CN101226329B

CN101226329B - Radiation sensitive resin composition, laminated insulating film, micro lens and preparation method thereof

Info

Publication number: CN101226329B
Application number: CN200810003519XA
Authority: CN
Inventors: 花村政晓; 内池千浩; 三谷浩司; 饭岛孝浩; 滨田谦一; 长屋胜也; 大泽友希
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2007-01-18
Filing date: 2008-01-18
Publication date: 2012-09-05
Anticipated expiration: 2028-01-18
Also published as: CN101226329A; JP4849251B2; JP2008176037A

Abstract

A radio-sensitized resin composition comprises a copolymer (A) of (a1), (a2) and (a3), 1,2-diazido quinone compound (B), and a siloxane oligomer (C) with functional group for performing cross linking reaction with the copolymer (A) by heat, wherein the (a1) is unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, the (a2) is unsaturated compound containing epoxy group and/or trimethylene oxide group, and the (a3) is unsaturated compound except the (a1) and (a2). The radio-sensitized resin composition with high rediation sensibility has development allowance for forming good pattern shape even though exceeding the optimal developing time during developing and can easily form pattern shaped film with excellent compliance.

Description

Radiation sensitive resin composition, interlayer dielectric and lenticule and their preparation method

Technical field

The present invention relates to radiation sensitive resin composition, interlayer dielectric and lenticule and their preparation method.

Background technology

In the electronic units such as thin film transistor (TFT) (below be designated as " TFT ") type liquid crystal display cells, magnetic head element, integrated circuit component, solid-state imager,, interlayer dielectric is set usually in order to insulate between the wiring that makes the stratiform configuration.As the material that forms interlayer dielectric; Because it is few and have the material of enough flatness to be preferably the process number that obtains necessary pattern form, radiation sensitive resin composition (opening 2001-354822 communique and Te Kai 2001-343743 communique with reference to the spy) therefore is widely used.

In the above-mentioned electronic unit; For example through on above-mentioned interlayer dielectric, forming ELD and then forming the operation of liquid crystal orientation film above that and make TFT type liquid crystal display cells; Therefore interlayer dielectric is exposed under the hot conditions in the formation operation of ELD; Or the pattern that is exposed to electrode form in the stripper of employed resist, so must enough patience be arranged to above-mentioned condition.

In recent years; For TFT type liquid crystal display cells; Trends such as big pictureization, high brightnessization, height become more meticulous, high-speed responsiveization, slimming are arranged; Therefore the composition that requires wherein to be used to form interlayer dielectric is high sensitive, and requires higher performance at aspects such as low-k, high-transmission rates for the interlayer dielectric that forms.

On the other hand; As the brilliant optical system material that carries the imaging optical system such as color filter or the joints of optical fibre such as facsimile recorder, electronic copier, solid-state imager, use to have the lenticule of the lens diameter about diameter 3～100 μ m or the microlens array that these lenticules are regularly arranged.

The method of formation lenticule or microlens array is known to be had: after forming the resist pattern corresponding to lens, make it melt flows through heat treated, the method for directly utilizing as lens thus; Shelter the lens pattern of melt flows, lens shape is transferred to the method for substrate etc. through dry ecthing.During the said lens pattern formed, radiation sensitive resin composition was widely used (opening flat 6-18702 communique and the flat 6-136239 communique of Te Kai with reference to the spy).

Form like the above-mentioned lenticule or the element of microlens array; Then it is supplied in following operation: form the various dielectric films on the pad partly in order to remove as wiring; Resist film is used in coating planarization film and etching; Make public, develop through desirable mask; Remove the etching of pad portion and use resist; Then remove planarization film or various dielectric film, the operation that pad is exposed through etching.Therefore, form in operation and the etching work procedure,, need solvent resistance or thermotolerance for lenticule and microlens array filming of planarization film and etching resist.

It is high sensitive being used to form so lenticular radiation sensitive resin composition, has desirable radius-of-curvature by its lenticule that forms, and requires high-fire resistance, high-transmission rate etc.

In addition; Interlayer dielectric that obtains like this or lenticule; In the developing procedure that forms at that time; Even development time only than the Best Times surplus a bit; Then developer solution infiltration between pattern and substrate; And peel off easily, therefore essential strict control development time is arranged, and aspect the yield rate of goods, have problems.

Like this; When forming interlayer dielectric or lenticule by radiation sensitive resin composition; Require high sensitive as composition; Even development time is superfluous than the stipulated time in the developing procedure in forming operation in addition; Peeling off of pattern not taken place and shows good stickiness yet; And require high-fire resistance for the interlayer dielectric that forms by it; High solvent resistance; Low-k; High-transmission rate etc.; On the other hand; When forming lenticule; Except as the lenticular good melt shape (desirable radius-of-curvature); Also require high-fire resistance; High solvent resistance; High-transmission rate, but the radiation sensitive resin composition that satisfies such requirement is ignorant in the past.

Summary of the invention

The present invention accomplishes in view of above situation.Therefore the object of the present invention is to provide radiation sensitive resin composition; It has high radiation-sensitive; And has a development surplus (margin) that is described below; Can easily form stickiness excellent pattern shape film, even said development surplus is meant that in developing procedure, surpassing optimum development time still can form good pattern form.

Another object of the present invention is to provide radiation sensitive resin composition; It can form the interlayer dielectric of high-fire resistance, high solvent resistance, high-transmission rate, low-k when the formation that is used for interlayer dielectric, when being used for lenticular form, can form the lenticule with high-transmission rate and good melt shape in addition.

Another object of the present invention is to provide and use above-mentioned radiation sensitive resin composition to form interlayer dielectric and lenticular method.

Another object of the present invention is to provide interlayer dielectric and the lenticule that forms through method of the present invention.

Further other purposes of the present invention and advantage are illustrated by following explanation.

According to the present invention, above-mentioned purpose of the present invention and advantage realize through following the 1st aspect,

Radiation sensitive resin composition is characterized in that, contains: (a1), (a2) and multipolymer (a3) [A], 1,2-two nitrine naphtoquinone compounds [B] and containing through the siloxane oligomer [C] of heat with the functional group of [A] composition cross-linking reaction,

Said (a1): unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides,

Said (a2): contain epoxy radicals and/or oxetanyl unsaturated compound and

Said (a3): be selected from alkyl methacrylate; Alkyl acrylate; The methacrylic acid cycloalkyl ester; Methacrylate with hydroxyl; The acrylic acid cycloalkyl ester; Aryl methacrylate; The acrylic acid aryl ester; The unsaturated dicarboxylic diester; Two ring unsaturated compounds; Maleimide compound; Unsaturated aromatics; Conjugated diolefine; Has the tetrahydrofuran skeleton; The furans skeleton; The oxinane skeleton; The unsaturated compound of the phenolic hydroxyl group that the unsaturated compound of the skeleton shown in pyrans skeleton or the following formula (3) and following formula (I) expression contain; With (a1) composition and (a2) different at least a other unsaturated compounds of composition

(in formula (3), R < > 7 <> Be hydrogen atom or methyl, n is the integer more than 1)

Wherein, R < > 1 <> The alkyl of expression hydrogen atom or carbon number 1～4, R < > 2 <>～R < > 6 <> Identical or different, be the alkyl of hydrogen atom, hydroxyl or carbon number 1～4, B be singly-bound ,-COO-or-CONH-, m is 0～3 integer, wherein, R < > 2 <>～R < > 6 <> At least one be hydroxyl.

Above-mentioned purpose of the present invention and advantage realize through following the 2nd aspect:

Interlayer dielectric or lenticular formation method is characterized in that, comprise following operation according to the order of the following stated:

(1) operation of filming of the above-mentioned radiation sensitive resin composition of formation on substrate,

(2) to the operation of this at least a portion of filming irradiation radioactive ray,

(3) developing procedure, and

(4) heating process.

Above-mentioned purpose of the present invention and advantage realize through following the 3rd aspect:

Interlayer dielectric or lenticule through said method formation.

The accompanying drawing summary

Fig. 1 is the mode chart of lenticule cross sectional shape.

Embodiment

Below the present invention is elaborated.

Multipolymer [A]

Multipolymer [A] can be through in solvent, under the existence of polymerization initiator, with compound (a1), compound (a2) and compound (a3) carry out the incompatible preparation of radical polymerization.Based on by compound (a1), (a2) and the (a3) total of repeat units derived, the multipolymer that uses among the present invention [A] preferably contains by compound (a1) structural unit 5～40 weight % that derive, preferred especially 5～25 weight %.If use the multipolymer of this structural unit less than 5 weight %, then in developing procedure, becoming is difficult to be dissolved in aqueous alkali, on the other hand, and the tendency that the multipolymer that surpasses 40 weight % exists the dissolubility to aqueous alkali to become excessive.

Compound (a1) be to have free-radical polymerised unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, can enumerate the acid anhydrides like monocarboxylic acid, dicarboxylic acid, dicarboxylic acid, single [(methyl of polybasic carboxylic acid) acryloxyalkyl] ester, two ends have list (methyl) acrylic ester of the polymkeric substance of carboxyl and hydroxyl, the polycyclic compund with carboxyl and its acid anhydrides etc.

As their concrete example, can enumerate respectively: as monocarboxylic acid, for example acrylic acid, methacrylic acid, crotonic acid etc.;

As dicarboxylic acid, for example maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid etc.;

As the acid anhydrides of dicarboxylic acid, for example as acid anhydrides of the compound of above-mentioned dicarboxylic acid example etc.;

Single [(methyl as polybasic carboxylic acid) acryloxyalkyl] ester, for example mono succinate [2-(methyl) the acryloxy ethyl] ester, phthalic acid list [2-(methyl) the acryloxy ethyl] ester etc.;

Have list (methyl) acrylic ester of the polymkeric substance of carboxyl and hydroxyl, for example ω-carboxyl polycaprolactone list (methyl) acrylic ester etc. as two ends.

As the polycyclic compund with carboxyl and its acid anhydrides; For example 5-carboxyl two encircles [2.2.1] hept-2-ene", 5; 6-dicarboxyl two ring [2.2.1] hept-2-ene", 5-carboxyl-5-methyl bicyclic [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl two ring [2.2.1] hept-2-ene", 5-carboxyl-6-methyl bicyclic [2.2.1] hept-2-ene", 5-carboxyl-6-ethyl two ring [2.2.1] hept-2-ene", 5,6-dicarboxyl two ring [2.2.1] the hept-2-ene" acid anhydrides etc.

Wherein, preferably use the acid anhydrides of monocarboxylic acid, dicarboxylic acid,, especially preferably use acrylic acid, methacrylic acid, maleic anhydride from copolyreaction property, for the dissolubility of aqueous alkali and the angle that obtains easily.These compounds (a1) can be used alone or in combination.

Based on by compound (a1), (a2) and the (a3) total of repeat units derived, the multipolymer that uses among the present invention [A] preferably contains by compound (a2) structural unit 10～80 weight % that derive, preferred especially 30～80 weight %.If this structural unit is during less than 10 weight %; There are the tendency that reduces in interlayer dielectric that then obtains or lenticular thermotolerance, skin hardness and stripper patience; On the other hand; When if this amount that constitutes the unit surpasses 80 weight %, then there is the tendency of the storage stability reduction of radiation sensitive resin composition.

Compound (a2) be to have the free-radical polymerised unsaturated compound that contains epoxy radicals and/or oxetanyl; Can enumerate for example glycidyl acrylate as the unsaturated compound that contains epoxy radicals; GMA; The α-Yi Jibingxisuan ethylene oxidic ester; α-n-pro-pyl glycidyl acrylate; α-normal-butyl glycidyl acrylate; Acrylic acid 3; 4-epoxy butyl ester; Methacrylic acid 3; 4-epoxy butyl ester; Acrylic acid 6; 7-epoxy heptyl ester; Methacrylic acid 6; 7-epoxy heptyl ester; α-Yi Jibingxisuan 6,7-epoxy heptyl ester; Adjacent vinyl benzyl glycidyl ether; Between the vinyl benzyl glycidyl ether; To vinyl benzyl glyceryl ether etc.Wherein, Preferably use GMA, methacrylic acid 6 from improving copolyreaction property with the interlayer dielectric or the lenticular thermotolerance that obtain, the angle that shows hardness; 7-epoxy heptyl ester, adjacent vinyl benzyl glycidyl ether, a vinyl benzyl glycidyl ether, to vinyl benzyl glycidyl ether, methacrylic acid 3,4-epoxycyclohexyl ester etc.Can enumerate respectively as the unsaturated compound that contains oxetanyl: 3-(acryloyl-oxy ylmethyl for example) oxetanes acryloyl-oxy ylmethyl)-2-methyl oxetanes acryloyl-oxy ylmethyl)-3-ethyl oxetanes acryloyl-oxy ylmethyl)-2-trifluoromethyl oxetanes acryloyl-oxy ylmethyl)-2-pentafluoroethyl group oxetanes acryloyl-oxy ylmethyl)-2-phenyl oxetanes acryloyl-oxy ylmethyl)-2; 2-difluoro oxetanes acryloyl-oxy ylmethyl)-2; 2; 4-trifluoro oxetanes acryloyl-oxy ylmethyl)-2; 4; 4-tetrafluoro oxetanes acryloxy ethyl) oxetanes acryloxy ethyl)-2-ethyl oxetanes acryloxy ethyl)-3-ethyl oxetanes acryloxy ethyl)-2-trifluoromethyl oxetanes acryloxy ethyl)-2-pentafluoroethyl group oxetanes acryloxy ethyl)-2-phenyl oxetanes acryloxy ethyl)-2; 2-difluoro oxetanes acryloxy ethyl)-2; 2; 4-trifluoro oxetanes acryloxy ethyl)-2, acrylic ester such as 4-tetrafluoro oxetanes;

3-(methacryloxy methyl) oxetanes methacryloxy methyl)-2-methyl oxetanes methacryloxy methyl)-3-ethyl oxetanes methacryloxy methyl)-2-trifluoromethyl oxetanes methacryloxy methyl)-2-pentafluoroethyl group oxetanes methacryloxy methyl)-2-phenyl oxetanes methacryloxy methyl)-2; 2-difluoro oxetanes methacryloxy methyl)-2; 2; 4-trifluoro oxetanes methacryloxy methyl)-2; 4; 4-tetrafluoro oxetanes methacryloxyethyl) oxetanes methacryloxyethyl)-2-ethyl oxetanes methacryloxyethyl)-3-ethyl oxetanes methacryloxyethyl)-2-trifluoromethyl oxetanes methacryloxyethyl)-2-pentafluoroethyl group oxetanes methacryloxyethyl)-2-phenyl oxetanes methacryloxyethyl)-2; 2-difluoro oxetanes methacryloxyethyl)-2; 2; 4-trifluoro oxetanes methacryloxyethyl)-2, methacrylates such as 4-tetrafluoro oxetanes.These compounds (a2) can be used alone or in combination.

Compound (a3) be and compound (a1), (a2) different have a free-radical polymerised unsaturated compound.Compound (a3) be alkyl methacrylate; Alkyl acrylate; The methacrylic acid cycloalkyl ester; Methacrylate with hydroxyl; The acrylic acid cycloalkyl ester; Aryl methacrylate; The acrylic acid aryl ester; The unsaturated dicarboxylic diester; Two ring unsaturated compounds; Maleimide compound; Unsaturated aromatics; Conjugated diolefine; Has the tetrahydrofuran skeleton; The furans skeleton; The oxinane skeleton; The unsaturated compound of the phenolic hydroxyl group that the unsaturated compound of the skeleton shown in pyrans skeleton or the following formula (3) or following formula (I) expression contain.

Concrete example as them can be enumerated respectively: as alkyl methacrylate, and the for example secondary butyl ester of methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, methacrylic acid, metering system tert-butyl acrylate, methacrylic acid 2-Octyl Nitrite, isodecyl methacrylate, the positive Lauryl Ester of methacrylic acid, methacrylic acid three decyl ester, the positive stearate of methacrylic acid etc.;

As alkyl acrylate, for example methyl acrylate, isopropyl acrylate etc.;

As the methacrylic acid cycloalkyl ester, for example cyclohexyl methacrylate, methacrylic acid 2-methyl cyclohexane ester, methacrylic acid three encircle [5.2.1.0 < > 2,6 <> ] decane-8-base ester, methacrylic acid three ring [5.2.1.0 < > 2,6 <> ] decane-8-base oxygen base ethyl ester, methacrylic acid isoborneol (ィソボロニ Le) ester etc.;

As methacrylate with hydroxyl; For example methacrylic acid hydroxymethyl ester, methacrylic acid 2-hydroxyethyl ester, methacrylic acid 3-hydroxy-propyl ester, methacrylic acid 4-hydroxybutyl ester, diglycol monotertiary methacrylate, methacrylic acid 2,3-dihydroxypropyl ester, 2-methacryloxyethyl glucoside, methacrylic acid 4-hydroxy phenyl ester etc.;

As the acrylic acid cycloalkyl ester, for example cyclohexyl acrylate, acrylic acid 2-methyl cyclohexane ester, acrylic acid three encircle [5.2.1.0 < > 2,6 <> ] decane-8-base ester, acrylic acid three ring [5.2.1.0 < > 2,6 <> ] decane-8-base oxygen base ethyl ester, IBOA etc.;

As aryl methacrylate, for example phenyl methacrylate, benzyl methacrylate etc.;

As acrylic acid aryl ester, for example phenyl acrylate, benzyl acrylate etc.;

As the unsaturated dicarboxylic diester, for example diethyl maleate, DEF, diethyl itaconate etc.;

As two ring unsaturated compounds; For example two encircle [2.2.1] hept-2-ene"; 5-methyl bicyclic [2.2.1] hept-2-ene"; 5-ethyl two ring [2.2.1] hept-2-ene"; 5-methoxyl two ring [2.2.1] hept-2-ene"; 5-ethoxy two ring [2.2.1] hept-2-ene"; 5; 6-dimethoxy two ring [2.2.1] hept-2-ene"; 5; 6-diethoxy two ring [2.2.1] hept-2-ene"; 5-tert-butoxycarbonyl two ring [2.2.1] hept-2-ene"; 5-cyclohexyl oxygen base carbonyl two ring [2.2.1] hept-2-ene"; 5-phenyloxycarbonyl two ring [2.2.1] hept-2-ene"; 5; 6-two (tert-butoxycarbonyl) two ring [2.2.1] hept-2-ene"; 5; 6-two (cyclohexyl oxygen base carbonyl) two ring [2.2.1] hept-2-ene"; 5-(2 '-hydroxyethyl) two ring [2.2.1] hept-2-ene"; 5; 6-dihydroxy two ring [2.2.1] hept-2-ene"; 5; 6-two (hydroxymethyl) two ring [2.2.1] hept-2-ene", 6-two (2 '-hydroxyethyl) two ring [2.2.1] hept-2-ene"; 5-hydroxy-5-methyl base two ring [2.2.1] hept-2-ene"; 5-hydroxyl-5-ethyl two ring [2.2.1] hept-2-ene"; 5-hydroxymethyl-5-methyl bicyclic [2.2.1] hept-2-ene" etc.;

As maleimide compound, for example N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-(4-hydroxy phenyl) maleimide, N-(4-hydroxybenzyl) maleimide, N-succinimido-3-maleimide benzoate, N-succinimido-4-maleimide butyrate, N-succinimido-6-maleimide caproate, N-succinimido-3-maleimide propionate, N-(9-acridinyl) maleimide etc.;

As unsaturated aromatics, for example styrene, AMS, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxy styrene etc.;

As conjugated diolefine, for example 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene etc.;

As the unsaturated compound that contains the tetrahydrofuran skeleton, for example (methyl) acrylic acid tetrahydro furfuryl ester, 2-methacryloxy-propionic acid tetrahydro furfuryl ester, 3-(methyl) acryloxy tetrahydrofuran-2-ketone etc.;

As the unsaturated compound that contains the furans skeleton, for example 2-methyl-5-(3-furyl)-1-penten-3-one, (methyl) acrylic acid furfuryl group ester, 1-furans-2-butyl-3-alkene-2-ketone, 1-furans-2-butyl-3-methoxyl-3-alkene-2-ketone, 6-(2-furyl)-2-methyl-1-hexene-3-one, 6-furans-2-base-oneself-1-alkene-3-ketone, acrylic acid 2-furans-2-base-1-methyl ethyl ester, 6-(2-furyl)-6-methyl-1-heptene-3-ketone etc.;

As the unsaturated compound that contains the oxinane skeleton; Methacrylic acid (oxinane-2-yl) methyl esters, 2 for example, 6-dimethyl-8-(oxinane-2-base oxygen base)-suffering-1-alkene-3-ketone, 2-methacrylic acid oxinane-2-base ester, 1-(oxinane-2-oxygen base)-butyl-3-alkene-2-ketone etc.;

As the unsaturated compound that contains the pyrans skeleton, 4-(1 for example, 4-dioxa-5-oxo-6-heptenyl)-6-methyl-2-pyrone, 4-(1,5-dioxa-6-oxo-7-octenyl)-6-methyl-2-pyrone etc.;

As the unsaturated compound that contains the skeleton shown in the above-mentioned formula (3), for example polyglycol (n=2～10) single (methyl) acrylic ester, polypropylene glycol (n=2～10) single (methyl) acrylic ester etc.;

As the unsaturated compound that contains the phenol skeleton, in the compound shown in the above-mentioned formula (I),, the compound shown in following formula (4)～(8) etc. is arranged through definition B and m;

(in the formula (4), n is 1 to 3 integer, R < > 1 <> , R < > 2 <> , R < > 3 <> , R < > 4 <> , R < > 5 <> And R < > 6 <> Definition identical with above-mentioned formula (I).)

(in the formula (5), R < > 1 <> , R < > 2 <> , R < > 3 <> , R < > 4 <> , R < > 5 <> And R < > 6 <> Definition identical with above-mentioned formula (I).)

(in the formula (6), n is 1 to 3 integer.R < > 1 <> , R < > 2 <> , R < > 3 <> , R < > 4 <> , R < > 5 <> And R < > 6 <> Definition identical with above-mentioned formula (I).)

(in the formula (7), R < > 1 <> , R < > 2 <> , R < > 3 <> , R < > 4 <> , R < > 5 <> And R < > 6 <> Definition identical with above-mentioned formula (I).)

(in the formula (8), R < > 1 <> , R < > 2 <> , R < > 3 <> , R < > 4 <> , R < > 5 <> And R < > 6 <> Definition identical with above-mentioned formula (I).)

As other unsaturated compounds, for example vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylic amide, Methacrylamide, vinyl acetate.

The unsaturated compound that contains phenolic hydroxyl group shown in preferred use alkyl methacrylate, methacrylic acid cycloalkyl ester, maleimide compound, tetrahydrofuran skeleton, furans skeleton, oxinane skeleton, pyrans skeleton, unsaturated compound, the following formula (1) among them with the skeleton shown in the above-mentioned formula (3); Consider special optimization styrene, methacrylic acid tertiary butyl ester, methacrylic acid three ring [5.2.1.0 from copolyreaction property and to the dissolubility aspect of aqueous alkali < > 2,6 <> ] decane-8-base ester, to methoxy styrene, acrylic acid 2-methyl cyclohexane ester, N-phenylmaleimide, N-cyclohexyl maleimide, (methyl) acrylic acid tetrahydro furfuryl ester, polyglycol (n=2～10) single (methyl) acrylic ester, 3-(methyl) acryloxy tetrahydrofuran-2-ketone, (methyl) acrylic acid 4-hydroxybenzyl ester, (methyl) acrylic acid 4-hydroxy phenyl ester, o-hydroxy ethene, para hydroxybenzene ethene, Alpha-Methyl para hydroxybenzene ethene.These cyclisation things (a3) can use or make up use separately.

For example can enumerate methacrylic acid/methacrylic acid three ring [5.2.1.0 as the preferred object lesson of the multipolymer that uses among the present invention [A] < > 2,6 <> ] decane-8-base ester/acrylic acid 2-methyl cyclohexane ester/GMA/N-(3,5-dimethyl-4-hydroxybenzyl) Methacrylamide, methacrylic acid/methacrylic acid tetrahydro furfuryl ester/GMA/N-cyclohexyl maleimide/methacrylic acid Lauryl Ester/Alpha-Methyl para hydroxybenzene ethene, styrene/methacrylic acid/GMA/methacrylic acid (3-ethyl oxetanes-3-yl) ester/methacrylic acid three encircle [5.2.1.0 < > 2,6 <> ] decane-8-base ester.

The polystyrene conversion weight-average molecular weight of the multipolymer that uses among the present invention [A] (below be called " Mw ") is preferably 2 * 10 < > 3 <>～1 * 10 < > 5 <> , more preferably 5 * 10 < > 3 <>～5 * 10 < > 4 <> Mw is less than 2 * 10 < > 3 <> , development surplus become reduction or interlayer dielectric that obtains or variation such as lenticular pattern form, thermotolerance such as inadequate situation, the residual film ratio of the tunicle that obtains are then arranged, on the other hand, surpass 1 * 10 < > 5 <> , then susceptibility reduction, pattern form variation.Molecular weight distribution (below be called " Mw/Mn ") is preferred below 5.0, more preferably below 3.0.Mw/Mn surpasses 5.0, interlayer dielectric that then obtains or lenticular pattern form variation.The radiation sensitive resin composition that contains above-mentioned multipolymer [A] can not produce when developing and develop residually, can form the pattern of regulation shape easy as can.

As the solvent that in the preparation of multipolymer [A], uses, can enumerate like alcohol, ether, glycol ether, monoethylene glycol alkyl ether acetic acid esters, diglycol ether, propylene-glycol monoalky lether, propylene glycol alkyl ether acetic acid ester, propylene glycol alkyl ether propionic ester, aromatic hydrocarbons, ketone, ester etc.

As their object lesson, can enumerate respectively:

As alcohol, for example methyl alcohol, ethanol, benzylalcohol, 2-phenylethanol, 3-phenyl-1-propyl alcohol etc.;

As ether, tetrahydrofuran etc. for example;

As glycol ether, for example glycol monoethyl ether, ethylene glycol monoethyl ether etc.;

As monoethylene glycol alkyl ether acetic acid esters, for example methylcellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetic acid esters, ethylene glycol monomethyl ether acetate etc.;

As diglycol, for example diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethyl carbitol, diglycol ethyl-methyl ether etc.;

As propylene-glycol monoalky lether, for example propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether etc.;

As propylene glycol alkyl ether propionic ester, for example methyl proxitol propionic ester, propylene glycol ethylether propionic ester, propylene glycol propyl ether propionic ester, propylene glycol butyl ether propionic ester etc.;

As propylene glycol alkyl ether acetic acid ester, for example methyl proxitol acetate, propylene glycol ethylether acetic acid esters, propylene glycol propyl ether acetic acid esters, propylene glycol butyl ether acetic acid esters etc.;

As aromatic hydrocarbons, for example toluene, xylene etc.;

As ketone, for example MEK, cyclohexanone, 4-hydroxy-4-methyl-2 pentanone etc.;

As ester, methyl acetate for example; Ethyl acetate; Propyl acetate; Butyl acetate; The 2 hydroxy propanoic acid ethyl ester; 2-hydroxy-2-methyl methyl propionate; 2-hydroxy-2-methyl ethyl propionate; Hydroxy methyl acetate; Hydroxyl ethyl acetate; The glycolic acid butyl ester; Methyl lactate; Ethyl lactate; Propyl lactate; Butyl lactate; The 3-hydroxy methyl propionate; 3-hydracrylic acid ethyl ester; 3-hydracrylic acid propyl ester; 3-hydracrylic acid butyl ester; 2-hydroxy-3-methyl methyl butyrate; Methoxy menthyl acetate; The methoxyacetic acid ethyl ester; The methoxyacetic acid propyl ester; The methoxyacetic acid butyl ester; Ethoxy acetate; Ethoxy ethyl acetate; The ethoxyacetic acid propyl ester; The ethoxyacetic acid butyl ester; The propoxyl group methyl acetate; Propoxyl group ethyl acetate; The propoxyl group propyl acetate; The propoxyl group butyl acetate; The butoxy acetic acid methyl esters; The butoxy acetic acid ethyl ester; The butoxy acetic acid propyl ester; The butoxy acetic acid butyl ester; 2-methoxypropionic acid methyl esters; 2-methoxy propyl acetoacetic ester; 2-methoxy propyl propyl propionate; 2-methoxy propyl acid butyl ester; 2-ethoxy-propionic acid methyl esters; The 2-ethoxyl ethyl propionate; 2-ethoxy-c propyl propionate; 2-ethoxy-c acid butyl ester; 2-butoxy methyl propionate; 2-butoxy ethyl propionate; 2-butoxy propyl propionate; 2-butoxy butyl propionate; 3-methoxypropionic acid methyl esters; 3-methoxy propyl acetoacetic ester; 3-methoxy propyl propyl propionate; 3-methoxy propyl acid butyl ester; 3-ethoxy-propionic acid methyl esters; The 3-ethoxyl ethyl propionate; 3-ethoxy-c propyl propionate; 3-ethoxy-c acid butyl ester; 3-propoxyl group methyl propionate; 3-propoxyl group ethyl propionate; 3-propoxyl group propyl propionate; 3-propoxyl group butyl propionate; 3-butoxy methyl propionate; 3-butoxy ethyl propionate; 3-butoxy propyl propionate; Esters such as 3-butoxy butyl propionate.

Among them; Preferred monoethylene glycol alkyl ether acetic acid esters, diglycol, propylene-glycol monoalky lether, propylene glycol alkyl ether acetic acid ester etc., preferred especially diethylene glycol dimethyl ether, diglycol ethyl-methyl ether, methyl proxitol, propylene glycol ethylether, methyl proxitol acetate, 3-methoxypropionic acid methyl esters.

As the polymerization initiator that in the preparation of multipolymer [A], uses, can use known radical polymerization initiator usually.Can enumerate as 22 '-azoisobutyronitrile, 2,2 '-azo, two (2,4-methyl pentane nitrile), 2,2 '-azo two azo-compounds such as (4-methoxyl-2,4-methyl pentane nitriles); Benzoyl peroxide, lauroyl peroxide, the peroxidating valeric acid tert-butyl ester, 1,1 '-two-(tert-butyl peroxides) organic peroxide such as cyclohexane; With hydrogen peroxide etc.When using superoxide, also can use superoxide to be used as the oxidation-reduction type initiating agent with reductive agent as radical polymerization initiator.

In the preparation of multipolymer [A],, can use molecular weight regulator in order to regulate molecular weight.As its object lesson, can enumerate halogenated hydrocarbons such as chloroform, carbon tetrabromide; Mercaptan such as positive hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, uncle's lauryl mercaptan, TGA; Xanthates such as two (methyl yellow ortho esters) sulfide, two (isopropyl xanthan acid esters) disulfide; Terpinolene, AMS dimer etc.

[B] composition

[B] composition that uses among the present invention is that the irradiation through radioactive ray produces 1 of carboxylic acid, and 2-two nitrine naphtoquinone compounds can use phenoloid or alcohol property compound (below be called " parent nucleus ") and 1, the condensation product of 2-diazido naphthoquinone sulfonic acid halide.

As above-mentioned parent nucleus, can enumerate like trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxy benzophenone, (polyhydroxy phenyl) alkane, other parent nucleus.

As their object lesson, can enumerate, as trihydroxybenzophenone, for example 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone etc.;

As tetrahydroxybenzophenone, for example 2,2 ', 4,4 '-tetrahydroxybenzophenone, 2,3,3 '-tetrahydroxybenzophenone, 2,3,4,4 '-tetrahydroxybenzophenone, 2,3,2 '-tetrahydroxy-4 '-methyldiphenyl ketone, 2,3,4,4 '-tetrahydroxy-3 '-methoxy benzophenone etc.;

As pentahydroxybenzophenone, for example 2,3,4,2 ', 6 '-pentahydroxybenzophenone etc.;

As the hexahydroxy benzophenone, for example 2,4,6,3 ', 4 ', 5 '-hexahydroxy benzophenone, 3,4,5,3 ', 4 ', 5 '-hexahydroxy benzophenone etc.;

As (polyhydroxy phenyl) alkane, for example two (2,4-dihydroxy phenyl) methane; Two (p-hydroxybenzene) methane; Three (p-hydroxybenzene) methane, 1-three (p-hydroxybenzene) ethane; Two (2,3; 4-trihydroxy phenyl) methane, the two (2 of 2-, 3; 4-trihydroxy phenyl) propane, 3-three (2,5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane '-[1-[4-[1-[4-hydroxy phenyl Methylethyl] phenyl] ethylidene] bis-phenol; Two (2; 5-dimethyl-4-hydroxy phenyl)-2-hydroxy phenyl methane, 3,3 ' 3 '-tetramethyl,-1 '-spirobindene-5, pure of 7,5 ' ' '-six, 2,4-trimethyl-7 ', 4 '-trihydroxy flavane etc.;

As other parent nucleus; 2-methyl-2-(2 for example; The two {(5-isopropyls of 4-dihydroxy phenyl)-4-(4-hydroxy phenyl)-7-hydroxychroman, 2-[-4-hydroxy-2-methyl) phenyl } methyl], 1-[1-(3-{1-(4-hydroxy phenyl)-1-Methylethyl }-4; 6-dihydroxy phenyl)-1-Methylethyl hydroxy phenyl)-1-Methylethyl }-4; 6-dihydroxy phenyl)-1-Methylethyl) benzene, 4; The two {1-(4-hydroxy phenyl)-1-Methylethyls of 6-}-1, the 3-dihydroxy benzenes.

Also preferably use ester bond to become 1 of amido link, 2-two azido benzoquinone sulfonamide, for example 2,3,4-trihydroxybenzophenone-1,2-diazido naphthoquinone-4-sulfonamide etc. with above-mentioned illustrative parent nucleus.

In these parent nucleus, preferred 2,3,4,4 '-tetrahydroxybenzophenone, 4,4 '-[1-[4-[1-[4-hydroxy phenyl Methylethyl] phenyl] ethylidene] bis-phenol.

As 1,2-diazido naphthoquinone sulfonic acid halide, preferred 1,2-diazido naphthoquinone sulfonic acid chloride, its object lesson can enumerate 1,2-diazido naphthoquinone-4-sulfonic acid chloride and 1,2-diazido naphthoquinone-5-sulfonic acid chloride wherein, preferably uses 1,2-diazido naphthoquinone-5-sulfonic acid chloride.

In condensation reaction, with respect to the OH group number in phenoloid or the alcohol property compound, can preferably use be equivalent to 30～85 moles of %, more preferably 50～70 moles of % 1,2-diazido naphthoquinone sulfonic acid halide.

Condensation reaction can be implemented through known method.

These [B] compositions can use or make up two or more uses separately.

The usage ratio of [B] composition is with respect to multipolymer [A weight portion, preferred 5～100 weight portions, more preferably 10～50 weight portions.This ratio is during less than 5 weight portions; For little as the difference of the radiation exposure part of the aqueous alkali of developer solution and the solubleness of illuminated portion not; Have to form the pattern situation of difficult that becomes, the interlayer dielectric that obtains or the situation of lenticular thermotolerance and solvent resistance deficiency are arranged.On the other hand, when this ratio surpasses 100 weight portions, in the radio exposure part, the solubleness of above-mentioned aqueous alkali is become not enough, the development situation of difficult is arranged.

[C] composition

[C] composition that uses among the present invention is to have the siloxane oligomer that carries out the functional group of cross-linking reaction with above-mentioned [A] composition through heat; Can enumerate; The siloxane oligomer of the alkoxy silane cohydrolysis of preferably following formula (1) and following formula (2) being represented respectively and the siloxane oligomer for preparing (below be called siloxane oligomer I) or following formula (9) expression, be the condensation product (below, be called siloxane oligomer II) of silicic acid oxetanyl ester.

Si(R ⁸) _s(R ⁹) _t(OR ¹⁰) _u (1)

Wherein, R < > 8 <> Expression contains the substituting group of epoxy radicals, oxetanyl, epithio base, vinyl, allyl, (methyl) acryloyl group, carboxyl, hydroxyl, sulfydryl, NCO, amino, urea groups or styryl, R < > 9 <> , R < > 10 <> Can be the same or different, be respectively hydrogen atom or 1 valency organic group, s is 1～3 integer, and t is 0～2 integer, and u is 1～3 integer.Wherein, s+t+u=4.

Si(R ¹¹) _x(OR ¹²) _4-x (2)

R < > 11 <> , R < > 12 <> Can be the same or different, be respectively 1 valency organic group, x is 0～2 integer.

For above-mentioned cohydrolysis thing, being construed as a product and the one of which partial hydrolysis part that whole hydrolysis of also comprising in the raw material part that can hydrolysis obtain does not have hydrolysis and residual product.

Object lesson as the compound that contains epoxy radicals (1); Can enumerate 3-glycidoxy MTMS; 3-glycidoxy MTES; 3-glycidoxy methyl three positive propoxy silane; 3-glycidoxy methyl three isopropoxy silane; 3-glycidoxy methyl triacetic acid base silane; 3-glycidoxy methyl dimethoxy silane; 3-glycidoxy methyl diethoxy silane; 3-glycidoxy methyl two positive propoxy silane; 3-glycidoxy methyl diisopropoxy silane; 3-glycidoxy methyl diacetoxyl silane; 3-glycidoxy Methylethyl dimethoxy silane; 3-glycidoxy Methylethyl diethoxy silane; 3-glycidoxy Methylethyl two positive propoxy silane; 3-glycidoxy Methylethyl diisopropoxy silane; 3-glycidoxy Methylethyl diacetoxyl silane; 3-glycidoxy aminomethyl phenyl dimethoxy silane; 3-glycidoxy aminomethyl phenyl diethoxy silane; 3-glycidoxy aminomethyl phenyl two positive propoxy silane; 3-glycidoxy aminomethyl phenyl diisopropoxy silane; 3-glycidoxy aminomethyl phenyl diacetoxyl silane; 3-glycidoxy ethyl trimethoxy silane; 3-glycidoxy ethyl triethoxysilane; 3-glycidoxy ethyl three positive propoxy silane; 3-glycidoxy ethyl three isopropoxy silane; 3-glycidoxy ethyl triacetic acid base silane; 3-glycidoxy ethyl-methyl dimethoxy silane; 3-glycidoxy ethyl-methyl diethoxy silane; 3-glycidoxy ethyl-methyl two positive propoxy silane; 3-glycidoxy ethyl-methyl diisopropoxy silane; 3-glycidoxy ethyl-methyl diacetoxyl silane; 3-glycidoxy ethyl diethyldithiocarbamate dimethoxy silane; 3-glycidoxy ethyl diethyldithiocarbamate diethoxy silane; 3-glycidoxy ethyl diethyldithiocarbamate two positive propoxy silane; 3-glycidoxy ethyl diethyldithiocarbamate diisopropoxy silane; 3-glycidoxy ethyl diethyldithiocarbamate diacetoxyl silane; 3-glycidoxy ethylphenyl dimethoxy silane; 3-glycidoxy ethylphenyl diethoxy silane; 3-glycidoxy ethylphenyl two positive propoxy silane; 3-glycidoxy ethylphenyl diisopropoxy silane; 3-glycidoxy ethylphenyl diacetoxyl silane; The 3-glycidoxypropyltrime,hoxysilane; 3-glycidoxy propyl-triethoxysilicane; 3-glycidoxy propyl group three positive propoxy silane; 3-glycidoxy propyl group three isopropoxy silane; 3-glycidoxy propyl group triacetic acid base silane; 3-glycidoxy propyl group methyl dimethoxysilane; 3-glycidoxy propyl group methyldiethoxysilane; 3-glycidoxy propyl group methyl two positive propoxy silane; 3-glycidoxy propyl group methyl diisopropoxy silane; 3-glycidoxy propyl group methyl diacetoxyl silane; 3-glycidoxy propyl group ethyl dimethoxy silane; 3-glycidoxy propyl group ethyl diethoxy silane; 3-glycidoxy propyl group ethyl two positive propoxy silane; 3-glycidoxy propyl group ethyl diisopropoxy silane; 3-glycidoxy propyl group ethyl diacetoxyl silane; 3-glycidoxy propyl group phenyl dimethoxy silane; 3-glycidoxy propyl group phenyl diethoxy silane; 3-glycidoxy propyl group phenyl two positive propoxy silane; 3-glycidoxy propyl group phenyl diisopropoxy silane; 3-glycidoxy propyl group phenyl diacetoxyl silane; The 4-epoxycyclohexyl) MTMS; The 4-epoxycyclohexyl) MTES; The 4-epoxycyclohexyl) methyl three positive propoxy silane; The 4-epoxycyclohexyl) methyl triacetic acid base silane; The 4-epoxycyclohexyl) methyl dimethoxy silane; The 4-epoxycyclohexyl) methyl diethoxy silane; The 4-epoxycyclohexyl) methyl two positive propoxy silane; The 4-epoxycyclohexyl) methyl diacetoxyl silane; The 4-epoxycyclohexyl) Methylethyl dimethoxy silane; The 4-epoxycyclohexyl) Methylethyl diethoxy silane; The 4-epoxycyclohexyl) Methylethyl two positive propoxy silane; The 4-epoxycyclohexyl) Methylethyl diacetoxyl silane; The 4-epoxycyclohexyl) aminomethyl phenyl dimethoxy silane; The 4-epoxycyclohexyl) aminomethyl phenyl diethoxy silane; The 4-epoxycyclohexyl) aminomethyl phenyl two positive propoxy silane; The 4-epoxycyclohexyl) aminomethyl phenyl diacetoxyl silane; The 4-epoxycyclohexyl) ethyl trimethoxy silane; The 4-epoxycyclohexyl) ethyl triethoxysilane; The 4-epoxycyclohexyl) ethyl three positive propoxy silane; The 4-epoxycyclohexyl) ethyl triacetic acid base silane; The 4-epoxycyclohexyl) ethyl-methyl dimethoxy silane; The 4-epoxycyclohexyl) ethyl-methyl diethoxy silane; The 4-epoxycyclohexyl) ethyl-methyl two positive propoxy silane; The 4-epoxycyclohexyl) ethyl-methyl diacetoxyl silane; The 4-epoxycyclohexyl) ethyl diethyldithiocarbamate dimethoxy silane; The 4-epoxycyclohexyl) ethyl diethyldithiocarbamate diethoxy silane; The 4-epoxycyclohexyl) ethyl diethyldithiocarbamate two positive propoxy silane; The 4-epoxycyclohexyl) ethyl diethyldithiocarbamate diacetoxyl silane; The 4-epoxycyclohexyl) ethylphenyl dimethoxy silane; The 4-epoxycyclohexyl) ethylphenyl diethoxy silane; The 4-epoxycyclohexyl) ethylphenyl two positive propoxy silane; The 4-epoxycyclohexyl) ethylphenyl diacetoxyl silane; The 4-epoxycyclohexyl) propyl trimethoxy silicane; The 4-epoxycyclohexyl) propyl-triethoxysilicane; The 4-epoxycyclohexyl) propyl group three positive propoxy silane; The 4-epoxycyclohexyl) propyl group triacetic acid base silane; The 4-epoxycyclohexyl) propyl group methyl dimethoxysilane; The 4-epoxycyclohexyl) propyl group methyldiethoxysilane; The 4-epoxycyclohexyl) propyl group methyl two positive propoxy silane; The 4-epoxycyclohexyl) propyl group methyl diacetoxyl silane; The 4-epoxycyclohexyl) propyl group ethyl dimethoxy silane; The 4-epoxycyclohexyl) propyl group ethyl diethoxy silane; The 4-epoxycyclohexyl) propyl group ethyl two positive propoxy silane; The 4-epoxycyclohexyl) propyl group ethyl diacetoxyl silane; The 4-epoxycyclohexyl) propyl group phenyl dimethoxy silane; The 4-epoxycyclohexyl) propyl group phenyl diethoxy silane; The 4-epoxycyclohexyl) propyl group phenyl two positive propoxy silane; 2-(3, the 4-epoxycyclohexyl) propyl group phenyl diacetoxyl silane etc.;

Object lesson as the compound that contains the epithio base (1); Can enumerate 2; 3-epithio propoxyl group MTMS; 2; 3-epithio propoxyl group MTES; 2; 3-epithio propoxyl group methyl three positive propoxy silane; 2; 3-epithio propoxyl group methyl three isopropoxy silane; 2; 3-epithio propoxyl group methyl triacetic acid base silane; 2; 3-epithio propoxyl group methyl dimethoxy silane; 2; 3-epithio propoxyl group methyl diethoxy silane; 2; 3-epithio propoxyl group methyl two positive propoxy silane; 2; 3-epithio propoxyl group methyl diisopropoxy silane; 2; 3-epithio propoxyl group methyl diacetoxyl silane; 2; 3-epithio propoxyl group Methylethyl dimethoxy silane; 2; 3-epithio propoxyl group Methylethyl diethoxy silane; 2; 3-epithio propoxyl group Methylethyl two positive propoxy silane; 2; 3-epithio propoxyl group Methylethyl diisopropoxy silane; 2; 3-epithio propoxyl group Methylethyl diacetoxyl silane; 2; 3-epithio propoxyl group aminomethyl phenyl dimethoxy silane; 2; 3-epithio propoxyl group aminomethyl phenyl diethoxy silane; 2; 3-epithio propoxyl group aminomethyl phenyl two positive propoxy silane; 2; 3-epithio propoxyl group aminomethyl phenyl diisopropoxy silane; 2; 3-epithio propoxyl group aminomethyl phenyl diacetoxyl silane; 2; 3-epithio propoxyl group ethyl trimethoxy silane; 2; 3-epithio propoxyl group ethyl triethoxysilane; 2; 3-epithio propoxyl group ethyl three positive propoxy silane; 2; 3-epithio propoxyl group ethyl three isopropoxy silane; 2; 3-epithio propoxyl group ethyl triacetic acid base silane; 2; 3-epithio propoxyl group ethyl-methyl dimethoxy silane; 2; 3-epithio propoxyl group ethyl-methyl diethoxy silane; 2; 3-epithio propoxyl group ethyl-methyl two positive propoxy silane; 2; 3-epithio propoxyl group ethyl-methyl diisopropoxy silane; 2; 3-epithio propoxyl group ethyl-methyl diacetoxyl silane; 2; 3-epithio propoxyl group ethyl diethyldithiocarbamate dimethoxy silane; 2; 3-epithio propoxyl group ethyl diethyldithiocarbamate diethoxy silane; 2; 3-epithio propoxyl group ethyl diethyldithiocarbamate two positive propoxy silane; 2; 3-epithio propoxyl group ethyl diethyldithiocarbamate diisopropoxy silane; 2; 3-epithio propoxyl group ethyl diethyldithiocarbamate diacetoxyl silane; 2; 3-epithio propoxyl group ethylphenyl dimethoxy silane; 2; 3-epithio propoxyl group ethylphenyl diethoxy silane; 2; 3-epithio propoxyl group ethylphenyl two positive propoxy silane, 3-epithio propoxyl group ethylphenyl diisopropoxy silane, 3-epithio propoxyl group ethylphenyl diacetoxyl silane; 2; 3-epithio propoxyl group propyl trimethoxy silicane; 2; 3-epithio propoxyl group propyl-triethoxysilicane, 3-epithio propoxyl group propyl group three positive propoxy silane, 3-epithio propoxyl group propyl group three isopropoxy silane; 2; 3-epithio propoxyl group propyl group triacetic acid base silane; 2; 3-epithio propoxyl group propyl group methyl dimethoxysilane, 3-epithio propoxyl group propyl group methyldiethoxysilane, 3-epithio propoxyl group propyl group methyl two positive propoxy silane; 2; 3-epithio propoxyl group propyl group methyl diisopropoxy silane; 2; 3-epithio propoxyl group propyl group methyl diacetoxyl silane, 3-epithio propoxyl group propyl group ethyl dimethoxy silane, 3-epithio propoxyl group propyl group ethyl diethoxy silane; 2; 3-epithio propoxyl group propyl group ethyl two positive propoxy silane; 2; 3-epithio propoxyl group propyl group ethyl diisopropoxy silane, 3-epithio propoxyl group propyl group ethyl diacetoxyl silane, 3-epithio propoxyl group propyl group phenyl dimethoxy silane; 2; 3-epithio propoxyl group propyl group phenyl diethoxy silane; 2; 3-epithio propoxyl group propyl group phenyl two positive propoxy silane, 3-epithio propoxyl group propyl group phenyl diisopropoxy silane, 3-epithio propoxyl group propyl group phenyl diacetoxyl silane etc.;

As the object lesson of the compound that contains vinyl (1), can enumerate vinyltrimethoxy silane; VTES; Vinyl three positive propoxy silane; Vinyl silane triisopropoxide; Vinyl triacetic acid base silane; Vinyl three (methoxy ethoxy) silane; The vinyl methyl dimethoxysilane; The vinyl methyldiethoxysilane; Vinyl methyl two positive propoxy silane; Vinyl methyl diisopropoxy silane; Vinyl methyl diacetoxyl silane; Vinyl ethyl dimethoxy silane; Vinyl ethyl diethoxy silane; Vinyl ethyl two positive propoxy silane; Vinyl ethyl diisopropoxy silane; Vinyl ethyl diacetoxyl silane; Vinyl ethyl two (methoxy ethoxy) silane; Ethenylphenyl dimethoxy silane; The ethenylphenyl diethoxy silane; Ethenylphenyl two positive propoxy silane; Ethenylphenyl diisopropoxy silane; Ethenylphenyl diacetoxyl silane; Ethenylphenyl two (methoxy ethoxy) silane etc.;

As the object lesson that contains allylic compound (1), can enumerate allyltrimethoxysilanis; Allyltriethoxysilane; Allyl three positive propoxy silane; Allyl three isopropoxy silane; Allyl triacetic acid base silane; Allyl three (methoxy ethoxy) silane; Allyl methyl dimethoxy silane; The allyl methyl diethoxy silane; Allyl methyl two positive propoxy silane; Allyl methyl diisopropoxy silane; Allyl methyl diacetoxyl silane; Allyl ethyl dimethoxy silane; Allyl ethyl diethoxy silane; Allyl ethyl two positive propoxy silane; Allyl ethyl diisopropoxy silane; Allyl ethyl diacetoxyl silane; Allyl ethyl two (methoxy ethoxy) silane; Allyl phenyl dimethoxy silane; The allyl phenyl diethoxy silane; Allyl phenyl two positive propoxy silane; Allyl phenyl diisopropoxy silane; Allyl phenyl diacetoxyl silane; Allyl phenyl two (methoxy ethoxy) silane etc.;

Comprising the (meth) acryloyl group of the compound (1) Specific examples include 3 - (meth) acryloyloxy methyl trimethoxy silane, 3 - (meth) acryloyloxy methyltriethoxysilane ethoxy silane, 3 - (meth) acryloyloxy propyl methyl tri-silane, 3 - (meth) acryloyloxy methyl triisopropoxysilane, 3 - (meth) acrylic acyloxymethyl triacetoxy silane, 3 - (meth) acryloyloxy-methyl dimethoxy silane, 3 - (meth) acryloyloxy-methyl diethoxy silane, 3 - (meth) acryloyloxy-methyl di-n-propoxy silane, 3 - (meth) acryloyloxy diisopropyl methyl silane, 3 - (meth) acrylic acid alkoxy methyl diacetoxy-silane, 3 - (meth) acryloyloxy ethyl methyl dimethoxy silane, 3 - (meth) acryloyloxy ethyl methyl diethoxy silane 3 - (meth) acryloyloxy ethyl methyl di-n-propoxy silane, 3 - (meth) acryloyloxy ethyl diisopropyl methyl silane, 3 - (meth) acrylic acyloxy-methylethyl diacetoxy-silane, 3 - (meth) acryloyloxy-phenyl dimethoxy silane, 3 - (meth) acryloxy diethoxy-methylphenyl silane, 3 - (meth) acryloyloxy-phenyl di-n-propoxy silane, 3 - (meth) acryloyloxy-diisopropyl-phenyl silane, 3 - (meth) acryloyloxymethyl phenyl diacetoxy-silane, 3 - (meth) acryloyl-oxyethyl trimethoxysilane, 3 - (meth) acryloyloxy ethyl triethoxysilane, 3 - (meth) acryloyloxyethyl tri-n-propoxy silane, 3 - (meth) acryloyloxy ethyl triisopropoxysilane, 3 - (meth) acryloyloxy ethyltriphenylphosphonium acetoxy silane, 3 - (meth) acryloyloxy ethyl methyl dimethoxy silane, 3 - (meth) acryloyloxy ethyl methyl diethoxy silane, 3 - (meth) acryloyloxyethyl methyl-di-n-propoxy silane, 3 - (meth) acryloyloxy ethyl methyl iso-propoxy silane, 3 - (meth) acryloyloxy ethyl methyl diacetoxy-silane, 3 - (meth) acryloyloxyethyl ethyl dimethoxy silane, 3 - (meth) acryloyloxyethyl ethyl diethoxy silane, 3 - (methyl- ) acryloyloxyethyl ethyl di-n-propoxy silane, 3 - (meth) acryloyloxyethyl diisopropyl ethyl trimethoxysilane, 3 - (meth) acryloyloxy ethyl yl diacetoxy-silane, 3 - (meth) acryloyloxy-ethyl-phenyl dimethoxy silane, 3 - (meth) acryloyloxy-ethyl-phenyl diethoxy silane, 3 - (methyl yl) acryloyloxyethyl phenyl di-n-propoxy silane, 3 - (meth) acryloyloxy ethyl diisopropyl phenyl silane, 3 - (meth) acryloyloxyethyl phenyl-diacetoxy-silane, 3 - (meth) acryloxy propyl trimethoxy silane, 3 - (meth) acryloxy propyl triethoxy silane, 3 - (meth) acrylic acid tri-n-propoxy-propyl silane, 3 - (meth) acryloxypropyl triisopropoxysilane, 3 - (meth) acryloxy propyl-triacetoxy-silane, 3 - ( meth) acryloxypropyl methyl dimethoxy silane, 3 - (meth) acryloxy propyl methyl diethoxy silane, 3 - (meth) acryloxy propyl methyl bis n-propoxy silane, 3 - (meth) acryloxy propyl methyl-propoxy silane, 3 - (meth) acryloxy propyl methyl-diacetoxy-silane, 3 - (meth) acryloxy propyl ethyl dimethoxy silane, 3 - (meth) acryloxy propyl ethyl diethoxy silane, 3 - (meth) acryloxy propyl ethyl-di-n-propoxy silane, 3 - (meth) acryloxy propyl trimethoxysilane diisopropyl ethyl, 3 - (meth) acryloxy propyl-ethyl-diacetoxy-silane, 3 - (meth) acryloxy propyl-phenyl dimethoxy silane, 3 - (meth) acryloxy propyl-phenyl diethoxy silane, 3 - (meth) acryloyloxy C phenyl di-n-propoxy silane, 3 - (meth) acryloxy propyl trimethoxysilane diisopropyl-phenyl, 3 - (meth) acryloxy propyl-phenyl-diacetoxy-silane ;

As the object lesson of the compound that contains carboxyl (1), can enumerate the carboxyl MTMS; The carboxyl MTES; Carboxyl methyl three positive propoxy silane; Carboxyl methyl three isopropoxy silane; Carboxyl methyl triacetic acid base silane; Carboxyl methyl three (methoxy ethoxy) silane; Carboxyl methyl dimethoxy silane; Carboxyl methyl diethoxy silane; Carboxyl methyl two positive propoxy silane; Carboxyl methyl diisopropoxy silane; Carboxyl methyl diacetoxyl silane; Carboxyl Methylethyl dimethoxy silane; Carboxyl Methylethyl diethoxy silane; Carboxyl Methylethyl two positive propoxy silane; Carboxyl Methylethyl diisopropoxy silane; Carboxyl Methylethyl diacetoxyl silane; Carboxyl Methylethyl two (methoxy ethoxy) silane; Carboxyl aminomethyl phenyl dimethoxy silane; Carboxyl aminomethyl phenyl diethoxy silane; Carboxyl aminomethyl phenyl two positive propoxy silane; Carboxyl aminomethyl phenyl diisopropoxy silane; Carboxyl aminomethyl phenyl diacetoxyl silane; Carboxyl aminomethyl phenyl two (methoxy ethoxy) silane; 2-carboxy ethyl trimethoxy silane; 2-carboxy ethyl triethoxysilane; 2-carboxy ethyl three positive propoxy silane; 2-carboxy ethyl three isopropoxy silane; 2-carboxy ethyl triacetic acid base silane; 2-carboxy ethyl three (methoxy ethoxy) silane; 2-carboxy ethyl methyl dimethoxysilane; 2-carboxy ethyl methyldiethoxysilane; 2-carboxy ethyl methyl two positive propoxy silane; 2-carboxy ethyl methyl diisopropoxy silane; 2-carboxy ethyl methyl diacetoxyl silane; 2-carboxy ethyl ethyl dimethoxy silane; 2-carboxy ethyl ethyl diethoxy silane; 2-carboxy ethyl ethyl two positive propoxy silane; 2-carboxy ethyl ethyl diisopropoxy silane; 2-carboxy ethyl ethyl diacetoxyl silane; 2-carboxy ethyl ethyl two (methoxy ethoxy) silane; 2-carboxy ethyl phenyl dimethoxy silane; 2-carboxy ethyl diethylamino phenyl TMOS; 2-carboxy ethyl phenyl two positive propoxy silane; 2-carboxy ethyl phenyl diisopropoxy silane; 2-carboxy ethyl diethylamino phenyl acyloxysilanes; 2-carboxy ethyl phenyl two (methoxy ethoxy) silane etc.;

As the object lesson of the compound that contains hydroxyl (1), can enumerate the hydroxymethyl trimethoxy silane; The hydroxymethyl triethoxysilane; Hydroxymethyl three positive propoxy silane; Hydroxymethyl three isopropoxy silane; Hydroxymethyl triacetic acid base silane; Hydroxymethyl three (methoxy ethoxy) silane; The hydroxymethyl methyl dimethoxysilane; The hydroxymethyl methyldiethoxysilane; Hydroxymethyl methyl two positive propoxy silane; Hydroxymethyl methyl diisopropoxy silane; Hydroxymethyl methyl diacetoxyl silane; Hydroxymethyl ethyl dimethoxy silane; Hydroxymethyl ethyl diethoxy silane; Hydroxymethyl ethyl two positive propoxy silane; Hydroxymethyl ethyl diisopropoxy silane; Hydroxymethyl ethyl diacetoxyl silane; Hydroxymethyl ethyl two (methoxy ethoxy) silane; Hydroxymethyl phenyl dimethoxy silane; Hydroxymethyl diethylamino phenyl TMOS; Hydroxymethyl phenyl two positive propoxy silane; Hydroxymethyl phenyl diisopropoxy silane; Hydroxymethyl diethylamino phenyl acyloxysilanes; Hydroxymethyl phenyl two (methoxy ethoxy) silane; 2-hydroxyethyl trimethoxy silane; 2-hydroxyethyl triethoxysilane; 2-hydroxyethyl three positive propoxy silane; 2-hydroxyethyl three isopropoxy silane; 2-hydroxyethyl triacetic acid base silane; 2-hydroxyethyl three (methoxy ethoxy) silane; 2-hydroxyethyl methyl dimethoxysilane; 2-hydroxyethyl methyldiethoxysilane; 2-hydroxyethyl methyl two positive propoxy silane; 2-hydroxyethyl methyl diisopropoxy silane; 2-hydroxyethyl methyl diacetoxyl silane; 2-hydroxyethyl ethyl dimethoxy silane; 2-hydroxyethyl ethyl diethoxy silane; 2-hydroxyethyl ethyl two positive propoxy silane; 2-hydroxyethyl ethyl diisopropoxy silane; 2-hydroxyethyl ethyl diacetoxyl silane; 2-hydroxyethyl ethyl two (methoxy ethoxy) silane; 2-hydroxyethyl phenyl dimethoxy silane; 2-hydroxyethyl diethylamino phenyl TMOS; 2-hydroxyethyl phenyl two positive propoxy silane; 2-hydroxyethyl phenyl diisopropoxy silane; 2-hydroxyethyl diethylamino phenyl acyloxysilanes; 2-hydroxyethyl phenyl two (methoxy ethoxy) silane; 3-hydroxypropyl trimethoxy silane; 3-hydroxypropyl triethoxysilane; 3-hydroxypropyl three positive propoxy silane; 3-hydroxypropyl three isopropoxy silane; 3-hydroxypropyl triacetic acid base silane; 3-hydroxypropyl three (methoxy ethoxy) silane; 3-hydroxypropyl methyl dimethoxysilane; 3-hydroxypropyl methyldiethoxysilane; 3-hydroxypropyl methyl two positive propoxy silane; 3-hydroxypropyl methyl diisopropoxy silane; 3-hydroxypropyl methyl diacetoxyl silane; 3-hydroxypropyl ethyl dimethoxy silane; 3-hydroxypropyl ethyl diethoxy silane; 3-hydroxypropyl ethyl two positive propoxy silane; 3-hydroxypropyl ethyl diisopropoxy silane; 3-hydroxypropyl ethyl diacetoxyl silane; 3-hydroxypropyl ethyl two (methoxy ethoxy) silane; 3-hydroxypropyl phenyl dimethoxy silane; 3-hydroxypropyl diethylamino phenyl TMOS; 3-hydroxypropyl phenyl two positive propoxy silane; 3-hydroxypropyl phenyl diisopropoxy silane; 3-hydroxypropyl diethylamino phenyl acyloxysilanes; 3-hydroxypropyl phenyl two (methoxy ethoxy) silane; 4-hydroxyl-(p-hydroxybenzene ketonic oxygen base) benzyl trimethoxy silane; 4-hydroxyl-(p-hydroxybenzene ketonic oxygen base) benzyl triethoxysilane; 4-hydroxyl-(p-hydroxybenzene ketonic oxygen base) benzyl three positive propoxy silane; 4-hydroxyl-(p-hydroxybenzene ketonic oxygen base) benzyl three isopropoxy silane; 4-hydroxyl-(p-hydroxybenzene ketonic oxygen base) benzyl triacetic acid base silane; 4-hydroxyl-(p-hydroxybenzene ketonic oxygen base) benzyl three (methoxy ethoxy) silane; 4-hydroxyl-(p-hydroxybenzene ketonic oxygen base) benzyl methyl dimethoxysilane; 4-hydroxyl-(p-hydroxybenzene ketonic oxygen base) benzyl methyldiethoxysilane; 4-hydroxyl-(p-hydroxybenzene ketonic oxygen base) benzyl methyl two positive propoxy silane; 4-hydroxyl-(p-hydroxybenzene ketonic oxygen base) benzyl methyl diisopropoxy silane; 4-hydroxyl-(p-hydroxybenzene ketonic oxygen base) benzyl methyl diacetoxyl silane; 4-hydroxyl-(p-hydroxybenzene ketonic oxygen base) benzyl ethyl dimethoxy silane; 4-hydroxyl-(p-hydroxybenzene ketonic oxygen base) benzyl ethyl diethoxy silane; 4-hydroxyl-(p-hydroxybenzene ketonic oxygen base) benzyl ethyl two positive propoxy silane; 4-hydroxyl-(p-hydroxybenzene ketonic oxygen base) benzyl ethyl diisopropoxy silane; 4-hydroxyl-(p-hydroxybenzene ketonic oxygen base) benzyl ethyl diacetoxyl silane; 4-hydroxyl-(p-hydroxybenzene ketonic oxygen base) benzyl ethyl two (methoxy ethoxy) silane; 4-hydroxyl-(p-hydroxybenzene ketonic oxygen base) benzyl phenyl dimethoxy silane; 4-hydroxyl-(p-hydroxybenzene ketonic oxygen base) benzyl phenyl diethoxy silane; 4-hydroxyl-(p-hydroxybenzene ketonic oxygen base) benzyl phenyl two positive propoxy silane; 4-hydroxyl-(p-hydroxybenzene ketonic oxygen base) benzyl phenyl diisopropoxy silane; 4-hydroxyl-(p-hydroxybenzene ketonic oxygen base) benzyl phenyl diacetoxyl silane; 4-hydroxyl-(p-hydroxybenzene ketonic oxygen base) benzyl phenyl two (methoxy ethoxy) silane etc.;

As the object lesson of the compound that contains sulfydryl (1), can enumerate the mercapto methyl trimethoxy silane; The mercapto methyl triethoxysilane; Mercapto methyl three positive propoxy silane; Mercapto methyl three isopropoxy silane; Mercapto methyl triacetic acid base silane; Mercapto methyl three (methoxy ethoxy) silane; The mercapto methyl methyl dimethoxysilane; The mercapto methyl methyldiethoxysilane; Mercapto methyl methyl two positive propoxy silane; Mercapto methyl methyl diisopropoxy silane; Mercapto methyl methyl diacetoxyl silane; Mercapto methyl ethyl dimethoxy silane; Mercapto methyl ethyl diethoxy silane; Mercapto methyl ethyl two positive propoxy silane; Mercapto methyl ethyl diisopropoxy silane; Mercapto methyl ethyl diacetoxyl silane; Mercapto methyl ethyl two (methoxy ethoxy) silane; Mercapto methyl phenyl dimethoxy silane; Mercapto methyl diethylamino phenyl TMOS; Mercapto methyl phenyl two positive propoxy silane; Mercapto methyl phenyl diisopropoxy silane; Mercapto methyl diethylamino phenyl acyloxysilanes; Mercapto methyl phenyl two (methoxy ethoxy) silane; 2-mercaptoethyl trimethoxy silane; 2-mercaptoethyl triethoxysilane; 2-mercaptoethyl three positive propoxy silane; 2-mercaptoethyl three isopropoxy silane; 2-mercaptoethyl triacetic acid base silane; 2-mercaptoethyl three (methoxy ethoxy) silane; 2-mercaptoethyl methyl dimethoxysilane; 2-mercaptoethyl methyldiethoxysilane; 2-mercaptoethyl methyl two positive propoxy silane; 2-mercaptoethyl methyl diisopropoxy silane; 2-mercaptoethyl methyl diacetoxyl silane; 2-mercaptoethyl ethyl dimethoxy silane; 2-mercaptoethyl ethyl diethoxy silane; 2-mercaptoethyl ethyl two positive propoxy silane; 2-mercaptoethyl ethyl diisopropoxy silane; 2-mercaptoethyl ethyl diacetoxyl silane; 2-mercaptoethyl ethyl two (methoxy ethoxy) silane; 2-mercaptoethyl phenyl dimethoxy silane; 2-mercaptoethyl diethylamino phenyl TMOS; 2-mercaptoethyl phenyl two positive propoxy silane; 2-mercaptoethyl phenyl diisopropoxy silane; 2-mercaptoethyl diethylamino phenyl acyloxysilanes; 2-mercaptoethyl phenyl two (methoxy ethoxy) silane; 3-sulfydryl propyl trimethoxy silicane; 3-sulfydryl propyl-triethoxysilicane; 3-sulfydryl propyl group three positive propoxy silane; 3-sulfydryl propyl group three isopropoxy silane; 3-sulfydryl propyl group triacetic acid base silane; 3-sulfydryl propyl group three (methoxy ethoxy) silane; 3-sulfydryl propyl group methyl dimethoxysilane; 3-sulfydryl propyl group methyldiethoxysilane; 3-sulfydryl propyl group methyl two positive propoxy silane; 3-sulfydryl propyl group methyl diisopropoxy silane; 3-sulfydryl propyl group methyl diacetoxyl silane; 3-sulfydryl propyl group ethyl dimethoxy silane; 3-sulfydryl propyl group ethyl diethoxy silane; 3-sulfydryl propyl group ethyl two positive propoxy silane; 3-sulfydryl propyl group ethyl diisopropoxy silane; 3-sulfydryl propyl group ethyl diacetoxyl silane; 3-sulfydryl propyl group ethyl two (methoxy ethoxy) silane; 3-sulfydryl propyl group phenyl dimethoxy silane; 3-sulfydryl propyl group phenyl diethoxy silane; 3-sulfydryl propyl group phenyl two positive propoxy silane; 3-sulfydryl propyl group phenyl diisopropoxy silane; 3-sulfydryl propyl group phenyl diacetoxyl silane; 3-sulfydryl propyl group phenyl two (methoxy ethoxy) silane etc.;

As the object lesson of the compound that contains NCO (1), can enumerate the isocyanates MTMS; The isocyanates MTES; Isocyanates methyl three positive propoxy silane; Isocyanates methyl three isopropoxy silane; Isocyanates methyl triacetic acid base silane; Isocyanates methyl three (methoxy ethoxy) silane; Isocyanates methyl dimethoxy silane; Isocyanates methyl diethoxy silane; Isocyanates methyl two positive propoxy silane; Isocyanates methyl diisopropoxy silane; Isocyanates methyl diacetoxyl silane; Isocyanates Methylethyl dimethoxy silane; Isocyanates Methylethyl diethoxy silane; Isocyanates Methylethyl two positive propoxy silane; Isocyanates Methylethyl diisopropoxy silane; Isocyanates Methylethyl diacetoxyl silane; Isocyanates Methylethyl two (methoxy ethoxy) silane; Isocyanates aminomethyl phenyl dimethoxy silane; Isocyanates aminomethyl phenyl diethoxy silane; Isocyanates aminomethyl phenyl two positive propoxy silane; Isocyanates aminomethyl phenyl diisopropoxy silane; Isocyanates aminomethyl phenyl diacetoxyl silane; Isocyanates aminomethyl phenyl two (methoxy ethoxy) silane; 2-isocyanates ethyl trimethoxy silane; 2-isocyanates ethyl triethoxysilane; 2-isocyanates ethyl three positive propoxy silane; 2-isocyanates ethyl three isopropoxy silane; 2-isocyanates ethyl triacetic acid base silane; 2-isocyanates ethyl three (methoxy ethoxy) silane; 2-isocyanates ethyl-methyl dimethoxy silane; 2-isocyanates ethyl-methyl diethoxy silane; 2-isocyanates ethyl-methyl two positive propoxy silane; 2-isocyanates ethyl-methyl diisopropoxy silane; 2-isocyanates ethyl-methyl diacetoxyl silane; 2-isocyanates ethyl diethyldithiocarbamate dimethoxy silane; 2-isocyanates ethyl diethyldithiocarbamate diethoxy silane; 2-isocyanates ethyl diethyldithiocarbamate two positive propoxy silane; 2-isocyanates ethyl diethyldithiocarbamate diisopropoxy silane; 2-isocyanates ethyl diethyldithiocarbamate diacetoxyl silane; 2-isocyanates ethyl diethyldithiocarbamate two (methoxy ethoxy) silane; 2-isocyanates ethylphenyl dimethoxy silane; 2-isocyanates ethylphenyl diethoxy silane; 2-isocyanates ethylphenyl two positive propoxy silane; 2-isocyanates ethylphenyl diisopropoxy silane; 2-isocyanates ethylphenyl diacetoxyl silane; 2-isocyanates ethylphenyl two (methoxy ethoxy) silane; 3-isocyanates propyl trimethoxy silicane; 3-isocyanates propyl-triethoxysilicane; 3-isocyanates propyl group three positive propoxy silane; 3-isocyanates propyl group three isopropoxy silane; 3-isocyanates propyl group triacetic acid base silane; 3-isocyanates propyl group three (methoxy ethoxy) silane; 3-isocyanates propyl group methyl dimethoxysilane; 3-isocyanates propyl group methyldiethoxysilane; 3-isocyanates propyl group methyl two positive propoxy silane; 3-isocyanates propyl group methyl diisopropoxy silane; 3-isocyanates propyl group methyl diacetoxyl silane; 3-isocyanates propyl group ethyl dimethoxy silane; 3-isocyanates propyl group ethyl diethoxy silane; 3-isocyanates propyl group ethyl two positive propoxy silane; 3-isocyanates propyl group ethyl diisopropoxy silane; 3-isocyanates propyl group ethyl diacetoxyl silane; 3-isocyanates propyl group ethyl two (methoxy ethoxy) silane; 3-isocyanates propyl group phenyl dimethoxy silane; 3-isocyanates propyl group phenyl diethoxy silane; 3-isocyanates propyl group phenyl two positive propoxy silane; 3-isocyanates propyl group phenyl diisopropoxy silane; 3-isocyanates propyl group phenyl diacetoxyl silane; 3-isocyanates propyl group phenyl two (methoxy ethoxy) silane etc.;

As amino group-containing compound (1) Specific examples include aminomethyl trimethoxysilane, aminomethyl-triethoxysilane, methyl tri-n-propoxy silane amino, aminomethyl triisopropoxide silane, amino acid methyl silane, amino methyl tris (methoxyethoxy) silane, amino methyl dimethoxy silane, methyl diethoxy silane group, methyl group bis n-propoxy silane, methyl diisopropyl amino silane, amino methyl diacetoxy-silane, amino methyl ethyl dimethoxy silane, methyl ethyl amino diethoxy silane, amino methyl ethyl di-n-propoxy silane, methyl ethyl diisopropyl amino-silane, amino-methylethyl diacetoxy-silane, amino methyl ethyl bis (methoxyethoxy) silane, amino methyl phenyl dimethoxy silane, methyl phenyl diethoxy silane amino, aminomethyl-phenyl di-n-propoxy silane, amino silane diisopropyl-phenyl, carbamoyl phenyl diacetoxy-silane, amino-phenyl bis (methoxyethoxy) silane 2 - aminoethyl trimethoxysilane 2 - aminoethyl triethoxysilane 2 - aminoethyl tri-n-propoxy silane 2 - aminoethyl triisopropoxysilane 2 - aminoethyl triacetoxy silane 2 - amino-ethyl-tri (methoxyethoxy) silane 2 - aminoethyl dimethoxysilane 2 - amino-ethyl-methyl-diethoxy silane 2 - amino-ethyl-methyl-di-n-propyl silane 2 - amino-ethyl-diisopropyl methyl silane, 2 - amino-ethyl-methyl-diacetoxy-silane 2 - amino-ethyl ethyl dimethoxysilane 2 - diethyl aminoethyl triethoxysilane 2 - amino-ethyl-ethyl-di-n-propoxy silane 2 - aminoethyl trimethoxysilane diisopropyl ethyl 2 - amino-ethyl-ethyl-diacetoxy-silane 2 - amino-ethyl-ethyl-di (methoxyethoxy) silane 2 - aminoethyl Diphenyldimethoxysilane 2 - aminoethyl Diphenyldiethoxysilane 2 - amino-ethyl-phenyl di-n-propoxy silane 2 - amino-ethyl-diisopropyl-phenyl silane, 2 - amino-ethyl-phenyl-diacetoxy-silane 2 - amino-ethyl-phenyl-bis (methoxyethoxy) silane, 3 - aminopropyl trimethoxy silane, 3 - aminopropyl triethoxysilane 3 - amino propyl tri-n-propoxy silane, 3 - amino-propyl triisopropoxy silane, 3 - aminopropyl triacetoxy silane, 3 - amino-propyl-tri (methoxyethoxy) silane 3 - amino propyl methyl dimethoxy silane, 3 - amino propyl methyl diethoxy silane, 3 - amino-propyl-methyl-n-propoxy silane, 3 - aminopropyl methyl isobutyl propoxy silane, 3 - aminopropyl methyl diacetoxy-silane, 3 - amino-propyl ethyl dimethoxy silane, 3 - amino-propyl ethyl diethoxy silane, 3 - aminopropyl-ethyl di-n-propoxy silane, 3 - aminopropyl trimethoxysilane diisopropyl ethyl 3 - amino-propyl-ethyl-diacetoxy-silane, 3 - amino-propyl-ethyl-bis (methoxyethoxy) silane 3 - amino-propyl-phenyl dimethoxy silane, 3 - amino-propyl-phenyl diethoxy silane, 3 - amino-propyl-phenyl di-n-propoxy silane, 3 - amino-propyl-phenyl di-iso- propoxy silane, 3 - amino-propyl-phenyl-diacetoxy-silane, 3 - amino-propyl-phenyl-bis (methoxyethoxy) silane, N-2-(aminoethyl) -3 - aminopropyl trimethoxysilane, N-2-(aminoethyl) -3 - aminopropyl triethoxysilane, N-2-(aminoethyl) -3 - aminopropyl tri-propoxy silane, N- 2 - (aminoethyl) -3 - aminopropyl-triisopropoxysilane, N-2-(aminoethyl) -3 - aminopropyl triacetoxy silane, N-2-(aminoethyl) - 3 - amino-propyl-tri (methoxyethoxy) silane, N-2-(aminoethyl) -3 - aminopropyl methyl dimethoxy silane, N-2-(aminoethyl) - aminopropyl methyl diethoxy silane, N-2-(aminoethyl) -3 - amino-propyl-methyl-n-propoxy silane, N-2-(aminoethyl) -3 - aminopropyl diisopropyl methyl silane, N-2-(aminoethyl) -3 - aminopropyl methyl-diacetoxy-silane, N-2-(aminoethyl) -3 - aminopropyl-diethyl methoxy silane, N-2-(aminoethyl) -3 - diethyl aminopropyl triethoxysilane, N-2-(aminoethyl) -3 - aminopropyl-ethyl di-n-propoxy silane, N-2-(aminoethyl)-3 - ethyl-diisopropyl-aminopropyl trimethoxysilane, N-2-(aminoethyl)-3 - ethyl-amino-propyl-diacetoxy-silane, N- 2 - (amino-ethyl) -3 - amino-propyl-ethyl-bis (methoxyethoxy) silane, N-2-(aminoethyl) -3 - amino-propyl-phenyl dimethoxy silane, N -2 - (amino-ethyl) -3 - Methylene-aminopropyl triethoxysilane, N-2-(aminoethyl) -3 - amino-propyl-phenyl di-n-propoxy silane, N-2- (aminoethyl) -3 - phenyl-diisopropyl-aminopropyl trimethoxysilane, N-2-(aminoethyl) -3 - amino-propyl-phenyl-diacetoxy-silane, N-2-(aminoethyl ) -3 - amino-propyl-phenyl-bis (methoxyethoxy) silane, N-phenyl-3 - aminopropyl trimethoxy silane, N-phenyl-3 - aminopropyl triethoxysilane , N-phenyl-3 - amino propyl tri-n-propoxy silane, N-phenyl-3 - amino-propyl triisopropoxysilane, N-phenyl-3 - aminopropyl acid silane , N-phenyl-3 - amino-propyl-tri (methoxyethoxy) silane, N-phenyl-3 - amino propyl methyl dimethoxy silane, N-phenyl-3 - aminopropyl methyl diethoxy silane, N-phenyl-3 - aminopropyl methyl n-propoxy silane, N-phenyl-3 - amino propyl methyl diisopropyl silane, N-phenyl- -3 - methyl-diacetoxy-aminopropyl silane, N-phenyl-3 - amino-propyl ethyl dimethoxy silane, N-phenyl-3 - amino-propyl ethyl diethoxy silane, N - phenyl-3 - amino-propyl-ethyl-di-n-propoxy silane, N-phenyl-3 - ethyl-diisopropyl-aminopropyl trimethoxysilane, N-phenyl-3 - aminopropyl-diethyl acetoxy silane, N-phenyl-3 - amino-propyl-ethyl-bis (methoxyethoxy) silane, N-phenyl-3 - amino-propyl-phenyl dimethoxy silane, N-phenyl - 3 - Methylene aminopropyl triethoxysilane, N-phenyl-3 - amino-propyl-phenyl di-n-propoxy silane, N-phenyl-3 - aminopropyl trimethoxysilane diisopropyl-phenyl , N-phenyl-3 - amino-propyl-phenyl-diacetoxy-silane, N-phenyl-3 - amino-propyl-phenyl-bis (methoxyethoxy) silane, 3 - trimethoxysilyl group - N-(1,3 - dimethyl - butylene) propylamine 3 - triethoxysilyl group-N-(1,3 - dimethyl - butylene) propylamine 3 - tri silyl propoxy-N-(1,3 - dimethyl - butylene) propyl amine;

As the object lesson of the compound that contains urea groups (1), can enumerate the urea groups MTMS; The urea groups MTES; Urea groups methyl three positive propoxy silane; Urea groups methyl three isopropoxy silane; Urea groups methyl triacetic acid base silane; Urea groups methyl three (methoxy ethoxy) silane; Urea groups methyl dimethoxy silane; Urea groups methyl diethoxy silane; Urea groups methyl two positive propoxy silane; Urea groups methyl diisopropoxy silane; Urea groups methyl diacetoxyl silane; Urea groups Methylethyl dimethoxy silane; Urea groups Methylethyl diethoxy silane; Urea groups Methylethyl two positive propoxy silane; Urea groups Methylethyl diisopropoxy silane; Urea groups Methylethyl diacetoxyl silane; Urea groups Methylethyl two (methoxy ethoxy) silane; Urea groups aminomethyl phenyl dimethoxy silane; Urea groups aminomethyl phenyl diethoxy silane; Urea groups aminomethyl phenyl two positive propoxy silane; Urea groups aminomethyl phenyl diisopropoxy silane; Urea groups aminomethyl phenyl diacetoxyl silane; Urea groups aminomethyl phenyl two (methoxy ethoxy) silane; The 2-ureidoethyltrimethoxsilane; 2-urea groups ethyl triethoxysilane; 2-urea groups ethyl three positive propoxy silane; 2-urea groups ethyl three isopropoxy silane; 2-urea groups ethyl triacetic acid base silane; 2-urea groups ethyl three (methoxy ethoxy) silane; 2-urea groups ethyl-methyl dimethoxy silane; 2-urea groups ethyl-methyl diethoxy silane; 2-urea groups ethyl-methyl two positive propoxy silane; 2-urea groups ethyl-methyl diisopropoxy silane; 2-urea groups ethyl-methyl diacetoxyl silane; 2-urea groups ethyl diethyldithiocarbamate dimethoxy silane; 2-urea groups ethyl diethyldithiocarbamate diethoxy silane; 2-urea groups ethyl diethyldithiocarbamate two positive propoxy silane; 2-urea groups ethyl diethyldithiocarbamate diisopropoxy silane; 2-urea groups ethyl diethyldithiocarbamate diacetoxyl silane; 2-urea groups ethyl diethyldithiocarbamate two (methoxy ethoxy) silane; 2-urea groups ethylphenyl dimethoxy silane; 2-urea groups ethylphenyl diethoxy silane; 2-urea groups ethylphenyl two positive propoxy silane; 2-urea groups ethylphenyl diisopropoxy silane; 2-urea groups ethylphenyl diacetoxyl silane; 2-urea groups ethylphenyl two (methoxy ethoxy) silane; 3-urea groups propyl trimethoxy silicane; 3-urea groups propyl-triethoxysilicane; 3-urea groups propyl group three positive propoxy silane; 3-urea groups propyl group three isopropoxy silane; 3-urea groups propyl group triacetic acid base silane; 3-urea groups propyl group three (methoxy ethoxy) silane; 3-urea groups propyl group methyl dimethoxysilane; 3-urea groups propyl group methyldiethoxysilane; 3-urea groups propyl group methyl two positive propoxy silane; 3-urea groups propyl group methyl diisopropoxy silane; 3-urea groups propyl group methyl diacetoxyl silane; 3-urea groups propyl group ethyl dimethoxy silane; 3-urea groups propyl group ethyl diethoxy silane; 3-urea groups propyl group ethyl two positive propoxy silane; 3-urea groups propyl group ethyl diisopropoxy silane; 3-urea groups propyl group ethyl diacetoxyl silane; 3-urea groups propyl group ethyl two (methoxy ethoxy) silane; 3-urea groups propyl group phenyl dimethoxy silane; 3-urea groups propyl group phenyl diethoxy silane; 3-urea groups propyl group phenyl two positive propoxy silane; 3-urea groups propyl group phenyl diisopropoxy silane; 3-urea groups propyl group phenyl diacetoxyl silane; 3-urea groups propyl group phenyl two (methoxy ethoxy) silane etc.;

As the object lesson of the compound that contains styryl (1), can enumerate the styryl trimethoxy silane; The styryl triethoxysilane; Styryl three positive propoxy silane; Styryl three isopropoxy silane; Styryl triacetic acid base silane; Styryl three (methoxy ethoxy) silane; The styryl methyl dimethoxysilane; The styryl methyldiethoxysilane; Styryl methyl two positive propoxy silane; Styryl methyl diisopropoxy silane; Styryl methyl diacetoxyl silane; Styryl ethyl dimethoxy silane; Styryl ethyl diethoxy silane; Styryl ethyl two positive propoxy silane; Styryl ethyl diisopropoxy silane; Styryl ethyl diacetoxyl silane; Styryl ethyl two (methoxy ethoxy) silane; Styryl phenyl dimethoxy silane; Styryl diethylamino phenyl TMOS; Styryl phenyl two positive propoxy silane; Styryl phenyl diisopropoxy silane; Styryl diethylamino phenyl acyloxysilanes; Styryl phenyl two (methoxy ethoxy) silane etc.;

Among them; The preferred use contained epoxy radicals; Oxetanyl; Hydroxyl; The compound (1) of sulfydryl; From considering with the reactivity of [A] composition and the aspect of storage stability; Preferred especially 3-glycidoxypropyltrime,hoxysilane; 3-glycidoxy propyl-triethoxysilicane; 3-glycidoxy propyl group methyl dimethoxysilane; 3-glycidoxy propyl group methyldiethoxysilane; The 4-epoxycyclohexyl) ethyl trimethoxy silane; 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane ethyl oxetanes-3-yl) propyl trimethoxy silicane ethyl oxetanes-3-yl) propyl-triethoxysilicane; 3-sulfydryl propyl trimethoxy silicane; 3-sulfydryl propyl-triethoxysilicane.

As the object lesson of compound (2), can enumerate tetraalkoxysilanes such as tetramethoxy-silicane, tetraethoxysilane (common name TEOS), four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane; Monoalkyltrialkoxysi.ane such as MTMS, MTES, methyl three positive propoxy silane, ethyl triethoxysilane, cyclohexyl triethoxysilane; Single aryl trialkoxy silanes such as phenyl triethoxysilane, naphthyl Ethoxysilane, 4-chlorphenyl triethoxysilane, 4-cyano-phenyl triethoxysilane, 4-aminophenyl triethoxysilane, 4-nitrobenzophenone triethoxysilane, 4-aminomethyl phenyl triethoxysilane, 4-hydroxy phenyl triethoxysilane; Single aryloxy group trialkoxy silanes such as phenoxy group triethoxysilane, naphthoxy triethoxysilane, 4-chlorophenoxy triethoxysilane, 4-cyano-phenyl three oxygen base oxethyl silane, 4-amino-benzene oxygen triethoxysilane, 4-nitrophenoxy triethoxysilane, 4-methylphenoxy triethoxysilane, 4-hydroxyphenoxy triethoxysilane; Monohydroxy trialkoxy silanes such as monohydroxy trimethoxy silane, monohydroxy triethoxysilane, monohydroxy three positive propoxy silane; Dialkyl dialkoxy silicanes such as dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyl two positive propoxy silane, methyl (ethyl) diethoxy silane, methyl (cyclohexyl) diethoxy silane; Monoalkyl aryl dialkoxy silicanes such as methyl (phenyl) diethoxy silane; Diaryl dialkoxy silicanes such as diphenyl diethoxy silane; Two aryloxy group dialkoxy silicanes such as two phenoxy group diethoxy silanes; Monoalkyl aryloxy group dialkoxy silicanes such as methyl (phenoxy group) diethoxy silane; Single aryl aryloxy group dialkoxy silicanes such as phenyl (phenoxy group) diethoxy silane; Dihydroxy dialkyl silanes such as dihydroxy dimethoxy silane, dihydroxy diethoxy silane, dihydroxy two positive propoxy silane; Monoalkyl monohydroxy dialkoxy silicanes such as methyl (hydroxyl) dimethoxy silane; Single aryl monohydroxy dialkoxy silicanes such as phenyl (hydroxyl) dimethoxy silane; Trialkyl-single alkoxy silanes such as trimethyl methoxy silane, trimethylethoxysilane, trimethyl positive propoxy silane, dimethyl (ethyl) Ethoxysilane, dimethyl (cyclohexyl) Ethoxysilane; Dialkyl group list aryl monoalkoxy silane such as dimethyl (phenyl) Ethoxysilane; Monoalkyl diaryl monoalkoxy silane such as methyl (diphenyl) Ethoxysilane; Three aryloxy group monoalkoxy silane such as triple phenoxyl Ethoxysilane; Monoalkyl two aryloxy group monoalkoxy silane such as methyl (two phenoxy groups) Ethoxysilane; Single aryl two aryloxy group monoalkoxy silane such as phenyl (two phenoxy groups) Ethoxysilane; Dialkyl group list aryloxy group monoalkyl silane such as dimethyl (phenoxy group) Ethoxysilane; Diaryl list aryloxy group monoalkoxy silane such as diphenyl (phenoxy group) Ethoxysilane; Monoalkyl list aryl list aryloxy group monoalkoxy silane such as methyl (phenyl)(phenoxy group) Ethoxysilane; Trihydroxy monoalkoxy silane such as trihydroxy methoxy silane, trihydroxy Ethoxysilane, trihydroxy positive propoxy silane.

Among them; From reactive, to the stickiness aspect of substrate, preferred tetramethoxy-silicane, tetraethoxysilane, MTMS, MTES, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane.

These compounds can be to form and multiple with arbitrarily arbitrarily.

The siloxane oligomer I that above-claimed cpd can be prepared [C] composition of the present invention's use through cohydrolysis.

Hydrolysis reaction preferably carries out in appropriate solvent.Examples of such a solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol methyl ether, propylene glycol methyl ether acetate, tetrahydrofuran, diethyl

dioxane, acetonitrile, or a water-soluble solvent.

Since after operation in remove these water-soluble solvents; The lower solvents of boiling point such as particular methanol, ethanol, n-propanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran; Consider from raw material dissolubility aspect; Ketones such as further preferred acetone, methyl ethyl ketone, methyl isobutyl ketone, the most preferable isobutyl ketone.

The hydrolysis reaction that is used to synthesize [C] composition siloxane oligomer I preferably carries out in the presence of acid catalyst or base catalyst.As acid catalyst, can enumerate example hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetate, trifluoroacetic acid, TFMS, acid-exchange resin, various lewis acids etc.As base catalyst, go out like carboxylates such as carbonate such as oxyhydroxide such as nitrogen-containing aromatic compound, deacidite, NaOH, sal tartari, sodium acetate, lewis bases etc. such as ammonia, primary amine class, secondary amine class, tertiary amines, pyridines.Can suitably set consumption, temperature of reaction, the reaction time of water.For example can adopt following condition.

With respect to 1 mole of the total amount of alkoxy in the compound of above-mentioned formula (1) or (2) expression and halogen atom, the consumption of water is preferred below 1.5 moles, more preferably below 1 mole, further preferred amount below 0.9 mole.

Preferred 40～200 ℃, more preferably 50～150 ℃ of temperature of reaction.

Preferred 30 minutes～24 hours, more preferably 1～12 hour reaction time.

Above-mentioned siloxane oligomer II representes with following formula (9).

Wherein, R < > 21 <>～R < > 24 <> Separate, expression hydrogen atom, alkyl, naphthenic base or following formula (10) oxetanyl of expression, m is 1～10 integer.Wherein, R < > 21 <>～R < > 24 <> At least one be following formula (10) expression oxetanyl.

Wherein, R < > 25 <> , R < > 13 <> , R < > 14 <> , R < > 15 <> And R < > 16 <> Separate, expression hydrogen atom, fluorine atom, carbon number are that 1～4 alkyl, phenyl or carbon number are 1～4 perfluoroalkyl, and l is 1～6 integer.

These siloxane oligomers can be through with following formula (11) and (12) the alkoxy silane hydrolysis of expression prepare.

Si(R ¹⁷) _p(OR ¹⁸) _q …(11)

Wherein, R < > 17 <> Expression contains the substituting group of oxetanyl, R < > 18 <> Expression hydrogen atom or 1 valency organic group, p is 1～3 integer, q is respectively 0～3 integer.Wherein.p+q＝4。

Si(R ¹⁹) _x(OR ²⁰) _4-x …(12)

Wherein, R < > 19 <> , R < > 20 <> The substituting group of expression oxygen-free heterocycle butane group can be the same or different, and is respectively hydrogen atom or 1 valency organic group, and x is 0～3 integer.

Above-mentioned formula (11) and compound (12) be the reactive siloxane oligomer.The reactive siloxane oligomer imports silicone structure in the polysiloxane with oxetanes ring and silsesquioxane structure, with the molecular weight that reduces oxetanyl concentration in this polysiloxane, makes silsesquioxane compound do not reduce and reduce viscosity, reduce cure shrinkage, give the solidfied material stickiness through reducing cross-linking density, chemical proofing, the purpose of giving the solidfied material flexibility be imported into.As the reactive siloxane oligomer among the present invention, preferably has the wire silicone of side chain or side chain.

Having an oxetanyl group of the compound (11) Specific examples of the p = 1, it can be mentioned (oxetan-3 - yl) methyl trimethoxysilane, (oxetane -3 - yl) methyl triethoxysilane, (oxetan-3 - yl) methyl tri-n-propoxy silane, (oxetan-3 - yl) methyl-triisopropyl oxygen silane, (oxetan-3 - yl) methyl-triacetoxy silane, (oxetan-3 - yl) methyl dimethoxysilane, (oxetan-3 - yl) methyl diethoxy silane, (oxetan-3 - yl) methyl di-n-propyl silane, (oxetan-3 - yl) methyl diisopropyl silane, (oxetan-3 - yl) methyl diacetoxy-silane, (oxetan-3 - yl) ethyl methyl dimethoxy silane, (oxygen oxetane -3 - yl) ethyl methyl diethoxy silane, (oxetan-3 - yl) methyl-ethyl di-n-propyl silane, (oxetan-3 - yl) methyl ethyl diisopropyl silane, (oxetan-3 - yl) methyl-ethyl-diacetoxy-silane, (oxetan-3 - yl) methyl phenyl dimethoxy silane, (oxetan-3 - yl) methyl phenyl diethoxy silane, (oxetan-3 - yl) methyl-phenyl di-n-propyl silane, (oxa cyclobutan-3 - yl) methyl-diisopropyl-phenyl silane, (oxetan-3 - yl) methyl-phenyl-diacetoxy-silane.

When p=2, can enumerate two (oxetanes-3-yl) methyl dimethoxysilane; Two (oxetanes-3-yl) methyldiethoxysilane; Two (oxetanes-3-yl) methyl, two positive propoxy silane; Two (oxetanes-3-yl) methyl diisopropoxy silane; Two (oxetanes-3-yl) methyl diacetoxyl silane; Two (oxetanes-3-yl) methyl methoxy silane; Two (oxetanes-3-yl) methyl Ethoxysilane; Two (oxetanes-3-yl) methyl positive propoxy silane; Two (oxetanes-3-yl) methyl isopropoxy silane; Two (oxetanes-3-yl) methyl acetate silane; Two (oxetanes-3-yl) Methylethyl methoxy silane; Two (oxetanes-3-yl) Methylethyl Ethoxysilane; Two (oxetanes-3-yl) Methylethyl positive propoxy silane; Two (oxetanes-3-yl) Methylethyl isopropoxy silane; Two (oxetanes-3-yl) ethyl methyl acetic acid base silane; Two (oxetanes-3-yl) aminomethyl phenyl methoxy silane; Two (oxetanes-3-yl) aminomethyl phenyl Ethoxysilane; Two (oxetanes-3-yl) aminomethyl phenyl positive propoxy silane; Two (oxetanes-3-yl) aminomethyl phenyl isopropoxy silane; Two (oxetanes-3-yl) aminomethyl phenyl acetate silane etc.

When p=3, can enumerate three (oxetanes-3-yl) methyl methoxy base silane, three (oxetanes-3-yl) methyl ethoxy silane, three (oxetanes-3-yl) methyl positive propoxy silane, three (oxetanes-3-yl) methyl isopropyl TMOS, three (oxetanes-3-yl) methyl acetic acid base silane etc.

As compound (12 with oxetanyl) object lesson; Can enumerate tetramethoxy-silicane; Tetraethoxysilane; MTMS; MTES; Methyl tripropoxy silane; Methyl three isopropoxy silane; Ethyl trimethoxy silane; Ethyl triethoxysilane; Propyl-triethoxysilicane; Butyl trimethoxy silane; Cyclohexyl trimethoxy silane; The cyclohexyl triethoxysilane; Phenyltrimethoxysila,e; Phenyl triethoxysilane; Dimethyldiethoxysilane; Dimethyldiethoxysilane; Diethyl dimethoxy silane; The diethyl diethoxy silane; Dimethoxydiphenylsilane; The diphenyl diethoxy silane; Aminomethyl phenyl dimethoxy silane; The aminomethyl phenyl diethoxy silane; The trimethyl silicane alkanol; Triethyl silicane alcohol; The tripropyl silanol; The tributyl silanol; Tri-phenyl-silane alcohol; The trimethyl methoxy silane; Trimethylethoxysilane; The triethyl methoxy silane; Triethyl-ethoxy-silicane alkane; The tripropyl methoxy silane; The tripropyl Ethoxysilane; Trimethylsilyl acetate; The trimethyl silyl benzoic ether; The triethylsilyl acetic acid esters; The triethylsilyl benzoic ether; The benzyl dimethyl methoxy silane; The benzyl dimethyl Ethoxysilane; Diphenyl methoxy ylmethyl silane; Diphenyl (ethoxymethyl) base silane; Acetyltriphenylsilane; The ethoxy tri-phenyl-silane; Hexamethyldisiloxane; Hexaethyl dimethyl two silicon ethers; Six propyl-dimethyls, two silicon ethers; 1; 3-dibutyl-1; 3; 3-tetramethyl two silicon ethers; 1; 3-diphenyl-1; 3; 3-tetramethyl two silicon ethers; 1; 3-dimethyl-1,3-tetraphenyl two silicon ethers etc.

Other compositions

Radiation sensitive resin composition of the present invention contains above-mentioned multipolymer [A], [B] and [C] composition as necessary composition, can contain [D] thermonasty according to other needs and become acid compound, [E] to have polymerizable compound, [F] other epoxy resin, [G] surfactant or [H] bonding auxiliary agent different with multipolymer [A] of at least one ethylenic unsaturated double-bond.

Above-mentioned [D] thermonasty becomes acid compound can be used to improve thermotolerance, hardness.Specific examples include sulfonium salts, benzothiazole salts, ammonium salts, salt

salt.

Can enumerate alkyl sulfonium salt, benzyl sulfonium salt, dibenzyl sulfonium salt, substituted benzyl sulfonium salt etc. as the object lesson of above-mentioned sulfonium salt.

As their object lesson; Can enumerate respectively as the alkyl sulfonium salt, for example 4-acetyl phenyl dimethyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl dimethyl sulfonium hexafluoro arsenate, dimethyl-4-(benzyloxycarbonyloxy base) phenyl sulfonium hexafluoro antimonate, dimethyl-4-(benzoyloxy) phenyl sulfonium hexafluoro antimonate, dimethyl-4-(benzoyloxy) phenyl sulfonium hexafluoro arsenate, dimethyl-3-chloro-4-acetoxyl group phenyl sulfonium hexafluoro antimonate etc.;

As the benzyl sulfonium salt, for example benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, benzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate, 4-acetoxyl group phenyl benzyl methyl sulfonium hexafluoro antimonate, benzyl-4-methoxybenzene ylmethyl sulfonium hexafluoro antimonate, benzyl-2-methyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, benzyl-3-chloro-4-hydroxy phenyl methyl sulfonium hexafluoro arsenate, 4-methoxy-benzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate etc.;

As the dibenzyl sulfonium salt, for example dibenzyl-4-hydroxy phenyl sulfonium hexafluoro antimonate, dibenzyl-4-hydroxy phenyl sulfonium hexafluorophosphate, 4-acetoxyl group phenyl dibenzyl sulfonium hexafluoro antimonate, dibenzyl-4-methoxyphenyl sulfonium hexafluoro antimonate, dibenzyl-3-chloro-4-hydroxy phenyl sulfonium hexafluoro arsenate, dibenzyl-3-methyl-4-hydroxyl-5-tert-butyl-phenyl sulfonium hexafluoro antimonate, benzyl-4-methoxy-benzyl-4-hydroxy phenyl sulfonium hexafluorophosphate etc.;

As the substituted benzyl sulfonium salt; For example p-chlorobenzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, to nitrobenzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, p-chlorobenzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate, to nitrobenzyl-3-methyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, 3,5-dichloro benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, o-chlorobenzyl-3-chloro-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate etc.

As the benzothiazole Salt Specific examples include 3 - benzyl benzothiazole

hexafluoroantimonate 3 - benzyl benzothiazole

hexafluorophosphate 3 - benzyl benzothiazole

tetrafluoroborate 3 - (p-methoxy-benzyl) benzothiazole

hexafluoroantimonate 3 - benzyl-2 - methyl-benzothiazole

hexafluoroantimonate 3 - benzyl-5 - chlorobenzothiazole

six hexafluoroantimonate other benzothiazole

salts.

Among them, preferred to use sulfonium salts and benzothiazole

salts, particularly preferably a 4 - acetyl-phenyl dimethyl sulfonium hexafluoroarsenate, benzyl-4 - hydroxyphenyl methyl sulfonium hexafluoroantimonate 4 - acetoxy methyl benzyl phenyl sulfonium hexafluoroantimonate, dibenzyl-4 - hydroxyphenyl sulfonium hexafluoroantimonate 4 - acetoxy-benzyl phenyl sulfonium hexafluoroantimonate 3 - benzyl benzothiazole hexafluoroantimonate.

As their commercially available article, can enumerate サ Application ェィ De SI-L85, サ Application ェィ De SI-L110, サ Application ェィ De SI-L145, サ Application ェィ De SI-L150, サ Application ェィ De SI-L160 (three new chemical industry (strain) system) etc.

With respect to multipolymer [A weight portion, below preferred 20 weight portions of the usage ratio of [D] composition, more preferably below 5 weight portions.If this consumption surpasses 20 weight portions, then in the formation operation of filming, separate out precipitate, there is the situation of bringing obstacle for the formation of filming.

As the polymerizable compound with at least 1 ethylenic unsaturated double-bond of above-mentioned [E] composition, preferably enumerate for example above (methyl) acrylic ester of simple function (methyl) acrylic ester, difunctionality (methyl) acrylic ester or trifunctional.

As above-mentioned simple function (methyl) acrylic ester, for example can enumerate (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) carbitol acrylate, (methyl) IBOA, (methyl) acrylic acid 3-methoxyl butyl ester, 2-(methyl) acryloxy ethyl-2-hydroxypropyl phthalic ester etc.As their commercially available article, for example can enumerate アロニ Star Network ス M-101, アロニ Star Network ス M-111, more than the アロニ Star Network ス M-114(, East Asia synthetic (strain) system); KAYARAD TC-110S, more than the KAYARAD TC-120S(, Japanese chemical drug (strain) system); PVC スコ one ト 158, more than the PVC スコ one ト 311(, Osaka organic chemistry industry (strain) system) etc.

As above-mentioned difunctionality (methyl) acrylic ester; Can enumerate for example monoethylene glycol (methyl) acrylic ester, 1; 6-hexanediol two (methyl) acrylic ester, 1,9-nonanediol two (methyl) acrylic ester, polypropylene glycol two (methyl) acrylic ester, tetraethylene glycol two (methyl) acrylic ester, two phenoxetol fluorenes diacrylates, two phenoxetol fluorenes diacrylates etc.As their commercially available article, for example can enumerate アロニ Star Network ス M-210, アロニ Star Network ス M-240, more than the アロニ Star Network ス M-6200(, East Asia synthetic (strain) system); KAYARAD HDDA, KAYARAD HX-220, more than the KAYARAD R-604(, Japanese chemical drug (strain) system); PVC スコ one ト 260, PVC スコ one ト 312, more than the PVC スコ one ト 335HP(, Osaka organic chemistry industry (strain) system) etc.

As (methyl) acrylic ester more than the above-mentioned trifunctional; Can enumerate for example trimethylolpropane tris (methyl) acrylic ester; Pentaerythrite three (methyl) acrylic ester; Three ((methyl) phosphate acryloxy ethyl); Pentaerythrite four (methyl) acrylic ester; Dipentaerythritol five (methyl) acrylic ester; Dipentaerythritol six (methyl) acrylic ester etc.; As its commercially available article; Can enumerate for example アロニ Star Network ス M-309; アロニ Star Network ス M-400; アロニ Star Network ス M-405; アロニ Star Network ス M-450; アロニ Star Network ス M-7100; アロニ Star Network ス M-8030; More than the アロニ Star Network ス M-8060(, East Asia synthetic (strain) system); KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, more than the KAYARAD DPCA-120(, Japanese chemical drug (strain) system); PVC スコ one ト 295, PVC スコ one ト 300, PVC スコ one ト 360, PVC スコ one ト GPT, PVC スコ one ト 3PA, more than the PVC スコ one ト 400(, Osaka organic chemistry industry (strain) system) etc.

Wherein, preferably use above (methyl) acrylic ester of trifunctional, wherein preferred especially trimethylolpropane tris (methyl) acrylic ester, pentaerythrite four (methyl) acrylic ester, dipentaerythritol six (methyl) acrylic ester.

Above (methyl) acrylic ester of these simple functions, difunctionality or trifunctional can be used alone or in combination.With respect to multipolymer [A weight portion, below preferred 50 weight portions of the usage ratio of [E] composition, more preferably below 30 weight portions.

Through containing [E] composition with such ratio, can make interlevel insulator or the raisings such as lenticular thermotolerance and skin hardness that obtain by radiation sensitive resin composition of the present invention.If this use amount surpasses 50 weight portions, on substrate, in the operation of filming of formation radiation sensitive resin composition the coarse situation of film that occurs is arranged.

Other epoxy resin different with multipolymer [A] as above-mentioned [F] composition do not limit in the limit that does not influence compatibility.Preferred bisphenol A type epoxy resin, phenol novolac-type epoxy resin, cresols novolac-type epoxy resin, cycloaliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, heterocyclic ring epoxy resins, make GMA (be total to) polymerization and must resin etc.Wherein preferred especially bisphenol A type epoxy resin, cresols line style phenol aldehyde type epoxy resin, glycidyl ester type epoxy resin etc.

With respect to multipolymer [A weight portion, the usage ratio of [F] composition is preferably below 30 weight portions.Thermotolerance through containing [F] composition with such ratio, can further improve the diaphragm that obtains by radiation sensitive resin composition of the present invention or dielectric film and skin hardness etc.When if this ratio, then forms filming of radiation sensitive resin composition above 30 weight portions on substrate, the situation that exists the thickness homogeneity of filming to become not enough.

Multipolymer [A] also can be called " epoxy resin ", but have aspect the alkali solubility different with [F] composition.[F] composition is that alkali is insoluble.

In radiation sensitive resin composition of the present invention, can use surfactant as above-mentioned [G] composition in order further to improve coating.As at this operable [G] surfactant, can preferably use fluorine is surfactant, silicone-based surfactant and non-ionics.

As fluorine is the object lesson of surfactant, except 1,1, and 2; 2-tetrafluoro octyl group (1,1,2,2-tetrafluoro propyl group) ether, 2,2-tetrafluoro octyl group hexyl ether; Eight glycol, two (1,1,2-tetrafluoro butyl) ether; Hexaethylene glycol (1,1,2,3,3-hexafluoro amyl group) ether; Eight propylene glycol, two (1,1,2-tetrafluoro butyl) ether; Six propylene glycol, two (1,1,2,3,3-hexafluoro amyl group) ether; Perfluor sodium dodecylsulphonate, 2,2,8,9,10,10-ten fluorine dodecane, 2,2 outside the 3-hexafluoro decane etc., can also enumerate the fluoro-alkyl benzene sulfonic acid sodium salt; Fluoro-alkyl ethylene oxide ether; The fluoro-alkyl ammonium iodide; The fluoro-alkyl polyoxyethylene ether; Perfluoroalkyl poly oxyethanol (Port リォキシェタノ one Le); The perfluoroalkyl alkoxide; Fluorine is an Arrcostab etc.Can enumerate more than BM-1000 as their commercially available article is BM Chemie corporate system); メガ Off ア Star Network F142D; メガ Off ア Star Network 172; メガ Off ア Star Network 173; メガ Off ア Star Network 183; メガ Off ア Star Network 178; メガ Off ア Star Network F191; メガ Off ア Star Network 471(is above to be big Japanese ink chemical industry (strain) system); Off ロラ one De FC-170C is above to be Sumitomo スリ one ェ system (strain) system; サ one Off ロ Application S-112; サ one Off ロ Application S-113; サ one Off ロ Application S-131; サ one Off ロ Application S-141; サ one Off ロ Application S-145; サ one Off ロ Application S-382; サ one Off ロ Application SC-101; サ one Off ロ Application SC-102; サ one Off ロ Application SC-103; サ one Off ロ Application SC-104; サ one Off ロ Application SC-105; サ one Off ロ Application SC-106(Asahi Glass (strain) system), ェ Off ト Star プ EF301; ェ Off ト Star プ 303; The new autumn fields of ェ Off ト Star プ 352(changes into (strain) system) etc.

As above-mentioned silicone-based surfactant; For example can enumerate: trade name C3PA, DC7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032(be above to be eastern レダウコ one ニ Application グシリコ one Application (strain) system), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452(is above be that GE Toshiba シリコ one Application (strain) is made) etc. commercially available product.

As above-mentioned non-ionics, can use like polyoxyethylene alkyl ether classes such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ethers; Polyoxyethylene aryl ethers such as NONIN HS 240, polyoxyethylene nonylplenyl ether; Polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate, polyoxyethylene distearate etc.; (methyl) acrylic acid series copolymer Port リ Off ロ one No.57,95(common prosperity society chemistry (strain) system) etc.

These surfactants can use separately, or make up more than 2 kinds and use.

With respect to multipolymer [A weight portion, these [G] surfactants preferably use below 5 weight portions, more preferably use below 2 weight portions.[G] then forms when filming on substrate if amount of surfactant surpasses 5 weight portions, and becoming sometimes, it is coarse to be easy to produce the film of filming.

In addition, in the radiation sensitive resin composition of the present invention,, can use bonding auxiliary agent as [H] composition in order to improve the cementability with matrix.As so bonding auxiliary agent, can preferably use the functional silanes coupling agent, can enumerate for example have carboxyl, methacryl, NCO, the substituent silane coupling agent of epoxy radicals isoreactivity.Specifically can enumerate trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxy silane, vinyl triacetic acid base silane, vinyltrimethoxy silane, γ-isocyanates propyl-triethoxysilicane, γ-glycidoxypropyltrime,hoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane etc.With respect to multipolymer [A weight portion, preferably to use below 20 weight portions, more preferably use with the amount below 10 weight portions as the bonding auxiliary agent of such [H] composition.When the amount of bonding auxiliary agent surpassed 20 weight portions, in developing procedure, it was residual to be easy to development to occur sometimes.

Radiation sensitive resin composition

Radiation sensitive resin composition of the present invention can be through preparing above-mentioned multipolymer [A], [B] and [C] composition and any as stated even mixing of other compositions that add.Usually, radiation sensitive resin composition of the present invention is preferably dissolved in the appropriate solvent and uses with solution state.For example can prepare the radiation sensitive resin composition of solution state through mixing multipolymer [A], [B] and [C] composition and any as stated other compositions that add to scale.

As preparation radiation sensitive resin composition of the present invention used solvent, can use to make multipolymer [A], [B] and [C] composition and each composition uniform dissolution of other compositions of cooperation arbitrarily, and the solvent that does not react with each composition.

As such solvent, can enumerate and the identical solvent of solvent as the aforementioned solvent institute example of when being used to prepare multipolymer [A], using.

In the middle of such solvent, from the dissolubility of each composition, with the reactivity of each composition, form the viewpoints such as easness of filming and consider, can preferably use alcohol, glycol ether, monoethylene glycol alkyl ether acetic acid esters, ester and diglycol.Wherein, can especially preferably use benzylalcohol, 2-phenylethyl alcohol, 3-phenyl-1-propyl alcohol, ethylene glycol monobutyl ether acetic acid esters, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diglycol ethyl-methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, methoxypropionic acid methyl esters, ethoxyl ethyl propionate.

In order to improve the inner evenness of thickness, can be further with above-mentioned solvent and use high boiling solvent.As can and the high boiling solvent of usefulness; Can enumerate N-NMF, N are for example arranged; Dinethylformamide, N-methyl formyl aniline, N-methylacetamide, DMAC N,N, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), benzylisoeugenol, hexyl ether, acetonyl acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, propylene carbonate, phenylacetic acid cellosolve etc.Wherein, preferred N-Methyl pyrrolidone, gamma-butyrolacton, DMAC N,N.

As the solvent of radiation sensitive resin composition of the present invention, and when using high boiling solvent, its consumption is with respect to below the preferred 50 weight % of solvent total amount, more preferably below the 40 weight %, further below the preferred 30 weight %.If the consumption of high boiling solvent surpasses this consumption, then there is the tendency of film thickness uniformity, susceptibility and the residual film ratio reduction of filming.

When being prepared into solution state to radiation sensitive resin composition of the present invention; The shared ratio of composition beyond desolventizing in the solution (just multipolymer [A], [B] and [C] composition and the total amount of other compositions of interpolation arbitrarily); Can set arbitrarily according to application target and desirable film thickness value etc.; Be preferably 5～50 weight %; More preferably 10～40 weight %, further preferred 15～35 weight %.

The composition solution of preparation like this, via hole diameter is after the millipore filter about 0.2 μ m etc. filters, and is available.

Interlayer dielectric, lenticular formation

Down in the face of using radiation sensitive resin composition of the present invention, form interlayer dielectric of the present invention, lenticular method is described.The order that interlayer dielectric of the present invention or lenticular formation method are the following stated comprises following operation.

(1) operation of filming of formation radiation sensitive resin composition of the present invention on substrate,

(3) developing procedure, and

(4) heating process.

(1) operation of filming of formation radiation sensitive resin composition of the present invention on substrate

In above-mentioned (1) operation, coating composition solution of the present invention on substrate surface preferably through carrying out prebake conditions except that desolvating, forms filming of radiation sensitive resin composition.

As the kind of operable substrate, can enumerate the substrate that is formed with various metals like glass substrate, silicon wafer with on their surface.

Coating process as composition solution; Not special the qualification; Can adopt like proper method such as spraying process, rolling method, method of spin coating (spin-coating method), slit mouth mould rubbing method, excellent rubbing method, ink-jet application methods preferred especially spin-coating method, slit mouth mould rubbing method.As the condition of prebake conditions, different according to the kind of each composition, usage ratio etc.For example, can be to carry out under 60～110 ℃ about 30 seconds～15 minutes.

As the thickness of filming that forms, as the value after the prebake conditions, when forming interlayer dielectric, for example be preferably 3～6 μ m, when forming lenticule, for example be preferably 0.5～3 μ m.

(2) to the operation of this at least a portion of filming irradiation radioactive ray

In the operation of above-mentioned (2), film through behind the mask irradiation radioactive ray with predetermined pattern to formed, use developer solution to carry out development treatment and assign to form pattern through the irradiating part of removing radioactive ray.As the radioactive ray that use this moment, can enumerate for example ultraviolet ray, far ultraviolet, X ray, charged particle ray etc.

Can enumerate for example g line (wavelength 436nm), i line (wavelength 365nm) etc. as above-mentioned ultraviolet ray.For example can enumerating as far ultraviolet, KrF swashs basic laser etc.Can enumerate for example synchrotron radioactive ray etc. as X ray.Can enumerate for example electron beam etc. as the charged particle ray.

In them, preferred ultraviolet ray wherein especially preferably contains the radioactive ray of g line and/or i line.

As exposure, preferred 50～1 when forming interlayer dielectric, 500J/m < > 2 <> , preferred 50～2 when forming lenticule, 000J/m < > 2 <>

(3) developing procedure

As developer solution used in development treatment; Can use for example NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-pro-pyl amine, diethylamide, diethylaminoethanol, di-n-propyl amine, triethylamine, methyl diethylamide, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrroles, piperidines, 1; 8-diazabicylo [5.4.0 undecylene, 1, the WS of alkali (alkali compounds) such as 5-diazabicylo [4.3.0 nonane.In addition, an amount of WS that adds water-miscible organic solvent such as methyl alcohol, ethanol or surfactant in the WS of above-mentioned alkali, or the various organic solvents that dissolve composition of the present invention can be used as developer solution.And then, as developing method, for example can utilize liquid hollow method, infusion process, shake proper methods such as infusion process, spray process.The development time of this moment is different with the composition of composition, for example can be made as 30～120 seconds.

For known in the past radiation sensitive resin composition; If development time surpassed Best Times about 20～25 seconds; The pattern that then forms is peeled off; Therefore have and strictly to control development time; For radiation sensitive resin composition of the present invention; Even surpass optimum development time more than 30 seconds, also can form good pattern, the advantage aspect the yield rate of goods is arranged.

(4) heating process

Behind (3) developing procedure of implementing as stated; Film to forming pattern preferably carries out the carrying out washing treatment as cleaning with circulating water; And then; Also preferred through shine radioactive ray (post-exposure) comprehensively by generations such as high-pressure sodium lamps; During this is filmed remaining 1; 2-two nitrine naphtoquinone compounds carry out resolution process, through heating arrangements such as hot plate, baking ovens this film are carried out heat treated (back baking processing) then, carry out the cured of this film.Exposure in the above-mentioned post-exposure operation is preferably 2,000～5,000J/m < > 2 <> About.In addition, the sintering temperature in this cured for example is 120～250 ℃.Heat time heating time is different and different with the kind of heating instrument, as when on hot plate, carrying out heat treated, being set at 5～30 minutes; When in baking oven, carrying out heat treated, can be set at 30～90 minutes.At this moment also can adopt sectional type baking that carries out heat treated more than 2 times etc.

On substrate surface, can form interlayer dielectric or the corresponding pattern-like film of lenticule like this with purpose.

As after to state embodiment said, the interlayer dielectric and the lenticule that form as stated are excellent at aspects such as stickiness, thermotolerance, solvent resistance and the transparencys.

Interlayer dielectric

The interlayer dielectric of the present invention that forms as stated is good to the stickiness of substrate, and solvent resistance and excellent heat resistance have high-transmission rate, and specific inductive capacity is low, is preferably used as the interlayer dielectric of electronic unit.

Lenticule

The lenticule of the present invention that forms as stated is good to the stickiness of substrate, solvent resistance and excellent heat resistance, and have high-transmission rate and good melt shape, be preferably used as the lenticule of solid photographic element.

In addition, lenticular shape of the present invention is like figure 1(a) shown in, semi-convex lens shape be.

As above; Radiation sensitive resin composition of the present invention has high radioactive ray susceptibility; Even have when in developing procedure, surpassing optimum development time, also have the development surplus that can form good pattern form, can easily form stickiness excellent pattern shape film.

By the interlayer dielectric of the present invention that above-mentioned composition forms, good to the stickiness of substrate, solvent resistance and excellent heat resistance have high-transmission rate, and specific inductive capacity is low, is preferably used as the interlayer dielectric of electronic unit.

In addition, good by the lenticule of the present invention that above-mentioned composition forms to the stickiness of substrate, solvent resistance and excellent heat resistance, and have high-transmission rate and good melt shape, be preferably used as the lenticule of solid photographic element.

[embodiment]

Below enumerate synthetic example, embodiment, the present invention more specifically is described, but the present invention is not limited to following embodiment.

The synthetic example of multipolymer [A]

Synthetic example 1

In the flask that possesses condenser pipe, stirring machine, add 2,2 '-azo, two (2,4-methyl pentane nitrile)7 weight portion, diglycol ethyl-methyl ether 200 weight portions.Then add methacrylic acid 16 weight portions, methacrylic acid three ring [5.2.1.0 < > 2,6 <> ] decane-8-base ester 16 weight portions, acrylic acid 2-methylcyclohexyl ester 20 weight portions, GMA 40 weight portions, styrene 10 weight portions and AMS dimer 3 weight portions, and after carrying out nitrogen replacement, beginning is slowly stirred.Make solution temperature rise to 70 ℃, kept this temperature 4 hours, obtain containing the polymer solution of multipolymer [A-1].

The weight-average molecular weight of polymkeric substance is 8,000, and molecular weight distribution (ratio of weight-average molecular weight/number-average molecular weight) is 2.3.In addition, the solid component concentration at this polymer solution that obtains is 34.4 weight %.

Weight-average molecular weight and number-average molecular weight are to use GPC(gel permeation chromatography (eastern Application one (strain) system HLC-8020) to measure the mean molecular weight of the polystyrene conversion that obtains.

Synthetic example 2

In the flask that possesses condenser pipe, stirring machine, add 2,2 '-azo, two (2,4-methyl pentane nitrile)8 weight portion and diglycol ethyl-methyl ether 220 weight portions.Then add methacrylic acid 11 weight portions, methacrylic acid tetrahydro furfuryl ester 12 weight portions, GMA 40 weight portions, N-cyclohexyl maleimide 15 weight portions, methacrylic acid Lauryl Ester 10 weight portions, Alpha-Methyl-para hydroxybenzene ethene 10 weight portions and AMS dimer 3 weight portions; And after carrying out nitrogen replacement, beginning is slowly stirred.Make solution temperature rise to 70 ℃, kept this temperature 5 hours, obtain containing the polymer solution of multipolymer [A-2].

The weight-average molecular weight of polymkeric substance is 8,000, and molecular weight distribution (ratio of weight-average molecular weight/number-average molecular weight) is 2.3.In addition, the solid component concentration at this polymer solution that obtains is 31.9 weight %.

Synthetic example 3

In the flask that possesses condenser pipe, stirring machine, add 2,2 '-azo, two (2,4-methyl pentane nitrile)8 weight portion and diglycol ethyl-methyl ether 220 weight portions.Then add styrene 10 weight portions, methacrylic acid 20 weight portions, GMA 40 weight portions, methacrylic acid (3-ethyl oxetanyl-3-yl) ester 10 weight portions and methacrylic acid three ring [5.2.1.0 < > 2,6 <> ] decane-8-base ester 20 weight portions, and after carrying out nitrogen replacement, beginning is slowly stirred.Make solution temperature rise to 70 ℃, kept this temperature 5 hours, obtain containing the polymer solution of multipolymer [A-3].

The weight-average molecular weight of polymkeric substance is 7,900, and molecular weight distribution (ratio of weight-average molecular weight/number-average molecular weight) is 2.4.In addition, the solid component concentration at this polymer solution that obtains is 31.6 weight %.

Synthetic example 4

In the flask that possesses condenser pipe, stirring machine, add 2,2 '-azo, two (2,4-methyl pentane nitrile)8 weight portion and diglycol ethyl-methyl ether 220 weight portions.Then add styrene 5 weight portions, methacrylic acid 16 weight portions, GMA 40 weight portions and N-(4-hydroxy phenyl) Methacrylamide 10 weight portions; And after carrying out nitrogen replacement; Add 1,3-butadiene 5 weight portions, beginning is slowly stirred.Make solution temperature rise to 70 ℃, kept this temperature 5 hours, obtain containing the polymer solution of multipolymer [A-4].

The weight-average molecular weight of polymkeric substance is 7,900, and molecular weight distribution (ratio of weight-average molecular weight/number-average molecular weight) is 2.4.In addition, the solid component concentration at this polymer solution that obtains is 31.5 weight %.

Synthetic example 5

In the flask that possesses condenser pipe, stirring machine, add 2,2 '-azo, two (2,4-methyl pentane nitrile)7 weight portion, propylene glycol monomethyl ether 220 weight portions.Then add methacrylic acid 22 weight portions, GMA 40 weight portions, methacrylic acid two cyclopentyl esters 28 weight portions, 3-ethyl-3-methacryloxy methyl oxetanes 10 weight portions, AMS dimer 3 weight portions; And carry out nitrogen replacement on one side, Yi Bian begin slow stirring.Make solution temperature rise to 70 ℃, heating is 4 hours under this temperature, obtains containing the polymer solution of multipolymer [A-5].The solid component concentration of the polymer solution that obtains is 31.8 weight %, and the weight-average molecular weight of polymkeric substance is 17,900, and molecular weight distribution (ratio of weight-average molecular weight/number-average molecular weight) is 1.8.

Synthetic example 6

In the flask that possesses condenser pipe, stirring machine, add 2,2 '-azo, two (2,4-methyl pentane nitrile)7 weight portion, diglycol ethyl-methyl ether 220 weight portions.Then add styrene 5 weight portions, methacrylic acid 22 weight portions, GMA 40 weight portions, 3-ethyl-3-methacryloxy methyl oxetanes 5 weight portions, methacrylic acid two cyclopentyl esters 28 weight portions; And carry out nitrogen replacement on one side, Yi Bian begin slow stirring.Make solution temperature rise to 70 ℃, heating is 4 hours under this temperature, obtains containing the polymer solution of multipolymer [A-6].The solid component concentration of the polymer solution that obtains is 31.9 weight %, and the weight-average molecular weight of polymkeric substance is 20,200, and molecular weight distribution (ratio of weight-average molecular weight/number-average molecular weight) is 1.9.

Synthetic example 7

In the flask that possesses condenser pipe, stirring machine, add 2,2 '-azo, two (2,4-methyl pentane nitrile)7 weight portion, diglycol ethyl-methyl ether 200 weight portions.Then add methacrylic acid 12 weight portions, cyclohexyl maleimide 12 weight portions, Alpha-Methyl-para hydroxybenzene ethene 9 weight portions, GMA 50 weight portions, 3-ethyl-3-methacryloxy methyl oxetanes 10 weight portions, methacrylic acid tetrahydro furfuryl ester 7 weight portions, AMS dimer 3 weight portions; And carry out nitrogen replacement on one side, Yi Bian begin slow stirring.Make solution temperature rise to 70 ℃, heating is 5 hours under this temperature, obtains containing the polymer solution of multipolymer [A-7].The solid component concentration of the polymer solution that obtains is 32.7 weight %, and the weight-average molecular weight of polymkeric substance is 21,500, and molecular weight distribution (ratio of weight-average molecular weight/number-average molecular weight) is 2.2.

Synthetic example 8

In the flask that possesses condenser pipe, stirring machine, add 2,2 '-azo, two (2,4-methyl pentane nitrile)8 weight portion, diglycol ethyl-methyl ether 220 weight portions.Then add styrene 20 weight portions, methacrylic acid 30 weight portions, 3-ethyl-3-methacryloxy methyl oxetanes 20 weight portions, GMA 30 weight portions, AMS dimer 4.0 weight portions; And carry out nitrogen replacement on one side, Yi Bian begin slow stirring.Make solution temperature rise to 70 ℃, heating is 5 hours under this temperature, obtains containing the polymer solution of multipolymer [A-8].The solid component concentration of the polymer solution that obtains is 31.0 weight %, and the weight-average molecular weight of polymkeric substance is 19,000, and molecular weight distribution (ratio of weight-average molecular weight/number-average molecular weight) is 1.7.

Relatively more synthetic example 1

In the flask that possesses condenser pipe, stirring machine, add 2,2 '-azo, two (2,4-methyl pentane nitrile)7 weight portion, diglycol methyl ethyl ether 220 weight portions.Then add methacrylic acid 23 weight portions, methacrylic acid two cyclopentyl esters 47 weight portions, GMA 20 weight portions, AMS dimer 2.0 weight portions, Yi Bian and carry out nitrogen replacement, Yi Bian begin slow stirring.Make solution temperature rise to 70 ℃, kept this temperature 5 hours, obtain containing multipolymer [A-1R] polymer solution.The solid component concentration of the polymer solution that obtains is 32.8 weight %, and the weight-average molecular weight of polymkeric substance is 24,000, and molecular weight distribution (ratio of weight-average molecular weight/number-average molecular weight) is 2.3.

Relatively more synthetic example 2

In the flask that possesses condenser pipe, stirring machine, add 2,2 '-azo, two (2,4-methyl pentane nitrile)7 weight portion, diglycol methyl ethyl ether 220 weight portions.Then add methacrylic acid 25 weight portions, methacrylic acid two cyclopentyl esters 35 weight portions, methacrylic acid 2-hydroxyethyl ester 40 weight portions, AMS dimer 2.0 weight portions, Yi Bian and carry out nitrogen replacement, Yi Bian begin slow stirring.Make solution temperature rise to 70 ℃, kept this temperature 5 hours, obtain containing multipolymer [A-2R] polymer solution.The solid component concentration of the polymer solution that obtains is 32.8 weight %, and the weight-average molecular weight of polymkeric substance is 25,000, and molecular weight distribution (ratio of weight-average molecular weight/number-average molecular weight) is 2.4.

The synthetic example of cyclosiloxane oligomer [C]

Synthetic example 1

In the three-neck flask of 500mL, add phenyltrimethoxysila,e 39.6g, (3-ethyl oxetanes-3-yl) propyl-triethoxysilicane 64.0g; Add methyl isobutyl ketone 100g and make its dissolving, on one side the mixed solution that obtains is heated to 60 ℃ with magnetic stirrer on one side.Therein, added the 8.6g ion exchange water that contains 1 weight % oxalic acid continuously through 1 hour.After 4 hours the reactant liquor that obtains is cooled to room temperature in reaction under 60 ℃ then.To as pure composition from the reactant liquor decompression distillation of byproduct of reaction remove thereafter.The weight-average molecular weight of this polymkeric substance [C-1] is 1,600.

Synthetic example 2

In the three-neck flask of 500mL, add dimethoxydiphenylsilane 48.8g, 2-(3; The 4-epoxycyclohexyl) ethyl trimethoxy silane 49.2g; Add methyl proxitol acetate 100g and make its dissolving, on one side the mixed solution that obtains is heated to 60 ℃ with magnetic stirrer on one side.Therein, added the 8.6g ion exchange water that contains 1 weight % oxalic acid continuously through 1 hour.After 4 hours the reactant liquor that obtains is cooled to room temperature in reaction under 60 ℃ then.To as pure composition from the reactant liquor decompression distillation of byproduct of reaction remove thereafter.The weight-average molecular weight of this polymkeric substance [C-2] is 2,000.

Synthetic example 3

In the three-neck flask of 500mL, add tetramethoxy-silicane 30.4g, 3-glycidoxypropyltrime,hoxysilane 47.2g, add methyl proxitol 100g and make its dissolving, on one side the mixed solution that obtains is heated to 60 ℃ with magnetic stirrer on one side.Therein, added the 8.6g ion exchange water that contains 1 weight % oxalic acid continuously through 1 hour.After 4 hours the reactant liquor that obtains is cooled to room temperature in reaction under 60 ℃ then.To as pure composition from the reactant liquor decompression distillation of byproduct of reaction remove thereafter.The weight-average molecular weight of this polymkeric substance [C-3] is 1,400.

Synthetic example 4

In the three-neck flask of 500mL, add MTMS 27.2g, 3-sulfydryl trimethoxy silane 39.2g, add methyl proxitol 100g and make its dissolving, on one side the mixed solution that obtains is heated to 60 ℃ with magnetic stirrer on one side.Therein, added the 8.6g ion exchange water that contains 1 weight % oxalic acid continuously through 1 hour.After 4 hours the reactant liquor that obtains is cooled to room temperature in reaction under 60 ℃ then.To as pure composition from the reactant liquor decompression distillation of byproduct of reaction remove thereafter.The weight-average molecular weight of this polymkeric substance [C-4] is 1,900.

Embodiment 1

[preparation of radiation sensitive resin composition]

The solution (as [A] composition synthetic in the above-mentioned synthesis example 1) that will contain polymer [A-1] is to be equivalent to the amount of polymer [A-1] 100 weight portions (solid constituent); With as 4 of composition [B]; 4 '-[1-[4-[1-[4- hydroxy phenyl]-1- Methylethyl] phenyl] ethylidene] bis-phenol (1.0 moles) and 1; Condensation product (B-1) 30 weight portions of 2- diazido naphthoquinone-5- sulfonic acid chloride (2.0 moles) and polymer [C-1] 3 weight portions (solid constituent) mix; Be dissolved to diethylene glycol (DEG) ethyl-methyl ether so that after solid component concentration is 30 weight %; Molecular filter with bore 0.2 μ m filters, the solution (S-1) of preparation radioactivity sensitive compositions.

Embodiment 2～16, comparative example 1

[preparation of radiation sensitive resin composition]

In embodiment 1, as [A] composition and [B] composition, uses outside kind as described in Table 1, the amount, likewise implements with embodiment 1, prepare the solution (S-2)～(S-16) of radiation sensitive resin composition and (s-1).

Among the embodiment 2,6,10,14, the record of [B] composition representes to share respectively 2 kind 1,2-two nitrine naphtoquinone compounds.

Embodiment 17

Except in embodiment 1; With diglycol ethyl-methyl ether/propylene glycol monomethyl ether=6/4 dissolving,, and add (F) in addition so that solid component concentration is 20 weight %; Likewise prepare composition with embodiment 1, the solution (S-17 of preparation radiation sensitive resin composition).

In the table 1, composition is called for short the following compound of expression.

(B-1) :4,4 '-[1-[4-[1-[4-hydroxy phenyl Methylethyl] phenyl] ethylidene] bis-phenol (1.0 mole) with 1,2-diazido naphthoquinone-5-sulfonic acid chloride (2.0 mole) condensation product

(B-2) :4,4 '-[1-[4-[1-[4-hydroxy phenyl Methylethyl] phenyl] ethylidene] bis-phenol (1.0 mole) with 1,2-diazido naphthoquinone-5-sulfonic acid chloride (1.0 mole) condensation product

(B-3) :2,3,4,4 '-tetrahydroxybenzophenone (1.0 mole) with 1,2-diazido naphthoquinone-5-sulphonic acid ester (2.44 moles)

(F):SH-28PA(east レダウコ one ニ Application グシリコ one Application (strain) system)

< > [0286] <> Embodiment 18～34, comparative example 2

< as the performance evaluation of interlayer dielectric >

Use the as above radiation sensitive resin composition of preparation, the following various characteristics of estimating as interlayer dielectric.

[evaluation of susceptibility]

For embodiment 18～33, comparative example 2, on silicon substrate, use spinner, behind the described composition of coating table 2,, form filming of thickness 3.0 μ m 90 ℃ of prebake conditions 2 minutes on hot plate.To embodiment 34, be coated with through slit mouth mould coating machine, under 0.5Torr, carry out vacuum drying after, 90 ℃ of prebake conditions 2 minutes on hot plate, form filming of thickness 3.0 μ m.Make filming of obtaining through having the pattern mask of predetermined pattern; Change after the time shutter makes public with Canon's (strain) system PLA-501F exposure machine (ultrahigh pressure mercury lamp); The tetramethylammonium hydroxide aqueous solution of his-and-hers watches 2 said concentration; Under 25 ℃; When using the developer solution of 0.4% concentration, developed 80 seconds, when using the developer solution of 2.38% concentration; Developed 50 seconds, and developed through the hollow method of liquid.With ultrapure water washing 1 minute, drying also formed pattern on wafer.Mensuration for the lines that make 3.0 μ m and at interval the intermittent pattern of (10 to 1) dissolve essential exposure fully.Should be worth as susceptibility, as shown in table 2.This is worth 1,000J/m < > 2 <> We can say when following that susceptibility is good.

[evaluation of development surplus]

For embodiment 18～33, comparative example 2, on silicon substrate, use spinner, behind the described composition of coating table 2,, form filming of thickness 3.0 μ m 90 ℃ of prebake conditions 2 minutes on hot plate.To embodiment 34, be coated with through slit mouth mould coating machine, under 0.5Torr, carry out vacuum drying after, 90 ℃ of prebake conditions 2 minutes on hot plate, form filming of thickness 3.0 μ m.Make filming of obtaining have the lines and a mask of the pattern of (10 to 1) at interval through 3.0 μ m; With the system PLA-501F of Canon's (strain) exposure machine (ultrahigh pressure mercury lamp); Through making public with above-mentioned " [evaluation of susceptibility] " middle suitable exposure of sensitivity value of measuring; The tetramethylammonium hydroxide aqueous solution of his-and-hers watches 2 said concentration; Under 25 ℃; Change development time, develop through the hollow method of liquid.With ultrapure water flowing water washing 1 minute, drying formed pattern on wafer then.At this moment, live width is reached the necessary development time of 3.0 μ m as optimum development time, be shown in Table 2.In addition, during from optimum development time continuation development, mensuration reaches the time that 3.0 μ m line patterns are stripped from, and is shown in Table 2 as the development surplus.This value we can say that the development surplus is good more than 30 seconds the time.

[evaluation of solvent resistance]

For embodiment 18～33, comparative example 2, on silicon substrate, use spinner, behind the described composition of coating table 2,90 ℃ of prebake conditions 2 minutes on hot plate, formation is filmed.To embodiment 34, be coated with through slit mouth mould coating machine, under 0.5Torr, carry out vacuum drying after, 90 ℃ of prebake conditions 2 minutes on hot plate, formation is filmed.Film with Canon's (strain) system PLA-501F exposure machine (ultrahigh pressure mercury lamp) exposure so that the accumulative total exposure reaches 3,000J/m to what obtain < > 2 <> , this silicon substrate was heated 1 hour down at 220 ℃ in the baking oven of cleaning, obtain the cured film of thickness 3.0 μ m.The thickness (T1 of the cured film that mensuration obtains).The silicon substrate that forms this cured film impregnated in the dimethyl sulfoxide (DMSO) that temperature is controlled in 70 ℃ 20 minutes, measures the thickness (t1 of this cured film then), calculate because Thickness Variation rate {|t1-T1|/T1} * 100[% that dipping produces].The result is as shown in table 2.This value we can say that 5% when following solvent resistance is good.

In addition, the film that forms in the evaluation of solvent resistance does not need patterning, therefore omits radiation exposure operation and developing procedure, and only film formation operation, back roasting procedure and heating process are used for estimating.

[stable on heating evaluation]

Likewise form cured film with the evaluation of above-mentioned solvent resistance, measure the cured film thickness (T2 that obtains).Then, with this cured film substrate in the baking oven of cleaning appending baking under 240 ℃ after 1 hour, measure the thickness (t2 of this cured film), calculate owing to append Thickness Variation rate {|t2-T2|/T2} * 100[% that baking produces].The result is as shown in table 2.This value we can say that 5% when following thermotolerance is good.

[evaluation of cured film stickiness]

Likewise form cured film with the evaluation of above-mentioned solvent resistance; The aluminum bolt pin with circular bonding plane (QUAD society system) of the diameter 0.27cm of pre-coating epoxy resin is bonded on the cured film so that the relative substrate of latching is vertical, in the baking oven of cleaning, under 150 ℃, carries out baking in 1 hour and make epoxy resin cure.Then, adopt cupping machine (Motorized StandSDMS-0201-100SL((strain) modern field makes made)) the tensile bolt pin, carry out the mensuration of substrate and the cured film power when peeling off thus.This moment, the value of this power was as shown in table 2.If this value is more than 150N then we can say the stickiness of substrate good.

[evaluation of the transparency]

Except in the evaluation of above-mentioned solvent resistance, and the use glass substrate " コ one ニ Application ダ 7059(コ one ニ Application グ society system) " replace likewise on glass substrate, forming cured film outside the silicon substrate.Under the wavelength of the scope of 400～800nm, measure the transmittance of glass substrate with this cured film with spectrophotometer " 150-20 type twin-beam ((strain) Hitachi's system) ".The minimum light transmission rate value of this moment is as shown in table 2.This value is 90% when above, we can say that the transparency is good.

[evaluation of relative dielectric constant]

For embodiment 18～34, comparative example 2, on the SUS304 system substrate of polishing, use spinner, behind the described composition of coating table 2,, form filming of thickness 3.0 μ m 90 ℃ of prebake conditions 2 minutes on hot plate.To embodiment 35, be coated with through slit mouth mould coating machine, under 0.5Torr, carry out vacuum drying after, 90 ℃ of prebake conditions 2 minutes on hot plate, form filming of thickness 3.0 μ m.Film with Canon's (strain) system PLA-501F exposure machine (ultrahigh pressure mercury lamp) exposure so that the accumulative total exposure reaches 3,000J/m to what obtain < > 2 <> , with this substrate in the baking oven of cleaning 220 ℃ of following sintering 1 hour, thereby obtain cured film.To this cured film, process specific inductive capacity mensuration through vapour deposition method formation Pt/Pd electrode pattern and use sample.With this substrate is under the frequency of 10kHz in frequency, uses Yokogawa ヒュ-レ Star トパ Star カ one De (strain) system HP16451B electrode and accurate LCR analyzer of HP4284A, measures the relative dielectric constant of this substrate through the CV method.The result is as shown in table 2.This value we can say that 3.9 when following specific inductive capacity is good.

In the evaluation of specific inductive capacity, the film of formation does not need pattern, therefore omits radiation exposure operation and developing procedure, and only film formation operation, back roasting procedure and heating process are used for estimating.

[0307]

< > [0309] <> Embodiment 35～50, comparative example 3

< as lenticular performance evaluation >

Use the as above radiation sensitive resin composition of preparation, estimate as lenticular various characteristics as follows.The evaluation of the evaluation of solvent resistance, stable on heating evaluation, the transparency is with reference to the result in the performance evaluation of above-mentioned interlayer dielectric.

[evaluation of susceptibility]

For embodiment 35～50, comparative example 3, on silicon substrate, use spinner, behind the described composition of coating table 3,, form filming of thickness 2.0 μ m 90 ℃ of prebake conditions 2 minutes on hot plate.Make filming of obtaining through having the pattern mask of predetermined pattern; With Nikon (strain) system NSR1755i7A reduced projection exposure machine (NA=0.50; λ=365nm) changes after the time shutter makes public; The tetramethylammonium hydroxide aqueous solution of his-and-hers watches 3 said concentration; Under 25 ℃, through the hollow Faxian shadow of liquid 1 minute.Use water washing, drying also forms pattern on wafer.Mensuration for the lines that make 0.8 μ m and intermittent pattern (1 than 1) the interval live width reach the essential time shutter of 0.8 μ m.Should be worth as susceptibility, as shown in table 3.This is worth 2,000J/m < > 2 <> We can say when following that susceptibility is good.

[evaluation of development surplus]

For embodiment 35～50, comparative example 3, on silicon substrate, use spinner, behind the described composition of coating table 3,, form filming of thickness 2.0 μ m 90 ℃ of prebake conditions 2 minutes on hot plate.Make filming of obtaining through having the pattern mask of predetermined pattern; With Nikon (strain) system NSR1755i7A reduced projection exposure machine (NA=0.50; The exposure of the value of the susceptibility of λ=365nm) measuring in above-mentioned to be equivalent to " [evaluation of susceptibility] " is made public; The tetramethylammonium hydroxide aqueous solution of his-and-hers watches 3 said concentration; Under 25 ℃, through the hollow Faxian shadow of liquid 1 minute.Use water washing then, on the wafer of drying, form pattern.With the lines that make 0.8 μ m and intermittent pattern (1 than 1) the interval live width reach the essential time shutter of 0.8 μ m as optimum development time, be shown in Table 3.In addition, when optimum development time continue to develop, measure the time (development surplus) that the pattern that reaches wide 0.8 μ m is stripped from, be shown in Table 3 as the development surplus.This value we can say that the development surplus is good more than 30 seconds the time.

[lenticular formation]

For embodiment 35～50, comparative example 3, on silicon substrate, use spinner, behind the described composition of coating table 3,, form filming of thickness 2.0 μ m 90 ℃ of prebake conditions 2 minutes on hot plate.Make filming of obtaining through having the pattern mask of 4.0 μ m points, 2.0 μ m intermittent patterns; With Nikon (strain) system NSR1755i7A reduced projection exposure machine (NA=0.50; λ=365nm) exposure of measuring sensitivity value in above-mentioned to be equivalent to " [evaluation of susceptibility] " is made public; Tetramethylammonium hydroxide aqueous solution with the described concentration of solution level in estimating as table 3 susceptibility; Under 25 ℃, through the hollow Faxian shadow of liquid 1 minute.Use water washing then, on the wafer of drying, form pattern.Then, reach 3,000J/m with Canon's (strain) system PLA-501F exposure machine (ultrahigh pressure mercury lamp) exposure so that add up exposure < > 2 <> Further made the pattern melt flows form lenticule in 10 minutes with 160 ℃ of heating after 10 minutes on the hot plate then with 230 ℃ of heating.

The size (diameter) and the cross sectional shape of the lenticular bottom (face that engages with substrate) that forms are as shown in table 3.The size of lenticule bottom surpasses 4.0 μ m and during less than 5.0 μ m, we can say good.If its size reaches more than the 5.0 μ m, is state of contact between the then adjacent lens, and is not preferred.In addition, good when cross sectional shape is (a) such semi-convex lens shape in mode chart shown in Figure 1, be (b) such being roughly when trapezoidal, bad.

< > [0321] <> Embodiment 51

The preparation of radiation sensitive resin composition

Mix the polymer solution that contains the multipolymer [A-5] that obtains in the synthetic example 5 and (be equivalent to multipolymer [A-5 weight portion (solid constituent)); With 4 '-[1-[4-[1-[4-hydroxy phenyl Methylethyls as composition [B]] phenyl] ethylidene] bis-phenol (1 mole) with 1; 2-diazido naphthoquinone-5-sulfonic acid chloride (2 mole) condensation product (4 '-[1-[4-[1-[4-hydroxy phenyl Methylethyl] phenyl] ethylidene] bis-phenol-1; 2-diazido naphthoquinone-5-sulphonic acid ester) 20 weight portions; Four [(3-ethyl oxetanes-3-yls) methyl] condensed polymer 2 weight portions of esters of silicon acis; And γ-metacryloxy propyl trimethoxy silicane 5 weight portions; Be dissolved to propylene glycol monomethyl ether so that after solid component concentration is 30 weight %; Millipore filter with aperture 0.5 μ m filters, the solution (S-51 of preparation radioactivity sensitive compositions).

The evaluation of interlayer dielectric

(I) formation of pattern-like film

On glass substrate, use spinner coating above-mentioned composition solution (S-51) afterwards, 80 ℃ of prebake conditions 3 minutes on hot plate, formation is filmed.

Above-mentioned filming of obtaining used the predetermined pattern mask to be radiated at wavelength 65nm place intensity to be 10mW/cm < > 2 <> 15 seconds of ultraviolet ray.After 1 minute, washed 1 minute in development under 25 ℃ with 0.5 weight % tetramethylammonium hydroxide aqueous solution afterwards with pure water.Through these operations, remove part not.

Intensity is 10mW/cm at wavelength 65nm place to the patterned illumination of above-mentioned formation < > 2 <> 30 seconds of ultraviolet ray after, through in 220 ℃ baking oven, being heating and curing 60 minutes, obtain the pattern-like film of thickness 3.0 μ m.

In addition,, carry out operation same as described above, obtain 3 kinds of different pattern-like films of prebake conditions temperature except the prebake conditions temperature is changed into 90 ℃, 100 ℃.

(II) the evaluation of resolution

To the pattern-like film that obtains by above-mentioned (I), with punching press pattern (5 μ m * 5 μ m holes) situation about can differentiate is " * " for " zero ", unresolvable situation.The result is shown in table 4.

(III) evaluation of heat-resisting dimensional stability

In above-mentioned (I), will in baking oven, heat 60 minutes down at 80 ℃ of Thinfilm patterns that form down of prebake conditions temperature at 220 ℃.The rate of change of the thickness before and after the heating is as shown in table 5.The size changing rate of this moment is in 5% before and after the heating time, we can say that heat-resisting dimensional stability is good, and size changing rate surpasses at 5% o'clock, we can say bad.

(IV) the evaluation of the transparency

In above-mentioned (I), use spectrophotometer (150-20 type twin-beam (Hitachi (strain) system)) to be determined at the transmissivity of the 400nm of 80 ℃ of pattern-like films that form down of prebake conditions temperature, carry out the evaluation of the transparency.The result is shown in Table 5.This moment, transmissivity was that situation 90% or more we can say that the transparency well, we can say bad less than 90% situation.

(V) evaluation of heat-resisting discolouration

In above-mentioned (I), the substrate that will have the pattern-like films that form down 80 ℃ of prebake conditions temperature heat 1 hour in 250 ℃ baking oven, and heat-resisting discolouration is estimated in the variation of the transmissivity of the pattern-like film through the heating front and back.The evaluation result of this moment is shown in Table 5.Rate of change we can say that less than 5% o'clock heat-resisting discolouration is good, surpasses at 5% o'clock and we can say bad.Transmissivity and (IV) transparency evaluation likewise obtain.

(VI) the evaluation of stickiness

In above-mentioned (I), through (120 ℃ of pressure cooker test, humidity 100%, 4 hour) after the gridiron pattern disbonded test estimate stickiness at 80 ℃ of pattern-like films that form down of prebake conditions temperature.The evaluation result of this moment is shown in table 5.Evaluation result is represented remaining gridiron pattern number among 100 of the gridiron patterns.

(VII) evaluation of storage stability

With baking oven for heating 1 week of above-mentioned composition solution, estimate storage stability through viscosity change before and after the heating with 40 ℃.The viscosity rate of change of this moment is shown in Table 4.Rate of change we can say that less than 5% o'clock storage stability is good, and 5% we can say that storage stability is bad when above.

Lenticular evaluation

(I) lenticular formation

Spin coating above-mentioned composition solution (S-51 on 6 inches silicon substrates) so that reach the thickness of 2.5 μ m, under 70 ℃ on hot plate prebake conditions 3 minutes, formation is filmed.

To as above-mentioned filming of obtaining use the predetermined pattern mask to be radiated at wavelength 36nm place intensity to be 10mW/cm < > 2 <> Ultraviolet ray.Utilize 2.38 weight % tetramethylammonium hydroxide aqueous solutions afterwards after carrying out development in 1 minute under 25 ℃, through pure water washing 1 minute.Through these operations, remove part not, form pattern.

Then, intensity is 10mW/cm at wavelength 36nm place to the patterned illumination of above-mentioned formation < > 2 <> Ultraviolet 200mJ/cm < > 2 <> Afterwards,, and then under 230 ℃, heated 10 minutes, make the pattern melt flows form lenticule through after heating 10 minutes under 160 ℃.

(II) the evaluation of susceptibility

The minimum exposure of interval live width that can differentiate 0.8 μ m lines and the intermittent pattern (10 to 1) of the microlens pattern after the melt flows that is obtained by above-mentioned (I) is shown in table 6.This value is 100mJ/cm < > 2 <> When following, we can say that resolution is good, susceptibility surpasses 100mJ/cm < > 2 <> The time, we can say that resolution is bad.

(III) evaluation of the transparency

On glass substrate, likewise form the pattern-like film with above-mentioned (I).

To the formation after the melt flows glass substrate of microlens pattern, use spectrophotometer (150-20 type twin-beam (Hitachi (strain) system) to measure the transmissivity of 400nm, carry out transparency evaluation.Transmissivity under the 400nm of this moment is shown in table 6.Transmissivity is 90～100% o'clock, we can say that transmissivity is good, less than 90% o'clock, we can say that transmissivity is bad.

(IV) the evaluation of the heat-resisting transparency

With 250 ℃ baking oven for heating 1 hour, the transmission change of the pattern-like film through the heating front and back was estimated the heat-resisting transparency with the glass substrate with pattern-like film that forms in above-mentioned (III).The transmission change rate of this moment is shown in table 6.Rate of change we can say that less than 5% o'clock the heat-resisting transparency is good, surpasses at 5% o'clock, we can say bad.Transmissivity is likewise obtained with (III) transparent evaluation.

(V) evaluation of stickiness

Through (120 ℃ of pressure cooker test, humidity 100%, 4 hour) after the gridiron pattern disbonded test estimate the stickiness of the pattern-like film of formation in above-mentioned (I).The evaluation result of this moment is shown in table 6.Evaluation result is represented remaining gridiron pattern number among 100 of the gridiron patterns.

(VII) evaluation of solvent resistance

To impregnated in 50 ℃ the isopropyl alcohol 10 minutes with the glass substrate that above-mentioned (III) likewise forms, estimate Thickness Variation with pattern-like film.The rate of change of this moment is shown in table 6.Rate of change is 0～5% o'clock, we can say that solvent resistance is good, surpasses at 5% o'clock and because the dissolving thickness when reducing, we can say that solvent resistance is bad.

Embodiment 52

Mix the polymer solution contain the multipolymer [A-6] that obtains in the synthetic example 6 (be equivalent to multipolymer [A-6 weight portion (solid constituent)),

With as 4 of composition [B]; 4 '-[1-[4-[1-[4- hydroxy phenyl]-1- Methylethyl] phenyl] ethylidene] bis-phenol (1 mole) and 1; The condensation product (4 of 2- diazido naphthoquinone-5- sulfonic acid chloride (2 moles); 4 '-[1-[4-[1-[4- hydroxy phenyl]-1- Methylethyl] phenyl] ethylidene] bis-phenol-1; 2- diazido naphthoquinone-5- sulphonic acid ester) condensation polymer 2 weight portions of 20 weight portions, four [(3- ethyl oxetanes-3- yl) methyl] esters of silicon acis; And γ-metacryloxy propyl trimethoxy silicane 5 weight portions; Be dissolved to propylene glycol monomethyl ether so that after solid component concentration is 31 weight %; Millipore filter with aperture 0.5 μ m filters; The solution (S-52) of preparation radioactivity sensitive compositions, and estimate.The result is shown in table 4～6.

Embodiment 53

Mix the polymer solution contain the multipolymer [A-7] that obtains in the synthetic example 7 (be equivalent to multipolymer [A-7 weight portion (solid constituent)),

With as 4 of composition [B]; 4 '-[1-[4-[1-[4- hydroxy phenyl]-1- Methylethyl] phenyl] ethylidene] bis-phenol (1 mole) and 1; The condensation product (4 of 2- diazido naphthoquinone-5- sulfonic acid chloride (2 moles); 4 '-[1-[4-[1-[4- hydroxy phenyl]-1- Methylethyl] phenyl] ethylidene] bis-phenol-1; 2- diazido naphthoquinone-5- sulphonic acid ester) condensation polymer 2 weight portions of 18 weight portions, four [(3- ethyl oxetanes-3- yl) methyl] esters of silicon acis; And γ-metacryloxy propyl trimethoxy silicane 5 weight portions; Be dissolved to propylene glycol monomethyl ether so that after solid component concentration is 30 weight %; Millipore filter with aperture 0.5 μ m filters; The solution (S-53) of preparation radioactivity sensitive compositions, and estimate.The result is shown in table 4～6.

Embodiment 54

Mix the polymer solution contain the multipolymer [A-8] that obtains in the synthetic example 8 (be equivalent to multipolymer [A-8 weight portion (solid constituent)),

With as 4 of composition [B]; 4 '-[1-[4-[1-[4- hydroxy phenyl]-1- Methylethyl] phenyl] ethylidene] bis-phenol (1 mole) and 1; The condensation product (4 of 2- diazido naphthoquinone-5- sulfonic acid chloride (2 moles); 4 '-[1-[4-[1-[4- hydroxy phenyl]-1- Methylethyl] phenyl] ethylidene] bis-phenol-1; 2- diazido naphthoquinone-5- sulphonic acid ester) condensation polymer 2 weight portions of 30 weight portions, four [(3- ethyl oxetanes-3- yl) methyl] esters of silicon acis; And γ-metacryloxy propyl trimethoxy silicane 5 weight portions; Be dissolved to propylene glycol monomethyl ether so that after solid component concentration is 31 weight %; Millipore filter with aperture 0.5 μ m filters; The solution (S-54) of preparation radioactivity sensitive compositions, and estimate.The result is shown in table 4～6.

Comparative example 4

Mix and to contain the multipolymer [A-1R that obtains in the comparative example synthetic 1] polymer solution (be equivalent to multipolymer [A-1R weight portion (solid constituent)),

With as 4 of composition [B]; 4 '-[1-[4-[1-[4- hydroxy phenyl]-1- Methylethyl] phenyl] ethylidene] bis-phenol (1 mole) and 1; The condensation product (4 of 2- diazido naphthoquinone-5- sulfonic acid chloride (2 moles); 4 '-[1-[4-[1-[4- hydroxy phenyl]-1- Methylethyl] phenyl] ethylidene] bis-phenol-1; 2- diazido naphthoquinone-5- sulphonic acid ester) 30 weight portions and γ-metacryloxy propyl trimethoxy silicane 5 weight portions; Be dissolved to propylene glycol monomethyl ether so that after solid component concentration is 31 weight %; Millipore filter with aperture 0.5 μ m filters; The solution (S-1R) of preparation radioactivity sensitive compositions, and estimate.The result is shown in table 4～6.

Comparative example 5

Mix and to contain the multipolymer [A-2R that obtains in the comparative example Synthetic 2] polymer solution (be equivalent to multipolymer [A-2R weight portion (solid constituent)),

With as 4 of composition [B]; 4 '-[1-[4-[1-[4- hydroxy phenyl]-1- Methylethyl] phenyl] ethylidene] bis-phenol (1 mole) and 1; The condensation product (4 of 2- diazido naphthoquinone-5- sulfonic acid chloride (2 moles); 4 '-[1-[4-[1-[4- hydroxy phenyl]-1- Methylethyl] phenyl] ethylidene] bis-phenol-1; 2- diazido naphthoquinone-5- sulphonic acid ester) 18 weight portions and γ-metacryloxy propyl trimethoxy silicane 5 weight portions; Be dissolved to propylene glycol monomethyl ether so that after solid component concentration is 31 weight %; Millipore filter with aperture 0.5 μ m filters; The solution (S-2R) of preparation radioactivity sensitive compositions, and estimate.The result is shown in table 4～6.

Table 4

Table 5

Table 6

Claims

1. a radiation sensitive resin composition is characterized in that, contains: (a1), (a2) and multipolymer (a3) [A], 1,2-two nitrine naphtoquinone compounds [B] and contain the siloxane oligomer [C] that carries out the functional group of cross-linking reaction through heat and [A] composition,

Said (a2): contain oxetanyl unsaturated compound and/or; Glycidyl acrylate; GMA; The α-Yi Jibingxisuan ethylene oxidic ester; α-n-pro-pyl glycidyl acrylate; α-normal-butyl glycidyl acrylate; Acrylic acid 3; 4-epoxy butyl ester; Methacrylic acid 3; 4-epoxy butyl ester; Acrylic acid 6; 7-epoxy heptyl ester; Methacrylic acid 6; 7-epoxy heptyl ester; α-Yi Jibingxisuan 6; 7-epoxy heptyl ester; Adjacent vinyl benzyl glycidyl ether; Between the vinyl benzyl glycidyl ether or to vinyl benzyl glyceryl ether and

Said (a3) :) composition and (a2) different at least a other unsaturated compounds of composition with (a1; Said (a3) is selected from alkyl methacrylate; Alkyl acrylate; The methacrylic acid cycloalkyl ester; Methacrylate with hydroxyl; The acrylic acid cycloalkyl ester; Aryl methacrylate; The acrylic acid aryl ester; The unsaturated dicarboxylic diester; Two ring unsaturated compounds; Maleimide compound; Styrene; AMS; Vinyltoluene; To methoxy styrene; Conjugated diolefine; Has the tetrahydrofuran skeleton; The furans skeleton; The oxinane skeleton; The unsaturated compound that contains phenolic hydroxyl group of the unsaturated compound of the skeleton shown in pyrans skeleton or the following formula (3) and following formula (I) expression

In formula (3), R < > 7 <> Be hydrogen atom or methyl, n is the integer more than 1,

Wherein, R < > 1 <> The alkyl of expression hydrogen atom or carbon number 1～4, R < > 2 <>～R < > 6 <> Identical or different, be the alkyl of hydrogen atom, hydroxyl or carbon number 1～4, B be singly-bound ,-COO-or-CONH-, m is 0～3 integer, wherein, R < > 2 <>～R < > 6 <> At least one be hydroxyl,

Wherein, [C] composition is the alkoxy silane cohydrolysis that following formula (1) and following formula (2) are represented respectively and the siloxane oligomer that obtains,

Si(R ⁸) _s(R ⁹) _t(OR ¹⁰) _u (1)

Wherein, R < > 8 <> Expression contains the substituting group of epoxy radicals, epithio base, vinyl, allyl, (methyl) acryloyl group, carboxyl, hydroxyl, sulfydryl, NCO, amino, urea groups or styryl, R < > 9 <> , R < > 10 <> Identical or different, be respectively 1 valency organic group, s is 1～3 integer, and t is 0～2 integer, and u is 1～3 integer, wherein, s+t+u=4,

Si(R ¹¹) _x(OR ¹²) _4-x (2)

Wherein, R < > 11 <> , R < > 12 <> Identical or different, be respectively 1 valency organic group, x is 0～2 integer.

2. the described radiation sensitive resin composition of claim 1, wherein, [C] composition is the alkoxy silane cohydrolysis that following formula (1) and following formula (2) are represented respectively and the siloxane oligomer that obtains,

Si(R ⁸) _s(R ⁹) _t(OR ¹⁰) _u (1)

Wherein, R < > 8 <> Expression contains the substituting group of oxetanyl, R < > 9 <> , R < > 10 <> Identical or different, be respectively 1 valency organic group, s is 1～3 integer, and t is 0～2 integer, and u is 1～3 integer, wherein, s+t+u=4,

Si(R ¹¹) _x(OR ¹²) _4-x (2)

3. the described radiation sensitive resin composition of claim 1, it is used to form interlayer dielectric.

4. the formation method of an interlayer dielectric is characterized in that, comprises following operation according to the order of the following stated:

(1) operation of filming of the described radiation sensitive resin composition of formation claim 1 on substrate,

(3) developing procedure, and

(4) heating process.

5. interlayer dielectric, its method by claim 4 forms.

6. the described radiation sensitive resin composition of claim 1, it is used to form lenticule.

7. a lenticular formation method is characterized in that, comprises following operation according to the order of the following stated:

(3) developing procedure, and

(4) heating process.

8. lenticule, its method by claim 7 forms.