CA2473121A1

CA2473121A1 - Transparent composite composition

Info

Publication number: CA2473121A1
Application number: CA 2473121
Authority: CA
Inventors: Sumio Shibahara; Yasuo Shimobe; Hiromitsu Kuramoto
Original assignee: Individual
Current assignee: Sumitomo Bakelite Co Ltd
Priority date: 2002-01-25
Filing date: 2003-01-22
Publication date: 2003-08-07
Also published as: EP1477529A1; JP4285242B2; KR100969835B1; CN100503733C; US20040126592A1; JPWO2003064535A1; WO2003064535A1; US7250209B2; NO20043486L; AU2003211873B2; CN1606600A; EP1477529A4; KR20040089121A

Abstract

A transparent composite composition which has a low coefficient of linear expansion, is excellent in transparency, heat resistance, and solvent resistance, and is usable as a glass substitute as, e.g., an optical sheet f or liquid-crystal display elements and organic EL display elements. The transparent composite composition comprises a transparent resin (a) and a glass filler (b), wherein the transparent resin (a) is a copolymer obtained from at least one reactive monomer which, through crosslinking, comes to hav e a lower refractive index than the glass filler (b) and at least one reactive monomer which, through crosslinking, comes to have a higher refractive index than the glass filler (b).

Description

DESCRIPTION
TRANSPARENT COMPOSITE COMPOSITION
TECHNICAL FIELD
The present invention relates to a transparent composite composition which is low in coefficient of linear expansion, is excellent in transparency, heat resistance and solvent resis-tance and can serve as a substitute for glass. This transparent composite composition can judiciously be used in producing liq-uid crystal display panel substrates, organic EL (electrolumi-nescent) display device substrates, color filter substrates, touch panel substrates, solar cell substrates and like optical sheets, transparent sheets, optical lenses, optical devices, op-tical waveguides, LED (light-emitting diode) sealing materials, and so forth.
BACKGROUND ART
Those display panel or device substrates for use in ac-tive matrix type liquid crystal display devices and organic EL
display devices, color filter substrates, solar cell substrates and the like which are made of glass are generally in wide use.
In recent years, however, for the reasons that glass sheets are breakable, inflexible, and unsuited to weight reduction, various plastics materials have been investigated as substitutes there-for.
For example, Laid-open Japanese Patent Application (JP
Kokai) H10-77321 describes that a member obtained by curing a resin composition comprising a noncrystalline thermoplastic resin and an actinic radiation-curable bis(meth)acrylate with an actinic ray can be used as a substitute for a glass substrate, such as a liquid crystal panel substrate. Further, JP Kokai H10-90667 describes a liquid crystal display device in which a transparent substrate obtained by curing/molding a composition comprising a specific alicyclic-structured or aromatic bis(meth)acrylate with an actinic radiation or the like is used.

However, these known plastics materials as substitutes for glass are all high in coefficient of linear expansion as compared with glass sheets and, when used as display device sub-strates, in particular active matrix display device substrates, they may cause such troubles as warping and aluminum wiring breaking in the production process and, accordingly, it is dif-ficult to apply them to such fields of use. Thus, plastics ma-terials satisfying the transparency, solvent resistance and heat resistance requirements, among others, imposed on display device substrates, in particular active matrix display device sub-strates and, at the same time, showing a small coefficient of linear expansion are demanded.
For reducing the coefficient of linear expansion, at-tempts have been made in the art to produce composite materials by incorporating an inorganic filler, such as a glass powder or glass fiber, in resins. In the case of such resin-inorganic filler composite materials, however, the transparency of the substrates is often impaired. The main cause is the difference in refractive index between the inorganic filler and resin, which causes diffused refraction of the light passing through the resin.
To solve such problems, various methods have been pro-posed, for example the method comprising adjusting the composi-tion of a styrene-methacrylate copolymer to thereby equalize its refractive index with that of glass fiber, the method of refrac-tive index adjustment which comprises blending an acrylic resin with a styrene-acrylonitrile copolymer and, further, the method of refractive index adjustment which comprises adjusting the composition of an N-substituted maleimi.de-olefin copolymer (e. g.
JP Kokai S54-24993, Japanese Patent Publication (JP Kokoku) H06-94523, Japanese Patent No. 3216179). However, these materials are not sufficient in heat resistance and solvent resistance for their use as active matrix display device substrates in lieu of glass substrates.
It is an object of the present invention to provide a transparent composite composition low in coefficient of linear " CA 02473121 2004-07-08 expansion, excellent in transparency, heat resistance and sol-vent resistance and capable of serving as a substitute for glass.
The composite composition of the invention is suited for use in such fields of application as liquid crystal display device sub-strates, inclusive of active matrix type ones, organic EL dis-play device substrates, color filter substrates, touch panel substrates, solar cell substrates and like optical sheets, transparent sheets, optical lenses, optical devices, optical waveguides, and LED sealing materials.
DISCLOSURE OF THE INVENTION
The present inventors made intensive investigations in an attempt to solve such problems. As a result, they found that a transparent composite composition comprising a glass filler (b) and a transparent resin (a) which is a copolymer obtained by crosslinking at least one reactive monomer lower in refractive index after crosslinking than the glass filler (b) and at least one reactive monomer higher in refractive index after crosslink-ing than the glass filler (b), with the difference in refractive index between (a) and (b) being not more than 0.01, is highly transparent, as evidenced by a light transm_issivity at the wave-length 550 nm of not less than 80~, and, in addition, is low in coefficient of linear expansion and is excellent in heat resis-tance and solvent resistance as well. This and other findings have now led to completion of the present invention.
Thus, the present invention provides a transparent compo-site composition comprising a transparent resin (a) and a glass filler (b) and showing a light transmissivity at the wavelength 550 nm of not less than 80~.
Preferred as the transparent composite composition ac-cording to the invention is a resin composition comprising a transparent resin (a) obtained by crosslinking an acrylate (al) having an alicyclic structure and at least one acrylate (a2) se-lected form among sulfur-containing acrylates and fluorene skeleton-containing acrylates and a glass filler (b).

171ETAIT.Fn DESCRIPTION OF THE INVENTION
In the following, the present invention is described more specifically.
The transparent resin (a) to be used in the transparent composite composition of the invention is highly transparent to the visible light and, when it is molded into a sheet with a thickness of 200 um, the light transmissivity thereof at the wavelength 550 nm is preferably not less than 80~, more prefera-bly not less than 85~s, most preferably not less than 90~. In the case of the production of display device substrates, in par-ticular, the transmissivity should preferably be not less than 85~.
The transparent resin (a) preferably has a glass transi-tion temperature of not lower than 150°C, more preferably not lower than 180°C, still more preferably not lower than 200°C.
If the glass transition temperature of the resin is lower, de-formation or warping will possibly occur in the step of TFT de-vice formation in particular in the case of active matrix type display device substrates.
As examples of such transparent resin (a), there may be mentioned, among others, such thermoplastic resins as polycar-bonates, polyarylates, polysulfones, polyethersulfones and cy-cloolefin polymers, and resins produced by crosslinking a reac-tive monomers) such as an acrylate(s) with actinic radiation.
Among these, those resins resulting from crosslinking of a reac-tive monomers) such as an acrylate(s) with actinic radiation and/or by heating are preferred since they are excellent in sol-vent resistance.
Such reactive monomer may be any of those capable of crosslinking upon heating or exposure to actinic radiation.
Preferred from the transparency and heat resistance viewpoint are (meth)acrylates having two or more functional groups. Those resins may be used singly or two or more of them may be used in combination.
When the transparent composite composition of the inven-tion is used in producing plastics substrates far use as display device substrates, the light transmissivity thereof at the wave-length 550 nm is required to be not less than 80~, more prefera-bly not less than 85~, most preferably not less than 88$. When the light transmissivity at the wavelength 550 nm is less than 80~, the display performance will be unsatisfactory.
For attaining a light transmissivity at the 550 nm of not less than 80~ with such composite composition, either (1) the method comprising equalizing the refractive index of the trans-parent resin with that of the glass filler or (2) the method comprising using, as the glass filler, a fine one not larger than the wavelength of the light may be employed. In view of the ready material availability, however, the method involving refractive index adjustment is preferred.
For attaining better transparency, the difference in re-fractive index between the transparent resin (a) and glass filler (b) should be not more than 0.01, more preferably not more than 0.005. When such difference in refractive index is greater than 0.01, the resulting composite composition becomes poor in transparency.
The method employable for attaining a difference in re-fractive index between the transparent resin (a) and glass filler (b) of not more than 0_01 may comprise (1) selecting, as the glass filler (b), one matching in refractive index to the transparent resin (a), (2) selecting, as the transparent resin (a), one matching in refractive index to the glass filler (b), or (3) combinedly using a resin whose refractive index is higher than that of the glass filler (b) and a resin whose refractive index is lower than that of the glass filler (b) to thereby equalize the refractive index of the resin combination with that of the glass filler (b) , for instance .
However, since resin species which when used singly, can match in refractive index to some or other glass filler are re-stricted, it is preferred that refractive index matching or ad-justment be realized by combining two or more resins differing in refractive index or using two or more reactive monomers dif-fering in refractive index after crosslinking. Since polymer species differing in refractive index and mutually compatible are also restricted, the refractive index is more preferably controlled by adjusting the proportion of two or more reactive monomers differing in refractive index and carrying out the po-lymerization. By such method, it is possible to adjust the re-fractive index of the resin to the refractive index of a glass filler in general use, such as E glass.
For adjusting the difference in refractive index between the resin and glass filler being not more than 0.01, the use of at least one reactive monomer higher in refractive index than the glass filler and at least one reactive monomer lower in re-fractive index than the glass filler is preferred.
(al) Low refractive index monomer Usable as the reactive monomer lower in refractive index than the glass filler are various (meth)acrylates having an ali-cyclic structure or an aliphatic chain. From the transparency and heat resistance viewpoint, in particular, (meth)acrylates having an alicyclic structure are preferred. The alicyclic structure-containing (meth)acrylate to be used in preparing the composite composition of the invention may be any of those (meth)acrylates containing an alicyclic structure and having two or more functional groups. From the reactivity, heat resistance and transparency viewpoint, at least one (meth)acrylate selected from among the (meth)acrylates of the formulas (1) and (2) given below:
R~ R2 CH2=C-C-0-CHZ CH-O-C-C=CH (1 ) 2 ~~ 2 O O
a b wherein R1 and RZ each independently represents a hydrogen atom or a methyl group, a represents 1 or 2 and b represents 0 or 1;
CHZ O-C-C=CHZ
C2) _CHz O-C-C=CHZ
O

' ' CA 02473121 2004-07-08 wherein X represents a hydrogen atom, -CH3, -CHZOH, NHZ, -CHZ-O-C (~) -C (CH3) =CH2 or -CHz-O-C (=O) -CH=CH2, R3 and R4 each indepen-dently represents H or -CH3 and p is 0 or 1.
Among the (meth)acrylates of formula (~), dicyclopentadi-enyl diacrylate having a structure such that R1 and RZ each is a hydrogen atom, a is 1 and b is 0 is particularly preferred from the viewpoint of physical properties such as viscosity.
Among the (meth)acrylates of formula (2), at least one acrylate selected from among perhydro-1,4:5,8-dimethanonaphthalene-2,3,7-(oxymethyl)triacrylate having a structure such that X is -CH20COCH=CH2, R3 and R9 each is a hydro-gen atom and p is 1 and the acrylate having a structure such that X, R3 and R4 each is a hydrogen atom and p is 0 or 1 is par-ticularly preferred. From the viscosity viewpoint, among others, norbornane dimethylol diacrylate having a structure such that X, R3 and R, each is a hydrogen atom and p is 0 is most preferred.
The (meth) acrylates of formula (2) can be obtained by the method disclosed in JP Kokai H05-70523.
Desirable as the reactive monomer lower in refractive in-dex than glass fibers from the transparency and heat resistance viewpoint are cyclic ether (meth)acrylates of the following for-mula ( 6) R~$ CH3 O-CHZ~CH2 CH3 CH2=C-C-O-CH2 C-CH ~C~ R,s O CH3 O'CH2 CH2 O-G-C=CH2 wherein Rle and Rl9 each independently represents a hydrogen atom or a methyl group.
(a2) Higher refractive index monomer Various sulfur- and/or aromatic ring-containing (meth)acrylates can be used as the reactive monomer higher in refractive index than glass fillers (glass fiber cloths), and sulfur-containing (meth)acrylates and fluorene skeleton-containing (meth)acrylates are preferred from the high refrac-tive index viewpoint, in particular.

Sulfur-containing (meth_) ac late The sulfur-containing (meth)acrylate to be used in the practice of the invention may be any of sulfur-containing (meth)acrylates having two or more functional groups. From the heat resistance and transparency viewpoint, however, (meth)acrylates represented by the following formula (3) are preferred:
R~ Re R
('' ~s HiC=C-C~O-CHz CH~Y ~ \ X ~ , Y~CHZ CHi O~C-C=CH2 (3) p ~ O
Rya wherein X represents a sulfur atom or a S02 group, Y represents an oxygen or sulfur atom, RS to Rlo each independently represents a hydrogen atom or a methyl group, and n and m each is 0 to 2.
.Among the (meth) acrylates of formula (3) , bis [4-(acryloyloxyethoxy)phenyl] sulfide having a structure such that X is sulfur, Y is oxygen, R5 to Rla each is hydrogen and n and m each is 1 is most preferred from the reactivity, heat resistance and easy handling viewpoint.
Fluorene skeleton-containing (meth)acrvlate The fluorene skeleton-containing (meth)acrylate to be used in the practice of the invention is not particularly re-stricted but may be any of those fluorene skeleton-containing (meth)acrylates which have two or more functional groups. From the heat resistance and transparency viewpoint, however, at least one (meth)acrylate selected from the (meth)acrylates rep-resented by the formula (4) and (5) given below is preferred:
r R~z H2C=C-C~0-CH- O~CH2 CH-O~C-C=CH2 (4) p L LL JS O
wherein Rll to R14 each independently represents a hydrogen atom or a methyl group and r and s each is 0 to 2;

R~s Rye H2C=C-C-O- HZ CH-CH2 O-C-C=CHZ
O OH O
wherein R15 to R1~ each independently represents a hydrogen atom or a methyl group.
Among these, bis[4-(acryloyloxyethoxy)phenyl]fluorene having a structure such that, in formula (4) , R11 to R14 each is hydrogen and r and s each is 1 is most preferred.
These lower refractive index monomer and higher refrac-tive index monomer can be mixed together in an appropriate pro-portion according to the desired refractive index and subjected to crosslinking so that the refractive index of the transparent resin may be matched with the refractive index of the glass filler to be combined therewith.
In the practice of the invention, a monofunctional (meth)acrylate may be used in combination with the (meth)acrylate having two or more functional groups for the pur-pose of providing flexibility, for instance, in an addition lev-el range in which the desired characteristics'will not be sacri-ficed. In this case, the monomer composition is adjusted so that the refractive index of the resulting whole resin component may match with the refractive index of the glass filler.
(b) Glass filler The refractive index of the glass filler (b) to be incor-porated in the transparent composite composition of the inven-tion is not particularly restricted but is preferably within the range of 1.50 to 1.57 so that the refractive index of the resin to be used in combination may be adjusted with ease. In par-ticular when the refractive index of the glass filler is 1.50 to 1.54, it is favorably possible to select a resin close in Abbe number to the glass filler. When the resin and glass are close in Abbe number to each other, the refractive indexes of both agree in a wide wavelength range and a high light transmissivity ' CA 02473121 2004-07-08 ZO
can be obtained in the wide wavelength range.
The glass filler (b) to be used in the practice of the invention includes glass fibers, glass cloths, nonwoven glass fabrics and other glass fiber cloths, glass beads, glass flakes, glass powders, milled glass species and so forth. Among them, glass fibers, glass cloths and nonwoven glass fabrics are preferred in view of their being highly effective in reducing the coefficient of linear expansion. Glass cloths are most pre-ferred.
As for the glass species, there may be mentioned E glass, C glass, A glass, S glass, D glass, NE glass, T glass, quartz, low inductivity glass, high inductivity glass and so forth.
Preferred among them are E glass, S glass, T glass and NE glass, which are poor in ionic impurities such as alkali metals and readily available.
In cases where a glass cloth or nonwoven glass fabric is used as the glass filler, the manner of weaving of filaments is not restricted but includes plain weave, moss stitch-like weave, satin weave, and twill weave, among others. Plain weave is pre-ferred, however. Generally, the glass cloth thickness is pref-erably 30 to 200 dun, more preferably 40 to 150 dam. The glass cloth, nonwoven glass fabric or other glass fiber fabric may be used either in the form of one single sheet or in the form of a laminate comprising a plurality of sheets.
(Transparent composite composition) The content of the glass filler in the transparent compo-site composition is preferably 1 to 90~ by weight, more prefera-bly 10 to 80~ by weight, still more preferably 30 to 70~ by weight. When the glass filler content is lower, the composite composition will not show any substantial linear expansion coef-ficient reducing effect and, when it is higher, the appearance of the moldings tends to deteriorate.
The closer the contact between the glass filler, such as a glass fiber fabric, and the resin is, the more improved the transparency of plastics substrates or the like produced from ' ' CA 02473121 2004-07-08 the transparent composite composition is. Therefore, the glass filler surface is preferably treated with a surface modifier known in the art, for example a silane coupling agent. More specifically, when a (meth)acrylate(s) having two or more func-tional groups is(are) used as the reactive monomer(s), acrylic silane compound treatment is preferred.
(Other ingredients) In the composite composition of the invention, there may be incorporated, where necessary, a thermoplastic or thermoset-ting oligomer or polymer may be used combinedly within an addi-tion level range within which the transparency, solvent resis-tance, heat resistance and other characteristics will not be im-paired. In such case, an oligomer or polymer having an alicy-clic structure or cardo skeleton is preferably used for the pur-pose of reducing the water absorbency, for instance. When such thermoplastic or thermosetting oligomer or polymer is combinedly used, the composition of the mixture is to be adjusted so that the refractive index of the whole may match with the refractive index of the glass filler.
In the composite composition of the invention for produc-ing plastics substrates and the like, there may further be in-corporated, according to need, an antioxidant, an ultraviolet absorber, a dye or pigment, a loading material such as another inorganic filler, and/or a further additive, each in a small amount so that such characteristics as transparency, solvent re-sistance and heat resistance may not be impaired.
(Manufacturing method) The method of molding the composite composition is not restricted. When a reactive monomer composition is used as the transparent resin, for instance, it includes, among others, (1) the method comprising directly mixing the reactive monomer com-position with the glass filler and casting the mixture into a required mold, followed by crosslinking, (2) the method compris-ing dissolving the reactive monomer composition in a solvent, dispersing the glass filler in the solution, casting the disper-sion, followed by crosslinking, and, further, (3) the method ' CA 02473121 2004-07-08 comprising impregnating the glass fiber cloth with the reactive monomer composition, crosslinking the monomer composition and subjecting the whole to sheet formation according to need.
Available for crosslinking the above reactive monomer composition are the method comprising causing curing by means of actinic radiation, the method comprising causing thermal polym-erixation by heating, and so forth. These methods may be used in combination. When the reactive monomer composition comprises a (meth)acrylate monomer having two or more functional groups, preferably two or more such monomers differing in.refractive in-dex, the method comprising causing crosslinking by actinic ra-diation is preferred. For the purpose of driving the reaction to completion, lowering the retardation value and/or lowering the coefficient of linear expansion, for instance, it is preferred that the step of curing by means of actinic radiation and/or thermal polymerization by means of application of heat be followed by further high temperature heat treatment employed in combination. Ultraviolet light is preferred as the actinic ra-diation to be used. As the source of ultraviolet light, there may be mentioned, for example, metal halide lamps, high-pressure mercury lamps, and the like.
(Polymerization initiator) In crosslinking/curing the reactive monomer composition by actinic irradiation, for example by ultraviolet irradiation, a radical-generating photopolymerization initiator is preferably added to the resin composition. As such photopolymerization initiator, there may be mentioned, for example, benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Two or more of these photopolymerization initiators may be used combinedly.
The content of the photopolymerization initiator in the composite composition may be such that an adequate level of cur-ing can be secured. It is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 1 part by weight, most preferably 0.1 to ' ' CA 02473121 2004-07-08 0.5 part by weight, per 100 parts by weight of the sum of the (meth)acrylates having two or more functional groups. When the level of addition of the photopolymerization initiator is exces-sive, the polymerization will progresses abruptly, causing such problems as increased birefringence, discoloration, and cracking upon curing. When it is too low, the composition cannot be cured to a sufficient extent and problems may arise, for example the composition after curing may remain sticking to the mold, making it difficult to release the same from the mold.
When high temperature heat treatz~nt is carried out after crosslinking by actinic radiation curing and/or thermal polym-erization, it is preferred that a step of 1 to 24 hours of heat treatment at 250-300°C in a nitrogen atmosphere or under vacuum be carried out additionally in the process of the heat treatment for the purpose of reducing the coefficient of linear expansion, for instance.
In cases where the transparent composite composition of the invention is used in the field of optical applications, namely for producing/preparing transparent sheets, optical lenses, plastics substrates for liquid crystal display devices, color filter substrates, plastics substrates for organic EL dis-play devices, solar cell substrates, touch panels, optical de-vices, optical waveguides, LED sealing materials, it is preferred that these products have an average coefficient of linear expansion, at 30-150°C, of not more than 50 ppm, more preferably not more than 40 ppm. In particular, when the trans-parent composite composition is used in sheet form in producing active matrix type display device substrates, the average coef-ficient of linear expansion is preferably not more than 30 ppm, more preferably not more than 20 ppm. When the coefficient ex-ceeds the above value, such problems as Warping and aluminum wiring breakage may possibly occur in the production process.
When the coefficient of linear expansion does not exceed the above value, the TFT formation steps can be carried out without substantial modification of the existing equipment for the con-ventional glass substrates.

In cases where the transparent composite composition of the invention is used far the production of plastics substrates for liquid crystal display devices, color filter substrates, plastics substrates for organic LE display devices, solar panel substrates, touch panels and the like, the substrate thickness is preferably 50 to 2,000 pm, more preferably 50 to 1,000 dun.
When the substrate thickness in within this range, the sub-strates are excellent in flatness and can be lightweight as com-pared with the corresponding glass substrates.
When the composite composition of the invention is used as optical sheets, the sheets may be provided with a coat layer made of a resin on both sides for improvement in smoothness.
The coat resin is preferably one having good transparency, heat resistance and chemical resistance, specifically a polyfunction-al acrylate or epoxy resin, for instance. The coat layer pref-erably has a thickness of 0.1 to 50 ptn, more preferably 0.5 to 30 ~a~m.
When such optical sheets of the invention are used as plastics substrates for display devices, a gas barrier layer against water vapor and oxygen and/or a transparent electrode layer may be provided thereon according to need.
EXAMPLES
The following examples illustrate the present invention in more detail. They are, however, by no means limitative of the scope of the invention.
[Example 1]
A glass cloth made of E glass (thickness 50 prn, refrac-tive index 1.560, Unitika Cloth's E06B (#1080)) was deprived of organic matter by burning and then treated with acryloyloxypro-pyltriethoxysilane (acrylic silane compound). This glass cloth was impregnated with a resin composition (refractive index after crosslinking 1.560) composed of 58 parts by weight of dicyclo-pentadienyl diacrylate (formula 1) (M-203, product of Toagosei Co., Ltd.), 42 parts by weight of bis[4-(acryloyloxyethoxy)phenyl] sulfide (formula 3) (TO-2066, trial product of Toagosei, refractive index after crosslinking 1.606) and 0.5 part by weight of a photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone, Irgacure 184, product of Ciba Specialty Chemicals), followed by degassing. The cloth obtained was subjected to lamination in the manner of resin/cloth/resin/cloth/resin, and the laminate was sandwiched between release agent-treated glass sheets and irradiated from both sides with UV rays at about 500 mJ/cmz for curing. The laminate was then heated, in a vacuum oven, at about 100°C for 3 hours and, further, at about 250°C for 3 hours to give a sheet-like plastic substrate (thickness 0.2 m~n)_ The glass filler content of the substrate was 30~ by weight.
[Example 2]
The same glass cloth as used in Example 1 was impregnated with a resin composition (refractive index after crosslinking 1.560) prepared from 53 parts by weight of norbornanedimethylol diacrylate (formula 2) (trial product of Toagosei, refractive index after crosslinking 1.520), 47 parts by weight of bis[4-(acryloyloxyethoxy)phenyl] sulfide (formula 3) (TO-2066, trial product of Toagosei, refractive index after crosslinking 1.606) and 0_5 part by weight of the photopolymerization initiator, followed by degassing. This glass cloth was subjected to lami-nation and the laminate subjected to W light irradiation and heating treatment in the same manner as in Example 1 to give a sheet-like plastic substrate (thickness 0.2 mm). The glass filler content of the substrate was 30~ by weight.
[Example 3]
An E glass-based glass cloth (thickness 100 dun, refrac-tive index 1.560, Unitika Cloth's ElOA (#2117)) deprived of or-ganic matter by burning and treated with acryloyloxypropyltri-ethoxysilane (acrylic silane compound) was used as the glass cloth. This cloth was impregnated with the same resin composi-tion as used in Example 1, followed by degassing. This glass cloth was sandwiched between release agent-treated glass sheets and irradiated from both sides with W rays at about 500 mJ/cm2 for curing. The subsequent 3 hours of heating at about 100°C

and further 3 hours of heating at about 250°C in a vacuum oven gave a sheet-like plastic substrate With a thickness of 0.1 man.
The glass filler content of the substrate was 50~ by weight.
[Example 4]
An E glass-based glass cloth having a thickness of 100 ~.un and treated in the same manner as in Example 3 was prepared as the glass cloth. This glass cloth was impregnated with the same resin composition as used in Example 2, followed by degassing.
This glass cloth was sandwiched between glass sheets, cured by W light irracliation and heated in the same manner as in Example 3 to give a plastic substrate (thickness 0.1 man). The glass filler content of the substrate was 50~ by weight.
[Example 5]
An S glass-based glass cloth (thickness 100 dam, refrac-tive index 1.530, product of Unitika Cloth (#2117 type) was used as the glass cloth and treated in the same manner as in Example 1. A resin composition (refractive index after crosslinking 1.533) composed of 92 parts by weight of dicyclopentadienyl diacrylate (formula 1) (M-203, product of Toagosei, refractive index after crosslinking 1.527), 8 parts by Weight of bis[4-(acryloyloxyethoxy)phenyl] sulfide (formula 3) (TO-2066, trail product of Toagosei, refractive index after crosslinking 1.606) and 0.5 part by weigh of the photopolymerization initiator was used as the resin composition. The glass cloth was impregnated with the resin composition and, after degassing, sandwiched be-tween release agent-treated glass sheets and irradiated from both sides with W rays at about 10 J/cm2 for curing. The subse-quent 3 hours of heating at 250°C in a vacuum oven gave a sheet-like plastic substrate (thickness 0.1 ~rtn). The glass filler content of the substrate was 50~ by weight_ [Example 6]
A resin composition (refractive index after crosslinking 1.531) composed of 96 parts by weight of dicyclopentadienyl diacrylate (formula 1) (M-203, product of Toagosei, refractive index 1.527), 4 parts by weight of bis[4-(acryloyloxyethoxy)phenyl]fluorene (formula 4) (TO-2065, trial product of Toagosei, refractive index after crosslinking 1.624) and 0.5 part of the photopolymerization initiator was prepared as the resin composition. The S glass-based glass cloth pre-pared in the same manner as in Example 5 was impregnated with this resin composition, followed by degassing. The glass cloth thus obtained was sandwiched between release agent-treated glass sheets and cured by W light irradiation and heat treatment un-der the same conditions as in Example 5 to give a sheet-like plastics substrate (thickness 0.1 mm). The glass filler content of the substrate was 50~ by weight.
[Example 7]
A 50-dun-thick T glass-based glass cloth (product of Nit-tobo, refractive index 1.530) deprived of organic matter by burning and treated with acryloyloxypropyltriethoxysilane (ac-rylic silane compound) was prepared as the glass cloth. This glass cloth was impregnated with the same resin composition as used in Example 6, followed by degassing. Two sheets of this glass cloth, one on the other, were sandwiched between release agent-treated glass sheets and irradiated with W rays and heat-treated for curing under the same conditions as in Example 5 to give a sheet-like plastic substrate (thickness 0.1 mm).
The glass filler content of the substrate was 50~ by weight.
[Example 8]
An NE glass-based cloth (thickness 100 pm, refractive in-dex 1.510, product of Nittobo (#2116 type)) was used as the glass cloth and treated in the same manner as in Example 1. The resin composition used (refractive index after crosslinking 1.512) was composed of 90 parts by weight of norbornanedimethy-lol diacrylate (formula 2) (trial product of Toagosei, refrac-tive index after crosslinking 1.520), 10 parts by weight of hy-droxypivalaldehyde-trimethylolpropane acetal diacrylate (formula 6) (Kayarad R-604, Product of Nippon Kayaku, refractive index after crosslinking 1.496) and 0.5 part by weight of the photo-polymerization initiator. The above glass cloth was impregnated with the resin composition and, after degassing, sandwiched be-tween release agent-treated glass sheets, followed by UV light irradiation, curing and heating treatment under the same condi-tions as in Example 5. A sheet-like plastic substrate (thick-ness 0.1 mm) was thus obtained. The glass filler content of the substrate was 50~ by weight.
[Comparative Example 1]
The photopolymerization initiator (0.5 part by Weight) was added to 100 parts by weight of dicyclopentadienyl diac-rylate (formula 1) (M-203, product of Toagosei, refractive index after crosslinking 1.527), and the mixture was sandwiched be-tween release agent-treated glass sheets and irradiated from both sides with UV rays at about 500 mJ/cmz. Further, in a vac-uum oven, it was heated at about 100°C for 3 hours and then at about 250°C for 3 hours to give a sheet-like plastic substrate ( 0 . 2 man) .
[Comparative Example 2]
A glass cloth made of E glass (thickness 50 um, refrac-tive index 1.560, Unitika Cloth's E06H (#1080)) was deprived of organic matter by burning and then treated with acryloyloxypro-pyltriethoxysilane (acrylic silane compound). This glass cloth was impregnated with a resin composition prepared by adding 0.5 part by weight of the photopolymerization initiator to 100 parts by weight of dicyclopentadienyl diacrylate (M-203, product of Toagosei Co., refractive index after crosslinking 1.527), fol-lowed by degassing. The cloth obtained was subjected to lamina-tion in the manner of resin/cloth/resin/cloth/resin, and the laminate was sandwiched between release agent-treated glass sheets and irradiated from both sides with UV rays at about 500 mJ/cm2 for curing. The laminate was then heated, in a vacuum oven, at about 100°C for 3 hours and, further, at about 250°C
for 3 hours to give a sheet-like plastic substrate (thickness 0.2 mm). The glass filler content of the substrate was 30~ by weight.
[Comparative Example 3]
An E glass-based glass cloth (thickness 100 ~atn, refrac-tive index 1.560, Unitika Cloth's ElOA (#2117)) was deprived of organic matter by burning and treated with acryloyloxypropyltri-ethoxysilane (acrylic silane compound). This cloth was impreg-nated with a resin composition composed of 100 parts by weight of the above-mentioned dicyclopentadienyl diacrylate and 0.5 part by weight of the photopolymerization initiator, followed by degassing. This glass cloth was sandwiched between release agent-treated glass sheets and irradiated from both sides with W rays at about 500 mJ/cm2 for curing. The subsequent 3 hours of heating at about 100°C and further 3 hours of heating at about 250°C in a vacuum oven gave a sheet-like plastic substrate (thickness 0.1 mm). The glass filler content of the substrate was 50~ by weight.
(Methods of evaluation) The sheet-like plastic substrates (optical sheets) pro-duced in the above examples and comparative examples were meas-ured for various characteristics by the following evaluation methods.
(a) Average linear expansion coefficient The coefficient was determined by carrying out measure-ments in a nitrogen atmosphere using a Seiko Instruments model TMA/SS120C thermal stress strain measuring apparatus within the range of 30°C to 150°C while raising the temperature at a rate of 5°C per minute after once raising the temperature from 30°C
to 250°C at a rate of 5°C per minute and then cooled to 0°C.
For the measurements, originally designed tension chucks (material: quartz, coefficient of linear expansion 0.5 ppm) were used. The Inconel-made chucks in general use have problems, namely they are themselves high in coefficient of linear expan-sion and unsatisfactory with respect to the mode of supporting samples and, thus, when they are applied to sheets having a thickness exceeding 100 dam, greater linear expansion coefficient values are obtained as compared with the results of measurement in the compression mode and the variation becomes greater.
Therefore, the quartz-made tension chucks were originally des-igned and used in linear expansion coefficient measurements. It has been confirmed that when these tension chucks are used, al-most the same values can be measured as in the compression mode.
(b) Heat resistance (Tg) Measurements were made on a Seiko Instruments model DMS-210 viscoelasticity measuring apparatus. The maximum value of tan8 at 1 Hz was recorded as the glass transition temperature (Tg).
(c) Solvent resistance Each specimen was immersed in diethyl sulfoxide (DMSO) at 60°C and allowed to stand therein for 60 minutes. After tak-ing out the specimen, its appearance Was checked by visual ob-servation. When the shape and color were fully retained and there was no erosion, the appearance was evaluated as ~~ other-wise, it was evaluated as X.
(d) Alignment material resistance Each specimen was placed on a spin coater. CRD-8201 (pro-duct of Sumitomo Bakelite) was dropped onto the surface thereof, and spin coating was carried out at 2,500 rpm. After 60 minutes of drying at 180°C, the appearance was evaluated by visual ob-servation.
(e) Liquid crystal resistance On drop of Merck's ZIL-4792 was dropped onto the surface of each substrate specimen. The whole was placed in an oven at 80°C and allowed to stand there for 60 minutes. After taking out the specimen, its appearance was evaluated by visual obser-vation.
(f) Light transmissivity Light transmissions at 400 nm and 550 nm were measured on a spectrophotometer U3200 (product of Hitachi Ltd.).
(g) Refractive index The refractive index at the wavelength 589 nm was meas-ured at 25°C using an Atago model DR-M2 Abbe refractometer.
(h) Evaluation of deformation such as warping and/or flexure A 3,000 A-thick aluminum layer was formed on each sub-strate specimen by sputtering, a pseudo wiring pattern, 100 dun wide and 30 mm long, was formed by photolithography, and a 2,000 A-thick gold layer was formed on each 5-mm end portion of the pattern by sputtering to form 5-mm2 electrodes for resistance value measurement. Then, a metal mask having an opening of 10 mmz was disposed in the middle of the wiring pattern, and SiN
(2,000 A)/amorphous Si (500 A)/SiN (2,000 A) layers were formed by continuous CVD. Further, the whole was placed in an oven at 180°C and, after 1 hour, allowed to cool to ordinary temperature, and the appearance was checked by visual observation.
The results of the evaluations of the samples obtained in the above-mentioned examples and comparative examples by these evaluation methods are shown below in Tables 1 to 3.
[Table 1]

a~

N ' r O O

M I~ Ifs ~PCO0 n ~ 00~
I I X o 0 0 o ~ ,~'~ o ~ ,~a ,~N ~ ~

[d ~ T r X

w O

O
T

'- O O

o X ~ ; O O O ~ O

~ o N ~

(Q ~ T T

X

w O

O
r N

rr d d N t N O O

I M ~ I ~ ~ tna ~ T"' cco0 O X N N

tp r r X

O

H

+~

t !v N O O

d I Lt~ O O O O

. o X ~ N N tDGO

X

w ...
E

~, ., M +r C
N

_ U_ t ~

U
~ n O ~ L a.~ O C C
' O

N v d O O ~ O O

(C t0v ~CN U ~-U ~0 O 1f?

S ~ C ~ +~ etu7 ..~+r C N N
o U ' _ ~ o . v, _ ~ .
~

~ U d ~ v ~ C
C

O ~.. L
tC~ O N 4-4-~ ~ h-. N ~

_ p _ ~+~ O O O ~ t > 7 _N X ~ ~ U ~ ~
~

C ~ N X X ~ U N N ~ C tntn ~0 N ' _ -'~ "a'~U ~ U +~ ,,,~,,. N j ~ N

'ip N N c c s y ~ ~ m .N~ ~ x E , -~v cn ~ _ +~ ~,m E , N

~ m ~ ~ '~ a~a~o .~n ,.~ a~c c _ ~ ~ ~ ~ . ~
O

_U U U ~ ) N ~ p U +~

I p N U U W p L ~ Z ~ +~+~ G
V U ~ L 3 (6c0 _ +~+~
U ' O ~ ~' ~ O > C ~ a U ~' O 4 4-~ U .. ..
' - ' Q Q gina a w tx~ cna i Q ~ cn~ ~ ~

[Table 2]
+~

N

a~

~ ~ O

I I I ~ I I x '- ~ O O O O
~

O T T ~ ~ , T

X

O

O
I

N

N

r-O p I 1 ~ I ~ 1 N I ~ ~ O ~

X

uJ

O

r N

N

c0 s N

N T - O O

I ~ I O X I I ~ ~ O ~ N o o o o ~ ~ o cC ~ T T I~

x O

O
T

N

a~ r" c"~O

~ I o0I i ~ I I ~ ~ O O O

X , ~ ,_N OpCOO

Ifl ~ T T

X

O

O
T

/1 ~/

~

U_ L L

O ~ ~ L +~ N C C

r N v ~ 3 O ~ O U

t0 N N ~ ~ tip ~ U ca O 1>

t ~ ~ _ ~ E ~ C ~ O U y ~ ~ U ~ V
n ~

E ~ ~ ~ _ U V ~ u1Q C
- "

L L - N N O - C O c0 O i ~ N ~ ~

a v f0 c0O IAtAl0~ 4' f- H

N O N _ _ N t0- O O V x " V ,N 'N> >
+-N ~ - - ~ X X ~ ~ N _ f O H jj f '~- ' f _ ~ ~ ~ ~ ~ .D'D U N C +'N _ _ O

N N N C C S O ~ .N l0 ~

U U U ~ ~ V!U7m . .NC ,~,~ E +~. U
.

cu cvO ~ S '~C7O O V1' +r N

_ ~ ~ - _ C C

U U U ~ ~ O I I N +,~, ~ N ~ , O V

.~" ~
C

U U L N U O N Vf~0U U ~ ~ L ~ .~+ v C
.-7. > i .-+, cac0_ ~ ~ ofL .~..~07C ._-r~+, ~ O _ _ > 3 ..Cs L
U U ~

~ p j,L UJd N 7 > N p --a a ~n~ v a cn~ z ~ ~ cna z cna J _JJ

(Table 3]
+~

a~

a~

a~

> m c~

r O I I 1 0 X ~ ~ O ~ O O O ~ M O

r N

E r r w T

N

7 s N

fop N 1"~O
4?

O I 1 1 o ~ ~ ~' O O O ~ O

N N N

X r T

~
w U

a~

y T

~ ' o 1 1 1 0 1 ~ N ~ N O O O o ~ x v r o x ~

U

E

n v N C

O

_ _ U

L

U
O ~ 1. ~ O C C

r N v ~ O O o C O O

m m i;3 m N E c . .sc ~
o N - --E c o -~,N _ U . , N . .

L _ U O !Wr N v 0 o a ~ c N ~ N o ~

m ...o N ~ .-N m ~ ~ N +r a~a~ v a-_mo o ,~ x ..v ,m-N '>->
~

+~ ~ x x = a1~ C ~ a7 N ~ut ~ N ' t ~ ~ . .'O V s.U ~ +~
O y t0 N ~ ZI~ t N t0 C ~ X

U ~ N - ~ +r N l0~ ~ ~.,.
~

t6lCp N ~ j ; O '~N i N >'C

_ _ C \
U U U ~ O O

_ U (n U i L C O ~ ~

C_ U o ~D

7 L ~ ~ dot N d +rN C +r+r C

4-O L > > .Gt U U O ~ ~+-w s7 U t3 ~

a a cn~ a w ~ ~ cn Q z cnQ :~ _I~ ~

INDUSTRIAL AP:~~,f,ABILITY
The transparent composite composition of the invention has a low coefficient of linear expansion and is excellent in transparency, heat resistance and solvent resistance, among oth-ers and, therefore, can be utilized, for example, in the form of transparent sheets, optical lenses, plastics substrates for liq-uid crystal display devices, color filter substrates, plastics substrates for organic EL display devices, solar cell substrates, touch panels, optical devices, optical waveguides, LED sealing materials and so forth, preferably in the form of optical sheets for use as active matrix type liquid crystal display device sub-strates and organic EL display device substrates, in particular.

Claims

1. A transparent resin composition which comprises a trans-parent resin (a) and a glass filler (b) and shows a light trans-missivity at the wavelength 550 nm of not less than 80%.

2. A transparent composite composition which comprises a transparent resin (a) and a glass filler (b), said transparent resin (a) being a copolymer obtained from at least one reactive monomer lower in refractive index after crosslinking than the glass filler (b) and at least one reactive monomer higher in re-fractive index after crosslinking than the glass filler (b).

3. The transparent composite resin according to Claim 2, wherein at least one of the reactive monomers is a (meth)acrylate having two or more functional groups.

4. The transparent composite composition according to Claims 1 to 3, wherein the transparent resin (a) has a glass transition temperature of not Lower than 150°C.

5. The transparent composite composition according to Claims 1 to 4, wherein the difference in refractive index between the transparent resin (a) and glass filler is not more than 0.01.

6. The transparent composite composition according to any of Claims 1 to 5, wherein the transparent resin (a) is a copolymer obtained by crosslinking an acrylate (a1) having an alicyclic structure and at least one acrylate (a2) selected from among sulfur-containing acrylates and fluorene skeleton-containing ac-rylates.

7. The transparent composite composition according to Claim 6, wherein the alicyclic structure-containing (meth)acrylate comprises at least one (meth)acrylate selected from among the (meth) acrylates of the following formulas (1) and (2):

wherein R1 and R2 each independently represents a hydrogen atom or a methyl group, a represents 1 or 2 and b represents 0 or 1;
wherein X represents a hydrogen atom, a methyl group, -CH2OH, -NH2, -CH2-O-C(=O)-C(CH3)=CH2 or -CH2-O-C(=O)-CH=CH2, R3 and R4 each independently represents a hydrogen atom or a methyl group and p represents 0 or 1.

8. The transparent composite composition according to Claim 6, wherein the sulfur-containing (meth)acrylate is a (meth)acrylate represented by the following formula (3):
wherein X represents S or SO2, Y represents O or S, R5 to R10 each independently represents a hydrogen atom or a methyl group, and n and m each is 0 to 2.

9. The transparent composite composition according to Claim 6, wherein the fluorene skeleton-containing (meth)acrylate com-prises at least one (meth)acrylate selected from among the (meth) acrylates of the following formulas (4) and (5):
wherein R11 to R14 each independently represents a hydrogen atom or a methyl group and r and s each represents 0 to 2;
wherein R15 to R17 each independently represents a hydrogen atom or a methyl group.

10. The transparent composite composition according to any of Claims 1 to 9, wherein the transparent resin (a) is a resin ob-tained by crosslinking of two or more reactive monomers differ-ing in refractive index by actinic irradiation and/or heating.

11. The transparent composite composition according to any of Claims 1 to 10, wherein the glass filler (b) is a glass fiber cloth.

12. The transparent composite composition according to any of Claims 1 to 11, wherein the glass filler (b) has a refractive index of 1.50 to 1.57.

13. The transparent composite composition according to any of Claims 1 to 12 which has an average linear expansion coefficient of not more than 50 ppm within the temperature range of 30 to 150°C.

14. The transparent composite composition according to any of Claims 1 to 13 which occurs as a sheet having a thickness of 50 to 2,000 µm.

15. The transparent composite composition according to any of Claims 1 to 14 which occurs as an optical sheet, display device plastic substrate or active matrix type display device substrate.