CN103467967A

CN103467967A - Thermosetting resin composition and use thereof

Info

Publication number: CN103467967A
Application number: CN2013104228737A
Authority: CN
Inventors: 孟运东; 方克洪
Original assignee: Shengyi Technology Co Ltd
Current assignee: Shengyi Technology Co Ltd
Priority date: 2013-09-16
Filing date: 2013-09-16
Publication date: 2013-12-25

Abstract

The invention relates to a thermosetting resin composition. The thermosetting resin composition comprises (A) polyphenylene ether resin; (B) epoxy resin; (C) a curing agent and (D) an initiating agent. The thermosetting resin composition can also comprise a compound which simultaneously contains an epoxy group and an olefinic bond type unsaturated group, the curing agent, a flame retardant, an accelerant and the like. The thermosetting resin composition has the characteristics of low dielectric constant and dielectric loss, high heat resistance, flame retardance and the like, and is suitable for laminated boards and the like for prepregs and printed circuits.

Description

A kind of compositions of thermosetting resin and uses thereof

Technical field

The present invention relates to a kind of compositions of thermosetting resin, and the prepreg and the used for printed circuit veneer sheet that use this resin combination.

Background technology

Current, electric industrial development is swift and violent, and the developing direction of electronic product is lightening, high performance, high reliability and environmental protection etc.The specific requirement of used for printed circuit veneer sheet also shows as high heat-resisting, low thermal coefficient of expansion, high wet-heat resisting, environmental protection flame retardant, low-k and dielectric loss and high elastic coefficient etc.Therefore, traditional epoxy resin can't meet the growth requirement of used for printed circuit veneer sheet fully, and it is also more and more outstanding to have the application of polyphenylene oxide resin in the used for printed circuit veneer sheet of high heat resistance, low-k and dielectric loss, good-toughness.

The thermoplastic material that traditional polyphenylene oxide resin is high molecular, flow temperature is high, and melt viscosity is high, poorly soluble, Shortcomings still aspect processibility.In the application of making at the used for printed circuit veneer sheet, generally the polyphenylene oxide resin of high molecular can be carried out to degraded modification, it be mixed to use with thermosetting resin.Such as in patent CN101796132A, number-average molecular weight being used in combination at the polyphenylene oxide resin below 5000 and cyanate etc., in patent EP2412740A1, number-average molecular weight is defined as to 500～3000 polyphenylene oxide resin and epoxy resin etc. and is used in combination and is used in conjunction with.The copper-clad plate of using above resin combination to make has lower specific inductivity and dielectric loss with respect to pure cyanate or epoxy-resin systems, has better thermotolerance, and water absorption decreased.But, low molecular weight polycaprolactone phenylate resin active group quantity used in patent CN101796132A, EP2412740A1 is few, active low, participate in hardly the curing reaction of epoxy resin or cyanate, the cured article of its resin combination can only become half interpenetrating network structure (IPN), crosslinking curing can not occur in the polyphenylene oxide resin self in this IPN structure yet, can only intert among the cross-linked network of thermosetting resin with free state.And the consistency between polyphenylene oxide and other thermosetting resins is very poor, is prone to resin and divides equal problem.Generally all there are the insoluble defects such as thermal expansivity is higher, thermostability is poor in the sheet material that this based resin composition is made.

The low problem for the polyphenylene oxide reactive behavior, some,, by the further modification of degraded polyphenylene oxide resin, access active group on its molecular chain, especially refer to an access the functional groups such as unsaturated double-bond.Such as in CN101624467, CN1745142A etc., mentioning the end group of polyphenylene oxide or side chain are carried out to modification, increase unsaturated double-bond, thereby it is crosslinked that polyphenylene oxide resin can be occurred, such modified polyphenylene ether resin is coordinated and can obtain compositions of thermosetting resin with components such as the linking agents such as cyanuric acid triallyl ester (TAIC) and initiators; In CN102807658, will have larger molecular weight containing the isostructural olefin resin of divinyl as linking agent, with functionalized polyphenylene ether resins, and the component such as initiator coordinates and obtains the resin combination for the used for printed circuit veneer sheet.Said composition has good dielectric properties and thermotolerance, is applicable to the application of high-frequency high-speed electronic circuit board.But in CN101624467 etc., solely adopt TAIC etc. as linking agent, because its boiling point is lower, volatile, cause existing in process of production unstable, and can make the cured article cross-linking density reduce, over-all properties incurs loss.In CN102807658, olefin resin used is unfavorable for improving the larger problem of system viscosity that the polyphenylene oxide stiff chain causes.The polarity of the resin combination in above-mentioned patent is lower, the cohesiveness of resin cured matter and glass-fiber-fabric and Copper Foil etc. is poor, and its curing reaction mechanism is radical polymerization, solidify reaction process is difficult to control, and has certain difficulty in the application of used for printed circuit veneer sheet.In patent US2009/023371A1, a kind of polyphenylene oxide resin of vinyl difunctionality is coordinated with the components such as cyanate, bisphenol A cyanate ester, brominated flame retardant and mineral filler with naphthalene ring, obtain a kind ofly thering is fine mobility, and can guaranteeing to obtain good stripping strength, humidity resistance and flame retardant resistance under the prerequisite of better dielectric properties.The cyanate ester resin of introducing in this patent has obvious water-absorbent, and the storage period of cyanate ester resin and prepreg thereof is shorter with respect to epoxy resin, and this two aspect is all very important problem in the production of used for printed circuit veneer sheet.

Mention the polymer network of allylic cpd and epoxy resin solidifying system IPN in patent CN1131955A, but wherein allylic cpd is the low-molecular weight compounds such as cyanuric acid triallyl ester (TAC) and performed polymer thereof etc., its toughness, thermotolerance and dielectric properties are relative is weaker than functionalized polyphenylene oxide resin, and the low-molecular weight compound boiling point such as TAC is lower, volatile, processing stability is very poor.

Mention in CN1193081C the epoxy resin with propenyl or vinyl is added to performances such as can in the resin of radical polymerization or silicon oxidation polymerization, improving bounding force, but abandoned common epoxy resin in patent, and only adopt the kind epoxy resin with propenyl or vinyl seldom on market, the application space of its resin combination is dwindled, and high expensive.

Curing system and a kind of allyl group network of mentioning epoxy resin and acid anhydride type curing agent composition in CN1160407A form the resin combination that compound forms, wherein allylic cpd used is mainly the low-boiling compounds such as cyanuric acid triallyl ester (TAC), the process for processing less stable, and its dielectric properties and mechanical property are inferior to functionalized polyphenylene ether resins.

Summary of the invention

Prepreg, used for printed circuit veneer sheet that main purpose of the present invention is to provide a kind of compositions of thermosetting resin containing polyphenylene oxide and uses this composition, this compositions of thermosetting resin has low-k and dielectric dissipation factor, low water absorption, high glass-transition temperature, high-adhesion, high heat resistance, the excellent excellent over-all properties such as processed-type, high tenacity and flame retardant resistance, be applicable to prepreg, used for printed circuit veneer sheet etc., can meet the integration requirement of laminate for printed circuit board.

In order to achieve the above object, the present invention has adopted following technical scheme:

A kind of compositions of thermosetting resin, described compositions of thermosetting resin comprises:

(A) polyphenylene oxide resin that contains unsaturated double-bond;

(B) epoxy resin;

(C) solidifying agent;

(D) initiator.

Polyphenylene oxide resin, be called for short PPO, and commonly used is the thermoplastic resin that the disubstituted phenol of 2,6-forms through oxidative coupling polymerization, and structural formula is as follows:

The present invention's polyphenylene oxide resin used is the polyphenylene oxide resin that end group or side chain contain unsaturated double-bond that can curing cross-linked.This resinoid generally with the compound that contains unsaturated double-bond, replaces the end group of degraded polyphenylene oxide resin or the hydrogen atom on side chain is made.This resinoid molecular size range affects the performance of its complete processing and final cured article, and its molecular weight is larger, and resin or soltion viscosity are larger, and reactive group is fewer, poorer with the consistency of other components; Molecular weight is less, and the viscosity of resin or solution is less, and reactive group is more, and better with the consistency of other components, but too little dielectric properties and the loss in toughness that can make again cured article of molecular weight.Therefore, the number-average molecular weight of the described polyphenylene oxide resin that contains unsaturated double-bond is 1000～7000, and preferably the number-average molecular weight of the described polyphenylene oxide resin that contains unsaturated double-bond is 1000～4000.

Component (B) and (C) form the curing network system of epoxy resin, formed semi-intercrossing network (IPN) with together with the network system of the crosslinked generation of component (A), forms the main body of resin combination of the present invention.The mass fraction ratio of two network systems does not significantly limit, and it is foundation that its consumption be take the demand of reality in using.Consumption increase that it is generally acknowledged epoxy systems has favourable influence to the cohesiveness with whole system, and for specific inductivity and dielectric dissipation factor, negative impact is arranged, and the network system of component (A) is contrary.

In the present invention, preferably with (A), (B) with (C) summation of component, be 100 mass parts meters, the consumption of described (A) component is 1～99 mass parts, 3 mass parts for example, 5 mass parts, 10 mass parts, 15 mass parts, 22 mass parts, 32 mass parts, 41 mass parts, 53 mass parts, 65 mass parts, 74 mass parts, 85 mass parts, 93 mass parts, 46 mass parts, 37 mass parts, 80 mass parts, 71 mass parts, preferably the consumption of (A) component is 20～90 mass parts, further preferred 30～80 mass parts, correspondingly (B) and (C) component consumption summation be that 100 mass parts are removed component (A) mass parts in addition.

Preferably, take (A), (B) is 100 mass parts with (C) summation of component, and (B) and (C) component consumption summation is 1～99 mass parts.Described (B) and (C) component consumption summation be for example 5 mass parts, 10 mass parts, 15 mass parts, 20 mass parts, 25 mass parts, 35 mass parts, 45 mass parts, 55 mass parts, 60 mass parts, 65 mass parts, 70 mass parts, 75 mass parts, 80 mass parts, 85 mass parts, 90 mass parts or 95 mass parts.

Epoxy resin, this component can be any resin, as long as the epoxide group that contains two (or more than two) in the molecular structure of described resin.Exemplary epoxy resin is selected from bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol aldehyde type epoxy resin, brominated epoxy resin, phosphorous epoxy resin, nitrogen-containing epoxy thermoset, biphenyl epoxy resin, containing naphthalene nucleus epoxy resin, containing fluorene structured epoxy resin or containing the mixture of any one or at least two kinds in dicyclo fluorenes diene structure epoxy resin.Described mixture for example contains dicyclo fluorenes diene structure epoxy resin and contains the mixture of fluorene structured epoxy resin, the mixture of bisphenol A type epoxy resin and biphenyl epoxy resin, mixture containing naphthalene nucleus epoxy resin and biphenyl epoxy resin, the mixture of brominated epoxy resin and phenol aldehyde type epoxy resin, the mixture of phosphorous epoxy resin and nitrogen-containing epoxy thermoset, the mixture of phenol aldehyde type epoxy resin and bisphenol-s epoxy resin, the mixture of bisphenol f type epoxy resin and bisphenol A type epoxy resin.Consider the requirement of flame retardant resistance, in the structure of epoxy resin, can contain the ignition-proof elements such as bromine, nitrogen, phosphorus, also can not contain this dvielement, by increasing fire retardant, play fire retardation.

Described epoxy resin does not have clear and definite requirement to molecular structure and molecular weight etc., the epoxy resin that described epoxy resin preferred molecular structure is symmetrical and epoxy equivalent (weight) is less than 700, for the epoxy resin that does not contain the elements such as bromine, phosphorus, nitrogen, the epoxy resin that preferably epoxy equivalent (weight) is less than 400, perhaps preferably in epoxy resin composition, contain mass fraction and be not less than the epoxy resin that 10% epoxy equivalent (weight) is less than 300 bifunctional, contribute to like this compatible between each component, be conducive to the over-all properties after resin combination solidifies.

Described epoxy resin preferred molecular structure symmetry, in molecular structure without alkyl group side chain, the epoxy resin that contains the elements such as chlorine, bromine, phosphorus or nitrogen, fire-retardant after contributing to resin combination to solidify.

Solidifying agent, described solidifying agent be selected from can with acid anhydride type curing agent, imidazole curing agent, amine curing agent, organo-metallic salt solidifying agent or the resol class solidifying agent of epoxy resin generation curing reaction in the mixture of any one or at least two kinds.Described mixture is the mixture of resol class solidifying agent and imidazole curing agent for example, the mixture of amine curing agent and imidazole curing agent, the mixture of imidazole curing agent and acid anhydride type curing agent, the mixture of acid anhydride type curing agent and amine curing agent, the mixture of resol class solidifying agent and acid anhydride type curing agent, the mixture of resol class solidifying agent, imidazole curing agent and acid anhydride type curing agent, the mixture of acid anhydride type curing agent, amine curing agent and imidazole curing agent.Solidifying agent makes veneer sheet have good thermotolerance and reliability, and its kind be there is no to significant limitation, but preferably it can be dissolved in the homogeneous solvent system with component (A), (B), is mixing and the phenomenon such as can not separate, separate out in reaction process.

The effect of solidifying agent is and epoxy resin generation chemical reaction, forms cross-linked network.The mol ratio of the group that can react with epoxide group in epoxide group and solidifying agent in epoxy resin is 1:0～1.5, described 0～1.5 does not comprise 0, described molar ratio is as be 1:0.1,1:0.2,1:0.3,1:0.4,1:0.5,1:0.6,1:0.7,1:0.8,1:0.9,1:1,1:1.1,1:1.2,1:1.3,1:1.4, preferably 1:0.2～1.2.

Described compositions of thermosetting resin also comprises (D) initiator, and described initiator can impel the polyreaction of unsaturated double-bond, for regulating and improve the reaction conditions of (A) component polymerization reaction take place.Can polymerization reaction take place at component (A) temperature certain in the condition that does not have initiator, form cross-linked network, but general consuming time very long, and speed of reaction is difficult to control, so the present invention preferably uses initiator.Can play and promote the compound of unsaturated double-bond polyreaction all to can be used as this component, preferably peroxide initiator is or/and azo-initiator.

Preferably, described peroxide initiator is selected from α, α '-bis-(sec.-propyl between tert-butyl hydroperoxide) benzene, 2,5-dimethyl-2,5-bis-(tert-butyl hydroperoxide)-3-hexin, benzoyl peroxide, 3,3 ', 5,5 '-tetramethyl--Isosorbide-5-Nitrae-hexichol oxygen quinone, chloranil, 2, the mixture of any one in 4,6-tri-(tertiary butyl phenoxy group) or single carbonic acid tert-butyl hydroperoxide isopropyl ester or at least two kinds.

Preferably, described azo-initiator is selected from the mixture of any one or at least two kinds in Diisopropyl azodicarboxylate, azo isobutyl cyano group methane amide, 2,2'-Azobis(2,4-dimethylvaleronitrile) or azo-bis-iso-dimethyl etc.

The example of described initiator is as α, α '-bis-(sec.-propyl between tert-butyl hydroperoxide) benzene and 2, 5-dimethyl-2, the mixture of 5-bis-(tert-butyl hydroperoxide)-3-hexin, benzoyl peroxide and 3, 3 ', 5, 5 '-tetramethyl--1, the mixture of 4-hexichol oxygen quinone, chloranil and 2, 4, the mixture of 6-tri-(tertiary butyl phenoxy group), the mixture of single carbonic acid tert-butyl hydroperoxide isopropyl ester and Diisopropyl azodicarboxylate, the mixture of azo isobutyl cyano group methane amide and 2,2'-Azobis(2,4-dimethylvaleronitrile), the mixture of azo isobutyl cyano group methane amide and azo-bis-iso-dimethyl, α, the mixture of α '-bis-(sec.-propyl between tert-butyl hydroperoxide) benzene and azo-bis-iso-dimethyl.

Take (A) component as 100 mass parts, the consumption of described initiator is 0.1～20 mass parts, for example 0.5 mass parts, 1.2 mass parts, 1.8 mass parts, 2 mass parts, 3 mass parts, 4 mass parts, 5 mass parts, 7 mass parts, 9 mass parts, 11 mass parts, 13 mass parts, 15 mass parts, 17 mass parts, 19 mass parts, preferred 1～19.5 mass parts, further preferred 2.4～18.5 mass parts.If necessary, can further add metal carboxylate further to promote curing reaction.

One of ordinary skill in the art can be according to the formula of disclosed compositions of thermosetting resin in prior art, select suitable cooperation component as linking agent, promotor, fire retardant and filler etc., with (A), (B), (C) and (D) component coordinate, obtain compositions of thermosetting resin of the present invention.When the used for printed circuit veneer sheet, possess excellent flame retardant properties after requiring resin combination to solidify when described compositions of thermosetting resin.When described epoxy resin is chosen as the epoxy resin of ignition-proof elements such as not containing bromine or phosphorus, can coordinate the component fire retardant to reach the purpose that resin cured matter possesses excellent flame retardant properties by interpolation.

Described compositions of thermosetting resin also comprises the compound that (E) contains epoxide group and ethylenic unsaturated group.This component have can with the ethylenic unsaturated group of (A) polymerization reaction take place, and have and can participate in epoxy resin (B) and (C) epoxide group of curing reaction, therefore, this component under certain reaction conditions can by (A) and (B)/(C) two cross-linking systems link together, thereby increase resin combination cured article force of cohesion and stability.And component (E) all has fine consistency to two kinds of network systems, it can serve as compatilizer, contributes to the compatible of resin combination integral body.

Described (E) component can be any compound, but as long as the unsaturated link(age) and the epoxide group that contain copolymerization in described molecular structure of compounds.The glycidyl ester of the described preferred unsaturated carboxylic acid of compound that contains epoxide group and ethylenic unsaturated group and/or containing the glycidyl ether of thiazolinyl, more preferably glycidyl acrylate, limonene dioxide, 2, the mixture of any one in 6-2-glycidyl phenyl allyl ether, glycidyl methacrylate, methylene-succinic acid list glycidyl ester, butylene tricarboxylic acid list glycidyl ester, vinyl glycidyl ether, glycidyl allyl ether or glycidyl oxygen ethyl vinyl ether or at least two kinds.Described mixture is the mixture of glycidyl oxygen ethyl vinyl ether and glycidyl allyl ether for example, the mixture of vinyl glycidyl ether and butylene tricarboxylic acid list glycidyl ester, the mixture of methylene-succinic acid list glycidyl ester and glycidyl methacrylate, the mixture of glycidyl acrylate and glycidyl allyl ether, the mixture of vinyl glycidyl ether and methylene-succinic acid list glycidyl ester, the mixture of butylene tricarboxylic acid list glycidyl ester, glycidyl methacrylate and glycidyl oxygen ethyl vinyl ether.Both contain unsaturated double-bond in the molecular structure of above-mentioned substance, contained again epoxide group.

Some compound boiling point in the described compound that contains epoxide group and ethylenic unsaturated group is lower, be easy to volatilization, have different restrictions in the course of processing, the compound boiling point that contains epoxide group and ethylenic unsaturated group of the present invention is more than 120 ℃, preferably boiling point is more than 150 ℃, and further preferred boiling point is more than 170 ℃.

Take (A) component as 100 mass parts, the described compound amount that contains epoxide group and ethylenic unsaturated group is 0～50 mass parts, for example 0.01 mass parts, 0.001 mass parts, 0.5 mass parts, 0.8 mass parts, 2 mass parts, 8 mass parts, 12 mass parts, 16 mass parts, 22 mass parts, 28 mass parts, 32 mass parts, 36 mass parts, 40 mass parts, 45 mass parts, 48 mass parts, preferred 5～46 mass parts, further preferred 9～42 mass parts.

Described compositions of thermosetting resin also comprises (F) linking agent.Described linking agent is selected from the compound with two or at least three ethylenic unsaturation hydrocarbon structures, preferably the mixture of a kind of in trialkenyl isocyanuric acid ester, trialkenyl cyanurate, aryl polyenoid propyl diester, fatty polyenoid propyl diester, carbonic acid polyenoid propyl diester and the olefin resin that contains butadiene structure or at least two kinds.This component can participate in the polyreaction of component (A), increases cross-linking density, improves thermotolerance and mechanical property etc., and it also can be regulated and improve this component (A) and the reaction conditions of component polymerization reaction take place such as (F) by initiator.And do not contain the polyphenylene oxide structure in linking agent, be easy to and epoxy-resin systems and other component compatibility, can improve component (A) and the consistency of component such as (B).

Take (A) component as 100 mass parts, the consumption of described linking agent is 0～50 mass parts, for example 0.002 mass parts, 0.004 mass parts, 0.2 mass parts, 0.4 mass parts, 0.5 mass parts, 5 mass parts, 8 mass parts, 13 mass parts, 18 mass parts, 23 mass parts, 28 mass parts, 32 mass parts, 36 mass parts, 39 mass parts, 42 mass parts, 45 mass parts, 47 mass parts, 49 mass parts, preferred 0～50 mass parts, do not comprise 0 mass parts, further preferred 0.1～50 mass parts.

Preferably, described compositions of thermosetting resin also comprises (G) promotor, and described promotor is selected from glyoxal ethyline, the 2-phenylimidazole, 2-ethyl-4-methylimidazole, tri-n-butylamine, triphenyl phosphorus, thiocarbamide, thiourea derivative, boron trifluoride complex, sad metal-salt, the isocaprylic acid metal-salt, acetyl acetone salt, metallic naphthenate, the mixture of any one in salicylic acid metal salt or Metallic stearates or at least two kinds, described mixture is the mixture of Metallic stearates and salicylic acid metal salt for example, the mixture of metallic naphthenate and acetyl acetone salt, the mixture of sad metal-salt and boron trifluoride complex, the mixture of triphenyl phosphorus and tri-n-butylamine, the mixture of 2-ethyl-4-methylimidazole and 2-phenylimidazole, the mixture of sad metal-salt and tri-n-butylamine, 2-ethyl-4-methylimidazole, the mixture of tri-n-butylamine and 2-phenylimidazole, wherein, described metal is selected from zinc, copper, iron, tin, the mixture of any one in cobalt or aluminium or at least two kinds.Promotor being mainly used in regulated component (B) and crosslinking reaction speed (C).

Take (B) component as 100 mass parts, the consumption of described promotor is 0.01～1.0 mass parts, for example 0.05 mass parts, 0.08 mass parts, 0.15 mass parts, 0.25 mass parts, 0.35 mass parts, 0.45 mass parts, 0.55 mass parts, 0.65 mass parts, 0.75 mass parts, 0.85 mass parts, 0.95 mass parts, preferred 0.10～0.90 mass parts, further preferred 0.18～0.84 mass parts.

Component (G) and (D) select kind and consumption respectively to (B) in compositions of thermosetting resin and (C), (A) and (F) and each component and (E) initial reaction temperature and the speed of reaction of component have vital effect, (G) with the selecting so that in combining, the temperature of reaction of each component is consistent with speed is advisable of (D) two components, in actual the use with in solidification process without noted phase separation phenomena, the cured article physical strength is good is advisable.In addition, part component (C) solidifying agent and (G) promotor the decomposition of component (D) initiator is also had to promoter action, wherein outstanding with some amine curing agents and tertiary amines promotor, therefore when selecting, need consider to some extent.

(A) polyphenylene oxide resin that contains unsaturated double-bond;

(B) epoxy resin;

(C) solidifying agent;

(D) initiator;

(E) compound that contains epoxide group and ethylenic unsaturated group.

Wherein, take (A), (B) is 100 mass parts with (C) summation of component, and the consumption of described (A) component is 1～99 mass parts, and (B) and (C) component consumption summation is 1～99 mass parts; The mol ratio of the group that can react with epoxide group in epoxide group and solidifying agent in epoxy resin is 1:0～1.5, and described 0～1.5 does not comprise 0; (A) component of take calculates as 100 mass parts, and the described compound amount that contains epoxide group and ethylenic unsaturated group is 0～50 mass parts, and the consumption of described initiator is 0.1～20 mass parts.

(A) polyphenylene oxide resin that contains unsaturated double-bond;

(B) epoxy resin;

(C) solidifying agent;

(D) initiator;

(E) compound that contains epoxide group and ethylenic unsaturated group;

(F) linking agent;

(G) promotor;

Wherein, take (A), (B) is 100 mass parts with (C) summation of component, and the consumption of described (A) component is 1～99 mass parts, and (B) and (C) component consumption summation is 1～99 mass parts; The mol ratio of the group that can react with epoxide group in epoxide group and solidifying agent in epoxy resin is 1:0～1.5, and described 0～1.5 does not comprise 0; (A) component of take calculates as 100 mass parts, and the described compound amount that contains epoxide group and ethylenic unsaturated group is 0～50 mass parts, and the consumption of described linking agent is 0～50 mass parts, and the consumption of described initiator is 0.1～20 mass parts; Take (B) component as 100 mass parts, and the consumption of described promotor is 0.01～1.0 mass parts.

In order to increase the flame retardant resistance of resin combination, described compositions of thermosetting resin also comprises (H) fire retardant, and preferably, described fire retardant is selected from decabromodiphynly oxide, TDE, the two tetrabromo phthalimides of ethylene, melamine phosphate, melamine polyphosphate, two melamine pyrophosphates, three (tribromo phenyl) cyanurate, three (2,6-3,5-dimethylphenyl) phosphorus, 10-(2,5-dihydroxy phenyl)-9, mix-10-phosphorus phenanthrene-10-oxide compound of 10-dihydro-9-oxy, 2,6-bis-(2,6-3,5-dimethylphenyl) phosphorus base benzene, 10-phenyl-9, the 10-dihydro-9-oxy is assorted-mixture of any one or at least two kinds in 10-phosphorus phenanthrene-10-oxide compound or phosphonitrile compounds, preferably three (2,6-3,5-dimethylphenyl) phosphorus, 10-(2,5-dihydroxy phenyl)-9, mix-10-phosphorus phenanthrene-10-oxide compound of 10-dihydro-9-oxy, 2,6-bis-(2,6-3,5-dimethylphenyl) phosphorus base benzene, 10-phenyl-9, mix-10-phosphorus phenanthrene-10-oxide compound of 10-dihydro-9-oxy, hexachlorocyclotriphosphazene, alkoxycyclotriphosphderivative, phenoxy cyclotriphosphazene, six amino ring three phosphonitriles, poly-bromo alkoxyl group phosphonitrile or polyaryloxyphosphazene etc. contain halogen, nitrogen, the mixture of any one in the fire retardant of the elements such as phosphorus or at least two kinds.

Described fire retardant also comprises the inorganic combustion inhibitors such as aluminium hydroxide, magnesium hydroxide, and described inorganic combustion inhibitor can mix with other fire retardants use, does not generally advise independent use;

Take the compositions of thermosetting resin gross weight as 100 mass parts, the consumption of described fire retardant is 0～50 mass parts, for example 0.02 mass parts, 0.004 mass parts, 0.8 mass parts, 1.5 mass parts, 2 mass parts, 5 mass parts, 8 mass parts, 12 mass parts, 16 mass parts, 20 mass parts, 25 mass parts, 28 mass parts, 32 mass parts, 36 mass parts, 38 mass parts, 42 mass parts, 46 mass parts, 48 mass parts, 49 mass parts, preferably 10～30 mass parts.

Can also add the performance that (I) inorganic filler components is regulated composition in compositions of thermosetting resin of the present invention, this mineral filler is selected from the mixture of any one or at least two kinds of silicon-dioxide, boron nitride, aluminium hydroxide, boehmite, talcum, clay, mica, kaolin, barium sulfate, calcium carbonate, magnesium hydroxide or zinc borate.Described mixture is the mixture of silicon-dioxide and boron nitride for example, the mixture of aluminium hydroxide and boehmite, the mixture of talcum and clay, mica and kaolinic mixture, the mixture of barium sulfate and calcium carbonate, the mixture of magnesium hydroxide and zinc borate, the mixture of silicon-dioxide, boron nitride and aluminium hydroxide, the mixture of boehmite, talcum and clay, the mixture of mica, kaolin and barium sulfate, the mixture of calcium carbonate, magnesium hydroxide and zinc borate.

This mineral filler can be carried out suitable ratio adjustment according to application target, take the compositions of thermosetting resin gross weight as 100 mass parts, the consumption of described mineral filler is 0～70 mass parts, for example 0.004 mass parts, 0.02 mass parts, 1 mass parts, 2 mass parts, 8 mass parts, 12 mass parts, 17 mass parts, 20 mass parts, 24 mass parts, 26 mass parts, 32 mass parts, 36 mass parts, 40 mass parts, 45 mass parts, 50 mass parts, 55 mass parts, 60 mass parts, 62 mass parts, 66 mass parts, 68 mass parts, 69 mass parts, preferably 5～40 mass parts.

In order better mineral filler to be dispersed in resin combination, can also add (J) coupling agent in compositions of thermosetting resin of the present invention.Described coupling agent can prevent the mineral filler reunion, improve the bonding force between resin and mineral filler, the defect that reduces to add mineral filler and cause, reduce water-intake rate, and coupling agent can also improve the surface tension of resin combination, further improve the mobility of resin combination, strengthen effect of impregnation.Described coupling agent can be silane coupling agent, silane pre-polymer, the mixture of any one in titanate ester compound etc. or at least two kinds, it can improve capillary compound, coupling agent preferred silane coupling agent of the present invention, further preferred epoxy silane coupling, the amino containing silane coupling agent, the anilino silane coupling agent, vinyl silicane coupling agent, the isocyanato silanes coupling agent, the propenyl silane coupling agent, the iso-butylene silane coupling agent, the mixture of any one in vinylbenzene silane coupling agent or ureido silane coupling agent etc. or at least two kinds.The consumption of coupling agent there is no especially and limits, and preferably, take the compositions of thermosetting resin gross weight as 100 mass parts calculating, the consumption of coupling agent is 0～5 mass parts, wherein do not comprise 0 mass parts, more preferably 0.005～4 mass parts, further preferred 0.05～3 mass parts.

The consumption of described coupling agent is for example 0.5 mass parts, 1 mass parts, 1.5 mass parts, 2 mass parts, 2.5 mass parts, 3 mass parts, 3.5 mass parts, 4 mass parts or 4.5 mass parts.

(A) polyphenylene oxide resin that contains unsaturated double-bond

(B) epoxy resin

(C) solidifying agent

(D) initiator

(E) compound that contains epoxide group and ethylenic unsaturated group

(F) linking agent

(G) promotor

(H) fire retardant

(I) mineral filler;

Wherein, take (A), (B) is 100 mass parts with (C) summation of component, and the consumption of described (A) component is 1～99 mass parts, and (B) and (C) component consumption summation is 1～99 mass parts; The mol ratio of the group that can react with epoxide group in epoxide group and solidifying agent in epoxy resin is 1:0～1.5, and described 0～1.5 does not comprise 0; (A) component of take calculates as 100 mass parts, and the described compound amount that contains epoxide group and ethylenic unsaturated group is 0～50 mass parts, and the consumption of described linking agent is 0～50 mass parts, and the consumption of described initiator is 0.1～20 mass parts; Take (B) component as 100 mass parts, and the consumption of described promotor is 0.01～1.0 mass parts; Take the compositions of thermosetting resin gross weight as 100 mass parts, and the consumption of described fire retardant is 0～50 mass parts, and the consumption of described mineral filler is 0～70 mass parts.

The present invention, by combination of components such as the polyphenylene oxide resin of unsaturated double-bond modification and epoxy resin, has unexpectedly obtained a kind of good fluidity, solidifies the aspect excellences such as rear thermotolerance, cohesiveness and processibility, and can guarantee the resin combination of better dielectric properties.More beyond thought is that add a kind of compound that had not only contained unsaturated double-bond but also contained epoxide group in said composition after, the performance of the aspects such as the dielectric properties of resin combination, thermotolerance, cohesiveness and processibility is better.In said composition, add solidifying agent, linking agent, initiator, fire retardant and filler etc. to contribute to control the curing reaction of resin combination, make the structure of cured article more stable, performance is more excellent.Introduced epoxy resin solidifying system in the present invention, reduced the consumption of lower molecular weight, volatile olefin(e) compound, and lower molecular weight, volatile olefin(e) compound are not selected as unique linking agent in invention, even can avoid the application to it, there is good stability in process of manufacture.Therefore, according to content of the present invention, can obtain a kind ofly in dielectric properties, and the aspects such as thermotolerance, cohesiveness, flame retardant resistance and processibility have outstanding representation, are applicable to the resin combination of high-frequency high-speed with electronic circuit board.

" comprising " of the present invention, mean it except described component, can also comprise other components, these other components give described resin combination different characteristics.In addition, " comprising " of the present invention, can also replace with enclosed " being " or " by ... form ".

For example, compositions of thermosetting resin of the present invention can add the thermosetting resin of cooperation, as concrete example, can enumerate cyanate ester resin, resol, urethane resin, melamine resin etc., solidifying agent or the solidifying agent promotor that also can add these thermosetting resins.

In addition, described compositions of thermosetting resin can also contain various additives, as concrete example, can enumerate silane coupling agent, titanate coupling agent, oxidation inhibitor, thermo-stabilizer, static inhibitor, UV light absorber, pigment, tinting material, lubricant etc.These thermosetting resins and various additive can be used separately, also can two kinds or two or more mixing use.

Preparation method as one of resin combination of the present invention, the compound, solidifying agent, promotor, initiator, fire retardant, the mineral filler that can coordinate by known method, stir, mix the described polyphenylene oxide resin that contains unsaturated double-bond, epoxy resin, contain epoxide group and ethylenic unsaturated group, and various thermosetting resins, various additive, prepare.

Two of purpose of the present invention is to provide a kind of resin adhesive liquid, and it is compositions of thermosetting resin as above to be dissolved or is dispersed in solvent obtain.

As the solvent in the present invention, be not particularly limited, as concrete example, can enumerate the alcohols such as methyl alcohol, ethanol, butanols, the ethers such as ethyl cellosolve, ethylene glycol butyl ether, ethylene glycol-methyl ether, Trivalin SF, diethylene glycol monobutyl ether, the ketones such as acetone, butanone, ethyl methyl ketone, hexone, pimelinketone, toluene, dimethylbenzene, sym-trimethylbenzene etc. are aromatic hydrocarbon based, the ester classes such as ethoxyethyl group acetic ester, vinyl acetic monomer, N, the nitrogenous kind solvents such as dinethylformamide, N,N-dimethylacetamide, METHYLPYRROLIDONE.Above-mentioned solvent can be used separately a kind of, also can two kinds or two or more mixing use, preferably the aromatic hydrocarbon solvents such as toluene, dimethylbenzene, sym-trimethylbenzene mix use with ketone flux such as acetone, butanone, ethyl methyl ketone, hexone, pimelinketone.Usage quantity those skilled in the art of described solvent can select according to the experience of oneself, and the resin adhesive liquid that makes to obtain reaches the viscosity that is suitable for using and gets final product.

In resin combination as above dissolves or is dispersed in the process of solvent, can add emulsifying agent.Disperseed by emulsifying agent, can make powder filler etc. be uniformly dispersed in glue.

The preparation method of exemplary resin adhesive liquid is: above-mentioned (A)～(D) component is mixed at normal temperatures, add solvent, stir until after dissolving fully, add (H) and (I) component, continue the high speed shear balance that is uniformly dispersed, make the resin adhesive liquid that solid content is 45～75%.

Three of purpose of the present invention is to provide a kind of prepreg, and it is that after base-material is infiltrated to resin adhesive liquid as above, drying obtains.Described base-material is fabric or nonwoven fabric.Described drying conditions for to toast 2～10min under 100～200 ℃.

Four of purpose of the present invention is to provide a kind of veneer sheet, and described copper-clad plate contains at least one prepreg as above.Veneer sheet be prepared as prior art.

Five of purpose of the present invention is to provide a kind of insulcrete, and described insulcrete contains at least one prepreg as above.

Six of purpose of the present invention is to provide a kind of printed circuit board, and described printed circuit board is by least one veneer sheet preparation as above.The lamination of the preparation of veneer sheet is at 2～5MPa pressure and 180～250 ℃ of temperatures system 1～4h.

Compared with prior art, the present invention has following beneficial effect:

(1) the thermosetting polyphenylene ether resin that the present invention will contain unsaturated double-bond coordinates with epoxy resin solidifying system, obtains a kind of both had lower specific inductivity and dielectric loss, has again cohesiveness and stable on heating resin combination preferably;

(2) adopt a kind of compound that had not only contained unsaturated double-bond but also contained epoxide group that polyphenylene oxide and two cross-linked networks of epoxy resin are joined together, make resin combination there is more excellent over-all properties, prepared metal foil laminate has excellent tinsel stripping strength, thermotolerance and dielectric properties, is applicable to the high-frequency high-speed electronic circuit board.

Embodiment

For the present invention is described better, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:

Embodiment 1

By 70 parts of methacrylic acid blocking polyphenyl ether resin (SABIC, trade(brand)name: SA9000), 28 parts of tetrabromo-bisphenol type epoxy resin (Changchun artificial resin factories, BEB400), 12 parts of acid anhydride type curing agent styrene-maleic anhydride copolymer (Sartomers, SMA EF40), 3 parts of dicumyl peroxide DCP and 70 parts of toluene mix, and stir until dissolve fully.0.2 part of 2 ethyl-4 Methylimidazole is dissolved in 10 parts of butanone, then adds above-mentioned solution.Above-mentioned composition is fully stirred at normal temperature, obtain finely dispersed resin combination.This resin combination is impregnated into to NE type glasscloth, and (Co., Ltd. is spun in day east, NEA2116), and, in 155 ℃ of oven dry 2～10min, except desolventizing, obtains the prepreg of resin content in 55% left and right.

Respectively cover the Copper Foil of a 1Oz on the two sides of eight overlapping prepregs, under the pressure of the temperature of 200 ℃ and 3.0MPa, hot pressing 90min, obtain doublesided copperclad laminate.

Embodiment 2

By 30 parts of methacrylic acid blocking polyphenyl ether resin (SABIC, trade(brand)name: SA9000), the acetone soln (Dow Chemical of 53 parts of brominated bisphenol A type epoxy resins, D.E.R.530A80, solid content 80wt%), 5 parts of tetrabromo-bisphenol type epoxy resin (Changchun artificial resin factories, BEB350), (Japan is bright and change into for 22 parts of biphenyl type resol, MEH-7851H), 0.05 part of 2 ethyl-4 Methylimidazole, 1.3 parts of dicumyl peroxide DCP and 60 parts of toluene mix, and dissolve fully.Above-mentioned composition is fully stirred at normal temperature, obtain finely dispersed resin combination.This resin combination is impregnated into to NE type glasscloth, and (Co., Ltd. is spun in day east, NEA2116), and, in 155 ℃ of oven dry 2～10min, except desolventizing, obtains the prepreg of resin content in 55% left and right.

Respectively cover the Copper Foil of a 1Oz on the two sides of eight overlapping prepregs, under the pressure of the temperature of 190 ℃ and 3.0MPa, hot pressing 90min, obtain doublesided copperclad laminate.

Embodiment 3

By 70 parts of methacrylic acid blocking polyphenyl ether resin (SABIC, trade(brand)name: SA9000), 28 parts of tetrabromo-bisphenol type epoxy resin (Changchun artificial resin factories, BEB400), 12 parts of acid anhydride type curing agent styrene-maleic anhydride copolymer (Sartomers, SMA EF40), 10 part 2,6-Racemic glycidol phenyl allyl ether (commercial reagent), 3 parts of dicumyl peroxide DCP and 70 parts of toluene mix, and dissolve fully.0.2 part of 2 ethyl-4 Methylimidazole is dissolved in 10 parts of butanone, then adds above-mentioned solution.Above-mentioned composition is fully stirred at normal temperature, obtain finely dispersed resin combination.This resin combination is impregnated into to NE type glasscloth, and (Co., Ltd. is spun in day east, NEA2116), and, in 155 ℃ of oven dry 2～10min, except desolventizing, obtains the prepreg of resin content in 55% left and right.

Embodiment 4

By 50 parts of methacrylic acid blocking polyphenyl ether resin (SABIC, trade(brand)name: SA9000), 26 parts of tetrabromo-bisphenol type epoxy resin (Changchun artificial resin factories, BEB400), 20 parts of phenol type novolac epoxy (Changchun artificial resin factories, PNE177), 33 parts of acid anhydride type curing agent styrene-maleic anhydride copolymer (Sartomers, SMA EF40),, 0.05 part of 2 ethyl-4 Methylimidazole, 25 parts of methyl propenoic acid glycidyl ethers (commercial reagent), 2 parts of dicumyl peroxide DCP and 90 parts of toluene mix, and dissolve fully.Above-mentioned composition is fully stirred at normal temperature, obtain finely dispersed resin combination.This resin combination is impregnated into to NE type glasscloth, and (Co., Ltd. is spun in day east, NEA2116), and, in 155 ℃ of oven dry 2～10min, except desolventizing, obtains the prepreg of resin content in 55% left and right.

Embodiment 5

By 70 parts of methacrylic acid blocking polyphenyl ether resin (SABIC, trade(brand)name: SA9000), 28 parts of tetrabromo-bisphenol type epoxy resin (Changchun artificial resin factories, BEB400), 12 parts of acid anhydride type curing agent styrene-maleic anhydride copolymer (Sartomers, SMA EF40), 0.05 part of 2 ethyl-4 Methylimidazole, 10 parts of methyl propenoic acid glycidyl ethers (commercial reagent), 4 parts of dicumyl peroxide DCP, 30 parts of styrene-butadiene copolymer (Sartomer companies, R181) and 90 parts of toluene mix, and dissolve fully.Above-mentioned composition is fully stirred at normal temperature, obtain finely dispersed resin combination.This resin combination is impregnated into to NE type glasscloth, and (Co., Ltd. is spun in day east, NEA2116), and, in 155 ℃ of oven dry 2～10min, except desolventizing, obtains the prepreg of resin content in 55% left and right.

Embodiment 6

By 70 parts of methacrylic acid blocking polyphenyl ether resin (SABIC, trade(brand)name: SA9000), 28 parts of tetrabromo-bisphenol type epoxy resin (Changchun artificial resin factories, BEB400), 12 parts of acid anhydride type curing agent styrene-maleic anhydride copolymer (Sartomers, SMA EF40), 0.05 part of 2 ethyl-4 Methylimidazole, 10 parts of methyl propenoic acid glycidyl ethers (commercial reagent), 3 parts of dicumyl peroxide DCP, 10 parts of styrene-butadiene copolymer (Sartomer companies, R181) and 90 parts of toluene mix, and dissolve fully.Above-mentioned composition is fully stirred at normal temperature, obtain finely dispersed resin combination.This resin combination is impregnated into to NE type glasscloth, and (Co., Ltd. is spun in day east, NEA2116), and, in 155 ℃ of oven dry 2～10min, except desolventizing, obtains the prepreg of resin content in 55% left and right.

Embodiment 7

By 70 parts of vinylbenzene blocking polyphenyl ether resin (Mitsubishi Chemical Inds, trade(brand)name: St-PPE-2), 26 parts of ortho-cresol type novolac epoxy (Momentive, EPON164), 20 parts of acid anhydride type curing agent styrene-maleic anhydride copolymer (Sartomers, SMA EF40), 0.1 part of 2 ethyl-4 Methylimidazole, 10 parts of methyl propenoic acid glycidyl ethers (commercial reagent), 3 parts of dicumyl peroxide DCP, 10 parts of styrene-butadiene copolymer (Sartomer companies, R181) and 80 parts of toluene mix, and dissolve fully.Above-mentioned composition is fully stirred at normal temperature, obtain finely dispersed resin combination.This resin combination is impregnated into to NE type glasscloth, and (Co., Ltd. is spun in day east, NEA2116), and, in 155 ℃ of oven dry 2～10min, except desolventizing, obtains the prepreg of resin content in 55% left and right.

Embodiment 8

By 70 parts of vinylbenzene blocking polyphenyl ether resin (Mitsubishi Chemical Inds, trade(brand)name: St-PPE-2), 26 parts of ortho-cresol type novolac epoxy (Momentive, EPON164), 20 parts of acid anhydride type curing agent styrene-maleic anhydride copolymer (Sartomers, SMA EF40), 0.1 part of 2 ethyl-4 Methylimidazole, 10 parts of methyl propenoic acid glycidyl ethers (commercial reagent), 3 parts of dicumyl peroxide DCP, 10 parts of styrene-butadiene copolymer (Sartomer companies, R181) and 135 parts of toluene mix, and dissolve fully.Add the two tetrabromo phthalimide of 28 parts of brominated flame-retardant ethylenes (U.S. Albemarle Corporation in above-mentioned solution, BT-93w), the 50 parts of molten silicon micro mist (East Sea, Lianyun Harbour silicon powders, FS1002) and 0.05 part of silane coupling agent (chemical company of SHIN-ETSU HANTOTAI, KBM-403).Said components is fully stirred, and obtain finely dispersed resin combination after high speed shear is disperseed.This resin combination is impregnated into to NE type glasscloth, and (Co., Ltd. is spun in day east, NEA2116), and, in 155 ℃ of oven dry 2～10min, except desolventizing, obtains the prepreg of resin content in 55% left and right.

Embodiment 9

By 70 parts of vinylbenzene blocking polyphenyl ether resin (Mitsubishi Chemical Inds, trade(brand)name: St-PPE-2), 26 parts of ortho-cresol type novolac epoxy (Momentive, EPON164), 20 parts of acid anhydride type curing agent styrene-maleic anhydride copolymer (Sartomers, SMA EF40), 0.1 part of 2 ethyl-4 Methylimidazole, 10 parts of methyl propenoic acid glycidyl ethers (commercial reagent), 3 parts of dicumyl peroxide DCP, 10 parts of styrene-butadiene copolymer (Sartomer companies, R181) and 115 parts of toluene mix, and dissolve fully.Add the two tetrabromo phthalimide of 28 parts of brominated flame-retardant ethylenes (U.S. Albemarle Corporation in above-mentioned solution, BT-93w), the 17 parts of molten silicon micro mist (East Sea, Lianyun Harbour silicon powders, FS1002) and 0.05 part of silane coupling agent (chemical company of SHIN-ETSU HANTOTAI, KBM-403).Said components is fully stirred, and obtain finely dispersed resin combination after high speed shear is disperseed.This resin combination is impregnated into to NE type glasscloth, and (Co., Ltd. is spun in day east, NEA2116), and, in 155 ℃ of oven dry 2～10min, except desolventizing, obtains the prepreg of resin content in 55% left and right.

Embodiment 10

By 70 parts of methacrylic acid blocking polyphenyl ether resin (SABIC, trade(brand)name: SA9000), 26 parts of biphenyl type novolac epoxy (Japanese chemical drugs, NC3000H), 20 parts of acid anhydride type curing agent styrene-maleic anhydride copolymer (Sartomers, SMA EF40), 0.1 part of 2 ethyl-4 Methylimidazole, 10 parts of methyl propenoic acid glycidyl ethers (commercial reagent), 3 parts of dicumyl peroxide DCP, 10 parts of styrene-butadiene copolymer (Sartomer companies, R181) and 115 parts of toluene mix, and dissolve fully.Add the two tetrabromo phthalimide of 28 parts of brominated flame-retardant ethylenes (U.S. Albemarle Corporation in above-mentioned solution, BT-93w), the 17 parts of molten silicon micro mist (East Sea, Lianyun Harbour silicon powders, FS1002) and 0.05 part of silane coupling agent (chemical company of SHIN-ETSU HANTOTAI, KBM-403).Said components is fully stirred, and obtain finely dispersed resin combination after high speed shear is disperseed.This resin combination is impregnated into to NE type glasscloth, and (Co., Ltd. is spun in day east, NEA2116), and, in 155 ℃ of oven dry 2～10min, except desolventizing, obtains the prepreg of resin content in 55% left and right.

Embodiment 11

By 70 parts of methacrylic acid blocking polyphenyl ether resin (SABIC, trade(brand)name: SA9000), 26 parts of biphenyl type novolac epoxy (Japanese chemical drugs, NC3000H), 20 parts of acid anhydride type curing agent styrene-maleic anhydride copolymer (Sartomers, SMA EF40), 0.1 part 2 ethyls-4 Methylimidazole, 10 parts of methyl propenoic acid glycidyl ethers (commercial reagent), 3 parts of dicumyl peroxide DCP, 10 parts of styrene-butadiene copolymer (Sartomer companies, R181) and 105 parts of toluene mix, after dissolving fully, add 28 parts of brominated flame-retardant ethyls-bis-(tetrabromo phthalimide) (U.S. Albemarle Corporation, BT-93w).Said components is fully stirred, and obtain finely dispersed resin combination after high speed shear is disperseed.This resin combination is impregnated into to NE type glasscloth, and (Co., Ltd. is spun in day east, NEA2116), and, in 155 ℃ of oven dry 2～10min, except desolventizing, obtains the prepreg of resin content in 55% left and right.

Embodiment 12

By 30 parts of methacrylic acid blocking polyphenyl ether resin (SABIC, trade(brand)name: SA9000), 63 parts of biphenyl type novolac epoxy (Japanese chemical drugs, NC3000H), 50 parts of acid anhydride type curing agent styrene-maleic anhydride copolymer (Sartomers, SMA EF40), 0.2 part 2 ethyls-4 Methylimidazole, 5 parts of methyl propenoic acid glycidyl ethers (commercial reagent), 1.3 part dicumyl peroxide DCP, 5 parts of styrene-butadiene copolymer (Sartomer companies, R181) and 120 parts of toluene mix, after dissolving fully, add 30 parts of phosphonium flame retardant (German Ke Laien, OP935).Said components is fully stirred, and obtain finely dispersed resin combination after high speed shear is disperseed.This resin combination is impregnated into to NE type glasscloth, and (Co., Ltd. is spun in day east, NEA2116), and, in 155 ℃ of oven dry 2～10min, except desolventizing, obtains the prepreg of resin content in 55% left and right.

Embodiment 13

By 30 parts of methacrylic acid blocking polyphenyl ether resin (SABIC, trade(brand)name: SA9000), 63 parts of biphenyl type novolac epoxy (Japanese chemical drugs, NC3000H), 50 parts of acid anhydride type curing agent styrene-maleic anhydride copolymer (Sartomers, SMA EF40), 0.2 part 2 ethyls-4 Methylimidazole, 10 parts of methyl propenoic acid glycidyl ethers (commercial reagent), 1.3 part dicumyl peroxide DCP, 10 parts of styrene-butadiene copolymer (Sartomer companies, R181) and 120 parts of toluene mix, after dissolving fully, add 30 parts of polyphosphoric acid melamine (Korea S DOOBON, nonfla601), 17 parts of silicon powder (Japanese Adamtech, SO-C2, D50:0.5 μ m) and 0.5 part of silane coupling agent (chemical company of SHIN-ETSU HANTOTAI, KBM-403).Said components is fully stirred, and obtain finely dispersed resin combination after high speed shear is disperseed.This resin combination is impregnated into to NE type glasscloth, and (Co., Ltd. is spun in day east, NEA2116), and, in 155 ℃ of oven dry 2～10min, except desolventizing, obtains the prepreg of resin content in 55% left and right.

Comparative Examples 1

3 parts of Dyhard RU 100 Dicy are dissolved in 40 parts of DMF solvents, then add acetone soln (Dow Chemical, D.E.R.530A80, solid content 80wt%) and 0.1 part of 2 ethyl-4 Methylimidazole of 120 parts of brominated bisphenol A type epoxy resins.Above-mentioned composition is fully stirred at normal temperature, obtain finely dispersed resin combination.This resin combination is impregnated into to NE type glasscloth, and (Co., Ltd. is spun in day east, NEA2116), and, in 155 ℃ of oven dry 2～10min, except desolventizing, obtains the prepreg of resin content in 55% left and right.

Comparative Examples 2

By 80 parts of methacrylic acid blocking polyphenyl ether resin (SABIC, trade(brand)name: SA9000), 3 parts of dicumyl peroxide DCP, 20 parts of triallyl isomelamines (TAIC) and 50 parts of toluene mix, after dissolving fully, add the two tetrabromo phthalimides of 28 parts of brominated flame-retardant ethylenes (U.S. Albemarle Corporation, BT-93w).45 parts of silicon powders (Japanese Adamtech, SO-C2, D50:0.5 μ m) and 0.5 part of silane coupling agent (chemical company of SHIN-ETSU HANTOTAI, KBM-403).Said components is fully stirred, and obtain finely dispersed resin combination after high speed shear is disperseed.This resin combination is impregnated into to NE type glasscloth, and (Co., Ltd. is spun in day east, NEA2116), and, in 155 ℃ of oven dry 2～10min, except desolventizing, obtains the prepreg of resin content in 55% left and right.

Copper-clad laminate to embodiment 1-13 carries out performance test, and result as shown in Table 1 and Table 2.

Table 1

Table 2

The testing method of above characteristic is as follows:

1) glass transition temperature Tg: use dynamic thermomechanometry (DMA) test, according to the DMA test determines of IPC-TM-6502.4.24 defined;

2) mobility: measure according to known degree of mobilization method in industry;

3) volatility: the prepreg prepared is toasted to 10min under 155 ℃, measure the mass loss of prepreg, loss surpasses 2% explanation volatilization;

4) stripping strength (PS): refer at room temperature every millimeter Copper Foil be peeled off the required pulling force of copper-clad plate;

5) specific inductivity (Dk) and dielectric dissipation factor (Df): use Resonant-cavity Method (SPDR) to measure;

6) fire-retardant: as according to the test of UL94 " 50W(20mm) testing vertical flammability: V-0, V-1 and V-2 " testing method, to assert that V-0 is fire-retardant.

Physical Property Analysis:

From the sample physical property characteristic of embodiment 1～13 and Comparative Examples 1～2, in Comparative Examples 1, the pure epoxy resin curing system has excellent cohesiveness, but second-order transition temperature is lower, and specific inductivity and loss factor are higher; And in Comparative Examples 2, the dielectric properties excellence of functionalized polyphenylene ether resins system, cohesiveness is very poor.In embodiment 1～13, above-mentioned two kinds of curing systems are coordinated, the specific inductivity of gained sample and loss factor slightly increase with respect to Comparative Examples 2, but other properties all have better performance, especially increase a certain amount of linking agent and contain epoxide group and the components such as compound of ethylenic unsaturated group after, the over-all propertieies such as the thermotolerance of veneer sheet and stripping strength obviously increase.

As mentioned above, the scheme of the present invention's explanation is in the application of used for printed circuit veneer sheet, with simple functionalized polyphenylene ether resins system, compare, although sacrificed certain specific inductivity and dielectric dissipation factor, but the aspects such as thermotolerance, cohesiveness and processibility have better performance, it has excellent over-all properties, can meet the integration requirement of used for printed circuit veneer sheet.

Simultaneously, from embodiment 3-13 and embodiment 1-2 contrast, can find out, in the polyphenylene oxide resin that contains unsaturated double-bond and epoxy-resin systems, after adding the compound that contains epoxide group and ethylenic unsaturated group, thermotolerance and the stripping strength of veneer sheet improve greatly, and specific inductivity and loss factor all decrease, and over-all properties obviously improves.

By the above, those of ordinary skill in the art can make corresponding change and the distortion of other kinds according to technical scheme of the present invention and technical conceive, but all these changes and distortion all should belong to the protection domain of the claims in the present invention.

Applicant's statement, the present invention illustrates detailed composition of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed composition, does not mean that the present invention must rely on above-mentioned detailed composition and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., within all dropping on protection scope of the present invention and open scope.

Claims

1. a compositions of thermosetting resin, is characterized in that, described compositions of thermosetting resin comprises:

(A) polyphenylene oxide resin that contains unsaturated double-bond;

(B) epoxy resin;

(C) solidifying agent;

(D) initiator.

2. compositions of thermosetting resin as claimed in claim 1, is characterized in that, the number-average molecular weight of the described polyphenylene oxide resin that contains unsaturated double-bond is 1000～7000, preferably 1000～4000;

Preferably, take (A), (B) is 100 mass parts with (C) summation of component, and the consumption of described (A) component is 1～99 mass parts, preferred 20～90 mass parts, further preferred 30～80 mass parts;

Preferably, take (A), (B) is 100 mass parts with (C) summation of component, and (B) and (C) component consumption summation is 1～99 mass parts;

Preferably, described epoxy resin be selected from bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol aldehyde type epoxy resin, brominated epoxy resin, phosphorous epoxy resin, nitrogen-containing epoxy thermoset, biphenyl type epoxy resin, containing naphthalene nucleus epoxy resin, containing fluorene structured epoxy resin or containing the mixture of any one or at least two kinds in dicyclo fluorenes diene structure epoxy resin;

Preferably, described solidifying agent be selected from can with acid anhydride type curing agent, imidazole curing agent, amine curing agent, organo-metallic salt solidifying agent or the resol class solidifying agent of epoxy resin generation curing reaction in the mixture of any one or at least two kinds;

Preferably, the mol ratio of the group that can react with epoxide group in epoxide group and solidifying agent in epoxy resin is 1:0～1.5, and described 0～1.5 does not comprise 0, preferably 1:0.2～1.2;

Preferably, described initiator is selected from peroxide initiator or/and azo-initiator;

Preferably, described peroxide initiator is selected from α, α '-bis-(sec.-propyl between tert-butyl hydroperoxide) benzene, 2,5-dimethyl-2, the mixture of any one in 5-bis-(tert-butyl hydroperoxide)-3-hexin, benzoyl peroxide, single carbonic acid tert-butyl hydroperoxide isopropyl ester or at least two kinds;

Preferably, described azo-initiator is selected from the mixture of any one or at least two kinds in Diisopropyl azodicarboxylate, azo isobutyl cyano group methane amide, 2,2'-Azobis(2,4-dimethylvaleronitrile) or azo-bis-iso-dimethyl etc.;

Preferably, take (A) component as 100 mass parts, the consumption of described initiator is 0.1～20 mass parts, preferred 1～19.5 mass parts, further preferred 2.4～18.5 mass parts;

Preferably, described compositions of thermosetting resin also comprises the compound that (E) contains epoxide group and ethylenic unsaturated group;

Preferably, the glycidyl ester of the described preferred unsaturated carboxylic acid of compound that contains epoxide group and ethylenic unsaturated group and/or containing the glycidyl ether of thiazolinyl, more preferably 2, the mixture of any one in 6-2-glycidyl phenyl allyl ether, glycidyl acrylate, limonene dioxide, glycidyl methacrylate, methylene-succinic acid list glycidyl ester, butylene tricarboxylic acid list glycidyl ester, vinyl glycidyl ether, glycidyl allyl ether or glycidyl oxygen ethyl vinyl ether or at least two kinds;

Preferably, the boiling point of the described compound that contains epoxide group and ethylenic unsaturated group is more than 120 ℃, preferably more than 150 ℃, further preferably more than 170 ℃;

Preferably, take (A) component as 100 mass parts, the described compound amount that contains epoxide group and ethylenic unsaturated group is 0～50 mass parts, preferred 5～46 mass parts, further preferred 9～42 mass parts;

Preferably, described compositions of thermosetting resin also comprises (F) linking agent;

Preferably, described linking agent is selected from the compound with two or at least three ethylenic unsaturation hydrocarbon structures, preferably the mixture of a kind of in trialkenyl isocyanuric acid ester, trialkenyl cyanurate, aryl polyenoid propyl diester, fatty polyenoid propyl diester, carbonic acid polyenoid propyl diester or the olefin resin that contains butadiene structure or at least two kinds;

Preferably, take (A) component as 100 mass parts, the consumption of described linking agent is 0～50 mass parts, and preferably 0～50 mass parts, do not comprise 0 mass parts, further preferred 0.1～50 mass parts;

Preferably, described compositions of thermosetting resin also comprises (G) promotor;

Preferably, described promotor is selected from the mixture of any one or at least two kinds in glyoxal ethyline, 2-phenylimidazole, 2-ethyl-4-methylimidazole, tri-n-butylamine, triphenyl phosphorus, quaternary phosphonium compound, thiocarbamide, thiourea derivative, boron trifluoride complex, sad metal-salt, isocaprylic acid metal-salt, acetyl acetone salt, metallic naphthenate, salicylic acid metal salt or Metallic stearates, wherein, described metal is selected from the mixture of any one or at least two kinds in zinc, copper, iron, tin, cobalt or aluminium;

Preferably, take (B) component as 100 mass parts, the consumption of described promotor is 0.01～1.0 mass parts, preferred 0.10～0.90 mass parts, further preferred 0.18～0.84 mass parts.

3. compositions of thermosetting resin as claimed in claim 1 or 2, is characterized in that, described compositions of thermosetting resin comprises:

(A) polyphenylene oxide resin that contains unsaturated double-bond;

(B) epoxy resin;

(C) solidifying agent;

(D) initiator;

(E) compound that contains epoxide group and ethylenic unsaturated group;

Take (A), (B) is 100 mass parts with (C) summation of component, and the consumption of described (A) component is 1～99 mass parts, and (B) and (C) component consumption summation is 1～99 mass parts; The mol ratio of the group that can react with epoxide group in epoxide group and solidifying agent in epoxy resin is 1:0～1.5, and described 0～1.5 does not comprise 0; (A) component of take calculates as 100 mass parts, and the described compound amount that contains epoxide group and ethylenic unsaturated group is 0～50 mass parts, and the consumption of described initiator is 0.1～20 mass parts;

Preferably, described compositions of thermosetting resin comprises:

(A) polyphenylene oxide resin that contains unsaturated double-bond;

(B) epoxy resin;

(C) solidifying agent;

(D) initiator;

(E) compound that contains epoxide group and ethylenic unsaturated group;

(F) linking agent;

(G) promotor;

Take (A), (B) is 100 mass parts with (C) summation of component, and the consumption of described (A) component is 1～99 mass parts, and (B) and (C) component consumption summation is 1～99 mass parts; The mol ratio of the group that can react with epoxide group in epoxide group and solidifying agent in epoxy resin is 1:0～1.5, and described 0～1.5 does not comprise 0; (A) component of take calculates as 100 mass parts, and the described compound amount that contains epoxide group and ethylenic unsaturated group is 0～50 mass parts, and the consumption of described linking agent is 0～50 mass parts, and the consumption of described initiator is 0.1～20 mass parts; Take (B) component as 100 mass parts, and the consumption of described promotor is 0.01～1.0 mass parts.

4. compositions of thermosetting resin as described as one of claim 1-3, is characterized in that, described compositions of thermosetting resin also comprises (H) fire retardant;

Preferably, described fire retardant is selected from decabromodiphynly oxide, TDE, the two tetrabromo phthalimides of ethylene, melamine phosphate, melamine polyphosphate, two melamine pyrophosphates, three (tribromo phenyl) cyanurate, three (2,6-3,5-dimethylphenyl) phosphorus, 10-(2,5-dihydroxy phenyl)-9, mix-10-phosphorus phenanthrene-10-oxide compound of 10-dihydro-9-oxy, 2,6-bis-(2,6-3,5-dimethylphenyl) phosphorus base benzene, 10-phenyl-9, the 10-dihydro-9-oxy is assorted-mixture of any one or at least two kinds in 10-phosphorus phenanthrene-10-oxide compound or phosphonitrile compounds, preferably three (2,6-3,5-dimethylphenyl) phosphorus, 10-(2,5-dihydroxy phenyl)-9, mix-10-phosphorus phenanthrene-10-oxide compound of 10-dihydro-9-oxy, 2,6-bis-(2,6-3,5-dimethylphenyl) phosphorus base benzene, 10-phenyl-9, mix-10-phosphorus phenanthrene-10-oxide compound of 10-dihydro-9-oxy, hexachlorocyclotriphosphazene, alkoxycyclotriphosphderivative, phenoxy cyclotriphosphazene, six amino ring three phosphonitriles, the mixture of any one in poly-bromo alkoxyl group phosphonitrile or polyaryloxyphosphazene or at least two kinds,

Preferably, take the compositions of thermosetting resin gross weight as 100 mass parts, the consumption of described fire retardant is 0～50 mass parts, preferably 10～30 mass parts;

Preferably, also comprise (I) mineral filler in described compositions of thermosetting resin;

Preferably, described mineral filler is selected from the mixture of any one or at least two kinds of silicon-dioxide, boron nitride, aluminium hydroxide, boehmite, talcum, clay, mica, kaolin, barium sulfate, calcium carbonate, magnesium hydroxide or zinc borate;

Preferably, take the compositions of thermosetting resin gross weight as 100 mass parts, the consumption of described mineral filler is 0～70 mass parts, preferably 5～40 mass parts;

Preferably, described compositions of thermosetting resin also comprises (J) coupling agent;

Preferably, described coupling agent is selected from the mixture of any one or at least two kinds in silane coupling agent, silane pre-polymer or titanate ester compound, preferred silane coupling agent, the further preferably mixture of any one in epoxy silane coupling, amino containing silane coupling agent, anilino silane coupling agent, vinyl silicane coupling agent, isocyanato silanes coupling agent, propenyl silane coupling agent, iso-butylene silane coupling agent, vinylbenzene silane coupling agent or ureido silane coupling agent or at least two kinds;

Preferably, take the compositions of thermosetting resin gross weight as 100 mass parts, the consumption of coupling agent is 0～5 mass parts, does not wherein comprise 0 mass parts, preferred 0.005～4 mass parts, further preferred 0.05～3 mass parts.

5. compositions of thermosetting resin as claimed in claim 4, is characterized in that, described compositions of thermosetting resin comprises:

(A) polyphenylene oxide resin that contains unsaturated double-bond;

(B) epoxy resin;

(C) solidifying agent;

(D) initiator;

(E) compound that contains epoxide group and ethylenic unsaturated group;

(F) linking agent;

(G) promotor;

(H) fire retardant;

(I) mineral filler;

Take (A), (B) is 100 mass parts with (C) summation of component, and the consumption of described (A) component is 1～99 mass parts, and (B) and (C) component consumption summation is 1～99 mass parts; The mol ratio of the group that can react with epoxide group in epoxide group and solidifying agent in epoxy resin is 1:0～1.5, and described 0～1.5 does not comprise 0; (A) component of take calculates as 100 mass parts, and the described compound amount that contains epoxide group and ethylenic unsaturated group is 0～50 mass parts, and the consumption of described linking agent is 0～50 mass parts, and the consumption of described initiator is 0.1～20 mass parts; Take (B) component as 100 mass parts, and the consumption of described promotor is 0.01～1.0 mass parts; Take the compositions of thermosetting resin gross weight as 100 mass parts, and the consumption of described fire retardant is 0～50 mass parts, and the consumption of described mineral filler is 0～70 mass parts.

6. a resin adhesive liquid, is characterized in that, it is compositions of thermosetting resin as described as one of claim 1-5 to be dissolved or is dispersed in solvent obtain.

7. a prepreg, is characterized in that, it is that after base-material is infiltrated to resin adhesive liquid as claimed in claim 6, drying obtains.

8. an insulcrete, is characterized in that, described insulcrete contains at least one prepreg as claimed in claim 7.

9. a veneer sheet, is characterized in that, comprises at least one prepreg as claimed in claim 7, carries out laminated into type preparing.

10. a printed circuit board, is characterized in that, described printed circuit board is by least one veneer sheet preparation as claimed in claim 9.