CN103724999A

CN103724999A - A kind of cyanate ester resin composition and its application

Info

Publication number: CN103724999A
Application number: CN201410004397.1A
Authority: CN
Inventors: 唐军旗; 许永静
Original assignee: Shengyi Technology Co Ltd
Current assignee: Shengyi Technology Co Ltd
Priority date: 2013-05-30
Filing date: 2014-01-02
Publication date: 2014-04-16

Abstract

本发明涉及一种氰酸酯树脂组合物及使用其制作的预浸料、层压板、覆金属箔层压板以及印刷线路板，所述氰酸酯树脂组合物包括氰酸酯树脂（A）、具有式（Ⅰ）结构的环氧树脂（B）和马来酰亚胺化合物（C）。本发明的氰酸酯树脂组合物及使用其制得的预浸料、层压板与覆金属箔层压板具有良好的耐湿性、耐热性、阻燃性和可靠性，低的平面方向热膨胀系数，适合用于制作高密度印刷线路板的基板材料。The present invention relates to a cyanate resin composition and a prepreg, a laminate, a metal foil-clad laminate and a printed circuit board made using the same. The cyanate resin composition comprises a cyanate resin (A), an epoxy resin (B) having a structure of formula (I) and a maleimide compound (C). The cyanate resin composition of the present invention and the prepreg, the laminate and the metal foil-clad laminate made using the same have good moisture resistance, heat resistance, flame retardancy and reliability, and a low thermal expansion coefficient in the plane direction, and are suitable for use in making substrate materials for high-density printed circuit boards.

Description

A kind of cyanate resin composition and uses thereof

Technical field

The present invention relates to a kind of resin combination, relate in particular to a kind of cyanate resin composition and use prepreg, veneer sheet, metal-clad laminate and the printed-wiring board (PWB) of its making.

Background technology

Along with the development of computer, electronics and information communication device miniaturization, high performance, multifunction, printed-wiring board (PWB) is also had higher requirement: miniaturization, slimming, highly integrated and high reliability.This has more excellent wet fastness, thermotolerance and reliability etc. with regard to requiring for making the metal-clad laminate of printed-wiring board (PWB).

Meanwhile, due to the raising of semiconductor packages density, in order to reduce the warpage issues producing in encapsulation process, strong request in recent years reduces the in-plane thermal expansivity of veneer sheet.

Cyanate ester resin has excellent dielectric properties, thermotolerance, mechanical property and processes, and it is making high-end printed-wiring board (PWB) with in metal-clad laminate being a kind of conventional matrix resin.But the humidity resistance of cyanate ester resin after due to its self cure is poor, therefore generally by epoxy resin etc., to after its modification, use again.

But, current conventional bisphenol-type epoxy resin, although processes is excellent, Shortcomings aspect thermotolerance, wet fastness; Although linear phenol aldehyde type epoxy resin improves aspect thermotolerance, the Shortcomings still at aspects such as wet fastness, processibilities.

In addition, for making the resin combination of metal-clad laminate, conventionally need to there is flame retardant resistance, therefore also need with brominated fire retardant, to realize fire-retardant simultaneously.Yet, owing in recent years the concern of environmental problem being improved, need to halide-containing, not realize fire-retardant.The phosphorus compounds that use as fire retardant more at present, but the various intermediates of phosphorus compound and production process all have certain toxicity, phosphorus compound may produce toxic gas (as methylphosphine) and toxic substance (as triphenylphosphine etc.) in the process of burning, and its waste may cause potential hazard to aquatic environment.Therefore, even if need to develop the veneer sheet that does not use halogen compound, phosphorus compound also to have flame retardant resistance and have high reliability, so this just requires resin itself to have more excellent flame retardant resistance.

Although phenol phenyl aralkyl-type epoxy resin, phenol naphthyl aralkyl-type epoxy resin have been improved wet fastness, Shortcomings aspect thermotolerance, flame retardant resistance, in-plane thermal expansivity.

Naphthols xenyl aralkyl-type epoxy resin, naphthols naphthyl aralkyl-type epoxy resin although flame retardant resistance is improved, are brought the rising of resin melting viscosity thereupon, and workability declines.

Summary of the invention

One of object of the present invention is to provide a kind of cyanate resin composition, and this cyanate resin composition has good wet fastness, thermotolerance, flame retardant resistance and reliability, and low in-plane thermal expansivity has good workability simultaneously.

For achieving the above object, the present invention has adopted following technical scheme:

A cyanate resin composition, comprises cyanate ester resin (A), has epoxy resin (B) and the maleimide compound (C) of formula I structure;

Wherein, R ₁be selected from phenyl and naphthyl, and R ₁the mol ratio of middle naphthyl/(naphthyl+phenyl) is that 0.05～0.95, R is aryl, the integer that n is 1～20.

Described n is for example 2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19.

The molar ratio of described naphthyl/(naphthyl+phenyl) is as being 0.08,0.12,0.15,0.21,0.26,0.32,0.38,0.45,0.51,0.56,0.62,0.67,0.71,0.76,0.81,0.88,0.92,0.94.

Preferably, the integer that n is 1～15, the integer that preferably n is 1～10, n is in 1～10 scope time, and the epoxy resin (B) with formula I structure is better to the wetting property of base material.

Preferably, the mol ratio of naphthyl/(naphthyl+phenyl) is 0.1～0.8, preferably 0.2～0.7.

Described R is phenyl, naphthyl or xenyl, and preferably R is naphthyl or xenyl.

Described naphthyl is Alpha-Naphthyl or betanaphthyl.

Preferably, described in, there is the melt viscosity≤1.0Pas at 150 ℃ of the epoxy resin (B) of formula I structure.

The epoxy resin with formula I structure (B) exemplary in the present invention is as follows:

Wherein, R ₁be selected from phenyl and naphthyl, and R ₁the mol ratio of middle naphthyl/(naphthyl+phenyl) is that 0.2～0.7, R is aryl, the integer that n is 1～10.

Melt viscosity≤1.0Pas at 150 ℃ of described epoxy resin (B) with formula I structure.This epoxy resin (B) with formula I structure can significantly improve humidity resistance, flame retardant resistance and the processes of cyanate resin composition, reduces in-plane thermal expansivity.

The inventor finds through research, by cyanate ester resin (A), maleimide compound (C) and have and can produce a kind of resin combination with good wet fastness, thermotolerance, flame retardant resistance, reliability, processes and low in-plane thermal expansivity while using together with the epoxy resin (B) of formula I structure---in molecular structure, the content of naphthalene nucleus, phenyl ring is controlled within the specific limits, thereby reduced the melt viscosity of resin, processes is improved; Because the rigid structure of resin matrix has kept good thermotolerance, and there is good wet fastness, flame retardant resistance and reliability, low in-plane thermal expansivity.Based on above-mentioned discovery, the inventor has completed the present invention.

The not special restriction of cyanate ester resin of the present invention (A), is selected from molecular structure and contains at least two cyanate ester based cyanate ester resins or cyanate prepolymer, preferably from bisphenol A cyanate ester resin, Bisphenol F type cyanate ester resin, tetramethyl bisphenol F cyanate resin, bis-phenol M type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol E-type cyanate resin, bis-phenol P type cyanate ester resin, linear Novolac Cyanate Ester Resins, cresols Novolac Cyanate Ester Resins, naphthol type cyanate ester resin, Naphthol phenolic cyanate ester resin, dicyclopentadiene type ethylene rhodanate resin, phenolphthalein type cyanate ester resin, aralkyl-type cyanate ester resin, aralkyl Novolac Cyanate Ester Resins, bisphenol A cyanate ester prepolymer, Bisphenol F type cyanate prepolymer, tetramethyl-Bisphenol F type cyanate prepolymer, bis-phenol M type cyanate prepolymer, bisphenol S type cyanate prepolymer, bisphenol E-type cyanate prepolymer, bis-phenol P type cyanate prepolymer, linear Novolac Cyanate Eater Resin prepolymer, cresols Novolac Cyanate Eater Resin prepolymer, naphthol type cyanate prepolymer, naphthol novolac type cyanate prepolymer, dicyclopentadiene type ethylene rhodanate prepolymer, phenolphthalein type cyanate prepolymer, the mixture of any one in aralkyl-type cyanate prepolymer or aralkyl Novolac Cyanate Eater Resin prepolymer or at least two kinds, described mixture is the mixture of bisphenol A cyanate ester resin and Bisphenol F type cyanate ester resin for example, the mixture of tetramethyl bisphenol F cyanate resin and bis-phenol M type cyanate ester resin, the mixture of bisphenol S type cyanate ester resin and bisphenol E-type cyanate resin, the mixture of bis-phenol P type cyanate ester resin and linear Novolac Cyanate Ester Resins, the mixture of cresols Novolac Cyanate Ester Resins and Naphthol phenolic cyanate ester resin, the mixture of dicyclopentadiene type ethylene rhodanate resin and phenolphthalein type cyanate ester resin, aralkyl-type cyanate ester resin, the mixture of aralkyl Novolac Cyanate Ester Resins and bisphenol A cyanate ester prepolymer, Bisphenol F type cyanate prepolymer, the mixture of tetramethyl-Bisphenol F type cyanate prepolymer and bis-phenol M type cyanate prepolymer, bisphenol S type cyanate prepolymer, the mixture of bisphenol E-type cyanate prepolymer and bis-phenol P type cyanate prepolymer, linear Novolac Cyanate Eater Resin prepolymer, cresols Novolac Cyanate Eater Resin prepolymer, the mixture of naphthol novolac type cyanate prepolymer and dicyclopentadiene type ethylene rhodanate prepolymer, phenolphthalein type cyanate prepolymer, the mixture of aralkyl-type cyanate prepolymer and aralkyl Novolac Cyanate Eater Resin prepolymer, in order to improve the thermotolerance of cyanate resin composition, flame retardant resistance, this cyanate ester resin (A) is preferred linear Novolac Cyanate Ester Resins further, naphthol type cyanate ester resin, Naphthol phenolic cyanate ester resin, phenolphthalein type cyanate ester resin, aralkyl-type cyanate ester resin, aralkyl Novolac Cyanate Ester Resins, linear Novolac Cyanate Eater Resin prepolymer, naphthol type cyanate prepolymer, naphthol novolac type cyanate prepolymer, phenolphthalein type cyanate prepolymer, the mixture of any one in aralkyl-type cyanate prepolymer or aralkyl Novolac Cyanate Eater Resin prepolymer or at least two kinds, particularly preferably linear Novolac Cyanate Ester Resins, Naphthol phenolic cyanate ester resin, aralkyl Novolac Cyanate Ester Resins, linear Novolac Cyanate Eater Resin prepolymer, the mixture of any one in naphthol novolac type cyanate prepolymer or aralkyl Novolac Cyanate Eater Resin prepolymer or at least two kinds.Cyanate ester resin (A) can be used separately, also can mix as required use.

The consumption of described cyanate ester resin (A) has no particular limits, its preferably account for cyanate ester resin (A) and have formula I structure epoxy resin (B) gross weight 10～90%, for example 12%, 15%, 21%, 26%, 32%, 36%, 45%, 52%, 58%, 63%, 67%, 72%, 77%, 85%, 88%, further preferably 20～80%, particularly preferably 30～70%.

The epoxy resin (B) with formula I structure can be used separately, also can as required at least two kinds of epoxy resin (B) with formula I structure be mixed to use.

The described consumption with the epoxy resin (B) of formula I structure has no particular limits, its preferably account for cyanate ester resin (A) and have formula I structure epoxy resin (B) gross weight 10～90%, for example 12%, 15%, 21%, 26%, 32%, 36%, 45%, 52%, 58%, 63%, 67%, 72%, 77%, 85%, 88%, further preferably 20～80%, particularly preferably 30～70%.

The described synthetic method with the epoxy resin (B) of formula I structure has no particular limits, and those skilled in the art can select according to prior art and the expertise of oneself.Particularly, for example can obtain in the following way the epoxy resin (B) with formula I structure: exist under the condition of basic cpd, the aralkyl-type phenol resin of structure as shown in formula II is reacted in inert organic solvents with epoxy chloropropane, obtain having the epoxy resin (B) of formula I structure.

There is no particular limitation for maleimide compound of the present invention (C), be selected from the compound that contains at least one maleimide base group in molecular structure, the compound that contains at least two maleimide base groups in preferred molecular structure, further preferably from N-phenylmaleimide, N-(2-aminomethyl phenyl) maleimide, N-(4-aminomethyl phenyl) maleimide, N-(2,6-3,5-dimethylphenyl) maleimide, two (4-dimaleoyl imino phenyl) methane, 2,2-bis-(4-(4-maleimide phenoxyl)-phenyl) propane, two (3,5-dimethyl-4-dimaleoyl imino phenyl) methane, two (3-ethyl-5-methyl-4-dimaleoyl imino phenyl) methane, two (3,5-diethyl-4-dimaleoyl imino phenyl) methane, polyphenylene methane bismaleimides (Polyphenylmethanebismaleimide), N-phenylmaleimide prepolymer, N-(2-aminomethyl phenyl) maleimide prepolymer, N-(4-aminomethyl phenyl) maleimide prepolymer, N-(2,6-3,5-dimethylphenyl) maleimide prepolymer, two (4-dimaleoyl imino phenyl) methane prepolymer, 2,2-bis-(4-(4-maleimide phenoxyl)-phenyl) propane prepolymer, two (3,5-dimethyl-4-dimaleoyl imino phenyl) methane prepolymer, two (3-ethyl-5-methyl-4-dimaleoyl imino phenyl) methane prepolymer, two (3,5-diethyl-4-dimaleoyl imino phenyl) methane prepolymer, polyphenylene methane bismaleimides prepolymer, the prepolymer of N-phenylmaleimide and aminated compounds, N-(2-aminomethyl phenyl) prepolymer of maleimide and aminated compounds, N-(4-aminomethyl phenyl) prepolymer of maleimide and aminated compounds, N-(2,6-3,5-dimethylphenyl) prepolymer of maleimide and aminated compounds, the prepolymer of two (4-dimaleoyl imino phenyl) methane and aminated compounds, 2,2-bis-(4-(4-maleimide phenoxyl)-phenyl) prepolymer of propane and aminated compounds, the prepolymer of two (3,5-dimethyl-4-dimaleoyl imino phenyl) methane and aminated compounds, the prepolymer of two (3-ethyl-5-methyl-4-dimaleoyl imino phenyl) methane and aminated compounds, two (3, 5-diethyl-4-dimaleoyl imino phenyl) mixture of any one in methane and the prepolymer of aminated compounds or the prepolymer of polyphenylene methane bismaleimides and aminated compounds or at least two kinds, most preferably two (4-dimaleoyl imino phenyl) methane, 2,2-bis-(4-(4-maleimide phenoxyl)-phenyl) mixture of any one in propane or two (3-ethyl-5-methyl-4-dimaleoyl imino phenyl) methane or at least two kinds.

Maleimide compound (C) can be used separately as required or multiple combination is used.The consumption of described maleimide compound (C) has no particular limits, it preferably accounts for cyanate ester resin (A) and 5～80% of maleimide compound (C) gross weight, for example 7%, 12%, 18%, 25%, 32%, 38%, 44%, 48%, 54%, 60%, 64%, 69%, 75%, 78%, further preferably 10～70%.

This cyanate resin composition also includes mineral filler (D).In cyanate resin composition, add mineral filler (D), can obtain the resin combination of the halogen-free flameproof that flame retardant properties, in-plane thermal expansivity are more excellent.Mineral filler of the present invention (D) has no particular limits, and is selected from silicon-dioxide, metal hydrate, molybdenum oxide, zinc molybdate, titanium oxide, zinc oxide, strontium titanate, barium titanate, barium sulfate, boron nitride, aluminium nitride, silicon carbide, aluminum oxide, zinc borate, zinc, clay, kaolin, talcum, mica, comprehensive silicon micro mist, E glass powder, D glass powder, L glass powder, M glass powder, S glass powder, T glass powder, NE glass powder, fused silica powder, the mixture of any one in short glass fiber or hollow glass or at least two kinds, preferably powdered quartz, fused silica, soft silica, preparing spherical SiO 2, hollow silicon dioxide, aluminium hydroxide, boehmite, magnesium hydroxide, molybdenum oxide, zinc molybdate, titanium oxide, zinc oxide, strontium titanate, barium titanate, barium sulfate, boron nitride, aluminium nitride, silicon carbide, aluminum oxide, zinc borate, zinc, clay, kaolin, talcum, mica, comprehensive silicon micro mist, E glass powder, D glass powder, L glass powder, M glass powder, S glass powder, T glass powder, NE glass powder, fused silica powder, the mixture of any one in short glass fiber or hollow glass or at least two kinds, described mixture is the mixture of powdered quartz and fused silica for example, the mixture of soft silica and preparing spherical SiO 2, the mixture of hollow silicon dioxide and aluminium hydroxide, the mixture of boehmite and magnesium hydroxide, the mixture of molybdenum oxide and zinc molybdate, titanium oxide, the mixture of zinc oxide and strontium titanate, the mixture of barium titanate and barium sulfate, boron nitride, the mixture of aluminium nitride and silicon carbide, aluminum oxide, the mixture of zinc borate and zinc, clay, the mixture of kaolin and talcum, comprehensive silicon micro mist, E glass powder, D glass powder, the mixture of L glass powder and M glass powder, S glass powder, T glass powder, the mixture of NE glass powder and fused silica powder, mica, the mixture of short glass fiber and hollow glass, further preferred molten silicon-dioxide is or/and boehmite.Wherein, fused silica has the characteristic of low thermal coefficient of expansion, the flame retardant resistance of boehmite and excellent heat resistance, therefore preferably it.

There is no particular limitation for the median size (d50) of mineral filler (D), but consider from dispersed angle, median size (d50) is preferably 0.1～10 micron, for example 0.2 micron, 0.8 micron, 1.5 microns, 2.1 microns, 2.6 microns, 3.5 microns, 4.5 microns, 5.2 microns, 5.5 microns, 6 microns, 6.5 microns, 7 microns, 7.5 microns, 8 microns, 8.5 microns, 9 microns, 9.5 microns, more preferably 0.2～5 micron.Can use separately as required or multiple combination is used the mineral filler (D) of dissimilar, variable grain size distribution or different median sizes.

The consumption of mineral filler of the present invention (D) has no particular limits, preferably with cyanate ester resin (A), there is the epoxy resin (B) of formula I structure and the gross weight of maleimide compound (C) is 100 weight part meters, the amount of described mineral filler (D) is 10～300 weight parts, 20 weight parts for example, 40 weight parts, 60 weight parts, 80 weight parts, 100 weight parts, 120 weight parts, 140 weight parts, 160 weight parts, 180 weight parts, 200 weight parts, 220 weight parts, 240 weight parts, 260 weight parts, 280 weight parts, 290 weight parts, be preferably 30～200 weight parts, 50～150 weight parts more preferably.

Mineral filler of the present invention (D) can mating surface treatment agent or wetting agent, dispersion agent use together.There is no particular limitation for effects on surface treatment agent, and it is selected from the conventional surface treatment agent of inorganics surface treatment.It is specially tetraethoxy compounds, organic acid compound, aluminate compound, titanate ester compound, silicone oligomer, macromole treatment agent, silane coupling agent etc.Silane coupling agent is had no particular limits, it is selected from the conventional silane coupling agent of inorganics surface treatment, and it is specially amino silicane coupling agent, epoxy silane coupling, vinyl silicane coupling agent, phenyl silane coupling agent, cationic silane coupling agent, mercaptosilane coupling agents etc.Wetting agent, dispersion agent are had no particular limits, and it is selected from wetting agent, the dispersion agent that is usually used in coating.The surface treatment agent that the present invention can use separately as required or appropriately combined use is dissimilar or wetting agent, dispersion agent.

Cyanate resin composition of the present invention can also comprise organic filler (E).To organic filler (E), there is no particular limitation, be selected from the mixture of any one or at least two kinds in organosilicon, liquid crystalline polymers, thermosetting resin, thermoplastic resin, rubber or core shell rubbers, further preferably organosilicon powder or/and core shell rubbers.Described organic filler (E) can be powder or particle.Wherein, organosilicon powder has good flame-retarding characteristic, and core shell rubbers has good toughening effect, thus preferably it.

The consumption of organic filler of the present invention (E) has no particular limits, preferably take cyanate ester resin (A), there is the epoxy resin (B) of formula I structure and the gross weight of maleimide compound (C) is 100 weight parts, the amount of described organic filler (E) is 1～30 weight part, for example 2 weight parts, 5 weight parts, 7 weight parts, 9 weight parts, 12 weight parts, 15 weight parts, 18 weight parts, 21 weight parts, 24 weight parts, 27 weight parts, 29 weight parts, be preferably 3～25 weight parts, more preferably 5～20 weight parts.

" 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 ".

Cyanate resin composition of the present invention can also be used together in conjunction with the epoxy resin in addition of the epoxy resin (B) with formula I structure, as long as it does not damage the proper property of cyanate resin composition.Can be selected from bisphenol A type epoxy resin, bisphenol f type epoxy resin, linear phenol aldehyde type epoxy resin, cresols phenol aldehyde type epoxy resin, bisphenol-A phenolic type epoxy resin, tetramethyl-bisphenol f type epoxy resin, bis-phenol M type epoxy resin, bisphenol-s epoxy resin, bisphenol E-type epoxy resin, bis-phenol P type epoxy resin, trifunctional phenol-type epoxy resin, four sense phenol-type epoxy resins, naphthalene type epoxy resin, naphthol type epoxy resin, naphthol novolac type epoxy resin, anthracene type epoxy resin, phenoxy group type epoxy resin, norbornene-type epoxy resin, diamantane type epoxy resin, Cong type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, aralkyl-type epoxy resin, aralkyl phenol aldehyde type epoxy resin, the epoxy resin that contains arylene ether structure in molecule, cycloaliphatic epoxy resin, polyvalent alcohol type epoxy resin, containing epoxy silicone, nitrogen-containing epoxy thermoset, phosphorous epoxy resin, glycidyl amine epoxy resin, ethylene oxidic ester epoxy resin etc.These epoxy resin can be used separately as required or multiple combination is used.

Cyanate resin composition of the present invention can also be used together in conjunction with various superpolymer, as long as it does not damage the proper property of cyanate resin composition.Concrete example is as being liquid crystalline polymers, thermosetting resin, thermoplastic resin, different flame-retardant compound or additive etc.They can use separately as required or multiple combination is used.

Cyanate resin composition of the present invention can also be used in conjunction with curing catalyst as required together, to control curing reaction speed.Described curing catalyst has no particular limits, it can be selected from the curing catalyst that is usually used in promoting solidifying cyanate ester resin, epoxy resin, maleimide compound, and it is specially the organic salt, imidazole and its derivants, tertiary amine, organo-peroxide, azo-compound, phenols, inorganic metal salt etc. of the metal of copper, zinc, cobalt, nickel, manganese, tin and so on.

In addition, described cyanate resin composition can also contain various additives, as concrete example, can enumerate oxidation inhibitor, thermo-stabilizer, static inhibitor, UV light absorber, pigment, tinting material, lubricant etc.

As the preparation method of one of resin combination of the present invention, prepared by the epoxy resin with formula I structure (B) described in can coordinating by known method, stirring, mix, cyanate ester resin (A), maleimide compound (C) etc.

Another object of the present invention is to provide a kind of prepreg that uses above-mentioned cyanate resin composition to prepare, veneer sheet, metal-clad laminate and printed-wiring board (PWB), the veneer sheet and the metal-clad laminate that use this prepreg to make have good wet fastness, thermotolerance, flame retardant resistance and reliability, low in-plane thermal expansivity, there is good workability simultaneously, be suitable for preparing the baseplate material of high density printed circuit board.

The invention provides a kind of prepreg that uses above-mentioned cyanate resin composition to prepare, described prepreg comprises base material and is dried the cyanate resin composition as above on postadhesion base material by impregnation.Base material of the present invention has no particular limits, and it can be selected from known to making the base material of various printed wiring panel materials.Be specially inorganic fibre (glass fibre such as E glass, D glass, L glass, M glass, S glass, T glass, NE glass, quartz), organic fibre (such as polyimide, polymeric amide, polyester, polyphenylene oxide, liquid crystalline polymers etc.).The form of base material is yarn fabric, non-woven fabrics, rove, staple fibre, fibrous paper etc. normally.In above-mentioned base material, base material preferred glass fibers cloth of the present invention.

The preparation method of prepreg of the present invention does not have concrete restriction, as long as it is by cyanate resin composition of the present invention is combined to prepare the method for prepreg with base material.

Can be as required with an organic solvent in the above-mentioned cyanate resin composition of preparing prepreg, to organic solvent, there is no particular limitation, so long as with the epoxy resin (B) with formula I structure, the compatible solvent of mixture of cyanate ester resin (A) and maleimide compound (C), described solvent, as concrete example, can enumerate: methyl alcohol, ethanol, the alcohols such as butanols, ethyl cellosolve, ethylene glycol butyl ether, ethylene glycol-methyl ether, diethylene glycol ether, the ethers such as Diethylene Glycol butyl ether, acetone, butanone, ethyl methyl ketone, hexone, the ketones such as pimelinketone, toluene, dimethylbenzene, sym-trimethylbenzene etc. are aromatic hydrocarbon based, ethoxyethyl group acetic ester, the ester classes such as vinyl acetic monomer, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, the nitrogenous kind solvent such as METHYLPYRROLIDONE.Above-mentioned solvent can be used separately, also can be as required by two kinds or two or more mixing use.

The present invention also provides a kind of veneer sheet and metal-clad laminate that uses above-mentioned prepreg to prepare.Described veneer sheet comprises at least one prepreg as above, and the prepreg lamination after superimposed is solidified and obtains veneer sheet.Described metal-clad laminate comprises at least one prepreg as above, and the one or both sides of the prepreg after superimposed are covered with tinsel, and lamination solidifies and obtains metal-clad laminate.Use veneer sheet and metal-clad laminate prepared by this prepreg to there is good wet fastness, thermotolerance, flame retardant resistance and reliability, low in-plane thermal expansivity, there is good workability simultaneously, be therefore suitable for preparing the baseplate material of high density printed circuit board.

The preparation method of veneer sheet of the present invention can be prepared by known method, for example: an above-mentioned prepreg is placed or by two or two above prepregs stacking, as required, tinsel is placed in a side or both sides at prepreg or stacking prepreg, and curing veneer sheet or the metal-clad laminate of obtaining of lamination.Described tinsel has no particular limits, and it is optional from the tinsel for printed-wiring board (PWB) material.Veneer sheet and multiple-plate general lamination that lamination can select printed-wiring board (PWB) to use.

The present invention also provides a kind of printed-wiring board (PWB), and described printed-wiring board (PWB) comprises at least one prepreg as above.The preparation method of printed-wiring board (PWB) of the present invention does not have concrete restriction, can prepare by known method.

Beneficial effect of the present invention: cyanate resin composition provided by the invention, there is good wet fastness, thermotolerance, flame retardant resistance and reliability, low in-plane thermal expansivity has good workability simultaneously.The prepreg, veneer sheet and the metal-clad laminate that use this cyanate resin composition to make, also there is good wet fastness, thermotolerance, flame retardant resistance and reliability, low in-plane thermal expansivity, there is good workability simultaneously, be suitable for making the baseplate material of high density printed 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:

The metal-clad laminate of making for cyanate resin composition of the present invention, detect its thermotolerance (Tg), resistance to immersed solder, humidity resistance, flame retardant resistance and in-plane thermal expansivity (CTE), its test result further gives to illustrate in detail and describe as following embodiment.

Synthesis example 1: naphthyl aralkyl-type phenol resin synthetic

In flask, add 2-Naphthol 46g, phenol 271g, dichloromethyl naphthalene 215g and chlorobenzene 300g, rising temperature for dissolving slowly while stirring under nitrogen protection is reacted 2 hours at approximately 80 ℃.Then, limit distills chlorobenzene limit and is warmed up to 180 ℃, reacts 1 hour at 180 ℃.After reaction, by underpressure distillation, solvent and unreacted monomer are removed, obtained the naphthyl aralkyl-type phenol resin of brown.From the unreacted monomer reclaiming, analyzed, the mol ratio that enters 2-Naphthol/(2-Naphthol+phenol) in resin is 0.23.

Synthesis example 2: naphthyl aralkyl-type phenol resin synthetic

In flask, add 2-Naphthol 96g, phenol 251g, dichloromethyl naphthalene 150g and chlorobenzene 450g, rising temperature for dissolving slowly while stirring under nitrogen protection is reacted 2 hours at approximately 80 ℃.Then, limit distills chlorobenzene limit and is warmed up to 180 ℃, reacts 1 hour at 180 ℃.After reaction, by underpressure distillation, solvent and unreacted monomer are removed, obtained the naphthyl aralkyl-type phenol resin of brown.From the unreacted monomer reclaiming, analyzed, the mol ratio that enters 2-Naphthol/(2-Naphthol+phenol) in resin is 0.50.

Synthesis example 3: naphthyl aralkyl-type phenol resin synthetic

In flask, add 2-Naphthol 224g, phenol 272g, dichloromethyl naphthalene 100g and chlorobenzene 300g, rising temperature for dissolving slowly while stirring under nitrogen protection is reacted 2 hours at approximately 80 ℃.Then, limit distills chlorobenzene limit and is warmed up to 180 ℃, reacts 1 hour at 180 ℃.After reaction, by underpressure distillation, solvent and unreacted monomer are removed, obtained the naphthyl aralkyl-type phenol resin of brown.From the unreacted monomer reclaiming, analyzed, the mol ratio that enters 2-Naphthol/(2-Naphthol+phenol) in resin is 0.70.

Synthesis example 4: naphthyl aralkyl-type novolac epoxy synthetic

The naphthyl aralkyl-type phenol resin 100g obtaining in synthesis example 1 is dissolved in epoxy chloropropane 307g and diethylene glycol dimethyl ether 48g, decompression, at 60 ℃ with 4 hours dropping 48% aqueous sodium hydroxide solution 40g.During this by the water of generation by removing outside system with the azeotropic of epoxy chloropropane, the epoxy chloropropane distilling out turns back in system.After dropping finishes, then continue reaction 1 hour.Then by underpressure distillation, epoxy chloropropane and diethylene glycol dimethyl ether are removed, added 295g methyl iso-butyl ketone (MIBK) stirring and dissolving even, by washing, the salt of generation is removed.Then, add 48% aqueous sodium hydroxide solution 9g, at 80 ℃, react 2 hours.After reaction, wash with water until washing lotion is neutral, by underpressure distillation, methyl iso-butyl ketone (MIBK) is removed afterwards, obtained naphthyl aralkyl-type novolac epoxy, the melt viscosity at 150 ℃ is 0.4Pas.

Synthesis example 5: naphthyl aralkyl-type novolac epoxy synthetic

The naphthyl aralkyl-type phenol resin 100g obtaining in synthesis example 2 is dissolved in epoxy chloropropane 298g and diethylene glycol dimethyl ether 45g, decompression, at 60 ℃ with 4 hours dropping 48% aqueous sodium hydroxide solution 38g.During this by the water of generation by removing outside system with the azeotropic of epoxy chloropropane, the epoxy chloropropane distilling out turns back in system.After dropping finishes, then continue reaction 1 hour.Then by underpressure distillation, epoxy chloropropane and diethylene glycol dimethyl ether are removed, added 295g methyl iso-butyl ketone (MIBK) stirring and dissolving even, by washing, the salt of generation is removed.Then, add 48% aqueous sodium hydroxide solution 9g, at 80 ℃, react 2 hours.After reaction, wash with water until washing lotion is neutral, by underpressure distillation, methyl iso-butyl ketone (MIBK) is removed afterwards, obtained naphthyl aralkyl-type novolac epoxy, the melt viscosity at 150 ℃ is 0.5Pas.

Synthesis example 6: naphthyl aralkyl-type novolac epoxy synthetic

The naphthyl aralkyl-type phenol resin 100g obtaining in synthesis example 3 is dissolved in epoxy chloropropane 300g and diethylene glycol dimethyl ether 45g, decompression, at 60 ℃ with 4 hours dropping 48% aqueous sodium hydroxide solution 38.5g.During this by the water of generation by removing outside system with the azeotropic of epoxy chloropropane, the epoxy chloropropane distilling out turns back in system.After dropping finishes, then continue reaction 1 hour.Then by underpressure distillation, epoxy chloropropane and diethylene glycol dimethyl ether are removed, added 295g methyl iso-butyl ketone (MIBK) stirring and dissolving even, by washing, the salt of generation is removed.Then, add 48% aqueous sodium hydroxide solution 9g, at 80 ℃, react 2 hours.After reaction, wash with water until washing lotion is neutral, by underpressure distillation, methyl iso-butyl ketone (MIBK) is removed afterwards, obtained naphthyl aralkyl-type novolac epoxy, the melt viscosity at 150 ℃ is 0.6Pas.

Synthesis example 7: xenyl aralkyl-type novolac epoxy synthetic

By xenyl aralkyl-type phenol resin (by bright and change into Co., Ltd. and provide, the mol ratio of naphthyl alcohol/(naphthyl alcohol+phenol) is 0.70) 100g is dissolved in epoxy chloropropane 257g and diethylene glycol dimethyl ether 48g, at decompression, 60 ℃ with 4 hours dropping 48% aqueous sodium hydroxide solution 32.5g.During this by the water of generation by removing outside system with the azeotropic of epoxy chloropropane, the epoxy chloropropane distilling out turns back in system.After dropping finishes, then continue reaction 1 hour.Then by underpressure distillation, epoxy chloropropane and diethylene glycol dimethyl ether are removed, added 295g methyl iso-butyl ketone (MIBK) stirring and dissolving even, by washing, the salt of generation is removed.Then, add 48% aqueous sodium hydroxide solution 9g, at 80 ℃, react 2 hours.After reaction, wash with water until washing lotion is neutral, by underpressure distillation, methyl iso-butyl ketone (MIBK) is removed afterwards, obtained xenyl aralkyl-type novolac epoxy, the melt viscosity at 150 ℃ is 0.6Pas.

Embodiment 1

By the linear Novolac Cyanate Ester Resins (PT-30 of 25 weight parts, by LONZA, provided), 5 weight parts two (3-ethyl-5-methyl-4-dimaleoyl imino phenyl) methane (BMI-70, by KI Chemical Industry Co., Ltd. provide), the naphthyl aralkyl-type novolac epoxy obtaining in 70 weight part synthesis examples 6, 0.02 weight part zinc octoate is dissolved in DMF, butanone also mixes, add afterwards 150 weight part boehmite (APYRAL AOH30, by Nabaltec, provided), 1.5 weight part epoxy silane coupling (Z-6040, by DOW CORNING, provided), 1 weight part dispersion agent (BYK-W903, by BYK, provided), and be adjusted to appropriate viscosity with butanone, be uniformly mixed, make glue.The E glasscloth that is 0.1mm with thickness floods above glue, after then solvent is removed in oven dry, makes prepreg.Respectively the above-mentioned prepreg of 1,4,8 is superimposed, and at its electrolytic copper foil that both sides cover 18um thickness separately, carries out solidifying for 2 hours in press, solidifying pressure is 45Kg/cm ², solidification value is 220 ℃, acquisition thickness is the copper-clad laminate of 0.1,0.4,0.8 millimeter.

Embodiment 2

By 35 weight part naphthyl alcohol aralkyl-type cyanate ester resins (the naphthyl alcohol aralkyl resin SN485 being provided by Nippon Steel reacts and makes with mauguinite), 15 weight parts two (3-ethyl-5-methyl-4-dimaleoyl imino phenyl) methane (BMI-70, by KI Chemical Industry Co., Ltd. provide), the naphthyl aralkyl-type novolac epoxy obtaining in 50 weight part synthesis examples 6, 0.02 weight part zinc octoate is dissolved in DMF, butanone also mixes, add afterwards 110 weight part spherical fused silica (SC2050, by Admatechs, provided), organosilicon powder (the KMP-605 of 5 weight part nucleocapsid structures, by SHIN-ETSU HANTOTAI's chemistry, provided), 1 weight part epoxy silane coupling (Z-6040, by DOW CORNING, provided), and be adjusted to appropriate viscosity with butanone, be uniformly mixed, make glue.According to the manufacture craft identical with embodiment 1, acquisition thickness is the copper-clad laminate of 0.1,0.4,0.8 millimeter.

Embodiment 3

By the linear Novolac Cyanate Ester Resins (PT-30 of 5 weight parts, by LONZA, provided), 28 weight part naphthyl alcohol aralkyl-type cyanate ester resins (the naphthyl alcohol aralkyl resin SN485 being provided by Nippon Steel reacts and makes with mauguinite), 22 weight parts two (3-ethyl-5-methyl-4-dimaleoyl imino phenyl) methane (BMI-70, by KI Chemical Industry Co., Ltd. provide), the naphthyl aralkyl-type novolac epoxy obtaining in 45 weight part synthesis examples 5, 0.02 weight part zinc octoate is dissolved in DMF, butanone also mixes, add afterwards 50 weight part spherical fused silica (SC2050, by Admatechs, provided), 70 weight part boehmite (APYRAL AOH30, by Nabaltec, provided), 10 weight part organosilicon powder (KMP-590, by SHIN-ETSU HANTOTAI's chemistry, provided), organosilicon powder (the KMP-605 of 5 weight part nucleocapsid structures, by SHIN-ETSU HANTOTAI's chemistry, provided), 1 weight part epoxy silane coupling (Z-6040, by DOW CORNING, provided), 1 weight part dispersion agent (BYK-W903, by BYK, provided), and be adjusted to appropriate viscosity with butanone, be uniformly mixed, make glue.According to the manufacture craft identical with embodiment 1, acquisition thickness is the copper-clad laminate of 0.1,0.4,0.8 millimeter.

Embodiment 4

By 60 weight part naphthyl alcohol aralkyl-type cyanate ester resins (the naphthyl alcohol aralkyl resin SN485 being provided by Nippon Steel reacts and makes with mauguinite), 15 weight parts two (3-ethyl-5-methyl-4-dimaleoyl imino phenyl) methane (BMI-70, by KI Chemical Industry Co., Ltd. provide), the naphthyl aralkyl-type novolac epoxy obtaining in 15 weight part synthesis examples 6, 10 weight part naphthylidene ether type naphthols epoxy resin (EXA-7311, by Dainippon Ink Chemicals, provided), 0.02 weight part zinc octoate is dissolved in DMF, butanone also mixes, add afterwards 60 weight part boehmite (APYRAL AOH30, by Nabaltec, provided), 20 weight part organosilicon powder (KMP-590, by SHIN-ETSU HANTOTAI's chemistry, provided), 1 weight part epoxy silane coupling (Z-6040, by DOW CORNING, provided), 1 weight part dispersion agent (BYK-W903, by BYK, provided), and be adjusted to appropriate viscosity with butanone, be uniformly mixed, make glue.According to the manufacture craft identical with embodiment 1, acquisition thickness is the copper-clad laminate of 0.1,0.4,0.8 millimeter.

Embodiment 5

By the linear Novolac Cyanate Ester Resins (PT-30 of 40 weight parts, by LONZA, provided), 10 weight part Naphthol phenolic cyanate ester resins (the method reaction providing in Chinese patent CN102911502A synthesis example 2 makes), 5 weight parts two (3-ethyl-5-methyl-4-dimaleoyl imino phenyl) methane (BMI-70, by KI Chemical Industry Co., Ltd. provide), the naphthyl aralkyl-type novolac epoxy obtaining in 25 weight part synthesis examples 4, 20 weight part phenol xenyl aralkyl-type epoxy resin (NC-3000-FH, by Nippon Kayaku K. K, provided), 0.02 weight part zinc octoate is dissolved in DMF, butanone also mixes, add afterwards 100 weight part boehmite (APYRAL AOH30, by Nabaltec, provided), 50 weight part spherical fused silica (SC2050, by Admatechs, provided), 1 weight part epoxy silane coupling (Z-6040, by DOW CORNING, provided), 1 weight part dispersion agent (BYK-W903, by BYK, provided), and be adjusted to appropriate viscosity with butanone, be uniformly mixed, make glue.According to the manufacture craft identical with embodiment 1, acquisition thickness is the copper-clad laminate of 0.1,0.4,0.8 millimeter.

Embodiment 6

By the linear Novolac Cyanate Ester Resins (PT-30 of 25 weight parts, by LONZA, provided), 5 weight parts two (3-ethyl-5-methyl-4-dimaleoyl imino phenyl) methane (BMI-70, by KI Chemical Industry Co., Ltd. provide), the naphthyl aralkyl-type novolac epoxy obtaining in 40 weight part synthesis examples 6, the naphthyl aralkyl-type novolac epoxy obtaining in 30 weight part synthesis examples 4, 0.02 weight part zinc octoate is dissolved in DMF, butanone also mixes, add afterwards 220 weight part spherical fused silica (SC2050, by Admatechs, provided), 2.0 weight part epoxy silane coupling (Z-6040, by DOW CORNING, provided), 1 weight part dispersion agent (BYK-W903, by BYK, provided), and be adjusted to appropriate viscosity with butanone, be uniformly mixed, make glue.According to the manufacture craft identical with embodiment 1, acquisition thickness is the copper-clad laminate of 0.1,0.4,0.8 millimeter.

Embodiment 7

By 60 weight part naphthyl alcohol aralkyl-type cyanate ester resins (the naphthyl alcohol aralkyl resin SN485 being provided by Nippon Steel reacts and makes with mauguinite), 15 weight parts two (3-ethyl-5-methyl-4-dimaleoyl imino phenyl) methane (BMI-70, by KI Chemical Industry Co., Ltd. provide), the naphthyl aralkyl-type novolac epoxy obtaining in 25 weight part synthesis examples 6, 0.02 weight part zinc octoate is dissolved in DMF, butanone also mixes, add afterwards 15 weight part spherical fused silica (SC2050, by Admatechs, provided), 30 weight part organosilicon powder (KMP-590, by SHIN-ETSU HANTOTAI's chemistry, provided), 1 weight part epoxy silane coupling (Z-6040, by DOW CORNING, provided), 1 weight part dispersion agent (BYK-W903, by BYK, provided), and be adjusted to appropriate viscosity with butanone, be uniformly mixed, make glue.According to the manufacture craft identical with embodiment 1, acquisition thickness is the copper-clad laminate of 0.1,0.4,0.8 millimeter.

Embodiment 8

By 50 weight part naphthyl alcohol aralkyl-type cyanate ester resins (the naphthyl alcohol aralkyl resin SN485 being provided by Nippon Steel reacts and makes with mauguinite), 10 weight parts two (3-ethyl-5-methyl-4-dimaleoyl imino phenyl) methane (BMI-70, by KI Chemical Industry Co., Ltd. provide), the xenyl aralkyl-type novolac epoxy obtaining in 40 weight part synthesis examples 7, 0.02 weight part zinc octoate is dissolved in DMF, butanone also mixes, add afterwards 90 weight part spherical fused silica (SC2050, by Admatechs, provided), 10 weight part organosilicon powder (KMP-590, by SHIN-ETSU HANTOTAI's chemistry, provided), organosilicon powder (the KMP-600 of 15 weight part nucleocapsid structures, by SHIN-ETSU HANTOTAI's chemistry, provided), 1 weight part epoxy silane coupling (Z-6040, by DOW CORNING, provided), 1 weight part dispersion agent (BYK-W903, by BYK, provided), and be adjusted to appropriate viscosity with butanone, be uniformly mixed, make glue.According to the manufacture craft identical with embodiment 1, acquisition thickness is the copper-clad laminate of 0.1,0.4,0.8 millimeter.

Comparative example 1

With 70 weight part bisphenol A type epoxy resins (

1055, by Dainippon Ink Chemicals, provided) replace the 70 weight part naphthyl aralkyl-type novolac epoxys that use in embodiment 1, other obtain thickness according to the method identical with embodiment 1 is the copper-clad laminate of 0.1,0.4,0.8 millimeter.

Comparative example 2

With 50 weight part phenol phenyl aralkyl-type epoxy resin (NC-2000, by Nippon Kayaku K. K, provided) replace the 50 weight part naphthyl aralkyl-type novolac epoxys that use in embodiment 2, other obtain thickness according to the method identical with embodiment 2 is the copper-clad laminate of 0.1,0.4,0.8 millimeter.

Comparative example 3

With 25 weight part bisphenol A type epoxy resins (

1055, by Dainippon Ink Chemicals, provided) replace the 25 weight part naphthyl aralkyl-type novolac epoxys that use in embodiment 7, other obtain thickness according to the method identical with embodiment 7 is the copper-clad laminate of 0.1,0.4,0.8 millimeter.

Comparative example 4

By 35 weight part phenyl aralkyl-type phenol resin (MEH-7800H, by bright and change into Co., Ltd. and provide), 15 weight parts two (3-ethyl-5-methyl-4-dimaleoyl imino phenyl) methane (BMI-70, by KI Chemical Industry Co., Ltd. provide), the naphthyl aralkyl-type novolac epoxy obtaining in 50 weight part synthesis examples 6, 0.075 weight part diethyl tetramethyl-imidazoles is dissolved in butanone and mixes, add afterwards 110 weight part spherical fused silica (SC2050, by Admatechs, provided), organosilicon powder (the KMP-605 of 5 weight part nucleocapsid structures, by SHIN-ETSU HANTOTAI's chemistry, provided), 1 weight part epoxy silane coupling (Z-6040, by DOW CORNING, provided), and be adjusted to appropriate viscosity with butanone, be uniformly mixed, make glue.According to the manufacture craft identical with embodiment 1, acquisition thickness is the copper-clad laminate of 0.1,0.4,0.8 millimeter.

The physical property measurement data of the copper-clad laminate that above-described embodiment 1-8 and comparative example 1-4 make as shown in Table 1 and Table 2.

The physical property measurement data of the copper-clad laminate that table 1 embodiment 1-6 makes

?

Embodiment 1

Embodiment 2

Embodiment 3

Embodiment 4

Embodiment 5

Embodiment 6

Tg,℃

255

250

260

270

280

250

Resistance to immersed solder, S

＞120

Humidity resistance

0/3

Flame retardant resistance

V-0

CTE,ppm/℃

10.5

9.5

10

12

10.5

8.2

The physical property measurement data of the copper-clad laminate that table 2 embodiment 7-8, comparative example 1-4 make

?

Embodiment 7

Embodiment 8

Comparative example 1

Comparative example 2

Comparative example 3

Comparative example 4

Tg,℃

270

250

215

220

235

190

Resistance to immersed solder, S

＞120

≥120

Humidity resistance

0/3

3/3

0/3

3/3

0/3

Flame retardant resistance

V-1

V-0

Burning

V-1

Burning

V-1

CTE,ppm/℃

12.8

9.3

12.6

11.1

14.6

12.5

In table 1 and table 2, the testing method of physical data is as follows:

Tg: testing tool and condition: DMA, 5 ℃/min of temperature rise rate, test sample specification: Copper Foil is removed in etching, 0.8 millimeter.

Resistance to immersed solder: by the tin stove of 288 ℃ of the sample immersions of 50 * 50 millimeters, observation layering foaming situation also records the corresponding time.Test sample specification: etching Copper Foil not, 0.4 millimeter.

Flame retardant resistance: pass judgment on according to UL94 testing vertical flammability standard.Test sample specification: Copper Foil is removed in etching, 0.4 millimeter.

Humidity resistance: the sample of 50 * 50 millimeters is dried to 2 hours at 105 ℃.Then, sample is processed 3 hours under 121 ℃ and two normal atmosphere with steam pressure pot machine, then by sample wicking 60 seconds in the tin stove of 260 ℃, whether layering (layering sample number/test sample number) of observing samples.Test sample specification: Copper Foil is removed in etching, 0.4 millimeter.

CTE: measurement direction is along glass-fiber-fabric warp thread direction; Testing tool and condition: TMA, is warmed up to 300 ℃ with the temperature rise rate of 10 ℃/min from 25 ℃ of room temperatures, the in-plane thermal expansivity measuring from 50 ℃ to 130 ℃.Test sample specification: Copper Foil is removed in etching, 0.1 millimeter.

Physical Property Analysis:

Described embodiment compares with comparative example, and the thermotolerance of embodiments of the invention 1～8, humidity resistance and flame retardant resistance are all better than using comparative example 1 and the comparative example 3 of bisphenol A type epoxy resin; The thermotolerance of embodiments of the invention 1～6, embodiment 8 and flame retardant resistance are all better than comparative example 4 and use the comparative example 2 of phenol phenyl aralkyl-type epoxy resin; The thermotolerance of embodiments of the invention 1,2,7, flame retardant resistance and in-plane thermal expansivity are all better than the comparative example 1 that uses bisphenol A type epoxy resin to replace naphthyl aralkyl-type novolac epoxy, the comparative example 2 that uses phenol phenyl aralkyl-type epoxy resin replacement naphthyl aralkyl-type novolac epoxy, use bisphenol A type epoxy resin to replace the comparative example 3 of naphthyl aralkyl-type novolac epoxy.

Especially, comparative example 4 is owing to having used phenolic resin curing naphthyl aralkyl-type novolac epoxy, although its filling kind and content, manufacture craft are all identical with embodiment 2, the thermotolerance of embodiment 2, flame retardant resistance and in-plane thermal expansivity are all better than comparative example 4.

In sum, cyanate resin composition of the present invention and use its prepreg making, veneer sheet and metal-clad laminate to have good wet fastness, thermotolerance, flame retardant resistance and reliability, low in-plane thermal expansivity is suitable for making the baseplate material of high density printed circuit board.

Above embodiment, not the content of composition of the present invention is imposed any restrictions, any trickle modification, equivalent variations and modification that the weight part of every foundation technical spirit of the present invention or composition or content are done above embodiment, all still belong in the scope of technical solution of 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.Person of ordinary skill in the field should understand, any improvement in the present invention, to the selection of the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.

Claims

1. A cyanate resin composition, characterized in that, the cyanate resin composition comprises cyanate resin (A), epoxy resin (B) with the structure of formula (I) and maleic acid Amine compound (C);

Wherein, R ₁ is selected from phenyl and naphthyl, and the molar ratio of naphthyl/(naphthyl+phenyl) in R ₁ is 0.05-0.95, R is aryl, and n is an integer of 1-20.

2. The cyanate resin composition according to claim 1, wherein n is an integer of 1 to 15 in the epoxy resin (B) having the structure of formula (I), preferably n is 1 to 10 an integer of

Preferably, the molar ratio of naphthyl/(naphthyl+phenyl) is 0.1-0.8, preferably 0.2-0.7;

Preferably, the R is phenyl, naphthyl or biphenyl, preferably naphthyl or biphenyl;

Preferably, the melt viscosity of the epoxy resin (B) having the structure of formula (I) at 150°C is ≤1.0 Pa·s.

3. The cyanate resin composition as claimed in claim 1 or 2, wherein the cyanate resin (A) is selected from the group consisting of cyanate resins containing at least two cyanate groups in the molecular structure or Cyanate prepolymers, preferably selected from bisphenol A type cyanate resins, bisphenol F type cyanate resins, tetramethylbisphenol F type cyanate resins, bisphenol M type cyanate resins, bisphenol S type cyanate resin, bisphenol E type cyanate resin, bisphenol P type cyanate resin, novolak type cyanate resin, cresol novolac type cyanate resin, naphthol type cyanate resin, Naphthol novolac cyanate resin, dicyclopentadiene cyanate resin, phenolphthalein cyanate resin, aralkyl cyanate resin, aralkyl phenolic cyanate resin, bisphenol A cyanate resin Ester prepolymer, bisphenol F cyanate prepolymer, tetramethyl bisphenol F cyanate prepolymer, bisphenol M cyanate prepolymer, bisphenol S cyanate prepolymer polymer, bisphenol E cyanate prepolymer, bisphenol P cyanate prepolymer, novolac cyanate prepolymer, cresol novolac cyanate prepolymer, naphthol cyanate prepolymer Ester prepolymer, naphthol novolac cyanate prepolymer, dicyclopentadiene cyanate prepolymer, phenolphthalein cyanate prepolymer, aralkyl cyanate prepolymer or aromatic Any one or a mixture of at least two of the alkylphenol novolac cyanate prepolymers, further preferably novolac cyanate resins, naphthol cyanate resins, naphthol novolac cyanate resins, phenolphthalein Type cyanate ester resin, aralkyl type cyanate ester resin, aralkyl novolak type cyanate ester resin, novolak type cyanate ester prepolymer, naphthol type cyanate ester prepolymer, naphthol novolac type cyanate resin Any one or a mixture of at least two of ester prepolymers, phenolphthalein cyanate prepolymers, aralkyl cyanate prepolymers or aralkyl phenolic cyanate prepolymers;

Preferably, the cyanate resin (A) accounts for 10-90% of the total weight of the cyanate resin (A) and the epoxy resin (B) having the structure of formula (I), more preferably 20-80%, especially Preferably 30-70%;

Preferably, the epoxy resin (B) having the structure of formula (I) accounts for 10-90% of the total weight of the cyanate resin (A) and the epoxy resin (B) having the structure of formula (I), more preferably 20-80%, particularly preferably 30-70%.

4. The cyanate ester resin composition according to any one of claims 1-3, wherein the maleimide compound (C) is selected from compounds containing at least one maleimide group in its molecular structure Group compounds, preferably compounds containing at least two maleimide groups in the molecular structure, further preferably selected from N-phenylmaleimide, N-(2-methylphenyl)maleimide , N-(4-methylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, bis(4-maleimidophenyl)methane , 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, bis(3,5-dimethyl-4-maleimidophenyl)methane , bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, poly Phenylmethane bismaleimide, N-phenylmaleimide prepolymer, N-(2-methylphenyl)maleimide prepolymer, N-(4-methylbenzene base) maleimide prepolymer, N-(2,6-dimethylphenyl)maleimide prepolymer, bis(4-maleimidophenyl)methane prepolymer , 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane prepolymer, bis(3,5-dimethyl-4-maleimidobenzene base) methane prepolymer, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane prepolymer, bis(3,5-diethyl-4-maleimidoyl Iminophenyl)methane prepolymer, polyphenylmethane bismaleimide prepolymer, N-phenylmaleimide and amine compound prepolymer, N-(2-methyl Prepolymer of phenyl)maleimide and amine compound, prepolymer of N-(4-methylphenyl)maleimide and amine compound, N-(2,6-dimethyl phenyl)maleimide and amine compound prepolymer, bis(4-maleimidophenyl)methane and amine compound prepolymer, 2,2-bis(4-( Prepolymers of 4-maleimidophenoxy)-phenyl)propane and amines, bis(3,5-dimethyl-4-maleimidophenyl)methane and amines Prepolymers of compounds, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane and prepolymers of amine compounds, bis(3,5-diethyl- 4-maleimidophenyl) methane and amine compound prepolymer or polyphenylmethane bismaleimide and amine compound prepolymer any one or a mixture of at least two , most preferably bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane or bis(3-ethane Any one or a mixture of at least two of the 5-methyl-4-maleimidophenyl)methanes;

Preferably, the amount of the maleimide compound (C) accounts for 5-80%, preferably 10-70%, of the total weight of the cyanate resin (A) and the maleimide compound (C).

5. The cyanate resin composition according to any one of claims 1-4, characterized in that, the cyanate resin composition also includes an inorganic filler (D);

Preferably, the inorganic filler (D) is selected from silica, metal hydrate, molybdenum oxide, zinc molybdate, titanium oxide, zinc oxide, strontium titanate, barium titanate, barium sulfate, boron nitride, nitride Aluminum, silicon carbide, aluminum oxide, zinc borate, zinc stannate, clay, kaolin, talc, mica, composite silica powder, E glass powder, D glass powder, L glass powder, M glass powder, S glass powder, T glass powder , NE glass powder, quartz glass powder, short glass fiber or hollow glass, or a mixture of at least two, preferably crystalline silica, fused silica, amorphous silica, spherical silica, Hollow silica, aluminum hydroxide, boehmite, magnesium hydroxide, molybdenum oxide, zinc molybdate, titanium oxide, zinc oxide, strontium titanate, barium titanate, barium sulfate, boron nitride, aluminum nitride, carbide Silicon, alumina, zinc borate, zinc stannate, clay, kaolin, talc, mica, composite silica powder, E glass powder, D glass powder, L glass powder, M glass powder, S glass powder, T glass powder, NE glass Powder, quartz glass powder, short glass fiber or hollow glass, or a mixture of at least two, more preferably fused silica or/and boehmite;

Preferably, the average particle diameter (d50) of the inorganic filler (D) is 0.1-10 microns, preferably 0.2-5 microns;

Preferably, the inorganic filler (D ) is 10 to 300 parts by weight, preferably 30 to 200 parts by weight, more preferably 50 to 150 parts by weight.

6. The cyanate resin composition according to any one of claims 1-5, characterized in that, the cyanate resin composition can also include an organic filler (E);

Preferably, the organic filler (E) is selected from one or a mixture of at least two of silicone, liquid crystal polymer, thermosetting resin, thermoplastic resin, rubber or core-shell rubber, more preferably silicone powder or/and core shell rubber;

Preferably, the organic filler (E ) is 1 to 30 parts by weight, preferably 3 to 25 parts by weight, more preferably 5 to 20 parts by weight.

7. A prepreg, characterized in that the prepreg comprises a substrate and the cyanate resin composition according to any one of claims 1-6 attached to the substrate after being impregnated and dried.

8. A laminate, characterized in that the laminate comprises at least one prepreg according to claim 7.

9. A metal-clad laminate, characterized in that the metal-clad laminate comprises at least one prepreg as claimed in claim 7 and metal foil covering one or both sides of the prepreg.

10. A printed circuit board, characterized in that the printed circuit board comprises at least one prepreg according to claim 7.