TW201422673A - Thermosetting cyanate resin composition and application of thermosetting cyanate resin composition - Google Patents

Abstract

The invention relates to a thermosetting cyanate resin composition, which comprises the following components: polyfunctional cyanate, epoxy resin, flame retardant agent and inorganic filler. The thermosetting cyanate resin composition is used for preparing resin substrates, resin compound metal copper foils, prepregs, laminating plates, copper-coating plate laminating plates, printed circuit boards and the like. The thermosetting cyanate resin composition has good heat resistant property, humidity resistant property and flame retardant property and low heat expansion coefficient.

Description

Thermosetting cyanate ester and application thereof

The present invention relates to the field of polymer resin technology, and in particular to a thermosetting cyanate resin composition and a resin sheet thereof, a resin composite metal foil, a prepreg, a laminate, a metal foil-clad laminate, and a printed circuit. The application in the board.

With the rapid development of the electronic and electrical industry in the world, the toxic substances in electrical and electronic products and electrical and electronic products are increasingly harmful to the environment. Faced with the pressure to protect the environment, the industry switched from using lead-containing solders to using lead-free solders. The temperature of lead-free solders is 20-30 °C higher than that of leaded solders. For some harsh process conditions, the temperature of lead-free solders has reached 260 ° C or even 270 ° C. This directly leads to the need for the circuit substrate material to face more stringent reliability tests during processing, thereby increasing the risk of cracking and blasting of the substrate.

On the other hand, with the development of electronic information technology, the trend of short and light electronic components requires more precise wiring and higher wiring density of printed circuit boards, which in turn requires more excellent electrical and mechanical properties of the circuit board substrate. , low coefficient of thermal expansion and heat resistance.

Conventional FR-4 uses dicyandiamide-cured epoxy resin. Due to insufficient heat resistance of dicyandiamide-cured epoxy resin, it is no longer sufficient for lead-free solder. Heat resistance requirements under the generation. As a new type of thermosetting resin, cyanate ester has excellent thermal stability and mechanical properties, and is mixed with epoxy resin and used on printed circuit boards (eg, JP 1998-145019, JP 2001-071981). However, the conventional bisphenol A type difunctional cyanate still needs to be further improved in thermal expansion coefficient, moisture resistance, and moist heat resistance.

The researchers found that the use of novolac type cyanate can further increase the glass transition temperature, but the novolac type cyanate resin is prone to insufficient curing, and the cured product has a large water absorption rate and reduces the moist heat resistance.

Japanese Patent No. 2011-126963, JP 2009-298981, and JP 1991-084040 disclose a bisphenolate-containing phenolic cyanate composition. However, the cross-linking density of the dicyclopentadiene-containing phenol aldehyde cyanate is low, and thus the water absorption rate, thermal expansion coefficient, heat resistance, and moist heat resistance are further required to be further improved.

One of the objects of the present invention is to provide a cyanate ester in view of the deficiencies of the prior art. The cyanate ester has a structure of the formula (I): Wherein n is an arbitrary natural number, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 15, 20, etc., and is preferably any integer between 0 and 10.

The cyanate ester of the formula (I) is a resorcinol type dicyclopentane Alkene cyanate (structural formula (II)), catechol type dicyclopentadiene cyanate (structural formula (III)) or hydroquinone type dicyclopentadiene cyanate (structural formula (IV) A mixture of one or at least two of the resins.

Wherein n is an arbitrary natural number, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 15, 20, etc., and is preferably any integer between 0 and 10.

Wherein n is an arbitrary natural number, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 15, 20, etc., and is preferably any integer between 0 and 10.

Wherein n is an arbitrary natural number, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 15, 20, etc., and is preferably any integer between 0 and 10.

Preferably, the cyanate ester of the formula (I) has a number average molecular weight of from 400 to 5,000, more preferably from 450 to 4,500, particularly preferably from 700 to 3,500. . Too large a molecular weight results in too fast reactivity, resulting in a small flow window, a difficult lamination process, and a decrease in adhesion between the layers of the sheet.

The method for synthesizing the cyanate ester in the formula (I) is not particularly limited, and any cyanate ester preparation route can be selected. First, the cyanogen halide is dissolved in an inert organic solvent, and the compound of the formula (V) and the basic catalyst are dissolved in the same inert organic solvent and added dropwise to the cyanogen halide solution, and the reaction temperature is controlled at -20 to -10 ° C. The reaction time is controlled to be 0.5 to 5 hours to obtain a cyanate ester of the formula (I).

The compound of the formula (V) is a mixture of one or at least two of a resorcinol type, a catechol type or a hydroquinone type dicyclopentadiene resin. The resin synthesis method of the structural formula (V) is not particularly limited. The synthetic method of the phenolic resin represented by the structural formula (V) is described by taking the resorcinol type biscyclopentadiene phenol resin as an example: resorcinol is reacted with dicyclopentadiene under the action of a catalyst. The resorcinol is dissolved by heating, and a catalyst is added to form a homogeneous solution, and dicyclopentadiene is added dropwise at 50 to 180 ° C (preferably 70 to 140 ° C). The amounts of dicyclopentadiene, catalyst and resorcin are respectively 1 mol, 0.001 to 0.5 mol (preferably 0.005 to 0.1 mol) and 0.1 to 10 mol (preferably 0.5 to 5 mol). Throughout the process, the dropwise addition of dicyclopentadiene to a mixture of resorcin or resorcinol and the catalyst should be carried out slowly, and the dropwise addition time is controlled between 1 and 10 hours, and the dicyclopentadiene is added dropwise. After the reaction for a while. Thereafter, the unreacted product is distilled off under reduced pressure, and washed with water to obtain a compound of the formula (I).

Wherein n is an arbitrary natural number, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 15, 20, etc., and is preferably any integer between 0 and 10.

Due to the increasingly stringent processing conditions, higher requirements are placed on the heat resistance, thermal expansion coefficient, moisture resistance and moist heat resistance of the material. The bisphenol A cyanate resin still has thermal expansion coefficient, moisture resistance and moist heat resistance. Need to be further improved. The phenol novolak type resin has an increase in heat resistance, but due to its small cyanate ester equivalent, the adhesion of the phenol novolac type cyanate resin cured product to the copper foil, the moisture resistance and the moist heat resistance are insufficient. At the office. The cyanate ester structure of the structural formula (I) of the present invention introduces a dicyclopentadiene structure, and has superior heat resistance, thermal expansion coefficient, moisture resistance and moist heat resistance compared with the bisphenol A cyanate resin. Compared with phenol novolac type cyanate, it has more excellent moisture resistance and moist heat resistance.

The cyanate structure of the structural formula (I) incorporates a dicyclopentadiene structure, and the present invention contains more cyanate groups in the structure than the conventional dicyclopentadiene phenol ocyanate, the composition The denser crosslink density can further reduce the water absorption rate, lower the thermal expansion coefficient, and improve heat resistance and moist heat resistance.

It is also an object of the present invention to provide a thermosetting cyanate resin composition which is characterized by heat resistance, low coefficient of thermal expansion, moisture resistance and heat and humidity resistance.

The thermosetting cyanate resin composition comprises the structural formula (I) Cyanate ester.

Preferably, the thermosetting cyanate resin composition comprises a cyanate ester of the formula (I), an epoxy resin, and a flame retardant. The invention finds that in the thermosetting cyanate composition, the cyanate ester, the epoxy resin and the flame retardant of the specific structural formula (I) are reasonably matched, so that the product has heat resistance, and the low thermal expansion coefficient and moisture resistance are ensured. Sexuality and resistance to heat and humidity. Based on the above findings, the present invention has been completed.

Preferably, the cyanate content of the structural formula (I) in the thermosetting cyanate resin composition is from 5 to 90% by weight, for example, 5.1% by weight, 5.2% by weight, 6% by weight, 9% by weight, 11% by weight, and 14% by weight. 16 wt%, 20 wt%, 40 wt%, 60 wt%, 69 wt%, 71 wt%, 79 wt%, 81 wt%, 85 wt%, 88 wt%, 89 wt%, etc., further preferably 10 to 80 wt%, particularly preferably 15 to 70 wt%, Too much or too little will affect heat resistance, water absorption or heat and humidity resistance.

Preferably, the epoxy resin is an epoxy resin containing two or more epoxy groups, and more preferably a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or a phenol novolac type epoxy resin. , methyl phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, brominated bisphenol A type epoxy resin, brominated phenolic epoxy resin, biphenyl type epoxy resin, naphthalene epoxy resin , aralkyl epoxy resin, polybutadiene epoxy resin, phosphorus-containing epoxy resin, antimony-containing epoxy resin, nitrogen-containing epoxy resin, alicyclic epoxy resin, resorcinol epoxy Resin, polyethylene glycol epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, bisphenol S epoxy resin, bisphenol oxime epoxy resin, TDI modified epoxy resin or MDI modified ring One or a mixture of at least two of oxygen resins, particularly preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, methyl phenol novolac type epoxy resin, bisphenol A linear One or at least two of a phenolic epoxy resin, a brominated bisphenol A epoxy resin, a brominated phenolic epoxy resin, a biphenyl epoxy resin, a naphthalene epoxy resin or an aralkyl epoxy resin Kind of mixture.

Preferably, the epoxy resin is one or a mixture of at least two of the epoxy resins of the formula (VI), (VII), (VIII) or (IX): Wherein R _{1 is} selected from a hydrogen atom, a halogen, a substituted or unsubstituted C ₁ -C ₈ linear alkyl group, a substituted or unsubstituted C ₁ -C ₈ branched alkyl group, a substituted or unsubstituted alicyclic alkyl group a substituted or unsubstituted C ₁ -C ₁₀ alkoxy group, a substituted or unsubstituted phenyl group; n ₁ is an arbitrary natural number, for example, 0, ₁ , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 15, 20, etc.; X is selected from the group consisting of -CH ₂ -, -O-, -CO-, -SO ₂ -, -S-, -CH(C ₆ H ₅ )-, -C(C ₆ H ₅ ) ₂ -, -CH(CH ₃ )- , -C(CH ₃ ) ₂ - or Any of them; Wherein R ₂ is a hydrogen atom, a halogen atom, a C ₁ -C ₈ linear alkyl group, a C ₁ -C ₈ branched alkyl group, a C ₁ -C ₈ cycloalkyl group, a C ₁ -C ₁₀ alkoxy group, a substitution Or any one of unsubstituted phenyl groups; n ₂ is an integer from 0 to 20, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 15, 20, etc.; Wherein R ₃ is a hydrogen atom, a halogen atom, a C ₁ -C ₈ linear alkyl group, a C ₁ -C ₈ branched alkyl group, a C ₁ -C ₈ cycloalkyl group, a C ₁ -C ₁₀ alkoxy group, a substitution Or any one of unsubstituted phenyl groups; n ₃ is an integer from 0 to 20, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 15, 20, etc.; Wherein R ₅ is a hydrogen atom, a halogen atom, a C ₁ -C ₈ linear alkyl group, a C ₁ -C ₈ branched alkyl group, a C ₁ -C ₈ cycloalkyl group, a C ₁ -C ₁₀ alkoxy group, a substitution or Any one of unsubstituted phenyl groups; n ₄ is an integer of 0-20, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 15, 20, and the like.

Preferably, the epoxy resin content in the thermosetting cyanate resin composition is 5 to 90 wt%, for example, 5.1 wt%, 5.2 wt%, 6 wt%, 9 wt%, 11 wt%, 14 wt%, 16 wt%, 20 wt% 40 wt%, 60 wt%, 69 wt%, 71 wt%, 79 wt%, 81 wt%, 85 wt%, 88 wt% 89% by weight, etc., further preferably 10 to 70% by weight, particularly preferably 15 to 65% by weight.

Preferably, the flame retardant is selected from the group consisting of a halogen flame retardant, a phosphorus flame retardant or an inorganic flame retardant, or a combination of at least two, and further preferably a bromine flame retardant, phosphorus flame retardant Any one or a combination of at least two of the agents or inorganic flame retardants.

The halogen-based flame retardant may be a chlorine-based flame retardant, a bromine-based flame retardant, and/or an iodine-based flame retardant; and the halogen-based flame retardant may, for example, be a halogen-containing acrylic resin [halogenated polycondensation] a benzyl (meth) acrylate resin, for example, brominated poly(benzyl) methacrylate such as poly(pentabromobenzyl (meth) acrylate) or poly(pentachlorobenzyl (meth) acrylate) Halogenated benzyl (meth) acrylate homopolymer or copolymer, etc.], halogen-containing styrene resin [halogenated polystyrene (permeating styrene based on brominated polystyrene, chlorinated polystyrene, etc.) a halide obtained by halogenating a resin, a homopolymer or a copolymer of a halogenated styrene monomer, or the like], or a halogen-containing polycarbonate resin (halogenated such as a brominated polycarbonate or a chlorinated polycarbonate) Polycarbonate, etc., halogen-containing epoxy compound (halogenated epoxy resin such as brominated epoxy resin or chlorinated epoxy resin; halogenated phenoxy resin such as brominated phenoxy resin), halogen-containing Phosphate ester [eg, tris(bromoethyl)phosphate, tris(mono or dibromopropyl) phosphate, tris(mono or dibromobutyl)phosphate , tris(mono-tribromo-p-pentyl) phosphate, bis(tribromoneopentyl)phenyl phosphate, bis(mono-tribromophenyl)phosphate, etc., etc., halogen-containing a triazine compound [for example, a bromine-containing triazine compound such as tris(tribromophenoxy)triazine], or a halogen-containing trimeric isocyanate compound [for example, tris(2,3-dibromopropyl) Cyanurate, tris(2,3,4-tribromobutyl)isocyanurate, bromine-containing trimeric isocyanate, etc., etc., halogenated a polyaryl ether compound [for example, a bis(halogenated aryl)ether such as octadecaBDE or octadecyldiphenyl ether (for example, bis(halophenyl)ether); brominated poly A halogen-containing polyphenylene ether resin such as phenylene ether or the like] or a halogenated aromatic quinone imine compound [for example, a brominated aromatic quinone imine such as ethylenedibromophthalimide. a compound (for example, a diimine compound or the like) or the like, a halogenated bisaryl compound [for example, a bis(halogenated C ₆ -C ₁₀ aryl group) such as a bromodiphenyl group; a bromodiphenylmethane group; bis (halogenated C ₆ -C ₁₀ aryl) C ₁ -C ₄ paraffins; brominated bisphenol a or a halogenated bisphenol Organisms (brominated polyesters obtained by polymerization of halogenated bisphenol ethylene oxide adducts, etc.), halogenated alicyclic hydrocarbons (crosslinked cyclic saturated or unsaturated halogenated alicyclic hydrocarbons) For example, a halogenated polycyclic hydrocarbon diene such as dodecylpentacyclostearyl-7,15-diene or the like). The halogen-based flame retardants may be used singly or in combination of two or more.

Preferably, the bromine-based flame retardant is selected from the group consisting of tetrabromobisphenol A, decabromodiphenyl ether, hexabromobenzene, brominated polycarbonate, decabromodiphenylethane or ethylene bis-tetrabromophthalic acid One or a mixture of at least two of quinones, for example: a mixture of tetrabromobisphenol A and decabromodiphenyl ether; a mixture of decabromodiphenyl ether and hexabromobenzene; hexabromobenzene, brominated polycarbonate a mixture with decabromodiphenylethane; a mixture of hexabromobenzene, brominated polycarbonate, decabromodiphenylethane and ethylene bistetrabromophthalimide; tetrabromobisphenol A, decabromo a mixture of diphenyl ether, hexabromobenzene and brominated polycarbonate; tetrabromobisphenol A, decabromodiphenyl ether, hexabromobenzene, brominated polycarbonate, decabromodiphenylethane and ethylene bistetrabromo a mixture of phthalimin and the like.

The phosphorus-based flame retardant may be, for example, an alkylphosphonic acid having a substituent [dialkylphosphonic acid (di-C _1-10 alkylphosphonic acid, etc.), for example, dimethylphosphonic acid, methyl ethyl Phosphonic acid, diethylphosphonic acid, ethyl (n-, iso- or tert-)butylphosphonic acid, di-n-propylphosphonic acid, diisopropylphosphonic acid, di-n-butylphosphonic acid, diiso a dialkylphosphonic acid such as butylphosphonic acid, di-tert-butylphosphonic acid, dipentylphosphonic acid or dioctylphosphonic acid; (hydroxymethyl)methylphosphonic acid, (hydroxyethyl)methylphosphonic acid a hydroxyl group-containing dialkylphosphonic acid such as bis(hydroxymethyl)phosphonic acid or bis(hydroxyethyl)phosphonic acid; or a carboxyl group-containing dialkylphosphoric acid such as (2-carboxyethyl)methylphosphonic acid; An alkoxy-containing dialkylphosphonic acid such as (methoxymethyl)methylphosphonic acid, etc.], an arylphosphonic acid (C _6-10 arylphosphonic acid such as phenylphosphonic acid; diphenylphosphine; a di-C _{6-10 arylphosphonic} acid such as an acid or the like, an alkyl arylphosphonic acid (C _1-4 alkyl-C _6-10 aryl-phosphonic acid or the like such as methylphenylphosphonic acid), and a salt of these organic phosphonic acids; and may, for example, be 1-hydroxy-1H-phosphorane-1-oxide, 2-carboxy-1-hydroxy-1H-phosphorane-1-oxide, etc., which may have a substituent Alkylene a phosphinic acid (C _3-8 alkylene phosphonic acid, etc.); a 1-hydroxyphosphorane-1-oxide or the like, an alkenylene phosphonic acid (C _3-8 alkenylene phosphonic acid, etc.) which may have a substituent; a cycloalkylene phosphine such as 1,3-cyclopentylenephosphonic acid, 1,3-cyclopentylphosphonic acid, 1,4-cyclooctylphosphonic acid or 1,5-cyclooctylphosphonic acid An acid (C _4-10 cycloalkylenephosphonic acid, etc.); or a salt thereof.

Preferably, the phosphorus-based flame retardant is selected from the group consisting of tris(2,6-dimethylphenyl)phosphine, resorcinol bis[bis(2,6-dimethylphenyl)phosphate], and m-benzene. Diphenol tetraphenyl diphosphate, triphenyl phosphate, bisphenol A bis(diphenyl phosphate), phosphazene flame retardant, 10-(2,5-dihydroxyphenyl)-10-hydrogen-9 -oxa-10-phosphinophen-10-oxide, 10-(2,5-dihydroxynaphthyl)-10-hydro-9-oxa-10-phosphinophen-10-oxide or 9,10- Any one or a mixture of at least two dihydro-9-oxa-10-phosphaphenanthrene-10-oxide flame retardants, for example: three (2,6-di) a mixture of methylphenyl)phosphine and resorcinol bis[bis(2,6-dimethylphenyl)phosphate]; tris(2,6-dimethylphenyl)phosphine, resorcinol double a mixture of [bis(2,6-dimethylphenyl)phosphate] and resorcinol tetraphenyl diphosphate; resorcinol tetraphenyl diphosphate, triphenyl phosphate and bisphenol A double a mixture of (diphenyl phosphate); a phosphazene flame retardant, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphinophen-10-oxide, 10- (2,5-dihydroxynaphthyl)-10-hydro-9-oxa-10-phosphinophen-10-oxide and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- a mixture of oxide flame retardants; tris(2,6-dimethylphenyl)phosphine, resorcinol bis[bis(2,6-dimethylphenyl)phosphate], resorcinol tetraphenyl a mixture of bisphosphonate, triphenyl phosphate and bisphenol A bis(diphenyl phosphate); resorcinol bis[bis(2,6-dimethylphenyl)phosphate], resorcinol Tetraphenyl diphosphate, triphenyl phosphate, bisphenol A bis(diphenyl phosphate), phosphazene flame retardant and 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxygen A mixture of hetero-10-phosphaphenanthrene-10-oxides, and the like.

Preferably, the inorganic flame retardant is selected from one or a mixture of at least two of red phosphorus, aluminum hydroxide, magnesium hydroxide or antimony trioxide.

Preferably, the flame retardant accounts for 2 to 40% by weight, preferably 5 to 30% by weight, still more preferably 10 to 25% by weight based on the mass of the thermosetting resin composition.

Preferably, the thermosetting cyanate resin composition of the present invention further comprises a filler. In the patent of the present invention, the filler is an inorganic filler selected from the group consisting of cerium oxide, kaolin, talc, magnesium hydroxide, aluminum hydroxide, boehmite or a mixture of at least two, for example, a mixture of cerium oxide and kaolin. a mixture of talc, magnesium hydroxide and aluminum hydroxide; a mixture of magnesium hydroxide, aluminum hydroxide and boehmite; kaolin, talc, hydroxide a mixture of magnesium and aluminum hydroxide; a mixture of cerium oxide, kaolin, talc, magnesium hydroxide and aluminum hydroxide; a mixture of cerium oxide, kaolin, talc, magnesium hydroxide, aluminum hydroxide and boehmite, etc. . The cerium oxide may be crystalline cerium oxide, molten cerium oxide or spherical cerium oxide.

Preferably, the filler has a median diameter of from 0.1 to 10 microns.

Preferably, the filler accounts for 10 to 60% by weight, further preferably 15 to 55% by weight, particularly preferably 20 to 40% by weight based on the mass of the thermosetting resin composition, and if the amount of the inorganic filler is less than 10% by weight, the coefficient of thermal expansion is not significantly lowered, and on the other hand, the inorganic filler When the amount exceeds 60% by weight, the viscosity of the resin system increases, and the laminate after curing of the composition may be difficult to process in the PCB.

The filler of the thermosetting resin composition of the present invention may further contain, and inorganic fillers such as hydrotalcite, titanium oxide, calcium silicate, cerium oxide, boron nitride, glass powder, zinc borate, aluminum nitrogen compound, and the like may be mentioned. Niobium nitride, niobium carbide, magnesia, zirconia, mullite, titanium dioxide, potassium titanate, hollow glass microspheres, polytetrafluoroethylene powder and polystyrene powder, and potassium titanate, tantalum carbide Single crystal fibers such as tantalum nitride and alumina, and glass short fibers.

In the thermosetting resin composition of the present invention, a catalyst is additionally added as needed, and the catalyst includes a tertiary amine, a tertiary phosphine, a quaternary ammonium salt, a quaternary phosphonium salt, an organic metal complex or an imidazole compound. Examples of tertiary amines are: triethylamine, tributylamine, dimethylamine ethanol, N,N-dimethyl-aminomethylphenol, and benzyldimethylamine; Examples include: triphenylphosphine, etc.; examples of quaternary ammonium salts include: tetramethylammonium bromide, tetramethylammonium chloride , tetramethylammonium iodide, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, cetyltrimethylammonium bromide, etc.; specific examples of quaternary phosphonium salts include: tetrabutyl chloride Antimony, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, ethyltriphenylphosphonium chloride, propyl three Phenylphosphonium chloride, propyltriphenylphosphonium bromide, propyltriphenylphosphonium iodide, butyltriphenylphosphonium chloride, butyltriphenylphosphonium bromide, and butyltriphenylphosphonium iodide Etc. Examples of organometallic complexes include: zinc acetate, copper acetate, nickel acetate, zinc octoate, copper octoate, iron octoate, cobalt octoate, acetoacetone ketone, zinc acetonate, nickel acetonitrile, iron acetonitrile , zinc naphthenate, cobalt acetonate, copper naphthenate, iron naphthenate and cobalt naphthenate; examples of imidazoles include: 2-methylimidazole, 2-ethyl-4-methylimidazole, 2 -phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-dodecylimidazole and 1-cyanoethyl-2-methyl The above catalysts may be used singly or in combination.

The amount of the catalyst used depends on the type of the epoxy resin, the type of the curing agent, and the type of the catalyst. The amount of the catalyst in the present invention is from 0.001 to 5.0% by weight, preferably from 0.02 to 4.0% by weight, more preferably from 0.005 to 3.0% by weight based on the mass of the thermosetting resin composition. Excessive use of the catalyst (more than 5.0% by weight) will result in too fast reactivity of the thermosetting composition, adversely affecting the formation of by-products and the uniformity of conversion of the curing reaction; if the amount of the catalyst in the composition is less than 0.005 Wt%, the reactivity is too slow, which is not conducive to the preparation of prepreg. One principle of using a catalyst is that the gelation time of the glue should not be less than 120 s.

The thermosetting resin composition of the present invention may further contain various high molecular polymers such as an oxazine ring-containing compound, melamine and a derivative thereof, a phenoxy resin, an anthracene resin, a polyvinyl acetal, an acrylic resin, an alkyd resin, and a core. Shell rubber, polyimine, bismaleimide, polyphenylene ether, polytetrafluoroethylene, polyether oxime, polycarbonate, phthalocyanine resin, ultraviolet absorber, antioxidant, photosensitizer, pigment, defoaming A dispersing agent, a thickening agent and the like; one or a mixture of at least two may be selected as needed.

The thermosetting resin composition of the present invention may further contain other types of cyanate esters other than the structural formula (I), and other types of cyanate esters may be selected from the group consisting of novolac type cyanate, bisphenol A type cyanate, bisphenol. A mixture of one or at least two of an E-type cyanate, a bisphenol F-type cyanate, a bisphenol M-type cyanate, a phosphorus-containing cyanate, a guanidate-containing ester, and a fluorine-containing cyanate.

In the present invention, the thermosetting resin composition may further contain other additives, for example, other flame retardants (nitrogen flame retardants, etc.), antioxidants (phenolic antioxidants, amine antioxidants, hydroquinone antioxidants). , quinoline-based antioxidants, sulfur-based antioxidants or phosphorus-based antioxidants, stabilizers (ultraviolet absorbers, weather-resistant (light) stabilizers, heat stabilizers, processing stabilizers, phosphorus stabilizers, or reactive stability Agents, etc.), antistatic agents, lubricants, mold release agents, nucleating agents, plasticizers, colorants (dyes or pigments, etc.), lubricants, and trickle preventers. These other additives may be used singly or in combination of two or more.

The thermosetting resin composition of the present invention can be prepared by mixing with a solvent to form a glue. Examples of solvents that can be used include ketones (such as acetone, methyl ethyl ketone, and methyl isobutyl ketone); hydrocarbons (such as toluene and xylene); alcohols (such as Alcohols, ethanol and primary alcohols; ethers (such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether); esters (such as propylene glycol methyl ether acetate and ethyl acetate); aprotic solvents (such as N, N-two) Methylformamide and N,N-diethylformamide), the above solvents may be used singly or in combination of at least two.

In the present invention, the content of each component of the thermosetting resin composition is calculated by the total content of the components other than the solvent in the thermosetting resin composition being 100% by weight.

It is also an object of the present invention to provide a prepreg comprising the above-described thermosetting resin composition. The thermosetting resin composition is attached to the base after being impregnated and dried. The prepreg has the characteristics of heat resistance, low coefficient of thermal expansion, moisture resistance and heat and humidity resistance.

The method for producing a prepreg using the epoxy resin composition of the present invention is as follows, however, the method for producing the prepreg is not limited thereto: the epoxy resin composition glue (here, solvent-adjusted viscosity has been used) is impregnated on the base material, The prepreg impregnated with the epoxy resin composition is dried by heating, so that the epoxy resin composition in the prepreg is in a semi-curing stage (B-Stage), and a prepreg is obtained. The binder used therein may be an inorganic or organic material. Examples of the inorganic material include woven fabrics or nonwoven fabrics or papers such as glass fibers, carbon fibers, boron fibers, and metals. Among the glass fiber cloths or nonwoven fabrics, E-glass, Q-type cloth, NE cloth, D-type cloth, S-type cloth, and high-oxygen cloth can be used. Woven fabrics or nonwoven fabrics or papers made of organic fibers such as polyester, polyamine, polyacrylic acid, polyimine, aramid, polytetrafluoroethylene, and syndiotactic polystyrene. However, the binder (ie reinforcing material) is not limited this. The heating temperature for the prepreg sheet is 80 to 250 ° C and the time is 1 to 30 minutes. The resin content in the prepreg is between 30 and 80% by weight.

It is also an object of the present invention to provide a laminate for a printed circuit comprising one or more laminated prepregs as described above. The printed circuit board laminate comprises one or more laminated prepregs, and a single-sided or double-sided metal foil on the laminated prepreg, each prepreg comprising a base material and adhered to the base material after being impregnated and dried. The thermosetting resin composition as described above.

Further, the resin composition of the present invention can also be used as a resin sheet or prepreg, a resin composite metal copper foil, a laminate, and a printed circuit board.

Laminates, copper clad laminates, and printed circuit boards can be produced using the above-described resin sheets, resin composite metal foils, and prepregs. This production method will be described by taking a copper clad laminate as an example, but is not limited thereto. When a copper-clad laminate is produced using a prepreg, one or more prepregs are cut into a certain size, laminated, and then fed into a laminating apparatus for lamination, while the metal foil is placed on one side or both sides of the prepreg, Hot press forming presses the prepreg to form a metal foil laminate. As the metal foil, copper, brass, aluminum, nickel, and an alloy of these metals or a composite metal foil can be used. As the pressing conditions of the laminate, suitable lamination curing conditions should be selected according to the actual conditions of the epoxy resin composition. If the pressing pressure is too low, there will be voids in the laminate, and the electrical properties will be lowered. Excessive lamination pressure will cause excessive internal stress in the laminate, which will reduce the dimensional stability of the laminate. The molding pressure is met to compress the sheet to meet the desired requirements. A general guideline for conventional pressed laminates is that the lamination temperature is 130-250 ° C, the pressure is 3-50 kg/cm ² , and the hot pressing time is 60-240 minutes. A printed circuit board or a complicated multilayer circuit board can be produced by a addition or subtraction method using a resin sheet, a resin composite metal foil, a prepreg or a metal foil-clad laminate.

The thermosetting resin composition of the present invention can be used for making adhesives, coatings, and composites in addition to resin sheets, resin composite metal copper foils, prepregs, laminates, copper clad laminates, and printed circuit boards. Materials can also be used in the construction, aerospace, marine and automotive industries.

Compared with the prior art, the present technology has the following beneficial effects:

The cyanate ester of the structural formula (I) of the present invention overcomes the disadvantages of insufficient heat resistance, thermal expansion coefficient, moisture resistance and moist heat resistance of the bisphenol A type cyanate resin, and the water absorption rate of the phenol novolac type cyanate ester. The disadvantage of being too high; it further increases the crosslinking density and improves the heat resistance as compared with the conventional dicyclopentadiene novolac type cyanate. The cyanic acid of the structural formula (I) is mixed with an epoxy resin and a flame retardant, and the obtained thermosetting resin composition has good heat resistance, low coefficient of thermal expansion, moisture resistance, and moist heat resistance.

To facilitate an understanding of the invention, the invention is set forth below. It should be understood by those skilled in the art that the present invention is not to be construed as limited.

The product models used in the following examples and comparative examples are as follows: (1) NC3000H is DIC biphenyl epoxy resin; (2) HP7200H is DIC dicyclopentadiene epoxy resin; (3) EXA9900 is DIC containing naphthalene Epoxy resin; (4) N695 is DIC o-methyl phenolic epoxy resin; (5) BRENS is a brominated phenolic epoxy resin of Nippon Chemical; (6) HF-10 is Shanghai Huifeng Science and Trade Co., Ltd. Cyanate resin; (7) DT4000 is a common dicyclopentadiene phenolic cyanate of Longsha Group; (8) PT-30 is a phenol novolac type cyanate of Longsha Group; (9) SC2050 is made by Admatech (10) brominated styrene is produced by Albemarle; (11) BT93 is ethylene bis-tetrabromophthalimide produced by Albemarle; (12) SAYTEX 8010 is decabromo produced by Albemarle Diphenylethane; (13) 2-PI is a commonly used catalyst for the industry 2-phenylimidazole.

Synthesis Example 1:

Using 1000 parts by weight of resorcin, 7 parts by weight of boron trifluoride monoethylamine, adding to a reaction kettle equipped with a thermometer, a cooler, a stirring device, and a dropper, stirring at 100 ± 5 ° C until completely mixed and dissolved, 415 parts by weight of dicyclopentadiene was dropped over 4 hours, and after dropwise addition, it was kept at 100 ± 5 ° C for 1 hour, and then washed with water under reduced pressure to obtain Compound A of the structural formula (V).

Cyanate ester synthesis of formula (I):

The compound A in the structural formula (V) having an OH content of 0.5 mol was dissolved in acetone, the acetone was 5 times by weight of the structural formula (V), and 2 mol of triethylamine was added thereto and stirred uniformly.

200 mL of acetone was placed in a four-necked flask, cooled to -5 ° C, and then 1 mol of cyanogen bromide was added. The reaction temperature was controlled from -5 ° C to 0 ° C, and the above mixed liquid was added to an acetone solution of cyanogen bromide, and the mixture was added dropwise for 2 hours. After the completion of the dropwise addition, the reaction was continued for 30 minutes, and then filtered and washed with water to obtain a composition 1. The substance of the composition 1 was subjected to a GPC test with a number average molecular weight of 1,120. In the infrared absorption spectrum, an absorption peak at 2270 cm ^-1 was confirmed to be a cyanate group, and there was no hydroxyl absorption peak.

Synthesis Example 2-3:

Composition 2 and Composition 3 were prepared using hydroquinone and catechol, respectively. The synthesis method is referred to Synthesis Example 1. The number average molecular weight of the composition 2 was 400, and the number average molecular weight of the composition 3 was 5,000. It was confirmed by infrared absorption spectrum that the cyanate group was contained and there was no hydroxyl absorption peak.

Example 1:

10 parts by weight of the composition 1, 15 parts by weight of the biphenyl-containing epoxy resin NC3000H, 60 parts by weight of SC2050, 15 parts by weight of brominated styrene, and an appropriate amount of the catalyst zinc octoate and 2-PI were added to the beaker, and 70 was used. The parts by weight of MEK are dissolved and formulated into a glue of suitable viscosity. Use 7628 A type of electronic grade glass cloth was used to wet the glue, and the solvent was removed in an oven at 155 ° C to obtain a B-stage prepreg sample.

Eight sheets of 7628 prepreg laminations were used, and one ounce of electrolytic copper foil was placed one on top of the other and laminated by a hot press to obtain a double-sided copper clad laminate. The lamination conditions are as follows: (1) when the temperature of the material is 80-120 ° C, the heating rate is controlled at 1.0-3.0 ° C / min; (2) the pressure is set to 20 kg / cm ² ; (3) the curing temperature is 220 ° C, and remains This temperature is 90 minutes. The corresponding performance is shown in Table 1.

Example 2:

20 parts by weight of the composition 1, 20 parts by weight of the epoxy resin containing the naphthalene structure EXA9900, 40 parts by weight of SC2050, 20 parts by weight of SAYTEX 8010 and an appropriate amount of the catalyst zinc octoate and 2-PI were added to the beaker and dissolved in 70 parts by weight of toluene. And formulated into a glue of suitable viscosity. The glue was infiltrated with a 7628 type electronic grade glass cloth, and the solvent was removed in an oven at 155 ° C to obtain a B-stage prepreg sample.

A double-sided copper clad laminate was obtained by laminating 8 sheets of 7628 prepreg sheets, one ounce of electrolytic copper foil on the top and bottom, and laminating through a hot press. The lamination conditions are as follows: (1) when the temperature of the material is 80-120 ° C, the heating rate is controlled at 1.0-3.0 ° C / min; (2) the pressure is set to 20 kg / cm ² ; (3) the curing temperature is 220 ° C, and remains This temperature is 90 minutes. The corresponding performance is shown in Table 1.

Example 3:

30 parts by weight of the composition 1, 40 parts by weight of the brominated phenolic epoxy resin BREN-S, 25 parts by weight of SC2050, 5 parts by weight of SAYTEX 8010, and an appropriate amount of the catalyst zinc octoate and 2-PI were added to the beaker, using 70 weights. The DMF is dissolved and formulated into a glue of suitable viscosity. Use 7628 type electricity The sub-glass cloth was wetted with the glue, and the solvent was removed in an oven at 155 ° C to obtain a B-stage prepreg sample.

A double-sided copper clad laminate was obtained by laminating 8 sheets of 7628 prepreg sheets, one ounce of electrolytic copper foil on the top and bottom, and laminating through a hot press. The lamination conditions are as follows: (1) when the temperature of the material is 80-120 ° C, the heating rate is controlled at 1.0-3.0 ° C / min; (2) the pressure is set to 20 kg / cm ² ; (3) the curing temperature is 220 ° C, and remains This temperature is 90 minutes. The corresponding performance is shown in Table 1.

Example 4:

20 parts by weight of the composition 1, 30 parts by weight of the dicyclopentadiene novolac type epoxy resin HP7200H, 20 parts by weight of SC2050, 30 parts by weight of SAYTEX 8010, and an appropriate amount of the catalyst zinc octoate and 2-PI were added to the beaker, using 70 parts by weight. The MEK dissolves and is formulated into a glue of suitable viscosity. The glue was infiltrated with a 7628 type electronic grade glass cloth, and the solvent was removed in an oven at 155 ° C to obtain a B-stage prepreg sample.

A double-sided copper clad laminate was obtained by laminating 8 sheets of 7628 prepreg sheets, one ounce of electrolytic copper foil on the top and bottom, and laminating through a hot press. The lamination conditions are as follows: (1) when the temperature of the material is 80-120 ° C, the heating rate is controlled at 1.0-3.0 ° C / min; (2) the pressure is set to 20 kg / cm ² ; (3) the curing temperature is 220 ° C, and remains This temperature is 90 minutes. The corresponding performance is shown in Table 1.

Example 5:

60 parts by weight of the composition 1, 10 parts by weight of o-methylphenol novolac type epoxy resin N695, 10 parts by weight of SC2050, 20 parts by weight of BT93, and an appropriate amount of catalyst zinc octoate and 2-PI were added to a beaker, using 70 parts by weight. The MEK dissolves and is formulated into a glue of suitable viscosity. Use 7628 type electricity The sub-glass cloth was wetted with the glue, and the solvent was removed in an oven at 155 ° C to obtain a B-stage prepreg sample.

A double-sided copper clad laminate was obtained by laminating 8 sheets of 7628 prepreg sheets, one ounce of electrolytic copper foil on the top and bottom, and laminating through a hot press. The lamination conditions are as follows: (1) when the temperature of the material is 80-120 ° C, the heating rate is controlled at 1.0-3.0 ° C / min; (2) the pressure is set to 20 kg / cm ² ; (3) the curing temperature is 220 ° C, and remains This temperature is 90 minutes. The corresponding performance is shown in Table 1.

Example 6

90 parts by weight of the composition 2, 7 parts by weight of o-methylphenol novolac type epoxy resin N695, 3 parts by weight of BT93 and an appropriate amount of zinc octoate and 2-PI were added to a beaker, dissolved in 70 parts by weight of MEK, and matched Make glue of suitable viscosity. The glue was infiltrated with a 7628 type electronic grade glass cloth, and the solvent was removed in an oven at 155 ° C to obtain a B-stage prepreg sample.

A double-sided copper clad laminate was obtained by laminating 8 sheets of 7628 prepreg sheets, one ounce of electrolytic copper foil on the top and bottom, and laminating through a hot press. The lamination conditions are as follows: (1) when the temperature of the material is 80-120 ° C, the heating rate is controlled at 1.0-3.0 ° C / min; (2) the pressure is set to 20 kg / cm ² ; (3) the curing temperature is 220 ° C, and remains This temperature is 90 minutes. The corresponding performance is shown in Table 1.

Example 7

7 parts by weight of the composition 3, 80 parts by weight of the brominated phenolic epoxy resin BREN-S, 10 parts by weight of SC2050, 3 parts by weight of SAYTEX 8010 and an appropriate amount of the catalyst zinc octoate and 2-PI were added to the beaker, using 70 weight The DMF is dissolved and formulated into a glue of suitable viscosity. Use 7628 type electricity The sub-glass cloth was wetted with the glue, and the solvent was removed in an oven at 155 ° C to obtain a B-stage prepreg sample.

A double-sided copper clad laminate was obtained by laminating 8 sheets of 7628 prepreg sheets, one ounce of electrolytic copper foil on the top and bottom, and laminating through a hot press. The lamination conditions are as follows: (1) when the temperature of the material is 80-120 ° C, the heating rate is controlled at 1.0-3.0 ° C / min; (2) the pressure is set to 20 kg / cm ² ; (3) the curing temperature is 220 ° C, and remains This temperature is 90 minutes. The corresponding performance is shown in Table 1.

Example 8

70 parts by weight of the composition 2, 15 parts by weight of the naphthalene-containing epoxy resin EXA9900, 10 parts by weight of SC2050, 5 parts by weight of SAYTEX 8010, and an appropriate amount of the catalyst zinc octoate and 2-PI were added to a beaker, and dissolved in 70 parts by weight of toluene. And formulated into a glue of suitable viscosity. The glue was infiltrated with a 7628 type electronic grade glass cloth, and the solvent was removed in an oven at 155 ° C to obtain a B-stage prepreg sample.

A double-sided copper clad laminate was obtained by laminating 8 sheets of 7628 prepreg sheets, one ounce of electrolytic copper foil on the top and bottom, and laminating through a hot press. The lamination conditions are as follows: (1) when the temperature of the material is 80-120 ° C, the heating rate is controlled at 1.0-3.0 ° C / min; (2) the pressure is set to 20 kg / cm ² ; (3) the curing temperature is 220 ° C, and remains This temperature is 90 minutes. The corresponding performance is shown in Table 1.

Example 9

9 parts by weight of the composition 3, 11 parts by weight of the biphenyl-containing epoxy resin NC3000H, 40 parts by weight of SC2050, 40 parts by weight of brominated styrene, and an appropriate amount of the catalyst zinc octoate and 2-PI were added to the beaker, using 70 The parts by weight of MEK are dissolved and formulated into a glue of suitable viscosity. Use 7628 A type of electronic grade glass cloth was used to wet the glue, and the solvent was removed in an oven at 155 ° C to obtain a B-stage prepreg sample.

Eight sheets of 7628 prepreg laminations were used, and one ounce of electrolytic copper foil was placed one on top of the other and laminated by a hot press to obtain a double-sided copper clad laminate. The lamination conditions are as follows: (1) when the temperature of the material is 80-120 ° C, the heating rate is controlled at 1.0-3.0 ° C / min; (2) the pressure is set to 20 kg / cm ² ; (3) the curing temperature is 220 ° C, and remains This temperature is 90 minutes. The corresponding performance is shown in Table 1.

Comparative example 1:

20 parts by weight of PT30 phenol novolac type cyanate, 40 parts by weight of o-methylphenol novolac type epoxy resin N695, 20 parts by weight of SC2050, 20 parts by weight of brominated styrene and an appropriate amount of catalyst zinc octoate and 2-PI are added In a beaker, it was dissolved using 70 parts by weight of MEK and formulated into a glue of suitable viscosity. The glue was infiltrated with a 7628 type electronic grade glass cloth, and the solvent was removed in a 155 degree oven to obtain a B-stage prepreg sample.

Eight sheets of 7628 prepreg laminations were used, and one ounce of electrolytic copper foil was placed one on top of the other and laminated by a hot press to obtain a double-sided copper clad laminate. The lamination conditions are as follows: (1) when the material temperature is 80-120 degrees, the heating rate is controlled at 1.0-3.0 degrees/min; (2) the pressure is set to 20 kg/cm ² ; (3) the curing temperature is 220 degrees, and is maintained. This temperature is 90 minutes. The corresponding performance is shown in Table 1.

Comparative example 2:

15 parts by weight of HF-10 bisphenol A type bifunctional cyanate, 40 parts by weight of biphenyl-containing epoxy resin NC3000H, 20 parts by weight of SC2050, 25 parts by weight of brominated styrene and an appropriate amount of catalyst zinc octoate and 2- PI is added to the beaker, dissolved in 70 parts by weight of MEK, and formulated into a suitable viscosity. Glue. The glue was infiltrated with a 7628 type electronic grade glass cloth, and the solvent was removed in a 155 degree oven to obtain a B-stage prepreg sample.

Eight sheets of 7628 prepreg laminations were used, and one ounce of electrolytic copper foil was placed one on top of the other and laminated by a hot press to obtain a double-sided copper clad laminate. The lamination conditions are as follows: (1) when the material temperature is 80-120 degrees, the heating rate is controlled at 1.0-3.0 degrees/min; (2) the pressure is set to 20 kg/cm ² ; (3) the curing temperature is 220 degrees, and is maintained. This temperature is 90 minutes. The corresponding performance is shown in Table 1.

Comparative example 3:

10 parts by weight of DT4000 dicyclopentadiene type cyanate, 15 parts by weight of biphenyl-containing epoxy resin NC3000H, 60 parts by weight of SC2050, 15 parts by weight of brominated styrene and an appropriate amount of catalyst zinc octoate and 2-PI are added to In a beaker, it was dissolved using 70 parts by weight of MEK and formulated into a glue of suitable viscosity. The glue was infiltrated with a 7628 type electronic grade glass cloth, and the solvent was removed in a 155 degree oven to obtain a B-stage prepreg sample.

Eight sheets of 7628 prepreg laminations were used, and one ounce of electrolytic copper foil was placed one on top of the other and laminated by a hot press to obtain a double-sided copper clad laminate. The lamination conditions are as follows: (1) when the material temperature is 80-120 degrees, the heating rate is controlled at 1.0-3.0 degrees/min; (2) the pressure is set to 20 kg/cm ² ; (3) the curing temperature is 220 degrees, and is maintained. This temperature is 90 minutes. The corresponding performance is shown in Table 1.

The laminates obtained in Examples 1-9 and Comparative Examples 1-3 were tested using the following method:

(1) Glass transition temperature (Tg): The DSC test was used, and the measurement was carried out in accordance with the DSC test method specified in IPC-TM-650 2.4.25.

(2) Humidity and heat resistance measurement (PCT): The copper-clad laminate was immersed in a copper etching solution to remove the surface copper foil evaluation substrate. The substrate was placed in a pressure cooker, treated at 121 ° C and 2 atm for 2 hours, and then immersed in a tin furnace at 288 ° C until the sheet was layered and foamed. The stratification foaming time of the substrate is recorded. If the time exceeds 5 minutes, the substrate has excellent heat and humidity resistance, and the test can be stopped.

(3) Evaluation of solder resistance: The copper-clad laminate was immersed in a tin furnace at a temperature of 288 ° C until the sheet was layered and foamed, and the time of layering and foaming of the sheet was recorded. Sexual limit.

(4) Water absorption rate: The board was treated at 85 degrees and 85% humidity for 196 hours.

(5) PCT water absorption rate: The board was placed in a pressure cooker and treated at 121 ° C and 2 atm for 2 hours.

(6) CTE: The TMA test was used, and the heating rate was 10 ° C / min.

(7) Peel strength: The test was carried out in accordance with the method of IPC-TM-650 2.4.8.

Examples 1 to 9 show that the thermosetting resin composition of the present invention has excellent heat resistance, low coefficient of thermal expansion, moisture resistance, and moist heat resistance, and is excellent in overall performance. Comparative Example 1 shows that the water absorption of the phenol novolac type cyanate system is too high, and the immersion tin limit is slightly shorter, and the peel strength is slightly smaller. In the comparative example 2, the water absorption rate of the difunctional cyanate system was too high, the glass transition temperature was slightly lower, the thermal expansion coefficient was too large, the immersion tin limit was short, and the moist heat resistance was slightly poor. In Comparative Example 3, the peel strength and the glass transition temperature were slightly lower than those of Example 1, the water absorption rate was slightly higher, and the dip solderability was slightly shorter.

The Applicant declares that the present invention illustrates the detailed process equipment and process flow of the present invention through the above embodiments, but the present invention is not limited to the above detailed process equipment and process flow, that is, does not mean that the present invention must rely on the above detailed process equipment and The process can only be implemented. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.

Claims (10)

A cyanate ester having the structure of formula (I): Where n is an arbitrary natural number. The cyanate ester according to claim 1, wherein n is an arbitrary integer between 0 and 10; preferably, the cyanate ester is resorcinol type dicyclopentadienoyl cyanate, a mixture of one or at least two of catechol-type dicyclopentadiene cyanate or hydroquinone-type biscyclopentadiene cyanate resin; and preferably, the cyanate number average molecular weight is 400 -5000, further preferably 450-4500, particularly preferably 700-3500. A thermosetting cyanate resin composition, characterized in that the thermosetting cyanate resin composition comprises the cyanate ester according to claim 1 or 2. The thermosetting cyanate resin composition according to claim 3, wherein the thermosetting cyanate resin composition comprises the cyanate ester, the epoxy resin, and the flame retardant according to claim 1 or 2; Preferably, the epoxy resin is an epoxy resin containing two or more epoxy groups, and more preferably a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or a phenol novolac type epoxy resin. , methyl phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, brominated bisphenol A type epoxy resin, brominated phenolic epoxy resin, biphenyl type epoxy resin, naphthalene system Epoxy resin, aralkyl epoxy resin, polybutadiene epoxy resin, phosphorus-containing epoxy resin, antimony-containing epoxy resin, nitrogen-containing epoxy resin, alicyclic epoxy resin, resorcinol Epoxy resin, polyethylene glycol epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, bisphenol S epoxy resin, bisphenol oxime epoxy resin, TDI modified epoxy resin or MDI One or a mixture of at least two modified epoxy resins, particularly preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, methyl phenol novolac type epoxy resin, double One of phenol A novolac type epoxy resin, brominated bisphenol A type epoxy resin, brominated phenolic epoxy resin, biphenyl type epoxy resin, naphthalene epoxy resin or aralkyl type epoxy resin Or a mixture of at least two. The thermosetting cyanate resin composition according to claim 3 or 4, wherein the epoxy resin is an epoxy resin of the formula (VI), (VII), (VIII) or (IX) One or a mixture of at least two: Wherein R _{1 is} selected from a hydrogen atom, a halogen, a substituted or unsubstituted C ₁ -C ₈ linear alkyl group, a substituted or unsubstituted C ₁ -C ₈ branched alkyl group, a substituted or unsubstituted alicyclic alkyl group a substituted or unsubstituted C ₁ -C ₁₀ alkoxy group, a substituted or unsubstituted phenyl group; n ₁ is an arbitrary natural number; and X is selected from -CH ₂ -, -O-, -CO- , -SO ₂ -, -S-, -CH(C ₆ H ₅ )-, -C(C ₆ H ₅ ) ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ - or Any of them; Wherein R ₂ is a hydrogen atom, a halogen atom, a C ₁ -C ₈ linear alkyl group, a C ₁ -C ₈ branched alkyl group, a C ₁ -C ₈ cycloalkyl group, a C ₁ -C ₁₀ alkoxy group, a substitution Or any one of unsubstituted phenyl groups; n ₂ is an integer from 0 to 20; Wherein R ₃ is a hydrogen atom, a halogen atom, a C ₁ -C ₈ linear alkyl group, a C ₁ -C ₈ branched alkyl group, a C ₁ -C ₈ cycloalkyl group, a C ₁ -C ₁₀ alkoxy group, a substitution Or any of the unsubstituted phenyl groups; n ₃ is an integer from 0 to 20; Wherein R ₅ is a hydrogen atom, a halogen atom, a C ₁ -C ₈ linear alkyl group, a C ₁ -C ₈ branched alkyl group, a C ₁ -C ₈ cycloalkyl group, a C ₁ -C ₁₀ alkoxy group, a substitution or Any one of unsubstituted phenyl groups; n ₄ is an integer of 0-20. The thermosetting cyanate resin composition according to any one of claims 3 to 5, wherein the flame retardant is selected from the group consisting of a halogen flame retardant, a phosphorus flame retardant or an inorganic flame retardant. Any one or a combination of at least two, further preferably a bromine-based flame retardant, a phosphorus-based flame retardant or an inorganic flame retardant Any one or a combination of at least two; preferably, the bromine-based flame retardant is selected from the group consisting of tetrabromobisphenol A, decabromodiphenyl ether, hexabromobenzene, brominated polycarbonate, decabromodiphenylethane or One or a mixture of at least two of ethylene bis-tetrabromophthalimide; preferably, the phosphorus-based flame retardant is selected from the group consisting of tris(2,6-dimethylphenyl)phosphine and m-benzene Diphenol bis[bis(2,6-dimethylphenyl)phosphate], resorcinol tetraphenyl diphosphate, triphenyl phosphate, bisphenol A bis(diphenyl phosphate), phosphazene Flame retardant, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphinophen-10-oxide, 10-(2,5-dihydroxynaphthyl)-10 Any one or at least two of hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide or 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide flame retardant a mixture; and preferably, the inorganic flame retardant is selected from one or a mixture of at least two of red phosphorus, aluminum hydroxide, magnesium hydroxide or antimony trioxide. The thermosetting cyanate resin composition according to any one of claims 3 to 6, wherein the cyanate content in the thermosetting cyanate resin composition is from 5 to 90% by weight, further preferably It is 10 to 80% by weight, particularly preferably 15 to 70% by weight; preferably, the epoxy resin content in the thermosetting cyanate resin composition is 5 to 90% by weight, further preferably 10 to 70% by weight, particularly preferably 15 -65 wt%; and preferably, the flame retardant content in the thermosetting cyanate resin composition is from 2 to 40% by weight, preferably from 5 to 30% by weight, still more preferably from 10 to 25% by weight. The thermosetting cyanate resin composition according to any one of claims 3 to 7, wherein the thermosetting cyanate resin composition further comprises a filler; preferably, the filler is selected from the group consisting of cerium oxide, kaolin, talc, magnesium hydroxide, aluminum hydroxide, boehmite, or a mixture of at least two; preferably, the filler has a median diameter of 0.1 to 10 μm; and preferably, the filler accounts for 10 to 60% by weight, further preferably 15 to 55% by weight, particularly preferably 20 to 40% by weight based on the mass of the thermosetting resin composition. A prepreg comprising the thermosetting cyanate resin composition according to any one of claims 3 to 8. A laminate for printed circuit boards, characterized in that the laminate for printed circuit boards comprises one or more laminated prepregs as described in claim 9.