CN1803916A - Resin composite and prepreg and laminate materials used thereof - Google Patents
Resin composite and prepreg and laminate materials used thereof Download PDFInfo
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- CN1803916A CN1803916A CN 200610001192 CN200610001192A CN1803916A CN 1803916 A CN1803916 A CN 1803916A CN 200610001192 CN200610001192 CN 200610001192 CN 200610001192 A CN200610001192 A CN 200610001192A CN 1803916 A CN1803916 A CN 1803916A
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Abstract
The provided is a resin composition containing as essential components a cyanic acid ester resin (A) composition shown in the formula (1) and an epoxy resin (B), wherein, the R means hydrogen atom or cymene, and n is integer of 1 to 50, the precondition is the cyanic acid ester resin (A) is a mixture of component shown in the formula (1) with different value of n and prepreg and laminated sheet made from the said resin composition.
Description
Technical field
The present invention relates to be suitable for to form the resin combination of the printed wiring panel material of circuit thereon, also relate to the prepreg (prepreg) and the laminating material that use this resin combination.
Background technology
Printed-wiring board (PWB) (printed wiring board) is widely used for electronics, communication device and PC, and adopts high-density wiring and high integration just day by day in printed-wiring board (PWB).According to above-mentioned situation, need have excellent properties for example after thermotolerance, low water absorbable, the moisture absorption clad with metal foil lamination material (metal-foil-cladlaminate) of thermotolerance and insulating reliability as the clad with metal foil lamination material that uses in the printed-wiring board (PWB).Be extensive use of FR-4 type laminating material traditionally, wherein use the Dyhard RU 100 cured epoxy resin, the laminating material of using as printed-wiring board (PWB).Yet aspect the high heat resistance requirement, this method has limitation.As the resin with excellent heat resistance that is used for printed-wiring board (PWB), cyanate ester resin is known.Cyanate ester resin is known to be to have the excellent high heat resistance and the thermosetting resin of dielectric characteristics.Its resin combination technology (for example, referring to JP-B-54-30440) that contains maleimide compound simultaneously is known as " BT resin ".Based on above-mentioned technology, in recent years, the resin combination that contains the BT resin extensively is used in the used high function printed wiring panel material of plastic semiconductor encapsulation.Use this resin combination of bisphenol A cyanate ester resin to have excellent mechanical property, for example electrical characteristic, high heat resistance and Young's modulus, chemical resistant properties and binding property.Yet its absorption coerfficient is very high, and also requires further improvement on the mechanical property of Young's modulus and so on.
Yet, under mal-condition, these resin combinations under low water absorbable or some situation after moisture absorption deficiency aspect the thermotolerance.In order further to improve its performance, after deliberation the cyanate ester resin of other structure.
As cyanate ester resin, found phenol line style phenol aldehyde type (phenol novolak type) cyanate ester resin (for example, referring to JP-A-11-124433) in many places with other structure.Yet phenol line style phenol aldehyde type cyanate ester resin solidifies not enough under general condition of cure easily, and the gained solidifying product has the problem that thermotolerance reduces after big absorption coerfficient and the moisture absorption.As the method for improving phenol line style phenol aldehyde type cyanate ester resin, the prepolymer (for example, referring to JP-A-2000-191776) of itself and bisphenol A cyanate ester resin is disclosed.Although above-mentioned prepolymer improves to some extent aspect solidified nature, the improvement on its performance is still not enough.In addition, the resin combination that is used for printed-wiring board (PWB) need have resistivity against fire usually, therefore also uses bromated fire retardant (for example, referring to JP-A-11-021452) usually simultaneously.Yet, owing to, need not use the resin combination of halogen compound recently to the raising of environmental problem degree of concern.Therefore, earnestly need a kind of cyanate resin composition with stable on heating halogen-free flameproof after excellent low water absorbable and the moisture absorption.
Summary of the invention
An object of the present invention is to provide the cyanate resin composition that is used for the printed wiring panel material, said composition has thermotolerance and insulating reliability after improved absorption coerfficient, the moisture absorption.
Another object of the present invention provides a kind of cyanate resin composition that is used for the halogen-free flameproof of printed wiring panel material, and said composition has thermotolerance and insulating reliability after improved solidified nature, absorption coerfficient, the moisture absorption.
Another purpose of the present invention provides a kind of compositions of thermosetting resin that contains cyanate ester resin and maleimide compound, and said composition has excellent more performance in the mechanical properties of water-absorbent and Young's modulus and so on.
A further object of the present invention provides a kind of prepreg and laminating material, and they use any above-mentioned resin combination separately.
Phenol line style phenol aldehyde type cyanate ester resin has less cyanate ester based equivalent, and since their rigid-skeleton, very likely residual many unreacted cyanate groups when solidifying.Therefore, the performance deficiency of thermotolerance and so on after the binding property of phenol line style phenol aldehyde type cyanate ester resin and tinsel, absorption coerfficient or the moisture absorption.The inventor has been found that, in having the cyanate ester resin of ad hoc structure, add Resins, epoxy and can produce following resin combination---because the reaction that above-mentioned interpolation has reduced based on the cyanate ester resin molecular structure suppresses factor, its solidified nature is improved, owing to the rigid structure of resin matrix has kept thermotolerance, and has thermotolerance after excellent water-absorbent and the moisture absorption.Based on above-mentioned discovery, the inventor has finished the present invention.
In addition, the inventor has been found that, in having the cyanate ester resin of ad hoc structure, add halogen-free epoxy resin and mineral filler, can produce the resin combination of following halogen-free flameproof---because the reaction that above-mentioned interpolation has reduced based on the cyanate ester resin molecular structure suppresses factor, its solidified nature is improved, owing to the rigid structure of resin matrix has kept thermotolerance, and has thermotolerance after excellent water-absorbent and the moisture absorption.Based on above-mentioned discovery, the inventor has finished the present invention.
In addition, the inventor has been found that being used in combination maleimide compound with the cyanate ester resin with ad hoc structure can produce the resin combination with excellent absorption coerfficient and Young's modulus.Based on above-mentioned discovery, the inventor has finished the present invention.
That is to say that the present invention 1 provides a kind of resin combination that contains the cyanate ester resin (A) shown in the formula (1) and Resins, epoxy (B) as basal component
Wherein R represents hydrogen atom or methyl, and n is 1 to 50 integer,
Prerequisite is that cyanate ester resin (A) can be the mixture of the compound of the mutually different formula of n value (1).
The present invention 2 provides a kind of resin combination that contains the cyanate ester resin (A) shown in the formula (1), halogen-free epoxy resin (B ') and mineral filler (C) as basal component
Wherein R represents hydrogen atom or methyl, and n is 1 to 50 integer,
Prerequisite is that cyanate ester resin (A) can be the mixture of the compound of the mutually different formula of n value (1).
The present invention 3 provides a kind of resin combination that contains the cyanate ester resin (A) shown in maleimide compound (E) and the formula (1) as basal component
Wherein R represents hydrogen atom or methyl, and n is 1 to 50 integer,
Prerequisite is that cyanate ester resin (A) can be the mixture of the compound of the mutually different formula of n value (1).
A kind of the present invention of containing 1, the present invention 2 or the present invention's 3 resin combination and the prepreg of base material (D) and laminating material or the clad with metal foil lamination material that obtains by the above-mentioned prepreg of curing have been the present invention further provides.
The invention effect
The present invention 1 resin combination has good solidified nature, have thermotolerance and insulating reliability after excellent thermotolerance, absorption coerfficient, the moisture absorption by solidifying laminating material that the prepreg that obtained by this resin combination get or clad with metal foil lamination material, so it is suitable for preparing to be used as the printed wiring panel material of high density printed circuit board.Therefore, its commercial availability is very high.In addition, the present invention 2 resin combination also has following characteristics except the effect of the present invention 1 resin combination---and promptly do not use brominated flame-retardant can have high flame retardant.
The present invention 3 resin combination has good solidified nature and excellent thermotolerance, water-absorbent and Young's modulus, so it has overcome the weakness of traditional cyanate ester resin-maleimide compound resin combination.Therefore, its commercial availability is very high.
Detailed Description Of The Invention
The cyanate ester resin (A) that uses among the present invention is had no particular limits, as long as it is that per molecule contains at least two cyanate groups and cyanate ester resin as the formula (1) or its prepolymer.Cyanate ester resin (A) can use separately, also can as required at least two kinds of cyanate ester resins (A) be mixed and use.By cyanic acid and by the naphthols such as naphthyl alcohol or 2-Naphthol with such as p-Xylol glycol, α, α '-dimethoxy-p-Xylol or 1, the polycondensation of the naphthols aralkyl resin that the reaction of the condensing agent of 4-two (2-hydroxyl-2-propyl group) benzene and so on obtains obtains the cyanate ester resin (A) of formula (1).That is to say, the manufacture method of cyanate ester resin (A) is had no particular limits, and it can be selected from the manufacture method that is called the cyanate synthesis method.Particularly, for example, following acquisition cyanate ester resin (A): exist under the condition of basic cpd, naphthols aralkyl resin and the halogen cyan shown in the formula (2) reacted in inert organic solvents,
Wherein R represents hydrogen atom or methyl, and n is 1 to 50 integer, and prerequisite is that naphthols aralkyl resin can be the mixture of the compound of the mutually different formula of n value (2).
In addition, cyanate ester resin (A) also can synthesize by the following method: form the identical naphthols aralkyl resin and the salt of basic cpd in aqueous solution, make the reaction in the two-phase interface reaction of this salt and halogen cyan then.Cyanate ester resin (A) is preferably naphthyl alcohol aralkyl-type cyanate ester resin, and wherein R is a hydrogen atom.Can be used in combination multiple cyanate ester resin (A) as required.
Amount to cyanate ester resin (A) among the present invention 1 and the present invention 2 has no particular limits.When the amount of cyanate ester resin (A) too hour, the thermotolerance of gained laminating material can reduce.When it was too big, dissolution with solvents degree or solidified nature reduced.Therefore, the amount of cyanate ester resin (A) preferably accounts for 10 to 90 weight % of cyanate ester resin (A) and Resins, epoxy (B) total amount, preferred especially 30 to 70 weight %.
Amount to cyanate ester resin (A) among the present invention 3 has no particular limits.When its too hour, the hygroscopic property of gained laminating material reduces.When it was too big, thermotolerance reduced.Therefore, the amount of cyanate ester resin (A) preferably accounts for 25 to 95 weight % of cyanate ester resin (A) and maleimide compound (E) total amount, preferred especially 30 to 90 weight %.
The Resins, epoxy (B) that uses among the present invention 1 is had no particular limits, as long as it is the compound that per molecule contains at least two epoxide groups.Its example comprises bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol line style phenol aldehyde type epoxy resin (novolac: the line style phenolic aldehyde), cresols line style phenol aldehyde type epoxy resin, dihydroxyphenyl propane line style phenol aldehyde type epoxy resin, brominated bisphenol a type epoxy resin, brominated phenols line style phenol aldehyde type epoxy resin, the trifunctional phenol-type epoxy resin, four sense phenol-type epoxy resins, naphthalene type Resins, epoxy, biphenyl type epoxy resin, the phenol aralkyl-type epoxy resin, the biphenyl aralkyl-type epoxy resin, the naphthols aralkyl-type epoxy resin, cycloaliphatic epoxy resin, polyvalent alcohol type Resins, epoxy, phosphorous epoxy resin, glycidyl amine, glycidyl ester, the compound that double bond epoxidation by divinyl and so on obtains and by the silicone resin of hydroxyl and the compound of the reaction acquisition of Epicholorohydrin.The preferred example of Resins, epoxy (B) comprises bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol line style phenol aldehyde type epoxy resin, cresols line style phenol aldehyde type epoxy resin, dihydroxyphenyl propane line style phenol aldehyde type epoxy resin, brominated bisphenol a type epoxy resin, brominated phenols line style phenol aldehyde type epoxy resin, biphenyl type epoxy resin, phenol aralkyl-type epoxy resin, biphenyl aralkyl-type epoxy resin and naphthols aralkyl-type epoxy resin.These Resins, epoxy (B) can be as required separately or be used in combination.Amount to Resins, epoxy (B) has no particular limits.It preferably accounts for 10 to 90 weight % of cyanate ester resin (A) and Resins, epoxy (B) total amount, preferred especially 30 to 70 weight %.
The halogen-free epoxy resin that uses among the present invention 2 (B ') is not particularly limited, as long as it is the non-halogen compound that per molecule contains at least two epoxide groups.The example of halogen-free epoxy resin (B ') comprises bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol line style phenol aldehyde type epoxy resin, cresols line style phenol aldehyde type epoxy resin, dihydroxyphenyl propane line style phenol aldehyde type epoxy resin, the trifunctional phenol-type epoxy resin, four sense phenol-type epoxy resins, naphthalene type Resins, epoxy, biphenyl type epoxy resin, the phenol aralkyl-type epoxy resin, the biphenyl aralkyl-type epoxy resin, the naphthols aralkyl-type epoxy resin, cycloaliphatic epoxy resin, polyvalent alcohol type Resins, epoxy, phosphorous epoxy resin, glycidyl amine, glycidyl ester, the compound that double bond epoxidation by divinyl and so on obtains and by the silicone resin of hydroxyl and the compound of the reaction acquisition of Epicholorohydrin.Its preferred example comprises phenol line style phenol aldehyde type epoxy resin, biphenyl type epoxy resin, phenol aralkyl-type epoxy resin, biphenyl aralkyl-type epoxy resin, naphthols aralkyl-type epoxy resin and phosphorous epoxy resin.These halogen-free epoxy resins (B ') can be as required separately or be used in combination.Amount to halogen-free epoxy resin (B ') has no particular limits.It preferably accounts for 10 to 90 weight % of cyanate ester resin (A) and halogen-free epoxy resin (B ') total amount, preferred especially 30 to 70 weight %.
Can use curing catalyst with resin combination of the present invention as required, with the control curing speed.Curing catalyst is had no particular limits, as long as it is selected from the curing catalyst of the curing catalyst that is commonly used for cyanate ester resin (A), Resins, epoxy (B) or halogen-free epoxy resin (B ').Its object lesson comprises organic salt, imidazoles and derivative thereof and the tertiary amine of the metal of copper, zinc, cobalt, nickel and so on.
Can be used in combination mineral filler (C) with resin combination of the present invention.Use the basal component of mineral filler (C) as the present invention 2.(C) has no particular limits to mineral filler, as long as it is selected from mineral filler commonly used.Its object lesson comprises silicon-dioxide, for example native silicon dioxide, fused silica, soft silica and hollow silicon dioxide; Metal hydrate, for example aluminium hydroxide, heat treated aluminium hydroxide (by thermal treatment aluminium hydroxide and reduce partial crystallization water obtains), boehmite and magnesium hydroxide; Molybdenum compound, for example molybdenum oxide and zinc molybdate; Zinc borate; Zinc; Aluminum oxide; Clay; Kaolin; Talcum; Calcined clay; Calcined kaolin; Calcination of talc; Mica; Short glass fiber (fine powder of E glass or D glass and so on glass) and hollow glass.The median size of mineral filler (C) is 0.1 to 10 micron, preferred 0.2 to 5 micron.Can be used in combination mineral filler as required with variable grain size distribution or different median sizes.Amount to mineral filler (C) has no particular limits.The amount of the mineral filler (C) that the total amount of per 100 weight part cyanate ester resins (A) and Resins, epoxy (B) or halogen-free epoxy resin (B ') is corresponding is preferably 10 to 300 weight parts, is preferably 30 to 200 weight parts especially.
Can be used in combination silane coupling agent or moistening and dispersion agent with the mineral filler (C) used among the present invention.Silane coupling agent is had no particular limits, as long as it is selected from inorganics surface treatment silane coupling agent commonly used.Its object lesson comprises amino silicane coupling agent, for example γ-An Bingjisanyiyangjiguiwan and N-β-(aminoethyl)-γ-An Bingjisanjiayangjiguiwan; Epoxy silane coupling agent, for example γ-glycidoxypropyltrime,hoxysilane; Vinyl silicane coupling agent, for example γ-methacryloxypropyl trimethoxy silane; Cationic silane coupling agent, for example N-β-(N-vinyl benzyl amino-ethyl)-gamma-amino propyl trimethoxy silicane hydrochloride; With the phenyl silane coupling agent.These silane coupling agents can be as required separately or be used in combination.Moistening and dispersion agent are had no particular limits, as long as it is selected from the dispersion stabilizer that is used for coating.Its example comprises the moistening and dispersion agent based on the multipolymer that contains acidic group, for example the Disperbyk-110,111 of Big Chemie Japan supply, 996 and W903.
Can be used in combination maleimide compound (E) with resin combination of the present invention.Maleimide compound is had no particular limits, as long as it is that per molecule contains at least one maleimide base group, the compound of preferred at least two maleimide base groups.In the present invention 3, require to add maleimide compound (E) in essence.Its object lesson comprises two (4-maleimide aminophenyl) methane, 2,2-two { 4-(4-maleimide amino-benzene oxygen)-phenyl } propane, two (3,5-dimethyl-4-maleimide aminophenyl) methane, two (3-ethyl-5-methyl-4-maleimide aminophenyl) methane, two (3,5-diethyl-4-maleimide aminophenyl) methane, polyphenylene methane maleimide, the prepolymer of these maleimide compounds and the prepolymer of maleimide compound and amine compound.Maleimide compound can be as required separately or be used in combination.Maleimide compound is two (4-maleimide aminophenyl) methane, 2 more preferably, 2-two { 4-(4-maleimide amino-benzene oxygen)-phenyl } propane or two (3-ethyl-5-methyl-4-maleimide aminophenyl) methane.
Can be used in combination cyanate ester resin (A) cyanate ester resin in addition of formula (1) with resin combination of the present invention, only otherwise the inherent nature of infringement resin combination.Cyanate ester resin (A) cyanate ester resin in addition of formula (1) can be selected from known cyanate ester resin.Its example comprises bisphenol A cyanate ester resin, Bisphenol F type cyanate ester resin, bis-phenol M type cyanate ester resin, bis-phenol P type cyanate ester resin, bisphenol E-type cyanate resin, phenol line style phenol aldehyde type cyanate ester resin, cresols line style phenol aldehyde type cyanate ester resin, Dicyclopentadiene (DCPD) line style phenol aldehyde type cyanate ester resin, tetramethyl-Bisphenol F type cyanate ester resin, bisphenol type cyanate ester resin and their prepolymer.Cyanate ester resin (A) cyanate ester resin in addition of these formulas (1) can be as required separately or be used in combination.
Can be used in combination various superpolymer with resin combination of the present invention, for example different thermosetting resins, thermoplastic resin and oligopolymer thereof and elastomerics, different flame-retardant compound or additive, only otherwise the inherent nature of infringement resin combination.They are had no particular limits, as long as they are selected from type commonly used.The example of flame-retardant compound comprises for example for example compound and the silicone compounds of trimeric cyanamide or benzo guanamine, Han oxazine ring of phosphoric acid ester or melamine phosphate, nitrogenous compound of phosphorus compound.The example of additive comprises UV light absorber, antioxidant, photopolymerization inhibitor, white dyes, photosensitizers, dyestuff, pigment, thickening material, lubricant, defoamer, dispersion agent, levelling agent (aleveling agent), brightener and polymerization retarder.They can be used in combination as required.
Can be as required with an organic solvent with resin combination of the present invention.It organic solvent is had no particular limits, as long as can dissolve the mixture of cyanate ester resin (A) and Resins, epoxy (B) or halogen-free epoxy resin (B ') or maleimide compound (E) aptly.Its object lesson comprises ketone for example acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) and pimelinketone; Aromatic hydrocarbons is benzene, toluene and dimethylbenzene for example; With acid amides for example dimethyl formamide and N,N-DIMETHYLACETAMIDE.
The base material that is used for various printed wiring panel materials that the preferred base material (D) that uses can be selected oneself and be known among the present invention.Its example comprises for example for example polyimide, polymeric amide and polyester of E glass, D glass, S glass, NE glass and quartz and organic fibre of inorganic fibre.Base material (D) can suitably be selected according to required purposes or performance.These base materials (D) can separately or be used in combination.The form of base material (D) is yarn fabric, non-woven fabrics, rove, short-cut original silk silk felt and face felt normally.Thickness to base material (D) has no particular limits.Usually, it is about 0.01 to 0.3 millimeter.In addition, consider thermotolerance after the moisture absorption, preferred (physically-opening-treated) yarn fabric handled with surface-treated base material of silane coupling agent or analogue and physics perforate that uses.In addition, can also use the organic membrane of polyimide, polymeric amide, polyester or analogue as base material (D).Thickness to film has no particular limits, and it is preferably about 0.002 to 0.05 millimeter.More preferred by the organic membrane that plasma treatment or similar approach are surface-treated.
The method of making prepreg of the present invention is had no particular limits, as long as it is by resin combination is combined the method for making prepreg with base material (D), wherein said resin combination contain cyanate ester resin (A) and Resins, epoxy (B) as basal component or contain cyanate ester resin (A), halogen-free epoxy resin (B ') and mineral filler (C) as basal component.For example, its normally a kind of like this method---wherein, above-mentioned resin combination is immersed or be coated in the base material (D), for example immerse or the resin combination semicure of coating then, make prepreg thus by in moisture eliminator, making in 1 to 60 minute with 100 to 200 ℃ of heating.The total amount of the resin of resin combination and mineral filler is preferably 20 to 95 weight % of base material (D) in the prepreg.
Obtain laminating material of the present invention by using above-mentioned prepreg to carry out the lamination molding.Particularly, prepare laminating material of the present invention according to following mode: the above-mentioned prepreg of a slice is placed or two or multi-disc prepreg are piled up, as required prepreg pile up surface of prepreg or two surfaces on put the tinsel of Copper Foil or aluminium foil and so on and lamination molding gained assembly.Used tinsel is had no particular limits, as long as it is selected from the tinsel that is used for the printed wiring panel material.As for condition of moulding, laminating material and multiple-plate current techique that can use printed-wiring board (PWB) to use.For example, use multi-platen press, multi-platen vacuum press, continuously moulding, autoclave mould machine or similar devices usually, temperature is generally 100 to 300 ℃, and pressure is generally 2 to 100kgf/cm
2, and be generally 0.05 to 5 hour heat-up time.In addition, can also be by prepreg of the present invention and the merging of internal layer circuit plate and the lamination molding gained assembly of preparation be separately made multi-ply wood.
Amount to maleimide compound (E) among the present invention 3 has no particular limits.When its too hour, the thermotolerance of gained solidifying product reduces.When it was too big, hygroscopic property reduced.Therefore, the amount of maleimide compound (E) preferably accounts for 5 to 75 weight % of cyanate ester resin (A) and maleimide compound (E) total amount, preferred especially 10 to 70 weight %.
The maleimide compound of having explained among used maleimide compound (E) and the present invention 1 and the present invention 2 among the present invention 3 (E) is identical.(E) has no particular limits to maleimide compound used among the present invention 3, as long as it is that per molecule contains at least one maleimide base group, and the compound of preferred at least two maleimide base groups.
In the present invention 3, the method that preparation is contained the resin combination of cyanate ester resin (A) and maleimide compound (E) has no particular limits.For example, can be with cyanate ester resin (A) and maleimide compound (E) melt blending simply, perhaps can be dissolved in organic solvent for example behind methyl ethyl ketone, N-Methyl pyrrolidone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, toluene or the dimethylbenzene, cyanate ester resin (A) is mixed with maleimide compound (E) at cyanate ester resin (A) and maleimide compound (E).In addition, can after one of cyanate ester resin (A) and maleimide compound (E) or both change into oligopolymer, cyanate ester resin (A) be mixed with maleimide compound (E).In addition, cyanate ester resin (A) can be mixed with maleimide compound (E), then they be changed into oligopolymer.
Can be used in combination Resins, epoxy with the present invention 3 resin combination.Used Resins, epoxy is selected from known Resins, epoxy.Resins, epoxy is had no particular limits, as long as it is the compound that per molecule contains at least two epoxide groups.Its example comprises bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol line style phenol aldehyde type epoxy resin, cresols line style phenol aldehyde type epoxy resin, dihydroxyphenyl propane line style phenol aldehyde type epoxy resin, brominated bisphenol a type epoxy resin, brominated phenols line style phenol aldehyde type epoxy resin, the trifunctional phenol-type epoxy resin, four sense phenol-type epoxy resins, naphthalene type Resins, epoxy, biphenyl type epoxy resin, the phenol aralkyl-type epoxy resin, the biphenyl aralkyl-type epoxy resin, the naphthols aralkyl-type epoxy resin, cycloaliphatic epoxy resin, polyvalent alcohol type Resins, epoxy, phosphorous epoxy resin, glycidyl amine, glycidyl ester, the compound that double bond epoxidation by divinyl and so on obtains and by the silicone resin of hydroxyl and the compound of the reaction acquisition of Epicholorohydrin.These Resins, epoxy can be as required separately or be used in combination.
The present invention 3 resin combination carries out self cure under heating, can add known curing catalyst simultaneously to promote curing.The example of this compound comprises organo-peroxide, and for example benzoyl peroxide, lauroyl peroxide, acetyl peroxide, chloro benzoyl peroxide and di-t-butyl-two-the mistake phthalic ester (perphthalate); Azo-compound, for example azo dintrile; Imidazoles, the for example carboxylic acid adducts of glyoxal ethyline, 2-undecyl imidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-Methylimidazole, 1-1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl imidazol(e), 1-cyanoethyl-2-undecyl imidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-Methylimidazole and 1-guanidine amino-ethyl-glyoxal ethyline, these imidazoles, and the carboxylic acid anhydride adducts of these imidazoles; Tertiary amine, N for example, N-dimethyl benzylamine, N, accelerine, N, N-dimethyl methyl aniline, 2-N-ethylbenzene amido ethanol, three-n-Butyl Amine 99, pyridine, quinoline, N-methylmorpholine, trolamine, triethylenediamine, tetramethyl butane diamine and N-methyl piperidine; Phenols, for example phenol, xylenol, cresols, Resorcinol and catechol; Organic metal salt, for example lead naphthenate, lead stearate, zinc naphthenate, zinc octoate, oleic acid tin, toxilic acid dibutyl tin, manganese naphthenate, cobalt naphthenate and ferric acetyl acetonade; Compound by in these organo-metallic any being dissolved in hydroxyl is the material that obtains of phenol or bis-phenol for example; Inorganic metal salt, for example tin chloride, zinc chloride and aluminum chloride; And organo-tin compound, for example di-n-octyltin oxide, other tin alkyl and oxidation of alkyl tin.These curing catalysts can add with usual amounts.For example, the amount of curing catalyst accounts for 10 weight % or lower of resin combination, usually about 0.01 to 2 weight %.
The present invention 3 resin combination can further contain various superpolymer, for example different thermosetting resins, thermoplastic resin and oligopolymer thereof and elastomerics, different flame-retardant compound or additive, only otherwise the inherent nature of infringement resin combination.They are had no particular limits, as long as they are selected from type commonly used.Its example comprises phosphorus compound for example phosphoric acid ester or melamine phosphate; Nitrogenous compound is trimeric cyanamide or benzo guanamine for example; The compound of Han oxazine ring; Silicone compounds; Polyimide; Polyvinyl acetal; Phenoxy resin; Acrylic resin; The acrylic resin of hydroxyl or carboxyl; Synolac; TPU(Thermoplastic polyurethanes); Elastomerics is polyhutadiene, perbutan, polymeric 2-chlorobutadiene, butadiene-styrene copolymer, polyisoprene, isoprene-isobutylene rubber, viton and natural rubber for example; Vinyl compound polymer is styrene isoprene rubber, acrylic rubber, their core-shell rubber, epoxidation divinyl, toxilic acid divinyl, polyethylene, polypropylene, polyethylene-propylene copolymer, poly--4-methylpentene-1, polyvinyl chloride, poly-inclined to one side 1 for example, 1-Ethylene Dichloride, polystyrene, polymethyl benzene base ethene, polyvinyl phenol, AS resin, ABS resin, MBS resin, poly--the 4-vinyl fluoride, vinyl fluoride-propylene copolymer, 4-vinyl fluoride-6-fluoride copolymers and vinylidene fluoride; Thermoplastic resin is polycarbonate, polyestercarbonate, polyphenylene ether, polysulfones, polyester, polyethersulfone, polymeric amide, polyamidoimide, polyester-imide and polyphenylene sulphite (polyphenylenesulfite) and their low-molecular(weight)polymer for example; Poly-(methyl) acrylate is (methyl) acrylate, epoxy (methyl) acrylate and two (methyl) acryloxy-bis-phenol for example; Poly-allylat compound and prepolymer thereof be vinylbenzene, vinyl pyrrolidone, diallyphthalate acyl ester, Vinylstyrene, diallyl benzene, diallyl ether bis-phenol and trialkenyl isocyanuric acid ester for example; Dicyclopentadiene and prepolymer thereof; Phenol resins; Contain for example unsaturated polyester of the monomer of polymerizable double bond and prepolymer thereof; With curable monomer or prepolymer polymeric polyisocyanate for example.The example of additive comprises UV light absorber, antioxidant, photopolymerization inhibitor, white dyes, photosensitizers, dyestuff, pigment, thickening material, lubricant, defoamer, dispersion agent, levelling agent, brightener and polymerization retarder.They can be used in combination as required.
In the present invention 3 resin combination, can use inorganic or organic fibre supporting material.Example inorganic or the organic fibre supporting material comprises inorganic fibre, is glass fibre, quartz glass fibre, carbon fiber, sapphire whisker, silicon carbide fiber, asbestos, rock wool, slag wool and the gypsum palpus brilliant (plaster whisker) of representative, yarn fabric or the non-woven fabrics or their mixture of inorganic fibre with E, NE, D, S and T glass for example; Organic fibre, for example yarn fabric of wholly-aromatic polyamide fiber, polyimide fiber, liquid crystal polyester, trevira, fluorine fiber, polybenzoxazole fibers, cotton, flax and half carbon fiber, organic fibre or non-woven fabrics or their mixture; BLENDED FABRIC, for example glass fibre and wholly-aromatic polyamide fiber, glass fibre and carbon fiber, glass fibre and tynex, glass fibre and liquid crystal aromatic polyester; Inorganic paper, for example glassine paper, mica paper and aluminum oxide paper; Kraft paper, cotton paper, paper-glass mixed paper, or the like, and suitably by at least two kinds constitute in the above-mentioned materials blend fiber supporting material.Preferably these supporting materials are carried out known surface treatment to improve the binding property of itself and resin.In addition, can use polyimide film, wholly-aromatic polyamide film, polybenzoxazole film or liquid crystal polyester film as thin material.
Can be used in combination mineral filler with the present invention 3 resin combination.Mineral filler is had no particular limits, as long as it is selected from mineral filler commonly used.Its object lesson comprises silicon-dioxide, for example native silicon dioxide, fused silica, soft silica and hollow silicon dioxide; Metal hydrate, for example aluminium hydroxide, heat treated aluminium hydroxide (by thermal treatment aluminium hydroxide and reduce partial crystallization water obtains), boehmite and magnesium hydroxide; Molybdenum compound, for example molybdenum oxide and zinc molybdate; Zinc borate; Zinc; Aluminum oxide; Clay; Kaolin; Talcum; Calcined clay; Calcined kaolin; Calcination of talc; Mica; Short glass fiber (fine powder of E glass or D glass and so on glass) and hollow glass.
The condition of cure of the present invention 3 resin combination according to the constituent ratio of resin combination, whether have factors such as curing catalyst difference and difference.For pectisation or curing in advance, can use 100 ℃ or lower temperature by selecting curing catalyst.In order to finish curing, the present invention 3 resin combination is heated the scheduled time under common 100 ℃ to 300 ℃ temperature, to obtain solidifying product.In this case, stress level is had no particular limits, but preferably exert pressure usually.Usually, pressure is selected in preferred 0.5 to 15MPa the scope 0.01 to 50MPa.The present invention 3 resin combination is because its excellent physicals and processability can be used for multiple use.For example, it is suitable as the printed wiring panel material, and for example prepreg or copper-clad laminate also are suitable as structured material and casting resin.
Explain the present invention in detail with reference to synthesis example, embodiment and Comparative Examples below.
Embodiment
Synthesizing of (synthesis example 1) naphthyl alcohol aralkyl-type cyanate ester resin
The mixture of n=1 to 5
With the naphthyl alcohol aralkyl resin (SN475L shown in 0.47 mole of (getting) following formula (3) with the calculating of OH group, OH group equivalent: 216g/eq., by Nippon Steel Chemical Co., Ltd. provides) be dissolved in 500 milliliters of chloroforms, add 0.7 mole of triethylamine and mix with gained solution.In mixture, dropwise add 300 of 0.93 mole of mauguinite with 1.5 hours down at-10 ℃ and restrain chloroformic solutions.The gained mixture was stirred 30 minutes.Then, dropwise add the mixing solutions of 0.1 mole of triethylamine and 30 gram chloroforms, and the gained mixture is stirred 30 minutes to finish reaction.The triethylamine hydrochloride that filtering separation generates.Thus obtained filtrate with 500 milliliters of 0.1N salt acid elutions, is used 500 ml water repeated washings 4 times then.After dried over sodium sulfate, evaporate and at 90 ℃ of decompression degassings, the brown solid naphthyl alcohol aralkyl-type cyanate ester resin shown in the acquisition formula (4) at 75 ℃.Near about 2264cm-1 on the infrared absorption spectrum, confirm the absorption of cyanate group.
The mixture of n=1 to 5
Embodiment 1
(Epikote 1001 with the naphthyl alcohol aralkyl-type cyanate ester resin that obtains in the 70 weight part synthesis examples 1 and 30 weight part bisphenol A type epoxy resins, by Japan Epoxy Resins Co., Ltd. provide) be dissolved in methyl ethyl ketone, and 0.04 weight part zinc octoate is mixed with gained solution to obtain varnish.With this varnish methyl ethyl ketone solvent cut, making varnish after the dilution immerse thickness is in 0.1 millimeter the E woven fiber glass, and with submerged varnish 160 ℃ of following heat dryings 4 minutes, be the prepreg of 41 weight % to obtain resin content.Four described prepregs are piled up and on upper surface that piles up prepreg and lower surface, place the electrolytic copper foil of 18 micron thickness, Copper Foil on the upper surface, Copper Foil on the lower surface, and with the gained assembly at 30kgf/cm
2Pressure and 220 ℃ temperatures system 120 minutes, obtain thickness and be 0.4 millimeter copper-clad laminate.Table 1 has shown the measuring result of the physicals of the copper-clad laminate that makes thus.
Embodiment 2
With naphthyl alcohol aralkyl-type cyanate ester resin, the 45 weight part brominated phenols line style phenol aldehyde type epoxy resin (BREN-S that obtain in the 30 weight part synthesis examples 1, by Nippon Kayaku Co., Ltd provides) and 25 weight part cresols line style phenol aldehyde type epoxy resin (ESCN-220F, provide by Sumitomo Chemical Co.Ltd.) be dissolved in methyl ethyl ketone, and 0.04 weight part zinc octoate is mixed with gained solution to obtain varnish.Then, except that using above-mentioned varnish, obtaining resin content according to the method identical with embodiment 1 is the prepreg of 43 weight %.Carry out subsequently program according to the method identical, obtain thickness and be 0.4 millimeter copper-clad laminate with embodiment 1.Table 1 has shown the measuring result of the physicals of the copper-clad laminate that makes thus.
Embodiment 3
With naphthyl alcohol aralkyl-type cyanate ester resin, the 50 weight part biphenyl aralkyl-type epoxy resin (NC-3000H that obtain in the 50 weight part synthesis examples 1, by Nippon Kayaku Co., Ltd provides) be dissolved in methyl ethyl ketone, and 0.04 weight part zinc octoate is mixed with gained solution to obtain varnish.Then, except that using above-mentioned varnish, obtaining resin content according to the method identical with embodiment 1 is the prepreg of 41 weight %.Carry out subsequently program according to the method identical, obtain thickness and be 0.4 millimeter copper-clad laminate with embodiment 1.Table 1 has shown the measuring result of the physicals of the copper-clad laminate that makes thus.
Comparative Examples 1
Except with 70 weight parts 2,2-two (4-cyanato-phenyl) propane prepolymer (BT2070, Mitsubishi Gas Chemical Company, Inc. providing) outside the 70 weight part naphthyl alcohol aralkyl-type cyanate ester resins that replace using among the embodiment 1, obtaining thickness according to the method identical with embodiment 1 is 0.4 millimeter copper-clad laminate.Table 1 has shown the measuring result of the physicals of the copper-clad laminate that makes thus.
Comparative Examples 2
Except with 70 weight part phenol line style phenol aldehyde type cyanate ester resin (Primaset PT-30, providing by LONZA) outside the 70 weight part naphthyl alcohol aralkyl-type cyanate ester resins that replace using among the embodiment 1, obtaining thickness according to the method identical with embodiment 1 is 0.4 millimeter copper-clad laminate.Table 3 has shown the measuring result of the physicals of the copper-clad laminate that makes thus.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | Comparative Examples 2 | ||
| Copper Foil stripping strength (kgf/cm) | 1.1 | 1.1 | 1.2 | 1.0 | 0.9 | |
| Second-order transition temperature (℃) | 230 | 210 | 240 | 230 | 240 | |
| Thermotolerance after the moisture absorption | 0/4 | 0/4 | 0/4 | 2/4 | 4/4 | |
| Absorption coerfficient (weight %) | 0.5 | 0.5 | 0.4 | 0.9 | 1.1 | |
| Insulation resistance (Ω) | 100 hours | 5×10 13 | 4×10 15 | 3×10 14 | 3×10 11 | 2×10 9 |
| 200 hours | 1×10 13 | 6×10 13 | 1×10 14 | 5×10 10 | 8×10 8 | |
(measuring method)
1) Copper Foil stripping strength: measure according to JIS C6481.
2) second-order transition temperature: measure by the DMA method according to JIS C6481.
3) thermotolerance after the moisture absorption:, rather than remove half lip-deep Copper Foil of sample by the whole Copper Foils on 50 millimeters * 50 millimeters samples of etching removal.With pressure cooker trier (the PC-3 type is provided by Hirayama Manufacturing Corporation) under 121 ℃ and 2 normal atmosphere with sample preparation 3 hours, then sample was soaked 30 seconds visual inspection appearance change then in 260 ℃ scolder.(expansion number/given the test agent number).
4) absorption coerfficient: according to JIS C6481 with pressure cooker trier (the PC-3 type is provided by Hirayama Manufacturing Corporation) under 121 ℃ and 2 normal atmosphere with sample preparation 3 hours, measure its absorption coerfficient then.
5) insulation resistance: according to JIS C6481 with pressure cooker trier (the PC-3 type is provided by Hirayama Manufacturing Corporation) under 121 ℃ and 2 normal atmosphere with the sample preparation scheduled time, measure its insulation resistance then.
Embodiment 4
With the naphthyl alcohol aralkyl-type cyanate ester resin that obtains in the 70 weight part synthesis examples 1,30 weight part phenol line style phenol aldehyde type epoxy resin (EPICLON N-770, by Dainippon Ink AndChemicals, Incorporated provides), 1 weight part silane coupling agent (silane A187, NihonYunika provides) and 1 weight part is moistening and dispersion agent (BYK-W903, provide by Big ChemieJapan) dissolve and be blended in the methyl ethyl ketone, and with 100 weight part aluminium hydroxide (CL-303, provide by Sumitomo Chemical Co.Ltd.) and 0.04 weight part zinc octoate further mix with gained solution, to obtain varnish.With this varnish methyl ethyl ketone solvent cut, making varnish after the dilution immerse thickness is in 0.1 millimeter the E woven fiber glass, and with submerged varnish 160 ℃ of following heat dryings 4 minutes, be the prepreg of 48 weight % to obtain resin content.Four described prepregs are piled up and on upper surface that piles up prepreg and lower surface, place the electrolytic copper foil of 18 micron thickness, Copper Foil on the upper surface, Copper Foil on the lower surface, and with the gained assembly at 30kgf/cm
2Pressure and 220 ℃ temperatures system 120 minutes, obtain thickness and be 0.4 millimeter copper-clad laminate.Table 2 has shown the measuring result of the physicals of the copper-clad laminate that makes thus.
Embodiment 5
With naphthyl alcohol aralkyl-type cyanate ester resin, the 50 weight part bis-phenol aralkyl-type epoxy resin (NC-3000-H that obtain in the 50 weight part synthesis examples 1, by Nippon Kayaku Co., Ltd provides), 1 weight part silane coupling agent (silane A187) and 1 weight part is moistening and dispersion agent (BYK-W903) dissolves and be blended in the methyl ethyl ketone.Aluminium hydroxide (the BS40 that 30 weight parts are heat treated, boehmite conversion rate: 40%, provide by Kawai Lime Industry Co.Ltd.), 20 weight part boehmite (BS100, provide by Kawai Lime Industry Co.Ltd.), 3 weight parts scribble talcum (the Kemgard 911C of zinc molybdate, zinc molybdate carrier: 10 weight %, provide by Sherwin Williams) and 0.01 weight part zinc octoate further mix with gained solution, to obtain varnish.With this varnish methyl ethyl ketone solvent cut, making varnish after the dilution immerse thickness is in 0.1 millimeter the E woven fiber glass, and with submerged varnish 160 ℃ of following heat dryings 3 minutes, be the prepreg of 47 weight % to obtain resin content.Carrying out subsequently program according to the method identical with embodiment 4, is 0.4 millimeter copper-clad laminate to obtain thickness.
Table 2 has shown the measuring result of the physicals of the copper-clad laminate that makes thus.
Embodiment 6
With naphthyl alcohol aralkyl-type cyanate ester resin, the 50 weight part phosphorated Resins, epoxy (FX-305 that obtain in the 40 weight part synthesis examples 1, by Tohto Kasei Co., Ltd. provide), 10 weight part phenol aralkyl-type epoxy resin (E-XLC-LL, by Mitsui Chemicals, Inc. provides) and 1 weight part silane coupling agent (silane A187) dissolve and be blended in the methyl ethyl ketone.50 weight part calcination of talc (BST-200L, by NIPPON TALC CO., LTD. provides) and 0.04 weight part zinc octoate are further mixed with gained solution, to obtain varnish.With this varnish methyl ethyl ketone solvent cut, making varnish after the dilution immerse thickness is in 0.1 millimeter the E woven fiber glass, and with submerged varnish 160 ℃ of following heat dryings 3 minutes, be the prepreg of 47 weight % to obtain resin content.Carrying out subsequently program according to the method identical with embodiment 4, is 0.4 millimeter copper-clad laminate to obtain thickness.Table 2 has shown the measuring result of the physicals of the copper-clad laminate that makes thus.
Embodiment 7
Naphthyl alcohol aralkyl-type cyanate ester resin, 50 weight part biphenyl aralkyl-type epoxy resin (NC-3000-H), the 1 weight part silane coupling agent (silane A187) that obtains in the 50 weight part synthesis examples 1 dissolved and be blended in the methyl ethyl ketone.Spherical synthetic silica (SC-2050, by ADMATECHS Co., LTD provides) of 150 weight parts and 0.04 weight part zinc octoate are further mixed with gained solution, to obtain varnish.With this varnish methyl ethyl ketone solvent cut, making varnish after the dilution immerse thickness is in 0.1 millimeter the E woven fiber glass, and with submerged varnish 160 ℃ of following heat dryings 5 minutes, be the prepreg of 47 weight % to obtain resin content.Carrying out subsequently program according to the method identical with embodiment 4, is 0.4 millimeter copper-clad laminate to obtain thickness.Table 2 has shown the measuring result of the physicals of the copper-clad laminate that makes thus.
Comparative Examples 3
Except with 50 weight parts 2,2-two (4-cyanato-phenyl) propane prepolymer (BT2070, Mitsubishi Gas Chemical Company, Inc. providing) outside the 50 weight part naphthyl alcohol aralkyl-type cyanate ester resins that replace using among the embodiment 5, obtaining thickness according to the method identical with embodiment 5 is 0.4 millimeter copper-clad laminate.Table 2 has shown the measuring result of the physicals of the copper-clad laminate that makes thus.
Comparative Examples 4
Except with 50 weight part phenol line style phenol aldehyde type cyanate ester resin (Primaset PT-30, providing by LONZA) outside the 50 weight part naphthyl alcohol aralkyl-type cyanate ester resins that replace using among the embodiment 5, obtaining thickness according to the method identical with embodiment 5 is 0.4 millimeter copper-clad laminate.Table 2 has shown the measuring result of the physicals of the copper-clad laminate that makes thus.
Table 2
| Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative Examples 3 | Comparative Examples 4 | |
| The Copper Foil stripping strength | 1.1 | 1.2 | 1.1 | 1.1 | 1.0 | 0.9 |
| Insulation resistance (Ω) | 1.4×10 10 | 2.8×10 11 | 4.2×10 10 | 2.9×10 11 | 5.1×10 8 | 5.7×10 7 |
| Absorption coerfficient (weight %) | 0.3 | 0.3 | 0.4 | 0.2 | 0.5 | 0.6 |
| Thermotolerance after the moisture absorption | 0/4 | 0/4 | 0/4 | 0/4 | 1/4 | 3/4 |
| Flame retardant resistance | V-0 | V-0 | V-0 | V-0 | Burning | V-0 |
(measuring method)
1) Copper Foil stripping strength: measure (units f/cm) according to JIS C6481.
2) insulation resistance: according to JIS C6481 with pressure cooker trier (the PC-3 type is provided by Hirayama Manufacturing Corporation) under 121 ℃ and 2 normal atmosphere with sample preparation 500 hours, measure its insulation resistance then.
3) absorption coerfficient: according to JIS C6481 with pressure cooker trier (PC-3 type) under 121 ℃ and 2 normal atmosphere with sample preparation 5 hours, measure its absorption coerfficient then.
4) thermotolerance after the moisture absorption:, rather than remove half lip-deep Copper Foil of sample by the whole Copper Foils on 50 millimeters * 50 millimeters samples of etching removal.With pressure cooker trier (PC-3 type) under 121 ℃ and 2 normal atmosphere with sample preparation 3 hours, then sample was soaked 30 seconds visual inspection appearance change then in 260 ℃ scolder.(expansion number/given the test agent number).
5) flame retardant resistance: measure according to UL 94 vertical test methods.
Embodiment 8
With the naphthyl alcohol aralkyl-type cyanate ester resin that obtains in the 70 weight part synthesis examples 1 and 30 weight parts two (4-maleimide aminophenyl) methane (BMI-H is provided by K I KASEI KK) 160 ℃ of melt blendings 10 minutes.With the mixture of melt blending pour in the mold, vacuum and 165 ℃ of following froth breakings 15 minutes, be heating and curing 4 hours at 180 ℃ then, being heating and curing 4 hours at 200 ℃, and being heating and curing 4 hours at 250 ℃, is the solidifying product that 3 millimeters solidifying product and thickness are 4 millimeters to obtain thickness.Table 3 has shown the measuring result of solidifying product physicals.
Embodiment 9
With the naphthyl alcohol aralkyl-type cyanate ester resin that obtains in the 50 weight part synthesis examples 1 and 50 weight parts two (4-maleimide aminophenyl) methane (BMI-H) 160 ℃ of melt blendings 10 minutes.The mixture of melt blending is processed according to the method identical with embodiment 8, to obtain solidifying product.Table 3 has shown the measuring result of solidifying product physicals.
Comparative Examples 5
Except with 70 weight parts 2,2-two (4-cyanato-phenyl) propane (CX, Mitsubishi GasChemical Company, Inc. provides) outside the 70 weight part naphthyl alcohol aralkyl-type cyanate ester resins that replace using among the embodiment 8, obtain solidifying product according to the method identical with embodiment 8.
Table 3 has shown the measuring result of solidifying product physicals.
Comparative Examples 6
Except with 50 weight parts 2, outside the 50 weight part naphthyl alcohol aralkyl-type cyanate ester resins that 2-two (4-cyanato-phenyl) propane (CX) replaces using among the embodiment 9, obtain solidifying product according to the method identical with embodiment 8.Table 3 has shown the measuring result of solidifying product physicals.
Table 3
| Embodiment 8 | Embodiment 9 | Comparative Examples 5 | Comparative Examples 6 | |
| Absorption coerfficient (%) | 2.9 | 3.7 | 8.9 | 10.0 |
| Appearance change after the processing | Do not have | Do not have | Have *) | Have *) |
| Flexural strength (MPa) | 163 | 162 | 149 | 128 |
| Bend elastic constant (GPa) | 3.9 | 4.2 | 3.6 | 3.9 |
| Second-order transition temperature (℃) | 264 | 275 | 261 | 266 |
*)Solidifying product was transparent before handling, and is muddy but solidifying product becomes after handling.
(measuring method)
1) absorption coerfficient and processing back appearance change:
Under 121 ℃ and 2 normal atmosphere, will be of a size of 30 millimeters * 30 millimeters * 3 millimeters sample preparation 96 hours with pressure cooker trier (the PC-3 type is provided by HirayamaManufacturing Corporation) according to JIS C6481.Measure its absorption coerfficient then, and judge the appearance change of suction back sample by range estimation.
2) flexural strength and bend elastic constant:
Using autoplotter (AG5000B is provided by SHIMADZUCORPORATION) measurement size at normal temperatures according to JIS-K6911 is 10 millimeters * 60 millimeters * 4 millimeters sample.
3) second-order transition temperature:
With TMA equipment (TA Instrumen model 2940) under 5 gram load and under 10 ℃/minute the temperature rise rate measurement size be 5 millimeters * 5 millimeters * 3 millimeters sample.
Claims (10)
1. resin combination that contains the cyanate ester resin (A) shown in Resins, epoxy (B) and the formula (1) as basal component
Wherein R represents hydrogen atom or methyl, and n is 1 to 50 integer,
Prerequisite is that cyanate ester resin (A) can be the mixture of the compound of the mutually different formula of n value (1).
2. resin combination according to claim 1, wherein Resins, epoxy (B) is halogen-free epoxy resin (B ').
3. resin combination according to claim 1, wherein the amount of cyanate ester resin (A) accounts for 10 to 90 weight % of cyanate ester resin (A) and Resins, epoxy (B) total amount.
4. resin combination according to claim 1, wherein this resin combination further contains mineral filler (C).
5. prepreg, it contains resin combination according to claim 1 and base material (D).
6. laminating material, it obtains by at least one prepreg according to claim 5 of lamination molding.
7. laminating material according to claim 6, wherein this laminating material is the clad with metal foil lamination material that obtains in the following manner: place tinsel on one or two surface of the laminating material that contains at least one prepreg, then lamination molding tinsel and laminating material.
8. resin combination that contains the cyanate ester resin (A) shown in maleimide compound (E) and the formula (1) as basal component
Wherein R represents hydrogen atom or methyl, and n is 1 to 50 integer,
Prerequisite is that cyanate ester resin (A) can be the mixture of the compound of the mutually different formula of n value (1).
9. resin combination according to claim 8, wherein cyanate ester resin (A) is that (A) 25 is to 95:(E with the weight ratio of maleimide compound (E)) 5 to 75.
10. by solidifying the solidifying product that resin combination according to claim 8 obtains.
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| JP2005006162A JP4843944B2 (en) | 2005-01-13 | 2005-01-13 | Resin composition and prepreg and laminate using the same |
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| JP2005-006162 | 2005-01-13 | ||
| JP2005233331 | 2005-08-11 | ||
| JP2005-233331 | 2005-08-11 | ||
| JP2005233331A JP4784198B2 (en) | 2005-08-11 | 2005-08-11 | Thermosetting resin composition |
| JP2005-233931 | 2005-08-12 | ||
| JP2005233931A JP4997727B2 (en) | 2005-08-12 | 2005-08-12 | Flame retardant resin composition, and prepreg and laminate using the same |
| JP2005233931 | 2005-08-12 |
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Also Published As
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|---|---|
| JP2006193607A (en) | 2006-07-27 |
| CN1803916B (en) | 2010-10-13 |
| JP4843944B2 (en) | 2011-12-21 |
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