JPH11171980A - Epoxy resin composition for laminate and prepreg and laminate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition that swiftly hardens, when it is hot-formed, and can provide molded products of high quality by homogeneously dissolving an epoxy resin, an epoxy resin curing agent, and a specific quaternary phosphonium borate in an organic solvent. SOLUTION: This composition is a homogeneous solution in an organic solvent including the following components: (A) an epoxy resin, (B) one epoxy resin-curing agent selected from polyamine, polyphenol of acid anhydride and (C) a quaternary phosphonium borate of the formula (R1 -R4 are each an organic group having the aromatic ring or the heterocyclic ring and the P-atoms and individual substituents form the P-C bonds, respectively; at least on of X1 -X4 is a group that is formed when a proton donor releases a proton therefrom and the other groups are monovalent organic group bearing an aromatic ring or a heterocyclic ring). The amount of the component (C) is 0.01-10 pts.wt. per 100 pts.wt. of the component A. Thus, this composition can be expected to have good moldability and long-term storage stability at room temperature.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an epoxy resin composition for a laminate which can be rapidly cured. More specifically, printed wiring, which quickly cures when heated during molding, can provide a molded article of good moldability and high quality, and can be stably stored at about room temperature for a long period of time. The present invention relates to a resin composition for a laminate useful for a board, and a prepreg and a laminate using the same.

[0002]

2. Description of the Related Art In recent years, in order to automate processing equipment, save energy, and further improve productivity, epoxy resin multilayer printed wiring boards have been required to exhibit desired performance by heat molding in a short time. I have. By adding a large amount of catalyst to the varnish, heat molding can be performed in a short time.However, although the curability at the time of heat molding is improved, the melt viscosity at the time of molding is significantly increased, and the circuit pattern is reduced. It is difficult to control in terms of moldability such as resin embedding. Further, by increasing the amount of the catalyst, the curing reaction of the resin proceeds during storage at around room temperature, and the characteristics are reduced. Thus, it has been difficult to achieve both fast curing at high temperatures, moldability, and room temperature storage stability.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made as a result of intensive studies to solve such problems of the epoxy resin composition for a laminated board. The present invention provides an epoxy resin composition for a laminate, and a prepreg and a laminate using the same, which have excellent moldability and can be stably stored at around normal temperature for a long period of time. The purpose is to:

[0004]

That is, the present invention provides an epoxy resin (A), an epoxy resin curing agent (B) which is one selected from polyamines, polyphenols or acid anhydrides, and a curing acceleration effect. It is an epoxy resin composition for a laminate obtained by uniformly dissolving a quaternary phosphonium borate (C) in an organic solvent, wherein the quaternary phosphonium borate (C) is represented by the following general formula [1] or general formula [ 2] or represented by the general formula [3]. Furthermore, a prepreg using the epoxy resin composition for a laminate and a laminate.

[0005]

Embedded image In the formula, R ₁ , R ₂ , R ₃ and R ₄ are an organic group having an aromatic ring or a heterocyclic ring, or a monovalent aliphatic group, and a phosphorus atom and each substituent form a PC bond. And they may be the same or different from each other. Also,
At least one of X ₁ , X ₂ , X ₃ and X ₄ is a group in which a proton donor having at least one proton that can be released outside the molecule releases at least one proton, and Is a monovalent organic group having an aromatic ring or a heterocyclic ring, or a monovalent aliphatic group, which may be the same or different.

[0006]

Embedded image In the formula, R ₅ , R ₆ , R ₇ and R ₈ are an organic group having an aromatic ring or a heterocyclic ring, or a monovalent aliphatic group, and a phosphorus atom and each substituent form a PC bond. And they may be the same or different from each other. Also,
Z ₁ is an organic group having substituents Y ₁ and Y ₂ . Y ₁ , Y
Reference numeral ₂ denotes a group in which a monovalent proton-donating substituent emits a proton, and the substituents Y ₁ and Y ₂ in the same molecule are bonded to a boron atom to form a chelate structure. Z
₂ is an organic group having substituents Y ₃ and Y ₄ . Y ₃ , Y ₄
Is a group in which a monovalent proton donating substituent emits a proton, and the substituents Y ₃ and Y ₄ in the same molecule are bonded to a boron atom to form a chelate structure.
Z _1, Z ₂ may be the same or different, Y _1,
Y ₂ , Y ₃ , and Y ₄ may be the same or different from each other.

[0007]

Embedded image In the formula, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are an organic group having an aromatic ring or a heterocyclic ring, or a monovalent aliphatic group, and each substituent forms a PC bond with a phosphorus atom. To do
They may be the same or different from each other. Z ₃ is an organic group having substituents Y ₅ and Y ₆ .
Y ₅ and Y ₆ are groups in which a monovalent proton donating substituent emits a proton, and the substituents Y ₅ and Y ₆ in the same molecule are bonded to a boron atom to form a chelate structure. is there. X ₅ and X ₆ each represent a group in which a proton donor having at least one proton capable of being released outside the molecule releases at least one proton, a monovalent organic group having an aromatic ring or a heterocyclic ring, or 1 Are aliphatic groups, which may be the same or different from each other.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As described above, in order to shorten the time required for heat molding an epoxy resin laminate, it is common practice to add a catalyst having a curing promoting effect.
While the curing speed is improved, the melt viscosity at the time of molding is significantly increased, making it difficult to control the moldability such as embedding a resin in a circuit pattern. In addition, a curing reaction of the resin proceeds during storage at around room temperature, and there is a disadvantage that the resin composition and the prepreg cannot be stored at room temperature for a long period of time.

In the present invention, in order to solve such a problem, a catalyst having a curing promoting effect is studied and is represented by the general formula [1], the general formula [2], or the general formula [3]. By using the quaternary phosphonium borate (C), it has become possible to achieve both a reduction in the time for heat molding and a long-term storage of the resin composition and the prepreg. In particular, in the B stage state, which is the use state of the prepreg, the curing speed up to the final curing is high at the molding temperature without sacrificing the moldability and the storability at room temperature, and the curability, moldability,
The technical feature is a latent catalyst that satisfies storage stability to a high degree and at the same time.

As the epoxy resin (A) used in the present invention, any resin having two or more epoxy groups which has been conventionally used for electric insulation can be used. As an example, bisphenol A type epoxy resin,
Bisphenol F epoxy resin, novolak epoxy resin, isocyanurate epoxy resin, glycidylamine epoxy resin, epoxy resin with biphenyl skeleton, epoxy resin with naphthalene skeleton, epoxy resin with dicyclopentadiene skeleton, limonene Epoxy resin having a skeleton, or polyfunctional epoxy resin such as trifunctional or tetrafunctional glycidylamine type epoxy resin, polyglycidyl ester of polycarboxylic acid, polyglycidyl ester of aliphatic polyhydroxy compound, silicone-modified epoxy resin, Rubber-modified epoxy resins and the like can be mentioned. Furthermore, in order to impart flame retardancy, a flame-retardant epoxy resin obtained by halogenating the above-described epoxy resin, or a co-condensate of the above-described epoxy resin with tetrabromobisphenol A, bisphenol A, or the above-described epoxy resin Tetrabromobisphenol A, bisphenol A
And a mixture of the above-described epoxy resin and diglycidyl ether tetrabromobisphenol A.

As the epoxy resin curing agent (B), a compound having a functional group capable of reacting with an epoxy group is used, and polyamine, polyphenol, or acid anhydride is preferably used. As polyamines, for example,
4,4'-diaminodiphenylmethane, 4,4'-didiaminodiphenylsulfone, metaphenylenediamine, 4,4'-diamino-3,3'-didiethyl-5,5'-di4,4'-didimethyldiphenylmethane , 3,3'-didimethoxy-4,4'-didiaminodiphenyl, 3,3'-didimethyl-4,4'-di-4,4'-didiaminodiphenyl, 2,2'-didichloro-4,4 '-Didiamino-5,5'-didimethoxydimethyl, 2,2', 5,5'-tetrachloro-4,4'-didiaminodiphenyl, 4,4'-dimethylenebis (2-chloroaniline), 2, 2 ', 3,3'-tetrachloro-4,4'-didiaminodiphenylmethane, 4,4'-didiaminodiphenyle-
Ter, 4,4'-didiaminobenzanilide, 3,3'-dihydroxy-4,4'-didiaminobiphenyl, 9,9'-dibis (4-
Examples thereof include (aminophenyl) fluorene, 9,9′-dibis (4-aminophenyl) anthracene, ethylenediamine, diethylaminopropylamine, hexamethylenediamine, isophoronediamine, and bis (4-amino-3-methylcyclohexyl) methane.

When a guanidine derivative is used in combination as a polyamine, it is effective in improving properties such as storage stability and curability. Examples of such guanidine derivatives include:
Dicyandiamide, dicyandiamide aniline adduct, dicyandiamide aromatic amine adduct, 1-ortho tolyl diguanide, α-2,5-dimethyl guanide, α, ω-diphenyl diguanidide, α, α'-bisguanyl guanidino diphenyl ether , P-chlorophenyldiguanide, α, α'-hexamethylenebis [ω- (p-chlorophenol)] diguanide, phenyldiguanide oxale
And mono- or disubstituted alkyl-modified phenyldiguanide, acetylguanidine, diethylcyanoacetylguanidine and the like.

Examples of the polyphenols include phenol novolak, o-cresol novolak, p-cresol novolak, pt-butylphenol novolak, hydroxynaphthalene novolak, bisphenol A novolak, bisphenol F novolak, terpene-modified novolak, and dicyclopentadiene-modified Novolak, paraxylene-modified novolak, polybutadiene-modified phenol and the like are exemplified.

Examples of acid anhydrides include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, nadic anhydride, chlorendic anhydride and the like. Is an example.

The quaternary phosphonium borate (C) as a latent curing promoting catalyst is represented by the general formulas [1], [2] and [3] as described above. In the formula, substituents R _{1 to} R ₄ , R _{5 to} R ₈ , and R ₉ on the phosphonium side
To R ₁₂ are an organic group having an aromatic ring or a heterocyclic ring, or a monovalent aliphatic group, and the phosphorus atom and each substituent are P-
They form C bonds, and they may be the same or different from each other. Examples of such a group include a methyl group, an ethyl group, a butyl group, an allyl group, a phenyl group, a tolyl group, a benzyl group, an ethylphenyl group, a phenoxy group, and a naphthyl group.

Examples of the phosphonium group constituting each of the general formulas include, for example, tetraphenylphosphonium group, tetratolylphosphonium group, tetraethylphosphonium group, tetramethoxyphosphonium group, tetranaphthylphosphonium group, tetrabenzylphosphonium group, ethyltriphenyl Examples include a phosphonium group, an n-butyltriphenylphosphonium group, a 2-hydroxyethyltriphenylphosphonium group, a trimethylphenylphosphonium group, a methyldiethylphenylphosphonium group, a methyldiallylphenylphosphonium group, and a tetra-n-butylphosphonium group. .

In the general formula [1], at least one of the substituents X ₁ , X ₂ , X ₃ and X ₄ on the borate group side is a proton donor having at least one proton which can be released outside the molecule. Is a group that releases at least one proton, and the other is a monovalent organic group having an aromatic ring or a heterocyclic ring, or a monovalent aliphatic group. Is also good.

Examples of the proton donor providing such a substituent include carboxylic acids, phenol compounds, isocyanuric acid, benzotriazole, and alcohols. Among these proton donors, aromatic carboxylic acids and phenol compounds are particularly preferred. Examples of aromatic carboxylic acids include, for example, benzoic acid, naphthoic acid, biphenylcarboxylic acid, o-phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, hydroxybenzoic acid,
Naphthalenedicarboxylic acid, hydroxynaphthoic acid, 4,4 '
-Didicarboxydiphenylmethane, trimellitic acid, pyromellitic acid and the like. Examples of the phenol compound include, for example, phenol, o-cresol, m
-Cresol, p-cresol, p-phenylphenol, methyl p-hydroxybenzoate, hydroquinone, catechol, resorcin, dihydroxynaphthalene, 4,4 '
-Dibiphenol, 4,4'-didihydroxydiphenylmethane, 2,2'-dibis (4-hydroxyphenyl) propane,
4,4'-didihydroxydiphenyl-2,2'-hexafluoropropane, bis (3,5-dimethyl-4-dihydroxyphenyl) methane, bis (3,5-dimethyl-4-dihydroxyphenyl) sulfone, 4'-didihydroxystilbene, 4,
4'-didihydroxy-α-methylstilbene, bisphenolfluorene and the like. The above compounds are mentioned as an example, but are not limited to them.

In the general formula [2], the organic group Z ₁ on the borate group side is an organic group having substituents Y ₁ and Y ₂ ,
Y ₁ and Y ₂ are groups formed by a monovalent proton donating substituent releasing a proton. The organic group Z ₂ is an organic group having substituents Y ₃ and Y ₄ , and Y ₃ and Y ₄ are groups formed by a monovalent proton donating substituent releasing a proton. The organic groups Y ₁ -Z ₁ -Y ₂ and Y ₃ -Z ₂ -Y ₄ composed of these are groups formed by two or more proton donors releasing two protons. Substituent Y
₁ , Y ₂ and Y ₃ and Y ₄ combine with a boron atom to form a chelate structure. Z ₁ and Z ₂ may be the same or different from each other, and Y ₁ , Y ₂ , Y ₃ , and Y ₄ may be the same or different from each other.

Such substituents Y ₁ -Z ₁ -Y ₂ and Y ₃
A proton donor HY ₁ -Z ₁ -Y ₂ to give -Z ₂ -Y ₄
Examples of H and HY ₃ -Z ₂ -Y ₄ H, contains a carboxylic acid or a phenol compound, or polyhydric alcohols. Among these proton donors, aromatic carboxylic acids having at least two carboxyl groups in the molecule,
An aromatic carboxylic acid having at least one carboxyl group and at least one hydroxyl group in the molecule, or a phenol compound having at least two hydroxyl groups in the molecule and having no carboxyl group is preferable. Examples of aromatic carboxylic acids having at least two carboxyl groups in the molecule include, for example, o-phthalic acid, isophthalic acid, 1,8-naphthalic acid, 2,3-pyridinecarboxylic acid, trimellitic acid, pyromellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid is exemplified. Examples of aromatic carboxylic acids having at least one carboxyl group and at least one hydroxyl group in the molecule include salicylic acid, 3-hydroxy-2-naphthoic acid, and 2-hydroxy-2-naphthoic acid.
Examples include hydroxybiphenyl-3-carboxylic acid, 4-hydroxybiphenyl-3-carboxylic acid, and 2,2′-biphenol-4-carboxylic acid. Examples of the phenol compound having at least two hydroxyl groups in the molecule and not having a carboxyl group include catechol, resorcinol, 2,3-dihydroxynaphthalene, and 2,2′-biphenol. . The above compounds are mentioned as an example, but are not limited to them.

In the general formula [3], the organic group Z ₃ on the borate group side is an organic group having substituents Y ₅ and Y ₆ , and Y ₅ and Y ₆ are monovalent proton donating substituents. Is a group that emits a proton. The organic group Y ₅ -Z ₃ -Y ₆ composed of these is a group formed by a divalent or higher proton donor releasing two protons.
₅ and Y ₆ combine with a boron atom to form a chelate structure. Y ₅ and Y ₆ may be the same or different from each other.

Examples of proton donors HY ₅ -Z ₃ -Y ₆ H which provide such substituents Y ₅ -Z ₃ -Y ₆ include:
Includes carboxylic acids, phenolic compounds, or polyhydric alcohols. Among these proton donors, aromatic carboxylic acids having at least two carboxyl groups in the molecule, aromatic carboxylic acids having at least one carboxyl group and at least one hydroxyl group in the molecule, or at least one in the molecule Phenolic compounds having two hydroxyl groups and no carboxyl group are preferred. Examples of aromatic carboxylic acids having at least two carboxyl groups in the molecule include, for example, o-phthalic acid, isophthalic acid, 1,8-naphthalic acid, 2,3-pyridinecarboxylic acid, trimellitic acid, pyromellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid is exemplified. Examples of aromatic carboxylic acids having at least one carboxyl group and at least one hydroxyl group in the molecule include salicylic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxybiphenyl-3-carboxylic acid, and 4-hydroxybiphenyl -3-carboxylic acid, 2,2'-biphenol
-4-carboxylic acid. Examples of the phenol compound having at least two hydroxyl groups in the molecule and not having a carboxyl group include catechol, resorcinol, 2,3-dihydroxynaphthalene, and 2,2′-biphenol. . The above compounds are mentioned as an example, but are not limited to them.

At least one of the substituents X ₅ and X ₆ is
A proton donor having at least one proton that can be released outside the molecule is a group that releases at least one proton, and the other is a group having an aromatic ring or a heterocyclic ring.
A monovalent organic group or a monovalent aliphatic group, which may be the same or different from each other. Examples of the proton donor providing such a substituent include carboxylic acids, phenol compounds, isocyanuric acid, benzotriazole, and alcohols. Among these proton donors, aromatic carboxylic acids and phenol compounds are particularly preferred. Examples of aromatic carboxylic acids include:
For example, benzoic acid, naphthoic acid, biphenylcarboxylic acid, o-phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, hydroxybenzoic acid, naphthalenedicarboxylic acid, hydroxynaphthoic acid, 4,4′-didicarboxydiphenylmethane, trimellitic acid, pyromellitic Acids and the like. Examples of the phenol compound include, for example,
Phenol, o-cresol, m-cresol, p-cresol, p-phenylphenol, methyl p-hydroxybenzoate, hydroquinone, catechol, resorcin, dihydroxynaphthalene, 4,4'-dibiphenol, 4,4'-didihydroxy Diphenylmethane, 2,2'-dibis (4-hydroxyphenyl) propane, 4,4'-didihydroxydiphenyl-2,2'-hexafluoropropane, bis (3,5-dimethyl-4-dihydroxyphenyl) methane, bis (3,5-dimethyl-4-dihydroxyphenyl) sulfone, 4,4'-didihydroxystilbene, 4,4'-didihydroxy-α-methylstilbene, bisphenolfluorene and the like. The above compounds are mentioned as an example, but are not limited to them.

In the present invention, the quaternary phosphonium borate (C) represented by the general formula [1], the general formula [2], or the general formula [3] is a compound in which a phosphonium cation and a borate anion, which are active species, are mutually bonded. The catalyst activity is suppressed at room temperature because it is protected by forming an ion pair.However, at the temperature during molding, the ion pair dissociates into anions and cations and rapidly develops the catalytic activity. It becomes possible to achieve both the room temperature storage property and the rapid curing property of the resin composition. The combination of these phosphonium borates and the amount added to the epoxy resin composition make it possible to easily adjust the curing rate of the resin composition, which is advantageous in terms of moldability.

The latent catalysts composed of quaternary phosphonium borates represented by the general formulas [2] and [3] include Y ₁ -Z ₁ -Y ₂ , Y ₃ -Z ₂ -Y ₄ , and Y ₅ −Z ₃ −
The organic group represented by Y ₆ is bonded to a boron atom to form a chelate ring structure, whereby the suppression of catalytic activity at a low temperature is more effective than in the case of a proton donor that does not form a cyclic chelate structure. The long-term stable storage of the resin composition at room temperature is particularly excellent.

The quaternary phosphonium borates represented by the general formulas [1] to [3] may be obtained by repeating the quaternary phosphonium borates represented by the general formula depending on conditions such as the temperature at the time of production and the composition of the raw materials. As a unit, a multimer in which a plurality is linked is produced. That is, 4 represented by the general formula [1]
X ₁ , X ₂ , X ₃ , and X ₄
A quaternary phosphonium borate represented by the general formula [1], wherein at least one proton donor releases two or more protons and binds between different boron atoms. (C) A plurality of units are linked.

In the quaternary phosphonium borate represented by the general formula [2], the substituents Y ₁ -Z ₁ -Y ₂ and Y ₃ -Z ₂ -Y ₄
And a quaternary phosphonium borate represented by the general formula [2], wherein the proton donor binds between different boron atoms through at least one of the groups formed by releasing two protons. A plurality of units based on (C) are linked. In the quaternary phosphonium borate represented by the general formula [3], the proton donor represented by the substituent Y ₅ -Z ₃ -Y ₆ releases two protons, or X ₅ and A quaternary phosphonium represented by the general formula [3], wherein at least one proton donor contained in X ₆ is bonded between different boron atoms via a group formed by releasing two or more protons; A plurality of units based on borate (C) are linked.

Even when these multimers occupy a part or all of the quaternary phosphonium borate, they can be used as a latent catalyst to be added to the epoxy resin composition and are included in the scope of the present invention. Of course.

In the resin composition for a laminate, the quaternary phosphonium borate (C) is added to the epoxy resin in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the epoxy resin.
Desirably, parts by weight are used. When the blending amount of the quaternary phosphonium borate (C) is more than 10 parts by weight, the viscosity rise at the time of molding becomes faster, and the moldability decreases. Further, the preservability of the varnish also deteriorates, and it is difficult to achieve both fast curing property, moldability and varnish preservability. Further, the influence of the decrease in the physical properties accompanying the increase in the added amount cannot be ignored. On the other hand, if the amount of the quaternary phosphonium borate (C) is less than 0.01, satisfactory quick-curing properties cannot be obtained.

The quaternary phosphonium borate (C) acts as a curing accelerator for the epoxy resin. The quaternary phosphonium borate (C), which has been conventionally used as a curing accelerator for epoxy resin laminates, is used. -Methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-
It is also possible to use imidazoles such as 4-methylimidazole, 2-methylimidazole / isocyanuric acid adduct, and 2-methylimidazole / trimellitic acid adduct.

Solvents for preparing the epoxy resin composition for laminates of the present invention include acetone, methyl ethyl ketin, toluene, xylene, ethylene glycol monoethyl ether and its acetate compound, propylene glycol monoethyl ether and its acetate. monster,
Dimethylformamide, methanol, ethanol and the like can be used. In addition, a reactive diluent can also be used. Examples of the reactive diluent include n-butyl glycidyl ether, allyl glycidyl ether, styrene oxide, phenyl glycidyl ether, glycidyl methacrylate, Glycidyl ether, diglycidyl aniline, trimethylolpropane triglycidyl ether,
Glycerin triglycidyl ether and the like can be mentioned.

In order to produce a laminate using the epoxy resin composition solution (varnish) of the present invention, the varnish is first prepared by using a base such as paper, glass woven fabric, glass nonwoven fabric, or a cloth containing a component other than glass. By applying, impregnating and drying the material in a drying oven at a temperature in the range of 80 to 200 ° C,
Prepare prepreg. This is heated and pressed to produce a laminate or a metal-clad laminate for a printed wiring board. Depending on the method of application and impregnation, an inorganic filler may be added as necessary to impart thixotropy to the varnish. Examples of the inorganic filler include aluminum oxide, hydrated silica alumina, antimony oxide, barium titanate, colloidal silica, calcium carbonate, calcium sulfate, mica, silica, silicon carbide, talc, titanium oxide, quartz, zirconium oxide, and silicate. Examples include fine particle powders of zirconium, boron nitride, carbon, graphite and the like.

Further, a coupling agent can be added for improving the adhesion to a metal foil such as copper or the like and the inorganic filler. As the coupling agent, a silane coupling agent, a titanate coupling agent, an aluminum chelate coupling agent and the like can be used. For example, chloropropyltrimethoxysilane, vinyltrichlorosilane, γ-glycidoxypropyltrimethoxy Silane, γ-mercaptopropyltrimethoxysilane, N-
β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, isopropyl triisostearoyl titanate, isopropyl trimethacryl titanate, isopropyl tri (dioctyl phyllophosphate) titanate, isopropyl isostearoyl di (4 -Aminobenzoyl) titanate and the like.

[0034]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention.

(Examples 1 to 9 and Comparative Examples 1 to 6) A multilayer printed wiring board was prepared and, for property evaluation, moldability at the time of heat molding, glass transition temperature of resin of the obtained laminated board, moisture absorption The solder heat resistance and the storage stability of the prepreg were evaluated. Each evaluation method was as follows.

1. Glass transition temperature of resin Only the cured prepreg layer is cut from the multilayer printed wiring board after heat molding, and an automatic viscoelasticity measuring device RHEOV
IBRON DDV-3-EP (Orientec Co., Ltd.)
Was measured in a tensile mode at a frequency of 11 Hz and a temperature rising rate of 5 ° C./min. Tan in dynamic viscoelastic curves
The δ peak temperature was taken as the glass transition temperature.

2. Moldability After the outer layer copper foil of the multilayer printed wiring board after the heat molding was removed by the etching treatment, the resin embedded state in the inner layer circuit pattern visible from the exposed cured prepreg layer was comparatively evaluated.

3. Moisture Absorption Solder Heat Resistance The obtained multilayer printed circuit board is subjected to PCT (pressure cooker test) moisture absorption treatment at 125 ° C., 2.3 atm and 30 minutes, and further floated in a solder bath at 260 ° C. for 2 minutes. The presence or absence of swelling at the time was observed.

4. Preservability of Prepreg Prepreg immediately after coating and drying is stored at 40 ° C for 7 days,
The fluidity after storage was compared.

(Examples 1 to 9) First, the substrate thickness was 0.1 m.
The glass-epoxy double-sided copper-clad laminate with a thickness of 35 μm and a copper foil thickness of 35 μm was polished and soft-etched to remove the rust-proofing film, and then a circuit was formed by etching. This was subjected to an oxidation treatment generally called black treatment to roughen the circuit surface to prepare an inner circuit board. Next, an epoxy resin composition solution was prepared by blending each component at a composition ratio as shown in Table 1, and this was impregnated with a conventional method into a glass cloth having a thickness of 180 μm, and dried to obtain a prepreg. . Example 1
The chemical structural formulas of the six types of curing accelerators (quaternary phosphonium borates) used in Nos. To 9 are shown in Formulas [4] to [9].

This prepreg is superimposed one by one on both sides of the inner circuit board, and a thickness of 1
8 μm copper foils were stacked one by one and heat-formed by a vacuum press to obtain a multilayer printed wiring board. The heat molding was started from room temperature, and the material was heated at a rate of 8 ° C./min. The maximum temperature of the material was 170 ° C., and the time required for molding including heating and cooling was 60 minutes. The moldability at this time, the glass transition temperature of the resin of the obtained laminate, the moisture absorption solder heat resistance,
Table 1 summarizes the evaluation results of the storage stability of the prepreg.

(Comparative Examples 1 to 6) First, an inner layer circuit board having a roughened circuit surface was prepared in the same manner as in the example. next,
Each component was blended at a composition ratio as shown in Table 2 to prepare an epoxy resin composition solution, which was impregnated and dried in the same manner as in the example to obtain a prepreg of a comparative example. Further, a multilayer printed wiring board was prepared in the same manner as in the examples, and the characteristics were evaluated. The evaluation results are summarized in Table 2.

[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

[Table 1]

[0050]

[Table 2]

The glass transition temperature of the cured resin in each of the examples was 140 ° C. or higher, which was higher than that of the comparative example. In addition, the moldability, the moisture absorption solder heat resistance, and the fluidity of the prepreg after storage at 40 ° C. for 7 days were all good results. On the other hand, in each of the comparative examples, the fluidity of the prepreg after storage was all gelling or poor fluidity, and any of the moldability and the heat resistance to moisture absorption solder caused voids and swelling. The results were poor and none were satisfactory.

[0052]

The epoxy resin composition for laminates of the present invention is excellent in curability, can be sufficiently cured even in a short lamination molding time, and has a storage stability near room temperature, and furthermore has a good molding property. It is excellent in property and can be suitably used for manufacturing a laminated board or a printed wiring board. In particular, because of its excellent fast-curing properties, it is possible to reduce the time required for heat molding from 150 minutes or more in a single press to about 60 minutes, greatly reducing manufacturing costs, quality control and inventory. The man-hours spent on management will be greatly reduced. In addition, moldability, varnish preservability, and other physical properties can maintain the conventional quality, and are extremely effective in satisfying both fast curing properties at high temperatures, moldability, and varnish storability at room temperature.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08J 5/24 CFC C08J 5/24 CFC C08L 63/00 C08L 63/00 B (72) Inventor Akiko Okubo Higashishinagawa, Shinagawa-ku, Tokyo 2-5-8 Sumitomo Bakelite Co., Ltd. (72) Inventor Minoru Kobayashi 2-5-8 Higashishinagawa, Shinagawa-ku, Tokyo Sumitomo Bakelite Co., Ltd.

Claims (11)

[Claims] 1. An epoxy resin (A), an epoxy resin curing agent (B) selected from polyamines, polyphenols or acid anhydrides, and a quaternary phosphonium borate represented by the general formula [1]: An epoxy resin composition for a laminate obtained by uniformly dissolving (C) in an organic solvent. Embedded image In the formula, R ₁ , R ₂ , R ₃ and R ₄ are an organic group having an aromatic ring or a heterocyclic ring, or a monovalent aliphatic group, and a phosphorus atom and each substituent form a PC bond. And they may be the same or different from each other. Also,
At least one of X ₁ , X ₂ , X ₃ and X ₄ is a group in which a proton donor having at least one proton that can be released outside the molecule releases at least one proton, and Is a monovalent organic group having an aromatic ring or a heterocyclic ring, or a monovalent aliphatic group, which may be the same or different. 2. A quaternary phosphonium borate (C) represented by the general formula [1], wherein at least one of X ₁ , X ₂ , X ₃ and X ₄ contains a proton as a proton donor. The laminate according to claim 1, wherein the released group is a group obtained by releasing a proton from an aromatic carboxylic acid or a phenol compound having at least one carboxyl group or hydroxyl group in the molecule. Epoxy resin composition for use. 3. A proton donor wherein at least one of X ₁ , X ₂ , X ₃ and X ₄ contains at least one part or all of a quaternary phosphonium borate represented by the general formula [1]. Two or more quaternary phosphonium borate (C) units represented by the above general formula [1] linked through different boron atoms through a group that releases two or more protons. The epoxy resin composition for a laminate according to claim 1 or 2, wherein: 4. An epoxy resin (A), an epoxy resin curing agent (B) selected from polyamines, polyphenols or acid anhydrides, and a quaternary phosphonium borate represented by the general formula [2]. An epoxy resin composition for a laminate obtained by uniformly dissolving (C) in an organic solvent. Embedded image In the formula, R ₅ , R ₆ , R ₇ and R ₈ are an organic group having an aromatic ring or a heterocyclic ring, or a monovalent aliphatic group, and a phosphorus atom and each substituent form a PC bond. And they may be the same or different from each other. Also,
Z ₁ is an organic group having substituents Y ₁ and Y ₂ . Y ₁ , Y
Reference numeral ₂ denotes a group in which a monovalent proton-donating substituent emits a proton, and the substituents Y ₁ and Y ₂ in the same molecule are bonded to a boron atom to form a chelate structure. Z
₂ is an organic group having substituents Y ₃ and Y ₄ . Y ₃ , Y ₄
Is a group in which a monovalent proton donating substituent emits a proton, and the substituents Y ₃ and Y ₄ in the same molecule are bonded to a boron atom to form a chelate structure.
Z _1, Z ₂ may be the same or different, Y _1,
Y ₂ , Y ₃ , and Y ₄ may be the same or different from each other. 5. The substituents Y ₁ -Z ₁ -Y ₂ and Y ₃ -Z of the quaternary phosphonium borate (C) represented by the general formula [2]
Represented by ₂ -Y _4, group proton donor is by releasing two protons, aromatic carboxylic acids having at least two carboxyl groups in the molecule, at least one carboxyl group in the molecule and a hydroxyl group 4. An aromatic carboxylic acid having at least one phenol or a phenol compound having at least two hydroxyl groups in the molecule and having no carboxyl group is a group formed by releasing a proton. The epoxy resin composition for a laminate according to the above. 6. A quaternary phosphonium borate represented by the general formula [2] is partially or entirely substituted with a substituent Y ₁ -Z ₁ -Y.
₂ and Y ₃ -Z ₂ -Y ₄ , a proton donor is bonded between different boron atoms via at least one of groups that release two protons, and the above-mentioned general formula [ The epoxy resin composition for a laminate according to claim 4 or 5, wherein a plurality of units based on the quaternary phosphonium borate (C) represented by [2] are linked. . 7. An epoxy resin (A), an epoxy resin curing agent (B) selected from polyamines, polyphenols or acid anhydrides, and a quaternary phosphonium borate represented by the general formula [3]. An epoxy resin composition for a laminate obtained by uniformly dissolving (C) in an organic solvent. Embedded image In the formula, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are an organic group having an aromatic ring or a heterocyclic ring, or a monovalent aliphatic group, and each substituent forms a PC bond with a phosphorus atom. To do
They may be the same or different from each other. Z ₃ is an organic group having substituents Y ₅ and Y ₆ .
Y ₅ and Y ₆ are groups in which a monovalent proton donating substituent emits a proton, and the substituents Y ₅ and Y ₆ in the same molecule are bonded to a boron atom to form a chelate structure. is there. X ₅ and X ₆ each represent a group in which a proton donor having at least one proton capable of being released outside the molecule releases at least one proton, a monovalent organic group having an aromatic ring or a heterocyclic ring, or 1 Are aliphatic groups, which may be the same or different from each other. 8. A proton donor of a quaternary phosphonium borate (C) represented by the general formula [3], represented by a substituent Y ₅ -Z ₃ -Y _6, which emits two protons. The group is an aromatic carboxylic acid having at least two carboxyl groups in the molecule, an aromatic carboxylic acid having at least one carboxyl group and at least one hydroxyl group in the molecule, or at least two hydroxyl groups in the molecule. A phenol compound having no carboxyl group is a group formed by releasing a proton, and a group formed by releasing a proton by at least one proton donor contained in X ₅ and X ₆ is formed in the molecule. 6. The laminated board according to claim 5, wherein the aromatic carboxylic acid or phenol compound having at least one carboxyl group or hydroxyl group is a group that releases protons. Carboxymethyl resin composition. 9. A quaternary phosphonium borate represented by the general formula [3] is partially or entirely substituted with a substituent Y ₅ -Z ₃ -Y.
_{A group} in which the proton donor represented by ₆ releases two protons, or a group in which at least one proton donor contained in X ₅ and X ₆ releases two or more protons. Quaternary phosphonium borate (C) represented by the general formula [3]
The epoxy resin composition for a laminate according to claim 7 or 8, wherein a plurality of units based on are connected. 10. A prepreg, which is basically composed of the epoxy resin composition for a laminate according to any one of claims 1 to 9 and a substrate. 11. A laminate, which is basically composed of the epoxy resin composition for a laminate according to any one of claims 1 to 9 and a base material.