JP2002167427A - Epoxy resin composition for laminated sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an epoxy resin composition for laminated sheets excellent in dielectric constant, dielectric loss tangent, moldability and processability together with the characteristics of an epoxy resin excellent in heat resistance, adhesivity, dimensional stability and chemical resistance, and to provide an electric insulation material and a printed board wherein the composition is applied. SOLUTION: The epoxy resin composition for laminated sheets containing (A) a bi- or more functional epoxy compound or epoxy resin, (B) a bi- or more functional phenolic compound or phenolic resin, as a hardening agent, wherein the hydroxyl group of 10-100 mol% is subjected to esterification by an acyl group and (C) a hardening accelerator is characterized in that the accelerator contains a phosphioxide derivative represented by formula (1) [wherein R1-R6 may be the same or different and denote such hydrogen atom, a 1-10C linear, branched or cyclic alkyl group or a 6-10C aryl group or aralkyl group].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate such as a printed board and a resin composition used for the laminate.

[0002]

2. Description of the Related Art In recent years, progress in electronic information equipment has been remarkable, for example, high-density mounting of components, high integration of semiconductors, and miniaturization of semiconductor packages. In addition, as the performance of personal computers, mobile phones, and portable information devices has increased, the speed and performance of information processing have been required to be higher, and energy saving has been required.
Hz.

Meanwhile, among thermosetting resins used for electric and electronic parts, a composition mainly composed of a combination of a bisphenol type epoxy resin and dicyandiamide has been used as a material for a printed circuit board.

However, in recent years, multilayered printed circuit boards and higher density devices have been used to increase the speed of signals, and the dielectric constant of resins has also been reduced. Tangentization is required. Therefore, a method using a composition in which an epoxy resin and a low-dielectric-constant thermoplastic resin, for example, a reactive polybutadiene or polytetrafluoroethylene resin are combined has been proposed for these uses (Japanese Patent Laid-Open No. 6-199989). ). On the other hand, the method of manufacturing a multilayer printed circuit board is a so-called build-up method in which an organic insulating film is alternately built up on a conductor layer without using a glass cloth disadvantageous to dielectric properties, instead of a conventional laminating press. Are actively developing multilayer wiring boards.

[0005]

However, in any of the compositions used in any of the methods, the epoxy resin as a basic component has a high dielectric property. The ratio of resin must be increased, and the heat resistance, adhesiveness,
Dimensional stability, chemical resistance, workability, etc. are impaired.

In the build-up method, a rubber component is sometimes added to improve the adhesive strength between the insulating layer and the conductor layer. However, since the rubber component remains in the insulating layer, heat resistance and electrical insulation properties are increased. Etc. may be a cause of deteriorating the characteristics.

Accordingly, an object of the present invention is to provide a laminate having the characteristics of an epoxy resin having excellent heat resistance, adhesiveness, dimensional stability, chemical resistance, etc., and also having an excellent dielectric constant, dielectric loss tangent, moldability, and workability. It is to provide a resin composition for use, an electrical insulating material to which the composition is applied, and a printed circuit board.

[0008]

Means for Solving the Problems The present inventors diligently studied the above-mentioned problems of the epoxy resin composition used for the laminate, and as a result, the epoxy resin composition comprises a bifunctional or more functional epoxy resin, a curing agent and a curing accelerator. In the resin composition, a bifunctional or more functional phenol compound or phenolic resin in which 10 to 100 mol% of hydroxyl groups are esterified by an acyl group is used as a curing agent, and a phosphine oxide derivative having a specific structure is used as a curing accelerator. By using a resin composition containing as an essential component in combination, it has been found that a laminated board excellent in various properties such as dielectric properties, hygroscopicity, moldability, and workability can be obtained, and the present invention described below has been completed. Was. [1] Bifunctional or higher functional epoxy compound or epoxy resin (A) and a bifunctional or higher functional phenolic compound or phenolic resin (B) in which 10 to 100 mol% of hydroxyl groups are esterified by an acyl group as a curing agent And a curing accelerator (C), wherein the curing accelerator (C) is represented by the following general formula (1)

[0009]

Embedded image

(Wherein R _{1 to} R ₆ may be the same or different and each represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or aralkyl). An epoxy resin composition for a laminate, comprising a phosphoxide derivative represented by the following formula: [2] The epoxy equivalent of the epoxy resin is 170 to 10
The epoxy resin composition for a laminate according to [1], wherein the composition is 00 g / eq. [3] The epoxy resin composition for a laminate according to [1] or [2], wherein the component (B) is contained in a proportion of 2 to 150 parts by weight with respect to 100 parts by weight of the component (A). [4] The epoxy resin for a laminate according to any one of [1] to [3], wherein the component (B) is a novolak resin substituted with an alkyl group having 1 to 10 carbon atoms or a resin containing an alicyclic skeleton. Composition. [5] A prepreg comprising a substrate impregnated with the resin composition for a laminate according to any one of [1] to [4]. [6] A laminate, wherein two or more prepregs according to [5] are stacked and heated and pressed.

The resin composition of the present invention comprises, as a curing agent for an epoxy resin, a phenol compound esterified with an acyl group or a phenol resin and a specific phosphine oxide derivative as a curing catalyst.
The catalyst not only increases the curing speed, but also reacts with the secondary OH formed by the opening of the epoxy ring and the acyl group to form a new ester bond. It has excellent properties and hygroscopicity.

Further, the epoxy resin composition according to the present invention has a characteristic that the time until complete curing is relatively long despite the high initial curing speed. For this reason, when it is used for laminates, advantages such as good moldability are obtained.

The resin composition for a laminate of the present invention comprises a substrate using a glass cloth, a copper foil with a resin for use in build-up,
It can be suitably used for a laminated board formed by laminating insulating sheets and the like.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific examples of the bifunctional or higher functional epoxy resin which is the component (A) of the epoxy composition of the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, Bisphenol B epoxy resin, brominated epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, alkylphenol novolak epoxy resin, trisphenol epoxy resin, tetraphenol epoxy resin, naphthalene epoxy resin, alicyclic skeleton Epoxy resin, phenol aralkyl type epoxy resin, phosphorus atom-containing epoxy resin, and the like.

Here, the alkyl group of the alkylphenol novolak type epoxy resin may have, for example, 4 to 9 carbon atoms. Among them, a glycidylated product of p-octylphenol novolak resin, and an epoxy resin having an alicyclic skeleton is terpene. Glycidylation of diphenol,
Glycidylated terpene-2,6-dixylenol is mentioned, and glycidylated terpene-2,6-dixylenol is particularly preferred because of its excellent dielectric properties.

Examples of the epoxy resin having a halogen substituent include, for example, tetrabromobisphenol A, tetrachlorobisphenol A, tetrabromobisphenol F
And diglycidylated bisphenols. Among these, diglycidyl ether of tetrabromobisphenol A is preferable in terms of economy and high flame retardancy.

The epoxy resin may be used alone or in combination of two or more kinds, or an epoxy resin obtained by previously reacting with tetrabromobisphenol A may be used.

A specific example of a phenolic compound or a phenolic resin having two or more functional groups in which 10 to 100 mol% of hydroxyl groups, which is the component (B) of the epoxy composition of the present invention, is esterified with an acyl group, includes: Examples include phenol novolak, acylated cresol novolak, acylated alkylphenol novolak, acylated terpene diphenol, acylated terpene-2,6-dixylenol, acylated dicyclopentadiene phenol resin, and acylated aralkyl type resin. Among these, a novolak resin substituted with an alkyl group having 1 to 10 carbon atoms and a resin containing an alicyclic skeleton are preferably used from the viewpoint of dielectric properties and hygroscopicity. For example, carbon number 1
Preferred are an acylated alkylphenol novolak substituted with 10 alkyl groups, an acylated terpene-2,6-dixylenol, an acylated dicyclopentadiene phenol resin, and an acylated phenol aralkyl resin. Here, examples of the acyl group include a benzoyl group, an alkyl-substituted benzoyl group, a butyroyl group, and an octanoyl group. A benzoyl group is preferred in terms of economy.

As the method for esterifying the component (B), a known method can be used. As the esterifying agent used when esterifying the phenolic hydroxyl group, an organic carboxylic anhydride, an organic carboxylic acid halide, an organic carboxylic acid, or the like can be used. Just choose. Specific examples of the esterifying agent include acetic anhydride, acetyl chloride, acetyl bromide, acetic acid, propionic anhydride, propionic chloride, propionic bromide, propionic acid, butyric anhydride, butyric chloride, butyric acid,
Valeric anhydride, valeric chloride, valeric bromide, valeric acid, pivalic chloride, pivalic acid, phenylacetic chloride, phenylacetic acid, 2-phenylpropionic acid, 3-phenylpropionic acid, o-tolylacetic acid, m-
Tolylacetic acid, p-tolylacetic acid, cumene acid, 2-phenylbutyric acid, 4-phenylbutyric acid, benzoic anhydride, benzoic chloride, benzoic bromide, benzoic acid, o-methylbenzoic chloride, m-methylbenzoic chloride, p
-Methylbenzoic acid chloride, o-methylbenzoic acid, m
-Methylbenzoic acid, p-methylbenzoic acid, 2,3-dimethylbenzoic acid, 2,4-dimethylbenzoic acid, 2,5-dimethylbenzoic acid, 2,6-dimethylbenzoic acid, 3,4-
Examples thereof include dimethylbenzoic acid and 3,5-dimethylbenzoic acid.

Among these, preferred are acetic anhydride, acetyl chloride, benzoic anhydride, benzoic acid chloride and the like.

These esterifying agents can be used alone or in combination of two or more.

The amount of the esterifying agent used is preferably 10 mol% or more based on the hydroxyl groups. There is no particular upper limit to the amount used, but in practice, from the viewpoint of reaction volume efficiency, cost, etc., the molar amount is preferably 10 times or less, preferably 5 times or less, more preferably 3 times or less with respect to the hydroxyl group. When the esterification is sufficiently advanced by using an excessive amount, the excess esterifying agent may be removed after the completion of the reaction.

The reaction temperature of the esterification reaction is, for example, 6
The range is from 0 ° C to 200 ° C, preferably from 80 ° C to 180 ° C. The reaction time largely depends on the type of the reactants and the reaction temperature, but is in a range of about 1 hour to 25 hours.

The solvent in the reaction may or may not be used. If the hydroxyl group-containing substance is sufficiently molten at the reaction temperature and the esterifying agent is a liquid, or if it is molten at the reaction temperature or if it dissolves in the resin and does not hinder the reaction, the reaction is carried out without solvent. Should be performed. When a solvent is required, a solvent inert to the reaction is selected. Specifically, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene, diphenyl ether, N, N-dimethylformamide,
Aprotic polar solvents such as N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N, N-dimethyl-2-imidazolidinone, dimethylsulfoxide, sulfolane, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether And the like, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in any combination.

The reaction is carried out at normal pressure, pressure (in an autoclave),
Any of reduced pressure may be used, and the atmosphere of the reaction system is in air,
Any of inert gases such as nitrogen, argon and helium may be used, but preferably under a nitrogen atmosphere.

The esterification ratio of the component (B) is from 10 to 100.
Although it is in the range of mol%, it is possible to control the physical properties of the obtained cured product by arbitrarily changing the esterification ratio. In other words, when it is desired to reduce the water absorption rate while placing emphasis on heat resistance, the esterification rate is suppressed to a low level, and in order to reduce the dielectric properties and the water absorption rate, the esterification rate is increased to improve the cured physical properties. Can control. The esterification rate of the component (B) is preferably 50 to 100 mol%, more preferably 75 to 100 mol%, and still more preferably 9 to 100 mol%.
The range is 0 to 100 mol%. By setting the content in such a range, the balance of various properties required for a laminated board, such as dielectric properties and water absorption, is remarkably improved.

The curing accelerator phosphine oxide derivative, which is the component (C) of the epoxy composition of the present invention, is represented by the following general formula (1).

[0028]

Embedded image

In the formula, R _{1 to} R ₆ may be the same or different.
Specific examples of R _{1 to} R ₆ include, for example, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group,
Examples include alkyl groups such as n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-octyl group and cyclohexyl group, and aryl groups such as phenyl group and toluyl group. And an ethyl group is preferred.

The phosphine derivative is GNKoian et, al Jo
urnal of General Chemistry of The USSR, 55, 1453 (19
As described in (85), it can be synthesized by reacting phosphorus oxytrichloride with three molecules of iminotrisaminophosphorane. Further, if purification is necessary, it can be purified by a commonly used method such as column chromatography, distillation and recrystallization. The phosphine oxide derivative thus obtained is usually a solid.

In the epoxy resin composition of the present invention, the amount of the phosphine oxide derivative (C) used as a curing accelerator is determined by weight based on the total epoxy resin composition (resin component: the sum of the epoxy resin and the curing agent). 0.001 to 25%
(G / 100 g), preferably 0.01 to 15
%, More preferably in the range of 0.1 to 5%.
Compared with conventional imidazoles and phosphines, this curing accelerator not only increases the curing speed, but also promotes the esterification reaction between the secondary OH generated by opening the epoxy ring and the acyl group. It is. Therefore, a cured product having excellent mechanical properties, flexibility, water resistance, and dielectric properties can be obtained.

When a conventional curing accelerator, for example, imidazoles, phosphines, tertiary amines, diazabicyclos, etc., is used, the use of a curing agent having an increased esterification rate does not sufficiently increase the crosslink density. It was difficult to obtain good curing properties. In contrast, in the present invention,
Since a phosphine oxide derivative having a specific structure is used as a curing accelerator, curing proceeds sufficiently even if the esterification ratio of the component (B) is increased, and good characteristics are obtained. As described above, the esterification ratio of the component (B) is preferably 50%.
-100 mol%, more preferably 75-100 mol%,
Even more preferably, the content is in the range of 90 to 100 mol%, but according to the present invention, the curing reaction sufficiently proceeds even with the use of the component (B) having a high esterification rate, and good characteristics are obtained. be able to.

In the epoxy resin cured product of the present invention, the fact that the epoxy group and the ester group efficiently react is as follows.
It is supported by the physical properties of the cured product, but is also proved by the very low solvent extraction rate of the cured product. The cured product of the resin composition according to the present invention preferably has an extraction content of 10 wt% or less when extracted with refluxing acetone for 2 hours. By doing so, various characteristics required for the laminate are improved.

In the epoxy resin composition of the present invention,
Other generally used curing accelerators other than the phosphoxide derivative, such as imidazoles such as 2-ethyl-4-methylimidazole, phosphines such as triphenylphosphine, and tertiary amines such as triethylamine;
1,8-diazabicyclo (5,4,0) undecene-7
And the like may be used in combination with the phosphoxide derivative as long as the characteristics of the present invention are not lost. The content of the phosphoxide derivative with respect to the entire curing accelerator is preferably 50 mol% or more, more preferably 80 mol% or more, and most preferably 100 mol%.

The cured product of the resin composition according to the present invention is characterized in that the moisture absorption is greatly reduced as compared with the epoxy-phenol cured product, and that the resin composition has excellent flexibility due to the effect of having an ester group. No. And
A cured product is formed in a form in which a hydroxyl group is esterified with respect to an epoxy-phenol cured product in which a hydroxyl group is generated in a structure after curing, so that dielectric properties and the like are improved.

The mixing ratio of the epoxy resin and the curing agent is such that the ester group or the total of the ester group and the hydroxyl group per 1 equivalent of the epoxy group, that is, 0.5 to 1.5 equivalents, preferably 0 to 1.5 equivalents of the active group to the epoxy group. It is in the range of 0.7 to 1.3 equivalents, and it is more preferable to adjust the equivalent ratio to obtain the optimum cured physical properties. In addition, the epoxy resin and the curing agent may be used alone one by one,
A plurality may be used in combination.

The laminate according to the present invention may have a form in which a copper foil or a wiring layer is formed on at least one surface.
The production of the copper-clad laminate can be performed according to a known method. For example, a resin varnish is prepared by dissolving the resin composition of the present invention in an organic solvent. The resin varnish is impregnated into a base material, heat-treated to form a prepreg, and then the prepreg and a copper foil are laminated, heated and pressed to form a copper-clad laminate. Specific examples of this organic solvent include methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, toluene, aromatic hydrocarbons such as xylene, cellosolve, cellosolves such as butyl cellosolve,
Carbitol, carbitols such as butyl carbitol, ethyl acetate, butyl acetate, cellosolve acetate,
There are acetates such as butyl cellosolve acetate, and these can be used alone or in combination of two or more.

A filler may be added to the epoxy composition of the present invention, if necessary. Examples of the filler include an organic filler and an inorganic filler. Specific examples of the organic filler include a powder epoxy resin (for example, TEPI).
C), a melamine resin, a benzoguanamine resin, a urea resin, a crosslinked acrylic polymer, and the like. Specific examples of the inorganic filler include magnesium oxide, calcium carbonate, zirconium silicate, zirconium oxide, calcium silicate, calcium hydroxide, and silica. And the like.
Among them, calcium carbonate is particularly preferable because the surface can be easily roughened when used as an insulating sheet and the adhesive strength to a conductor can be increased.

A rubber component and various additives may be added to the epoxy composition of the present invention, if necessary. Specific examples of the rubber component include polybutadiene rubber (for example, R-45HT manufactured by Idemitsu Kosan Co., Ltd.). Etc.), CTBN (eg, 1300-X31 manufactured by Ube Industries), CTBN-modified epoxy resin (eg, SR3542 manufactured by Mitsui Chemicals, YR102 manufactured by Toto Kasei), urethane-modified, maleated, epoxy-modified, (meth) acryloyl-modified, etc. Of various polybutadiene derivatives (for example, epoxy-modified Idemitsu Kosan R
-45EPI). Further, as various additives, fillers such as barium sulfate, silicon sulfide, talc, clay, bentonite, kaolin, glass fiber, carbon fiber, mica, asbestos, thixotropic agents such as Aerosil, phthalocyanine, phthalocyanine green, and phthalocyanine Coloring pigments such as blue, titanium oxide and carbon black, flame retardants, flame retardant aids, defoamers, adhesion promoters,
Leveling agents and the like.

[0040]

EXAMPLES The present invention will be described more specifically with reference to Synthesis Examples, Examples and Comparative Examples of the present invention, but the present invention is not limited to these Examples.

Curing Agent Synthesis Example 1 A phenol novolak resin (PS) was placed in a 3 L glass reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser.
321 g (3 mol with respect to OH) of M-4261 (OH equivalent 107 g / eq, manufactured by Gunei Chemical Co., Ltd.) was added, and the internal temperature was raised to 125 ° C. While stirring at the same temperature, 464 g (3.3 mol) of benzoic acid chloride was added dropwise over 4 hours. Thereafter, the reaction was carried out for 2 hours while maintaining the temperature at 125 ° C., and the temperature was further raised to 150 ° C.
Stirred for hours. Hydrochloric acid by-produced by the reaction was promptly distilled out of the system by a nitrogen stream and neutralized with an alkali trap.

The resin obtained here was treated with toluene 2500
g, washed with a 5% aqueous sodium hydroxide solution and separated. After that, the organic layer is washed with hot water at 60 to 70 ° C. until the organic layer becomes neutral.
The solvent was distilled off under the condition of mHg to obtain 750 g of a resin in which hydroxyl groups were completely benzoylated. Melt viscosity of this resin (IC
480 mP at 125 ° C)
a · S, 130 mPa · S at 150 ° C., and hydroxyl equivalent was 3000 g / eq (not detected).

Curing Agent Synthesis Example 2 In Synthesis Example 1, a phenol aralkyl resin (Mirex XLC-4L, OH equivalent 1
507 g (69 g / eq, Mitsui Chemical)
mol)), except that 783 g of the target resin was obtained in the same manner as in Synthesis Example 1. The melt viscosity of this resin is 12
520 mPa · S at 5 ° C, 150 mPa · S at 150 ° C
And the hydroxyl equivalent is 1780 g / eq (not detected)
Met.

Curing Agent Synthesis Example 3 A phenol aralkyl resin (trade name:) was placed in a glass container equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser.
Millex XLC-4L, 507 g (3 mol) of hydroxyl equivalent 169 g / eq: manufactured by Mitsui Chemicals, Inc. were charged, and the internal temperature was raised to 125 ° C. While maintaining the internal temperature at the same temperature, 336.9 g (3.3 mol) of acetic anhydride was added dropwise over 2 hours while stirring. Thereafter, the reaction was carried out for 2 hours while maintaining the temperature at 125 ° C., and the temperature was further raised to 140 ° C. 140-1
After aging at 50 ° C. for 2 hours, excess acetic anhydride and by-produced acetic acid were distilled off under reduced pressure at a maximum of 150 ° C./10 mmHg.

The resin obtained here was mixed with toluene 1400
g and washed with hot water at 60 to 70 ° C. until the wastewater becomes neutral.
The residue was distilled under the condition of g to obtain 609 g of a resin in which hydroxyl groups were completely acetylated.

The melt viscosity of this resin (according to the ICI cone type melt viscosity type; the same applies hereinafter) is 3.4 poise at 100 ° C.
1.0 poise at 125 ° C., 0.5 poise at 150 ° C., and the hydroxyl equivalent is 3000 g / eq or more (not detectable)
Met.

Example 1, Comparative Examples 1-3 Epoxidized ortho-cresol novolak resin (EOC
N-102S, manufactured by Nippon Kayaku, epoxy equivalent 195g / e
q) 49.3 g, 50.7 g of the benzoylated phenol novolak resin obtained in Synthesis Example 1 as a curing agent, and PZO (R _{1 in the} aforementioned general formula (1)) as a curing catalyst.
To R ₆ : methyl group) 2.0 g of methyl ethyl ketone 67
g to prepare a varnish. 14 of the varnish obtained
The gel time at 0 ° C. was 8 minutes. Apply this varnish to a glass substrate (100 μm, E glass cloth, manufactured by Nitto Bo)
And dried at 140 ° C. for 5 minutes to obtain a prepreg. The obtained prepreg was tack-free and excellent in workability. Stack 10 prepregs, 18 on each side
電解 μm thick electrolytic copper foil (made by Mitsui Kinzoku)
Lamination was performed at a molding pressure of 2.45 MPa for 2 hours to obtain a double-sided copper-clad laminate having a resin content of 50% and a thickness of 1.2 mm.

The dielectric constant, dielectric loss tangent, solder heat resistance, moisture absorption, copper foil peel strength and delamination strength of the obtained copper clad laminate were measured in accordance with JIS C6481. The dielectric properties were measured using a TR-10C dielectric loss measuring instrument (manufactured by Ando Electric).

The solder heat resistance was determined by treating a test piece in a steam bath at 121 ° C. and a pressure of 2.0 atm for 3 hours, and then immersing it in 260 ° C. solder for 20 seconds (C-3 / 121/100).
The appearance was checked for abnormalities (○: no abnormalities ×: abnormalities).

The flame retardancy test was evaluated by the vertical method according to the UL-94 standard. The glass transition temperature (Tg) is T
It was determined from the inflection point of thermal expansion by the MA method (thermomechanical analysis). Table 1 shows the results together with comparative examples in which the curing agent and the catalyst were changed.

The moldability was evaluated by the presence or absence of outflow of the molten resin at the time of molding (流出: no outflow Δ: slightly outflow ×: outflow) Also, the composition of the resin composition was changed as shown in Table 1. Other than using triphenylphosphine as a curing accelerator,
Comparative Examples 1 to 3 were performed in the same manner as described above.

Table 1 shows the results of evaluating various characteristics.

[0053]

[Table 1]

(Note) TPP: triphenylphosphine In Example 1, it was confirmed that the dielectric properties, heat resistance, peel strength, water absorption and moldability were excellent. In addition, it was confirmed that drilling workability of the laminate was also good.

On the other hand, in the case of the comparative example, sufficient characteristics could not be obtained. In Comparative Example 3, no cured product was obtained, and thus no evaluation could be performed.

Examples 2 to 8 Examples 2 to 8 were carried out in the same manner as in Example 1 except that the types and proportions of the epoxy resin and the curing agent were changed. Table 2 shows the results of evaluating various characteristics.

[0057]

[Table 2] (Note) VG3101: glycidylated product of 1- [α-methyl-α- (4-hydroxyphenyl) ethyl] -4- [α, α-bis (4-hydroxyphenyl) ethyl] benzene (EEW 210 g / Mitsui Chemicals) eq) Epoxy resin 1: glycidylated p-octylphenol novolak (EEW390 g / e, manufactured by Mitsui Chemicals, Inc.)
q) Epicron 153: tetrabromobisphenol A diglycidyl ether (EEW 400 g, manufactured by Dainippon Ink)
AO-30: 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane (OH equivalent 192 g / eq)

Reference Example Orthocresol novolak type epoxy resin (trade name: EOCN-102S, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 210 g / eq) as an epoxy resin, and acetylated phenol of Synthesis Example 3 of a curing agent as a curing agent The aralkyl resin (ester equivalent: 211 g / eq = calculated value) was sufficiently melt-kneaded at 80 ° C. in a molar ratio of epoxy group / functional group (hydroxyl group + ester group) = 1/1 to obtain a uniform resin mixture.

In the resin mixture, R represented by the general formula (1)
0.0055 mol of a phosphine oxide derivative (PZO) in which all of _{1 to} R ₆ are methyl groups was added and kneaded at 50 ° C. for 1 minute to obtain a resin composition.

Using the molding material thus obtained, 150
° C → 185 ° C / 5min, 185 ° C / 5min, 150
After obtaining a cured product under the condition of kg / cm ² , 185 ° C./8
After-curing was performed under the condition of Hr (nitrogen atmosphere) to sufficiently advance the curing.

After curing, a small crusher (sample mill, SK
-M10 type, manufactured by Kyoritsu Riko Co., Ltd.). 30 g of the pulverized powder was extracted with 300 g of acetone using a Soxhlet extractor for 2 hours. The extraction rate obtained by drying up the extract was 0.15% (N
O. 1).

On the other hand, except that 0.015 mol of triphenylphosphine was added instead of PZO as a curing accelerator, NO. NO. Two samples were made. However, NO. Sample No. 2 had poor curing, and the acetone extraction rate was 100%.

[0063]

[Table 3] According to the present invention as described above, heat resistance, adhesiveness,
A laminate having the characteristics of an epoxy resin having excellent dimensional stability, chemical resistance, and the like, and having excellent dielectric constant, dielectric loss tangent, moldability, and workability can be obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Terufumi Suzuki 3 Chigusa Kaigan, Ichihara City, Chiba Prefecture In-house (72) Inventor Tatsunori Urakami 580-32 Nagaura Sodegaura City, Chiba Prefecture Mitsui Chemicals, Inc. 72) Inventor Nao Maeda 580-32 Nagaura, Sodegaura-shi, Chiba F-term in Mitsui Chemicals Co., Ltd. JA11

Claims (6)

[Claims] 1. A bifunctional or more functional epoxy compound or epoxy resin (A) and a curing agent having a hydroxyl group of 10 to 1
In an epoxy resin composition containing a phenolic compound or a phenolic resin (B) having a functionality of at least 00 mol% esterified with an acyl group, and a curing accelerator (C), the curing accelerator (C ) Is represented by the following general formula (1): (Wherein, R _{1 to} R ₆ may be the same or different and represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group) An epoxy resin composition for a laminate, comprising a phosphoxide derivative represented by the formula: 2. An epoxy resin having an epoxy equivalent of 17
The epoxy resin composition for a laminate according to claim 1, wherein the amount is 0 to 1000 g / eq. (3) 100 parts by weight of the component (A)
The epoxy resin composition for a laminate according to claim 1 or 2, wherein the component (B) is contained in a proportion of 2 to 150 parts by weight. 4. The laminated board according to claim 1, wherein the component (B) is a novolak resin substituted with an alkyl group having 1 to 10 carbon atoms or a resin containing an alicyclic skeleton. Epoxy resin composition. 5. A prepreg obtained by impregnating a substrate with the resin composition for a laminate according to any one of claims 1 to 4. 6. A laminate, comprising two or more prepregs according to claim 5 stacked and heated and pressed.