JPH08311142A - Phenol resin composition and curing agent for epoxy resin - Google Patents

Abstract

(57) 【Abstract】 PROBLEM TO BE SOLVED: Epoxy resin curing agent composition capable of giving a cured product excellent in solvent solubility and compounding stability, flame retardancy, heat resistance and moisture resistance, and solubility in a solvent. And a phenol resin composition having excellent adhesion to metals and glass. A mixture or condensate of a phenol, a compound having a triazine ring and an aldehyde, wherein the mixture or the condensate does not substantially contain unreacted aldehydes and methylol groups, and methyl ethyl ketone and the mixture or The present invention relates to a phenol resin composition which dissolves in methyl ethyl ketone in a weight ratio of 80:20 to 20:80 with a condensate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a phenol resin composition, and in particular, it can provide a cured product having excellent compounding stability, flame retardancy, heat resistance and moisture resistance.
Suitable for various applications using epoxy resin such as encapsulation, lamination and paints, especially suitable as epoxy resin curing agent for glass epoxy laminates and IC encapsulation materials, and also excellent in solvent solubility and metal adhesion, so it is suitable for paint applications such as resists. The present invention relates to a coating resin composition used and a phenol resin composition suitable as a curable phenol resin composition used for friction materials.

[0002]

2. Description of the Related Art Epoxy resins are widely used mainly in electric and electronic material parts because of their excellent electric characteristics.

These electric and electronic material parts are required to have high flame retardancy as represented by a glass epoxy laminated plate and an IC encapsulant, but the epoxy resin alone cannot provide a sufficient effect. Currently, many halogen-based flame retardants are used together.

However, in recent years, the toxicity of organic halogen substances such as dioxin has become a serious problem, and the long-term reliability of halogen in an IC package is adversely affected. However, there is a strong demand for flame retardants or other flame retardant formulations that use other compounds that can substitute for halogen.

Therefore, for example, a method of adding a flame retardant such as a phosphorus compound has been devised. Although this method improves the flame retardancy, it is a basic resin of heat resistance and moisture resistance. It has the drawback of impairing the physical properties.

On the other hand, JP-A-57-195119 discloses a phenol composition modified with amines as an epoxy resin curing agent, and JP-A-59-13.
Japanese Patent Publication No. 768 discloses a triazine derivative using a polyhydric phenol.

However, when these compounds are used as curing agents,
Since the former is originally intended for curing at low to normal temperature, the compounding stability with the epoxy resin is extremely poor, the flame retardant effect is hardly seen, and the above-mentioned problems cannot be solved.

In the latter case, although the flame retardant effect is slightly observed, since it is originally intended to impart flexibility, it does not have sufficient strength and heat resistance, and the above problem is also solved. Not something to do.

On the other hand, Japanese Patent Publication No. 40-551 and Japanese Patent Publication No. 64-79253 disclose resin compositions comprising phenols and melamine.
-87122 discloses a method in which benzoguanamine as an epoxy resin curing agent is heated and dissolved in a novolak resin in advance.

However, the composition of the former Japanese Patent Publication No. 40-551 is poor in practical use because it is an intermediate composition of the reaction containing a large amount of unreacted phenol, melamine, and formaldehyde. When the above composition is used as an epoxy curing agent, flame retardancy, heat resistance and moisture resistance are not sufficient. Furthermore, since neither composition has a poor solubility in MEK or the like, it cannot be used for a laminated plate to be used after being impregnated.

Also in the latter Japanese Patent Laid-Open No. 58-87122, the heat resistance, moisture resistance and flame retardancy of the epoxy cured product are not sufficient due to non-uniform curing, and when it is dissolved in a solvent such as methyl ethyl ketone (hereinafter referred to as MEK). Benzoguanamine precipitates immediately and cannot be used for laminated plate applications and the like.

Further, a phenolic resin has been conventionally used as a binder of a friction material, but has a high friction coefficient,
A friction material having high wear resistance has been demanded, and therefore, a method of pulverizing and mixing melamine with a novolac type phenol resin has been adopted. However, in this method, there is a problem such as deterioration of heat resistance.

[0013]

DISCLOSURE OF THE INVENTION The present invention, when used as an epoxy resin curing agent, can provide a cured product having excellent compounding stability, flame retardancy, heat resistance and moisture resistance, Flame retardance is improved without using, and various applications using epoxy resin such as sealing, lamination, paints,
In particular, it is an object of the present invention to provide a phenol resin composition for coating, which is suitable for glass epoxy laminates and IC encapsulants, and is excellent in solvent solubility and metal adhesion, and therefore suitable for coating applications such as resists.

Another object of the present invention is to provide a curable phenolic resin composition which, when used as a binder for a friction material, has a high coefficient of friction and is capable of imparting high abrasion resistance and excellent heat resistance. To do.

[0015]

Means for Solving the Problems As a result of intensive studies in view of the above circumstances, the present inventors have found that a mixture or cocondensate having a specific composition such as a phenol resin and a compound having a triazine ring solves the above problems. After finding out that, the present invention has been completed.

That is, the present invention comprises a mixture or condensate of a phenol, a compound having a triazine ring and an aldehyde, wherein the mixture or the condensate does not substantially contain unreacted aldehydes and methylol groups, and MEK And 80:20 to 20:80 by weight ratio of the mixture or the condensate.
The present invention relates to a phenol resin composition and a curing agent for an epoxy resin, which are soluble in MEK within the range.

[0017]

The phenols for obtaining the phenol resin composition of the present invention are not particularly limited, and examples thereof include phenol, cresol, xylenol, ethylphenol, butylphenol, nonylphenol and octylphenol. Examples include polyphenols such as alkylphenols, bisphenol A, bisphenol F, bisphenol S, resorcin, and catechol, halogenated phenols, phenylphenols, and aminophenols. In addition, these phenols are not limited to one kind in use, and two or more kinds can be used in combination.

Further, the compound containing a triazine ring for obtaining the phenol resin composition of the present invention is not particularly limited, but is represented by the following general formula (I) and / or general formula (II). It is preferably a compound.

[0019]

Embedded image (In the formula, R1, R2, and R3 are an amino group, an alkyl group,
Represents any of phenyl group, hydroxyl group, hydroxylalkyl group, ether group, ester group, acid group, unsaturated group, cyano group, and halogen atom)

[0020]

[Chemical 4] (In the formula, R 4, R 5, and R 6 are a hydrogen atom, an alkyl group,
A phenyl group, a hydroxyl group, a hydroxylalkyl group, an ester group, an acid group, an unsaturated group, a cyano group, or a halogen atom) In the general formula (I), at least one of R1, R2, and R3 is amino. It is preferably a group.

As the compound represented by the general formula (I),
Specific examples include melamine, guanamine derivatives such as acetoguanamine and benzoguanamine, cyanuric acid, and cyanuric acid derivatives such as methylcyanurate, ethylcyanurate, acetylcyanurate, and cyanuric chloride. Among these, R1, R2, R3
More preferred are guanamine derivatives such as melamine, acetoguanamine, and benzoguanamine, in which any two or three of them are amino groups.

Further, in the general formula (II), at least one of R4, R5 and R6 is preferably a hydrogen atom. Specific examples of the compound represented by the general formula (II) include isocyanuric acid, methyl isocyanurate, ethyl isocyanurate, allyl isocyanurate, 2-hydroxyethyl isocyanurate, 2-carboxyethyl isocyanurate, and chlorinated isocyanuric acid. Isocyanuric acid derivatives and the like. Among these, R
Most preferred is isocyanuric acid in which all of 4, R5 and R6 are hydrogen atoms. Further, cyanuric acid which is a compound represented by the general formula (I) which is a tautomer is also a preferable compound.

These compounds are not limited to one kind in use, and it is possible to use two or more kinds in combination. The aldehydes for obtaining the phenol resin composition of the present invention are not particularly limited, but formaldehyde is preferable from the viewpoint of easy handling. The formaldehyde includes, but is not limited to, formalin, paraformaldehyde and the like as typical sources.

The phenol resin composition of the present invention is characterized in that it does not substantially contain unreacted aldehydes and methylol groups. When it is used as a curing agent for an epoxy resin because it contains substantially no unreacted aldehydes and methylol groups, it has the effect of significantly improving the compounding stability with the epoxy resin.

The unreacted monofunctional phenolic monomer contained in the phenolic resin composition of the present invention is preferably 3% by weight or less. By adjusting the content of the unreacted monofunctional phenol monomer to 3% or less, the compounding stability with the epoxy resin is improved, and the heat resistance and moisture resistance of the obtained epoxy resin cured product are improved.

The unreacted monofunctional phenolic monomer as used herein means a phenolic monomer containing only one phenolic hydroxyl group capable of reacting with an epoxy group in one molecule.

The above-mentioned phenol resin composition is M
It is characterized in that it dissolves in MEK in the range of 80:20 to 20:80 in weight ratio with EK. By dissolving in MEK in the above range, it can be applied to a wide range of impregnation lamination molding or coating applications. When it is used as an epoxy resin curing agent, a uniform cured product can be obtained, and heat resistance, moisture resistance, and metal adhesion can be extremely improved.

Next, a typical production method for obtaining the phenol resin composition of the present invention will be described below. First, the above-mentioned phenols, aldehydes and compounds having a triazine ring are added to the system at a pH of 4 to 10, preferably pH.
The reaction is carried out under the conditions of 5-9. At this time, the catalyst may or may not be used. The type of catalyst is not particularly limited, but it is preferable to use a basic catalyst because many compounds containing a triazine ring are easily dissolved in a basic solution. Examples of the basic catalyst include hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide and barium hydroxide, and oxides thereof, ammonia, primary to tertiary amines, hexamethylenetetramine. , Sodium carbonate and the like. Of these basic catalysts, when used as a curing agent for an epoxy resin for electric / electronic materials, it is not preferable that an inorganic substance such as a metal remains as a catalyst residue. Therefore, it is preferable to use amines.

The reaction order of each raw material is not particularly limited, and even if a compound having a triazine ring is added after first reacting a phenol and an aldehyde, a compound having a triazine ring is reacted with an aldehyde. The phenols may be added afterwards, or all the raw materials may be added at the same time and reacted. At this time, the molar ratio of the aldehyde to the phenol and the compound having a triazine ring is not particularly limited, but is preferably 1: 0.2 to 0.9, and more preferably 1: 0.4 to 0.8. preferable. The weight ratio of the compound having a triazine ring to the phenols is not particularly limited, but is preferably 10 to 98:90 to 2, and more preferably 30 to 95:70 to 5. When the weight ratio of the phenols is 10% by weight or less, it becomes difficult to make it into a resin, and when it is 98% by weight or more, a sufficient flame retarding effect cannot be obtained, which is not preferable.

From the viewpoint of reaction control, the reaction can be carried out in the presence of various solvents. At this time, the solvent is not particularly limited, and examples thereof include acetone, MEK, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, N, N-dimethylformamide, methanol, ethanol and the like.
These solvents can be used alone or as a mixed solvent of two or more kinds as appropriate.

Next, if necessary, neutralization and washing with water remove impurities such as salts. However, this step is not necessary when amines are used as the catalyst. After completion of the reaction, unreacted aldehydes, phenols, solvents and the like are removed by ordinary methods such as atmospheric distillation and vacuum distillation. At this time, in order to obtain a resin composition which is substantially free of unreacted aldehydes and methylol groups, which is a characteristic of the resin composition of the present invention,
It requires heat treatment at 0 ° C or higher. It is difficult to substantially eliminate the methylol group by heat treatment at 120 ° C. or lower. Further, if the temperature is 120 ° C. or higher, the methylol group can be eliminated by taking sufficient time, but it is preferable to perform heat treatment at a higher temperature, preferably 150 ° C. or higher for efficient elimination. . At this time, at high temperature, it is preferable to distill with heating according to the usual method for obtaining a novolac resin. Further, at this time, it is preferable that the unreacted monofunctional phenolic monomers are simultaneously adjusted to 3% by weight or less.

The phenol resin composition of the present invention obtained as described above can be used as a curing agent for epoxy resins. Examples of the epoxy resin in this case include bisphenol A type epoxy resin, polyphenol type epoxy resin, aliphatic epoxy resin, aromatic ester type epoxy resin, cycloaliphatic ester type epoxy resin, aliphatic ester type epoxy resin, ether ester type. Examples thereof include epoxy resins, non-glycidyl epoxy resins such as epoxidized soybean oil, and halogen-substituted products thereof such as bromine and chlorine. There is no problem even if these epoxy resins are used alone or as a mixture of several kinds. The solvent used for the epoxy resin composition at this time is not particularly limited, and the various solvents described above can be used as necessary. Further, various additives, flame retardants, fillers and the like can be appropriately blended if necessary.

Further, the phenol resin composition of the present invention can be used as a resin composition for coating a resist or the like.
The solvent in this case is not particularly limited,
For example, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate,
Examples thereof include cyclohexanone, dimethyl sulfoxide, dimethylformamide, dioxolane, tetrahydrofuran, propylene glycol monomethyl ether acetate, ethyl lactate and the like. These solvents can be used alone or as a mixed solvent of two or more kinds as appropriate.

A hardener may be added to the phenol resin composition of the present invention to prepare a curable phenol resin composition which can be used as a friction material. The curing agent is not particularly limited, and examples thereof include substances that generate formaldehyde by heating, such as hexamethylenetetramine and paraformaldehyde. If desired, a curing accelerator may be used in combination with these curing agents. As the curing accelerator, various ones generally used for curing an epoxy compound can be used. Examples thereof include imidazole and its derivatives, phosphine compounds, amines, and BF3 amine compounds.

When it is used as a binder for a friction material, it is produced by heat-curing the phenol resin composition in combination with a fiber base material and a curing agent according to a conventional method. In this case, as the fiber base material, for example, glass fiber, ceramic fiber, asbestos fiber, carbon fiber, inorganic fiber such as stainless fiber, cotton,
Examples include natural fibers such as hemp, and synthetic organic fibers such as polyester and polyamide. These fibers may be used alone or in combination of two or more. Among these, glass fiber is mainly used in consideration of performance, price and the like. The shape of the fiber base material is not limited at all, and short fibers, long fibers,
Any material such as yarn, mat, sheet, etc. may be used.
Further, as the curing agent, those described above can be used.

The conditions for heat-curing the curable phenol resin composition are not particularly limited, and it is possible to cure under ordinary conditions for curing a phenol resin.
If the temperature is equal to or higher than the temperature at which the resin component softens, there is no problem and usually 1
It is performed at a temperature of 20 ° C. or higher and 200 ° C. or lower. It is preferable to carry out in the range of 130 to 180 ° C. from the viewpoint that molding defects are unlikely to occur. In order to obtain a friction material having further excellent heat resistance, it is preferable to bake after molding.

Further, when the curable phenol resin composition of the present invention is used as a friction material, a filler, an additive and the like can be further added. As the filler and the additive,
Although those generally known can be used, for example, silica, barium sulfate, calcium carbonate, silicon carbide, cashew oil polymer, molybdenum disulfide, aluminum hydroxide,
Examples thereof include talc, clay, graphite, graphite, rubber particles, aluminum powder, copper powder and brass powder. These fillers and the like may be used alone or in combination of two or more. The amount used should also be adjusted depending on the application and required performance.

The effects of the present invention will be described in detail below with reference to examples.

[0039]

【Example】

Example 1 To 94 parts of phenol and 9.4 parts of benzoguanamine, 41.
51 parts of 5% formalin and 0.8 parts of 25% aqueous ammonia solution were added, and the temperature was gradually raised to 100 ° C while paying attention to heat generation. After reacting at 100 ° C for 5 hours, the temperature was raised to 180 ° C over 2 hours while removing water under normal pressure, and then unreacted phenol was removed under reduced pressure to obtain a softening point of 107 ° C. A phenol resin composition was obtained.

Hereinafter, this composition is abbreviated as "N1". The weight ratio of the phenols to the compound having a triazine ring, the amount of unreacted formaldehyde, the presence or absence of a methylol group, the amount of unreacted phenol monomer and the MEK solubility in the obtained composition were determined as follows. <Weight ratio of phenol to triazine ring-containing compound (benzoguanamine)> 180 ° C, the phenol content in the effluent removed outside the reaction system under reduced pressure was calculated by gas chromatography, and the composition was obtained by subtracting from the phenol part charged. It was defined as the amount of phenol present. Benzoguanamine was included in the composition as it was charged.
The ratio of both was defined as the abundance ratio. Column: 30% Celite 545 Carnauba wax 2m x
3 mmΦ Column temperature: 170 ° C. Inlet temperature: 230 ° C. Detector: FID Carrier gas: N2 gas 1.0 kg / cm2 Measuring method: internal standard method <Unreacted formaldehyde amount> About 5 g of a composition finely pulverized in 50 g of distilled water In addition, it was kept at room temperature for 24 hours.
Set to pH meter, add N / 10 hydrochloric acid aqueous solution to obtain pH =
It was adjusted to 4.0. 7% adjusted to pH = 4.0
50 ml of a hydroxylamine aqueous solution was added, and the mixture was sealed with an aluminum foil or the like and left for 30 minutes. Then set it on the pH meter,
Titrate with 1N sodium hydroxide solution until neutralization to pH = 4.0. The amount of free formaldehyde was determined by the following formula.

[0041] <Presence or absence of methylol group> The methylol group present in the resin composition was measured using C13-NMR. Apparatus: JEOL Ltd. GSX270 Proton: 270MHZ Measurement solvent: Deuterated methanol or deuterated acetone Reference substance: Tetramethylsilane Measurement conditions Pulse condition: 45 ° × 4000 times Pulse interval: 2 seconds Appeared in 60-70 ppm of the obtained chart , A peak that can be clearly distinguished from noise was used for the determination. The case where a peak was observed was defined as “Yes”, and the case where it was not observed was defined as “No”. <Amount of Unreacted Phenol Monomer> The content of phenol monomer in the composition was measured under the same measurement conditions as in the gas chromatography described above. <MEK solubility> Resin composition and MEK in a glass flask
Were added at the weight ratios of 30/70, 50/50, and 70/30, respectively, and heated at 70 to 80 ° C. for 4 hours. The obtained solution was cooled and stored at 10 ° C. for 7 days, and then the dissolved state was examined. A transparent uniform solution without any precipitate was evaluated as ◯, and a case where a precipitate or turbidity was observed was evaluated as x.

The amounts of each component thus obtained and the results of solubility are summarized in Table 1. Example 2 To 94 parts of phenol, 29 parts of 41.5% formalin and 0.47 part of triethylamine were added and reacted at 80 ° C. for 3 hours. After adding 19 parts of melamine and further reacting for 1 hour, the temperature was raised to 120 ° C. while removing water under normal pressure, and the reaction was continued for 2 hours while maintaining the temperature. While removing water under normal pressure, the temperature was raised to 180 ° C over 2 hours,
Next, unreacted phenol was removed under reduced pressure to obtain a phenol resin composition having a softening point of 136 ° C. The weight ratio of phenol and melamine, the amount of unreacted formaldehyde, the presence or absence of methylol groups, the amount of unreacted phenol monomer and the MEK solubility were determined, and the results are summarized in Table 1.

Hereinafter, this composition is abbreviated as "N2". Example 3 36 parts of 41.5% formalin and 0.47 part of triethylamine were added to 94 parts of phenol, and the mixture was reacted at 80 ° C. for 3 hours. Next, 14 parts of melamine and 14 parts of benzoguanamine were added and reacted for another 2 hours. Example 2 below
A phenol resin composition having a softening point of 130 ° C. was obtained by reacting in the same manner as above. In the same manner as in Example 1, the weight ratio of phenol to melamine and benzoguanamine, the amount of unreacted formaldehyde, the presence or absence of a methylol group, the amount of unreacted phenol monomer and MEK solubility were determined, and the results are shown in Table 1.
Are summarized in.

Hereinafter, this composition is abbreviated as "N3". Example 4 Phenol 94 parts, Benzoguanamine 70 parts, 41.5
% Formalin 47 parts and triethylamine 0.35 part were added and reacted at 80 ° C. for 4 hours. Then, while removing water under normal pressure, the temperature was raised to 120 ° C., and the temperature was kept 2
Allowed to react for hours. 180 ℃ while removing water under normal pressure
The temperature was raised to 2 hours, then unreacted phenol was removed under reduced pressure to obtain a phenol resin composition having a softening point of 132 ° C. The weight ratio of phenol and benzoguanamine, the amount of unreacted formaldehyde, the presence or absence of methylol groups, the amount of unreacted phenol monomer, and the MEK solubility were determined, and the results are summarized in Table 1.

Hereinafter, this composition is abbreviated as "N4". Comparative Example 1 94 parts of phenol and 340 parts of metaxylenediamine were charged into a reactor equipped with a stirrer and a thermometer, and the contents were heated to 90 ° C. under a nitrogen gas stream. After the temperature was raised, 146 parts of 37% formalin was added to the mixture over 2 hours. Then, the mixture is reacted for 2 hours while maintaining the temperature at 90 to 95 ° C., and then the water produced is distilled off while gradually raising the temperature to 180 ° C. to obtain the composition described in JP-A-57-195119. I got a thing. The weight ratio of phenol to metaxylenediamine, the amount of unreacted formaldehyde, the presence or absence of methylol groups, the amount of unreacted phenol monomer and the MEK solubility were determined, and the results are summarized in Table 1.

Hereinafter, this composition is abbreviated as "N5". Comparative Example 2 390 parts of hexamethoxymethylmelamine and 2052 parts of bisphenol A were heated to 138 ° C., and methanol was generated at that temperature. The temperature was raised to 177 ° C over 90 minutes and held at 177 ° C until the methanol evolution ceased,
A composition described in JP-A-59-13768 was obtained.

This composition and metaxylene diamine 340
Parts were charged into a reactor equipped with a stirrer and a thermometer, and the contents were heated to 90 ° C. under a nitrogen gas stream. After the temperature was raised, 37% formalin 146 was added to the mixture over 2 hours. Then, the mixture was reacted for 2 hours while maintaining the temperature at 90 to 95 ° C., and then the produced water was distilled off while gradually raising the temperature to 180 ° C. to obtain a transparent pale yellow product. The amount of unreacted formaldehyde, the presence or absence of methylol groups, the amount of unreacted phenol monomer and the MEK solubility were determined, and the results are summarized in Table 1.

Hereinafter, this composition is abbreviated as "N6". Comparative Example 3 Phenol 470 parts, 37% formalin 162 parts 1N
Hydrochloric acid was added to adjust the pH to 1.0. The temperature was raised on an oil bath, the mixture was reacted at reflux temperature for 2 hours, and then cooled to 50 ° C. After adding 44 parts of melamine and 41 parts of 37% formalin, 3
20 parts of 0% trimethylamine aqueous solution was added to adjust the pH to 8.5.
Adjusted to. After raising the temperature again and reacting at the reflux temperature for 3 hours, 470 parts of distilled water was added, and the mixture was stirred at 80 to 85 ° C.
After standing for 30 minutes, the upper aqueous layer was removed by decantation. After performing this washing operation again, the temperature is raised to a temperature of 150 to 160 ° C. and a vacuum degree of 50 to 100 Torr.
Vacuum distillation was carried out for 4 hours under the conditions described in JP-A-64-79.
A composition described in Japanese Patent No. 253 was obtained. The amount of unreacted formaldehyde, the presence or absence of methylol groups, the amount of unreacted phenol monomer and the MEK solubility were determined, and the results are summarized in Table 1.

Hereinafter, this composition is abbreviated as "N7". Example 5 When the unreacted phenol was removed under reduced pressure, the softening point 13 was changed in the same manner as in Example 2 except that the unreacted phenol remained by returning to normal pressure before the removal was completed.
A phenol resin composition at 0 ° C. was obtained. Weight ratio of phenol and melamine, amount of unreacted formaldehyde, presence or absence of methylol group, amount of unreacted phenol monomer and M
The EK solubility was determined and the results are summarized in Table 1.

Hereinafter, this composition is abbreviated as "N8".

[0051]

[Table 1] Examples 6-9 and Comparative Examples 4-8 Epiclon 850 (epoxy resin epoxy equivalent 190
[Dainippon Ink and Chemicals, Inc.]) 100 parts
Compounds N1 to N7 were mixed as curing agents at the ratios shown in Table 2, respectively. At this time, an accelerator was added to the compounds N1 to N7 in advance, N5 was removed and the temperature was maintained at 170 ° C. to melt. Similarly, add the heated epoxy resin, stir well, and pour it into a glass mold with a thickness of 3 mm,
It was heat-cured at 0 ° C. for 2 hours to obtain a cast plate. In Comparative Example 4, the epoxy resin and the curing agent were blended at room temperature. The curing agent of Comparative Example 4 was prepared by the following procedure. First, Phenolite TD-
2131 (phenol novolac softening point 80 ° C [Dainippon Ink and Chemicals Co., Ltd.]) is heated and melted at 130 ° C,
Benzoguanamine was added at the ratio shown in Table 2, and the mixture was stirred for 1 hour as it was to obtain a curing agent described in JP-A-58-87122. In Comparative Example 8, Phenolite TD-2131 was used as a curing agent, and a casting plate was obtained in the same manner as in Examples 6 to 9.

When the physical properties of the cast plate were tested, the results shown in Table 2 were obtained. Further, when a compounding stability test of the epoxy MEK solution was conducted, the results shown in Table 2 were obtained.

[0053]

[Table 2] * 1: Flame-extinguishing test A test piece with a width of 12.7 mm is set upright, exposed to a flame for 10 seconds, and then the time required for self-extinguishing. Also, if the combustion continued for 2 minutes or more, or if it burned up to 5 cm from the lower end, it was designated as "combustion". * 2: Compounding stability test The gelling time (seconds) of the compounded liquid on a 170 ° C hot plate was compounded. Immediately after and after storage for 7 days at 25 ° C., the value of (gelling time after storage) ÷ (gelling time immediately after compounding) was used as a guideline for storage stability.

Examples 10 to 12 and Comparative Example 9 100 parts of the N2, N3 and N8 phenol resin compositions were mixed with 10 parts of hexamethylenetetramine and pulverized to obtain a powdery curable resin composition. To 15 parts of this composition, 55 parts of glass fiber (chopped strand), 5 parts of aramid fiber, 8 parts of cashew oil polymer, graphite 7
Parts, 5 parts of barium sulfate and 5 parts of calcium carbonate were mixed by a mixer to obtain a thermosetting resin composition for friction materials. As Comparative Example 4, a phenol novolac resin was used and a thermosetting resin composition for a friction material was obtained according to the same formulation.

The thermosetting resin compositions for friction materials obtained in Examples 10 to 12 and Comparative Example 9 were put into a mold at 160 ° C. and compression-molded by using a press machine according to a well-known general method. This was processed to obtain a molded product. The one removed from the mold was then heated at 200 ° C. for 2 hours and then baked to obtain a molded product.
This molded product was cut into a predetermined size and subjected to a friction performance test (JIS D-4411) for comparative evaluation. The results are summarized in Table 3.

The unit of wear rate is 10-7 cm / kg.
・ It is m.

[0057]

[Table 3] Application Example 1 and Comparative Application Example 1 As 100 parts of Epicron 850, N as a curing agent
2 and TD-2131 were blended in the proportions shown in Table 4.
At this time, Epicron 850 and the curing agent were used after being dissolved in a mixed solvent of MEK / dimethylformamide = 50/50 in a weight ratio. Then, 2-ethyl 4-methylimidazole (hereinafter referred to as 2
Abbreviated as E4MZ. ) 0.2 parts was added, and the nonvolatile content of the solution was adjusted to 55% with methyl ethyl ketone.
The mixed solutions of Application Example 1 and Comparative Application Example 1 were prepared.

Thereafter, each mixed solution was impregnated in glass cloth and dried at 160 ° C. for 3 minutes to obtain a prepreg. Eight sheets of this prepreg were stacked, 35 μm of copper foil was stacked on both surfaces thereof, and heat and pressure molding was carried out at 170 ° C. and a pressure of 40 kgf / cm 2 for 1 hour to prepare a double-sided copper clad laminate having a thickness of 1.5 mm.

Then, the laminated plate was subjected to an etching treatment to remove the copper foil, and then each physical property test was conducted, and the results shown in Table 4 were obtained. * 1: Temperature rising speed 3 ° C / min * 2: Presure cooker test (PCT) is 120
The test pieces were treated for a predetermined time in steam at ℃.

The solder resistance test was evaluated by dipping in a solder bath at 260 ° C. for 20 seconds after the PCT treatment. The evaluation was carried out by visually judging the appearance of the test piece, especially the presence or absence of a measling.

◯: No abnormality at all Δ: Slight measling occurred ×: Mesling present

[0062]

[Table 4] Example 13 4 parts in 108 parts of m / p cresol (m: p = 60: 40)
51 parts of 1.5% formalin and 0.32 parts of triethylamine were added and reacted at 100 ° C. for 1 hour. After adding 5.4 parts of melamine and further reacting for 2 hours, the temperature was raised to 120 ° C. while removing water under normal pressure, and the reaction was continued for 2 hours while maintaining the temperature. While removing water under normal pressure, the temperature was raised to 180 ° C. over 2 hours, and then unreacted phenol was removed under reduced pressure to obtain a coating cresol resin composition having a softening point of 157 ° C.

The weight ratio of phenol and melamine, the amount of unreacted formaldehyde, the presence or absence of methylol groups, the amount of unreacted phenol monomer and the MEK solubility were determined, and the results are summarized in Table 5. Hereinafter, this composition is referred to as "N9".
Abbreviated.

[0064]

[Table 5] 2,3,4 trihydroxybenzophenone-1,2-naphthoquinonediazide-5 as a quinonediazide compound
-Sulfonic acid triester was blended in a weight ratio of alkali-soluble resin: quinonediazide compound: solvent = 24: 7: 69 using cellosolve acetate as a solvent to obtain a positive photoresist solution.

This solution was spin-coated on a glass substrate.
Coating to a film thickness of 1 μm, and dry at 90 ° C
Prebaking was performed for 30 minutes to form a positive photoresist film. The exposure was performed using an ultra-high pressure mercury lamp. The development was carried out by using a 2.4% aqueous solution of tetramethylammonium hydroxide, immersing it at 25 ° C. for 1 minute with shaking, and then washing with pure water.

The resist had a sensitivity of 23 mJ / cm 2 and a residual film ratio of 99%. Comparative Example 10 To 108 parts of m-cresol, 0.09 wt% of oxalic acid was added, and 80 parts of 37% formalin was charged and reacted at 100 ° C. for 5 hours. The temperature was raised to 200 ° C. and vacuum distillation was performed. An m-cresol novolac resin having a softening point of 162 ° C. was obtained.

Oxalic acid 1.8 against 108 parts of o-cresol
Add 5wt% and charge 88 parts of 37% formalin 100
The reaction was carried out at 0 ° C for 5 hours. The temperature was raised to 200 ° C. and vacuum distillation was performed. An o-cresol novolac resin having a softening point of 138 ° C. was obtained. These m-cresol novolac resins, o-
A mixture of cresol novolac resin in a weight ratio of 1: 1 was used as an alkali-soluble resin.

Using the same photosensitizer and solvent as in Example 13, m cresol novolak: o cresol novolak: photosensitizer: solvent was mixed in a weight ratio of 12: 12: 7: 69. As a result of film formation and development being carried out in exactly the same manner as in Example 1, the sensitivity of the resist was 30 mJ / cm 2 and the residual film ratio was 96%.

[0069]

EFFECTS OF THE INVENTION The phenol resin composition of the present invention, when used as an epoxy resin curing agent, can give a cured product which is excellent in solvent solubility and compounding stability and has good flame retardancy, heat resistance and moisture resistance. Can be used for a wide range of applications such as lamination, sealing, paint, molding,
In particular, it can be used for a glass epoxy laminated plate or an IC sealing material. Further, the phenol resin composition of the present invention has excellent solubility in a solvent and excellent adhesion to a metal, glass, etc., and thus can be used alone as a coating composition for coating applications such as resists. Furthermore, when the phenol resin composition of the present invention is used, a friction material having excellent wear resistance and heat resistance can be obtained.

Claims (11)

[Claims] 1. A mixture or condensate of a phenol, a compound having a triazine ring and an aldehyde, wherein the mixture or the condensate is substantially free of unreacted aldehydes and methylol groups, and methyl ethyl ketone and the mixture. Alternatively, a phenol resin composition which is soluble in methyl ethyl ketone in a weight ratio of 80:20 to 20:80 with a condensate. 2. The composition according to claim 1, wherein the compound having a triazine ring is a compound represented by the general formula (I) and / or a compound represented by the general formula (II). Embedded image (In the formula, R1, R2, and R3 are an amino group, an alkyl group,
Represents any of a phenyl group, a hydroxyl group, a hydroxylalkyl group, an ether group, an ester group, an acid group, an unsaturated group, a cyano group and a halogen atom. (In the formula, R 4, R 5, and R 6 are a hydrogen atom, an alkyl group,
Represents any of a phenyl group, a hydroxyl group, a hydroxylalkyl group, an ester group, an acid group, an unsaturated group, a cyano group, and a halogen atom) 3. The composition according to claim 2, wherein in the general formula (I), at least one of R1, R2 and R3 is an amino group. 4. The composition according to claim 3, wherein in the general formula (I), any two of R1, R2 and R3 are amino groups. 5. The composition according to claim 3, wherein R1, R2 and R3 in the general formula (I) are amino groups. 6. The composition according to any one of claims 2 to 5, wherein R4, R5 and R6 in the general formula (II) are hydrogen. 7. The composition according to claim 1, wherein an unreacted monofunctional phenolic monomer contained in the mixture or the condensate is 3% by weight or less. 8. A method of reacting a phenol, a compound having a triazine ring, and an aldehyde at pH 4 to 10 and then heat-treating at 120 ° C. or higher to substantially remove unreacted aldehydes and methylol groups. A method for producing a phenolic resin composition which is not contained in. 9. A curing agent for an epoxy resin, which comprises the phenol resin composition according to claim 1 as a main component. 10. A resin composition for coating comprising the phenol resin composition according to claim 1 as a main component. 11. A curable phenol resin composition comprising the phenol resin composition according to claim 1 and a curing agent.