JP5366263B2 - Phenol aralkyl resin, epoxy resin composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phenolaralkyl resin, an epoxy resin composition including the same, and cured material thereof having an excellent heat resistance, which can be used for an electric-electronic component insulating material (a high reliability semiconductor seal material and so on) and a laminate (a print wiring board and so on), or various composite materials such as CFRP, adhesives, paints and so on. <P>SOLUTION: This phenolaralkyl resin is obtained by reacting a 4,4'-bis(halogenomethyl)biphenyl represented by general formula (1) (wherein X is a halogen atom) with a phenol compound using an acid catalyst in the absence of a solvent, and has 50 ppm or less of a residual halogen amount. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention is used for insulating materials for electrical and electronic parts including those for highly reliable semiconductor sealing, and for various composite materials including laminated boards (printed wiring boards) and CFRP (carbon fiber reinforced plastics), adhesives, The present invention relates to a phenol aralkyl resin useful for paints and the like, an epoxy resin composition containing the same, and a cured product thereof.

  Phenol aralkyl resin is a compound useful as a semiconductor encapsulant epoxy resin curing agent and epoxy resin raw materials, adhesives, molding materials and paints, and has excellent electrical properties, heat resistance, adhesion and moisture resistance of the cured product. It is widely used in the fields of electrical and electronic parts, structural materials, adhesives, paints, etc. due to its properties (water resistance).

  However, in recent years, especially in the electric and electronic fields, with its development, heat resistance, moisture resistance, adhesion, low viscosity, low dielectric properties, fast curing, flame retardancy for high filler filling, etc. Further improvement of various characteristics such as these is demanded. Further, as a structural material, there is a demand for a material that is lightweight and excellent in mechanical properties for use in aerospace materials, leisure / sports equipment, and the like. In response to these requirements, many proposals have been made for phenolic resins (epoxy resin curing agents) and thermosetting resin compositions containing them. Specifically, Patent Document 1 describes a phenol aralkyl resin obtained by the reaction of bismethoxymethylbiphenyl and phenol, and when the phenol aralkyl resin is used as a curing agent for an epoxy resin, the cured product is flexible. There is a description that good mechanical properties such as can be expected. However, since the phenol aralkyl resin has a large hydroxyl equivalent, a cured product having a high glass transition point, which is expected to have a relatively low crosslinking density, has not been obtained. Patent Document 2 describes a method of reacting an aromatic bishalogenomethyl compound and a phenol compound without a catalyst, and 4,4′-bis (halogenomethyl) biphenyl is exemplified as the aromatic bishalogenomethyl compound. However, there is no description that specifically discloses or suggests the effects of the present invention.

JP-A-8-143648 Japanese Patent Laid-Open No. 6-100657

  The present invention has excellent heat resistance in the cured product, insulating materials for electrical and electronic parts (such as highly reliable semiconductor encapsulating materials), laminates (such as printed wiring boards), and various composite materials including CFRP. It is an object of the present invention to provide a phenol aralkyl resin useful for coatings, adhesives, paints and the like, an epoxy resin composition containing the same, and a cured product thereof.

That is, the present invention
(1) General formula (1)

（Ｘはハロゲン原子を示す。）
で表される４，４’−ビス（ハロゲノメチル）ビフェニルとフェノールとを酸触媒を使用し、無溶媒で反応させることで得られる残留ハロゲン量が５０ｐｐｍ以下であるフェノールアラルキル樹脂、
（２） 一般式（１）

(X represents a halogen atom.)
A phenol aralkyl resin having a residual halogen content of 50 ppm or less obtained by reacting 4,4′-bis (halogenomethyl) biphenyl represented by the formula (I) and phenol without using a solvent;
(2) General formula (1)

（Ｘはハロゲン原子を示す。）
で表される４，４’−ビス（ハロゲノメチル）ビフェニルとフェノールとを酸触媒を使用し、無溶媒で反応させることを特徴とする残留ハロゲン量が５０ｐｐｍ以下であるフェノールアラルキル樹脂の製造方法、
に関する。

(X represents a halogen atom.)
A process for producing a phenol aralkyl resin having a residual halogen content of 50 ppm or less, characterized by reacting 4,4′-bis (halogenomethyl) biphenyl represented by the formula:
About.

  Since the epoxy aralkyl resin of the present invention and the epoxy resin composition containing the phenol aralkyl resin of the present invention have excellent heat resistance in the cured product, insulating materials for electrical and electronic parts (highly reliable semiconductor encapsulating materials, etc.) And it is extremely useful when used for various composite materials such as laminated boards (printed wiring boards, etc.), CFRP, adhesives, paints and the like.

  The phenol aralkyl resin of the present invention can be obtained by reacting 4,4'-bis (halogenomethyl) biphenyl represented by the general formula (1) with a phenol compound.

  Specific examples of 4,4′-bis (halogenomethyl) biphenyl represented by the general formula (1) include 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis. (Bromomethyl) -1,1′-biphenyl, 4,4′-bis (fluoromethyl) -1,1′-biphenyl and the like. Of these, industrially preferred are compounds in which X is a chlorine atom.

  The phenol compound used in the present invention is a compound having at least one phenolic hydroxyl group in an aromatic ring. Specific examples include unsubstituted phenols such as phenol, resorcinol, hydroquinone, o-cresol, m-cresol, p-cresol, ethylphenol, n-propylphenol, isopropylphenol, t-butylphenol, octylphenol, nonylphenol, phenylphenol. , Substituted phenols such as cyclohexylphenol, xylenol, methylpropylphenol, methylbutylphenol, allylphenol and aminophenol, substituted phenols having a halogen atom such as brominated phenol, naphthols such as naphthol and methylnaphthol, biphenol, bisphenol- A, bisphenols such as bisphenol-F, bisphenol-S, thiodiphenol, etc. It is not limited to these as long as they have. In the present invention, among these, phenol, o-cresol, m-cresol or p-cresol is preferable. Moreover, these phenol compounds can be used individually or in mixture of 2 or more types.

  The usage-amount of the phenol compound with respect to the compound of Formula (1) is 1.1-10 mol normally with respect to 1 mol of compounds of Formula (1), Preferably it is 1.5-7.0 mol.

  In the present invention, an acid catalyst is used. Various acid catalysts can be used, but organic or inorganic acids such as sulfuric acid, p-toluenesulfonic acid and oxalic acid, Friedel-Crafts type catalysts such as stannic chloride, zinc chloride and ferric chloride are listed. It is done. Of these, stannic chloride, sulfuric acid, and p-toluenesulfonic acid are preferable. The amount of the acid catalyst used varies depending on the type of the catalyst, but an appropriate amount may be added within a range of 0.0005 to 1% by weight with respect to the compound of the formula (1).

  The reaction temperature is usually 40 to 200 ° C, preferably 50 to 150 ° C. The reaction time is 0.5 to 20 hours, preferably 1 to 15 hours. The reaction may be performed while charging all raw materials at once, or may be performed by sequentially adding 4,4′-bis (halogenomethyl) biphenyl in a state where the phenol compound is kept at a constant temperature in advance. . The reaction is carried out without solvent.

  The hydrochloric acid gas generated during the reaction may be removed from the system by flowing an inert gas such as nitrogen gas, or may be removed under reduced pressure.

  After completion of the reaction, impurities such as hydrogen chloride and acid catalyst generated during the reaction are neutralized and removed by washing with water. Then, the target phenol aralkyl resin can be obtained by recovering the unreacted phenol compound and the solvent. The unreacted phenol compound and the solvent are preferably distilled off under normal pressure or reduced pressure. It is also possible to blow off water vapor and distill it off with water vapor distillation. The temperature for phenol compound distillation recovery is 100 to 180 ° C., and the degree of vacuum is preferably about 0.1 to 25 kPa.

  The amount of halogen remaining in the phenol aralkyl resin of the present invention thus obtained is 50 ppm or less. The amount of residual halogen is derived from the unreacted halogenomethyl compound, and the smaller the residual halogen, the better the reliability of electrical and electronic parts as is known in the art, and the better the heat resistance. It is.

  Hereinafter, the epoxy resin composition of the present invention will be described. Specific examples of the epoxy resin in the epoxy resin composition of the present invention include bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, OH Roxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1, Polycondensates with 1′-biphenyl, 1,4′-bis (chloromethyl) benzene, 1,4′-bis (methoxymethyl) benzene, and their modified products, and halogenated bisphenols such as tetrabromobisphenol A Examples thereof include, but are not limited to, solid or liquid epoxy resins such as glycidyl etherified products derived from alcohols, alicyclic epoxy resins, glycidylamine epoxy resins, glycidyl ester epoxy resins, and the like. These may be used alone or in combination of two or more.

  The curing agent of the present invention comprises the phenol aralkyl resin of the present invention and, if necessary, another curing agent. When other curing agents are used in combination, the proportion of the phenol aralkyl resin of the present invention in the total curing agent is preferably 30% by weight or more, particularly preferably 40% by weight or more.

In the curing agent of the present invention, examples of other curing agents that can be used in combination with the phenol aralkyl resin of the present invention include amine compounds, acid anhydride compounds, amide compounds, and phenol compounds. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride Acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol Terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [1,1′-biphenyl] -4,4′-diol, Idroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxy Benzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl)- 1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1,4′-bis (chloromethyl) benzene, 1,4′-bis (methoxy) Chill) polycondensates and their modified products of benzene, halogenated bisphenols such as tetrabromobisphenol A, imidazole, BF 3 _- amine complex, but such guanidine derivatives, but the invention is not limited to . These may be used alone or in combination of two or more.

  The epoxy resin composition of the present invention contains an epoxy resin and the curing agent of the present invention. In the epoxy resin composition of the present invention, the amount of the curing agent used is preferably 0.5 to 1.5 equivalents, particularly preferably 0.6 to 1.2 equivalents, based on 1 equivalent of the epoxy group of the epoxy resin. When less than 0.5 equivalent or more than 1.5 equivalent with respect to 1 equivalent of an epoxy group, curing may be incomplete and good cured properties may not be obtained.

  Moreover, when using the said hardening | curing agent, a hardening accelerator may be used together. Examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, triethylenediamine, Triethanolamine, tertiary amines such as 1,8-diazabicyclo (5,4,0) undecene-7, organic phosphines such as triphenylphosphine, diphenylphosphine and tributylphosphine, metal compounds such as tin octylate, Tetraphenylphosphonium / tetraphenylborate, tetrasubstituted phosphonium / tetrasubstituted borate such as tetraphenylphosphonium / ethyltriphenylborate, 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmol Such as tetraphenyl boron salts such as phosphorus-tetraphenylborate and the like. 0.01-15 weight part is used for a hardening accelerator as needed with respect to 100 weight part of epoxy resins.

  Furthermore, an inorganic filler, a silane coupling material, a release agent, various compounding agents such as a pigment, and various thermosetting resins can be added to the epoxy resin composition of the present invention as necessary. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These may be used alone or in combination of two or more. These fillers are preferably used in a proportion of 50 to 90% by weight in the epoxy resin composition from the viewpoint of heat resistance, moisture resistance, mechanical properties, etc. of the cured product of the epoxy resin composition.

  The epoxy resin composition of the present invention can be obtained by uniformly mixing the above components. And the epoxy resin composition of this invention can be easily made into the hardened | cured material by the method similar to the method known conventionally. For example, an epoxy resin, the curing agent of the present invention, and if necessary, a curing accelerator and an inorganic filler, a compounding agent, various thermosetting resins until uniform using an extruder, kneader, roll, etc. as necessary The epoxy resin composition of the present invention is obtained by thoroughly mixing, and the epoxy resin composition is molded by a melt casting method, a transfer molding method, an injection molding method, a compression molding method, or the like, and further at 80 to 200 ° C. The cured product of the present invention can be obtained by heating for 2 to 10 hours.

  Further, by dissolving or dispersing each component of the epoxy resin composition of the present invention in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, ethylene glycol monomethyl ether, N-methyl-2-pyrrolidone, etc. It can also be mixed. In this case, a cured product may be obtained by hot press molding a prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and drying by heating. it can.

  The amount of the solvent used in this case is usually 10 to 70% by weight, preferably 15 to 65% by weight, based on the total weight of the epoxy resin composition of the present invention and the solvent.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. Moreover, a part means a weight part in a synthesis example, an Example, and a comparative example. The softening point, melt viscosity, and residual halogen content were measured under the following conditions.
-Softening point It measured by the method according to JIS K-7234.
Melt viscosity Melt viscosity in cone plate method at 150 ° C Measuring instrument: Corn plate (ICI) high temperature viscometer
(Made by RESEACH EQUIPMENT (LONDON) LTD.)
Corn No. : 3 (measurement range 0 to 2.00 Pa · s)
Sample amount: 0.15 ± 0.01 g
-Residual halogen content: After combustion decomposition in the sample combustion device, the product gas was absorbed into the absorption liquid (0.01% H2O2), and the absorption liquid was quantified by ion chromatography.

Example 1
A four-necked flask equipped with a stirrer, thermometer and condenser was charged with 180.8 parts of phenol and 0.05 part of p-toluenesulfonic acid monohydrate and stirred at 80 ° C. for 4,4 ′. -141.9 parts of -bis (chloromethyl) -1,1'-biphenyl was added over 2 hours. Thereafter, the reaction was further carried out at 80 ° C. under reduced pressure of 95 to 105 kPa for 2 hours. Thereafter, 500 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated until the washing water became neutral. Subsequently, unreacted phenol and MIBK were distilled off from the oil layer under heating and reduced pressure. As a result, 186.7 parts of the phenol aralkyl resin (P1) of the present invention was obtained. The obtained phenol aralkyl resin (P1) had a melt viscosity of 0.12 Pa · s, a softening point of 71 ° C., a residual halogen of 6 ppm, and a hydroxyl group equivalent of 207 g / eq.

Comparative Example 1
A four-necked flask equipped with a stirrer, thermometer, and condenser is charged with 611 parts of phenol, 485 parts of 4,4′-bis (methoxymethyl) -1,1′-biphenyl, and 8 parts of paratoluenesulfonic acid monohydrate. The reaction was continued for 4 hours while maintaining the reaction temperature at 125 ° C. During that time, the methanol produced was distilled out of the reaction system. After completion of the reaction, 1500 parts of MIBK was added, and washing with water was repeated until the washing water became neutral. Subsequently, unreacted phenol and MIBK were distilled off from the oil layer under heating and reduced pressure. As a result, 615 parts of phenol aralkyl resin (P2) was obtained. The obtained phenol aralkyl resin (P2) had a softening point of 71 ° C., a melt viscosity of 0.12 Pa · s, and a hydroxyl group equivalent of 207 g / eq.

Example 2 and Comparative Example 2
Example of using epoxy aralkyl type epoxy resin (Nippon Kayaku Co., Ltd., NC-3000P, Nippon Kayaku Co., Ltd., epoxy equivalent 274 g / eq.) As epoxy resin, with respect to 1 epoxy equivalent of epoxy resin 1 and the phenol aralkyl resins (P1) and (P2) obtained in Comparative Example 1 were blended with 1 equivalent of a hydroxyl group as a curing agent, and further 1 part by weight of a curing accelerator (triphenylphosphine) was blended per 100 parts by weight of epoxy resin. A resin molded body was prepared by transfer molding and cured at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours.

The results of measuring the physical properties of the cured product thus obtained are shown in Table 1. The physical property values were measured by the following methods.
Glass transition temperature (TMA): TM-7000 manufactured by Vacuum Riko Co., Ltd.
Temperature rising rate 2 ° C./min.

  From Table 1, the cured product of the present invention has a high glass transition temperature and excellent heat resistance.

Claims (2)

General formula (1)

(X represents a halogen atom.)
A phenol aralkyl resin having a residual halogen content of 6 ppm or less obtained by reacting 4,4′-bis (halogenomethyl) biphenyl represented by the formula (I) and phenol without using a solvent. General formula (1)

(X represents a halogen atom.)
The residual halogen content is 50 ppm, characterized by reacting 4,4′-bis (halogenomethyl) biphenyl represented by the formula (II) and phenol with an acid catalyst and removing the hydrochloric acid gas in a reduced pressure state without solvent. The manufacturing method of the phenol aralkyl resin which is the following.