JP2008231071A - New polyvalent hydroxy compound, and epoxy resin composition and its cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyvalent hydroxy compound which gives a cured product exhibiting excellent adhesion to a dissimilar material and having excellent flame retardancy and heat resistance. <P>SOLUTION: The new polyvalent hydroxy compound is expressed by formula (1), and is obtained by reacting 0.1-0.9 mol of a curing agent such as dichloromethyl diphenyl sulfide etc., with a mol of a hydroxy compound (in the formula A is a benzene or naphthalene ring which may be substituted with a 1-8C hydrocarbon group; R<SB>1</SB>and R<SB>2</SB>are the same or different and each a hydrogen atom or a 1-8C alkyl group; n is a number of 0-10; and m is an integer of 1-2). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a sulfide structure-containing polyvalent hydroxy compound useful as an epoxy resin curing agent, modifier, etc., and an epoxy resin composition and a cured product thereof, such as a printed wiring board and a semiconductor encapsulation. It is suitably used for insulating materials in the field of electrical and electronic fields.

  Epoxy resins have been used in a wide range of industrial applications, but their required performance has become increasingly sophisticated in recent years. For example, there is a semiconductor sealing material in a typical field of a resin composition mainly composed of an epoxy resin, but as the integration degree of semiconductor elements is improved, the package size is becoming larger and thinner, and the mounting method is also increased. The transition to surface mounting is progressing, and the development of materials with excellent solder heat resistance is desired. Therefore, as a sealing material, in addition to reducing moisture absorption, improvement in adhesion and adhesion at the interface between different materials such as lead frames and chips is strongly demanded. Similarly, for circuit board materials, in addition to improving low heat absorption, high heat resistance, and high adhesion from the viewpoint of improving solder heat resistance, it is desirable to develop materials with excellent low dielectric properties from the viewpoint of reducing dielectric loss. Yes. In order to meet these requirements, various new structures of epoxy resins and curing agents have been studied. Furthermore, recently, from the viewpoint of reducing environmental impact, there has been a movement to eliminate halogen-based flame retardants, and epoxy resins and curing agents with more excellent flame retardancy have been demanded.

Therefore, various epoxy resins and epoxy resin curing agents have been studied from the above background. As an example of the epoxy resin curing agent, a naphthalene-based resin is known, and Patent Document 1 discloses that a naphthol aralkyl resin is applied to a semiconductor sealing material. However, although the naphthol aralkyl resin is excellent in low hygroscopicity, low thermal expansion property, etc., it has a defect of poor curability. Moreover, although the hardening | curing agent which has a biphenyl structure is proposed in patent document 2 and it describes that it is effective for a flame retardance improvement, there existed a fault which is inferior to curability. Furthermore, both the naphthalene-based resin and the biphenyl-based resin have a main skeleton composed only of hydrocarbons, and thus are not sufficient for the expression of flame retardancy and adhesion.
Patent Document 3 discloses an epoxy resin composition containing a bifunctional hydroxy compound having a sulfide structure. However, since the bifunctional hydroxy compound has a high melting point, it is easy to handle as an epoxy resin curing agent. There was a problem. Furthermore, since it is a bifunctional compound, there was also a defect inferior in heat resistance as compared with a polyfunctional compound.
On the other hand, an epoxy resin that satisfies these requirements is not yet known. For example, the well-known bisphenol type epoxy resin is in a liquid state at room temperature and is widely used because it is excellent in workability and easy to mix with a curing agent, an additive, etc. There is a problem in terms of moisture resistance. Further, novolac type epoxy resins are known as improved heat resistance, but there are problems in adhesiveness, moisture resistance and the like. Furthermore, the conventional epoxy resin whose main skeleton is composed of only hydrocarbons has no flame retardancy.

  As a measure for improving flame retardancy without using a halogen flame retardant, a method of adding a phosphate ester flame retardant is disclosed. However, the method using a phosphate ester flame retardant does not have sufficient moisture resistance. In addition, the phosphoric acid ester is hydrolyzed under a high temperature and humidity environment, and there is a problem that the reliability as an insulating material is lowered.

  Patent Documents 2 and 4 disclose examples in which an aralkyl epoxy resin having a biphenyl structure is applied to a semiconductor encapsulant as a material that improves flame retardancy without containing phosphorus atoms or halogen atoms. Patent Document 5 discloses an example in which an aralkyl type epoxy resin having a naphthalene structure is used. However, these epoxy resins have insufficient performance in any of flame retardancy, adhesion, and heat resistance. Patent Documents 6, 7 and 8 disclose a naphthol-based aralkyl epoxy resin and a semiconductor encapsulant containing the naphthol-based aralkyl epoxy resin, but nothing focuses on flame retardancy. Patent Document 9 discloses a polyvalent hydroxy compound having a diphenyl ether skeleton and an epoxidized product thereof, but does not focus on adhesion and flame retardancy. Furthermore, Patent Document 10 discloses a semiconductor sealing material using a bifunctional epoxy resin having a sulfide structure. However, these epoxy resins have insufficient heat resistance and flame retardancy. It is not something that focuses on.

JP-A-5-109934 JP-A-11-140166 JP-A-6-145306 JP 2000-129092 A JP 2004-57992 A Japanese Patent Laid-Open No. 3-90075 JP-A-3-281623 Japanese Patent Laid-Open No. 4-173831 Japanese Patent Laid-Open No. 10-265554 JP-A-6-145300

  The purpose of the present invention is excellent in adhesion to a metal substrate and flame retardancy in applications such as lamination, molding, casting, and adhesion, and has excellent performance in heat resistance, etc. Providing sulfide structure-containing polyhydric hydroxy compounds useful as curing agents, modifiers, etc., electric and electronic materials that have excellent moldability and provide cured products with excellent adhesion, flame retardancy, heat resistance, etc. An object of the present invention is to provide an epoxy resin composition useful for sealing parts, circuit board materials, and the like, and to provide a cured product thereof.

  The sulfide structure-containing polyvalent hydroxy compound of the present invention is represented by the following general formula (1).

ここで、Ａは炭素数１〜８の炭化水素基で置換されてもよいベンゼン環又はナフタレン環を示し、Ｒ_１、Ｒ_２は同一又は異なってもよい水素原子、又は炭素数１〜６のアルキル基を示し、ｎは１〜１０の数を示し、ｍは１〜２の整数を示す。

Here, A represents a benzene ring or a naphthalene ring which may be substituted with a hydrocarbon group having 1 to 8 carbon atoms, and R ₁ and R ₂ may be the same or different hydrogen atoms, or have 1 to 6 carbon atoms. An alkyl group is shown, n shows the number of 1-10, m shows the integer of 1-2.

  This sulfide structure-containing polyvalent hydroxy compound contains 0.1 to 0.9 mol of a crosslinking agent represented by the following formula (4) with respect to 1 mol of the hydroxy compound represented by the following formula (2) or (3). It can be obtained by reacting.

ここで、Ｒ_３は炭素数１〜８のアルキル基を示し、ｐは０〜３の整数、ｍは１〜２の整数を示す。

Wherein, _{R 3} represents an alkyl group having 1 to 8 carbon atoms, p is an integer of 0 to 3, m is an integer of 1-2.

ここで、Ｒ_１、Ｒ_２は同一又は異なってもよい水素原子、又は炭素数１〜６のアルキル基を示し、Ｒ_４はOH、アルコキシ又はハロゲンを示す。

Wherein, R _1, R ₂ are the same or different and which may hydrogen atom, or an alkyl group having 1 to 6 carbon atoms, R ₄ represents OH, alkoxy or halogen.

The novel polyvalent hydroxy compound represented by the general formula (1) of the present invention can be obtained by reacting a specific hydroxy compound with a specific cross-linking agent. In the general formula (1), A represents a benzene ring or a naphthalene ring, and these rings may be substituted with a hydrocarbon group having 1 to 8 carbon atoms. Preferably, A is an unsubstituted or methyl-substituted benzene ring or naphthalene ring. R ₁ and R _{2 each} represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or a methyl group, and these may be the same or different. m is 1 or 2, but is preferably 1. n represents the average number of repetitions, and is 1 to 10, preferably 1 to 5. Such a polyvalent hydroxy compound can be obtained by reacting the hydroxy compound represented by the general formula (2) or (3) with the crosslinking agent represented by the general formula (4). In the general formula (2) or (3), R ₃ is a hydrocarbon group having 1 to 8 carbon atoms, preferably an alkyl group, more preferably a methyl group. p is an integer of 0 to 3, preferably 0.

  The sulfide structure-containing polyvalent hydroxy compound (hereinafter also referred to as SAR) of the present invention is represented by the general formula (1). Moreover, since SAR can be converted into an epoxy resin by epoxidation, SAR is also an intermediate of epoxy resin.

  The softening point of SAR is preferably 40 to 200 ° C, preferably 50 to 160 ° C, more preferably 60 to 120 ° C. Here, the softening point refers to a softening point measured based on the ring and ball method of JIS-K-2207. When lower than this, when this is mix | blended with an epoxy resin, the heat resistance of hardened | cured material will fall, and when higher than this, the fluidity | liquidity at the time of shaping | molding will fall.

  The SAR of the present invention is useful as a curing agent and a modifier for epoxy resins, and when applied to an epoxy resin composition, has excellent adhesion to different materials, and is excellent in flame retardancy and heat resistance. It is possible to give a cured product and to use it suitably for applications such as sealing of electric / electronic parts, circuit board materials, and the like. If the epoxy resin composition containing the SAR of the present invention is cured by heating, an epoxy resin cured product can be obtained. This cured product is excellent in terms of adhesion, flame retardancy, high heat resistance and the like. It can be suitably used for applications such as sealing of electric / electronic parts, circuit board materials, and the like.

The present invention will be described in detail.
The SAR of the present invention can itself be a component of a phenol resin composition or an epoxy resin composition. In some cases, an haloalkyl compound, an alkenyl halide compound, an epihalohydrin is added to a sulfide structure-containing polyvalent hydroxy compound. By reacting the compound or the like, a part or all of the hydrogen atoms of the OH group in the sulfide structure-containing polyvalent hydroxy compound can be substituted with an alkyl group, an alkenyl group, a glycidyl group, or the like.
The SAR of the present invention can be synthesized by reacting the hydroxy compound represented by the formula (2) or (3) with the crosslinking agent represented by the formula (4). The amount of the crosslinking agent used in this case is in the range of 0.1 to 0.9 mol, preferably in the range of 0.2 to 0.8 mol, with respect to 1 mol of the hydroxy compound. If it is smaller than this, the amount of unreacted hydroxy compounds increases during synthesis, the softening point of the synthesized SAR is lowered, and the heat resistance of the cured product when used as an epoxy resin curing agent is lowered. On the other hand, if it is larger than this, the softening point of SAR becomes high, and in some cases, SAR may gel during synthesis.

  This reaction can be carried out without a catalyst or in the presence of an acid catalyst. The acid catalyst can be appropriately selected from known inorganic acids and organic acids. For example, mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, dimethyl sulfuric acid, diethyl sulfuric acid, zinc chloride, aluminum chloride, iron chloride, trifluoride. Examples thereof include Lewis acids such as boron fluoride or ion exchange resins, activated clay, silica-alumina, zeolite and other solid acids.

  Moreover, this reaction is normally performed at 10-250 degreeC for 1 to 20 hours. Further, during the reaction, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl ether, diethyl ether, diisopropyl ether, Ethers such as tetrahydrofuran and dioxane, aromatic compounds such as benzene, toluene, chlorobenzene, and dichlorobenzene can be used as the solvent.

  Examples of the phenols represented by the general formula (2) or the naphthols represented by the general formula (3) include phenol, o-cresol, m-cresol, p-cresol, ethylphenols, isopropylphenols, and tarsha. Libutylphenols, allylphenols, phenylphenols, 2,6-xylenol, 2,6-diethylphenol, hydroquinone, resorcin, catechol, 1-naphthol, 2-naphthol, 1,5-naphthalenediol, 1,6- Examples include naphthalene diol, 1,7-naphthalene diol, 2,6-naphthalene diol, 2,7-naphthalene diol, and the like. These phenols or naphthols may be used alone or in combination of two or more.

In the general formula _{(4), R 1, R} 2 are the same or different and which may hydrogen atom, or an alkyl group having 1 to 6 carbon atoms, _{R 4} represents OH, alkoxy or halogen. As the crosslinking agent represented by the general formula (4), a dichloromethyl compound, a dimethylol compound of diphenyl sulfide, or a dialkyl ether thereof can be used. Examples of such a crosslinking agent include 4,4′-dichloromethyl diphenyl sulfide, 2,4′-dichloromethyl diphenyl sulfide, 2,2′-dichloromethyl diphenyl sulfide, 4,4′-dihydroxymethyl diphenyl sulfide, 2 , 4′-dihydroxymethyl diphenyl sulfide, 2,2′-dihydroxymethyl diphenyl sulfide, 4,4′-dimethoxymethyl diphenyl sulfide, 2,4′-dimethoxymethyl diphenyl sulfide, 2,2′-dimethoxymethyl diphenyl sulfide, 4, , 4′-diisopropoxymethyl diphenyl sulfide, 2,4′-diisopropoxymethyl diphenyl sulfide, 2,2′-diisopropoxymethyl diphenyl sulfide, 4,4′-dibutoxymethyl diphenyl sulfide, 2,4 ′ − Examples include dibutoxymethyl diphenyl sulfide and 2,2′-dibutoxymethyl diphenyl sulfide.

The substitution position for the diphenyl sulfide of the chloromethyl group and methylol group or its alkyl ether group may be any of 4,4′-position, 2,4′-position, and 2,2′-position, but is a desirable compound as a crosslinking agent. Is a 4,4′-form, and the total condensing agent preferably contains 50% by weight or more of the 4,4′-form. If it is less than this, there are disadvantages such as a decrease in the curing rate when the synthesized resin is cured, and the obtained cured product becomes brittle.

  The phenol resin composition of the present invention comprises the above SAR in polyhydric phenolic compounds. The content of SAR is in the range of 2 to 200 parts by weight, preferably 5 to 100 parts by weight, and more preferably 10 to 80 parts by weight with respect to 100 parts by weight of the polyhydric phenolic compounds. If it is less than this, the modification effects such as low hygroscopicity, heat resistance, adhesion, and flame retardancy are small, and if it is more than this, the viscosity becomes high and the moldability deteriorates.

  The polyhydric phenolic compounds mentioned here refer to all compounds having two or more phenolic hydroxyl groups in one molecule, for example, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, Divalent phenols such as 2,2′-biphenol, hydroquinone, resorcin, naphthalenediol, or tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, There are trivalent or higher phenols represented by phenol novolak, o-cresol novolak, naphthol novolak, polyvinylphenol and the like. Furthermore, divalent phenols such as phenols, naphthols, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, naphthalenediol, Formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene glycol, p-xylylene glycol dimethyl ether, 4,4'-dimethoxymethylbiphenyl, 4,4'-dimethoxymethyldiphenyl ether, divinylbenzenes, divinylbiphenyls, There are polyhydric phenolic compounds synthesized by reaction with a crosslinking agent such as divinylnaphthalene. Hereinafter, the polyhydric phenolic compounds may be described as a phenol resin.

  The softening point of the phenol resin is usually in the range of 40 to 200 ° C, preferably 60 to 150 ° C. When lower than this, the heat resistance of the hardened | cured material obtained by using as a hardening | curing agent of an epoxy resin will fall. Moreover, when higher than this, the mixability with SAR will fall.

  The phenol resin composition of the present invention is obtained by dissolving both in a melt mixing method in which mixing is performed uniformly by stirring, kneading, etc. at a temperature equal to or higher than the softening point of either the phenol resin or SAR, and a solvent for dissolving each. Thus, it can be obtained by a method such as a solution mixing method in which the mixture is uniformly mixed by stirring, kneading or the like. Examples of the solvent used in the solution mixing method include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, and ethyl cellosolve, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, dimethyl ether, diethyl ether, and diisopropyl ether. And ethers such as tetrahydrofuran and dioxane, and aromatic solvents such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene. In addition, when obtaining this composition, an epoxy resin, an inorganic filler, another phenol resin, and another additive (material) can also be mix | blended.

The phenol resin composition of this invention can be made into a phenol resin hardened | cured material by using together with the hardening | curing agent generally used for phenol resin molding materials, such as hexamethyltetramine.
The epoxy resin composition of the present invention contains at least an epoxy resin and a curing agent, and is a composition in which the SAR is blended as part or all of the curing agent.
In the case of the said composition, the compounding quantity of SAR is 2-200 weight part normally with respect to 100 weight part of epoxy resins, Preferably it is the range of 5-80 weight part. If it is less than this, the effect of improving the adhesion, flame retardancy and heat resistance is small, and if it is more than this, there is a problem that the moldability and the strength of the cured product are lowered.

When the SAR of the present invention is used as the total amount of the curing agent, the amount of SAR is usually determined in consideration of the equivalent balance between the —OH group of SAR and the epoxy group in the epoxy resin. The equivalent ratio of the epoxy resin and the curing agent is usually in the range of 0.2 to 5.0, preferably in the range of 0.5 to 2.0. If it is larger or smaller than this, the curability of the epoxy resin composition is lowered, and the heat resistance, mechanical strength and the like of the cured product are lowered.
A curing agent other than the SAR of the present invention can be used in combination as a curing agent. The blending amount of the other curing agent is determined so that the blending amount of SAR is usually 2 to 200 parts by weight, preferably 5 to 80 parts by weight with respect to 100 parts by weight of the epoxy resin. . If the amount of SAR is less than this, the effect of improving the adhesion, flame retardancy and heat resistance is small, and if it is more than this, there is a problem that the moldability and the strength of the cured product are lowered.

  As the curing agent other than SAR, any of those generally known as epoxy resin curing agents can be used, and examples thereof include dicyandiamide, acid anhydrides, polyhydric phenols, aromatic and aliphatic amines. Among these, polyhydric phenols are preferably used as a curing agent in a field where high electrical insulation properties such as a semiconductor sealing material are required. Below, the specific example of a hardening | curing agent is shown.

  Examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl hymic anhydride, dodecynyl succinic anhydride, nadic anhydride, There are trimellitic anhydride and the like.

  Examples of the polyhydric phenols include divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, naphthalenediol, or the like. , Tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak, naphthol novolak, polyvinylphenol, There are phenols. Furthermore, divalent phenols such as phenols, naphthols, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, naphthalenediol, Examples thereof include polyhydric phenolic compounds synthesized by a crosslinking agent such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene glycol, and dimethoxymethylbiphenyl. Moreover, the phenol resin composition of the present invention can be blended.

Examples of amines include aromatic amines such as 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenylsulfone, m-phenylenediamine, and p-xylylenediamine, ethylenediamine, There are aliphatic amines such as hexamethylenediamine, diethylenetriamine, and triethylenetetramine.
One or more of these curing agents can be mixed and used in the composition.

  The epoxy resin used in the composition is selected from those having two or more epoxy groups in one molecule. For example, divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, tetrabromobisphenol A, hydroquinone, resorcin, or tris- (4 -Hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, novolak resins such as phenol, cresol and naphthol, and aralkyl resins such as phenol, cresol and naphthol There are glycidyl etherified compounds of the active compound. These epoxy resins can be used alone or in combination of two or more.

  In the epoxy resin composition of the present invention, an oligomer or a polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene resin, indene-coumarone resin, phenoxy resin, etc. is used as another modifier. You may mix | blend suitably. The addition amount is usually in the range of 2 to 30 parts by weight with respect to 100 parts by weight of the epoxy resin.

  In addition, the epoxy resin composition of the present invention can contain additives such as inorganic fillers, pigments, refractory agents, thixotropic agents, coupling agents, fluidity improvers and the like. Examples of inorganic fillers include silica powder such as spherical or crushed fused silica and crystalline silica, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, hydrated alumina, and the like. A preferable blending amount when used for a stopper is 70% by weight or more, and more preferably 80% by weight or more.

Examples of the pigment include organic or inorganic extender pigments, scaly pigments, and the like. Examples of the thixotropic agent include silicon-based, castor oil-based, aliphatic amide wax, polyethylene oxide wax, and organic bentonite.
Furthermore, a curing accelerator can be used in the epoxy resin composition of the present invention as necessary. Examples include amines, imidazoles, organic phosphines, Lewis acids, etc., specifically 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, Tertiary amines such as ethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2- Imidazoles such as heptadecylimidazole, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenyl Tetraphenyl such as ruphosphonium / ethyltriphenylborate, tetrabutylphosphonium / tetrabutylborate, tetrasubstituted phosphonium / tetrasubstituted borate, 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate, etc. There is boron salt. The addition amount is usually in the range of 0.2 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin.

  Further, if necessary, the resin composition of the present invention includes a release agent such as carnauba wax and OP wax, a coupling agent such as γ-glycidoxypropyltrimethoxysilane, a colorant such as carbon black, and trioxide. Flame retardants such as antimony, low stress agents such as silicone oil, lubricants such as calcium stearate, etc. can be used.

  The epoxy resin composition of the present invention is made into a varnish in which an organic solvent is dissolved, and then impregnated into a fibrous material such as glass cloth, aramid nonwoven fabric, polyester nonwoven fabric such as liquid crystal polymer, etc., and then the solvent is removed, It can be. Moreover, it can be set as a laminated body by apply | coating on sheet-like materials, such as copper foil, stainless steel foil, a polyimide film, and a polyester film depending on the case.

  If the epoxy resin composition of the present invention is cured by heating, an epoxy resin cured product can be obtained, and this cured product is excellent in terms of low hygroscopicity, high heat resistance, adhesion, flame retardancy, and the like. Become. This cured product can be obtained by molding the epoxy resin composition by a method such as casting, compression molding, transfer molding or the like. The temperature at this time is usually in the range of 120 to 220 ° C.

Hereinafter, the present invention will be described more specifically with reference to examples.
Here, the viscosity was measured using a B-type viscometer, and the softening point was measured by the ring and ball method according to JIS K-6911. GPC measurement conditions were as follows: apparatus; HLC-82A (manufactured by Tosoh Corp.), column; TSK-GEL2000 × 3 and TSK-GEL4000 × 1 (both manufactured by Tosoh Corp.), solvent: tetrahydrofuran, flow rate 1 ml / min, temperature; 38 ° C., detector; RI, and polystyrene standard solution was used for the calibration curve.

Example 1
A 500 ml 4-necked flask was charged with 50.0 g (0.53 mol) of phenol as a hydroxy compound component and 60.2 g (0.21 mol) of dichloromethyldiphenyl sulfide as a crosslinking agent, and reacted at 120 ° C. for 3 hours with stirring. I let you. During this time, the generated hydrochloric acid was removed from the system. After the reaction, excess phenol was distilled off under reduced pressure to obtain 60.2 g of a brown resin (polyvalent hydroxy compound). This compound is referred to as SAR-A. The softening point of this compound was 71 ° C., and the melt viscosity at 150 ° C. was 0.31 Pa · s. FIG. 1 shows the ¹ H-NMR spectrum of SAR-A, FIG. 2 shows the infrared absorption spectrum, FIG. 3 shows the GPC chart, and FIG. 4 shows the FD-MS chart.

Example 2
Using 10.0-naphthol (0.35 mol) of 1-naphthol as a hydroxy compound component and 29.5 g (0.10 mol) of dichloromethyldiphenyl sulfide as in Example 1 as a crosslinking agent, the reaction was conducted in the same manner as in Example 1. As a result, 47.0 g of a brown resin (polyvalent hydroxy compound) was obtained. This compound is referred to as SAR-B. The softening point of this compound was 80 ° C., and the melt viscosity at 150 ° C. was 0.53 Pa · s.

Example 3
In 50 g of phenol novolak (softening point 82 ° C., OH equivalent 103) melted at 150 ° C., 50 g of SAR-A obtained in Example 1 was added and uniformly melted to obtain 100 g of a phenol resin composition (resin Composition A). The obtained phenol resin composition had a softening point of 75 ° C. and a melt viscosity at 150 ° C. of 0.28 Pa · s.

Examples 4-7 and Comparative Examples 1-2
O-Cresol novolak type epoxy resin (OCNE; epoxy equivalent 200, softening point 65 ° C.) as an epoxy resin component, SAR-A, SAR-B obtained in Examples 1 and 2 as a curing agent, phenol obtained in Example 3 Resin composition (resin composition A), phenol novolak (curing agent A: manufactured by Gunei Chemical Co., Ltd., PSM-4261; OH equivalent 103, softening point 82 ° C.), phenol aralkyl resin (curing agent B; manufactured by Meiwa Kasei Co., Ltd., MEH- 7800SS, OH equivalent 175, softening point 67 ° C.), silica (average particle size 18 μm) as a filler, and triphenylphosphine as a curing accelerator are kneaded with the formulations shown in Tables 1 and 3 to obtain an epoxy resin composition. It was. This epoxy resin composition was molded at 175 ° C. and post-cured at 175 ° C. for 12 hours to obtain a cured product test piece, which was then subjected to various physical property measurements.

  The glass transition point (Tg) and linear expansion coefficient (CTE) were measured at a rate of temperature increase of 10 ° C./min using a thermomechanical measuring device. Further, the water absorption is 50 mm in diameter and 3 mm in thickness using a circular test piece, and the water absorption obtained by absorbing moisture for 100 hours at 85 ° C. and 85% RH is 50 mm in diameter using the present epoxy resin composition. A disk with a thickness of 3 mm was formed, and the weight change rate after post-curing and after absorbing moisture at 133 ° C., 3 atm for 96 hours. The adhesive strength was obtained by molding a molded product of 25 mm × 12.5 mm × 0.5 mm between two copper plates at 175 ° C. with a compression molding machine, post-curing at 180 ° C. for 12 hours, and then adjusting the tensile shear strength. Evaluated by seeking. Flame retardance was measured by molding a 1/16 inch thick test piece, evaluated according to the UL94V-0 standard, and expressed as the total burning time of 5 test pieces. The results are shown in Table 2.

¹ H-NMR spectrum of SAR-A Infrared absorption spectrum of SAR-A SAR-A GPC chart SAR-A FD-MS chart

Claims (5)

The following general formula (1)

Here, A represents a benzene ring or a naphthalene ring which may be substituted with a hydrocarbon group having 1 to 8 carbon atoms, and R ₁ and R ₂ may be the same or different hydrogen atoms, or have 1 to 6 carbon atoms. An alkyl group is shown, n shows the number of 1-10, m shows the integer of 1-2.
A novel polyvalent hydroxy compound represented by   The polyvalent hydroxy compound according to claim 1, which has a softening point of 40 to 200 ° C. The cross-linking agent represented by the following formula (4) is reacted with 0.1 to 0.9 mol of the hydroxy compound represented by the following formula (2) or (3). Or the manufacturing method of the polyvalent hydroxy compound of 2.

Wherein, _{R 3} represents an alkyl group having 1 to 8 carbon atoms, p is an integer of 0 to 3, m is an integer of 1-2.

_Wherein, R 1, _{R 2} are the same or different and which may hydrogen atom, or an alkyl group having 1 to 6 carbon atoms, _{R 4} represents OH, alkoxy or halogen.   In the epoxy resin composition which consists of an epoxy resin and a hardening | curing agent, 2 to 200 weight part of polyvalent hydroxy compounds of Claim 1 or 2 are mix | blended with respect to 100 weight part of epoxy resins as some or all of a hardening | curing agent. An epoxy resin composition characterized by comprising:   An epoxy resin cured product obtained by curing the epoxy resin composition according to claim 4.

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