WO2008114766A1

WO2008114766A1 - Novel polyvalent hydroxy compound, method for producing the compound, epoxy resin and epoxy resin composition each using the compound, and cured product of the composition

Info

Publication number: WO2008114766A1
Application number: PCT/JP2008/054846
Authority: WO
Inventors: Hisashi Yamada; Hideyasu Asakage
Original assignee: Tohto Kasei Co., Ltd.
Priority date: 2007-03-12
Filing date: 2008-03-11
Publication date: 2008-09-25

Abstract

Disclosed are a novel polyvalent hydroxy compound and an epoxy resin, each represented by the general formula (1) below. The resin is excellent in close adhesion to a different material, and enables to obtain a cured product having excellent flame retardancy and heat resistance. H-L1-(X-L1)n-H (1) In the general formula (1), L1 represents a group represented by the following formula (2): (wherein R1 represents a hydrogen atom, a hydroxy group, a glycidyloxy group, an alkoxy group having 1-8 carbon atoms, a halogen atom or a hydrocarbon group having 1-8 carbon atoms; and G represents a hydrogen atom or a glycidyl group); and X represents a crosslinking group represented by the following formula (a) or the following formula (b). In the formulae (a) and (b), R2, R3, R4 and R5 independently represent a hydrogen atom or a hydrocarbon group having 1-6 carbon atoms; B represents a group composed of a benzene ring, a biphenyl ring or a naphthalene ring; and n represents a number of 0-20.

Description

Specification

TECHNICAL FIELD The present invention relates to a novel polyhydric hydroxy compound, a method for producing the compound, an epoxy resin using the compound, an epoxy resin composition, and a cured product thereof.

The present invention relates to a novel sulfide structure-containing polyhydric hydroxy compound, a sulfide structure-containing epoxy resin obtained by epoxidizing the compound, the epoxy resin-containing epoxy resin composition, and a cured product thereof, a printed wiring board, It is suitably used for insulating materials in the electrical and electronic fields such as semiconductor encapsulation. Background art

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, semiconductor encapsulating materials are a typical field of resin compositions based on epoxy resins, but as the degree of integration of semiconductor elements increases, the package size is becoming larger and thinner, and the mounting method However, 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 low 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. ing. To meet these demands, various new structures of epoxy resins and curing agents are being investigated. More 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 better 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 shows that a naphthol aralkyl resin is applied to a semiconductor sealing material. However, naphthol aralkyl resins are excellent in low hygroscopicity, low thermal expansion, etc., but are curable. There was a disadvantage inferior to. Further, Patent Document 2 proposes a curing agent having a bifunil structure and describes that it is effective for improving flame retardancy, but has a disadvantage of poor curability. Furthermore, both naphthalene-based resins and biphenyl-based resins have a main skeleton composed of only hydrocarbons, so that they were not sufficient for the development 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, an epoxy resin curing agent is disclosed. As a result, there was a problem in handling. Furthermore, since it is a bifunctional compound, it has a disadvantage that it is inferior in heat resistance as compared with a polyfunctional compound.

On the other hand, no epoxy resin that satisfies these requirements has been known yet. For example, the well-known bisbuenol-type epoxy resin is widely used because it is liquid at room temperature and has excellent workability and is easy to mix with curing agents, additives, etc. There is a problem in terms of moisture resistance. In addition, novolac type epoxy resins are known as improved heat resistance, but there are problems in adhesion, moisture resistance, and the like. Furthermore, conventional epoxy resins whose main skeleton is composed only of hydrocarbons have 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 phosphate ester flame retardants does not have sufficient moisture resistance. In addition, the phosphoric acid ester is hydrolyzed under high temperature and high humidity, which reduces the reliability as an insulating material.

Patent Documents 2 and 4 disclose an example in which a aralkyl epoxy resin having a biphenyl structure is applied to a semiconductor encapsulant as one 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 naphthol-based aralkyl-type epoxy resins and semiconducting materials containing them, but nothing focuses on flame retardancy. Patent Document 9 includes Although aralkyl type resins using phenols are disclosed, they do 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 are difficult to perform. It does not focus on flammability.

Patent document 1: Japanese Patent Laid-Open No. 5-10093 4

Patent Document 2: Japanese Patent Laid-Open No. 11 1 1 4 0 1 6 6

Patent Document 3: Japanese Patent Application Laid-Open No. 6-1 4 5 3 0 6

Patent Document 4: Japanese Patent Laid-Open No. 2 00 0 1 2 9 0 9 2

Patent Document 5: Japanese Patent Laid-Open No. 2 0 4 5 9 7 9 2

Patent Document 6: Japanese Patent Laid-Open No. 3-90 075

Patent Document 7: Japanese Patent Laid-Open No. 3-2 8 1 6 2 3

Patent Document 8: Japanese Patent Laid-Open No. 4 1 1 7 3 8 3 1

Patent Document 9: Japanese Patent Application Laid-Open No. 6-222071

Patent Document 10: Japanese Patent Application Laid-Open No. 6-1 4 5 300 Disclosure of Invention

The object of the present invention is to have excellent performance in heat resistance and the like in addition to excellent adhesion to a metal substrate and flame retardancy in applications such as lamination, molding, casting and adhesion, and a thermosetting resin composition Provided with a sulfide structure-containing polyhydric hydroxy compound that is useful as a material hardener, modifier, etc., as well as excellent adhesion to metal substrates and flame retardancy, as well as excellent heat resistance Providing a sulfide structure-containing epoxy resin that has performance and is useful for applications such as lamination, molding, casting, and adhesion, as well as excellent moldability, adhesion, flame resistance, and heat resistance An object of the present invention is to provide an epoxy resin composition useful for sealing electric and electronic parts that give excellent cured products, circuit board materials, and the like, and to provide cured products thereof.

The sulfide structure-containing polyhydric hydroxy compound and the sulfide structure-containing epoxy resin of the present invention are represented by the following general formula (1). H- L!-(X- (1)

Where

Is the following formula (2)

Is a hydrogen atom, a hydroxyl group, a glycidyloxy group, an alkoxy group having 1 to 8 carbon atoms, a halogen atom, or a hydrocarbon group having 1 to 8 carbon atoms, and X is the following ( a) or formula (b)

R

(a)

R 3

R ₂ , R ₃ , R ₄ and R ₅ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and B represents a benzene ring, biphenyl ring or naphthalene. A group consisting of a ring,

G represents either a hydrogen atom or a glycidyl group, and n represents a number from 0 to 20.

When d is a glycidyl group, the epoxy resin containing a sulfide structure is represented by the general formula (3) H- L _2- (X-L ₂ ) n -H (3) Where

L ₂ is the following formula (4)

Represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and X has the same meaning as in the general formula (1). N represents a number from 0 to 20;

It can be obtained by reacting a sulfido structure-containing polyhydric hydroxy compound represented by the following formula with epichlorohydrin.

This sulfido structure-containing polyhydric hydroxy compound is represented by the following formula (6), (7), (8) or (9) with respect to 1 mol of the hydroxy compound represented by the following formula (5). It can be obtained by reacting 0.1 to 0.9 mol of a crosslinking agent.

R ₂ CHO (6) R ₂ R ₃ C = 0 (7)

However, represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ₂ , R ₃ , R ₄ and R ₅ independently represent a hydrogen atom or A hydrocarbon group having 1 to 6 carbon atoms, B represents a group consisting of a benzene ring, a biphenyl ring or a naphthalene ring, and Y and Z independently represent OH, alkoxy or halogen.

The sulfido structure-containing polyhydric compound (hereinafter also referred to as SAR) represented by the general formula (1) according to the present invention is epoxidized to sulfide structure-containing epoxy resin (hereinafter also referred to as SAE). SAR is also an intermediate of epoxy resin (S AE). Brief Description of Drawings

FIG. 1 is a ¹ H-NMR spectrum of SAR-A obtained in Example 1.

Figure 2 shows the infrared absorption spectrum of SAR-A obtained in Example 1.

FIG. 3 is a G P C chart of SAR-A obtained in Example 1.

Figure 4 is a ¹ H- NMR spectrum of SAE- A obtained in Example 1 1 Figure 5 is an infrared absorption space of S AE one A obtained in Example 1 1 It is.

FIG. 6 is a GP C chart of SAE A obtained in Example 11. BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be described in detail.

In the general formula (1), is a group represented by the formula (2). X is a group represented by the formula (a) or (b), and n represents a number from 0 to 20. If n = 20 is exceeded, the softening point and melt viscosity will be too high and the handling will be poor.

In the formula (2), G represents either a hydrogen atom or a glycidyl group, and represents a hydrogen atom, a hydroxyl group, a glycidyloxy group, an alkoxy group having 1 to 8 carbon atoms, a halogen atom, or a carbon atom having 1 to 8 carbon atoms. One of hydrogen groups is shown.

X is a bridging group represented by the formula (a) or (b), but R ₂ , R ₃ , R ₄ and R ₅ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. , B represents a group consisting of a benzene ring, a biphenyl ring or a naphthalene ring. In addition, these rings constituting B may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. X crosslinks 1 ^, but the substitution position of X with respect to the group represented by the formula (2) constituting Li is not particularly limited.

The softening point of SAR is preferably 40 to 20 and is preferably in the range of 50 to: I 60 ° C., more preferably 60 to 120. Here, the softening point refers to a softening point measured based on the ring and ball method of JIS—K—2 2 0 7. If it is lower than this, the heat resistance of the cured product is lowered when it is added to the epoxy resin, and if it is higher than this, the fluidity during molding is lowered.

The SAR according to the present invention can itself be a component of a thermosetting resin composition. In some cases, a sulfido structure-containing polyhydric hydroxy compound is added to a halogenated alkyl compound or a halogenated alkenyl compound. By reacting an epihalohydrin compound or the like, part or all of the hydrogen atoms of the OH group in the sulfido structure-containing polyhydric hydroxy compound can be substituted with an alkyl group, an alkenyl group, a glycidyl group, or the like.

The SAR according to the present invention is synthesized by reacting a hydroxy compound represented by the formula (5) with a crosslinking agent represented by the formula (6), the formula (7), (8) or (9). can do. In this case, the amount of the crosslinking agent used 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 the 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 decreases. 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, dimethylsulfuric acid, and jetylsulfuric acid, zinc chloride, aluminum chloride, iron chloride, trifluoride Examples thereof include Lewis acids such as fluorine fluoride or ion exchange resins, activated clays, silica-alumina, and solid acids such as zeolite.

In addition, this reaction is usually performed at 10 to 25 ° C. for 1 to 20 hours. Furthermore, during the reaction, alcohols such as methanol, ethanol, prono "? Norole, butanol, ethylene glycolate, methyl cetylsolve, ethylcetol sorb, ketones such as acetone, methylethyl ketone, methylisobutylketone, Usable as solvents are ethers such as dimethyl ether, jetyl ether, diisopropyl ether, tetrahydrofuran, dioxane and the like, and aromatic compounds such as benzene, toluene, black benzene and dichlorobenzene.

Examples of the hydroxy compound used as a raw material include dihydroxy diphenyl sulfide substituted with a hydroxyl group, an alkoxy group, a halogen atom, or a hydrocarbon group as a substituent, in addition to dihydroxy diphenyl sulfide. For example, a halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, etc., and an alkoxy group includes a methoxy group, a ethoxy group, a butyl ether group, an isopropoxy group, a allyloxy group, a propargyl ether group, a ptoxy group, a phenoxy group. Is mentioned. Hydrocarbon groups include methyl, ethyl, bur, ethyne, isopropyl, aryl, propargyl, buty Various substituted dihydroxydiphenyl sulfides having an alkyl group, an amyl group, a phenyl group, a benzyl group and the like can be used, and dihydroxydiphenyl sulfide is preferred.

Examples of the crosslinking agent include aldehydes such as formaldehyde, acetoaldehyde, propyl aldehyde, butyl aldehyde, amyl aldehyde and benzaldehyde represented by the formula (6), with formaldehyde being preferred. Preferred formaldehyde raw material forms for use in the reaction include formalin aqueous solution, paraformaldehyde, trioxane and the like. Also, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetophenone represented by the formula (7) can be used as a crosslinking agent.

Further, the crosslinking agent represented by the formula (8) includes P-xylylene glycol, p-xylylene glycol dimethyl ether, p-xylylene dichloride, 4, 4'-dimethylmethylbiphenyl, 4 , 4'-dichloromethylbiphenyl, dimethoxymethylnaphthalene, dichloromethylnaphthalene. In addition, divinylbenzenes, divinylbiphenyls, dibulaphthalenes and the like represented by the formula (9) can also be used as a crosslinking agent.

The sulfide structure-containing epoxy resin (S A E) of the present invention is represented by the general formula (1). The sulfido structure-containing polyhydric hydroxy compound (S A R) is represented by the general formula (3). S A E can be obtained by epoxidizing S A R.

In the formula (2), G represents a hydrogen atom or a glycidyl group, and represents a hydrogen atom, a hydroxyl group, a glycidyloxy group, an alkoxy group having 1 to 8 carbon atoms, a halogen atom, or a carbon atom having 1 to 8 carbon atoms. Indicates a hydrogen group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a butyl ether group, an isopropoxy group, a allyloxy group, a propargyl ether group, a ptoxy group, a phenoxy group, and a benzyloxy group, and a halogen atom. Is exemplified by fluorine atom, chlorine atom, bromine atom and the like. Hydrocarbon groups include methyl, ethyl, bur, ethyne, n-propyl, isopropyl, and aryl. Group, propargyl group, n-butyl group, sec-butyl group, tert-butyl group, n-amyl group, sec-amyl group, tert-amyl group, hexyl group, phenyl group, benzyl group, etc. It is done.

X is a bridging group represented by the formula (a) or (b), but R ₂ , R ₃ , R ₄ and Shaku ₅ are independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. B represents a group consisting of a benzene ring, a biphenyl ring or a naphthalene ring. Note that these rings constituting B may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. X bridges L i, but the substitution position of X with respect to the group represented by the formula (2) constituting L i is not particularly limited. The SAE of the present invention is advantageously produced by reacting the SAR represented by the general formula (3) with epichlorohydrin, but is not limited to this reaction.

In addition to the reaction of SAR with epichlorohydrin, SAR and a halogenated halide can be reacted to form a allylic ether compound and then reacted with a peroxide. The reaction of reacting the above SAR with epichlorohydrin can be carried out in the same manner as a normal epoxidation reaction. ,

For example, after dissolving the above SAR in an excess of epichlorohydrin, in the presence of an alkali metal hydroxide such as sodium hydroxide or hydroxy hydroxide, 20 to 150 ° C, preferably And a method of reacting in the range of 30 to 80 for 1 to 10 hours. In this case, the amount of the alkali metal hydroxide used is in the range of 0.8 to 1.5 mol, preferably 0.9 to 1.2 mol, per 1 mol of the SAR hydroxyl group. In addition, epichlorohydrin is used in excess relative to 1 mol of hydroxyl group in SAR, but usually 1.5 to 30 mol, preferably 2 to 1 mol, relative to 1 mol of hydroxyl group in SAR. The range is 5 moles. After completion of the reaction, excess epichlorohydrin is distilled off, and the residue is dissolved in a solvent such as toluene or methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the solvent is distilled off. The target epoxy resin can be obtained.

The epoxy resin composition of the present invention contains at least an epoxy resin and a curing agent, and there are the following two types. 1) The composition which mix | blended said SAE as a part or all of an epoxy resin.

2) A composition in which the SAE and SAR are blended as part or all of the epoxy resin and the curing agent.

In the case of the above composition 2), the amount of SAR is usually in the range of 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 it is less than this, the effect of improving the adhesion and flame retardancy 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 SAR is used as the total amount of curing agent, the amount of SAR is usually determined in consideration of the equivalent balance of SAR OH groups and epoxy groups 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, and 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 and mechanical strength of the cured product are lowered.

Curing agents other than SAR can be used in combination. The amount of the other curing agent is such that the amount of the SAR is usually in the range of 2 to 200 parts by weight, preferably 5 to 80 parts by weight with respect to 100 parts by weight of the epoxy resin. Determined within. If the amount of SAR is less than this, the effect of improving low moisture absorption, adhesion and flame retardancy 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 curing agents other than SAR, all of those generally known as epoxy resin curing agents can be used, such as dicyandiamide, acid anhydrides, polyhydric phenols, aromatic and aliphatic amines. . Among these, polyhydric phenols are preferably used as curing agents in fields where high electrical insulation properties such as semiconductor encapsulants are required. Specific examples of curing agents are shown below.

Examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrohydrous phthalic acid, methylhydric anhydride, Examples include dodecyl succinic anhydride, nadic anhydride, and trimellitic anhydride. Examples of the polyhydric phenols include bisphenol A, bisphenol F, bisphenolore S, funoleolene bisphenolate, 4, 4 '— biphenolate, 2, 2' — biphenolate, hydrodroquinone, resornoresin, naphthalene. Divalent phenol / Les such as dioreno, or tris- (4-hydroxyphenyl) methane, 1, 1, 2, 2-tetraxyl (4-hydroxyphenyl) ethane, phenol monovolak, There are trihydric or higher phenols such as 0-cresol novolac, naphthol novolak, and polybuhlphenol. Furthermore, phenols, naphthols, bisphenol A, bisphenol enole F, bisphenol nore S, funole ren bisphenolenore, 4, 4'-biphenolate, 2, 2'-biphenol, hydroquinone, Multivalent phenolic compounds synthesized by divalent phenols such as resorcinol and naphthalene diol, and condensing agents such as formaldehyde, acetoaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene render alcohol, etc. There are compounds. Moreover, the above-mentioned phenol resin composition can also be blended. -Amines include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfone, m-phenylenediamine, p-xylylenediamine Aromatic amines such as ethylenediamine, 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, bisphenol A, bisphenol F, bisphenol nore S, funoleolene bisphenol nore, 4, 4'—biphenolate, 2,2'—biphenol, tetrabromobisphenol A, hydroquinone, resorcin Divalent phenols such as Tris mono (4-Hydroxyphenyl) methane, 1, 1, 2, 2—Tetrakis (4-Hydroxyphenyl) Ethaneya, phenol, Cresol, naphthol and other novolaks Aralkyls such as resin, phenol, cresol, naphthol, etc. There are darcidyl etherified products of trihydric or higher phenolic compounds such as resins. These epoxy resins can be used alone or in combination of two or more.

In the case of the above compositions 1) and 2), any of the curing agents generally known as epoxy resin curing agents can be used. For example, there are dicyandiamide, polyhydric phenols, acid anhydrides, aromatic and aliphatic amines, and the like. Further, S A R represented by the general formula (3) is also preferably exemplified. One or more of these hardeners can be mixed and used in this resin composition.

Moreover, in this epoxy resin composition, you may mix | blend another kind of epoxy resin other than SAE represented by General formula (1) as an epoxy resin component. As the epoxy resin in this case, all ordinary epoxy resins having two or more epoxy groups in the molecule can be used. For example, bisphenol A, bisphenol S, fluorene bisphenol nore, 4, 4 '— biphenolate, 2, 2' — bivalent phenols such as biphenolate, hydroquinone, resorcin, or trisou (4 -Hydroxyphenyl) methane, 1, 1, 2, 2—Tetrakis (4-Hydroxyphenyl) ethane, phenol novolak, o-chloro novolak, etc. Trivalent or higher phenols, phenolic aralkyl resins, naphth Examples include toll-based aralkyl resins, and darcidyl ethers derived from halogenated bisphenols such as tetrabromobisphenol A. These epoxy resins can be used alone or in combination of two or more. In the case of a composition containing the SAE of the present invention as an essential component, the amount of SAE represented by the general formula (1) is 5 to 100%, preferably 60 to 1% in the whole epoxy resin. It should be in the range of 0 0%.

In the epoxy resin composition of the present invention, other oligomers or polymer compounds such as polyester, polyamide, polyimide, polyester, polyurethane, petroleum resin, indene resin, indene coumarone resin, and phenoxy resin are used. You may mix | blend suitably as a modifier of this. 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 may contain additives such as inorganic fillers, pigments, flame retardants, thixotropic agents, coupling agents, and fluidity improvers. Examples of the inorganic filler include spherical or fractured fused silica, silica powder such as crystalline silica, alumina powder, glass powder, or my strength, talc, calcium carbonate, alumina, hydrated alumina, and the like. A preferable blending amount when used for a sealing material 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, castor oil, aliphatic amide wax, oxidized polyethylene wax, and organic bentonite.

Furthermore, a curing accelerator can be used in the epoxy resin composition of the present invention as needed. Examples include amines, imidazoles, organic phosphines, Lewis acids, etc., specifically 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, Tertiary amines such as triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl 1-methylimidazole, 2-imidazole such as 2-heptadecylimidazole, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylenophosphine, diphenylenophosphine, and phenylenophosphine, Norrephosphonium Te Tetra-substituted phosphonium tetrasubstituted borates such as rough enoreborate, tetrafuenore phosphonium ethyltriphenyl borate, tetrabutyl phosphonium tetrabutyl borate, etc. Tetraphenylboron salts such as methylmorpholine.tetrafenyl borate. 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-glycidoxyprovir trimethoxysilane, Colorants such as Nblack, flame retardants such as antimony trioxide, low stress reducing agents such as silicon oil, lubricants such as calcium stearate, and the like 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, a polyamide nonwoven fabric, a polyester nonwoven fabric such as a liquid crystal polymer, and the like, and then the solvent is removed. It can be a pre-preda. In some cases, a laminate can be formed by coating on a sheet-like material such as a copper foil, a stainless steel foil, a polyimide film, or a polyester film.

If the epoxy resin composition of the present invention is cured by heating, an epoxy resin cured product can be obtained. 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 120-20. Example

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-2207. The GPC measurement conditions were as follows: equipment: HLC-8 2 A (manufactured by Tosohichi Co., Ltd.), column: TSK-GE L 2 000 X 3 and TSK-GE L 400 0 X 1 (both Tosoh Co., Ltd.), solvent: tetrahydrofuran, flow rate: 1 m 1 Zmin, temperature: 38, detector: RI, polystyrene standard solution was used for the calibration curve.

Example 1

In a 1 L, 3 separable flask equipped with a stirrer, condenser, and nitrogen inlet tube, 40.0 'g dihydroxydiphenylsulfide 20.0 g, p-xylylene dichloride 48.2 g Monoclonal benzene 1 65 g was charged and heated to 80 0 to dissolve while introducing nitrogen. Thereafter, the mixture was heated to 150 ° C. with stirring under reduced pressure and reacted for 3 hours. During this time, hydrochloric acid and monochlorobenzene produced by the reaction were removed from the system. afterwards, Hydrochloric acid was removed under reduced pressure to obtain a hydroxy compound 2 2 8.lg. This compound is called SAR-A. The softening point of the obtained resin was 66, and the melt viscosity at 150 was 0. IIP a -s.

Fig. 1 shows the ¹ H-NMR spectrum of SAR-A, Fig. 2 shows the infrared absorption spectrum, and Fig. 3 shows the GPC chart.

Example 2

4, 4'-dihydroxydiphenyl sulfide 200.0 g, 4,4'-bisclomethyl methylbiphenyl 69.1 g, monochrome benzene 1 7 9 g, and nitrogen introduced into 80 Heat to dissolve. Thereafter, while stirring under reduced pressure, the temperature was raised to 150 and reacted for 3 hours. During this time, hydrochloric acid and monochlorobenzene produced by the reaction were removed from the system. Thereafter, hydrochloric acid was removed under reduced pressure to obtain 249.0 g of a hydroxy compound. This compound is called SAR-B. The softening point of the obtained resin was 82, and the melt viscosity at 150 was 0.60 Pa · s.

Example 3

The reaction was conducted in the same manner as in Example 2 using 200,0 g of 4,4′-dihydroxydiphenylsulfide, 61.9 g of bischloromethylnaphthalene, and 17.5 g of monochlorobenzene. Droxy compound 240. lg was obtained. This compound is called SAR-C. The softening point of the obtained resin was 93, and the melt viscosity at 150 3 was 0.75 Pa ′s. Example 4

Charge 4,4'-dihydroxydiphenylsulfide 300.0 g, 9 2% paraformaldehyde 13.5 g, 200 g of monochlorobenzene benzene, heat to 90 while introducing nitrogen and dissolve I let you. Thereafter, 0.52 g of oxalic acid was added with stirring and reacted for 3 hours. During this time, water produced by the reaction was removed from the system. Furthermore, the temperature was raised to 120 and the reaction was carried out for 1 hour. After that, the temperature was raised to 150 ^ under reduced pressure to remove the condensed water and the monochrome benzene. Thereafter, 450 g of methylisobutyl ketone was added, and the mixture was washed with water at 80 "C. Further, methylisobutyl ketone was distilled off under reduced pressure at 15 and then hydroxylated. Compound 3 0 3. lg was obtained. This compound is called SAR—D. The softening point of the obtained resin was 73, and the melt viscosity at 150 was 0.20 Pa's.

Example 5

Into 100 g of phenol novolak (softening point 82, OH equivalent 10 3) melted at 150, add SAR—AlOO g obtained in Example 1 and melt evenly As a result, 200 g of a phenol resin composition was obtained (resin composition A). The softening point of the obtained funinol resin composition was 76, and the melt viscosity at 1550 was 0.18 Pa * s.

Examples 6 to 1 1 and Comparative Examples 1 to 2

0-cresol novolac type epoxy resin (OCNE; epoxy equivalent 2 200, softening point 65 ° C) as epoxy resin component, SAR-A obtained in Examples 1, 2, 3, and 4 as curing agent, S AR—B, S AR — C, S AR—D, phenol resin composition (resin composition A) obtained in Example 5, phenol novolak (curing agent A: manufactured by Gunei Chemical Co., Ltd., P SM— 4 2 6 1; 0 H equivalent 10 3, softening point 8 2), phenol aralkyl resin (curing agent B; made by Meiwa Kasei, ME H—780 0 SS, OH equivalent 1 75, softening point 6 7 ° ) Was used, and kiri force (average particle size 18 μm) as a filler and triphenylphosphine as a curing accelerator were mixed and kneaded to obtain a thermosetting resin composition. Table 1 shows the composition of the thermosetting resin. Using this thermosetting resin composition, it was molded at 1755, and was bombarded at 1755 for 12 hours to obtain a cured specimen, which was then subjected to various physical property measurements.

The glass transition point (T g) and the coefficient of linear expansion (CTE) using this thermosetting resin composition were measured at a heating rate of 10 / min using a thermomechanical measuring device. The water absorption rate is 85 mm and 85 mm RH using a circular test piece with a diameter of 50 mm and a thickness of 3 mm. A disk having a diameter of 50 mm and a thickness of 3 mm was formed using the object, and the weight change rate after post-curing and absorbing moisture for 1 3 3 ^, 3 atm, 96 hours. The adhesive strength was 25 mm 'x 1 2.5 mm x 0.5 mm between two copper plates, molded in 1 75 5 ¾ with a compression molding machine, and post-pressed for 1 2 hours at 1800. After performing tocure, the tensile shear strength was evaluated. 'Flame Retardation Thickness 1 Z 16 inch test Specimens were molded and evaluated according to the UL 94 V-0 standard and expressed as the total burn time for five specimens. The results are summarized in Table 2.

table 1

Table 2

The glass transition point (T g) and the coefficient of linear expansion (CTE) using this epoxy resin composition were measured at a heating rate of 10 / min using a thermomechanical measuring device. The water absorption rate is Using a circular test piece with a diameter of 5 Omm and a thickness of 3 mm, the water absorption rate obtained by absorbing moisture for 10 hours under the conditions of 85% and 85% RH was 50 mm in diameter and thick with this epoxy resin composition. A 3 mm-thick disk was formed, and the rate of weight change after post-curing was 1 3 3 and absorbed moisture at 3 atm for 96 hours. Adhesive strength is 25 mm X 1 2.5 mm X 0.5 mm between two copper plates, molded at 1 75 with a compression molding machine, and postcured at 180 for 12 hours Evaluation was made by determining the tensile shear strength. Flame retardancy was measured by UL 94 V-0 standard after molding a test specimen with a thickness of 1 Z 16 inches and expressed as the total burning time of five specimens.

Example 1.2

In a four-separable flask, 30 g of SAR-A 1 obtained in Example 1, 48 5 g of epichlorohydrin, and 7 3 g of diethylene glycol dimethyl ether were stirred and dissolved. After uniform dissolution, keep it at 65 5 under reduced pressure of 13 OmmH g, and add 47.4% aqueous solution of sodium hydroxide 87.4 g over 4 hours. The epichlorohydrin was separated in a separation tank, the epichlorohydrin was returned to the reaction vessel, and water was removed from the system to react. After completion of the reaction, the salt produced by filtration was removed, and after further washing with water, epichlorohydrin was distilled off to obtain 17.9.9 g of epoxy resin (S AE-A). The melt viscosity of the obtained resin at 15 was 0.14 Pa · s, and the epoxy equivalent was 205 g / eq. Fig. 4 shows the ¹ H-NMR spectrum of SAE-A, Fig. 5 shows the infrared absorption spectrum, and Fig. 6 shows the GPC chart.

Examples 1 3 to 16 and Comparative Examples 3 to 5

As an epoxy resin component, SAE-A, 0-cresol novolac type epoxy resin synthesized in Example 12 (OCNE; epoxy equivalent of 200, with softening point 65), diphenyl sulfide type epoxy resin (Toto) Kasei, YS LV—50 TE; epoxy equivalent 1700, melting point 45 V), and as a curing agent component, SAR—A synthesized in Example 1, phenol novolak (curing agent A: manufactured by Gunei Chemical Co., Ltd.) , P SM— 4 26 1; OH equivalent of 10 3 with softening point of 8 2), 1—naphthol aralkyl type resin (curing agent B: manufactured by Tohto Kasei, SN—4 7 5; 0 20

H equivalent 2 1 0, softening point 7 7) was used. Furthermore, an epoxy resin composition was obtained with the composition shown in Table 3, using spherical silica (average particle size 18 / zm) as a filler and triphenylphosphine as a curing accelerator. The numerical value in a table | surface shows the weight part in a mixing | blending.

Using this epoxy resin composition, it was molded in 1 75 ¾, and further post cured at 1 75 for 12 hours to obtain a cured product test piece, which was then subjected to various physical property measurements. The results are shown in Table 4.

Table 3

Table 4

Industrial applicability The SAR of the present invention is useful as a curing agent and modifier for epoxy resins, and is excellent in adhesiveness to dissimilar materials when applied to thermosetting resin compositions, particularly epoxy resin compositions. At the same time, it gives a cured product with excellent flame resistance and heat resistance, and can be suitably used for applications such as sealing of electric / electronic parts and circuit board materials. In addition, the sulfide structure-containing epoxy resin (SAE) of the present invention, when applied to an epoxy resin composition, is excellent in high adhesion with different materials and gives a cured product excellent in flame retardancy and heat resistance. It can be used suitably for applications such as sealing of electric / electronic parts, circuit board materials, and the like. If the epoxy resin composition containing the SAE or sulfide structure-containing polyhydric hydroxy compound (hereinafter also referred to as SAR) of the present invention is cured by heating, it can be made into an epoxy resin cured product, and this cured product is adhered closely Excellent in terms of heat resistance, flame retardancy, high heat resistance, etc., and can be suitably used for applications such as sealing of electric and electronic parts and circuit board materials.

Claims

The scope of the claims

The following general formula (1)

Where

L! Is the following formula (2)

R i is a hydrogen atom, a hydroxyl group, a glycidyloxy group, an alkoxy group having 1 to 8 carbon atoms, a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms, G is a hydrogen atom, g Lysidyl group,

X is the following formula (a) or formula (b)

(b)

R ₂ , R ₃ , R 4 and R ₅ independently represent a hydrogen atom or a hydrocarbon group having carbon number:! To 6 and B represents a benzene ring, biphenyl ring or naphthalene ring N represents a number from 0 to 20;

A novel epoxy resin or polyhydric hydroxy compound represented by

2. General formula (3)

H- L ₂ 1 (X— (3)

here,

L, is the following formula (4)

R i represents a hydrogen atom, a hydroxyl group, an aralkoxy group having 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms,

X is the following (a) or formula (b)

R ₂ , R ₃ , R ₄ and R ₅ independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and B represents a benzene ring, a biphenyl ring or a naphthalene ring. N represents a number from 0 to 20;

2. The method for producing an epoxy resin according to claim 1, wherein the polyhydric hydroxy compound represented by the formula is reacted with epichlorohydrin.

3. An epoxy resin composition comprising an epoxy resin and a curing agent, according to claim 1. An epoxy resin composition comprising 24 epoxy resins and / or polyhydric hydroxy compounds as essential components.

4. A cured product obtained by curing the epoxy resin composition according to claim 3.

5. 0.1 to 0.9 mol of a cross-linking agent represented by the following formula (6), (7), (8) or (9) with respect to 1 mol of the hydroxy compound represented by the following formula (5) The method for producing a polyhydric hydroxy compound according to claim 2, wherein

2CHO (6)

R ₂ R ₃ C = 0 (7)

In the formula, represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ₂ , R ₃ , R ₄ and R ₅ are independently a hydrogen atom. Alternatively, it represents a hydrocarbon group having 1 to 6 carbon atoms, B represents a group consisting of a benzene ring, biphenyl ring or naphthalene ring, and Y and Z independently represent OH, alkoxy or halogen.

6. The polyhydric hydroxy compound according to claim 1, which has a softening point of 40 to 200.