WO2006043524A1

WO2006043524A1 - Resin containing indole skeleton, epoxy resin containing indole skeleton, epoxy resin composition and cured product therefrom

Info

Publication number: WO2006043524A1
Application number: PCT/JP2005/019079
Authority: WO
Inventors: Hisashi Yamada; Masashi Kaji
Original assignee: Nippon Steel Chemical Co., Ltd.; Tohto Kasei Co., Ltd.
Priority date: 2004-10-21
Filing date: 2005-10-18
Publication date: 2006-04-27

Abstract

The present invention relates to an epoxy resin providing a cured product being excellent in high heat resistance, moisture resistance and flame resistance, and in the adhesion with a different type of material, and also to a resin containing an indole skeleton used as an intermediate for the epoxy resin. The above resin containing an indole skeleton is prepared by reacting 100 moles in total of an indole and a phenol with 10 to 90 moles of a crosslinking agent such as an aldehyde and a xylylene glycol. The above epoxy resin containing an indole skeleton is prepared by the epoxidation of the above resin containing an indole skeleton with epichlorohydrin. The resin containing an indole skeleton can be represented by the following general formula (1): H-L-(X-L)n-H (1) wherein L is a divalent group formed from an indole or a phenol, the presence ratio (mole ratio) of an indole-derived group and a phenol-derived group is in the range of 1:9 to 9:1, X is a divalent group formed from a crosslinking agent such as an aldehyde, a ketone, xylylene glycol or divinyl benzene, and n represents a number of 1 to 10.

Description

Specification

Indole skeleton-containing resin, indole skeleton-containing epoxy resin, epoxy resin composition and cured product thereof

Technical field

The present invention relates to an indole skeleton-containing resin useful as an intermediate of epoxy resin, a curing agent, etc., an indole skeleton-containing epoxy resin, an epoxy resin composition using these, and a cured product thereof. It is preferably used as an insulating material in the electric and electronic fields such as printed wiring boards and semiconductor encapsulation. Background art

[0002] Epoxy resin has been used in a wide range of industrial applications, but its required performance has become increasingly sophisticated in recent years. For example, there is a semiconductor encapsulating material in a typical field of a resin composition mainly composed of epoxy resin, but as the integration degree of semiconductor elements increases, the package size is becoming larger and thinner. The mounting method is also shifting to surface mounting, 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, the viewpoint power of improving solder heat resistance In addition to the improvement of low moisture absorption, high heat resistance, and high adhesion, development of materials with excellent low dielectric properties is desired from the viewpoint of reducing dielectric loss. Speak. In order to meet these demands, various new structures of epoxy resins and curing agents have been studied. More recently, from the viewpoint of reducing the environmental load, there has been a movement to eliminate halogen-based flame retardants, and there has been a demand for epoxy resins and hardeners with better flame retardancy.

[0003] There are the following documents as prior art related to the present invention.

Patent Document 1: JP-A-5-1099345

Patent Document 2: JP-A-11-140166

Patent Document 3: Japanese Patent Application Laid-Open No. 2004-46522

Patent Document 4: Japanese Patent Application Laid-Open No. 2004-59792

Patent Document 5: Japanese Patent Laid-Open No. 4-173831 Patent Document 6: Japanese Unexamined Patent Publication No. 2000-129092

Patent Document 7: Japanese Patent Laid-Open No. 3-90075

Patent Document 8: JP-A-3-281623

[0004] Accordingly, various epoxy resins and epoxy resin curing agents with the above background power have been studied. As an example of an epoxy resin hardener, naphthalene-based resin is known, and Patent Document 1 shows the application of naphthol aralkyl resin to semiconductor encapsulants. However, although naphthol aralkyl rosin is excellent in low hygroscopicity, low thermal expansion, etc., it has a disadvantage of poor curability. Further, Patent Document 2 proposes a curing agent having a biphenyl structure and describes that it is effective for improving flame retardancy, but has a drawback of being inferior in curability. Furthermore, both naphthalene-based and biphenyl-based resins have a main skeleton composed only of hydrocarbons, so they were not sufficient for the development of flame retardancy. Patent Document 3 describes indole oligomers copolymerized with aromatic olefins.

[0005] On the other hand, an epoxy resin that satisfies these requirements has not been known yet. For example, the well-known bisphenol 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 and additives. There is a problem in terms of resistance and moisture resistance. Further, novolac type epoxy resin is known as an improved heat resistance, but there are problems in moisture resistance, adhesion and the like. Furthermore, conventional epoxy resins whose main skeleton is composed only of hydrocarbons have no flame retardancy.

[0006] As a measure for improving flame retardancy without using a rogen-based flame retardant, a method of adding a phosphate-based flame retardant is known. However, the method using a phosphate ester flame retardant does not have sufficient moisture resistance. In addition, the phosphoric acid ester is hydrolyzed under high temperature and humidity, and there is a problem that the reliability as an insulating material is lowered.

[0007] Patent Documents 2, 5, and 6 disclose examples in which 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. ing. Patent Document 4 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, moisture resistance, and heat resistance. Patents References 7 and 8 disclose naphthol-based aralkyl-type epoxy resins and semiconductor encapsulating materials containing them, but nothing focuses on flame retardancy.

Disclosure of the invention

Problems solved by the invention

H

[0008] An object of the present invention is to contain an indole skeleton useful for an intermediate of epoxy resin, a curing agent, etc.

H N

Providing grease, excellent flame retardancy, and excellent performance in moisture resistance, heat resistance, adhesion to metal substrate, etc., useful for applications such as lamination, molding, casting and adhesion Providing a new indole skeleton-containing epoxy resin, having excellent moldability, and providing electrical and electronic parts that provide cured products with excellent moisture absorption, heat resistance, adhesion, and flame retardancy Another object of the present invention is to provide an epoxy resin composition useful for circuit board materials and the like, and to provide a cured product thereof.

Means for solving the problem

[0009] The indole skeleton-containing coffin of the present invention is represented by the following general formula (1).

H-L- (X-L) -H (1)

here,

L is the following formula (2) and formula (3)

Ri

(2)

(3) R is 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 A is a group having 1 carbon atom. Even if the alkyl group or hydroxyl group of ˜8 is substituted, it represents a group having a benzene ring or naphthalene ring force, and the abundance ratio (molar ratio) of the groups represented by the formulas (2) and (3) is 1: 9-9: 1, where X is the following (a) or formula (b)

R, R, R

2 3 4 and R

5 independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, B represents a group having a benzene ring, biphenyl ring or naphthalene ring force,

n represents 1 to: the number of LOs.

This indole skeleton-containing rosin has a molar ratio of indole represented by the following formula (4) and phenol represented by the following formula (5) in the range of 1: 9 to 9: 1. It is obtained by reacting 10 to 90 mol of a crosslinking agent represented by the following formula (6), (7), (8) or (9) with respect to 100 mol.

(7)

However,

R represents a hydrogen atom, a hydroxyl group, an alkoxy group having 8 carbon atoms, a halogen atom or a hydrocarbon group having 8 to 8 carbon atoms,

A represents an alkyl group having 1 to 8 carbon atoms or a group having a benzene ring or naphthalene ring which may be substituted by a hydroxyl group,

R, R, R and R independently represent a hydrogen atom or a hydrocarbon group having a carbon number], B represents a group having a benzene ring, biphenyl ring or naphthalene ring,

Z and Z independently represent OH, alkoxy or halogen.

1 2

The indole skeleton-containing epoxy resin of the present invention is represented by the following general formula (10).

H-L-(X-L) -H (10)

1 1 n

Niko,

L is the following formula (11) or formula (12)

A OI ¾ 一

Any one of the groups represented by (1 2), wherein R is a hydrogen atom, a glycidyloxy group, having 1 to 8 carbon atoms.

6

An alkoxy group, a halogen atom, or a hydrocarbon group having 1 to 8 carbon atoms, and A represents a group having a benzene ring or naphthalene ring force, which may be substituted by an alkyl group or glycidyloxy group having 1 to 8 carbon atoms. The ratio of the groups represented by the formulas (11) and (12) (molar ratio) is in the range of 1: 9 to 9: 1,

Y represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms or a glycidyl group, G represents a glycidyl group,

X has the same meaning as in general formula (1),

n represents 1 to: the number of L0.

[0012] This indole skeleton-containing epoxy resin can be advantageously obtained by reacting the indole skeleton-containing resin represented by the general formula (1) with epichlorohydrin.

[0013] The phenolic resin composition of the present invention is obtained by blending 2 to 200 parts by weight of an indole skeleton-containing resin with 100 parts by weight of a polyhydric phenolic compound. The epoxy resin composition comprising the epoxy resin and the curing agent of the present invention comprises 2 to 200 parts by weight of an Indian skeleton-containing resin as part or all of the curing agent with respect to 100 parts by weight of the epoxy resin. The indole skeleton-containing epoxy resin is blended as a part of or the entire power of the epoxy resin. The epoxy resin cured product of the present invention can be obtained by hardening this phenol resin composition.

[0014] The indole skeleton-containing rosin (hereinafter also referred to as ISR) of the present invention is represented by the general formula (1). The indole skeleton-containing epoxy resin (hereinafter also referred to as ISE) of the present invention has the general formula (10) It is represented by Since ISE can be obtained by epoxidizing ISR, ISR is also an intermediate of ISE.

[0015] In the general formula (1), L is a group selected from the basic forces represented by the formulas (2) and (3), and the abundance ratio thereof is 1: 9 to 9: 1, preferably 3: 7-7: 3. X is a group represented by formula (a) or formula (b), and n is a number from 1 to 10. Here, n + 1 L and n X in the formula (1) may be the same or different from each other, but L is the above-mentioned abundance ratio in the fat and oil in the formula (2) and the formula There is a group represented by (3). However, since rosin is a mixture, it only needs to exist as an average. As for n, since rosin is a mixture, its average (number average) is preferably in the above range.

In the formulas (2) and (3), R is a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, preferably an alkoxy group having 1 to 6 carbon atoms, a halogen atom, or a carbon atom having 1 to 8, preferably 1 to 7 Represents a hydrocarbon group. A may be substituted with an alkyl group or a hydroxyl group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, or from phenols (may be polyhydric or polycyclic aromatic funols). The resulting group is indicated.

[0017] X is a bridging group represented by formula (a) or formula (b). Forces R, R, R and R are independently water

2 3 4 5

An elementary atom or a hydrocarbon group having 1 to 6 carbon atoms, and B represents a group consisting of a benzene ring, biphenyl ring or naphthalene ring. In addition, these rings constituting B may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. X bridges L, but the substitution position of X with respect to the groups represented by formulas (2) and (3) constituting L is not particularly limited. For example, the 1-position force of the indole ring is also 7-position. A structure in which a hydrogen atom is substituted with a bridging group and linked can be taken, but it is preferable that the hydrogen atom at the 1-position of the indole ring in formula (2) remains. It is not necessary that the 1-position hydrogen atom of all indole rings remain, but if the 1-position hydrogen atom of all indole rings is substituted, the indole skeleton-containing resin of the present invention functions as a curing agent. Is not fully expressed.

[0018] The softening point of the ISR is preferably 40 to 200 ° C, more preferably 50 to 160 ° C, and more preferably 60 to 120 ° C. Here, the softening point refers to the softening point measured based on the ring and ball method of JISK-6911. 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. [0019] The ISR of the present invention can itself be a component of a phenol resin composition or an epoxy resin composition, but in some cases, a halogen-alkyl compound, an alkenyl halide is added to an indole skeleton-containing resin. By reacting compounds, epino-hydrohydrin compounds, etc., some or all of the -NH- and -OH hydrogen atoms in the indole skeleton-containing resin are replaced with alkyl groups, alkenyl groups, glycidyl groups, etc. can do.

[0020] The ISR of the present invention includes an indole represented by the formula (4) and a phenol represented by the formula (5), a formula (6), a formula (7), (8) or (9). It can be synthesized by reacting the represented crosslinking agent. 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 total of indoles and phenols. is there. If it is smaller than this, the amount of unreacted indoles and phenols will increase during the synthesis, resulting in lower ISR productivity and lower soft point of the synthesized ISR, which was used as an epoxy resin curing agent. In this case, the heat resistance of the cured product is lowered. On the other hand, if it is larger than this, the softening point of ISR becomes high, and in some cases, ISR may be gelled during synthesis. The proportions of indoles and phenols are adjusted so that they are the above-mentioned proportions. However, since indoles are more reactive with the crosslinking agent, phenols are somewhat less than the theoretical amount. There are cases where there are many cases.

[0021] 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, jetyl sulfuric acid, zinc chloride, aluminum chloride, iron chloride, Examples include Lewis acids such as boron fluoride, or solid acids such as ion-exchange resin, activated clay, silica-alumina, and zeolite.

[0022] This reaction is usually performed at 10 to 250 ° C for 1 to 20 hours. Furthermore, during the reaction, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycolol, methinoreserosolve, ethyl acetate, etc., ketones such as acetone, methylethyl ketone, methylisobutylketone, dimethyl ether, jetyl Ethers such as ether, diisopropyl ether, tetrahydrofuran and dioxane, and aromatic compounds such as benzene, toluene, chlorobenzene and dichlorobenzene can be used as the solvent. [0023] Examples of indoles used as a raw material include indoles substituted with a hydroxyl group, an alkoxy group, a halogen atom or a hydrocarbon group as a substituent, in addition to indoles. For example, the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and the like, and the alkoxy group includes a methoxy group, an ethoxy group, a vinyl ether group, an isopropoxy group, a allyloxy group, a propargyl ether group, a butoxy group, and a phenoxy group. It is done. In addition, as the hydrocarbon group, various substituted indoles having a methyl group, an ethyl group, a vinyl group, an ethyne group, an isopropyl group, an aryl group, a propargyl group, a butyl group, an amyl group, a fullyl group, a benzyl group, etc. The power that can be used is preferably indole.

[0024] The phenols include, in addition to phenols, alkylphenols such as talesols and xylenols, polyhydric phenols such as hydroquinone, polycyclic phenols such as naphthols and naphthalenediols, bisphenol A and bisphenols. Examples thereof include bisphenols such as F, and polyfunctional phenolic compounds such as phenol novolak and phenol aralkyl resin. These monomers can be used singly or in combination of two or more. However, from the viewpoint of the physical properties of the cured product obtained by containing ISR, the content of the indole skeleton is high. There are no particular restrictions.

[0025] The cross-linking agent is preferably a formaldehyde represented by formula (6) such as aldehydes such as formaldehyde, acetoaldehyde, propyl aldehyde, butyraldehyde, amyl aldehyde, and benzaldehyde. Preferred formaldehyde raw materials used in the reaction include an aqueous formalin solution, paraformaldehyde, trioxane and the like. Further, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetophenone represented by the formula (7) can also be used as a crosslinking agent.

[0026] Further, the cross-linking agent represented by the formula (8) includes P-xylylenedaricol, P-xylylene glycol dimethyl ether, ρ-xylylene dichloride, 4, 4, -dimethoxymethyl biphenyl. 4,4'-dichloromethylbiphenyl, dimethoxymethylnaphthalene, dichloromethylnaphthalene.

In addition, dibutenebenzenes, dibibiphenols, divinylnaphthalenes and the like represented by the formula (9) can also be used as a crosslinking agent.

[0027] After completion of the reaction, in some cases, the obtained ISR contains unreacted indole and phenol. Ru remains. Unreacted remaining indoles and phenols are usually removed out of the system by methods such as distillation under reduced pressure or solvent separation. It is desirable that the amount of unreacted indole and phenols remaining in the ISR be small, usually 5% or less, preferably 3% or less, more preferably 1% or less. If the amount of the remaining indoles and phenols is large, they volatilize during the production of the molded product, which may reduce the molding workability and cause voids in the molded product. In addition, the flame retardancy of the molded product is also reduced.

[0028] The phenolic resin composition of the present invention comprises the above ISR in a polyhydric phenolic compound. The content of ISR is 2 to 200 parts by weight, preferably 5 to: LOO parts by weight, and more preferably 10 to 80 parts by weight with respect to 100 parts by weight of the polyvalent phenolic compound. If it is less than this, the effects of modification such as low hygroscopicity, heat resistance, adhesion and flame retardancy will be small in winter, and the viscosity will increase and the moldability will decrease.

[0029] The polyhydric phenol compound referred to here refers to any compound having two or more phenolic hydroxyl groups in one molecule, for example, bisphenol A, bisphenol F, bisphenol S, fluorene bis. Divalent phenols such as phenol, 4, 4, -biphenol, 2, 2, -biphenol, hydrin quinone, resorcin, naphthalenediol, or tris- (4-hydroxyphenol) methane, 1, 1 , 2,2-tetrakis (4-hydroxyphenol) ethane, phenol novolak, o-cresol novolak, naphthol novolak, polyvinyl phenol and the like. Furthermore, divalent phenols such as phenols, naphthols, bisphenolanol A, bisphenolanol F, bisphenolanol S, fluorenebisphenol, 4,4, -biphenol, 2,2, biphenol, hydroquinone, resorcinol, naphthalenediol, etc. And formaldehyde, acetoaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene glycol, p-xylylene glycol dimethyl ether, 4,4, -dimethoxymethylbiphenyl, 4,4, -dimethoxymethyldiphenyl There are polyhydric phenolic compounds synthesized by reaction with cross-linking agents such as diethers, divinylbenzenes, dibibiphenols, dibutanaphthalenes.

[0030] The softening point of the polyhydric phenolic compound is usually in the range of 40 to 200 ° C, preferably 60 to 150 ° C. Lower than this, the cure obtained using epoxy hardener as a curing agent The heat resistance of the object decreases. In addition, the mixing property between ISR and higher is lowered.

[0031] The phenolic resin composition of the present invention includes a melt mixing method in which mixing is performed by stirring, kneading, and the like at a temperature equal to or higher than the softening point of either the polyhydric phenolic compound or the ISR, It can be obtained by a method such as a solution mixing method in which both are dissolved in a solvent that dissolves each and mixed uniformly by stirring, kneading or the like. Solvents used in the solution mixing method include, for example, alcohols such as methanolol, ethanol, propanol, butanol, ethylene glycolol, methinoresellosonol, ethyl acetate sorb, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Ketones, dimethyl ether, jetyl ether, diisopropyl ether, tetrahydrofuran, dioxane, and other ethers, and aromatic solvents such as benzene, toluene, xylene, black benzene, and dichlorobenzene. In obtaining this composition, epoxy resin, inorganic filler, other phenolic compounds, and other additives can be blended.

[0032] The phenol resin composition of the present invention can be made into a phenol resin composition by using in combination with a curing agent generally used for phenol resin compositions such as hexamethyltetramine.

Next, the ISE of the present invention represented by the general formula (10) will be described.

In the general formula (10), L is a group selected by the basic force represented by the formula (11) or the formula (12), and the abundance ratio thereof is 1: 9 to 9: 1, preferably 3: 7 to 7 : 3 X is a group represented by the formula (a) or (b), and n is a number from 1 to 10. Here, when there are a plurality of L and X in the formula (10), they may be the same or different, but L is the formula (11) and (12 ) Is present. However, since rosin is a mixture, it should be present as an average.

[0034] In the formulas (11) and (12), R is a hydrogen atom having 1 to 8 carbon atoms, preferably 1

It represents a 6 to 6 alkoxy group, a glycidyloxy group, a halogen atom or a hydrocarbon group having 1 to 8, preferably 1 to 7 carbon atoms. Here, 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 putoxy group, a phenoxy group, and a benzyloxy group, and the halogen atom includes a fluorine atom and a chlorine atom. Examples thereof include a child and a bromine atom. Hydrocarbon groups include methyl, ethyl, and biphenyl. Group, ethyne group, n-propyl group, isopropyl group, aryl group, propargyl group, n-butyl group, sec-butyl group, tert-butyl group, n-amyl group, sec-amyl group, tert-amyl group Group, cyclohexyl group, phenol group, benzyl group and the like. A is a group formed by epoxy-forming phenols (which may be polyhydric or polycyclic aromatic funols) and has 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms. A group having a benzene ring or naphthalene ring force that may be substituted by the alkyl group or glycidyloxy group.

[0035] X and n have the same meaning as X and n in formula (1). That is, X is a bridging group represented by formula (a) or formula (b). n is a number from 1 to 10. In addition, rosin is a mixture, but its average (number average) n is preferably in the above range.

[0036] The ISE of the present invention is advantageously produced by reacting ISR represented by the general formula (1) with epichlorohydrin, but is not limited to this reaction. The ISR represented by the above general formula (1) is a resin that is at least partly, preferably all of which is H or OH, that is epoxyd with epichlorohydrin. In the formulas (10) to (12), this corresponds to a compound in which the glycidyl ether group is OH and the glycidyl group is H. In general formula (10), it is advantageous in terms of flame retardancy to epoxidize such that Y is partly H and part is an oxyglycidyl group.

[0037] In addition to the reaction of reacting ISR with epichlorohydrin, a method of reacting ISR with a allylic halide to form a allylic ether compound and then reacting with a peracid hydrate can also be used. The reaction of reacting the ISR with epichlorohydrin can be carried out in the same manner as a normal epoxy reaction.

[0038] For example, after dissolving the ISR in an excess of epichlorohydrin, in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, 20 to 150 ° C, preferably 30 In the range of ˜80 ° C., 1˜: a method of reacting for L0 hours is mentioned. The amount of alkali metal hydroxide used in this case is in the range of 0.8 to 1.5 mol, preferably 0.9 to 1.2 mol, per 1 mol of the hydroxyl group of ISR. In addition, epichlorohydrin is used in excess of 1 mol of hydroxyl group in ISR. Usually, 1.5 to 30 mol, preferably 2 to 15 mol, per 1 mol of hydroxyl group in ISR. Range. After completion of the reaction, excess epichlorohydrin is distilled off, and the residue is dissolved in a solvent such as toluene or methylisobutyl ketone, filtered, washed with water and washed with an inorganic salt. The desired epoxy resin can be obtained by removing the solvent and then distilling off the solvent.

[0039] The epoxy resin composition of the present invention contains at least an epoxy resin and a curing agent, and there are the following three types.

1) A composition containing the ISR as a part or all of the curing agent.

2) The composition which mix | blended the said ISE as some or all of epoxy resin.

3) Composition containing ISR and ISE as part or all of epoxy resin and curing agent

[0040] In the case of the composition 1), the amount of ISR 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 low hygroscopicity, adhesion and flame retardancy is small. If it is more than this, there is a problem that the moldability and the strength of the cured product are lowered.

[0041] When the ISR of the present invention is used as the total amount of hardener, the amount of ISR is usually determined in consideration of the equivalent balance of -NH- groups and -OH groups of ISR and epoxy groups in the epoxy resin. Mix. The equivalent ratio of epoxy resin and curing agent (epoxy group Z (NH group + OH group) molar ratio) is usually in the range of 0.2 force to 5.0, preferably ί or 0.5 force. The range is 0. If it is larger or smaller than this, the curability of the epoxy resin composition is lowered, and the heat resistance, mechanical strength, etc. of the cured product are lowered.

[0042] As the curing agent, a curing agent other than the ISR of the present invention can be used in combination. The amount of the other curing agent is determined within a range in which the range of the ISR is usually within 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 the amount of ISR is less than this, the effect of improving low moisture absorption, adhesion and flame retardancy is small. If it is more than this, there is a problem that the moldability and the strength of the cured product are lowered.

[0043] As curing agents other than ISR, all those generally known as epoxy resin hardeners can be used, such as dicyandiamide, acid anhydrides, polyhydric phenols, aromatic and aliphatic amines. Etc. Among these, polyhydric phenols are preferably used as curing agents in fields where high electrical insulation properties such as semiconductor encapsulants are required. The following are specific examples of curing agents.

[0044] Examples of the acid anhydride hardener include phthalic anhydride, tetrahydrophthalic anhydride, and methyl. Examples include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl hymic anhydride, dodecyl succinic anhydride, nadic anhydride, and trimellitic anhydride.

[0045] Examples of polyhydric phenols include bisphenol A, bisphenol F, bisphenol 3, fluorene bisphenol, 4, 4, -biphenol, 2, 2, -biphenol, hydroquinone, resorcin, naphthalenediol Divalent phenols such as tris- (4-hydroxyphenol) methane, 1,1,2,2-tetrakis (4-hydroxyphenol) ethane, phenol novolak, o-cresol novolak In addition, trivalent or higher phenols such as naphthol novolac and polyvinyl phenol are available. Furthermore, divalent compounds such as phenols, naphthols, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4, 4, -biphenol, 2, 2, -biphenol, hydroquinone, resorcin, naphthalene diol, etc. And polyhydric phenolic compounds synthesized by a condensing agent such as formaldehyde, acetoaldehyde, benzaldehyde, P-hydroxybenzaldehyde, P-xylylene diol and the like. Further, the above-described phenolic resin composition of the present invention can be blended.

[0046] Examples of amines include 4,4, -diaminodiphenylmethane, 4,4, -diaminodiphenylpropan, 4,4, -diaminodiphenylsulfone, m-phenylenediamine, and p-xylylenediamine. There are aromatic amines such as amine, and aliphatic amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine.

[0047] One or more of these curing agents can be mixed and used in the composition.

[0048] The epoxy resin used in the yarn and composite is selected from those having two or more epoxy groups in one molecule. For example, divalent phenols such as bisphenol A, bisphenol F, bisphenol 3, fluorene bisphenol, 4, 4, -biphenol, 2, 2, -biphenol, tetrabromobisphenol A, hydroquinone, resorcin, etc. Or, tris- (4-hydroxyphenol) methane, 1,1,2,2-tetrakis (4-hydroxyphenol) ethane, novolac sesame such as phenol, cresol, naphthol, phenol, sauce There are glycidyl ethers of phenolic compounds having a valence of 3 or more, such as aralkyl resins such as sol and naphthol. These epoxy resins can be used alone or in combination of two or more. It is possible to be.

[0049] In the case of the above composition 2), as the curing agent, any one generally known as a curing agent for epoxy resin can be used. Examples include dicyandiamide, polyvalent phenols, acid anhydrides, aromatic and aliphatic amines described above. In addition, an ISR represented by the general formula (1) is also preferably exemplified. One or more of these hardeners can be mixed and used in the resin composition.

[0050] In addition to the ISE represented by the general formula (10), another type of epoxy resin may be blended in the epoxy resin composition as an epoxy resin component. As the epoxy resin in this case, all normal epoxy resins having two or more epoxy groups in the molecule can be used. For example, divalent phenols such as bisphenol A, bisphenol S, fluorene bisphenol, 4, 4, 1 biphenol, 2, 2, 1 biphenol, hydroquinone, resorcin, or tris mono (4- Hydroxyphenol) methane, 1,1,2,2-tetrakis (4-hydroxyphenol) ethane, phenol novolak, o-cresol novolak and other trivalent phenols, phenolic aralkyl fats, Examples include naphthol-based aralkyl resins, or darcidyl ether derivatives that are derived from halogen-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 ISE of the present invention as an essential component, the amount of ISE represented by the general formula (1) is 5 to: L00 wt%, preferably 60 to 100 wt% in the entire epoxy resin. It should be in the range!

[0051] In the case of the above composition 3), ISR and ISE are used as part or all of the epoxy resin and curing agent, but the preferred amount of ISR and ISE when used as a part is as described above. The same as in the case of the composition of 1) or 2). As other epoxy resin or curing agent when other epoxy resin and curing agent are used, the same epoxy resin or curing agent as described in the composition can be used.

[0052] In the epoxy resin composition of the present invention, an oligomer or a polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, inden resin, inden'coumarone resin, phenoxy resin, etc. May be appropriately blended as other modifiers. The amount added is usually in the range of 2 to 30 parts by weight per 100 parts by weight of the epoxy resin. [0053] The epoxy resin composition of the present invention may contain additives such as inorganic fillers, pigments, retardants, 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, or my strength, talc, calcium carbonate, alumina, hydrated alumina, and the like. A preferable blending amount when used for a semiconductor encapsulant is 70 wt% or more, and more preferably 80 wt% or more.

[0054] 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, acid-polyethylene nitrate, and organic bentonite-based.

[0055] 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, benzyldimethyl. Tertiary amines such as amine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-phenolimidazole, 2-ethyl-4-methylimidazole, 2-phenol -Ru 4-methylimidazole, imidazoles such as 2-heptadecylimidazole, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylenophosphine, and phenylophosphine, tetraphenylphosphonium 'Tetraphenolate, tetraphenylphospho-um・ Ethyl trifluorate, tetrabutyl phosphorum ・ Tetra-substituted phosphomumes such as tetrabutyl borate, tetra-substituted borate, 2-ethyl 4-methylimidazole “tetraphenol porate, N-methylmorpholine” tetraphenyl borate And tetraphenylboron salts. 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.

[0056] 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 y-glycidoxypropyltrimethoxysilane, carbon black and the like. Colorants, flame retardants such as antimony trioxide, anti-stress agents such as silicone oil, and lubricants such as calcium stearate.

[0057] The epoxy resin composition of the present invention is made into a varnish in which an organic solvent is dissolved, After impregnating fibrous materials such as glass cloth, aramid nonwoven fabric, and polyester nonwoven fabric such as liquid crystal polymer, the solvent can be removed to prepare a pre-preda. 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.

[0058] If the epoxy resin composition of the present invention is cured by heating, an epoxy resin composition can be obtained. This cured product has low moisture absorption, high heat resistance, adhesion, flame retardancy, and the like. Excellent in terms. This cured product can be obtained by molding the epoxy resin composition by casting, compression molding, transfer molding or the like. The temperature at this time is usually in the range of 120 to 220 ° C.

Brief Description of Drawings

[0059] [Fig.1] ¹ H—NMR ^ vector of ISR—A

[Figure 2] Infrared absorption spectrum of ISR-A

[Figure 3] GSR chart of ISR—A

[Fig.4] ¹ H-NMR spectrum of ISE—A

[Figure 5] Infrared absorption spectrum of ISE—A

[Fig.6] GPC chart of ISE—A

Example

[0060] Hereinafter, the present invention will be described more specifically with reference to Examples.

Here, the viscosity was measured by a ring-and-ball method using a B-type viscometer according to the softening point ί and IS K-6911. The GPC measurement conditions were as follows: apparatus; HLC-82A (manufactured by Tosohichi Co., Ltd.), column; Tetrahydrofuran, flow rate; lml / miiu temperature; 38 ° C, detector; RI, polystyrene standard solution was used for the calibration curve.

[0061] Example 1

Stirrer, a cooling tube, in marked with 500mL, 3 b separable flask with a nitrogen inlet tube was charged India one Norre 72. 5g, Fuenonore 233. lg, 92 ^_0/0 Nora phosphono REM § Norre dehydrogenase 27. 9g, the, While introducing nitrogen, it was heated to 90 ° C to dissolve. Then, the temperature was raised to 130 ° C with stirring and the reaction was allowed to proceed for 3 hours. During this time, water produced by the reaction was removed from the system. Then under reduced pressure, The temperature was raised to 180 ° C., and condensed water, unreacted phenol and indole were removed to obtain 150 g of rosin (ISR-A). The softening point of the obtained resin (ISR-A) was 83 ° C, and the melt viscosity at 150 ° C was 0.12 Pa's. The residual monomer amount determined by GPC measurement was 0.5 wt%. Yeah! Fig. 1 shows the NMR ^ vector, Fig. 2 shows the infrared absorption spectrum, and Fig. 3 shows the GPC chart.

[0062] Example 2

Indonore 106. 3 g, the reaction was carried out in the same manner as Fuenonore 199. 2g, 92 ^_0/0 Nora phosphono REM § Honoré dehydropeptidase 27. Example 1 2g of Te use!ヽto give榭脂(ISR- B) 130g. The resulting resin (ISR-B) had a soft melting point of 135 ° C and a melt viscosity at 180 ° C of 0.58 Pa's. The residual monomer amount determined by GPC measurement was 0.4 wt%.

[0063] Example 3

In lOOg phenol novolak (softening point 82 ° C, OH equivalent 103) melted at 150 ° C, add ISR-AlOOg obtained in Example 1 and melt uniformly to obtain 200 g of phenolic resin composition. (Coffin composition A). The resulting phenolic resin composition had a softening point of 82 ° C and a melt viscosity at 150 ° C of 0.18 Pa's.

[0064] Examples 4 to 9 and Comparative Examples 1 to 2

0-cresol novolak type epoxy resin (OCNE; epoxy equivalent 200, softening point 70 ° C) as epoxy resin component, ISR-A, ISR-B obtained in Examples 1 and 2 as curing agent, Example 3 Phenol resin composition (resin composition A), phenol novolac (curing agent A; OH equivalent 103, soft soft point 82 ° C), phenol aralkyl resin (curing agent B; Mitsui) Glossary, XL 225-LL, OH equivalent 172, softening point 74 ° C), silica (average particle size 2 2 m) as filler, and 2-ethyl-4-methylimidazole as curing accelerator in Table 1. The resulting mixture was kneaded to obtain an epoxy resin composition. This epoxy resin composition was used and 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.

[0065] The glass transition point (Tg) and the coefficient of linear expansion (CTE) were measured at a rate of temperature increase of 10 ° CZ using a thermomechanical measurement device. Also, the water absorption rate is the rate of change in weight after forming a disk with a diameter of 50 mm and a thickness of 3 mm using an epoxy resin thread and post-curing, and absorbing moisture at 133 ° C, 3 atm for 96 hours. did. However, in Table 4, a round test with a diameter of 50 mm and a thickness of 3 mm was used. Using the specimen, the rate of change in weight after absorbing moisture for 100 hours under the conditions of 85 ° C. and 85% RH was used. The adhesive strength was 175 ° C, formed on a copper foil with a compression molding machine using an epoxy resin composition. After post-curing at C for 12 hours, the tensile shear strength was determined and evaluated. However, in Table 4, the adhesive strength is 25 mm X 12.5 mm X O. 5 mm molded product between two copper plates at 175 ° C with a compression molding machine and post-cured at 180 ° C for 12 hours. Then, the tensile shear strength was evaluated. Flame retardancy was measured by the UL94V-0 standard after molding a 1Z16 inch thick test piece and expressed as the total burn time for five test pieces. The results are summarized in Table 2.

[0066] [Table 1]

[0067] [Table 2]

[0068] Example 10 100 g of ISR-A obtained in Example 1 was dissolved in 178 g of epichlorohydrin and 36 g of diethylene glycol dimethyl ether. Thereafter, 33.7 g of 96% potassium potassium hydroxide was added over 3 hours at 50 ° C. with stirring, and the reaction was continued for another hour after the addition was completed. After completion of the reaction, the salt produced by filtration was removed, and after further washing with water, epiclorhydrin was distilled off to obtain 110 g of epoxy resin (ISE-A). The obtained epoxy resin had a soft soft point of 78 ° C, a melt viscosity of 0.28 Pa's, and an epoxy equivalent of 278 g / eq. The results of NMR, IR and GPC measurements on ISE-A are shown in FIGS.

[0069] Examples 11 to 14 and Comparative Examples 3 to 5

As the epoxy resin component, ISE-A, 0-cresol novolac type epoxy resin synthesized in Example 10 (epoxy resin B: Nippon Kayaku Co., Ltd., EOCN-1020-65; epoxy equivalent 200, hydrolyzable Chlorine 400ppm, softening point 65 ° C), biphenyl type epoxy resin (Epoxy resin C: made by Japan Epoxy Resin, YX4000HK; epoxy equivalent 195, hydrolyzable chlorine 450ppm, melting point 105 ° C) As an agent component, IS R-A synthesized in Example 1, phenol novolak (curing agent A: manufactured by Gunei Chemical Co., Ltd., PSM-4261; OH equivalent 103, softening point 80 ° C), 1-naphthol aralkyl-type soot Fat (curing agent B: manufactured by Nippon Steel Engineering Co., Ltd., SN-4 75; OH equivalent 210, softening point 77 ° C.) was used. Further, an epoxy resin composition was obtained with the formulation shown in Table 3, using spherical silica (average particle size 18 m) as a filler and triphenylphosphine as a curing accelerator. The numerical value in a table | surface shows the weight part in a mixing | blending.

[0070] Using this epoxy resin composition, it was molded at 175 ° C and further post-cured at 180 ° C for 12 hours to obtain a cured specimen, which was then subjected to various physical property measurements. The results are shown in Table 4.

[0071] [Table 3]

Table 4]

* 1) The flame reaches the upper end of the test piece without extinguishing itself.

Industrial applicability

The ISR of the present invention is useful as an epoxy resin intermediate, an epoxy resin curing agent, and a modifier. When applied to an epoxy resin composition, the ISR has excellent high heat resistance and moisture resistance. It gives a cured product with excellent flame retardancy and high adhesion to different materials, and can be suitably used for applications such as sealing of electronic components and circuit board materials. If an epoxy resin composition containing ISR or ISE of the present invention is cured by heating, an epoxy resin is obtained. It is possible to make a cured oil, and this cured product is excellent in terms of flame retardancy, low moisture absorption, high heat resistance, adhesion, etc., and is suitable for applications such as sealing electrical and electronic parts, circuit board materials, etc. It can be used for

Claims

The following general formula (1)

H-L- (X-L) -H (1)

here,

L is the following formula (2) and formula (3)

R 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 A represents a carbon group having 1 to 8 carbon atoms. Even if an alkyl group or a hydroxyl group is substituted, it indicates a group having a benzene ring or naphthalene ring force, and the abundance ratio (molar ratio) of the groups represented by formula (2) and formula (3) is 1: 9-9 : Range of 1, X is the following (a) or formula (b)

R, R, R and R are independently a hydrogen atom or a carbon number of 1-6. B represents a group having a benzene ring, biphenyl ring or naphthalene ring,

n represents 1 to: the number of LOs;

An indole skeleton-containing rosin represented by:

[2] The indole skeleton-containing resin according to claim 1, wherein the soft anchor point is 40 ° C to 200 ° C.

[3] Molar specific force between the indole represented by the following formula (4) and the phenol represented by the following formula (5) ^: 9 to 9: 1 range, , The following formula (6), (7), (8) or

A method for producing an indole skeleton-containing resin, comprising reacting 10 to 90 mol of the crosslinking agent represented by (9).

R is a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, a halogen atom or a carbon number] Represents ~ 8 hydrocarbon groups,

R, R, R and R independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms,

2 3 4 5

B represents a group consisting of a benzene ring, a biphenyl ring or a naphthalene ring,

Z and Z independently represent OH, alkoxy or halogen.

1 2

[4] A phenol resin composition comprising 2 to 200 parts by weight of the indole skeleton-containing resin according to claim 1 or 2 based on 100 parts by weight of the polyvalent phenolic compound.

[5] In an epoxy resin composition comprising an epoxy resin and a curing agent, the indole skeleton-containing resin according to claim 1 or 2 is used as a part or all of the curing agent. 2 to 200 parts by weight of an epoxy resin composition,

[6] An epoxy resin cured product obtained by curing the epoxy resin composition according to claim 5.

[7] The following general formula (10)

H-L-(X-L) -H (10)

1 1 n

here,

L is the following formula (11) or formula (12)

OG

-A (1 2) is one of the groups represented by the formula, R is a hydrogen atom, a glycidyloxy group, having 1 to 8 carbon atoms

6

An alkoxy group, a halogen atom, or a hydrocarbon group having 1 to 8 carbon atoms, Y represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms or a glycidyl group, G represents a glycidyl group, and A represents 1 carbon atom. ~ 8 alkyl group or glycidyloxy group may be substituted benzene ring or Represents a group having a naphthalene ring force, and the abundance ratio (molar ratio) of the groups represented by the formulas (11) and (12) is in the range of 1: 9 to 9: 1.

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

(a)

R ₃

F

One B—

(b)

R, R, R and R are independently a hydrogen atom or a carbon number of 1-6.

2 3 4 5

B represents a group having a benzene ring, biphenyl ring or naphthalene ring,

n represents 1 to: the number of LOs;

Indole skeleton-containing epoxy resin represented by

[8] An epoxy resin composition comprising the epoxy resin according to claim 7 as an essential component in an epoxy resin composition comprising an epoxy resin and a curing agent.

[9] A cured product obtained by curing the epoxy resin composition according to claim 8.

[10] In the method for producing an epoxy resin according to claim 7, the following general formula (1)

H-L- (X-L) -H (1)

here,

L is the following formula (2) or formula (3)

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 A represents an alkyl group having 1 to 8 carbon atoms. A group having a benzene ring or a naphthalene ring force, even if substituted with a ruthenium group or a hydroxyl group, the abundance ratio (molar ratio) of the groups represented by the formulas (2) and (3) is 1: 9-9: A range of 1 and X and n have the same meaning as in formula (10);

A process for producing an epoxy resin characterized by reacting an indole skeleton-containing resin represented by the formula with epichlorohydrin _n