JP2006117790A - Indole skeleton-containing resin, epoxy resin composition and its cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin useful as a curing agent, a modifier, etc., for epoxy resins, providing a cured product having excellent high heat resistance and moisture resistance and excellent in flame retardance and high adhesiveness between different kind of materials and suitable for applications such as sealing of electric/electronic parts and circuit board materials. <P>SOLUTION: The indole skeleton-containing resin is represented by general formula (1): H-L-(X-L)<SB>n</SB>-H [wherein L is a divalent group derived from indoles and phenols and existence ratio (molar ratio) of indoles to phenols is 1:9 to 9:1 and X is divalent group derived from a crosslinking agent such as an aldehyde, ketone, xylylene glycol or divinylbenzene; n is a number of 1 to 10]. The indole skeleton-containing resin is obtained by reacting 100 mol total of indoles and phenols with 10-90 mol crosslinking agent such as aldehyde and xylylene glycol. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an indole skeleton-containing resin useful as an epoxy resin curing agent, modifier, etc., and electrical / electronic components that give cured products excellent in low moisture absorption, heat resistance, adhesion, flame retardancy, etc. The present invention relates to a phenol resin composition useful for sealing, circuit board materials, and the like, and an epoxy resin composition and a cured product thereof.

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

  Therefore, various epoxy resin curing agents have been studied from the above background. As an example, a naphthalene-based resin is known, and Patent Document 1 shows that a naphthol aralkyl resin is applied to a semiconductor sealing material. However, although the naphthol aralkyl resin is excellent in low hygroscopicity, low thermal expansion property, etc., it has a defect of poor curability. Moreover, although the hardening | curing agent which has a biphenyl structure is proposed in patent document 2 and it describes that it is effective for a flame retardance improvement, there existed a fault which is inferior to curability. Furthermore, both the naphthalene-based resin and the biphenyl-based resin have a main skeleton composed only of hydrocarbons, and thus are not sufficient for the expression of flame retardancy. Patent Document 3 describes an indole oligomer copolymerized with an aromatic olefin.

Japanese Patent Laid-Open No. 5-1093945 JP-A-11-140166 JP 2004-46522 A

  An object of the present invention is to provide an indole skeleton-containing resin useful as a curing agent, a modifier, and the like of an epoxy resin composition, and has excellent moldability, low moisture absorption, heat resistance, adhesion, and difficulty. An object of the present invention is to provide an epoxy resin composition useful for sealing electrical and electronic parts, circuit board materials, and the like that provide a cured product having excellent flammability and the like, and to provide a cured product thereof. Moreover, the objective of this invention is providing the phenol resin composition useful for the hardening | curing agent etc. of an epoxy resin.

で表される基のいずれかであり、Ｒ₁は水素原子、水酸基、炭素数１〜６のアルコキシ基、ハロゲン原子又は炭素数１〜７の炭化水素基を示し、Ａは炭素数１〜６のアルキル基若しくは水酸基が置換してもよいベンゼン環又はナフタレン環からなる基を示し、式（２）と式（３）で表される基の存在割合（モル比）が1：9〜9：1の範囲であり、Ｘは下記（ａ）又は式（ｂ）

で表される架橋基であり、Ｒ₂、Ｒ₃、Ｒ₄及びＲ₅は独立に、水素原子又は炭素数１〜６の炭化水素基を示し、Ｂはベンゼン環、ビフェニル環又はナフタレン環からなる基を示し、ｎは１〜１０の数を示す。）で表されるインドール骨格含有樹脂である。このインドール骨格含有樹脂の軟化点は、４０〜２００℃の範囲にあることが好ましい。 That is, the present invention provides the following general formula (1)
HL- (XL) _n -H (1)
(Where L is the following formula (2) and formula (3)

R ₁ represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, or a hydrocarbon group having 1 to 7 carbon atoms, and A represents a group having 1 to 6 carbon atoms. A group consisting of a benzene ring or a naphthalene ring which may be substituted by an alkyl group or a hydroxyl group, wherein the abundance ratio (molar ratio) of the groups represented by the formulas (2) and (3) is 1: 9 to 9: 1, 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 of 1 to 10. ) -Containing indole skeleton-containing resin. The softening point of the indole skeleton-containing resin is preferably in the range of 40 to 200 ° C.

（但し、Ｒ₁は水素原子、水酸基、炭素数１〜６のアルコキシ基、ハロゲン原子又は炭素数１〜７の炭化水素基を示し、Ａは炭素数１〜６のアルキル基若しくは水酸基が置換してもよいベンゼン環又はナフタレン環からなる基を示し、Ｒ₂、Ｒ₃、Ｒ₄及びＲ₅は独立に、水素原子又は炭素数１〜６の炭化水基を示し、Ｂはベンゼン環、ビフェニル環又はナフタレン環からなる基を示し、Y及びZは独立にOH、OR又はハロゲンを示す。） In the present invention, the molar ratio of the indole represented by the following formula (4) and the phenol represented by the following formula (5) is in the range of 1: 9 to 9: 1, and the total of both is 100 mol. On the other hand, it is a method for producing an indole skeleton-containing resin characterized by reacting 10 to 90 mol of a crosslinking agent represented by the following formula (6), (7), (8) or (9).

(However, R ₁ represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a hydrocarbon group having 1 to 7 carbon atoms, and A represents an alkyl group or hydroxyl group having 1 to 6 carbon atoms substituted. And a group consisting of a benzene ring or a naphthalene ring, 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 or biphenyl. A group consisting of a ring or a naphthalene ring, and Y and Z independently represent OH, OR or halogen.)

  Furthermore, this invention is a phenol resin composition formed by blending 2 to 200 parts by weight of the indole skeleton-containing resin with respect to 100 parts by weight of polyhydric phenolic compounds. Further, the present invention provides an epoxy resin composition comprising an epoxy resin and a curing agent, wherein 2 to 200 parts by weight of the indole skeleton-containing resin is blended as a part or all of the curing agent with respect to 100 parts by weight of the epoxy resin. It is the epoxy resin composition formed. Furthermore, this invention is an epoxy resin hardened | cured material formed by hardening | curing this epoxy resin composition.

  In the above general formula (1), L is a group selected from the groups represented by formula (2) and formula (3), and the abundance ratio is 1: 9 to 9: 1, preferably 3: 7 to 7 : 3. X is a group represented by formula (a) or formula (b), and n is a number from 1 to 10. Here, L and X in the formula (1) may be the same or different, but L is a group represented by the formula (2) and the formula (3) in the presence ratio in the resin. To do. However, since the resin is a mixture, it may be present as an average. As for n, since the resin is a mixture, the average (number average) is preferably in the above range.

In Formula (2) and Formula (3), R ₁ represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, or a hydrocarbon group having 1 to 7 carbon atoms, and A represents a phenol (polyvalent A group derived from phenols or polycyclic aromatic phenols).

X is a bridging group represented by formula (a) or formula (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 bridges L, but the substitution position of X with respect to the groups represented by the formulas (2) and (3) constituting L is not particularly limited. For example, the 1-position to the 7-position of the indole ring In the formula (2), it is preferable that the hydrogen atom at the 1-position of the indole ring remains. The hydrogen atom at the 1-position of all indole rings does not need to remain, but if the hydrogen atom at the 1-position of all indole rings is substituted, the function of the indole skeleton-containing resin of the present invention as a curing agent Is not expressed.

  The softening point of the indole skeleton-containing resin of the present invention is preferably 40 to 200 ° C, preferably 50 to 160 ° C, more preferably 60 to 120 ° C. Here, the softening point refers to a softening point measured based on the ring and ball method of JISK-6911. When lower than this, when this is mix | blended with an epoxy resin, the heat resistance of hardened | cured material will fall, and when higher than this, the fluidity | liquidity at the time of shaping | molding will fall.

  The indole skeleton-containing resin of the present invention can itself be a component of a phenol resin composition or an epoxy resin composition. In some cases, the indole skeleton-containing resin is added to a halogenated alkyl compound, a halogenated alkenyl compound, an epihalohydrin. By reacting a compound or the like, part or all of the —NH— and —OH— hydrogen atoms in the indole skeleton-containing resin can be substituted with an alkyl group, an alkenyl group, a glycidyl group, or the like.

  The indole skeleton-containing resin 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 synthesize | combine by making the represented crosslinking agent react. 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 a total of 1 mol of indoles and phenols. is there. If it is smaller than this, the unreacted indole and phenols increase during the synthesis, the productivity of the indole skeleton-containing resin is lowered, and the softening point of the synthesized indole skeleton-containing resin is lowered, and the epoxy resin curing agent As a result, the heat resistance of the cured product decreases. On the other hand, if it is larger than this, the softening point of the indole skeleton-containing resin is increased, and in some cases, the indole skeleton-containing resin may gel during synthesis. In addition, the use ratio of indoles and phenols is adjusted so as to be the above ratio, but since indoles are more reactive with a crosslinking agent, it is better to make phenols somewhat higher than the theoretical amount. There is a case.

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

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

  As indoles used as a raw material, in addition to indoles, there are indoles substituted with a hydroxyl group, an alkoxy group, a halogen atom or a hydrocarbon group as a substituent. 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, an allyloxy group, a propargyl ether group, a putoxy group, and a phenoxy group. . 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 allyl group, a propargyl group, a butyl group, an amyl group, a phenyl group, a benzyl group, etc. should be used. Indole is preferable.

  Examples of phenols include phenols, alkylphenols such as cresols and xylenols, polyhydric phenols such as hydroquinone, polycyclic phenols such as naphthols and naphthalenediols, bisphenols such as bisphenol A and bisphenol F, Or polyfunctional phenol compounds, such as a phenol novolak and a phenol aralkyl resin, are illustrated. These monomers can be used singly or in combination of two or more. From the physical properties of the cured product obtained by containing an indole skeleton-containing resin, inclusion of the indole skeleton of the indole skeleton-containing resin is included. Higher rates are better, but there are no particular restrictions.

  Examples of the crosslinking agent include aldehydes such as formaldehyde, acetaldehyde, propyl aldehyde, butyraldehyde, amyl aldehyde, and benzaldehyde represented by the formula (6), and formaldehyde is preferable. Preferred formaldehyde raw materials used in the reaction include an aqueous formalin solution, paraformaldehyde, trioxane and the like. In addition, 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.

Furthermore, the crosslinking agent represented by the formula (8) includes p-xylylene glycol, p-xylylene glycol dimethyl ether, p-xylylene dichloride, 4,4′-dimethoxymethylbiphenyl, 4,4′-dichloromethyl. Biphenyl, dimethoxymethylnaphthalene and dichloromethylnaphthalene are mentioned.
In addition, divinylbenzenes, divinylbiphenyls, divinylnaphthalenes and the like represented by the formula (9) can also be used as a crosslinking agent.

  After completion of the reaction, in some cases, unreacted indoles and phenols remain in the obtained indole skeleton-containing resin. Unreacted remaining indoles and phenols are usually removed from the system by a method such as distillation under reduced pressure or solvent separation. The amount of unreacted indoles and phenols remaining in the indole skeleton-containing resin is desirably small, and is usually 5% by weight or less, preferably 3% by weight or less, more preferably 1% by weight or less. If the amount of the remaining indoles and phenols is large, it volatilizes during the production of the molded product, which may reduce molding workability and cause voids in the molded product. Moreover, the flame retardance of a molded product also falls.

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

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

  The softening point of the phenol resin is usually in the range of 40 to 200 ° C, preferably 60 to 150 ° C. When lower than this, the heat resistance of the hardened | cured material obtained by using as a hardening | curing agent of an epoxy resin will fall. On the other hand, if it is higher than this, the mixing property with the indole skeleton-containing resin is lowered.

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

  The phenol resin composition of this invention can be made into a phenol resin hardened | cured material by using together with the hardening | curing agent generally used for phenol resin molding materials, such as hexamethyltetramine.

  The epoxy resin composition of the present invention contains at least an epoxy resin and a curing agent, and the indole skeleton-containing resin is blended as part or all of the curing agent. The amount of the indole skeleton-containing resin 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 low hygroscopicity, 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 the indole skeleton-containing resin of the present invention is used as the total amount of the curing agent, the compounding amount of the indole skeleton-containing resin is usually equivalent to the —NH— group and —OH— group of the indole skeleton-containing resin and the epoxy group in the epoxy resin. Mix in consideration of balance. The equivalent ratio of epoxy resin and curing agent is usually in the range of 0.2 to 5.0, preferably in the range of 0.5 to 2.0. If it is larger or smaller than this, the curability of the epoxy resin composition is lowered, and the heat resistance, mechanical strength and the like of the cured product are lowered.

  The epoxy resin composition of the present invention can be used in combination with a curing agent other than the indole skeleton-containing resin of the present invention as a curing agent. The blending amount of the other curing agent is such that the blending amount of the indole skeleton-containing resin is usually 2 to 200 parts by weight, preferably 5 to 80 parts by weight with respect to 100 parts by weight of the epoxy resin. It is determined. If the amount of the indole skeleton-containing resin is less than this, the effect of improving the low hygroscopicity, adhesion and flame retardancy is small, and if it is more than this, the moldability and the strength of the cured product are lowered.

  As the curing agent other than the indole skeleton-containing resin, any 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 a curing agent in a field where high electrical insulation properties such as a semiconductor sealing material are required. Below, the specific example of a hardening | curing agent is shown.

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

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

  Examples of amines include aromatic amines such as 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenylsulfone, m-phenylenediamine, and p-xylylenediamine, ethylenediamine, There are aliphatic amines such as hexamethylenediamine, diethylenetriamine, and triethylenetetramine.

  In the epoxy resin composition of the present invention, one or more of these curing agents can be mixed and used.

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

  Furthermore, in the epoxy resin composition of the present invention, an oligomer or a polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene resin, indene coumarone resin, phenoxy resin or the like is used as another modifier. Etc. may be blended as appropriate. The addition amount is usually in the range of 2 to 30 parts by weight with respect to 100 parts by weight of the epoxy resin.

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

  Examples of the pigment include organic or inorganic extender pigments, scaly pigments, and the like. Examples of the thixotropic agent include silicon-based, castor oil-based, aliphatic amide wax, oxidized polyethylene wax, and organic bentonite-based.

  Furthermore, a curing accelerator can be used in the epoxy resin composition of the present invention as necessary. Examples include amines, imidazoles, organic phosphines, Lewis acids, etc., specifically 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, Tertiary amines such as ethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2- Imidazoles such as heptadecylimidazole, triphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, organic phosphines such as phenylphosphine, tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltrifer Ruboreto, tetra-substituted phosphonium tetra-substituted borate such as tetrabutylphosphonium-tetrabutyl borate, 2-ethyl-4-methylimidazole · tetraphenyl borate, and the like tetraphenyl boron salts such as N- methylmorpholine tetraphenylborate. The addition amount is usually in the range of 0.2 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin.

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

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

  If the epoxy resin composition of the present invention is cured by heating, an epoxy resin cured product can be obtained, and this cured product is excellent in terms of low hygroscopicity, high heat resistance, adhesion, flame retardancy, and the like. Become.

  The indole skeleton-containing resin of the present invention is useful as a curing agent and a modifier for epoxy resins, and when applied to an epoxy resin composition, has excellent high heat resistance and moisture resistance, flame retardancy, and different types. It can give a cured product with excellent adhesion to the material, and can be suitably used for applications such as sealing of electric and electronic parts, circuit board materials, and the like.

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

Example 1
A 500 mL, 3-neck separable flask equipped with a stirrer, a condenser tube, and a nitrogen inlet tube was charged with 72.5 g of indole, 233.1 g of phenol, and 27.9 g of 92% paraformaldehyde, and the temperature was increased to 90 ° C. while introducing nitrogen. Heat to dissolve. Then, it heated up at 130 degreeC, stirring, and was made to react for 3 hours. During this time, water produced by the reaction was removed from the system. Thereafter, the temperature was raised to 180 ° C. under reduced pressure to remove condensed water, unreacted phenol and indole, thereby obtaining 150 g of an indole skeleton-containing resin (oligomer A). The resulting resin had a softening point of 83 ° C. and a melt viscosity at 150 ° C. of 0.12 Pa · s. The residual monomer amount determined by GPC measurement was 0.5 wt%. ^{The 1} H-NMR spectrum is shown in FIG. 1, the infrared absorption spectrum is shown in FIG. 2, and the GPC chart is shown in FIG.

Example 2
The reaction was carried out in the same manner as in Example 1 using 106.3 g of indole, 199.2 g of phenol, and 27.2 g of 92% paraformaldehyde to obtain 130 g of an indole skeleton-containing resin (oligomer B). The resulting resin had a softening 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%.

Example 3
In 100 g of phenol novolak (softening point 82 ° C., OH equivalent 103) melted at 150 ° C., 100 g of the oligomer A obtained in Example 1 was added and uniformly melted to obtain 200 g of a phenol resin composition (resin composition) Object A). The resulting phenol resin composition had a softening point of 82 ° C. and a melt viscosity at 150 ° C. of 0.18 Pa · s.

Examples 4-8 and Comparative Examples 1-2
The o-cresol novolak type epoxy resin (epoxy equivalent 200, softening point 70 ° C.) as the epoxy resin component, the indole skeleton-containing resins (oligomers A and B) obtained in Examples 1 and 2 as the curing agent, and obtained in Example 3. Phenol resin composition (resin composition A), phenol novolak (curing agent A; OH equivalent 103, softening point 82 ° C.), phenol aralkyl resin (curing agent B; manufactured by Mitsui Chemicals, XL-225-LL, OH equivalent 172, Using a softening point of 74 ° C., silica (average particle size 22 μm) as a filler and 2-ethyl-4-methylimidazole as a curing accelerator were kneaded in the formulation shown in Table 1 to obtain an epoxy resin composition. This epoxy resin composition was molded at 175 ° C. and post-cured at 175 ° C. for 12 hours to obtain a cured product test piece, which was then subjected to various physical property measurements.

  The glass transition point was calculated | required on the conditions of the temperature increase rate of 10 degree-C / min with the thermomechanical measuring apparatus. The water absorption is the value obtained when a disc having a diameter of 50 mm and a thickness of 3 mm is molded using this epoxy resin composition, and after post-curing, the moisture is absorbed at 133 ° C. and 3 atm for 96 hours. Evaluation of adhesiveness was performed by compression-molding on a copper foil at 175 ° C. using an epoxy resin composition, post-curing at 175 ° C. for 12 hours, and measuring peel strength. Flame retardance was measured by molding a 1/16 inch thick test piece, evaluated according to the UL94V-0 standard, and expressed as the total burning time of 5 test pieces. The results are summarized in Table 2.

¹ H-NMR spectrum of oligomer A Infrared absorption spectrum of oligomer A GPC chart of oligomer A

Claims (6)

The following general formula (1)
HL- (XL) _n -H (1)
(Where L is the following formula (2) and formula (3)

R ₁ represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, or a hydrocarbon group having 1 to 7 carbon atoms, and A represents a group having 1 to 6 carbon atoms. A group consisting of a benzene ring or a naphthalene ring which may be substituted by an alkyl group or a hydroxyl group, wherein the abundance ratio (molar ratio) of the groups represented by the formulas (2) and (3) is 1: 9 to 9: 1, 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 of 1 to 10. ) -Containing indole skeleton-containing resin.   The indole skeleton-containing resin according to claim 1, which has a softening point of 40 ° C to 200 ° C. The molar ratio of the indoles represented by the following formula (4) and the phenols represented by the following formula (5) is in the range of 1: 9 to 9: 1. 6), (7), (8) or a method for producing an indole skeleton-containing resin characterized by reacting 10 to 90 mol of the crosslinking agent represented by (9).

(However, R ₁ represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a hydrocarbon group having 1 to 7 carbon atoms, and A represents an alkyl group or hydroxyl group having 1 to 6 carbon atoms substituted. And a group consisting of a benzene ring or a naphthalene ring, 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 or biphenyl. A group consisting of a ring or a naphthalene ring, and Y and Z independently represent OH, OR or halogen.)   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 polyhydric phenolic compounds.   In an epoxy resin composition comprising an epoxy resin and a curing agent, the indole skeleton-containing resin according to claim 1 or 2 as a part or all of the curing agent is blended in an amount of 2 to 200 parts by weight with respect to 100 parts by weight of the epoxy resin. An epoxy resin composition characterized by comprising: An epoxy resin cured product obtained by curing the epoxy resin composition according to claim 5.

Images