JP2018044069A - Flame-retardant epoxy resin composition, and prepreg and laminate prepared therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant epoxy resin composition that does not use halogen and therefore has excellent environmental suitability and also excellent workability; and prevents the bleeding phenomenon of a flame retardant at the time of curing and does not cause the deterioration of the physical properties of the cured product.SOLUTION: A flame-retardant epoxy resin composition contains (A) an epoxy resin, (B) a curing agent, (C) a phosphorus-containing compound represented by formula (1), and (D) at least one flame retardant selected from the group consisting of a phosphorus-containing compound other than (C) component, a nitrogen-containing compound, and a boron-containing compound.SELECTED DRAWING: None

Description

  The present invention relates to a flame retardant epoxy resin composition, and in particular, a flame retardant epoxy excellent in environmental compatibility by using a phosphorus-based reactive flame retardant together with a specific flame retardant other than the reactive flame retardant. The present invention relates to a resin composition and an epoxy resin laminate using the flame-retardant epoxy resin composition.

  Epoxy resins have been used in a wide range of industrial applications, but the performance required for epoxy resins has become increasingly sophisticated in recent years with the development of the industry. For example, epoxy resins have been used for copper-clad laminates and casting materials used in electronic components and electronic devices, but these epoxy resins are safe for fire prevention and delay of fire spread. From the standpoint of safety, brominated epoxy resins that provide flame retardant effects have been used. However, from the viewpoint of environmental problems, in recent years, materials that exhibit a flame retardant effect in place of halogen have been actively developed.

  As a prior art for imparting flame retardancy to an epoxy resin, a method using a wide variety of organic phosphorus-containing compounds has already been presented. Increasing the phosphorus content in the composition is one of the effective means to bring about the flame retardant effect, and a method of adding a flame retardant having a high phosphorus content to the epoxy resin composition is known. (For example, Patent Document 1). However, in the case of the above method, the epoxy resin composition is heated and cured in order not to react with the epoxy resin, although it can increase the effectiveness to some extent in terms of imparting flame retardancy to the epoxy resin composition. In such a case, a bleed phenomenon in which a part of the flame retardant is liberated occurs, or the Tg of the cured product is greatly reduced.

  Moreover, the resin composition which uses a dialkyl phosphinate as a phosphorus compound which shows high flame retardance with respect to a thermoplastic polyester resin is provided (for example, patent document 2). The dialkylphosphinate used in this method has high performance as a flame retardant for thermoplastic resins such as polyester, but in the hope of high flame retardancy, this compound is converted into a thermosetting epoxy resin. When applied, satisfactory results in flame retardancy could not be obtained.

JP 2004-051907 A JP 2010-037375 A

  Accordingly, the problem to be solved by the present invention is that a flame retardant bleed phenomenon does not occur at the time of curing, the physical properties of the cured product do not deteriorate, and the workability is excellent, especially a laminated board used for a printed wiring board and the like. It is providing the flame-retardant epoxy resin composition suitable for.

  Therefore, the present inventors diligently studied, and in an epoxy resin curing system, by combining a reactive flame retardant and a specific flame retardant, an epoxy resin composition having excellent cured properties and good flame retardancy can be obtained. The headline, the present invention has been reached. That is, the present invention includes (A) an epoxy resin, (B) a curing agent, (C) a phosphorus-containing compound represented by the following formula (1), and (D) a phosphorus-containing compound other than the component (C), a nitrogen-containing compound. A flame retardant epoxy resin composition comprising a compound and at least one flame retardant selected from the group consisting of boron-containing compounds.

上記式（１）中、ｍは２〜１０の整数を表し、Ｒ¹及びＲ²はそれぞれ独立に、アルキル基、又はアリール基を表し、Ｒ³は、酸素原子、硫黄原子、又は窒素原子を含んでいる場合がある炭化水素基を表し、Ｘは酸素原子又は硫黄原子を表し、Ｙは、酸素原子、硫黄原子、又は―ＮＲ⁴―を表し、Ｒ⁴は、水素原子、アルキル基、又はアリール基を表す。

In the above formula (1), m represents an integer of 2 to 10, R ¹ and R ² each independently represents an alkyl group or an aryl group, and R ³ represents an oxygen atom, a sulfur atom, or a nitrogen atom. Represents a hydrocarbon group that may contain, X represents an oxygen atom or a sulfur atom, Y represents an oxygen atom, a sulfur atom, or —NR ⁴ —, and R ⁴ represents a hydrogen atom, an alkyl group, or Represents an aryl group.

  According to the present invention, since no halogen is used, the flame retardant epoxy resin composition has excellent environmental suitability and excellent workability, and does not cause a bleed phenomenon of a flame retardant upon curing, and has excellent physical properties of a cured product. Is obtained. In addition, by using the epoxy resin composition, a laminate having excellent flame resistance as well as environmental suitability can be obtained.

  Hereinafter, from (A) an epoxy resin, (B) a curing agent, (C) a phosphorus-containing compound, and (D) a phosphorus-containing compound other than the component (C), a nitrogen-containing compound, and a boron-containing compound used in the present invention. At least one flame retardant selected from the group consisting of:

  The use of the flame retardant epoxy resin composition of the present invention is not particularly limited, and examples thereof include a laminate used for an electronic circuit board, a sealant used for an electronic component, a casting material, a film material, and an adhesive. It can be used for electrical insulating paints, flame retardant composites, powder paints, and the like. In this invention, it is preferable to use for the laminated board especially used for an electronic circuit board, the sealing agent used for an electronic component, a casting material, etc., and it is most preferable to use for a laminated board.

  The (A) epoxy resin used in the present invention is not particularly limited in molecular structure, molecular weight, etc. as long as it has at least two epoxy groups in the molecule, and can be appropriately selected from known epoxy resins. Although it is possible, it is preferable to use properly depending on the application to be used.

  Examples of the epoxy resin include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene Bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene) 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxy Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as sphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, terpene phenol; ethylene glycol, propylene glycol, butylene glycol, hexanediol, Polyglycol, thiodiglycol, dicyclopentadiene dimethanol, 2,2-bis (4-hydroxycyclohexylpropane (hydrogenated bisphenol A), glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct, etc. Polyglycidyl ethers of polyhydric alcohols; maleic acid, fumaric acid, itako Acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, Glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as hexahydrophthalic acid and endomethylenetetrahydrophthalic acid and homopolymers or copolymers of glycidyl methacrylate; N, N-diglycidylaniline, bis ( 4- (N-methyl-N-glycidylamino) phenyl) methane, diglycidyl orthotoluidine, N, N-bis (2,3-epoxypropyl) -4- (2,3-epoxypropoxy) -2-methylaniline N, N-bis (2,3-epoxypropyl) -4- (2,3-epoxypropo Xyloxy) aniline, N, N, N ′, N′-tetra (2,3-epoxypropyl) -4,4′-diaminodiphenylmethane and other epoxy compounds having a glycidylamino group; vinylcyclohexene diepoxide, dicyclopentane Endeepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methyl Epoxidized products of cyclic olefin compounds such as (cyclohexylmethyl) adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymer, and heterocyclic compounds such as triglycidyl isocyanurate. These epoxy resins may be those internally crosslinked by terminal isocyanate prepolymers or those having a high molecular weight with polyvalent active hydrogen compounds (polyhydric phenols, polyamines, carbonyl group-containing compounds, polyphosphates, etc.). Good.

  The above epoxy resins may be used alone or in combination of two or more. When the flame retardant epoxy resin composition is for a laminated plate, it is preferable to use a polyglycidyl ether compound of a polynuclear polyphenol compound as the (A) epoxy resin, and among them, a novolac type epoxy resin and / or It is more preferable to use a bisphenol type epoxy resin because it is inexpensive and easily available.

  When the flame retardant epoxy resin composition is used for a sealant, (A) the epoxy resin is preferably a polyglycidyl ether of a polyhydric alcohol or a polyglycidyl ether compound of a polynuclear polyhydric phenol compound. It is more preferable to use at least one epoxy resin selected from an epoxy resin, a dicyclopentadiene type epoxy resin, a novolac type epoxy resin, and a naphthalene type epoxy resin.

  When the flame retardant epoxy resin composition is for a casting material, (A) the epoxy resin is preferably a polyglycidyl ether of a polyhydric alcohol, a polyglycidyl ether compound of a polynuclear polyhydric phenol compound, a bisphenol type epoxy resin, More preferred are novolak epoxy resins and glycidyl ether of hydrogenated bisphenol A.

  In the flame-retardant epoxy resin composition of the present invention, in order to adjust the flame-retardant epoxy resin composition to a desired viscosity, a reactive diluent can be used in combination with (A) the epoxy resin. As such a reactive diluent, a diluent having at least one epoxy group is used from the viewpoint of suppressing a decrease in heat resistance and glass transition temperature of the cured product when the epoxy resin composition is cured. It is preferable.

The number of epoxy groups contained in the reactive diluent may be one or more, and is not particularly limited. Examples of the reactive diluent having one epoxy group include n-butyl glycidyl ether, C _{12 to} C ₁₄ alkyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, Examples include glycidyl ether, p-sec-butylphenyl glycidyl ether, t-butylphenyl glycidyl ether, glycidyl methacrylate, and tertiary carboxylic acid glycidyl ester.
Examples of the reactive diluent having two epoxy groups include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and neopentyl glycol diester. A glycidyl ether etc. are mentioned. Examples of the reactive diluent having 3 epoxy groups include trimethylolpropane triglycidyl ether and glycerin triglycidyl ether.

  Although the compounding quantity with respect to the epoxy resin of the said reactive diluent is not specifically limited, It is preferable to use properly by the use to be used. In the case of the epoxy resin composition used for the laminate, it is preferable not to use a reactive diluent from the viewpoint of avoiding a decrease in the glass transition temperature of the product. In the case of the epoxy resin composition used for the sealant, it is preferable to blend 3 to 50 parts by mass, and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of (A) epoxy resin. Moreover, also in the case of the epoxy resin composition used for a casting material, it is preferable to mix | blend 3-50 mass parts with respect to 100 mass parts of epoxy resins, and it is more preferable to mix | blend 5-30 mass parts.

  Next, (B) the curing agent used in the present invention will be described. Examples of the (B) curing agent include phenol resins, aliphatic amines, aromatic amines, latent curing agents, and acid anhydrides. In the present invention, it is preferable to use these curing agents properly depending on applications.

  Specifically, when the flame retardant epoxy resin composition of the present invention is used for the production of a laminate, it is preferable to use a phenol resin or a latent curing agent as the (B) curing agent, a phenol novolac resin, More preferably, a cresol novolac resin or a dicyandiamide type latent curing agent is used. When used as a sealant, it is preferable to use phenol resins, latent curing agents or acid anhydrides as the (B) curing agent. When used as a casting material, it is preferable to use an aliphatic amine, aromatic amine, or acid anhydride as the (B) curing agent. These curing agents may be used alone or in combination of two or more.

  Examples of the phenol resins include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin (Zylok resin), naphthol aralkyl resin, trisphenylol methane resin. , Tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol co-condensation novolak resin, naphthol-cresol co-condensation novolak resin, biphenyl-modified phenol resin (polyhydric phenol compound in which phenol nucleus is linked by bismethylene group), biphenyl-modified naphthol Resin (polyvalent naphthol compound in which phenol nucleus is linked by bismethylene group), aminotriazine modified phenolic resin (phenol skeleton, A compound having a gin ring and a primary amino group in the molecular structure), and an alkoxy group-containing aromatic ring-modified novolak resin (a polyhydric phenol compound in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde). A phenol compound is mentioned.

  Although the compounding quantity with respect to the (A) epoxy resin of the (B) hardening | curing agent which consists of the said phenol resin is not specifically limited, The hydroxyl group in a phenol resin is 0 with respect to one epoxy group in an epoxy resin. It is preferable to mix | blend so that it may become 3-1.5 pieces, and it is more preferable to mix | blend so that it may become 0.8-1.2 pieces.

Examples of the aliphatic amines include ethylenediamine, hexamethylenediamine, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 4,4′-diaminodicyclohexylpropane, bis (4-aminocyclohexyl) sulfone, 4,4′-diaminodicyclohexyl ether, 2,2′-dimethyl-4,4 Examples include '-diaminodicyclohexane, 4,4'-diaminodicyclohexane, isophorone diamine, norbornene diamine, and meta-xylene diamine. These can be used singly or as an appropriately mixed mixture.
The blending amount of the (B) curing agent composed of the above aliphatic amines with respect to the (A) epoxy resin is not particularly limited, but the active hydrogen in the aliphatic amine with respect to one epoxy group in the epoxy resin. It is preferable to mix | blend so that it may become 0.6-1.5 pieces, and it is more preferable to mix | blend so that it may become 0.8-1.2 pieces.

Examples of the aromatic amines include diethyltoluenediamine, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3,3 Examples include 5-triethyl-2,6-diaminobenzene, 3,3′-diethyl-4,4′-diaminodiphenylmethane, and 3,5,3 ′, 5′-tetramethyl-4,4′-diaminodiphenylmethane. These can be used alone or in a mixture of any proportions.
Although the compounding quantity with respect to (A) epoxy resin of the (B) hardening | curing agent which consists of said aromatic amines is not specifically limited, The active hydrogen in aromatic amine with respect to one epoxy group in epoxy resin It is preferable to mix so that it may become 0.6-1.5 pieces, and it is more preferable to mix | blend so that it may become 0.8-1.2 pieces.

  Examples of the latent curing agent include latent curing agents such as a dicyandiamide type, an imidazole type, and a polyamine type compound that, when mixed with an epoxy resin at room temperature, have little change in viscosity and change in physical properties of the mixture.

  Examples of the dicyandiamide type latent curing agent include dicyandiamide alone or, if necessary, a combination of an epoxy resin curing accelerator described later.

The imidazole-type latent curing agent is obtained, for example, by reacting an epoxy compound with an active hydrogen-containing imidazole compound at 50 to 150 ° C. for 1 to 20 hours using a solvent as necessary. be able to. When a solvent is used, the solvent is removed at 80 to 200 ° C. under normal pressure or reduced pressure after completion of the reaction.
Examples of the imidazole compound used in the production of the imidazole-type latent curing agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and 2-phenylimidazole. Etc.
As said epoxy compound used for manufacture of the said imidazole type | mold latent hardening | curing agent, the compound illustrated by the said (A) epoxy resin is mentioned, for example.
Examples of the solvent used for the production of the imidazole-type latent curing agent include methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, propylene glycol monomethyl ether acetate, cyclohexanone and other ketones; tetrahydrofuran, 1,2- Ethers such as dimethoxyethane, 1,2-diethoxyethane and propylene glycol monomethyl ether; esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as benzene, toluene and xylene; carbon tetrachloride, chloroform, Halogenated aliphatic hydrocarbons such as trichloroethylene and methylene chloride; halogenated aromatic hydrocarbons such as chlorobenzene.

The polyamine-type latent curing agent can be obtained, for example, by reacting an epoxy compound with a solvent exemplified above at 50 to 150 ° C. for 1 to 20 hours, if necessary. it can. When a solvent is used, the solvent is removed at 80 to 200 ° C. under normal pressure or reduced pressure after completion of the reaction.
As said polyamine used for manufacture of the said polyamine type | mold latent hardening | curing agent, the compound illustrated by the said aliphatic amines and aromatic amine is mentioned, for example. As the epoxy compound and the solvent used for the production of the polyamine type latent curing agent, those similar to those used for the production of the imidazole type latent curing agent can be used.

  The latent curing agent may be used in combination with the phenol resins exemplified above in order to improve the storage stability of the composition.

  Specific examples of the latent curing agent include ADEKA HARDNER EH-3636AS (manufactured by ADEKA, dicyandiamide type latent curing agent), ADEKA HARDNER EH-4351S (manufactured by ADEKA, dicyandiamide type latent), which are commercially available products. ADEKA HARDNER EH-5011S (manufactured by ADEKA, imidazole type latent curing agent), ADEKA HARDNER EH-5046S (manufactured by ADEKA, imidazole type latent curing agent), ADEKA HARDNER EH-4357S (stock) Company ADEKA, polyamine type latent curing agent), ADEKA HARDNER EH-5057P (made by ADEKA, polyamine type latent curing agent), and ADEKA HARDNER EH-5057PK (made by ADEKA, polyamine type latent curing agent) ), And the like. These can be used alone or as a mixture in which they are appropriately mixed.

  Although the compounding quantity with respect to the epoxy resin (A) of the hardening | curing agent (B) which consists of the said latent hardener is not specifically limited, It is preferable that it is 1-70 mass parts with respect to 100 mass parts of epoxy resins. 3 to 60 parts by mass is more preferable.

Examples of the acid anhydrides include hymic anhydride, phthalic anhydride, maleic anhydride, methyl hymic anhydride, succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydroanhydride. Examples thereof include phthalic acid, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, benzophenone tetracarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and hydrogenated methylnadic acid anhydride.
Although the compounding quantity with respect to the epoxy resin (A) of the hardening | curing agent (B) which consists of the said acid anhydrides is not specifically limited, The acid in acid anhydrides with respect to one epoxy group in an epoxy resin The number of anhydride groups is preferably 0.7 to 1.6, and more preferably 0.9 to 1.2.

  In this invention, a well-known epoxy resin hardening accelerator can be used together with the said (B) hardening | curing agent as needed. Specific examples of these curing accelerators include phosphine compounds such as triphenylphosphine; phosphonium salts such as tetraphenylphosphonium bromide; 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2 -Imidazoles such as undecylimidazole and 1-cyanoethyl-2-methylimidazole; Imidazoles which are salts of the imidazoles with trimellitic acid, isocyanuric acid, boron and the like; benzyldimethylamine, 2,4,6- Amines such as tris (dimethylaminomethyl) phenol; quaternary ammonium salts such as trimethylammonium chloride; 3- (p-chlorophenyl) -1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1,1 -Dimethylurea, 3-fu Examples include ureas such as nyl-1,1-dimethylurea, isophorone diisocyanate-dimethylurea, tolylene diisocyanate-dimethylurea; and complex compounds of boron trifluoride with amines and ether compounds. it can. These curing accelerators may be used alone or in combination of two or more. There is no restriction | limiting in particular in content of the epoxy resin hardening accelerator in the flame-retardant epoxy resin composition of this invention, According to the use of a flame-retardant epoxy resin composition, it can set suitably.

  Next, the phosphorus-containing compound of the component (C) represented by the following formula (1) used in the present invention will be described.

上記式（１）中のｍは２〜１０の整数を表し、Ｒ¹及びＲ²はそれぞれ独立に、アルキル基、又はアリール基を表し、Ｒ³は、酸素原子、硫黄原子、又は窒素原子を含んでいる場合がある炭化水素基を表し、Ｘは酸素原子又は硫黄原子を表し、Ｙは、酸素原子、硫黄原子、又は―ＮＲ⁴―を表し、Ｒ⁴は、水素原子、アルキル基、又はアリール基を表す。

M in the above formula (1) represents an integer of 2 to 10, R ¹ and R ² each independently represents an alkyl group or an aryl group, and R ³ represents an oxygen atom, a sulfur atom, or a nitrogen atom. Represents a hydrocarbon group that may contain, X represents an oxygen atom or a sulfur atom, Y represents an oxygen atom, a sulfur atom, or —NR ⁴ —, and R ⁴ represents a hydrogen atom, an alkyl group, or Represents an aryl group.

  The phosphorus-containing compound of component (C) used in the present invention is a compound that reacts with an epoxy group according to the reaction formula shown in the following formula (3).

上記式（３）中のｍは２〜１０の整数を表し、Ｒ¹及びＲ²はそれぞれ独立に、アルキル基又はアリール基を表し、Ｒ³は、酸素原子、硫黄原子、又は窒素原子を含んでいる場合がある炭化水素基を表し、Ｒ⁸はアルキル基又はアリール基を表し、Ｘは酸素原子又は硫黄原子を表し、Ｙは、酸素原子、硫黄原子、又は―ＮＲ⁴―を表し、Ｒ⁴は、水素原子、アルキル基、又はアリール基を表す。

M in the above formula (3) represents an integer of 2 to 10, R ¹ and R ² each independently represents an alkyl group or an aryl group, and R ³ contains an oxygen atom, a sulfur atom, or a nitrogen atom. R ⁸ represents an alkyl group or an aryl group, X represents an oxygen atom or a sulfur atom, Y represents an oxygen atom, a sulfur atom, or —NR ⁴ —, R ⁴ represents a hydrogen atom, an alkyl group, or an aryl group.

  M in the above formula (1) is preferably 2 to 7, and more preferably 2 to 5. When m is 1, the number of functional groups that react with the epoxy group is one, and the glass transition temperature and strength of the cured product when the epoxy resin is cured are significantly reduced, which is not preferable. When m is a number larger than 10, it is not preferable since the viscosity becomes high and the production becomes difficult when the phosphorus-containing compound is produced.

Examples of the alkyl group represented by R ¹ , R ² and R ^{4 in the} above formula (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, and an amyl group. , Isoamyl group, tertiary amyl group, hexyl group, isohexyl group, octyl group, 2-ethylhexyl group, tertiary octyl group, nonyl group, decyl group and the like. Examples of the aryl group represented by R ₁ or R ₂ include a phenyl group and a naphthyl group.
In the present invention, among these, R ¹ and / or R ² is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 2 to 5 carbon atoms, Is particularly preferably an alkyl group of 1 to 4, most preferably an ethyl group or a propyl group.

Examples of the hydrocarbon group represented by R ³ in the above formula (1) include alkanediyl groups such as a methylene group, an ethylene group, a propylene group, an ethanediyl group, and an octanediyl group; Alkanetriyl groups such as 3-ethylenetriyl groups; alkanetetrayl groups such as 1,1,2,2-ethylenetriyl; and mononuclear polyhydric phenols such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol Compound residues: dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3- Screw (4- Droxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) Examples include polynuclear polyhydric phenol compound residues such as ethane, thiobisphenol, sulfonylbisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, terpene phenol.

  The flame retardant epoxy resin composition of the present invention is preferably such that X is an oxygen atom and Y is an oxygen atom from the viewpoint that raw materials for production are easily available.

  From the viewpoint of the physical properties of a cured product obtained by curing the flame retardant epoxy resin composition of the present invention, the phosphorus-containing compound (C) used in the present invention is a compound containing at least one aromatic ring in the skeleton. Are preferable, and a compound containing a group represented by the following formulas (2-1), (2-2), and (2-4) to (2-6) is particularly preferable.

上記式（２−１）中、Ｒ⁵は水素原子、もしくは炭素数が１〜４のアルキル基を表す。

In the above formula (2-1), R ⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

上記式（２−２）中のｎは０〜３の整数、ｏは０〜５０の整数を表し、Ｒ⁶は、水素原子又は炭素数が１〜４のアルキル基を表し、Ｒ⁷は、酸素原子又は硫黄原子を含んでもよい炭化水素基を表し、Ｚは水酸基又は下記式（２−３）で表される官能基である；

In the above formula (2-2), n represents an integer of 0 to 3, o represents an integer of 0 to 50, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁷ represents Represents a hydrocarbon group which may contain an oxygen atom or a sulfur atom, and Z is a hydroxyl group or a functional group represented by the following formula (2-3);

上記式（２−３）中、Ｒ₁及びＲ₂は、それぞれ独立に、アルキル基又はアリール基を表す；

In the above formula (2-3), R ₁ and R ₂ each independently represents an alkyl group or an aryl group;

The alkyl group having a carbon number of 1 to 4 represented by R ⁶ in R ^5, and the formula (2-2) in the above formula (2-1), R ¹ in the formula (1), Examples of the alkyl group represented by R ² and R ⁴ include those having 1 to 4 carbon atoms.
Examples of the hydrocarbon group represented by R ⁷ in the above formula (2-2) include the same hydrocarbon groups represented by R ³ in the above formula (1).
As the alkyl group and aryl group represented by R ₁ and R ₂ in the above formula (2-3), the alkyl group and aryl group represented by R ¹ , R ² and R ⁴ in the above formula (1) The same thing is mentioned.

Among the phosphorus-containing compounds in which R ³ in the above formula (1) is a group represented by the above (2-1) to (2-6), R ³ is the above (2-1) or (2-2 It is particularly preferable to use one having a structure represented by Moreover, among the structures of (2-1), it is particularly preferable that R ¹ and R ² are each independently an ethyl group or a propyl group, and R ⁵ is a hydrogen atom or a methyl group.
On the other hand, in the case of the above structure (2-2), n is 0 or 1, the average value of o is a number of 1 to 5, R ¹ and R ² are each independently an ethyl group or a propyl group, R It is preferable that ⁶ is a methyl group and R ⁷ is a methylene group, an ethanediyl group, or a propanediyl group.

  Examples of such a compound include compounds represented by the following formulas (4-1) to (4-4).

上記式（４−４）におけるｐは１〜５０の整数である。

P in the above formula (4-4) is an integer of 1 to 50.

  Although the compounding quantity of the said (C) phosphorus containing compound in the flame-retardant epoxy resin composition of this invention is not specifically limited, (A) component of an epoxy resin composition, (B) component, (C ) Component, the (D) component described later, and the optional reactive diluent used, the phosphorus content attributable to the component (C) is 0.1 to 5% by mass. The amount is preferably 0.5 to 3% by mass. If the phosphorus content is less than 0.1% by mass, the flame retardancy of the epoxy resin composition may be significantly reduced. On the other hand, when there is more phosphorus content than the quantity used as 5 mass%, the water resistance of an epoxy resin composition may fall remarkably.

上記式（５）中におけるｍは２〜１０の整数、Ｒ¹及びＲ²はそれぞれ独立に、アルキル基又はアリール基を表し、Ｒ³は、酸素原子、硫黄原子、又は窒素原子を含んでいる場合がある炭化水素基、Ｘは酸素原子又は硫黄原子、Ｙは、酸素原子、硫黄原子、または―ＮＲ⁴―を表し、Ｒ⁴は水素原子、アルキル基又はアリール基を表す。 Although the manufacturing method of the phosphorus-containing compound used by this invention is not restrict | limited in particular, For example, it can manufacture by the method etc. which were represented to following formula (5).

In the above formula (5), m is an integer of 2 to 10, R ¹ and R ² each independently represents an alkyl group or an aryl group, and R ³ contains an oxygen atom, a sulfur atom, or a nitrogen atom. In some cases, a hydrocarbon group, X represents an oxygen atom or a sulfur atom, Y represents an oxygen atom, a sulfur atom, or —NR ⁴ —, and R ⁴ represents a hydrogen atom, an alkyl group, or an aryl group.

  Examples of the base used in the above formula (5) include tertiary amines such as triethylamine, tributylamine, diazabicycloundecene, diazabicyclononene, 1,4-diazabicyclo [2.2.2] octane; Examples thereof include pyridines such as pyridine and N, N-dimethylaminopyridine; imidazoles such as 1-methylimidazole; phosphines such as triphenylphosphine, tributylphosphine and tricyclohexylphosphine; In the present invention, among these bases, a tertiary amine is preferably used, and triethylamine is most preferably used.

  Examples of the solvent used in the above formula (5) include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, propylene glycol monomethyl ether acetate, and cyclohexanone; tetrahydrofuran, 1,2-dimethoxyethane Ethers such as 1,2-diethoxyethane and propylene glycol monomethyl ether; esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as benzene, toluene and xylene; carbon tetrachloride, chloroform, trichloroethylene, And halogenated aliphatic hydrocarbons such as methylene chloride; halogenated aromatic hydrocarbons such as chlorobenzene. Among these solvents, ethers or halogenated aliphatic hydrocarbons are preferable, and ethers are particularly preferable.

  The above reaction can be carried out at −80 to 100 ° C., preferably room temperature to 50 ° C., for 0.5 hour to 72 hours, preferably 1 hour to 24 hours.

  The component (D) used in the present invention is at least one flame retardant selected from the group consisting of phosphorus-containing compounds other than the component (C), nitrogen-containing compounds, and boron-containing compounds. In the present invention, by combining the component (C), which is a phosphorus-containing compound having reactivity with the epoxy resin, and the component (D), flame retardance that cannot be achieved alone can be expressed.

  Examples of phosphorus-containing compounds other than the above component (C) include aliphatic phosphate esters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate; triphenyl phosphate, cresyl diphenyl phosphate, dicrete Dilphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, xylenyl diphenyl phosphate, tris (isopropylphenyl) phosphate, isopropylphenyl diphenyl phosphate, diisopropylphenylphenyl phosphate, tris (trimethylphenyl) phosphate, tris (t-butylphenyl) ) Phosphate, hydroxyphenyl diphenyl phosphate, octyl diphenyl phosphate Aromatic phosphate esters such as: resorcinol polyphenyl phosphate, 1,3-phenylenebis (2,6-dimethylphenyl phosphate), resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, Bisphenol A polyphenyl phosphate, hydroquinone poly (2,6-xylyl) phosphate and condensed phosphates such as condensates thereof; phosphates such as ammonium phosphate and melamine phosphate; ammonium polyphosphate and melamine polyphosphate Condensed phosphate; aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, aluminum triphosphinate, zinc bisdiethylphosphinate, bis Zinc ethyl ethylphosphinate, zinc bisdiphenylphosphinate, zinc triphosphinate, titanyl bisdiethylphosphinate, titanium tetrakisdiethylphosphinate, titanyl bismethylethylphosphinate, titanium tetrakismethylethylphosphinate, titanyl bisdiphenylphosphinate, tetrakis Metal salts of phosphinic acids such as titanium diphenylphosphinate, titanyl tetraphosphinate, phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter referred to as HCA) Phosphinic acid ester such as HCA and acrylic ester, addition reaction product of HCA and epoxy resin, addition reaction of HCA and hydroquinone HCA-modified compounds such as products, phosphazene derivatives such as diphenylvinylphosphine oxide, triphenylphosphine oxide, trialkylphosphine oxide, tris (hydroxyalkyl) phosphine oxide, phosphazene derivatives such as hexaphenylcyclotriphosphazene, red Phosphorus etc. are mentioned.

  Examples of phosphorus-containing compounds other than the component (C) include phosphorus-containing phenoxy resins (for example, phenototo ERF-001M30 and TX-0924K30 manufactured by Nippon Steel Chemical Co., Ltd.), hydroxyl-containing phosphate esters (for example, Daihachi Chemical Industry Co., Ltd. DAIGUARD-580 and DAIGUARD-610 etc.), HCA derivatives (for example, Sanko Co., Ltd. HCA-HQ, M-Ester, ME-P8 etc.) etc. are already on the market. ing.

  Examples of the nitrogen-containing compound include a compound that forms a salt of cyanuric acid or isocyanuric acid with silicon nitride, aluminum nitride, or a triazine-based compound. A triazine compound and a salt of cyanuric acid or isocyanuric acid are adducts of a triazine compound and cyanuric acid or isocyanuric acid, usually 1 to 1 (molar ratio), sometimes 2 to 1 (molar ratio). ). Of the triazine compounds, those that do not form a salt with cyanuric acid or isocyanuric acid are excluded.

  Examples of the triazine compounds include melamine, mono (hydroxymethyl) melamine, di (hydroxymethyl) melamine, tri (hydroxymethyl) melamine, benzoguanamine, acetoguanamine, 2-amido-4,6-diamino-1,3. , 5-triazine and the like.

上記式（６）中のｑは２〜１０の整数を表し、Ｒ⁸〜Ｒ¹¹はそれぞれ独立に、水素原子、アルキル基、又はアリール基を表し、Ｒ¹²は、酸素原子、硫黄原子、又は窒素原子を含んでいる場合がある炭化水素基を表す。 Moreover, as a nitrogen-containing compound, the compound containing a phosphorus atom and a nitrogen atom as represented by following formula (6) is mentioned.

Q in the formula (6) represents an integer of 2 to 10, R ^{8 to} R ¹¹ each independently represents a hydrogen atom, an alkyl group, or an aryl group, and R ¹² represents an oxygen atom, a sulfur atom, or Represents a hydrocarbon group that may contain a nitrogen atom.

  Although the manufacturing method of the compound represented by the above formula (6) component is not particularly limited, for example, it is manufactured by using a base together in a solvent by the method shown in the following formula (7). can do.

上記式（７）中、ｑは２〜１０の整数を表し、Ｒ⁸〜Ｒ¹¹はそれぞれ独立に、水素原子、アルキル基、又はアリール基を表し、Ｒ¹²は、酸素原子、硫黄原子、又は窒素原子を含んでいる場合がある炭化水素基を表す。

In the above formula (7), q represents an integer of 2 to 10, each R ⁸ to R ¹¹ independently represents a hydrogen atom, an alkyl group, or aryl group, R ¹² represents an oxygen atom, a sulfur atom, or Represents a hydrocarbon group that may contain a nitrogen atom.

  Examples of the solvent and base that can be used in the above formula (7) include the same ones as exemplified in the reaction of the above formula (5).

  Q in the above formulas (6) and (7) is preferably an integer of 2 to 7, and more preferably an integer of 2 to 5. When q is 1, the number of functional groups that react with the epoxy group is one, and the Tg and strength of the cured product obtained by curing the epoxy resin are remarkably lowered. When q is a number larger than 10, the viscosity at the time of producing the nitrogen-containing compound becomes high and the production becomes difficult, which is not preferable.

Examples of the alkyl group represented by R ^{8 to} R ¹¹ in the above formulas (6) and (7) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, Examples include amyl group, isoamyl group, tertiary amyl group, hexyl group, isohexyl group, octyl group, 2-ethylhexyl group, tertiary octyl group, nonyl group, and decyl group. Moreover, as an aryl group represented by said R < ⁸ > -R < ¹¹ >, a phenyl group, a naphthyl group, etc. are mentioned, for example.
In Among these, R ⁸ to R ¹¹ is a hydrogen atom, or preferably an alkyl group having 1 to 6 carbon atoms, in either a hydrogen atom of R ^8, R ^9, or a methyl group, or More preferably, it is an ethyl group, and any one of R ¹⁰ and R ¹¹ is a hydrogen atom, and any one is a methyl group or an ethyl group.

Examples of the hydrocarbon group represented by R ¹² in the above formulas (6) and (7) include alkanediyl groups such as a methylene group, an ethylene group, a propylene group, an ethanediyl group, and an octanediyl group; Alkanetriyl groups such as 1,1,3-ethylenetriyl groups; alkanetetrayl groups such as 1,1,2,2-ethylenetriyl; and simple units such as hydroquinone, resorcin, pyrocatechol, phloroglucinol Nuclear polyphenol compounds; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1, 3-bis 4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxy Phenyl) ethane, thiobisphenol, sulfonylbisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, terpene phenol, and other aromatic groups of polynuclear polyhydric phenol compounds. .

From the viewpoint of physical properties of a cured product obtained by curing the flame retardant epoxy resin composition of the present invention, R ¹² of the compounds represented by the above formulas (6) and (7) is represented by the following formula (8). Those are preferred.

上記式（８）中の、ｒは０〜３の数を表し、Ｒ¹³は、水素原子又は炭素数が１〜４のアルキル基を表し、Ｒ¹⁴は単結合、メチレン基、又は−Ｃ（ＣＨ₃）₂−を表し、Ｒ¹⁵、Ｒ¹⁶は、独立して、水素原子、又は炭素数が１〜６のアルキル基を表す。

In the above formula (8), r represents a number of 0 to 3, R ¹³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹⁴ represents a single bond, a methylene group, or —C ( CH ₃ ) ₂ — and R ¹⁵ and R ¹⁶ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹³ in the above formula (8) are those exemplified as the alkyl groups represented by R ¹ , R ² and R ⁴ in the above formula (1). Among them, those having 1 to 4 carbon atoms can be mentioned.
The alkyl group having 1 to 6 carbon atoms represented by R ¹⁵ and R ¹⁶ in the above formula (8) is an alkyl group represented by R ¹ , R ² and R ⁴ in the above formula (1). The thing of C1-C6 in what was illustrated is mentioned.

  Examples of the boron-containing compound include boric acid (orthoboric acid, metaboric acid, etc.), borate (alkali metal borate such as sodium tetraborate, alkaline earth metal salt such as barium metaborate, zinc borate, etc. Transition metal salts, etc.), condensed boric acid (salt) (pyroboric acid, tetraboric acid, pentaboric acid, octaboric acid or metal salts thereof), boron nitride and the like. These boron-containing compounds may be hydrated materials (for example, borax which is hydrated sodium tetraborate). These boron-containing compounds may be used alone or in combination of two or more.

  In the present invention, the flame retardant as the component (D) is preferably a phosphorus-containing compound other than the component (C) or a nitrogen-containing compound in terms of being able to express more flame retardancy, and other than the component (C) The phosphorous compound is more preferably ammonium polyphosphate, melamine polyphosphate, aluminum trisdiethylphosphinate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA), 10- (2, 5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA-HQ manufactured by Sanko Co., Ltd.), hexaphenylcyclotriphosphazene, or the following formula (9 It is more preferable that the flame retardant is represented by any one of -1) to (9-11).

S in the formula (9-1) represents an integer of 1 to 50; t in the formula (9-2) represents an integer of 1 to 20;
A, b, and c in formulas (9-3) to (9-5) each independently represent an integer of 1 to 5;
D and e in formulas (9-6) and (9-7) each independently represents an integer of 1 to 10;
F in Formula (9-8) represents an integer of 1 to 50, A in Formula (9-11) represents a hydrogen atom or —OR ¹⁷ , and R ¹⁷ represents an alkyl group having 1 to 6 carbon atoms. Represent.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹⁷ in A in Formula (9-11) are the alkyl groups represented by R ¹ , R ² and R ⁴ in Formula (1). Among them, those having 1 to 6 carbon atoms are mentioned.

  Among the above phosphorus-containing compounds, aluminum trisdiethylphosphinate, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-, in that the flame-retardant effect is very excellent. 10-phosphaphenanthrene-10-oxide is particularly preferred.

  In this invention, as usage-amount of (D) component, it is preferable that it is 1-1000 mass parts with respect to 100 mass parts of phosphorus compounds which are (C) component, 20-200 mass parts is more preferable, 50- 150 parts by mass is more preferable.

  When the phosphorus atom is contained in the flame retardant as the component (D), the amount of the component (D) used is the component (A), component (B), component (C), (D) of the epoxy resin composition. It is preferable that the phosphorus content derived from the component (D) in the total mass of the component and optional reactive diluent is 0.1 to 5% by mass, preferably 0.5 to 3% by mass. It is more preferable that the amount is%. If the phosphorus content is less than 0.1% by mass, the flame retardancy of the epoxy resin composition may be significantly reduced. On the other hand, when there is more phosphorus content than the quantity used as 5 mass%, the water resistance of an epoxy resin composition may fall remarkably.

By the way, as a general flame retardant, a halogen-based flame retardant is known as a flame retardant other than the component (D) of the present invention. For example, tetrabromobisphenol A, carbonate oligomer of tetrabromobisphenol A, tetrabromo Bisphenol A bis (2,3-dibromopropyl ether), tetrabromobisphenol A bis (2-bromoethyl ether), tetrabromobisphenol A diglycidyl ether and brominated bisphenol adduct epoxy oligomer, tetrabromobisphenol A diglycidyl ether Tetrabromobisphenol A derivatives such as tribromophenol adducts; decabromodiphenyl ether, octabromodiphenyl ether, ethylenebistetrabromophthalimide, hexabromocyclododeca 1,2-bis (pentabromophenyl) ethane, 2,3-dibromopropylpentabromophenyl ether, 1,2-bis (2,4,6-tribromophenoxy) ethane, 2,4,6-tris ( 2,4,6-tribromophenoxy) -1,3,5-triazine, brominated polystyrene, polybrominated styrene, pentabromobenzyl acrylate (monomer) and the like brominated aromatic compounds; chlorinated paraffin; chlorinated naphthalene Tris (chloroethyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris (2-chloropropyl) phosphate, tris (2,3-bromopropyl) phosphate, tris (bromochloropropyl) phosphate, 2,3- Dibromopropyl-2,3-chloropropyl phosphate, Tris Tribromophenyl) phosphate, tris (dibromophenyl) phosphate, etc. halogen-containing phosphoric acid esters such as tris (tribromoneopentyl) phosphate can be mentioned.
These halogen flame retardants are considered to be sufficient materials for improving the flame retardancy of the epoxy resin composition as an alternative to the component (D) of the present invention in terms of flame retardancy. It is known that printed wiring boards using halogen-based flame retardants generate toxic gases in the event of a fire or disposal after use. Is an undesirable material.

  The flame retardant epoxy resin composition of the present invention may contain an organic solvent as a viscosity modifier as necessary. Examples of the organic solvent include amides such as N, N-dimethylformamide, ethers such as ethylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol and ethanol, and aromatics such as benzene and toluene. Group hydrocarbons and the like. In the present invention, at least one solvent selected from these solvents is used as component (A), component (B), component (C), component (D), and optionally used reaction. For example, it can mix | blend so that it may become the range of 1-90 mass% with respect to the total mass of a soluble diluent.

  The flame retardant epoxy resin composition of the present invention may contain an inorganic filler as necessary. Examples of such inorganic filler include silica such as fused silica and crystalline silica, magnesium hydroxide, aluminum hydroxide, zinc molybdate, calcium carbonate, silicon carbide, calcium silicate, potassium titanate, beryllia, zirconia, zircon. , Powders such as fosterite, steatite, spinel, mullite, titania, or beads formed by spheroidizing these, and glass fiber. These inorganic fillers may be used alone or in combination of two or more.

In the present invention, it is preferable to use the above-mentioned inorganic filler properly depending on the application to be used. For the use of the laminate, it is preferable to use fused silica, aluminum hydroxide or the like. As for the use of the sealant, it is preferable to use fused silica, crystalline silica or the like, and it is particularly preferable to use fused silica. Regarding the use of the casting material, it is preferable to use fused silica, crystalline silica, aluminum hydroxide or the like, and it is particularly preferable to use fused silica.
The blending amount of the inorganic filler is preferably 20 to 90% by mass, and more preferably 25 to 80% by mass with respect to the total solid content of the epoxy resin composition. If the blending amount of the inorganic filler is less than 20% by mass, the effect of reducing the coefficient of thermal expansion of the cured product tends to be low. Tend to.

  Moreover, the flame retardant epoxy resin composition of the present invention may contain additives other than the inorganic filler as necessary. Examples of the additive include non-reactive diluents (plasticizers) such as dioctyl phthalate, dibutyl phthalate, benzyl alcohol, and coal tar; fibrous fillers such as glass fiber, pulp fiber, synthetic fiber, and ceramic fiber; Reinforcing materials such as glass cloth, aramid cloth, carbon fiber; pigment; γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -N '-Β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-anilinopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane , Vinyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl ) Silane coupling agents such as -γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane; candelilla wax, carnauba wax, wood Lubricants such as wax, ibota wax, beeswax, lanolin, whale wax, montan wax, petroleum wax, aliphatic wax, aliphatic ester, aliphatic ether, aromatic ester, aromatic ether; thickener; thixotropic agent; oxidation Common additives such as inhibitor, light stabilizer, ultraviolet absorber, antifoaming agent, rust inhibitor, colloidal silica, and colloidal alumina can be mentioned. In the present invention, adhesive resins such as xylene resin and petroleum resin can be used in combination.

  The flame-retardant epoxy resin composition of the present invention is a laminate used for electronic circuit boards, a sealant used for electronic components, a casting material, a film material, an adhesive, an electrical insulating paint, and a composite that requires flame retardancy. It can be used for materials, powder coatings, etc., and is particularly suitable for use in laminates used in electronic circuit boards, sealants used in electronic components, and casting materials.

  The laminated board of the present invention is a prepreg using the flame retardant epoxy resin composition of the present invention, one sheet or a predetermined number of sheets, for example, 2 to 20 sheets, and a metal foil such as copper or aluminum on one or both sides thereof. Can be manufactured by thermocompression bonding at a predetermined temperature, for example, 100 to 250 ° C., using a multistage press, a multistage vacuum press or the like. The organic components contained in the laminate (components (A) to (D), and optionally added reactive diluents, and the total amount of organic substances among the additives) are not particularly limited, Preferably it is 46 mass%-50 mass%. When the amount is less than 46% by mass, there is no problem with respect to heat resistance and flame retardancy, but there is a concern that the interlayer adhesion in the laminate is lowered, the insulation is lowered, the adhesion with the circuit forming metal is lowered, and the smoothness is deteriorated. Yes, there is a possibility that the performance of the laminated board is lowered overall, and when it is more than 50% by mass, there is a possibility that the dimensional stability (linear expansion) is deteriorated and the flame retardancy is lowered.

  A prepreg using the flame retardant epoxy resin composition of the present invention is produced by impregnating or coating the flame retardant epoxy resin composition of the present invention on a substrate and semi-curing (B-stage) by heating or the like. be able to.

  As the base material of the prepreg, known materials such as glass fibers, polyimide, polyester, tetrafluoroethylene, and other organic fibers, and mixtures thereof can be used.

  Examples of the shape of the substrate include woven fabric, non-woven fabric, robink, chopped strand mat, and surfacing mat. The material and shape of these base materials are selected according to the intended use and performance of the molded product. The flame-retardant epoxy resin composition of the present invention can be used alone or in combination of two or more materials and shapes.

The sealant of the present invention used for electronic parts can be produced by stirring, melting, mixing, and dispersing the flame retardant epoxy resin composition of the present invention while being heat-treated as necessary. In this case, the apparatus used for stirring, melting, mixing, and dispersion is not particularly limited, and in the present invention, a stirrer, a raikai machine equipped with a heating device, a three-roll mill, a ball mill, a planetary mixer, A bead mill or the like can be used. Moreover, you may use combining these apparatuses suitably.
The casting material using the flame retardant epoxy resin composition of the present invention is manufactured using, for example, a mold after mixing the flame retardant epoxy resin composition of the present invention using a mixer or the like and vacuum degassing. can do.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to these Examples.
In the following examples and the like,% is based on mass unless otherwise specified.

  Items evaluated in the examples include the appearance of the prepreg, the moldability of the copper clad laminate, the resin content (the amount of resin in the prepreg, (A) component, (B) component, (C) component, (D ) Component and the total amount of organic components such as reactive diluents and additives optionally added, the same applies hereinafter), glass transition temperature (Tg), and flame retardancy.

When the appearance of the prepreg was visually observed, a uniform appearance was evaluated as good, and a non-uniform appearance was regarded as defective.
In the resin content in a prepreg, the thing of 46 mass%-50 mass% was set as the pass. The resin content was calculated as follows by measuring the total mass of the manufactured laminate and the total mass of the glass cloth used.
<Calculation method of resin content>
Resin content (mass%) = {(total mass of laminated plate−total mass of glass cloth) / total mass of laminated plate} × 100

  The formability of the copper-clad laminate was evaluated by visually observing the appearance after producing a double-sided copper-clad laminate by pressure-curing using a prepreg. Uniform curing and prepreg molding were considered good in moldability, and non-uniformly cured prepreg was evaluated as poor moldability.

  Regarding the flame retardancy, UL (Underwriters Laboratories) “Plastic material flammability” was used for test pieces that had been processed to have a length of 127 mm and a width of 12.7 mm by removing the copper foil of the double-sided copper-clad laminate by etching. The test was conducted in accordance with “Test UL 94” and judged as follows.

<Judgment method>
The test piece was kept vertical, and the burner was fired at the lower end for 10 seconds, then the burner was removed, and the time until the fire that ignited the test piece disappeared was measured. Next, at the same time when the fire was extinguished, the second flame contact was performed for 10 seconds, and the time until the ignited fire was extinguished was measured in the same manner as the first time. The average value of the time until the first fire extinguishes after performing the operation five times (hereinafter referred to as T1) The average value of the time until the second fire extinguishes (hereinafter referred to as T2) Calculated. At the same time, the total burning time for five operations was calculated. In addition, it was also evaluated whether or not the cotton placed under the test piece was ignited by the falling fire type.
The combustion rank was evaluated according to the UL-94V standard from the results such as the total combustion time and the presence or absence of cotton ignition. V-0 is the highest combustion rank, and the flame retardancy decreases as V-1 and V-2. However, those not corresponding to any of the ranks V-0 to V-2 were defined as NR.

  The glass transition temperature (Tg) of the cured product was measured using TMA (thermomechanical analyzer, manufactured by Hitachi High-Tech Science Co., Ltd., EXSTAR TMA / SS-6100).

  In the Example of this invention, the resin content in a laminated board is 46 mass%-50 mass% made evaluation favorable, and the thing outside the range was made bad evaluation. In general, when there are many organic components such as resin content, the resulting laminated board tends to have poor flame retardancy. Conversely, when there are few organic components, the organic component has a flame-retardant effect. Even if not, the evaluation is good in the flame retardancy test, but other performances such as interlayer adhesion and insulation tend to deteriorate. For those having flame retardancy of V-1 or higher, those having a Tg of 180 ° C. or higher were evaluated as good. For those having flame retardancy of V-0, those satisfying the above-mentioned evaluation of the resin content were evaluated as good. In addition, the appearance of the prepreg and the moldability of the copper clad laminate were also evaluated, and the overall evaluation was judged as acceptable or unacceptable.

[Production Example 1: Synthesis of phosphorus-containing compound (PH-1)]
A 500 mL five-necked flask equipped with a stirring blade, a reflux tube, a thermometer, a dropping funnel, and a septum was thoroughly dried and purged with nitrogen to obtain 45.7 g (0.20 mol) of bisphenol A and 42.5 g (0.42 mol) of triethylamine. , And 300 mL of ultra-dehydrated tetrahydrofuran were charged. The dropping funnel was charged with 59.0 g (0.42 mol) of diethylphosphinic chloride and dropped so that the reaction temperature did not exceed 50 ° C. After completion of dropping, the mixture was stirred overnight. The reaction solution was transferred to a separatory funnel, and 500 mL of chloroform and 300 mL of saturated aqueous sodium hydrogen carbonate solution were added and stirred well. After oil-water separation, the aqueous layer was removed. The organic layer was washed twice with 200 mL of distilled water, dried over anhydrous magnesium sulfate, the solvent was removed with an evaporator, and phosphorus-containing compound (PH-1, corresponding to the compound of the above formula (4-3)) 78.1 g (Yield 89.4%) was obtained. The theoretical phosphorus content of the phosphorus-containing compound PH-1 is 14.2% by mass.

[Production Example 2: Synthesis of phosphorus-containing compound (PH-2)]
A 500 mL five-necked flask equipped with a stirring blade, a reflux tube, a thermometer, a dropping funnel and a septum was thoroughly dried and purged with nitrogen, and HF-1M (phenol novolac resin, hydroxyl group equivalent: 107 g / eq., Meiwa Kasei) 34.2 g (0.16 mol), triethylamine 34.4 g (0.34 mol), and super dehydrated tetrahydrofuran 300 mL were charged. Into the dropping funnel, 47.8 g (0.34 mol) of diethylphosphinic chloride was added and added dropwise so that the reaction temperature did not exceed 50 ° C. After completion of dropping, the mixture was stirred overnight. The reaction solution was transferred to a separatory funnel, and 500 mL of chloroform and 300 mL of saturated aqueous sodium hydrogen carbonate solution were added and stirred well. After oil-water separation, the aqueous layer was removed. The organic layer was washed twice with 200 mL of distilled water, dried over anhydrous magnesium sulfate, the solvent was removed with an evaporator, and phosphorus-containing compound (PH-2, corresponding to the compound of the above formula (4-4)) 66.4 g (Yield 98.3%) was obtained. The theoretical phosphorus content of the phosphorus-containing compound PH-2 is 14.6% by mass.

[Production Example 3: Synthesis of phosphorus-containing compound (PH-3)]
A 500 mL five-necked flask equipped with a stirring blade, a reflux tube, a thermometer, a dropping funnel and a septum was thoroughly dried and purged with nitrogen, to 29.8 g (0.16 mol) of 4,4′-biphenol and 34.4 g of triethylamine. (0.34 mol) and 300 mL of ultra-dehydrated tetrahydrofuran were charged. Into the dropping funnel, 47.8 g (0.34 mol) of diethylphosphinic chloride was added and added dropwise so that the reaction temperature did not exceed 50 ° C. After completion of dropping, the mixture was stirred overnight. The reaction solution was transferred to a separatory funnel, and 500 mL of chloroform and 300 mL of saturated aqueous sodium hydrogen carbonate solution were added and stirred well. After oil-water separation, the aqueous layer was removed. The organic layer was washed twice with 200 mL of distilled water, dried over anhydrous magnesium sulfate, the solvent was removed with an evaporator, and phosphorus-containing compound (PH-3, corresponding to the compound of the above formula (4-1)) 60.6 g (Yield 96.1%) was obtained. The theoretical phosphorus content of the phosphorus-containing compound PH-3 is 15.7% by mass.

[Production Example 4: Synthesis of phosphorus-containing compound (PA-1) <Synthesis of phosphorus-containing chloride P-1>
In a 300 mL round bottom flask equipped with a rotor, reflux tube, thermometer and nitrogen inlet, 22.8 g (0.1 mol) of bisphenol A, 306.7 g (2.0 mol) of phosphoryl chloride, and anhydrous magnesium chloride Was added until the reaction solution was refluxed and stirred for 24 hours. At that time, hydrogen chloride gas generated in the reaction was introduced into the sodium hydroxide aqueous solution from the upper part of the reflux pipe and trapped. After completion of the reaction, excess phosphoryl chloride was removed using an evaporator to obtain phosphorus-containing chloride P-1. The obtained P-1 was dissolved in 100 mL of THF to obtain a THF solution of P-1.

<Reaction of chloride and amine>
In a 500 mL round bottom flask equipped with a stirring blade, a reflux tube, a dropping funnel and a thermometer, 210 mL (2.0 mol / L, methylamine: 0.42 mol) of methylamine in THF and 42.5 g (0. 42 mol). While stirring and cooling the reaction solution in a nitrogen atmosphere, the THF solution of P-1 was added dropwise so that the reaction temperature did not exceed 0 ° C., and the mixture was stirred at 25 ° C. for 24 hours. After completion of the reaction, the solvent and excess raw material were removed with an evaporator, and the residue was dissolved in 300 mL of chloroform and transferred to a separatory funnel. The organic layer was washed twice with 100 mL of distilled water, dried over anhydrous magnesium sulfate, the solvent was removed with an evaporator, and the phosphorus-containing compound (PA-1, R ⁸ and R ¹⁰ are methyl groups in the above formula (6). R ⁹ and R ¹¹ are hydrogen, q is 2, R ¹² is the above formula (8), R ¹³ and R ¹⁵ are hydrogen in formula (8), and R ¹⁴ is —C 18.8 g (yield 85.3%) of (CH ₃ ) ₂ —, corresponding to a compound in which R ¹⁶ is a methyl group and r is 0.16). The theoretical phosphorus content of the phosphorus-containing compound PA-1 is 14.1% by mass.

[Example 1]
EOCN-104S (cresol novolak type epoxy resin, manufactured by Nippon Kayaku Co., Ltd.) 49.1 g, HP-350 (aluminum hydroxide, manufactured by Showa Denko KK) 59.2 g and SFP-130MC (spherical silica, electrochemistry) 59.2 g (manufactured by Kogyo Co., Ltd.) was added to 100 g of methyl ethyl ketone and dispersed with three rolls. Subsequently, 8.34 g of PH-1 obtained in Production Example 1 and OP-1230 (aluminum trisdiethylphosphinate, manufactured by Clariant) were dissolved in 5.15 g and methanol 20 g and added. Further, 50.9 g of EOCN-104S, 5 g of ADEKA HARDNER EH-3636AS (Dicyandiamide type latent curing agent, manufactured by ADEKA) (5 phr with respect to 100 parts by mass of epoxy resin), and 100 g of methyl ethyl ketone were added to the disper. The resin varnish was prepared by dispersing.

The obtained resin varnish was impregnated into a glass cloth (# 7628, manufactured by Nitto Boseki Co., Ltd.) and dried by heating in a hot air circulating furnace at 120 ° C. for 10 minutes to prepare a prepreg. Furthermore, 4 sheets of the prepared prepregs were stacked, 35 μm thick copper foil (made by Fukuda Metal Foil Powder Co., Ltd.) was placed on both sides, and thermocompression bonded at 190 ° C. under a pressure of 10 kg / cm ² for 120 minutes. Thus, a double-sided copper-clad laminate was obtained. The appearance, moldability, Tg, and flame retardancy tests of the prepreg appearance, resin content, and double-sided copper-clad laminate were performed as described above. The evaluation is shown in Table 1.

[Examples 2-7, Comparative Examples 1-5]
A prepreg and a double-sided copper-clad laminate were prepared and subjected to various evaluations in the same manner as in Example 1 except that the formulation shown in Tables 1 and 2 was changed. The results are shown in Tables 1 and 2.

  All the prepregs using the flame-retardant epoxy resin composition of the present invention have good appearance without bleeding and crystallization of components such as flame retardant, and have a certain amount of resin content. However, a copper clad laminate having a good balance between flame retardancy and Tg could be obtained. In Examples 3, 4, 5, and 6, it was found that the copper-clad laminate was particularly excellent in flame retardancy and Tg evaluation. Copper-clad laminates obtained using the flame retardant epoxy resin compositions of Comparative Examples 1 and 2 with high resin content did not provide satisfactory results with respect to the overall evaluation of flame retardancy and Tg. In Comparative Examples 3 and 4, good results were obtained with respect to flame retardancy. However, since the resin content was lower than that of Comparative Example 1, the interphase adhesion decreased, the insulation decreased, and the adhesion to the circuit-forming metal. As a result, there is a concern about deterioration of the property, smoothness, etc., which is not good for evaluation of a copper clad laminate. In Comparative Example 5, since the component considered to be HCA-HQ was crystallized on the prepreg surface, a uniform prepreg could not be obtained, and the subsequent evaluation could not be performed. In Comparative Example 6, the flame retardancy was poor due to the absence of the component (C).

  Since the flame-retardant epoxy resin composition of the present invention does not use halogen, it is not only excellent in environmental suitability, but also has good flame retardancy and has two or more reactive sites with the epoxy group of the epoxy resin. Since the phosphorus-containing compound is used, the Tg of the cured product can be greatly improved, and the workability is also good. Since the laminated board etc. which were manufactured using the flame-retardant epoxy resin composition of this invention are excellent in physical properties, such as heat resistance, this invention is very useful industrially.

Claims (7)

(A) epoxy resin, (B) curing agent, (C) phosphorus-containing compound represented by the following formula (1), and (D) phosphorus-containing compounds other than component (C), nitrogen-containing compounds, and boron-containing compounds A flame retardant epoxy resin composition comprising at least one flame retardant selected from the group consisting of:

In the above formula (1), m represents an integer of 2 to 10, R ¹ and R ² each independently represents an alkyl group or an aryl group, and R ³ represents an oxygen atom, a sulfur atom, or a nitrogen atom. Represents a hydrocarbon group that may contain, X represents an oxygen atom or a sulfur atom, Y represents an oxygen atom, a sulfur atom, or —NR ⁴ —, and R ⁴ represents a hydrogen atom, an alkyl group, or Represents an aryl group. The flame retardant epoxy resin composition according to claim 1, wherein R ³ in the formula (1) is a hydrocarbon group having at least one aromatic ring. In the above formula (1), X and Y are both oxygen atoms, R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms, and R ³ is represented by the following formulas (2-1), ( The flame-retardant epoxy resin composition according to claim 1 or 2, which is a group having any structure selected from 2-2) and (2-4) to (2-6);

In the above formula (2-1), R ⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In the above formula (2-2), n represents an integer of 0 to 3, o is an integer of 0 to 50, R ⁶ is a hydrogen atom or a carbon atoms represent 1-4 alkyl, R ⁷ Represents a hydrocarbon group that may contain an oxygen atom or a sulfur atom, and Z represents a hydroxyl group or a functional group represented by the following formula (2-3);

R ¹ and R ² in the above formula (2-3) each independently represent an alkyl group or an aryl group;

  (D) The flame retardant according to any one of claims 1 to 3, wherein the flame retardant is at least one flame retardant selected from the group consisting of a phosphorus-containing compound other than the component (C) and a nitrogen-containing compound. Flammable epoxy resin composition.   The prepreg which consists of a sheet-like base material which consists of at least 1 sort (s) of fiber which could be selected from an inorganic fiber and an organic fiber, and the flame-retardant epoxy resin composition described in any one of Claims 1-4.   An epoxy resin laminate comprising the prepreg according to claim 5 or a laminate obtained by laminating at least two of the prepregs, wherein metal foil is disposed and laminated on at least one surface, and thermocompression-bonded. Production method.   An epoxy resin laminate produced by the method according to claim 6.