JP2019038891A - Flame-retardant epoxy resin composition, and prepreg and laminate using the same - Google Patents

Abstract

To provide an epoxy resin composition which improves the glass transition temperature (Tg) of a cured product and is excellent in flame retardancy.SOLUTION: The 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) a flame retardant other than the component (C). In the formula (1), m represents an integer of 1-10; Rand Reach independently represent an alkyl group or an aryl group; Rrepresents a hydrocarbon group which may contains an oxygen atom, a sulfur atom or a nitrogen atom; X represents an oxygen atom or a sulfur atom; Y represents an oxygen atom, a sulfur atom or -NR-; and Rrepresents a hydrogen atom, an alkyl group or an aryl group.SELECTED DRAWING: None

Description

  The present invention relates to a flame retardant epoxy resin composition, and more specifically, a glass transition temperature (Tg) of a cured product by using a phosphorus-based reactive flame retardant together with a flame retardant other than the reactive flame retardant. It is related with the epoxy resin composition excellent in the flame retardance while being improved, and can be used suitably for a laminated board use.

  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 parts and electronic devices. However, these epoxy resins have safety features such as fire prevention and delay of fire spread. From the standpoint of safety, brominated epoxy resins that provide flame retardant effects have been used.

  On the other hand, 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.
Furthermore, it has been proposed to use a phosphorus-containing compound having reactivity with an epoxy group (for example, Patent Documents 3 and 4). Although this method can impart flame retardancy while giving the glass transition temperature (Tg) of the cured product, a sufficient flame retardancy imparting effect cannot be obtained yet.

JP 2004-051907 A JP 2010-037375 A International Publication No. 2015/025904 International Publication No. 2016/121750

  Therefore, the problem to be solved by the present invention is to provide a flame retardant epoxy resin composition that is excellent in workability, in particular, a laminated board used for a printed wiring board, etc. Is to provide.

  Accordingly, the present inventors have intensively studied, and in an epoxy resin curing system, by combining a specific phosphorus-based reactive flame retardant and another flame retardant, an epoxy resin having excellent cured properties and excellent flame retardancy. The inventors have found that a composition can be obtained and have reached the present invention. That is, the present invention contains (A) an epoxy resin, (B) a curing agent, (C) a phosphorus-containing compound represented by the following formula (1), and (D) a flame retardant other than the component (C). Is a flame retardant epoxy resin composition characterized by

In the above formula (1), m represents an integer of 1 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, it is possible to obtain a flame retardant epoxy resin composition that is excellent in workability, does not cause a bleed phenomenon of a flame retardant during curing, and has excellent physical properties of a cured product. Moreover, the laminated board excellent in the flame retardance can be obtained by using this epoxy resin composition.

  The flame retardants other than (A) epoxy resin, (B) curing agent, (C) phosphorus-containing compound, and (D) (C) component used in the present invention will be described below.

  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 has at least two epoxy groups in the molecule and can be appropriately selected from known epoxy resins without any particular limitation on the molecular structure, molecular weight, etc. It is preferable to use them properly depending on the intended use.

  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, Polyethylene glycol, polypropylene glycol, thioglycol, dicyclopentadiene dimethanol, 2,2-bis (4-hydroxycyclohexyl) propane (hydrogenated bisphenol A), glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide addition Polyglycidyl of polyhydric alcohol compounds such as Ether compounds; maleic acid, fumaric acid, itaconic 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, trimesin Homopolymers or copolymers of glycidyl ester compounds and glycidyl methacrylates of aliphatic, aromatic or alicyclic polybasic acids such as acids, pyromellitic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid; N, N-di Glycidylaniline, 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 -Epoxy compounds having a glycidylamino group such as (2,3-epoxypropoxy) aniline, N, N, N ', N'-tetra (2,3-epoxypropyl) -4,4-diaminodiphenylmethane; vinylcyclohexenedi Epoxide, cyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3,4- Epoxy products of cyclic olefin compounds such as epoxy-6-methylcyclohexylmethyl) adipate; Epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymer; Heterocycles such as triglycidyl isocyanurate Compounds, and the like. In addition, these epoxy resins are those internally cross-linked by a prepolymer of a terminal isocyanate, or those having a high molecular weight with a polyvalent active hydrogen compound (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphate ester, etc.) But you can.

  The said epoxy resin may be used independently, or may use 2 or more types together. When the flame retardant epoxy resin composition is for a laminate, it is preferable to use a polyglycidyl ether compound of a polynuclear polyhydric phenol 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, a biphenyl type epoxy resin, and a naphthalene type epoxy resin.

  When the flame retardant epoxy resin composition is a casting material, (A) the epoxy resin is preferably a polyglycidyl ether of a polyhydric alcohol, a polyglycidyl ether compound of a polynuclear polyphenol 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, C12-C14 alkyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, and cresyl. Examples thereof 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 diglycidyl ether. Etc. Examples of the reactive diluent having three 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 for a sealing material, it is preferable to use phenol resins, latent curing agents or acid anhydrides as (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'-diaminodicyclohexyl Examples include methane, isophoronediamine, norbornenediamine, and metaxylenediamine. Further, a modified product of these amines may be used. Examples of the amine modification method include dehydration condensation with carboxylic acid, addition reaction with epoxy resin, addition reaction with isocyanate, Michael addition reaction, Mannich reaction, condensation reaction with urea, condensation reaction with ketone, and the like. These can be used alone or in combination at any ratio.
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-diaminebenzene, 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. It is done. Further, a modified product of these amines may be used. Examples of the amine modification method include dehydration condensation with carboxylic acid, addition reaction with epoxy resin, addition reaction with isocyanate, Michael addition reaction, Mannich reaction, condensation reaction with urea, condensation reaction with ketone, and the like. These can be used alone or in combination at any ratio.
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 | 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 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. Is mentioned.
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 in the production of the imidazole-type latent curing agent include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, propylene glycol monomethyl ether acetate, and cyclohexane; 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, if necessary, at 50 to 150 ° C. for 1 to 20 hours. 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 amines 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-3636S (manufactured by ADEKA Corporation; dicyandiamide type latent curing agent) and ADEKA HARDNER EH-4351S (manufactured by ADEKA Corporation; 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), ADEKA HARDNER EH-5057PK (made by ADEKA; polyamine type latent curing agent), Micure PN-23 (Ajinomoto Fine Techno Co., Ltd .; amine adduct based latent curing agent), Amicure PN-40 (Ajinomoto Fine Techno Co., Ltd .; amine adduct based latent curing agent), Amicure VDH (Ajinomoto Fine Techno Co., Ltd.) Hydrazide-based latent curing agent), Fuji Cure FXR-1020 (manufactured by T & K TOKA; latent curing agent), and the like. These can be used alone or in appropriate combination.

  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 phosphines such as triphenylphosphine; phosphonium salts such as tetraphenylphosphonium bromide; 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-un Imidazoles such as decylimidazole and 1-cyanoethyl-2-methylimidazole; imidazole salts which are salts of the imidazoles with trimellitic acid, isocyanuric acid, boron and the like; benzyldimethylamine, 2,4,6-tris ( Amines such as dimethylaminomethyl) phenol; quaternary ammonium salts such as trimethylammonium chloride; 3- (p-chlorophenyl) -1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethyl Urea, 3-pheni Examples include ureas such as -1,1-dimethylurea, isophorone diisocyanate-dimethylurea, tolylene diisocyanate-dimethylurea; and complex compounds of boron trifluoride with amines and ether compounds. . 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.

In the above formula (1), m represents an integer of 1 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).

In the above formula (3), m represents an integer of 1 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.

  In said formula (1), it is preferable that m is 2-7, and it is more preferable that it is 2-5. 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.

In the above formula (1), examples of the alkyl group represented by R ¹ , R ² and R ⁴ 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. 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 and R ² include a phenyl group and a naphthyl group.
In the present invention, among these, R ¹ , R ² and R ⁴ are preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 2 to 5 carbon atoms, An alkyl group having a number of 2 to 4 is particularly preferable, and an ethyl group or a propyl group is most preferable.

In the above formula (1), examples of the hydrocarbon group represented by R ³ include alkanediyl groups such as methylene group, ethylene group, propylene group, ethanediyl group, and octanediyl group; methanetriyl, 1,1,2- Alkanetriyl groups such as ethanetriyl groups; alkanetetrayl groups such as 1,1,2,2-ethanetetrayl; hydroxyl groups are removed from mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol Residues: dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumyl) benzene, 1,4-bis (4-hydroxycumyl) benzene, 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4- Residues obtained by removing hydroxyl groups from polynuclear polyhydric phenol compounds such as hydroxyphenyl) ethane, thiobisphenol, sulfonylbisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, terpene phenol Is mentioned.

  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 any one of the following formulas is particularly preferable.

  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.

  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 represents an integer of 1 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.

  Examples of the base used in the above formula (5) include triethyleneamine, tributylamine, diazabicycloundecene, diazabicyclononene, 1,4-diazabicyclo [2.2.2] octane, and the like. Pyridines such as pyridine and N, N-dimethylaminopyridine; imidazoles such as 1-methylimidazole; and 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 (solv) used in the above formula (5) include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, and cyclohexanone; tetrahydrofuran, 1,2-dimethoxyethane, 1, Ethers such as 2-diethoxyethane and propylene glycol monomethyl ether; esters such as ethyl acetate, n-butyl acetate and propylene glycol monomethyl ether acetate; halogenated aliphatic carbonization such as carbon tetrachloride, chloroform, trichloroethylene and methylene chloride Hydrogen: 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 ° C. to 100 ° C., preferably 0 ° C. 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 a flame retardant other than the component (C), and is selected from, for example, phosphorus-containing compounds other than the component (C), nitrogen compounds, boron compounds, halogen compounds, silicon compounds, and inorganic compounds. And at least one flame retardant. 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, isopropylphenyldiphenyl phosphate, bis (isopropylphenyl) phenyl phosphate, tris (trimethylphenyl) phosphate, tris (t -Butylphenyl) phosphate, hydroxyphenyl diphenyl phosphate, octyl diphenyl phosphate Aromatic phosphate esters such as phosphate; resorcinol polyphenyl phosphate, 1,3-phenylenebis (2,6-dimethylphenyl phosphate), resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, Hydroquinone poly (2,6-xylyl) phosphate and condensed phosphates such as condensates thereof; phosphates such as ammonium phosphate and melamine phosphate; condensed phosphates such as ammonium polyphosphate and melamine polyphosphate; (Diethylphosphinic acid) aluminum, tris (methylethylphosphinic acid) aluminum, bis (diethylphosphinic acid) zinc, bis (methylethylphosphinic acid) zinc, bis (diphenylphosphinic acid) zinc, zinc triphosphinate, bis Metal salts of phosphinic acids such as diethylphosphinic acid) titanyl, tetrakis (diethylphosphinic acid) titanium, bis (methylethylphosphinic acid) titanyl, tetrakis (diphenylphosphinic acid) titanium, tetraphosphinic acid titanyl; phenyl diphenylphosphinate, diphenylphosphine Methyl acid, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter referred to as DOPO), 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa Phosphinic acid esters such as -10-phosphaphenanthrene-10-oxide; DOPO modification of DOPO and acrylic acid ester addition products, DOPO and epoxy resin addition reaction products, DOPO and hydroquinone addition reaction products, etc. Type compounds; phosphine oxide compounds such as diphenylvinylphosphine oxide, triphenylphosphine oxide, trialkylphosphine oxide, tris (hydroxyalkyl) phosphine oxide; phosphazene derivatives such as hexacyclotriphosphazene and hexaphenylcyclotriphosphazene; red Phosphorus etc. are mentioned.

  Among the phosphorus-containing compounds other than these components (C), for example, ammonium polyphosphate, melamine polyphosphate, aluminum tris (diethylphosphinate), 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.), hexaphenylcyclo More preferably, it is triphosphazene or a flame retardant represented by any one of the following formulas (6-1) to (6-11).

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

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹⁷ in A in Formula (6-11) 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 phosphorus-containing compounds, tris (diethylphosphinic acid) aluminum and 10- (2,5-phosphaphenanthrene-10-oxide are particularly preferable in that the effect of flame retardancy is very excellent.

  Examples of the nitrogen compound include compounds that form silicon nitride, aluminum nitride, a triazine-based compound and a salt of cyanuric acid or isocyanuric acid. A salt of a triazine compound and cyanuric acid or isocyanuric acid is an adduct of a triazine compound and cyanuric acid or isocyanuric acid, usually 1 to 1 (molar ratio), sometimes 2 to 1 (mole). Ratio) composition. 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.

  Moreover, as a nitrogen compound, the compound containing a phosphorus atom and a nitrogen atom as represented by following formula (7) is mentioned.

In the above formula (7), t represents an integer of 1 to ^10, R 11 ^{to R 14} each independently represent a hydrogen atom, an alkyl group, or aryl ^{group, R 15} 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 said Formula (7) component is not restrict | limited in particular, For example, it manufactures by using a base together in a solvent by the method shown by following formula (8). be able to.

上記式（８）中、ｑは１〜１０の整数を表し、Ｒ^１１〜Ｒ^１４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、Ｒ^１５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 formula (8), q represents an integer of 1 to ^10, R 11 ^{to R 14} each independently represent a hydrogen atom, an alkyl group, or aryl ^{group, R 15} represents an oxygen atom, a sulfur atom or Represents a hydrocarbon group that may contain a nitrogen atom.

  Examples of the solvent (solv) and the base (base) that can be used in the above formula (8) include the same ones as exemplified in the reaction of the above formula (5).

  T in the formulas (7) and (8) is preferably an integer of 2 to 7, and more preferably an integer of 2 to 5. When t is 1, there is only one functional group that reacts with the epoxy group, and the Tg and strength of the cured product obtained by curing the epoxy resin are remarkably lowered. When t is a number greater than 10, it is not preferable because the viscosity at the time of producing the nitrogen compound becomes high and the production becomes difficult.

Examples of the alkyl group represented by R ^{11 to} R ¹⁴ in the above formulas (7) and (8) 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 11 ^{to R 14} is preferably hydrogen atom, or an alkyl group having 1 to 6 carbon ^atoms, in either a hydrogen atom of R ^{11, R 12,} or a methyl group, or More preferably, it is an ethyl group, and any of R ¹³ and R ¹⁴ is a hydrogen atom, and either is a methyl group or an ethyl group.

Examples of the hydrocarbon group represented by R ¹⁵ in the above formulas (7) and (8) include alkanediyl groups such as a methylene group, an ethylene group, a propylene group, an ethanediyl group, and an octanediyl group; a methanetriyl group, 1 Alkanetriyl groups such as 1,2,2-ethanetriyl groups; Alkanetetrayl groups such as 1,1,2,2-ethanetetrayl groups; mononuclear polyhydric phenols such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol A group obtained by removing a hydroxyl group from a compound; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfonyl Examples thereof include groups obtained by removing hydroxyl groups from polynuclear polyhydric phenol compounds such as bisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, and terpene phenol.

From the viewpoint of physical properties of a cured product obtained by curing the flame retardant epoxy resin composition of the present invention, R ¹⁵ of the compound represented by the above formulas (7) and (8) is represented by the following formula (9). Those are preferred.

In the above formula (9), u represents a number of 0 to 3, R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹⁷ represents a single bond, a methylene group, or —C ( CH ₃ ) ₂ — and R ¹⁸ and R ¹⁹ 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 ¹⁶ in the above formula (9) 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.
As an alkyl group having 1 to 6 carbon atoms represented by R ¹⁸ and R ¹⁹ in the above formula (9), as an alkyl group represented by R ¹ , R ² and R ⁴ in the above formula (1) Among those exemplified, those having 1 to 6 carbon atoms can be mentioned.

  Examples of the boron 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), condensed boric acid (salts) (pyroboric acid, tetraboric acid, pentaboric acid, octaboric acid or metal salts thereof), boron nitride, and the like. These boron compounds may be hydrated materials (for example, borax which is hydrated sodium tetraborate). These boron compounds may be used alone or in combination of two or more.

  Examples of the halogen compound include tetrabromobisphenol A, carbonated oligomers of bisphenol A, tetrabromobisphenol A bis (2,3-dibromopropyl ether), tetrabromobisphenol A bis (2-bromoethyl ether), Tetrabromobisphenol A diglycidyl ether and tetrabromobisphenol A derivatives such as brominated bisphenol adducts; decabromodiphenyl ether, octabromodiphenyl ether, ethylenebistetrabromophthalimide, hexabromocyclododecane, 1,2-bis (pentabromophenyl) Ethane, 2,3-dibromopropylpentabromophenyl ether, 1,2-bis (2,4,6-tribromophenoxy) ethane, 2,4,6-to Brominated aromatic compounds such as bis (2,4,6-tribromophenoxy) -1,3,5-triazine, brominated polystyrene, polybrominated styrene, pentabromobenzyl acrylate (monomer); chlorinated paraffin; chlorine Naphthalene; tris (chloroethyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris (bromochloropropyl) phosphate, tris (2,3-dibromopyrrolyl) phosphate, tris (bromochlorophenyl) phosphate, 2,3 -Halogenated phosphates such as dibromopropyl-2,3-dichloropropyl phosphate, tris (tribromophenyl) phosphate, tris (dibromophenyl) phosphate, tris (tribromoneopentyl) phosphate, etc. .

  Examples of the inorganic compound include antimony trioxide, antimony pentoxide, aluminum hydroxide, magnesium hydroxide, boehmite, and graphite.

  Moreover, as a flame retardant marketed as (D) component, phosphoric acid ester (For example, ADEKA Corporation PN-600 and PFR), phosphorus containing phenoxy resin (For example, Nippon Steel Nippon Chemical Co., Ltd.) Phenototo ERF-001M30, TX-0924K30, etc., produced by a hydroxyl group (for example, DAIGUARD-580, DAIGUARD-610, etc., produced by Daihachi Chemical Industry Co., Ltd.), HCA derivatives (for example, Sanko ( HCA-HQ, M-Ester, ME-P8, etc. manufactured by Co., Ltd.), Intomesent flame retardant, which is a composite flame retardant (for example, FP-2100JC, FP-2200S, FP- manufactured by ADEKA Co., Ltd. 2500S).

  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, and it is more preferable that it is 20-200 mass parts. More preferably, it is 50-150 mass parts.

  When the phosphorus atom is contained in the flame retardant which is (D) component, as (D) component usage-amount, (A) component of an epoxy resin composition, (B) component, (C) component, ( It is preferable that the phosphorus content derived from the component (D) in the total mass of the component D) and the optional reactive diluent is 0.1 to 5% by mass, preferably 0.5 to 3 It is more preferable that the amount is 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.

  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 in the quantity used as the range which is 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 fillers include silica such as fused silica and crystalline silica; magnesium hydroxide, aluminum hydroxide, zinc molybdate, calcium carbonate, silicon carbonate, calcium silicate, potassium titanate, beryllia, zirconia. , Powders of zircon, fosterite, steatite, spinel, mullite, titania, or the like, beads formed by spheroidizing them, and glass fibers. 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, fused silica, aluminum hydroxide or the like is preferably used. 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.

  Moreover, the flame retardant epoxy resin composition of the present invention may contain additives other than the inorganic filler as necessary. Examples of the additives include non-reactive diluents (plasticizers) such as dioctyl phthalate, dibutyl phthalate, benzyl alcohol and coal tar; fiber fillers such as glass fiber, pulp fiber, synthetic fiber and ceramic fiber; glass cloth , Aramid cloth, carbon fiber and other reinforcing materials; pigments; γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -N′- β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-anilinopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, vinyl Triethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ- Silane coupling agents such as aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane; candelilla wax, carnauba wax, waxy wax, ibotarou, Lubricants such as beeswax, lanolin, whale wax, montan wax, petroleum wax, aliphatic wax, aliphatic ester, aliphatic ether, aromatic ester, aromatic ether; thickener; thixotropic agent; antioxidant; light Usable additives such as stabilizers; ultraviolet absorbers; antifoaming agents; rust preventives; colloidal silica and colloidal alumina. 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 sealing material 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, flooring materials, anti-corrosion coatings, concrete repair materials, etc., and is particularly suitable for use in laminates, semiconductor sealing materials, interlayer insulation films, and resin-coated copper foils. .

  The laminated board using the flame-retardant epoxy resin composition of the present invention has one or a predetermined number of prepregs using the flame-retardant epoxy resin composition of the present invention, for example, 2 to 20 sheets stacked on one side. Or after arranging metal foils, such as copper and aluminum, and laminating | stacking on both surfaces, using a multistage press machine, a multistage vacuum press machine, etc., it thermocompresses at predetermined temperature, for example, 100-250 degreeC, and can manufacture. it can. The organic components contained in the laminate (components (A) to (D) and optionally the reaction diluent and the total amount of organic substances among the additives) are not particularly limited, but are preferably Is 46% by mass to 50% by 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 applying the flame retardant epoxy resin composition of the present invention to a substrate and semi-curing (B-stage) by heating or the like. can do.

  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, low beating, 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 formed 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 used for the electronic material using the flame-retardant epoxy resin composition of the present invention stirs, melts, mixes, and disperses the flame-retardant epoxy resin composition of the present invention while being heat-treated as necessary. Can be manufactured. In this case, the apparatus used for stirring, melting, mixing, and dispersing is not particularly limited, and in the present invention, a raikai machine equipped with a stirrer and 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 Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples.
In addition,% in the following Examples etc. is a mass reference | standard unless there is particular description.

  Items evaluated in the examples are glass transition temperature (Tg) and flame retardancy (self-extinguishing).

  The glass transition temperature (Tg) was measured using TMA (Thermo-mechanical analyzer, manufactured by Hitachi High-Tech Science Co., Ltd., EXTER TMA / SS-6100) using the double-sided copper-clad laminate obtained in the following examples. .

  The copper foil of the double-sided copper-clad laminate obtained in the following examples was removed, cut into 5 mm squares, and the corners were ignited using a lighter while being held with tweezers. Those that self-extinguished were marked with ◯, and those that were completely burned were marked with ×.

[Example 1]
ECON-104S (Nippon Kayaku Co., Ltd .; Cresol Novolac Epoxy Resin) 49.1 g, HP-350 (Showa Denko Co., Ltd .; Aluminum Hydroxide) 62.5 g and SFP-130MC (Electrochemical Industry Co., Ltd.) ); Spherical silica) 62.5 g was added to 100 g of methyl ethyl ketone and dispersed with a three roll. Next, 10 g of phosphorus-containing compound (I) and 10 g of hexabromocyclodecane (HBCD) were dissolved in 20 g of methanol and added. Further, 50.9 g of EOCN-104S, 5 g of Adeka Hardener EH-3636AS (manufactured by ADEKA Corporation; dicyandiamide type latent curing agent) and 100 g of methyl ethyl ketone were added and dispersed with a disper to prepare a resin varnish.

The obtained resin varnish was impregnated with glass cloth (manufactured by Nitto Boseki Co., Ltd .; # 7628) and dried for 10 minutes in a hot air circulating furnace at 120 ° C. to prepare a prepreg. Furthermore, four prepregs prepared were stacked, and a 35 μm thick copper foil (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) was placed on both sides of the prepreg, and thermocompression bonded at 190 ° C. under a pressure of 10 kg / cm ² for 120 minutes. As a result, a double-sided copper-clad laminate was obtained. The glass transition temperature (Tg) was measured and flame retardancy was evaluated.

[Examples 2-372]
The glass transition temperature (Tg) was measured and the flame retardancy was evaluated in the same manner as in Example 1 except that the composition was changed as shown in [Table 1] to [Table 48] below.

  The phosphorus-containing compound represented by the formula (1) used in the following [Table 1] to [Table 48] is as follows.

  Flame retardants other than the components (D) and (C) used in the following [Table 1] to [Table 48] are as follows.

HBCD: Hexabromocyclodecane
DBP-TBBPA: Bis (dibromopropyl) tetrabromobisphenol A
TDBPIC: Tris (dibromopropyl) isocyanurate
TTBNPP: Tris (tribromoneopentyl) phosphate
DBDPO: Decabromodiphenyl oxide
TBBPA-EP: Tetrabromobisphenol A diglycidyl ether
BPBPE: Bis (pentabromo) phenylethane
TTBPTA: Tris (tribromophenoxy) triazine
EBTBPI: Ethylenebistetrabromophthalimide
PBPI: Polybromophenylindane
BrPS: Brominated polystyrene
TBBPA-PC: Tetrabromobisphenol A-polycarbonate
BrPPO: Brominated phenylene oxide
PPBBA: Polypentabromobenzyl acrylate

PCO 900：Thor社製：リン系難燃剤（AFLAMMIT）
APDE：ジエチルホスフィン酸アルミニウム TPP: Triphenyl phosphate
TCP: tricresyl phosphate
TXP: Trixinyl phosphate
TEP: Triethyl phosphate
CDPP: Cresyl diphenyl phosphate
XSPP: Xylyldiphenyl phosphate
CBXP: Cresylbis (di-2,6-xylenyl) phosphate
EHDPP: 2-ethylhexyl diphenyl phosphate
RDP: resorcinol bis (diphenyl) phosphate
HQDPP: Hydroquinone bis (diphenyl) phosphate
BPA-DP: Bisphenol A bis (diphenyl) phosphate
BPA-DC: Bisphenol A bis (dicresyl) phosphate
BPDPP: p-biphenol bis (diphenyl) phosphate
REBXP: Resorcinol bis (di-2,6-xylenyl) phosphate
BPBXP: p-biphenol bis (di-2,6-xylenyl) phosphate
TCEP: Tris (chloroethyl) phosphate
TCPP: Tris (chloropropyl) phosphate
TDCPP: Tris (dichloropropyl) phosphate
TTBPP: Tris (tribromopropyl) phosphate
DEBHEAMP: diethyl-N, N-bis (2-hydroxyethyl) aminomethyl phosphonate
AP: Ammonium phosphate
APPY: Ammonium pyrophosphate
APP: Ammonium polyphosphate
MP: Melamine phosphate
MPPY: Melamine pyrophosphate
MPP melamine polyphosphate
PP: Piperazine phosphate
PPPY: Piperazine pyrophosphate
PPP: Piperazine polyphosphate
Red phosphorus
HPTCP: Hexaphenoxycyclotriphosphazene
Fyrol PMP: ICL's reactive phosphate flame retardant
OL1001: FRX Polymers (Nofia) hydroxyl-terminated alkylphosphonate oligomer, molecular weight (Mn) 1500 g / mol
OL 3001: FRX Polymers (Nofia) hydroxyl-terminated alkylphosphonate oligomer, 2700 g / mol
DOPO: Sanko Co., Ltd. HCA
CNEP-DOPO: Reaction product of DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and cresol novolac epoxy resin
PN-DOPO: Reaction product with phenol novolac, formaldehyde and DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide)
DOPO-HQ: Sanko HCA-HQ
DOPO-dimer:

PCO 900: Thor: Phosphorus flame retardant (AFLAMMIT)
APDE: Aluminum diethylphosphinate

SbO3: Antimony trioxide
SbO5: Antimony pentoxide
MgOH: Magnesium hydroxide
AlOH: Aluminum hydroxide
AlO ・ OH (Boehmite)

melamine
MCY: Melamine cyanurate
ZnBO: Zinc borate

  As shown by the above examples, the flame retardant epoxy resin composition of the present invention has a high Tg of cured product and is excellent in flame retardancy, so it is particularly suitable for use in electronic materials. Can do.

Claims (14)

(A) An epoxy resin, (B) a curing agent, (C) a phosphorus-containing compound represented by the following formula (1), and (D) a flame retardant other than the component (C) Epoxy resin composition.

In the above formula (1), m represents an integer of 1 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. X and Y in the formula (1) 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 any one of the following formulae. The flame-retardant epoxy resin composition according to claim 1, wherein the flame-retardant epoxy resin composition is a group having a structure.

  The flame retardant as the component (D) is at least one selected from phosphorus-containing compounds other than the component (C), nitrogen compounds, boron compounds, halogen compounds, silicon compounds, and inorganic compounds. The flame-retardant epoxy resin composition according to any one of claims 1 to 3.   The prepreg which consists of a sheet-like base material which consists of at least 1 sort (s) of fiber selected from the inorganic fiber and the organic fiber, and the flame-retardant epoxy resin composition as 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 the 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.   The semiconductor sealing material formed by containing the flame-retardant epoxy resin composition as described in any one of Claims 1-4.   The interlayer insulation film formed by containing the flame-retardant epoxy resin composition as described in any one of Claims 1-4.   A resin-coated copper foil comprising the flame retardant epoxy resin composition according to any one of claims 1 to 4.   A casting material comprising the flame retardant epoxy resin composition according to any one of claims 1 to 4.   The adhesive agent containing the flame-retardant epoxy resin composition as described in any one of Claims 1-4.   The coating material containing the flame-retardant epoxy resin composition as described in any one of Claims 1-4.   A flooring comprising the flame retardant epoxy resin composition according to any one of claims 1 to 4.