TWI620762B - Method for producing cyanuric acid-denatured phosphorus-containing epoxy resin, resin composition containing the same, and curing product thereof - Google Patents

Abstract

The present invention provides a method for producing a cyanuric acid-denatured phosphorus-containing epoxy resin, which is obtained by denaturation of an epoxy resin using cyanuric acid and a phosphorus compound to obtain a flame-retardant cyanuric acid-containing phosphorus ring. In the production of an oxygen resin, it is possible to manufacture in a short period of time, and it is possible to obtain an epoxy resin cured product which has little residual of cyanuric acid and has excellent physical properties.

The present invention relates to a method for producing a cyanuric acid-denatured phosphorus-containing epoxy resin, a resin composition comprising the cyanuric acid-denatured phosphorus-containing epoxy resin and a hardener obtained by the production method, and hardening thereof The method for producing the cyanuric acid-denatured phosphorus-containing epoxy resin is a cyanuric acid-containing phosphorus-containing epoxy obtained by reacting a phosphorus compound, cyanuric acid, and an epoxy resin as essential components. a method for producing a resin, and for the specific phosphorus compound, the phosphorus compound is set to 2.5 to 50 mol with respect to 1 mol of cyanuric acid; and the phosphorous containing epoxy resin of the cyanuric acid is contained The ratio is 1.0 to 5.0% by mass, the nitrogen content is 0.1 to 2.0% by mass, and the sum of the phosphorus content and the nitrogen content is 2.5 to 5.5% by mass.

Description

Method for producing cyanuric acid-denatured phosphorus-containing epoxy resin, resin composition containing the same for cyanide-denatured phosphorus-containing epoxy resin, and cured product thereof

The present invention relates to a method for producing a halogen-free flame-retardant epoxy resin containing a phosphorus atom and a nitrogen atom in a molecular skeleton, and an epoxy resin composition comprising the epoxy resin obtained by the production method and another epoxy resin. A curable epoxy resin composition containing the epoxy resin composition and a curing agent, and an epoxy resin cured product obtained by curing the curable epoxy resin composition.

As represented by a brominated epoxy resin using tetrabromobisphenol A as a raw material, flame retardancy of an epoxy resin was previously carried out by halogenation. However, in the case of using a halogenated epoxy resin, there is a problem in that a highly toxic halide is formed by thermal decomposition reaction upon combustion of the cured product. In response to this problem, in recent years, a halogen-free flame-retardant technology using a phosphorus compound has been studied, and a phosphorus compound disclosed in Patent Document 1 to Patent Document 4 has been proposed. However, these phosphorus compounds are used because they are less soluble in an epoxy resin or a solvent, and are difficult to be used in an epoxy resin or dissolved in a solvent. Therefore, as disclosed in Patent Documents 5 to 10, It is used by reacting with an epoxy resin in advance to prepare a phosphorus-containing epoxy resin or a phosphorus-containing phenol resin, and to impart solvent solubility thereto.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. SHO 47-016436

[Patent Document 2] Japanese Patent Laid-Open Publication No. SHO 60-126293

[Patent Document 3] Japanese Patent Laid-Open No. 61-236787

[Patent Document 4] Japanese Patent Laid-Open No. Hei 05-331179

[Patent Document 5] Japanese Patent Laid-Open No. 04-11662

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2000-309623

[Patent Document 7] Japanese Patent Laid-Open No. Hei 11-166035

[Patent Document 8] Japanese Patent Laid-Open No. Hei 11-279258

[Patent Document 9] Japanese Patent Laid-Open Publication No. 2001-123049

[Patent Document 10] Japanese Patent Laid-Open Publication No. 2003-040969

[Patent Document 11] Japanese Patent Laid-Open Publication No. 2012-229364

[Non-patent literature]

[Non-Patent Document 1] Nishizawa, "Flame Retardation of Polymers" P60, right column, 22 rows to 27 rows, P166, 6-8-3, 1992, Dacheng Society

Regarding the flame retardancy by the phosphorus compound, if the flame retardancy is to be further improved, only the phosphorus content is increased, the molecular weight is increased, the crosslinking density is lowered, or a high-priced phosphorus-containing compound must be used. On the other hand, the inventors of the present invention have focused on the synergistic effect of phosphorus and nitrogen on the flame retardancy described in Non-Patent Document 1, and proposed to improve the flame retardancy by using cyanuric acid as a nitrogen compound (Patent Document 11). . However, it is known that the epoxy resin and the cyanuric acid are not sufficiently reacted according to the production method, and the unreacted cyanuric acid easily remains. The cyanuric acid remaining in the reaction system can only react with the epoxy resin at a very slow rate, and the unreacted cyanuric acid has poor solubility in the solvent, thereby further reducing the deterioration of the hardened physical properties. Affected unreacted cyanuric acid.

In order to solve the above problems, the present inventors have found that when a reaction between an epoxy resin and cyanuric acid is carried out, a specific ratio of a specific phosphorus compound coexists with respect to cyanuric acid is reversed. Therefore, the present invention is completed by the fact that the residual of cyanuric acid is extremely small and the reaction with the epoxy resin is easily carried out without a long reaction.

That is, the present invention relates to: (1) A method for producing a cyanuric acid-denatured phosphorus-containing epoxy resin, which comprises reacting a phosphorus compound, cyanuric acid, and an epoxy resin as essential components; A method for producing a cyanuric acid-denatured phosphorus-containing epoxy resin obtained, wherein the phosphorus compound is represented by the following formula (1):

[wherein, n represents 0 or 1, and R ₁ and R ₂ each independently represent a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, or may form a ring together with a phosphorus atom]

Or the following general formula (2):

[wherein, m represents 0 or 1, and R ₃ and R ₄ each independently represent a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, or may form a ring together with a phosphorus atom]

The phosphorus compound or the phosphorus compound containing the two, in relation to the trimerization The above-mentioned epoxy resin is preliminarily mixed with a phosphorus compound of 2.5 to 50 moles of phosphorus compound and cyanuric acid, and then reacted to have a phosphorus content of 1.0 to 5.0% by mass. The content ratio is 0.1 to 2.0% by mass, and the sum of the phosphorus content and the nitrogen content is 2.5 to 5.5% by mass; and (2) an epoxy resin composition which is produced by the production method of the above (1) (a) a curable epoxy resin composition obtained by the production method of the above (1) The cyanuric acid-denatured phosphorus-containing epoxy resin comprises: 1 equivalent of an epoxy group of the phosphorus-containing epoxy resin denatured with the cyanuric acid; and a hardening agent of 0.4 to 2.0 equivalents based on a functional group ratio; (4) A curable epoxy resin composition which is contained in the epoxy resin composition of the above (2), which contains 1 equivalent of the epoxy group based on the epoxy resin composition, and is 0.4 based on the functional group ratio. (2.0) an epoxy resin cured product which is a hardened epoxy resin group as described in (3) or (4) above. It was obtained by hardening.

The present invention is a cyanuric acid-denatured phosphorus-containing epoxy resin which is copolymerized with an epoxy resin by coexisting a specific phosphorus compound at a molar ratio of 2.5 to 50 mol with respect to 1 mol of cyanuric acid. According to the reaction, the cyanuric acid-denatured phosphorus-containing epoxy resin can be produced in a short period of time, and an epoxy resin cured product having little residual of cyanuric acid and having excellent physical properties can be obtained.

Hereinafter, embodiments of the present invention will be described in detail. Specific examples of the phosphorus compound represented by the formula (1) or (2) of the present invention include dimethylphosphine, diethylphosphine, and diphenyl. Phosphine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), dimethylphosphine oxide, diethylphosphine oxide, dibutylphosphine oxide, diphenyl oxidation Phosphine, 1,4-cyclooctylphosphine oxide, 1,5-cyclooctylphosphine oxide (CPHO, manufactured by Nippon Chemical Industry Co., Ltd.), and the like. These phosphorus compounds may be used singly or in combination of two or more kinds, and are not limited thereto.

In the present invention, the term "cyanuric acid" means symmetry three as tautomerism. -2,4,6-triol, and symmetry three -2,4,6-trione, there is no special regulation on the ratio.

Although a technique of adding cyanuric acid as a nitrogen-based flame retardant has been disclosed, it is difficult to obtain a uniform resin because the solubility of cyanuric acid in a solvent is poor or the compatibility with an epoxy resin or a hardener is poor. The composition has a variation in flame retardancy. The cyanuric acid-denatured phosphorus-containing epoxy resin obtained by the production method of the present invention becomes uniform in the resin composition by reacting cyanuric acid with an epoxy resin, thereby obtaining stable flame retardancy. . Further, when it is referred to as a resin composition of the present invention, it is used in the sense of including both an epoxy resin composition and a curable epoxy resin composition unless otherwise specified. , indicating either.

Epoxy resins for producing the cyanuric acid-denatured phosphorus-containing epoxy resin of the present invention include Epotohto YD-128 and Epotohto YD-8125 (bisphenol A type epoxy manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) Resin), Epotohto YDF-170, Epotohto YDF-8170 (bisphenol F type epoxy resin manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), YSLV-80XY (tetramethyl double manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) Phenol F-type epoxy resin), Epotohto YDC-1312 (hydroquinone epoxy resin), jER YX-4000H (biphenyl type epoxy resin manufactured by Mitsubishi Chemical Corporation), Epotohto YDPN-638, Epotohto YDPN -63X (phenol novolak type epoxy resin manufactured by Nippon Steel Co., Ltd.), Epotohto YDCN-701 (cresol novolac type epoxy resin manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epotohto GK-5855, Epotohto TX-1210 (substituted phenolic epoxy resin manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epotohto ZX-1201 (bisphenol oxime epoxy resin manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), TX-0710 (Nippon Steel & Sumitomo Chemical Co., Ltd. Bisphenol S-type epoxy resin), NC-3000 (biphenyl aralkyl phenol epoxy resin manufactured by Nippon Kayaku Co., Ltd.), Epotohto ZX-1355, Epotohto ZX-1711 (Nippon Steel & Sumitomo Chemical Co., Ltd. Naphthalenediol-type epoxy resin manufactured by the company, Epotohto ESN-155 (β-naphthol aralkyl epoxy resin manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epotohto ESN-355, Epotohto ESN- 375 (Nina-Tiejin Shoujin Chemical Co., Ltd. bisphthol aralkyl epoxy resin), Epotohto ESN-475V, Epotohto ESN-485 (α-naphthol aralkyl manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) Base type epoxy resin), EPPN-501H (triphenylmethane type epoxy resin manufactured by Nippon Kayaku Co., Ltd.), YSLV-120TE (disulfide type epoxy resin manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. ), Epotohto ZX-1684 (Nippon Steel & Sumitomo Chemical Co., Ltd. manufactures a resorcinol type epoxy resin), EPICLON HP-7200H (dicyclopentadiene type epoxy resin manufactured by DIC Corporation), Epotohto YDG-414 (four functionals manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. Oxygen resin, etc. Epoxy resin made of phenolic compound of polyphenol resin and epihalohydrin; TX-0929, TX-0934, ZX-1542, TX-1032 (Extension manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) An epoxy resin produced from an alcohol compound and an epihalohydrin, such as an alkyl glycol type epoxy resin; Celloxide 2021 (aliphatic epoxy resin manufactured by Daicel Chemical Industry Co., Ltd.), Epotohto YH-434 ( N-aminodiphenylmethanetetraglycidylamine manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., jER 630 (aminophenol-based epoxy resin manufactured by Mitsubishi Chemical Corporation), and the like, and an amine compound and epihalohydrin Epoxy resin produced; Epotohto FX-289B, Epotohto FX-305, TX-0940 (phosphorus-containing epoxy resin manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), urethane-modified epoxy resin, The epoxy resin of the oxazolidinone ring, etc.; but it is not limited to these.

Further, these epoxy resins may be used singly or in combination of two or more kinds, and a bisphenol type epoxy resin, a phenol novolac type epoxy resin, or a cresol novolac type epoxy resin can be preferably used. Resin.

The reaction of the phosphorus compound represented by the formula (1) or (2) with cyanuric acid and an epoxy resin is carried out by reacting an epoxy resin in the presence of a phosphorus compound and cyanuric acid, relative to trimerization. The cyanic acid is 1 molar and requires 2.5 to 50 moles of phosphorus compound. The molar ratio of the preferred phosphorus compound is 2.7 to 25 moles, preferably 3 to 10 moles per mole of cyanuric acid. . If the phosphorus compound is less than 2.5 mol with respect to 1 mol of cyanuric acid, the reaction of cyanuric acid and epoxy resin is insufficient, and the residual amount of cyanuric acid is increased. If the phosphorus compound exceeds 50 mol with respect to 1 mol of cyanuric acid, the reaction of the cyanuric acid and the epoxy resin proceeds sufficiently, but the introduction effect of the nitrogen atom obtained by cyanuric acid is The synergistic effect of phosphorus and nitrogen on flame retardancy almost disappeared. Further, when the coexistence conditions of the phosphorus compound and the cyanuric acid are satisfied, the epoxy resin and the phosphorus compound can be reacted before or after the reaction between the epoxy resin and the cyanuric acid.

The reaction temperature for obtaining the cyanuric acid-denatured phosphorus-containing epoxy resin of the present invention is preferably a temperature which is usually set at the time of synthesis of the epoxy resin, and is 100 to 250 ° C, preferably 120 to 200 ° C.

In order to shorten the time or lower the reaction temperature during the reaction, a catalyst may also be used. The catalyst which can be used is not particularly limited, and a user who is usually used in the synthesis of an epoxy resin can be used. For example, a tertiary amine such as dimethylbenzylamine; a quaternary ammonium salt such as tetramethylammonium chloride; a phosphine such as triphenylphosphine or tris(2,6-dimethoxyphenyl)phosphine; a sulfonium salt such as ethyltriphenylphosphonium bromide; a catalyst such as 2-methylimidazole or 2-ethyl-4-methylimidazole; and these may be used alone or in combination of two or more. It is not limited to these. Also, it can be divided into several uses in batches.

The amount of the catalyst to be used in the reaction is not particularly limited, and is preferably 5% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less based on the epoxy resin to be used. When the amount of the catalyst exceeds 5% by mass, the self-polymerization reaction of the epoxy group is likely to occur, and the resin viscosity tends to increase, which is not preferable.

Further, an inert solvent can also be used in the reaction. Specifically, various kinds of hexane, heptane, octane, decane, dimethylbutane, pentene, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, etc. can be used. Hydrocarbon; ether, diisopropyl ether, dibutyl ether, diisoamyl ether, methyl phenyl ether, ethyl phenyl ether, amyl phenyl ether, ethyl benzyl ether, two An ether such as an alkane, methylfuran or tetrahydrofuran; methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, cellulolytic acetate, ethylene glycol isopropyl ether, diethylene glycol dimethyl ether, Methyl ethyl carbitol, propylene glycol monomethyl ether, dimethylformamide, dimethyl hydrazine, etc., but not limited thereto, these may be used singly or in combination of two or more.

The epoxy equivalent of the cyanuric acid-denatured phosphorus-containing epoxy resin obtained in the present invention is preferably from 100 to 700 g/eq, more preferably from 200 to 600 g/eq. When the epoxy equivalent is less than 100 g/eq, the adhesion of the cured product is likely to be deteriorated, and when it is more than 700 g/eq, the glass transition temperature (Tg) of the cured product is lowered, and the resin composition becomes highly viscous. The workability is prone to deterioration.

The phosphorus-containing epoxy resin of the cyanuric acid-modified epoxy resin obtained in the present invention has a phosphorus content of 1.0 to 5.0% by mass, preferably 1.5 to 4.0% by mass, more preferably 2.0 to 3.5% by mass. The nitrogen content is 0.1 to 2.0% by mass, preferably 0.5 to 1.0% by mass. Further, the sum of the phosphorus content rate and the nitrogen content rate is 2.5 to 5.5% by mass, preferably 3.0 to 4.5% by mass, and more preferably 3.0 to 4.0% by mass. The flame retardancy of the cyanuric acid-denatured phosphorus-containing epoxy resin obtained in the present invention is exerted by the synergistic effect of phosphorus and nitrogen, so that it is meaningless to specify the range of either one, and the phosphorus content rate must be specified. The range of sums with the nitrogen content. When the sum of the phosphorus content rate and the nitrogen content rate is less than 2.5% by mass, the flame retardancy may not be sufficiently exhibited depending on the resin composition. In addition, when the sum of the phosphorus content and the nitrogen content exceeds 5.5% by mass, the flame retardancy can be sufficiently exhibited, but the resin composition has a high viscosity and adversely affects solvent solubility. Therefore, the range of the sum of the phosphorus content rate and the nitrogen content rate is preferably 2.5 to 5.5% by mass.

As the other epoxy resin used in the epoxy resin composition of the present invention, it can be omitted Within the scope of the characteristics of the present invention, an epoxy resin similar to the above epoxy resin is used in combination with a cyanuric acid-denatured phosphorus-containing epoxy resin.

The cyanuric acid-denatured phosphorus-containing epoxy resin or epoxy resin composition of the present invention can be made into a curable epoxy resin composition by blending a hardener. As the curing agent, a curing agent for an epoxy resin which is usually used, such as various phenol compounds, acid anhydrides, amines, anthraquinones, and acidic polyesters, may be used. These curing agents may be used alone or in combination. 2 or more types. Among these, the curing agent contained in the curable epoxy resin composition of the present invention is preferably dicyandiamide or a phenol compound.

In the curable epoxy resin composition of the present invention, the curing agent is preferably used in an amount of 1 equivalent to the epoxy group as a functional group of the epoxy resin, and the functional group of the curing agent is 0.4 to 2.0 equivalents. Preferably, it is 0.5 to 1.5 equivalents, and particularly preferably 0.5 to 1.0 equivalents. When the amount of the curing agent is less than 0.4 equivalents per equivalent of the epoxy group, or when it exceeds 2.0 equivalents, the curing becomes incomplete and good cured physical properties cannot be obtained.

Specific examples of the phenol compound which can be used in the curable epoxy resin composition of the present invention include bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, and tetramethyl group. Bisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetramethylbisphenol Z, dihydroxydiphenyl sulfide, 4,4'-thiobis(3-methyl-6- Bisphenols such as tributyl phenol); catechol, resorcinol, methyl resorcinol, hydroquinone, monomethyl hydroquinone, dimethyl hydroquinone, top three Dihydroxybenzenes such as hydroquinone, mono-tert-butyl hydroquinone, di-tert-butyl hydroquinone; biphenols such as 4,4'-biphenol and tetramethylbiphenol; Phenolics; polyhydroxynaphthalenes such as dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxymethylnaphthalene, trihydroxynaphthalene; phenol novolac resin, DC-5 (cresol novolacs manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) Phenols such as varnish resin, naphthol novolac resin, or condensates of naphthols and aldehydes; phenols or naphthalenes such as SN-160, SN-395, and SN-485 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) The shrinkage of phenols and xylylene glycol Compound; GK-5855P (substituted phenol resin manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), phenols or naphthols and isopropenyl a condensate of acetophenone, a phenol or a reaction product of a naphthol and dicyclopentadiene, a condensate of a phenol or a naphthol and a biphenyl condensing agent, and the like, and two or more phenolic hydroxyl groups in one molecule. Phenolic compounds and the like.

Further, examples of the phenols include phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, butylmethylphenol, trimethylphenol, and phenylphenol, as the above naphthol. The class may, for example, be 1-naphthol or 2-naphthol. Further, examples of the aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, hexanal, benzaldehyde, chloral aldehyde, bromoaldehyde, glyoxal, malondialdehyde, succinaldehyde, and pentane Aldehyde, adipaldehyde, p-glyoxal, sebacaldehyde, acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, hydroxybenzaldehyde, etc., as the biphenyl-based condensing agent, bis(hydroxyl) Biphenyl, bis(methoxymethyl)biphenyl, bis(ethoxymethyl)biphenyl, bis(chloromethyl)biphenyl, etc., but is not limited thereto.

Other known hardeners which can be used in the curable epoxy resin composition of the present invention include methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, and o-benzene. Anhydrides such as dicarboxylic anhydride, trimellitic anhydride, methylic acid anhydride; dicyandiamide, di-ethyltriamine, tri-ethyltetramine, tetra-ethylpentamine, m-xylylenediamine, iso An aliphatic amine such as a ketone diamine; an aromatic amine such as a diaminodiphenylmethane, a diaminodiphenyl hydrazine, a diaminodiphenyl ether or a diaminoethyl benzene; An amine such as 2,4,6-tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecyl An imidazole such as imidazole or 1-cyanoethyl-2-methylimidazole; and an imidazolium salt as a salt of trimellitic acid, iso-cyanuric acid, boron or the like; as an acid such as a dimer acid An amine compound such as polyamine amine of a condensate of a polyamine; an anthracene such as diammonium adipate or diterpene sebacate; an aminobenzoate; a phosphine compound such as triphenylphosphine; Barium salt such as tetraphenylphosphonium; chlorine a quaternary ammonium salt such as trimethylammonium; a diazabicyclo compound; and a salt thereof with a phenol or a phenol novolak resin; a complex of boron trifluoride with an amine or an ether compound;鏻 or 錪 salt, etc.; but is not limited to these. Also, These two or more are used in combination.

In the curable epoxy resin composition of the present invention, an organic solvent for viscosity adjustment can also be used. Examples of the organic solvent that can be used include decylamines such as N,N-dimethylformamide; ethers such as ethylene glycol monomethyl ether; ketones such as acetone and methyl ethyl ketone; and methanol, ethanol, and the like. Alcohols; aromatic hydrocarbons such as benzene and toluene. One or a mixture of the above solvents may be blended in an amount of from 25 to 250 parts by mass based on 100 parts by mass of the epoxy resin component in the resin composition.

In the curable epoxy resin composition of the present invention, a curing accelerator may be used as needed. Examples of the hardening accelerator which can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole; 2-(dimethylaminomethyl)phenol a tertiary amine such as 1,8-diaza-bicyclo(5,4,0)undecene-7; a phosphine such as triphenylphosphine, tricyclohexylphosphine or triphenylphosphine triphenylborane a metal compound such as tin octylate. The amount of use of the curing accelerator is preferably 0.02 to 5.0 parts by mass based on 100 parts by mass of the epoxy resin component in the resin composition of the present invention. By using a hardening accelerator, the hardening temperature can be lowered and the hardening time can be shortened.

In the curable epoxy resin composition of the present invention, a filler may be used as needed. Specific examples thereof include inorganic fillers such as aluminum hydroxide, magnesium hydroxide, talc, calcined talc, clay, kaolin, titanium oxide, glass powder, boehmite, and silica balloon. Adjustable with pigments, etc. The reason why the inorganic filler is generally used is that the impact resistance is improved. Further, when a metal hydroxide such as aluminum hydroxide or magnesium hydroxide is used, it functions as a flame retardant auxiliary agent, and even if the phosphorus content in the resin composition is small, flame retardancy can be ensured. In particular, when the amount is not more than 10 parts by mass based on 100 parts by mass of the epoxy resin component, the effect of impact resistance is small. However, when the blending amount exceeds 150 parts by mass, the adhesion of the item necessary for the use of the laminate is lowered. Further, the resin composition may contain a fibrous filler such as glass fiber, pulp fiber, synthetic fiber or ceramic fiber, or a fine particle rubber or a thermoplastic elastomer. And other organic filling materials.

An epoxy resin cured product containing phosphorus and nitrogen can be obtained by curing the curable epoxy resin composition of the present invention. In the case of curing, for example, a resin sheet, a copper foil with a resin, a preform, or the like is laminated and heated and press-hardened to obtain a phosphorus-containing epoxy resin cured product as a laminate.

A curable epoxy resin composition using the cyanuric acid-denatured phosphorus-containing epoxy resin of the present invention, and a laminate obtained by heat-hardening the properties of the cured epoxy resin containing phosphorus and nitrogen The evaluation is carried out, and the results are compared with the cyanuric acid-denatured phosphorus-containing epoxy resin obtained by reacting the phosphorus compound outside the range of the molar ratio of the present invention with cyanuric acid and the epoxy resin, and the phosphorus compound and the ring. The previously known phosphorus-containing epoxy resin obtained from the oxyresin exhibits high adhesion and flame retardancy.

[Examples]

The present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited thereto. In the examples and comparative examples, "parts" means parts by mass, and "%" means mass% unless otherwise specified.

The epoxy equivalents of the epoxy resins measured in the examples and the comparative examples were measured in accordance with JIS K 7236.

The nitrogen content rate is a percentage of the phosphorus-containing epoxy resin denatured by the cyanuric acid from the nitrogen content and the amount of the cyanuric acid.

The phosphorus content of the epoxy resin synthesized in the examples and the comparative examples was measured by the following method. That is, 3 mL of sulfuric acid was added to 150 mg of the sample and heated for 30 minutes. After returning to room temperature, 3.5 mL of nitric acid and 0.5 mL of perchloric acid were added and decomposed by heating until the contents became transparent or yellow. The sample solution was diluted with pure water in a 100 mL measuring flask. 10 mL of this sample solution was placed in a 50 mL measuring flask, and 1 drop of phenolphthalein indicator was added, and 2 mol/L of ammonia water was added until it became reddish. Add 2 mL of 50% sulfuric acid solution and add pure water. Add 2.5 mL/L of ammonium metavanadate aqueous solution 5 mL and After 50 g of an aqueous ammonium molybdate solution of 50 g/L, the volume was adjusted to a volume of pure water. After leaving at room temperature for 40 minutes, the measurement was carried out using a spectrophotometer at a wavelength of 440 nm using pure water as a control, and the phosphorus content was determined from the absorbance.

With respect to the obtained phosphorus cyanide-denatured phosphorus-containing epoxy resin, the presence or absence of turbidity was observed by visual observation to confirm the presence or absence of residual cyanuric acid. In the case where no turbidity is present, no residual cyanuric acid (○) is present, and in the case where turbidity is present, residual cyanuric acid (x) is present.

Regarding the glass transition temperature of the cured product, the Exster 6000 manufactured by Seiko Instruments Co., Ltd. was used, and the value of the initial inflection point was set in DSC (Differential Scanning Calorimetry). For the glass transition temperature, the inflection point was set to the glass transition temperature in TMA (Thermomechanical Analysis).

The copper foil peeling strength was measured based on JIS C 6481 5.7, and the interlayer adhesion was measured based on JIS C 6481 5.7 and peeling between one sheet of the preform and the remaining three sheets.

The flame retardancy was measured based on the UL (Underwriter Laboratorics) standard. Further, the afterflame time is expressed by summing the flaming combustion durations of the five test pieces.

The reaction rate of cyanuric acid is the value of the initial epoxy equivalent, the theoretical epoxy equivalent, and the epoxy equivalent (final epoxy equivalent) of the cyanide-modified phosphorus-containing epoxy resin, and is obtained by the following formula Find out.

[(Final Epoxy Equivalent - Initial Epoxy Equivalent) / (Theoretical Epoxy Equivalent - Initial Epoxy Equivalent)] × 100

Wherein, in the case where the final epoxy equivalent is larger than the theoretical epoxy equivalent, the reaction rate is set to 100%.

Example 1.

Epotohto YDPN-638 was added to a glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device (Nippon Steel & Sumitomo Chemical Co., Ltd. has Phenolic novolac type epoxy resin manufactured by the company: 850 parts of epoxy equivalent 177g/eq), HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-produced by Sanko Co., Ltd. 127 parts of an oxide, a phosphorus content of 14.2%, and 23 parts of cyanuric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred while introducing nitrogen gas, and the mixture was heated and heated to 130 °C. The initial epoxy equivalent in the mixed state was 207 g/eq, and after the initial epoxy equivalent was measured, 0.14 parts of triphenylphosphine was added as a catalyst, and the reaction was carried out at 160 ° C for 4 hours. The obtained cyanuric acid-denatured phosphorus-containing epoxy resin (A-1) has a phosphorus content of 1.8%, a theoretical epoxy equivalent of 270 g/eq, and a final epoxy equivalent of 272 g/eq, and cyanuric acid. The reaction rate was 100%. The results are shown in Table 1.

Example 2.

The same operation as in Example 1 was carried out except that Epotohto YDPN-638 was changed to 758 parts, the cyanuric acid was changed to 3 parts, and the HCA was changed to 239 parts. The obtained cyanuric acid-denatured phosphorus-containing epoxy resin (A-2) has a phosphorus content of 3.4%, an initial epoxy equivalent of 232 g/eq, a theoretical epoxy equivalent of 320 g/eq, and a final epoxy equivalent of The reaction rate of 332 g/eq, cyanuric acid was 100%. The results are shown in Table 1.

Example 3.

Epotohto YDPN-63X (Narrow-dispersed phenol novolak-type epoxy resin manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) was placed in a glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device. 692 parts of epoxy equivalent (176 g/eq), 250 parts of HCA, and 58 parts of cyanuric acid were stirred while introducing nitrogen gas, and the mixture was heated and heated to 130 °C. The initial epoxy equivalent in the mixed state was 254 g/eq, and after the initial epoxy equivalent was measured, 0.33 part of triphenylphosphine was added as a catalyst, and the reaction was carried out at 160 ° C for 4 hours. The obtained cyanuric acid-denatured phosphorus-containing epoxy resin (A-3) has a phosphorus content of 3.6%, a theoretical epoxy equivalent of 701 g/eq, and a final epoxy equivalent of 669 g/eq, and cyanuric acid. The reaction rate was 93%. The results are shown in Table 1.

Example 4.

The same operation as in Example 3 was carried out except that the Epotohto YDPN-63X was changed to 640 parts, the cyanuric acid was changed to 15 parts, and the HCA was changed to 345 parts. The obtained cyanuric acid-denatured phosphorus-containing epoxy resin (A-4) has a phosphorus content of 4.9%, an initial epoxy equivalent of 275 g/eq, a theoretical epoxy equivalent of 592 g/eq, and a final epoxy equivalent of The reaction rate of 594 g/eq, cyanuric acid was 100%. The results are shown in Table 1.

Example 5.

Epotohto YDPN-638 507 parts and Epotohto YD-128 (bisphenol manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) were placed in a separable glass flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device. A type liquid epoxy resin: 300 parts of epoxy equivalent 186 g/eq), 162 parts of HCA, and 31 parts of cyanuric acid were stirred while introducing nitrogen gas, and heated to 130 ° C. The initial epoxy equivalent in the mixed state was 223 g/eq, and after the initial epoxy equivalent was measured, 0.25 parts of triphenylphosphine was added as a catalyst, and the reaction was carried out at 160 ° C for 4 hours. The obtained cyanuric acid-denatured phosphorus-containing epoxy resin (A-5) has a phosphorus content of 2.3%, a theoretical epoxy equivalent of 333 g/eq, and a final epoxy equivalent of 330 g/eq, and cyanuric acid. The reaction rate was 97%. The results are shown in Table 1.

Example 6.

Epotohto YDPN-638 433 parts, Epotohto YDCN-704 (Metrolol manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) was placed in a glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device. A novolac type epoxy resin: 300 parts of epoxy equivalent: 209 g/eq), 250 parts of HCA, and 17 parts of cyanuric acid were stirred while introducing nitrogen gas, and heated to 130 ° C. The initial epoxy equivalent in the mixed state was 258 g/eq, and after the initial epoxy equivalent was measured, 0.25 parts of triphenylphosphine was added as a catalyst, and the reaction was carried out at 160 ° C for 4 hours. The obtained cyanuric acid-denatured phosphorus-containing epoxy resin (A-6) had a phosphorus content of 3.6%, a theoretical epoxy equivalent of 429 g/eq, and a final epoxy equivalent of 428 g/eq, and cyanuric acid. The reaction rate was 99%. The results are shown in Table 1.

Example 7.

Epotohto YDPN-638 442 parts, YSLV-80XY (Tetramethyl by Nippon Steel & Sumitomo Chemical Co., Ltd.) was placed in a glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device. Bisphenol F-type epoxy resin: 300 parts of epoxy equivalent: 190 g/eq), 250 parts of HCA, and 6 parts of cyanuric acid were stirred while introducing nitrogen gas, and heated to 130 ° C. The initial epoxy equivalent in the mixed state was 245 g/eq, and after the initial epoxy equivalent was measured, 0.25 part of triphenylphosphine was added as a catalyst, and the reaction was carried out at 160 ° C for 4 hours. The obtained cyanuric acid-denatured phosphorus-containing epoxy resin (A-7) has a phosphorus content of 3.6%, a theoretical epoxy equivalent of 360 g/eq, and a final epoxy equivalent of 360/eq, and cyanuric acid. The reaction rate was 100%. The results are shown in Table 1.

Example 8.

Epotohto YDPN-638 860 parts, CPHO (1,5-extension cycline manufactured by Nippon Chemical Industry Co., Ltd.) was placed in a separable glass flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas introduction device. The base phosphine oxide, phosphorus content: 19.6%), 110 parts, and 30 parts of cyanuric acid were stirred while introducing nitrogen gas, and heated to 130 ° C. The initial epoxy equivalent in the mixed state was 206 g/eq, and after the initial epoxy equivalent was measured, 0.14 parts of triphenylphosphine was added as a catalyst, and the reaction was carried out at 160 ° C for 4 hours. The obtained cyanuric acid-denatured phosphorus-containing epoxy resin (A-8) has a phosphorus content of 2.2%, a theoretical epoxy equivalent of 289 g/eq, and a final epoxy equivalent of 290 g/eq, and cyanuric acid. The reaction rate was 100%. The results are shown in Table 1.

Comparative Example 1.

Into a glass separable flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas introduction device, 954 parts of Epotohto YDPN-638 and 46 parts of cyanuric acid were added, and the mixture was stirred while introducing nitrogen gas, and heated. Warm up. The temperature was raised to 130 °C. The initial epoxy equivalent in the mixed state was 185 g/eq, and after the initial epoxy equivalent was measured, 0.05 part of triphenylphosphine was added as a catalyst, and the reaction was carried out at 160 ° C for 4 hours. Obtained The final epoxy equivalent of the cyanuric acid-modified epoxy resin (A-9) was 194 g/eq, and the phosphorus content was 0%. The theoretical epoxy equivalent is 230 g/eq and the reaction rate of cyanuric acid is 20%. The results are shown in Table 1.

Comparative Example 2.

The same operation as in Example 1 was carried out except that Epotohto YDPN-638 was changed to 843 parts and cyanuric acid was changed to 31 parts. The obtained cyanuric acid-denatured phosphorus-containing epoxy resin (A-10) has a phosphorus content of 1.8%, an initial epoxy equivalent of 209 g/eq, a theoretical epoxy equivalent of 287 g/eq, and a final epoxy equivalent of The reaction rate of 263 g/eq and cyanuric acid was 69%. The results are shown in Table 1.

Comparative Example 3.

The same operation as in Example 1 was carried out except that Epotohto YDPN-638 was changed to 882 parts, the cyanuric acid was changed to 23 parts, and the HCA was changed to 95 parts. The obtained cyanuric acid-denatured phosphorus-containing epoxy resin (A-11) has a phosphorus content of 1.35%, an initial epoxy equivalent of 200 g/eq, a theoretical epoxy equivalent of 248 g/eq, and a final epoxy equivalent of The reaction rate of 231 g/eq and cyanuric acid was 65%. The results are shown in Table 1.

Comparative Example 4.

Epotohto YDPN-638 788 parts, 23 parts of cyanuric acid, and HCA-HQ (manufactured by Sanko Co., Ltd.) were placed in a glass separable flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas introduction device. 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, phosphorus content: 9.6%) 189 parts, stirred while introducing nitrogen gas, and heated Warm up. The temperature was raised to 130 °C. The initial epoxy equivalent in the mixed state was measured and found to be 223 g/eq. After the initial epoxy equivalent was measured, 0.2 part of triphenylphosphine was added as a catalyst, and the reaction was carried out at 160 ° C for 4 hours to cause gelation. No epoxy resin was obtained. Further, cyanuric acid remains as a solid in the gelate.

Comparative Example 5.

Change Epotohto YDPN-638 to 855 parts, change cyanuric acid to 15 parts, The same operation as in Comparative Example 4 was carried out except that the HCA-HQ was changed to 130 parts. The obtained cyanuric acid-denatured phosphorus-containing epoxy resin (A-12) has a phosphorus content of 1.2%, an initial epoxy equivalent of 206 g/eq, a theoretical epoxy equivalent of 271 g/eq, and a final epoxy equivalent of The reaction rate of 224 g/eq and cyanuric acid was 28%. The results are shown in Table 1.

Comparative Example 6.

Epotohto YDPN-638 683 parts, Epotohto YDF-2001 (bisphenol manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) was placed in a glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device. F-type solid epoxy resin: 190 parts of epoxy equivalent 469 g/eq) and 127 parts of HCA, and stirred while introducing nitrogen gas, heating and heating. The temperature was raised to 130 °C. The initial epoxy equivalent in the mixed state was 235 g/eq, and after the initial epoxy equivalent was measured, 0.13 parts of triphenylphosphine was added as a catalyst, and the reaction was carried out at 160 ° C for 4 hours. The phosphorus-containing epoxy resin (A-13) obtained had a final epoxy equivalent of 272 g/eq and a phosphorus content of 1.8%. The theoretical epoxy equivalent is 272 g/eq. The results are shown in Table 1.

Examples 9 to 12 and 14 to 16, and comparative examples 7 to 11.

The phosphorus-containing epoxy resin denatured with cyanuric acid of Examples 1 to 5, Comparative Examples 1 to 3, and Comparative Example 5, and the phosphorus-containing epoxy resin of Comparative Example 6, and DICY (Nippon as a curing agent) were used. A curable epoxy resin composition was produced by dicyandiamide manufactured by Carbide Co., Ltd. The formulation of the formulation based on the solid content is shown in Table 2. When blending, the epoxy resin is dissolved in methyl ethyl ketone and used. DICY is used by being dissolved in methoxypropanol or N,N-dimethylformamide. 2E4MZ (2-ethyl-4-methylimidazole manufactured by Shikoku Chemical Industry Co., Ltd.) is used by being dissolved in methoxypropanol. After the formulation, the non-volatile component was adjusted to 50% by using methyl ethyl ketone or methoxypropanol to obtain a resin varnish of a homogeneous solution.

The obtained resin varnish was impregnated into a glass cloth WEA 7628 XS13 (manufactured by Nitto Textile Co., Ltd., thickness: 0.18 mm). The impregnated glass cloth was dried by a hot air circulating furnace at 150 ° C for 8 minutes to obtain a preform. Four pieces of the obtained preform were superposed, and copper foil (3EC manufactured by Mitsui Mining & Mining Co., Ltd.) was superposed on top and bottom, and heated at 130 ° C × 15 minutes and 170 ° C × 20 kg / cm ² × 70 minutes. Pressurization is performed to obtain a laminate. The physical properties of the obtained laminated sheets are shown in Table 2.

Further, TX-1210-90 in the table indicates Epotohto TX-1210-90 (substituted phenol type epoxy resin manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.: epoxy equivalent: 293 g/eq).

Examples 13 and 17.

An epoxy resin composition was produced using the cyanuric acid-denatured phosphorus-containing epoxy resin obtained in Examples 2 and 8, and BRG-557 (a phenol novolak resin manufactured by Showa Denko Co., Ltd.) as a curing agent. . The formulation of the formulation based on the solid content is shown in Table 2. At the time of preparation, epoxy resin and BRG-557 were used by being dissolved in methyl ethyl ketone. 2E4MZ is used by being dissolved in methoxypropanol. After the formulation, the non-volatile component was adjusted to 50% by using methyl ethyl ketone or methoxypropanol to obtain a resin varnish of a homogeneous solution.

The obtained resin varnish was impregnated into a glass cloth WEA 7628 XS13 (manufactured by Nitto Textile Co., Ltd., thickness: 0.18 mm). The impregnated glass cloth was dried by a hot air circulating furnace at 150 ° C for 8 minutes to obtain a preform. Four pieces of the obtained preform were superposed, and copper foil (3EC manufactured by Mitsui Mining & Mining Co., Ltd.) was superposed on top and bottom, and heated at 130 ° C × 15 minutes and 190 ° C × 20 kg / cm ² × 80 minutes. Pressurization is performed to obtain a laminate. The physical properties of the obtained laminated sheets are shown in Table 2.

It can be seen from the examples that by reacting a specific molar ratio of the phosphorus compound with the epoxy resin with respect to 1 mol of cyanuric acid, the cyanuric acid can be sufficiently reacted in a short reaction. A turbid-free cyanuric acid-denatured phosphorus-containing epoxy resin was obtained. Further, the laminated plate was evaluated by using a phosphorus-free cyanuric acid-denatured phosphorus-containing epoxy resin obtained by sufficiently reacting cyanuric acid, and as a result, a cyanuric acid of a comparative example having a turbidity due to unreacted reaction was used. Compared with the case of denatured epoxy resin, it exhibits high heat resistance, adhesion, and flame retardancy.

[Industrial availability]

The present invention relates to a production method for reacting a specific phosphorus compound with cyanuric acid at a specific molar ratio and reacting with an epoxy resin, and the cyanuric acid-denatured phosphorus-containing epoxy resin obtained by the production method It can be used as an epoxy resin for an electronic circuit board excellent in flame retardancy, heat resistance, and adhesion.

Claims (5)

A method for producing a cyanuric acid-denatured phosphorus-containing epoxy resin, which comprises a reaction of cyanuric acid obtained by reacting a phosphorus compound, cyanuric acid, and an epoxy resin as essential components A method for producing a phosphorus epoxy resin, wherein the phosphorus compound is represented by the following formula (1): [wherein, n represents 0 or 1, and R ₁ and R ₂ each independently represent a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, or may form a ring together with a phosphorus atom] or Equation (2): [wherein, m represents 0 or 1, and R ₃ and R ₄ each independently represent a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, or may form a ring together with a phosphorus atom] a compound or a phosphorus compound containing the same, premixed with the epoxy resin in a coexistence of a phosphorus compound of 8.78 to 50 mol with respect to 1 mol of cyanuric acid and cyanuric acid Then, the reaction is carried out, and the phosphorus content is 1.0 to 5.0% by mass, the nitrogen content is 0.5 to 2.0% by mass, and the sum of the phosphorus content and the nitrogen content is 2.5 to 5.5% by mass. An epoxy resin composition obtained by blending other epoxy resins in a cyanuric acid-denatured phosphorus-containing epoxy resin obtained by the production method of claim 1. A curable epoxy resin composition containing a phosphorus-containing epoxy resin denatured with respect to the cyanuric acid, which is obtained by a process for producing a phosphorus cyanate denatured by the method of claim 1 The epoxy group of the oxygen resin is one equivalent of 0.4 to 2.0 equivalents of a hardener based on a functional group ratio. A curable epoxy resin composition, which is contained in the epoxy resin composition of claim 2, having an epoxy group equivalent of from 0.4 to 2.0 equivalents per 1 equivalent of the epoxy group of the epoxy resin composition. Made of hardener. An epoxy resin cured product obtained by hardening a curable epoxy resin composition according to claim 3 or 4.