KR20150052011A - Method for producing cyanuric acid-modified phosphorus-containing epoxy resin, resin composition containing cyanuric acid-modified phosphorus-containing epoxy resin, and cured product of same - Google Patents

Abstract

The present invention relates to a method for producing a flame-retardant cyanuric acid-modified phosphorus-containing epoxy resin obtained by modifying an epoxy resin using cyanuric acid and a phosphorous compound, which enables production in a short time, The present invention also provides a method for producing a cyanuric acid-modified phosphorus-containing epoxy resin capable of obtaining an epoxy resin cured product having excellent physical properties. A method for producing a cyanuric acid-modified phosphorus-containing epoxy resin obtained by reacting a phosphorus compound, cyanuric acid, and an epoxy resin as essential components, which method comprises reacting a specific phosphorus compound with 2.5 to 50 mol of the phosphorus compound per mole of cyanuric acid, A process for producing a cyanuric acid-modified phosphorus-containing epoxy resin, and a process for producing the cyanuric acid-modified phosphorus-containing epoxy resin, which comprises obtaining a cyanuric acid having a phosphorus content of 1.0 to 5.0 mass%, a nitrogen content of 0.1 to 2.0 mass%, and a phosphorus content and a nitrogen content of 2.5 to 5.5 mass% A resin composition comprising an acid-modified phosphorus-containing epoxy resin and a curing agent, and a cured product thereof.

Description

METHOD FOR PRODUCING CYANURIC ACID-MODIFIED PHOSPHORUS-CONTAINING EPOXY RESIN, RESIN COMPOSITION CONTAINING CYANURIC ACID, AND RESIN COMPOSITION CONTAINING CYANURIC ACID -MODIFIED PHOSPHORUS-CONTAINING EPOXY RESIN, AND CURED PRODUCT OF SAME}

The present invention relates to a method for producing a halogen-free flame-retardant epoxy resin containing phosphorus atoms and nitrogen atoms in a molecular skeleton, an epoxy resin composition containing an epoxy resin and other epoxy resins obtained from the above-mentioned production method, and an epoxy resin composition and a curing agent And an epoxy resin cured product obtained by curing the curable epoxy resin composition.

The flame retardancy of the epoxy resin has been conventionally carried out by halogenation as represented by a brominated epoxy resin using tetrabromobisphenol A as a raw material. However, when a halogenated epoxy resin is used, there is a problem that generation of a halide which is highly toxic by pyrolysis reaction is observed when the cured product is burned. On the other hand, halogen-free flame retarding techniques using phosphorus compounds have recently been studied, and it has been proposed to apply phosphorus compounds disclosed in Patent Documents 1 to 4. However, since these phosphorus compounds are low in solubility with epoxy resins or solvents, and are difficult to be mixed with or dissolved in an epoxy resin, as disclosed in Patent Documents 5 to 10, Containing phenol resin is used by imparting solvent solubility to phosphorus-containing epoxy resin and phosphorus-containing phenol resin.

Japanese Patent Application Laid-Open No. 47-016436 Japanese Patent Application Laid-Open No. 60-126293 Japanese Patent Application Laid-Open No. 61-236787 Japanese Patent Application Laid-Open No. 05-331179 Japanese Patent Laid-Open No. 04-11662 Japanese Patent Application Laid-Open No. 2000-309623 Japanese Patent Laid-Open No. 11-166035 Japanese Patent Application Laid-Open No. 11-279258 Japanese Patent Laid-Open No. 2001-123049 Japanese Patent Application Laid-Open No. 2003-040969 Japanese Patent Laid-Open Publication No. 229364/1991

Nishizawa Hitoshi "Polymerization of Polymer" P60 Right column, line 22 to line 27, P166, paragraph 6-8-3 1992,

When the flame retardancy is to be further improved, the phosphorus content has to be increased, and the phosphorus compound-containing compound has to be used in order to increase the molecular weight and decrease the crosslinking density or to use expensive phosphorus-containing compounds. On the other hand, the present inventors have focused on the synergistic effect on the flame retardancy of phosphorus and nitrogen described in Non-Patent Document 1, and proposed to improve flame retardancy by using cyanuric acid as a nitrogen compound (Patent Document 11). However, depending on the production method, it was found that the epoxy resin and cyanuric acid did not sufficiently react with each other and unreacted cyanuric acid was liable to remain. The cyanuric acid remaining in the reaction system reacts only with the epoxy resin at a very low rate and the unreacted cyanuric acid has a poor solubility in the solvent and further the reduction of the unreacted cyanuric acid which adversely affects the curing properties is further required .

In order to solve the above problems, the present inventors have found that when a specific phosphorus compound is allowed to coexist with a cyanuric acid in the reaction between an epoxy resin and cyanuric acid, the cyanuric acid remains in a very small amount, And the reaction with the epoxy resin proceeds easily without requiring the use of the epoxy resin. Thus, the present invention has been completed.

That is,

(1) A process for producing a cyanuric acid-modified phosphorus-containing epoxy resin obtained by reacting a phosphorus compound, cyanuric acid and an epoxy resin as essential components,

(1): < EMI ID =

[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 be a cyclic structure together with the phosphorus atom]

(2): < EMI ID =

[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 be a cyclic structure together with the phosphorus atom]

, Or a phosphorus compound containing both of them, and the epoxy resin is preliminarily mixed in the coexistence of phosphorus compound and cyanuric acid in which 2.5 to 50 mol of the phosphorus compound is added per mole of cyanuric acid , And the reaction is carried out thereafter to obtain a phosphorus content of 1.0 to 5.0 mass%, a nitrogen content of 0.1 to 2.0 mass%, and a total content of phosphorus content and nitrogen content of 2.5 to 5.5 mass% A method for producing an epoxy resin,

(2) An epoxy resin composition obtained by blending another epoxy resin with a cyanuric acid-modified phosphorus-containing epoxy resin obtained by the production method described in (1) above,

(3) A cyanuric acid-modified phosphorus-containing epoxy resin obtained by the production method described in (1) above, which contains 0.4 to 2.0 equivalents of a curing agent based on 1 equivalent of the epoxy group of the cyanuric acid- Curable epoxy resin composition,

(4) A curable epoxy resin composition containing the curing agent in an amount of 0.4 to 2.0 equivalents based on one equivalent of the epoxy group of the epoxy resin composition,

(5) The epoxy resin cured product obtained by curing the curable epoxy resin composition according to (3) or (4)

.

The present invention relates to a cyanuric acid-modified phosphorus-containing epoxy resin obtained by co-existence of a specific phosphorus compound in a molar ratio of 2.5 to 50 mol with respect to 1 mol of cyanuric acid, followed by reaction with an epoxy resin, , A cured epoxy resin having a very small residual amount of cyanuric acid and having excellent physical properties can be obtained.

Hereinafter, embodiments of the present invention will be described in detail. The phosphorus compound represented by the formula (1) or (2) of the present invention specifically includes dimethylphosphine, diethylphosphine, diphenylphosphine, 9,10-dihydro-9-oxa-10- The transition metal complex oxide may be at least one selected from the group consisting of trhene-10-oxide (DOPO), dimethylphosphine oxide, diethylphosphine oxide, dibutylphosphine oxide, diphenylphosphine oxide, 1,4-cyclooctylenephosphine oxide, Octylenphosphine oxide (CPHO, manufactured by Nippon Kayaku Kagaku Co., Ltd.), and the like. These phosphorus compounds may be used singly or in combination of two or more, but the present invention is not limited thereto.

In the present invention, cyanuric acid refers to tautomeric s-triazine-2,4,6-triol and s-triazine-2,4,6-trione, none.

Although cyanuric acid has been disclosed as a nitrogen-based flame retardant, it is difficult to obtain a uniform resin composition due to poor solubility of a cyanuric acid in a solvent, compatibility with an epoxy resin or a curing agent, there was. The cyanuric acid-modified phosphorus-containing epoxy resin obtained from the production process of the present invention is uniform in the resin composition by reacting the cyanuric acid with the epoxy resin, so that stable flame retardancy is obtained. The resin composition of the present invention is used in the meaning including both epoxy resin composition and curable epoxy resin composition, unless otherwise specified, but it shows either of them in the context clearly.

The epoxy resin used for producing the cyanuric acid-modified phosphorus-containing epoxy resin of the present invention is Epototo YD-128, Epototo YD-8125 (manufactured by Shinnitetsu Sumitomo Chemical Co., Ltd., bisphenol A type epoxy (Manufactured by Shinnitetsu Sumitomo Chemical Co., Ltd., Bisphenol F type epoxy resin), YSLV-80XY (manufactured by Shinnitetsu Sumitomo Chemical Co., Ltd.), Epotohto YDF- (Biphenyl-type epoxy resin, manufactured by Mitsubishi Chemical Corporation), Epitoto YDPN-638 (manufactured by Mitsubishi Chemical Co., Ltd.), epoxy resin (Phenol novolak type epoxy resin manufactured by Shin-Nittsu Kabushiki Kaisha), Epoto YDCN-701 (manufactured by Shin-Nittsu Sumitomo Chemical Co., Ltd., cresol novolak type epoxy resin) GK-5855, Ephotoot TX-1210 (manufactured by Shinnitetsu Sumi Kagakuga Co., Epoxy phenol type epoxy resin), Ecototo ZX-1201 (bisphenol fluorene type epoxy resin, manufactured by Shin-Tetsu Sumitomo Chemical Co., Ltd.), TX-0710 (manufactured by Shinnitetsu Sumitomo Chemical Co., (Bisphenol S type epoxy resin), NC-3000 (biphenylaralkylphenol type epoxy resin, manufactured by Nippon Kayaku Kabushiki Kaisha), Epitoto ZX-1355, and Eptotoz ZX-1711 (Naphthalene diol type epoxy resin made by Nippon Kayaku Co., Ltd.), Epitoto ESN-155 (棺 -naphthol aralkyl type epoxy resin made by Shin-Nittsu Sumitomo Chemical Co., Ltd.) Epitothets ESN-475V, Eptoto ESN-485 (manufactured by Shin-Tetsu Sumitomo Chemical Co., Ltd., epoxy resin: Dinaphthol aralkyl type epoxy resin) naphthol aralkyl type epoxy resin), EPPN-501H (manufactured by Nippon Kayaku Kabushiki Co., Ltd. Epoxy resin), YSLV-120TE (manufactured by Shin-Nittsu Sumitomo Chemical Co., Ltd., bis-thioether type epoxy resin), Epitoto ZX-1684 (manufactured by Shinnitetsu Sumitomo Chemical Co., Epiclon HP-7200H (manufactured by DIC Corporation, dicyclopentadiene type epoxy resin), Epotohto YDG-414 (manufactured by Shinnitetsu Sumitomo Chemical Co., Ltd., tetrafunctional epoxy resin) TX-0929, ZX-1542, TX-1032 (manufactured by Shin-Tetsu Sumitomo Chemical Co., Ltd.) and epoxy resin made of epihalohydrin and phenol compound of polyhydric phenol resin such as epoxy resin Epoxy resin prepared from epichlorohydrin and alcohol compound such as epoxy resin, alkylene glycol type epoxy resin), Celloxide 2021 (aliphatic cyclic epoxy resin, manufactured by Daicel Chemical Industries, Ltd.), Epotoh YH-434 Shinnitetsu Sumi 낑 Kagakugabushi (Diaminodiphenylmethane tetraglycidylamine), jER 630 (manufactured by Mitsubishi Chemical Corporation, aminophenol type epoxy resin), and epoxy resins prepared from epihalohydrin, Epoxy FX-305, and TX-0940 (phosphorus-containing epoxy resins, available from Shin-Nittsu Sumitomo Chemical Co., Ltd.), urethane-modified epoxy resins, and oxazolidinone-containing epoxy resins. But are not limited thereto.

These epoxy resins may be used singly or in combination of two or more kinds. Bisphenol-type epoxy resins, phenol novolak-type epoxy resins, and cresol novolak-type epoxy resins may be suitably used.

The reaction between the phosphorus compound represented by the formula (1) or (2) and the cyanuric acid and the epoxy resin is carried out by reacting the phosphorus compound with the epoxy resin in the presence of cyanuric acid, And a preferable molar ratio of the phosphorus compound is 2.7 to 25 moles, preferably 3 to 10 moles per 1 mole of cyanuric acid. If the amount of the phosphorus compound is less than 2.5 moles per mole of cyanuric acid, the progress of the reaction between the cyanuric acid and the epoxy resin becomes insufficient and the amount of residual cyanuric acid increases. If the phosphorus compound exceeds 50 moles per mole of cyanuric acid, the reaction between the cyanuric acid and the epoxy resin proceeds sufficiently, but the effect of introducing nitrogen atoms by cyanuric acid, that is, the synergistic effect of phosphorus and nitrogen on flame retardancy, . In addition, when the condition of coexistence of the phosphorus compound and the cyanuric acid is satisfied, the epoxy resin and the phosphorus compound can be reacted both before and after the reaction of the epoxy resin and the cyanuric acid.

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

A catalyst may be used for the reaction for shortening the time or reducing the reaction temperature. The catalyst that can be used is not particularly limited and those generally used for the synthesis of an epoxy resin can be used. For example, tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine, Phosphonium salts such as phenylphosphonium bromide and the like, imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole, and the like, and they may be used alone or in combination of two or more But are not limited to these. It is also possible to divide it into several circuits and use it.

The amount of the catalyst to be used in the reaction is not particularly limited, but is preferably 5% by mass or less, more preferably 1% by mass or less, and most preferably 0.5% by mass or less, based on the epoxy resin to be used. When the amount of the catalyst exceeds 5 mass%, the autopolymerization reaction of the epoxy group tends to proceed and the resin viscosity tends to increase, which is not preferable.

An inert solvent may also be used for the reaction. Specific examples thereof include various hydrocarbons such as hexane, heptane, octane, decane, dimethylbutane, pentene, cyclohexane, methylcyclohexane, benzene, toluene, xylene and ethylbenzene, ethylether, isopropylether, butylether, diisooamylether , Methylphenyl ether, ethyl phenyl ether, amyl phenyl ether, ethyl benzyl ether, dioxane, methylfuran and tetrahydrofuran, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, cellosolve acetate, But are not limited to, ethylene glycol isopropyl ether, diethylene glycol dimethyl ether, methyl ethyl carbitol, propylene glycol monomethyl ether, dimethyl formamide, and dimethyl sulfoxide. They may be used in combination.

The epoxy equivalent of the cyanuric acid-modified phosphorus-containing epoxy resin obtained in the present invention is preferably 100 to 700 g / eq, more preferably 200 to 600 g / eq. If the epoxy equivalent is less than 100 g / eq, the adhesion of the cured product tends to deteriorate. If the epoxy equivalent is more than 700 g / eq, the glass transition temperature (Tg) of the cured product is lowered, easy.

The phosphorus content of the cyanuric acid-modified phosphorus-containing epoxy resin obtained in the present invention is 1.0 to 5.0 mass%, preferably 1.5 to 4.0 mass%, more preferably 2.0 to 3.5 mass%. The nitrogen content is 0.1 to 2.0% by mass, preferably 0.5 to 1.0% by mass. The total content of phosphorus content and nitrogen content is 2.5 to 5.5 mass%, preferably 3.0 to 4.5 mass%, more preferably 3.0 to 4.0 mass%. Since the flame retardancy of the cyanuric acid-modified phosphorus-containing epoxy resin obtained in the present invention is exhibited by the synergistic effect of phosphorus and nitrogen, it is not meaningful to specify either range, and it is necessary to define the total sum of the phosphorus content and the nitrogen content . If the sum of the phosphorus content and the nitrogen content is less than 2.5 mass%, there is a possibility that flame retardancy can not be sufficiently exhibited depending on the resin composition. If the sum of the phosphorus content and the nitrogen content exceeds 5.5 mass%, the flame retardancy can be sufficiently exhibited, but the resin composition may have a high viscosity and adversely affect the solvent solubility. Therefore, it is preferable that the sum of the phosphorus content and the nitrogen content is in the range of 2.5 to 5.5% by mass.

As the other epoxy resin used in the epoxy resin composition of the present invention, the same epoxy resin as the above epoxy resin can be used in combination with the epoxy resin containing the cyanuric acid modified phosphorus within the range not impairing the characteristics of the present invention.

The cyanuric acid-modified phosphorus-containing epoxy resin or epoxy resin composition of the present invention can be made into a curable epoxy resin composition by blending a curing agent. As the curing agent, conventionally used epoxy resin curing agents such as phenol compounds, acid anhydrides, amines, hydrazides, and acidic polyesters can be used. These curing agents may be used alone or in combination of two or more. Among them, dicyandiamide or a phenol compound is preferable as a curing agent contained in the curable epoxy resin composition of the present invention.

The amount of the curing agent to be used in the curable epoxy resin composition of the present invention is preferably 0.4 to 2.0 equivalents, more preferably 0.5 to 1.5 equivalents, and more preferably 0.5 to 1.0 equivalents, relative to 1 equivalent of the epoxy group as the functional group of the epoxy resin desirable. When the amount of the curing agent is less than 0.4 equivalents or more than 2.0 equivalents based on 1 equivalent of the epoxy group, the curing is incomplete and good curing properties may not be obtained.

Specific examples of the phenol compounds usable in the curable epoxy resin composition of the present invention include bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol S, Bisphenols such as tetramethyl bisphenol Z, dihydroxydiphenyl sulfide and 4,4'-thiobis (3-methyl-6-tert-butylphenol), catechol, resorcin, methylresorcinol, hydroquinone, mono Dihydric phenols such as dihydroxybenzenes such as methylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, mono-tert-butylhydroquinone, and di-tert-butylhydroquinone, and biphenols such as 4,4'-biphenol and tetramethylbiphenol , Polyhydroxynaphthalenes such as dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxymethylnaphthalene and trihydroxynaphthalene, phenol novolak resins such as phenol novolak resin, DC-5 (available from Shin-Nittsu Sumi-kega Phenols such as naphthol novolak resin or condensates of naphthols and aldehydes, SN-160, SN-395, and SN-485 (manufactured by Shin Nittsu Sumitomo Chemical Co., Ltd.) ) Or a condensate of naphthol and xylylene glycol, a condensate of GK-5855P (a substituted phenol resin manufactured by Shin-Nittsu Sumitomo Chemical Co., Ltd.), phenols or naphthols with isopropenyl acetophenone, A phenol compound having two or more phenolic hydroxyl groups in a molecule such as a reaction product of naphthols and dicyclopentadiene, a condensate of phenols or naphthols with a biphenyl-based condensing agent, and the like.

Examples of the phenols include phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, butylmethylphenol, trimethylphenol and phenylphenol. Examples of the naphthol include 1-naphthol, 2- . Examples of the aldehydes include formaldehyde, acetaldehyde, propylaldehyde, butylaldehyde, valeraldehyde, capronaldehyde, benzaldehyde, chloroaldehyde, bromoaldehyde, glyoxal, maronaldehyde, succinaldehyde, glutaraldehyde, (Methylol) biphenyl, bis (methoxy) biphenyl, and the like can be given as the above-mentioned biphenyl-based condensing agent, and examples thereof include aldehyde, pimelaldehyde, sebacic aldehyde, acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, Methyl) biphenyl, bis (ethoxymethyl) biphenyl, bis (chloromethyl) biphenyl, and the like.

Examples of other known curing agents that can be used in the curable epoxy resin composition of the present invention include acid anhydrides such as methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, anhydrous pyromellitic acid, phthalic anhydride, trimellitic anhydride, But are not limited to, aliphatic amines such as dicyandiamide, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, metaoxylenediamine and isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylether , Aromatic amines such as diaminoethylbenzene, amines such as benzyldimethylamine and 2,4,6-tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-phenylimidazole, 2- Imidazoles such as methylimidazole, 2-undecylimidazole and 1-cyanoethyl-2-methylimidazole, and imidazoles such as trimellitic acid, isocyanuric acid and boron, Salt, die Amine compounds such as polyamide amine which are condensates of polyamines with acids such as acid, hydrazides such as adipic acid dihydrazide and sebacic acid dihydrazide, aminobenzoic acid esters, phosphine compounds such as triphenylphosphine, Tetraphenylphosphonium bromide and the like, quaternary ammonium salts such as trimethylammonium chloride, diazabicyclo compounds and their salts with salts such as phenols, phenol novolak resins, boron trifluoride, amines, ether compounds and the like, Aromatic phosphonium salts, iodonium salts, and the like, but are not limited thereto. Two or more kinds of these may also be used in combination.

In the curable epoxy resin composition of the present invention, an organic solvent may also be used for viscosity adjustment. Examples of the organic solvent that can be used 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, Aromatic hydrocarbons and the like. These solvents alone or in combination of plural kinds may be blended in a range of 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 if necessary. Examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) Tertiary amines such as diazabicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, tricyclohexylphosphine, triphenylphosphine triphenylborane, tin octylate, etc. Of a metal compound. The curing accelerator is preferably used in an amount of 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 curing accelerator, the curing temperature can be lowered and the curing time can be shortened.

In the curable epoxy resin composition of the present invention, a filler may be used if necessary. Specific examples thereof include inorganic fillers such as aluminum hydroxide, magnesium hydroxide, talc, calcined talc, clay, kaolin, titanium oxide, glass powder, boehmite and silica balloons. The reason for using a general inorganic filler is to improve the impact resistance. Further, when a metal hydroxide such as aluminum hydroxide or magnesium hydroxide is used, it acts as a flame retarding auxiliary agent, and the phosphorus content in the resin composition can be ensured at least at the flame retardancy. Particularly, when the blending 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, adhesiveness, which is a necessary item for laminated board applications, is lowered. Further, fibrous fillers such as glass fibers, pulp fibers, synthetic fibers and ceramic fibers, and organic fillers such as fine particle rubber and thermoplastic elastomer may be contained in the resin composition.

The curable epoxy resin composition of the present invention is cured to obtain a phosphorus- and nitrogen-containing epoxy resin cured product. At the time of curing, for example, a resin sheet, a copper foil with a resin, a prepreg or the like is laminated and heated and cured to obtain a phosphorus-containing epoxy resin cured product as a laminate.

The curable epoxy resin composition containing the cyanuric acid-modified phosphorus-containing epoxy resin of the present invention was prepared and the properties of the phosphorus- and nitrogen-containing epoxy resin cured product were evaluated as a laminate obtained by heat curing. As a result, Containing epoxy resin which is obtained by reacting an epoxy resin with a cyanuric acid compound and cyanuric acid, and a phosphorus-containing epoxy resin obtained from a phosphorus compound and an epoxy resin.

Example

The present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In Examples and Comparative Examples, " parts " and "% " indicate parts by mass unless otherwise specified.

The epoxy equivalent of the epoxy resin measured in Examples and Comparative Examples was measured according to JIS K 7236.

The percentage of nitrogen was calculated from the content and amount of nitrogen in cyanuric acid to the percentage of cyanuric acid-modified phosphorus-containing epoxy resin.

The phosphorus content of the epoxy resin synthesized in Examples and Comparative Examples was measured by the following method. That is, 3 ml of sulfuric acid is added to 150 mg of the sample, and the mixture is heated for 30 minutes. After returning to room temperature, 3.5 mL of nitric acid and 0.5 mL of perchloric acid are added, and the mixture is heated and decomposed until the content becomes transparent or yellow. Dilute this solution with pure water in a 100 mL volumetric flask. Add 10 mL of this sample solution into a 50 mL volumetric flask, add one drop of the phenolphthalein indicator, and add 2 mol / L ammonia water until it turns red. Add 2 mL of 50% sulfuric acid solution and add pure water. Add 5 mL of an aqueous solution of ammonium metavanadate 2.5 g / L and 5 mL of an aqueous 50 g / L ammonium molybdate solution, and then use pure water to make the solution. After standing at room temperature for 40 minutes, pure water was measured as a control using a spectrophotometer under the condition of a wavelength of 440 nm, and the phosphorus content was determined from the absorbance.

With respect to the resulting epoxy resin containing cyanuric acid-modified phosphorus, the presence or absence of residual cyanuric acid was confirmed by the presence or absence of visible fog. No cloudiness was defined as no residual cyanuric acid (?), And cloudiness was determined as residual cyanuric acid (?).

The glass transition temperature of the cured product was measured using Exster 6000 manufactured by Seiko Instruments Inc. The value of the first inflection point was set to the glass transition temperature in DSC and the inflection point was set to the glass transition temperature in TMA.

The copper foil peel strength was measured in accordance with JIS C 6481 5.7, and the interlaminar adhesive strength was measured by peeling between one prepreg and the other three sheets in accordance with JIS C 6481 5.7.

The flame retardancy was measured according to UL (Underwriter Laboratories) standards. In addition, the time of the flushing is indicated by the total duration of the five test pieces of the flame.

The reaction rates of cyanuric acid were determined by the following equations using the values of initial epoxy equivalent, theoretical epoxy equivalent, and epoxy equivalent (epoxy equivalent) of epoxy resin containing cyanuric acid-modified phosphorus.

[(Final epoxy equivalent - initial epoxy equivalent) / (theoretical epoxy equivalent - initial epoxy equivalent)] 100

However, when the final epoxy equivalent weight is larger than the theoretical epoxy equivalent weight, the reaction rate is set to 100%.

Example  One.

To a four-neck glass separable flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas introducing apparatus, Epototo YDPN-638 (phenol novolak type epoxy resin, manufactured by Shin-Nittsu Sumitomo Kagaku Kogyo Co., / eq), 127 parts of HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phosphorus content of 14.2%, manufactured by Sanko Kabushiki Kaisha) (Manufactured by Tokyo Kasei Kogyo Co., Ltd.) were charged, stirred while introducing nitrogen gas, heated and heated to 130 캜. The initial epoxy equivalent in the mixed state was 207 g / eq. After the initial epoxy equivalent amount was measured, 0.14 part of triphenylphosphine was added as a catalyst, and the reaction was carried out at 160 ° C for 4 hours. The phosphorus content of the resulting cyanuric acid-modified phosphorus-containing epoxy resin (A-1) was 1.8%, the theoretical epoxy equivalent was 270 g / eq, the final epoxy equivalent was 272 g / eq, and the reaction rate of cyanuric acid was 100%. The results are shown in Table 1.

Example  2.

The same operation as in Example 1 was carried out except that 755 parts of epotato YDPN-638, 3 parts of cyanuric acid and 239 parts of HCA were used. The phosphorus content of the resulting cyanuric acid-modified phosphorus-containing epoxy resin (A-2) was 3.4%, the initial epoxy equivalent was 232 g / eq, the theoretical epoxy equivalent was 320 g / eq, the final epoxy equivalent was 332 g / Was 100%. The results are shown in Table 1.

Example  3.

To a four-neck glass separable flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas introducing device were placed 10 g of Epototo YDPN-63X (manufactured by Shinnitetsu Sumitomo Chemical Co., Ltd., narrow dispersion phenol novolak type epoxy resin: epoxy 696 parts of an equivalent weight of 176 g / eq), 250 parts of HCA and 58 parts of cyanuric acid, stirring was conducted while introducing nitrogen gas, and the mixture was heated and heated to 130 캜. The initial epoxy equivalent weight in the mixed state was 254 g / eq. After the initial epoxy equivalent weight was measured, 0.33 part of triphenylphosphine was added as a catalyst, and the reaction was carried out at 160 DEG C for 4 hours. The phosphorus content of the resulting cyanuric acid-modified phosphorus-containing epoxy resin (A-3) was 3.6%, the theoretical epoxy equivalent was 701 g / eq, the final epoxy equivalent was 669 g / eq and the reaction rate of cyanuric acid was 93%. The results are shown in Table 1.

Example  4.

The procedure of Example 3 was repeated except that 640 parts of epotato YDPN-63X, 15 parts of cyanuric acid and 345 parts of HCA were used. The phosphorus content of the resulting cyanuric acid-modified phosphorus-containing epoxy resin (A-4) was 4.9%, the initial epoxy equivalent was 275 g / eq, the theoretical epoxy equivalent was 592 g / eq, the final epoxy equivalent was 594 g / Was 100%. The results are shown in Table 1.

Example  5.

507 parts of Eptoto YDPN-638, 4 parts of Eptoto YD-128 (manufactured by Shin-Tetsu Sumitomo Chemical Co., Ltd.), and 10 parts of Nippon Kayaku Co., Ltd. were added to four glass separable flasks equipped with a stirrer, a thermometer, 300 parts of bisphenol A type liquid epoxy resin: epoxy equivalent 186 g / eq), 162 parts of HCA and 31 parts of cyanuric acid, stirring was conducted while nitrogen gas was introduced, and the mixture was heated and heated to 130 占 폚. The initial epoxy equivalent weight in the mixed state was 223 g / eq. After the initial epoxy equivalent weight was measured, 0.25 part of triphenylphosphine was added as a catalyst, and the reaction was carried out at 160 DEG C for 4 hours. The phosphorus content of the obtained cyanuric acid-modified phosphorus-containing epoxy resin (A-5) was 2.3%, the theoretical epoxy equivalent was 333 g / eq, the final epoxy equivalent was 330 g / eq, and the reaction rate of cyanuric acid was 97%. The results are shown in Table 1.

Example  6.

Into four glass separable flasks equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas introducing device, 433 parts of Ephotoot YDPN-638, 5 parts of Eptotol YDCN-704 (manufactured by Shinnitetsu Sumitomo Kagaku Kikai Co., 300 parts of cresol novolac epoxy resin: epoxy equivalent 209 g / eq), 250 parts of HCA and 17 parts of cyanuric acid, stirring was conducted while nitrogen gas was introduced, and the mixture was heated to 130 캜. The initial epoxy equivalent weight in the mixed state was 258 g / eq. After the initial epoxy equivalent weight 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 phosphorus content of the obtained cyanuric acid-modified phosphorus-containing epoxy resin (A-6) was 3.6%, the theoretical epoxy equivalent was 429 g / eq, the final epoxy equivalent was 428 g / eq and the reaction rate of cyanuric acid was 99%. The results are shown in Table 1.

Example  7.

In a four-neck separable glass flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas introducing device, 442 parts of Ephotoot YDPN-638, 30 parts of YSLV-80XY (manufactured by Shinnitetsu Sumitomo Kagaku Kagaku Co., Ltd., F type epoxy resin: epoxy equivalent 190 g / eq), 250 parts of HCA and 6 parts of cyanuric acid, stirring was carried out while nitrogen gas was introduced, and the mixture was heated and heated to 130 占 폚. The initial epoxy equivalent weight in the mixed state was 245 g / eq. After the initial epoxy equivalent weight was measured, 0.25 part of triphenylphosphine was added as a catalyst, and the reaction was carried out at 160 캜 for 4 hours. The phosphorus content of the resulting cyanuric acid-modified phosphorus-containing epoxy resin (A-7) was 3.6%, the theoretical epoxy equivalent was 360 g / eq, the final epoxy equivalent was 360 / eq and the reaction rate of cyanuric acid was 100%. The results are shown in Table 1.

Example  8.

To a four-glass separable flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas introducing apparatus, 860 parts of Epitoto YDPN-638, 5 parts of CPHO (1,5-cyclooctylene (trade name, manufactured by Nippon Oil Chemical Co., Phosphorus content: 19.6%), and 30 parts of cyanuric acid were charged. While nitrogen gas was introduced, the mixture was stirred and heated to 130 ° C. The initial epoxy equivalent weight in the mixed state was 206 g / eq. After the initial epoxy equivalent weight was measured, 0.14 part of triphenylphosphine was added as a catalyst, and the reaction was carried out at 160 ° C for 4 hours. The phosphorus content of the resulting cyanuric acid-modified phosphorus-containing epoxy resin (A-8) was 2.2%, the theoretical epoxy equivalent was 289 g / eq, the final epoxy equivalent was 290 / eq and the reaction rate of cyanuric acid was 100%. The results are shown in Table 1.

Comparative Example  One.

Into four glass separable flasks equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas introducing device, 954 parts of Epitoto YDPN-638 and 46 parts of cyanuric acid were charged, stirring was conducted while introducing nitrogen gas, Heating was performed to raise the temperature. And the temperature was raised to 130 deg. The initial epoxy equivalent weight in the mixed state was 185 g / eq. After the initial epoxy equivalent weight was measured, 0.05 part of triphenylphosphine was added as a catalyst, and the reaction was carried out at 160 DEG C for 4 hours. The final epoxy equivalent weight of the resulting cyanuric acid-modified epoxy resin (A-9) was 194 g / eq, and the phosphorus content was 0%. Theoretical epoxy equivalent was 230 g / eq, and the reaction rate of cyanuric acid was 20%. The results are shown in Table 1.

Comparative Example  2.

The same operation as in Example 1 was carried out except that 843 parts of epotato YDPN-638 and 31 parts of cyanuric acid were used. The phosphorus content of the resulting cyanuric acid-modified phosphorus-containing epoxy resin (A-10) was 1.8%, the initial epoxy equivalent was 209 g / eq, the theoretical epoxy equivalent was 287 g / eq, the final epoxy equivalent was 263 g / Was 69%. The results are shown in Table 1.

Comparative Example  3.

The procedure of Example 1 was repeated except that 885 parts of epotato YDPN-638, 23 parts of cyanuric acid and 95 parts of HCA were used. The phosphorus content of the resulting cyanuric acid-modified phosphorus-containing epoxy resin (A-11) was 1.35%, the initial epoxy equivalent was 200 g / eq, the theoretical epoxy equivalent was 248 g / eq, the final epoxy equivalent was 231 g / Was 65%. The results are shown in Table 1.

Comparative Example  4.

Into four glass separable flasks equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas introducing device, 788 parts of Epotato YDPN-638, 23 parts of cyanuric acid, and 10 parts of HCA-HQ (manufactured by Sanko Kabushiki Kaisha, - (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, phosphorus content: 9.6%) was added, stirring was conducted while introducing nitrogen gas, Heating was performed to raise the temperature. And the temperature was raised to 130 deg. The initial epoxy equivalent weight in the mixed state was measured and found to be 223 g / eq. After the initial epoxy equivalent weight was measured, 0.2 part of triphenylphosphine was added as a catalyst and the reaction was carried out at 160 캜 for 4 hours to obtain a gelled epoxy resin I did. In addition, cyanuric acid remained in a solid form in the gel.

Comparative Example  5.

The same operation as in Comparative Example 4 was carried out except that 855 parts of epotato YDPN-638, 15 parts of cyanuric acid and 130 parts of HCA-HQ were used. The phosphorus content of the resulting cyanuric acid-modified phosphorus-containing epoxy resin (A-12) was 1.2%, the initial epoxy equivalent was 206 g / eq, the theoretical epoxy equivalent was 271 g / eq, the final epoxy equivalent was 224 g / Was 28%. The results are shown in Table 1.

Comparative Example  6.

683 parts of Epitoto YDPN-638, 4 parts of Eptoto YDF-2001 (manufactured by Shinnitetsu Sumitomo Chemical Co., Ltd.) were added to four glass separable flasks equipped with a stirrer, a thermometer, 190 parts of bisphenol F type solid epoxy resin: epoxy equivalent 469 g / eq) and 127 parts of HCA were charged, stirred while introducing nitrogen gas, heated and heated. And the temperature was raised to 130 deg. The initial epoxy equivalent weight in the mixed state was 235 g / eq. After the initial epoxy equivalent weight was measured, 0.13 part of triphenylphosphine was added as a catalyst, and the reaction was carried out at 160 DEG C for 4 hours. The resulting epoxy-containing epoxy resin (A-13) had a final epoxy equivalent of 272 g / eq and a phosphorus content of 1.8%. The theoretical epoxy equivalent weight was 272 g / eq. The results are shown in Table 1.

Example  9 to 12 and 14 to 16, and Comparative Example  7-11.

The epoxy resin containing cyanuric acid modified phosphorus 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 (dicyandiamide manufactured by Nippon Kayabite Co., Ltd., ) Was used to prepare a curable epoxy resin composition. Table 2 shows the formulation for the solid content. The epoxy resin was dissolved in methyl ethyl ketone at the time of blending. DICY was dissolved in methoxypropanol and N, N-dimethylformamide. 2E4MZ (2-ethyl-4-methylimidazole, manufactured by Shikoku Chemical Industry Co., Ltd.) was dissolved in methoxypropanol and used. After mixing, the mixture was adjusted to a non-volatile content of 50% with methyl ethyl ketone and methoxypropanol to obtain a resin varnish as a homogeneous solution.

The obtained resin varnish was impregnated with glass fiber WEA 7628 XS13 (0.18 mm thick, made by Nitto Boseki Co., Ltd.). The impregnated glass fiber was dried in a hot air circulation furnace at 150 캜 for 8 minutes to obtain a prepreg. Overlapping the prepreg 4 sheets of the obtained superposed copper foils (manufactured by MITSUI long jokku Kogyo whether or sikki manufactured claim, 3EC) above and below, 130 ℃ × 15 minutes and ^{170 ℃ × 20kg / cm 2 ×} 70 bungan heated, subjected to pressing to obtain a laminated board . The physical properties of the obtained laminate are shown in Table 2.

In the table, TX-1210-90 represents Eptoto TX-1210-90 (phenol-type epoxy resin substituted by epoxy resin: epoxy equivalent: 293 g / eq, manufactured by Shin-Nittsu Sumitomo Chemical Co., Ltd.).

Example  13 and 17.

Epoxy resin compositions were prepared using the cyanuric acid-modified phosphorus-containing epoxy resin obtained in Examples 2 and 8 and BRG-557 (phenol novolak resin, manufactured by Showa Denko K.K.) as a curing agent. Table 2 shows the formulation for the solid content. The epoxy resin and BRG-557 were dissolved in methyl ethyl ketone and used in the blending. 2E4MZ was dissolved in methoxypropanol and used. After mixing, the mixture was adjusted to a non-volatile content of 50% with methyl ethyl ketone and methoxypropanol to obtain a resin varnish as a homogeneous solution.

The obtained resin varnish was impregnated with glass fiber WEA 7628 XS13 (0.18 mm thick, made by Nitto Boseki Co., Ltd.). The impregnated glass fiber was dried in a hot air circulation furnace at 150 캜 for 8 minutes to obtain a prepreg. Overlapping the prepreg 4 sheets of the obtained superposed copper foils (manufactured by MITSUI long jokku Kogyo whether or sikki manufactured claim, 3EC) above and below, 130 ℃ × 15 minutes and ^{190 ℃ × 20kg / cm 2 ×} 80 bungan heated, subjected to pressing to obtain a laminated board . The physical properties of the obtained laminate are shown in Table 2.

As can be seen from the Examples, cyanuric acid was sufficiently reacted in a short time reaction by reacting a phosphorus compound having a predetermined molar ratio with respect to 1 mole of cyanuric acid and an epoxy resin, and a fog-free cyanuric acid-modified phosphorus-containing epoxy A resin can be obtained. Further, laminate evaluation was carried out using fog-free cyanuric acid-modified phosphorus-containing epoxy resin which was sufficiently reacted with cyanuric acid. As a result, it was found that the laminated board was superior in heat resistance and adhesiveness than the cyanuric acid- And flame retardancy.

A cyanuric acid-modified phosphorus-containing epoxy resin obtained from this process is a process for producing a cyanuric acid-modified phosphorus-containing epoxy resin by reacting a specific phosphorus compound and cyanuric acid in a specific molar ratio in the presence of an epoxy resin. It can be used as an epoxy resin for a substrate.

Claims (5)

A process for producing a cyanuric acid-modified phosphorus-containing epoxy resin obtained by reacting a phosphorus compound, cyanuric acid and an epoxy resin as essential components,
(1): < EMI ID =

[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 be a cyclic structure together with the phosphorus atom]
(2): < EMI ID =

[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 be a cyclic structure together with the phosphorus atom]
, Or a phosphorus compound containing both of them, wherein the epoxy resin is preliminarily mixed in the presence of a phosphorus compound and cyanuric acid, wherein the amount of the phosphorus compound is 2.5 to 50 moles relative to 1 mole of cyanuric acid, The reaction is carried out to obtain a phosphorus-containing phosphorus-containing epoxy resin having a phosphorus content of 1.0 to 5.0 mass%, a nitrogen content of 0.1 to 2.0 mass%, and a total content of phosphorus content and nitrogen content of 2.5 to 5.5 mass% A method for producing a resin. An epoxy resin composition comprising a cyanuric acid-modified phosphorus-containing epoxy resin obtained by the production method according to claim 1 mixed with another epoxy resin. A curable epoxy resin composition containing 0.4 to 2.0 equivalents of a curing agent based on 1 equivalent of an epoxy group of the cyanuric acid-modified phosphorus-containing epoxy resin, which is obtained by the production method described in claim 1, . A curable epoxy resin composition comprising the epoxy resin composition according to claim 2 in an amount of 0.4 to 2.0 equivalents of a curing agent based on one equivalent of the epoxy group of the epoxy resin composition. A cured epoxy resin cured product obtained by curing the curable epoxy resin composition according to claim 3 or 4.