JP2002088138A - Epoxy resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an epoxy resin composition without generating a harmful halogen compound in combustion having excellent flame retardance and excellent physical properties of a cured product. SOLUTION: This epoxy resin composition is obtained by compounding (a) a polyepoxy compound represented by general formula (I) (n is a number of 0.1-20; Z is a direct bond, a 1-4C alkylidene group or SO2; X is a hydrogen atom or a glycidyl group; X in an amount of >=10% is a glycidyl group) with at least one kind of a phosphorus compound selected from the group consisting of an aromatic phosphinic acid ester, an aromatic phosphonic acid ester and an aromatic phosphoric ester which contain at least one phenolic hydroxy group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition and, more particularly, to an epoxy resin composition which has excellent flame retardancy and is used for electric and electronic applications.
The present invention relates to an epoxy resin composition that can be suitably used for automotive applications, paints, and the like.

[0002]

2. Description of the Related Art Epoxy resins have excellent adhesiveness to various substrates, heat resistance, chemical resistance, electrical properties, mechanical properties, and the like.
It is widely used as molded products such as electric devices and automobile parts, paints, adhesives, and fiber treatment agents.

[0003] Since epoxy resins are flammable, brominated epoxy resins have been used for the purpose of preventing or delaying fire when used in applications such as electric equipment, electronic parts, and automobile parts. By introducing a halogen such as bromine into an epoxy resin, flame retardancy is imparted, and a cured product excellent due to high reactivity of an epoxy group is obtained. However, the use of these brominated epoxy resins has caused a problem of adverse effects on the environment due to the generation of harmful substances such as hydrogen halides during combustion. For this reason, there is an increasing demand for flame-retardant epoxy resins that do not use halogen compounds.

[0004] In order to solve the above problems, attempts have been made to impart flame retardancy by using a phosphorus compound instead of a halogen compound. As a phosphorus-based flame retardant, triphenyl phosphate is used. Generally known. However, triphenyl phosphate not only has a high volatility and a small flame-retarding effect, but also has a drawback in that bleeding impairs the appearance of the resin or lowers the softening point of the resin, which greatly affects the physical properties. ing. As a method of suppressing the influence on the resin properties, Japanese Patent Publication No. 54-32818, Japanese Patent Application Laid-Open No. Hei 7-233184, and the like have proposed to add a hydroxyl group-containing polyphosphate to a thermosetting resin. The flame retardant effect was still insufficient.

On the other hand, there has been proposed a polyfunctional bisphenol-type epoxy resin obtained by reacting a normal diglycidyl ether of a bisphenol compound with epichlorohydrin to a secondary hydroxyl group (for example, US Pat. No. 4,623,701). Specification, JP-A-1-1687
No. 22, JP-A-3-255934, JP-A-6
JP-A-248055, JP-A-6-298904, JP-A-7-173250 and the like. Here, too, it has been proposed to use a diglycidyl ether compound of a brominated bisphenol compound. However, no attempt has been made to achieve flame retardancy by combining a bisphenol-type epoxy resin with a phosphorus-containing compound.

Accordingly, it is an object of the present invention to reduce the generation of harmful halogen compounds during combustion, to provide excellent flame retardancy,
An object of the present invention is to provide an epoxy resin composition having excellent physical properties of a cured product.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that an epoxy resin composition obtained by combining a specific polyepoxy compound and a specific phosphorus-containing compound has a low flame retardancy. It has been found that a cured product which is excellent and has various physical properties can be provided, and the present invention has been achieved.

That is, (A) a polyepoxy compound represented by the following general formula (I) and (B) an aromatic phosphinate having at least one phenolic hydroxyl group:
An epoxy resin composition comprising at least one phosphorus-containing compound selected from the group consisting of aromatic phosphonates and aromatic phosphates.

[0009]

Embedded image (Wherein, n represents a number from 0.1 to 20, Z is a direct bond,
X represents an alkylidene group having 1 to 4 carbon atoms or SO ₂ ; X represents a hydrogen atom or a glycidyl group;
0% or more represents a glycidyl group. )

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the epoxy resin composition of the present invention will be described in detail.

In the general formula (I), examples of the alkylidene group having 1 to 4 carbon atoms represented by Z include groups such as methylidene, ethylidene, propylidene and butylidene. Further, n is 0.1 to 20, particularly 1 to 15
X represents a hydrogen atom or a glycidyl group, and 10% or more, particularly 30% or more of X is a glycidyl group. When n is less than 0.1 or less than 10% of X is a glycidyl group, the content of the trifunctional or higher polyfunctional epoxy compound decreases, and thus, for example, a problem such as a decrease in the strength of the cured product occurs. It is not preferable because there is a possibility of it.

The polyepoxy compound represented by the above-mentioned general formula (I) as the component (A) of the present invention can be used to convert a diglycidyl ether of a bisphenol having a secondary hydroxyl group in one molecule and epichlorohydrin into an alkali and an interlayer transfer catalyst. Can be easily produced by reacting in the presence of

Here, examples of the alkali include sodium hydroxide, potassium hydroxide, calcium hydroxide and the like, and examples of the interlayer transfer catalyst include tetramethylammonium chloride, tetrabutylammonium bromide, methyltrioctylammonium Chloride,
Methyltridecyl ammonium chloride, N, N-dimethylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium iodide, N-butyl-N-methylpyrrolidinium bromide, N-benzyl-N-methylpyrrolidide Nium chloride, N-ethyl-N-methylpyrrolidinium bromide, N-butyl-N-methylmorpholinium bromide, N-butyl-N-methylmorpholinium iodide, N-allyl-N-methylmorpholinium Bromide, N-methyl-N-benzylpiperidinium chloride, N-methyl-N-benzylpiperidinium bromide, N, N-dimethylpiperidinium iodide, N-methyl-N-ethylpiperidinium acetate, N -Methyl-N-ethylpiperidinium iodide; Moniumukurorido is preferable.

The amount of epichlorohydrin used in this reaction is 1 to 1 equivalent of hydroxyl group of diglycidyl ether.
The equivalent is used in an amount of at least equivalent, particularly 2 to 10 equivalents, and the alkali is used in an amount of 0.1 to 1 equivalent to 1 equivalent of the hydroxyl group to be glycidylated.
2.0 mol, in particular 0.3 to 1.5 mol, are used, and the interlayer transfer catalyst is used in an amount of 0.01 to 10 mol%, especially 0.2 to 2 mol%, based on the total weight of the reactants. This reaction can be carried out in a solvent such as a hydrocarbon, ether or ketone, but an excess of epichlorohydrin can also be used as a solvent. The reaction is carried out at 20 to 100 ° C, especially
The reaction is carried out at a temperature in the range of 0 to 80 ° C. If the temperature is lower than 20 ° C, the reaction becomes slow and a long-time reaction is required. Regarding this production method, for example, H. BATZER AND SA ZAHIR, JOURNAL O
F APPLIED POLYMER SCIENCE VOL 19 PP. 609-617 (1975)
And so on. Further, Japanese Patent Application Laid-Open No. 5-239181
Japanese Patent Laid-Open Publication No. H11-15083 proposes a method for producing a glycidyl ether of a secondary alcohol, but the method can also be applied. Further, Japanese Patent Application Laid-Open Nos. 1-168722 and 5-5020 propose a method using dimethyl sulfoxide, which can be produced by this method.

The diglycidyl ether of a bisphenol compound having at least one hydroxyl group in one molecule is a known compound, and is a one-step method produced by reacting a bisphenol compound with epichlorohydrin, or a low-molecular-weight bisphenol. Any of the two-step methods of producing by reacting a diglycidyl ether of a compound with a bisphenol compound may be used. Examples of the bisphenol compound that can be provided include methylidene bisphenol (bisphenol F), ethylidene bisphenol, and isopropylidene. Bisphenol (bisphenol A), butylidene bisphenol, biphenol,
Sulfone bisphenol (bisphenol S) and the like.

The epoxy resin composition of the present invention includes (a)
Other polyepoxy compounds may be used in combination with the component polyepoxy compound. In this case, it is preferable that the polyepoxy compound of the component (a) accounts for 20% by weight or more, especially 40% by weight or more of the total polyepoxy compound. There is a possibility that it is not preferable.

These other polyepoxy compounds include:
For example, hydroquinone, resorcinol, pyrocatechol, phloroglucinol, dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis (orthocresol), ethylidenebisphenol, isopropylidenebisphenol (bisphenol A), isopropylidenebis (orthocresol), Tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1, 1,2,2
-Tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcinol novolak, bisphenol A novolak, bisphenol F novolak, terpene diphenol , (1-
(4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) a polyglycidyl ether compound of a polyhydric phenol compound such as bisphenol; an adduct of ethylene oxide and / or propylene oxide with the above polyhydric phenol compound A polyglycidyl ether compound; a hydrogenated polyglycidyl ether compound of the above polyhydric phenol compound; ethylene glycol;
Polyglycidyl ethers of polyhydric alcohols such as propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, dicyclopentadiene dimethanol; maleic acid, fumaric acid, itacone Acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, Homopolymers or copolymers of glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as hexahydrophthalic acid, endomethylenetetrahydrophthalic acid and glycidyl methacrylate; N, N- Glycidyl aniline, bis (4
Epoxy compounds having a glycidylamino group such as-(N-methyl-N-glycidylamino) phenyl) methane; vinylcyclohexene diepoxide, dicyclopentanedienediepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane Epoxidized cyclic olefin compounds such as carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized polybutadiene; Examples include epoxidized conjugated diene polymers such as epoxidized styrene-butadiene copolymer and heterocyclic compounds such as triglycidyl isocyanurate. These epoxy resins may be those internally crosslinked with a prepolymer of terminal isocyanate or those having a high molecular weight with a polyvalent active hydrogen compound.

The phosphorus-containing compound as the component (b) of the present invention has at least one phenolic hydroxyl group and at least one selected from the group consisting of aromatic phosphinates, aromatic phosphonates and aromatic phosphates. And specific examples include compounds represented by the following general formula (II).

[0019]

Embedded image (In the formula, m represents a number of 1 to 5, and X ₁ and X ₂ represent —O
—, —N (R ₃ ) — or a direct bond, R ₁ and R ₂ represent an alkyl group, an aryl group or —Ar—OH, R ₃ represents a hydrogen atom or an alkyl group, or R ₃ represents R _{1 and} R ₂ may be combined with each other to form a ring, and Ar represents a group represented by the following formula. )

[0020]

Embedded image(Where R_Four~ R₁₆Are each independently a hydrogen atom,
Y represents a direct bond when p = 0.
-CH_Two-, -C (CH_Three)_Two-Or -SO _Two−
And when p = 1, -CR₁₇=, R₁₇Is hydrogen
Represents an atom or an alkyl group, and l represents 0 to 2. )

In the general formula (II), examples of the alkyl group represented by R ₁ and R ₂ include methyl, ethyl,
Propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, sec-amyl,
Tertiary amyl, hexyl, isohexyl, heptyl, octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and the like. The aryl group includes, for example, phenyl and naphthyl, which may be substituted by 1 to 5 with the above alkyl group. Examples of the alkyl group represented by R ₃ and R _{4 to} R ₁₇ include, for example,
Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, sec-amyl, tert-amyl, hexyl, isohexyl, heptyl, octyl, isooctyl, tert-octyl, 2-ethylhexyl, Nonyl, isononyl, decyl, isodecyl and the like can be mentioned. Examples of the ring that can be formed by R ₃ and R ₁ or R ₂ include a piperidine ring.

The phosphorus-containing compound represented by the general formula (II) is specifically described below.

[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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Among these phosphorus-containing compounds, those having only one phenolic hydroxyl group in the skeleton are preferred because of their excellent stability when combined with a polyepoxy compound. Further, Ar in the general formula (II) L in the group represented
Is preferably 1 or 2 because of excellent water resistance.

The method for synthesizing the phosphorus-containing compound of the component (b) of the present invention is not particularly limited, and it can be synthesized in the same manner as a usual phosphate ester compound.
o. In the case of 1, the compound can be easily synthesized by heating and dehydrochlorinating 2,6-dimethylphenol and phosphorus oxychloride in the presence of an amine-based catalyst, and then further reacting hydroquinone with a Lewis acid catalyst. Here, as a side reaction product, a compound obtained by phosphorylation at both ends may be obtained, or unreacted hydroquinone may remain. However, the content of the phosphorus-containing compound of the present invention is 50% by weight. %
If it exceeds, it can be used as it is.
However, if tri (substituent-containing) phenyl phosphate remains, it is not preferable because physical properties may be adversely affected. By using a phenol having a methyl group at the 2,4-position (in general formula (II), R ₄ and R ₅ in the group represented by Ar are methyl groups), a diphenyl compound can be selectively formed. It is preferable because it can be obtained.

The present invention provides an epoxy resin composition having excellent flame retardancy by using a combination of the polyepoxy compound (A) and the phosphorus-containing compound (B). When the component (a) and the polyepoxy other than the component (a) are used, a total of 100% of the polyepoxy compound other than the component (a) is used.
Component (b) phosphorus-containing compound (1-100)
Parts by weight, preferably 5 to 50 parts by weight,
When a polyepoxy other than the component (a), the component (b), and the component (a) is used, the phosphorus content is 0.1 relative to the total amount of the polyepoxy compound and the curing agent other than the component (a).
It is preferable to use an amount of from 10 to 10% by weight, and preferably from 0.5 to 8% by weight, since a material having excellent flame retardancy and various physical properties can be obtained.

When the component (b) is mixed with the component (a), a part or all of the glycidyl group of the component (a) and the component (b) undergo an addition reaction in the cured product, and the following formula (II)
I) is considered to form a partial structure, but if the amount of the unreacted (ii) component is large, the alkali resistance tends to decrease. Therefore, an epoxy ring-opening catalyst capable of accelerating the above addition reaction should be used. It is preferable to use them in combination or to carry out an addition reaction of the components (a) and (b) in advance.

[0044]

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Considering the above, an amount of less than 1 mol, preferably 0.1 to 0.8 mol, of the phosphorus-containing compound of the component (b) relative to 1 epoxy equivalent of the polyepoxy compound of the component (a). It is desired to be used.

The method of adding the component (b) to the component (a) in advance can be performed by a known method. The reaction uses an epoxy ring opening catalyst as needed,
The reaction is carried out by using a suitable solvent and stirring under heating at 30 to 200 ° C., if necessary, under reduced pressure. As the reaction solvent, for example, acetone, methyl ethyl ketone, ketones such as isobutyl ketone, ethyl acetate, esters such as butyl acetate, dioxane, ethers such as tetrahydrofuran, toluene, aromatic hydrocarbons such as xylene, dimethylformamide, Examples thereof include amides such as dimethylacetamide, sulfoxides such as dimethylsulfoxide, and a mixed solvent of two or more of these.

As the above-mentioned epoxy ring-opening catalyst, for example,
Tertiary amines such as benzyldimethylamine; quaternary ammonium salts such as tetramethylammonium chloride; phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine; ethyltriphenylphosphonium bromide; Examples include phosphonium salts such as phenylphosphonium chloride, and imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole.

Here, the amount of the epoxy ring-opening catalyst used is:
When a polyepoxy compound other than the component (a), the component (b), and the component (a) is used, the total amount of the polyepoxy compound other than the component (a) is 0.1 part by weight to 100 parts by weight.
001 to 10 parts by weight, preferably 0.01 to 1 part by weight.

The epoxy resin composition of the present invention can be used by dissolving or dispersing in water or an organic solvent. Examples of the organic solvent include acetone, methyl isopropyl ketone, propylene glycol monomethyl ether, propylene glycol Ketones such as monomethyl ether acetate and cyclohexanone; ethers such as tetrahydrofuran, 1,2-dimethoxyethane and 1,2-diethoxyethane; ethyl acetate and acetic acid n
Esters such as -butyl; alcohols such as iso- or n-butanol, iso- or n-propanol and amyl alcohol; aromatic hydrocarbons such as benzene, toluene and xylene; turpentine oil, D-limonene, pinene and the like. Terpene hydrocarbon oils; mineral spirits,
Paraffin solvents such as Swazol # 310 (Maruzen Petrochemical Co., Ltd.) and Solvesso # 100 (Exxon Chemical Co., Ltd.); halogenated aliphatic hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene and methylene chloride; chlorobenzene and the like Halogenated aromatic hydrocarbons; aniline, triethylamine, pyridine, dioxane, acetic acid,
Acetonitrile, carbon disulfide and the like. These solvents can be used alone or arbitrarily as a mixed solvent of two or more kinds.

Further, the epoxy resin composition of the present invention comprises:
Usually, a curing agent for epoxy resin can be used,
Examples of the curing agent include polyalkylpolyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; and fats such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane and isophoronediamine. Cyclic polyamines; and aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone. Further, these polyamines and various epoxy resins such as glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, and glycidyl esters of carboxylic acid are used in a conventional manner. A modified polyepoxy produced by reacting the compound with a carboxylic acid such as phthalic acid, isophthalic acid, dimer acid, or the like, by an ordinary method; These polyamines and aldehydes such as formaldehyde and phenols having at least one aldehyde-reactive site in the nucleus such as phenol, cresol, xylenol, tert-butylphenol, and resorcinol; Such as Mannich-modified product is prepared by reacting in a conventional manner and the like. Further, latent curing agents such as dicyandiamide, acid anhydrides and imidazoles can be used.

Further, the epoxy resin composition of the present invention includes:
If necessary, a curing catalyst; monoglycidyl ethers,
Reactive or non-reactive diluents (plasticizers) such as dioctyl phthalate, dibutyl phthalate, benzyl alcohol, and coal tar; glass fiber, carbon fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, Talc, silica, finely divided silica, titanium dioxide, carbon black, graphite,
Fillers or pigments such as iron oxide and bituminous substances; γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β
-(Aminoethyl) -N'-β- (aminoethyl) -γ
-Aminopropyltriethoxysilane, γ-anilinopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, vinyltriethoxysilane, N-β- Silane coupling agents such as (N-vinylbenzylaminoethyl) -γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane; candelilla Wax, carnauba wax, wax, wax, wax, bee wax, lanolin, whale wax, montan wax, petroleum wax, fatty acid wax, fatty acid ester,
Lubricants such as fatty acid ethers, aromatic esters and aromatic ethers; thickeners; thixotropic agents; antioxidants;
Light stabilizers; UV absorbers; Flame retardants; Defoamers; Rust inhibitors; may contain conventional additives such as colloidal silica and colloidal alumina, and may be adhesive resins such as xylene resins and petroleum resins. Can also be used in combination.

The epoxy resin composition of the present invention is used for copper-clad laminates used for electronic circuit boards, sealing materials, casting materials, adhesives, electric insulating paints, etc .; Can be suitably used for various applications requiring

[0053]

The following examples illustrate the epoxy resin composition of the present invention in more detail, but the present invention is not limited to these examples.

Production Example 1 (Production of Compound No. 7) After dissolving 114 parts by weight of bisphenol A and 110 parts by weight of triethylamine in 200 parts by weight of methyl ethyl ketone, 297 parts by weight of bis (2,6-dimethylphenyl) phosphoric acid chloride was heated at a temperature of 25%. While maintaining the temperature at ３０30 ° C., the mixture was added dropwise to perform esterification. After completion of dropping, at 25-30 ° C
Allowed to react for hours. After completion of the reaction, salts formed in the system were removed by filtration, and the filtrate was washed with acidic hydrochloric acid and then desolvated to obtain the desired product (hydroxyl equivalent 485, phosphorus content 5.95%). Other phosphorus-containing compounds used in Examples were produced in the same manner.

Production Example 2 (Production of polyepoxy compound) A polyepoxy compound (bisphenol A) was placed in a flask equipped with a reflux device, a stirrer, a pressure reducing device and a dropping device.
Diglycidyl ether, epoxy equivalent 475, n = 2.
1, EP-1) 475 parts by weight, epichlorohydrin 92
5 parts by weight and tetramethylammonium chloride 5
Charge 1 part by weight of a 0% by weight aqueous solution, and add 48%
108 parts by weight of an aqueous solution of sodium hydroxide are put in advance. An aqueous sodium hydroxide solution was added dropwise at reflux at an internal temperature of 50 to 60 ° C. at 60 torr over 2 hours, and water was simultaneously removed by azeotropic distillation. The produced salt and unreacted sodium hydroxide were adsorbed and filtered using an alkali adsorbent (Kyowa Chemical Co., Ltd. Kyoward 600S) and a filter aid Celite to obtain an epichlorohydrin solution. Epichlorohydrin was removed from this solution at 120 ° C. and 10 torr, and an epoxy equivalent of 265 (G [in the general formula (I),
X = glycidyl group ratio = 86%) to obtain a polyepoxy compound (EP-2).

Production Example 3 (Production of Polyepoxy Compound) A polyepoxy compound (bisphenol A) was placed in a flask equipped with a reflux device, a stirring device, a decompression device, and a dropping device.
Diglycidyl ether, epoxy equivalent 650, n = 3.
4, EP-3) 650 parts by weight, epichlorohydrin 46
3 parts by weight and tetramethylammonium chloride 5
Charge 1 part by weight of a 0% by weight aqueous solution, and add 48%
85 parts by weight of an aqueous solution of sodium hydroxide is added. The aqueous solution of sodium hydroxide is refluxed at an internal temperature of 50 to 60 ° C.
The solution was added dropwise at 0 torr over 2 hours, and at the same time, water was removed by azeotropic distillation. Using an alkali adsorbent (Kyowa Chemical Co., Ltd. Kyoward 600S) and a filter aid Celite, the generated salt and unreacted sodium hydroxide are adsorbed and filtered,
An epichlorohydrin solution was obtained. This solution is heated at 120 ° C.
Epichlorohydrin was removed at 10 torr and a polyepoxy compound (EP having an epoxy equivalent of 340 (G = 65%)) was obtained.
-4) was obtained.

Production Example 4 100 parts by weight of polyepoxy compound (EP-2) and 20 parts by weight of compound No. 7 were uniformly dissolved at 120 to 140 ° C. Thereafter, the temperature was lowered to 100 ° C., and ethyltriphenylphosphonium bromide (ETPPBr) 0.5
The mixture was reacted at 140 to 150 ° C. for 2 hours to obtain a phosphorus-containing polyepoxy compound (P-EP-1) having an epoxy equivalent of 395 and a phosphorus content of 1.0% by weight.

Production Example 5 100 parts by weight of a polyepoxy compound (EP-2) and 40 parts by weight of Compound No. 740 were uniformly dissolved at 120 to 140 ° C. Thereafter, the temperature was lowered to 100 ° C., and ethyltriphenylphosphonium bromide (ETPPBr) 0.5
The mixture was reacted at 140 to 150 ° C. for 2 hours to obtain a phosphorus-containing polyepoxy compound (P-EP-2) having an epoxy equivalent of 520 and a phosphorus content of 2.1% by weight.

Production Example 6 100 parts by weight of a polyepoxy compound (EP-2) and 15 parts by weight of Compound No. 7 were uniformly dissolved at 120 to 140 ° C. Thereafter, the temperature was lowered to 100 ° C., and ethyltriphenylphosphonium bromide (ETPPBr) 0.5
The mixture was reacted at 140 to 150 ° C. for 2 hours to obtain a phosphorus-containing polyepoxy compound (P-EP-3) having an epoxy equivalent of 360 and a phosphorus content of 0.7% by weight.

Production Example 7 100 parts by weight of polyepoxy compound (EP-2) and 40 parts by weight of compound No. 7 were uniformly dissolved at 120 to 140 ° C. Thereafter, the temperature was lowered to 100 ° C., and ethyltriphenylphosphonium bromide (ETPPBr) 0.5
Parts by weight and mixed to obtain a phosphorus-epoxy blend (P-EP-) having an epoxy equivalent of 385 and a phosphorus content of 2.0% by weight.
4) was obtained.

Production Example 8 100 parts by weight of a polyepoxy compound (EP-2) and 40 parts by weight of Compound No. 7 were uniformly dissolved at 120 to 140 ° C. to obtain a phosphorus having an epoxy equivalent of 385 and a phosphorus content of 2.0% by weight. -An epoxy blend product (P-EP-5) was obtained.

Production Example 9 Polyepoxy compound (EP-2) 50 parts by weight, polyepoxy compound (orthocresol novolak epoxy resin, epoxy equivalent 210, softening point 55 ° C., EP-5) 5
0 parts by weight and 40 parts by weight of Compound No. 7
Dissolved uniformly at 40 ° C. Thereafter, the temperature was lowered to 100 ° C., and ethyltriphenylphosphonium bromide (ET
PPBr) 0.5 part by weight was added and mixed, and an epoxy equivalent of 4 was added.
15. A phosphorus-epoxy blend (P-EP-6) having a phosphorus content of 2.1% by weight was obtained.

Production Example 10 100 parts by weight of a polyepoxy compound (EP-4) and 40 parts by weight of Compound No. 7 were uniformly dissolved at 120 to 140 ° C. Thereafter, the temperature was lowered to 100 ° C., and ethyltriphenylphosphonium bromide (ETPPBr) 0.5
The mixture was reacted at 140 to 150 ° C. for 2 hours to obtain a phosphorus-containing polyepoxy compound (P-EP-7) having an epoxy equivalent of 685 and a phosphorus content of 2.1% by weight.

Production Example 11 100 parts by weight of a polyepoxy compound (EP-2) and 40 parts by weight of Compound No. 840 were uniformly dissolved at 120 to 140 ° C. Thereafter, the temperature was lowered to 100 ° C., and ethyltriphenylphosphonium bromide (ETPPBr) 0.5
The mixture was reacted at 140 to 150 ° C. for 2 hours to obtain a phosphorus-containing polyepoxy compound (P-EP-8) having an epoxy equivalent of 540 and a phosphorus content of 2.2% by weight.

Production Example 12 100 parts by weight of polyepoxy compound (EP-2) and 40 parts by weight of Compound No. 10 were uniformly dissolved at 120 to 140 ° C. After that, the temperature was lowered to 100 ° C., and ethyltriphenylphosphonium bromide (ETPPBr) was added to a pH of 0.1.
5 parts by weight, and reacted at 140 to 150 ° C. for 2 hours,
A phosphorus-containing polyepoxy compound (P-EP-9) having an epoxy equivalent of 500 and a phosphorus content of 2.1% by weight was obtained.

Production Example 13 100 parts by weight of a polyepoxy compound (EP-2) and 40 parts by weight of Compound No. 11 were uniformly dissolved at 120 to 140 ° C. After that, the temperature was lowered to 100 ° C., and ethyltriphenylphosphonium bromide (ETPPBr) was added to a pH of 0.1.
5 parts by weight, and reacted at 140 to 150 ° C. for 2 hours,
A phosphorus-containing polyepoxy compound (P-EP-10) having an epoxy equivalent of 520 and a phosphorus content of 2.1% by weight was obtained.

Production Example 14 100 parts by weight of polyepoxy compound (EP-1) and 40 parts by weight of compound No. 740 were uniformly dissolved at 120 to 140 ° C. Thereafter, the temperature was lowered to 100 ° C., and ethyltriphenylphosphonium bromide (ETPPBr) 0.5
The mixture was reacted at 140 to 150 ° C. for 2 hours to obtain a phosphorus-containing polyepoxy compound (HP-EP-1) having an epoxy equivalent of 1200 and a phosphorus content of 2.1% by weight.

Production Example 15 100 parts by weight of a polyepoxy compound (EP-2) and 40 parts by weight of a phosphorus-containing compound represented by the following formula
A phosphorus-epoxy blend product (HP-EP) which is uniformly dissolved at 0 ° C. and has an epoxy equivalent of 390 and a phosphorus content of 2.2% by weight.
-2) was obtained.

Production Example 16 100 parts by weight of a polyepoxy compound (EP-1) and 40 parts by weight of a phosphorus-containing compound represented by the following formula
A phosphorus-epoxy blend product (HP-EP) which is uniformly dissolved at 0 ° C. and has an epoxy equivalent of 390 and a phosphorus content of 2.2% by weight.
-3) was obtained.

[0070]

Embedded image

Example 1 The following evaluation test was carried out using the phosphorus-containing polyepoxy compound and the phosphorus-epoxy blend obtained in the above Production Examples. The results are shown in Tables 1, 2 and 3.

(Flame Retardancy) Using the compounds shown in Tables 1, 2 and 3, test specimens in accordance with the UL-94 standard were prepared under the conditions of 50 ° C. × 1 hour and 180 ° C. × 30 minutes. And UL-
The flame retardancy was evaluated according to the 94 standard.

(Glass transition temperature [Tg]) Using the formulations shown in Tables 1, 2 and 3, 50 ° C. × 1 hour, 18 hours
A test piece was prepared under the conditions of 0 ° C. × 30 minutes, and the glass transition temperature was measured by a Vibron dynamic viscoelasticity tester.

(Alkali Resistance) The formulations shown in Tables 1, 2 and 3 were applied to tinplates, and heated at 50 ° C. × 1 hour for 18 hours.
A coating film was formed under the conditions of 0 ° C. × 30 minutes. The tinplate on which the coating film was formed was placed in a 10% by weight sodium hydroxide solution for 8 hours.
The coating was immersed at 0 ° C. for 24 hours, and the coating film was visually evaluated. The evaluation criteria were: no change, 剥離, slight peeling, and large peeling x.

[0075]

[Table 1]

[0076]

[Table 2]

[0077]

[Table 3]

As is clear from the above results, when the polyepoxy compound is used alone (Comparative Examples 1-4 and 1-5), it has no self-extinguishing property. When a general-purpose bisphenol-type epoxy resin is combined with a phosphorus-containing compound different from the component (b) of the present invention (Comparative Example 1)
In the case of -3), the flame retardancy is improved to V-0, but only those having extremely poor physical properties such as alkali resistance can be obtained. When a general-purpose bisphenol-type epoxy resin is combined with the phosphorus-containing compound of the present invention (Comparative Example 1-1), the polyepoxy compound of the component (A) of the present invention and the (B) of the present invention are also used.
When a phosphorus compound different from the component is combined (Comparative Example 1
-2) Similarly, the flame retardancy is improved to V-0,
Only extremely poor physical properties such as alkali resistance can be obtained.

On the other hand, by using the polyepoxy compound of the component (a) of the present invention in combination with the phosphorus-containing compound of the component (b), the flame retardancy is improved to V-0, and the alkali resistance and the like are improved. (See Examples 1-1 to 1-12.)

[0080]

The epoxy resin composition of the present invention has a low generation of harmful halogen compounds upon burning, has excellent flame retardancy, and has excellent physical properties of a cured product. It can be suitably used for the intended use.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hirofumi Waki F-term (reference) in Asahi Denka Kogyo Co., Ltd. 20-20 Showa-numa, Shobu-cho, Minami-Saitama-gun, Saitama 4J036 AA02 AD01 AD08 AD20 AK19 DA01 DB05 DB30 DD07 JA01 JA06

Claims (5)

[Claims] 1. A polyepoxy compound represented by the following general formula (I) and (b) an aromatic phosphinate, an aromatic phosphonate and an aromatic phosphoric acid having at least one phenolic hydroxyl group: An epoxy resin composition comprising at least one phosphorus-containing compound selected from the group consisting of esters. Embedded image (Wherein, n represents a number from 0.1 to 20, Z is a direct bond,
X represents an alkylidene group having 1 to 4 carbon atoms or SO ₂ ; X represents a hydrogen atom or a glycidyl group;
0% or more represents a glycidyl group. ) (2) A phosphorus-containing compound represented by the following general formula (I)
The epo according to claim 1, which is a phosphorus-containing compound represented by I).
Xy resin composition. Embedded image(Where m represents a number of 1 to 5, X₁And X_TwoIs -O
-, -N (R_Three)-Or a direct bond;₁and
R_TwoRepresents an alkyl group, an aryl group or -Ar-OH
Then R_ThreeRepresents a hydrogen atom or an alkyl group, or
Is R_ThreeIs R₁Or R_TwoForms a ring with
Ar represents a group represented by the following formula:
You. )(Where R_Four~ R₁₆Are each independently a hydrogen atom,
Y represents a direct bond when p = 0.
-CH_Two-, -C (CH_Three)_Two-Or -SO _Two−
And when p = 1, -CR₁₇=, R₁₇Is hydrogen
Represents an atom or an alkyl group, and l represents 0 to 2. ) 3. The polyepoxy compound of the component (a) is a polyepoxy compound in which n is 1 to 15 in the general formula (I) and 30% or more of X is a glycidyl group.
Or the epoxy resin composition according to 2. 4. The polyepoxy compound 100 of the component (a)
The epoxy resin composition according to any one of claims 1 to 3, wherein the epoxy resin composition is used in an amount of 1 to 100 parts by weight based on the weight of the component (b). 5. The epoxy resin composition according to claim 1, further comprising an epoxy ring-opening catalyst.