JP2000080251A - Phosphorus-modified flame-retardant epoxy resin composition and its production and molded product and laminate using the phosphorus-modified flame-retardant epoxy resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having good flame retardancy, capable of being easily produced at a low cost and having excellent heat resistance and flame resistance by mixing an epoxy resin with a specific phosphorus- containing compound and a curing agent. SOLUTION: This phosphorus-modified flame-retardant epoxy resin composition having a phosphorus content of 0.5-13 wt.% and preferably not containing a halogen comprises (A) an epoxy resin, (B) a phosphorus-containing compound of formula I [R1 is a compound containing two or more phenolic OH groups; (n) is 0-3; R2 is a 1-8C alkyl, cyclohexyl, cyclopentyl, an aryl or the like, or R2 forms a ring together with P; (m) is 0 or 1] or formula II preferably in an amount of 10-100 pts.wt. per 100 pts.wt. of the component A, (C) a curing agent in a (component A + component B)/(component C) weight ratio of (1-80)/1, and, if necessary, (D) 5-300 pts.wt. of (i) one or more other components and/or (ii) a filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a phosphorus-modified flame-retardant epoxy resin composition containing an epoxy resin, a phosphorus-containing compound and a curing agent, a method for producing the same, and a method for using the same.

[0002]

BACKGROUND OF THE INVENTION Epoxy resins are currently used in the production of molding compositions and coating materials having good thermal, mechanical and electrical properties. They are suitable for encapsulation of electrical and electronic components and are suitable for dipping and impregnation processes. In the field of electrical engineering, the epoxy resin composition used is mainly subjected to a flame retarding treatment.

[0003] Generally, epoxy resin compositions are flame-retarded using a bromine-containing aromatic compound, particularly tetrabromobisphenol A. With fully brominated flame retardants, a bromine content of about 20% is required to ensure that the molding composition is self-extinguishing. Antimony trioxide is often used as a synergist. In the event of a fire, hydrogen bromide will be released, which can cause corrosion damage. Under adverse conditions, polybrominated dibenzodioxins and furans may be formed. Accordingly, there has been a demand for an epoxy resin composition that can achieve the required flame retardancy without adding a brominated compound.

[0004] For the flame retarding treatment of epoxy resin compositions, fillers having a fire extinguishing action, for example, aluminum oxide hydrate (DE-A 35 40 524) have been proposed. Further, by adding ammonium polyphosphate alone or in combination with aluminum oxide hydrate, appropriate flame retardancy can be obtained. Instead of ammonium polyphosphate, red phosphorus can also be used (DE-A 17 45 796).

[0005] Numerous liquid organophosphorus compounds have been proposed as flame retardant plastic additives. However, a disadvantage of these systems lies in the significant "plasticizing effect" of these additives. In the case of a cured epoxy resin, the plasticizing effect appears in a remarkable decrease in the glass transition temperature, and further, the drillability and abrasion of the molded product are reduced.

Although epoxy resins can be flame retarded using epoxide-functional phosphonates,
The synthesis of phosphonates becomes very complicated. Furthermore, phosphorus-modified epoxy resins can be obtained by reacting polyepoxide compounds with phosphonic or phosphinic anhydrides and exhibit significantly better flame retardancy. Phosphorus-containing dicarboxylic acids or phosphorus-containing carboxylic anhydrides can be obtained industrially more easily than phosphonic anhydrides, which are used, for example, for flame retarding polyester fibers. Furthermore, it has good flame retardancy,
A phosphorus-modified epoxy resin composition which can be easily and inexpensively manufactured and whose phosphorus content can be changed is disclosed in JP-A-1998-63636. However, the disclosed resin skeleton has a high proportion of fatty chains and may be inferior in heat resistance and flame retardancy.

[0007]

An object of the present invention is to provide a phosphorus-modified flame-retardant epoxy resin which has good flame retardancy, can be easily and inexpensively manufactured, and has excellent heat resistance and flame retardancy. It is to provide a composition.

[0008]

This object is achieved by the following chemical structural formula (I)

[0009]

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This is achieved by a phosphorus-containing epoxy resin composition of the type mentioned at the outset containing a phosphorus-containing compound represented by the formula:

The phosphorus-modified flame-retardant epoxy resin composition is preferably used in an amount of 1 to 100 parts by weight of the epoxy resin.
0 to 100 parts by weight of a phosphorus-containing compound represented by the chemical structural formula (I) or (II), wherein the entire epoxy resin and the phosphorus-containing compound represented by the chemical structural formula (I) and a curing agent Is (1 to 80): 1. This phosphorus-modified flame-retardant epoxy resin composition preferably does not contain halogen.

This phosphorus-modified flame-retardant epoxy resin composition preferably contains 5 to 300 parts by weight of a phosphorus-free epoxy resin. The phosphorus-modified flame-retardant epoxy resin composition preferably contains 5 to 300 parts by weight of other components and / or fillers. Preferably, the filler is an inorganic filler, and further, the inorganic filler is a hydroxide. This phosphorus-modified flame-retardant epoxy resin composition,
It preferably contains 0.5 to 13% by weight of phosphorus.

It is particularly preferable that the phosphorus-modified flame-retardant epoxy resin composition contains 1 to 6% by weight of phosphorus. The phosphorus-modified flame-retardant epoxy resin composition preferably contains an accelerator. This phosphorus-modified flame-retardant epoxy resin composition has the following chemical structural formula (II)

[0014]

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It is preferable to contain a compound represented by the formula: The present invention also provides a method for producing a phosphorus-modified flame-retardant epoxy resin composition containing an epoxy resin, a phosphorus-containing compound and a curing agent, wherein the phosphorus-containing compound represented by the chemical structural formula (I) and the epoxy resin are cured. The present invention also relates to a method for producing a phosphorus-modified flame-retardant epoxy resin composition using the agent to produce a phosphorus-modified flame-retardant epoxy resin composition, and further relates to a phosphorus-modified flame-retardant epoxy resin composition containing an epoxy resin, a phosphorus-containing compound and a curing agent In a method for producing a flame-retardant epoxy resin composition, an epoxy resin is reacted with a phosphorus-containing compound represented by a chemical structural formula (I) in a first reaction step, and then a reaction is formed using a curing agent in a second reaction step. To a phosphorus-modified flame-retardant epoxy resin composition.

This first reaction step can be carried out without solvent or in a solvent. When carried out in a solvent, aprotic polar solvents that can be used include N-methylpyrrolidone, dimethylformamide, tetrahydrofuran, dioxane, dialkyl ether, glycol ether, ketone and / or ester, other methoxypropanol, halogenated carbon Hydrogen, aliphatic, cycloaliphatic and / or aromatic hydrocarbons, respectively, or mixtures thereof, can be used as the solvent. Further, after the first reaction means is completed, a solvent may be added for cooling.

The reaction in the first reaction stage is preferably carried out between 0 and +
It is performed at a temperature of 250 ° C. This reaction is 100-200
It is particularly preferred to work at a temperature of ° C. The reaction of the second reaction stage is preferably carried out at a temperature of from 0 to 200C. It is particularly preferred to carry out this reaction at a temperature of from 100 to 180 ° C. The present invention also relates to a method of using a novel epoxy resin composition for a molded article, a molding composition, a coating material, a resin-coated copper foil or a laminate.

The present invention further relates to prepregs and laminates based on inorganic or organic reinforcing materials in the form of fibers, nonwovens or woven fabrics, produced using the epoxy resin compositions obtained.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION

The phosphorus-containing compound used in the present invention has the following chemical structural formula (I)

[0021]

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A compound having a reactivity with an epoxy resin, wherein R1 is a compound containing two or more phenolic OH groups, n is an integer of 0 to 3,
Is, for example, the following chemical structural formula group A

[0023]

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And the like. In addition, R2
Is a linear or branched alkyl group having 1 to 8 carbon atoms, a cyclohexyl group, a cyclopentyl group or an aryl group or an alkyl or alkoxy-substituted alkyl group or an aryl group having 1 to 18 carbon atoms. Yes, R2 may form a ring with the P atom,
m is 0 or 1, for example, the following chemical structural formula group B

[0025]

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Are shown. The phosphorus compound is obtained by a reaction between phosphine oxide and benzoquinone or a reaction between phosphine oxide and a polyfunctional phenol having an allyl group.

The halogen-free epoxide compounds (hereinafter also referred to as polyepoxide compounds) used in the present invention can be saturated or unsaturated and include aliphatic, alicyclic, aromatic and / or heterocyclic compounds. Can be an expression. In addition, they may contain substituents which do not cause disturbing side reactions under the mixing or reaction conditions, such as alkyl or aryl substituents, ether groups and the like. Mixtures of different polyepoxide compounds can also be used. The average molecular weight Mn of these polyepoxide compounds can be up to about 9000, but is generally about 150-4000.

These polyepoxide compounds include, for example, polyhydric, preferably dihydric alcohols, phenols, hydrogenation products of these phenols and / or novolaks (mono- or polyhydric phenols in the presence of an acidic catalyst). Polyglycidyl ethers based on phenols and / or cresols and aldehydes, preferably formaldehyde), which are known in the art, for example by reacting a polyol with epichlorohydrin. can get.

Examples of suitable polyhydric phenols are resorcinol, hydroquinone, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), a mixture of isomers of dihydroxydiphenylmethane (bisphenol F),
4'-dihydroxydiphenylcyclohexane, 4,4'-dihydroxy-3,3'-dimethyldiphenylpropane, 4,4'-
Dihydroxybiphenyl, 4,4'-dihydroxybenzophenone, 1,1-bis (4-hydroxyphenyl) ethane, 1,
1'-bis (4-hydroxyphenyl) isobutane, 2,2-bis (4-hydroxytert-butylphenyl) propane, bis (2-hydroxynaphthyl) methane, 1,5-dihydroxynaphthalene, tris (4-hydroxyphenyl ) Methane, 1,
1'-bis (4-hydroxyphenyl) ether.

Here, bisphenol A and bisphenol F are preferred. Polyglycidyl ethers of polyhydric aliphatic alcohols are also suitable as polyepoxide compounds. Preferred examples of such polyhydric alcohols are 1,
4-butanediol, 1,6-hexanediol, polyalkylene glycol, glycerol, trimethylolpropane, 2,2-bis (4-hydroxycyclohexyl) propane and pentaerythritol.

Other suitable polyepoxide compounds include:
(Poly) glycidyl esters, which convert epichlorohydrin or similar epoxy compounds with aliphatic, cycloaliphatic or aromatic polycarboxylic acids such as oxalic acid, adipic acid, glutaric acid, phthalic acid, isophthalic acid, It is obtained by reacting terephthalic acid, tetrahydrophthalic acid or hexahydrophthalic acid, 2,6-naphthalenedicarboxylic acid and dimerized fatty acids. Examples of these are diglycidyl terephthalate and diglycidyl hexahydrophthalate.

A polyepoxide compound containing epoxide groups randomly arranged along a molecular chain, comprising emulsification using an olefinically unsaturated compound containing these epoxide groups, for example, a glycidyl ester of acrylic acid or methacrylic acid. Polyepoxide compounds which can be produced by copolymerization can be used advantageously in some cases.

Other examples of polyepoxide compounds which can be used are those based on heterocyclic systems,
For example, hydantoin epoxy resin, triglycidyl isocyanurate and / or its oligomer, triglycidyl-p-aminophenol, triglycidyl-p-aminodiphenyl ether, tetraglycidyldiaminodiphenylmethane, tetraglycidyldiaminodiphenylether, tetrakis (4-glycidyloxyphenyl) ethane , Urazole epoxide, uracil epoxide, and oxazolidinone-modified epoxy resin. Other polyepoxides are aromatic amines, such as aniline, such as
N, N-diglycidylaniline, diaminodiphenylmethane and N, N'-dimethylaminodiphenylmethane or N,
It is based on N'-dimethylaminodiphenyl sulfone. Another suitable polyepoxide compound is He
"Handbook of Epoxy R by nry Lee and Kris Neville
esins ", McGraw-Hill Book Company, 1967, Henry Lee
Paper "Epoxy Resins", American Chemical Societ
y, 1970, Wagner / Sarx, "Lackkunstharze", CarlHanse
r Verlag (1971), 5th edition, 174 ff., "Angew. Mak
romol. Chemie ", Vol. 44 (1975), pages 151 to 163,
It is described in DE-A 27 57 733 and EP-A 0 384 939.

The polyepoxide compounds preferably used are bisglycidyl ethers based on bisphenol A, bisphenol F and bisphenol S (reaction products of these bisphenols with epichloro (halo) hydrin) or oligomers thereof, phenol-
Polyglycidyl ethers of formaldehyde and / or cresol-formaldehyde novolak, and diglycidyl esters of phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid and / or hexahydrophthalic acid and trimellitic acid, aromatic amines and heterocyclic nitrogen bases N-glycidyl compounds such as N,
N-diglycidylaniline, N, N, O-triglycidyl-p-aminophenol, triglycidylisocyanurate and N, N, N ', N'-tetraglycidylbis (p-aminophenyl) methane, hydantoin epoxy resin and Arachid
(aracid) epoxy resin, and polyhydric aliphatic alcohol,
For example, di- and polyglycidyl compounds of 1,4-butanediol, trimethylolpropane and polyalkylene glycol.

Further, oxazolidinone-modified epoxy resins are also suitable. These compounds are known ("Ange
w. Makromol. Chem. ", Vol. 44 (1975), pages 151 to
163, and US Patent No. 3,334,110). A preferred example of these is the reaction product of bisphenol A diglycidyl ether with diphenylmethane diisocyanate (in the presence of a suitable accelerator). For the production of novel coating compositions, polyepoxy resins are:
It can be present alone or as a mixture. As used herein, the term "curing" generally refers to the conversion of a soluble, fusible polyepoxide from a soluble, fusible polyepoxide to a solid, insoluble, infusible, three-dimensionally cross-linked product with concomitant modeling. For example, providing impregnated structures, coatings and adhesive bonds.

Examples of curing agents that can be used include aliphatic, cycloaliphatic, aromatic and heterocyclic amines such as bis (4-aminophenyl) methane, aniline-formaldehyde resin, bis (4-aminophenyl) ) Sulfone, ethylenediamine, 1,3-propanediamine, hexamethylenediamine, diethylenetriamine, triethylenetetraamine, 2,2,4-trimethyl-1,6-hexanediamine, m-
Xylylenediamine, bis (4-aminocyclohexyl)
Methane, 2,2-bis (4-aminocyclohexyl) propane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine), polyamidoamine, polyphenols such as hydroquinone, resorcinol, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and phenol-aldehyde resins, polycarboxylic acids and their anhydrides such as phthalic anhydride,
Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and pyromellitic dianhydride. In addition, it is also possible to use catalytic hardeners, for example cyanoguanidine, or Friedel-Crafts catalysts, for example boron trifluoride.

When using an amine as a curing agent,
They are usually from 0.35 to 1.2 per epoxide equivalent.
Used in an amount of 5 equivalents. In the case of polycarboxylic acid or its anhydride, 0.4 to 1.1 per epoxide equivalent
Equivalents are used. Particularly suitable accelerators are imidazole derivatives such as 2-methylimidazole, 2-phenylimidazole and 2-heptadecylimidazole, and also phosphines, metal soaps and acetylacetonate.

Suitable reactive diluents are, for example, low molecular weight mono- or polyfunctional alcohols which react with epichlorohydrin. By changing the equivalent ratio of the polyepoxide compound to the phosphorus-containing dicarboxylic acid or the phosphorus-containing carboxylic anhydride, the phosphorus content of the novel resin can be adjusted. The equivalent ratio is preferably from 1: 0.1 to 1: 0.8, particularly preferably from 1: 0.1 to 1: 0.4. The reaction of the epoxy resin with a phosphorus-containing dicarboxylic acid or a phosphorus-containing carboxylic anhydride results in a phosphorus-modified epoxy resin that is still fusible and / or soluble, which may be stored even in solution. It is stable and easy to handle.

If solvents are used, they are aprotic, preferably polar. For example, N-methylpyrrolidone, dimethylformamide, ether, diethyl ether, tetrahydrofuran, dioxane, 1 to
Ethyl glycol ether, propylene glycol ether, butyl glycol ether, ketone, acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, ester, ethyl Acetate, butyl acetate, ethylene glycol acetate and methoxypropyl acetate, methoxypropanol, other halogenated hydrocarbons and alicyclic and / or aromatic hydrocarbons, among which hexane, heptane,
Solvents such as cyclohexane, toluene and dixylene are preferred. These solvents can be used alone or as a mixture thereof.

The epoxy resin composition is preferably reinforced with glass cloth or glass fiber. This epoxy resin composition is a filler, for example, melamine, a flame retardant of a phosphorus component, silica, talc, quartz powder as an inorganic filler,
Aluminum oxide, aluminum oxide hydrate, aluminum hydroxide, magnesium hydroxide, or the like can be filled, and the phosphorus content can be adjusted by the amount of these fillers. This epoxy resin composition can be used for surface coating. These can be used as an encapsulating material for an electronic component, and for a laminate, a copper foil with resin, a laminate, and an adhesive.

[0041]

The following examples illustrate the invention. In Examples 1 to 10, a phosphorus compound represented by the following chemical structural formula (II) was used.

[0042]

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Example 1 A 1 L flask was charged with a phosphorus compound (10 (2,5-dihydroxyphenyl) -10H-9oxa-10-phosphaphenanthrene-10-oxide) represented by the chemical structural formula (II). (HCA-HQ, manufactured by Sanko Co., Ltd.) 161
g, bisphenol A type epoxy resin (EPICLON850S, manufactured by Dainippon Ink and Chemicals, Inc.) (380 g) and triphenylphosphine (0.5 g) were added and heated at 148 ° C. for 1 hour to obtain a brownish transparent liquid. The liquid material was applied on a fluororesin sheet and cooled to obtain a solidified material.
The solidified product is pulverized to obtain a white resin powder A. 54 g of the obtained white resin powder A and 9.5 g of a phenol curing agent having a triazine skeleton (KA-7752, manufactured by Dainippon Ink and Chemicals, Inc.) were mixed well on a hot plate at 170 ° C. to obtain a plate-like gel. Was. The gelled product was sandwiched between iron plates provided with 2 mm spacers and heated at 170 ° C. for 70 minutes under a pressure of 30 kg / cm ² to obtain a plate-like cured product. (Example 2) In a 300 mL beaker, a phosphorus compound represented by the chemical structural formula (II) (10 (2,5-dihydroxyphenyl)-
16 g of 10H-9 oxa-10-phosphaphenanthrene-10-oxide (HCA-HQ, manufactured by Sanko Co., Ltd.), 38 g of a bisphenol A type epoxy resin (YD128, manufactured by Toto Kasei), a phenol curing agent having a triazine skeleton (KA -7052, manufactured by Dainippon Ink and Chemicals, Inc.) and 0.1 g of triphenylphosphine, and mixed well. Thereafter, the mixture is poured onto a hot plate at 170 ° C., and a plate-like gel is obtained while mixing well. This gel was sandwiched between iron plates provided with 2 mm spacers, and pressed at 30 kg / cm ² at 170 ° C.
Heating was performed for 0 minutes to obtain a plate-shaped cured product. (Example 3) In a 300 mL beaker, a phosphorus compound represented by the chemical structural formula (II) (10 (2,5-dihydroxyphenyl)-
16 g of 10H-9 oxa-10-phosphaphenanthrene-10-oxide (HCA-HQ, manufactured by Sanko Co., Ltd.) and a 75% MEK solution of a gresol novolac epoxy resin (YDCN704-EK)
75, manufactured by Toto Kasei), 1 g of dicyandiamide and 0.1 g of triphenylphosphine are added and mixed well. Thereafter, the mixture is poured onto a hot plate at 170 ° C., and a plate-like gel is obtained while mixing well. This gel is sandwiched between iron plates with 2 mm spacers, and is 30 kg / cm ²
The mixture was heated at 170 ° C. for 70 minutes under the above pressure to obtain a plate-like cured product. (Example 4) In a 300 mL beaker, a phosphorus compound represented by the chemical structural formula (II) (10 (2,5-dihydroxyphenyl)-
16 g of 10H-9 oxa-10-phosphaphenanthrene-10-oxide (HCA-HQ, manufactured by Sanko Co., Ltd.), 42 g of triazine-based epoxy resin (TEPIC-S, manufactured by Nissan Chemical), 2 g of dicyandiamide, 0.1 g of triphenylphosphine And mix well. Thereafter, the mixture is poured onto a hot plate at 170 ° C., and a plate-like gel is obtained while mixing well. The gelled product was sandwiched between iron plates with a 2 mm spacer, and heated at 170 ° C. for 70 minutes at a pressure of 30 kg / cm ² to obtain a plate-shaped cured product. Example 5 A 1 L flask was charged with a phosphorus compound (10 (2,5-dihydroxyphenyl) -10 represented by the chemical structural formula (II)).
161 g of H-9 oxa-10-phosphaphenanthrene-10-oxide (HCA-HQ, manufactured by Sanko Co., Ltd.), 380 g of bisphenol A type epoxy resin (YD128, manufactured by Toto Kasei) and 0.5 g of triphenylphosphine were added. The mixture was heated at 145 ° C. for 2.5 hours to obtain a brownish transparent liquid.
39 g of dimethylformamide while cooling the liquid,
Methoxypropanol 129 g, methyl ethyl ketone 77 g
Was added to obtain a resin solution A having a solid content of 69 wt%. Then 1L
89 g of a 60% MEK solution of a phenolic curing agent having a triazine skeleton (KA7052-M60, manufactured by Dainippon Ink and Chemicals, Inc.), 55 g of methyl ethyl ketone, and a resin solution A3
A resin varnish was obtained by adding 50 g and stirring.
This resin varnish was impregnated into a glass cloth having a thickness of 200 μm and weighing 210 g / cm ² and dried at 160 ° C. for 5 minutes to obtain a prepreg. The resin content of the obtained prepreg was 40%. Three prepregs were stacked and heated and pressed at a temperature of 170 ° C. under a pressure of 30 kg / cm ² for 70 minutes to obtain a laminate. (Example 6) A phosphorus compound (10 (2,5-dihydroxyphenyl) -10 represented by the chemical structural formula (II)) was placed in a 1-L flask.
161 g of H-9 oxa-10-phosphaphenanthrene-10-oxide (HCA-HQ, manufactured by Sanko Co., Ltd.), 380 g of bisphenol A type epoxy resin (YD128, manufactured by Toto Kasei) and 0.5 g of triphenylphosphine were added. The mixture was heated at 165 ° C. for 1 hour to obtain a brownish transparent liquid. While cooling the liquid, 39 g of dimethylformamide, 129 g of methoxypropanol and 77 g of methyl ethyl ketone were added to obtain a resin solution A having a solid content of 69 wt%. Next, a phenol curing agent having a triazine skeleton was placed in a 1 L flask.
67 g of 60% MEK solution (KA7052-M60, manufactured by Dainippon Ink and Chemicals, Inc.), 50 g of methyl ethyl ketone, resin solution A35
A resin varnish was obtained by adding 0 g and stirring. This resin varnish was impregnated into a glass cloth having a thickness of 200 μm and weighing 210 g / cm ² , and dried at 160 ° C. for 5 minutes to obtain a prepreg. The resin content of the obtained prepreg was 40%. Three prepregs were stacked and heated and pressed at a temperature of 170 ° C. under a pressure of 30 kg / cm ² for 70 minutes to obtain a laminate. Example 7 A 1-L flask was charged with a phosphorus compound (10 (2,5-dihydroxyphenyl) -10 represented by the chemical structural formula (II)).
161 g of H-9 oxa-10-phosphaphenanthrene-10-oxide (HCA-HQ, manufactured by Sanko Co., Ltd.), 380 g of bisphenol A type epoxy resin (YD128, manufactured by Toto Kasei) and 0.5 g of triphenylphosphine were added. The mixture was heated at 145 ° C. for 2.5 hours to obtain a brownish transparent liquid.
39 g of dimethylformamide while cooling the liquid,
Methoxypropanol 129 g, methyl ethyl ketone 77 g
Was added to obtain a resin solution A having a solid content of 69 wt%. Then 1L
45 g of a 60% MEK solution (KA7052-M60, manufactured by Dainippon Ink and Chemicals, Inc.) and 45 g of methyl ethyl ketone, a resin solution A
A resin varnish was obtained by adding 350 g and stirring.
This resin varnish was impregnated into a glass cloth having a thickness of 200 μm and weighing 210 g / cm ² and dried at 160 ° C. for 5 minutes to obtain a prepreg. The resin content of the obtained prepreg was 40%. Three prepregs were stacked and heated and pressed at a temperature of 170 ° C. under a pressure of 30 kg / cm ² for 70 minutes to obtain a laminate. Example 8 A 1 L flask was charged with a phosphorus compound (10 (2,5-dihydroxyphenyl) -10 represented by the chemical structural formula (II)).
161 g of H-9 oxa-10-phosphaphenanthrene-10-oxide (HCA-HQ, manufactured by Sanko Co., Ltd.), 380 g of bisphenol A type epoxy resin (YD128, manufactured by Toto Kasei) and 0.5 g of triphenylphosphine were added. The mixture was heated at 145 ° C. for 2.5 hours to obtain a brownish transparent liquid.
39 g of dimethylformamide while cooling the liquid,
Methoxypropanol 129 g, methyl ethyl ketone 77 g
Was added to obtain a resin solution A having a solid content of 69 wt%. Then 1L
A phenol curing agent (Tamanol 752, Arakawa Chemical Co., Ltd.) (47 g) was dissolved in methyl ethyl ketone (80 g) in the flask (1), 350 g of the resin solution A was added, and the mixture was stirred to obtain a resin varnish. This resin varnish is 200 μm thick,
A prepreg was obtained by impregnating a glass cloth weighing 210 g / cm ² and drying at 160 ° C. for 5 minutes. The resin content of the obtained prepreg was 40%. Three prepregs were stacked and heated and pressed at a temperature of 170 ° C. under a pressure of 30 kg / cm ² for 70 minutes to obtain a laminate. (Example 9) A phosphorus compound (10 (2,5-dihydroxyphenyl) -10 represented by the chemical structural formula (II) was placed in a 1 L flask.
161 g of H-9 oxa-10-phosphaphenanthrene-10-oxide (HCA-HQ, manufactured by Sanko Co., Ltd.), 380 g of bisphenol A type epoxy resin (YD128, manufactured by Toto Kasei) and 0.5 g of triphenylphosphine were added. The mixture was heated at 145 ° C. for 2.5 hours to obtain a brownish transparent liquid.
While cooling the liquid, 39 g of dimethylformamide,
Methoxypropanol 129 g, methyl ethyl ketone 77 g
Was added to obtain a resin solution A having a solid content of 69 wt%. Then 1L
75 of cresol novolak epoxy resin in a flask
127 g of a% MEK solution (YDCN704-EK75, manufactured by Toto Kasei), 22 g of dimethylformamide and 65 g of methyl ethyl ketone were added, and the mixture was stirred well to obtain a uniform solution. There resin solution A35
0 g, 0.7 g of imidazole (2E4MZ, manufactured by Shikoku Chemicals) and 9 g of dicyandiamide were added and stirred to obtain a resin varnish. Apply this resin varnish to a thickness of 200
μm, weigh 210 g / cm ² glass cloth
A prepreg was obtained by drying at 5 ° C. for 5 minutes. The resin content of the obtained prepreg was 40%.
Three prepregs are stacked, and the temperature is 30 kg / cm ²
It was heated and pressed at 170 ° C. for 70 minutes to obtain a laminate. Example 10 A 1 L flask was charged with a phosphorus compound (10 (2,5-dihydroxyphenyl) -10 represented by the chemical structural formula (II)).
161 g of H-9 oxa-10-phosphaphenanthrene-10-oxide (HCA-HQ, manufactured by Sanko Co., Ltd.), 380 g of bisphenol A type epoxy resin (YD128, manufactured by Toto Kasei) and 0.5 g of triphenylphosphine were added. The mixture was heated at 145 ° C. for 2.5 hours to obtain a brownish transparent liquid.
39 g of dimethylformamide while cooling the liquid,
Methoxypropanol 129 g, methyl ethyl ketone 77 g
Was added to obtain a resin solution A having a solid content of 69 wt%. Then 1L
67 g of a 60% MEK solution of a phenol curing agent having a triazine skeleton (KA7052-M60, manufactured by Dainippon Ink and Chemicals, Inc.), 75 g of methyl ethyl ketone, and a resin solution A35
0 g and 120 g of aluminum hydroxide (manufactured by Nacalai Tesque) were added and stirred to obtain a resin varnish. This resin varnish was impregnated into a glass cloth having a thickness of 200 μm and weighing 210 g / cm ² and dried at 160 ° C. for 5 minutes to obtain a prepreg. The resin content of the obtained prepreg was 42%. Three prepregs were stacked and heated and pressed at a temperature of 170 ° C. under a pressure of 30 kg / cm ² for 70 minutes to obtain a laminate. Example 11 A 1 L flask was charged with a phosphorus compound (10 (2,5-dihydroxyphenyl) -10 represented by the chemical structural formula (II)).
161 g of H-9 oxa-10-phosphaphenanthrene-10-oxide (HCA-HQ, manufactured by Sanko Co., Ltd.), 380 g of bisphenol A type epoxy resin (YD128, manufactured by Toto Kasei) and 0.5 g of triphenylphosphine were added. The mixture was heated at 145 ° C. for 2.5 hours to obtain a brownish transparent liquid.
39 g of dimethylformamide while cooling the liquid,
Methoxypropanol 129 g, methyl ethyl ketone 77 g
Was added to obtain a resin solution A having a solid content of 69 wt%. Then 1L
Bisphenol A epoxy resin (YD128,
90 g of Toto Kasei, 25 g of dimethylformamide, and 60 g of methyl ethyl ketone were added and stirred well to obtain a uniform solution. There 350g of resin solution A, imidazole (2E4MZ,
1.0g, 10g of dicyandiamide
Was added and stirred to obtain a resin varnish. This resin varnish was impregnated into a glass cloth having a thickness of 200 μm and weighing 210 g / cm ² , and dried at 160 ° C. for 5 minutes to obtain a prepreg. The resin content of the obtained prepreg was 40%. Overlay three prepregs,
The laminate was formed by heating and pressing at a temperature of 170 ° C. under a pressure of 30 kg / cm ² for 70 minutes. Example 12 A 1 L flask was charged with a phosphorus compound (10 (2,5-dihydroxyphenyl) -10 represented by the chemical structural formula (II)).
161 g of H-9 oxa-10-phosphaphenanthrene-10-oxide (HCA-HQ, manufactured by Sanko Co., Ltd.), 900 g of bisphenol A type epoxy resin (YD128, manufactured by Toto Kasei) and 0.5 g of triphenylphosphine were added. The mixture was heated at 145 ° C. for 2.5 hours to obtain a brownish transparent liquid.
39 g of dimethylformamide while cooling the liquid,
Methoxypropanol 129 g, methyl ethyl ketone 77 g
Was added to obtain a resin solution A having a solid content of 81% by weight. Then 1L
50 g of dimethylformamide, 30 g of methyl ethyl ketone and 100 g of magnesium hydroxide (manufactured by Nacalai Tesque, Inc.) were added to the flask, and 350 g of the resin solution A and 15 g of dicyandiamide were further added and stirred to obtain a resin varnish. This resin varnish is 200 μm thick and weighs 210
g / cm ² of glass cloth and dried at 160 ° C. for 5 minutes to obtain a prepreg. The resin content of the obtained prepreg was 42%. Three prepregs were stacked and heated and pressed at a temperature of 170 ° C. under a pressure of 30 kg / cm ² for 70 minutes to obtain a laminate. (Comparative Example) In a 300 mL beaker, 50 g of bisphenol A type epoxy resin (YD128, manufactured by Toto Kasei), 3 g of dicyandiamide, and 0.1 g of imidazole (2E4MZ, manufactured by Shikoku Chemical Industry Co., Ltd.) are added and mixed well. Thereafter, the mixture is poured onto a hot plate at 170 ° C., and a plate-like gel is obtained while mixing well. This gel was sandwiched between iron plates with a 2 mm spacer, and was heated at 170 ° C. 70 under a pressure of 30 kg / cm ^2.
After heating for a minute, a plate-like cured product was obtained.

Table 1 below shows the resin formulations of the above Examples and Comparative Examples.

[0045]

[Table 1]

(Evaluation) The plate-shaped cured products and laminates obtained in the above Examples 1 to 12 and Comparative Example were each 125 mm in length.
A 13 mm wide test piece was cut out.

"Test for Underwriters Laboratories"
In accordance with Flammability of Plastic Materials-UL 94 ", a test piece having a length of 125 mm, a width of 13 mm and a thickness of 2 mm was tested for combustion behavior.

The test pieces obtained in the examples using the resin composition of the present invention were able to obtain an evaluation of V-0. The test piece of the comparative example could not be evaluated.

[0049]

According to the phosphorus-modified flame-retardant epoxy resin composition of the present invention, a phosphorus-modified flame-retardant epoxy resin composition containing an epoxy resin, a phosphorus-containing compound and a curing agent has the following chemical structural formula (I)

[0050]

Embedded image

Since it contains a phosphorus-containing compound represented by the formula (1), it has a smaller proportion of fatty chains, has better flame retardancy, can be easily and inexpensively produced, as compared with conventional flame-retardant epoxy resin compositions, Moreover, a phosphorus-modified epoxy resin composition having excellent heat resistance and flame retardancy can be provided. Further, using the phosphorus-modified epoxy resin composition of the present invention, molded articles,
Molding composition, coating material, can also be used for laminates, copper foil with resin, laminates and adhesives,
A material having excellent heat resistance and flame retardancy can be formed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08K 5/5313 C08K 5/5313 (72) Inventor Naoki Ito 1048 Odakadoma, Kazuma, Osaka Matsushita Electric Works, Ltd. In-company (72) Inventor Koichi Nogami 1048 Kadoma, Kazuma, Osaka Pref.Matsushita Electric Works Co., Ltd. (72) Inventor Takuya Asano 1048 Kadoma, Kazuma, Kadoma, Osaka Pref. Matsushita Electric Works F-term (reference) 4F072 AA07 AB09 AC15 AD23 AE07 AF16 AG03 AG17 AH02 AH31 AJ04 AL13 4F100 AA00A AA00H AA17A AA17H AB17B AB33B AH10A AK53A AK53K AL06A BA01 BA02 BA10A BA10B CA02A CA23A CC00A DG12A DG15A DH01A DH02A JJ03 JJ07A 4J002 AA031 CD011 CD021 CD051 CD111 DK007 EF007 EN027 EN037 EN047 EV237 EW146 FD018 FD147 FD159 GF00 GH01

Claims (22)

[Claims] 1. A flame-retardant epoxy resin composition containing an epoxy resin, a phosphorus-containing compound and a curing agent, comprising a compound represented by the following chemical structural formula (I): (In the formula, R1 is a compound containing two or more phenolic OH groups, n is an integer of 0 to 3. R2 is a straight or branched chain having 1 to 8 carbon atoms. Alkyl group,
A cyclohexyl, cyclopentyl or aryl group or an alkyl or alkoxy-substituted alkyl or aryl group having 1 to 18 carbon atoms,
May form a ring together with a P atom, and m is 0 or 1.) A phosphorus-modified flame-retardant epoxy resin composition, characterized by comprising: 2. 10 per 100 parts by weight of epoxy resin
１００100 parts by weight of the phosphorus-containing compound represented by the chemical structural formula (I), wherein the weight ratio of the entire epoxy resin and the phosphorus-containing compound represented by the chemical structural formula (I) to the curing agent is The phosphorus-modified flame-retardant epoxy resin composition according to claim 1, wherein (1 to 80): 1. 3. The method according to claim 1, which does not contain halogen.
3. The phosphorus-modified flame-retardant epoxy resin composition according to item 1. 4. The phosphorus-modified flame-retardant epoxy resin composition according to claim 1, comprising 5 to 300 parts by weight of a phosphorus-free epoxy resin. 5. The phosphorus-modified flame-retardant epoxy resin composition according to claim 1, further comprising 5 to 300 parts by weight of another component and / or filler. 6. A phosphorus-modified flame-retardant epoxy resin composition wherein the filler according to claim 5 is an inorganic filler. 7. The phosphorus-modified flame-retardant epoxy resin composition according to claim 6, wherein the inorganic filler is a hydroxide. 8. The phosphorus-modified flame-retardant epoxy resin composition according to claim 1, which contains 0.5 to 13% by weight of phosphorus. 9. The composition according to claim 1, which contains 1 to 6% by weight of phosphorus.
9. The phosphorus-modified flame-retardant epoxy resin composition according to any one of claims 1 to 8. 10. The phosphorus-modified flame-retardant epoxy resin composition according to claim 1, further comprising an accelerator. 11. The following chemical structural formula (II): The phosphorus-modified flame-retardant epoxy resin composition according to claim 1, comprising a compound represented by the formula: 12. A method for producing a phosphorus-modified flame-retardant epoxy resin composition containing an epoxy resin, a phosphorus-containing compound and a curing agent, the method comprising the steps of: A method for producing a phosphorus-modified flame-retardant epoxy resin composition, comprising producing a phosphorus-modified flame-retardant epoxy resin composition using the above. 13. A method for producing a phosphorus-modified flame-retardant epoxy resin composition containing an epoxy resin, a phosphorus-containing compound and a curing agent, wherein the epoxy resin is represented by the chemical formula (I) in the first reaction step. A method for producing a phosphorus-modified flame-retardant epoxy resin composition, which comprises reacting a reaction product with a compound-containing compound and then using a curing agent in a second reaction step to convert the reaction product into a phosphorus-modified flame-retardant epoxy resin composition. . 14. The method according to claim 1, wherein the first reaction step is performed in a solvent.
4. The method for producing the phosphorus-modified flame-retardant epoxy resin composition according to 3. 15. The phosphorus-modified flame retardant according to claim 14, wherein an aprotic polar solvent such as N-methylpyrrolidone, dimethylformamide, tetrahydrofuran, dioxane, dialkyl ether, glycol ether, ketones and / or esters is used. Method for producing water-soluble epoxy resin composition. 16. The phosphorus-modified flame-retardant epoxy resin according to claim 14, wherein the solvent used is a halogenated hydrocarbon, an aliphatic, alicyclic and / or aromatic hydrocarbon or a mixture thereof. Manufacturing method. 17. The reaction of the first reaction step is carried out at 0 to +250
The method for producing a phosphorus-modified flame-retardant epoxy resin according to any one of claims 13 to 16, which is carried out at a temperature of ° C. 18. The method for producing a phosphorus-modified flame-retardant epoxy resin according to claim 17, wherein the reaction is carried out at a temperature of 100 to 200 ° C. 19. The reaction of the second reaction stage is carried out at 0 to 200 ° C.
The method for producing a phosphorus-modified flame-retardant epoxy resin according to any one of claims 13 to 18, which is carried out at a temperature of: 20. The method for producing a phosphorus-modified flame-retardant epoxy resin according to claim 19, wherein the reaction is carried out at a temperature of 100 to 180 ° C. 21. An epoxy resin produced by the method for producing the epoxy resin composition according to any one of claims 1 to 11 or the phosphorus-modified flame-retardant epoxy resin composition according to any one of claims 12 to 20. Molded articles, molding compositions, coating materials, resin-coated copper foils and laminates using the compositions. 22. A phosphorus-modified product produced by the method for producing the epoxy resin composition according to any one of claims 1 to 11 or the phosphorus-modified flame-retardant epoxy resin composition according to any one of claims 12 to 20. Prepregs and laminates based on inorganic or organic reinforced materials in the form of fibers, non-woven fabrics or woven fabrics produced using a flame-retardant epoxy resin composition.