JPS60184524A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:A resin composition excellent in processability and curability and also excellent in the heat resistance, electrical properties, mechanical properties, moisture resistance, etc., of a curing, prepared by mixing a reaction product between an epoxy compound and a diamine with a cyanate ester component and a maleimide component. CONSTITUTION:A thermosetting resin composition containing (A) a reaction product between an epoxy compound having at least two epoxy groups in the molecule and a diamine, (B) a polycyanate ester having at least two cyanato groups in the molecule, a prepolymer thereof, or a prepolymer thereof with an amine, and (C) a polymaleimide having at least two N-maleimido groups in the molecule, prepolymer thereof, or a prepolymer thereof with an amine. Examples of components (B) which can be suitably used include compounds of the formula (wherein m>=2, R1 is an aromatic organic group, and each of the cyanato groups is bonded to the aromatic ring of said organic group).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel thermosetting resin composition, and more specifically, a reaction product of an epoxy compound having two or more epoxy groups in the molecule and a diamine, B6. A polyfunctional cyanate ester containing two cyanato groups in the molecule, a prepolymer of the cyanate ester or a prepolymer of the cyanate ester and an amine, and two or more N-maleimide groups in the C1 molecule. It is a thermosetting resin composition containing as essential components a polyfunctional maleimide, a prepolymer of the maleimide, or a prepolymer of the maleimide and an amine.

Conventionally, a curable resin composition prepared by mixing components B and C of the present invention with an epoxy resin has been known as Japanese Patent Publication No. 31279/1982, and is a cured product with excellent heat resistance and various other properties. It is something that can be obtained. However, this curable resin composition has insufficient workability and processability, particularly in terms of solvent solubility.

As a result of extensive research in order to eliminate the above-mentioned drawbacks, the present inventors used a reaction product of an epoxy resin and a diamine as an epoxy resin, added a cyanate ester component and a maleimide component to this, and pre-reacted as desired. As a result, it is easily dissolved in low boiling point solvents, has excellent processability and workability,
In addition, the inventors succeeded in obtaining a thermosetting resin composition whose cured product has excellent heat resistance, electrical properties, mechanical properties, moisture resistance, etc., leading to the present invention.

The present invention will be explained below.

The epoxy compound having two or more epoxy groups in the molecule of component A of the present invention may be any known epoxy resin, but typical examples include glycidyl ether type, glycidyl ester type, glycidyl amine type, Examples include aliphatic epoxide type and alicyclic epoxide type. In particular, representative glycidyl ether type epoxy resins include glycidyl ethers of hisphenol A (bisphenol A type), polyhalogenated bisphenol A type, and glycidyl ether of phenol novolac (phenol novolac type), which are easy to obtain. , and exhibits performance suitable for the purpose of the present invention. Further, it is preferable to use monoepoxy compounds such as phenyl glycidyl ether, butyl glycidyl ether, etc. in combination, since this has the effect of improving workability.

The diamines to be reacted with the above epoxy compounds include:
Any organic primary diamine represented by R(NH2)2 (R in the formula is an organic group having two or more carbon atoms) may be used (but is not particularly limited. Such diamines include meta or para diamines). phenylenediamine, meta- or paraxylylenediamine, 1,4- or 1,3-cyclohexanediamine, hexahydroxylylenediamine, 4,4-diaminobiphenyl, bis(4-aminophenyl)methane,
Bis(4-aminophenyl)ether, bis(4-aminophenyl)sulfone, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3,5-dimethylphenyl)methane, bis( 4-aminophenyl)cyclohexane, 2.2-bis(4-aminophenyl)propane, 2.2-bis(4-amino-3-methylphenyl)propane, 2.2-bis(4-amino-3-chlorophenyl) ) propane, bis(4-amino-3-chlorophenyl)methane, 2,2-bis(4-amino-3,5-
dibromophenyl)propane, bis(4-aminophenyl)phenylmethane, 3,4-diaminophenyl-4-
Specific examples include aminophenylmethane, 1-bis(4-aminophenyl)-1-phenylethane, and benzoguanamine.

The above epoxy compound and cyamine are reacted to prepare component A of the present invention. The equivalent ratio used is epoxy group:amine group-1: (1,05~1, preferably t:o,i~
0.8, dissolved in a solvent-free medium or in a medium such as methyl ethyl ketone, methyl cellosolve, or methyl isophyl ketone, usually at 20 to 250°C, preferably at 50 to 200°C, for 1 minute to 10 hours. Select as appropriate.

Suitable polyfunctional cyanate esters as component B of the curable resin composition of the present invention have the following general formula (1) % formula % (1) (where m is 2 or more, usually 5 or less). is an integer, R1 is an aromatic organic group, and the cyanato group is bonded to the aromatic ring of the organic group. To give a concrete example, ll3-
or 1,4-dicyanatobenzene, R3,5-1-licyanatobenzene, 1.3-, R4-,1,6-,1,8
-,2,6- or 2,7-dicyanatonaphthalene, R3
, 6-tricyanatonaphthalene, 4,4-diaminobiphenyl, bis(4-diaminophenyl)methane, 2,2
-Bis(4-cyanatophenyl)propane, 2,2-bis(3,5-dichloro-4-cyanatophenyl)propane, 2,2-bis(3,5-dibromo-4-cyanatophenyl)propane , his(4-cyanatophenyl) ether, bis(4-cyanatophenyl) thioether, bis(4-cyanatophenyl) sulfone, tris(4-cyanatophenyl) phosphite, tris(4-cyanatophenyl) These include phosphate, and cyanate ester obtained by the reaction of Nophora Sok and cyanogen halide. In addition to these, Tokuko Sho 41-1928, Sho 4
3-18468, 44-4791, 45-117
Cyanic acid esters described in No. 12, No. 46-41112, No. 47-26853, and JP-A No. 51-63149 may also be used.

Furthermore, it can be used as a prepolymer obtained by polymerizing the above-mentioned polyfunctional cyanate ester in the presence of a mineral acid, a Lewis acid, a salt such as sodium carbonate or lithium chloride, or a phosphate ester such as tributylphosphine. can.

These prepolymers generally have a sym-triazine ring in the molecule, which is formed by trimerization of the cyanide group in the cyanate ester. In the present invention, it is preferable to use the prepolymer having a number average molecular weight of 300 to 6,000.

Furthermore, the polyfunctional cyanate esters described above can also be used in the form of prepolymers with amines.

Examples of amines that can be suitably used include those exemplified as those used in the reaction with the epoxy resin described above.

Of course, the polyfunctional cyanate esters mentioned above, their prepolymers and prepolymers with amines can be used in the form of mixtures.

A preferred polyfunctional maleimide as component C of the present invention is represented by the following general formula (2) (wherein R is an aromatic or alicyclic organic group having a valence of 2 or more and usually 5 or less, is hydrogen, halogen, or an alkyl group, and n is usually an integer of 2 to 5.) The maleimide represented by the above formula has a maleic anhydride and an amino group of 2 to 5. It can be produced by a method known per se in which maleamic acid is prepared by reacting with polyamines containing polyamines, and then the maleamic acid is cyclized by dehydration. However, if flexibility and flexibility of the resin are desired, alicyclic amines may be used alone or in combination.Also, polyamines are preferably primary amines. Although desirable in terms of reactivity, secondary amines can also be used. Suitable amines include the amines listed above as those used for preparing component A, and melamines having a sym-) lyazine ring; These are polyamines made by reacting aniline with formalin and linking benzene rings with methylene bonds.

In the present invention, the above-mentioned polyfunctional maleimide can be used in the form of a prepolymer or a monomer with the above-mentioned amine, instead of being used in the form of a so-called monomer.

The curable resin composition of the present invention is prepared by mixing or preliminarily reacting the above A, B, and C.

The preparation methods include a simple mixing method; a method of mixing as a liquid in a liquid such as methyl ethyl ketone, methyl cellosolve, methyl isophyl ketone, etc.; a method of preliminarily reacting components B and C and mixing component A therewith. ; A method of pre-reacting components A and C and mixing component B; Furthermore, any method of further pre-reacting after mixing may be used;
The usage ratio of each component is not particularly limited.

Although the curable resin composition of the present invention itself is cured by heating, a thermosetting catalyst or curing agent is usually used to accelerate curing. These include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-7" -Methylimitasole, l-cyanoethyl-2-methylimidazole, 1-
Cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, l-cyanoethyl-2-
Imidazoles exemplified by ethyl-4-methylimidazole and 1-guanamineethyl-2-methylimidazole, as well as adducts of carboxylic acid or its anhydride to these imidazoles, N,'N-dimethyl Benzylamine, N,N-dimethylaniline, N,N
-dimethyltoluicine, N,N-dimethyl-p-anisidine, p-halogeno-N,N-dimethylaniline, 2-
N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, N, N, N
'.

Tertiary amines such as N-tetramethylbutanediamine and N-methylpiperidine; Phenols such as phenol, xylenol, cresol, resorcinol, catechol, and phloroglycine; Lead naphthenate, lead stearate, zinc naphthenate, octylic acid Organic metal salts such as zinc, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetonate; 5n
CI4- inorganic metal salts such as ZnCl2, AlCl3;
Peroxides such as benzoyl peroxide, lauroyl peroxide, caprylic anhydride, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl di-bar phthalate; maleic anhydride, phthalic anhydride, lauryl anhydride Acids, acid anhydrides such as pyromellitic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, hexahydro trimellitic anhydride, and hexahydrobylomellitic anhydride; and azo compounds such as azobisisobutylnitrile and epoxy Examples include resin curing catalysts. The amount of these catalysts to be added is sufficient within a general range of catalytic amounts, and may be used, for example, in an amount of 5 wt % or less based on the total composition.

The curable resin composition of the present invention may contain various additives as desired, as long as the original properties of the composition are not impaired. These additives include natural or synthetic resins such as rosin, shellank, copal,
Natural products such as oil-modified rosin, esters of (meth)acrylic acid of monofunctional or polyfunctional hydroxy compounds, (meth)
Esters of (meth)acrylic acid such as epoxy esters of acrylic acid and alkenyl esters of (meth)acrylic acid, and prepolymers thereof; polyallyl compounds such as diallyl phthalate, dihinylbenzene, diallylhensen, trialkenyl isocyanurate, etc. and prepolymers thereof ; dicyclopentadiene and its prepolymer;
Phenol resin; polyvinyl acecool resin such as polyvinyl formal, erichinyl acecool, polyvinyl butyral; phenoxy resin; OH group or C00I
Acrylic resin with I group; silicone resin; alkyd resin; petroleum resin; polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, butadiene-
Low molecular weight liquid to high molecular weight elastic rubber such as styrene copolymer, polyisoprene, butyl rubber, natural rubber; polyethylene, polypropylene, polybutene,
Poly-4-methylpentene-1, polystyrene, polyvinyl chloride, polyvinylphenol, AS resin, A B
Vinyl compound polymers such as S resin, MBS resin, poly-4-fluorinated ethylene, fluorinated ethylene-propylene copolymer, 4-fluorinated ethylene-6-monofluorinated ethylene copolymer, vinylidene fluoride; polycarbonate , polyphenylene ether, polysulfone, polyester, nylon, polyimide, polyaimide, polyesterimide, polyphenylene sulfide, and low molecular weight prepolymers or oligomers thereof are exemplified and used as appropriate. In addition, as reinforcing materials and fillers, various glass cloths such as cloth, roving cloth, Chosopto cloak, and surfacing mat, quartz glass cloth, carbon fiber cloth, other inorganic fibers such as ashest, rock wool, and slag wool, and wholly aromatic fibers can be used. Nylon cloth, blended cloth of glass fiber and fully aromatic nylon fiber, synthetic fiber cloth such as acrylic, vinylon, polyester, nylon, polyimide, cotton cloth, linen cloth, felt, kraft paper, cotton paper, paper-glass blend Paper, semi-carbon fiber cloth, etc., and chopped fibers that make up these cloths and papers; glass powder, glass bulbs, silica, alumina, silica alumina, aluminum hydroxide, asbestos, calcium carbonate, calcium silicate, wollastonite. , carbon black, kaolin clay, calcined kaolin, mica, talc, aluminum, copper, iron, iron oxide, synthetic mica, natural mica, semiconductors, boron nitride, other ceramics, and various other materials. In addition to these, various additives known as resin additives such as dyes, pigments, thickeners, lubricants, campling agents, and flame retardants may be used in appropriate combinations as desired.

The curing temperature of the curable resin composition of the present invention described in detail above varies depending on the presence or absence of a curing agent and catalyst, the types of composition components, etc., but it may be normally selected within the range of 100 to 300°C. Further, when manufacturing molded products, laminate products, bonded structures, etc., it is preferable to apply pressure, and generally speaking, the pressure is appropriately selected within the range of 0.1 to 500 kg/cnl.

The thermosetting resin composition of the present invention can be used as a composition with a catalyst, an inorganic filler, etc. as necessary for use as an electric insulating paint powder ring for automobile starter motors and generator motors; for coating metal plates, etc. It is used for various purposes such as coatings, cast products, molded products, laminates, tapes, sheets, and films.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. In addition, parts in Examples and Comparative Examples are parts by weight unless otherwise specified.

Example-1 Bisphenol A type epoxy resin (trade name: Epicote 828, manufactured by Yuka Shell Epoxy@, epoxy equivalent: 19
2) 576 parts and 1 bis(4-aminophenyl)methane
98 parts (equivalent ratio 1:0.67) were reacted for 50 minutes while melting at 110°C to obtain a prepolymer (hereinafter referred to as (a)).

In this (a), bis(4-maleimidophenyl)methane 1
074 parts of 2.2-bis(4-cyanatophenyl)propane was added, pre-reacted at 110°C for 11 minutes, and 1 part of 2.2-bis(4-cyanatophenyl)propane
074 parts were added and mixed uniformly to obtain a curable resin composition.

This curable resin composition was soluble in methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, and dioxane as a solid content concentration of 65 wt % or more.

100 parts of this curable resin composition, 50 parts of powdered graphite carbon, tert-butyl peroxide 04
3 parts and 0.1 part of zinc octylate were added and kneaded uniformly with a hot roll at 80°C to obtain a molding material. This molding material was compression molded at 170° C. and 1300 kg/c for 2 minutes, and then cured in an oven at 230° C. for 12 hours to obtain a good molded product.

The test results for this molded article are shown in Table 1.

Example-2 Novolac type epoxy resin (Product name: ECN-127
3, Epoxy equivalent 225, Chiha Geiki + 4W M
) 2250 parts and his(4-aminophenyl)methane 19
8 parts (equivalent ratio 1:0.2) were reacted for 50 minutes while melting at 110°C to obtain a prepolymer (hereinafter referred to as (bl)).

2,880 parts of bis(4-maleimidophenyl)ether was added to this (b), and a preliminary reaction was carried out at 110°C for 12 minutes. To this was added 2,780 parts of 2,2-bis(4-cyanatophenyl)propane and mixed uniformly to obtain a curable resin composition.

This curable resin composition was soluble in methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, and dioxane as a solid content concentration of 65 wt % or more.

0 parts of zinc octylate was added to 1000 parts of this curable resin composition.
．． 2 parts and 0.3 part of triethylenediamine were added and dissolved in methyl ethyl ketone.

This solution was impregnated into a glass woven fabric with a thickness of 0.2 mm and dried to obtain a B-stage prepreg.
Stack the sheets, place 35μ electrolytic copper foil on both sides, and heat to 180℃.
°C for 180 minutes at a pressure of 30 kg/cnl;
Lamination molding was performed at 200°C and 240 kg/cnl for 120 minutes to obtain a copper-clad laminate. The test results for this failure are shown in Table 2.

Example-3 In Example-2, bis(4) was added to the prepolymer fb).
-maleimidophenyl)ether 2880 parts and 2,
A prepolymer prepared by preliminarily reacting 2,780 parts of 2-his(4-cyanatophenyl)propane at 160° C. for 2 hours was added and mixed uniformly to obtain a curable resin composition.

This curable resin composition was soluble in methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, and dioxane at a solid content of 65 w L % or more.

0 parts of zinc octylate was added to 1000 parts of this curable resin composition.
．． 2 parts and 0.3 part of triethylenediamine were added and dissolved in methyl ethyl ketone.

Impregnate a glass woven fabric with a thickness of 0.211111 with this solution.
Dried to form a B-stage prepreg, stacked 8 sheets of this prepreg, placed 35μ electrolytic copper foil on both sides, and heated at a temperature of 180℃ and a pressure of 30kg/ctA for 180 minutes.
Furthermore, lamination molding was performed at 200° C. and 40 kg/cthl for 120 minutes to obtain a copper-clad laminate. The test results for this board are shown in Table 2.

Example-4 250 parts of bisphenol A epoxy resin (trade name: Epicote 828, epoxy 1192, manufactured by Yuka Shell Epoxy Co., Ltd.) and 100 parts of bis(4-aminophenyl) ether (equivalence ratio 1:0.77) was reacted for 50 minutes while melting at 100°C to obtain a prepolymer (hereinafter referred to as (C1
).

540 parts of bis(4-maleimidophenyl)ether was added to this tel, and a preliminary reaction was carried out at 110°C for 10 minutes.

361 parts of 2,2-bis(4-cyanatophenyl)propane was added to this and mixed uniformly to obtain a curable resin composition.

This curable resin composition was soluble in methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, and dioxane at a solid content of 60 wt % or more.

0 parts of zinc octylate was added to 1000 parts of this curable resin composition.
．． 2 parts and 0.3 part of triethylenediamine were added and dissolved in methyl ethyl ketone.

This was impregnated into a glass woven fabric with a thickness of Q of 21111 and dried to produce a prepreg of 1313-5ta. 8 sheets of this prepreg were stacked, 35μ electrolytic copper foil was placed on both sides, and the temperature was 180℃ and the pressure was 30kg/ell! for 180 minutes at 200° C. and further for 120 minutes at 140 kg/cJ to obtain a copper-clad laminate. The test results for this board are shown in Table 2.

Comparative Example-1 In Example-3, the novolanc type epoxy resin and bis(4-aminophenyl)methane were not pre-reacted,
Bis(4-maleimidophenyl)ether and 2,2
When -bis(4-cyanatophenyl)propane was blended, the gelling time at 160°C was 0 w, making it impossible to manufacture prepreg in m order.

Comparative example-2 Polyano bismaleide resin (product name: Kerimid
601, Loos-Boulin '5k) 700 parts and Novolank type epoxy resin (Product name: ECN-1273)
, Epoxy Photon 225, Chiha Geigy (411)! v
) 300 parts were dissolved and mixed in N-methylpyrrolidone, impregnated into a glass woven fabric having a thickness of 0.2 fins, and dried to prepare a prepreg.The results are shown in Table 2 in the same manner as in Example 2.

Comparative Example-3 100 parts of bis(4-aminophenyl)methane, bisphenol A type epoxy resin (trade name: Epicote 100
1. 1000 parts of oil-based shell epoxy (41%) and 20 parts of 2-ethylimidazole were dissolved in methyl ethyl ketone, impregnated into a 0.2-fin thick glass woven fabric and dried to make a prepreg, which was stacked with 8 sheets. , 35μ on both sides
electrolytic copper foil, temperature 175°C, pressure 30 kg
/ cnT for 90 minutes to obtain a copper-clad laminated N slope. The test results for this board are shown in Table 2.

Claims (1)

[Scope of Claims] A reaction product of an epoxy compound having two or more epoxy groups in the Δ0 molecule and a diamine, a polyfunctional cyanate ester containing two or more cyanato groups in the B6 molecule, and the cyanate ester A prepolymer or a prepolymer of the cyanate ester and an amine, a polyfunctional maleimide containing two or more N-maleimide groups in the C9 molecule, the maleimide prepolymer, or the prepolymer of the maleimide and an amine as essential components. A thermosetting resin composition.