JPS60184523A - 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 product, prepared by mixing a reaction product between an epoxy compound and a polyphenol with a cyanate ester component and a maleimide component. CONSTITUTION:A thermosetting composition containing (A) a reaction product between an epoxy compound having at least two epoxy groups in the molecule and a polyphenol having at least two phenolic hydroxyl groups in the molecule, (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-maleimid group in the molecule, a prepolymer thereof, or a prepolymer thereof with an amine. Examples of componevt (B) which can be suitably used include compounds of the formula (wherein m>=2, R 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, the present invention relates to a novel thermosetting resin composition, and more specifically, an epoxy compound having two or more epoxy groups in the molecule and two or more phenolic hydroxyl groups in the molecule. A reaction product with the polyhydric phenol contained, a polyfunctional cyanate ester containing two or more cyanato groups in the B1 molecule, the cyanate ester prepolymer or a prepolymer of the cyanate ester and an amine, and the C6 molecule. It is a thermosetting resin composition containing as an essential component a polyfunctional maleimide containing two or more N-maleimide groups, 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 some disadvantages in terms of workability, processability, especially solvent solubility.

The inventors of the present invention have conducted intensive research to solve the above-mentioned drawbacks, and as a result of the epoxy resin, they used a reaction product of an epoxy resin and a polyhydric phenol containing two or more phenolic hydroxyl groups in the molecule. By adding a cyanate ester component and a maleimide component and pre-reacting as desired, a thermosetting resin with excellent processability and workability, as well as excellent heat resistance, electrical properties, mechanical properties, moisture resistance, etc. of the cured product. They succeeded in obtaining a composition, leading to the present invention.

The present invention will be explained below.

The epoxy compound having two or more epoxy compounds 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, chain type, etc. Examples include aliphatic epoxyte type and alicyclic epoxide type. In particular, representative glycidyl ether type epoxy resins include glycidyl ethers to bisphenol (bisphenol A type), polyhalogenated bisphenol A type, and glycidyl ether of phenol novolak (phenol novolac type), which are easily available. Moreover, it 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.

Polyhydric phenols containing two or more phenolic hydroxyl groups in the molecule that react with the above epoxy compounds include:
A compound represented by the following formula (in the formula, R,, R2 is a hydrocarbon group having 1 to 6 carbon atoms, -1-〇-1-S-1-so2
-1 or O=P (0), X is a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms, p, q, r are O or an integer of 1 to 4, S, t, u are 0 is an integer of ~3, s,
t.

The sum of U is 2 or more, p is an integer from 1 to 4, m is 0 or 1,
n represents an integer of 0 to 4. ) is preferred. Such compounds include 4゜4'-dihydroxybiphenyl,
Bis(4-hydroxyphenyl)methane, tri(4-
hydroxyphenyl)methane, Ll,l-tri(4-
hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-
Bis(4-hydroxy-3,5-dichlorophenyl)propane, His(4-hydroxyphenyl)thioether, His(4-hydroxyphenyl)ether, Bis(4-hydroxyphenyl)
-hydroxyphenyl) sulfone, tris(4-hydroxyphenyl)bosphite, tris(4-hydroxyphenyl)phosphe-1~, phloroglycin, 4.6-
cymethyl-2.4.6- tri(4-hydroxyphenyl)hebutene-2,4,6-cymethyl-2.4.6-
) li(4-hydroxyphenyl)hebutane, 1,3
．． 5-1-li(4-hydroxyphenyl)benzene;
Examples include alkylphenol novolac resins such as phenol novolac resins and cresol novolac resins; low molecular weight polyP-hinylphenol, phenol-modified xylene resins, and the like.

Component A of the present invention is prepared by reacting the above epoxy compound with a polyhydric phenol containing two or more phenolic hydroxyl groups in the molecule. The equivalent ratio used is epoxy group: hydroxyl group-1: 0.05 to 2, preferably 170.1 to 1.
The solution is either solvent-free or dissolved in a solvent such as methyl ethyl ketone, methyl cellosolve, methyl isobutyl ketone, shioxane, etc., usually at 20 to 300°C, preferably at 80 to 250°C, for 1 minute to 20 hours. I will do it.

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, R is an aromatic organic group, and the cyanato group is bonded to the aromatic ring of the organic group. A specific example is 1.3-
or 1,4-dicyanatohensene, L3,5-tricyanatophenyl, 1.3-, L4-. 1.6-. 1.8-
．． 2.6- or 2.7-dicyanatonaphthalene, L3,
6-tricyanatonaphthalene, 4,4-diaminobiphenyl, bis(4-diaminophenyl)methane, 2,2-
Bi(4-cyanatophenyl)propane, 2,2-bis(3,5-dichloro-4-cyanatophenyl)propane, 2,2-bis(3,5-dibromo-4-cyanatophenyl)propane , bis(4-cyanatophenyl) ether, bis(4-cyanatophenyl) thioether, bis(4-cyanatophenyl) sulfone, tris(4-cyanatophenyl) phosphite, tris(4-cyanatophenyl) phosphates, and cyanate esters obtained by the reaction of novolacs with cyanogen halides. In addition to these, Tokuko Sho 41-1928, Sho 43
-18468, 44-4791, 45-1171
Cyanic acid esters described in JP-A No. 2, 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 meta- or para-phenylene diamine, meta- or para-xylylene diamine, 1
．． 4- or L3-cyclohexanediamine, hexahydroxylylenecyamine, 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
1bis(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-amino-3,5-dibromophenyl)propane Specific examples include -aminophenyl)phenylmethane, 3,4-diaminophenyl-4-aminophenylmethane, 1.1-<su(4-aminophenyl)-1-phenylethane, hensocanamine, and the like.

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 the C component 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, xLx is hydrogen, It is a halogen or an alkyl group, and n is usually an integer of 2 to 5. The maleimide represented by the above formula is produced by a method known per se, in which maleic anhydride I is reacted with a polyamine containing 2 to 5 amino groups to prepare maleamic acid, and then the maleamic acid is cyclized by dehydration. can do. It is preferable that the polyamines used are aromatic polyamines in terms of the heat resistance of the final resin, but if flexibility and flexibility of the resin are desired, alicyclic amines may be used alone or in combination. Good too. Further, it is desirable that the polyamines be primary amines from the viewpoint of reactivity, but secondary amines can also be used. Suitable amines include the amines exemplified as those used for preparing the preliminary reactant in the above-mentioned B component, and sym-)
These include melamines with a riazine ring, and polyamines made by reacting aniline with formalin and linking benzene rings with methylene bonds.

In the present invention, the above-mentioned polyfunctional maleimide can also be used in the form of a prepolymer, or a prepolymer 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 simply mixing; mixing as a solution of a solvent such as methyl ethyl ketone, methyl cellosolve, and methyl isobutyl ketone; pre-reacting components B and C, and mixing component A with this; A and C Any method may be used, such as a method of preliminarily reacting the components and mixing component B; or a method of further preliminarily reacting after mixing, and 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-hensyl-2-methylimidazole, 1-propyl-2- Methylimidazole, 1-cyanoethyl-2-methylimidazole, ■-cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-
Imidazoles exemplified by 2-phenylimidazole, l-cyanoethyl-2-ethyl-4-methylimidazole, and ■-guanaminoethyl-2-methylimidazole, and carboxylic acids or their Adducts of anhydrides, etc. iN, N-dimethylbenzylamine, N, N-dimethylaniline, N, N
-dimethyltoluidine, N,N-dimethyl-p-anisidine, p-halogeno-N,N-dimethylaniline, 2-
N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, tritanolamine, triethylenediamine, N, N,
N'.

Tertiary amines such as W-tetramethylbutanediamine, N-methylpiperidine; phenol, xylenol,
Phenols such as cresol, resorcin, catechol, phloroglycin; lead naphthenate, lead stearate,
Organic metal salts such as zinc naphthenate, zinc octylate, tin oleate, nbutyltin male, manganese naphthenate, cobalt naphthenate, iron acetylacetonate; 5nC
Inorganic metal salts such as 141, ZnCl2, and 81c13; peroxides such as benzoyl peroxide, lauroyl peroxide, caprylic peroxide, acetyl peroxide, parachlorobenzoyl peroxide, and di-tert-butyl perphthalate. ;maleic anhydride,
Acid anhydrides such as phthalic anhydride, lauric anhydride, pyromellitic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, hexahydrotrimellitic anhydride, hexahydropyromellitic anhydride; and azobisisobutyl Examples include azo compounds such as nitrile and curing catalysts for epoxy resins. The amount of these catalysts to be added is sufficient within a general range of catalytic amounts, and for example, it is sufficient that they are used 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, schlag, 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; diallyl phthalate,
Polyallyl compounds and their prepolymers such as divinylbenzene, diallylbenzene, and trialkenyl isocyanurate; dicyclopentadiene and some prepolymers; phenolic resins; polyvinyl acecool resins such as polyvinyl formal, polyvinyl acecool, and polyvinyl butyral; phenoxy resin iOH group or C0O
Acrylic resin with H 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-methylhentene-1, polystyrene, polyhinyl chloride, polyvinylphenol, As resin, A B
S 41 fat, M B S +A (fat, poly-4-fluorinated ethylene, fluorinated ethylene-propylene copolymer, 4-
Vinyl compound polymers such as fluorinated ethylene-6 monofluorinated ethylene copolymer and vinylidene fluoride; high molecular weight polymers such as polycarbonate, polyphenylene ether, polysulfone, polyester, nylon, polyimide, polyaimide, borie 4-thylimide, and polyphenylene sulfide. and low molecular weight prepolymers or oligomers thereof are exemplified and used as appropriate. In addition, various glass cloths such as cloth, roving cloth, Chosopto cloak, surfacing mat, quartz glass cloth, carbon fiber cloth, and other asbestos can be used as reinforcing materials and fillers.
Inorganic fibers such as rock wool and slag wool, fully aromatic nylon cloth, blended fabrics of glass fiber and fully aromatic nylon fibers, synthetic fiber cloths such as acrylic, vinylon, polyester, nylon, and polyimide, cotton cloth, linen cloth, and felt. , kraft paper, cotton paper, paper-glass mixed paper, semi-carbon fiber cloth, etc., as well as chopped fibers that make up these cloths and papers; glass powder, glass bulbs, silica, alumina, silica alumina, aluminum hydroxide, asbestos. , calcium carbonate, silicate, wollastonite, carbon black, kaolin clay, calcined kaolin, mica, talc, aluminum, copper, iron, iron oxide, synthetic mica, natural mica, semiconductors, boron nitride, other ceramics, There are various other examples. In addition to these, various additives known as resin additives, such as dyes, pigments, thickeners, lubricants, coupling agents, and flame retardants, may be used in appropriate combinations as desired.

The curing temperature of the curable resin composition of the present invention explained in detail above is determined by the curing agent and catalyst. (Although it varies depending on the type of composition, etc., it is usually selected within the range of 100 to 300°C. In addition, it is preferable to apply pressure when manufacturing molded products, laminates, adhesive structures, etc. Generally speaking, it is appropriately selected within the range of 0°1 to 500 kir/crA.

The thermosetting resin composition of the present invention can be used in various applications such as paint powder, paint, 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 Novolac-type epoxy resin (trade name: E(:N-12)
73, epoxy equivalent weight 225, manufactured by Chiha Geigy ■) and 10 parts (0.1 equivalent) of phenol novolak resin (average molecular weight 571, 5.5 hydroxyl groups) were melted at 200°C. A seprepolymer was obtained after reacting for 80 minutes (hereinafter referred to as (a+)).

A prepolymer prepared by pre-reacting 40 parts of bis(4-maleimidophenyl)methane and 60 parts of 2,2-bis(4-cyanatophenyl)propane at 160°C for 60 minutes was uniformly mixed into this f8). , with jetter as a catalyst.
2.0 parts of t-butylperoxide, 0.7 parts of zinc octylate, and 1 to 200 parts of wolastonite were added and extrusion kneaded at 100 to 110°C to form pellets.

This pellet was heated at 170°C, 130fl kg/cn.
! After compression molding for 3 minutes, the molded product was post-cured in an oven at 200°C for 30 minutes.

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

History Example 2 In Example 1, a prepolymer prepared by pre-reacting 60 parts of 2,2-bis(4-cyanatophenyl)propane at 160°C for 150 minutes and bis(4-maleimidophenyl) were added to (a). ) Add 40 parts of methane, add 2.0 parts of di-tert-butyl peroxide as a catalyst, 0.7 parts of zinc octylate, and 200 parts of wollastonite, and extrude and knead at 100 to 110 °C. The same procedure was used except that pellets were used.

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

Example-3 Novolac type epoxy resin (Product name: HCN-127
3. Epoxy equivalent 225, Chiha Geigy Co., Ltd. 22
5 parts (1 equivalent) and 2,2-bis(4-hydroxyphenyl)propane (molecular weight 22B>90 parts (0,8 equivalent)
was reacted for 120 minutes while melting at 160°C to obtain a prepolymer (hereinafter referred to as (bl)).

This (bl, 2,2-bis(4-cyanatophenyl)
126 parts of propane and bis(4-maleimidophenyl)
A prepolymer pre-reacted with 190 parts of ether at 160°C for 60 minutes is mixed uniformly, and 6.3 parts of dicumyl peroxide and 1 part of iron acetylacetonate are added as a catalyst.
．． 0 parts, and 632 parts of wollastonite were added, and 1
The mixture was extruded and kneaded at a temperature of 00 to 110:C to form pellets.

The pellets were compression molded at 170°C and 300 kg/c+a for 3 minutes, and after t9, they were placed in an oven at 200°C.
; After curing for 1 minute, a molded article was obtained.

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

Comparative Example-1 The same procedure as Example-1 was carried out except that the phenol novolak resin was not used.

The results are shown in Table 1.

Comparative Example-2 In Example-1, novolac type epoxy resin (trade name: ECN-1273, epoxy equivalent weight 225, Ciba
Geigy Co., Ltd. 90 parts (0.4 equivalent) and phenol novolac resin (average molecular weight 571, 5.5 hydroxyl groups) 1
The same procedure was followed except that 0 part (0.1 equivalent) was used without pre-reaction.

The results are shown in Table 1.

Comparative Example 3 The same procedure as Example 3 was carried out except that 2,2-bis(4-hydroxyphenyl)propane was not used.

The results are shown in Table 1.

In Table 1, *1 and *2 are as follows, respectively.

*After heat treatment for 1100 hours (%) *2 Blocking property: Pulverize the pellets, take the powder that passed through a 150 mesh sieve, and sieve it into a 40 mm diameter
Put 7g of each into a glass container and heat in an oven at 40°C.
After leaving it for a week, I turned it upside down and looked at its blocking properties.

◎: Forms lumps and falls.

○: Forms clumps, but falls apart when touched lightly Ru.

×: Forms a lump and does not crumble even when touched.

Table 1

Claims (1)

[Scope of Claims] A reaction product of an epoxy compound having two or more epoxy groups in one molecule and a polyhydric phenol containing two or more phenolic hydroxyl groups in the molecule, B9 having two or more cyanato groups in the molecule. a polyfunctional cyanate ester containing two or more N-maleimide groups, a prepolymer of the cyanate ester or a prepolymer of the cyanate ester and an amine, and a polyfunctional maleimide containing two or more N-maleimide groups in the C1 molecule; A thermosetting resin composition containing a maleimide prepolymer or a prepolymer of the maleimide and an amine as an essential component.