JPS60184521A - Method for producing curable resin composition solution - Google Patents

Abstract

PURPOSE:To produce a resin composition which can give a curing product excellent in moldability, heat resistance, adhesiveness, etc., by reacting a polymaleimide with an aromatic diamine till complete elimination of all of the amino groups and mixing the reaction mixture with a polycyanate ester. CONSTITUTION:A polymaleimide having at least two N-maleimide groups in the molecule is prereacted with an aromatic diamine at an amino group/maleimido group numerical ratio of 0.0015-0.3 at a temperature of 60-160 deg.C in a solvent till all of the amino groups are eliminated. The reaction product is mixed and, if desired, reacted by heating with a polycyanate ester having at least two cyanato groups in the molecule, or a prepolymer of this cyanate ester to obtain the purpose curable resin composition. Examples of the polymaleimides which can be suitably used include compounds of the formula (wherein R1 is an at least bivalent aromatic or alicyclic organic group, X<1> and X<2> are each H, a halogen, or an alkyl, and n is 2-5).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a curable resin composition that provides a cured product with excellent moldability, heat resistance, adhesiveness, etc.
A polyfunctional maleimide containing two or more N-maleimide groups in the molecule and an aromatic diamine are arranged in a ratio of 1 maleimide group to 1 amino group in a solvent,
After pre-reacting at a temperature of 60 to 160 ° C to substantially eliminate all amino groups, mixing a polyfunctional cyanate ester or the cyanate ester prepolymer containing two or more cyanato groups in the molecule, This is a method for producing a curable resin composition solution by carrying out a heating reaction if necessary.

Conventionally, curable resin compositions containing polyfunctional cyanate esters and polyfunctional maleimides as essential components have high heat resistance,
Although it has excellent chemical resistance, adhesiveness, and moisture resistance,
In resin compositions containing a large amount of polyfunctional maleimides, is the polyfunctional maleimide component a solvent? 81a property, it was not possible to obtain a highly concentrated and uniform resin solution with excellent practicality, and the workability was poor.

A method of using polyfunctional amines as a curing agent in a composition of polyfunctional cyanate esters and polyfunctional maleimides is to reacts easily and has poor storage stability, and in these preliminary reactions, the reaction between polyfunctional maleimides and polyfunctional amines is rapid, and the reaction between polyfunctional cyanate ester and polyfunctional amine is rapid. Because an imine carbonate bond is formed by the reaction with the compound, the heat resistance of the cured product and the storage stability of the uncured composition are poor.

The inventors of the present invention have conducted extensive research to solve the above-mentioned drawbacks, and as a result, we have developed a prepolymer made by heating and reacting polyfunctional maleimides and polyfunctional amines. By combining polyfunctional cyanate esters with polyfunctional cyanate esters, it has excellent heat resistance, moisture resistance, chemical resistance, electrical properties, mechanical strength, etc., and has excellent storage stability and workability in processing. The inventors succeeded in obtaining a heat-resistant resin composition with good properties, leading to the present invention.

The present invention will be explained below.

A preferred polyfunctional maleimide of the present invention is represented by the following general formula (1) (wherein R1 is an aromatic or alicyclic organic group with a valence of 2 (+1i or more, usually 5 or less), hydrogen, halogen,
or an alkyl group, and n is usually an integer of 2 to 5. ) is a compound represented by Maleimides represented by the above formula are produced by a method known per se, in which maleic anhydride and polyamines containing 2 to 5 amino groups are reacted to prepare maleamic acid, and then maleamic acid is cyclized by dehydration. be able to. The polyamines used are preferably 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. 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 meta- or para-phenylenediamine, meta- or para-xylylenediamine, R4- or 1°3-cyclohexanediamine, hexahydroxylylenediamine, 4, t-diaminopiphenyl, 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-
Aminol 3-chlorophenyl)propane, bis(4-amino-3-chlorophenyl)methane, 2,2-his(4
-amino-3,5-dibromophenyl)propane, bis(4-aminophenyl)phenylmethane, 3,4-diaminophenyl-4'-aminophenylmethane, 1,1-
These include melamines having a bis(4-aminophenyl>-i-phenylethane and sym-) lyazine ring, and polyamines having Hensen's rings linked with methylene bonds by reacting aniline and pomarine.

The aromatic diamine of the present invention is the following general formula (2)% formula%
(2) A compound represented by (R2 in the formula is an aromatic organic group). Specific examples include meta or paraphenylenecyamine, meta or paraxylylenediamine,
4. Todiaminodiphenylmethane, bis(4-aminophenyl)ether, his(4-aminophenyl)sulbone, bis(4-amino-3-methylphenyl)methane,
Bis(4-amino-3,5-dimethylphenyl)methane, his(4-aminophenyl)cyclohexane, 2.2
-His(4-aminophenyl)propane, 2゜2-bis(4-amino-3-methylphenyl)propane, 2,2
-bis(4-aminol3-chlorophenyl)propane,
2,2-bis(4-amino-3,5-dibromophenyl)propane, bis(4-amino-3-chlorophenyl)
Methane, bis(4-aminophenyl)phenylmethane,
1. l-bis(4-aminophenyl)-1-phenylethane, bis(4-aminophenyl)diphenylsilane,
Examples include bis(4-aminophenyl)methylphosphine oxide, bis(3-aminophenyl)methylphosphine oxide, bis(4-aminophenyl)phenylphosphine oxide, and 1,5-diaminonaphculene.

Suitable polyfunctional cyanate esters of the present invention have the following general formula (3) % formula % (3) (m in the formula is an integer of 2 or more, generally under 5J22, and R
3 is an aromatic organic group, and the cyanato group is bonded to the aromatic ring of the organic group. To give a concrete example, 1.3-
or 1,4-dicyanatobenzene, R3,5-) lycyanatobenzene, 1,3. -, R4-, 1,6-, 1,8
-,2,6- or 2,7-dicyanatonaphthalene, R3
, 6-) dicyanatonaphthalene, 4,4′-dicyanatobiphenyl, bis(4-dicyanatophenyl)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, bis(4-cyanatophenyl)ether, his(4-cyanatophenyl)thioether, bis(4-cyanatophenyl) Surpone, 1-lis(4-cyanatophenyl)bosphite, tris(4-
cyanatophenyl) phosphate, and cyanic acid esters obtained by the reaction of novolacs with cyanogen halides. In addition to these, special public interest public works in 1928
, 43-18468, 44-4791, 45
-11712, 46-41112, 47-2685
Cyanic acid esters described in No. 3 and JP-A-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 are sym-4, which is formed by trimerization of cyanide groups in the cyanate ester.
Generally has a riazine ring in the molecule. In the present invention, it is preferable to use the prepolymer having a number average molecular weight of 300 to 6,000.

The solvent used in the present invention may be a compound that dissolves the polyfunctional maleimide when the polyfunctional maleimide is pre-reacted with the aromatic diamine. Specific examples include acetin, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, chloroform, dimethyl ether, dioxane, tetrahydrofuran, ethyl acetate-1-, acetonyl-1-lyl, dimethylborumamide, dimethylacetamide, diethylene glycol dimethyl sulfoxide, N-methyl-2-pyrrolidone, toluene, xylene, butyl phthalate, etc.

The curable resin composition of the present invention is manufactured using the above components as essential components.

In the curable resin composition of the present invention, the preliminary reaction between the polyfunctional maleimide and the aromatic diamine is performed so that the polyfunctional maleimide and the aromatic diamine are mixed with 0.0015 to 0.0015 amino groups per 1 maleimide group. 0.25, preferably a ratio of amine groups of 0.011 to 0.11, a solvent preferably of 10 to 200 parts by weight per 100 parts of polyfunctional maleimide, and a reaction temperature of 60 to 160°C. Preferably 8
Hydroquinone, tertiary-butylcatechol, A radical polymerization inhibitor such as hydroquinone monomethyl ether is added and reacted. This reaction is necessary to prevent or suppress the precipitation of monomer crystals of polyfunctional maleimide, and also to prevent deterioration of storage stability due to unreacted amino groups and cured products. is essential to prevent deterioration of physical properties. That is, when the number of amine groups is more than 0.25 fil per 1 maleimide group, excess unreacted amino groups remain and react with polyfunctional cyanate esters to form imine carbonate bonds, This is not preferable because it deteriorates the heat resistance and also reduces the storage stability of the uncured resin composition. Further, if the reaction temperature exceeds 160° C., it will gel before becoming a homogeneous pre-reactant, and if it is too low, the reaction will not proceed or will be too slow, which is not preferable.

Next, a polyfunctional cyanate ester is mixed with the above preliminary reaction solution or reacted by heating at a temperature of usually 160° C. or lower to obtain a resin composition solution of the present invention.

There is no particular limitation on the ratio of the solid content in the pre-reaction solution to the polyfunctional cyanate ester, but usually the solid content in the pre-reaction solution: polyfunctional cyanate ester-1; 99 ~90:10, preferably 10:90-8
A range of 0:20 is preferred.

The curable resin composition of the present invention itself has the property of becoming a heat-resistant resin by bonding and reticulating when heated, but it may also contain a catalyst for the purpose of promoting cross-linking and reticulating. . Such catalysts 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, 1-cyanoethyl-2-ethylimidazole, ■-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2
-Phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-guanamineethyl-
imidazoles exemplified by 2-methylimidazole,
Furthermore, adducts of carboxylic acids or their anhydrides to these imidazoles, N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, N,N-dimethyl-p -anisidine,
p-ha, 0geno N, N-dimethylaniline, 2-N-
Ethylanilinoethanol, tri-n-butylamine,
Pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, N, N,
Tertiary amines such as N', 1-tetramethylbutanediamine and N-methylpiperidine; phenolics such as phenol, xylenol, cresol, resorcin, catechol, and phloroglycin; lead naphthenate, lead stearate, naphthenic acid Organic metal salts such as zinc, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetone; inorganic metal salts such as 5nC14, ZnCl2, ^ICl3; hendiyl peroxide, lauroyl peroxide' , cabryl peroxide, acetyl peroxide, parachlorohenzoyl peroxide, ter
Peroxides such as t-butyl di-barphthalate; maleic anhydride, phthalic anhydride, lauric anhydride, pyromellitic anhydride, l-limerisotic anhydride, hexahydrophthalic anhydride, hexahydro trimellitic anhydride, hexahydro anhydride Acid anhydrides such as pyromellitic acid; further, azo compounds such as azobisisobutyl L-tolyl, and the like. The amount of these catalysts to be added is sufficient within a general range of catalytic amounts, and for example, it may be used in an amount of 5 wt% or less based on the total composition.

The temperature for curing the curable resin composition of the present invention is:
The temperature may vary depending on the presence or absence of a curing agent or catalyst, the types of composition components, etc., but it is usually selected within the range of 100 to 250°C. This composition is used for various purposes, including molded products,
When used in the production of laminated products, adhesive structures, etc., it is preferable to apply pressure during heat curing, generally speaking 1 to 500 kg/cd, preferably 5 to 15Q.
Appropriately selected within the range of kg/cJ.

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 thermosetting or thermoplastic resins and their low molecular weight products, fibrous reinforcements, fillers, dyes, pigments, thickeners, lubricants, coupling agents, and flame retardants. It contains various known additives such as, and may be used in appropriate combinations as desired. Examples of thermoplastic resins or low molecular weight compounds thereof include polyvinyl acecool resins such as polyvinyl polymer, polyvinyl acecool, and polyvinyl butyral; mature plastic polyurethane resins; polybutadiene, butadiene-acrylonitrile copolymers, and polychloroprene. , butadiene-styrene copolymer, polyisoprene,
Non-crosslinked (non-vulcanized) rubber such as butyl rubber and natural rubber; polyethylene, polypropylene, polybutene, poly-
4-methylpentene-1, polyvinyl chloride, vinylidene chloride resin, polystyrene, polyvinyltoluene, polyvinylphenol, AS resin, ABS resin, MBS resin,
Vinyl compound polymers such as poly-4-fluorinated ethylene, fluorinated ethylene-propylene copolymer, 4-fluorinated ethylene-6-monofluorinated ethylene copolymer, and vinylidene fluoride; polycarbonate, polyester carbonate, polyphenylene ether , polysulfone, polyester,
polyether zalvon, polyamide, polyaimide,
Examples include resins such as polyesterimide, polyphenylene, and sulfide, and low molecular weight polymers (prepolymers) of thermoplastic resins having a molecular weight of 10,000 or less, usually 1,000 to several thousand.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Note that the parts in Examples and Comparative Examples are heavy parts unless otherwise specified.

Example-1 900g of bis(4-maleimidophenyl)methane (2,
51 mol) to bis(4-aminophenyl)methane 100
g (0.51 mol, equivalent ratio t: 0.2>) and 429 g of N,N-dimethylborumamide were mixed, 12
A heating reaction was carried out at 0° C. for 2 hours to obtain a prepolymer solution. This prepolymer solution was preliminarily reacted with 2.2-bis(4-cyanatophenyl)propane at 150°C for 1 hour, and 250g of prepolymer and N,N-dimethylformamide 5
After adding 94 g and mixing at 80° C. for 1 hour, the mixture was cooled to obtain a brown transparent resin solution.

Zinc octylate o, e g is added to this resin solution as a catalyst.
, 1.2 g of dicumyl peroxide was added and mixed]I
A B-stage prepreg was obtained by impregnating a 0.2 inch I-me glass woven fabric and drying it by heating.

Electrolytic copper foil with a thickness of 35 μm was layered on both sides of these 8 sheets of prepreg, and the temperature was 180°C and the pressure was 50 kg/'c+a.
Lamination molding was carried out for 20 minutes, and post-curing was further carried out at 240° C. for 24 hours.

The test results of the obtained copper-clad laminates are shown in Table 1.

Example-2 990g of bis(4-maleimidophenyl)methane (2,
77 mol) to bis(4-aminophenyl)sulfone 10
g (0,046 mol, equivalent ratio 1:0.017
), 1 g of hydroquinone and 4 N-methylpyrrolidone
29 g were mixed and reacted by heating at 130° C. for 2 hours to obtain a prepolymer solution. 667 g of 2.2-bis(4-cyanatophenyl)propane and 682 g of dimethylacetamide were added to this prepolymer solution, mixed at 130°C for 1 hour, and then cooled to obtain a brown transparent resin solution (at 25°C). Ta.

A copper-clad laminate was obtained and tested in the same manner as in Example-1 except that this resin liquid was used.

The test results are shown in Table 1.

Example-3 950 g of bis(4-maleimidophenyl)methane (2,
65 mol) of bis(4-aminophenyl)methane 50
g (0.25 mol, equivalent ratio 1:0.094) and 429 g of N,N-dimethylpolamide were mixed,
A heating reaction was performed at 130° C. for 2.5 hours to obtain a prepolymer solution. This prepolymer solution was preliminarily reacted with 2,2-bis(4-cyanatophenyl)propane at 150°C for 5 hours to obtain 100g of prepolymer and N.

1207 g of N-dimethylformamide was added and mixed at room temperature to obtain a brown transparent resin solution.

In this resin solution, 0.6 g of zinc octylate was added as a catalyst.
Add and mix 1.2g of dicumyl peroxide to a thickness of 0.
．． B-
It was made into a stage prepreg.

Electrolytic copper foil with a thickness of 35 μm was layered on both sides of these 8 sheets of prepreg, and the temperature was 180°C and the pressure was 50 kg/cnT.
Lamination molding was carried out for 20 minutes, and further stepwise curing was performed at 240°C for 24 hours.

Table 1 shows the test results for the copper-clad laminates.

Comparative Example-1 In Example-1, bis(4-maleimidophenyl)
methane, bis(4-aminophenyl)methane and N,
A mixed solution of N-dimethylbormamide and 2,2-bis(4-cyanatophenyl)propane was prepared without pre-reacting the mixture.

The resulting resin solution caused precipitation at room temperature (25°C).

Using this solution, stir and mix until just before impregnating a glass woven fabric to prepare a B-stage prepreg, and prepare a copper-clad laminate No. 14 in the same manner. The test results are shown in Table 1.

Comparative Example 2 The same method as in Example 2 was attempted except that bis(4-aminophenyl)sulfone was not used.

The resulting resin solution formed a precipitate at room temperature.

Table 1 shows the results of the same procedure as Comparative Example 1 except that the resin solution was used.

Table 1

Claims (1)

[Claims] A polyfunctional maleimide containing two or more N-maleimide groups in the molecule and an aromatic diamine at a ratio of 0.0015 to 0.3 amino groups to 1 maleimide group in a solvent,
After pre-reacting at a temperature of 60 to 160°C to substantially eliminate all amino groups, a polyfunctional cyanate ester containing two or more cyanato groups in the molecule or the cyanate ester prepolymer is mixed. and, if necessary, a method for producing a curable B fat composition solution, which is subjected to a heating reaction.