JPS58179229A - Thermosetting resin composition and prepolymer thereof - Google Patents

Abstract

PURPOSE:A thermosetting resin composition, containing a polyphenylmethylene polycyanamide compound expressed by a specific formula and a polyfunctional imide having unsaturated bonds, and capable of giving cured articles having the heat resistance in the C-stage. CONSTITUTION:A composition obtained by incorporating (A) a polyphenylmethylene polycyanamide of formula I (n is O or an integer >=1), e.g. a reaction product of a polyphenylmethylene polymine of formula II with cyanogen bromide, with (B) a polyfunctional imide having unsaturated bonds, e.g. N, N'- 4,4'-diphenylmethane bismaleimide, and preferably further (C) a polymerizable compound, e.g. an epoxy compound, phenolic compound or triallyl isocyanurate compound. The amounts of the componets are as follows: 7-3 mole component (A), 3-7 moles component (B) and 2-50wt%, based on the composition, component (C). The resultent composition is preliminarily reacted to give the B- stage and the aimed prepolymer. USE:Varishes for the impregnation, lamination, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermosetting resin composition and a prepolymer thereof, in which the curing reaction progresses by heating, the B state shifts to the C state, and a cured product with excellent heat resistance is obtained. .

Addition polymerization type polyimides such as bismaleimide are well known as heat-resistant class H class resin molding materials. This maleimide is often used in combination with a diamine or an epoxy resin.
According to the specification, cyanamide (NC) is added to mono- or bisimide to improve heat resistance and chemical stability.
A product cured by adding NH, ) has been proposed. However, even in these cases, the heat resistance of the cured product has not been sufficiently improved. Furthermore, the curability is not sufficient.

An object of the present invention is to provide a thermosetting resin composition that provides a cured product having the heat resistance of a C-shaped bell.

The thermosetting resin composition of the present invention comprises: (1) a polyphenylmethylene poly(I) cyanamide compound having the general formula α) and (B) a polyvalent imide having an unsaturated bond;
The present invention is characterized in that it further contains at least one polymerizable compound selected from an epoxy compound, a phenol compound, and a triallyl isocyanurate compound as a component (0).

In the present invention, due to the reaction between the dicyanade and the polyvalent imide, the isomelamine ring and the imide ring, which are heat-resistant skeletons represented by the following general formula A cured product with high heat resistance is produced. Also,
By stopping the reaction midway, a prepolymer can be obtained.

On the other hand, when polyphenylmethylene polycyanamide, polyvalent imide, and a polymerizable compound as component 0 are used in combination, the following combination occurs.For example, when an epoxy compound is used as component C), the dicyanide compound is Amino groups and epoxy groups react, and in the case of phenolic compounds, they react with unsaturated bonds in polyvalent imides. In the case of a triallylisocyanurate compound, it undergoes radical polymerization with the cyano group of cyanamide and the unsaturated bond of polyvalent imide. It is also effective to use a curing accelerator or catalyst such as idendazole or peroxide in these reaction systems.

The polyphenylmethylene polycyanide represented by the general formula (I) according to the present invention can be obtained by reacting a polyphenylmethylene polyamine represented by the general formula (ff[) with a cyanogen halide such as bromcyan.

Examples of polyvalent indocarbons having unsaturated bonds include maleic anhydride, citraconic anhydride, itaconic anhydride, pyc/conic anhydride, dichloromaleic anhydride, and Diels-Alder adducts of these compounds with synchrodienes. Bisimides obtained by reaction of diamines with acid anhydrides such as N.

N/-methylene bismaleimide, N, N'-ethylene bismaleimide, N, N'-hekytemethylene bismaleimide (mi)", N, N'-)rimethylene bismaleimide% N
, N'-m-phenylene bismaleimi)-% N, N
'-p-phenylene bismaleimide, N, N'-4,4
'-diphenylmethane bismaleimide, N, N'-4,
4'-diphenyl ether bismaleimide, N, N'-
Methylenebis(3-chloro-p-phenylene)bismaleimide, N.

N'-4,4'-diphenylsulfone bismaleimide, N, N'-4,4'-dicyclohexylmethane bismale(mi)', N, N'-α, α'-4゜4'-dimethylene bismaleimide compounds such as cyclohexane bismaleimide, N,N'-m-xylene bismaleimide, N,N'-4,4'-diphenylcyclohexytine bismaleimide, a condensate of aniline and formaldehyde, and maleic anhydride. At least one type of polyvalent maleimide represented by the following formula M obtained by reacting with is used.

(n is 0.1 to 3) t+, in the present invention, the following monomaleimide compounds can also be combined 0 For example, N-methylmaleimide, N-ethylmaleimide, N-furobylmaleimide, N-butyl Maleind, N-71J Le Maley? )”,
N-bismaleimide, N-phenylmaleimide, N-3
-riαrofeni-"Rei? )', N-0-) Lil Male iY, N-m-) Lil Male Kendo, N-p-) Lil Male (t1', N-0-methoxyphenyl male (()'
, N-■-methoxyphenylmaleimide, N-rime)xyphenylmaleimide, N-benzyl! Reimido,
Monomaleimide compounds such as N-pyridylmaleimide, N-hydroxyphenylmaleimide, N-acetoxyphenylmaleimide, N-dichlorophenylmaleimide, N-benzophenonemaleimide, N-diphenyl ethermaleimide, N-acetylphenylmaleimide, N-cyclohexylmaleimide, etc. At least ldan can be used in combination.

Furthermore, the following polyvalent imide prepolymers can also be used. That is, it is a prepolymer obtained by reacting the aforementioned polyvalent imide with diamide, an epoxy compound, a phenol compound, or triallyl isocyanurate.

Here, examples of the epoxy compound include diglycidyl ether of bisphenol A, 3.4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 4.4'-(1,2-epoxyethyl)biphenyl, and 4.4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate. '-di(1,2-epoxyethyl)diphenyl ether, resol 7in diglycidyl ether,
Bis(2,3-epoxycyclobentyl)ether, N
, N'-m-phenylenebis(4,5'-epoxy-
difunctional poxy compounds such as (1,2-cyclohexanedicarbodiimide), triglycidyl compounds of p-aminophenol, 1.3.5-)su(1,2-epoxyethyl)benzene, tetraglycidoxytetra7ethyl At least one type of epoxy compound containing a halogen atom such as a trifunctional or higher functional epoxy compound such as polyglycidyl ether of dilethane or phenol formaldehyde novolac resin, an epoxy compound having a hydantoin skeleton, or a brominated epoxy compound is used. Phenolic compounds include phenol, cresol, m-cresol, p-cresol, 2.5-xylenol, 2.6-xylenol, O-chlorophenol, m-chlorophenol, p-chloro7-esol, O-phenylphenol, m-phenylphenol, p-phenylphenol,
At least 1m of saligenin or bisphenol A and formalin or paraformaldehyde,
Liquid or resinous condensates obtained by reaction under acidic or alkaline catalysts, diphenyl ether resins, xylene-modified phenolic resins, parahydroquine polystyrene resins, brominated parahydroxypolystyrene resins, bisphenol-furfural resins, etc. are useful. It is. In addition, prepolymers obtained by directly reacting bisphenol A, resorcinol, catechol, hydroquinone, pyrogallol, etc. with polyvalent maleiodine can also be used.

A cured product having good heat resistance can be obtained even if the blending ratio of the polycyanamide compound and the polyvalent indium is varied over a fairly wide range. In terms of the flexibility of the cured product, polycyana tends to decrease when the ratio is extremely unbalanced, whether it is a do compound or a polyvalent imide. Furthermore, in terms of the solubility of the polycyanamide compound and polyvalent imide prepolymer in the solvent, it is preferable to increase the amount of the polycyanamide compound. Generally, a range of polycyanamide compounds is suitable. Preferably, polycyanide compound 7-
The amount is in the range of 3 to 7 moles per 3 moles of polyvalent imide.

The resin composition of the present invention reacts and cures by heating as an organic solvent solution or festival, or in the absence of a solvent. The latter is a happy reaction to Tokomoe. In this reaction, when a solvent is used, it is heated once at about 50 to 220 tsoc, and then the temperature increases to s 150 to 220 C1i.
On the other hand, in the case of a melt reaction, the temperature is relatively high from the beginning, that is, 150 to 220 ri! This can be done by heating to a certain degree. In order to obtain a prepolymer, heating may be stopped when the reactant is in state B; in the case of reaction in a solvent, heating is stopped before solid matter (cured material) is precipitated. In the present invention, a cured product may be directly produced without temporarily stopping the reaction in the B state. For example, methyl ethyl ketone, methyl acetyl ketone, 2-methoxyethanol, 2-(methoxymethine)ethanol, 2-improxyethanol, 2-(
(ethoxyethoxy) ethanol, dioxane, dimethyldiochitin, seven-a-pyrene glycol methyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, or two or more thereof. A mixed solvent of can be used. Particularly preferred are methyl ethyl ketone, 2-methoxyethanol, N,N-dimethylformamide, N-
Methyl-2-pyrrolidone and diochitin.

In the present invention, by using diamine in combination, curability and flexibility of the cured product can be improved. Diamine is a system of polycyanamide compound and polyvalent imide.
This may be achieved by direct mixing, or by heating the diamine and the polyvalent imide or the polyvalent imide prepolymer in a solvent or in the absence of a solvent at 70 to 180 C for about 120 minutes. 1. When synthesizing a polyvalent imide prepolymer, a diamine may be added to moxibustion the ternary prepolymer. Examples of the diamine include 4-4'-cya inodicyclohexylmethane, 1°4-cya Cyclohexane, 2.6-diamithulysine, m-phenylenediamine, p-7 nylenediamine% +, 4/-diaminodiphenylmethane, 2.2'-bis(4-aminophenyl)propane, benzine, 4.4'-diaminophenyl Oxid, 4-4'-diaminophenylsulfone bis(4-aminophenyl)methylphosphine oxide, his(4-aminophenyl)phenylphosphine oxide, bis(4-aminophenyl)methylamine, 1
．． 5-diaminonaphthalene, m-xylylenediamine,
1.1-bis(p-azunophenyl)furatane, p-xylylenediamine, hexamethylenediamine, 6.6'
-Diaono2.2-dipyridyl, 4.4'-diaminobenzophenone, 4.4'-diaminoazobenzene bis(4-amino2enyl)phenylmethane, l.

! -bis(4-aminophenyl) Schiff-coated 1xane, 1.
1-bis(4-7minor-3-methylphenyl)cyclohexane, 2,5-bis(m-aminophenyl)-1,3
, 4-oxadiazole, 2.5-bis(p-aminophenyl)-1,3,4-oxadiazole, 2.5-bis(m-aminophenyl)thiazolo(4,5-d)thiazole, 5゜5-di(m-aminophenyl)-(2,2
') bis(1,3,4-oxadiazole), 4.41
-diaminodiphenyl ether 4,4/-bis(
p-aminophenyl)-2,2'-dithiazole, m-
Bis(4-p-aminophenyl-2-thiazolyl)benzene, 4.4'-diaminobenzanilide, 4.4'-
Diaminophenyl benzoate, N,N'-bis(4-
aminobenzyl)-p-phenylenediamine, 4.4'
At least one of -1fV bis(2-dichloroaniline), benzoguanamine, methylguanamine, etc.
used. The amount of diamine blended is generally in the range of 1.0 to 30% by coul, preferably 10 to 2% of the total composition.
It is appropriate to use it in a range of 0% by weight.

Further, in the present invention, in order to promote the reaction, a curing catalyst such as a conventional curing catalyst for maleimide or a curing catalyst for epoxy resin can be used in combination. Specific examples include tetramethylbutanecyamine, benzyldimethylamine, 2.4.6-tris(dimethylaminophenol), tetramethylguanidine, guanidine, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- Ethylimidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 2-phenylimidazole, 2.4'-
Imidazole compounds such as dimethyl-Zdazole, azine derivatives of the above imidazole compounds, tinium salts, trimellitates, nitrile ethyl derivatives, tetraphenylphosphonicum tetraphenylborate, tetraphenylammonium tetraphenylborate, tetrabutylammonium tetra7 Examples include aleborate and tetramethylammonium fluoride. The general amount of these curing catalysts used is O, 1 to 5% by weight of the entire composition.
is appropriate.

The resin composition of the present invention includes a known inorganic filler, a fuel agent, i.
A flexibilizing agent, an antioxidant, a pigment, a cupping agent, a mold release agent, etc. can be added.

The resin composition of the present invention as detailed above may be further used in combination with at least one elliptic compound selected from epoxy compounds, phenolic compounds, and 13allylisocyanurate compounds. . Specific examples include those similar to the above-mentioned examples. The appropriate blending ratio is generally 2 to 50% by weight.

When made into an organic solvent solution (varnish), the resin composition of the present invention is useful as a varnish for impregnation, lamination, adhesives, films, films, and prepregs. On the other hand, as a solvent-free type, it can be used as a molding powder. Examples of organic solvents include acetone, methyl ethyl ketone, methyl cellosolve, N-methyl-2-pyrrolidone, and N.

Many compounds such as N'-dimethylformamide and N,N-dimethylacetoand can be used in the resin composition of the present invention, which can maintain the B state by preliminary reaction.

This B-state material, the so-called prepolymer, has the advantage that its solubility in organic solvents is further improved and that it can be dissolved in containers even in low-boiling point solvents.

Next, examples of the present invention will be shown. In addition, the numerical value in the chemical structural formula shown in each Example shows an average value.

Polyphenylmethylene polycyanamide represented by 5
5 parts by weight (0.20 mol) a) N,N'-4,4'-diphenylmethane bismaleimide No. 5 parts by weight (0.13 mol) The above two components were dissolved in methyl cellosolve (50 parts by weight) at 80 to 120C. The mixture was reacted for 40 minutes to obtain a prepolymer. Next, 50 parts by weight of methyl ethyl ketone was added to this prepolymer to obtain a varnish with a solid content of 50% by weight. Next, apply this varnish onto the color board.
C111 cloth, dry and remove the solvent at 100-120 tll', and then react for 10 minutes at 170-200C to produce an insoluble and infusible cured product.

Polyphenylmethylene polycyanamide represented by Example 2 4
0 coulometric parts (0.11 mol) (11) 2.2-bisC4-(4-maleimidophenoxy)phenyl]propane 60 ttffll (0,
tt mol) The above secondary fraction was dissolved in a mixed solvent of methyl cellosolve and methyl ethyl ketone (1:l by weight), and 0.1 part by weight of 2-ethyl-4-methylimidazole was added thereto.
The varnish had a solid content of 50% by weight. ('K) After applying this varnish on a glass plate, drying and removing the solvent at 80 to tzoc, and further reacting at 170 to 200 C for 100 minutes, an insoluble and invincible cured product is produced.

Polyphenylmethylene poly7 anamide 3 represented by Example 3
5 parts by weight (0.08 mol) 033N,N'-4,4'-diphenylmethane bislimide 30 parts by weight (0.09 mol) 0 Epoxy resin manufactured by Dow Chemical Company DER-322 (epoxy equivalent: 17
4) 35 parts by weight (0.l 0 mol) The above tertiary portion was added to Methyl Cellosolve 5031! 5 in weight part
React for 0 minutes and bind the prepolymer. Then 5 more
0 parts by weight of methyl ethyl ketone and α3 parts by weight of an azine derivative of 2-ethyl-methyl-imidazole were added to prepare a varnish with a solid content of 50% by coul. Next, apply this varnish onto a glass plate.

After drying and removing the solvent at 100-120C, heat at 170C-
The reaction was carried out at 200C for 100 minutes to obtain an insoluble and infusible cured product.

Polyphenylmethylene poly7 anamide represented by 5
5 parts by weight (0,10 mol) CB) N,N'-4,4'-diphenyl ether bismaleimide 45 parts by weight 1 t (0,13 mol) 0.2 parts by weight of azine derivative of 2-ethyl-4-methyl-imidazole A varnish with a solid content of 50% by weight was prepared by dissolving the above tertiary portion in 100 parts by weight of ON-methyl-2-pyrrolidone, and a skin was prepared. Next, apply VC coating of this varnish on the glass plate and apply it to 80~1
Dry the solvent at 30C to remove 9 bales, and dry at 170-200C for 1
We are good at producing cured products that are insoluble and infusible after 00 minutes of reaction.

Polyphenylmethylene polyanamide 2 represented by Example 5 4
0 parts by weight (α15 mol) @ N# N' -L 4'-diphenylmethane bismaleinde 30 parts by weight (0.09 mol) 0 Epoxy resin CY-179 (Epoxy life equivalent 1311) 30 parts by weight (0,114 ) Convert the above 3rd order into methyl cellosolve 5
Next, 50 parts by weight of methyl ethyl ketone was added to make a varnish with a solid content of 50% by weight. Apply on a glass plate, 100~
After drying and removing the solvent at 120C, further boiling at 170~2
Insoluble after reacting at 00C for 100 minutes.

An infusible cured product was obtained.

Polyphenylmethylene polycyanamide represented by Example 6 5
0 parts by weight (α15 mol) (6) 4.4'-diaminodiphenylmethane 6 parts by weight (0.03 mol) (Q N,N'-4,4'-diphenylmethane bismaleimide 44 parts by weight (α13 mol) 3 above 50 ingredients
Approximately 1 at 80-120C in 11 parts of methyl cellosolve
It was dried for 0 minutes to obtain a bripolymer. Next, 50 parts by weight of methyl ethyl ketone was added to obtain a varnish with a solid content of 50% by weight.

Next, apply this varnish on a glass plate and apply 100 to 12
After drying off the solvent at 0C, further [170-200C
The mixture was reacted for 100 minutes to obtain an insoluble and infusible cured product.

Polyphenylmethylene polycyanamide represented by Example 7 3
0 parts by weight @)2.2'-bis(4-(4-limidophenoxy)
Phenyl] propy 50m1110 Phenol noselac resin (softening point 75c1 active hydrogen equivalent of phenol group 100) 20 parts by weight 0.2 parts by weight of azine derivative of 2-methyl-imidazole After solid blending the above four components, 170 to 200C After reaction for 100 minutes, an insoluble and infusible cured product was obtained.

polyphenylmethylene polymaleimide represented by polyphenyl methylene boriciana 40 parts by weight (α08 mol) 0 triallyl isocyanurate 20 parts by weight (O, O
■ Dicumyl peroxidide α3-fold tS Dissolve the above four ingredients in N-methyl-2-pyrrolidone, mix well, and add 1
Dry and remove solvent at 00~tsoc, 170~200c
React for 80 minutes and produce cured products that are insoluble and infusible.

Next, a glass cloth treated with aminosilane was impregnated with the varnish of the above example, and then dried at 80 to 140 C for about 10 minutes to prepare a coated cloth having a resin content of about 40% by weight. Layer 8 sheets of this coated cloth and set the temperature at 40 odor/cN.
Laminate molding was carried out at 170 to 200 C for 100 minutes under a pressure of 1.6 to obtain a laminate with a nickname of 1.6.

In addition, the resin collected from the coated cloth was heated to 1700~zooc,
When cured for too long and measured the infrared absorption spectrum, it was found that the cyanamide group VC' of 2220cWR-''
At 4h, the absorption and the absorption based on the epoxy group at 918 m'''1 almost disappeared, and a new peak of 1620 cm'''
1, characteristic absorption based on isomelamine IIK was confirmed.

Conventional example Amino bismaleimide resin (softening point 85-95C)
N-methyl-2-pyrrolidone (boiling point 202tll')
A varnish with a solid content of 50% by weight was prepared by dissolving it in 9. Next, the same glass cloth as in the above example was impregnated with varnish.
Dry at 20-150C for 10 minutes, solid content 40% by weight
Create a coated cloth and peel. Next, using 8 sheets of this coated cloth, 8
After lamination adhesion for 90 minutes at 180 rK under a pressure of 0 Kt/ly*'', temporary curing was further performed at 220 C for 180 minutes to create a laminate with a thickness of approximately 1.6 mm.

In addition, the residual volatile content of each coated fabric of Examples 1 to 5 and the conventional example was measured, and the results were 0.2 to 0.4 in each of Examples.
In terms of weight%, HL was as high as 2% by weight in the conventional example.

Therefore, Examples 1 and 2 of the present invention in which a low boiling point solvent can be used
, 3.5.6Fi, it has superior workability compared to conventional imide-based resins that use high-boiling point solvents, and there is no fear of performance deterioration due to residual solvent.

this! Samples were taken from each coated fabric prepared by pressing, and various properties of the resin and laminate were measured, and the results are shown in the table below. In addition,
In the table, the temperature zone at which weight loss starts is the temperature at which weight loss starts when heating in air at a heating rate of 4 C/min and measuring weight loss characteristics.
The weight loss at 500C is the weight loss rate when 500cK is reached. The bending strength is the bending strength UK at 20C.
Retention rate of bending strength at each temperature, bending strength FI after deterioration
L is.

This is the retention rate of the bending strength with respect to the initial value after heat deterioration for a predetermined period of time in air at 220C. The measurement temperature was 20C.

The results 1-board made using the resin composition and prepolymer of the present invention were 228% lower than conventional imide-based laminates.

Claims (1)

[Claims] 1. (A) Contains a polyphenylmethylene polycyanamide compound represented by general formula (I) (wherein n is an integer of 0 or 1 or more) and a polyvalent imide having 0 unsaturated bonds A thermosetting resin composition characterized by: 2, (A) a polyphenylmethylene polycyanamide compound represented by the general formula (I) (in the formula, n is ot or an integer of 1 or more), (B) a polyvalent imide and a zero-functional poxy compound having an unsaturated bond, A thermosetting resin composition comprising at least one polymerizable compound selected from phenolic compounds and triallylisocyanurate compounds. 3. (A) Preliminarily reacting a polyphenylmethylene polycyanand compound represented by the general formula (I) c (where n is Ol or an integer of 1 or more) and a composition containing a polyvalent imide having an unsaturated bond. TeB
A prepolymer characterized by nine conditions. 4, (A) polyphenylmethylene polycyanamide compound represented by general formula (I) (in the formula, n is Ol or an integer of 1 or more), a) polyvalent imide and zero-functional poxy compound having an unsaturated bond, phenol % indicates that the composition containing the compound and the triallyl isocyanurate compound is pre-reacted to state B.
A prepolymer with a characteristic.