JPS62169825A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition excellent in curability, heat resistance of a cured product, etc., less corrosive to electronic components and suitable as, e.g., a sealant for electronic components, by mixing a polymaleimide compound with a specified polyphenol and a curing catalyst. CONSTITUTION:The purpose thermosetting resin composition is prepared by mixing a polymaleimide (A) having at least two maleimide groups in the molecule (e.g., N,N'-ethylenebismaleimide) with a polyphenol (B) of formula I (wherein X and Y are each H or a halogen, a 1-4C alkyl or alkoxy, n is 0-10 and m and p are each 1 or 2) and a curing catalyst (C) (e.g., triethylamine). Component B can be obtained by reacting an aromatic monoaldehyde of formula II (e.g., o-hydroxybenzaldehyde) with a monovalent phenol (e.g., phenol) in the presence of an acidic catalyst (e.g., hydrochloric acid).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to thermosetting resin compositions with excellent heat resistance, curability and storage stability. In particular, the present invention relates to thermosetting resin compositions useful as molding materials, sliding materials, single component sealants and protective coatings, conductive pastes, and multilayer laminated materials.

[Conventional technology]

Conventionally, polyamino bismaleimide resins have been used in the fields of 4-piece component sealants, multilayer FIT laminates, etc., which require high heat resistance, dimensional stability, and one-layer customization. However, this polyamino bismaleimide prepolymer requires curing at high temperature for a long time (e.g., 200°C, 48 hours;
Temporary curing is required at 50°C for about 10 hours) or N-
It has the problem that it is only soluble in special solvents with a high fluoride point such as methyl-2-pyrrolidone, which is unfavorable from the production environment.

Furthermore, in protective films for electronic components, polyamines eat away at lead wires and the like, causing failures, and therefore, an amine-free curing system is desired.

In order to solve the above problems, for example, JP-A-50-96
No. 696 describes a polyadduct obtained by reacting bismaleimide with bisphenol or novolac phenol in the presence of a basic compound. However, these compositions have significantly poor curability, and require long periods of heating before gelation occurs. Also, probably because decomposition occurs during curing, the resulting cured product has foaming, blistering, etc.
There is a problem that good fecal matter is not broken down.

[Problem that the invention seeks to solve]

The present invention was made in order to improve the curability of the conventional polymaleimide resin described above and the heat resistance of the cured product, and to reduce the corrosion of sterile parts.

[Failure to resolve the discrepancy]

The above object is achieved by using a composition comprising a polymaleimide compound, a specific polyphenol, and a curing catalyst.

That is, the present invention provides: (A) component: a polymaleimide compound having at least two maleimide groups in one molecule (B) component; a polyphenol represented by the following general formula (1) [wherein X
and Y are each a hydrogen atom, a halogen atom, or a carbon number of 1 to
4 represents an alkyl group or an alkoxy group. n is 0
An integer of ~10, m and p represent an integer of 1 or 2. ]
Component (C): Provides a thermosetting resin composition containing a curing catalyst.

(Polymaleimide Compound) (A) Examples of the polymaleimide compound having at least two maleimide groups in one molecule include the following.

(i) N,N'-ethylene bismaleimide, N,N'-
Hexamethylene bismaleimide, N*N'-m-7 22lene bismaleimide, N, N'-p-phenylene bismaleimide, N, N'-4,4'-diphenylmethane pismaleimide)', N, N '-4,4'-diphenyl ether bismaleimide, N,N'-methylenebis(3-chloro-p-phenylene)bismaleimide, NIN'-41
4'-diphenylsul7one bismaleimito, N,N'
-4,4'-dicyclohexylmethane bismaleimide,
N, N'-α, α/ 44/-dimethylenecyclohexane bismaleimide, N, N'-m-xylylene bismaleimide, N, N'-4,4'-dimethylenecyclohexane bismaleimide, N, N'-4,4'-diphenyl-1,l-propane bismaleimide, NrN'-4#4
'-) +)-y Uniru 1.1.1-ethane bismaleimide, N, N'-4゜4'-) rif x nylmethane bismaleimide, N, N1-3.5-triazole-1
, 2,4-bismaleimide and the like.

(ii) Poly(N-phenylmethylene)maleimide represented by the following general formula 0=CC=0 0=CC=O0=CC=0 [in the formula, n
is a number from O to 4. ] (iii) Polymaleimide represented by the following general formula (see JP-A-59-12931) [In the formula, X is a hydrogen atom, a hydrogen atom, or a carbon number of 1
~4 alkyl group or alkoxy group] (1■) For 1 mol of aldehydes consisting of a mixture of 5 to 95% by weight of formaldehyde and 95 to 5% by weight of aromatic dialdehyde, the general formula, [wherein, X is a hydrogen atom, a rogen atom, or a carbon number of 1
~4 alkyl group or alkoxy group] React an aromatic amine represented by 2 to 60 moles to obtain a polyamine, and then add maleic anhydride to the polyamine to obtain a polyamic acid. , a mixture containing a polymaleimide represented by the following formula obtained by dehydrating and cyclizing the polyamic acid, and a polymaleimide represented by
(See Publication No. 0-26032).

[In the formula, X is a hydrogen atom,] ・Rogen atom or carbon number 1
~4 alkyl group or alkoxy group, n is 0
is an integer from 4 to 4].

(Polyphenol) The polyphenol represented by the general formula (1) as component (B) is composed of: - an aromatic monoaldehyde represented by the following general formula (n) having at least one phenolic hydroxyl group in the molecule; and a monohydric phenol. It can be obtained by reacting these in the presence of an acidic catalyst.

[In the formula, Y is a hydrogen atom,] ・Rogen atom or carbon number 1
to 4 alkyl or alkoxy groups, m and p are integers of 1 or 2, and include azaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, vanillin, syringaldehyde, β-resorcyl aldehyde, proto- Examples include catechualdehyde.

-valent phenols include phenol, 〇-cresol, m-cresol, p-cresol, 0-ethylphenol, m-ethylphenol, p-ethylphenol, 2-isopropylphenol, p-5ec-butylphenol, p- tert-butylphenol,
O-methoxyphenol, m-methoxyphenol, p
-Methoxyphenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, O-bromophenol, m-bromophenol, p-bromophenol and the like.

The reaction between aromatic monoaldehyde and monovalent phenols is carried out in the presence of an acidic catalyst such as mineral acids such as hydrochloric acid and sulfuric acid, and organic acids such as oxalic acid, trichloroacetic acid, and paratoluenesulfonic acid. The reaction is carried out at a temperature of 40 to 150 DEG C. for 1 to 10 hours at a ratio of 0.5 to 60%, preferably 1 to 30 mol, of monohydric phenol based on the mole. After the reaction is completed, the reaction mixture is washed with water and excess phenol is removed under reduced pressure to obtain a polyphenol that is solid at room temperature (20° C.).

The polyphenol of component (B) is usually 5 to 100 parts by weight per 100 parts of polymaleimide of component (A)! Used in Tsujibe's ratio. (B) Component polyphenol is
(A) For 100 fi parts of component polymerimide,
If it is less than 5 parts by weight, the bending strength and impact resistance of the cured product will be low.

If it exceeds 100 eyelids, the cured product will not have sufficient heat resistance.

(Curing Catalyst) As the curing catalyst for component (C), tertiary amines, tertiary amine salts, quaternary ammonium salts, basic catalysts such as imidazoles, and Lewis acid amine complex catalysts are used. By blending these catalysts, effects such as shortening the curing time and improving moldability (molding cycle) can be obtained. In this case, the most practical blending ratio is 0.1 to 10 parts by weight of component (A), polymaleimide 100, based on the bone part.

Examples of tertiary amines include triethylamine, tri-n-
Butylamine, tri-n-octylamine, benzyldimethylamine, dimethylaminemethylphenol, trisdimethylaminomethylphenol, triethylenediamine, NININfN'-tetramethylethylenediamine, tetramethylguanidine, heptamethylisoguanide, 1,8-diazabicyclo(5 ,4,0) undecene-7,N,N-dimethylaniline, N,N,N? N'-
Tetramethyldiaminodiphenylmethane, N, N, N?
N'-tetramethyl-m-phenylenediamine, N,N
,N? Examples include N'-tetramethyl-p-phenylenediamine. Examples of the tertiary amine salts include salts of the above-mentioned tertiary amines and triacetate or tribenzoate. Examples of quaternary ammonium salts include tetramethylammonium chloride, tetramethy7ammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, trimethylcetylammonium chloride, trimethylcetylammonium bromide, triethylcetylammonium chloride, triethylacetylammonium bromide,
Examples include tetraethylammonium iodide.

Examples of imidazoles include 2-methylimidazole, 2
-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-ingrobylimidazole or their azine derivatives,
Examples include trimellitic acid derivatives and nitrile ethyl derivatives.

As Lewis acid amine complexes, BF3, ZnC/ask
Examples include complexes of Lewis acids such as lct3.5ict4, SnC14, and FeCl2 and amine compounds such as heptanoethylamine, n-hexylamine, benzylamine, triethylamine, and aniline piperidine.

These curing catalysts can be used in combination of 14 or 2 or more.

(Optional Components) The following components can be added to the curable composition of the present invention as necessary.

(1) Powdered reinforcing agents and fillers, such as metal oxides such as aluminum oxide and magnesium oxide, metal hydroxides such as aluminum hydroxide, calcium carbonate,
Metal carbonates such as magnesium carbonate, diatomaceous earth powder, basic magnesium silicate, fired clay, fine powder silica, fused silica, crystalline silica, carbon black, kaolin,
Finely powdered mica, quartz powder, metal hydroxides such as aluminum hydroxide, graphite, asbestos, molybdenum distributary, antimony dioxide, etc. Furthermore, fibrous reinforcements and fillers, such as inorganic fibers such as glass fibers, rock wool, ceramic fibers asbestos, and carbon fibers, and synthetic fibers such as paper, pulp, wood flour, linters, and polyamide fibers. The amount of these powder or fibrous reinforcing materials and fillers used varies depending on the application, but as a laminated material or molding material, the resin composition 100%
You can use up to 500 heavy weight parts.

(2) A coloring agents, pigments, refueling agents such as titanium dioxide, yellow lead carbon black, iron black, molybdenum red, navy blue, oxidation, cadmium yellow, cadmium red, red phosphorus, and other inorganic phosphorus triphenyl phosphates; These include organic phosphorus.

(3) Furthermore, various synthetic resins can be blended for the purpose of improving the properties of the resin in the final coating film, adhesive layer, resin molded product, etc. For example, epoxy resin, alkyd resin, melamine resin, fluororesin, vinyl chloride resin,
181 such as acrylic resin, silicone resin, polyester resin, or a combination of two or more types of 4gi.

The amount of these resins to be used is preferably within a range that does not impair the inherent properties of the resin composition of the present invention, that is, less than 9 times 50 times the total resin weight.

Methods for blending component (A), component (B), component (C), and various additives include heating melt mixing, cross-mixing using a roll kneader, mixing using an appropriate organic solvent, dry mixing, etc. can be given.

The resin composition of the present invention provides a cured product with excellent curability and heat resistance compared to conventional polymaleimide resins.

[Experiment example]

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example of production of polyphenol (Example-1)
-Hydroxypenzaldehy)' 61 F (0,5
188.29 (2.0 mol) of phenol, and 0.6 f of concentrated hydrochloric acid were charged, and the mixture was reacted for 4 hours at a temperature of 100°C. After the reaction is completed, the reaction solution is washed with water, and unreacted phenol is removed under reduced pressure (100 to 1 min Hg).
/lo o ~ 180℃), and the residue was
Pour off at 0℃, cool to room temperature, melting point 110-12
Red-brown polyphenol 13 with 0°C (capillary method)
8.89 was obtained.

(Example-2) Same procedure as Example-1 except that aldehyde in Example-1 was changed to o-hydroxybenzaldehyde, melting point 81-92°C.
A reddish-brown polyphenol 139.19 having the following properties was obtained.

(Example-3) Same procedure as Example-1 except that the aldehyde in Example-1 was changed to vanillin 76y (o, s mol), melting point 100-105.
A brown polyphenol having a temperature of 142.8 F was obtained.

(Example-4) The phenol of Example-1 was converted into 0-cresol 216.29 (
A brown polyphenol 152 having a black point of 115 to 125° C. was prepared in the same manner as in Example 1, except that it was changed to
．． 1 f was obtained.

(Example-5) Same procedure as Example-1 except that the aldehyde in Example-1 was changed to 0-hydroxybenzaldehyde and the phenol was changed to m-cresol 216.2f (2.0 mol).
152.59 of a brown polyphenol with a temperature of 4°C was obtained.

[Example-1] 100 parts by weight of NUN'-414'-diphenylmethane bismaleimide and 27.0 parts of the polyphenol obtained in Production Example 1.
2Tl (2 parts of dimethylaminomethylphenol as a slip and catalyst were mixed at cn degree 150tl), and after defoaming, poured into a metal mold at 180°C for 3 hours, then 2
Cured at 30°C for 5 hours, measuring 127 meters long and 12.7 meters wide.
A cured product with a thickness of 6.4 m was obtained.

Table 1 shows the physical properties of this cured product.

[Examples 2 to 11] Cured products were obtained in the same manner as in Example 1 using the maleimide compound, polyphenol, and curing catalyst shown in Table 1. The results are shown in Table 1.

[Comparison Example-1] The same procedure as in Example 1 was carried out except that the polyphenol was changed to a phenol novolac 28.59 with a softening temperature of 100° C. obtained by a condensation reaction of formaldehyde and phenol.

However, foaming occurred during the curing process, and a good cured product could not be obtained.

[Comparative Example-2] The same procedure as in Example 1 was carried out except that the polyphenol was changed to 31.8-4i parts of bisphenol A and 2 parts by weight of N, N, NζN/-tetramethyldiaminodiphenylmethane was used as the curing catalyst.

However, the surface of the obtained cured product appeared to be unevenly wavy, and subsequent evaluation was not performed.

[Comparative Example-3] A cured product was obtained in the same manner as in Example 1 using 100 parts by weight of NUN'-4,4'-Schiff x nylmethane bismaleimide and 22.1 parts by weight of 4,4'-diaminodiphenylmethane. Ta. The results are shown in Table 1.

Claims (2)

[Claims] (1) A thermosetting resin composition containing the following components (A) to (C). (A) Component: Polymaleimide compound having at least two maleimide groups in one molecule (B) Component: Polyphenol represented by the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X and Y are Each represents a hydrogen atom, a halogen atom, or an alkyl group or alkoxy group having 1 to 4 carbon atoms. n represents an integer of 0 to 10; m and p represent an integer of 1 or 2; ] (C) Curing catalyst (2) Component (B) is blended in a proportion of 5 to 100 parts by weight and component (C) is blended in a proportion of 0.1 to 10 parts by weight to 100 parts by weight of component (A). The composition according to item 1.