JPS6234922A - resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having excellent heat-resistance, curability and storage stability, and suitable especially as a molding material, sliding material, sealing material, etc., by compounding a specific polymaleimide, a polyhydric phenolic compound and a curing catalyst at specific ratios. CONSTITUTION:The objective composition can be produced by compounding (A) 100pts.(wt.) of a polymaleimide obtained by (1) reacting 1mol of an aldehyde consisting of a mixture of 5-95(wt)% formaldehyde and 95-5% aromatic dialdehyde with 2-60mol of aromatic amine of formula (X is H, halogen or 1-4C alkyl or alkoxy) to obtain a polyamine, (2) producing a polyamic acid by the addition reaction of the polyamine and maleic anhydride and (3) carrying out the dehydrative cyclization of the polyamic acid, (B) 5-100pts. of a polyhydric phenol having >=2 hydroxyl groups in a molecule and (C) 0.1-10pts. of a curing catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the invention, industrial field of application] The present invention relates to a resin composition having excellent heat resistance, curability and storage stability. Especially molding materials, sliding materials,
Useful as encapsulation materials and multilayer laminate materials.

[Conventional technology]

BACKGROUND OF THE INVENTION In recent years, with the advancement of technology for electronic equipment, electrical equipment, transportation equipment, etc., materials with excellent mechanical properties and excellent heat resistance have been desired.

Polyimide is the most well-known material with excellent heat resistance, but condensed ash requires high temperatures and produces moisture as a by-product, which is considered a difficulty in molding operations. An aminobismaleimide resin is an example of a material that improves this point. However, to use them in liquid form requires a high boiling point and expensive solvent such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, etc., which causes problems in terms of workability and in the production of cured products. There was a problem with heat resistance.

In addition, a composition of poly(phenylmethylene)polymaleimide represented by the general formula, [wherein 1m is an integer of 0 to 4] and noramine has a slight solubility in solvents, unlike aminobismaleimide resins. However, in terms of curing speed, like aminobismaleimide resins, they require heating at high temperatures for long periods of time, and they have problems in that they dissolve in solvents and have poor storage stability when in a varnished state.

[Problem that the invention seeks to solve]

The present invention has been made to improve the curability, solubility in solvents, storage stability, and heat resistance of cured products of conventional polymaleimide resins.

[Structure of the invention]

That is, in the present invention, component (A): per mole of an aldehyde consisting of a mixture of 5 to 95 weight parts of aromatic dialdehyde and 95 to 5 weight part of formaldehyde, [wherein X is a hydrogen atom, a halodane atom, or Carbon number 1~
The aromatic amine represented by 4 is an alkyl group or an alkoxy group] is reacted in a ratio of 2 to 60 moles to obtain a polyamine, and then the polyamine and maleic anhydride are subjected to an addition reaction to obtain a polyamic acid. , Polymaleimide 100'ML obtained by cyclodehydration of the polyamic acid Dobe (B) component, 5 to 100 parts of polyhydric phenol compound having at least two hydroxyl groups in one molecule (C) component : Curing catalyst 0.1 to 10 parts by weight (A) above
The present invention provides a heat-resistant resin composition in which components (B) and (C) are blended in equal proportions.

[Polymaleimide]

In the examples of the present invention, the aromatic dialdehyde, one of the aldehydes used in the production of the polyamine that is the raw material for the polymaleimide component (A), is a compound represented by the general formula (1), specifically 1 .2-benzenedialdehyde, 1.3-benzenedialdehyde, and 1.4-benzenedialdehyde are preferred, and these may have a substituent such as a halogen group or an alkyl group.

The other formaldehyde may be formalin, which is a water bath solution, or i4 formaldehyde, which is a polymer thereof.

The aromatic dialdehyde represented by the above formula (summer) has a weight ratio of 5 to 95, preferably 10 to 90, in aldehydes.
Used in percentages. If the amount of aromatic dialdehyde used is less than 5 parts by weight, the effect of improving the curability of the resulting polymaleimide is small. On the other hand, if the weight ratio exceeds 95, the effect of improving solubility in solvents is not sufficient.

Next, the aromatic amines include aniline, o-) luidine, m-) luidine, p-) cycloaniline, 6-fluoraniline, O-isopropylaniline, p-butylaniline, 0-anisidine, m- Examples include anisidine, p-anisidine, 0-phenetidine, chloranilines, bromoanilines, and the like.

The reaction between aldehydes and aromatic amines is carried out in the presence of an acidic catalyst such as mineral acids such as hydrochloric acid and sulfuric acid, organic acids such as oxalic acid and radruenesulfonic acid, and other organic acid salts. The condensation reaction is carried out at a temperature of 40 to 150° C. for 1 to 10 hours at a ratio of 2 to 60 mol, preferably 2 to 40 mol, of the aromatic amine.

After the reaction is completed, the reaction mixture is hydroxylated) The polyamine can be obtained by neutralizing with an alkali represented by IJum, washing with water, and removing excess aromatic amine under reduced pressure.

The obtained polyamine is liquid to solid at room temperature. Dissolve 1 mol of maleic anhydride in a suitable organic solvent per 1 equivalent of the amino group of this polyamine,
Addition reaction is carried out for 4 hours to obtain polyamic acid. Examples of the organic solvent include N,N-dimethylformamide, acetone, methyl ethyl ketone, dioxane, N,N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone.

Next, acetic anhydride is added as a dehydrating agent for this polyamic acid, a catalyst and a tertiary amine are added as necessary, and 2
Heating at 0 to 80°C for 1 to 5 hours to perform a cyclodehydration reaction,
Obtain the desired polymaleimide.

Catalysts include alkali metal salts, alkaline earth metal salts, 2
nickel salts, divalent or trivalent iron salts, and cobalt salts. In addition, chlorides, bromides, carbonates, acetates, etc. of these metals can also be used.

As the tertiary amine, triethylamine, tri-n-zorobylamine, tri-n-butylamine, etc. can be used.

The produced polymaleimide reaction solution is precipitated with a precipitant such as water, and washed with water or neutralized with a basic substance such as sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, etc. as necessary. After being combined, it is purified by drying.

The polymaleimide obtained in this way is generally a mixture, and its weight ratio of 50 or more is of the general formula (
It is a mixture of II) and (III).

[In the formula, X is a hydrogen atom,) a gun atom or carbon #1
1 to 4 alkyl group or alkoxy (]2) (IIJ [wherein, In addition to polymaleimide, polymaleimides represented by the following formulas (F/), (V), etc. coexist.

C in formula x toz C is the same as formula (II): Yj
*Y21Y, 51Y4 are H or λ; 芭', Y,', Y3' are H or λ, and Y''2. is H or λ].

and n is an integer of 5 or less] The method for producing this polymerimide is disclosed in Japanese Patent Application Laid-Open No. 60-2603.
It is described in the specification of No. 2.

(Polyhydric phenol compound) Examples of the polyhydric phenol compound having at least two hydroxyl groups in one molecule of the component 0) include the following.

Resorcinol, catechol, hydroquinone, bisphenol F1 bisphenol A and phenol, 0-
Cresol, m-cresol, p-cresol, 2,5
-xylenol, 3,4-xylenol, 2,6-xylenol, 0-chlorophenol, m-chlorophenol, p-chlorophenol, 0-phenylphenol,
Using monohydric phenol such as m-phenylphenol and p-phenylphenol; or bisphenol A as a raw material, this is reacted with formalin, formaldehyde, and dialdehyde such as glyoxal in the presence of an acidic or alkaline catalyst. It is a resinous condensate obtained by In addition, diphenyl ether resin,
Also effective are xylene-modified phenol resin, hydroxystyrene resin, bisphenol A-7#7 seal resin, and the like.

(4) For 100 parts by weight of component polymerimide, (B
) The polyhydric phenol compound is used in an amount of 5 to 100 parts by weight.

For example, when a polymaleimide compound and a polyhydric phenol compound are cured through a reaction mode between a maleimide group and a hydroxyl group as shown in the above formula (wherein R4 represents a monovalent organic group and R2 represents a divalent organic group), Presumed. Although the polymaleimide compound itself is polymerized by heat, the resulting cured product is very brittle.By introducing a phenolic compound as described above, a tough cured product can be obtained.

If the polyhydric phenol compound (B) is added to 100 parts by weight of the polymaleimide (A) component, if it is less than 5 parts by weight, the bending strength and impact resistance of the cured product will be low. In this case, the heat resistance of the cured product becomes insufficient.

(Curing Catalyst) The curing catalyst of component (C) is a basic catalyst such as tertiary amines, tertiary amine salts, quaternary ammonium salts, and imidazoles. 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 in the range of 0.1 to 10 parts by weight based on the polymaleimide 100]i lid part of component (A).

Examples of tertiary amines include triethylamine, tri-n-
Butylamine, tri-n-octylamine, benzyldimethylamine, dimethylaminomethylphenol, triethylenediamine, N, N, N', N'-detramethylethylenenoamine, tetramethylguanidine, to! Tamethylinoguanide, 1,8-diazabicyclo(5,4,
0) undecene-7 and the like. 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, tetramethylammonium bromide,
Examples include tetraethylammonium chloride, tetraethylammonium bromide, trimethylcetylammonium chloride, trimethylcetylammonium bromide, triethylcetylammonium chloride, triethylacetylammonium bromide, and tetraethylammonium iodide.

Examples of imidazoles include 2-methylimidazole, 2
-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-methylimidazole, 2,4-dimethylimidazole, 2-isoglobylimidazole or their azine derivatives,
Examples include trimellitic acid derivatives and 2) IJ ethyl derivatives.

These curing catalysts can be used alone or in combination of two 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 disulfide, antimony trioxide, and fibrous reinforcements and fillers such as glass fiber, rock wool, and ceramics. These include fiber asbestos, inorganic fibers such as carbon fiber, and synthetic fibers such as paper, wood powder, 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 10
Up to 500 parts by weight can be used compared to 0 parts by weight.

(2) Coloring agents, pigments, flame retardants such as titanium trioxide, yellow lead carpet black, iron black, molybdenum red, navy blue,
These include inorganic phosphorus such as ultramarine blue, cadmium yellow, cadmium red, and red phosphorus, and organic phosphorus such as triphenyl phosphate.

(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,
Examples include acrylic resin, silicone resin, polyester resin, etc., or a combination of two or more thereof.

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 50% by weight of the total resin amount.

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 polymaleimides.

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

Production Example of Polymaleimide Example 1 500 equipped with a thermometer, cooler, dropping funnel, and stirring device
- In a four-day flask, 33.517 N of 1,4-benzenedialdehyde and 195.5 N of nirine.

Concentrated hydrochloric acid 18.3F was charged, and then 20.3M formaldehyde aqueous solution (proportion of formaldehyde in aldehydes: 18.3%) was added dropwise. After the completion of the dropwise addition, water was refluxed (temperature 102°C). Let it react for 5 hours.

After the reaction is complete, add 10% sodium hydroxide aqueous solution 79.21%
Add 1 to the flask and stir for 5 minutes. Next, add 500ml of methyl isobutyl ketone to the system to make it an alkaline solution.
After adding and dissolving g in the flask, add 300 g of pure water,
Washing with water was performed a total of three times to remove by-product sodium chloride and excess sodium hydroxide.

Next, the solution was heated under reduced pressure (100~1■Hg/80~1
Methyl isobutyl ketone and unreacted aniline were completely removed at 180° C.), and the residue was poured off at 180° C. and cooled to give an orange solid 1519.

A solution obtained by dissolving this polyamine 591 in acetone 118I was placed in a dropping funnel.

50 equipped with thermometer, condenser, dropping funnel and stirring device
In a 0ml four-day flask, 51.5N maleic anhydride
and acetone 103I were charged and stirred to dissolve maleic anhydride.

Next, a polyamine solution dissolved in acetone was dropped onto the surface of the flask while keeping the temperature at 20 to 30°C, and after the dropping was completed,
Stirring was continued for 30 minutes at the same temperature.

Next, in this flask, 1.211 liters of lithium bromide, 12.5 N of triethylamine, and 63.8 JF of acetic anhydride were added.
was added and stirred under reflux (65°C) for 3 hours to perform a dehydration cyclization reaction.

After the reaction is complete, the reaction product is poured into 1 ton of water to precipitate the polymaleimide, which is then filtered, neutralized with an aqueous sodium carbonate solution, washed with a large amount of water, and dried to form a yellow-brown polyester. 97.311 particles of maleimide powder (yield: 98%) was obtained.

The melting point (capillary method) of this polymaleimide is 132-14
The temperature was 4°C.

Examples 2 to 8 Polymaleimides having the physical properties shown in Table 1 were obtained in the same manner as in Example 1, except that the aldehyde and amine used in Example 1 were changed to those shown in Table 1.

[Example-1] 100 parts by weight of the polymeric resin obtained in Example 1, 29 parts by weight of bisphenol A, and 2 parts by weight of tri-n-butylamine were dissolved in 130 parts by weight of methyl cellosolve.
The reaction was carried out at a temperature of 0° C. for 2 hours.

Next, add 1 part of "Kiazol 2E4MZ-CNS" (trade name manufactured by Shikoku Kasei Co., Ltd.) and impregnate a 0.16-thick aminosilane-treated glass cloth with the dissolved varnish.
Glyshireg was produced by drying at 30℃ for 10 minutes◎ 9 sheets of this prepreg were stacked at 180℃ and 60kg/cm.
'' for 60 minutes to create a 1.6-thick laminate.

Table 2 shows the results of measuring various heat resistance properties of this laminate.

[Examples 2 to 8] Laminated plates having the physical properties shown in Table 2 were obtained in the same manner as in Example 1, except that the composition was changed as in 2-2.

[Comparative example]

A varnish prepared by dissolving 100 parts by weight of aminobismaleimide-based grepolymer (trade name: Kerimide 601, sold by Roth Seelan Co., Ltd.) in 120 parts by weight of N-methyl-2-pyrrolidone was treated with aminosilane to a thickness of 0.16 m. A glass cloth was impregnated with the mixture and dried at 150°C for 15 minutes to obtain glycileg.

Nine sheets of this Glyshireg were stacked and inserted into a press at 180°C, held at contact pressure for 5 minutes, and then the pressure was increased to 60 kg/m'' and press-molded for 2 hours to obtain a laminate with a thickness of 1.6 vm. .

Table 2 shows the results of measuring the mechanical characteristics.

[Stability test]

The varnishes obtained in Examples 1 to B and Comparative Examples were stored in a constant temperature bath at 30°C, and changes in viscosity were measured to determine stability. The results are shown in Table-3.

Claims (1)

[Scope of Claims] 1) Component (A): For 1 mole 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 ▲ Numerical formula, chemical formula, table, etc. Yes▼ [In the formula, X is a hydrogen atom, a halogen atom, or a carbon number of 1 to
4 is an alkyl group or an alkoxy group] to obtain a polyamine by reacting an aromatic amine represented by 2 to 60 moles, and then adding maleic anhydride to the polyamine to obtain a polyamic acid, 100 parts by weight of polymaleimide obtained by cyclodehydration of the polyamic acid (B) Component: 5 to 100 parts by weight of a polyhydric phenol compound having at least two hydroxyl groups in one molecule (C) Component: Curing catalyst 0. A resin composition characterized in that 1 to 10 parts by weight of the above components (A), (B), and (C) are blended in the above proportions. 2) The polymaleimide is a mixture containing at least a polymaleimide represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and a polymaleimide represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ The resin composition according to claim 1, characterized in that: [In the formula, X is a hydrogen atom, a halogen atom, or a carbon number of 1 to
4 alkyl group or alkoxy group; m is an integer from 0 to 4. ]