JPS603089B2 - Heat resistant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a novel resin composition that can be cured into a resin with excellent heat resistance by heating.

[Background of the Invention] In recent years, with the increase in the capacity of electrical equipment and the concomitant increase in the operating temperature due to the miniaturization of electronic devices, as well as the increase in reliability of electronic components, it has become necessary to There is a strong need to develop organic materials with stability, good mechanical strength, and excellent dielectric properties.

At the same time, these materials also require good moldability. Conventionally, epoxy resins, silicone resins, and the like have been mainly used for these purposes.

The former has good workability and moldability, but cannot be used for a long period of time under conditions equivalent to the insulation material heat resistance class (use temperature limit 18 pi○), and the latter is an H class material, but cannot be used at high temperatures. has low strength and adhesion and high moisture permeability. In addition, H such as diphenyl ether resin and polyimide resin
There are several types of heat-resistant materials, but they have drawbacks such as high cost, long curing times, and poor moldability, which limits their application as molding materials or solvent-free varnishes. In order to improve these momme points, an addition polymerization type thermosetting resin composition containing a polyfunctional epoxy compound and a polyfunctional isocyanate compound has been proposed.
However, even in this case, the isocyanate compound, which is one of the components, easily reacts with moisture in the atmosphere and deteriorates, which poses a major problem in terms of storage stability, which is an important property in use. In particular, storage stability is an essential characteristic for applications such as molding materials, prepregs, and powder coatings, and unless this property is excellent, commercialization will be difficult.

[Object of the Invention] An object of the present invention is to provide a new heat-resistant resin composition that overcomes the drawbacks of the above-mentioned prior art and has excellent storage stability.

[Summary of the invention]

The present invention has been made in view of the above, and is represented by the following general formula (1
) (wherein R is a divalent aliphatic group, a cycloaliphatic group, an araliphatic group,
(representing an aromatic group) and a carboxylic acid anhydride having three or more carboxyl groups in the molecule, at least two of which form an acid anhydride ring. Features.

Typical carboxylic anhydride compounds used in the present invention include monoanhydrides represented by the general formula (0). The carboxylic anhydride in the present invention has three or more carboxylic anhydrides in the molecule. Contains carboxyl groups and at least 2 of them
It is sufficient that these carboxyl groups form an anhydride ring.

Further, in the present invention, in addition to this carboxylic acid anhydride, a free acid represented by the following general formula (m) may be used in combination. the above(
0), (m) In both formulas, R has at least 3 carbon atoms and is an aliphatic, aromatic or alicyclic group, or at least one nitrogen, oxygen or sulfur group. Represents a trivalent organic group containing at least one group selected from atom-containing polycyclic groups.

As the carboxylic acid or carboxylic acid anhydride in the above formula (0) (m), R in these formulas includes some of the above-mentioned groups, and these may be directly or
10-, 1CO-, 1NY-CO-X- CO-NY-, 1CO-NY-X-NY-CO-, 1C
It is preferable that they are bonded through at least one of O-○1×-○-CO-, 10-CO-X-SO-0-1, and -CO-NY-NY-CO-.

Thus, X is an alkyl, dioxyalkyl, cycloanilidene or allyl divalent group, Y is an alkyl, allyl or cycloanyl group or hydrogen, and Y is an alkyl, allyl or cycloanilyl group.

The monoanhydrides of tricarboxylic acids which are preferably used are as follows.

Namely, trimellitic acid anhydride, naphthalene-2.
2,3-monoanhydride of 3,6-tricarboxylic acid, 3,4-mono/anhydride of diphenyl 3,4,4'-tricarboxylic acid, 1,8 of naphthalene-1,8,4-tricarboxylic acid
-monoanhydride, 1,2-monoanhydride of naphthalene-1,2,5-tricarboxylic acid, diphenylsulfone-3,4
・3,4-monoanhydride of 3-tricarboxylic acid, 3,4-monoanhydride of berylene-3,4,9-tricarboxylic acid,
diphenyl ether-3,4,4'tricarboxylic acid 3
・4-monoanhydride, monoanhydride of tricarbalic acid, 1 of cyclobesotagenyl-1,2,4-tricarboxylic acid
・2-monoanhydride, benzophene-3,4,4'-tricarboxylic acid monoanhydride, 2-(3',4'-dicarpoxyphenyl)-5-(3'-carpoxylphenyl)-1・3,4'-monoanhydride of 3,4-oxadiazole, 2-(3',4'-dicarboxyphenyl)
-5-3,4'-monohydrate of carboxybenzimidazole, 2-(3,4'-dicarboxyphenyl)-
3'/4'-monoanhydride of 5-lupoxy-penzoxazole, 3'/4'-monoanhydride of 2-(3'/4'-dicarboxyphenyl)-5-carpoxy-penzothiazole, 2- (3', 4'-dicarboxydiphenyl ether)-151 (4-carboxydiphenyl ether)-1, 3, 4-oxadiazole 3', 4'-monoanhydride, (3, 4- dicarpoxyphenyl)-4'
-carpoxymethane monoanhydride, (3,4-dicarboxyphenyl)-4'-carboxypropane monoanhydride, etc. Further, when tricarboxylic acid is used in combination as a free acid, an acid corresponding to the monoanhydride shown above is used. Therefore, if a mixture of a monoanhydride and a free acid is used, it is desirable that the free acid used corresponds to the monoanhydride. In addition to the above, the carboxylic acid anhydride used in the present invention includes tetracarboxylic dianhydride (the following general formula (W)), and this carboxylic acid anhydride and free carboxylic acid (the following general formula (V) )) is also possible. In the formulas (W) and (V), R2 contains at least two carbon atoms and has the same meaning as the symbol R used above.

In the formula, R2 includes the same several groups as R, and these groups are bonded either directly or through at least one of the same groups as the bonding group represented by R.
Examples of dianhydrides include the following.

That is, for example, dianhydride of pyromellitic acid, 2.3.6.
7-naphthalene-tetracarboxylic acid dihydrate, 3.3
・4,4'-diphenyl-tetracarboxylic acid dianhydride, 1,4,5,8 naphthalene-tetracarboxylic acid dianhydride, 1,2,5,6 naphthalene-tetracarboxylic acid dianhydride , bis(3,4-dicarboxyphenyl)sulfone dianhydride, 3,4,9,10-berylene-tetracarboxylic acid dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride Anhydride, ethylene-tetracarboxylic acid dianhydride, cyclobentadienyl-tetracarboxylic acid dianhydride, 3.4.3', 4'-benzophenone-tetracarboxylic acid dianhydride, 2.5 -bis(3',4'-dicarboxy-phenyl)-1,3.
4-oxadiazole monoanhydride, bis(3', 4'
-dicarboxyphenyl-1,3,4-oxadiazole) paraphenyl dianhydride, 2-(3',4'-dicarboxyphenyl)-15,6-dicarboxybenzimidazole dianhydride, 2 -(3',4'-dicarboxy-phenyl)-5,6-dicarboxybenzoxazole dianhydride, 2-(3',5-dicarboxyphenyl)-5,6-dicarboxy-penzthiazole dianhydride , dianhydride of 2,5-bis(3',5-dicarboxydiphenyl ether)-1,3,4-oxadiazole, dianhydride of bis(3,4-dicarboxyphenyl)methane dianhydride of bis(3,4-dicarboxyphenyl)propane. Further, the free acid tetracarboxylic acid compound used in combination may be the same as that corresponding to the dianhydride described above. Balavanic acid diisocyanate compounds can be produced, for example, by the method described in Tokkoku Seki No. 135972/1983.

That is, as described in the lower left column on page 5 to the upper left column on page 6 of the same publication, a diisocyanate represented by OCN-R-NH1CO-NH-R-NCO is suspended in methylene chloride, and then chlorocarbamoyl Cyanate (CICO-NCO) or oxalyl chloride (CICO-COCI)
) is added. Immediately, hydrogen chloride is generated and a reaction as shown in the following formula occurs, thus obtaining a parabanic acid diisocyanate compound, which is one of the components of the present invention. OCN-
R-NH1CO1NH1R-NCO+CICO1COC
I→In addition, this compound is named parabanic acid diisocyanate, for example, in the description in the same publication, page 6, upper left column 16-16, and in the Iwanami Rikagaku Dictionary, 3rd edition (Iwanami Shoten 1971, May 5).
This is clear from the "parabanic acid" section on page 1046 (published on May 20th), right column.

The blending ratio of the valavanic acid diisocyanate compound and the carboxylic acid compound (anhydride or a mixture of anhydride and free carboxylic acid) is preferably 0.25 to 4 mol of the latter per 1 mol of the former. Although there are no particular limitations on the production conditions, there are three conventional polyimide production methods, such as N2 in a polar solvent such as N-methyl-2-pyrrolidone, dimethyl sulfoxide, phenol, or m-cresol. Gas was passed into the reaction solution to create a dehydration condition by adding acetic acid, sulfuric acid, etc.
It is sufficient to proceed with 1 to 1 melon reaction with 5 pi○.

The generated reaction product itself is a brown solid and has excellent heat resistance, but depending on the blending ratio of valabanic acid diisocyanate and carboxylic acid compound (anhydride or a mixture of anhydride and free acid), terminal isocyanate groups may be formed. Alternatively, it becomes an imide compound having a terminal carboxylic acid anhydride.

For example, the reaction to form an imide compound is as follows. Note that old' represents a divalent group, and m represents a positive integer. Example 1 Example 2 The obtained reactants were an epoxy compound, a phenolic resin,
It can also be used in combination with unsaturated polyester resins, aniline resins, amine compounds, urea resins, melamine resins, and the like.

Furthermore, various catalysts such as amines and dioxylic acid derivatives can be added to these polyimide resin compositions to complete the cured product.

In addition, the composition of the present invention may include, depending on various uses and purposes,
One or more of the following materials may be used in combination.

For example, considering the use as a molding material, zircon, silica, fused silica glass, clay, alumina hydroxide, calcium carbonate, quartz glass, glass, asbestos, whisker, gypsum, magnesite, mica, kaolin, talc, graphite , cement, carbonyl iron, barium, ferrite, lead compounds, molybdenum disulfide, zinc white, titanium white, carbon black, silica sand, inorganic fillers such as wollastonite, fatty acids, mold release agents such as waxes, epoxysilane, vinyl silane , a poran compound, an alkoxy titanate compound, and the like can be used.

Further, if necessary, an elutriation agent made of antimony, phosphorus, etc., or an elutriation agent may be used. Furthermore, so-called solvents can be used for applications such as varnishes.

For example, organic polar solvents include N-methyl-2-pyrrolidone, N.N-dimethylacetoacide, N.N-dimethylformamide, N.N-diethylformamide, N.
-Methylformamide, dimethyl sulfoxide, N.
N-diethylacetamide, N/N-diethylmethoxyacetamide, hexamethylphasphoramide, pyridine, dimethylsulfone, tetramethylene sulfone, dimethyltetramethylene sulfone, etc., and phenolic soluble groups include phenol, cresol, etc. , xylenol, and other ketones such as methyl ethyl ketone and acetone.

The above materials may be used alone or in combination of two or more. In addition, a non-solvent such as toluene, xylene, petroleum naphtha, etc. can be used in combination if the amount thereof is small.

[Embodiments of the invention]

Next, the present invention will be specifically explained by showing examples.

Example i A predetermined proportion of 1.3-di (phenylisocyanate)-imidazolidine trione and various acid salts shown in the table below were mixed with N2 in 70 kinds of N-methyl-2-pyrrolidone.
While blowing gas into the reaction solution, heat at 130 to 0°C.
After reacting for 1q hours, filter, wash and dry.
Each reactant was obtained.

Table: Among these reactants, common to A to C, as a result of measuring infrared absorption spectra, 173 ratio Ne-1, 177 E-1 have characteristic absorption due to imide bond, 1670 ratio Ne-1 and 153 ratio S A characteristic absorption due to the amide bond was observed in -1.

In addition, all of the reactants A to C were 60% RH, 2yo
The fluidity of the composition during molding hardly decreased even after it was left in this environment for 3 months. This shows that the composition of the present invention has excellent storage stability. Example 2 Reactant AIOO part in Example 1, Fer/-
Formaldehyde nopolac compound (softening point 55°C) 3
Base part, bisphenol A type epoxy resin EP828 (manufactured by Shell) 15 base part, 2 parts of stearic acid as a hairstyle agent,
As a coupling agent, epoxysilane (KBM403
(manufactured by Oyo Kagaku) 0.5 part, as filler, silica powder, 65
2 parts were added and kneaded for 7 pi, lq minutes using two rolls of 8 inch diameter to obtain a molding material composition.

Using this material, transfer molding was carried out under the conditions of 18 mm, 200 k9/young, and 5 minutes to obtain molded and cured products for various tests.

The fluidity of this material under the above molding conditions is 35 inches in spiral flow, and the curability is 60 in Bacall cure. In addition, the heat distortion temperature of the cured product is 20 pi○ or more, 18 pi
The bending strength is 70k9/m. Example 3 Reactants B and C in Example 1 were each separately added to 1
A varnish was made by removing 0 base and adding 13 parts of N-methyl-2-pyrrolidone.

This was coated onto a glass cloth to obtain a prepreg with a resin content of 37%. lq woman's brep rig 1
A laminate was obtained by carrying out loading under the conditions of 70° C., 200° C., and 2 hours. The obtained laminate was flame retardant (V-○) and had a rating of 2
No blistering occurred even when exposed to a solder bath of No. 60.

[Effects of the Invention] As explained above, according to the present invention, a resin composition having excellent storage stability and heat resistance can be obtained.

Claims (1)

[Claims] 1. A parabanic acid diisocyanate compound represented by the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is a divalent aliphatic group, a cycloaliphatic group, an aromatic aliphatic group) (representing an aromatic group) and a carboxylic acid anhydride having three or more carboxyl groups in the molecule, at least two of which form an acid anhydride ring. Heat-resistant resin composition.