JPS61252224A - Heat-resistant resin composition - Google Patents

Abstract

PURPOSE:The titled composition having a high glass transition point and excellent heat resistance and mechanical and electrical properties and being suitable for painting, lamination, molding, etc., consisting essentially of a specified epoxy compound, an alkenylphenol polymer and a cure accelerator. CONSTITUTION:An epoxy resin (A) consisting essentially of an epoxy compound of a tri(hydroxyphenyl)alkane of formula I and/or formula II (wherein R is H or a 1-10C alkyl and m is 0-5) in combination with, optionally, an epoxy resin of, e.g., bisphenol type or novolak type is mixed with an alkenylphenol polymer (B) of a degree of polymerization of 10-80 (e.g., poly-p-vinylphenol) in an amount corresponding to a molar ratio of the epoxy groups of component A to the OH groups of component B of 0.8-1.2 and 0.5-10wt%, based on component A, cure accelerator (C) (e.g., triethylamine tetraphenylborate).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a heat-resistant resin composition, and particularly to a heat-resistant thermosetting resin composition suitable for applications such as painting (coating material), lamination, and molding.

[Background of the invention]

In recent years, heat resistance requirements for plastic parts have become increasingly strict in order to reduce the size and weight of various electrical equipment, improve reliability, and reduce costs.j) Materials with heat resistance of 200°C or higher are strongly desired. ing. Conventionally, aromatic polyimides, aromatic polyamideimides, and the like have been known as heat-resistant resins for such uses. However, aromatic polyimide and aromatic polyamide-imide produce water during the curing reaction process, so they tend to have problems with molding workability and are limited to applications such as films.

On the other hand, epoxy resins are widely used as resins that do not produce by-products such as water during the reaction process. Epoxy resins cured with phenolic compounds have good electrical and mechanical properties, so they are used in electrical equipment, electronic parts, and laminated materials. It is considered useful due to its good physical and mechanical properties (for example, the
(See Publication No. 522).

However, for use at high temperatures of 200° C. or higher, materials with further improved heat resistance are required.

[Purpose of the invention]

An object of the present invention is to provide a thermosetting heat-resistant resin composition that is particularly suitable for painting (coating material), lamination, molding, etc. as a material with a high glass transition temperature and excellent heat resistance.

[Summary of the invention]

To summarize the present invention, the present invention relates to a heat-resistant resin composition, (a) the following general formula I and/or II: [...] (wherein, R is hydrogen or the number of carbon atoms 1 to 10 alkyl groups,
m is zero or a positive integer from 1 to 5)
hydroxyphenyl)alkane epoxy compounds, (
1) It is characterized by comprising an alkenylphenol polymer and (C) a curing accelerator as essential components.

The epoxy compounds are essentially tri(hydroxyphenyl)alkaline epoxy compounds, but conventionally known epoxy resins can be used in combination as long as the purpose of the present invention is not impaired. Specifically, bisphenol-type epoxy resin obtained by reacting bisphenol A with shrimp chlorohydrintocara, novolac plastic epoxy resin obtained by reacting novolac resin with shrimp chlorohydrin, and reacting xylene with formalin or toluene with paraformaldehyde. A polyphenol-based epoxy resin obtained by reacting a condensate of chlorohydrin, a condensate of a toluene resin or a toluene resin with phenols, and a polyphenol epoxy resin obtained by reacting a polyhydric phenol resin such as resol or hydroquinone with chlorohydrin. polyhydroxybenzene-based epoxy resins obtained from vinyl polymers, epoxy resins obtained from polyhydric alcohols such as glycerin, and epoxy resins obtained from alicyclic compounds such as cyclohexene, cyclobe/tashiene, and dicyclopentadiene. Epoxy resin, epoxy resin obtained from natural products such as starch or unsaturated higher fatty acids, nitrogen-containing epoxy resin obtained from aniline or aliphatic amines, epoxy resin having a nitrogen-containing heterocycle obtained from incyanuric acid, epoxy resin A silicon-containing epoxy resin obtained by reacting silanol with a silicon-containing epoxy resin obtained by oxidizing a silicon compound having a carbon-carbon double bond, a phosphite having an olefinically unsaturated group with peracetic acid. Epoxidized epoxy phosphorous acid, silicon,
Epoxy resins containing heavy metals other than phosphorus in the form of chelates may be used, and these may be used alone or in combination of two or more.

Furthermore, various modifiers such as maleimide compounds, polyamino bismaleimide compounds, melamine resins, silicone resins, silicone rubbers, polybutadiene rubbers, polyethylene, nylon, Teflon, glass fibers, carbon fibers, potassium titanate fibers, olanetonite fibers, Alumina fibers, zirconia fibers, ceramic fibers, metal fibers such as copper, aluminum and stainless steel, organic fibers such as cellulose, nylon and Kepler, calcium carbonate, magnesium carbonate, zircon, mica, clay, kaolin, aluminum hydroxide, hydroxide Magnesium, alumina, silica, fused silica glass, glass beads, white titanium, gypsum, barium sulfate, graphite, carbon black, graphite fluoride, molybdenum disulfide, boron nitride,
Fillers such as beryllium oxide and various metal powders, mold release agents such as higher fatty acids and waxes, coupling agents such as epoxysilanes, vinylsilanes, aminosilanes, borane compounds, alkoxyctitanate compounds, and aluminum chelate compounds, etc. is used.

Examples of alkenylphenol polymers used in the present invention include polymers obtained by thermal polymerization or ionic polymerization of vinylphenol, impropenylphenol, n-7" tenylphenol, or derivatives thereof. There are various types of polymerization, from polymers to dispersed polymers, but the degree of polymerization is 1 due to ease of handling, properties of the cured product, etc.
It is preferably in the range of 0 to 80 (weight average molecular weight of about 1,500 to 8,000).

The blending ratio of the above resin components is not particularly limited, but the ratio of the epoxy compounds (a) and the alkenylphenol polymer (b) is the number of moles of the epoxy group in (a)/(b).
The number of moles of hydroxyl groups is preferably in the range of 0.8 to 1.2.

The curing accelerator is one used to accelerate the curing reaction of epoxy compounds and alkenylphenol polymers, and various amines, imidazoles, and salts thereof are preferably used. Particularly useful are tetra-substituted boron salts of ammonium compounds, phosphonium compounds, arsonium compounds, imidazole compounds, pyridinium compounds, or morpholinium compounds, and urea compounds. As a specific example, 3-(parachlorophenyl)-
1,1-dimethylurea, 3-(44-dichlorophenyl)-pre-1-dimethylurea, 5-(S,4-dichlorophenyl)-1-methoxy-1-methylurea, 3-(
3,4-dichlorophenyl)-tl-diethylurea,
1-(2-methylfuclohexyl)-3-phenylurea, trimethylammonium tetraphenylborate,
Triethylammonium tetraphenylborate, triphenylammonium tetraphenylborate, diethylmethylammonium tetraphenylborate, tetrabuterammonium tetraptylborate, tetrabutylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetrabutylborate, tetra Butylphosphonium tetrabutylborate, tetramethylalunnicum tetraphenylborate, tetraphenylarsonium tetraphenylborate, dimethyldiethylarsonium tetraphenylborate or imidazolium tetraphenylborate, 2-ethyl-4-methylimidazolium tetraphenylborate, 2-ethyl-t
4-dimethylimidazolium tetraphenylborate,
1-cyanoethyl-2-phenylimidazolium tetraphenylborate), 1-7ly-2-methylimidazolium tetraphenylborate, pyridinium tetraphenylborate, morpholinium tetraphenylborate, methylmorpholinium tetraphenylborate, etc. , at least one kind of these is used.

The curing accelerator is [L5
It is preferable to use it in a range of 10 parts by weight.

[Embodiments of the invention]

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The invention is not limited to these examples.

Note that FIG. 1 shows Example 1, and FIG. 2 shows Example 2 and 3.
The figure is a graph showing the characteristics of the resin composition of Comparative Example 2 in terms of the relationship between temperature (° C., horizontal axis), elastic modulus (dyn/m'' vertical axis), and tan δ (vertical axis).

Examples 1 and 2 As the epoxy resin, 1.1.1-1-ly(hydroxyphenyl)propane epoxy compound (manufactured by Yuka Shell Co., Ltd.,
100 parts by weight of epoxy equivalent (174), 9-p-vinylphenol (manufactured by Maruzen Sekiyu Co., Ltd., molecular weight 1800-600)
0) 69 parts by weight and 1 part by weight of triethylamine-tetraphenylborate were heated and dissolved at 80°C, and a casting mold VC was prepared.
, Pour, 130℃ 73 hours + 180℃ 15 hours + 2
Heating was performed at 30° C. for 16 hours to obtain a cured resin plate with a thickness of 2 cm. From this molded plate, the heating loss was 1
The electrical characteristics were measured using a 00×100× piece. The results are shown in Table 1, and the dynamic viscoelasticity measurement results are shown in the faI diagram for Example 1 and in FIG. 2 for Example 2.

Examples 5 and 4 1,1.1-') as epoxy resin! J (hi)”O
Xyphenylene #) Propane epoxy compound (manufactured by Dow Chemical Co., epoxy equivalent f62) 100 in amount S, polyarvinylphenol (manufactured by Maruzen Sekiyu Co., Ltd., molecular weight 1800)
~600 Q) Using 74 parts by weight and 1 part by weight of triethylamine-tetraphenylborate, Examples 1 and 2
Various characteristics were measured in the same manner. The results are shown in Table 1.

Example 5 As Ebo chrysanthemum resin 1. XD9053 (Dow), an oligomer of tl-tri(hydroxyphenyl)propane
100 parts by weight (manufactured by Chemical Co., Ltd.), 54 parts by weight of p-9-p-vinylphenol (manufactured by Maruzen Sekiyu Co., Ltd.), and 1 part by weight of triethylamine-tetraphenylborate were heated and dissolved at 80°C, poured into a casting mold, and heated at 130°C. /3 hours +180c
The resin plate was cured by heating at 230°C for 5 hours and 16 hours to obtain a resin plate with a thickness of 2 cm. The electrical properties of this molded plate were measured using a 100×100×10×18 scale heat loss test.

The results are shown in Table 1. As is clear from Table 1, the monomer (
Formula (■) and Shioligoma H (formula (1)) are superior in various properties.

Example 6 100 parts by weight of the epoxy resin of Example 1, 54 parts by weight of poly-p-vinylphenol (molecular weight 400G), 2 parts by weight of montanic acid ester wax as a mold release agent, and γ-glycidoxyprobyl as a coupling agent. Trimethoxysilane 2
parts by weight, [52 parts by weight of tetraphenylphosphonium tetraphenylbore as an accelerator, 1 part by weight of carbon black as a coloring agent, and 380 parts by weight of fused silica glass powder as a filler, and 15 parts by weight in a kneader heated to about 75°C.
A molding material was prepared by kneading for a minute. This mold temperature is 180
A test piece was prepared at a pressure cuff of 0 KC973'' at ℃.The results are shown in Table 2.

Example 7 100 parts by weight of the epoxy resin of Example 1, 69 parts by weight of poly-p-vinylphenol (molecular weight 4000), and 1iif part of tetraphenylphosphonium (tetraphenylbore) as a curing accelerator were mixed with methyl ethyl ketone-methyl cellosolve (1:1). The varnish created by melting the varnish to a thickness of α
Impregnated with 18-rin epoxy silane treated glass cloth,
It was dried at 100°C for 15 minutes. Eight sheets of this prepreg were stacked and molded at a temperature of 180° C. and a pressure of 40 to 9151 inches. The properties of the sheets are shown in Table 2.

Comparative Example 1 100 parts by weight of the epoxy resin of Example 1, 61 parts by weight of 7-C-nol novolac resin (manufactured by Nippon Kayaku Co., Ltd.), 2 parts by weight of montanic acid ester wax as a mold release agent, and T-glycan as a coupling agent. Sidokykupropyltrimethoxysila/2 parts by weight, tetraphenylphosphonyl A as curing accelerator?
) 2 parts by weight of raphenylborate, 1 part by weight of carbon black as a coloring agent, 3 parts by weight of fused silica glass powder as a filler
A test piece was prepared in the same manner as in Example 6 by adding 80 parts by weight, and measured. The results are shown in Table 2.

Comparative Example 2 100 parts by weight of the epoxy resin of Example 1, 61 parts by weight of phenol novolak resin (manufactured by Sumitomo Chemical Co., Ltd.), and 1 part by weight of triethylamine tetraphenylborate were used to measure the properties in the same manner as in Examples 1 and 2. The results are shown in Table 1, and the viscoelasticity measurement results are shown in FIG.

Table 2 [Effects of the Invention] As explained above, the resin composition of the present invention has a very high glass transition temperature and excellent mechanical properties at high temperatures (230°C).
It has electrical properties and is suitable for applications such as casting, impregnation, molding, and lamination.

[Brief explanation of drawings]

1 and 2 are graphs showing the characteristics of the resin composition of the present invention, and FIG. 3 is a graph showing the characteristics of the resin composition of the comparative example.

Claims (1)

[Claims] 1. (a) The following general formula I and/or II: ▲There are mathematical formulas, chemical formulas, tables, etc.▼… [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼…[II] (Formula where R is hydrogen or an alkyl group having 1 to 10 carbon atoms,
m is zero or a positive integer from 1 to 5)
hydroxyphenyl)alkane epoxy compounds, (
A heat-resistant resin composition comprising (b) an alkenylphenol polymer and (c) a curing accelerator as essential components.