JPH03275712A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition useful for sealing, having excellent compatibility with various epoxy resins, comprising a silicon-containing epoxy compound having a specific structural unit and a compound capable of starting ring opening polymerization of epoxy group. CONSTITUTION:The objective composition comprising (A) an organosilicon compound shown by the formula (n is 2 or 3; R is substituent group and 1-20C alkyl, alkoxy or substituted alkyl; m is 0-4) containing three or more structural units directly bonded Si in one molecule and (B) a compound containing two or more functional groups, which can be subjected to addition reaction with epoxy group, in one molecule and/or a compound (e.g. 2-methylimidazole) capable of starting ring opening polymerization of epoxy ring as essential components.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention provides a cured product that has excellent compatibility with various epoxy resins, is cured by heating, and has excellent moisture resistance, heat resistance, and visibility. The present invention relates to a ripeable resin composition based on a silicon-containing epoxy compound that can be cured.

<Prior Art> In the field of electrical and electronic components, epoxy resins are widely used because of their excellent electrical properties, mechanical properties, and adhesive properties.

In recent years, as products in the electrical and electronic fields have become more multi-functional and high-performance, it has become desirable to give resins more advanced properties, such as visibility, and to reduce stress caused by ripening shrinkage. ing. Resins containing both an epoxy resin and an organosilicon compound in the molecule for the purpose of imparting flexibility to the resin, such as epoxy-modified silicone resins (
Japanese Patent Publication No. 63-24624) and silicone-modified epoxy resins (Japanese Patent Application Laid-open No. 63-22822) have been proposed.

<Problems to be Solved by the Invention> However, conventional modified vIJ resins generally have poor compatibility with epoxy resins and curing agents, and even when the compatibility is slightly improved, the visibility when made into a cured resin,
It was not possible to satisfy both heat resistance and moisture resistance in a well-balanced manner.

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to provide a resin composition that can satisfy mutual solubility, visibility, and other properties at the same time. It was discovered that by using a silicon-containing epoxy compound, it is possible to provide a cured product with excellent compatibility, flexibility, moisture resistance, and heat resistance, leading to the present invention.

That is, the present invention provides: (A) an organosilicon compound containing in one molecule three or more of the following structural units directly bonded to a silicon atom <n=2.3;
R is the same or different substituent and has 1 to 2 carbon atoms;
0 alkyl group, alkoxy group, substituted alkyl group; m - an integer from 0 to 4) and (B) a compound containing two or more functional groups in one molecule that can undergo an addition reaction with an epoxy group, and The present invention relates to a mature curable resin composition containing as an essential component a compound capable of initiating ring-opening polymerization of an epoxy ring.

In the present invention, component (8) is an organosilicon compound containing an epoxy group (hereinafter referred to as a silicon-containing epoxy compound).
It is important to use

The substituents R, R', and R'' in the organosiloxane structural unit RR' /\ in the silicon-containing epoxy compound may be the same or different, and may include an alkyl group having 1 to 4 carbon atoms, a substituted alkyl group, Substituent rt, R', R representing an alkenyl group, an alkenyl group or a phenyl group, a substituted phenyl group
Specific examples of "" include a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group, an allyl group, and a phenyl group.

Specific examples of the silicon-containing epoxy compound used in the present invention include those represented by the following formula.

(m-0,1) (k is an integer of 3 or more, l is an integer) The method for producing the silicon-containing epoxy compound used in the present invention is not particularly limited, but for example, olefin name of chloroplatinic acid or platinum chloride can be used as a catalyst. Examples include a method in which allyl phenyl glycidyl ether and a siloxane compound having a silicon-bonded hydrogen are subjected to a hydrosilylation reaction in the presence of a body, or a method in which allylphenol and a siloxane compound are subjected to a hydrosilylation reaction and then the hydroxyl group is glycidylated.

Compounds capable of initiating ring-opening polymerization of epoxy rings used in the present invention include, but are not limited to, the following compounds.

2-methylimidazole, 2-ethyl-4methylimidazole, 2-phenylimidazole, 2-phenyl-4
-Imidazole compounds such as methyl-5-hydroxymethylimidazole, addition salts thereof, addition reaction products of epoxy compounds and imidazoles, N,N-dimethylbenzylamine, 2.4.6-tris(dimethylaminemethyl ) Phenol, 1,8-diazabicyclo(5
,4,0) Tertiary amino compounds such as undecene-7,4, dimethylaminopyridine.

The amount of component B added to the composition of the invention is usually 1 part by weight per 100 parts by weight of component A.

The properties of the silicon-containing epoxy compound used in the present invention can be further improved by mixing it with other epoxy resins. When a cured resin is obtained by mixing and using in this way, it is important whether or not the mixed resins are mutually dissolved immediately before gelation.

The silicon-containing epoxy compound used in the present invention has excellent compatibility with most other epoxy resins. Fl! ! The epoxy resin is not particularly limited as long as it has one or more epoxy groups per molecule, such as bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, tetrabromobisphenol A diglycidyl ether, phloroglucinol triglycidyl ether, etc. Glycidyl ether, tetraglycidyldiaminodiphenylmethane, triglycidylmethaminophenol, phenol novolac type epoxy, cresol novolac type epoxy, diglycidyl ether of 15-naphthalenediol, diglycidyl ether of 1,6-naphthalenediol, 4,4'-bis (2,3-epoxypropoxy)
-3,3', 5.5'-tetramethylbiphenyl, 4,4'-bis(2,3-epoxypropoxy)biphenyl, 4,4-bis<2,3-epoxypropoxy)
-3,3', 5.5' ~ Tetraethyl biphenyl, resorcin diglycidyl ether, neopentyl glycol diglycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, P-tert-butylphenyl glycidyl ether, adipic acid diglycidyl ester, 0 -phthalic acid diglycidyl ester, dibromophenyl glycidyl ether, chrycidyl phthalimide, methyl glycidyl ether -p-tert-butylphenol, vinylcyclohexene dioxide,
Triglycidyl ether of tris(4-hydroxyphenyl)methane, dimer acid-modified epoxy v! Examples include Jti, castor oil-modified epoxy resin, and the like. These epoxy resins should be used within a range that does not impair the properties of the silicon-containing epoxy compound used in the present invention, that is, the silicon-containing epoxy compound 1! It is possible to mix 0.01 to 100 parts by weight based on the amount.

Furthermore, the thermosetting resin composition of the present invention can be blended with other thermosetting resins to further exhibit its properties. Examples of thermosetting resins that can be blended include phenol resins, urea resins, melamine resins, furan resins, diallyl phthalate resins, silicone resins, and urethane resins.

Compounds containing two or more functional groups capable of undergoing an addition reaction with epoxy groups used in the present invention include the following compounds, but are not particularly limited to these. Phenol novolac, cresol novolac, 3
．． Phenolic compounds such as 3'-diallyl-4,4'-dihydrooxybisphenol A, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-methylenebis(2-ethylaniline) ), 4,4'-methylenebis(2,6-dinitylaniline), 4,4'-methylenebis(2-ethyl-6
- amine compounds such as phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, dicyandiamide, tetramethylguanidine, diaminomaleonitrile, Melamine and its 'L
Examples include A conductor, amine imide compounds, polyamines, and hydrazide compounds such as adipic acid dihydrazide and isophthalic acid dihydrazide.

A known curing accelerator can be added to the thermosetting resin composition of the present invention, if necessary.

Specific examples of the curing accelerator include amine compounds such as 2,4.6 tris(dimethylaminomethyl)phenol, t,8-diazabicyclo(5,4,0)undecene-7,4,dimethylaminopyridine, and the like; acid addition salts such as hydroxybenzoic acid or dihydroxybenzoic acid, triphenylphosphine, tricyclohexylphosphine, bis(diphenylphosphino)methane, tris(2,6-cymethoxyphenyl)phosphine,
Bosphine compounds such as triphenylphosphine-triphenylborane and tetraphenylphosphonium tetraphenylborate, boron-containing compounds such as triethylammonium-tetraphenylborate and pyridinium-tetraphenylborate, and metals such as aluminum acetylacetonate and cobalt acetylacetonate. Examples include acetylacetonates.

A rubber component, a powdered filler, a diluent, a coloring agent, a pigment, a flame retardant, and the like are added to the composition of the present invention as necessary.

Examples of rubber components are not particularly limited, and include silicone rubber, nitrile rubber modified with a carboxyl group-containing compound, nitrile rubber modified with an amino group-containing compound,
Examples include polystyrene, polybutadiene, triblock copolymers of polystyrene, and hydrogenated polymers thereof.

Examples of powdered fillers include metal oxides such as aluminum oxide and magnesium oxide, metal hydroxides such as aluminum hydroxide, metal carbonates such as calcium carbonate and magnesium carbonate, diatomaceous earth powder, and basic magnesium silicate. , fired clay, finely powdered silica, fused silica, crystalline silica, carbon black, kaolin, finely powdered mica, quartz powder, graphite, asbestos, molybdenum disulfide, antimony trioxide, etc., as well as reinforcing agents and fillers for TIII fibers, Examples include inorganic fibers such as glass fiber, rock wool, ceramic W4 fiber, asbestos and carbon fiber, and synthetic fibers such as polyamide fiber.

Examples of diluents include cellosolves such as butyl cellosolve acetate, ethyl cellosolve, butyl cellosolve, γ-
Lactones such as butyrolactone, ε-caprolactone, and 4-valerolactone; aromatic compounds such as benzene, toluene, and xylene; esters such as ethyl acetate and methyl acetate; ketones such as methyl ethyl getone and methyl isobutyl ketone; Examples include carbonates such as honate and propylene carbonate.

Examples of colorants and pigments and flame retardants include titanium dioxide, yellow lead carbon black, iron black, molybdenum red, red blue,
Inorganic phosphorus such as cadmium yellow, cadmium red, red phosphorus,
Examples include organic phosphorus such as triphenyl phosphate, decabromodiphenyl ether, and bromine compounds such as hexabromobenzene.

The composition of the present invention may be mixed, if necessary, by melting at a high temperature, or by using a Banbury mixer, kneader, roll, screw or twin screw extruder, co-kneader, etc. at a temperature of about room temperature to 150°C. A method of using and kneading is applied.

Effects> Since the mature cured resin composition of the present invention uses a compound having both an organosiloxane skeleton and a crisitoxyphenyl group in one molecule as its main component, it has excellent properties in both moist heat resistance and visibility. A cured product can be obtained.

Method for evaluating characteristics> The method for evaluating characteristics in the present invention is as follows.

1. Glass transition temperature test piece (5 tar x 5 cm x 10 ma)
Create pj! , using a mechanical analyzer (Seiko Electronics Industries - 'rMAIO type), from 30 to 330 °C.
The inflection point in the displacement-temperature curve when the temperature was raised at 0° C./man was measured and determined as the glass transition temperature.

2. Water absorption molded plate (50mφ x 3-thickness) by Ruscher, Kutzker,
The water absorption rate was calculated by measuring the weight increase after absorbing water for 100 hours at 121°C1 relative humidity of 100% using a test device (PCT).

3. IPC3M with Cufi thickness 30IJI+ on insulation resistance alumina substrate
- After making a pattern of type 840B, applying varnish and curing it,
A voltage of DC 1,00 V was applied using a mold), and the resistance value after 1 minute was measured and used as the insulation resistance value.

Reference Example 1 (Synthesis of trifunctional silicon-containing poxy compound) 405 g of 0-allylphenyl glycidyl ether and 0.1 g of 3% chloroplatinic acid in isopropyl alcohol were mixed at 1.0
OOa+ was placed in a Mitsuro flask, and 89 g of methyltris(dimethylsiloxane) silane CH35i (O3i (CH3)2H)3 ('I'SL8242 manufactured by Toshiba Silicone ■) was added dropwise from the dropping funnel over 1 hour while stirring. After the completion of 0 dropwise addition, the reaction temperature was adjusted to 60°C using a heating bath, the mixture was stirred at that temperature for 1 hour, and then the temperature was raised to 70″C and stirring was continued for an additional 2 hours.

The reaction solution was heated to 200°C under vacuum (3ai+ll() or less).
The unreacted substances were distilled off to obtain the desired trifunctional silicon-containing poxy compound (Formula 1) (Formula ■) (Yield: 122 g, Yield = 94%, Viscosity: 500 Cp)
s (25°C)) was obtained. 1'l, this compound is abbreviated as silicon-containing epoxy compound 4S-3.

Reference Example 2 (Synthesis of tetrafunctional silicon-containing poxy compound) 41.7 g of 0-allylphenyl glycidyl ether and 0.1 f of a 3% chloroplatinic acid isoglobil alcohol solution were mixed into 1.0 OO
Tetrakis(dimethylsiloxanesilane)Sl(O
31 (CH3) 28) 4 (TSL manufactured by Toshiba Silicone ■
8248) was added dropwise over 1 hour.

During the dropwise addition, the temperature of the reaction mixture was adjusted using a heating bath to be 60°C. After the completion of the dropwise addition, the temperature was stirred for 1 hour, and then the temperature was raised to 70°C and stirring was continued for an additional 3 hours.

Thereafter, the post-reaction treatment was carried out in the same manner as in Example 1, and the objective 4
A functional silicon-containing poxy compound (formula ■) was obtained (yield: 1
28g, yield 93%, viscosity 1,0OOcps (25°C)
) 48g of 0-allylphenylglycidyl ether dissolved in 3% chloroplatinic acid in isopropyl alcohol.
A heating bath was used to adjust the reaction temperature to 60° C. during the 4 dropwise additions in which 156 g of tetramethyl was added dropwise over 1 hour from the dropping funnel while stirring.

After the dropwise addition was completed, stirred at the same temperature for 1 hour, and then
The temperature was raised to 0.degree. C., and stirring was continued for an additional 3 hours. Thereafter, the post-reaction treatment was carried out in the same manner as in Example 1, and the desired tetrafunctional silicon-containing poxy compound (Formula 11() <48-c
(abbreviated as ) was obtained. [! rate 93%
, viscosity 15. OO0cps) (25°C) This compound will be hereinafter abbreviated as silicon-containing epoxy compound 5S-8.

Reference Example 3 (Synthesis of a tetrafunctional silicon-containing poxy compound) Actual tumor example 1 Orthocresol novolac type epoxy resin (EOCN1020 manufactured by Nippon Kayaku) 100-layer plate part, silicon-containing epoxy compound synthesized by the method of Reference Example 1 43-333 parts by weight, phenol novolac resin (H-1 manufactured by Meiso Kasei ■) 6
2 parts by weight, triphenylphosphine (manufactured by Hokuxingkaji ■) 1
．． 33 parts by weight and 1.33 parts by weight of γ-glycidoxyglobyltrimethoxysilane were weighed and mixed, melt-kneaded for 15 minutes with a mixing roll heated to 100°C, cooled, and then pulverized to form a thermoset powder. A synthetic resin composition was obtained. This composition was heated to 100°C for several minutes to melt it, then vacuum degassed, poured into a mold, heated to 120°C for 2 hours,
It was cured by heating at ℃ for 3 hours to obtain a test piece for physical property evaluation.

The glass transition temperature determined by TMA method was 164°C. P
CT test (121°C, 2 atm, 100% RI-1,10
After 0 hours), the water absorption rate was 2.30% by weight, and the glass transition temperature decreased to 140°C. 40 parts by weight of the above powdered thermosetting resin composition (mixed solvent of xylene/n-butanol/methyl isobutyl ketone, weight ratio: 50:
10:40) 60 parts by weight were added and uniformly dissolved.

This varnish is applied onto the comb-shaped electrode and the film thickness after drying is:
50ull) PCT test II (121℃, 2 atm, 10
The insulation resistance between the wires before and after (0% RH 1100 hours) was evaluated. Insulation resistance before PCT test is 4. t x i O)
4Ω, insulation resistance after PCT test is 6.2 x 1011
It was Ω.

Example 2 Silicon-containing epoxy compound used in Example 1! II
Cured 5f JIJ physical properties were evaluated using the same procedure as in Example 1 except that 33 parts by weight of silicon-containing epoxy compound 51-3 was used instead of 33 parts by weight of J43-833.

The glass transition temperature determined by TMA method was 169°C. P
After CT test (121℃, 2 atm, 100%RH5100
The water absorption rate (time) was 2.38% by weight, and the glass transition temperature was lowered to 143°C. The insulation resistance value measured by the comb electrode method was 4.6X1014Ω before the PCT test.
After the test, it was 8.7×10 IoΩ.

Example 3 Silicon-containing epoxy compound 4S used in Example 1
-33 parts by weight of silicon-containing epoxy compound 43-C was used instead of 333 parts by weight, and the other operations were the same as in Example 1 to evaluate the physical properties of the cured product.

The glass transition temperature by TMA method was 171'C.

After PCT test (121°C, 2 atm, 100% Rl-[,
The water absorption rate after 100 hours) was 2.41% by weight, and the glass transition temperature decreased to 147°C. Comb type t4iF! The insulation resistance value according to the method is 4.4x10M before the PCT test.
After the PCT test, it was 3.8×10 sum Ω.

Comparative Example Silicon-containing compound 4S-333 used in Example 1
Instead of 11 parts by weight, 33 parts by weight of epoxy-modified silicone oil shown by the formula m below (BX16-855 manufactured by Toshi Dow Corning Silicone ■, average f11 #16 of n, epoxy equivalent 755) was used. The other operations were the same as in Example 1, and the physical properties of the cured product were evaluated.

The glass transition temperature determined by the TMA method was 152°C. PCT test @ f & (121℃, 2 atm, 100% RH,
The water absorption rate for 100 hours was 2.73% by weight, and the glass transition temperature was lowered to 125°C. The insulation resistance value determined by the comb electrode method was 2.3×10 Ω before the F) C'r test and 7.6×10 9 Ω after the PCT test.

<Effects of the Invention> The mature hardening resin composition of the present invention has excellent compatibility with various epoxy resins, and furthermore, when made into a cured product, visibility, moisture resistance, and sharpness are all satisfied in a well-balanced manner. It has the following. By taking advantage of these characteristics, it is possible to apply it to a wide range of areas, especially to sealing and adhesive applications.

Claims (1)

[Claims] (A) An organosilicon compound containing three or more of the following structural units directly bonded to a silicon atom in one molecule ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (n = 2, 3; R are the same or different substituents, and represent an alkyl group, an alkoxy group, or a substituted alkyl group having 1 to 20 carbon atoms; m = an integer of 0 to 4) and (B) can undergo an addition reaction with an epoxy group. A thermosetting resin composition containing as essential components a compound containing two or more functional groups in one molecule and/or a compound capable of initiating ring-opening polymerization of an epoxy ring.