JPH02167331A - Silicone-epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition suitable for sealing or adhesion giving a cured material having excellent water-vapor resistance, heat resistance and flexibility, having excellent mutual solubility and curing by heat, comprising a specific silicone-epoxy resin and curing agent. CONSTITUTION:The aimed composition is composed of (A) a silicone-epoxy resin expressed by formula I (R<1>-R<4> are 1-4C alkyl, 1-4C alkenyl or phenyl; n is 1-100) (e.g. compound expressed by formula II) and (B) a curing agent (e.g. bisphenol A). Besides, (C) a curing accelerator (e.g. 2-methyl imidazole) may be added, as necessary.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention provides a silicone which has excellent mutual solubility and can further be cured by heating to provide a cured product having excellent moisture resistance, heat resistance, and flexibility. The present invention relates to an epoxy till fat composition.

<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 versatile and high-performance, it has become desirable to provide resins with even more advanced properties, such as visibility, and to reduce stress caused by thermal contraction. ing. For the purpose of imparting flexibility to resins, a method has been proposed in which a modified dimethylsiloxane compound having epoxy groups at both ends as shown in the following formula is added (``Thermosetting Resins'', Vol. 8, No. 3, 3
4-35, published in 1987).

(n is, for example, 1 to 19) <Problem to be solved by the invention> However, this modified dimethylsiloxane compound
Mutual solubility with epoxy resins and curing agents is generally poor, and even if mutual solubility is slightly improved, flexibility, heat resistance, and moisture resistance cannot be satisfied in a well-balanced manner when made into a cured resin. Ta.

Means for Solving the Problems> Therefore, as a result of extensive research in order to provide a resin composition that can simultaneously satisfy mutual solubility, flexibility, and other properties, the present inventors have found a specific The present inventors have discovered that by using a silicone epoxy resin composition, it is possible to provide a cured product that has excellent mutual solubility and is also highly flexible, moisture resistant, and heat resistant.

That is, the present invention is a silicone epoxy resin composition comprising a silicone epoxy resin represented by the following formula (1) and a curing agent.

(In the formula, Rj, R2, R3, and 4 may be the same or different, and each is an alkyl group having 1 to 4 carbon atoms,
It represents an alkenyl group or a phenyl group having 1 to 4 carbon atoms, and n represents a number from 1 to 100.) In the present invention, it is important to use a silicone epoxy resin represented by the above formula (2). In the above formula, n represents a number from 1 to 100, but when n is large, it becomes a polymer compound and is usually obtained as a mixture. In that case,
n is shown as an average value. In the present invention, n is preferably 1-10. Further, specific examples of R1, R2, R3R4 include methyl group, ethyl group, propyl group, butyl group, vinyl group, allyl group, phenyl group, etc.
R1, R2, R3R4 may be the same or different. Specific examples of the silicone epoxy resin used in the present invention include those represented by the following formula.

/\ The method for producing the silicone epoxy resin used in the present invention is not particularly limited, but for example, a siloxane compound having allyl phenyl glycidyl ether and silicon-bonded hydrogen in the presence of an olefin complex of chloroplatinic acid or platinum chloride as a catalyst. Examples include a method in which allylphenol and a siloxane compound are subjected to a hydrosilylation reaction, and then a hydroxyl group is glycidylated.

The curing agent used in the present invention is not particularly limited as long as it is a normal epoxy resin curing agent that cures the silicone epoxy resin represented by the above formula (2).For example, bisphenol A, bisphenol F, 4.4'- Dihydroxybiphenyl, 2,2'-diallylbisphenol A
, hydroquinone, phloroglucinol, salicylic acid,
Phenol compounds such as phenol novolak resin and cresol novolak resin, 4,4-diaminodiphenylsulfone, 4,4'methylenebis(2-ethylaniline), 4,4'-diaminodiphenylmethane, diaminomaleonitrile and its derivatives, amine imide compounds, etc. Amine compounds, acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, hydrazide compounds such as adipic acid dihydrazide, isophthalic acid dihydrazide, dicyandiamide, epoxy and Examples include addition reaction products consisting of imidazole.

Further, in the present invention, among conventionally known curing accelerators, those having an action as a curing agent are also included as the curing agent of the present invention. For example, 2
- Imidazole compounds such as methylimidazole, 2-ethyl-4-methylimidazole, 2phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, or their hydroxybenzoic acid or dihydroxybenzoic acid, etc. acid addition salts,
N,N'-dimethylpiperazine, 2,4,6-tris(
Dimethylaminomethyl> Phenol, amine compounds such as 1,8-diazabicyclo(5,4,0)undecene-7,4-dimethylaminopyridine, or acid addition salts thereof such as hydroxybenzoic acid or dihydroxybenzoic acid, etc. .

The amount of curing agent added to the composition of the present invention is usually 0.1 to 20 parts by weight per 100 parts by weight of silicone epoxy resin.
This is 0ffl and part.

The silicone epoxy resin composition of the present invention may optionally contain a known curing accelerator that is commonly used.

Examples of curing accelerators include triphenylphosphine, tricyclohexylphosphine, bis(diphenylphosphino)methane, tris(2,6-cymethoxyph), among the compounds that can be included as curing agents mentioned above. Examples include phosphine compounds such as enyl) phosphine, and metal acetylacetonates such as aluminum acetylacetonate and cobalt acetylacetonate.

When adding the above-mentioned curing accelerator to the composition of the present invention,
Usually 0 parts per 100 parts by weight of silicone epoxy resin.
．． 1 to 200 parts by weight are added.

The properties of the silicone epoxy resin 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 silicone epoxy resin used in the present invention has excellent compatibility with most other epoxy resins.

Other epoxy resins are not particularly limited as long as they have one or more epoxy groups per molecule, such as bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, tetrabromobisphenol A diglycidyl ether, and fluorolog. Rucinol triglycidyl ether, tetraglycidyldiaminodiphenylmethane, triglycidylmethaminophenol,
Phenol novolak polyglycidyl ether, cresol novolak polyglycidyl ether, bisphenol C diglycidyl ether, 1,5-naphthalenediol diglycidyl ether, 1,6-naphthalenediol diglycidyl ether, 3.3', 5.5'-tetramethyl -4,4'biphenol diglycidyl ether, 4
．． 4'biphenol diglycidyl ether, tris(4
-hydroxyphenyl)methane triglycidyl ether, resorcin diglycidyl ether, neopentyl glycol diglycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, p-tert-butylphenyl (methylglycidyl) ether, Examples include vinyl cyclohexene dioxide, dibromophenyl glycidyl ether, glycidyl phthalimide, diglycidyl adipate, dicrycidyl phthalate, dimer acid-modified epoxy resin, and castor oil-modified epoxy resin. These epoxy resins can be mixed in a range that does not impair the properties of the silicone epoxy resin used in the present invention, that is, 0.01 to 100 parts by weight per 1 part by weight of the silicone epoxy resin.

Furthermore, the silicone epoxy 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 phenolic resins, urea resins, Examples include melamine resin, furan resin, diallyl phthalate resin, silicone resin, and urethane resin.

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

Examples of components are not particularly limited, and examples include silicone rubber, nitrile rubber modified with a carboxyl group-containing compound, nitrile rubber modified with an amino group-containing compound, a triblock copolymer of polystyrene, polybutadiene, and polystyrene, or its hydrogenation. Examples include polymers.

Examples of fillers include oxides such as aluminum oxide, magnesium oxide, silica, quartz, and antimony trioxide; hydroxides such as aluminum hydroxide and magnesium hydroxide; carbonates such as calcium carbonate and magnesium carbonate; Examples include diatom, calcined clay, kaolin, mica, asbestos, pulp, and wood flour.

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 ketone and methyl isobutyl getone, ethylene carbonate, and propylene. Examples include carbonates such as carbonate.

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

The method of mixing the silicone epoxy resin composition of the present invention may be a method of melting at a high temperature or a Banbury mixer or a kneader at a temperature of about room temperature to 150°C.
, a method of kneading using a roll, a -screw or twin-screw extruder, a co-kneader, etc. is applicable.

<Examples> Next, examples will be shown to specifically explain the present invention, but these examples do not limit the present invention.

Reference Example 1 (Synthesis of silicone epoxy resin) 0-allylphenyl glycidyl ether 25otr and 3
% chloroplatinic acid i-propatool solution 0.1g to 1j!
Pour 88 g of 1.1.3.3-tetramethyldisiloxane into a Mitsuro flask and add 1.1.3.3-tetramethyldisiloxane from the dropping funnel while stirring.
It dripped over time.

During the dropwise addition, the reaction temperature was adjusted to 50-60°C. After stirring at the same temperature for 1 hour, the temperature was raised to 70°C and stirring was continued for an additional 2 hours.

The reaction solution was degassed under vacuum to obtain the desired 1,3-bis[3-(0-
glycysiloxyphenyl)propyl]1゜1.3.3-
Tetramethyldisiloxane (hereinafter referred to as "silicone epoxy resin A") was obtained.

Thereafter, silicone epoxy resins B and C were each synthesized using the raw materials shown in Table 1 according to the above procedure.

Table 1 shows the raw materials used in the synthesis and the corresponding reaction products.

Table 1 Examples 1 to 9 Silicone epoxy resins A, B, and C synthesized in Reference Example 1
4,4-monodiaminodiphenylsulfone (DDS), 4,4-diaminodiphenylmethane (
DDM), phenol novolak resin H-1 (OH equivalent Jl 108 g/eq, manufactured by Meiso Kasei ■), methyltetrahydrophthalic anhydride (Me-HHPA), salicylic acid (SA), 2-ethyl-4-methylimidazole (2E4MZ>, 2,4-dihydroxybenzoic acid addition salt of 2-phenyl-4-methylimidazole (2P4M
A silicone epoxy resin composition (rIj) was obtained by blending each of the following compounds in the proportions shown in Table 2. However, Example 4
and No. 5, triphenylphosphine (TPP) was used in combination as a curing accelerator.

As a comparative epoxy resin, 1,6-hexanethiol diglycidyl ether (11 denacol"EX212,
Nagase Kasei Kogyo ■), bisphenol F type epoxy resin ("Epicron" 830-3, manufactured by Dainippon Ink & Chemicals ■), epoxy-modified silicone oil (formula ○, B
X16-855, epoxy per jt750. n=16.3
, manufactured by Toto Silicone ■), ...... O and bis(3-glycidoxyprobyl)tetramethyldisiloxane (formula below @, B2405, manufactured by Chisso ■) in the proportions shown in Table 2. A silicone epoxy resin composition was obtained.

Next, 10% of each silicone epoxy resin composition was applied.
After melting by heating in a heating bath at 0 to 150°C, the mixture was degassed under vacuum, poured into a mold, and cured at 180°C for 5 hours to obtain a molded plate.

Various physical properties of the composition before curing or the molded plate after curing were measured by the methods described below. Table 2 shows the results.
Shown below.

Mutual solubility 2 The mutual solubility of the silicone epoxy resin and other epoxy resins or curing agents is shown when each composition in Table 2 is dissolved at 100 to 150°C.

Judgment is by visual inspection, marked with ○ is not separated during dissolution. Indicates that the x mark is separated into two layers. represents something.

Water absorption rate: Molded plate (3 spaces x 20 spaces x 60 mm)
The water absorption rate was calculated by measuring the weight increase after absorbing water for 20 hours at 121 °C and relative humidity of 100% using a pressure cutter test device (PCT).

Shore hardness: AS'l''MD22404: 1m Therefore, the hardness (Shore A or Shore D) of the cured product was measured.

Heating loss: The weight loss was measured when the cured product was heated at a rate of 10°C/1 lin from 30°C to 300°C using a differential thermogravimetry simultaneous measurement device ff (Seiko Electronics Co., Ltd., TG/DTA200 model). The weight loss was determined by heating.

The silicone epoxy resin composition of the present invention has excellent mutual solubility with other epoxy resins and curing agents, and when made into a cured product, all physical properties such as water absorption, hardness, and weight loss at high temperatures are well balanced. It can be said that it has been removed.

<Effects of the Invention> The silicone epoxy resin composition of the present invention has excellent mutual solubility, and furthermore, when made into a cured product, it has the property of satisfying all of flexibility, moisture resistance, and heat resistance in a well-balanced manner. . 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 silicone epoxy resin composition comprising a silicone epoxy resin represented by the following general formula (I) and a curing agent. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, R^1, R^2, R^3, and R^4 may be the same or different, and each represents the number of carbon atoms. It represents an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 1 to 4 carbon atoms, or a phenyl group, and n represents a number from 1 to 100.)