JPH02151624A - New silicone-epoxy compound - Google Patents

Abstract

PURPOSE:To increase curing speed and to improve flexibility of a cured product by incorporating a specified structural formula. CONSTITUTION:The title compd. of formula II is obtd. by performing hydrosilylation of eugenol glycidyl ether (A) and a siloxane compd. (B) having H bound to Si of formula I (wherein R is a 1-4C alkyl, an alkenyl or phenyl; n is 1-1,000) in the presence of a catalyst (C) which is chloroplatinic acid or a complex of platinum chloride at room temp. to 200 deg.C. This compd. is, if necessary, compounded with a curing agent (a curing accelerator), another epoxy resin and another thermosetting resin and cured.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel silicone epoxy compound that has fast curing properties and provides a cured product with excellent visibility.

<Prior Art> In recent years, when epoxy resins are used in the field of electrical and electronic components, the resins are required to have well-balanced properties in order to increase the functionality and performance of the products.

For example, 1,3-bis(3-glycidoxyprobyl) 1,1,3,3-tetramethyldisiloxane is known as a silicone epoxy resin having excellent heat resistance and moisture resistance and low viscosity. Taking advantage of its low viscosity, this epoxy resin is used for epoxy adhesives that do not require a reactive diluent (Japanese Patent Publication No. 63-53234). provil) −
1,1,3,3-tetramethyldisiloxane is a relatively long-chain bifunctional epoxy resin, and in terms of molecular structure,
It is similar to epoxy resins that have epoxy groups at both ends of the aliphatic chain, such as tetraethylene glycol diglycidyl ether (Journal of Japan Adhesive Association, Vol. 19, No. 1, p. 12, published in 1983), making it a flexible epoxy resin. It is also used as a resin.

<Problem to be solved by the invention> 1.3-bis(3-glycidoxy 10 pyru)-1,1,
Although 3,3-tetramethyldisiloxane has excellent properties as described above, its reactivity as an epoxy resin is low, so the drawback is that the curing reaction takes a long time and productivity is poor.

<Means for Solving the Problems> Therefore, the present inventors conducted intensive studies in order to provide a compound that has fast curing properties and also exhibits flexibility when made into a cured product. The inventors have discovered that by using a silicone epoxy resin, it is possible to provide a cured product with excellent flexibility while having fast curing characteristics, leading to the present invention.

That is, the present invention provides a new compound represented by the following general formula (I).
It is a silicone epoxy compound.

(In the formula, R may be the same or different and represents an alkyl group, alkenyl group, or phenyl group having 1 to 4 carbon atoms, and n represents a number of 1 to 1,000.) The configuration of the invention will be explained in detail.

In the compound of the present invention, n is 1 to 1,00 in the above formula
It shows the number of 0, but when n is large, it becomes a high molecular compound and is usually obtained as a mixture. Specific examples of R in the above formula include a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group, an aryl group, a phenyl group, and the like.

Specific examples of the compounds of the present invention include compounds represented by the following formula.

CH=CH2CI(s As a compound (In the formula, R and n are the same as the above formula 〇.) It is a compound represented by

Specific examples of the raw materials used include, for example, compounds represented by the following formula.

The method for producing the silicone epoxy compound of the present invention is not particularly limited, but for example, a method using a hydrosilylation reaction of glycidyl ether of eugenol and a siloxane compound having silicon-bonded hydrogen using chloroplatinic acid or an olefin complex of platinum chloride as a catalyst. It can be synthesized by Here, siloxane (n=1
~1.000) The same below (n++nt=2~1.000) The same reaction below may be carried out in stoichiometric amounts, but it is preferable to use an excess of glycidyl ether of eugenol.

The reaction temperature of the hydrosilylation reaction is preferably in the range of room temperature to 200°C; below room temperature, the reaction is slow;
If the temperature is higher than 0.degree. C., by-products are formed, resulting in a decrease in yield.

This reaction can proceed smoothly regardless of whether or not a reaction solvent is added601! There are no particular restrictions on the solvents that can be used, and examples include aromatic compounds such as toluene and xylene, diethyl ether, tetrahydrofuran,
Ethers such as dioxane, nitriles such as acetonitrile and propionitrile, etc. are used.

Also, another of the compounds of the present invention! ! ! As a production method, there is also a method in which a hydrosilylation reaction of eugenol and a siloxane compound having silicon-bonded hydrogen is performed, and then the hydroxyl group is glycidylated with epichlorohydrin or the like.

The compound of the present invention can be used in the form of a composition together with a curing agent. Furthermore, a curing accelerator can be added and used if necessary.

Moreover, it can be used in combination with other epoxy resins or silicone compounds.

As curing agents that can be used, common epoxy resin curing agents are used, such as phenol novolac,
Cresol novolak, 3゜3'-diallyl-4,4'
- phenolic compounds such as dihydroxybisphenol A, 4.4=diaminodiphenylsulfone, 3.
3'diaminodiphenyl sulfone, 4,4'-methylenebis(2,6-dinitylaniline), 4,4'methylenebis(2-ethyl-6-methylaniline, 4,4'-
Amine-based compounds such as methylenebis(2-ethylaniline), acid anhydrides such as phthalic anhydride, tetradrophthalic anhydride, trimellitic anhydride, and pyromellitic anhydride;
Dicyandiamide, aromatic amine adducts of dicyandiamide (modified dicyandiamide), adducts of dicyandiamide and epoxy resins, diaminomaleonitrile and its derivatives, melamine and its derivatives, amine imide compounds, polyamines, addition compounds consisting of imidazoles and epoxy resins, adipine Examples include hydrazide compounds such as acid dihydrazide and isophthalic acid dihydrazide.

As the curing accelerator that can be used, ordinary curing accelerators for epoxy resins are used, such as N, N'-
Dimethylpiperazine, 2,4゜6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5
,4,0) undecene-7,4-dimethylaminopyridine or their acid addition salts, triphenylphosphine, tricyclohexylphosphine, bis(diphenylphosphino)ethane, tris(2,6-
Phosphine compounds such as (cymethoxyphenyl)phosphine, imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, or these Examples include acid addition salts and metal acetylacetonates such as aluminum acetylacetonate and cobalt acetylacetonate.

Furthermore, the properties can be optimized by mixing with other epoxy resins having different physical properties.

Other epoxy resins are not particularly limited as long as they have one or more epoxy groups per molecule; for example, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, tetrabromo bisphenol A diglycidyl ether, roglucinol triglycidyl ether, tetraglycidyldiaminodiphenylmethane, triglycidylmethaminophenol,
Phenol novolac type epoxy, cresol novolac type epoxy, bisphenol C glycidyl ether,
diglycidyl ether of 1,5-naphthalenediol,
diglycidyl ether of 1,6-naphthalenediol,
4.4'-bis(2,3-epoxygloboxy-3゜3
', 5.5'-tetramethylvininyl, 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, dibromophenylglycidyl ether, glycidyl phthalimide, methylglycidyl ether-p-tashabutylphenol, vinylcyclohexene oxide, triglycidyl ether of tris(4-hydroxyphenyl)methane, dimer acid-modified epoxy resin, castor oil-modified epoxy Examples include resin. These epoxy resins can be mixed with the silicone epoxy compound of the present invention within a range that does not impair the properties.

Furthermore, other thermosetting resins can be blended to exhibit their 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.

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

Example 1 20 g of eugenol glycidyl ether and 0.02 g of an i-propatool solution of 3% chloroplatinic acid were charged into a 100 ml Mitsuro flask, and 1.0 g was added from the dropping funnel while stirring.
．． 1,3.3~6.1g of tetramethyldisiloxane 2
It was added dropwise over 0 minutes.

During the dropwise addition, the reaction temperature was adjusted to 48 to 52°C using a heating water bath. After continuing stirring for 1 hour, the temperature was further increased to 70°C.
Next, the reaction solution was degassed under vacuum to obtain 23 g of a reaction product ("Silicone epoxy compound P").
).

The infrared absorption (IR) spectrum and 1H nuclear magnetic resonance (NMR) spectrum of this reaction product are shown in FIG. 1 and FIG. 2, respectively.

From these analysis results, silicone epoxy compound P can be identified as a compound represented by the following formula.

Example 2 20 g of eugenol glycidyl ether and 0.02 g of a 3% i-propanol solution of chloroplatinic acid were charged into a 100 ml Mitsuro flask, and the same procedure as in Example 1 was carried out to obtain 1.1
, 3,3, 5,5, 7.7-octamethyltetrasiloxane (12.8 g). The reaction product obtained after vacuum degassing was 28 g (referred to as Pasilicone Eboxy Compound Q II).

The IR spectrum of this reaction product is shown in Figure 3.
The R spectrum is shown in FIG.

From these analysis results, silicone epoxy compound Q can be identified as a compound represented by the following formula.

I prepared something like this.

Next, 15% of each silicone epoxy resin composition was
After heating at 0° C. for several minutes to uniformly dissolve the mixture, the mixture was degassed under reduced pressure, poured into a mold, and cured at 150° C. for 4 hours to obtain a molded plate.

The gelation time of the composition before heating was measured, and the elastic modulus of the molded plate after curing was measured.

Reference Examples 1 to 2, Comparative Example 1 Silicone epoxy compound P and silicone epoxy compound Q obtained in Examples 1 and 2 were used as epoxy resins, and 2-phenyl-4-
A 2,4-dihydroxybenzoic acid addition salt of methylimidazole (abbreviated as 2P4MZ acid addition salt) was added in the proportions shown in Table 1 to prepare a sample. As a comparative epoxy resin, 1.
3-bis(3-glycidoxypropyl)-1゜1.3.
Using 3-tetramethyldisiloxane [Silicone Epoxy Compound B2405, manufactured by Chisso ■], a curing accelerator was added in the same manner as above, and gelation time was produced on a hot plate at 150°C according to JIS 5909. The time was measured.

The elastic modulus was measured according to JIS K7113 (Plastic tensile test method).

The results obtained are shown in Table 1.

table

[Brief explanation of the drawing]

Figures 1 and 3 show silicone epoxy compound P, respectively.
2 and 4 respectively show the IR spectrum and NMR spectrum of silicone epoxy compound Q. Patent Publishing Co., Ltd. (Note) a) 1.3-bis(3-glycidoxyglobil)
-1,1,3,3-Tetramethyldisiloxane <Effects of the Invention> The silicone epoxy compound obtained by the present invention has rapid curing characteristics and is characterized by excellent flexibility when made into a cured product. Thus, for example, adhesives,
Transmittance (%) that can be used as raw material for flexible epoxy resin Transmittance (%)

Claims (1)

[Claims] A novel silicone epoxy compound represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, R may be the same or different and represents an alkyl group, alkenyl group, or phenyl group having 1 to 4 carbon atoms, n indicates a number from 1 to 1,000.)