JPS6274919A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition whose curing rate can be controlled over a wide range and which is excellent in workability, by mixing an epoxy compound with a specified silanol-blocked polyisocyanate compound and an organometallic compound. CONSTITUTION:A silanol-blocked polyisocyanate compound (B) is obtained by reacting an active isocyanate group-containing organic isocyanate compound (e.g., 1,6-hexamethylene diisocyanate) with a silanol compound having at least one Si-bond aryl group, represented by formula I or II (wherein R1-6 are each H, Br, methyl or trifluoromethyl, R7-9 are each a 1-3C alkyl, n is 1-3 and land m are each 0-2). 100pts.wt. compound (A) having at least one epoxy group in the molecule is mixed with 1-30pts.wt. component B and 0.001-10pts. wt. organometallic compound (C) (e.g., acetylacetonatoaluminum) and, optionally, a compound having 0.1-1.5 equivalent of active hydrogen per equivalent of the epoxy group in component A.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to an epoxy resin composition, and more specifically, it is possible to control the curing rate over a wide range, has excellent workability, and is suitable for use in paints, adhesives, etc. , relates to an epoxy resin composition suitable as an electrical insulating material, a casting material, a molding material, and a material for laminates.

[Technical background of the invention and its problems]

Methods for curing epoxy resins include, for example, adding BF3 complex, dicyandiamide, etc. to the epoxy resin in advance and curing it by heating as needed during use, or using various amine compounds, carboxylic acids, phenolic compounds, etc. There are various methods such as a method in which a relatively highly active curing agent containing so-called active hydrogen is blended into an epoxy resin and cured at room temperature or by heating.

These methods generally include a curing accelerator necessary to control the curing speed of the epoxy resin. Usually, they are tertiary amine compounds or imidazole compounds.

However, once these curing accelerators are incorporated into a resin system, the curing accelerators begin to work anyway, and the resin system may exist in a state lacking storage stability or in a state with a rapid curing rate. Since the curing rate varies over a wide range, it has been extremely difficult to control the curing rate. This impedes workability when using epoxy resins and at the same time limits the fields in which the resins can be used, and there has been a strong desire for improvement.

[Purpose of the invention]

The object of the present invention is to solve the above-mentioned problems and provide an epoxy resin composition that can control the curing rate over a wide range, has excellent workability, and can be used for a wide variety of applications.

[Summary of the invention]

That is, the present invention comprises: (a) a compound having at least one epoxy group in the molecule; (b) an organic isocyanate compound having an active isocyanate group; and a silanol compound having at least one aryl group directly bonded to a silicon atom. The present invention relates to an epoxy resin composition comprising a silanol-blocked polyisocyanate compound (c) an organometallic compound.

At least one of the first essential components of the composition of the invention
Examples of compounds having epoxy groups include the following.

Namely, bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, Talesol novolac type epoxy resin, alicyclic epoxy resin, triglycidyl isocyanate and hydantoin. Heterocyclic epoxy resins such as epoxy, hydrogenated bisphenol A type epoxy resins, aliphatic epoxy resins such as propylene glycol diglycidyl ether and pentaerythritol polyglycidyl ether, aromatic, aliphatic or alicyclic carboxyl Glycidyl ester type epoxy resin obtained by the reaction of acid and epichlorohydrin, spiro ring-containing epoxy resin, glycidyl ether type epoxy resin which is the reaction product of ortho-allyl-phenol novolanc compound and epichlorohydrin, and the respective hydroxyl groups of bisphenol A. glycidyl ether type epoxy resin, which is a reaction product of a diallylbisphenol compound having an allyl group at the ortho position of , and epichlorohydrin.

Further, derivatives such as ethylene oxide, propylene oxide, styrene oxide, cyclohexene oxide, and phenyl glycidyl ether can also be used as necessary.

These epoxy resins may be used alone or as a mixture of two or more.

The organic isocyanate compound having an active isocyanate group, which is one of the components for synthesizing the silanol-blocked polyisocyanate compound of component (b), which is the second essential component, includes 1,6-hexamethylene diisocyanate, 1,8-octamethylene Diisocyanate, 1.12
-Dodecamethylene diisocyanate, 2,2.4-1-
Alkylene diisocyanates such as lymethylhexamethylene diisocyanate; 3-methyl isocyanate-3
, 5,5-trimethylcyclohexyl isocyanate,
Cyclopenticine-1,3-diisocyanate, cyclohexylene-1,4-diisocyanate, methyl-2,
Unsaturated isocyanates such as 6-diycyanatocaproate, bis(2-isocyanatoethyl) fumarate, 4-methyl-1,3-diisocyanatecyclohexane, transvinylene diisocyanate, 4,4-methylene-bis(cyclohexylisocyanate), Methane diisocyanate, N, N', N''-tris(6-
itcyanate hexamethylene) biuret, bis(2
Carbonates of diisocyanates such as -isocyanatoethyl) carbonate; other well-known isocyanates derived from aliphatic polyamines; toluene diisocyanate, xylylene diisocyanate, dianisidine diisocyanate, 4,4'-diphenylmethane diisocyanate, 1-ethoxy-2 , 4-diisocyanatebenzene, 1-chloro 2,4-diisocyanatebenzene, tris(4-isocyanatephenyl)methane, naphthalene diisocyanate, phleolein diisocyanate,
Aromatic isocyanates such as 4,4°-biphenyl diisocyanate; etc. and dimers or trimers thereof, phenylene diisocyanate, 3,3”-dimethyl-4,4”-biphenyl diisocyanate, p-isocyanate benzyl isocyanate, tetra Chloro-1゜3-phenylene diisocyanate, 2,4,6-dribromo 1,3-phenylene diisocyanate, bis(2
-isocyanatoethyl)benzene, 3-isocyanatomethyl-3,3,5-)limethylcyclohexyl isocyanate, and also 2-isocyanateethyl-6-
such as isocyanate caproate and prepolymers such as polyether or polyester polyol,
Examples include prepolymers obtained from polyisocyanate and polyhydroxy compounds or polyamine compounds. Furthermore, block compounds of the above-mentioned various diisocyanate compounds and other compounds such as trimethylolpropane, polyether, polyesteramide, diethylene glycol, etc. can also be used as the organic isocyanate compound.

The silanol compound in which at least one oryl group, which is the other component to synthesize component (b), is directly bonded to a silicon atom is represented by the following formula; (wherein, even if R1 to R6 are the same, They may be different and each represents a hydrogen atom, a bromine atom, a methyl group, a trifluoromethyl group, or a vinyl group.

n is a positive integer from 1 to 3, and m represents 0.1°2), or a compound represented by the following formula; (wherein R7 to R, are the same or different; Moyo (each represents an alkyl group having 1 to 3 carbon atoms, n is a positive integer from 1 to 3, l represents o, 1°2) can be used. Specific examples of compounds represented by the general formula include compounds represented by the following.

The method for synthesizing a silanol-blocked polyisocyanate compound by reacting an organic isocyanate compound having an active isocyanate group with a silanol compound in which at least one aryl group is directly bonded to a silicon atom is not particularly limited, but examples include methyl ethyl ketone, acetone, It is carried out by heating to about 75 to 90°C in the presence of a solvent such as toluene, xylene, or tetrahydrofuran.

This silanol block polyisocyanate compound is
One or more types can be used, and the blending amount is (a)
The amount is 1 to 30 parts by weight, preferably 3 to 15 parts by weight, based on 100 parts by weight of the components.

Organometallic compounds, which are the third essential component, include gold muds such as aluminum, titanium, chromium, zirconium, copper, iron, manganese, nickel, vanadium, and cobalt.
Examples include those in which various organic groups are directly bonded and various complexes.

Particularly useful are organoaluminum compounds.

Specifically, alkoxy groups having 1 to 10 carbon atoms such as methoxy, ethoxy and isopropoxy groups; acyloxy groups such as acetoxy, stearoyl, butyryloxy, propionyloxy and isopropionyloxy groups; phenoxy groups , an aryloxy group such as a p-methylphenoxy group; and a complex having acetylacetone, trifluoroacetylacetone, pentafluoroacetylacetone, ethylacetoacetate, salicylaldehyde, diethylmalonate, etc. as a ligand. can.

These organometallic compounds may be used alone or in a suitable mixture of two or more, and the amount added is 0.001 to 10 parts by weight per 100 parts by weight of component (a).
Parts by weight, preferably 0.5 to 5 parts by weight.

A compound having active hydrogen can also be added to the composition of the present invention consisting of components (a) to (c), if necessary.

Examples of compounds having active hydrogen include phenolic compounds, amine compounds, imide compounds, amide compounds,
Examples include thiophenol compounds and carboxylic acid compounds.

Among these compounds, phenolic compounds and amine compounds are particularly useful, and compounds in which an 10H group, -NH2 group, or ═NH group is directly bonded to an oryl group are particularly effective.

Examples of these phenolic compounds include the following. Namely, phenol, resorcinol, 0-cresol, m-cresol, p-cresol, chlorophenol, nitrophenol, bromophenol, dinitrophenol, picric acid, hydroquinone, bitecatechol, pyrogallol, hydroxyhydroquinone, 2-methoxyphenol, 2,4 -di-butoxyphenol, 2.5-dichlorophenol, 3-acetoxyphenol, m-aminophenol, p~ruaminophenol 4.4'-dihydroxydiphenylpropane, 4.4'-dihydroxydiphenylmethane,
3.3°-dihydroxydiphenylpropane, 4.4
° -dihydroxydiphenyl ether, 4.4'
-dihydroxydiphenyl sulfone, 4,4°-dihydroxy-2,2° dimethyl diphenyl ether, 4.4
' -dihydroxydiphenylethane, 4.4' -
Examples include dihydroxydiphenylketone, 2-allylphenol, and 2-allylcresol, as well as phenol derivatives obtained by reacting the above-mentioned phenolic compounds with various aldehyde compounds such as formalin and acetaldehyde. These phenol compounds can be used alone or in a mixture of two or more.

In addition, examples of amine compounds include phenylenediamine,
In addition to diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminodiphenyl sulfide, aromatic amine compounds consisting of halogen or alkyl substituted products thereof, and various amine compounds obtained by reaction of aniline or aniline derivatives with aldehydes, Aminophenol derivatives having a hydroxyl group and an amine group in one molecule can be mentioned.

The amount of the above-described active hydrogen-containing compound is usually 0.1 to 1.5 equivalents, preferably 0.5 to 1.2 equivalents, per equivalent of the epoxy compound as the first essential component.
It is equivalent.

Furthermore, a curing agent, a filler, a mold release agent, a coupling agent, a pigment, etc. can be added to the composition of the present invention, if necessary.

[Embodiments of the invention]

Hereinafter, the present invention will be explained in further detail with reference to Examples.

2 g of trisacetylacetonadoaluminum was added to 98 g of Epicote 828 (trade name, manufactured by Shell Co., Ltd., epoxy equivalent weight 189) and heated to 85° C. to prepare a uniform resin liquid. This is called liquid A. Similarly Epicote 828 9
7 g of silanol block polyisocyanate obtained by reacting a block copolymer obtained by reacting trimethylolpropane and TDI-80 with triphenylsilanol at 80 to 85 ° C in the presence of xylene.
was added and heated to 80°C to prepare a uniform resin liquid. This is called liquid B.

These solutions A and B were left at room temperature for 3 months.

No increase in the viscosity of each resin liquid was observed.

Next, mix this A liquid and B liquid, and further add bisphenol A, bisphenol S, bisphenol, and diaminophenylmethane (DAM).

Diaminodiphenyl ether (DDE) and diaminodiphenylsulfone (DDS) were blended as shown in Table 1, and the resulting resin liquid was placed on a hot plate maintained at the indicated temperature to determine the time required for gelation. Established.

The results are shown in Table 1.

Instead of the 2 g of trisacetylacetonadoaluminum used in each solution A in Example 1 and Example 4, the same amount of Ti, Cr, and Zr acetylacetonato complexes were blended into 98 g of Epicote 828. A-1 (Ti) liquid, A-2
CCr> solution and A-3 (Zr) solution were prepared. No increase in viscosity was observed in any of these solutions even after being left at room temperature for 3 months.

By replacing these liquids with liquid A in Table 1, six types of resin compositions shown in Table 2 were prepared.
The gelation time at °C was measured.

The results are summarized in Table 2.

The components shown in Table 3 were blended in the composition shown in Table 4 to obtain the composition of the present invention. This composition was heated at 175°C for 3 minutes, and then further heated and cured at 175°C for 8 hours to form a test piece. Using this test piece, the following tests were conducted.

The results are shown in Table 4.

The linear expansion coefficient, glass transition point, and volume resistivity tests are conducted by J.
According to IS K-6911. The passipation klassock and A1 slide are each subjected to a cold cycle (-65
The incidence of PSG cracks that occurred in the test piece after 60°C - room temperature H2O0°C, or the deviation width of the outermost AJ wiring of the 6 mm x 6 mm test piece was observed using a microscope. The viscosity is determined by increasing the value at 175℃ using a flow tester (
(manufactured by Shimabara Seisakusho).

〔Effect of the invention〕

As explained above, the composition of the present invention has good curability, and the curing rate can be controlled by selecting the heating temperature. Furthermore, the heat resistance, mechanical properties,
It has excellent electrical insulation properties, and its industrial value is extremely large.

Claims (3)

[Claims] (1) (a) A compound having at least one epoxy group in the molecule (b) A silanol obtained by reacting an organic isocyanate compound having an active isocyanate group with a silanol compound in which at least one aryl group is directly bonded to a silicon atom. An epoxy resin composition comprising a blocked polyisocyanate compound (c) an organometallic compound. (2) The epoxy resin composition according to claim 1, wherein the organometallic compound is an organoaluminum compound. (3) A patent claim in which 0.1 to 1.5 equivalents of a compound having active hydrogen are further added to each component (a) to (c) based on 1 equivalent of the epoxy group in component (a). The epoxy resin composition according to item 1.