JPS60190421A - Curable resin composition - Google Patents

Abstract

PURPOSE:The titled resin composition that is composed of an epoxy resin, an aluminum compound, a specific silicon compound and hydroquinone, thus being cured by irradiation for a short time to give an insulation material suitable for electric appliances, because of its good electric properties. CONSTITUTION:The objective resin composition is composed of (A) an epoxy resin, (B) an aluminum compound, (C) a silicon compound bearing peroxysilyl groups, which is represented by formula I (R<1>, R<2> are substituted or unsubstituted monovalent hydrocarbon; n is 1-3), concretely the compound of formula II and (D) hydroquinone. It is preferred to contain 1-5wt% of component B, 1-10wt% of C and 0.5-10wt% of D, based on component A, respectively.

Description

Detailed Description of the Invention [Technical Field of the Invention] The present invention relates to a photocurable resin composition having improved photocurability, and more particularly, to a photocurable resin composition for use as an insulating material and a resist material for electrical equipment. The present invention relates to a photocurable composition that exhibits a cured product having electrical properties suitable for use in a photocurable composition.

[Technical background of the invention and its problems] In recent years, there has been interest in the process of curing resin with light in relation to energy saving and workability. Among these, the process of photo-curing epoxy resin has a wide range of applications (and is important.Currently, there are two types of processes used for photo-curing epoxy resin.

One of them is to modify an epoxy resin with a vinyl group-containing compound such as a photopolymerizable acrylic compound, and photopolymerize it via the vinyl group. However, this modified epoxy resin has considerably lower heat resistance than the epoxy resin itself.

The other type is one in which the epoxy resin itself is cured using a completely photodegradable catalyst. The catalyst used at this time has a linear formula: % formula % (wherein Ar represents a phenyl group, etc.; X represents an iodine atom, a sulfur atom, a diazo group, etc.; Y represents BF4.
PF, AsF6. Represents SbF6 etc. ) [Macro, Molecules, Vol. 10, p. 1000, 1977 (Mao
romoleoules, 10, 1307 (197
7)l; Journal of Radiation Curing, Volume 5, Page 2, 1978 (Journal
of Radiation Curing, mutual, 2(1
978) l; Journal of Polymer Science, Polymer Chemistry, Editorial, No. 17
Volume, 2877 pages, 1979 (Journal of
Polymer 5oience PolymerOh
emistry Edltion, 17, 2877
(1979) ; ide., Vol. 17, p. 1047,
1979 1 Ibid., 17.1047 (197?)); Journal of Polymer Science Polymer Letters Edition, Vol. 17, p. 759, 1979
Year (Journal of Polytoer Soi
enoePO1ym6r Lesters Editi
on, 17, 759 (1979));
-755219; US Pat. No. 4,069,054; British Patent No. 1,516,511; British Patent No. 1,518,141, etc.].

However, when an epoxy resin is cured with these catalyst components, the resulting cured product is

Although it has good mechanical properties and heat resistance, the catalyst component becomes ionic impurities, so when this cured product is used in electrical equipment, it may cause deterioration of electrical properties such as poor electrical insulation and corrosion phenomena. There is a risk that this may occur.

Tomo, in order to solve these problems, we requested
The composition described in No. 58889 has been proposed. That is, it is a composition consisting of an epoxy resin, an aluminum compound, and a silicon compound having a peroxy group, and has the characteristics that it is photocurable and the resulting cured product is an epoxy resin with excellent electrical properties. It had the disadvantage of a long curing time.

[Purpose of the invention]

An object of the present invention is to provide an epoxy resin-based photocurable composition that has good photocurability and the resulting cured product has excellent electrical properties.

[Structure of the Invention] The present invention provides a curable resin composition consisting of (A) an epoxy resin, (B) an aluminum compound, (0) a silicon compound having a peroxinyl group, and (D) a human quinone. relating to things.

The epoxy resin (A) used in the present invention may be any resin as long as it is normally used as an epoxy resin composition (specific examples include bisphenol A epoxy resin; bisphenol Y epoxy resin). ; Phenol novolak type epoxy resin; Alicyclic epoxy resin; Complex-containing epoxy resin such as triglycidyl incyanate and hydantoin epoxy; Hydrogenated bisphenol A type epoxy resin; Globylene glycol diglycidyl ether, pentaerythritol polyglycidyl ether, etc. Aliphatic epoxy resin; aromatic,
Epoxy resin obtained by the reaction of aliphatic or alicyclic carboxylic acid with epichlorohydrin; Spiro ring-containing epoxy resin; Glycidyl ether type epoxy resin which is the reaction product of 0-allylphenol novolac compound and epichlorohydrin: Bisphenol derivative Rezo J
Examples include glycidyl ether type epoxy resin which is a reaction product of a diallyl bisphenol compound having an allyl group at the ortho position of the hydroxyl group of l and shrimp chlorohydrin.

The aluminum compound (B) is a compound formed by bonding an organic group selected from the group such as an alkoxy group, a phenoxy group, an acyloxy group, a β-diketonato group, and an o-carbonylphenolad group.

Among the above organic groups, examples of the alkoxy group include methoxy, ethoxy, impropoxy, butoyac, and pe/toxy; examples of the phenococc group include phenoxy, 0-methylphenoxy, O-methoxyphenoxy, p-=trophenoxy group, 2,6-dimethylphenoxy group; Examples of the acyloxy group include a7tato, propionato, ingrobionato, butyrado, stearado, ethylacetoacetate, probylacetoacetate. , butylacetoacetato, diethylmalato, dipivaloylmethanato; β-diketonato groups include acetylacetonato, trifluoroacetylacetonato, hexafluoroacetylacetonato, 0-carbonylphenorad group. Examples include salicylaldehydate.

Specific examples of aluminum compounds include trismethoxyaluminum, trisethoxyaluminum, triswingloboxyaluminum, trisphenoxyaluminum, trisparamethylphenoxyaluminum, ingloboxydiethoxyaluminum, trisethoxyaluminum, trisacetoxyaluminum, and tris. stearad aluminum, trisbutyrad aluminum,
Aluminum tripropionate, aluminum triswinglobionato, aluminum trisacetylacetonado, aluminum aluminum trifluoroacetylacetonado, aluminum aluminum trispentafluoroacetylacetonado, aluminum aluminum trisethylacetoacetato, aluminum aluminum trissalicylaldehyda, trisdiethylmaloradoaluminum, trisingrovir acetoacetatoaluminum, trisingrovir acetoacetatoaluminum, trisbutylacetoacetatoal(nium), trisdihybaloylmethanatoaluminum, diacetylacetonatodipivaloylmethanatoaluminum, these The aluminum compound may be used alone or in a mixed system of two or more.
．． The range is 0.001 to 10%, more preferably 1 to 5%. If the amount is less than 0.001% by weight, sufficient curing properties cannot be obtained, and if it exceeds 10% by weight, it will cause increased costs and deterioration of electrical properties.

The silicon compound having the peroxysilyl group (0) has the following formula; Aryl groups such as alkyl groups; cycloalkyl groups such as cyclohexyl and cyclooctyl groups; aryl groups such as phenyl, naphthyl, anthranyl, tolyl and xylyl groups; araaryl such as becumyl, styryl and cumyl groups Groups; alkenyl groups such as vinyl, allyl, and cyclohexenyl groups; and groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms, etc. Examples: ebachlormethyl group, p-chlorophenyl group, m- Chlorphenyl group, o-chlorophenyl group,
p-trifluoromethylphenyl group, m-)! Examples include J fluoromethylphenyl group, 〇-trifluoromethylphenyl M, 3,5.3- ) +) fluoropropyl group, but due to strong catalytic activity and ease of synthesis, phenyl group, Must be p-chlorophenyl group, m-chlorophenyl group, 〇-chlorophenyl group, p-)lifluoromethylphenyl group, m-17 fluoromethylphenyl group, O-chlorophenyl group, methyl group, vinyl group is preferred.

In addition, R2 in the above formula may be essentially the same as R1 in the above example, but from the viewpoint of ease of synthesis and availability of raw materials, t-butyl group, -amyl group, cumyl group, etc. preferable.

Specific examples of silicon compounds containing peroxysilyl groups include compounds represented by the following formula;

The amount of these silicon compounds added is preferably in the range of 40.1 to 20% by weight, more preferably 1 to 10% by weight, based on the epoxy resin.

If the amount is less than 0.1% by weight, sufficient curing properties will not be obtained, and although it is possible to use more than 20% by weight, it will increase the cost and cause decomposition products of the catalyst component. This may become a problem.

(DJ's hydroquinone is the most special feature of the present invention; it becomes benzoquinone when irradiated with light, generates protons, attacks all the peroxysilyl groups of the above-mentioned peroxysilyl group-containing silicon compound, and quickly becomes catalytic. It acts as a photo-curing reaction initiator that can produce silanol compounds in high yield in a short time and drastically shorten the curing time of the above epoxy resin.Hydroquinone has an ultraviolet absorption band in the ultraviolet region. For,
It is particularly effective in photocuring reactions, and can overcome the drawback of conventional photocurable resins, such as poor deep curing properties.

The amount of hydroquinone added in the composition of the present invention is:
The amount is preferably in the range of 0.1 to 20% by weight, more preferably 0.5 to 10% by weight based on the epoxy resin. If the blending amount is less than 0.1% by weight, sufficient sensitizing effect will not be obtained, and it is possible to use more than 20% by weight, but the effect of just adding it is expected. It can't be done and there's no point.

The photocurable composition of the present invention can be photocured at room temperature, photocured by heating,
It is then cured and put into practical use by a method such as after-curing after photo-curing. The wavelength required for photocuring varies depending on the components of the composition, but is usually 150 to 600 nm, preferably 200 to 400 nm; the heating temperature for heating photocuring varies depending on the composition of the epoxy resin and the type of catalyst. Usually 20-200℃, preferably 40-1
It is 00℃. As a light insert, a high pressure mercury lamp, a carbon arc lamp, a xeno/lamp, an argon glow discharge tube metal halide lamp, etc. can be used. Further, after-curing after photocuring is an effective means for stabilizing the physical properties of the epoxy resin, but it may or may not be carried out depending on the application. When the entire after-cure is carried out, it is usually carried out at 50 to 200'C, preferably 100 to 180C, for a period of up to 4 hours.

In order to improve the mechanical strength of the composition of the present invention, fillers such as fumed silica, wet silica, silanized silica, fine quartz powder, charcoal, aluminum hydroxide, and talc are added to the composition, as well as pigments and antioxidants. It is okay to add agents etc.

〔Effect of the invention〕

The photocurable composition of the present invention is cured by short-time light irradiation,
Furthermore, a cured product having excellent electrical properties can be obtained. The composition of the present invention is used as an insulating material for electrical equipment, a protective layer for semiconductors, a photoresist, and the like.

[Embodiments of the invention]

The present invention will be described below with reference to Examples. Parts in the examples indicate parts by weight.

Example 1 To 100 parts of epoxy resin gut, 4221 (Union Carbide Corporation product name; compound of the following formula fil epoxy equivalent weight 130, molecule 'jk 260), 1 part aluminum trisethylacetoacetate and 4 parts t-butylperoxytriphenylsilane. Completely complete? aM
A base resin (Sample 11) was obtained. One part of hydroquinone was dissolved in this base resin to obtain sample 12, which is a composition of the present invention.

These compositions were uniformly coated to a thickness of 10 μ on an aluminum plate with a thickness of f 0.5 Ill, and irradiated with light from a distance of 6.5 m using a metal halide lamp of aoW,/m to determine the time required to become tack-free ( curing time) and pencil hardness. In addition, these samples were poured into an aluminum petri dish, exposed to light for 120 seconds under the same conditions, and cured.The results shown in Table 1 were obtained when the thicknesses were compared.

27- Table 1 Example 2 Chinnox 206 (trade name manufactured by Chisso Corporation; compound of the following formula (2), epoxy equivalent: 70
, Molecule 1159), 0.5 parts of tris-inpropylacetoacetate aluminum and 2.0 parts of cumylperoxytriphenylsilane were completely dissolved to obtain a base resin (sample 21)'. 2.0 parts of hydroquinone was added to this base resin to obtain sample 22, which is a composition of the present invention.

Using these as samples, the same operation as in Example 1 was performed to generate 80 W/(
The curing time, pencil hardness, and cured thickness were measured using a high-pressure mercury lamp of
The results are shown below.

Example 3 As an epoxy resin, 100 parts of Epicor) 828 (M1 product name, manufactured by Shell Chemical Co., Ltd.; bisphenol A type epoxy 190 to 210 molecules Iit! 180), 2 parts of trisethylacetoacetoaluminum, and tertiary-butylperoxytri A base resin (Sample 61) was obtained by completely dissolving all 5 parts of phenylsilane. Six parts of hydroquinone was added to this base resin to obtain sample 52, which is a composition of the present invention. Using these samples as samples, the curing time, pencil hardness, and thickness after curing were measured using a 1 dOw/m high-pressure mercury lamp in the same manner as in Example 1, and the results shown in Table 3 were obtained.

Table 3 Example 4 Samples 11 and 12 of Example 1 were poured and applied onto the aluminum plates, and heated to 10 (I
From a distance of n, sample 11 was irradiated for 120 seconds, and sample 1 was irradiated for 120 seconds.
Sample No. 2 was irradiated for 30 seconds and a good cured resin surface was obtained. When the electrical tangent of this cured resin surface was completely measured, the results shown in Table 4 were obtained.

Table 4 51- Teitosei Arizen 111 Sansho (Voluntary) 1. Indication of the case Patent Application No. 1982-46691 2. Name of the invention Curable resin composition 3. Relationship with the case by the person making supplement 1F 4+f permission Applicant: Toshiba Silicone Corporation 4, Agent: 1-3, Mekibashi Yokoyama-cho, Chuo-ku, Tokyo Nakai Building Column 6 of the detailed explanation of the invention in the specification, Contents of the amendment (1) Specification, page 3, lines 5-6 [[Macro Molecule (1)
Page 8, line 8 “Tripropionatoaluminum, J” was corrected to “trispropionatoaluminum” (+) Page 11, line 14 “0-chlorophenyl group” was changed to “
〇-Trifluoromethylphenyl group” and revised Volume 1r (1) Same page 27, line 6 “Pigment” was corrected as “color dye pigment” (1) After “metal halide lamp” in line 6 from the bottom of page 28 “(4) (1) At the end of page 29, insert r (4k
w) Insert J (1) Insert r (8kw) J after "High pressure mercury lamp" in the 3rd to 2nd rows from the bottom on page 30 (1) Insert 3rd to 4th rows from the bottom of Table 3 on page 31 "High pressure mercury lamp"
Insert “(4 wise)” after

Claims (1)

[Claims] 1. A curable resin composition containing % of (Al epoxy resin; (B) an aluminum compound; (0) a peroxysilyl-based silicon compound; (D) hydroquinone. 2. The amounts of the aluminum compound, the silicon compound having a peroxysilyl group, and hydroquinone are o, ooi to 10% by weight, and 0.1% by weight, respectively, based on the epoxy resin.
5. The curable resin composition according to claim 4, wherein the percentage is 20% by weight and 0.1-20% by weight.