JPS6119624A - Curable composition - Google Patents

Abstract

PURPOSE:The titled composition which can be cured by light irradiation within a short time and is suitable for protective layers of semiconductors, photoresists, etc., comprising an epoxy resin, an Al compound, a specified Si compound and a peroxide containing no Si in the molecule. CONSTITUTION:The titled composition is obtained by mixing 100pts.wt. epoxy resin (e.g., bisphenol A-derived epoxy resin) with a catalyst component comprising 0.001-10pts.wt. Al compound [e.g., tris(ethylacetoacetato)aluminum] and 0.1-20pts.wt. Si compound having a peroxysilyl group of the formula [wherein R<1-2> are each H or an (un)substituted hydrocarbyl group and n is 0-3] and a promotor comprising 0.1-20pts.wt. hydroperoxy group-containing peroxide having no Si in the molecule (e.g., cumene hydroperoxide). This composition is cured by irradiation with light at a wavelength of 180-600nm and then after-cured at 50-200 deg.C up to 4hr.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application] The present invention relates to a curable composition having improved curability, and more particularly to a curable composition having improved curability that is photocurable. It is.

[Conventional technology]

In recent years, there has been interest in the process of curing resins with light in connection with energy savings and workability. Among these, the process of photocuring epoxy resins has a wide range of applications and is important. There are currently two types of processes used to photocure epoxy resins.

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 this vinyl group. However, this modified epoxy resin has considerably lower heat resistance than the epoxy resin itself.

The other method is to cure the epoxy resin itself using a photodegradable catalyst. The catalyst used at this time has the following formula: %Formula% (In the formula, Ar is an aryl group such as a phenyl group, X is an iodine atom, a sulfur atom, a diazo group, etc., Y is BF4,
Represents PF6, ASF6, SbF6, etc. ) [Macro Molecusis, Vol. 10, p. 1307, 1977 (Macro
molecules, 10.1307 (1977))
; Journal of Radiation Curing.

Volume 5, page 2, 1978 (Journal of R
adiationCuring, 5, 2 (19
7B) ; Journal of Polymer Science Polymer Chemistry Edition, Vol.
Volume 7, page 2877.

1979 (Journal of Polymer
5science Polymer Chemistry
y Edition, 17, 2877 (1979
) ; Ibid., Vol. 17, p. 1047, 197! It
Year (Ibid., 17, '1047 (1979))
; Journal of Polymer Science Polymer Letters Edition, Volume 17, Page 759, 19
1979 (Journal of Polymer 5c
ience Polymer Letters Edit
ion, 17, 759 (1979)) i JP-A-55-6521.9; US Patent No. 4069
Specification No. 054; British Patent No. 1516511;
See the specification of British Patent No. 1518141, etc.].

However, although the resulting cured product obtained by curing epoxy resin with these catalyst components has good mechanical properties and heat resistance, the catalyst component becomes ionic impurities, so this cured product cannot be used in electrical equipment. When used for this purpose, there is a risk of deterioration of electrical properties such as deterioration of electrical insulation properties and corrosion phenomena.

[Problem that the invention seeks to solve]

The present invention aims to solve the above-mentioned problems of the conventional technology and to provide an epoxy resin-based photopolymerizable composition that has good photocurability and the resulting cured product has excellent electrical properties. This is the purpose.

[Means for solving problems]

The present invention comprises: (8) 100 parts by weight of epoxy resin, (B) 0.001 to 10 parts by weight of aluminum compound, (
C) Silicon compound having peroxysilyl group 0.1~
20 parts of sodium bicarbonate, (D) 0.1 to 0.1 parts of peroxide that does not contain silicon atoms in the molecule
A specific curable composition comprising 20 parts by weight solves the above-mentioned conventional problems and achieves the objective.

The epoxy resin (A) used in the present invention is:
Any material that is normally used as an epoxy resin composition may be used, and specific examples include bisphenol A epoxy resin; bisphenol F epoxy resin; phenol novolak epoxy resin; alicyclic epoxy resin; triglycidyl isocyanate. coffoxy resins containing i-rings such as hydantoin epoxy; hydrogenated bisphenol A type epoxy resins; aliphatic epoxy resins such as propylene glycol diglycidyl ether and pentaerythritol polyglycidyl ether; aromatic, aliphatic or cycloaliphatic Epoxy resin obtained by the reaction of the carboxylic acid of and epichlorohydrin; Spiro ring-containing epoxy resin; Glycidyl ether type epoxy resin which is the reaction product of O-allylphenol novolac compound and epichlorohydrin; Ortho position of each hydroxyl group of bisphenol A Examples include glycidyl ether-type synthetic resin, which is a reaction product of a diallylbisphenol compound having an allyl group and epichlorohydrin.

The aluminum compound (B) combines an organic group selected from the group such as an alkyl group, a phenyl group, a haloalkyl group, an alkoxy group, a phenoxy group, an acyloxy group, a β-゛diketonato group, and an 〇-carbonylphenorad group. It is a compound consisting of

Among the above organic groups, examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group,
Examples include 5ec-butyl group, t-butyl group, and n-pentyl group; Examples of the fluorinyl group include phenyl group, p-methoxyphenyl group, 0-methoxyphenyl group, and p-ethoxyphenyl group; haloalkyl Examples of the group include chloromethyl group, chloroethyl group, and chloropropyl group; examples of alkoxy group include methoxy group, ethoxy group, isopropoxy group, butoxy group, and pentoxy group; examples of phenoxy group include phenoxy group, 0 Examples include -methylphenoxy group, O-methoxyphenoxy group, O-nitrophenoxy group, and 2,6-dimethylphenoxy group; Examples of the acyloxy group include acetato group, propionato group, isopropionato group, butyrad group, stearado group, Examples include ethyl acedoacet group, propylacetacetate group, butylacetacetate group, diethyl malorado, dipivaloylmethanato group; β-diketonato group includes acetylacetonato group, trifluoroacetylacetonato group , Hegizafluoroacetylacetonato group, and 0-carboxyphenolado group include salicylaldehydato.

Specific examples of aluminum compounds include trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, triphenoxyaluminum, tri(p-methylphenoxy)aluminum, isopropoxyjethoxyaluminum, tributoxyaluminum, triacetoxyaluminum, triste Arado aluminum, tributyrad aluminum, tripropionato aluminum, triisopropionato aluminum, tris(acetylacetonato)aluminum, tris(trifluoroacetylacetonato)aluminum,
tris(pentafluoroacetylacetonato)aluminum, tris(ethylacedoacetate)aluminum,
Ethylacedoacet diisopropoxyaluminum,
Tris(salicylaldehydato)aluminum, Tris(diethylmalorado)aluminum, Tris(propylacedoacetate)aluminum, Tris(butylacedoacetate)aluminum, Tris(isopropylacedoacetate)aluminum, Tris(dipivaloylmethanato) ) Aluminum, diacetylacetonatodipivaloylmethanatoaluminum, ethylacedoacetodiisopropoxyaluminum, and the like. Among these, tris(ethyl acetoacetate)aluminum is preferred in terms of catalytic activity and reaction rate.

These aluminum compounds may be used alone, or in a mixed system of two or more, and the amount added is 0.001 to 10 parts by weight, preferably 1 to 5 parts by weight, per 100 parts by weight of the epoxy resin. is within the range of The blending amount is 0.00
If it is less than 1% 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 a peroxysilyl group (C) is
The following formula: %Formula% (In the formula, R+ and R2 may be the same or different and each represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, and n represents the number of O to 3. ).

Substituted or unsubstituted hydrocarbon groups in the above formula include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, undecyl group, dodecyl group, hexadecyl group. , Alkyl groups such as octadecyl group; Aryl groups such as phenyl group, naphthyl group, chindranyl group, methylphenyl group, xylyl group, dodecylphenyl group; benzyl group, phenylethyl group, α-methylstyryl group, cumyl group Araryl groups such as; cycloalkyl groups such as cyclohexyl and cyclooctyl; alkenyl groups such as vinyl, allyl, and cyclohexenyl; or some or all of the hydrogen atoms of these groups replaced with halogen atoms, etc.
I-substituted groups, such as chloromethyl group, β-cyanoethyl group, p-chlorophenyl group, m-chlorophenyl group, 0-chlorophenyl group, p-trifluoromethylphenyl group, m-trifluoromethylphenyl group, 〇-trifluoro Methylphenyl group, 3.3.3”-)
Examples include a lifluoropropyl group, a pentafluorophenyl group, and a chloromethylphenyl group.

Specific examples of silicon compounds having a peroxysilyl group include compounds represented by the following formula; Among these, t-butylperoxytriphenylsilane and cumylperoxytriphenylsilane are preferred because of their strong catalytic activity.

The amount of these silicon compounds added is 1 epoxy resin.
0.1 to 20 parts by weight, preferably 1
-10 parts by weight.

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

In addition to hydrogen peroxide, the peroxide (D) which does not contain a silicon atom may be any commonly used organic peroxide, and specific examples include the following.

Hydrogen peroxide; Ketone peroxide such as C11°; 1.1-bis(t-butylperoxy) 3,3.5-
Trimethylcyclohexane, 1,1-bis(butylperoxy)cyclohexane, n-glatyl-4,4-
Bis(1-butylperoxy)valerate, 2. ．． 2-
Peroxyketals such as bis(t-butylperoxy)butane; t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-mencune hydroperoxide, 2゜5-dimethylhexane-2,5-dihydroperoxide, 1.
Hydroperoxides such as L3,3-tetramethylbutyl hydroperoxide; di-t-butyl peroxide;
t-Butylcumyl peroxide, dicumyl peroxide, α,α゛-bis(t-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl -2,5-
Dialkyl peroxides such as di(t-butylperoxy)hexyne-3; acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5.5
-) diacyl peroxides such as limethylhexanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-) lyoyl peroxide; diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate , di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate, di(3-methyl-3-methoxybutyl)beroxydicarbonate, acetylcyclo Peroxy dicarponates such as hexylsulfonyl peroxide; t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxypivalate, t-butylperoxyneodecanoate, cumylperoxyneodecanoate , t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5-
Trimethylhexanoate, t-butylperoxylaurate, t-butylperoxyhenzoate, dibutyldiperoxyisophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t~
Examples include peroxy esters such as 1-butylperoxyisopropylcarphonate. Among these, hydroperoxides are preferred from the viewpoint of strong catalytic activity, and cumene hydroperoxide and methyl ethyl alcohol peroxide are particularly preferred.

The amount of these peroxides added is as follows: (8) epoxy resin 1
0.1 to 20 parts by weight, preferably 0.00 parts by weight
．． It is 1 to 10 parts by weight. If the amount is less than 0.1 part by weight, a sufficient curing accelerating effect will not be obtained, and if it exceeds 20 parts by weight, decomposition products of the catalyst component will remain in the epoxy resin after curing. , may affect the electrical properties and thermal stability of the resin. Of these peroxides,
In view of the magnitude of the curing accelerating effect and the stability of the composition, those containing a hydroperoxy group are preferred.

[Effect]

The curable composition of the present invention is put into practical use after being cured by a method such as room temperature photocuring, heating photocuring, or after-curing after photocuring. The wavelength of light required for photocuring varies depending on the components of the composition, but is usually 180 to 6 () Onm, preferably 200 to 400 nm.

Light sources include high-pressure mercury lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, xenon lamps,
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 performing after-cure, the temperature is usually 50-200°C, preferably 100-180°C.
It is preferable to carry out the test within 4 hours. The heating temperature in the case of thermal photocuring varies depending on the composition of the epoxy resin and the type of catalyst, but is usually 20 to 200°C, preferably 40 to 100°C.

To improve the mechanical strength of the compositions of the present invention, fillers such as fumed silica, wet silica, silanized silica, fine quartz powder, calcium carbonate, aluminum hydroxide, talc, etc., as well as colored dyes, pigments, oxidized It is okay to add inhibitors, etc.

〔Effect of the invention〕

The curable composition of the present invention uses an aluminum compound and a silicon compound having a peroxysilane group as catalyst components, and uses peroxide as a cocatalyst for the decomposition of the peroxysilane group, so the curing time by light irradiation is significantly shortened. can do. Therefore, the energy saving effect associated with shortening the curing time is extremely large.

The composition of the present invention can be used in various applications such as insulating materials for electrical equipment, protective layers for semiconductors, and photoresists.

〔Example〕

Hereinafter, the present invention will be explained by examples. In the examples, all parts represent parts by weight.

Example 1 F, RL4221 (trade name, U
Manufactured by CC; compound of the following formula (1), epoxy equivalent: 130,
Base resin composition 1 was prepared by dissolving 1 part of 1-lis(ethyl acetoacetate) aluminum and 4 parts of t-butylperoxytriphenylsilane in 100 parts of molecular weight 260).
I got 1.

1 part of peroxide shown in Table 1 was added to this base resin composition to obtain Compositions 12 to 18 of the present invention. These compositions were uniformly coated to a thickness of 10μ on an aluminum plate with a thickness of 0.3 mm, and irradiated with light from a distance of 6.5 c+w using a high-pressure mercury lamp of 80 W/c+w to determine the curing time and pencil hardness. The results of the measurements are shown in Table 1.

Table 1 Example 2 As an epoxy resin, jTsonosox 206-(trade name,
Manufactured by Chisso ■; Compound of formula (2) below, epoxy equivalent 70,
Base resin 21 was obtained by completely dissolving 0.5 part of tris(isobutylacedoacet)aluminum and 2.0 parts of cumylperoxytriphenylsilane in 100 parts of the resin having a molecular weight of 139).

Add this base resin to Permec N (trade name, NOF special product, main component methyl ethyl ketone peroxide, active oxygen content 10% or more)2. ．． 0 parts were added to obtain Composition 22. These compositions were applied to a 0.3 am thick steel plate with a thickness of 5 μm.
Apply it evenly to the thickness of
A cured film was obtained by light irradiation. The curing time and pencil hardness were measured and the results in Table 2 were obtained.

Table 2 Example 3 Epikote 828 (trade name, manufactured by Shell Chemical Co., Ltd.; bisphenol A type, epoxy equivalent: 190) as an epoxy resin
Composition 31 was obtained by completely dissolving 2 parts of tris(ethylacedoacet)aluminum and 8 parts of t-butylperoxytri(4-chlorophenyl)silane in 100 parts of tris(ethylacedoacet)aluminum and 8 parts of t-butylperoxytri(4-chlorophenyl)silane.

Composition 32 of the present invention was obtained by adding 5 parts of cumene hydroperoxide to this composition. These compositions
It was applied to a thickness of 30μ on an aluminum plate with a thickness of IIl, and was irradiated with light from a distance of 10c+n using a 160 h/cm high pressure mercury lamp (8kW) to measure the curing time and pencil hardness. The results are shown in Table 3.

Table 3

Claims (1)

[Claims] 1 (A) 100 parts by weight of an epoxy resin, (B) 0.001 to 10 parts by weight of an aluminum compound, (C) 0.1 part by weight of a silicon compound having a peroxysilyl group.
~20 parts by weight, and (D) 0.1~ of peroxide containing no silicon atoms in the molecule
A curable composition comprising 20 parts by weight. 2. The composition according to claim 1, wherein the aluminum compound of 2(B) is tris(ethylacetoacetato)aluminum. 2. The composition according to claim 1, wherein the amount of aluminum compound 3(B) is 1 to 5 parts by weight. Claim 1, wherein the silicon compound having a peroxysilyl group (4(C)) is t-butylperoxytriphenylsilane or cumylperoxytriphenylsilane.
Compositions as described in Section. The composition according to claim 1, wherein the amount of the silicon compound having 5(C) peroxysilyl group is 1 to 10 parts by weight. The composition according to claim 1, wherein the peroxide in 6(D) is a peroxide containing a hydroperoxy group. 7. The composition according to claim 6, wherein the peroxide in 7(D) is cumene hydroperoxide. 7. The composition according to claim 6, wherein the peroxide in 8(D) is methyl ethyl ketone peroxide. The composition according to claim 1, wherein the amount of peroxide in 9(D) is 0.1 to 10 parts by weight.