JPS5998127A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To provide a photopolymerizable composition having excellent photo- setting property and giving a cured product having excellent electrical characteristics such as high dielectric loss tangent, etc., by compounding an epoxy resin with an acid anhydride and a catalyst composed of an aluminum compound and a specific silicon compound. CONSTITUTION:The objective composition is prepared by compounding (A) an epoxy resin with (B) an acid anhydride (e.g. methyl tetrahydrophthalic anhydride) and (C) a catalyst composed of (i) preferably 1-5wt% of an aluminum compound (preferably an organic aluminum compound such as trispropylacetoacetato aluminum) and (ii) preferably 1-10wt% of a silicon compound having o-nitrobenzyl group [e.g. di(o-nitrobenzyloxy)diphenylsilane]. The composition is cured e.g. by heating at 60-100 deg.C under irradiation with light having a wavelength of 300-400nm for 1-60min.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a novel photopolymerizable composition, and more particularly, it has electrical properties suitable for use as insulating materials and resist materials for electrical equipment. The present invention relates to a photopolymerizable composition that provides a cured product.

[Technical background of the invention and its problems]

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. One of the two lies about the process currently used to photocure epoxy resins is that the epoxy resin is modified with a photopolymerizable vinyl group-containing compound such as acrylic, and this vinyl It is photopolymerized via the 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;
PF6. ASF6. Represents SbF6 etc. ) [Macromolecules, Vol. 10, p. 1307, 1977 (Macro
+Nocleles.

Ship, 1307 (1977)); Journal
Of Radiation Curing, Volume 5, Page 2,
1978 (Journal of Hadia-ti
on Curing, 5, 2 (1978));
Journal of Polymer Science Polymers
Chemistry Edition, Volume 17.

2877 pages, 1979 (Journal of p.
polymer
Mistry Bdition, 17, 2877
(1979); Vol. 17, p. 1047, 1
979 (ibid., beans.

1047 (1979)); Journal of Polymer Science Polymer Letters Edition.

Volume 17, page 759, 1979 (Tournal
of polymerSience Polymer
r Letters' Edition, 17,
759 (1979)); JP-A-55-65219; U.S. Patent No. 4069054, iJl Invasion; British Patent I 1516511; British Patent No. 151
8141 specification, etc.] 0 However, when an epoxy resin is cured with these catalyst components, the resulting cured product has good geometrical properties and heat resistance; If this cured product is used in electrical equipment, it will cause ionic impurities.
[Objective of the Invention] The present invention provides a cured product that has good photocurability and has good electrical properties. The object of the present invention is to provide an epoxy resin-based photopolymerizable composition with excellent properties.

[i in invention is snow]

The photopolymerizable composition of the present invention is comprised of an epoxy resin, an acid anhydride, an aluminum compound, and a silicon compound having a .

The epoxy resin used in the present invention may be any resin as long as it is normally used as an epoxy resin composition, and specific examples include bisphenol A epoxy resin; bisphenol F 7jQ epoxy resin; phenol novolac type. Epoxy resin; alicyclic epoxy resin; heterocyclic epoxy resin such as triglycidyl isocyanate and hydantoin epoxy; hydrogenated bisphenol, AW epoxy 411 resin; fluoropylene gellicol diglycidyl ether and pentaerythritol Aliphatic epoxy resin such as polyglycidyl ether; Reaction of aromatic, aliphatic or alicyclic carboxylic acid with epichlorohydrin <Thus 1; Glycidyl ether type epoxy resin which is a reaction product of an O-allylphenol novolac compound and epichlorohydrin; a glycidyl ether which is a reaction product of a diallylbisphenol compound having an allyl group at the ortho position of the hydroxyl group of bisphenol A and epichlorohydrin Examples include molded epoxy resin.

The acid anhydrides used in the present invention include phthalic anhydride,
Hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, chlorendic anhydride, dodecynylconophosphate anhydride, methyl Examples include cono-phosphoric anhydride, benzophenonetetracarboxylic anhydride, pyromellitic anhydride, and maleic anhydride.

The aluminum compound that is a component of the present invention includes an alkyl group, a phenyl group, a noroalkyl group, an alkoxy group, a phenoxy group, an acyloxy group, a β-diketonato group, an 〇-
It is a compound formed by bonding an organic group selected from the group such as carbonyl phenolate group.

Among the above organic groups, examples of the alkyl group include methyl group, ethyl IM% n-propyl group, isopropyl group, n-butyl group, 5ec-butyl group, t-)ethyl group,
Examples of the phenyl group include phenyl group, p-methoxyphenyl group, and 0-methoxyphenyl71. p-Ethoxyphenyl group; Examples of the loalkyl group include chloromethyl group, chloroethyl group, and chloropropyl group; Examples of the alkoxy group include methoxy, ethoxy, isopropoxy, butoquino, and bentoxy. Examples of the phenoxy group include phenoxy group, O-methylphenoxy group, O-methoxyphenoxy group, p-nitrophenoxy group, and 2,6-dimethylphenoxy group h1; Examples of the acyloxy group include , acetato,
Propionate, Impropionate, Butyrad, Stearad, Ethylacetoacetate, Provylacetoacetate,
Examples of the β-diketonato group include acetylacetoacetato, diethylmalato, and dipivaloylmetanato; examples include acetylacetonato, trifluoroacetylacetonato, hexafluoroacetylacetonato, H3CH
Examples of the 30-carbonylphenolad group include salicylaldehydate. Specific examples of aluminum compounds include trismethoxyaluminum, trisethoxyaluminum, trisisopropoxyaluminum, trisphenoxyaluminum, trisparamethylphenoxyaluminum, isopropoxyjethoxyaluminum, trisbutquinaluminum, trisacetoxyaluminum, trisstearadoaluminum, trisbutyradoaluminum,
Aluminum tripropionato, aluminum trisisopropionato, aluminum aluminum trisacetylacetonado, aluminum aluminum trifluoroacetylacetonado, aluminum aluminum trispentafluoroacetylacetonado, aluminum aluminum trisethylacetoacetato, aluminum aluminum trissalicylaldehyda, aluminum aluminum trisdiethylmalorado , trispropylacetoacetatoaluminum, trisbutylacetoacetatoaluminum, trisdipivaloylmethanatoaluminum, diacetylacetonatodipivaloylmethanatoaluminum, These aluminum compounds are one type or a mixed system of two or more types. The amount added is in the range of 0.001 to 10%, preferably 1 to 5 wt., based on the weight of the epoxy resin. If the blending amount is less than 0.001% by weight, sufficient curing properties may not be obtained;
Exceeding this percentage by weight causes increased costs and deterioration of electrical characteristics.

It is a component of the present invention. The silicon compound having -nitrobenzyloxy group has the following formula; represents an alkyl group of 1 to 5 or an alkyl group, R2 represents a halogen atom or an alkyl group having 1 to 5 carbon atoms, and m represents O-4 represents an integer of 0 to 3, and n represents an integer of 0 to 3. The plurality of 0-nitrobenzyloxy groups, R1 and R2, may be the same or different. In addition, when m is an integer of 3 or less, the above.

- A hydrogen atom is bonded to the benzene ring of the nitrobenzyloxy thread. ) In the above formula, as the alkyl group having 1 to 5 carbon atoms, weighted t%
Although it is possible to use the catalyst in excess of 100%, high cost and decomposition products of the catalyst components may become a problem.

The photopolymerizable composition of the present invention is put into practical use after curing by methods such as room temperature photocuring, heating photocuring, and after-curing after photocuring. The wave length required for photocuring varies depending on the components of the composition, but is usually 180 to 600 nm, preferably 300 to 4000 nm; the light irradiation time varies depending on the composition of the epoxy resin and the type of catalyst, but is usually 1
-180 minutes, preferably 1-60 minutes; The heating temperature for photocuring varies depending on the composition of the epoxy resin and the type of catalyst, but is usually 20-200°C, preferably 60-100°C. As a light source, a high pressure mercury lamp, a carbon arc lamp, a xenon lamp, an argon glow discharge tube, etc. can be used. The after-key after photocuring varies depending on the composition of the epoxy resin and the type of catalyst, but is usually 50 to 20σC1, preferably 100 to
180° OK, usually 1 to 10 hours, preferably 2 to 5 hours
Do time.

The obtained cured product has extremely excellent electrical properties.

[Embodiments of the invention]

Example 1 In a quartz polymer tube, 100 g of ERL4221 (trade name, manufactured by UCC; compound of the following formula (1), epoxy equivalent weight 130, molecular weight 260) and Evicron B 570 (compound of the following formula (2)
), 8 g of acid anhydride (manufactured by Dainippon Ink), 0.5 g of trisbrobyl acetoacetatoaluminum, and 0.5 g of di(O-nitrobenzyloxy)diphenylsilane,
At 40'O, high pressure mercury lamp (400W) 80w
When the reaction system was irradiated with light for 5 minutes using /CIIL, the reaction system had already turned into a gel. In addition, when no light was irradiated, Ge υ Example 2 Chissonox 206 (trade name, manufactured by Chisso Corporation; compound of the following formula (3), epoxy equivalent: 70. Molecule -1i139
) 12 g, Epicoat 828 (trade name, manufactured by Shell Chemical Co., Ltd.; bisphenol A type, epoxy ff119Q~
210, molecular weight 380) 8 g, Epicron B57
020g,) Lisethylacetoacetatoaluminum 0
．． When the same procedure as in Example 1 was carried out using 5 g of 1L4221 and 0.25 g of triphenyl O-nitrobenzyloxysilane and irradiation with light for 5 minutes, the reaction system was already gelled. Epicoat 154 (trade name, Shell Chemical Company; phenol novolac type, epoxy weight Q172-180) 100 g, Ehikun B570 100g, Epicoat 828: 30g, )
Lissalicylaldehydatoaluminum 30g and di(
2,6-sinitropendyloquino)diphenylsilane 4
g and the mixture was poured onto aluminum slabs.

Next, apply UV light from a mercury lamp (400W) to this plate for 6 hours.
When irradiated for 10 minutes at 0°C, a good cured resin surface was obtained. Dielectric loss tangent value (tanδ) of this cured resin surface
When measured, it was 2.0% at 100°C.

Next, after the cured resin surface was after-keyed at 130°C for 7 hours, the tan δ was measured again, and it was found to be 180
It was 3.6 mm at ℃.

Example 4 Epicor) 828: 100 g, Epicort 152 (trade name, manufactured by Shell Chemical Co., Ltd.; phenol novolac type, epoxy weight +?t 172-179) 50 g,
Proceed as in Example 3 using 20 g of bisphenol F, 150 g of hexahydrophthalic anhydride, 4 g of lissalicyaldehydatoaluminum and 10 g of di(0-nitrobenzyloxy)diphenylsilane,
A cured resin surface was obtained by irradiating light for 30 minutes. Next, after keying this cured resin surface at 150°C for 5 hours, the tan δ was measured to be 4.0 at 180°C.
He was in charge.

Comparative example l E-L4221: 10 g, Ebikuron B 570
The same procedure as in Example 1 was carried out using 10 g and di(0-nitrobenzyloxy)diphenylsilane, but no gelation occurred.

Comparative Example 2 ER, L4221: 100 g, -1-Biquat 154: 30 g, Epicoat 828: 30 g, Epico
The procedure was carried out in the same manner as in Example 3 using 100 g of 570g of B and 0.3 g of diphenyliodonium tetrafluoroborate salt. The tan δ of the cured resin surface obtained after after-keying could not be measured at 180°C.

From the above, it is clear that the P of the present invention! The first proboscis is rapidly cured by light irradiation, and the resulting cured product has extremely excellent electrical insulation properties.

[Effects of the Invention] Because the photopolymerizable composition of the present invention uses an aluminum compound and a silicon compound having an 0-nitrobenzyloxy group as catalyst components, it is cured in a short time by light irradiation. In addition, the obtained cured product does not contain ionic impurities (and has extremely excellent electrical properties such as dielectric + E contact value). Therefore, the cured product can be applied to a wide range of applications such as resist materials, electrical equipment, and especially coil insulators, and its industrial value is extremely high.

Agent: Patent Attorney Noriyuki Chika (Shiga or one person)

Claims (3)

[Claims] (1) A photopolymerizable composition comprising an epoxy resin, an acid anhydride, an aluminum compound, and a silicon compound having an orthonitrobenzyloxy group. (2) The photopolymerizable composition according to claim 1, wherein the aluminum compound is an organic aluminum compound. (3) The amounts of the aluminum compound and the silicon compound having an O-nitrobenzyloxy group are 0.001 to 10% by weight and 0.00% to the epoxy resin, respectively.
The photopolymerizable composition according to claim 1 or 2, which has a weight of 1 to 20 weights.