JPS5949226A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To provide titled composition of excellent photocurability, capable of giving cured products of good electrical properties, suitable for resist material, insulating medium for electrical apparatus, comprising an epoxy resin, titanium compound, and o-nitrobenzyloxy group-contg. silicon compound. CONSTITUTION:The objective composition can be obtained by incorporating (A) an epoxy resin (e.g., of bisphenol A type) with (B) pref. 1-5wt% of a titanium compound (e.g., of formula I ) and (C) pref. 1-10wt% of an o-nitrobenzyloxy group-contg. silicon compound (e.g., of formula II). This composition will be subjected to photocuring by irradiating with light pref. of 300-400nm wavelength.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a novel photopolymerizable composition, and more particularly, the present invention relates to a novel photopolymerizable composition, and more particularly, it has electrical properties suitable for use as an insulating material for electrical equipment, a resist stripping agent, etc. 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 first in relation to energy savings and workability. Among these, the process of photocuring epoxy resin has a wide range of applications and is essential for rlj'. Currently, the most popular process for photo-curing epoxy resin is 2F.
There are Ili species.

One of them is one that is made of a vinyl group-containing compound such as an epoxy tree 11F1tr or an acrylic resin having optical jj and Q properties, and is photopolymerized via this vinyl group.

However, this ready-made epoxy resin has considerably lower heat resistance than the epoxy resin itself.

The other method is to cure epoxy resin with a photodecomposition type catalyst. The catalyst used at this time is the following formula: % formula % (wherein, Ar represents a phenyl group, etc.; X represents an iodine atom, a sulfur atom, a diazo group, etc.; Y is a BF4
, PF6, AsF6 e 8bF6, etc.

) [Macromolecules, Vol. 10, p. 1307, 1977 (Macromolecules, 10 p. 13)
07 (1977) ): Journal of Radiation Curing Vol. 5, p. 2, 1978 (Journal of Radiation Curing)
Radiation Curing.

5, 2 (1978)); Journal of
Polymer Science Polymer Chemistry Edition, Volume 17, Page 2877, 1979 (J
ou, rnal of Polymer 5science
Polymer Cbemitry Edltlo
n, 17, 2877 (1979));
Volume 17, page 1047, 1979 (ibid., 17
．． 1047 (1979); Journal of Polymer Science Polymer Letters Edition, Vol. 17, p. 759, 1979 (Journa
l of Polymer 5science Polym
er Letters Edition, 17,
759 (1979)); JP-A-55-65219; US Pat. No. 4,069,054 Meiwa 1; British Patent No. 1,516,511; British Patent No. 1,518,141, etc.].

However, when epoxy resins are cured using these catalyst components, the resulting cured product has good mechanical properties and heat resistance, but the catalyst components become ionic impurities, so this cured product cannot be used with electricity. When used in equipment, there is a risk of deterioration of electrical properties such as poor electrical insulation and corrosion phenomena.

[Purpose of the invention]

The object of the present invention is to provide an epoxy 47p1 resin-based photopolymerizable composition having a photocurability of R1 and a cured product of I7 having excellent electrical properties.

[Summary of the invention]

Photopolymerizable compositions of the present invention t, l1, epoxy VI"・,1
fat, butane compound and O-nitropenziol i57
The 9°v sign indicates that it is made of a silicon compound having a group.

-1 used in the present invention. The boxy 4r'r1 resin is usually any resin used in epoxy resin compositions, such as bisphenol A y, (g epoxy resin; bisphenol F type). Evo resin; phenol novolak type epoxy 4"MA resin; alicyclic epoxy resin; triglycidyl isocyanate and [-dantoine epoxy etc. Aliphatic epoxy resins such as diglycidyl ether and polyglycidyl ether; epoxy resins prepared by the reaction of aromatic, aliphatic or alicyclic carboxylic acids with epichlorohydrin; epoxy resins containing nuviro rings; 〇-A glycidyl ether type epoxy resin which is a reaction product of an allylphenol novolak compound and epichlorohydrin; A reaction product of a diallylbisphenol compound having an allyl group at the ortho position of each hydroxyl group to bisphenol and epichlorohydrin. Examples include certain glycidyl ether type epoxy resins.

The atane compound, which is a component of the present invention, has an alkoxy group,
Phenoxy group, acyloxy group, β-diketonato group, 0
It is a compound formed by bonding an organic group selected from the group such as -carbonylphenorad group.

Among the above organic groups, examples of alkoxy groups include methoxy, ethoxy, isopropoxy, butoxy, and pentoxy; examples of noenoxy group include phenoxy group, 0-methylphenoxy group, 0-methoxyphenoxy group, p-nitro Phenoxy group and 2,6-dimethylphenoxy group are mentioned, and examples of the niacyloxy group include 1: Il, acetate, propionate, imbropionate, buburato, stearado, ethyl acedoacetate, propylacedoacetate, and pter. Examples include acetoacetate, jetermalat, dipivaloylmethanat; β-
Examples of the diketonato group include acebulacetonato, trifluoroacetylacetonato, hexafluoroacetylacetonato, and 0-carbonylphenolado group.

Specific examples of titanium compounds include: These titanium compounds may be used in a mixed system of 1f111 or two or more types, and the weight ratio of the titanium compounds to the epoxy resin is 0.001 to 1. 10%, preferably in the range of 1 to 5%). Formulation-Fll 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 an 0-nitrobenzyloxy group, which is a component of the present invention, has the following formula: (wherein R' is a hydrogen atom, a halogen atom, or
5 represents an alkyl group or an aryl group; R2 represents a halogen atom or an alkyl group having 1 to 5 carbon atoms; m is O
Represents an integer of ~4; n represents a difference number of 0~3. The plurality of 0-nitrobenzyloxy groups, R1 and R2, may be the same or different. When m is an integer of 3 or less, a hydrogen atom is bonded to the benzene ring of the 0-nitrobenzyloxy group. ) In the above formula, examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, isopropyl group, n-propyl group, n-butyl group, t-butyl group, 5ec-butyl group, n Examples of the aryl group include a benzyl group, a methoxy group, an ethoxy group, and a chloromethyl group;
The alkyl group and aryl group having 1 to 5 carbon atoms may have a pendant group such as a halogen atom, a nitro group, a cyano group, or a methoxy group.

Specific examples of silicon compounds having an 0-nitrobenzyloxy group include compounds represented by the following formula:

The amount of these silicon compounds added is 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the epoxy resin.
Weight range. If the weight of Formulation 11 is less than 01, sufficient curing properties cannot be obtained, and it is recommended to use more than 20% by weight. 1. i i+3- objects may be a problem.

The photopolymerizable composition of the present invention is '7+'+ i'a light 1ii
1! It is then put into practical use after being cured by heating, photocuring, after-curing by cooling, and by drying. )'l'
J Curing (- the required wavelength depends on the components of the composition)
H, usually 180 to 600 nm, preferably 3
00~40011m; Light irradiation time is 1
It varies depending on the composition of the fat and the type of catalyst, but usually 1
~180 minutes, preferably 1 to 60 minutes: curing with heating light
The heating temperature in the case of l) varies depending on the composition of the epoxy resin and the relatives of the catalyst, but is usually 20 to 200°C, preferably 60 to 100°C.As a light source, a high-pressure water lamp, a carbon arc lamp, etc. , a xenon lamp, an argon glow discharge tube, etc. can be used. After curing after photocuring, the composition of the epoxy resin and j!l!b!!
Although it varies depending on the type of fish, it is usually carried out at 50 to 200°C, preferably 100 to 180°C, for 1 to 10 hours, preferably 2 to 5 hours.

The obtained cured product has extremely excellent electrical properties.

[Embodiments of the invention]

Example 1 In a quartz polymerization tube, ERL4221 (trade name, manufactured by tJCC; compound of the following formula (1), epoxy equivalent: 130, min. Add 0.59% of 0-nitrobenzyloxy)diphenylsilane and heat at 40°C.
When light was irradiated for 10 minutes using a high-pressure mercury lamp (400 W), the reaction thread had completely gelled. Moreover, when no light was irradiated, gelation did not occur.

I Example 2 Terrajin Nox 206 (trade name, Chisso (preparation: compound of the following formula (2), epoxy compound j, t 70, molecule JN1
39) 10g, Ebiko) 828 (trade name, manufactured by Shell Chemical Co., Ltd.; bisphenol A type, epoxy 1.119)
0 to 21 O1 molecular weight 380) 49.7 dizalytyl aldehyda diphenoxytethane 0.3 g and triphenyl 0
- Using 07 g of nitrobenzyloxysilane, the same procedure as in Example 1 was carried out and the reaction system was irradiated with light for 7.1 minutes, resulting in 1-gelation of the reaction system.

Example 3 RRL 4221: 100 y, Ebicor l-15
4C product name, Shell Chemical Co., Ltd.; phenol novolac type,
Epoxy equivalent 172-180) 30g, Epicote 82
8: 309, 2g of tetraphenoxy titanium and)
4 g of (2,6-sinitropenzyloxy)diphenylsilane was mixed and the mixture was poured onto an aluminum plate.

Next, when this plate was irradiated with UV light from a mercury lamp (400 W) at 60° C. for 30 minutes, a good cured resin surface was obtained. Dielectric loss tangent value (tanδ) of this cured resin surface
When measured, it was 3.0% at 100°C.

Next, after curing this cured resin surface at 150°C for 5 hours, tan δ was measured again, and it was found to be 180°C.
It was 3.5%.

Example 4 Epicote 828: 100 Q, Epicote 15
2 (trade name, manufactured by Shell Chemical Co., Ltd.; phenol novolac type, epoxy equivalent: 172 A-179) 50 g, bisphenol F20Q, titanium oxide diacetylacetonate 5
The same procedure as in Example 3 was carried out using g and 6 g of di(0-nitropenzyloxy)diphenylsilane, and light was irradiated for 1 hour to obtain a cured resin surface. Next, after curing the cured resin surface at 150°C for 5 hours, tan
When δ was measured, it was 5.0% at 180°C.

Comparative Example I ERL4221: The same procedure as in Example 1 was carried out using 10y and di(0-nitrobenzyloxy)diphenylsilane, but no gelation occurred.

Comparative example 2 FiRL4221: 100 Q, shrimp: I-to 154: 30 g,
Example 3 using 30 g of Epicote 828 and 0.39 g of hydisoenyl iodonium tetrafluoroborate.
operated in the same way. The tan δ of the cured resin surface obtained after after-curing was immeasurable at 180°C.

From the above results, it is clear that the composition of the present invention is rapidly cured by light irradiation [7], and the electrical insulation properties of the obtained cured product are extremely excellent.

〔Effect of the invention〕

Since the photopolymerizable composition of the present invention uses a titanium 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, since the cured product does not contain ionic impurities (2), it has extremely poor electrical properties such as dielectric loss tangent value, and moreover, when this cured product is used in electrical equipment, it There is no risk of corroding equipment.For this reason, historic materials can be applied to a wide range of applications such as L/cyst materials, electrical equipment, and especially Nikoil insulators, and their industrial value is extremely high. It is what it is.

Agent Patent Attorney Noriyuki Chika (1 idiot) -19
:

Claims (1)

[Claims] (1) A photopolymerizable composition comprising an epoxy resin; a titanium compound; and a silicon compound having an O-nitrobenzyloxy group (2) A compounding process of an aluminum compound and a silicon compound having an O-nitrobenzyloxy group 2. The photopolymerizable composition according to claim 1, wherein d and are respectively 0001 to 10% by weight and 0.1 to 20% by weight based on the epoxy resin.