JPH0368949A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive compsn. reacting with high sensitivity even in the presence of oxygen by incorporating an arom. iodonium salt, a halogenated phthalocyanine pigment and a sensitizer having a specified photosensitive wavelength region into a cationic-polymerizable photosensitive compsn. CONSTITUTION:A cationic-polymerizable compd., an arom. iodonium salt, a halogenated phthalocyanine pigment and a sensitizer having 350-450nm photosensitive wavelength region are incorporated into a cationic-polymerizable photosensitive compsn. The halogenated phthalocyanine pigment hardly hinders cationic polymn., the cyan and green hues of the pigment highly transmit light in the wavelength region of 350-450nm and higher sensitivity can be rendered to the compsn. by adding the sensitizer having high sensitivity in the region. The compsn. an be cored with a simple exposing device and can be colored without lowering the sensitivity.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a photosensitive composition used for photosensitive inks, photosensitive paints, sealants, etc. In particular, it relates to a cationic polymerizable photosensitive composition that can be cured at high speed even in the presence of oxygen.

(Prior Art) Conventionally, many photosensitive compositions have been used that mainly consist of a compound having an acrylic group in its molecular structure and a photopolymerization initiator that generates radicals when irradiated with light.

However, in radical polymerization reactions, oxygen becomes an inhibitor of polymerization, and photocuring reactions in the atmosphere have problems such as slow polymerization rates and residual stickiness on the surface of the resin coating of photosensitive compositions. . For this reason, the photosensitive device has become expensive and large, and the cost has increased due to exposure to nitrogen, etc.

Furthermore, epoxy resins, which have good electrical properties as a cured product and are widely used as the main component of sealants, have a problem in that they cannot be cured by radical polymerization reactions.

As a method for photocuring epoxy resins and vinyl ether resins, General Electric Company has reported a photosensitive composition using an aromatic onium compound as a polymerization initiator (Japanese Patent Publication Nos. 50-151997 and 52-14278).

Photosensitive compositions produced by such cationic polymerization reactions have the advantage of being easily hardened even in the atmosphere because they are not inhibited by oxygen. However, when cationic radicals react with strongly basic molecules such as nitrogen atoms, Polymerization will stop. For this reason, when a compound having a nitrogen atom in its molecular structure, especially a colorant added to UV ink, UV paint, sealant, etc., is added to the photosensitive composition, an extremely large decrease in sensitivity occurs. This was one of the major reasons for preventing the spread of cationic polymerization photosensitive compositions.

[Problem to be solved by the invention]

An object of the present invention is to provide a photosensitive composition that cures with high sensitivity despite containing a colorant in a photosensitive composition that is cured by a cationic polymerization reaction.

(Means for Solving the Problems) The present invention provides a photosensitive composition that is cured by a cationic polymerization reaction, which contains at least a cationically polymerizable compound, an aromatic iodonium salt, a halogenated phthalocyanine pigment, and a photosensitive wavelength. A photosensitive composition containing a sensitizer having a wavelength range of 350 to 450 nm,
This is a photosensitive composition that can be rapidly cured in the presence of oxygen even though it contains a colorant.

The halogenated phthalocyanine pigment used as the colorant 21 in the present invention has particularly low inhibition of cationic polymerization reaction, and the cyan and green hues of the halogenated phthalocyanine pigment have high transmittance to light in the wavelength range of 350 to 450 nm. By adding a sensitizer highly sensitive to this wavelength, the sensitivity of the photosensitive composition can be further increased.

As the cationically polymerizable compound used in the present invention, an epoxy compound having two or more oxirane rings in one molecule or a vinyl ether compound having two or more vinyl ether groups in one molecule is particularly desirable.

Examples of the epoxy compound include bisphenol A epoxy resin, novolac epoxy resin, alicyclic epoxy resin, and epoxidized polybutadiene.

For example, as bisphenol A type epoxy resin, Epicoat 828°834, 8 manufactured by Yuka Shell Epoxy Co., Ltd.
36.1001.1004.1007, DER331, 332, 661, 664, 667 manufactured by Dow Chemical Company,
Araldite 260.280.60 manufactured by Ciba Geigy
71.6084.6097 etc. are mentioned.

Examples of novolac type epoxy resins include Epicort 152.154 manufactured by Yuka Shell Epoxy Co., Ltd. and Araldite EPN 1138 manufactured by Ciba Geigy. EPN1139゜E
(:N1235. ECN1273. ECN1280
．． ECN1299, DEN431 manufactured by Dow Chemical Company
．． Examples include DEN438.

As the alicyclic epoxy resin, CY manufactured by Ciba Geigy is used.
I75. CY177, CY179. GY184.
CY192, epoxidized polybutadiene,
Examples include EPB12B and EPB27 manufactured by Nippon Soda.

Examples of vinyl ether compounds include ethylene glycol divinyl ether, 2-chloroethyl vinyl ether,
-Hydroxyethyl vinyl ether, 4-chlorobutyl vinyl ether, 4-hydroxybutyl vinyl ether, and vinyl ether compounds synthesized from aromatic polyhydric alcohols.

Examples of aromatic polyhydric alcohols include cresol, hydroquinone, 1,2.4-trihydroxybenzene, 1
, 3,5-trihydroxybenzene, 1,4-dihydroxy-2-tert-butylbenzene, 1,4-dihydroxy-2,5-di-tert-butylbenzene, bisphenol A, bisphenol S, and the like.

The aromatic iodonium salt used as a photopolymerization initiator in the present invention releases a Lewis acid upon irradiation with ultraviolet rays and initiates cationic polymerization, and its production method is described in the literature (J, Am).

Cheol, .Soc., 75.2705 or 81.342).

The aromatic iodonium salt has the formula %] (RI R2 is each substituted with a phenyl group, a naphthyl group, an alkyl group, or a phenyl group, a phenoxydyl group, a halogen, a nitro group, an alkyl group, or an alkoxyl group) Represents a phenyl group, M is B, P, As, Sb,
An atom selected from Sn, Bi, and Fe, Q is a fluorine or chlorine atom, and n is a number larger by 1 than the valence of M. ). Specifically, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluoroantimonate, di(p-tolyl)-iodonium hexafluoroarsenate, di(
4-nitrophenyl)-iodonium bentafluorostanate, di(4-t-butylphenyl)-iodonium hexafluorostibiate, di-2-naphthyl-
Iodonium tetrafluoroborate, di(4-diphenylyl)-iodonium hexafluorophosphate, di(3-methoxyphenyl)-iodonium hexafluoroarsenate, phenyl-naphthyl-iodonium tetrafluoroborate, phenyl-4-fluorophenyl-iodonium Hexafluorophosphate, phenyl-(3,5-diisopropylphenyl)-
Examples include iodonium bentafluorostanate.

Generally, the higher the degree of halogenation of halogenated phthalocyanine pigments, the higher the sensitivity of the resulting photosensitive composition, but the hue changes from cyan to green to brown, so there is a balance between hue and sensitivity. It is desirable to select according to

Halogenated phthalocyanine pigments that can be used include C
I No. 74260. CI Pigment Gray
en 7, CI No.

74250, CI Pigment Blue 15,
CI No. 74200. (:IPigment Bl
ue 17 (:I No, 42040, 11:I
Pigment Green 2 and the like.

The sensitizer that can be used in the present invention is 350 to 450 nm.
Examples thereof include 2-chlorothioxanthone, diethylthioxanthone, di-t-butylthioxanthone, benzophenone, anthraquinone, and Michler's ketone.

Further, in the present invention, a binder may be added to improve the dispersibility of the pigment, photopolymerization initiator, and sensitizer.

Preferred binders include polymethyl methacrylate, polyvinyl chloride, polyamide, polyethylene oxide,
Polymer compounds such as polycarbonate and polystyrene.

In addition, fillers, reinforcing materials, flame retardants, antistatic agents,
There is no problem in mixing plasticizers, etc.

The amount of the halogenated phthalocyanine pigment contained in the photosensitive composition of the present invention is preferably in the range of 1 to 30% by weight. If it is less than 1% by weight, the desired coloring cannot be obtained;
Also, as the amount of pigment added increases, the sensitivity decreases, but 3
If it exceeds 0% by weight, the sensitivity and physical properties of the coating film will be significantly reduced.

Further, the amount of aromatic iodonium salt and sensitizer added is preferably 0.1 to 30% by weight.

If the amount added is numerically increased, the sensitivity will increase, but once added to a certain extent, the sensitivity will be saturated.

〔Example〕

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples.

Example 1 Chlorinated phthalocyanine (CI No. 74260,
15 parts of CIPigment Green 7 (manufactured by Dainichiseika Kagaku Kogyo Co., Ltd.) and 10 parts of polymethyl methacrylate (Elvacite 2041, manufactured by DuPont) as a binder were dispersed with a sand mill in 300 parts of dichloromethane, and the following structural formula (I ), 5 parts of diphenyliodonium hexafluoroarsenate, and 5 parts of diethylthioxanthone (manufactured by Nippon Kayaku) as a sensitizer were dissolved to prepare a photosensitive resin liquid.

Structural formula (1) is synthesized using 100 parts of hydroquinone and 2-
300 parts of chloroethyl vinyl ether was dissolved in 500 parts of dimethylformamide and reacted at 50°C for 8 hours.
Next, the reaction solution is washed twice with 100 parts of water, and excess 2-chloroethyl vinyl ether is removed under vacuum at 60°C.

Next, the resin liquid was applied to a thickness of 10p on an A11 plate using a bar coater, and the cure rate was measured by irradiating ultraviolet rays. Ultraviolet rays are irradiated using a quartz low-pressure mercury lamp (man-powered 201F
, manufactured by Ushio Inc.) was used. The results are shown in Table 1. Note that the sensitivity was expressed as the light irradiation time until the film surface lost its tackiness.

Comparative Examples 1 to 7 For comparison, the sensitivity of the pigments shown in Table 1 was measured in the same manner. The results are shown in Table 1.

As can be seen from Table 1, for chlorinated phthalocyanine, the sensitivity was 172, which is the same as the system without colorant, but for other colorants, the sensitivity was significantly lowered to 175 to 1/20.

Example 2 Epoxy-novolak resin (manufactured by Dow Chemical Company, DEN
431) 100 parts, 300 parts of dichloromethane, chlorinated phthalocyanine pigment (PI No, B-68KET B
20 parts of lueEx-1 (manufactured by Dainippon Ink Chemical Co., Ltd.) were dispersed in a sand mill, and 10 parts of diphenyliodonium hexasulfoloarsenate and 10 parts of 2-chlorothioxanthone (manufactured by Tokyo Kasei Co., Ltd.) were added thereto. Sensitivity was determined in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 8.9 Sensitivity was measured in the same manner as in Example 2 except that the pigments were changed to those shown in Table 2. The results are shown in Table 2.

It can be seen that even in photosensitive compositions made of epoxy resins, the decrease in sensitivity due to chlorinated phthalocyanine pigments is extremely small compared to other pigments.

(Effects of the Invention) As described above, according to the present invention, a photosensitive composition that reacts with high sensitivity even in the presence of oxygen can be provided, and can be cured using a simple exposure device. Further, according to the present invention, it has become possible to color a cationic polymerization type photosensitive composition without significantly reducing its sensitivity.

Claims (1)

[Scope of Claims] 1. A photosensitive composition that is cured by a cationic polymerization reaction, which contains at least a cationically polymerizable compound, an aromatic iodonium salt, a halogenated phthalocyanine pigment,
and a sensitizer having a photosensitive wavelength range of 350 to 450 nm. 2. The photosensitive composition according to claim 1, which contains 1 to 30% by weight of a halogenated phthalocyanine pigment. 3. The photosensitive composition according to claim 1, wherein the cationically polymerizable compound is an epoxy compound having two or more oxirane rings in its molecular structure. 4. The photosensitive composition according to claim 1, wherein the cationically polymerizable compound is a vinyl ether compound having two or more vinyl ether groups in its molecular structure.