JPH02157759A - Photodiscolorable photosensitive composition - Google Patents

Abstract

PURPOSE:To expand color hue by using specific substd. amino group-contg. triaryl compds, as the photodiscolorable compd. and using tribromomethylphenyl sulfone as a phottdiscoloration accelerator. CONSTITUTION:At least one kind of the substd. amino group-contg. triaryl compds, expressed by the formula I are used as the photodiscolorable compd. In the formula I, R1 denotes a phenyl group, naphthyl group, etc.; R2, R3 denote a hydrocarbonsubstd. amino group or alkoxy group; R4 to R7 denote a hydrogen atom, hydrocarbon group, alkoxy group, etc.; n denotes 0 or 1. This compsn. is polymerized by irradiation of UV rays, visible rays, electron rays, X rays, etc. and the tribromomethylphenyl sulfone used as the photodiscoloration accelerator has the capacity as a photosensitization initiator. The hue of photodiscolorability is expanded and the formation of the hue of the blue-green system with which the recognition under a yellow safety light is easy is facilitated.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a photosensitive resin composition.

More specifically, for example, photosensitive resin compositions used in various fields such as etching resists and plating resists used in the production of printed wiring boards, metal precision processing, etc., are used to facilitate the determination of the photosensitive state during use. This invention relates to a photosensitive composition that has photochromic properties.

(Conventional technology) In recent years, photosensitive resins have achieved low-temperature curability, energy savings as no heating is required, resource-saving and non-environmental pollution as they are solvent-free, process shortening due to high curing speeds, improved productivity, and It is used in a wide range of applications because of its ability to be processed precisely. For example, in the fields of printed wiring board manufacturing, printing plate manufacturing, metal precision processing, etc., it is used as an etching resist plating resist to protect unprocessed areas during processing such as etching and plating.

In this case, it goes without saying that chemical resistance, adhesion to the base material, and photosensitivity are required as etching resists and plating resists, but recently, workability such as shortening processing time and lowering the defective rate has become particularly important. Improvements are being made. For example, in the production of printed wiring boards, a light-transmitting peelable support and a photosensitive resin layer are used.

A photosensitive element consisting of three layers of peelable protective film, with the peelable protective film removed and a photosensitive resin layer laminated on the substrate surface, or a photosensitive resin composition directly applied to the substrate surface. Then, ultraviolet rays are passed through a pattern such as negative film.

Irradiation with visible light, electron beam, etc., and if necessary, wet development (after peeling off the flexible support, removing the non-irradiated areas with an organic solvent or alkaline aqueous solution, etc.) or separating the irradiated areas with the non-irradiated areas. Utilizing the difference in adhesion between the irradiated area and the removable support, either the non-irradiated area or the irradiated area is removed along with the removable support, followed by a dry development process, followed by etching, plating, etc. This method is often used.

At that time, it is necessary to know the degree of exposure at the time of exposure and defects such as disconnections and chips after exposure and development at an early stage, and to make corrections that usually require a long time and a heavy burden on the operator.

In order to facilitate reprocessing, reduce the defective rate, and facilitate work management, we use a photosensitive composition that changes color (including color development) when irradiated with light, and changes the hue and color density between irradiated and non-irradiated areas. It was proposed to make a difference between
147829, JP-A-55-1378 [1, JP-A-59-107344, etc.], and have been put into practical use in some cases.

However, conventional photochromic photosensitive compositions have problems such as insufficient contrast between irradiated and non-irradiated areas, insufficient photosensitivity, and limited hue.
Furthermore, there are problems with the stability of the composition itself, which causes discoloration during long-term storage or high temperatures, and highly volatile components that evaporate during processing, reducing sensitivity and reproducibility. There is.

For example, many of these photochromic photosensitive compositions contain carbon tetrabromide, carbon tetrabromide,
Carbon tetrachloride, bromoform, chloroform, iodoform, trichloroacetamide.

Compounds such as tribromoacetamide that are easily volatilized by evaporation or sublimation are used, and for example, they volatilize during high-temperature processing such as when laminating photosensitive elements in the production of printed wiring boards, or when applying photosensitive compositions, causing photosensitivity and It has drawbacks such as reduced reproducibility. In order to improve these drawbacks, JP-A-59-107344 discloses that organic halogen compounds, such as tribromomethylphenylsulfone, which have a large molecular weight and have almost no sublimability or volatility, are used to provide photochromic properties. It has been proposed to use it in combination with leuco crystal violet, etc.

(Problems to be Solved by the Invention) Although the method disclosed in JP-A-59-107344 is an excellent method, the photochromic dye is limited to leuco crystal violet and its trimethyl substituted product, and other Although dyes are used in combination, it cannot be said that there are many types of hues.

The present inventors, as a manufacturer of tribromomethylphenylsulfone, discovered that a combination of tribromomethylphenylsulfone and some photochromic compounds was equivalent to or better than that of JP-A-59-107344. The above discoloration results show that the hue can be expanded, and the storage stability is also improved.

The present invention was arrived at after learning that it also has excellent high-temperature stability.

(Means for solving problems) The present invention relates to a photopolymerizable compound and a photochromic compound.

In a photochromic photosensitive composition containing a photochromic accelerator as an essential component, a special substituted amino group-containing triaryl compound is used as the photochromic compound, and tribromomethylphenyl sulfone is used as the photochromic accelerator. The present invention relates to a photochromic composition characterized by the following, and a photochromic photosensitive composition further containing a photosensitization initiator and a film-forming polymer as necessary.

The photopolymerizable compound used in the present invention is ultraviolet light.

Compounds that can be polymerized by irradiation with visible light, electron beams, Compounds having two or more sexually unsaturated bonds are often used.

Examples of acrylic acid ester compounds having two or more ethylenically unsaturated bonds include ethylene glycol diacrylate, 1,2-propylene glycol diacrylate, and 1,3-propylene glycol diacrylate.

1.3-Butylene glycol diacrylate 1.4-Butylene glycol diacrylate.

Neopentyl glycol diacrylate, 1,6-hexane glycol diacrylate, diethylene glycol diacrylate tetraethylene glycol diacrylate, nonaethylene glycol diacrylate, polyethylene glycol diacrylate dipropylene glycol diacrylate-h, tetrapropylene glycol diacrylate nonapropylene Glycol diacrylate.

Polypropylene glycol diacrylate Polybutylene glycol diacrylate 2.2-bis(4-acryloxyethoxyphenyl)propane, glycerin diacrylate Pentaerythritol diacrylate Trimethylol ethane diacrylate Trimethylol propane diacrylate, glycerin triacrylate,
Pentaerythritol triacrylate Pentaerythritol tetraacrylate Trimethylolethane triacrylate, Trimethylolpropane triacrylate, Diglycerin tetraacrylate Dipentaerythritol pentaacrylate, Dipentaerythritol hexaacrylate.

and ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, pentaerythritol.

Trimethylol ethane, trimethylol propane.

Compounds called monomers such as polyacrylic acid adducts of polyhydric alcohols such as diglycerin and dipentaerythritol to polyglycidyl ethers, as well as phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, sebacic acid, and tetrahydrocarbons. Polybasic acids such as phthalic acid, hexahydrophthalic acid, and trimellitic acid and ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, neopentyl glycol, 1,6-hexanediol, and polyethylene glycol , polypropylene glycol, polybutylene glycol, 2,2-bis(4-β-hydroxyethoxyphenyl)propane, glycerin, trimethylolethane.

Trimethylolpropane, pentaerythritol.

Dipentaerythritol, etc., compounds obtained from polyhydric alcohols such as ethylene oxide adducts and propylene oxide adducts thereof, and acrylic acid, polyester acrylate prepolymers such as polycaprolactone diacrylate, the various polybasic acids mentioned above, and the various polybasic acids mentioned above. Hydroxyl group-containing polyesters obtained from alcohols and the various polyhydric alcohols mentioned above and tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate),
4. Polyurethane acrylate prepolymer bisphenol A type obtained by the reaction of polyvalent isocyanates such as 4'-methylenebis(cyclohexyl isocyanate), hydrogenated tolylene diisocyanate, and isophorone diisocyanate with hydroxyalkyl acrylates such as hydroxyethyl acrylate and hydroxypropyl acrylate. , epoxy acrylate prepolymers obtained by reacting various epoxy resins such as aliphatic polyhydric alcohol types and novolac types with acrylic acid, silicone acrylate prepolymers, various vinyl polymers, various diene polymers, melamine resin prepolymers,
There are prepolymers such as urea resin prepolymers into which acrylic acid ester bonds are introduced, and compounds called prepolymers such as so-called unsaturated polyesters. Of course, it is also possible to use compounds in which the acrylic ester structure portion of these compounds becomes a methacrylic ester structure, an acrylamide structure, a methacrylamide structure, or another vinyl structure such as an allyl group.

These compounds can be used alone or in combination of two or more, but if a film-forming polymer is not used, favorable results can be obtained by using a combination of a so-called monomer type compound and a prepolymer type compound. There are many cases.

In addition, these compounds include compounds having one ethylenically unsaturated compound, ethylene glycol dimercaptopropionate, trimethylolethane tris (β-mercaptopropionate), trimethylolpropane tris (
β-mercaptopropionate), pentaerythritol tetrakis (β-mercaptopropionate), trimethylolethane tris (thioglycolate), trimethylolpropane tris (thioglycolate).

Pentaerythritol tetrakis (thioglycolate)
It is also possible to use polythiol compounds such as, and good results are often obtained.

Examples of monoethylenically unsaturated compounds include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, S-butyl acrylate, and t-butyl acrylate.
Butyl acrylate neopentyl acrylate 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2
-Hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, propoxyethyl acrylate butoxyethyl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, 2
-Hydroxy-3-phenoxyprobyl acrylate
2-Hydroxy-3-chloropropyl acrylate Methoxyethoxyethyl acrylate, ethoxyethoxyethyl acrylate, propoxyethoxyethyl acrylate, butoxyethoxyethyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, dicyclopentadienyl acrylate, dicyclopentadienyloxy Acrylic acid esters such as ethyl acrylate and 2-hydroxyethyl acryloyl phosphate; compounds in which the acrylic ester structure of these compounds has a methacrylic ester structure, an acrylamide structure, a methacrylamide structure, etc.; and acrylic acid; Methacrylic acid, acrylamide, methacrylamide.

Acrylonitrile, methacrylonitrile, styrene,
These include vinyl acetate and N-vinylpyrrolidone.

In the present invention, the photochromic compound has the general formula (wherein R1 is a phenyl group, a naphthyl group, a phenyl group having a hydrocarbon-substituted amino group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms at the 4-position, At least one carbon number 1-12
A naphthyl group having an alkoxy group, a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a carboxylic acid (salt) group, a sulfonic acid (salt) group, or a group substituted with a halogen atom and R2 and R3 have 1 to 1 carbon atoms.
12 hydrocarbon-substituted amino group or an alkoxy group having 1 to 12 carbon atoms, R4゜Rs, R6, and R7 are hydrogen atoms, hydrocarbon groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, and carbon atoms. Indicates an acid (salt) group, sulfonic acid (salt) group or halogen atom, n represents 0 or 1, at least one substituted amino group is present, and when n is 0 and the number of substituted amino groups is 1 or 2 is a small number (if one alkoxy group is present, n is O, and the number of substituted amino groups is 3, the nitrogen atom of the alkyl group-substituted amino group and the cycloalkyl group, aryl group, aralkyl group, or amino group) and at least one non-alkyl group-substituted amino group such as a group forming a cyclic structure that may also contain an oxygen atom). use

For example, 4-methylamino-4'-methoxy-
Triphenylmethane, 4-methylamino-4'
4'-dimethoxy-triphenylmethane, 4-dimethylamino-4'-methoxy-triphenylmethane,
4-dimethylamino-4'4'-dimethoxy-triphenylmethane, 4-methylamino-3-methyl-4'
4#-dimethoxy-triphenylmethane, 4-
Dimethylamino-3-methyl-4'4#-dimethoxy-triphenylmethane, 4-dimethylamino-4
'4''-dimethoxy-3', 3'dimethyl-triphenylmethane, 4-dimethylamino-4', 4-jethoxy-triphenylmethane, 4-benzylamino-
4',4''-dimethoxy-triphenylmethane, 4-benzylamino-3,4'4''-trimethoxytriphenylmethane, 4-benzylmethylamino-4'
4'-dimethoxy-triphenylmethane, 4.4'-di(methylamino)-4#-methoxy-triphenylmethane.

4',4'-di(methylamino)-4#-methoxy-3
,3',3''-trimethyl-triphenylmethane,
4.4'-bis(dimethylamino)-41-methoxy-
Triphenylmethane, 4゜4'-bis(dimethylamino)-4'-methoxy-3#-methyl-triphenylmethane, 4゜4'-bis(dimethylamino)-3',4
'-dimethoxy-triphenylmethane, 4.4'-bis(dimethylamino)-3',4',5'-)rimethoxytriphenylmethane, 4.4'-bis(dimethylamino)-4#- Methoxy-3-butyl-triphenylmethane, 4,4'-bis(dimethylamino)-
41-ethoxy-triphenylmethane, 4,4'-bis(dimethylamino)-42-ethoxy-31-methyl-
Triphenylmethane, 4.4'-bis(dimethylamino)-4#-ethoxy-31-cyclohexyl-triphenylmethane, 4.4'-bis(diethylamino)-
4'-Ethoxy-triphenylmethane.

4.4'-di(benzylamino)-4'-methoxy-triphenylmethane, 4.4'-di(benzylamino)-
4#-ethoxy-triphenylmethane, 4,4'-di(
benzylmethylamino)-4'-methoxy-triphenylmethane, 4゜4'-di(benzylmethylamino)
-4#-ethoxy-31-methyl-triphenylmethane, 4゜4'-di(pyrrolidino)-4#-ethoxy-triphenylmethane, 4.4'-di(pyrrolidino)-4#-
Ethoxy-31-methyl-triphenylmethane, 4.4
'-di(morpholino)-4'methoxy-3'-t-butyrotriphenylmethane, 4.4'-di(methylamino)-41-benzylamino-triphenylmethane, 4.
4'bis(dimethylamino)-41-benzylamino-
Triphenylmethane, 4.4'-bis(dimethylamino)-4'-(benzylmethylamino)-triphenylmethane, 4.4'-bis(dimethylamino)-4'-
(o-chlorobenzylmethylamino)-triphenylmethane, 4.4'bis(dimethylamino)-4'-(
p-chlorobenzylmethylamino)-triphenylmethane.

4.4'-bis(dimethylamino)-4'-(p-methylbenzylmethylamino)-triphenylmethane, 4.
4'-bis(dimethylamino)-41-dibenzylamino-triphenylmethane.

4.4'-bis(dimethylamino)-4'-pyrrolidino-triphenylmethane, 4°4'
-bis(dimethylamino')-4'-morpholino-triphenylmethane, 4-dimethylamino-4', 4
'-di(benzylamino)-triphenylmethane,
4-dimethylamino-4',4'-di(benzylmethylamino)-triphenylmethane.

4-dimethylamino-4,41-di(p-methylbenzylmethylamino)-triphenylmethane.

Bis(4-dimethylaminophenyl)-2'-methoxynaphthyl-1-methane, bis(4-dimethylaminophenyl)-4'-methoxynaphthyl-1-methane, bis(4-dimethylaminophenyl)-4', 8'-
Dimethoxynaphthyl-1-methane.

Bis(4-dimethylaminophenyl)-4'-methoxy-6'-(sulfonic acid)-naphthyl-1-methane, bis(4-dimethylaminophenyl)-4'-ethoxy-
8'-Carboxylic acid-naphthyl-1-methane, di(4-methylaminophenyl)-β-styrylmethane, di(4-
ethylaminophenyl)-β-styrylmethane, bis(
4-dimethylaminophenyl)-β-styrylmethane,
Bis(4-diethylaminophenyl)-β-styrylmethane, di(4-phenylaminophenyl)-β-styrylmethane, di(4-benzylaminophenyl)-β-styrylmethane, di(4-benzylmethylaminophenyl) -β-styrylmethane.

di(4-morpholinophenyl)-β-styrylmethane,
Bis(4-dimethylamino-2-methylphenyl)-β
-Styrylmethane, bis(4-diethylamino-3-methylphenyl)-β-styrylmethane, di(4-benzylamino-3-methylphenyl)-β-styrylmethane, bis(4-dimethylaminophenyl)-β- p-dimethylaminostyrylmethane, bis(4-dimethylaminophenyl)-β-p-methoxystyrylmethane, bis(
4-dimethylaminophenyl)-β-p-ethoxystyrylmethane, bis(4-dimethylaminophenyl)-β
-(3',4',5'-trimethoxystyrylmethane, bis(4-diethylaminophenyl)-β-(3
'-Methoxy-4'-ethoxystyryl)methane, di(
4-methylaminophenyl)-β-(3-methyl-4-
ethoxystyryl)-methane, di(3-methyl-4methylaminophenyl)-β-(3-methyl-4-ethoxystyryl)-methane, bis(4-dimethylaminophenyl)-β-(3'-methyl -4'-ethoxystyryl)-methane, di(4-morpholinophenyl)-β-(3
'-phenyl-4'-methoxystyryl)-methane,
Di(4-morpholinophenyl)-β-(3'-cyclohexyl-4'ethoxystyryl)-methane, Di(
4-methoxyphenyl)-β-(p-dimethylaminostyryl)-methane, di(3-methyl-4-ethoxyphenyl)-β-(p-diethylaminostyryl)-methane, 4-diethylaminophenyl-4'methoxyphenyl -β-(m-t.butyl-p-diethylaminostyryl)-methane and the like. It goes without saying that these substituted amino group-containing triaryl compounds can be used in combination for the purpose of adjusting hue and density.

The composition of the present invention is sensitive to ultraviolet rays, visible light, and electron beams.

Polymerization is performed by irradiation with X-rays, etc., and the tribromomethylphenylsulfone used as a photodiscoloration accelerator also has the ability as a photosensitization initiator, so there is no need to add a photosensitization initiator. However, in the case of UV irradiation or visible light irradiation, by adding a photosensitization initiator,
In many cases, polymerization can be promoted. Of course, in the case of electron beam irradiation or X-ray irradiation, the effect of adding a photosensitization initiator is hardly recognized.

As a photosensitization initiator, various commonly known compounds can be used. Examples of compounds having an ethylenically unsaturated bond as a photopolymerizable compound include acetophenone, 2,2-jetyl, Toxiacetophenone, p
-t-butyl-2゜2,2-trichloroacetophenone, p-phenoxy-2,2,2-dichloroacetophenone.

0-Nitro-2,2-tribromoacetophenone.

Acetophenones such as 4-dimethylaminoacetophenone, 2-hydroxy-2-methylpropiophenone,
1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone.

1-(4-t-butylphenyl)-2-hydroxy-2
-Propiophenones such as methyl-1-propanone and 4-dimethylaminopropiophenone, benzophenone, Michler's ketone, and 4°4'-bis(diethylamino)benzophenone.

4-methoxy-4'-dimethylaminobenzophenone, 4.4'-dimethoxybenzophenone.

4.4'-Diaminobenzophenone, 2-chlorobenzophenone, 4.4'-dichlorobenzophenone, benzophenones such as methyl-0-benzoylbenzoate, benzoin, benzoin methyl ether, benzoin ethyl ether.

Benzoin-n-propyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin phenyl ether, α-methylbenzoin.

Benzoins such as α-ethylbenzoin, benzyl, benzyls such as benzyl dimethyl ketal, anthraquinone, 2-methylanthraquinone.

2-ethylanthraquinone, 2-t-butylanthraquinone, octamethylanthraquinone.

1,4-dimethylanthraquinone, 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone, 1-chloroanthraquinone.

2-chloroanthraquinone, 2-phenylanthraquinone, 2.3-diphenylanthraquinone,
Anthraquinones such as 1,2-benzanthraquinone and 2.3-benzanthraquinone, cyclic ketones such as benzoquinone, naphthoquinone, phenanthraquinone, xanthone, retinquinone, cyclohexanone, and dibenzosuberone, diacetyl, 1-hydroxycyclohexyl Phenylketone, acetoin, vivaloin, furoin,
Other ketones such as toluoine, thioxanthone.

2-chlorothioxanthone, 2-methylthioxanthone, diphenyl disulfide, tetramethylthiuram monosulfide, tetramethylthiuram disulfide,
Sulfur compounds such as 2-mercaptooxazole, n-
Amines such as butylamine, di-n-butylamine, triethylamine, dimethylaminoethanol, N-methyljetanolamine, triethanolamine, p-fuynylenediamine, pentachlorobutadiene, octachlorobutene, trichloromethylnaphthalene, etc. It is a halogenated hydrocarbon, other 2.4.5-triarylimidazole compounds, etc. alone or a mixture of two or more thereof.

In the composition of the present invention, a film-forming polymer can also be used in combination, and particularly good results are often obtained when a prepolymer-based photopolymerizable compound is not used.

Various polymers can be used as the film-forming polymer used in the present invention. An example of this is methyl acrylate.

Methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-ethylhexyl acrylate, 2
- Homopolymers and copolymers of esters of acrylic acid and methacrylic acid such as ethylhexyl methacrylate, and small amounts of acrylic acids such as acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, etc. Copolymers of these esters with styrene, vinyl acetate, vinyl chloride, etc., and modified products thereof, polystyrene, polyvinyl acetate, polyvinyl chloride, polyvinyl alcohol.

Vinyl polymers such as polyvinyl formal and polyvinyl butyral, cellulose polymers such as cellulose acetate butyrate, and polyamides.

Condensation polymers such as polyester and polyether are used depending on the purpose.

Although the content of each component in the composition of the present invention varies depending on the compound used and the purpose of use, it is usually 0.01 to 20 parts by weight of the photochromic compound per 100 parts by weight of the photopolymerizable compound and the film-forming polymer. parts by weight, preferably 0.1
~5 parts by weight, 0.01 to 20 parts by weight, preferably 0.1 to 5 parts by weight, of a photochromic accelerator, 0 to 20 parts by weight, preferably 0 to 10 parts by weight, of a photosensitization initiator, and a film-forming polymer. 0 to 90 parts by weight, preferably 0 to 80 parts by weight are used. If the amount of the photochromic compound and photochromic accelerator is less than the above amount, sufficient photochromic property will not be obtained, and if the amount is greater than the above amount, the photochromic property will hardly increase. Problems may arise in the compatibility of the composition, etc. Also, if the amount of the photosensitization initiator is larger than the above amount, not only will the photopolymerization rate hardly increase, but also problems may arise in the compatibility, etc. of the composition. Furthermore, if the film-forming polymer is used in an amount larger than the above amount, the physical properties after photopolymerization, such as chemical resistance, will deteriorate.

In the composition of the present invention, pigments such as methylene blue, Nile blue, eosin, fluorescein, and phthalocyanine compounds are used for the purpose of improving workability, adjusting color tone, emphasizing photochromic effect, increasing photopolymerization rate, etc. before irradiation with light. It goes without saying that other photochromic compounds can be used in combination, and in this case the amount used is usually about 10 parts by weight, preferably 1
Up to about 1 part by weight, and even if the amount is increased beyond the above amount, there is almost no increase in the above effect, and in the case of ordinary dyes,
There are cases where the coloring before light irradiation becomes so large that it becomes difficult to align the irradiation pattern.

The composition of the present invention is made into a photosensitive element consisting of three layers: a peelable support, a photosensitive resin layer, and a peelable protective film, and then the peelable protective film is peeled off to form a photosensitive resin layer. A method in which the photosensitive composition of the present invention is applied directly to the surface of a predetermined substrate, irradiated with ultraviolet rays, etc., and developed; The photosensitive composition of the present invention can be used in various methods such as printing only the necessary portions of the photosensitive composition and irradiating it with ultraviolet light or the like. Of course, it is also possible to expose the entire surface to light after coating and drying for the purpose of painting, primer, adhesion, etc., and this has the effect of facilitating process control.

In order to adjust various physical properties of the composition of the present invention, such as coatability and printability, depending on the method and purpose of use,
Solvents such as methyl ethyl ketone and toluene, thickeners, fillers, plasticizers, and leveling agents.

Adhesion improvers such as antifoaming agents, stirring agents, phosphate esters, and silanes, tribromomethylphenylsulfone itself has flame retardant properties, and flame retardant 1 extender pigments for further flame retardancy. , stabilizers such as thermal polymerization inhibitors, etc. can be added.

Although irradiation with radiation is possible for discoloration and polymerization of the composition of the present invention, since safety measures are costly, ultraviolet rays, visible light, electron beams, X-rays, etc. are usually used.

With the composition of the present invention, it is possible to expand the photochromic hue, and of course, it is easy to generate a blue-green hue that is easy to distinguish under a yellow safety light.

The present invention will be explained below with reference to Examples. Of course, the present invention is not limited to the examples.

Example 1 The following composition was prepared.

Copolymer of methyl methacrylate (60%) (20%) p-methoxyphenol 0.05 parts by weight Benzophenone 0.6 parts by weight 4-
dimethylamino-4'4'-dimethoxy-3',
3'-Dimethyl 1 part by weight - Triphenylmethaneethyl cellosolve 110 parts Methyl ethyl ketone 100 parts by weight The above composition was uniformly coated on a polyethylene terephthalate film with a thickness of 25 μm, dried at 100° C., and a film with a thickness of about 25 μm was coated.
A thick coating film was obtained. This coating film was laminated onto a cleaned copper-clad laminate (substrate) and exposed using a negative film to a high-pressure mercury lamp for 20 seconds at a distance of 50 cm. ``The exposed area was completely cured and colored orange. The unexposed areas were not cured and remained colorless, and the contrast between the exposed and unexposed areas was good.

Comparative example 1 4-dimethylamino-4'4'-dimethoxy-3'
When the same treatment as in Example 1 was carried out using leuco crystal violet [4,4'4'-tris(dimethylamino)-triphenylmethane] instead of 3'-dimethyl-triphenylmethane, the exposed area was Colored blue. However, the contrast between the exposed and unexposed areas was not sufficient and it was not easy to distinguish them under a yellow safety light.

Examples 2-10 4-dimethylamino-4'4"-dimethoxy-3,
When the same treatment as in Example 1 was carried out using each compound in the table below in place of 3'-dimethyl-triphenylmethane, the contrast between the exposed and unexposed areas was as shown in the table below. It was good.

Example 11 Methyl methacrylate (60%), methacrylic acid (20%)
%), an unsaturated acrylic polymer in which 50% of the methacrylic acid component in the above copolymer was reacted with 2-hydroxyethyl acrylate was used instead of the copolymer of 2-ethyl ethyl acrylate (20%). Then, the same treatment as in Example 1 was performed, and the same results as in Example 1 were obtained.

Example 12 The following composition was prepared.

Esterified product of ethylene (80%) and acrylic acid (20%) copolymer with hydroxyethyl acrylate 60 parts by weight (30% esterified product of acrylic acid units) 2.2-bis(4-
Acryloxypolyethoxyphenyl)-propane 35 parts by weight (contains about 10 ethoxy units) 2-hydroxy-3-chloropropyl-2-acryloyloxyethyl-〇-phthalate 5 parts by weight 4.4'-bis(dimethylamino) -4'-morpholino-triphenylmethane parts by weight Toluene methanol 100 parts by weight The above composition was applied onto a cleaned stainless steel plate and dried to obtain a coating film. When the entire surface of this coating film was irradiated with an electron beam of approximately 5 megarads, it was completely cured and colored blue.

Claims (3)

[Claims] (1) In a photochromic photosensitive composition containing a photopolymerizable compound, a photochromic compound, and a photochromic accelerator as essential components, the photochromic compound has a general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (formula R_1 is a phenyl group, a naphthyl group, a hydrocarbon-substituted amino group having 1 to 12 carbon atoms at the 4-position, or a carbon number 1 to 1
phenyl group having 2 alkoxy groups, naphthyl group having at least one alkoxy group having 1 to 12 carbon atoms, and hydrocarbon groups having 1 to 12 carbon atoms thereof;
12 alkoxy group, carboxylic acid (salt) group, sulfonic acid (salt) group, or a group substituted with a halogen atom, R_2
, R_3 represents a hydrocarbon-substituted amino group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, R_4, R_
5, R_6, R_7 are hydrogen atoms, hydrocarbon groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, carboxylic acid (
salt) group, sulfonic acid (salt) group, or halogen atom, n
indicates 0 or 1, at least one substituted amino group is present, when n is 0 and the number of substituted amino groups is 1 or 2, at least one alkoxy group is present, and n is 0 and the number of substituted amino groups is present. is 3, non-containing groups such as those that form a cyclic structure with an alkyl-substituted amino group and a cycloalkyl group, an aryl group, an aralkyl group, or an amino group that contains a nitrogen atom and may also contain an oxygen atom. A photochromic photosensitive composition characterized by using a substituted amino group-containing triaryl compound represented by (at least one alkyl group-substituted amino group is present) and using tribromomethylphenyl sulfone as a photochromic accelerator. . (2) The composition according to claim (1), which contains a photosensitization initiator. (3) A composition according to claims (1) and (2) in which a film-forming polymer is added.