JPH07196632A - Photosensitive trihalomethyl-s-triazine compound and photopolymerizable composition containing the same - Google Patents

Abstract

PURPOSE:To obtain a new free radical producing agent, causing remarkably slight coloring itself or by decomposition products, capable of producing a photopolymerizable composition with slight optical coloring in exposing an image to light or preservation in the light. CONSTITUTION:This compound is expressed by formula I [X is Cl or Br; Y is an alkyl, CF3, CF2Cl, an alkyl substituted with a group other than a halogen, Z-CO-OR<3> (R<3> is H or an alkyl; Z is C2H4, C3H6, CH=CH or o-phenylene), C6F5, C6H4-R4 (R4 is H, OH, an alkyl, an aryl, an alkoxy, a halogen, CN, an acyl, etc.); R<1> and R<2> each is H, OH, an alkyl, an aryl, an alkoxy, a halogen, formula II (R<5> and R<6> each is H, an alkyl, an aryl or bound to form a ring) or NR<7>R<8> (R<7> and R<8> each is R<5>, R<6> or an acyl)]. The compound is obtained by reacting an N-iminoacyl-trihaloacetamidine expressed by formula III with an acid chloride expressed by formula IV. The compound is especially useful in use as a radical photopolymerization initiator in a photopolymerizable composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel compound capable of generating a free radical upon exposure to light, which is useful in the fields of photosensitive protective film, printing plate, photoresist, recording material such as proof, and the like. The present invention relates to a photopolymerizable composition to be contained. More specifically, the novel photosensitive trihalomethyl-s-
The present invention relates to a triazine compound and a photopolymerizable composition containing the same.

[0002]

2. Description of the Related Art Compounds (free radical generators) that decompose to form free radicals when exposed to light are known as graphic arts,
It is well known in the field of photosensitive recording materials. They are widely used as photoradical polymerization initiators in photopolymerizable compositions, photoactivators in free-radical photographic compositions, and photoinitiators of reactions catalyzed by photogenerated acids. Such free radical generators have been used to make a variety of light-sensitive materials useful in printing, reproduction, reproduction and other recording material systems.

A bis (trihalomethyl) -s-triazine compound has been proposed as a halogen free radical generator having a photosensitive wavelength in the near-ultraviolet to visible light region. For example, U.S. Pat. Nos. 3,954,475 and 3,987,0
No. 37, No. 4,189,323, No. 4,696,
No. 888, No. 4,837,128, JP-A-62-5
8241 and JP-A-2-149570. These compounds have a photosensitive wavelength in the near-ultraviolet to visible light region, but the decomposition product due to exposure is easily colored in a light yellow color, and further, in a system in which the photoradical polymerization initiator or its decomposition product remains in the recording layer, There is a problem in that, when stored in a bright place, these are decomposed by exposure to light and colored in yellow. With respect to such problems, the present inventors have diligently studied and found that the compound of the present invention exhibits good performance.

In connection with the compounds of the present invention, JP-A-58-
No. 40302 describes compounds represented by the following general formula (IV). General formula (IV)

[0005]

[Chemical 4]

(In the formula, R ⁹ , R ¹⁰ and R ¹¹ are optionally substituted alkyl group, aryl group, alkenyl group or piperidino group, --NR ₂ , --OR or --S
R (wherein R represents a hydrogen atom or an alkyl group), and at least one of them represents a mono-, di-, or trihalogen-substituted methyl group. )

However, in specific compound examples and examples, mono-, di-, or trihalogen-substituted methyl groups are disclosed in which the same triazine ring is substituted by two or three. Moreover, chlorine atoms and bromine atoms are described as halogen atoms, and no examples of fluorine atoms are found. As a matter of course, there is no description about the interesting performance of the photosensitive S-triazine compound having one trichloromethyl group or one tribromomethyl group according to the present invention.

[0008]

An object of the present invention is that the photosensitive wavelength region is in the near-ultraviolet to visible light region and that it is highly sensitive and does not cause coloration of the decomposed product upon exposure and the decomposed product during storage in a bright place. It is to provide a photosensitive trihalomethyl-s-triazine, and a photopolymerizable composition containing the same.

[0009]

The object of the present invention is to provide a photosensitive s-triazine having one trichloromethyl group or tribromomethyl group represented by the following general formula (I), and a photopolymerization containing the same. Achieved by the sexual composition.
General formula (I)

[0010]

[Chemical 5]

In the formula, X represents a chlorine atom or a bromine atom. Y is an alkyl group, CF ₃ group, CF ₂ Cl group, an alkyl group substituted with a non-halogen atom, Z-CO-OR ^3,
C ₆ F ₅ group, or a group represented by C ₆ H ^₄ -R _4. However, R ³ represents a hydrogen atom or an alkyl group, and Z is —C _{2
H 4 -, - C 3 H} 6 -, - CH = CH-, represents an o- phenylene group. R ⁴ is a hydrogen atom, hydroxyl group, alkyl group, substituted alkyl group, aryl group, alkoxy group, substituted alkoxy group, halogen atom, alkoxycarbonyl group, cyano group, acyl group, nitro group, formyl group, mercapto group, alkylthio group. Represents a group or a dialkylamino group. R ¹ and R ² are each a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, a substituted alkoxy group,
It represents an acyloxy group, a halogen atom, an alkoxycarbonyl group, a cyano group, a nitro group, a carboxyl group or a group represented by the general formula (II) or the general formula (III).
General formula (II)

[0012]

[Chemical 6]

General formula (III)

[0014]

[Chemical 7]

In the general formula (II), R^Five, R⁶Is that
Hydrogen atom, alkyl group, substituted alkyl group, aryl group
Or represents a substituted aryl group, and has the general formula (III)
R ⁷, R⁸Are hydrogen atom, alkyl group, and substituted
Kill group, aryl group, substituted aryl group or acyl group
Represent Also, R^FiveAnd R⁶, R⁷And R⁸Combine with each other to form a ring
It may be formed.

In the general formula (I), the alkyl group of Y is preferably one having 1 to 16 carbon atoms, and particularly preferably one having 1 to 10 carbon atoms. The alkyl group of R ³ preferably has 1 to 8 carbon atoms,
Particularly, those having 1 to 4 carbon atoms are preferable. Also, R ⁴
The alkyl group of is preferably one having 1 to 8 carbon atoms, particularly preferably one having 1 to 4 carbon atoms, and the alkoxy group or the alkoxy group of the alkoxycarbonyl group is preferably one having 1 to 8 carbon atoms. Particularly, those having 1 to 4 carbon atoms are preferable, those having 6 to 14 carbon atoms are preferable as the aryl group, those having 6 to 10 carbon atoms are particularly preferable, and those having an alkylthio group are those having carbon number. Those having 1 to 16 carbon atoms are preferable, and those having 1 to 8 carbon atoms are particularly preferable.

In the general formula (I), examples of the substituent of the alkyl group substituted by a halogen atom other than Y are aryl group, substituted aryl group, hydroxyl group, alkoxy group, carboxyl group, alkoxycarbonyl group and aryloxy. Examples thereof include a carbonyl group, a cyano group, an acyl group, a nitro group, a mercapto group, an alkylthio group, an arylthio group, and a dialkylamino group. Of these, particularly preferred are a hydroxyl group, an aryl group having 6 to 10 carbon atoms, and a carbon atom. An aryl group having 6 to 10 carbon atoms substituted with an alkoxy group having 1 to 8 carbon atoms or a dialkylamino group having 1 to 8 carbon atoms, a hydroxyl group, and 1 to 8 carbon atoms
Alkoxy group having 1 to 4 carbon atoms, alkoxycarbonyl group having 1 to 4 carbon atoms, cyano group, mercapto group, alkylthio group having 1 to 8 carbon atoms, arylthio group having 6 to 10 carbon atoms, dialkyl having 1 to 8 carbon atoms It is an amino group.

In the general formula (I), examples of the substituent of the substituted alkyl group and the substituted alkoxy group represented by R ⁴ are an aryl group, a halogen atom, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group and a cyano group. Group, an acyl group, a nitro group, a dialkylamino group, and the like. Of these, particularly preferable are a halogen atom, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group. , A cyano group or an acyl group.

In the general formula (I), the alkyl group represented by R ¹ and R ² preferably has 1 to 16 carbon atoms,
Particularly, those having 1 to 8 carbon atoms are preferable. The aryl group preferably has 6 to 14 carbon atoms, and particularly preferably has 6 to 10 carbon atoms.

In formula (I), the alkoxy group of R ¹ and R ² and the alkoxy group of the alkoxycarbonyl group are preferably those having 1 to 18 carbon atoms, and particularly preferably those having 1 to 8 carbon atoms.

In the general formula (I), examples of the substituent of the substituted alkoxy group for R ¹ and R ² include a hydroxyl group, an aryl group, a halogen atom, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group,
Examples thereof include a cyano group, an acyl group, a nitro group, and a dialkylamino group. Of these, particularly preferred are an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, and cyano. A group or an acyl group.

In the general formulas (II) and (III), the alkyl group represented by R ⁵ , R ⁶ , R ⁷ and R ⁸ has 1 carbon atom.
Those having 1 to 16 carbon atoms are preferable, and those having 1 to 8 carbon atoms are particularly preferable. The aryl group preferably has 6 to 14 carbon atoms, and particularly has 6 to 1 carbon atoms.
Those up to 0 are preferred.

In the general formulas (II) and (III), examples of the substituent of the substituted alkyl group of R ⁵ , R ⁶ , R ⁷ and R ⁸ include an aryl group, a halogen atom, an alkoxy group,
Examples thereof include a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, an acyl group, a nitro group and a dialkylamino group.

The substituent of the substituted aryl group of R ⁵ , R ⁶ , R ⁷ , and R ⁸ includes an alkyl group in addition to the above-mentioned substituents.

Of these substituents for the substituted alkyl group and substituted aryl group for R ⁵ , R ⁶ , R ⁷ , and R ⁸ , particularly preferred are halogen atoms, carboxyl groups, alkoxycarbonyl groups having 1 to 8 carbon atoms, It is a cyano group or an acyl group.

When R ⁵ and R ⁶ and R ⁷ and R ⁸ are bonded to each other to form a ring, those represented by the following (A) to (J) are mentioned.

[0027]

[Chemical 8]

Among the compounds represented by the general formula (I) as described above, particularly preferable compounds are those represented by the general formula (I), wherein X is a chlorine atom, and Y is a methyl group, an ethyl group, a propyl group or a butyl group. Group, pentyl group, hexyl group, decyl group, CF ₃ group, CF ₂ Cl group, benzyl group, diphenylmethyl group, triphenylmethyl group, p-methoxybenzyl group, p-diethylaminobenzyl group, hydroxymethyl group, methoxymethyl group Group, methoxypropyl group, cyanomethyl group, dimethylaminomethyl group, diethylaminopropyl group, mercaptomethyl group, methylthiomethyl group, phenylthiomethyl group, carboxylethyl group, methoxycarbonylethyl group, methoxycarbonylpropyl group,
Methoxycarbonyl ethenyl group, C ₆ F ₅ group, a phenyl group, a tolyl group, p- fluorophenyl group, p- chlorophenyl group, p- trifluoromethylphenyl group, o- trifluoromethylphenyl group, p- trichloromethylphenyl Group, p-methoxyphenyl group, p-ethoxyphenyl group, p-methoxyethoxyphenyl group, o-methoxycarbonylmethoxy group, p-cyanophenyl group, p-
A nitrophenyl group, an o-mercaptophenyl group, a p-methylthiophenyl group, or a p-diethylaminophenyl group, wherein R ¹ and R ² are hydrogen atoms, hydroxyl groups, halogen atoms, methyl groups, ethyl groups, propyl groups, methoxy groups , Ethoxy group, propoxy group, butoxy group, methoxycarbonylmethoxy group, ethoxycarbonylmethoxy group, cyanomethoxy group, cyanoethoxy group, acetoxy group, benzoyloxy group, hydroxyethoxy group, bromoethoxy group, chloroethoxy group, bromopropoxy group , Chloropropoxy group, phenylaminocarbonyl group, anisylaminocarbonyl group, diphenylaminocarbonyl group,
The compound is a dianisylaminocarbonyl group, a dimethylaminocarbonyl group, a diethylaminocarbonyl group, an acetylamino group or a benzoylamino group. Further, a particularly preferred one is that Y in the general formula (I) is C
It is of the F ₃ group.

Examples of compounds useful as the photosensitive trihalomethyl-s-triazine according to the present invention are shown below. However, the present invention is not limited to the following compounds.

[0030]

[Chemical 9]

[0031]

[Chemical 10]

[0032]

[Chemical 11]

[0033]

[Chemical 12]

[0034]

[Chemical 13]

[0035]

[Chemical 14]

[0036]

[Chemical 15]

[0037]

[Chemical 16]

[0038]

[Chemical 17]

[0039]

[Chemical 18]

[0040]

[Chemical 19]

[0041]

[Chemical 20]

[0042]

[Chemical 21]

[0043]

[Chemical formula 22]

[0044]

[Chemical formula 23]

[0045]

[Chemical formula 24]

[0046]

[Chemical 25]

[0047]

[Chemical formula 26]

[0048]

[Chemical 27]

[0049]

[Chemical 28]

[0050]

[Chemical 29]

[0051]

[Chemical 30]

[0052]

[Chemical 31]

Photosensitive trihalomethyl-related to the present invention
The s-triazine compound can be synthesized by the method of the following formula A or formula B.

[0054]

[Chemical 32]

[0055]

[Chemical 33]

That is, the formula A is for reacting N-iminoacyl-trihaloacetamidine with an acid chloride, and the formula B is for reacting N- (acetimidyl) trihaloacetamidine with a carboxylic acid derivative and methyl-trihalomethyl. -S-triazine is synthesized and a condensation reaction is performed with a specific aldehyde or aldehyde derivative.

The synthesis of trihalomethyl-s-triazine in formula A and the synthesis of methyl-trihalomethyl-s-triazine in formula B can be easily performed by the method described in British Patent No. 912,112. Further, the condensation reaction in the formula B can be synthesized according to the method described in US Pat. No. 3,987,037.

As the acid chloride in the formula A, a commercially available one or a compound synthesized from a carboxylic acid by a known method can be used. As the aldehyde in the formula B, a commercially available one or one synthesized by a known method can be used.

In the general formula (I), Y is -Z-C.
In the case of O—OR ¹² (R ¹² represents the alkyl group of R ³ ), it can also be synthesized by the method of the following formula C.

[0060]

[Chemical 34]

That is, the formula C is for reacting N- (acetimidyl) trihaloacetamidine with a cyclic acid anhydride, and an s-triazine derivative having a carboxyl group at the terminal can be synthesized. The resulting carboxyl group can be converted into an alkoxycarbonyl group by esterification by a conventional method.

The photosensitive trihalomethyl-s-triazine represented by formula (I) is particularly useful when used as a photoradical polymerization initiator in a photopolymerizable composition.

When the photosensitive trihalomethyl-s-triazine represented by the general formula (I) is used in the photopolymerizable composition, the photopolymerizable composition comprises a polymerizable compound having an ethylenically unsaturated bond and a photopolymerizable compound. It is composed of a radical polymerization initiator, a binder if necessary, and a sensitizer if necessary, and is particularly useful for a photosensitive layer of a photosensitive printing plate, a color proof, a photoresist and the like.

Further, for example, it is preferably used in the following recording materials using a photopolymerizable composition. However, it is not limited to these applications.

That is, a latent image is formed on the photocurable composition by exposure, and a component relating to coloring or decoloring upon heating moves in the light-sensitive material according to the latent image to form a color image. In this system, at least one kind of components involved in color development or decolorization is encapsulated in microcapsules, and the photocurable composition contains an ethylenically unsaturated compound and the above-mentioned photosensitive trihalomethyl-
Examples thereof include light and heat sensitive recording materials containing s-triazine. In this light and heat sensitive recording material, the components relating to color development or decolorization preferably consist of an electron donating colorless dye and an electron accepting compound.

The polymerizable compound having an ethylenically unsaturated bond in the photopolymerizable composition of the present invention is a compound having at least one ethylenically unsaturated bond in its chemical structure, which is a monomer or a prepolymer. Polymers, that is, dimers, trimers and other oligomers, mixtures thereof and copolymers thereof, and the like. Specifically, it is described in U.S. Pat. Nos. 2,760,863, 3,030,023, Japanese Patent Publications 35-5,093, 35-14,719, 44-28,727 and the like. There are compounds. Examples of these include acrylic acid and salts thereof, acrylic acid esters, methacrylic acid and salts thereof, methacrylic acid esters, acrylamide, methacrylamide, maleic anhydride, maleic acid esters, itaconic acid, itaconic acid esters, Examples thereof include styrenes, vinyl ethers, vinyl esters, and aryl esters.

Of these, compounds having two or more terminal unsaturated groups are particularly preferred, and acrylic acid esters, methacrylic acid esters, itaconic acid esters of polyhydric alcohols, acrylic acid amides of polyhydric amines, and methacrylic acid amides are preferred. And acrylate or methacrylate terminal epoxy resin and the like are preferable, and specific examples thereof include acrylic acid esters such as ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate,
Tetraethylene glycol diacrylate, propylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, 1,4-cyclohexanediol diacrylate,
Pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate , Sorbito
There are hexyl acrylate, polyester acrylate oligomer and the like. As the methacrylic acid ester, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetramethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, 1,
Examples include 3-butanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, sorbitol tetramethacrylate, and 1,2,4-butanetriol trimethacrylate. As itaconic acid esters, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate,
Examples include pentaerythritol diitaconate and sorbitol-lutetitaconate. Examples of acrylic acid amides include methylenebis-acrylamide, 1,6-hexamethylenebis-acrylamide, and diethylenetriaminetrisacrylamide. Examples of methacrylic acid amides include methylenebis-methacrylamide, 1,6-hexamethylenebis-methacrylamide, and xylylenebismethacrylamide.

As another example, an electron-accepting compound having one or more polymerizable ethylene groups is preferable, and specifically, a benzoic acid meta group having a hydroxy group described in JP-A-63-173682 is used. Acryloxyethyl ester and acryloxyethyl ester which can be synthesized by a similar synthetic method, Nos. 59-83693 and 60-14158.
Nos. 7 and 62-99190, and esters of hydroxybenzoic acid having a hydroxy group with hydroxymethylstyrene, hydroxystyrene described in European Patent 29323, and JP-A-62-167077 and 62-62.
N- of zinc halides described in No. 16708
Examples thereof include a vinylimidazole complex, a developer monomer described in JP-A-63-317558, and a compound represented by the following general formula (V). General formula (V)

[0069]

[Chemical 35]

In the above formula, T represents a hydrogen atom or a halogen atom, M represents a monovalent group having a polymerizable ethylene group, and Q represents a hydrogen atom, an alkyl group, a hydroxy group, an acyloxy group or an alkoxy group. Among the monovalent groups having a polymerizable ethylene group represented by M in the above formula (V), an aralkyl group having a vinyl group, an acryloyloxyalkyl group and a methacryloyloxyalkyl group are preferable.

Specifically, 3-chloro-4-hydroxybenzoic acid vinylphenethyl ester, 3-chloro-4-
Hydroxybenzoic acid vinyl phenylpropyl ester,
3-chloro-4-hydroxybenzoic acid- (2-acryloyloxyethyl) ester, 3-chloro-4-hydroxybenzoic acid- (2-methacryloyloxyethyl) ester, 3-chloro-4-hydroxybenzoic acid- (6 −
Methacryloyloxyhexyl) ester, 3-chloro-4-hydroxybenzoic acid- (6-acryloyloxyhexyl) ester, 3-chloro-4-hydroxybenzoic acid- (3-acryloyloxypropyl) ester,
3-Chloro-4-hydroxybenzoic acid- (3-methacryloyloxypropyl) ester, 3-chloro-4-hydroxybenzoic acid- (4-acryloyloxybutyl)
Ester, 3-chloro-4-hydroxybenzoic acid- (4
-Methacryloyloxybutyl) ester, 3-fluoro-4-hydroxybenzoic acid- (2-acryloyloxyethyl) ester, 2,4-dihydroxy-6-methylbenzoic acid vinylbenzyl ester, 2,4-dihydroxy-5-methyl Benzoic acid vinyl benzyl ester, 2,
4-Dihydroxy-3-methylbenzoic acid vinylbenzyl ester, 2,4-dihydroxy-3-chlorobenzoic acid vinylbenzyl ester, 2,4-dihydroxy-6-
Phenylbenzoic acid vinylbenzyl ester, 2,4-dihydroxybenzoic acid vinylphenethyl ester, 2,4
-Dihydroxybenzoic acid vinylphenylpropyl ester, 2,4-dihydroxybenzoic acid vinylbenzyl ester, 2-acryloyloxy-4-hydroxybenzoic acid- (2-acryloyloxyethyl) ester, 2
-Methacryloyloxy-4-hydroxybenzoic acid- (2
-Methacryloyloxyethyl) ester, 2,4-dihydroxybenzoic acid (2,3-bismethacryloyloxypropyl) ester, 2,4-dihydroxybenzoic acid (2,3-bisacryloyloxypropyl) ester and the like.

When the photosensitive trihalomethyl-s-triazine represented by the general formula (I) is used as a photoradical polymerization initiator in the photopolymerizable composition, it is optionally bonded to the photopolymerizable composition. Agents can be included.

The binder used in the photopolymerizable composition of the present invention has compatibility with the polymerizable ethylenically unsaturated compound and the photoradical polymerization initiator in the preparation, coating and drying of the coating solution of the composition. All the manufacturing steps of the light-sensitive material, and good enough not to cause demixing during storage of the resulting mixture, and image exposure when used in a light-sensitive layer or resist layer which is developed by an alkaline aqueous solution. After development is possible, photosensitive layer,
Although it is required to have characteristics such as being able to form a tough film as a resist layer or a protective layer, usually,
It is properly selected from a wide variety of synthetic, semi-synthetic and natural polymeric substances.

Specific examples of the binder include (meth) acrylic acid and (meth) acrylic acid ester (as the ester, methyl ester, ethyl ester, butyl ester, 2-ethylhexyl ester, benzyl ester,
2-hydroxyethyl ester, etc.), poly (meth) acrylic acid, a copolymer of styrene and an unsaturated dibasic acid anhydride such as maleic anhydride, a reaction product of the polymer with alcohols, Examples include, but are not limited to, a reaction product of cellulose with a polybasic acid anhydride, gelatin, and polyvinyl alcohol.

These binders may be used alone as binders, but they have good compatibility and are demixed during the manufacturing process from preparation of coating liquid to coating, drying and storage of the resulting mixture. Two or more polymers that do not cause the above may be mixed at an appropriate ratio and used as a binder.

The molecular weight of the polymeric substance used as the binder can take a wide range depending on the kind of the polymer, but it is generally in the range of 5,000 to 2,000,000, preferably 10,000 to 1,000,000. Is preferred.

In the photopolymerization composition containing the trihalomethyl-s-triazine derivative according to the present invention, a compound capable of initiating photopolymerization of another compound having an ethylenically unsaturated bond may be used in combination. Examples of these are: Examples of organic sulfur compounds, peroxides, redox compounds, azo and diazo compounds and substituted benzophenone derivatives, aromatic ketones, lophine dimers and organic halogen compounds other than the present invention described in Chapter 5 of "Light Sensitive Systems" by Coser .

The content of the photopolymerization initiator in the photopolymerizable composition is preferably 0.1% by weight based on the total weight of the photopolymerizable composition.
01-20% by weight, and more preferably 0.2-15
%, And the most preferable content is 0.5 to 10% by weight. If it is less than 0.01% by weight, the sensitivity is insufficient,
When it exceeds the weight%, an increase in sensitivity cannot be expected. The amount of the photosensitive trihalomethyl-s-triazine used in the present invention in the total photopolymerization initiator used is preferably 40% by weight or more, and more preferably 50% by weight or more.

The photopolymerizable composition according to the present invention may contain, in addition to the ethylenically unsaturated compound and the trihalomethyl-s-triazine derivative, a spectral sensitizing dye for adjusting its photosensitive wavelength. As the spectral sensitizing dye, various compounds known in the art can be used. Examples of spectral sensitizing dyes include patents relating to the above-mentioned photopolymerization initiator and
ch Diclosure, Vol.200, December 1980, Item20036 and "sensitizer" (Katsumi Tokumaru, Shin Okawara / ed. Kodansha, 1987)
160-163, etc.

Further, the photopolymerizable composition according to the present invention further comprises a reducing agent such as an oxygen scavenger and a chain transfer agent of an active hydrogen donor, and a chain transfer polymerization as an auxiliary agent for further promoting the polymerization. It is also possible to jointly use other compounds which promote. Oxygen scavengers are phosphines, phosphonates, phosphites, stannous salts and other compounds which are easily oxidized by oxygen. For example, N-phenylglycine, trimethylbarbituric acid, N, N-dimethyl-2,6-diisopropylaniline, N, N, N-
2,4,6-pentamethylaniline and the like. Further, thiols, thioketones, trihalomethyl compounds, lophine dimer compounds, iodonium salts, sulfonium salts, azinium salts, organic peroxides and the like as shown below are also useful as the polymerization accelerator.

In addition to these compounds, for example, polyvinyl cinnamate, polycinnamylidene vinyl acetate, and a photosensitive resin having an α-phenylmaleimide group can be added as a photocrosslinking composition.

Further, in addition to these compounds, a thermal polymerization inhibitor can be added if necessary. The thermal polymerization inhibitor is added in order to prevent thermal polymerization of the photopolymerizable composition or polymerization over time, whereby the chemical stability of the photopolymerizable composition during preparation or storage is improved. Can be increased.

In the photopolymerizable composition of the present invention, various surfactants may be used for various purposes such as coating aid, antistatic property, slip property improvement, emulsion dispersion, and adhesion prevention.

Examples of the surfactant include nonionic surfactants such as saponin, polyethylene oxide, and polyethylene oxide derivatives such as alkyl ethers of polyethylene oxide, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, and alkyl sulfates. Anionic surfactants such as esters, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, amphoteric surfactants such as alkyl betaines, alkyl sulfobetaines, and fats A cationic surfactant such as a quaternary ammonium salt of a genus or an aromatic group can be used if necessary.

A plasticizer may be added to the photopolymerizable composition of the present invention in order to control the physical properties of the film. Examples of plasticizers include phthalates such as diethyl phthalate, dibutyl phthalate, dioctyl phthalate,
Glycol esters such as triethylene glycol dicaprylic acid ester, phosphoric acid esters such as tricresyl phosphate, dioctyl adipate, aliphatic dibasic acid esters such as dibutyl sebacate, benzene sulfonamide, toluene sulfonamide, etc. Examples include amides.

An adhesion promoter may be added to the photopolymerizable composition of the present invention in order to improve the adhesion. Examples of adhesion promoters include JP-B Nos. 50-9177 and 54-52.
92, 55-22482, U.S. Pat. No. 4,62.
The compounds described in JP-A No. 9,679, JP-B No. 57-49894 and the like can be mentioned.

Various additives can be added to the recording material of the present invention, if necessary, including the additives described above. For example, typical examples of dyes, leuco dyes, ultraviolet absorbers, fluorescent whitening agents, matting agents, coating aids, curing agents, antistatic agents and slipperiness improving agents that prevent irradiation and halation are Research Disclosure, Vol. 176, 1978 12
Mon, Item17643, and Vol.187, November 1979, Item18716
It is described in.

The photopolymerizable composition of the present invention is dissolved or dispersed in a solvent to form a coating solution and applied to a support by a suitable method, or dispersed in water to form a coating solution and applied to a support. And applied as an image forming material.
Further, a protective layer or a protective film may be provided on the uppermost layer.

As the solvent used when preparing the coating solution, natural oil or synthetic oil can be used in combination. Examples of these solvents include cottonseed oil, kerosene, paraffin, naphthene oil, alkylated biphenyl, alkylated terphenyl, chlorinated paraffin, alkylated naphthalene and 1-phenyl-1-xylylethane, 1-phenyl-1-p-ethyl. Diarylethanes such as phenylethane and 1,1'-ditolylethane. Phthalates, phosphates, citrates, benzoates, alkylamides, fatty acid esters, trimesic acid esters secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, 1-methoxy- 2-propyl acetate, cyclohexanone, methanol, ethanol, propanol, acetone, methyl ethyl ketone, toluene,
Xylene, methyl chloroform, methylene chloride, ethylene glycol monoethyl ether, 1-methoxy-2-
Propanol, dimethylformamide, dimethylsulfoxide and the like can be mentioned.

To apply the coating liquid on the support, a blade coater, a rod coater, a knife coater, a roll doctor coater, a comma coater, a reverse roll coater, a transfer roll coater, a gravure coater, a kiss roll coater, a curtain coater, an ext. A rouge coater or the like can be used. Research Disclosure, Vol. 200, 1980 12
Month, Item 20036 can be referred to. A suitable thickness of the recording layer is 1.0 μ to 100 μ.

As the support, a support such as paper, coated paper, laminated paper or synthetic paper, a transparent film such as polyethylene terephthalate film, cellulose triacetate film, polyethylene film, polystyrene film or polycarbonate film, aluminum, zinc, Examples thereof include metal plates such as copper, and those obtained by subjecting the surface of the above-mentioned support to various treatments such as surface treatment, undercoating and metal vapor deposition treatment. Research Di as a support
You can also refer to the support of Item 20036, sclosure, Vol.200, December 1980. If necessary, these supports may be provided with an antihalation layer on the surface and a slip layer, an anti-stick layer, an anti-curl layer, a pressure-sensitive adhesive layer or the like on the back surface according to the purpose.

When the present invention is used as a resist for forming a printed wiring, a support having a thin layer of a metal such as copper provided on a plastic plate or a plastic film by vapor deposition or plating is used. When the present invention is applied to a printing plate, an aluminum plate, a plastic film provided with an aluminum layer, or the like is used. When the present invention is used for a photothermal recording material, paper,
Coated paper, laminated paper, synthetic paper or the like, or a transparent film such as a polyethylene terephthalate film, a cellulose triacetate film, a polyethylene film, a polystyrene film or a polycarbonate film is used.

The recording material of the present invention can record with high sensitivity by light in a wide range from ultraviolet light to visible light. As a light source, mercury lamp, xenon lamp, tungsten lamp,
Various lasers such as metal halide lamp, argon laser, helium neon laser, semiconductor laser, LE
A wide range of light sources such as D and fluorescent lamps can be used.

The image recording method includes contact exposure of a document such as a lith film, enlargement exposure of a slide or a liquid crystal image,
Various exposure methods such as reflection exposure using reflected light of the original can be used. After exposure on the image, the unexposed portion is eluted with an appropriate developing solution such as an organic solvent, an alkaline aqueous solution containing an organic solvent or an alkaline aqueous solution to obtain a photocured image on a substrate, or In that case, an image is obtained by direct thermal development. The photopolymerizable composition of the present invention is particularly a resist for printed wiring, a lithographic or relief printing plate,
It can be widely used for producing relief type, light and heat sensitive recording materials and the like.

Examples of the present invention will be shown below, but the present invention is not limited thereto.

[0096]

【Example】

 Example 1 (Synthesis of Compound-7)

A. Synthesis by the method of formula A N- (acetimidyl) trichloroacetamidine 2.8
g, p-methoxycinnamic acid chloride 4.7 g and benzene 60 ml were mixed and heated under reflux for 8 hours. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure. After purifying the residue by column chromatography,
The crystals were recrystallized from methanol to obtain 0.59 g of compound-7 as pale yellow needle crystals having a melting point of 138 ° C.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.33 (1H, d), 7.6
4 (2H, d), 7.06 (1H, d), 6.96 (2
H, d), 3.87 (3H, s), 2.89 (3H,
s) UV spectrum (CH ₃ CN) λ _max 351 nm (ε34800)

B. Synthesis by the method of formula B N- (acetimidyl) trichloroacetamidine 4.1 g
And 20 ml of acetic anhydride were mixed and heated under reflux for 1.5 hours. The internal temperature was returned to room temperature, the reaction solution was poured into ice water, and the produced solid was collected by filtration to obtain 3.3 g of 2,4-dimethyl-6-trichloromethyl-s-triazine. 2,4
3.3 g of dimethyl-6-trichloromethyl-s-triazine, 2.2 g of p-anisaldehyde, 1.0 g of piperidine acetate and 15 ml of toluene were mixed, heated under reflux for 20 hours, and the water released was Dane Stark. Collect with an extractor. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure. The residue was purified by column chromatography and then recrystallized from methanol to obtain 1.4 g of compound-7 as pale yellow needle crystals having a melting point of 138 ° C.

Example 2 (Synthesis of Compound-1) 4.8 g of 2,4-dimethyl-6-trichloromethyl-s-triazine, 3.2 g of benzaldehyde, 1.3 g of piperidine acetate and 20 toluene.
Mix ml, heat to reflux for 10 hours, and collect the water released in a Dean-Stark extractor. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure. After purifying the residue by column chromatography,
The crystals were recrystallized from methanol to obtain 0.4 g of white crystals of Compound-1 having a melting point of 80 ° C.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.35 (1H, d), 7.7
0-7.65 (2H, m), 7.46-7.40 (3
H, m), 7.20 (1H, d), 2.80 (3H,
s) UV spectrum (CH ₃ CN) λ _max 318 nm (ε27200)

Example 3 (Synthesis of Compound-2) Benzaldehyde of Example 2 3.
The same operation as in Example 2 was carried out except that 2 g of tolualdehyde was changed to 4.1 g to obtain 1.7 g of compound-2 as white crystals having a melting point of 117 ° C.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.33 (1H, d), 7.5
9 (2H, d), 7.24 (2H, d), 7.15 (1
H, d), 2.80 (3H, s), 2.40 (3H,
s) UV spectrum (CH ₃ CN) λ _max 331 nm (ε33100)

Examples 4 to 7 In the same manner as in Example 2, Compound-13, Compound-9,
Compound-3 and compound-5 were obtained. The physical properties of the obtained compound are shown below.

Compound-13 melting point 112-113 ° C. ¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.20 (1H, d), 7.6
3 (2H, d), 7.07 (1H, d), 6.96 (2
H, d), 4.70 (2H, s), 3.82 (3H,
s) 2.80 (3H, s) UV spectrum (CH ₃ CN) λ _max 345 nm (ε31900)

Compound-9 Melting point 115-117 ° C. ¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.73 (1H, d), 7.7
3-7.66 (1H, m), 7.42-7.24 (2
H, m) 7.05-6.95 (1H, m), 6.94 (1H,
d), 4.19 (2H, q), 2.80 (3H, s),
1.55 (3H, t) UV spectrum (CH ₃ CN) λ _max 355 nm (ε 19300)

Compound-3 Melting point 50-52 ° C. ¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.33 (1H, d), 7.6
0 (2H, d) 7.27 (2H, d), 7.15 (1H, d) 2.80 (3H, s), 2.70 (2H, q) 1.28 (3H, t) UV spectrum (CH ₃ CN) λ _max 332 nm (ε29000)

Compound-5 Melting point 72-74 ° C. ¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.33 (1H, d), 7.6
2 (2H, d), 7.30 (2H, d), 7.15 (1
H, d), 2.96 (1H, dq), 2.79 (3H,
s) 1.30 (6H, d) UV spectrum (CH ₃ CN) λ _max 331 nm (ε 29500)

Example 8 (Synthesis of Compound-61) 4.1 g of N- (acetimidyl) trichloroacetamidine and 20 m of propionic anhydride.
1 was mixed and heated under reflux for 2 hours. Return the internal temperature to room temperature,
The reaction solution was extracted with ethyl acetate, washed with water, the ethyl acetate solution was evaporated under reduced pressure, and the residue was purified by column chromatography to give 3.6 g of colorless liquid 2-methyl-4-ethyl-6-trichloromethyl-s-triazine. Obtained.

3.6 g of 2-methyl-4-ethyl-6-trichloromethyl-s-triazine, 2.2 g of p-anisaldehyde, 1.0 g of piperidine acetate and toluene 1
5 ml are mixed, heated under reflux for 10 hours and the water released is collected in a Dean-Stark extractor. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure. After purifying the residue by column chromatography,
The crystals were recrystallized from methanol to obtain 0.3 g of compound-61 which was a pale yellow crystal having a melting point of 92 ° C.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.72 (1H, d), 7.7
3-7.67 (1H, m), 7.42-7.24 (2
H, m), 7.05-6.92 (2H, m), 4.18.
(2H, q), 2.80 (3H, s), 1.55 (3
H, t) UV spectrum (CH ₃ CN) λ _max 350 m (ε30000)

Example 9 (Synthesis of Compound-91) 4.1 g of N- (acetimidyl) trichloroacetamidine
And 20 ml of trifluoroacetic anhydride were mixed and heated under reflux for 2 hours. The internal temperature was returned to room temperature, the reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure to give 4-methyl-4-trifluoromethyl-6-trichloromethyl-s-triazine as a colorless liquid to 4 0.0 g was obtained.

2-Methyl-4-trifluoromethyl-6
-Trichloromethyl-s-triazine (4.0 g), p-anisaldehyde (2.2 g), piperidine acetate (1.0 g) and toluene (15 ml) were mixed and heated under reflux for 10 hours, and the released water was recovered by a Dean-Stark extractor. To do. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure. The residue is purified by column chromatography and then recrystallized from methanol, melting point 125 ° C.
1.1 g of compound-91 which is a pale yellow crystal of was obtained.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.47 (1H, d), 7.7
0 (2H, d), 7.17 (1H, d), 6.99 (2
H, d), 3.90 (3H, s) UV spectrum (CH ₃ CN) λ _max 374 nm (ε 33800)

Example 10 (Synthesis of Compound-93) The same operation as in Example 9 was carried out except that 2.2 g of p-anisaldehyde of Example 9 was replaced with 4.4 g of cumylaldehyde, and the melting point was 77-. 0.2g of compound-93 which is a white crystal of 79 ° C was obtained.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.48 (1H, d), 7.6
6 (2H, d), 7.34 (2H, d), 7.22 (1
H, d), 2.98 (1H, dq), 1.30 (6H,
d) UV spectrum (CH ₃ CN) λ _max 350 nm (ε32600)

Example 11 (Synthesis of Compound-103) The same procedure as in Example 9 was carried out except that 4.2 g of p-anisaldehyde in Example 9 was replaced with 4.2 g of p-chlorobenzaldehyde, and the melting point was 118.
0.3 g of Compound-103 which is a white crystal at -119 ° C.
Obtained.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.45 (1H, d), 7.7
7 (2H, d), 7.46 (2H, d), 7.20 (1
H, d) UV spectrum (CH ₃ CN) λ _max 338 nm (ε34600)

Example 12 (Synthesis of Compound-88) 2-Methyl-4-trifluoromethyl-6-trichloromethyl-s-triazine 2.8
g, tolualdehyde 1.8 g, ammonium acetate 1.5
g and 10 ml of acetonitrile are mixed and heated under reflux for 10 hours. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure. The residue was purified by column chromatography and then recrystallized from methanol to obtain 1.6 g of white crystal compound-88 having a melting point of 108 ° C.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.48 (1H, d), 7.6
2 (2H, d), 7.29 (2H, d), 7.27 (1
H, d) 2.43 (3H, s) UV spectrum (CH ₃ CN) λ _max 349 nm (ε 25700)

Example 13 (Synthesis of Compound-95) The same operation as in Example 12 was carried out except that 1.8 g of tolualdehyde in Example 12 was replaced with 1.8 g of p-hydroxybenzaldehyde, and the melting point was 16
1.8 g of compound-95 which is a yellow crystal of 5-167 ° C
Obtained.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.45 (1H, d), 7.6
7 (2H, d), 7.24-7.10 (1H, m),
6.93 (2H, d), 5.17 (1H, brs) UV spectrum (CH ₃ CN) λ _max 375 nm (ε30600)

Example 14 (Synthesis of Compound-96) The same operation as in Example 12 was carried out except that 1.8 g of tolualdehyde in Example 12 was replaced with 2.0 g of vanillin to obtain yellow crystals having a melting point of 161 ° C. 1.0 g of a certain compound-96 was obtained.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.40 (1H, d), 7.3
2-7.10 (3H, m), 6.98 (1H, d),
6.05 (1H, brs), 3.98 (3H, s) UV spectrum (CH ₃ CN) λ _max 390 nm (ε 30500)

Example 15 (Synthesis of Compound-119) 20.3 g of N- (acetimidyl) trichloroacetamidine, 15.0 g of chlorodifluoroacetyl chloride and 200 ml of toluene were added at 0 ° C.
After mixing with, 13.9 ml of triethylamine was added, and the mixture was heated under reflux for 2 hours. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure. The residue was purified by column chromatography and colorless liquid 2-methyl-4-
Chlorodifluoromethyl-6-trichloromethyl-s-
7.7 g of triazine was obtained.

3.0 g of 2-methyl-4-chlorodifluoromethyl-6-trichloromethyl-s-triazine, 1.3 g of tolualdehyde, 0.8 g of ammonium acetate and 10 ml of acetonitrile were mixed and heated under reflux for 10 hours. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure. Recrystallize the residue from methanol,
Compound-11 which is a pale yellow crystal having a melting point of 120-122 ° C.
1.4 g of 9 was obtained.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.47 (1H, d), 7.6
3 (2H, d), 7.29 (2H, d), 7.25 (1
H, d), 2.43 (3H, s) UV spectrum (CH ₃ CN) λ _max 349 nm (ε32000)

Example 16 (Synthesis of Compound-118) Melting point of 155 ° C. was carried out in the same manner as in Example 15 except that 1.3 g of tolualdehyde of Example 15 was replaced with 1.6 g of p-chlorobenzaldehyde.
0.9 g of Compound-118, which is a white crystal of, was obtained.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.45 (1H, d), 7.6
7 (2H, d), 7.45 (2H, d), 7.30 (1
H, d), UV spectrum (CH ₃ CN) λ _max 338 nm (ε32000)

Example 17 (Synthesis of Compound-61) 10.2 g of N- (acetimidyl) trichloroacetamidine, pivaloyl chloride 6.2
After mixing 100 ml of toluene and 100 ml of toluene at 0 ° C.,
7 ml of triethylamine was added and the mixture was heated under reflux for 2 hours. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure to give colorless liquid 2-methyl-4-t-butyl-6.
10.5 g of -trichloromethyl-s-triazine was obtained.

2-Methyl-4-t-butyl-6-trichloromethyl-s-triazine (2.8 g), p-anisaldehyde (1.5 g), piperidine acetate (1.4 g) and toluene (10 ml) were mixed and heated under reflux for 10 hours. , And the water released was collected with a Dean-Stark extractor. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure. The residue was purified by column chromatography to give Compound-61 as a pale yellow crystal having a melting point of 93-94 ° C.
33 g was obtained.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.30 (1H, d), 7.6
5 (2H, d), 7.10 (1H, d), 6.96 (2
H, d), 3.89 (3H, s), 1.48 (9H,
s) UV spectrum (CH ₃ CN) λ _max 349 nm (ε35000)

Example 18 (Synthesis of Compound-62) The same operation as in Example 17 was conducted except that 1.5 g of p-anisaldehyde of Example 17 was replaced with 2.1 g of p-methoxycarbonylmethoxybenzaldehyde. Compound-62 which is a white crystal with a melting point of 92 ° C.
Was obtained.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.30 (1H, d), 7.6
5 (2H, d), 7.10 (1H, d), 6.95 (2
H, d), 4.70 (2H, s), 3.83 (3H,
s), 1.48 (9H, s) UV spectrum (CH ₃ CN) λ _max 340 nm (ε 25500)

Example 19 (Synthesis of Compound-60) The same operation as in Example 17 was carried out except that 1.5 g of p-anisaldehyde in Example 17 was replaced by 1.3 g of tolualdehyde, and the melting point was 95 ° C. 0.8g of compound-60 which is a white crystal was obtained.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.31 (1H, d), 7.5
9 (2H, d), 7.25 (2H, d), 7.20 (1
H, d), 2.40 (3H, s), 1.47 (9H,
s) UV spectrum (CH ₃ CN) λ _max 328 nm (ε32400)

Example 20 (Synthesis of Compound-71) 20.3 g of N- (acetimidyl) trichloroacetamidine, 13.9 ml of t-butylacetyl chloride and 200 ml of benzene were mixed at 0 ° C., and then 13.9 ml of triethylamine was mixed. The mixture was heated under reflux for 2 hours. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure to give 2-methyl-4 as a colorless liquid.
-9.6 g of neopentyl-6-trichloromethyl-s-triazine was obtained.

2.8 g of 2-methyl-4-neopentyl-6-trichloromethyl-s-triazine, 1.5 g of p-anisaldehyde, 1.5 g of piperidine acetate and 10 ml of toluene were mixed and heated under reflux for 10 hours, and The water released was collected with a Dean-Stark extractor. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure. The residue is purified by column chromatography,
Compound-71 which is a pale yellow crystal having a melting point of 100-101 ° C.
0.7 g was obtained.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.30 (1H, d), 7.6
5 (2H, d), 7.09 (1H, d), 6.96 (2
H, d), 3.87 (3H, s), 2.90 (2H,
s) 1.08 (9H, s) UV spectrum (CH ₃ CN) λ _max 350 nm (ε30300)

Example 21 (Synthesis of Compound-70) The same operation as in Example 20 was carried out except that 1.5 g of p-anisaldehyde of Example 20 was replaced with 2.2 g of p-methoxycarbonylmethoxybenzaldehyde. Compound-7 which is a white crystal with a melting point of 114 ° C.
0.4 g of 0 was obtained.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.30 (1H, d), 7.6
5 (2H, d), 7.10 (1H, d), 6.96 (2
H, d), 4.71 (2H, s), 3.84 (3H,
s) 2.91 (2H, s), 1.09 (9H, s) UV spectrum (CH ₃ CN) λ _max 345 nm (ε 29400)

Example 22 (Synthesis of compound-75) 20.3 g of N- (acetimidyl) trichloroacetamidine, 19.9 g of 1-adamantanecarbonyl chloride and 200 ml of benzene were added at 0 ° C.
After mixing with, 13.9 ml of triethylamine was added, and the mixture was heated under reflux for 2 hours. The reaction solution was evaporated under reduced pressure, washed with water, and recrystallized from methanol to give 2-methyl-4-adamantyl-6-trichloromethyl-s-triazine (1) as a white solid.
2.8 g was obtained.

2-Methyl-4-adamantyl-6-trichloromethyl-s-triazine (5.2 g), p-anisaldehyde (3.1 g), piperidine acetate (2.2 g) and toluene (15 ml) were mixed and heated under reflux for 10 hours. The water released was collected with a Dean-Stark extractor. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure. The residue is purified by column chromatography,
Compound-75 which is a pale yellow crystal having a melting point of 134 ° C. is 1.1
g was obtained.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.30 (1H, d), 7.6
6 (2H, d), 7.10 (1H, d), 6.97 (2
H, d), 3.89 (3H, s), 2.20-2.10.
(9H, brs), 1.85-1.80 (6H, br)
s) UV spectrum (CH ₃ CN) λ _max 349 nm (ε29600)

Example 23 (Synthesis of Compound-76) The same operation as in Example 22 was carried out except that 3.1 g of p-anisaldehyde of Example 22 was replaced with 4.4 g of p-methoxycarbonylmethoxybenzaldehyde. Compound-7 which is a white crystal having a melting point of 150 ° C.
0.26 g of 6 was obtained.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.30 (1H, d), 7.6
5 (2H, d), 7.10 (1H, d), 6.95 (2
H, d), 4.71 (2H, s), 3.84 (3H,
s) 2.20-2.10 (9H, brs), 1.85-1.
80 (6H, brs) UV spectrum (CH ₃ CN) λ _max 343 nm (ε26800)

Example 24 (Synthesis of Compound-122) 7.0 g of N- (acetimidyl) trichloroacetamidine, 10 g of triphenylacetyl chloride and 50 ml of toluene were mixed at 0 ° C., and then 4.8 ml of triethylamine was added for 2 hours. Heated to reflux. The reaction solution was evaporated under reduced pressure, washed with water, and recrystallized from methanol to give 2-methyl-4-triphenylmethyl-white solid.
5.5 g of 6-trichloromethyl-s-triazine was obtained.

2-Methyl-4-triphenylmethyl-6
-3.2 g of trichloromethyl-s-triazine, 1.0 g of p-anisaldehyde, 1.0 g of piperidine acetate and 7 ml of toluene were mixed and heated under reflux for 10 hours, and the released water was recovered by a Dean-Stark extractor. did.
The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure. The residue was purified by column chromatography to obtain 0.15 g of compound-122 as white crystals having a melting point of 140 ° C.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.13 (1H, d), 7.6
7 (2H, d) 7.32-7.20 (15H, m), 7.06 (1H,
d), 6.94 (2H, d), 3.88 (3H, s) UV spectrum (CH ₃ N) λ _max 358 nm (ε 29700)

Example 25 (Synthesis of Compound-135) 6.12 g of N- (acetimidyl) trichloroacetamidine, benzoyl chloride 6.
0 ml and 120 ml of benzene were mixed and heated under reflux for 2 hours. The reaction solution was evaporated under reduced pressure, washed with water and recrystallized from methanol to obtain 3.23 g of white solid 2-methyl-4-phenyl-6-trichloromethyl-s-triazine.

2-Methyl-4-phenyl-6-trichloromethyl-s-triazine (2.9 g), p-methoxycarbonylmethoxybenzaldehyde (2.9 g), piperidine acetate (0.7 g) and toluene (10 ml) were mixed and heated under reflux for 10 hours. , And the water released was collected with a Dean-Stark extractor. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure. The residue was purified by column chromatography to obtain 0.57 g of compound-135 as white crystals having a melting point of 134-135 ° C.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.67 (2H, d), 8.4
0 (1H, d), 7.69 (2H, d), 7.65-
7.52 (3H, m), 7.19 (1H, d), 6.9
8 (2H, d), 4.71 (2H, s) 3.83 (3H, s) UV spectrum (CH ₃ CN) λ _max 351 nm (ε 34000)

Example 26 (Synthesis of Compound-137) 20.3 g of N- (acetimidyl) trichloroacetamidine, 14.4 ml of pentafluorobenzoyl chloride and 200 ml of benzene were mixed with 0.
After mixing at ° C, 13.9 ml of triethylamine was added, and the mixture was heated under reflux for 2 hours. The reaction solution was extracted with ethyl acetate,
After washing with water, the ethyl acetate solution was distilled off under reduced pressure to obtain 23.0 g of colorless liquid 2-methyl-4-pentafluorophenyl-6-trichloromethyl-s-triazine.

2-Methyl-4-pentafluorophenyl-6-trichloromethyl-s-triazine 7.6 g, cumin aldehyde 4.5 g, piperidine acetate 1.5 g and toluene 20 ml are mixed and heated under reflux for 10 hours, and The water released was collected with a Dean-Stark extractor. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure. The residue was purified by column chromatography to obtain 0.9 g of compound-137 which was a pale yellow crystal having a melting point of 132-133 ° C.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.43 (1H, d), 7.7
6 (2H, d), 7.33 (2H, d), 7.26 (1
H, d), 2.97 (1H, dq), 1.30 (6H,
d) UV spectrum (CH ₃ CN) λ _max 345 nm (ε32500)

Example 27 (Synthesis of Compound-136) Melting point 112 was obtained in the same manner as in Example 26 except that 4.5 g of cumin aldehyde of Example 26 was changed to 5.8 g of p-methoxycarbonylmethoxybenzaldehyde. 1.13 g of compound-136 which is a pale yellow crystal of -113 ° C was obtained.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.40 (1H, d), 7.6
9 (2H, d), 7.17 (1H, d), 6.98 (2
H, d), 4.71 (2H, s), 3.84 (3H,
s) UV spectrum (CH ₃ CN) λ _max 359 nm (ε35800)

Example 28 (Synthesis of Compound-139) 20.3 g of N- (acetimidyl) trichloroacetamidine, 12.0 ml of p-fluorobenzoyl chloride and 200 ml of benzene were added at 0 ° C.
After mixing with, 13.9 ml of triethylamine was added, and the mixture was heated under reflux for 2 hours. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was distilled off under reduced pressure to obtain 15.0 g of white solid 2-methyl-4- (p-fluorophenyl) -6-trichloromethyl-s-triazine. .

2-Methyl-4- (p-fluorophenyl) -6-trichloromethyl-s-triazine 7.1
g, cumin aldehyde 4.5 g, piperidine acetate 1.5
g and 20 ml of toluene were mixed, heated under reflux for 10 hours, and the water released was collected in a Dean-Stark extractor. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure. The residue was purified by column chromatography to give compound-1 as white crystals having a melting point of 127 ° C.
0.7 g of 39 was obtained.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.70 (2H, d), 8.4
0 (1H, d), 7.67 (2H, d), 7.31 (2
H, d), 7.30-7.18 (3H, m), 2.97.
(1H, dq), 1.30 (6H, d) UV spectrum (CH ₃ CN) λ _max 340 nm (ε31200)

Example 29 (Synthesis of Compound-140) The melting point of 149 was obtained in the same manner as in Example 28 except that 4.5 g of cuminaldehyde of Example 28 was replaced with 5.8 g of p-methoxycarbonylmethoxybenzaldehyde. 1.3g of compound-140 which is a pale yellow crystal of -150 ° C was obtained.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.70 (1H, d), 8.6
7 (1H, d), 8.38 (1H, d), 7.69 (2
H, d), 7.24 (2H, d), 6.98 (2H,
d), 4.72 (2H, s), 3.85 (3H, s) UV spectrum (CH ₃ CN) λ _max 352 nm (ε32000)

Example 30 (Synthesis of Compound-141) 20.3 g of N- (acetimidyl) trichloroacetamidine, 14.9 ml of p-trifluoromethylbenzoyl chloride and benzene 200
After mixing ml at 0 ° C., triethylamine 13.9
ml was added and the mixture was heated under reflux for 2 hours. The reaction mixture was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure to give 2-methyl-4- (p-trifluoromethylphenyl) -6-trichloromethyl-s-triazine as a white solid in 27.
5 g was obtained.

2-methyl-4- (p-trifluoromethylphenyl) -6-trichloromethyl-s-triazine (7.1 g), cumin aldehyde (4.5 g), piperidine acetate (1.5 g) and toluene (20 ml) were mixed for 10 hours. The water was heated to reflux and the water released was collected in a Dean-Stark extractor. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure. The residue was purified by column chromatography to obtain 2.5 g of compound-141 as white crystals having a melting point of 164 ° C.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.78 (2H, d), 8.4
5 (1H, d), 7.82 (2H, d), 7.67 (2
H, d), 7.33 (2H, d), 7.29 (1H,
d), 2.98 (1H, dq), 1.30 (6H, d) UV spectrum (CH ₃ CN) λ _max 341 nm (ε35600)

Example 31 (Synthesis of Compound-142) The melting point 179 was the same as in Example 30 except that 4.5 g of cuminaldehyde of Example 30 was changed to 4.2 g of p-chlorobenzaldehyde.
0.5 g of compound-142 which is a white crystal at -180 ° C
Obtained.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.77 (2H, d), 8.4
0 (1H, d), 7.83 (2H, d), 7.68 (2
H, d), 7.45 (2H, d), 7.30 (1H,
d), UV spectrum (CH ₃ CN) λ _max 329 nm (ε34700)

Example 32 (Synthesis of Compound-143) 20.3 g of N- (acetimidyl) trichloroacetamidine, 14.7 ml of o-trifluoromethylbenzoyl chloride and benzene 200
After mixing ml at 0 ° C., triethylamine 13.9
ml was added and the mixture was heated under reflux for 2 hours. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was distilled off under reduced pressure to obtain 2-methyl-4- (o-trifluoromethylphenyl) -6-trichloromethyl-s-triazine as a white solid.
4 g was obtained.

2-Methyl-4- (o-trifluoromethylphenyl) -6-trichloromethyl-s-triazine (7.1 g), cumin aldehyde (4.5 g), piperidine acetate (1.5 g) and toluene (20 ml) were mixed for 10 hours. The water was heated to reflux and the water released was collected in a Dean-Stark extractor. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure. The residue was purified by column chromatography to obtain 2.6 g of compound-143 which was a light yellow liquid.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.43 (1H, d), 8.0
6 (1H, d), 7.90 (1H, d), 7.22 (2
H, m), 7.30 (2H, d), 7.17 (1H,
d), 2.97 (1H, dq), 1.30 (6H, d) UV spectrum (CH ₃ CN) λ _max 340 nm (ε 40200)

Example 33 (Synthesis of Compound-144) The melting point of 99 was obtained in the same manner as in Example 32 except that 4.5 g of cuminaldehyde of Example 32 was replaced with 5.8 g of p-methoxycarbonylmethoxybenzaldehyde. 4.0 g of compound-144, which is a pale yellow crystal at -100 ° C, was obtained.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.40 (1H, d), 8.0
5 (1H, d), 7.90 (1H, d), 7.22 (2
H, m), 7.17 (1H, d), 6.98 (2H,
d), 4.70 (2H, s), 3.83 (3H, s) UV spectrum (CH ₃ CN) λ _max 354 nm (ε32300)

Example 34 (Synthesis of Compound-147) 20.3 g of N- (acetimidyl) trichloroacetamidine, 18.6 g of p-nitrobenzoyl chloride and 200 ml of benzene were mixed at 0 ° C., and then 13.9 ml of triethylamine was added. The mixture was heated under reflux for 2 hours. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure to obtain 13.9 g of 2-methyl-4- (p-nitrophenyl) -6-trichloromethyl-s-triazine as a pale yellow liquid. It was

2-Methyl-4- (p-nitrophenyl)
6.7 g of -6-trichloromethyl-s-triazine, 4.5 g of cumin aldehyde, 1.5 g of piperidine acetate and 20 ml of toluene were mixed and heated under reflux for 10 hours, and the released water was recovered by a Dean-Stark extractor. did. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure. The residue was purified by column chromatography to obtain 0.7 g of compound-147 which is a reddish brown crystal having a melting point of 168-169 ° C.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.83 (2H, d), 8.4
7 (1H, d), 8.40 (2H, d), 7.69 (2
H, d), 7.34 (2H, d), 7.30 (1H,
d) 2.98 (1H, dq), 1.30 (6H, d) UV spectrum (CH ₃ CN) λ _max 342 nm (ε31700)

Example 35 (Synthesis of Compound-148) 20.3 g of N- (acetimidyl) trichloroacetamidine, 17.1 g of p-methoxybenzoyl chloride and 200 ml of benzene were mixed at 0 ° C., and 13.9 ml of triethylamine was added. Add 2
Heated to reflux for hours. The reaction solution was evaporated under reduced pressure, washed with water, and recrystallized from methanol to obtain 12.7 g of white solid 2-methyl-4- (p-methoxyphenyl) -6-trichloromethyl-s-triazine.

2-Methyl-4- (p-methoxyphenyl) -6-trichloromethyl-s-triazine 4.8
g, cumin aldehyde 3.3 g, piperidine acetate 1.1
g and 15 ml of toluene were mixed, heated under reflux for 10 hours, and the water released was collected with a Dean-Stark extractor. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure. The residue was purified by column chromatography to obtain 0.8 g of compound-148 as white crystals having a melting point of 136-137 ° C.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.62 (2H, d), 8.3
9 (1H, d), 7.65 (2H, d), 7.30 (2
H, d), 7.23 (1H, d), 7.05 (2H,
d) 3.91 (3H, s), 2.96 (1H, dq) 1.30 (6H, d) UV spectrum (CH ₃ CN) λ _max 334 nm (ε 48200)

Example 36 (Synthesis of Compound-149) The melting point 154 was the same as in Example 35 except that 3.3 g of cumin aldehyde of Example 35 was replaced with 4.4 g of p-methoxycarbonylmethoxybenzaldehyde. 1.31 g of compound-149 which is a white crystal at -155 ° C was obtained.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.62 (2H, d), 8.3
5 (1H, d), 7.67 (2H, d), 7.15 (1
H, d), 7.04 (2H, d), 6.97 (2H,
d) 4.70 (2H, s), 3.91 (3H, s) 3.83 (3H, s) UV spectrum (CH ₃ CN) λ _max 347 nm (ε38100)

Example 37 (Synthesis of Compound-152) 20.3 g of N- (acetimidyl) trichloroacetamidine, 16.6 g of p-cyanobenzoyl chloride and 200 ml of benzene were mixed at 0 ° C., and then 13.9 ml of triethylamine was added. The mixture was heated under reflux for 2 hours. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure to give a white solid 2-methyl-
4- (p-cyanophenyl) -6-trichloromethyl-
17.1 g of s-triazine was obtained.

2-Methyl-4- (p-cyanophenyl)
6.3 g of -6-trichloromethyl-s-triazine, 4.5 g of cumin aldehyde, 1.5 g of piperidine acetate and 20 ml of toluene were mixed and heated under reflux for 10 hours, and the released water was recovered by a Dean-Stark extractor. did. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure. The residue was purified by column chromatography to give Compound-152 as white crystals having a melting point of 170 ° C.
Was obtained.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.80 (2H, d), 8.4
5 (1H, d), 7.87 (2H, d), 7.68 (2
H, d), 7.35 (2H, d), 7.30 (1H,
d), 2.98 (1H, dq), 1.30 (6H, d) UV spectrum (CH ₃ CN) λ _max 341 nm (ε 25500)

Example 38 (Synthesis of Compound-154) The melting point of 186 was obtained in the same manner as in Example 37 except that 4.5 g of cuminaldehyde of Example 37 was replaced with 5.8 g of p-methoxycarbonylmethoxybenzaldehyde. 1.2g of compound-154 which is a pale yellow crystal of -188 degreeC was obtained.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.80 (2H, d), 8.4
2 (1H, d), 7.86 (2H, d), 7.70 (2
H, d), 7.20 (1H, d), 7.00 (2H,
d), 4.73 (2H, s), 3.85 (3H, s) UV spectrum (CH ₃ CN) λ _max 356 nm (ε 29600)

Example 39 (Synthesis of Compound-165) 20.3 g of N- (acetimidyl) trichloroacetamidine, maleic anhydride 19.6
g and 200 ml of toluene were mixed and heated under reflux for 4 hours. The reaction solution was evaporated under reduced pressure and washed with water to obtain 21.4 g of white solid 2-methyl-4-carboxylvinyl-6-trichloromethyl-s-triazine.

2-Methyl-4-carboxyl vinyl-6
-Trichloromethyl-S-triazine (21.4 g), boron trifluoride-diethyl ether complex (9.3 ml) and methanol (100 ml) were mixed and heated under reflux for 11 hours. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure. The residue was purified by column chromatography to obtain 4.5 g of white solid 2-methyl-4-methoxycarbonylvinyl-6-trichloromethyl-s-triazine.

3.0 g of 2-methyl-4-methoxycarbonylvinyl-6-trichloromethyl-S-triazine,
2.3 g of cumin aldehyde, 1.5 g of piperidine acetate and 10 ml of toluene were mixed and heated under reflux for 10 hours,
And the water released was collected in a Dean-Stark extractor. The reaction solution was extracted with ethyl acetate, washed with water, and the ethyl acetate solution was evaporated under reduced pressure. The residue was purified by column chromatography to obtain 1.6 g of compound-165 which was a pale yellow crystal having a melting point of 103-104 ° C.

¹ HNMR (CDCl ₃ ) δ (TMS, ppm) 8.38 (1H, d), 7.6
8 (1H, d), 7.64 (2H, d), 7.51 (1
H, d), 7.31 (2H, d), 7.21 (1H,
d), 3.89 (3H, s), 2.67 (1H, d
q), 1.30 (6H, d) UV spectrum (CH ₃ CN) λ _max 340 nm (ε26200)

Examples 40 to 96 It is shown that the compounds of the present invention are effective in reducing the coloration of the decomposed product by exposure and the coloration due to exposure to light when stored in a bright place.

1. Preparation of Photosensitive Solution of Photopolymerizable Composition and Preparation of Photosensitive Layer A mother liquor having the following formulation A was prepared. <Formulation A> -Benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 73/27, viscosity = 0.12) 144g-Pentaerythritol tetraacrylate 144g-Fluorine-based surfactant (Dainippon Ink Chemical Co., Ltd., Megafac F-176PF 1.4 g-Methyl cellosolve acetate 292 g-Methyl ethyl ketone 252 g-1-Methoxy-2-propyl acetate 126 g

To 90 g of the above mother liquor, 1.55 mmol of the compound shown in Table 1 was added and dissolved to obtain a photosensitive coating liquid. This photosensitive coating solution was applied onto a polyethylene terephthalate film having a thickness of 100 μm by a spin coater so as to have a dry film thickness of 10 μm and dried to form a photosensitive layer.

2. Preparation of Coating Solution for Protective Layer and Preparation of Protective Layer A coating solution having the following formulation B was coated on the above-mentioned photosensitive layer by a spin coater so as to have a dry film thickness of 1.5 μm and dried.

<Formulation B> -Polyvinyl alcohol (PVA205 manufactured by Kuraray Co., Ltd., saponification rate = 80%) 130 parts-Polyvinylpyrrolidone (PVP K-90 manufactured by GAF Corporation) 60 parts-Fluorine-based surfactant (Asahi Glass ( Co., Ltd. Surflon S-131) 10 parts-Distilled water 3350 parts

3. Evaluation of light-sensitive material 3-1. Sensitivity test Step wedge (density difference 0.15, density step number 1 to 15 steps, Fuji Step Guide-
P: 1.5 kW through Fuji Photo Film Co., Ltd.
After exposing for 24 seconds with an ultra-high pressure mercury lamp P-627GM (manufactured by Dainippon Screen Mfg. Co., Ltd.), a 5-fold diluted solution of color art developer CA-1 (trade name: Fuji Photo Film Co., Ltd.) was used. Automatic development (using Color Art Processor CA-600P: manufactured by Fuji Photo Film Co., Ltd.) was performed at 32 ° C. for 38 seconds. Film Thickness Meter (Alpha Step 200: TENCOR INSTRUMENTS
The maximum number of steps without change in film thickness was determined as a solid step according to the film thickness measurement by (manufactured by Co., Ltd.), and this number of steps was taken as the sensitivity.

3-2. Exposure color test 1.5 KW ultra high pressure mercury lamp P-
240 with 627GM (manufactured by Dainippon Screen Mfg. Co., Ltd.)
After exposure for 2 seconds, coloring was measured using a transmission densitometer TD904 (using a Y filter: manufactured by Macbeth Co., Ltd.). The value obtained by subtracting the value of the unexposed sample from the obtained value was defined as image exposure coloration.

3-3. Fluorescent color test 1.5KW ultra high pressure mercury lamp P-
240 with 627GM (manufactured by Dainippon Screen Mfg. Co., Ltd.)
After exposure for 2 seconds, 0.08 W / m ² xenon lamp (WEATHER-OMETER model C16
5: ATLASELECTRIC DEVICES
After exposure for 6 hours with a densitometer TD90
4 (using Y filter: manufactured by Macbeth Co., Ltd.) was used to measure the coloring. The value obtained by subtracting the value of the unexposed sample from the obtained value was defined as the time-dependent flash coloring.

Comparative Examples 1 to 9 The photoradical polymerization initiator used in the preparation of the photosensitive layer in Example 40 was replaced with the compounds of Comparative Examples shown below, and samples were obtained in the same manner. The same evaluation as in Example 40 was performed.

[0199]

[Table 1]

[0200]

[Table 2]

[0201]

[Table 3]

[0202]

[Table 4]

[0203]

[Table 5]

Comparative Method Comparison of the degree of photocoloring was made with compounds of similar sensitivity. Here, the compounds having a sensitivity of 1 to 4 steps are in the group A, the compounds having a sensitivity of 5 steps to 7 are in the group B, and the sensitivity is 8
Compounds from tier to tier 10 are set as group C. Group A, Group B,
And the evaluation results of the compounds of group C are shown in Tables 2 and 3, respectively.
And shown in Table 4.

[0205]

[Table 6]

[0206]

[Table 7]

[0207]

[Table 8]

[0208]

[Table 9]

[0209]

[Table 10]

From Tables 2, 3, and 4, it can be seen that the compounds of the present invention are excellent in exposure coloring and flash coloring when the sensitivity is similar to that of the compound of Comparative Example.

[0211]

INDUSTRIAL APPLICABILITY The photosensitive trihalimethyl-s-triazine compound of the present invention is remarkably little colored by itself and its decomposed product, and when it is used, a photopolymerizable composition which is less colored by light during image exposure and storage in a bright place. Is obtained.

Claims (2)

[Claims] 1. A compound represented by the following general formula (I):
And a photosensitive trihalomethyl-s-triazine compound.
General formula (I)In the formula, X represents a chlorine atom or a bromine atom. Y is Archi
Ru group, CF₃Group, CF₂Substitute with other than Cl group and halogen atom
Alkyl group, Z-CO-OR³, C₆F_FiveBase,
Is C₆H_Four-R^FourRepresents a group represented by. However, R³Is hydrogen
Represents a child or an alkyl group, and Z is -C₂H_Four-, -C₃H₆
-, -CH = CH-, represents an o-phenylene group. Also,
R^FourIs a hydrogen atom, hydroxyl group, alkyl group, substituted alkyl
Group, aryl group, alkoxy group, substituted alkoxy group, ha
Rogen atom, alkoxycarbonyl group, cyano group, reed
Group, nitro group, formyl group, mercapto group, alkyl
It represents a thio group or a dialkylamino group. R¹, R²Is
Hydrogen atom, hydroxyl group, alkyl group, aryl group,
Alkoxy group, substituted alkoxy group, acyloxy group, ha
Rogen atom, alkoxycarbonyl group, cyano group, nit
B group, carboxyl group or general formula (II) or general
It represents a group represented by the formula (III). General formula (II):General formula (III):R in the general formula (II)^Five, R⁶Are hydrogen atoms,
Alkyl group, substituted alkyl group, aryl group or substituted alkyl group
Represents a reel group, and R in the general formula (III) ⁷, R⁸Is
Hydrogen atom, alkyl group, substituted alkyl group, ant
Group, a substituted aryl group or an acyl group. Also,
R^FiveAnd R⁶, R⁷And R⁸Are linked together to form a ring
Good. 2. A photopolymerizable compound comprising a compound having at least one ethylenically unsaturated double bond capable of addition polymerization and at least one compound of the general formula (I) according to claim 1. Composition.