JPH10268514A - Photopolymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photopolymerizable composition high in sensitivity and restrained from occurrence of development sludge. SOLUTION: The photosensitive composition to be used contains a compound having an additionally polymerizable ethylenically unsaturated group, a photopolymerization initiator, and an amino acid salt represented by the formula in which each of R<1> and R<2> is an H atom or an alkyl or alkenyl or alkynyl group; each of R<3> and R<4> is an H or halogen atom or an alkyl, alkenyl, alkynyl, or aryl groups; each of optional pairs of R<1> -R<4> may form a ring; and (n) is an integer of 1-4; M<n+> is an n-valent counter ion, thus permitting the obtained composition to be high in sensitivity and to be good in the solubility of unexposed parts in a developing solution and to be restrained from occurrence of development sludge in the developing solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a photopolymerizable composition. More specifically, the present invention relates to a photopolymerizable composition containing at least a polymerizable compound having an ethylenically unsaturated bond capable of addition polymerization, a photopolymerization initiator, and a salt of an amino acid.

[0002]

2. Description of the Related Art A photosensitive composition comprising a compound having an ethylenically unsaturated bond capable of addition polymerization, a photopolymerization initiator, and, if necessary, a binder having a suitable film-forming ability and a thermal polymerization inhibitor. A method of duplicating an image by a photographic method using a technique known in the art is known, for example, from US Pat. Nos. 2,927,022 and 2,902,356.
No. 3,870,524 and the like. As described in these U.S. patents, this type of photosensitive composition undergoes photopolymerization upon irradiation with light, and cures and insolubilizes. The cured image of the desired photopolymerizable composition can be formed by irradiating light through the negative image and removing only the unexposed material with an appropriate solvent (hereinafter, simply referred to as development). This type of photosensitive composition is extremely useful as one used for producing a printing plate or the like.

[0003] In addition, it has been conventionally proposed that a compound having an ethylenically unsaturated bond capable of addition polymerization alone does not have sufficient photosensitivity, and that a photopolymerization initiator is added to enhance photosensitivity. Benzyl, benzoin, benzoin ethyl ether, Michler's ketone, anthraquinone, acridine, phenazine, benzophenone, 2-ethylanthraquinone and the like have been used as suitable photopolymerization initiators. However, when these photopolymerization initiators are used, it takes a long time for image exposure in image formation because the photopolymerizable composition has low sensitivity to curing. Therefore, in the case of a fine image, if there is a slight vibration in the operation, an image with good image quality cannot be reproduced, and further, since the amount of energy radiation of the light source for exposure must be increased, a large amount of heat generated thereby is generated. Radiation had to be considered. In addition, there has been a problem that the film of the composition is easily deformed and deteriorated by heat.

In recent years, the sensitivity to ultraviolet rays has been increased,
A method of forming an image using a laser has been studied, and UV projection exposure method, laser plate making, laser facsimile, holography, etc. in printing plate preparation are already in the practical stage, and a high-sensitivity photosensitive material corresponding to these is desired. It is rarely under development. However, it cannot be said that a photosensitive material having sufficient sensitivity has been found yet.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photopolymerizable composition having a high sensitivity, that is, a compound having an ethylenically unsaturated bond which can be widely and generally polymerized with a photopolymerization initiator. An object of the present invention is to provide a photopolymerizable composition containing a compound that increases the photopolymerization rate of the photopolymerizable composition containing the compound, and to suppress generation of development residue in a photosensitive material using the composition.

[0006]

The present inventors have made intensive studies to achieve the above object, and as a result, have found that a salt of an amino acid represented by the formula (I) has an addition-polymerizable ethylenically unsaturated bond. The present inventors have found that the photopolymerization rate of a copolymerizable composition containing a compound and a copolymerization initiator is significantly increased, and have reached the present invention. Further, as a further improvement effect by using the salt of the amino acid represented by the formula (I), suppression of development scum from a development waste liquid after development of the photosensitive material using the photopolymerizable composition is described. It was observed.

That is, the present invention provides the following (1). (1) A light comprising at least i) a compound having an ethylenically unsaturated bond capable of addition polymerization, ii) a photopolymerization initiator, and iii) a salt of an amino acid represented by the following formula (I). Polymerizable composition.

[0008]

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[In the formula (I), R ¹ and R ² each represent a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group. R ³ and R ⁴ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group. R ¹ , R ² , R ³ and R ⁴ may be combined in any combination to form a ring. n is an integer of 1 to 4, and M ^{n +} represents an n-valent counter cation. ]

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The photopolymerizable composition of the present invention comprises i) a compound having an ethylenically unsaturated bond capable of addition polymerization, ii) a photopolymerization initiator, and iii) a salt of an amino acid represented by the formula (I). It contains.

By including the salt of the amino acid represented by the formula (I) as described above, high sensitivity can be obtained. This, for example, considering the case of using the titanocene compound is preferably used as a photopolymerization initiator, wherein the isolated on N of a salt of an amino acid of formula (I) electron pair and -CO ₂ ^- the O ^- and It is considered that the coordination and chelation to Ti in the titanocene compound by the method described above advantageously proceeds because the electron density of the lone pair of electrons on N is increased by regulating the bonding atom or group to N. Such a phenomenon is considered to be the same in other metallocene compounds. Also,
It is presumed that the interaction with the photopolymerization initiator becomes appropriate by adopting the structure represented by the formula (I) in other types of photopolymerization initiators.

Further, in a photosensitive material using the photopolymerizable composition of the present invention, the solubility of the unexposed portion in the developing solution is good, and the generation of developing scum in the developing solution is suppressed.

On the other hand, if the salt of the amino acid represented by the formula (I) is not contained, the sensitivity is lowered, and if a similar amino acid which is not a salt is used, the sensitivity is lowered and the generation of development residue on the photosensitive material is increased. I do.

Hereinafter, each component of the photopolymerizable composition of the present invention will be described in detail.

The polymerizable compound having an addition-polymerizable unsaturated bond of the component i) used in the present invention is selected from compounds having at least one, and preferably two or more, terminal ethylenically unsaturated bonds.

Examples of the monomer include an ester of an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with an aliphatic polyhydric alcohol compound, and an unsaturated carboxylic acid and an fatty acid. And amides with group-III polyamine compounds.

Specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylates such as ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3.
-Butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate , 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate , So Bi penta acrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

Examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3- Methacryloxy-2-hi Rokishipuropokishi) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate,
There are 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate and the like.

As the crotonic acid ester, ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate,
Sorbitol tetradicrotonate and the like.

Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Further, a mixture of the above-mentioned ester monomers can also be mentioned.

Specific examples of the amide monomer of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6- Hexamethylene bis-methacrylamide,
Examples include diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like.

As another example, see JP-B-48-417.
JP-A-08-208, in which a hydroxyl group-containing vinyl monomer represented by the following general formula (A) is added to a polyisocyanate compound having two or more isocyanate groups in one molecule, two or more in one molecule: And a vinyl urethane compound containing a polymerizable vinyl group.

CH ₂ CC (R) COOCH ₂ CH (R ′) OH (A) (where R and R ′ represent H or CH ₃ )

Further, urethane acrylates described in JP-A-51-37193,
64183, JP-B-49-43191, JP-B-52
And polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in JP-A-30490. In addition, Journal of the Adhesion Society of Japan vol. 20, No. 7, 300-30
Those introduced as photocurable monomers and oligomers on page 8 (1984) can also be used. In the present invention, these monomers may be used in a chemical form such as a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof.

The amount of these used is 5 to 70% by weight (hereinafter abbreviated as%), preferably 10 to 55%, based on all components of the photopolymerizable composition. If the amount used is large, it is easy to cause poor coating formation (stickiness), and if the amount used is small, curing failure tends to occur, which is not preferable.

The photopolymerization initiator of the component ii) will be described later in detail, and then the salt of the amino acid represented by the formula (I) of the component iii) will be described in detail.

Describing the formula (I), the formula (I)
Wherein R ¹ and R ² each represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group or a substituted alkynyl group.

R ³ and R ⁴ represent a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aryl group or a substituted aryl group.

R ^{1 to} R ⁴ may be combined in any combination to form a ring.

N is an integer of 1 to 4, and M ^{n +} represents an n-valent counter cation of the amino acid anion. ^{Mn +} is more preferably an inorganic cation or an ammonium ion. Periodic Tables 1 (1A), 2 (2
A) Elements belonging to groups 11 to 13 (1B to 3B) and 8 to 9 (8) are preferably metal cations of 1 to 4 valences. The following are preferred as ammonium ions.

[0034]

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Here, R ⁵ , R ⁶ , R ⁷ and R ⁸ each represent an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, a substituted alkenyl group, an alkynyl group or a substituted alkynyl group. R ^{5 to} R ⁸ may form a nitrogen-containing heterocyclic ring in any combination.

In the above, examples of the alkyl group represented by R ^{1 to} R ⁸ include a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group,
Tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group,
Examples thereof include a 1-methylbutyl group, an isohexyl group, a 2-ethylhexyl group, a 2-methylhexyl group, a cyclohexyl group, a cyclopentyl group, and a 2-norbornyl group. Among them, a linear alkyl group having 1 to 12 carbon atoms and a branched alkyl group having 3 to 12 carbon atoms are preferable. Particularly, a linear alkyl group having 1 to 12 carbon atoms and a branched alkyl group having 3 to 12 carbon atoms are preferable.

As the substituent bonded to the alkylene group of the substituted alkyl group represented by R ^{1 to} R ⁸ , a monovalent nonmetallic atomic group other than hydrogen is used, and a preferable example is a halogen atom (—F , -Br, -Cl, -I), a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, an alkylthio group, an arylthio group, an alkyldithio group, an aryldithio group, an amino group, an N-alkylamino group,
N, N-dialkylamino group, N-arylamino group,
N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group , N '
An alkylureido group, an N ′, N′-dialkylureido group, an N′-arylureido group, an N ′, N′-diarylureido group, an N′-alkyl-N′-arylureido group, an N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N ′
-Alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N
-Alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'-diaryl-N-arylureido group, N'-alkyl-N '-Aryl-N-alkylureido groups, N'-alkyl-N'-aryl-N-
Arylureido group, alkoxycarbonylamino group,
Aryloxycarbonylamino group, N-alkyl-N-
Alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group,
Carboxyl group and its conjugate base (hereinafter referred to as carboxylate; also including metal salt), alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-
Alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl Group, sulfo group (—SO ₃ H) and its conjugate base group (also referred to as sulfonato group, including metal salt), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N -Dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-
Alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N -Alkyl-N-arylsulfamoyl group, N-acylsulfamoyl group and its conjugate base group, N-alkylsulfonylsulfamoyl group (—SO ₂ NHSO ₂ (alkyl): a
lkyl = alkyl group, hereinafter the same) and its conjugate base group, N
- allyl acylsulfamoyl group (-SO ₂ NHS
O ₂ (allyl): allyl = allyl group (hereinafter the same) and its conjugate base group, N-alkylsulfonylcarbamoyl group (-
CONHSO ₂ (alkyl) and its conjugate base group, N-allylsulfonylcarbamoyl group (—CONHSO ₂ (ally
l)) and its conjugate base group, alkoxysilyl group (—S
i (Oalkyl) ₃ ), allyloxysilyl group (-Si (Oally)
l) ₃ ), a hydroxysilyl group (—Si (OH) ₃ ) and its conjugate base group, a phosphono group (—PO ₃ H ₂ ) and its conjugate base group (also referred to as a phosphonate group, including a metal salt),
Dialkylphosphono group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group _{(-PO 3 (aryl) 2:} aryl = aryl group, hereinafter the same), an alkyl aryl phosphono group (-PO
₃ (alkyl) (aryl)), monoalkylphosphono group (-
PO ₃ (alkyl)) and its conjugated base group (referred to as alkylphosphonate group, including metal salt), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugated base group (arylphosphonate group) A metal salt), a phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (also called a phosphonatoxy group; also including a metal salt), a dialkylphosphonooxy group (—OPO ₃ H (alkyl) ₂ ),
Diarylphosphonooxy group (-OPO ₃ (aryl)
₂ ), an alkylarylphosphonooxy group (—OPO ₃
(Alkyl) (aryl)), monoalkyl phosphono group (-OPO ₃ H (alkyl) and its conjugated base group (. Referred to as alkylphosphonato group metal salts including also), monoarylphosphono group (- OPO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonatooxy group; also including metal salt), cyano group, nitro group, aryl group, alkenyl group, alkynyl group and the like.

Specific examples of the alkyl group as the substituent in these substituted alkyl groups include the aforementioned alkyl groups, and specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, and xylyl. Group, mesityl group, cumenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group,
Hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, Carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, nitrophenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group, phosphonate A phenyl group and the like can be mentioned.

Examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 1-butenyl group, a cinnamyl group and a 2-chloro-1-ethenyl group. Examples of the alkynyl group include an ethynyl group. Group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group, phenylethynyl group and the like.

The above acyl group (R ⁹ CO—) includes
R ⁹ is a hydrogen atom or the above alkyl group, aryl group,
Alkenyl groups and alkynyl groups can be mentioned.

On the other hand, examples of the alkylene group in the substituted alkyl group include those obtained by removing any one of the above hydrogen atoms on the alkyl group having 1 to 20 carbon atoms and forming a divalent organic residue. And preferably a linear alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms, and a cyclic alkylene group having 5 to 10 carbon atoms. Specific examples of the substituted alkyl group represented by R ^{1 to} R ⁸ obtained by combining such a substituent with an alkylene group include chloromethyl, bromomethyl, 2-chloroethyl, trifluoromethyl, and hydroxy. Methyl group, 2-hydroxyethyl group, methoxymethyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyl An oxymethyl group,
Benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxy Carbonylethyl group, methoxycarbonylmethyl group, methoxycarbonylbutyl group, ethoxycarbonylmethyl group,
Butoxycarbonylmethyl group, allyloxycarbonylmethyl group, benzyloxycarbonylmethyl group, methoxycarbonylphenylmethyl group, trichloromethylcarbonylmethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl Group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfopropyl group,
Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N
-Dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, the following groups,

[0042]

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A phosphonobutyl group, a phosphonatohexyl group, a diethylphosphonobutyl group, a diphenylphosphonopropyl group, a methylphosphonobutyl group, a methylphosphonatobutyl group, a tolylphosphonohexyl group, a tolylphosphonatohexyl group, a phosphonooxy group Propyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p
-Methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc. Can be mentioned.

The aryl group represented by R ^{3 to} R ⁸ is 1
Examples thereof include a group derived from a condensed ring of 1 to 3 benzene rings or a group derived from a condensed ring of a benzene ring and a 5-membered unsaturated ring. As a specific example,
Examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Of these, a phenyl group and a naphthyl group are more preferred.

The substituted aryl group represented by R ^{3 to} R ^{8 is one} in which a substituent is bonded to an aryl group, and a monovalent group excluding hydrogen is substituted as a substituent on a ring-forming carbon atom of the aforementioned aryl group. Having a non-metallic atomic group is used. Preferred examples of the substituent include the aforementioned alkyl group, substituted alkyl group, and those described above as the substituent for the substituted alkyl group. like this,
Preferred specific examples of the substituted aryl group include a biphenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group,
Chlorophenyl, bromophenyl, fluorophenyl, trifluorophenyl, chloromethylphenyl, trifluoromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, methoxyethoxyphenyl, allyloxyphenyl, phenoxy Phenyl, methylthiophenyl, tolylthiophenyl, phenylthiophenyl, ethylaminophenyl, diethylaminophenyl, morpholinophenyl, acetyloxyphenyl, benzoyloxyphenyl, N-cyclohexylcarbamoyloxyphenyl, N- Phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl , Allyloxycarbonyl phenyl group, chlorophenoxy carbonyl phenyl group, carbamoyl phenyl group, N- methylcarbamoyl-phenyl group,
N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N -Ethylsulfamoylphenyl group,
N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphono Phenyl group, diphenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group,
Allylphenyl group, 1-propenylmethylphenyl group,
Examples thereof include a 2-butenylphenyl group, a 2-methylallylphenyl group, a 2-methylpropenylphenyl group, a 2-propynylphenyl group, a 2-butylphenyl group, and a 3-butynylphenyl group.

The alkenyl groups represented by R ^{3 to} R ⁸ include those described above. A substituted alkenyl group is a compound in which a substituent is replaced by a hydrogen atom of an alkenyl group and bonded to the alkenyl group. As the substituent, the substituent in the above-mentioned substituted alkyl group is used, while the alkenyl group is the above-mentioned alkenyl group. Can be.

Examples of preferred substituted alkenyl groups include:
The following can be mentioned.

[0048]

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The alkynyl groups represented by R ^{1 to} R ⁸ include those described above. In a substituted alkynyl group, the substituent is replaced with a hydrogen atom of the alkynyl group,
The substituent is the same as the above-mentioned substituent in the substituted alkyl group, while the alkynyl group can be the above-mentioned alkynyl group.

The ring bonded to R ^{1 to} R ⁴ in an optional combination includes a 5- to 8-membered aliphatic ring. More preferably, a 5-membered ring and a 6-membered aliphatic ring can be mentioned. These may further have a substituent on the carbon atom constituting them (examples of the substituent include:
Substituents on the above-mentioned substituted alkyl groups may be mentioned), and a part of the ring-constituting carbons may be further substituted with a hetero atom (an oxygen atom, a sulfur atom, a nitrogen atom or the like). Further, this aliphatic ring may be condensed with an aromatic ring.

A ring formed by R ¹ and R ² is particularly preferable, and such a ring includes a morpholine ring.

As R ¹ and R ² , a hydrogen atom and an alkyl group (methyl, ethyl, isopropyl, n-butyl, etc.) are preferable, and a case where R ¹ and R ² form a morpholine ring is also preferable.

As R ³ and R ⁴ , a hydrogen atom, an alkyl group (methyl, benzyl, etc.) and an aryl group (phenyl, p-
Chlorophenyl, p-methoxyphenyl, etc.) are preferred.

The mono- to tetravalent metal cations represented by M ^{n +} include Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , Fr ⁺ , B
e ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Ra ²⁺ , Cu
⁺ , Cu ²⁺ , Ag ⁺ , Zn ²⁺ , Al ³⁺ , Fe ²⁺ , Fe ³⁺ ,
Co ²⁺ , Ni ²⁺ , Ti ⁴⁺ , and Zr ⁴⁺ .
More preferably, Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , F
r ⁺ , Cu ⁺ , and Ag ⁺ .

Further, as the ammonium ion, R ⁵ to
Specific examples of the alkyl group represented by R ⁸ include R ^{1 to} R
⁴ , the same ones as in M. Specific examples of the ammonium ion include the following.

[0056]

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As M ^{n +} , a monovalent metal cation such as Li ⁺ , Na ⁺ , K ⁺ is particularly preferable.

Preferred specific examples of the salt of the amino acid represented by the formula (I) are shown below, but the present invention is not limited thereto.

[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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The synthesis of the salt of the amino acid represented by the formula (I) can be carried out as follows.

In general, organic and inorganic salts of amino acids can be easily synthesized, for example, by neutralizing an amino acid with an organic alkali or inorganic alkali as shown in the scheme of Method 1.

[0066]

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The term “organic alkali” or “inorganic alkali” as used herein means M ⁺ OH ⁻ , which is a combination of the above-mentioned organic cation and hydroxide ion, or a combination of the inorganic cation and hydroxide ion, respectively. It is.

Alternatively, as shown in the scheme of Method 2, the compound can be easily synthesized by an ion exchange reaction between a silver salt of an amino acid and an organic chloride.

[0069]

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[0070] M ⁺ Cl The organic compound here ^- is that the one in which the chloride ions and the above-mentioned organic cations bound.

In the above scheme, R ^{1 to} R ⁴ and M have the same meaning as in formula (I).

As the starting amino acid, for example, a commercially available amino acid may be used, or published by Maruzen, edited by The Chemical Society of Japan, “New Experimental Chemistry Course” (Synthesis and Reaction of Organic Compounds [III] 1672) Pp. 1692 (1978)
It can be synthesized by a method for synthesizing amino acids or a method analogous thereto.

The obtained compound can be identified by a ¹ H nuclear magnetic resonance spectrum ( ¹ H NMR), a mass spectrum and the like.

The following shows a synthesis example. [Synthesis Example 1] Synthesis of Compound I-2 Commercially available N, N-dimethylglycine (5.20 g) and methanol (100 ml) were placed in a flask, and 1.0 M Na was added.
An OH aqueous solution (50.0 ml) was added dropwise. After 30 minutes, the solvent was removed under reduced pressure, and the concentrate was put in acetone (200 ml).
After stirring for 1 hour, white crystals were obtained. After filtering off the white crystals,
Vacuum drying yielded 4.96 g of the desired product. Structure is ¹
Confirmed by HNMR and mass spectrum. 80% yield
And the melting point was 270 to 273 ° C.

Synthesis Example 2 Synthesis of Compound I-5 Diisopropylamino (10.1 g), sodium chloroacetate (11.6 g), and methanol (150 ml) were placed in a flask, stirred at 50 ° C. for 3 hours, and then cooled to room temperature. After cooling, a 1.0 M aqueous NaOH solution (100 ml) was added dropwise,
The mixture was further stirred for 30 minutes. After the solvent was removed under reduced pressure, the concentrate was put in acetone (200 ml) and stirred for 1 hour to form white crystals. The white crystals were collected by filtration and vacuum dried to obtain 12.6 g of the desired product. The structure was confirmed by ¹ HNMR and mass spectrum. Yield 70%, melting point 255-
258 ° C.

The compounds I-2 and I- in the present invention
Compounds represented by formula (I) other than 5 can be easily synthesized by the same method.

The compounds represented by formula (I) used in the photopolymerizable composition of the present invention may be used alone or in combination of two or more.

The compound of the formula (I) is used in an amount of usually 0.05 to 50% by weight, preferably 0.5 to 35% by weight, more preferably 1 to 25% by weight, based on all components of the photopolymerizable composition.
Amounts by weight are used. If the amount is too large, poor coating formation (crack) tends to occur, and if too small, poor curing tends to occur, which is not preferable.

The photopolymerizable composition of the present invention contains the photopolymerization initiator of ii), and any known photopolymerization initiator can be used.

Examples of preferred photopolymerization initiators include (a)
Aromatic ketones, (b) aromatic onium salt compounds,
(C) organic peroxide, (d) thio compound, (e) hexaarylbiimidazole compound, (f) ketoxime ester compound, (g) borate compound, (h) azinium compound, (i) active ester compound, (J) a compound having a carbon-halogen bond, and (k) a metallocene compound.

Preferable examples of (a) aromatic ketones as an example of the component ii) include “RADIATION CURING IN POLY”.
MER SCIENCE AND TECHNOLOGY '' JPFOUASSIER JFRABE
Compounds having a benzophenone skeleton or a thioxanthone skeleton described in K (1993), pp. 77-117, for example, the following.

[0082]

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[0083]

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[0084]

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More preferred examples of the (a) aromatic ketones include α-thiobenzophenone compounds described in JP-B-47-6416 and benzoin ether compounds described in JP-B-47-3981. .

[0086]

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There are α-substituted benzoin compounds described in JP-B-47-22326, for example, the following compounds.

[0088]

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There are benzoin derivatives described in JP-B-47-23664, aroylphosphonic esters described in JP-A-57-30704, and dialkoxybenzophenones described in JP-B-60-26483, such as the following.

[0090]

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JP-B-60-26403, JP-A-62-206
The benzoin ethers described in JP 81345, for example, include the following.

[0092]

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JP-B-1-34242, US Pat. No. 43
Α-Aminobenzophenones described in EP 18791 and EP 0234561 A1, such as the following.

[0094]

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There are p-di (dimethylaminobenzoyl) benzene described in JP-A-2-21152, for example, the following.

[0096]

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The thio-substituted aromatic ketones described in JP-A-61-194062, for example, include the following.

[0098]

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Acylphosphine sulfides described in JP-B-2-9597, for example, include the following.

[0100]

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Acylphosphines described in JP-B-2-9596, for example, include the following.

[0102]

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Further, there may be mentioned thioxanthones described in JP-B-63-61950 and coumarins described in JP-B-59-42864.

The aromatic onium salt (b) which is another example of the component ii) includes 15 (5B) and 16 (5B) of the periodic table.
(6B), elements of group 17 (7B), specifically N, P,
Aromatic onium salts of As, Sb, Bi, O, S, Se, Te or I are included. Such aromatic onium salts are disclosed in JP-B-52-14277 and JP-B-52-1427.
No. 8, JP-B No. 52-14279, and specifically, the following compounds.

[0105]

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[0106]

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[0107]

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[0108]

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The (c) “organic peroxide” which is another example of ii) used in the present invention includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule. Examples thereof include methyl ethyl ketone peroxide, cyclohexanone peroxide,
3,5-trimethylcyclohexanone peroxide,
Methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane,
1-bis (t-butylperoxy) cyclohexane,
2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramethane hydroperoxide, 2,5-dimethylhexane-2,5-di Hydroperoxide,
1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, bis (t-butylperoxyisopropyl) benzene, 2,
5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, acetyl peroxide, isobutyryl peroxide, octa Noyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic peroxide, benzoyl peroxide,

2,4-dichlorobenzoyl peroxide, meta-toluoyl peroxide, diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-2-ethoxyethylperoxydicarbonate, dimethoxyisopropylperoxy Carbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, t-butylperoxyacetate, t-butylperoxypivalate, t-butylperoxyneodecanoate, t-butylperoxyoctano Ethate, t-butylperoxy-3,5,5
Trimethylhexanoate, t-butyl peroxy laurate, t-butyl peroxybenzoate, di-t
-Butylperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-
Butyl peroxide maleic acid, t-butyl peroxyisopropyl carbonate, 3,3 ', 4,4'-tetra-
(T-butylperoxycarbonyl) benzophenone,
3,3 ', 4,4'-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3 ', 4 4'-tetra (t-octylperoxycarbonyl) benzophenone, 3,3 ', 4
4'-tetra (cumylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate), carbonyldi (T-hexylperoxy dihydrogen diphthalate) and the like.

Among these, 3,3 ', 4,4'-tetra- (t-butylperoxycarbonyl) benzophenone and 3,3', 4,4'-tetra- (t-amylperoxycarbonyl) Benzophenone, 3,3 ', 4,4'
-Tetra (t-hexylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (t-octylperoxycarbonyl) benzophenone, 3,3',
4,4'-tetra (cumylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (p-isopropylcumylperoxycarbonyl) benzophenone,
Peroxide esters such as di-t-butyldiperoxyisophthalate are preferred.

The thio compound (d) as the component ii) used in the present invention is represented by the following formula [d].

[0113]

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R ¹⁰ represents an alkyl group, an aryl group or a substituted aryl group, and R ¹¹ represents a hydrogen atom or an alkyl group. R ¹⁰ and R ¹¹ represent a group of non-metallic atoms necessary to form a 5- or 7-membered ring which may combine with each other to contain a heteroatom selected from oxygen, sulfur and nitrogen atoms.

The alkyl group of R ¹⁰ in the formula [d] is preferably an alkyl group having 1 to 4 carbon atoms. The aryl group represented by R ¹⁰ is preferably a group having a carbon atom index of 6 to 10 such as a phenyl group or a naphthyl group. As the substituted aryl group, a halogen atom such as a chlorine atom, Examples include those substituted with an alkyl group such as a group and an alkoxy group such as a methoxy group and an ethoxy group.

R ¹¹ is preferably an alkyl group having 1 to 4 carbon atoms.

Specific examples of the thio compound represented by the formula [d] include the following compounds. R ¹⁰ , R
Shown in a combination such as ¹¹ .

[0118]

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Examples of (e) hexaarylbiimidazole, which is another example of the component ii) used in the present invention, include rosin dimers described in JP-B-45-37377 and JP-B-44-86516, such as 2,2. 2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetraphenyl Biimidazole, 2,2'-bis (o, p-dichlorophenyl)-
4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (o-chlorophenyl) -4,4 ',
5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl)
-4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole, 2,
2'-bis (o-methylphenyl) -4,4 ', 5
5'-tetraphenylbiimidazole, 2,2'-bis (o-trifluoromethylphenyl) -4,4 ', 5
5'-tetraphenylbiimidazole and the like.

The (f) ketoxime esters which are other examples of the component ii) used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, -Propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1
—One, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p-toluenesulfonyloxyimiminobtan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like. No.

Examples of the borate salt (g) which is another example of the component ii) in the present invention include a compound represented by the following formula [g].

[0122]

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In the formula [g], R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ may be the same or different and each is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted group. A substituted or unsubstituted alkynyl group or a substituted or unsubstituted heterocyclic group, wherein R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ represent two or more groups bonded to each other to form a ring structure; May be formed. However, at least one of R ¹² , R ¹³ , R ¹⁴ and R ¹⁵
One is a substituted or unsubstituted alkyl group. Z ⁺ represents an alkali metal cation or a quaternary ammonium cation.

The alkyl groups represented by R ^{12 to} R ¹⁵ include linear, branched and cyclic alkyl groups, and preferably have 1 to 18 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, stearyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. Examples of the substituted alkyl group include a halogen atom (for example, -Cl, -Br or the like), a cyano group, a nitro group, an aryl group (preferably a phenyl group), a hydroxy group, a -N
(R ¹⁶ ) (R ¹⁷ ) (where R ¹⁶ and R ^{17 each} independently represent a hydrogen atom, an alkyl group having 1 to 14 carbon atoms or an aryl group), —COOR ¹⁸ (where R ¹⁸ is hydrogen Represents an atom, an alkyl group having 1 to 14 carbon atoms, or an aryl group.), -COOR ¹⁹ or -OR ²⁰ (where R ¹⁹ , R
²⁰ represents an alkyl group having 1 to 14 carbon atoms or an aryl group. ) As a substituent.

The aryl group of R ^{12 to} R ¹⁵ includes a 1 to 3 ring aryl group such as a phenyl group and a naphthyl group, and the substituted aryl group includes Or a substituent having 1 to 14 carbon atoms
And those having an alkyl group of

As the alkenyl group for R ^{12 to} R ¹⁵ ,
It includes straight-chain, branched and cyclic ones having 2 to 18 carbon atoms, and examples of the substituent of the substituted alkenyl group include those described above as the substituent of the substituted alkyl group.

As the alkynyl group for R ^{12 to} R ¹⁵ ,
It includes straight or branched ones having 2 to 28 carbon atoms, and examples of the substituent of the substituted alkynyl group include those described above as the substituent of the substituted alkyl group.

The heterocyclic group represented by R ^{12 to} R ¹⁵ is a 5- or more-membered, preferably 5- to 7-membered heterocyclic group containing at least one of N, S and O. The ring group may include a condensed ring. Further, as the substituent, those described above as the substituent of the substituted aryl group may be included.

Specific examples of the compound represented by the formula [g] include US Pat. Nos. 3,567,453 and 4,434,891.
Nos., European Patent Nos. 109772 and 109773
And the compounds described below.

[0130]

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Examples of (h) azinium salt compounds which are other examples of the component ii) of the present invention are described in JP-A-63-1383.
No. 45, JP-A-63-142345, JP-A-63-1
No. 42346, JP-A-63-143537 and JP-B-46-42363.

Examples of (i) active ester compounds which are other examples of component ii) include imide sulfonate compounds described in JP-B-62-6223, JP-B-63-14340,
Active sulfonates described in JP-A-59-174831 can be exemplified.

Preferred examples of the compound having a carbon-halogen bond (j) which is an example of the component ii) include the following formula [j-
1] to [j-4], a carbonylmethylene heterocyclic compound having a trihalogenomethyl group represented by the following formula [j-5], and 4 represented by the following formula [j-6] -Halogeno-5-
(Halogenomethyl-phenyl) -oxazole derivatives,
Examples thereof include 2-halogenomethyl-phenyl) -4-halogeno-oxazole derivatives represented by the following formula [j-7].

[0134]

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In the formula [j-1], X ² represents a halogen atom. Y
^{2 _{-CX 3 2, -NH 2, -NHR}} 2 2, -N (R 22) 2,
It represents a -OR ^22. Here, R ²² represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. The R ²¹ is -CX ₃ ^2, alkyl group, substituted alkyl group, an aryl group,
Represents a substituted aryl group or a substituted alkenyl group.

[0136]

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In the formula [j-2], R ²³ represents an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a halogen atom, an alkoxy group, a substituted alkoxy group, a nitro group or a cyano group. X ³
Is a halogen atom, and k is an integer of 1 to 3.

[0138]

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In the formula [j-3], R ²⁴ is an aryl group or a substituted aryl group, and R ²⁵ is

[0140]

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Or a halogen atom, and Z ² represents —C
(= O) -, - C (= S) - or -SO ₂ -,
R ^26, R ²⁷ is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group, R ²⁸ is the same as R ²² in the formula [j-1], X ³ is M is 1 or 2;

[0142]

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In the formula [j-4], R ²⁹ is an optionally substituted aryl group or a heterocyclic group, and R ³⁰ is a carbon atom.
A trihaloalkyl or trihaloalkenyl group having from 3 to 3, and p is 1, 2 or 3.

[0144]

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In the formula [j-5], L is a hydrogen atom or a formula: CO
_{^{- (R 31) q (CX}} 3 4) are substituents of _r, Q is sulfur,
Selenium or oxygen atom, dialkylmethylene group, alkene-1,2-ylene group, 1,2-phenylene group or N
-R ³¹ group, M ¹ is a substituted or unsubstituted alkylene group or alkenylene group, or 1,2-arylene group, R ³² is an alkyl group, an aralkyl group or an alkoxyalkyl group, ³¹ is a carbocyclic or heterocyclic divalent aromatic group, X ⁴ is a chlorine, bromine or iodine atom, and q = 0 and r = 1, or q = 1 and r = 1 or 2.

[0146]

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In the formula [j-6], X ⁵ is a halogen atom, and t 5
Is an integer of 1 to 3, s is an integer of 1 to 4, R ³³
Is a hydrogen atom or a CH _3-t X ⁵ _t group, R ³⁴ is s-valent optionally substituted unsaturated organic group.

[0148]

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In the formula [j-7], X ⁵ is a halogen atom,
Is an integer of 1 to 3, u is an integer of 1 to 4, R ³⁵
Is CH _3-v X ⁶ _v group, R ³⁶ is an unsaturated organic group which may be substituted for u-valent.

Compounds having such a carbon-halogen bond include, for example, Wakabayashi et al., Bull. Chem. Soc.
apan, 42 , 2924 (1969), for example, 2-phenyl-4,6-bis (trichloromethyl)
-S-triazine (A-1 used in Examples described later), 2-
(P-chlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-tolyl) -4,6
-Bis (trichloromethyl) -S-triazine, 2-
(P-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -S
-Triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6-bis (trichloromethyl) -S-triazine, 2-n-nonyl-
4,6-bis (trichloromethyl) -S-triazine,
2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -S-triazine and the like. Other compounds described in British Patent No. 1388492, for example, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) ) -S-Triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4-amino-6-trichloromethyl-S-triazine Compounds described in JP-A-53-133428, for example, 2- (4-methoxy-naphth-1-)
Yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphth-1-yl) -4,
6-bis-trichloromethyl-S-triazine, 2-
[4- (2-ethoxyethyl) -naphth-1-yl]-
4,6-bis-trichloromethyl-S-triazine, 2
-(4,7-dimethoxy-naphth-1-yl) -4,6
Compounds such as -bis-trichloromethyl-S-triazine, 2- (acenaphth-5-yl) -4,6-bis-trichloromethyl-S-triazine, which are described in German Patent No. 3337024, such as the following compounds: Can be mentioned.

[0151]

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[0152]

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Also, J. Org. C by FC Schaefer et al.
hem., 29, 1527 (1964), for example, 2-methyl-4,6-bis (tribromomethyl) -S
-Triazine, 2,4,6-tris (tribromomethyl) -S-triazine, 2,4,6-tris (dibromomethyl) -S-triazine, 2-amino-4-methyl-
6-Tribromomethyl-S-triazine, 2-methoxy-4-methyl-6-trichloromethyl-S-triazine and the like can be mentioned.

Further, there may be mentioned the compounds described in JP-A-62-58241, for example, the following compounds.

[0155]

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[0156]

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Further, there may be mentioned the compounds described in JP-A-5-281728, for example, the following compounds.

[0158]

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Alternatively, MP Hutt, EF Elsla
ger and LM Werbel Journal of Heterocyclic
Chemistry, Volume 7 (No. 3), pp. 511 et seq. (19
(1970) which can be easily synthesized by those skilled in the art according to the synthesis method described in (1970).

[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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Alternatively, compounds such as those described in German Patent No. 2641100, for example 4- (4-methoxy-styryl) -6- (3,3,3-trichloropropenyl) -2-pyrone and 4- (3,4,5-Trimethoxy-styryl) -6-trichloromethyl-2-pyrone or the compounds described in German Patent No. 3333450, for example, the following compounds can be mentioned.

[0167]

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[0168]

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The following compounds can be exemplified from the compounds described in German Patent No. 3021590.

[0170]

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[0171]

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Further, from the compounds described in German Patent No. 3021599, for example, the following compounds can be mentioned.

[0173]

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Examples of (k) metallocene compounds which are other examples of component ii) include JP-A-59-152396, JP-A-61-151197, and JP-A-63-41484.
, The titanocene compounds described in JP-A-2-249 and JP-A-2-4705, and JP-A-1-304453.
And an iron-allene complex described in JP-A-1-152109.

Specific examples of the above titanocene compound include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-phenyl. 2,3
4,5,6-pentafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentadienyl-Ti- Bis-2,4,6-trifluorophenyl
1-yl, di-cyclopentadienyl-Ti-bis-
2,6-difluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,4-difluorophenyl
1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-
Yl, di-methylcyclopentadienyl-Ti-bis-
2,3,5,6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-
Difluorophenyl-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyri-1-
Yl) phenyl) titanium (A-
2),

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (methylsulfonamido) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N-butylbiaroyl-amino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N-ethylacetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-methylacetylamino) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3- (N-ethylpropionylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N-ethyl- (2,2-dimethylbutanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(N-butyl- (2,2-dimethylbutanoyl) amino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N-pentyl-
(2,2-Dimethylbutanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl)-(2,2-dimethylbutanoyl) phenyl] titanium Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-methylbutyrylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (N-methylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N-ethylcyclohexylcarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(N-ethylisobutyrylamino) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethylacetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,2, 5,5-tetramethyl-1,
2,5-azadisirolidin-1-yl) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (octylsulfonamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (4-tolylsulfonamido) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (4-dodecylphenylsulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (4
-(1-pentylheptyl) phenylsulfonylamido) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (ethylsulfonylamido) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3-((4-bromophenyl) -sulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-naphthylsulfonylamido) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3-
(Hexadecylsulfonylamide) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-methyl- (4-dodecylphenyl) -sulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro -3- (N-methyl-4- (1-pentylheptyl) phenyl) sulfonylamido) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (N-hexyl- (4-tolyl)
-Sulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (pyrrolidin-2,5-dion-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3,4-dimethyl-3-pyrrolidine-
2,5-Dion-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (phthalimido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-isobutoxycarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (ethoxycarbonylamino) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3-((2-chloroethoxy) -carbonylamino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (phenoxycarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-phenylthioureido) phenyl] titanium, bis (cyclo Pentadienyl) bis [2,6-difluoro-3- (3-butylthioureido) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (3-phenylureido) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (3-butylureido) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N, N-diacetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3,3-dimethylureido) phenyl] titanium, bis (cyclo Pentadienyl)
Bis [2,6-difluoro-3- (acetylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (butyrylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (decanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2 6-difluoro-3- (octadecanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (isobutyrylamino) phenyl] titanium, bis (cyclopentadienyl) Bis [2,6-difluoro-3- (2-ethylhexanoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (2-methylbutanoylamino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (pivaloylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,2- Dimethylbutanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-ethyl-2-methylheptanoylamino) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (cyclohexylcarbonylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (2,2-dimethyl-3-chloropropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3
-Phenylpropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-chloromethyl-2-methyl-3-chloropropanoylamino) phenyl] titanium, bis ( Cyclopentadienyl) bis [2,6-difluoro-3- (3,
4-xyloylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(4-ethylbenzoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (2,4,6-mesitylcarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (benzoylamino) phenyl] titanium, bis (cyclo Pentadienyl) bis [2,6-difluoro-3- (N- (3-phenylpropyl) benzoylamino) phenyl] titanium;
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-ethylheptyl) -2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2 , 6-Difluoro-3-
(N-isobutyl- (4-toluyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (N-isobutylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N-cyclohexylmethylpivaloylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(N- (oxolan-2-ylmethyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N- (3-ethylheptyl) -2,2-dimethylbutanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N- (3-phenylpropyl-
(4-toluyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (N- (oxolan-2-ylmethyl)-(4-toluyl) amino) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (4-toluylmethyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N- (4-toluylmethyl)-(4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N -(Butylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N- (butyl- (4-toluyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N- (hexyl- (4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2,
4-dimethylpentyl) -2,2-dimethylbutanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,4-dimethylpentyl) -2,2-dimethyl Pentanoylamino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-((4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (2,2-dimethylpentanoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (2,2-dimethyl-3-ethoxypropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(2,2-dimethyl-3-allyloxypropanolamino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N-allylacetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-ethylbutanoylamino) phenyl] titanium, Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexylmethylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexyl) Methyl- (4-toluyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N-2-ethylhexyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isopropylbenzoylamino) phenyl] titanium, bis ( Cyclopentadienyl) bis [2,6-difluoro-
3- (N- (3-phenylpropyl) -2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(N-hexylbenzoylamino) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexylmethyl-2,2-dimethylpentanoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (N-butylbenzoylamino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2-ethylhexyl) -2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) Screw [2
6-difluoro-3- (N-hexyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(N-isopropyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-phenylpropyl) pivaloylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (N-butyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N
-(2-methoxyethyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N-benzylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N-benzyl- (4
-Toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N
-(2-methoxyethyl)-(4-toluyl) amino)
Phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (N- (4-methylphenylmethyl) -2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N- (2-methoxyethyl)-
2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexylmethyl- (2-ethyl-2-methylheptanoyl) amino) phenyl ] Titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (4-chlorobenzoyl)
Amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (N-hexyl- (2-ethyl-
2-methylbutanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (N-cyclohexyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (oxolani-2-ylmethyl) -2, 2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexyl- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadi Enyl) bis [2,
6-difluoro-3- (N-cyclohexyl- (2-chlorobenzoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (3,3-dimethyl-2,2-azetidinoni-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis (2,6-difluoro-3-isocyanatophenyl) titanium, Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethyl-
(4-tolylsulfonyl) amino) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl- (4-tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3 -(N-butyl-
(4-tolylsulfonyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (N-isobutyl- (4-tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N
-Butyl- (2,2-dimethyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-
Phenylpropyl) -2,2-dimethyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N
-Cyclohexylmethyl- (2,2-dimethyl-3-chloropropanoyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (N-isobutyl- (2,2-dimethyl-3-chloropropanoyl) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (2-chloromethyl-2-methyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) ) Bis [2,6-difluoro-3- (butylthiocarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (phenylthiocarbonylamino) phenyl] titanium,

Bis (methylcyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl-2,2-
Dimethylbutanoylamino) phenyl] titanium, bis (methylcyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (methylcyclopenta Dienyl) bis [2,6-difluoro-3- (N-
Ethylacetylamino) phenyl] titanium, bis (methylcyclopentadienyl) bis [2,6-difluoro-
3- (N-ethylpropionylamino) phenyl] titanium, bis (trimethylsilylpentadienyl) bis [2,6-difluoro-3- (N-butyl-2,2-dimethylpropanoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (N- (2-methoxyethyl)-
Trimethylsilylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(N-butylhexyldimethylsilylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N-ethyl- (1,1,2-tolylmethylpropyl) dimethylsilylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (3-ethoxymethyl-3-methyl-2-azethiodinoni-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-allyloxy) Methyl-3-methyl-
2-azetidinoni-1-yl) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (3-chloromethyl-3-methyl-2-azetidinoni-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-benzyl- 2,2-dimethylpropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (5,5-dimethyl-2-pyrrolidinoni-1-yl) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (6,6-diphenyl-2-piperidinoni-1
-Yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-2,3-dihydro-1,2-benzinethiazolo-3-one (1,1
-Dioxide) -2-yl) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (N-hexyl- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-
Hexyl- (2-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N-isopropyl- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(N- (4-methylphenylmethyl)-(4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-
(4-methylphenylmethyl)-(2-chlorobenzoyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (N-butyl- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-benzyl-2,2-dimethyl) Pentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N- (2-ethylhexyl)-
4-tolyl-sulfonyl) amino) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-oxaheptyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N- (3,6-dioxadecyl) benzoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (trifluoromethylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (trifluoroacetylamino) phenyl] titanium, bis (cyclopentadi Enyl) bis [2,6-difluoro-3- (2-
Chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3,6-dioxadecyl) -2,
2-dimethylpentanoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (N- (3,7-dimethyl-7-
Methoxyoctyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexylbenzoylamino)
Phenyl] titanium, and the like.

More preferable examples of the component ii) in the present invention include the above-mentioned (j) compounds having a carbon-halogen bond and (k) metallocene compounds, and the most preferable examples are titanocene compounds. Can be mentioned.

In the present invention, component ii) may be used alone or
It is preferably used in combination of two or more kinds.

Further, the photopolymerizable composition of the present invention contains the component i
A spectral sensitizing dye or dye already known as v) may be allowed to coexist. Examples of preferred spectral sensitizing dyes or dyes include polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein,
Eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionin, methylene blue, toluidine blue), acridines (Eg, acridine orange, chloroflavin, acriflavine), phthalocyanines (eg, phthalocyanine, metal phthalocyanine), porphyrins (eg, tetraphenylporphyrin, metal porphyrin), chlorophylls (eg, chlorophyll,
Chlorophyllin, central metal-substituted chlorophyll), metal complexes such as:

[0209]

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Anthraquinones such as (anthraquinone) and squariums such as (squarium) are exemplified.

More preferred components iv) Examples of the spectral sensitizing dye or dye are listed below. First, styryl dyes described in JP-B-37-13034, for example, are as follows.

[0212]

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The cationic dyes described in JP-A-62-143044 include the following.

[0214]

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There are quinoxalinium salts described in JP-A-59-24147, for example, the following.

[0216]

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New methylene blue compounds described in JP-A-64-33104, for example, the following:

[0218]

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Anthraquinones described in JP-A-64-56767, for example, the following:

[0220]

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Benzoxanthene dyes described in JP-A-2-174.

JP-A-2-226148 and JP-A-2-2148
The acridines described in JP-A-226149, for example,

[0223]

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The pyrylium salts described in JP-B-40-28499 are, for example, the following.

[0225]

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Cyanines described in JP-B-46-42363, for example, the following.

[0227]

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Benzofuran dyes described in JP-A-2-63053, for example, those described below.

[0229]

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JP-A-2-85858, JP-A-2-21
Conjugated ketone dyes described in No. 6154, for example, the following.

[0231]

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Dyes described in JP-A-57-10605.

The azocinnamylidene derivatives described in JP-B-2-30321 are, for example, the following.

[0234]

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The cyanine dyes described in JP-A-1-287105 are, for example, the following.

[0236]

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JP-A-62-31844, JP-A-62-31844
No. 31848 and JP-A-62-143043, for example, the following xanthene dyes.

[0238]

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Aminostyryl ketones described in JP-B-59-28325, for example, the following:

[0240]

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It is a merocyanine dye represented by the following formulas [1] to [8] described in JP-B-61-9621.

[0242]

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In the general formulas [3] to [8], X ⁸ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxy group,
Represents an aryl group, a substituted aryl group, an aryloxy group, an aralkyl group or a halogen atom. In the general formula [2], Ph represents a phenyl group. In the general formulas [1] to [8], R ⁴⁸ , R ⁴⁹ and R ⁵⁰ are each an alkyl group,
Represents a substituted alkyl group, an alkenyl group, an aryl group, a substituted aryl group or an aralkyl group, which may be the same or different.

As the merocyanine dye, JP-A No.
The following general formulas [9] to [11] described in -179643
There is a dye represented by

[0245]

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In the general formulas [9] to [11], A represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, a nitrogen atom substituted with alkyl or aryl, or a carbon atom substituted with dialkyl.

Y ³ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an acyl group, or a substituted alkoxycarbonyl group.

R ⁵¹ and R ^{52 each} represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or a halogen atom (F,
Cl, Br, I), R 53 O -, - (CH 2 CH 2 O) x -
R ⁵³ represents a substituted alkyl group having 1 to 18 carbon atoms having the following groups.

[0249]

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However, R ⁵³ is a hydrogen atom or a group having 1 to 1 carbon atoms.
Represents an alkyl group of 0, and B represents a dialkylamino group, a hydroxyl group, an acyloxy group, a halogen atom, or a nitro group.

W represents an integer of 0 to 4, and x represents an integer of 1 to 20.

Further, there is a merocyanine dye represented by the following general formula [12] described in JP-A-2-244050.

[0253]

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In the general formula [12], R ⁵⁴ and R ⁵⁵
Each independently represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxycarbonyl group, an aryl group, a substituted aryl group or an aralkyl group. A ² represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, an alkyl or aryl substituted nitrogen atom, or a dialkyl substituted carbon atom. X ⁹ represents a nonmetallic atom group necessary for forming a nitrogen-containing 5-membered heterocyclic ring.

Y ⁴ represents a substituted phenyl group, an unsubstituted or substituted polynuclear aromatic hydrocarbon ring group, or an unsubstituted or substituted heteroaromatic ring group. Z ³ is a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, a substituted amino group, an acyl group or an alkoxycarbonyl group, together with Y ⁴ They may combine to form a ring.

Preferred specific examples of the merocyanine dye represented by the general formula [12] include the following and B-1 used in Examples described later.

[0257]

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Further, there is a merocyanine dye represented by the following formula [13] described in JP-B-59-28326.

[0259]

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In the general formula [13], R ⁵⁶ and R ⁵⁷
Represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl or an aralkyl group, which may be the same or different. X ¹⁰ is Hammett
(Hammett) represents a substituent having a sigma (σ) value in the range of -0.9 to +0.5.

Further, there is a merocyanine dye represented by the following general formula [14] described in JP-A-59-89303.

[0262]

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In the general formula [14], R ⁵⁸ and R ⁵⁹
Each independently represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or an aralkyl group. X ¹¹ has a Hammett's sigma (σ) value of −11.
Represents a substituent in the range from 0.9 to +0.5. Y ⁵
Represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an acyl group or an alkoxycarbonyl group.

Preferred specific examples of the merocyanine dye represented by the general formula [14] include the following.

[0265]

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Further, there is a merocyanine dye represented by the following general formula [15] described in Japanese Patent Application No. 6-269047.

[0267]

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In the general formula [15], R ⁶⁰ , R ⁶¹ , R
⁶² , R ⁶³ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ and R ⁷¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a hydroxyl group,
Substituted oxy group, mercapto group, substituted thio group, amino group,
Represents a substituted amino group, a substituted carbonyl group, a sulfo group, a sulfonato group, a substituted sulfinyl group, a substituted sulfonyl group, a phosphono group, a substituted phosphono group, a phosphonate group, a substituted phosphonate group, a cyano group or a nitro group. R ⁶⁰ and R
⁶¹ , ^R61 and ^R62 , ^R62 and ^R63 , ^R68 and ^R69 , ^R69 and ^R70 , ^R70 and ^R71 may be bonded to each other to form an aliphatic or aromatic ring. . R ⁶⁴ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group,, R ⁶⁵ represents a substituted or unsubstituted alkenyl group or a substituted or unsubstituted alkynyl group,, R ^66, R ⁶⁷ is each independently a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group,
Represents an aryl group, a substituted aryl group, or a substituted carbonyl group.

There is also a benzopyran dye represented by the following general formula [16] described in Japanese Patent Application No. 7-164585.

[0270]

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In the general formula [16], R ^{72 to} R ⁷⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group or an amino group. R ^{72 to} R ⁷⁵ may form a ring composed of a nonmetal atom together with the carbon atoms to which they can be respectively bonded.

R ⁷⁶ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaromatic group, a cyano group, an alkoxy group, a carboxy group or an alkenyl group. R ⁷⁷ is a group represented by R ⁷⁶ or —ZR ⁷⁶ , and Z represents a carbonyl group, a sulfonyl group, a sulfinyl group, or an arylenedicarbonyl group. R ⁷⁶ and R ⁷⁷ may together form a ring composed of a nonmetallic atom.

A ¹ represents an O atom, S atom, NH or N atom having a substituent.

B ¹ represents an O atom or the following group.

[0275]

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G ¹ and G ² may be the same or different,
Represents a hydrogen atom, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an arylcarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or a fluorosulfonyl group. However, G ¹ and G ² are not simultaneously hydrogen atoms. G ¹ and G ² may form a ring composed of a non-metal atom together with a carbon atom.

Specific examples of the benzopyran dye represented by the general formula [16] include B-2 used in Examples described later.

More preferred examples of the component iv) in the present invention include the merocyanine dyes described in JP-B-61-9621, the merocyanine dyes described in JP-A-2-179463, and the merocyanine described in JP-A-2-244050. Dyes; merocyanine dyes described in JP-B-59-28326; merocyanine dyes described in JP-A-59-89303; be able to.

In the present invention, the component iv) may be used alone or
It is preferably used in combination of two or more kinds.

Further, to the photopolymerizable composition of the present invention, a known compound having an effect of further improving sensitivity or suppressing polymerization inhibition by oxygen may be added as a cosensitizer.

Examples of such co-sensitizers include amines, for example, “Journal of Polymer Socie” by MRSander et al.
ty ", Vol. 10, p. 3173 (1972), Japanese Patent Publication No. 44-2
0189, JP-A-51-82102, JP-A-52-102
No. 134692, JP-A-59-138205, JP-A-60-84305, JP-A-62-18537, JP-A-64-33104, Research Disclosure 3382
No. 5, and the like, and specific examples thereof include triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline.

Other examples of the co-sensitizer include thiols and sulfides, for example, thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, and JP-A-56-142. No. 75643, specifically, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, and the like. Is mentioned.

Another example is an amino acid compound (eg, N-phenylglycine, etc.), Japanese Patent Publication No. 48-429.
No. 65, organometallic compounds (eg, tributyltin acetate, etc.), hydrogen donors described in JP-B-55-34414, sulfur compounds described in JP-A-5-91089 (eg,
Trithiane, etc.), phosphorus compounds described in Japanese Patent Application No. 5-32147 (diethyl phosphite, etc.), and Japanese Patent Application No. 6-1916.
Si-H and Ge-H compounds described in No. 05 are exemplified.

Components ii) and iii) in the composition of the present invention
And the amount of iv) is 0.01 to 6 with respect to the total amount of the photopolymerizable ethylenically unsaturated compound and the linear organic high molecular polymer as a binder which is optionally added.
0% by weight, more preferably 1 to 30% by weight.

The ratio of component ii) to component iii) used in the present invention is 0.01 to 50 parts by weight of component ii) per 1 part by weight of the salt of the amino acid represented by formula (I). It is suitably used in an amount of 0.02 to 20 parts by weight, most preferably 0.05 to 10 parts by weight.

The ratio of the component iii) to the component iv) used in the present invention is 0.01 to 50 parts by weight of the component iv) per 1 part by weight of the salt of the amino acid represented by the formula (I). It is suitably used in an amount of 0.02 to 20 parts by weight, most preferably 0.05 to 10 parts by weight.

When the above co-sensitizer is used, component ii
It is appropriate to use 0.01 to 50 parts by weight, more preferably 0.02 to 20 parts by weight, most preferably 1 part by weight of the salt of the amino acid represented by the formula (I) of i). 0.05 to 10 parts by weight.

The photopolymerizable composition of the present invention preferably contains a linear organic high molecular polymer as a binder. Such a “linear organic high molecular polymer” includes
Any linear organic high molecular polymer having compatibility with the photopolymerizable ethylenically unsaturated compound may be used. Preferably, a water-soluble or weakly alkaline water-soluble or swellable linear organic high molecular polymer that enables water development or weakly alkaline water development is selected. The linear organic polymer is appropriately selected and used depending on whether water, weakly alkaline water or an organic solvent is used as a developer as well as a film-forming agent of the photopolymerizable composition. For example, when a water-soluble organic high molecular polymer is used, water development becomes possible. Examples of such linear organic high molecular polymers include addition polymers having a carboxylic acid group in the side chain, for example, JP-A-59-44615 and JP-B-54-34327.
No., JP-B-58-12577, JP-B-54-2595
7, JP-A-54-92723, JP-A-59-538.
36, JP-A-59-71048, that is, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, There are esterified maleic acid copolymers and the like. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful.

In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomers] copolymer and [allyl (meth) acrylate / (meth) acrylic acid / Other addition-polymerizable vinyl monomers] copolymers are suitable, if necessary. In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful. These linear organic high molecular polymers can be incorporated in any amount into the entire composition. However, if it exceeds 90% by weight, no favorable result is obtained in view of the strength of the formed image and the like. Preferably 30 to 85
% By weight. The weight ratio of the photopolymerizable compound having an ethylenically unsaturated double bond and the linear organic high molecular weight polymer is preferably in the range of 1/9 to 7/3. A more preferred range is 3/7 to 5/5.

In the present invention, in order to prevent unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond which can be polymerized during the production or storage of the photosensitive composition in addition to the above basic components, It is desirable to add a small amount of a thermal polymerization inhibitor. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-
p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-
6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), cerium N-nitrosophenylhydroxyamine, and the like. The addition amount of the thermal polymerization inhibitor is preferably about 0.01% to about 5% by weight based on the weight of the whole composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be unevenly distributed on the surface of the photosensitive layer in a drying process after coating. . The added amount of the higher fatty acid derivative is preferably about 0.5% by weight to about 10% by weight of the whole composition. Further, a dye or a pigment may be added for the purpose of coloring the photosensitive layer. The amount of the dye or pigment added is preferably about 0.5% to about 5% by weight of the total composition. In addition, inorganic fillers and other known additives may be added to improve the physical properties of the cured film.

The photopolymerizable composition of the present invention is usually used after being coated on a support. When the photopolymerizable composition of the present invention is coated on a support, it is used after being dissolved in various organic solvents. As the solvent used here, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, methyl lactic acid And ethyl. These solvents can be used alone or as a mixture. The appropriate concentration of the solid content in the coating solution is 2 to 50% by weight. The coating amount is about 0.1 g / m ² to about 10 g by weight after drying.
A range of g / m ² is appropriate. More preferably 0.5 to 5 g /
a m ^2.

A dimensionally stable plate is used as the support. Dimensionally stable plate-like objects include paper,
Plastics (eg polyethylene, polypropylene,
Paper laminated with polystyrene, etc., for example, aluminum (including aluminum alloy), zinc,
Plates of metal such as copper, further, for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate,
Examples include plastic films such as polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, and polyvinyl acetal, and paper or plastic films on which the above-described metals are laminated or vapor-deposited. Among these supports, the aluminum plate is particularly preferable because it is extremely dimensionally stable and inexpensive. Further, a composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-B-48-18327 is also preferable.

In the case of a support having a surface of a metal, particularly aluminum, a surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodizing treatment. Is preferably performed.

Further, an aluminum plate grained and then immersed in an aqueous solution of sodium silicate can be preferably used. As described in JP-B-47-5125, an aluminum plate which is anodized and then immersed in an aqueous solution of an alkali metal silicate is preferably used. The anodizing treatment may be, for example, an aqueous solution or a non-aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or a salt thereof, or an electrolytic solution in which two or more kinds are combined. It is carried out by passing a current through an aluminum plate as an anode.

Electrodeposition of silicate as described in US Pat. No. 3,658,662 is also effective.

Further, the surface obtained by combining the electrolytic grain disclosed in JP-B-46-27481, JP-A-52-58602 and JP-A-52-30503 with the above-described anodic oxidation treatment and sodium silicate treatment. Processing is also useful.

Also preferred are those subjected to mechanical roughening, chemical etching, electrolytic graining, anodic oxidation treatment and sodium silicate treatment in that order as disclosed in JP-A-56-28893.

After these treatments, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having a sulfonic acid group in the side chain, polyacrylic acid, and water-soluble metal salts (eg, zinc borate) ) Or those undercoated with a yellow dye, an amine salt or the like are also suitable.

These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions of the photopolymerizable composition provided thereon and to adhere the photosensitive layer. This is performed for the purpose of improving the performance.

On the layer of the photopolymerizable composition provided on the support, for example, polyvinyl alcohol, in particular, having a saponification degree of 95, in order to prevent a polymerization inhibition effect due to oxygen in the air.
% Or more of a protective layer made of a polymer having excellent oxygen barrier properties such as polyvinyl alcohol and acidic celluloses. For the method of applying such a protective layer, see, for example, U.S. Pat. No. 3,458,311;
No. 49729.

The photopolymerizable composition of the present invention can be used for ordinary photopolymerization. Further, the present invention can be applied to various fields such as a photoresist for producing a printing plate, a printed board, and the like. Particularly, due to the high sensitivity and the wide spectral sensitivity characteristic up to the visible light region, which are characteristics of the photopolymerizable composition of the present invention,
When applied to a photosensitive material for a visible light laser such as an Ar ⁺ laser and a YAG-SHG laser, a good effect can be obtained.

Further, since the photopolymerizable composition of the present invention has high sensitivity and is sensitive to visible light, it can be particularly advantageously used for an image forming system using microcapsules.

[0303] For use in an image forming system using microcapsules, see, for example, JP-A-57-197538.
No. 61-130945, No. 58-88739,
No. 58-88740, EP 223,587 A1
References can be referred to. In this image forming method, for example, a photopolymerization initiator composition comprising an ethylenic vinyl compound and a photopolymerization initiator and a microcapsule containing a dye precursor are coated on a support, and the photosensitive sheet is exposed by imagewise exposure. After curing some of the microcapsules,
By overlapping the developer sheet and pressing the entire surface, the microcapsules in the unexposed areas are destroyed, and the color image forming substance (for example, a dye precursor) is transferred to an image receiving element (for example, a developer layer) to form a color. is there.

The photosensitive material using the photopolymerizable composition of the present invention is subjected to image exposure, and the unexposed portion of the photosensitive layer is removed with a developing solution to obtain an image. Preferred developers when these photopolymerizable compositions are used for preparing a lithographic printing plate include those described in JP-B-57-7427, such as sodium silicate and potassium silicate. Like sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. An aqueous solution of a suitable inorganic alkali agent or an organic alkali agent such as monoethanolamine or diethanolamine is suitable. Such an alkali agent has a solution concentration of 0.1 to
It is added so as to be 10% by weight, preferably 0.5 to 5% by weight.

Further, such an alkaline aqueous solution includes:
If necessary, a small amount of a surfactant or an organic solvent such as benzyl alcohol, 2-phenoxyethanol or 2-butoxyethanol can be contained. For example, those described in U.S. Pat. Nos. 3,375,171 and 3,615,480 can be mentioned. Further, Japanese Unexamined Patent Publication No.
No. 0-26601, No. 58-54341, Tokubo Sho56
The developing solutions described in JP-A-39464 and JP-A-56-42860 are also excellent.

The actinic ray used in the present invention may be in a wide range from ultraviolet light to visible light.

[0307]

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples.

Example 1 A 0.30 mm thick aluminum plate was coated with a nylon brush and
The surface was sand-grained with an aqueous suspension of pumicestone of 00 mesh, and then thoroughly washed with water. After etching by immersion in 10% by weight sodium hydroxide at 70 ° C. for 60 seconds, the plate was washed with running water, neutralized and washed with 20% by weight nitric acid, and then washed with water. This was converted to 160% in a 1% by weight aqueous nitric acid solution using a sinusoidal alternating current under the condition of _VA = 12.7V.
Electrolytic surface-roughening treatment was performed with an amount of electricity at the anode of Coulomb / dm ² . When the surface roughness was measured, it was 0.6 μm ( _Ra display). Subsequently, after immersing in a 30% by weight aqueous sulfuric acid solution and desmutting at 55 ° C. for 2 minutes, the thickness of the anodic oxide film was increased to 2.7 g / m ² at a current density of 2 A / dm ² in a 20% by weight aqueous sulfuric acid solution. Anodizing treatment was performed for 2 minutes.

On the thus treated aluminum plate, a photopolymerizable composition having the following composition was applied in a dry coating weight of 1.4.
g / m ² and dried at 80 ° C. for 2 minutes to form a photosensitive layer.

[Composition] Pentaerythritol tetraacrylate 2.0 g Allyl methacrylate / methacrylic acid copolymer 2.0 g (copolymer molar ratio 80/20) Component ii) Xg (Table 1) Component iii) Yg (Table 1) Component iv) Zg (Table 1) Methyl ethyl ketone 20 g Propylene glycol monomethyl ether acetate 20 g

An aqueous solution of 3% by weight of polyvinyl alcohol (degree of saponification: 98 mol%, degree of polymerization: 1000) was applied on the photosensitive layer so that the dry coating weight was 2 g / m ² ,
The sample was dried at 2 ° C. for 2 minutes to prepare a sample of the photosensitive material (Table 1). The following photosensitivity test was performed on a sample of this light-sensitive material.

In the photosensitivity test, visible light and monochromatic light of Ar ⁺ laser light (wavelength = 488 nm) were used. Visible light was obtained through a kenko optical filter BP-49 using a tungsten lamp as a light source. Sensitivity was measured using a Fuji PS step guide (a step tablet having a transmission optical density of 0.05 at the first stage and increasing by 0.15 to 15 stages sequentially, manufactured by Fuji Photo Film Co., Ltd.). Sensitivity is determined by the P at the time of exposure such that the exposure energy at the photosensitive material film surface is 0.25 mJ.
It is indicated by the number of clear steps in the S step guide. The higher the value of the number of stages, the higher the sensitivity.

The development was carried out by immersion in the following developer at 25 ° C. for 1 minute.

[0314] Potassium [developer] 1K silicate 30g hydroxide _{15g C 12 H 25 -C 6 H} 4 -O-C 6 H 4 -SO 3 Na 3g Water 1000g

Further, a development residue test was conducted at the same time. Model test of development scum, the photosensitive material of the unexposed created above (coating plate) was immersed in the developing solution (1 liter) at 2m ² increments in the range of 0～20M ^2, the waste developer week Nature It was left standing and visually observed for the presence or absence of a precipitate (developed residue). It was investigated in 5 m ² increments in the range of 0～20M ² the treated area of the light-sensitive material to development scum generated (m ²⁾ in this case. (Accordingly, it can be said that the larger the processing area (m ² ), the less sensitive a photosensitive material is development scum.)

The results are shown in Table 1. The structures of compounds A-1, A-2, B-1, B-2, C-1, and C-2 in Table 1 will be described later.

[0317]

[Table 1]

Example 2 A photosensitive material sample was prepared in the same manner as in Example 1 except that the photopolymerizable composition was changed to the following composition in the photosensitive material sample of Example 1 (Table 2). The test was performed. However, the same visible light as in Example 1 and each monochromatic light of YAG-SHG laser light (wavelength = 532 nm) were used for the sensitivity measurement.

[Composition] Pentaerythritol tetraacrylate 2.0 g Allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio 90/10) 2.0 g Component ii) Xg (Table 2) Component iii) Yg (Table 2) Methyl ethyl ketone 20 g Propylene glycol monomethyl ether acetate 20 g The results are shown in Table 2.

[0320]

[Table 2]

Tables 1 and 2 show that the sensitivity of the photopolymerizable composition of the present invention is increased due to the use of the component iii). In addition, it can be seen that the photosensitive material is less likely to generate development scum even when component iii) is added.

Compounds A-1 and A- in Tables 1 and 2
2, B-1, B-2, C-1 to C-4 are shown below.

[0323]

Embedded image

[0324]

The photopolymerizable composition of the present invention has high sensitivity to actinic rays in a wide range from ultraviolet to visible light, and the sensitivity of a photosensitive material obtained by using the same is improved. Further, development waste generated from the development waste liquid after the development of the photosensitive material is suppressed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/004 503 G03F 7/004 503Z

Claims (1)

[Claims] 1. A compound having at least i) an addition-polymerizable ethylenically unsaturated bond, ii) a photopolymerization initiator, and
iii) A photopolymerizable composition comprising a salt of an amino acid represented by the following formula (I). Embedded image [In the formula (I), R ¹ and R ² each represent a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group. R ³ and R ⁴ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group. R
¹ , R ² , R ³ and R ⁴ may be combined in any combination to form a ring. n is an integer of 1 to 4, and M ^{n +} is n
Represents a valent counter cation. ]