JPH06266102A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To obtain a photopolymerizable compsn. having high sensitivity by incorporating at least four kinds of specified compds. CONSTITUTION:This photopolymerizable compsn. contains a polymerizable compd. (1) having an addition-polymerizable unsatd. bond, a compd. (2) represented by formula I, etc., a compd. (3) having a carbon-halogen bond, an arom. onium salt., etc., and a compd. (4) represented by formula II, etc. In the formula I, each of Z<1> and Z<2> is a group of nonmetal atoms required to form a benzimidazole or naphthoimidazole ring, each of R<1>-R<4> is an optionally substd. alkyl, X1<-> is a counter anion and (n) is 0 or 1. In the formula II, Ar is an arom. group represented by formula III, etc., each of R<18> and R<19> is H or an alkyl and R<18> and R<19> may bond to each other to form an alkylene. In the formula III, each of R<20>-R<24> is H, a halogen, alkyl, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to photopolymerizable compositions. More specifically, it relates to a photopolymerizable composition containing a polymerizable compound having an addition polymerizable unsaturated bond, a photopolymerization initiator having a novel composition, and, if necessary, a linear organic polymer, The present invention also relates to a photopolymerizable composition useful for a photosensitive layer of a photosensitive printing plate which is sensitive to an argon laser light source.

[0002]

2. Description of the Related Art A photosensitive composition in which a polymerizable compound having an addition-polymerizable unsaturated bond, a photopolymerization initiator, and if necessary, a binder having an appropriate film forming ability and a thermal polymerization inhibitor are mixed. A method of reproducing an image by a photographic method using is currently known. That is, U.S. Pat.Nos. 2,927,022, 2,902,356 or 3,870,
As described in No. 524, since a photosensitive composition of this type undergoes photopolymerization upon irradiation with light and is cured and insolubilized, the photosensitive composition is formed into an appropriate film, and a desired negative image is formed through it. A desired cured image of the photopolymerizable composition can be formed by irradiating light and removing only the unexposed portion with a suitable solvent (hereinafter, simply referred to as development). It goes without saying that this type of photosensitive composition is extremely useful as a material used for producing printing plates and the like. Further, conventionally, a polymerizable compound having an addition polymerizable unsaturated bond alone does not have sufficient photosensitivity, and it has been proposed to add a photopolymerization initiator to enhance the photosensitivity. As such, benzyl, benzoin, benzoin ethyl ether, Michler's ketone, anthraquinone, acridine, phenazine, benzophenone, 2-ethylanthraquinone and the like have been used. However, when these photopolymerization initiators are used, the photosensitivity of curing of the photopolymerizable composition is low, and thus it took a long time for image exposure in image formation. Therefore, in the case of a fine image, if there is a slight vibration in the operation, an image of good image quality cannot be reproduced, and the amount of energy emitted from the exposure light source must be increased. It was necessary to consider the dissipation of fever. In addition, there is a problem that the coating film of the composition is easily deformed or deteriorated by heat.

Further, these photopolymerization initiators have a photopolymerization ability of 40 nm or less in the ultraviolet region of 40 nm or less.
The photopolymerization ability for a light source in the visible light region of 0 nm or more is remarkably low. Therefore, the application range of the conventional photopolymerizable composition containing the photopolymerization initiator is extremely limited. Several proposals have been made in the past regarding photopolymerization systems sensitive to visible light. As such a proposal, according to U.S. Pat. No. 2,850,445, certain photoreducible dyes such as rose bengal, eosin, and erythrosine are reported to have effective visible light sensitivity. As an improved technology,
Complex initiation system of dye and amine (Japanese Patent Publication No. 44-20189)
No.), a system of hexaaryldiimidazole and a radical generator and a dye (Japanese Patent Publication No. 45-37377), a system of hexaarylbiimidazole and P-dialkylaminobenzylidene ketone (Japanese Patent Publication No. 47-2528, Japanese Patent Laid-Open No. 5528/1982)
4-155292), a system of 3-keto-substituted coumarin compounds and active halogen compounds (JP-A-58-15503).
No.), a system of substituted triazine and merocyanine dye (JP-A-54-15102), and the like have been proposed. These techniques are certainly effective for visible light. However, the photosensitivity speed is not yet satisfactory,
Further improved techniques have been desired. In addition, in recent years, a method for forming an image using a laser and a high sensitivity to ultraviolet rays has been studied, and a UV projection exposure method, a laser direct plate making, a laser facsimile, in a printing plate making,
Holography and the like are already in the stage of practical use, and a highly sensitive light-sensitive material corresponding to them is being developed. However, it cannot be said that it still has sufficient sensitivity.

[0004]

An object of the present invention is to provide a photopolymerizable composition having high sensitivity. That is,
The object of the present invention is to provide a photopolymerizable composition containing a photopolymerization initiator that increases the photopolymerization rate of a photopolymerizable composition containing a polymerizable compound having an addition polymerizable unsaturated bond in general. is there. Another object of the present invention is 400 nm.
It is an object of the present invention to provide a photopolymerizable composition containing a photopolymerization initiator having high sensitivity to the above visible light, particularly light near 488 nm corresponding to the output of Ar ⁺ laser.

[0005]

Means for Solving the Problems As a result of earnest studies to achieve the above object, the present inventor has found that a specific photopolymerization initiator system is a photopolymerizable compound having an addition-polymerizable unsaturated bond. The present invention has been accomplished by finding that the polymerization rate is remarkably increased and that the composition has high sensitivity to visible light of 400 nm or more. That is, the present invention is a photopolymerizable composition containing the following components (i) to (iv). (i) A polymerizable compound having an addition-polymerizable unsaturated bond. (ii) A compound represented by the following general formula (I) or (II).

[0006]

[Chemical 7] In the formula, Z ¹ and Z ² represent a group of non-metal atoms necessary for forming a benzimidazole or naphthimidazole ring, and may be the same or different. R ¹ , R ² , R
³ and R ⁴ may be the same or different and each represents an optionally substituted alkyl group. X ₁ ⁻ represents a counter anion, and n is 0 or 1.

[0007]

[Chemical 8]In the formula, Q¹, Q²Is an oxygen atom, a sulfur atom or -C (R⁷)
(R⁸)-, -NR⁹Represents-and may be the same or different.
R^Five, R⁶, R⁷, R⁸, R⁹Are the same or different
Also represents an optionally substituted alkyl group. Q³
Represents an oxygen atom or a sulfur atom. Z³Is -C (R^Ten)
(R¹¹) -C (R¹²) (R¹³)-, -C (R¹⁴) = C (R¹⁵)-Or benzoi
Midazole, benzoxazole, benzothiazole,
Naphthoimidazole, naphthoxazole, naphthothia
Represents a group of non-metal atoms necessary to form a sol ring. R
^Ten~ R¹⁵Is R^FiveIs synonymous with or represents a hydrogen atom. (iii) (a) a compound having a carbon-halogen bond,
(B) Aromatic onium salt, (c) Organic peroxide, (d)
A thio compound represented by the following general formula (III):

[0008]

[Chemical 9] (Here, R ¹⁶ represents an alkyl group, an aryl group or a substituted aryl group, R ¹⁷ represents a hydrogen atom or an alkyl group, and R ¹⁶ and R ¹⁷ are bonded to each other to form an oxygen, sulfur or nitrogen atom. May contain selected heteroatoms 5
The non-metal atom group necessary for forming a 7-membered ring is shown. ), (E) hexaarylbiimidazole, and (f) at least one compound selected from the group consisting of ketoxime esters. (iv) At least one compound selected from the compounds represented by the following general formula (IV) or (V).

[0009]

[Chemical 10] In the formula, Ar represents an aromatic group selected from one of the following general formulas, R ¹⁸ and R ¹⁹ may be the same or different and represent a hydrogen atom or an alkyl group, and R ¹⁸ and R ^{19 19} may combine with each other to represent an alkylene group.

[0010]

[Chemical 11]Where R²⁰, R^{twenty one}, R^{twenty two}, R^{twenty three}And R^{twenty four}Are identical to each other
May be different from each other, and each may be a hydrogen atom or a halogen atom.
Child, alkyl group, alkenyl group, aryl group, substituted ant
Group, hydroxyl group, alkoxy group, substituted alkoxy group,-
SR²⁶Group, -SO-R²⁶Group or -SO₂R²⁶Represents a group
However, R²⁰, R^{twenty one}, R^{twenty two}, R^{twenty three}And R ^{twenty four}At least
One is -SR²⁶Group, -SO-R²⁶Group or -SO₂R²⁶
Represents R²⁶Is an alkyl group or an alkenyl group, R^{twenty five}Is water
Represents an elementary atom, an alkyl group or an acyl group, and Y¹Is hydrogen
Child or

[0011]

[Chemical 12] (In the formula, R ²⁹ , R ³⁰ , R ³¹ and R ³² may be the same or different from each other, and are each a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, A substituted or unsubstituted alkynyl group or a substituted or unsubstituted heterocyclic group is shown, and two or more groups of R ²⁹ , R ³⁰ , R ³¹ and R ³² may combine to form a cyclic structure. However, among R ²⁹ , R ³⁰ , R ³¹ and R ³² ,
At least one is an alkyl group. A ⁺ represents an alkali metal cation or a quaternary ammonium cation. ) At least one compound selected from the group consisting of:

Each component of the photopolymerizable composition of the present invention will be described in detail below. Component (i) used in the present invention
The polymerizable compound having an addition polymerizable unsaturated bond of
It is selected from compounds having at least one, and preferably two or more terminal ethylenically unsaturated bonds. For example, it has a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example,
Acrylic acid, methacrylic acid, itaconic acid, crotonic acid,
Isocrotonic acid, maleic acid and the like) and an ester of an aliphatic polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyhydric amine compound. Specific examples of the monomer of the ester of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylic acid ester,
Ethylene glycol diacrylate, triethylene glycol diacrylate, 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,
Examples include dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, and polyester acrylate oligomer.

Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 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. As the itaconic acid ester, ethylene glycol diitaconate,
Examples include propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol tetriconate.

As the crotonic acid ester, ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate,
Examples include sorbitol tetradicrotonate. 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. Furthermore, a mixture of the above-mentioned ester monomers can also be mentioned. Specific examples of the amide monomer of the aliphatic polyvalent amine compound and the unsaturated carboxylic acid include methylenebis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, 1,6-hexamethylenebis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide and the like.

As another example, Japanese Patent Publication No. 48-417.
No. 08, the polyisocyanate compound having two or more isocyanate groups in one molecule is added with a vinyl monomer having a hydroxyl group represented by the following general formula (A). Examples thereof include vinyl urethane compounds containing at least one polymerizable vinyl group. _{CH 2 = C (R) COOCH} 2 CH (R ') OH (A) ( wherein, R and R' each represents H or CH _3.)
Further, urethane acrylates as described in JP-A-51-37193, JP-A-48-64183,
No. 4, Japanese Patent Publication No. 49-43191, Japanese Patent Publication No. 52-3049
Examples thereof include 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-0. Furthermore, those introduced as photocurable monomers and oligomers in Japan Adhesive Association magazine vol. 20, No. 7, pages 300 to 308 (1984) can also be used. The amount of these used is 5 to 50% by weight based on all components.
(Hereinafter abbreviated as “%”), preferably 10 to 40%.

The component (ii) used in the present invention is at least one compound selected from the compounds represented by the above general formula (I) or (II). The general formula (I) will be further described. Examples of the benzimidazole ring or naphthimidazole ring formed by Z ¹ and Z ² include 1-alkylbenzimidazole, 1-alkyl-5-chlorobenzimidazole, 1-alkyl-5,6-dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole, 1-alkyl-5
-Cyanobenzimidazole, 1-alkyl-5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole, 1-alkyl-6-chloro-5-cyanobenzimidazole, 1-alkyl-
6-chloro-5-trifluoromethylbenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-
Aryl benzimidazole, 1-aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1-aryl-5-methoxybenzimidazole, 1-aryl-5-cyanobenzimidazole, 1-alkylnaphtho [1,2-d] imidazole and 1-arylnaphtho [1,2-d] imidazole are preferable, and the above-mentioned alkyl group has 1 to 8 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl and the like. The unsubstituted alkyl group and hydroxyalkyl group (for example, 2-hydroxyethyl, 3-hydroxypropyl) are preferable. Particularly preferred are methyl group and ethyl group. The aforementioned aryl group represents phenyl, halogen (eg chloro) substituted phenyl, alkyl (eg methyl) substituted phenyl, alkoxy (eg methoxy) substituted phenyl.

As R ¹ , R ² , R ³ and R ⁴ , an alkyl group having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, and particularly preferably 1 to 4 carbon atoms (for example, methyl group, ethyl group, propyl group, Isopropyl group, butyl group, isobutyl group, hexyl group, octyl group, dodecyl group, octadecyl group), substituted alkyl group (for example, aralkyl group (for example, benzyl group, 2-phenylethyl group), hydroxyalkyl group (for example, 2-hydroxy) Ethyl group, 3-hydroxypropyl group), carboxyalkyl group (for example, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, carboxymethyl group), alkoxyalkyl group (for example, 2-methoxyethyl group) , 2- (2-
Methoxyethoxy) ethyl group), sulfoalkyl group (for example, 2-sulfoethyl group, 3-sulfopropyl group, 3
-Sulfobutyl group, 4-sulfobutyl group, 2- [3-sulfopropoxy] ethyl group, 2-hydroxy-3-sulfopropyl group, 3-sulfopropoxyethoxyethyl group), sulfatoalkyl group (for example, 3-sulfato) Propyl group, 4-sulfatobutyl group), heterocyclic-substituted alkyl group (for example, 2- (pyrrolidin-2-one-1-yl) ethyl group, tetrahydrofurfuryl group, 2-morpholinoethyl group), 2-acetoxyethyl Group, carbomethoxymethyl group, 2-methanesulfonylaminoethyl group}
Is preferred.

X₁ ^-Include various anions
It For example, SO_Four ^2-, S₂O₃ ^2-, SO ₃-, Halogenio
ClO_Four ^-, BF_Four ^-, PF₆ ^-, SbF₆ ^-, BiCl_Five ^-, AsF₆
^-, SbCl₆ ^-, R-SO₃ ^-, R-COO^-And so on.
However, R is a hydrogen atom, an alkyl group, an aryl group or a compound.
Represents an elementary ring group. Table of the general formula (I) used in the present invention
Sensitizing dyes used are heterocyclic compounds
-Cyanine soybean and related compau
(Heterocyclic compounds-Cyanine dyes and r
elated compounds- ") chapter IV, V, VI, page86-
199, F. M. Hamer, John Wiley & So
ns (New York, London), 1964, Heterocycl
Rick Compounds-Special Topics Inn
・ Heterocyclic chemistry ("Heterocyclic
compounds-Special topics in heterocylic chemistr
y- ") chapter VIII, sec. IV page 482-515, D.
M. Sturmer, John Wiley & Sons (NewYork, Londo
n) Easily based on the method described in 1977
Can be synthesized. Of the general formula (I) used in the present invention
Representative examples of the compounds are shown below, but the scope of the present invention is
The present invention is not limited to the above compound.

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

[Table 3]

The general formula (II) will be further described. Examples of the benzimidazole ring or naphthimidazole ring formed by Z ³ include 1-alkylbenzimidazole, 1-alkyl-5-chlorobenzimidazole, 1-alkyl-5,6-dichlorobenzimidazole, 1-alkyl. -5-methoxybenzimidazole, 1-alkyl-5-cyanobenzimidazole, 1
-Alkyl-5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole,
1-alkyl-6-chloro-5-cyanobenzimidazole, 1-alkyl-6-chloro-5-trifluoromethylbenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-arylbenzimidazole, 1
-Aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1-aryl-5-methoxybenzimidazole, 1-aryl-5-cyanobenzimidazole, 1-alkylnaphtho [1,2- d] imidazole and 1-arylnaphtho [1,2-d] imidazole are preferred, and R ^{5 to} R ⁹ are alkyl groups having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, and particularly preferably 1 to 4 carbon atoms (for example, , Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, occlu group, dodecyl group, octadecyl group), substituted alkyl group (eg aralkyl group (eg benzyl group, 2-phenylethyl group)) , A hydroxyalkyl group (eg, 2-hydroxyethyl group, 3-hydroxypropyl group), Bokishiarukiru group (e.g., 2
-Carboxyethyl group, 3-carboxypropyl group, 4
-Carboxybutyl group, carboxymethyl group), alkoxyalkyl group (e.g., 2-methoxyethyl group, 2-
(2-methoxyethoxy) ethyl group), sulfoalkyl group (for example, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-
[3-sulfopropoxy] ethyl group, 2-hydroxy-
3-sulfopropyl group, 3-sulfopropoxyethoxyethyl group), sulfatoalkyl group (eg, 3-sulfatopropyl group, 4-sulfatobutyl group), heterocyclic-substituted alkyl group (eg, 2- (pyrrolidine-2) -On-
1-yl) ethyl group, tetrahydrofurfuryl group, 2-
Morpholinoethyl group), 2-acetoxyethyl group, carbomethoxymethyl group, 2-methanesulfonylaminoethyl group} are preferred.

The sensitizing dye represented by the general formula (II) used in the present invention is a heterocyclic compound-cyanine dyes and relat compound.
ed compounds- ") chapter IV, V, VI, page86-19
9. FM. Hamer, John Wiley & Sons (N
ew York, London), 1964, Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry ("Heterocyclic comp"
ounds-Special topics in heterocylic chemistry- ")
chapter VIII, sec. IV page 482-515, DM S
It can be easily synthesized based on the method described by turmer, John Wiley & Sons (New York, London), 1977. Representative examples of the compound represented by formula (II) used in the present invention are shown below, but the scope of the present invention is not limited to these compounds.

[0024]

[Table 4]

[0025]

[Table 5]

[0026]

[Table 6]

[0027]

[Table 7]

As the compound having a carbon-halogen bond which is an example of the component (iii) used in the preferred embodiment of the present invention, compounds represented by the following general formulas (VI) to (XII) are preferable. A compound represented by the general formula (VI).

[0029]

[Chemical 13] (In the formula, X ² represents a halogen atom. Y ² represents —CX ² ₃ ,
_{^{-NH 2, -NHR 34, -NR 34}} 2, represent -OR ^34. Here, R ³⁴ represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. R ³³ is —CX ² ₃ , an alkyl group,
It represents a substituted alkyl group, an aryl group, a substituted aryl group or a substituted alkenyl group. ) A compound represented by the general formula (VII).

[0030]

[Chemical 14] (However, R ³⁵ is 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, and X ³ is a halogen. An atom, and n is an integer of 1 to 3.) The compound represented by the general formula (VIII). _{^{R 36 -Z 5 -CH 2-m}} X 4 m -R 37 (VIII) ( provided that, R ³⁶ is an aryl group or a substituted aryl group, R ³⁷ is -CO-NR ³⁸ R ^39,

[0031]

[Chemical 15]Or halogen, Z^FiveIs -CO-, -CS- or-
SO₂− And R³⁸, R³⁹Is an alkyl group, substituted alk
Group, alkenyl group, substituted alkenyl group, aryl group or
Is a substituted aryl group, R⁴⁰Is R in the general formula (VI)³⁴
Is the same as X ^FourIs a halogen atom, m is 1 or
It is 2. ) A compound represented by the general formula (IX):

[0032]

[Chemical 16] Wherein R ⁴¹ is an optionally substituted aryl group or heterocyclic group, R ⁴² is a trihaloalkyl group or trihaloalkenyl group having 1 to 3 carbon atoms,
p is 1, 2 or 3. A carbonylmethylene heterocyclic compound having a trihalogenomethyl group represented by the general formula (X).

[0033]

[Chemical 17] (However, L is a hydrogen atom or a substituent of the formula: CO- (R ⁴³ ) _n (CX ⁵ ₃ ) _m , M is a substituted or unsubstituted alkylene group, and Q ⁴ is a sulfur, selenium, or oxygen atom. , A dialkylmethylene group, an alkene-1,2-ylene group, a 1,2-phenylene group or an N—R ⁴⁴ group, and M and Q ⁴ together form a 3- or 4-membered ring, and R ⁴⁴ is An alkyl group, an aralkyl group or an alkoxyalkyl group, R ⁴³ is a carbocyclic or heterocyclic aromatic group, X ⁵ is a chlorine, bromine or iodine atom, and q = 0 and r = 1. Or q =
1 and r = 1 or 2. ) 4-halogeno-5- (halogenomethyl-phenyl) represented by the general formula (XI)
-Oxazole derivatives.

[0034]

[Chemical 18] (However, X ⁶ and X ⁷ are halogen atoms, t is an integer of 1 to 3, s is an integer of 1 to 4, R ⁴⁵ is a hydrogen atom or a CH _{3 -t} X ⁷ _t group. , R ⁴⁶ is an s-valent optionally substituted unsaturated organic group). General formula (XI
2- (halogenomethyl-phenyl) -4 represented by I)
-Halogeno-oxazole derivatives.

[0035]

[Chemical 19] (However, X ⁸ and X ⁹ are halogen atoms, v is an integer of 1 to 3, u is an integer of 1 to 4, R ⁴⁷ is a hydrogen atom or a CH _{3 -v} X ⁹ _v group. , R ⁴⁸ is a u-valent optionally substituted unsaturated organic group).

Examples of such a compound having a carbon-halogen bond include, for example, Wakabayashi et al., Bull. Chem. Soc.
Japan, 42 , 2924 (1969), for example, 2-phenyl 4,6-bis (trichloromethyl) -S-triazine, 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. Others, British patent 138849
No. 2, compounds such as 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, etc., 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)-
Naphtho-1-yl] -4,6-bis-trichloromethyl-S-triazine, 2- (4,7-dimethoxy-naphth-1-yl] -4,6-bis-trichloromethyl-S-
Triazine, 2- (acenaphtho-5-yl) -4,6-
Bis-trichloromethyl-S-triazine, etc. German patent
The compounds described in the specification of 3337024, for example, the following compounds can be mentioned.

[0037]

[Chemical 20]

[0038]

[Chemical 21]

Also, J. Org Ch by FC Schaefer et al.
em .; 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-
Examples thereof include 6-tribromomethyl-S-triazine and 2-methoxy-4-methyl-6-trichloromethyl-S-triazine. Further, JP-A-62-5824
The compounds described in No. 1 such as the following compounds can be mentioned.

[0040]

[Chemical formula 22]

[0041]

[Chemical formula 23]

Or even MP Hutt, EF Elsl
Journal of Heterocyclic by ager and LM Werbel
Chemistry Volume 7 (No. 3), pp. 511 and after (197
The following compound groups that can be easily synthesized by those skilled in the art according to the synthetic method described in (0 years) can be mentioned.

[0043]

[Chemical formula 24]

[0044]

[Chemical 25]

[0045]

[Chemical formula 26]

[0046]

[Chemical 27]

[0047]

[Chemical 28]

[0048]

[Chemical 29]

[0049]

[Chemical 30]

[0050]

[Chemical 31]

[0051]

[Chemical 32]

[0052]

[Chemical 33]

[0053]

[Chemical 34]

Alternatively, compounds such as those described in DE 2641100, such as 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, such as

[0055]

[Chemical 35]

[0056]

[Table 8] Table 8 ───────────────────────────────── R ⁴⁴ Ma (CX ₃ ) _b ── ─────────────────────────────── 1 C ₂ H ₅ 1,2-phenylene 14-CCl ₃ 2 CH ₂ C ₆ H ₅ 1,2-phenylene 14-CCl ₃ 3 C ₂ H ₅ 1,2-phenylene 13-CCl ₃ 4 C ₂ H ₅ 1,2-phenylene 14-CF ₃ 5 C ₂ H ₅ 5- CH _{3-1,2-phenylene 0 CCl 3 6 CH 2 C 6} H 5 1,2- phenylene _{0 CCl 3 7 C 2 H 4} OCH 3 1,2- phenylene 1 4-CCl ₃ ─────── ───────────────────────── Alternatively, the compounds described in German Patent No. 3021590,

[0057]

[Chemical 36] Alternatively, the compound group described in German Patent No. 3021599, for example, the following compounds can be mentioned.

[0058]

[Chemical 37] The aromatic onium salt, which is another example of the component (iii), includes elements of groups V, VI and VII of the periodic table, specifically N, P, As, Sb, Bi, O and S. , Se, Te, or I aromatic onium salts are included. Such aromatic onium salts are disclosed in JP-B-52-14277 and JP-B-52-142.
No. 78 and Japanese Patent Publication No. 52-1279.

[0059]

[Chemical 38] Specifically, the following compounds can be mentioned.

[0060]

[Chemical Formula 39]

[0061]

[Chemical 40]

[0062]

[Chemical 41]

[0063]

[Chemical 42]

[0064]

[Chemical 43]

[0065]

[Chemical 44]

Preferred among these are BF ₄ salts,
Or more preferably a compound of PF ₆ salt is BF ₄ salt or PF ₆ salt of an aromatic iodonium salt. As the “organic peroxide” which is another example of the component (iii) used in the present invention, almost all organic compounds having one or more oxygen-oxygen bonds in the molecule are included. , Methylethylketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tertiarybutylperoxy) -3,3,5-trimethylcyclohexane 1,1, -bis (tertiary butyl peroxy) cyclohexane, 2,2-bis (tertiary butyl peroxy) butane, tertiary butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, para Methane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide,
1,1,3,3-Tetramethylbutyl hydroperoxide, ditertiary butyl peroxide, tertiary butyl cumyl peroxide, dicumyl peroxide, bis (tertiary butyl peroxyisopropyl) benzene, 2,5-dimethyl- 2,5-di (tertiarybutylperoxy) hexane, 2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexyne-3, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, Decanoyl peroxide, lauroyl peroxide, 3,5,5
-Trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, meta-toluoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di- 2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-)
(Methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxy neodecanoate, tert-butyl peroxyoctanoate, tert-butyl peroxy-3, 5,
5-trimethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxybenzoate, ditertiary butyl peroxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, tertiary Butyl peroxide maleic acid, tert-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-hexylperoxydihydrogen diphthalate)
Etc.

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 ester systems such as di-t-butyldiperoxyisophthalate are preferred.

The thio compound as the component (iii) (d) used in the present invention is represented by the above general formula (III). The alkyl group represented by R ¹⁶ in the general formula (III) preferably has 1 to 4 carbon atoms. The aryl group of R ¹⁶ has 6 to 10 carbon atoms such as phenyl and naphthyl.
The substituted aryl group is preferably a substituted aryl group as described above, which is substituted with a halogen atom such as a chlorine atom, an alkyl group such as a methyl group, an alkoxy group such as a methoxy group or an ethoxy group. Is included. Specific examples of the thio compound represented by the general formula (III) include the compounds shown in the table below. ──────────────────────────── No. R ¹⁶ R ¹⁷ ───────────────── ──────────── 1 HH 2 H CH ₃ 3 CH ₃ H 4 CH ₃ CH ₃ 5 C ₆ H ₅ C ₂ H ₅ 6 C ₆ H ₅ C ₄ H ₉ 7 C ₆ H ₄ Cl CH ₃ 8 C ₆ H ₄ Cl C ₄ H ₉ 9 C ₆ H ₄ -CH ₃ C ₄ H ₉ 10 C ₆ H ₄ -OCH ₃ CH ₃ 11 C ₆ H ₄ -OCH ₃ C ₂ H ₅ 12 C _{6 H 4 -OC 2 H 5 CH 3} 13 C 6 H 4 -OC 2 H 5 C 2 H 5 14 C 6 H 4 -OCH 3 C 4 H 9 15 - (CH 2) 3 - 16 - (CH 2) 2 -S- 17 -CH (CH ₃ ) -CH ₂ -S- 18 -CH ₂ -CH (CH ₃ ) -S- 19 -C (CH ₃ ) ₂ -CH ₂ -S- 20 -CH ₃ -C ( CH ₃ ) ₂ -S- 21-(CH ₂ ) ₃ -O-22 -CH (CH ₃ ) -CH ₂ -O-23 -C (CH ₃ ) ₂ -CH ₂ -O-24 -CH = CH- _{N (CH 3) - 25 -} (CH 2) 3 -S- 26 - (CH 2) 2 CH (CH 3) -S- 27 - (CH 2) 2 -O- 28 - (CH 2) 2 - 29 -C ₆ C ₄ -O- 30 -N = C (SCH ₃ ) -S- 31 -C ₆ H ₄ -NH- ────────────────────── ───────

[0069]

[Chemical formula 45]

[0070]

[Chemical formula 46]

Examples of the hexaarylbiimidazole include 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (o-bromophenyl)- 4,4 ', 5,5'-Tetraphenylbiimidazole, 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'-tetraphenyl biimidazole etc. are mentioned.
Ketooxime ester is 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutane-
2-one, 3-propionyloxyiminobutan-2-
On, 2-acetoxyiminopentan-3-one, 2-
Acetoxyimino-1-phenylpropan-1-one,
2-Benzyloxyimino-1-phenylpropane-1
-One, 3-p-toluenesulfonyloxyiminobutan-2-one, 2-ethoxycarbonyloxyimino-
1-phenylpropan-1-one and the like can be mentioned. Specific examples of the compound represented by the general formula (IV) or (V) include the following.

[0072]

[Chemical 47]

[0073]

[Chemical 48]

[0074]

[Chemical 49]

[0075]

[Chemical 50]

[0076]

[Chemical 51]

The content concentration of these photoinitiator systems in the compositions according to the invention is usually low. On the other hand, if the amount is inappropriately large, undesired results such as the blocking of effective rays will occur. The amount of the photopolymerization initiator system in the present invention is 0.01% to 60% based on the total amount of the photopolymerizable ethylenically unsaturated compound and the linear organic high molecular polymer optionally added. It is preferably used in the range. More preferably 1% to 30
Get good results with%. The ratio of the component (ii), which is a component as a photopolymerization initiator used in the present invention, to the components (iii) and (iv) is such that the ratio of the component (iii) to the organic dye of the component (ii) is 1 part by weight. , (Iv) is preferably 0.05 to 30 parts by weight, more preferably 0.1 to
10 parts by weight, most preferably 0.2 to 5 parts by weight. The photopolymerizable composition of the present invention preferably contains a linear organic high molecular polymer as a binder. As such a "linear organic high molecular polymer", any linear organic high molecular polymer having compatibility with the photopolymerizable ethylenically unsaturated compound may be used. Absent.
A linear organic high molecular polymer which is soluble or swellable in water or weak alkaline water, which enables water development or weak alkaline water development, is preferably selected. The linear organic high molecular polymer is selected and used not only as a film-forming agent for the composition but also as a developer for water, weak alkaline water or an organic solvent. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such a linear organic high molecular polymer include an addition polymer having a carboxylic acid group in the side chain,
For example, JP-A-59-44615 and JP-B-54-343.
No. 27, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25
957, JP-A-54-92723, and JP-A-59-5.
No. 3836, JP-A-59-71048, that is, methacrylic acid copolymer, alkaline acid copolymer, itaconic acid copolymer, crotonic acid copolymer,
Examples include maleic acid copolymers and partially esterified maleic acid copolymers. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in its side chain.

Besides these, addition polymers having a cyclic acid anhydride added to an addition polymer having a hydroxyl group are useful. In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / another addition-polymerizable vinyl monomer if necessary] copolymer and [allyl (meth) acrylate / (meth) acrylic acid / optionally And other addition-polymerizable vinyl monomers] copolymers are preferred. In addition, polyvinylpyrrolidone, polyethylene oxide, etc. are useful as the water-soluble linear organic polymer. In addition, alcohol-soluble nylon or 2,2-bis- (4-
Polyethers of hydroxyphenyl) -propane and epichlorohydrin are also useful. These linear organic high molecular weight polymers can be mixed in arbitrary amounts in the entire composition. However, when it exceeds 90% by weight, favorable results are not obtained in terms of the strength of the formed image. Preferably 30
~ 85%. The weight ratio of the photopolymerizable ethylenically unsaturated compound and the linear organic polymer is 1/9 to 7 /.
The range of 3 is preferable. A more preferable range is 3 /
It is 7 to 5/5.

Further, in the present invention, in addition to the above basic components, a small amount of thermal polymerization is prevented in order to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated compound during the production or storage of the photosensitive composition. It is desirable to add agents. Suitable thermal polymerization inhibitors include haloid quinone, 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), N-nitrosophenylhydroxyamine primary cerium salt and the like can be mentioned. The amount of the thermal polymerization inhibitor added is preferably about 0.01% to about 5% based on the weight of the entire composition. Further, 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 during the drying process after coating. . The amount of higher fatty acid derivative added is
About 0.5% to about 10% of the total composition is preferred. Further, a dye or a pigment may be added for the purpose of coloring the photosensitive layer. The amount of dye and pigment added is preferably about 0.5% to about 5% of the total composition. In addition, inorganic fillers and other known additives may be added to improve the physical properties of the cured film.

When the photopolymerizable composition of the present invention is coated on a support, it is dissolved in various organic solvents before use. 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, lactic acid For example, ethyl. These solvents can be used alone or as a mixture. Then, the concentration of the solid content in the coating solution is appropriately 2 to 50% by weight. The coating amount is about 0.1 g / m ² to about 10 g / by dry weight.
A range of m ² is appropriate. It is more preferably 0.5 to 5 g / m ² .

As the support, a dimensionally stable plate-like material is used. Examples of the dimensionally stable plate-like material include paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), and aluminum (including aluminum alloy), zinc, copper, etc. Metal plates, further, plastic films such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc. Examples include paper or plastic films laminated or vapor-deposited with the above metals. Of these supports,
Aluminum plates are particularly preferable because they are extremely dimensionally stable and inexpensive. Furthermore, Japanese Examined Japanese Patent Publication 48-183
Composite sheets in which an aluminum sheet is bonded onto a polyethylene terephthalate film as described in No. 27 are also preferred.

Further, in the case of a support having a surface of a metal, particularly aluminum, surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodization treatment. It is preferable that Furthermore, an aluminum plate that has been grained and then immersed in an aqueous sodium silicate solution can be preferably used. As described in JP-B-47-5125, an aluminum plate subjected to anodizing treatment and then immersed in an aqueous solution of an alkali metal silicate is preferably used. The anodizing treatment is, for example, 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 an aqueous solution or non-aqueous solution of a salt thereof, or an electrolytic solution obtained by combining two or more kinds. It is carried out by passing an electric current through the aluminum plate as an anode. Further, silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective. Further, JP-B-46-27481 and JP-A-52-586.
No. 02, JP-A No. 52-30503, and a surface treatment in which a support subjected to electrolytic graining is combined with the anodizing treatment and sodium silicate treatment are also useful.

Further, it is also preferable to use mechanical graining, chemical etching, electrolytic graining, anodizing treatment and sodium silicate treatment in that order, as disclosed in JP-A-56-28893. Further, after these treatments, a water-soluble resin, for example, polyvinylphosphonic acid, a polymer or copolymer having a sulfonic acid group in the side chain, polyacrylic acid, a water-soluble metal salt (for example, zinc borate), or Those undercoated with a yellow dye, an amine salt or the like are also suitable. These hydrophilization treatments are performed in order to make the surface of the support hydrophilic, prevent the harmful reaction of the photopolymerizable composition provided thereon, and improve the adhesion of the photosensitive layer. And so on. On the layer of the photopolymerizable composition provided on the support, in order to prevent the polymerization inhibiting action by oxygen in the air, for example, polyvinyl alcohol, particularly polyvinyl alcohol having a saponification degree of 99% or more, acidic celluloses, etc. You may provide the protective layer which consists of such a polymer excellent in oxygen barrier property. For the coating method of such a protective layer, see, for example, US Pat.
No. 3,458,311 and JP-A No. 55-49729. Further, the photopolymerizable composition of the present invention can be used in ordinary photopolymerization reaction. Further, it can be applied to various fields such as a photoresist when producing a printing plate, a printed circuit board and the like. In particular, the photopolymerizable composition of the present invention is characterized by high sensitivity and a wide range of spectral sensitivity characteristics up to the visible light region, so that when it is applied to a light-sensitive material for visible light laser such as Ar ⁺ laser, good effects can be obtained.

The photosensitive material using the photopolymerizable composition of the present invention is subjected to imagewise exposure, and then the unexposed portion of the photosensitive layer is removed with a developer to obtain an image. Preferred developing solutions for using these photopolymerizable compositions for preparing lithographic printing plates are JP-B-57-74.
No. 27, there may be mentioned developing solutions such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium triphosphate, dibasic sodium phosphate and triphosphorus. Ammonium acid,
Aqueous solutions of inorganic alkali agents such as dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. and organic alkali agents such as monoethanolamine or diethanolamine are suitable. It is added so that the concentration of the alkaline solution is 0.1 to 10% by weight, preferably 0.5 to 5% by weight. Further, the alkaline aqueous solution, if necessary, a surfactant, benzyl alcohol, 2-phenoxyethanol,
A small amount of organic solvent such as 2-butoxyethanol may be included. For example, those described in US Pat. Nos. 3,375,171 and 3,615,480 can be mentioned. Furthermore, JP-A-50-26601 and 58-54341.
The developing solutions described in JP-B Nos. 56-39464 and 56-42860 are also excellent.

[0085]

【The invention's effect】

The photopolymerizable composition of the present invention has high sensitivity to actinic rays in a wide range from ultraviolet light to visible light. Therefore, ultra-high pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet laser lamps, fluorescent lamps, tungsten lamps, and sunlight are used as light sources. it can.

[0086]

【Example】

The present invention is described below with reference to examples, but the present invention is not limited to these examples. Examples 1 to 24, Comparative Examples 1 to 15 An aluminum plate having a thickness of 0.30 mm was grained on its surface using a nylon brush and an aqueous suspension of 400 mesh pumice, and then washed thoroughly with water. 60% at 70 ° C in 10% sodium hydroxide
After dipping for 2 seconds for etching, it was washed with running water, neutralized with 20% nitric acid, and then washed with water. This is V _A = 12.7
Under the condition of V, electrolytic surface roughening treatment was performed in a 1% nitric acid aqueous solution using a sinusoidal alternating current with an electric quantity of 160 coulomb / dm ^{2 at} the anode time. When the surface roughness was measured,
It was 0.6 μ (Ra indication). Subsequent immersion in 30% sulfuric acid aqueous solution and desmutting at 55 ° C for 2 minutes followed by 2
Anodizing treatment was carried out for 2 minutes in a 0% sulfuric acid aqueous solution so that the thickness of the anodized film was 2.7 g / m ² at a current density of 2 A / dm ² . On the thus treated aluminum plate, a photosensitive composition having the following composition was applied so that the dry coating weight was 1.4 g / m ^2, and dried at 80 ° C. for 2 minutes to form a photosensitive layer.

Trimethylolpropane tri (acryloyl oxypropyl) ether 2.0 g Allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio 80/20) 2.0 g Photoinitiator X g Fluorine-based nonionic surfactant Agent 0.03 g Methyl ethyl ketone 20 g Propylene glycol monomethyl ether acetate 20 g Polyvinyl alcohol (saponification degree 86.5
~ 89 mol%, 3 wt% aqueous solution with a degree of polymerization of 1000) is applied so that the dry coating weight is 2 g / m ^2, and the temperature is 100 ° C.
/ Dried for 2 minutes. The photosensitivity test was conducted with visible light. As the visible light, a xenon lamp was used as a light source, and monochromatic light obtained through a Kenko optical filter BP-49 was used. Fuji PS step guide (made by Fuji Photo Film Co., Ltd., the transmission optical density of the first stage is 0.05 in sequence for the photosensitivity measurement)
0.15 step tablet with 15 steps to increase)
Was done using. Illuminance on photosensitive film surface is 0.0132m
The number of clear steps of the PS step guide when exposed for 240 seconds at W / cm ² is shown.

The development was carried out by immersing in the following developing solution at 25 ° C. for 1 minute. 1K Potassium silicate 30 g Potassium hydroxide 15 g C ₁₂ H ₂₅ -C ₆ H ₄ -OC ₆ H ₄ -SO ₃ Na 3 g Water 1000 g Sensitivity when the following compounds were used as photopolymerization initiators and their combinations were changed. The results are shown in Tables 1 and 2.

[0089]

[Chemical 52]

[0090]

[Chemical 53] From the results shown in Tables 1 and 2, it can be seen that the photopolymerizable composition of the present invention containing the component (iv) has high sensitivity.

[Table 9] Table 9 ─────────────────────────────────── Compound of Example (ii) (iii) ) Compound (iv) Compound BP-49 Filter No. (g) (g) (g) Number of clear steps at 240 seconds exposure ───────────────────── ─────────────── 1 I-6 (0.14) (iii) -1 (0.1) (iv) -1 (0.07) 15 2 〃 (iii) -2 (0 .1) 〃 12 3 〃 (iii) -3 (0.16) 〃 12 4 〃 (iii) -1 (0.1) (iv) -2 (0.065)> 15 5 〃 (iii) -2 (0.1 ) 〃 13 6 〃 (iii) -3 (0.16) 〃 13 7 I-11 (0.14) (iii) -1 (0.1) (iv) -1 (0.07) 13 8 〃 (iii) -2 (0 .1) 〃 10 9 〃 (iii) -3 (0.16) 〃 11 10 〃 (iii) -1 (0.1) (iv) -2 (0.065) 15 11 〃 (iii) -2 (0.1) 〃 11 12 〃 (iii) -3 (0.16) 〃 11 13 II-10 (0.087) (iii) -1 (0.1) (iv) -1 (0.07) 11 14 〃 (iii) -2 (0. 1) 〃 9 15 〃 (iii) -3 (0.16) 〃 10 16 〃 (i ii) -1 (0.1) (iv) -2 (0.065) 12 17 〃 (iii) -2 (0.1) 〃 10 18 〃 (iii) -3 (0.16) 〃 11 19 II-13 (0.16 ) (iii) -1 (0.1) (iv) -1 (0.07) 13 20 〃 (iii) -2 (0.1) 〃 10 21 〃 (iii) -3 (0.16) 〃 10 22 〃 (iii ) -1 (0.1) (iv) -2 (0.065) 14 23 〃 (iii) -2 (0.1) 〃 11 24 〃 (iii) -3 (0.16) 〃 11 ──────── ────────────────────────────

[Table 10] Table 10 ─────────────────────────────────── Compound of Comparative Example No (ii) ( Compound of iii) BP-49 filter Number of clear steps at 240 second exposure ──────────────────────────────────── 1 I-6 (0.14) (iii) -1 (0.1) 13 2 〃 (iii) -2 (0.1) 10 3 〃 (iii) -3 (0.16) 10 4 I-11 (0.14) ( iii) -1 (0.1) 11 5 〃 (iii) -2 (0.1) 8 6 〃 (iii) -3 (0.16) 8 7 II-10 (0.087) (iii) -1 (0.1) 9 8 〃 (iii) -2 (0.1) 7 9 〃 (iii) -3 (0.16) 8 10 II-13 (0.16) (iii) -1 (0.1) 11 11 〃 (iii) -2 ( 0.1) 8 12 〃 (iii) -3 (0.16) 8 ───────────────────────────────────

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area G03F 7/038

Claims (1)

[Claims] 1. A light containing the following components (i) to (iv):
Polymerizable composition. (i) A polymerizable compound having an addition-polymerizable unsaturated bond. (ii) A compound represented by the following general formula (I) or (II). [Chemical 1]Where Z¹And Z²Is benzimidazole or naphth
The non-metal atomic groups necessary to form the toymidazole ring
It may be the same or different. R¹, R², R
³And R^FourCan be the same or different, each
It represents an alkyl group which may be substituted. X₁ ^-Is a pair
Represents an anion, and n is 0 or 1. [Chemical 2]In the formula, Q¹, Q²Is an oxygen atom, a sulfur atom or -C (R⁷)
(R⁸)-, -NR⁹Represents-and may be the same or different.
R^Five, R⁶, R⁷, R⁸, R⁹Are the same or different
Also represents an optionally substituted alkyl group. Q³
Represents an oxygen atom or a sulfur atom. Z³Is -C (R^Ten)
(R¹¹) -C (R¹²) (R¹³)-, -C (R¹⁴) = C (R¹⁵)-Or benzoi
Midazole, benzoxazole, benzothiazole,
Naphthoimidazole, naphthoxazole, naphthothia
Represents a group of non-metal atoms necessary to form a sol ring. R
^Ten~ R¹⁵Is R^FiveIs synonymous with or represents a hydrogen atom. (iii) (a) a compound having a carbon-halogen bond,
(B) Aromatic onium salt, (c) Organic peroxide, (d)
A thio compound represented by the following general formula (III):(Where R¹⁶Is an alkyl group, an aryl group or a substituted group
Indicates a reel group, R¹⁷Represents a hydrogen atom or an alkyl group
You Also, R¹⁶And R¹⁷Are bound to each other by oxygen, sulfur,
And optionally containing a heteroatom selected from nitrogen atoms 5
The non-metallic atomic groups necessary to form a 7-membered ring
You ), (V) hexaarylbiimidazole, and
(F) A small amount selected from the group consisting of ketoxime esters.
At least one compound. (iv) a compound represented by the following general formula (IV) or (V)
At least one compound selected from. [Chemical 4]In the formula, Ar is an aromatic group selected from one of the following general formulas.
Indicates R¹⁸, R¹⁹Can be the same or different, water
Represents an elementary atom or an alkyl group, and R¹⁸And R¹⁹Are each other
They may be bonded to each other to represent an alkylene group. [Chemical 5]Where R²⁰, R^{twenty one}, R^{twenty two}, R^{twenty three}And R^{twenty four}Are identical to each other
May be different from each other, and each may be a hydrogen atom or a halogen atom.
Child, alkyl group, alkenyl group, aryl group, substituted ant
Group, hydroxyl group, alkoxy group, substituted alkoxy group,-
SR²⁶Group, -SO-R²⁶Group or -SO₂R²⁶Represents
However, R²⁰, R^{twenty one}, R^{twenty two}, R^{twenty three}And R^{twenty four}At least
One is -SR²⁶Group, -SO-R²⁶Group or -SO₂R²⁶
Represents a group, R²⁶Is an alkyl group or an alkenyl group, R^{twenty five}Is
Represents a hydrogen atom, an alkyl group or an acyl group, Y¹Is hydrogen
Atom or(In the formula, R²⁹, R³⁰, R³¹And R³²Are the same or different
Optionally substituted or unsubstituted alkyl
Group, substituted or unsubstituted aryl group, substituted or unsubstituted aryl group
A alkenyl group, a substituted or unsubstituted alkynyl group, or
A substituted or unsubstituted heterocyclic group, R²⁹, R³⁰, R³¹Over
And R³²Is a combination of two or more groups forming a cyclic structure.
May be. However, R²⁹, R³⁰, R³¹And R³²Out of
At least one is an alkyl group. A⁺Is alkaline gold
Indicates a genus cation or a quaternary ammonium cation
You ) At least one compound selected from the group consisting of
object.