JPH08262715A - Photopoylymerizable composition - Google Patents

Abstract

PURPOSE: To obtain a photopolymerizable compsn. having high sensitivity to active light in a wide region from UV to visible light. CONSTITUTION: This photopolymerizable compsn. contains an addition- polymerizable compd. having an ethylenically unsatd. double bond, a sensitizing dye represented by the formula and a titanocene compd. In the formula, each of X<100> and Y<100> is O, S, -C(R<300> )(R<400> ) or -NR<500> -, each of R<100> -R<500> is optionally substd. alkyl, Q<100> is O or S, Z<100> is -C(R<600> )(R<700> )-C(R<800> )(R<900> )-, -C(R<1000> )=C(R<1100> ) or a group of nonmetallic atoms required to form a benzimidazole, benzoxazole, benzothiazole, naphthimidazole, naphthoxazole or naphtho-thiazole ring and each of R<600> -R<1100> is H or has the same meanings as R<100> .

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photopolymerizable composition. In particular, the present invention relates to a photopolymerizable composition which has extremely high sensitivity to light rays in the visible light region and exhibits good sensitivity to, for example, Ar ⁺ laser and YAG-SHG laser light sources.

[0002]

2. Description of the Related Art Conventionally, many image forming methods using a photopolymerization system are known and used in a wide variety of fields such as printing plates, printed circuits, paints, inks, hologram recording, and three-dimensional modeling. For example, a photopolymerizable composition comprising a compound containing an addition-polymerizable ethylenic double bond, a photopolymerization initiator, and optionally an organic polymer binder and a thermal polymerization inhibitor is coated on a support. A method of forming a cured relief image by forming a layer, polymerizing and curing the exposed portion by imagewise exposing the desired image, and dissolving and removing the unexposed portion.
A layer of the above-mentioned photopolymerizable composition is provided between two supports, at least one of which is transparent, and the support is peeled off after image exposure from the transparent support side to induce a change in adhesive strength by light. To form an image, a photopolymerizable composition and a photosensitive material provided with a microcapsule layer having a color material such as a leuco dye in its contents, and the photosensitive material is imagewise exposed to expose the capsules of the exposed portion to light. Harden and destroy the unexposed part of the capsule by pressure treatment or heat treatment,
Color material: A method of forming a colored image by developing a color by contacting with a color developer, an image forming method utilizing a change in toner adhesion of a photopolymerizable composition by light, a light of a photopolymerizable composition An image forming method and the like utilizing changes in the refractive index are known.

Photopolymerization composition applied to these methods
Most of the products are benzyl and benzoyl as photopolymerization initiators.
Ether, Michler's ketone, anthraquinone, acryl
Gin, phenazine, benzophenone, etc. have been used
Was. However, these photopolymerization initiators have 400 nm
Compared with the following photopolymerization initiation ability to ultraviolet light, 400
Remarkably low photopolymerization initiation ability for visible light above nm
As a result, its application range was significantly limited. Near
Years, with the development of image forming technology,
There is a demand for a photopolymer having high sensitivity.
For example, non-contact type projection exposure plate making or visible light laser.
-It is a photosensitive material suitable for plate making. The visible light laser
As Ar ⁺Laser 488nm light, YAG-SHG
Lasers such as 532 nm light are considered promising.

Many proposals have hitherto been made for a photopolymerization initiation system capable of being sensitive to light rays in the visible light region. For example, certain photosensitive dyes described in U.S. Pat. No. 2,850,445, complex initiation system of dye and amine (Japanese Patent Publication No. 44-20189), combination system of hexaarylbiimidazole, radical generator and dye. (Japanese Patent Publication Sho 45-3
7377), a system of hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (Japanese Patent Publication No. 47-
No. 2528, JP-A-54-155292), a system of a cyclic cis-α-dicarbonyl compound and a dye (JP-A-54-8).
4183), a system of substituted triazine and merocyanine dye (JP-A-54-151024), and a system of 3-ketocoumarin and an activator (JP-A-52-112681, JP-A-58).
-15503), biimidazole, styrene derivative,
System of thiol (JP-A-59-140203), system of organic peroxide and dye (JP-A-59-140203, JP-A-59-189340), system of dye of rhodanine skeleton and radical generator ( JP-A-2-244050) and the like.

Further, the fact that titanocene is effective as a photopolymerization initiator is found in JP-A-59-152396, JP-A-61-151197, JP-A-63-10602, and JP-A-63-41484. It is described in JP-A-3-12403, and an example of use as a combination system is a system of titanocene and 3-ketocoumarin dye (JP-A-63-221).
No. 110), a system in which a titanocene, a xanthene dye, and an addition-polymerizable ethylenically unsaturated compound containing an amino group or a urethane group are combined (JP-A-4-22195).
No. 8, JP-A-4-219756), a system of titanocene and a specific merocyanine dye (JP-A-6-295061).
Etc. can be mentioned. However, although these prior arts are certainly effective for visible light, they have insufficient sensitivity or exhibit high sensitivity, but have problems such as poor storage stability and cannot be put to practical use.

[0006]

An object of the present invention is to provide a photopolymerizable composition having high sensitivity. Especially 400
It is an object of the present invention to provide a photopolymerizable composition having a high sensitivity to visible light having a wavelength of not less than nm, light having a wavelength of 488 nm or 532 nm, which corresponds to the output of an Ar ⁺ laser or a YAG-SHG laser light source. Still another object of the present invention is to provide a photopolymerizable composition having excellent storage stability.

[0007]

Means for Solving the Problems As a result of intensive research aimed at achieving the above object, the present inventor can generate active radicals upon irradiation with light in the presence of a dye having a specific structure and the sensitizing dye. The inventors have found that the combined system of the titanocene compounds has extremely high sensitivity to visible light of 400 nm or more and is excellent in storage stability, and arrived at the present invention. That is, the present invention comprises a photopolymerization containing an addition-polymerizable compound having at least one ethylenically unsaturated double bond, a sensitizing dye represented by the following general formula [I], and a titanocene compound. It is a sex composition. According to the present invention, a photopolymerizable composition having high sensitivity to light in the visible region and high storage stability can be obtained.

[0008]

Embedded image In the formula, X ¹⁰⁰ and Y ¹⁰⁰ are oxygen atom, sulfur atom or -C
(R ³⁰⁰ ) (R ⁴⁰⁰ ) −, —NR ⁵⁰⁰ —, which may be the same or different. R ¹⁰⁰ , R ²⁰⁰ , R ³⁰⁰ , R ⁴⁰⁰ and R
⁵⁰⁰ represents an alkyl group which may be substituted. Q ¹⁰⁰
Represents an oxygen atom or a sulfur atom. Z ¹⁰⁰ is -C (R
⁶⁰⁰ ) (R ⁷⁰⁰ ) -C (R ⁸⁰⁰ ) (R ⁹⁰⁰ )-, -C (R ¹⁰⁰⁰ )
═C (R ¹¹⁰⁰ ) — or a benzimidazole, benzoxazole, benzothiazole, naphthimidazole, naphthoxazole, or non-metal atom group necessary for forming a naphthothiazole ring. R ^{600 to} R ¹¹⁰⁰ is R ¹⁰⁰
Is synonymous with or represents a hydrogen atom.

In one embodiment of the present invention, the photopolymerization initiation system further contains at least one compound selected from the group consisting of (A) to (H). (A) Compound having carbon-halogen bond (b) Ketone compound represented by the following general formula [II]

[0010]

Embedded image Here, Ar represents an aromatic group selected from one of the following general formulas, R ³ and R ⁴ represent a hydrogen atom or an alkyl group, and R ³ and R ⁴ are bonded to each other to form an alkylene group. May be represented.

[0011]

[Chemical 4] However, in the formula, R ^{5 to} R ⁹ may be the same or different from each other, and each is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a substituted aryl group, a hydroxyl group, an alkoxy group, a —S—R ¹¹ group. , -SO-R ¹¹ group, -SO ₂
Represents an —R ¹¹ group, provided that at least one of R ^{5 to} R ⁹ represents a —S—R ¹¹ group or a —SO—R ¹¹ group, R ¹¹ represents an alkyl group, an alkenyl group, R ¹⁰ represents a hydrogen atom, Represents an alkyl group or an acyl group.

[0012]

Embedded image (C) a ketoxime compound represented by the following general formula [III]

[0013]

[Chemical 6] In the formula, R ¹² and R ¹³ are the same or different, and are a hydrocarbon group which may have a substituent and may contain an unsaturated bond,
Alternatively, it represents a heterocyclic group. R ¹⁴ and R ¹⁵ are the same or different and each is a hydrogen atom, a hydrocarbon group which may have a substituent and may contain an unsaturated bond, a heterocyclic group, a hydroxyl group, a substituted oxy group, a mercapto group, a substituted group. Represents a thio group. R ¹⁴ and R ¹⁵ are bonded to each other to form a ring,
-0-, -NR ^16- , -O-CO-, -NH-CO-, -S-, and / or -SO ₂ -may have 2 carbon atoms in the main chain.
To alkylene groups of 8 to 8 are represented. R ¹⁶ and R ¹⁷ are hydrogen atoms,
It represents a hydrocarbon group which may have a substituent or may contain an unsaturated bond, or a substituted carbonyl group. (D) Organic peroxide (e) Thio compound represented by the following general formula [IV]

[0014]

[Chemical 7] Here, R ¹⁸ represents an alkyl group, an aryl group or a substituted aryl group, and R ¹⁹ represents a hydrogen atom or an alkyl group. R ¹⁸ and R ¹⁹ represent a group of non-metal atoms necessary for forming a 5-membered to 7-membered ring which may be bonded to each other and may contain a hetero atom selected from oxygen, sulfur and nitrogen atoms. (He) Hexaarylbiimidazole (G) Aromatic onium salt (H) Keto oxime ester

The present invention will be described in detail below. The polymerizable compound having an addition-polymerizable unsaturated bond of the present invention is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. 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 esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid) with aliphatic polyhydric alcohol compounds, and unsaturated Examples thereof include amides of carboxylic acids and aliphatic polyvalent amine compounds.

Specific examples of the monomer of the ester of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylic acid esters 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.

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, propylene glycol diitaconate, 1,3-butanediol diitaconate,
1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate and the like. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and 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 tris acrylamide, xylylene bis acrylamide, xylylene bis methacrylamide 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 ′ represent H or CH ₃ ), and are described in JP-A-51-37193. Urethane acrylates such as those described in 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%.

Next, the photopolymerization initiation system which is the second essential component of the photopolymerizable composition of the present invention will be described. The photopolymerization initiation system of the present invention comprises a combination of at least two components, and the first component is a sensitizing dye represented by the general formula [I]. Examples of the benzimidazole ring or naphthimidazole ring formed by Z ¹⁰⁰ include 1-alkylbenzimidazole and 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,
1- Arirunafuto [1,2-d] imidazole is preferred, as the R ¹⁰⁰ to R ^500, 1 to 18 carbon atoms, preferably 1 to 7, particularly preferably 1 to 4 alkyl groups (e.g., methyl group, Ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, octyl group, dodecyl group, octadecyl group), substituted alkyl group (eg aralkyl group (eg benzyl group, 2-phenylethyl group), hydroxyalkyl group) (For example, 2-hydroxyethyl 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-sulfatopropyl 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, carbo Methoxymethyl group, 2-methanesulfonylaminoethyl group} is preferable.

The sensitizing dye represented by the general formula (I) used in the present invention is a heterocyclic compound-cyanine soybean and relayed compound ("Heterocyclic compounds-Cyanine dyes and related").
d compounds- ") chapter IV, V, VI, pages 86-19
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 St
It can be easily synthesized based on the method described by urmer, John Wiley & Sons (New York, London), 1977. Representative examples of the compound of the general formula (I) used in the present invention are shown below, but the scope of the present invention is not limited to these compounds.

[0024]

Embedded image

[0025]

[Chemical 9]

[0026]

[Chemical 10]

[0027]

[Chemical 11]

The sensitizing dye represented by the general formula [I] used in the photopolymerizable composition of the present invention can be preferably used alone or in combination of two or more kinds. Next, the titanocene compound which is important in the photopolymerization initiation system of the present invention will be described. The titanocene compound of the present invention is a titanocene compound capable of generating an active radical when irradiated with light in the presence of the above-mentioned sensitizing dye, and examples thereof include JP-A-59-15.
Known compounds described in JP-A No. 2396 and JP-A No. 61-151197 can be appropriately selected and used.

More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-
Ti-bis-2,3,4,5,6-pentafluorophen-1-yl (hereinafter referred to as A-1), di-cyclopentadienyl-Ti-bis-2,3,5,6-tetra Fluorophen-1-yl, di-cyclopentadienyl-Ti
-Bis-2,4,6-trifluorophen-1-yl,
Di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-cyclopentadienyl-
Ti-bis-2,4-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,
4,5,6-Pentafluorophen-1-yl (hereinafter A
-2), di-methylcyclopentadienyl-Ti
-Bis-2,3,5,6-tetrafluorophenyl-1-
Di-methylcyclopentadienyl-Ti-bis-
2,4-difluorophen-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyr-1-yl) phenyl) titanium (hereinafter referred to as A-3) and the like. be able to.

The titanocene compound used in the photopolymerizable composition of the present invention can be used alone or in combination of two or more kinds. The amount of the sensitizing dye constituting the photopolymerization initiation system used in the photopolymerizable composition of the present invention described above and the titanocene compound is 0.05 to 100 parts by weight of the ethylenic compound. 30 parts by weight, preferably 0.
1 to 20 parts by weight, more preferably 0.2 to 10 parts by weight, the titanocene compound is 0.5 to 100 parts by weight, preferably 1 to 80 parts by weight, more preferably 2 to 50 parts by weight. Appropriate.

The photopolymerizable composition of the present invention may contain, in addition to the sensitizing dye and the titanocene compound, compounds (a) to (h) described below for the purpose of improving sensitivity. As the compound (a) having a carbon-halogen bond, compounds represented by the following general formulas [V] to [XI] are preferable. General formula [V]

[Chemical 12]

(In the formula, X represents a halogen atom. Y²
Is −CX₃, -NH₂, -NHR^{twenty one}, -NR ^{twenty one} ₂, -OR^{twenty one}Represents
You Where R^{twenty one}Is an alkyl group, a substituted alkyl group, an aryl
And a substituted aryl group. Also R²⁰Is −CX₃, A
Alkyl group, substituted alkyl group, aryl group, substituted aryl
And a substituted alkenyl group. ) Compounds
Stuff.

General formula [VI]

[0034]

[Chemical 13]

(Wherein R ²² 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 Is a halogen atom, and n is an integer of 1 to 3.).

The general formula [VII] ^{_{R 23 -Z 3 -CH 2-m}} X m -R 24 ( provided that, R ²³ is an aryl group or a substituted aryl group, R ²⁴ is -CO-NR ²⁵ R ^26,

[0037]

Embedded image

Or halogen, Z ³ is --CO--,-
CS- or -SO ₂ - and is, R ^25, R ²⁶ is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl radical, R of R ²⁷ is the general formula [VI] ^The same as ²² and m is 1 or 2. ) The compound represented by. General formula [VIII]

[0039]

[Chemical 15]

However, in the formula, R ²⁸ is an optionally substituted aryl group or heterocyclic group, and R ²⁹ is 1 to 1 carbon atom.
It is a trihaloalkyl group or a trihaloalkenyl group having three, and p is 1, 2 or 3.

General formula [IX]

[0042]

Embedded image

However, L is a hydrogen atom or the formula: CO- (R ³⁰ ) _n
(CX ₃ ) _{m is} a substituent, M is a substituted or unsubstituted alkylene group, Q ² is a sulfur, selenium or oxygen atom, a dialkylmethylene group, an alkene-1,2-ylene group,
1,2-phenylene group or NR ³¹ group, M + Q together form a 3 or 4 membered ring, R ³¹ is an alkyl group, an aralkyl group or an alkoxyalkyl group, and R
³⁰ is a carbocyclic or heterocyclic aromatic group, X is a chlorine, bromine or iodine atom, q = 0 and r = 1, or q = 1 and r = 1 or 2. ) A carbonylmethylene heterocyclic compound having a trihalogenomethyl group represented by:

General formula [X]

[0045]

[Chemical 17]

(Wherein X is a halogen atom, t is an integer of 1 to 3, s is an integer of 1 to 4, R ³² is a hydrogen atom or a CH _{3 -t} X _t group, and R is ³³ is an s-valent optionally substituted unsaturated organic group),
4-halogeno-5- (halogenomethyl-phenyl) -oxazole derivative.

General formula [XI]

[0048]

Embedded image

(However, X is a halogen atom, v is an integer of 1 to 3, u is an integer of 1 to 4, R ³⁴ is a hydrogen atom or a CH _3-v X _v group, and R is R 3. ³⁵ is a u-valent unsaturated organic group which may be substituted).
2- (halogenomethyl-phenyl) -4-halogeno-oxazole derivative.

Examples of such a compound having a carbon-halogen bond include those described by 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. Other, 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)-
Naphth-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.

[0051]

[Chemical 19]

[0052]

Embedded image

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.

[0054]

[Chemical 21]

[0055]

[Chemical formula 22] Further, compounds described in JP-A-5-281728, for example,

[0056]

[Chemical formula 23]

And the like.

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.

[0059]

[Chemical formula 24]

[0060]

[Chemical 25]

[0061]

[Chemical formula 26]

[0062]

[Chemical 27]

[0063]

[Chemical 28]

[0064]

[Chemical 29]

[0065]

Embedded image

[0066]

[Chemical 31]

[0067]

Embedded image

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

[0069]

[Chemical 33]

[0070]

[Table 1] R ³⁸ M R ³⁶ a CX ₃ 1 C ₂ H ₅ 1,2-phenylene H 1 4-CCl ₃ 2 CH ₂ C ₆ H ₅ 1,2-phenylene H 1 4-CCl ₃ 3 C ₂ H ₅ 1,2 -Phenylene H 1 3-CCl ₃ 4 C ₂ H ₅ 1,2-phenylene H 1 4-CF ₃ 5 C ₂ H ₅ 5-CH ₃ -1,2-phenylene H 0 CCl ₃ 6 CH ₂ C ₆ H ₅ 1,2-phenylene _{H 0 CCl 3 7 C 2 H} 4 OCH 3 1,2- phenylene H 1 4-CCl ₃ or compounds described in German Patent No. 3,021,590,

[0071]

Embedded image

Alternatively, the group of compounds described in German Patent No. 3021599, for example,

[0073]

Embedded image

The following may be mentioned. Next, the ketone compound represented by the general formula [II] of the component (b) used in the present invention will be described. Here, R ³ and R ⁴ represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Also R ³ ,
R ⁴ may be bonded to represent an alkylene group. R ⁵ ~ R
⁹ is independently of each other a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, an aryl group, an alkoxy group having 1 to 12 carbon atoms, a hydroxyl group, S-R ¹¹ group, -SO-R ¹¹ group, -S
Represents an O ₂ -R ¹¹ group, R ¹¹ represents an alkyl group or an alkenyl group, R ¹⁰ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an acyl group having 2 to 13 carbon atoms. These alkyl groups, aryl groups, alkenyl groups,
The acyl group may be further substituted with a substituent having 1 to 6 carbon atoms. As a concrete example, US Pat.
The following compounds described in 8,791 and European Patent No. 0284561A can be mentioned.

[0075]

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[0076]

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[0077]

[Chemical 38]

Next, the ketoxime compound represented by the general formula [III] of the component (c) used in the present invention will be explained. In the formula, R ¹² and R ¹³ are the same or different and each represents a hydrocarbon group which may have a substituent and may contain an unsaturated bond, or a heterocyclic group. R ¹⁴ and R ¹⁵ are the same or different and each is a hydrogen atom, a hydrocarbon group which may have a substituent and may contain an unsaturated bond, a heterocyclic group, a hydroxyl group, a substituted oxy group, a mercapto group, a substituted group. Represents a thio group. R ¹⁴ and R ¹⁵ are bonded to each other to form a ring, and -0-, -NR ^16- , -O-CO-, -NH-CO-, -S-, and / or
Alternatively, it represents an alkylene group having 2 to 8 carbon atoms, which may contain -SO ₂ -in the linking main chain of the ring. R ¹⁶ and R ¹⁷ represent a hydrogen atom, a hydrocarbon group which may have a substituent and may contain an unsaturated bond, or a substituted carbonyl group. The following compounds can be mentioned as specific compounds, but the compounds are not limited thereto.

[0079]

[Chemical Formula 39]

[0080]

[Chemical 40]

[0081]

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[0082]

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[0083]

[Chemical 43]

[0084]

Examples of the organic peroxide of component (d) used in the present invention include compounds having an oxygen-oxygen bond in the molecule. For example, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,
3,5-trimethylcyclohexanone peroxide,
Methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tertiarybutylperoxy) -3,3,5-trimethylcyclohexane, 1,1, -bis (tertiarybutylperoxy)
Cyclohexane, 2,2-bis (tertiarybutylperoxy) butane, tert-butylhydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paraffin 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 peroxy. Carbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxy neodecanoate, tert-butyl peroxyoctano Ato,
Tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxybenzoate,
Ditertiary butyl peroxyisophthalate, 2,
5-dimethyl-2,5-di (benzoylperoxy) hexane, tert-butyl peroxymaleic 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) 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 ester systems such as di-t-butyldiperoxyisophthalate are preferred.

The thio compound as the component (e) used in the present invention is represented by the above general formula (IV). General formula (I
The alkyl group for R ¹⁸ and R ¹⁹ in V) is preferably one having 1 to 4 carbon atoms. The aryl group of R ¹⁸ 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 (IV) include the compounds shown in the table below.

[0090]

[Table 2] No. R ¹⁸ R ¹⁹ 1 H H 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 2 -C (CH _{3) 2 -S- 21 - (CH} 2) 2 -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 - _{- 26 - (CH 2) 2} CH (CH 3) -S- 27 - (CH 2) 3 -O- 28 - (CH 2) 5 - 29 -C 6 C 4 -O- 30 -N = C (SCH ₃ ) -S- 31 -C ₆ H ₄ -NH-

[0091]

[Chemical 44]

[0092]

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As the hexaarylbiimidazole of the component (f) used in the present invention, 2,2'-bis (o-
Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 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.

As the aromatic onium salt of the component (g) used in the present invention, there are V, VI and VII of the periodic table.
Group elements, specifically N, P, As, Sb, Bi, O, S, S
Included are aromatic onium salts of e, Te, or I. As such an aromatic onium salt, Japanese Examined Patent Publication No.
77, Japanese Patent Publication No. 52-14278, Japanese Patent Publication No. 52-14
The compound shown by No. 279 can be mentioned, and the following compounds can be specifically mentioned.

[0095]

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[0096]

[Chemical 47]

[0097]

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[0098]

[Chemical 49]

[0099]

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[0100]

[Chemical 51]

[0101]

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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. The ketooxyemster of the component (h) used in the present invention is 3
-Benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenyl Propan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p-toluenesulfonyloxyiminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropane-1- On and the like. These (A) to (H) additives can be used alone or in combination of two or more. The amount used is 0.05-10 with respect to 100 parts by weight of the ethylenic compound.
A range of 0 parts by weight, preferably 1 to 80 parts by weight, more preferably 3 to 50 parts by weight is suitable.

The content concentration of these photopolymerization initiation systems in the composition of the present 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 initiation system in the present invention is from 0.01% by weight to 6% 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 of 0% by weight. More preferably, 1 wt% to 30 wt% gives good results.

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 polymer may be used as long as it is a linear organic polymer having compatibility with the photopolymerizable ethylenically unsaturated compound. 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 not only used as a film forming agent for the composition,
Water, weakly alkaline water or an organic solvent is selected and used depending on the use as a developer. For example, when a water-soluble organic high molecular polymer is used, water development becomes possible. As such a linear organic high molecular polymer, an addition polymer having a carboxylic acid group in its side chain, for example, JP-A-59-44615 and JP-B-54 can be used.
-34327, Japanese Patent Publication 58-12577, Japanese Patent Publication 5
4-25957, JP-A-54-92723, JP-A-59-53836, and JP-A-59-71048, that is, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid. Examples thereof include copolymers, crotonic acid copolymers, maleic acid copolymers and partially esterified maleic acid copolymers. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition to these, addition polymers having a cyclic acid anhydride 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 / Other addition polymerizable vinyl monomers] copolymers are suitable if necessary. In addition, polyvinylpyrrolidone, polyethylene oxide, etc. are useful as the water-soluble linear organic polymer. Further, alcohol-soluble polyamide, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. are also useful for increasing the strength of the cured film. 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. It is preferably 30 to 85% by weight. The weight ratio of the photopolymerizable ethylenically unsaturated compound to the linear organic polymer is preferably in the range of 1/9 to 7/3. A more preferable range is 3/7 to 5/5.

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-nitrosophenylhydroxylamine primary cerium salt, N-nitrosophenylhydroxylamine aluminum salt and the like.
The amount of the thermal polymerization inhibitor added is about 0, based on the weight of the entire composition.
01 wt% to about 5 wt% is preferred. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide is added to prevent polymerization inhibition by oxygen,
It may be unevenly distributed on the surface of the photosensitive layer during the drying process after coating. The amount of the higher fatty acid derivative added is preferably about 0.5% by weight to about 10% by weight of the total composition.

Further, a dye or a pigment may be added for the purpose of coloring the photosensitive layer. Examples of colorants include phthalocyanine pigments, azo pigments, carbon black,
Pigments such as titanium oxide, ethyl violet, crystal violet, azo dyes, anthraquinone dyes,
There are cyanine dyes. The amount of dye and pigment added is preferably about 0.5% to about 5% by weight of the total composition. In addition, known additives such as an inorganic filler and other plasticizers may be added to improve the physical properties of the cured film. Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate,
There are triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like. When a binder is used, it is 10 relative to the total weight of the ethylenic compound and the binder. It can be added in an amount of up to wt%.

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, methoxymethoxy Ethanol, diethylene glycol monomethyl ether, diethylene 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, .gamma.-butyrolactone, methyl lactate and ethyl lactate. 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 was about 0.1 g / m ^{2 by} weight after drying.
A range of from about 10 g / m ² is suitable. More preferably 0.
It is 5 to 5 g / m ² . As the above 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. Among these supports, the aluminum plate is particularly preferable because it is dimensionally remarkably stable and inexpensive. Further, a composite sheet in which an aluminum sheet is bonded onto a polyethylene terephthalate film as described in JP-B-48-18327 is also preferable.

In the case of a support having a surface of metal, especially aluminum, surface treatment such as graining, dipping in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodization. It is preferable that Further, an aluminum plate that is grained and then immersed in an aqueous solution of sodium silicate can be preferably used. After anodizing the aluminum plate as described in JP-B-47-5125,
What is 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.

Also, silicate electrodeposition as described in US Pat. No. 3,658,662 is effective. Furthermore,
JP-B-46-27481, JP-A-52-58602
A surface treatment in which a support subjected to electrolytic graining as disclosed in JP-A-52-30503 and a combination of the above anodic oxidation treatment and sodium silicate treatment is also useful.

Further, it is also preferable to use mechanical graining, chemical etching, electrolytic graining, anodic oxidation 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. Furthermore, a sol-gel treated substrate having a functional group capable of causing an addition reaction by a radical covalently bonded, as disclosed in Japanese Patent Application No. 5-304358, is also preferably used.

These hydrophilization treatments are carried out not only to make the surface of the support hydrophilic, but also to prevent harmful reaction of the photopolymerizable composition provided thereon, and to adhere the photosensitive layer. It is given to improve the sex. 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. A method for applying such a protective layer is described in, for example, US Pat. No. 3,458,
311 and JP-A-55-49729.

The photopolymerizable composition of the present invention can be used in ordinary photopolymerization reactions. 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, due to the high sensitivity which is a feature of the photopolymerizable composition of the present invention and a wide spectral sensitivity characteristic up to the visible light region,
When applied to a photosensitive material for visible light laser such as Ar ⁺ laser and YAG-SHG-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 developing solution to obtain an image. Preferred developing solutions when these photopolymerizable compositions are used for preparing a lithographic printing plate are the developing solutions described in JP-B-57-7427, sodium silicate and potassium silicate. , Such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium phosphate tribasic, sodium phosphate dibasic, ammonium phosphate tribasic, ammonium phosphate dibasic, sodium metasilicate, sodium bicarbonate, aqueous ammonia etc. Aqueous inorganic alkaline agents and aqueous solutions of organic alkaline 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.

If necessary, the alkaline aqueous solution may contain a small amount of a surfactant or an organic solvent such as benzyl alcohol, 2-phenoxyethanol or 2-butoxyethanol. For example, U.S. Pat. No. 3,375,
Nos. 171 and 3,615,480 may be mentioned. Further, JP-A-50-266
No. 01, No. 58-54341, Japanese Patent Publication No. 56-3946
The developing solutions described in Nos. 4 and 56-42860 are also excellent.

[0117]

The photopolymerizable composition of the present invention has high sensitivity to actinic rays in a wide range from ultraviolet light to visible light.
Therefore, as the light source, 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, sunlight, etc. Can be used.

[0118]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Examples 1 to 15 and Comparative Examples 1 to 6 An aluminum plate having a thickness of 0.30 mm and a nylon brush 40
The surface was grained with a 0 mesh water suspension of pumice and then thoroughly washed with water. After immersing in 10% sodium hydroxide at 70 ° C for 60 seconds for etching,
It was washed with running water, neutralized and washed with 20% nitric acid, and then washed with water. This was subjected to 160 coulomb / dm in a 1% nitric acid aqueous solution using a sinusoidal alternating current under the condition of V _A = 12.7V.
^The electrolytic surface roughening treatment was performed with the amount of electricity at the time of ^{2 as} the anode. The surface roughness was measured and found to be 0.6 μ (Ra indication).
Subsequently, it was immersed in a 30% sulfuric acid aqueous solution and desmutted at 55 ° C for 2 minutes.
Anodizing treatment was performed for 2 minutes so that the thickness of the anodized film at A / dm ² was 2.7 g / m ² .

On the aluminum plate thus treated, a photosensitive composition having the following composition was applied at a dry coating weight of 1.4 g /
It was coated so as to be m ^2, and dried at 80 ° C. for 2 minutes to form a photosensitive layer. Pentaerythritol tetraacrylate 1.5 g Allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio 80/20) 2.0 g Photopolymerization initiation system X g Fluorine-based nonionic surfactant 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. For the photosensitivity measurement, a Fuji PS step guide (manufactured by Fuji Photo Film Co., Ltd., a step tablet having a first stage transmission optical density of 0.05 and increasing sequentially by 0.15 to 15 stages) was used. The number of clear steps of the PS step guide when exposed for 240 seconds at an illuminance of 0.0132 mW / cm ² on the photosensitive film surface portion is shown.

After that, heating was carried out at 100 ° C. for 1 minute, and development was carried out by immersing in the following developing solution at 25 ° C. for 20 seconds. As 1K potassium silicate 30g potassium hydroxide _{15g C 12 H 25 -C 6 H} 4 -OC 6 H 4 -SO 3 Na 3g Water 1000g photopolymerization initiation system, the sensitivity when using the compounds described below, changed its combination The results are shown in Table 3. The unit of the number in () is g.

[0122]

[Table 3] Table 3 ──────────────────────────────── Example No. Sensitizing dye Titanocene compound Gray scale step number (Clear) 1 I-1 (0.05) A-1 (0.1) 5.5 2 I-4 (0.05) A-1 (0.1) 5 3 I-6 (0.05) A-1 (0. 1) 5 4 I-10 (0.05) A-1 (0.1) 5.5 5 I-13 (0.05) A-1 (0.1) 6.5 6 I-15 (0.05) A-1 ( 0.1) 5 7 I-20 (0.05) A-1 (0.1) 5.5 8 I-21 (0.05) A-1 (0.1) 5 9 I-22 (0.05) A-1 (0. 1) 6 10 I-1 (0.05) A-2 (0.1) 6.5 11 I-6 (0.05) A-2 (0.1) 6.5 12 I-13 (0.05) A-2 ( 0.1) 7 13 I-1 (0.05) A-3 (0.1) 6.5 14 I-6 (0.05) A-3 (0.1) 6 15 I-13 (0.05) A-3 (0. 1) 6.5 Comparative example No 1 I-1 (0.1) ── 0 2 I-10 (0.1) ── 0 3 I-13 (0.1) ── 0 4 ── A-1 (0.1) 0 5 ─ ─ A-2 (0.1) 0 6 ── A 3 (0.1) 0

Examples 16 to 38 Samples were prepared in the same manner as in Example 1 except that the photopolymerization initiation system of Example 1 was replaced with the compounds shown in Table 4, and the photosensitivity test was conducted. The results are shown in Table 4.

[Table 4] Table 4 ─────────────────────────────────── Example Examples Increasing dyes titanocene (a) (H) Gray scale No. compound Compound number of stages (clear) 16 I-13 (0.05) A-1 (O.1) (A) -1 (0.1) 7 17 I-13 (0.1) A-1 (O .15) (B) -2 (0.1) 7 18 I-13 (0.08) A-1 (O.2) (B) -3 (0.2) 7 19 I-13 (0.05) A-1 (O.1 ) II-1 (0.2) 7.5 20 I-13 (0.05) A-1 (O.1) II-7 (0.2) 7.5 21 I-13 (0.1) A-1 (O.2) III -6 (0.2) 7.5 22 I-13 (0.1) A-1 (O.2) III-9 (0.2) 7 23 I-13 (0.05) A-1 (O.1) (D) -1 (0.3) 7 24 I-13 (0.05) A-1 (O.1) (e) -1 (0.4) 7.5 25 I-13 (0.05) A-1 (O.15) (e) -2 (0.2) 7.5 26 I-13 (0.05) A-1 (O.1) (G) -1 (0.2) 7 27 I-13 (0.05) A-1 (O.2) (F) -1 (0.5) 7.5 28 I-13 (0.05) A-1 (O.1) (CH) -1 (0.2) 7 29 I-10 (0.1) A-1 (O.1) (A) -1 (0.1) 7 30 I-10 (0.05) A-3 (O.1) II-1 (0.1) 8 31 I-10 (0.05) A-2 (O.1) III-6 (0.2) 8 32 I -10 (0.1) A-3 (O.2) (e) -1 (0.4) 7.5 33 I-10 (0.1) A-1 (O.15) (f) -1 (0.5) 7.5 34 I-13 (0.1) A-3 (O.2) (I) -4 (0.2) 7.5 35 I-13 (0.1) A-2 (O.2) II-3 (0.4) 8 36 I-13 (0.05) A-1 (O.2) III-9 (0.4) 8 .5 37 I-13 (0.05) A-1 (O.1) (e) -2 (0.3) 7.5 38 I-13 (0.05) A-1 (O.1) (g) -1 (0.2 ) 7.5

(A) -1: 2- (p-trifluoromethylphenyl) -4,6-bis (trichloromethyl) -S-triazine (ii) -2: 2-phenyl-4,6-bis (trichloro) Methyl) -S-triazine (A) -3: 2-dichloromethyl-5-phenyl-1,3
4-Oxadiazole (a) -4: 2- (p-styrylphenyl) -4,6-bis (trichloromethyl) -S-triazine (d) -1: 3,3 ', 4,4'-tetra -(T-Butylperoxycarbonyl) benzophenone (ho) -1: 2-mercaptobenzothiazole (ho) -2: 2-mercapto-5-methoxy-benzimidazole (f) -1: 2,2'-bis ( o-chlorophenyl) -4,
4 ', 5,5'-Tetraphenylbiimidazole (to) -1: diphenyliodonium hexafluorophosphate (thi) -1: 3-benzyloxyiminobutan-2-one

From the results shown in Tables 3 and 4, those of the photopolymerizable composition of the present invention containing the sensitizing dye represented by the general formula [I] and the titanocene compound as the photopolymerization initiation system were high. It is found that the sensitivity is high, and that the composition including at least one of (A) to (H) in addition to this has higher sensitivity.

Claims (1)

[Claims] 1. A photopolymerizable compound containing an addition-polymerizable compound having at least one ethylenically unsaturated double bond, a sensitizing dye represented by the following general formula [I], and a titanocene compound. Composition. Embedded image In the formula, X ¹⁰⁰ and Y ¹⁰⁰ are oxygen atom, sulfur atom or -C
(R ³⁰⁰ ) (R ⁴⁰⁰ ) −, —NR ⁵⁰⁰ —, which may be the same or different. R ¹⁰⁰ , R ²⁰⁰ , R ³⁰⁰ , R ⁴⁰⁰ and R
⁵⁰⁰ represents an alkyl group which may be substituted. Q ¹⁰⁰
Represents an oxygen atom or a sulfur atom. Z ¹⁰⁰ is -C (R
⁶⁰⁰ ) (R ⁷⁰⁰ ) -C (R ⁸⁰⁰ ) (R ⁹⁰⁰ )-, -C (R ¹⁰⁰⁰ )
═C (R ¹¹⁰⁰ ) — or a benzimidazole, benzoxazole, benzothiazole, naphthimidazole, naphthoxazole, or non-metal atom group necessary for forming a naphthothiazole ring. R ^{600 to} R ¹¹⁰⁰ is R ¹⁰⁰
Is synonymous with or represents a hydrogen atom.