JP2001305734A - Photopolymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photopolymerizable composition excellent in work efficiency, profitableness and shelf stability and used as a material of an original plate for a planographic printing plate for scanning exposure fit for a CTP system or a planographic printing plate having high sensitivity to the oscillation wavelength of a low-cost short-wavelength semiconductor laser. SOLUTION: The photopolymerizable composition is not sensitive to light of >=500 nm, accords with a short-wavelength laser having the wavelength of light for exposure in the range of 350-450 nm and contains one electron transferring initiation system selected from (i) a system comprising an electron donative initiator and a sensitizing dye, (ii) a system comprising an electron accepting initiator and a sensitizing dye and (iii) a system comprising an electron donative initiator, a sensitizing dye and an electron accepting initiator (a ternary initiation system).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel photoinitiating system, and more particularly to a photosensitive composition containing a photoinitiating system having high sensitivity and excellent stability. In addition, the present invention particularly relates to a photosensitive composition excellent as a material for a lithographic printing plate precursor that can be made by scanning exposure based on digital signals. Further, for example, it is used in image formation such as stereolithography, holography, and color hard copy, in the field of manufacturing electronic materials such as photoresists, and in photocurable resin materials such as inks, paints, and adhesives.

[0002]

2. Description of the Related Art Hitherto, as a lithographic printing plate, a PS plate having a structure in which a lipophilic photosensitive resin layer is provided on a hydrophilic support has been widely used. After the mask exposure (surface exposure), the non-image portion is dissolved and removed to obtain a desired printing plate.

In recent years, digitalization techniques for electronically processing, storing, and outputting image information using a computer have become widespread, and various new image output methods corresponding to the technology have come into practical use. As a result, computer-to-plate (CTP) technology for scanning a highly directional light such as a laser beam in accordance with digitized image information and directly manufacturing a printing plate without passing through a lithographic film is desired. It is an important technical issue to obtain an adapted printing plate precursor.

As one method of obtaining such a lithographic printing plate capable of scanning exposure, conventionally, an ink-receiving photosensitive resin layer (hereinafter referred to as a photosensitive layer) formed on a hydrophilic support has a photosensitive speed. A configuration using a photopolymerizable composition having excellent properties has been proposed and is already on the market. The original plate of this configuration is easy to develop, and furthermore has resolution, inking property,
It has desirable printing plate and printing performance such as excellent printing durability and stain resistance.

[0005] The photopolymerizable composition basically comprises an ethylenically unsaturated compound, a photopolymerization initiation system and a binder resin. In image formation, the photoinitiation system absorbs light to generate active radicals and the ethylenically unsaturated compound. It causes addition polymerization of a saturated compound and insolubilizes the photosensitive layer. Most of the proposals for conventional photopolymerizable compositions capable of scanning exposure disclose the use of a photoinitiating system excellent in photosensitivity, for example, Bruce M. Monroe et al., Chemical Revue, 93, 435 ( 1
993). And RSDavidson, Journal of Photochemistry a
nd biology A: Chemistry, 73.81 (1993).

An Ar laser (488 nm) or FD-YA is used as a light source for the photopolymerizable composition comprising these photoinitiating systems.
In a conventional CTP system using a visible light source having a long wavelength such as a G laser (532 nm), it is desired to perform writing at a higher speed in order to increase the productivity of the plate making process. Not achieved because it is not high or the sensitivity of the photosensitive material is not high enough.

On the other hand, in recent years, for example, a semiconductor laser using an InGaN-based material and capable of continuously oscillating in a range of 350 nm to 450 nm has been put into practical use. A scanning exposure system using these short-wave light sources has a sufficient output because a semiconductor laser can be manufactured at a low cost due to its structure.
It has the advantage that an economical system can be constructed.
Further, compared to a system using a conventional FD-YAG or Ar laser, a brighter safelight (500
A light-sensitive material having a short photosensitive area capable of working under a yellow light which cuts light of nm or less can be used.

Further, for example, J.P. Faussier "Photoi
nitiated Polymerization-Theoryand Applications "
: Rapra Review vol.9, Report, Rapra Technology (199
8) and M. Tsunooka et al., Prog.Polym.Sci., 21, 1 (1
As described in 996), obtaining a photoinitiating system with high sensitivity is a technique widely desired in the field of imaging.

However, from 350 nm to 450 nm
Has sufficient sensitivity for scanning exposure in the short wavelength range of 500 nm
A photoinitiating system not sensitive to the above light has not been known so far.

Heretofore, an initiation system in which a specific dye and a titanocene compound are combined has been disclosed as a photoinitiation system having relatively high sensitivity. JP-B-61-9621 discloses a combination of a dye having an acidic nucleus of oxazolidine and a triazine photoinitiator, but has poor storage stability and has a problem in production. JP-A-8-272096 discloses a combination of a dye having an oxazolone acidic nucleus and titanocene, and JP-A-10-101719 discloses a combination of a dye having a 5-membered heterocyclic acidic nucleus and titanocene. These are certainly high sensitivities, but are not sufficient, and when a laser light source having a wavelength of 450 nm or less is used, practically sufficient sensitivity cannot be obtained, which is not suitable for a short wavelength light source. Further, the titanocene compound has a problem of yellow lamp safety because it has an absorption of 450 nm or more due to dd transition specific to transition metals.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a lithographic printing plate for scanning exposure or an inexpensive short-wavelength semiconductor laser which is excellent in workability, economy and storage stability and is suitable for a CTP system. An object of the present invention is to provide a photopolymerizable composition used as a material for a highly sensitive lithographic printing plate precursor.
Another object of the present invention is to broadly cover the range from 350 nm to 450 nm.
An object of the present invention is to provide a photopolymerizable composition using a novel photopolymerization initiation system having high sensitivity to a wavelength of nm.

[0012]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that an electron transfer type starting system which is not sensitive to 500 nm or more, ie, which is not sensitive to 500 nm or more, A donor initiator and a sensitizing dye,
(ii) an electron-accepting initiator and a sensitizing dye, or (ii)
i) By using a photopolymerizable composition containing one of an electron-donating initiator, a sensitizing dye, and an electron-accepting initiator (a ternary initiator), it is sufficient for the oscillation wavelength of a short-wave semiconductor laser. It has been found that a photosensitive composition having excellent sensitivity and excellent storage stability can be obtained, and the present invention has been achieved.

Further, as the electron donating initiator, an anionic compound represented by the following general formula (I) is preferable.

[0014]

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In the formula (I), Y represents an element of Group III of the periodic table, B, Al or Ga, and R ¹ , R ² , R ³ and R ⁴ may be the same or different; Each represents an organic group. However, at least one of R ¹ , R ² , R ³ and R ⁴ is a substituted or unsubstituted alkyl group.
Zn ⁺ represents an n-valent cation, and n represents an integer of 1 to 6. ｝

As the electron accepting initiator, a cationic compound represented by the following general formula (II) is preferable.

[0017]

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In the formula (II), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹
And R ¹⁰ may be the same or different, and each represents an organic group. Here, at least one of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represents an organic group represented by the following general formula (III). X ^m- represents a m-valent anion;
Represents an integer of 1 to 6. ｝

[0019]

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In the formula (III), R ¹¹ , R ¹² and R ¹³ may be the same or different and each represents an organic group. L represents a divalent linking group containing a hetero atom. ｝

[0021]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described in detail. Photopolymerizable composition of the present invention (photosensitive composition)
Contains (A) a photopolymerization initiation system belonging to any of the above (i), (ii) and (iii), (B) a compound having an addition-polymerizable ethylenically unsaturated bond, and ,
(C) comprising a binder polymer. Hereinafter, these components will be specifically described.

(A) Photopolymerization initiation system The photopolymerization initiation system which is an essential component of the photosensitive composition of the present invention is
(1) an electron transfer initiator and (2) from 350 nm to 450 n
m contains a sensitizing dye having an absorption wavelength. It is considered that the initiation system in the present invention mainly absorbs light by the sensitizing dye and promotes generation of the initiation radical from the coexisting electron transfer initiator (such a process is hereinafter referred to as dye sensitization).

(A1) Photopolymerization initiator The electron transfer initiator used in the present invention includes (a)
Aromatic ketones, (b) aromatic oniums, (c) organic peroxides, (d) thio compounds, (e) hexaarylbiimidazole compounds, (f) ketoxime compounds,
(G) an azinium compound, (h) an active ester compound,
(J) a compound having a carbon-halogen bond, (k) a borate compound, and (l) a pyridium compound.

Preferred examples of the aromatic ketone (a) which is an example of the electron transfer initiator used in the present invention include:
`` RADIATION CURING IN POLYMER SCIENCE AND TECHNOLO
GY '' JP FOUASSIER JF RABEK (1993), pp. 77-117
Compound having a benzophenone skeleton or thioxanthone skeleton according to the description, for example,

[0025]

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[0026]

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[0027]

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And the like. More preferred examples of (a) aromatic ketones include α-thiobenzophenone compounds described in JP-B-47-6416 and JP-B-47-398.
No. 1 benzoin ether compound, for example,

[0029]

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Α-substituted benzoin compounds described in JP-B-47-22326, for example,

[0031]

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Benzoin derivatives described in JP-B-47-23664, aroylphosphonic esters described in JP-A-57-30704, dialkoxybenzophenones described in JP-B-60-26483, for example,

[0033]

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JP-B-60-26403, JP-A-62-26463
Benzoin ethers described in JP 81345, for example,

[0035]

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Japanese Patent Publication No. 1-34242, US Pat.
No. 318,791, European Patent 0284561A1
No. α-aminobenzophenones, for example,

[0037]

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P-Di (dimethylaminobenzoyl) benzene described in JP-A-2-21152, for example,

[0039]

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Thio-substituted aromatic ketones described in JP-A-61-194062, for example,

[0041]

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Acylphosphine sulfide described in JP-B-2-9597, for example,

[0043]

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Acylphosphines described in JP-B-2-9596, for example,

[0045]

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Thioxanthones described in JP-B-63-61950 and coumarins described in JP-B-59-42864 can be exemplified.

The (b) aromatic onium salt, which is another example of the electron transfer initiator, is exemplified by V and VI in the periodic table.
And Group VII elements, specifically N, P, As, Sb,
Bi, O, S, Se, Te or I aromatic onium salts are included. Examples of such aromatic onium salts include JP-B-52-14277 and JP-B-52-1427.
No. 8 and Japanese Patent Publication No. 52-14279. In particular,

[0048]

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[0049]

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[0050]

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[0051]

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And the like.

As the (c) "organic peroxide" which is another example of the electron transfer initiator used in the present invention, almost all organic compounds having one or more oxygen-oxygen bonds in the molecule are used. Although included, examples thereof include 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 (tertiary (Butylperoxy) cyclohexane, 2,2-bis (tertiarybutylperoxy) butane, tertiarybutylhydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramethane 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 (tert-butylperoxy) hexane, 2,5-xanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, metal-toluene Oil peroxide, diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-2-ethoxyethylperoxydicarbonate, dimethoxyisopropylperoxycarbonate,
Di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxy acetate, tert-butyl peroxy pivalate, tert-butyl peroxy neodecanoate, tert-butyl peroxy octanoate, Tertiary butyl peroxy-3,5,5-trimethylhexanoate, tertiary butyl peroxy laurate, tertiary 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 -Hexyl peroxy dihydrogen diphthalate) and the like.

Among these, 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
Peroxide esters such as 4'-tetra- (cumylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, di-t-butyldiperoxyisophthalate Systems are preferred.

The thio compound (d) as the component electron transfer initiator used in the present invention is preferably a compound represented by the following general formula [VI].

[0056]

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(In the formula [VI], R²⁹Is an alkyl group, aryl
A substituted or substituted aryl group; ³⁰Is a hydrogen atom or
Represents an alkyl group. Also, R²⁹And R³⁰Are connected to each other
A heteroatom selected from oxygen, sulfur and nitrogen atoms
Necessary to form a 5- to 7-membered ring which may contain
Shows a group of non-metallic atoms. )

The alkyl group represented by R ²⁹ in the above general formula [VI] preferably has 1 to 4 carbon atoms. As the aryl group for R ³⁰ , those having 6 to 10 carbon atoms such as phenyl and naphthyl are preferable. As the substituted aryl group, a halogen atom such as a chlorine atom and a methyl group And those substituted with an alkoxy group such as an alkyl group, a methoxy group and an ethoxy group.

R ³⁰ is preferably an alkyl group having 1 to 4 carbon atoms. Specific examples of the thio compound represented by the general formula [VI] include the following compounds.

[0060]

[Table 1]

The (e) hexaarylbiimidazole which is another example of the electron transfer initiator used in the present invention includes JP-B-45-37377 and JP-B-44-8651.
No. 6 lofin dimers, for example, 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-trifluorophenyl) -4,4 ', 5,5'-
And tetraphenylbiimidazole.

The (f) ketoxime ester which is another example of the electron transfer initiator used in the present invention includes 3-benzoyloximinobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentane-
3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p-toluenesulfonyloxyimiminobtan-2-one, 2- Ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

Another example of the azinium salt compound (g), which is another example of the electron transfer initiator of the present invention, is disclosed in
No. 138345, JP-A-63-142345, JP-A-63-142346, JP-A-63-143535, and JP-B-46-42363.

Examples of (h) active ester compounds which are other examples of electron transfer initiators include imide sulfonate compounds described in JP-B-62-6223 and JP-B-63-14340.
And active sulfonates described in JP-A-59-174831.

Preferred examples of the compound having a carbon-halogen bond (j), which is an example of an electron transfer initiator, include compounds represented by the following general formulas [VII] to [XIII].

[0066]

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(In the formula [VII], X ² represents a halogen atom. Y ² represents —CX ² , —NH ₂ , —NHR ^{3 2} —NR ³² or —OR ³² , wherein R ³² is an alkyl group. , .R ³¹ to represent a substituted alkyl group, an aryl group or a substituted aryl group
Represents -CX ^2, alkyl group, substituted alkyl group, an aryl group, a substituted aryl group or a substituted alkenyl group. )

[0068]

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(In the formula [VIII], R ³³ represents an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a halogen atom, an alkoxy group, a substituted alkoxyl group, a nitro group or a cyano group. And X ² is a halogen atom, and n is an integer of 1 to ^3. )

[0070]

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(In the formula [IX], R ³⁴ is an aryl group or a substituted aryl group, and R ³⁵ is

[0072]

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Or Z ² is —C (は O)
—, —C (＝ S) — or —SO ₂ —, and R ³⁶ , R ³⁷
Is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group;
³⁸ is the same as R ³² in formula [VII], X ³ is a halogen atom, and m is 1 or 2. )

[0074]

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(In the formula [X], R ³⁹ is an optionally substituted aryl group or a heterocyclic group, and R ⁴⁰ is a carbon atom.
A trihaloalkyl or trihaloalkenyl group having up to 3; and p is 1, 2 or 3. )

[0076]

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(In the formula [XI], L is a hydrogen atom or a formula: CO
_{^{- (R 41) q (CX}} 4 3) is a substituent _r, Q is sulfur,
Selenium or oxygen atom, dialkylmethylene group, alkene-1,2-ylene group, 1,2-phenylene group or NR
M is a substituted or unsubstituted alkylene group or alkenylene group, or a 1,2-arylene group, R ⁴² is an alkyl group, an aralkyl group or an alkoxyalkyl group, and R ⁴¹ is X ⁴ is a chlorine, bromine or iodine atom, wherein q = 0 and r = 1, or q = 1 and r = 1
Or 2. And a carbonylmethylene heterocyclic compound having a trihalogenomethyl group.

[0078]

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(In the formula [XII], X ⁵ is a halogen atom, t is an integer of 1 to 3, s is an integer of 1 to 4, R ⁴³ is a hydrogen atom or CH _{3 -t} X ⁵ a 4-halogeno-5- (halogenomethyl-phenyl) -oxazole derivative represented by the formula: _{t is a} group, and R ⁴⁴ is an s-valent optionally substituted unsaturated organic group.

[0080]

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(In the formula [XIII], X ⁶ is a halogen atom, v is an integer of 1 to 3, u is an integer of 1 to 4, R ⁴⁵ is a hydrogen atom or CH _{3 -v} X ⁶ a 2- (halogenomethyl-phenyl) -4-halogeno-oxazole derivative represented by the formula _v) wherein R ⁴⁶ is a u-valent, optionally substituted unsaturated organic group.

Specific examples of such a compound having a carbon-halogen bond include, for example, Wakabayashi et al., Bull.
em. 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 compounds described in British Patent 1,388,492, for example, 2-styryl-4,6-
Bis (trichloromethyl) -S-triazine, 2- (p
-Methylstyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl)
-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4-amino-6
JP-A-53-1 such as trichloromethyl-S-triazine
No. 33428, 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-naphtho-1
-Yl) -4,6-bis-trichloromethyl-S-triazine), 2- (acenaphth-5-yl) -4,6-bis-trichloromethyl-S-triazine and the like, German Patent 3,337,024. Compounds described in the above specification, for example,

[0084]

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[0085]

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And the like. Also, FC Sc
Haefer et al., J. Org. Chem. 29, 1527 (196
The compounds described in 4), for example, 2-methyl-4,6-bis (tribromomethyl) -S-triazine, 2,4,6-
Tris (tribromomethyl) -S-triazine, 2,
4,6-tris (dibromomethyl) -S-triazine,
2-amino-4-methyl-6-tribromomethyl-S-
Triazine, 2-methoxy-4-methyl-6-trichloromethyl-S-triazine and the like can be mentioned. Further, compounds described in JP-A-62-58241, for example,

[0087]

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[0088]

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And the like. Further, Japanese Patent Application Laid-Open
No. 281,728, for example,

[0090]

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And the like. Or even more
Jou by MP Hutt, EF Elslager and LM Herbel
rnalof Heterocyclic chemistry ", Vol. 7 (No.
3) The following compound groups that can be easily synthesized by those skilled in the art according to the synthesis methods described on pages 511 et seq. (1970).

[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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Alternatively, compounds such as those described in German Patent No. 2641100, for example 4- (4-methoxy-styryl) -6- (3,3,3-trichloropropenyl) -2-pyrone and 4- (3,4,5-trimethoxy-styryl) -6-trichloromethyl-2-pyrone or the compounds described in DE 33 33 450, for example,

[0099]

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[0100]

[Table 2]

Alternatively, a group of compounds described in German Patent No. 3021590,

[0102]

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

[0104]

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The following can be mentioned.

Further, more preferred electron donating initiators used in the present invention include (k) borate compounds, and those represented by the above formula (I) are particularly preferred. Hereinafter, the general formula (I) will be described in detail.

Y is an element of Group III of the periodic table, B, Al
Or, it represents Ga, and B is more preferable. R ¹ , R ² , R ³
And R ⁴ include, for example, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, a substituted alkenyl group, an alkynyl group and a substituted alkynyl group;
And heterocyclic groups. However, at least one of R ¹ , R ² , R ³ and R ⁴ is a substituted or unsubstituted alkyl group.

The alkyl group has 1 to 2 carbon atoms.
0, straight-chain, branched or cyclic alkyl groups, specific examples of which include methyl, ethyl, propyl, butyl, pentyl, hexyl,
Heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group,
Octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group,
Examples thereof include a cyclohexyl group, a cyclopentyl group, and a 2-norbornyl group. Among them, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

The substituted alkyl group is constituted by a bond between a substituent and an alkylene group. As the substituent, a monovalent nonmetallic atomic group other than hydrogen is used. As a preferred example, a halogen atom (-F,- Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino Group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-
Arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-ary Rucarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N ′
An alkylureido group, an N ′, N′-dialkylureido group, an N′-arylureido group, an N ′, N′-diarylureido group, an N′-alkyl-N′-arylureido group, an N-alkylureido group; N-aryl ureido group, N'-alkyl-N-alkyl ureido group, N '
-Alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N
-Alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'-diaryl-N-arylureido group, N'-alkyl-N '-Aryl-N-alkylureido groups, N'-alkyl-N'-aryl-N-
Arylureido group, alkoxycarbonylamino group,
Aryloxycarbonylamino group, N-alkyl-N-
Alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group,
Carboxyl group and its conjugate base group (hereinafter, referred to as carboxylate), alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter, sulfonato group) ), Alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl , N-alkyl-N-arylsulfinamoyl, sulfamoyl, N-alkylsulfamoyl, N, N-dialkylsulfamoyl, N-arylsulfamoyl, N, N-diarylsulfamoyl Group, N-alkyl-N-arylsulfamoyl group, N-acylsulfamoyl group and its conjugate base group, N-alkylsulfonylsulfamoyl group (—SO ₂ NHSO ₂ (alkyl)) and its conjugate base group ,
N-arylsulfonylsulfamoyl group (—SO ₂ N
HSO ₂ (allyl) and its conjugate base group, N-alkylsulfonylcarbamoyl group (—CONHSO ₂ (alky)
l)) and its conjugate base group, N-arylsulfonylcarbamoyl group (—CONHSO ₂ (allyl)) and its conjugate base group, alkoxysilyl group (—Si (Oalky)
l) ₃ ), an aryloxysilyl group (—Si (Oallyl) ₃ ),
A hydroxysilyl group (—Si (OH) ₃ ) and its conjugate base group, a phosphono group (—PO ₃ H ₂ ) and its conjugate base group (hereinafter, referred to as a phosphonate group), a dialkylphosphono group (—PO ₃ (alkyl ₂ )), a diarylphosphono group (-P
O ₃ (aryl) ₂ ), an alkylarylphosphono group (—PO
₃ (alkyl) (aryl)), monoalkylphosphono group (-P
O ₃ H (alkyl) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (-P
O ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonate group), phosphonooxy group (—OPO ₃
H ₂ ) and its conjugated base group (hereinafter referred to as phosphonatoxy group), dialkylphosphonooxy group (—OPO ₃ (a
lkyl) ₂ ), a diarylphosphonooxy group (—OPO)
₃ (aryl) ₂ ), an alkylarylphosphonooxy group (-
OPO ₃ (alkyl) (aryl)), monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonatooxy group), monoarylphosphonooxy group (− OPO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonatooxy group), cyano group, nitro group, aryl group, alkenyl group, and alkynyl group.

In these substituents, specific examples of the alkyl group include the aforementioned alkyl groups, and specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, and mesityl groups. , Cumenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, Phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, phenoxycarbonylphenyl group, N-phenylca Ba carbamoylphenyl group, a phenyl group, nitrophenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group,
Examples include a phosphonatophenyl group. Examples of the alkenyl group include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-
Examples thereof include a 1-ethenyl group, and examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group,
Examples include a trimethylsilylethynyl group and a phenylethynyl group.

As the above-mentioned acyl group (R ⁴ CO—),
R ^{4 includes a} hydrogen atom and the above-mentioned alkyl, aryl, alkenyl and alkynyl groups.

On the other hand, the alkylene group in the substituted alkyl group may be a divalent organic residue obtained by removing any one of the above hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. And preferably a linear alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms and a cyclic alkylene group having 5 to 10 carbon atoms.

Specific examples of preferred substituted alkyl groups include chloromethyl, bromomethyl, 2-chloroethyl, trifluoromethyl, methoxymethyl, methoxyethoxyethyl, allyloxymethyl, phenoxymethyl, methylthiomethyl. Group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group,
Benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxy Carbonylethyl group, methoxycarbonylmethyl group, methoxycarbonylbutyl group, ethoxycarbonylmethyl group,
Butoxycarbonylmethyl group, allyloxycarbonylmethyl group, benzyloxycarbonylmethyl group, methoxycarbonylphenylmethyl group, trichloromethylcarbonylmethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl Group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfopropyl group,
Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N
-Dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group,

[0114]

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

Examples of the aryl group include a group in which one to three benzene rings form a condensed ring, and a group in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Group, naphthyl group, anthryl group, phenanthryl group, indenyl group, acenabutenyl group,
Examples thereof include a fluorenyl group and the like, and among these, a phenyl group and a naphthyl group are more preferable.

The substituted aryl group is a group in which a substituent is bonded to an aryl group, and those having a monovalent nonmetallic atomic group other than hydrogen as a substituent on a ring-forming carbon atom of the aforementioned aryl group are used. Can be Preferred examples of the substituent include the aforementioned alkyl group, substituted alkyl group, and those described above as the substituent for the substituted alkyl group.

Preferred specific examples of these substituted aryl groups are biphenyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, fluorophenyl, chloromethylphenyl,
Trifluoromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group,
Methylthiophenyl group, tolylthiophenyl group, phenylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxy Phenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group,
Allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-
Methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfa Moylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, Phosphonophenyl, phosphonatophenyl, diethylphosphonophenyl, diphenylphosphonophenyl, methylphosphonophenyl, methylphosphonatophenyl, tolylphosphonophenyl, tolylphosphonatophenyl, allyl, 1 -Propenylmethyl group, 2 Butenyl, 2-methyl-allyl phenyl group, 2-methyl propenyl phenyl group, 2-propynyl phenyl group, 2-butynyl phenyl group, and a 3-butynylphenyl group.

Examples of the alkenyl group include those described above. A substituted alkenyl group is a compound in which a substituent is replaced by a hydrogen atom of an alkenyl group and bonded to the alkenyl group. As the substituent, the substituent in the above-mentioned substituted alkyl group is used, while the alkenyl group is the above-mentioned alkenyl group. Can be. Examples of preferred substituted alkenyl groups include

[0120]

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And the like. Examples of the alkynyl group include those described above. A substituted alkynyl group is a substituent in which a substituent is replaced by a hydrogen atom of an alkynyl group and bonded to the alkynyl group, and the substituent is the substituent in the above-mentioned substituted alkyl group, while the alkynyl group uses the alkynyl group described above. be able to.

The heterocyclic group is a monovalent group obtained by removing one hydrogen on the heterocyclic ring, and further removing one hydrogen from the monovalent group, and the substituent in the above-mentioned substituted alkyl group is bonded. The resulting monovalent group (substituted heterocyclic group). Examples of preferred heterocycles include

[0123]

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[0124]

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And the like.

Next, R¹And R^Two, R^TwoAnd R^ThreeAre connected to each other
An example in which a ring is formed by the following method will be described. R ¹And R^Two, R^TwoAnd R^ThreeBut
As the aliphatic ring formed by bonding to each other, a 5-membered ring, 6
And 7-membered and 8-membered aliphatic rings.
And more preferably a 5- or 6-membered aliphatic ring.
Can be These further include the carbon
May have a substituent on the atom (for example,
Can be a substituent on the above-mentioned substituted alkyl group.
Part of the ring-constituting carbon is a hetero atom (oxygen
Atom, sulfur atom, nitrogen atom, etc.)
No. Furthermore, a part of this aliphatic ring forms a part of an aromatic ring.
It may be formed.

Z ^{n +} is an alkali metal ion,
Grade ammonium, pyridinium, quinolinium, diazonium, monoholinium, tetrazolium, acridinium, phosphonium, sulfonium, oxosulfonium, sulfur, oxygen, carbon halide, Cu, Ag, H
g, Pd, Fe, Co, Sn, Mo, Cr, Ni, A
represents s or Se, and more preferably quaternary ammonium.

The preferred specific examples of the compounds represented by formula (I) are shown below, but the invention is not restricted thereto.

[0129]

[Table 3]

[0130]

[Table 4]

[0131]

[Table 5]

[0132]

[Table 6]

[0133]

[Table 7]

[0134]

[Table 8]

[0135]

[Table 9]

Among the above borate compounds, compounds containing at least one phenyl group substituted by fluorine at the m-position are more preferred.

Further, more preferred electron-accepting initiators in the present invention include (l) pyridium compounds, specifically, compounds represented by the above general formula (II).

In the formula (II), R ⁵ preferably represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, a substituted alkenyl group, an alkynyl group or a substituted alkynyl group. ^6, R ^7,
R ⁸ , R ⁹ and R ¹⁰ may be the same or different and represent a hydrogen atom, a halogen atom or a monovalent organic residue, at least one of which is represented by the general formula (III) Having a structure having the following structure: Also, R ⁵ and R ⁶ , R ⁵ and R ¹⁰ , R ⁶ and R
⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ may combine with each other to form a ring.

In the formula (III), R¹², R¹³Are independent
Hydrogen atom, halogen atom, alkyl group, substituted alkyl
Group, aryl group, substituted aryl group, alkenyl group,
Substituted alkenyl, alkynyl or substituted alkynyl
And R¹¹Is hydrogen atom, alkyl group, substituted alkyl
Group, aryl group, substituted aryl group, alkenyl group, substituted
Alkenyl, alkynyl, substituted alkynyl, hydride
Roxyl group, substituted oxy group, mercapto group, substituted thio
Represents a group, an amino group or a substituted amino group. Also, R ¹²When
R¹³, R¹¹And R¹², R¹¹And R¹³Combine with each other to form a ring
May be implemented.

X represents a counter anion. m represents an integer of 1 to 4.

In the general formula (II), R ⁵ , R ⁶ , R ⁷ ,
R ⁸ and R ⁹ are more preferably each independently a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, a hydroxyl group. Group, substituted oxy group, mercapto group, substituted thio group, amino group, substituted amino group, substituted carbonyl group, sulfo group, sulfonato group, substituted sulfinyl group, substituted sulfonyl group, phosphono group, substituted phosphono group, phosphonate group, cyano group , A nitro group or a silyl group can be used. Also, R ⁵ and R ⁶ , R ⁵ and R ¹⁰ , R ⁶ and R
⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ may combine with each other to form a ring.

Next, preferred examples of R ⁵ in formula (II) will be described in detail. Preferred examples of the alkyl group, the substituted alkyl group, the aryl group, the substituted aryl group, the alkenyl group, the substituted alkenyl group, the alkynyl group, and the substituted alkynyl group are the same as those described in the general formula (I). Can be

Next, R ⁶ , R ⁷ and R in the general formula (II)
Preferred examples of ⁸ , R ⁹ and R ¹⁰ other than the structure represented by the general formula (III) will be described in detail. As the halogen atom, a fluorine, chlorine, bromine or iodine atom is preferable. Alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, preferred examples of the substituted alkenyl group include those listed as examples of the aforementioned R ^5.

As the substituted oxy group (R ¹⁴ O—), R ¹⁴
Is a monovalent non-metallic atomic group other than hydrogen. Preferred substituted oxy groups include an alkoxy group, an aryloxy group, an acyloxy group, a carbamoyloxy group, an N-alkylcarbamoyloxy group, an N-arylcarbamoyloxy group, an N, N-dialkylcarbamoyloxy group, and an N, N-diarylcarbamoyloxy. Group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group,
Examples thereof include a phosphonooxy group and a phosphonatoxy group. Examples of the alkyl group and the aryl group in these include those described above as the alkyl group, the substituted alkyl group, the aryl group, and the substituted aryl group. Examples of the acyl group (R ¹⁵ CO—) in the acyloxy group include those in which R ¹⁵ is an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group described above. Among these substituents, an alkoxy group, an aryloxy group, an acyloxy group, and an arylsulfoxy group are more preferred.

Specific examples of preferred substituted oxy groups include:
Methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, allyloxy, phenethyloxy, carboxyethyloxy, methoxycarbonylethyloxy ,
Ethoxycarbonylethyloxy, methoxyethoxy, phenoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, morpholinoethoxy, morpholinopropyloxy, allyloxyethoxyethoxy, phenoxy, tolyloxy, xylyloxy, mesityloxy , Dimethyloxy, methoxyphenyloxy, ethoxyphenyloxy, chlorophenyloxy, bromophenyloxy, acetyloxy, benzoyloxy, naphthyloxy, phenylsulfonyloxy, phosphonooxy,
And a phosphonatoxy group.

As the substituted thio group (R ¹⁶ S-), those wherein R ¹⁶ is a monovalent non-metallic atomic group other than a hydrogen atom can be used.
Examples of preferred substituted thio groups include alkylthio, arylthio, alkyldithio, aryldithio,
An acylthio group can be mentioned. Alkyl group in these alkyl groups described above as the aryl group, a substituted alkyl group, and aryl group, those can be cited shown as substituted aryl group, R ¹⁵ of the acyl group in the acylthio group (R ¹⁵ CO-) in As described above. Among these, an alkylthio group and an arylthio group are more preferred. Specific examples of preferred substituted thio groups include methylthio, ethylthio, phenylthio, ethoxyethylthio, carboxyethylthio,
And a methoxycarbonylthio group.

The substituted amino group (R ¹⁷ NH—, (R ¹⁸ ) (R
¹⁹ ) As N-), those in which R ¹⁷ , R ¹⁸ and R ¹⁹ are monovalent non-metallic atomic groups excluding a hydrogen atom can be used. Preferred examples of the substituted amino group include an N-alkylamino group, N,
N-dialkylamino group, N-arylamino group, N,
N-diarylamino group, N-alkyl-N-arylamino group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N'-
Alkyl ureido group, N ′, N′-dialkyl ureide group, N′-aryl ureide group, N ′, N′-diaryl ureide group, N′-alkyl-N′-aryl ureide group, N-alkyl ureide group, N -Arylureido group, N'-alkyl-N-alkylureido group, N'-
Alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N-
Alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'-diaryl-N-arylureido group, N'-alkyl-N ' -Aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl —N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group and N-aryl-N-aryloxycarbonylamino group. As the alkyl group and the aryl group in these, the above-mentioned alkyl group,
Substituted alkyl group, and aryl group, those can be cited shown as substituted aryl group, an acylamino group, N- alkyl acyl amino group, R ¹⁵ of the acyl group (R ¹⁵ CO-) in the N- arylacylamino group As described above.

Of these, more preferred are an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, and an acylamino group. Specific examples of preferred substituted amino groups include a methylamino group, an ethylamino group, a diethylamino group, a morpholino group, a piperidino group, a piperidino group, a pyrrolidino group, a phenylamino group, a benzoylamino group, and an acetylamino group.

As the substituted carbonyl group (R ²⁰ —CO—), those wherein R ²⁰ is a monovalent nonmetallic atomic group can be used. Preferred examples of the substituted carbonyl group include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N-N-dialkylcarbamoyl group, N-arylcarbamoyl group, An N, N-diarylcarbamoyl group and an N-alkyl-N-arylcarbamoyl group are exemplified. Examples of the alkyl group and the aryl group in these include those described above as the alkyl group, the substituted alkyl group, and the aryl group and the substituted aryl group.

Of these, more preferred substituents include formyl, acyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, N-alkylcarbamoyl, N ', N-dialkylcarbamoyl, An N-arylcarbamoyl group is exemplified, and even more preferred are a formyl group, an acyl group, an alkoxycarbonyl group and an aryloxycarbonyl group. Specific examples of preferred substituted carbonyl groups include formyl, acetyl, benzoyl, carboxyl, methoxycarbonyl,
Examples include an allyloxycarbonyl group, an N-methylcarbamoyl group, an N-phenylcarbamoyl group, an N, N-diethylcarbamoyl group, and a morpholinocarbonyl group.

As the substituted sulfinyl group (R ²¹ —SO—), those wherein R ²¹ is a monovalent nonmetallic atomic group can be used. Preferred examples include an alkylsulfinyl group, an arylsulfinyl group, a sulfinamoyl group, an N-alkylsulfinamoyl group, an N, N-dialkylsulfinamoyl group, an N-arylsulfinamoyl group, and an N, N-diarylsulfinamoyl. And N-alkyl-N-arylsulfinamoyl groups. Examples of the alkyl group and the aryl group in these include those described above as the alkyl group, the substituted alkyl group, and the aryl group and the substituted aryl group. Among these, more preferred examples include an alkylsulfinyl group and an arylsulfinyl group. Specific examples of such a substituted sulfinyl group include a hexylsulfinyl group,
Examples include a benzylsulfinyl group and a tolylsulfinyl group.

As the substituted sulfonyl group (R25-SO2-), those wherein R25 is a monovalent nonmetallic atomic group can be used.
More preferred examples include an alkylsulfonyl group and an arylsulfonyl group. As the alkyl group and the aryl group in these, the above-mentioned alkyl group,
Examples include the substituted alkyl group, the aryl group, and the substituted aryl group. like this,
Specific examples of the substituted sulfonyl group include a butylsulfonyl group and a chlorophenylsulfonyl group.

As described above, the sulfonato group (SO ₃ ⁻ )
It means a conjugate base anion group of a sulfo group (—SO ₃ H), and it is usually preferably used together with a counter cation.
As such counter cations, those generally known,
That is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (Na ⁺ , K ⁺ , C
a ²⁺ , Zn ^2+, etc.).

The substituted phosphono group means a group in which one or two hydroxyl groups on the phosphono group are substituted by another organic oxo group. Preferred examples include the above-mentioned dialkylphosphono group, diarylphosphono group, Examples thereof include an alkylarylphosphono group, a monoalkylphosphono group, and a monoarylphosphono group. Among these, a dialkylphosphono group and a diarylphosphono group are more preferred. Specific examples include a diethylphosphono group, a dibutylphosphono group, and a diphenylphosphono group.

[0155] phosphonate group ^{_{(-PO 3 2-, -PO 3 H}} -)
As I mentioned above the means phosphono group (-PO ₃ H _2), first dissociation or acid, a conjugated base anion group derived from the second dissociation acid. Usually it is preferred to use it with a counter cation. Such counter cations are generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (N
a ⁺ , K ⁺ , Ca ²⁺ , Zn ^2+, etc.).

The substituted phosphonate group is the same as the aforementioned substituted phosphono group.
Of the groups, one obtained by replacing one hydroxyl group with an organic oxo group
Role base anion group, specific examples of which are
Alkyl phosphono group (-PO_ThreeH (alkyl)), monoary
Ruphosphono group (-PO_ThreeH (aryl) conjugate base
Can be. Usually used with counter cations
Good. Such counter cations are commonly known
, That is, various oniums (ammonium
, Sulfoniums, phosphoniums, iodonium
, Aziniums, etc.) and metal ions (N
a⁺, K⁺, Ca²⁺, Zn ²⁺Etc.).

The silyl group ((R ²³ ) (R ²⁴ ) (R ²⁵ ) Si
As-), those in which R ²³ , R ²⁴ , and R ²⁵ are monovalent nonmetallic atomic groups can be used, and preferred examples include those in which the aforementioned alkyl group, substituted alkyl group, aryl group, and substituted aryl group are used. Can be mentioned. Examples of preferred silyl groups include trimethylsilyl, tributylsilyl, t
-Butyldimethylsilyl group, dimethylphenylsilyl group and the like.

The above R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰
Among the examples, more preferred are a hydrogen atom, a halogen atom (-F, -Cl, -Br, -I), an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a substituted oxy group, and a substituted thio group. Group, substituted amino group, substituted carbonyl group, sulfo group, sulfonato group, cyano group,
Still more preferably, a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted carbonyl group can be mentioned.

Next, R ⁵ and R ⁶ , R ⁵ and R ¹⁰ , R ⁶ and R ⁷ ,
An example in which R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ are bonded to each other to form a ring will be described. An example of such is R ⁵
And R ⁶ , R ⁵ and R ¹⁰ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R
Examples include those in which ⁹ and R ¹⁰ are bonded to each other to form a saturated or unsaturated aliphatic ring.
Those which form a 5-membered ring, a 6-membered ring, a 7-membered ring and an 8-membered aliphatic ring in combination with the carbon atom to which they are bonded can be mentioned. Further more preferably, a 5-membered ring,
A 6-membered aliphatic ring can be exemplified. Further, they may further have a substituent on the carbon atom constituting them. (Examples of the substituent include the substituents on the substituted alkyl group described above as examples of R ⁸ and R ^11. And a part of the ring-constituting carbon atoms may be substituted with a hetero atom (an oxygen atom, a sulfur atom, a nitrogen atom, or the like). Further, a part of the aliphatic ring may form a part of an aromatic ring. Preferred examples of these include a cyclopentane ring, a cyclohexane ring,
Cycloheptane ring, cyclooctane ring, cyclo-1,3
-Dioxapentane ring, cyclopentene ring, cyclohexene ring, cycloheptene ring, cyclooctene ring, cyclo-1,3-dioxapentene ring, cyclo-1,3-dioxahexene ring, cyclohexadiene ring, benzocyclohexene ring, benzocyclohexa Cien ring, tetrahydropyranone ring and the like can be mentioned.

Next, R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹
And R ¹⁰ are bonded to each other to form an aromatic ring, examples of which include a quinoline ring, an isoquinoline ring, an acridine ring, a phenanthridine ring, and a benzquinoline ring in cooperation with a pyridine ring containing a carbon atom to which they are bonded. And those forming a benzisoquinoline ring, and more preferably those forming a quinoline ring. Further, these may have a substituent on the constituting carbon atom (an example of the substituent is the above-mentioned substituent on the substituted alkyl group).

Next, R in the general formula (III)¹², R¹³
A preferred example will be described in detail. As a halogen atom
Fluorine, chlorine, bromine and iodine atoms are preferred. Alkyl
Group, substituted alkyl group, aryl group, substituted aryl group,
Lucenyl, substituted alkenyl, alkynyl, and
Preferred examples of the substituted alkynyl group include the aforementioned R ^Five
Can be cited as examples. R¹², R
¹³Are more preferably a hydrogen atom or an alkyl group.
You.

Next, preferred examples of R ¹¹ in formula (III) will be described in detail. Alkyl group, substituted alkyl group, aryl group, substituted aryl group, alkenyl group, substituted alkenyl group, alkynyl group, substituted alkynyl group, hydroxyl group, substituted oxy group, mercapto group, substituted thio group, amino group, and substituted amino group Preferred examples include those described above as examples of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ . R ¹¹ is more preferably an alkyl group, a substituted alkyl group, an aryl group,
A substituted aryl group and an alkenyl group.

Further, R ¹² and R ¹³ , R ¹¹ and R ¹² , R ¹¹ and R ^12
13 may combine with each other to form a saturated or unsaturated aliphatic ring, and preferably form a 5-membered ring, a 6-membered ring, a 7-membered ring and an 8-membered ring together with the carbon atom to which they are attached. Those which form a cyclic aliphatic ring can be mentioned. further,
More preferably, a 5- or 6-membered aliphatic ring can be mentioned. Further, they may further have a substituent on the carbon atom constituting them (examples of the substituent include the above-mentioned examples of the substituent in the substituted alkyl group). , And a part of the ring-constituting carbon is
It may be substituted with a hetero atom (oxygen atom, sulfur atom, nitrogen atom, etc.). Further, a part of the aliphatic ring may form a part of an aromatic ring. Preferred examples of these include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclo-
1,3-dioxapentane ring, cyclopentene ring, cyclohexene ring, cycloheptene ring, cyclooctene ring,
Cyclo-1,3-dioxapentene ring, cyclo-1,3
-A dioxahexene ring, a cyclohexadiene ring, a benzocyclohexene ring, a benzocyclohexadiene ring, a perhydropyranone ring and the like.

Next, L in the general formula (III) will be described. L represents a divalent linking group containing a hetero atom,
Specifically, it has the following partial structure.

[0165]

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Here, "having the following partial structure" means that L as a linking group or terminal group has at least one of the above partial structures, and is a compound having a plurality of the above partial structures. Is also good. Accordingly, L may be the partial structure itself, or a group obtained by connecting a plurality of these, or a group obtained by connecting the partial structure to another hydrocarbon group or the like. Particularly preferred examples of L 'include the following structures.

[0167]

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Next, preferred examples of the counter anion Z- in formula (II) will be described in detail. Preferred examples of Z- include halide ions (F-, Cl-, Br-, I-
-), Sulfonate ion, organoboron anion, perchlorate ion (ClO ₄ ⁻ ) and anion represented by formula (a) or (b)

MX _r (a) MX _r-1 (OH) (b) (where M represents a boron atom, a phosphorus atom, an arsenic atom, or an antimony atom, X represents a halogen atom,
r represents an integer of 4 to 6. ).

Preferred examples of the sulfonate ion include:
Methanesulfonic acid ion, benzenesulfonic acid ion,
p-toluenesulfonic acid ion (TsO-), p-styrenesulfonic acid ion, β-naphthoquinone-4-sulfonic acid ion, anthraquinone-1,5-disulfonic acid ion, anthraquinone-1,8-disulfonic acid ion,
Anthraquinone-1-sulfonic acid ion, anthraquinone-2-sulfonic acid ion, quinoline-8-sulfonic acid ion, hydroquinonesulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 1-naphthalenesulfonic acid ion, 2-naphthalenesulfonic acid Ion, 2-amino-1-naphthalenesulfonic acid ion, 2-naphthol-
6-sulfonic acid ion, dibutylnaphthalenesulfonic acid ion, naphthalene-1,3,6-trisulfonic acid ion, m-benzenedisulfonic acid ion, p-phenolsulfonic acid ion, dodecylbenzenesulfonic acid ion, 2-hydroxy-4 -Methoxybenzophenone-5
-Sulfonic acid ion, 4-acetylbenzenesulfonic acid ion, 4-nitrotoluene-2-sulfonic acid ion,
o-benzaldehyde sulfonic acid ion, diphenylamine-4-sulfonic acid ion, benzaldehyde-2,
4-disulfonic acid ion, mesitylenesulfonic acid ion, trifluoromethanesulfonic acid ion, chlorosulfonic acid ion, fluorosulfonic acid ion, 9,10-
And dimethoxyanthracene-2-sulfonate ion.

Preferred specific examples of the compound represented by formula (II) are shown below, but the present invention is not limited thereto.

[0172]

[Table 10]

[0173]

[Table 11]

[0174]

[Table 12]

[0175]

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[0176]

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[0177]

[Table 13]

[0178]

[Table 14]

[0179]

[Table 15]

[0180]

[Table 16]

[0181]

[Table 17]

The method of using these electron transfer initiators can be appropriately set depending on the performance design of the light-sensitive material. The larger the amount of the electron transfer initiator used, the more advantageous in terms of photosensitivity.
Sufficient photosensitivity can be obtained when used in an amount of 1 part by weight, preferably 1 to 50 parts by weight.

(A2) Sensitizing dyes Examples of preferable sensitizing dyes in the present invention belong to the following compounds and are in the range of 350 nm to 450 nm.
Absorption in the region can be long. Polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanines, carbomerocyanines), thiazines (eg, thionin, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavin), anthraquinones (eg, anthraquinone), squariums (eg, squarium) ).

Examples of more preferable sensitizing dyes include compounds represented by the following formulas (XIV) to (XVIII).

[0185]

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(In the formula (XIV), A ¹ is a sulfur atom or NR
^{Represents 50} , R ⁵⁰ represents an alkyl group or an aryl group,
L ² represents a non-metallic atomic group which forms a basic nucleus of the dye together with adjacent A ² and an adjacent carbon atom, and R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent non-metallic atomic group. And R ⁵¹ and R ⁵² may combine with each other to form an acidic nucleus of the dye. W represents an oxygen atom or a sulfur atom. )

Preferred specific examples of the compound represented by formula (XIV) are shown below.

[0188]

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[0189]

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(In the formula (XV), Ar ¹ and Ar ² each independently represent an aryl group, and are linked via a bond by -L ^3- . Here, L ³ is -O- or -S- And W has the same meaning as in general formula (XIV).

Preferred examples of the compound represented by formula (XV) include the following.

[0192]

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[0193]

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(In the formula (XVI), A^TwoIs a sulfur atom or NR
⁵⁹And L^FourIs adjacent A^TwoAnd color in cooperation with carbon atom
Represents a nonmetallic atomic group that forms a basic nucleus of⁵³, R
⁵⁴, R ⁵⁵, R⁵⁶, R⁵⁷And R⁵⁸Are independently monovalent
Represents a group of a nonmetallic atomic group,⁵⁹Is an alkyl group or ant
Represents a hydroxyl group. )

Preferred examples of the compound represented by the formula (XVI) include the following.

[0196]

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[0197]

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[0198] (In the formula ^{(XVII), A 3, A} 4 are each independently -S- or -NR ⁶² - or -NR ⁶³ - represents, R
^63, R ⁶⁴ each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, L ^5,
L ⁶ each independently represents a nonmetallic atomic group which forms a basic nucleus of the dye in cooperation with adjacent A ³ , A ⁴ and an adjacent carbon atom, and R ⁶⁰ and R ⁶¹ each independently represent a monovalent group; Or can combine with each other to form an aliphatic or aromatic ring. )

Preferred examples of the compound represented by formula (XVII) include the following.

[0200]

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[0201]

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(In the formula (XVIII), R ⁶⁶ represents an aromatic ring or a heterocyclic ring which may have a substituent, and A ⁵ represents an oxygen atom, a sulfur atom or —NR ⁶⁷ —. R ⁶⁴ , R ⁶⁵ and R ⁶⁷ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁶⁷ and R ⁶⁴ , and R ⁶⁵ and R ⁶⁷ are each linked to each other to form an aliphatic or aromatic ring; can do.)

Preferred specific examples of the compound represented by the general formula (XVIII) include the following.

[0204]

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The sensitizing dye of the present invention, when used as a lithographic printing plate precursor, may be subjected to various chemical modifications to improve the characteristics of the photosensitive layer. For example, by combining a sensitizing dye with an addition-polymerizable compound structure (for example, an acryloyl group or a methacryloyl group) by a method such as a covalent bond, an ionic bond, or a hydrogen bond, it is possible to increase the strength of the exposed film or to increase the exposure. Unnecessary precipitation of the dye from the subsequent film can be suppressed.

Further, when the photosensitive composition of the present invention is used as a lithographic printing plate precursor, the photosensitive layer is preferably used in order to enhance the suitability for processing with an (alkali) aqueous developing solution. It is effective to introduce a hydrophilic site (a carboxyl group and its ester, a sulfonic acid group and its ester, an acid group such as an ethylene oxide group or a polar group). Particularly, the ester-type hydrophilic group has a relatively hydrophobic structure in the photosensitive layer and thus has excellent compatibility, and in a developer, generates an acid group by hydrolysis to increase the hydrophilicity. Having. In addition, for example, a substituent can be appropriately introduced for improving compatibility in the photosensitive layer and suppressing crystal precipitation. For example, in certain types of photosensitive systems, unsaturated bonds such as aryl groups and allyl groups may be very effective in improving compatibility. By introducing an obstacle, crystal precipitation can be significantly suppressed. Further, by introducing a phosphonic acid group, an epoxy group, a trialkoxysilyl group, or the like, it is possible to improve the adhesion to inorganic substances such as metals and metal oxides. In addition, a method such as polymerization of a sensitizing dye can be used depending on the purpose.

Which structure of these sensitizing dyes is used,
Details of how to use, such as whether to use them alone or in combination of two or more, and the amount of addition, can be appropriately set according to the final performance design of the light-sensitive material. For example, by using two or more sensitizing dyes in combination, the compatibility with the photosensitive composition layer can be increased. In selecting a sensitizing dye, the molar extinction coefficient at the emission wavelength of the light source used is an important factor in addition to the photosensitivity.
By using a dye having a large molar extinction coefficient, the amount of the dye added can be relatively small, so it is economical, and when used in a lithographic printing plate precursor, is advantageous in terms of the film physical properties of the photosensitive layer. It is. Since the photosensitivity and resolution of the photosensitive layer and the physical properties of the exposed film are greatly affected by the absorbance at the wavelength of the light source, the amount of the sensitizing dye to be added is appropriately selected in consideration of these factors. For example, the sensitivity is reduced in a low region where the absorbance is 0.1 or less. Also, the resolution becomes low due to the influence of halation.

However, for the purpose of curing a thick film having a thickness of, for example, 5 μm or more, such a low absorbance may sometimes increase the degree of curing. The absorbance is 3
In the high region as described above, most of the light is absorbed on the surface of the photosensitive layer, and the curing inside is more hindered. Becomes When used as a lithographic printing plate having a relatively thin film thickness, the amount of the sensitizing dye added is such that the absorbance of the photosensitive layer is in the range of 0.1 to 1.5, preferably 0.25.
Is preferably set to be in the range of 1 to 1. When used as a lithographic printing plate, it is usually used in an amount of 0.05 to 30 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.2 to 20 parts by weight, based on 100 parts by weight of the photosensitive layer component.
The range is 10 parts by weight.

(B) Compound having an addition-polymerizable ethylenically unsaturated bond The compound having an addition-polymerizable ethylenically unsaturated bond used in the present invention has at least one terminal ethylenically unsaturated bond, preferably Is selected from compounds having two or more. Examples of the monomer include an ester of an unsaturated carboxylic acid (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with an aliphatic polyhydric alcohol compound, and the unsaturated carboxylic acid and the fatty acid. And amides with group-III polyamine compounds.

Specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include 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 Acrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetra Acrylate, SO Bi penta acrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3 -Methacryloxy-2-h Rokishipuropokishi) phenyl] dimethyl methane, bis - [p- (acryloxy ethoxy)
Phenyl] dimethylmethane.

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

Examples of crotonates include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate,
Sorbitol tetradicrotonate and the like. Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate. Furthermore, a mixture of the above-mentioned ester monomers can also be mentioned. Specific examples of the amide monomer of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylenebis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, and 1,6-hexane. Methylene bis-
Examples include methacrylamide, diethylenetriaminetrisacrylamide, xylylenebisacrylamide, and xylylenebismethacrylamide.

Another example is described in JP-B-48-417.
JP-A-08-208, in which a hydroxyl-containing vinyl monomer represented by the following general formula (A) is added to a polyisocyanate compound having two or more isocyanate groups in one molecule. Vinyl urethane compounds containing the above polymerizable vinyl groups are exemplified.

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

In addition, urethane acrylates described in JP-A-51-37193,
64183, JP-B-49-43191, JP-B-52
And polyfunctional acrylates and methacrylates such as polyester acrylates described in JP-A-30490 and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid. Furthermore, the Journal of the Adhesion Society of Japan vol.20, No. 7, 300-308 (1984) as photocurable monomers and oligomers can also be used. In the present invention, these monomers may be used in a chemical form such as a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof.

The amount of these used is 5 to 50% by weight (hereinafter abbreviated as%), preferably 10 to 40%, based on all components of the photopolymerizable composition. If it is more than 50%, poor coating film formation (stickiness) will occur.
%, It is not preferable because curing failure occurs.

(C) Binder polymer When applied to a lithographic printing plate precursor, which is a preferred embodiment of the present invention, it is preferable to further use a binder polymer in the photosensitive layer. It is preferable to contain a linear organic high molecular polymer as the binder. Any of such “linear organic high molecular polymers” may be used. Preferably, a water-soluble or weakly alkaline water-soluble or swellable linear organic high molecular polymer that enables water development or weakly alkaline water development is selected. The linear organic high molecular polymer is selected and used not only as a film forming agent of the composition but also as a water, weakly alkaline water or organic solvent developing agent. For example, when a water-soluble organic high molecular 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 a side chain, for example, JP-A-59-44615.
No., JP-B-54-34327, JP-B-58-1257
7, JP-B-54-25957, JP-A-54-927
No. 23, JP-A-59-53836, JP-A-59-71
048, that is, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc. There is. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain.
In addition, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful.

In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomers] copolymer and [allyl (meth) acrylate / (meth) acrylic acid / Other addition-polymerizable vinyl monomers as needed) copolymer,
It is suitable because it has an excellent balance of film strength, sensitivity and developability.

In addition, Japanese Patent Publication No. 7-12004,
JP-A-120041, JP-B-7-120042, JP-B-8-12424, JP-A-63-287944, JP-A-63-287947, JP-A-1-271174,
The urethane-based binder polymer containing an acid group described in Japanese Patent Application No. 10-116232 is very excellent in strength, and therefore is advantageous in terms of printing durability and low exposure suitability.

Further, the binder having an amide group described in JP-A-11-171907 is preferable because it has excellent developability and film strength.

Further, as the water-soluble linear organic polymer, polyvinyl pyrrolidone, polyethylene oxide and the like are useful. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful. These linear organic high molecular polymers can be incorporated in any amount in the entire composition. However, if it exceeds 90% by weight, no favorable result is obtained in view of the strength of the formed image and the like. Preferably 30 to 85
% By weight. The weight ratio of the photopolymerizable compound having an ethylenically unsaturated double bond and the linear organic high molecular polymer is preferably in the range of 1/9 to 7/3.

In a preferred embodiment, a binder polymer which does not substantially require water and is soluble in alkali is used. By doing so, it is possible to use no organic solvent which is environmentally unfavorable or to use a very small amount as the developer. In such a usage, the acid value (acid content per gram of polymer represented by chemical equivalent number) and molecular weight of the binder polymer are appropriately selected from the viewpoint of image strength and developability. Preferred acid value is 0.4 to 3.0 m
eq / g, and the preferred molecular weight is in the range of 3,000 to 500,000, and more preferably the acid value is in the range of 0.6 to 2.0, and the molecular weight is in the range of 10,000 to 300,000.

(D) Other Components The photosensitive composition of the present invention may further contain other components suitable for its use, production method and the like.
Hereinafter, preferred additives will be exemplified.

(D1) Polymerization Inhibitor In the present invention, in addition to the above basic components, unnecessary heat of a compound having an ethylenically unsaturated double bond which can be polymerized during the production or storage of the photosensitive composition. It is desirable to add a small amount of thermal polymerization inhibitor to prevent polymerization. Suitable thermal polymerization inhibitors include hydroquinone, p
-Methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4- Methyl-
6-t-butylphenol), cerium N-nitrosophenylhydroxyamine, and the like. The amount of the thermal polymerization inhibitor added is about 0.01 to the weight of the whole composition.
% By weight to about 5% by weight is preferred. In addition, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide is added to prevent polymerization inhibition by oxygen, and when used as a lithographic printing plate precursor, after application to a support or the like, During the drying process, it may be unevenly distributed on the surface of the photosensitive layer. The amount of the higher fatty acid derivative to be added ranges from about 0.5% by weight to about 10% by weight of the total composition.
% By weight is preferred.

(D2) Other Additives When the photosensitive composition of the present invention is used for a lithographic printing plate precursor, an inorganic filler, other plasticizers, a surface of the photosensitive layer, and the like are used to improve the physical properties of the cured film. A known additive such as a sensitizing agent that can improve the ink adhesion of the ink may be added.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like. A binder was used. In this case, it can be added in an amount of 10% by weight or less based on the total weight of the compound having an ethylenically unsaturated double bond and the binder.

Further, UV light for enhancing the effects of heating and exposure after development for the purpose of improving the film strength (printing durability).
An initiator, a thermal crosslinking agent and the like can be added.

In addition, additives for improving the adhesion between the photosensitive layer and the support, and improving the development removal property of the unexposed photosensitive layer,
It is possible to provide an intermediate layer. For example, by adding or undercoating a compound having a relatively strong interaction with the substrate, such as a compound having a diazonium structure or a phosphone compound, the adhesion is improved, and the printing durability can be increased.
On the other hand, by adding or undercoating a hydrophilic polymer such as polyacrylic acid or polysulfonic acid, the developability of the non-image area is improved, and the stain resistance is improved.

When the photosensitive composition of the present invention is applied on a support to provide a lithographic printing plate, it is used after being dissolved in various organic solvents. As the solvent used here, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate,

3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, 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, γ-butyrolactone, methyl lactate, ethyl lactate and the like. These solvents can be used alone or as a mixture. The appropriate concentration of the solid content in the coating solution is 2 to 50% by weight.

The amount of the photosensitive layer coated on the support mainly affects the sensitivity of the photosensitive layer, the developability, and the strength and printing durability of the exposed film, and is desirably appropriately selected depending on the application. If the coating amount is too small, the printing durability will be insufficient. On the other hand, if the amount is too large, the sensitivity is lowered, and it takes a long time for exposure, and a longer time is required for the developing process, which is not preferable. The lithographic printing plate for scanning exposure, which is the main object of the present invention, has a coating amount of about 0.1 g / m 2 after drying.
The range of ² to about 10 g / m ² are suitable. More preferably, it is 0.5 to 5 g / m ² .

"Support" In order to obtain a lithographic printing plate, which is one of the main objects of the present invention, it is desirable to provide the photosensitive layer on a support having a hydrophilic surface. As the hydrophilic support, a conventionally known hydrophilic support used for a lithographic printing plate can be used without limitation. The support used is preferably a dimensionally stable plate-like material, for example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc) , Copper, etc.), plastic films (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.),
Paper or plastic film on which the metal is laminated or vapor-deposited as described above is included, and if necessary, a known physical or chemical property suitable for the purpose of imparting hydrophilicity or improving the strength to these surfaces, if necessary. May be applied.

Particularly preferred examples of the support include paper, a polyester film and an aluminum plate. Among them, the dimensional stability is good, the cost is relatively low, and the hydrophilicity and strength are excellent by surface treatment as required. Aluminum plates that can provide a surface are particularly preferred. In addition, Shoko 4
A composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-A-8-18327 is also preferable.

Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and a trace amount of a different element, and may be a plastic film on which aluminum is further laminated or vapor-deposited. The foreign elements contained in aluminum alloys include silicon, iron, manganese, copper,
There are magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The content of the foreign element in the alloy is at most 10% by weight or less. Particularly preferred aluminum in the present invention is pure aluminum. However, completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and a conventionally known and used raw material of A-luminium plate can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, particularly preferably 0.1 mm to 0.4 mm.
It is 2 mm to 0.3 mm.

In the case of a support having a metal surface, particularly an aluminum surface, a roughening (graining) treatment, a dipping treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodizing Preferably, a surface treatment such as a treatment is performed.

The surface roughening treatment of the aluminum plate is performed by various methods. For example, a method of mechanically roughening the surface, a method of electrochemically dissolving and roughening the surface, and a method of chemically roughening the surface. Is selectively dissolved. As the mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, a buffing method and a polishing method can be used. Further, as an electrochemical surface roughening method, there is a method of performing an alternating or direct current in an electrolytic solution such as hydrochloric acid or nitric acid. Further, as disclosed in JP-A-54-63902, a method in which both are combined can also be used. Prior to roughening the aluminum plate, if necessary, a degreasing treatment with, for example, a surfactant, an organic solvent or an alkaline aqueous solution is performed to remove rolling oil on the surface.

Further, an aluminum plate which has been roughened and then immersed in an aqueous solution of sodium silicate can be preferably used. As described in JP-B-47-5125, an aluminum plate which is anodized and then immersed in an aqueous solution of an alkali metal silicate is preferably used. The anodizing treatment is performed, for example, in an electrolytic solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or an aqueous solution or a non-aqueous solution of a salt thereof alone or in combination of two or more. This is performed by flowing a current using an aluminum plate as an anode.

Also, silicate electrodeposition as described in US Pat. No. 3,658,662 is effective. Furthermore, JP-B-46-27481 and JP-A-52-5860.
No. 2, JP-A-52-30503, and a surface treatment obtained by combining the anodizing treatment and the sodium silicate treatment with a support provided with electrolytic grains are also useful.

Further, it is also preferable to sequentially perform mechanical surface roughening, chemical etching, electrolytic graining, anodizing treatment and sodium silicate treatment as disclosed in JP-A-56-28893. Furthermore, after performing these treatments, a water-soluble resin such as polyvinylphosphonic acid, a polymer and a copolymer having a sulfonic acid group in a side chain, polyacrylic acid, a water-soluble metal salt (for example, zinc borate) or Those coated with a yellow dye, an amine salt or the like are also suitable.

Further, a sol-gel treated substrate having a functional group capable of causing an addition reaction by a radical covalently disclosed in JP-A-7-159983 is also preferably used.

As another preferred example, a support having a water-resistant hydrophilic layer as a surface layer on an arbitrary support can also be used. As such a surface layer, for example, US30
55295, a layer composed of an inorganic pigment and a binder described in JP-A-56-13168, a hydrophilic swelling layer described in JP-A-9-80744, a titanium oxide, a polyvinyl alcohol, and a silicate described in JP-A-8-507727. Sol-gel films and the like can be raised.

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

"Protective layer" is a desirable mode of the present invention.
In a lithographic printing plate for scanning exposure, usually, since the exposure is performed in the air, it is preferable to further provide a protective layer on the layer of the photopolymerizable composition. The protective layer prevents low-molecular compounds such as oxygen and basic substances present in the atmosphere that inhibit the image formation reaction caused by exposure in the photosensitive layer from entering the photosensitive layer, and enables exposure in the atmosphere. And Therefore, a desired property of such a protective layer is that the permeability of low molecular compounds such as oxygen is low, and further, the transmission of light used for exposure is not substantially inhibited, and the adhesion to the photosensitive layer is excellent. In addition, it is desirable that it can be easily removed in a developing step after exposure.

Such a device for the protective layer has been conventionally devised, and is described in detail in US Pat. No. 3,458,311 and JP-A-55-49729. As a material that can be used for the protective layer, for example, it is preferable to use a water-soluble polymer compound having relatively excellent crystallinity. Although water-soluble polymers such as acrylic acid are known, use of polyvinyl alcohol as a main component gives the best results in terms of basic characteristics such as oxygen barrier properties and development removability. The polyvinyl alcohol used for the protective layer may be partially substituted with an ester, an ether, or an acetal as long as it contains an unsubstituted vinyl alcohol unit for obtaining necessary oxygen barrier properties and water solubility. Similarly, a part thereof may have another copolymer component.

Specific examples of polyvinyl alcohol include 7
1-100% hydrolyzed, molecular weight 300-240
A range of 0 can be given. Specifically, Kuraray's PVA-105, PVA-110, P
VA-117, PVA-117H, PVA-120,
PVA-124, PVA-124H, PVA-C
S, PVA-CST, PVA-HC, PVA-20
3, PVA-204, PVA-205, PVA-21
0, PVA-217, PVA-220, PVA-2
24, PVA-217EE, PVA-217E, P
VA-220E, PVA-224E, PVA-40
5, PVA-420, PVA-613, L-8 and the like.

The components of the protective layer (selection of PVA, use of additives), the amount of coating, and the like are selected in consideration of fogging properties, adhesion, and scratch resistance in addition to oxygen barrier properties and development removability. Generally, the higher the hydrolysis rate of the PVA used (the higher the content of unsubstituted vinyl alcohol units in the protective layer) and the thicker the film thickness, the higher the oxygen barrier properties, which is advantageous in terms of sensitivity. However, when the oxygen barrier property is extremely increased, there arises a problem that an unnecessary polymerization reaction occurs at the time of production or raw storage, and that unnecessary fogging and thickening of an image occur at the time of image exposure. Further, the adhesion to the image area and the scratch resistance are also extremely important in handling the plate. That is, when a hydrophilic layer made of a water-soluble polymer is laminated on a lipophilic polymer layer, film peeling due to insufficient adhesive force is apt to occur, and the peeled portion causes defects such as poor film curing due to inhibition of oxygen polymerization.

On the other hand, various proposals have been made to improve the adhesiveness between these two layers. For example, US Patent No. 2
No. 92,501 and U.S. Pat. No. 44,563, an acrylic emulsion or a water-insoluble vinylpyrrolidone-vinyl acetate copolymer is mixed in a hydrophilic polymer mainly composed of polyvinyl alcohol in an amount of 20 to 60% by weight. It is described that sufficient adhesiveness can be obtained by laminating on a polymer layer. Any of these known techniques can be applied to the protective layer in the present invention. Regarding the method of applying such a protective layer,
For example, U.S. Pat. No. 3,458,311;
No. 49729.

When a photosensitive material using the photosensitive composition of the present invention is used as an image forming material, usually, after image exposure, an unexposed portion of the photosensitive layer is removed with a developing solution to obtain an image. Preferred developers for using these photopolymerizable compositions for preparing a lithographic printing plate include JP-B-57-742.
No. 7, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium tertiary phosphate, and the like.
An aqueous solution of an inorganic alkali agent such as dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia or an organic alkali agent such as monoethanolamine or diethanolamine. Is appropriate. The alkaline solution is added so that the concentration of the alkaline solution is 0.1 to 10% by weight, preferably 0.5 to 5% by weight.

In addition, such an alkaline aqueous solution includes:
If necessary, a small amount of a surfactant or an organic solvent such as benzyl alcohol, 2-phenoxyethanol or 2-butoxyethanol can be contained. For example, those described in U.S. Pat. Nos. 3,375,171 and 3,615,480 can be mentioned. further,
The developing solutions described in JP-A-50-26601, JP-A-58-54341, JP-B-56-39464 and JP-B-56-42860 are also excellent.

In addition, the plate-making process of a lithographic printing plate precursor using the photosensitive composition of the present invention may be, if necessary,
The entire surface may be heated before, during, or between exposure and development. By such heating, an image forming reaction in the photosensitive layer is promoted, and advantages such as improvement in sensitivity and printing durability and stabilization of sensitivity can be brought about. Further, for the purpose of improving image strength and printing durability, it is also effective to post-heat or expose the entire surface of the developed image. Usually, heating before development is preferably performed under mild conditions of 150 ° C. or less. If the temperature is too high, there arises a problem that the non-image portion is covered. Very strong conditions are used for heating after development. Usually, it is in the range of 200 to 500 ° C. If the temperature is too low, a sufficient image strengthening effect cannot be obtained.

As the method of exposing a lithographic printing plate for scanning exposure using the photosensitive composition of the present invention, known methods can be used without any limitation. Desirable light source wavelength is from 350 nm to 45
The thickness is 0 nm, and specifically, an InGaN-based semiconductor laser is preferable. The exposure mechanism may be any of an internal drum type, an external drum type, a flat bed type, and the like. Further, the photosensitive composition of the present invention can be made soluble in neutral water or weakly alkaline water by using a highly water-soluble one, but a lithographic printing plate precursor having such a configuration can be used. After loading on a printing machine, a method such as exposure-development can be performed on the machine.

As the available laser light source of 350 nm to 450 nm, the following can be used.

As a gas laser, an Ar ion laser (364 nm, 351 nm, 10 mW to 1 W) and a Kr ion laser (356 nm, 351 nm, 10 mW to 1 W) are used.
W), He-Cd laser (441 nm, 325 nm,
1mW to 100mW), Nd: Y as a solid laser
Combination of AG (YVO ₄ ) and SHG crystal × 2 times (3
55 nm, 5 mW to 1 W), Cr: LiSAF and SHG
Combination of crystals (430 nm, 10 mW),

As a semiconductor laser system, a KNbO ₃ ring resonator (430 nm, 30 mW), a combination of a waveguide type wavelength conversion element and an AlGaAs or InGaAs semiconductor (380 nm to 450 nm, 5 mW to 100 mW), a waveguide type wavelength conversion element and an AlGaInP , AlGaAs semiconductor combination (300 nm to 350 nm, 5 mW to 1
00mW), AlGaInN (350 nm to 450 n
m, 5 mW to 30 mW) In addition, N ₂ laser (337 nm, pulse 0.1 to 10 m) as a pulse laser
J), XeF (351 nm, pulse 10-250 mJ)

Particularly, among these, an AlGaInN semiconductor laser (commercially available InGaN semiconductor laser 380-410n)
m, 5 to 30 mW) is preferable in terms of wavelength characteristics and cost.

As the lithographic printing plate exposure apparatus of the scanning exposure system, there are an inner drum system, an outer drum system and a flat bed system as an exposure mechanism, and a light source capable of continuous oscillation among the above light sources is preferably used. be able to. Actually, the following exposure apparatus is particularly preferable in relation to the sensitivity of the photosensitive material and the plate making time.

Single-to-triple-beam exposure apparatus using one or more gas lasers or solid-state laser light sources so that a semiconductor laser with a total output of 20 mW or more can be obtained by the internal drum method. Multi-beam (1 to 10) exposure equipment using one or more semiconductor lasers, gas lasers or solid-state lasers ・ Semiconductor lasers, gas lasers or solid-states so that the total output is 20 mW or more by the external drum method Laser 1
Multi-beam (1 to 9) exposure equipment using more than one ・ Multi-beam (10 or more) exposure equipment using one or more semiconductor lasers or solid-state lasers so that the total output is 20 mW or more by the external drum method.

In the lithographic printing plate of the laser direct drawing type described above, the sensitivity of the photosensitive material X (J / cm ² ), the exposure area S (cm ² ) of the photosensitive material, the power q of one laser light source are generally used.
Equation (eq 1) holds between (W), the number of lasers n, and the total exposure time t (s).

X · S = n · q · t (eq 1)

I) In the case of the inner drum (single beam) system: Laser rotation speed f (radian / s), sub-scanning length L of photosensitive material
x (cm), resolution Z (dot / cm), total exposure time t
Equation (eq 2) generally holds during (s).

F.Z.t = Lx --- (eq 2)

Ii) In the case of the external drum (multi-beam) method: the drum rotation speed F (radian / s), the sub-scanning length Lx of the photosensitive material
(Cm), resolution Z (dot / cm), total exposure time t
(S) and the number of beams (n) generally have the formula (eq 3)
Holds.

F · Z · nt · L = Lx (eq 3)

Iii) In the case of the flat head (multi-beam) system The rotation number H (radian / s) of the polygon mirror, the sub-scanning length Lx (cm) of the photosensitive material, the resolution Z (dot / cm), the total exposure time t ( s) and the number of beams (n), the equation (eq 4) generally holds.

F · Z · nt · L = Lx (eq 4)

The resolution required for the actual printing plate (256
0 dpi), plate size (A1 / B1, sub-scan length 42 in)
ch), exposure conditions of about 20 sheets / hour and the photosensitive characteristics of the photosensitive composition of the present invention (photosensitive wavelength, sensitivity: about 0.1 mJ /
By substituting (cm ² ) into the above formula, it can be understood that a combination with a multi-beam exposure method using a laser having a total output of 20 mW or more is particularly preferable in a photosensitive material using the photosensitive composition of the present invention. Furthermore, by multiplying the operability, cost, and the like, the combination with an external drum type semiconductor laser multi-beam (10 or more) exposure apparatus is most preferable.

Other exposure light rays for the photosensitive composition of the present invention include ultrahigh-pressure, high-pressure, medium-pressure and low-pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, visible and ultraviolet lamps. Various laser lamps, fluorescent lamps, tungsten lamps, sunlight and the like can also be used. In addition, the photosensitive composition of the present invention can be applied without limitation to lithographic printing plates for scanning exposure and those widely known as uses of photocurable resins. For example, when applied to a liquid photosensitive composition used in combination with a cationically polymerizable compound as required, a material for stereolithography with high sensitivity can be obtained. In addition, a hologram material can be formed by utilizing a change in refractive index due to photopolymerization. It can be applied to various transfer materials (peeling-sensitive material, toner-developing material, etc.) by utilizing the change in surface tackiness accompanying photopolymerization. It can also be applied to light curing of microcapsules. It can also be applied to the manufacture of electronic materials such as photoresists, and photocurable resin materials such as inks, paints, and adhesives.

[0270]

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples. A synthesis example is also shown.

The borate compound (I-1) in the present invention
To (I-86) were synthesized according to the method described in JP-A-11-316458. The compound represented by the general formula (II) was synthesized by the following method.

Synthesis Example 1 Synthesis of Compound (II-1) 4-Pyridinemethanol (9.5 g) in benzene (10 g)
Benzoyl chloride (14.7 g) was added dropwise to the solution (0 g), and the mixture was stirred at room temperature for 4 hours. The reaction solution was poured into ice water and stirred for a while. The mixture was extracted three times with ethyl acetate (300 g), and the organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution (500 g).
g) and washed with saturated saline (500 g), dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. The obtained residue was dissolved in acetonitrile (50 g), and benzyl bromide (7 g) was added dropwise. After reacting at room temperature for 24 hours, the precipitated crystals were taken out by filtration. The obtained crystals were dissolved in a small amount of methanol, and then poured into a saturated aqueous solution of KPF6. The precipitated crystals are taken out by filtration,
14 g of compound (II-1) was obtained (40% yield). The structure of compound (II-1) was confirmed by ¹ H-NMR and MASS spectra. The melting point was 110-112 ° C.

Synthesis Example 2: Synthesis of Compound (II-27) To a solution of 2-chloromethylpyridine hydrochloride (12 g) in dimethylacetamide (150 g) was added thiophenoxyacetic acid (19 g), potassium carbonate (25 g), and tetrabutylammonium iodide. After the addition of 1 g (1 g), the mixture was heated to 90 ° C. and reacted for 3 hours. After cooling to room temperature, the reaction solution was poured into water and stirred for a while. The mixture was extracted four times with ethyl acetate (300 g), and the organic layer was extracted with water (500 g) and saturated saline (5 g).
After drying with magnesium sulfate and filtration, the solvent was distilled off under reduced pressure. 6 g of the obtained residue (13 g) was dissolved in acetonitrile (50 g), and pt-butylbenzyl bromide (5 g) was added dropwise. 24 hours,
After reacting at room temperature, the precipitated crystals were taken out by filtration. The obtained crystals were dissolved in a small amount of methanol, and then poured into a saturated aqueous solution of KPF6. The precipitated crystals were taken out by filtration to obtain 8 g of compound (II-27) (yield: 45).
%). The structure of compound (II-27) was confirmed by ¹ H-NMR and MASS spectra. Melting point 105-107
° C.

Synthesis Example 3: Synthesis of compound (II-18) In a solution of 4-chloromethylpyridine hydrochloride (10 g) in dimethylacetamide (150 g), sodium pt-butyl benzoate (19 g), potassium carbonate (10 g), After adding tetrabutylammonium iodide (1 g),
The mixture was heated to 90 ° C. and reacted for 3 hours. After cooling to room temperature,
The reaction solution was poured into water and stirred for a while. Ethyl acetate (3
00g), and the organic layer was washed with water (500 g) and saturated saline (500 g), dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. The obtained residue (1
5 g) was dissolved in acetonitrile (50 g),
Benzyl bromide (5 g) was added dropwise. After reacting at room temperature for 24 hours, the precipitated crystals were taken out by filtration. After dissolving the obtained crystals in a small amount of methanol,
aBF ₄ was poured into a saturated aqueous solution. The precipitated crystals were taken out by filtration to obtain 10 g of compound (II-18) (yield: 70).
%). The structure of compound (II-18) was confirmed by ¹ H-NMR and MASS spectra. Melting point 100-102
° C.

Synthesis Example 4 Synthesis of Compound (II-17) 4-Pyridinemethanol (5 g) in acetonitrile (5 g)
0g) to the solution was added triethylamine (6g),
Cooled down. Di-t-butyl dicarbonate (13
After dropping g), the mixture was reacted at room temperature for 24 hours. The reaction solution was poured into ice water and stirred for a while. Ethyl acetate (3
00g), and the organic layer was washed with a saturated aqueous solution of sodium hydrogencarbonate (500 g) and a saturated aqueous solution of sodium chloride (500 g), dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. N-Heptyl tosylate (6.5 g) was added to the obtained residue, heated to 100 ° C., and reacted for 1 hour. After cooling to room temperature, recrystallize with ethyl acetate,
5 g of compound (II-17) was obtained (40% yield). The structure of compound (II-17) was confirmed by ¹ H-NMR and MASS spectra. Melting point was 98-100 ° C.

Synthesis Example 5 Synthesis of Compound (II-45) In a solution of 4-chloromethylpyridine hydrochloride (12 g) in dimethylacetamide (150 g), phenylglyoxylic acid (13 g), potassium carbonate (25 g), tetrabutylammonium iodide After the addition of 1 g (1 g), the mixture was heated to 90 ° C. and reacted for 3 hours. After cooling to room temperature, the reaction solution was poured into water and stirred for a while. Ethyl acetate (300g)
The organic layer was washed with water (500 g) and saturated saline (500 g), dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure. The residue obtained (12 g)
Was dissolved in acetonitrile (50 g), and benzyl bromide (5 g) was added dropwise. After reacting at room temperature for 24 hours, the precipitated crystals were taken out by filtration. The resulting crystals were dissolved in a small amount of methanol, poured into KPF ₆ saturated solution. The precipitated crystals were taken out by filtration to obtain 4 g of compound (II-45) (yield: 40%). The structure of compound (II-45) was confirmed by ¹ H-NMR and MASS spectra. Melting point was 105-107 ° C.

Further, the compound (II-1) according to the present invention,
(II-27), (II-18), (II-17) and (II-
Pyridiniomethyl ester compounds other than 45) could be easily synthesized by the same method.

Examples 1 to 19 and Comparative Examples 1 to 3 (Preparation of Support)
After etching by immersion in 0% by weight sodium hydroxide at 60 ° C. for 25 seconds, the film was washed with running water, neutralized and washed with 20% by weight nitric acid, and then washed with water. This was converted to 300 coulomb / dm in a 1% by weight nitric acid aqueous solution using a sinusoidal alternating current.
Electrolytic surface-roughening treatment was performed with the quantity of electricity at the time of anode No. ² . Subsequently, it was immersed in a 1% by weight aqueous solution of sodium hydroxide at 40 ° C. for 5 seconds, and then immersed in a 30% by weight aqueous solution of sulfuric acid.
After desmutting for 0 second, anodizing was performed for 2 minutes in a 20% by weight sulfuric acid aqueous solution at a current density of 2 A / dm ^{2 so} that the thickness of the anodized film became 2.7 g / m ² . The surface roughness was measured to be 0.3 μm (J
Ra display according to IS B0601).

The following sol-gel reaction solution was applied to the back surface of the substrate thus treated with a bar coater,
The support was provided with a back coat layer having an applied amount of 70 mg / m ² after drying.

Sol-gel reaction liquid Tetraethyl silicate 50 parts by weight Water 20 parts by weight Methanol 15 parts by weight Phosphoric acid 0.05 parts by weight

When the above components were mixed and stirred, exotherm started in about 5 minutes. After reacting for 60 minutes, the following solution was added to prepare a backcoat coating solution.

Pyrogallol formaldehyde condensation resin (molecular weight: 2000) 4 parts by weight Dimethyl phthalate 5 parts by weight Fluorinated surfactant (N-butyl perfluorooctane 0.7 parts by weight) Sulfonamide ethyl acrylate / polyoxyethylene acrylate copolymer: molecular weight 2 10,000) Methanol silica sol (manufactured by Nissan Chemical Industries, Ltd., methanol 30% by weight) 50 parts by weight Methanol 800 parts by weight

(Preparation of Photosensitive Layer) A photopolymerizable composition having the following composition was applied onto the aluminum plate thus treated so that the dry coating amount was 1.0 g / m ² ,
After drying for a minute, a photosensitive layer was formed.

• Pentaerythritol tetraacrylate 1.7 g • Allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio 85/15) 2.0 g • Photopolymerization initiation system (described in Table 1) Sensitizing dye 0.1 g Electron-donating initiator 0.6 g Electron-accepting initiator 0.2 g ・ Fluorine nonionic surfactant (F-177P) 0.02 g ・ Thermal polymerization inhibitor N-nitrosophenylhydroxyl 0.01 g ・ Color pigment dispersion 2 0.0g

(Composition of Pigment Dispersion) Composition: Pigment Blue (15: 6) 15 parts by weight Allyl methacrylate / methacrylic acid copolymer 10 parts by weight (copolymerization molar ratio 83/17) Cyclohexanone 15 parts by weight methoxypropyl acetate 20 Parts by weight propylene glycol monomethyl ether 40 parts by weight

-Methyl ethyl ketone 20.0 g-Propylene glycol monomethyl ether 20.0 g

(Preparation of Protective Layer) A 3% by weight aqueous solution of polyvinyl alcohol (degree of saponification: 98 mol%, degree of polymerization: 550) was coated on the photosensitive layer so that the dry coating weight was 2 g / m ² . Dry at 100 ° C. for 2 minutes.

(Evaluation of photosensitivity and suitability for safelight) On the thus obtained light-sensitive material, a Fuji step guide manufactured by Fuji Photo Film Co., Ltd. (ΔD = 0.15, discontinuous transmission optical density (A gray scale in which the value changes), and exposure was performed using a xenon lamp passed through an optical filter (Kenko BP-40) so as to have a known exposure energy. As an optical filter, Kenko BP-40 capable of exposing with monochromatic light of 400 nm was used for the purpose of estimating the suitability for exposure to a short-wavelength semiconductor laser. Thereafter, the film was immersed in a developer having the following composition at 25 ° C. for 10 seconds, developed, and the image area was inked. The sensitivity (clear sensitivity) was calculated from the highest number of steps at which the image was completely removed (Table 1).
A). Here, the clear sensitivity indicates the minimum energy required for image formation, and the lower the value, the higher the sensitivity.

<Developers in Examples 1 to 19 and Comparative Examples 1 to 3> An aqueous solution having the following composition and having a pH of 13: 1K potassium silicate 3.0 parts by weight Potassium hydroxide 1.5 parts by weight A compound represented by the following formula (ぺRex NBL; (manufactured by Kao Atlas Co., Ltd.)) 0.2 parts by weight Water 95.3 parts by weight

[0290]

Embedded image

To further evaluate the suitability for safelight, the obtained photographic material was exposed to a yellow light (500 minutes) for 30 minutes before exposure.
, and exposed and developed in the same manner. A light-sensitive material in which fog occurred (without safelight suitability) was evaluated as x, and a light-sensitive material in which fog did not occur (with safelight suitability) was evaluated as ○ (see Table A).

In Comparative Example 1, the sensitizing dye was changed from A-1 (maximum absorption wavelength 409 nm) to AR-
3 (maximum absorption wavelength: 480 nm) was similarly evaluated. As Comparative Examples 2 and 3, titanocene compounds were used instead of the electron transfer initiator.

[0293]

[Table 18]

The sensitizing dyes in the examples are those exemplified in the present specification, and the structures of other compounds are as follows.

[0295]

Embedded image

As shown in Table-A, the lithographic printing plate of the present invention has a very high sensitivity, and shows a sufficient sensitivity for the scanning exposure method. It was also shown that there was no problem with yellow light safety.

[0297]

The photopolymerizable composition of the present invention, when used in the photosensitive layer of a lithographic printing plate precursor, can have sufficient sensitivity suitable for scanning exposure with a short-wavelength semiconductor laser such as InGaN. The lithographic printing plate for scanning exposure using the photopolymerizable composition of the present invention for the photosensitive layer has remarkably improved fog under a yellow lamp, and the workability of handling the plate can be greatly improved. The photopolymerizable composition of the present invention has a molecular weight of 350 to
It has excellent sensitivity to a wavelength of 450 nm and very excellent storage stability.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/032 G03F 7/032 (72) Inventor Yasufumi Murota 4000 Kawajiri, Yoshida-cho, Haribara-gun, Shizuoka Prefecture Makoto Fujisha Inside Film Co., Ltd. (72) Inventor Kazuto Kunida 4,000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Fujisha Shin-Film Co., Ltd. F-term (reference) 2H025 AA00 AA01 AB03 AC01 AC08 AD01 BC31 BC51 CA01 CA14 CA18 CA20 CA27 CA28 CA30 CA35 CA41 CA48 CA50 CB52 FA03 FA10 FA17 2H096 AA07 AA08 BA05 BA06 BA20 EA02 EA04 GA08 4J011 QA01 QA02 QA03 QA06 QA08 QA11 QA12 QA13 QA22 QA23 QA24 QB19 QB24 SA01 SA03 SA13 SA16 SA21 SA23 SA51 SA48 SA41 SA48 UA06 VA01 WA01

Claims (4)

[Claims] 1. It is not sensitive to light having a wavelength of 500 nm or more.
A photopolymerizable composition comprising an electron transfer initiation system according to any one of the following (i) to (iii) corresponding to a short wavelength laser having an exposure light source wavelength from nm to 450 nm. (i) Electron donating initiator and sensitizing dye (ii) Electron accepting initiator and sensitizing dye (iii) Electron donating initiator, sensitizing dye and electron accepting initiator (ternary initiator system) 2. The method according to claim 1, wherein the electron donating initiator is represented by the following general formula (I):
The photopolymerizable composition according to claim 1, which is a compound represented by the formula: Embedded image 中 In the formula (I), Y is an element of Group III of the periodic table, B, A
represents 1 or Ga, and R ¹ , R ² , R ³ and R ⁴ may be the same or different, and each represents an organic group. However, at least one of R ¹ , R ² , R ³ and R ⁴ is a substituted or unsubstituted alkyl group. Zn ⁺ represents an n-valent cation, and n represents an integer of 1 to 6. ｝ 3. An electron-accepting initiator represented by the following general formula (II):
The photopolymerizable composition according to claim 1, which is a compound represented by the formula: Embedded image 中 In the formula (II), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be the same or different and each represents an organic group. Here, at least one of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represents an organic group represented by the following general formula (III). X ^m- represents a m-valent anion, and m represents an integer of 1 to 6. ｝ (3) 中 In the formula (III), R ¹¹ , R ¹² and R ¹³ may be the same or different and each represents an organic group. L represents a divalent linking group containing a hetero atom. ｝ 4. It is not sensitive to light of 500 nm or more,
a photopolymerizable composition containing an electron donating initiator, a sensitizing dye, and an electron accepting initiator (ternary initiator) corresponding to a short wavelength laser having an exposure light source wavelength of from 450 nm to 450 nm. Lithographic printing plate.