JP2005227320A - Image recording material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image recording material having high sensitivity, good in highlighting, excellent in reproducibility of dots and thin lines, and capable of maintaining highlighting without lowering sensitivity even when a plate is stored over a prolonged period of time. <P>SOLUTION: The image recording material has on a support a photosensitive layer containing: (a) an addition polymerizable compound having an ethylenically unsaturated double bond as well as at least one photooxidizable group, or an addition polymerizable compound having an ethylenically unsaturated double bond obtained by reacting a polyepoxy compound with a (meth)acrylate having a hydroxyl group or a carboxyl group; (b) an organic linear polymeric binder; (c) a polymerization initiator; (d) a sensitizing dye; and (e) a compound having a sulfur atom and a carboxyl group within a molecule and having a molecular weight of ≤300. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an image recording material, and in particular, relates to an image recording material for a photosensitive lithographic printing plate having high sensitivity, excellent reproducibility of halftone dots and fine lines, and storage stability.

Conventionally, as a photosensitive lithographic printing plate, a PS plate having a configuration in which a lipophilic photosensitive resin is provided on a hydrophilic support is widely used. As a plate making method of a lithographic printing plate from the PS plate, Has obtained a desired printing plate by dissolving and removing the non-image area after mask exposure (surface exposure) through a lith film.
In recent years, digitization techniques for electronically processing, storing, and outputting image information using a computer have become widespread, and various new image output methods corresponding thereto have come into practical use. As a result, computer-to-plate (CTP) technology that scans highly directional light such as laser light according to digitized image information and directly manufactures printing plates without using a lith film is desired and applied. An original lithographic printing plate has been developed.

  In such a CTP system, violet LD (405 nm), Ar laser (488 nm), and FD-YAG laser (532 nm) need to form an image with less energy than a conventional lithographic printing plate that uses UV light as a mask. is there.

However, the laser-sensitive lithographic printing plate as described above generally has low sensitivity, and the highlight halftone dot disappears at a low exposure amount. In order to overcome this problem, for example, Patent Document 1 below includes a) a polymer binder, b) a compound having a polymerizable group and a photooxidizable group in the molecule, and c) a photoinitiator comprising a metallocene. Polymeric mixtures containing are proposed. However, the mixture has a problem in that the degree of deterioration with highlights increases with time, and the effect of increasing sensitivity is diminished.
JP-A-4-221958

  The object of the present invention is an image recording material that is highly sensitive, has good highlighting, is excellent in reproducibility of halftone dots and fine lines, and can maintain highlighting without lowering the sensitivity even when the plate is stored for a long period of time. Is to provide.

The present invention is as follows.
(1) An image recording material having a photosensitive layer containing the following components (a) to (e) on a support:
(A) An addition polymerizable compound having at least one photooxidizable group and having an ethylenically unsaturated double bond, or a reaction between a polyepoxy compound and a (meth) acrylate having a hydroxyl group or a carboxyl group An addition polymerizable compound having an ethylenically unsaturated double bond,
(B) an organic linear polymer binder,
(C) a polymerization initiator,
(D) a sensitizing dye, and (e) a compound having a molecular weight of 300 or less having a sulfur atom and a carboxyl group in the molecule.

According to the invention, an image recording material in which the organic pigment is a β and / or ε type phthalocyanine pigment is preferable.
Furthermore, according to the present invention, an image recording material in which the polymerization initiator is a titanocene compound is preferable.

  According to the present invention, there is provided an image recording material which has high sensitivity, good highlighting, excellent reproducibility of halftone dots and fine lines, and can maintain the highlighting without lowering the sensitivity even when the plate is stored for a long time. Provided.

Hereinafter, a photosensitive lithographic printing plate which is a preferred embodiment of the present invention will be described in detail.
The image recording material that is scanned and exposed with the laser beam of the present invention comprises (a) an addition polymerizable compound having at least one photooxidizable group and having an ethylenically unsaturated double bond, or a polyepoxy compound and a hydroxyl group or Addition polymerizable compound having ethylenically unsaturated double bond obtained by reaction with (meth) acrylate having carboxyl group, (b) organic linear polymer binder, (c) polymerization initiator, (d) increase A photosensitive layer containing a dye-sensitive dye and (e) a compound having a sulfur atom and a carboxyl group in the molecule and having a molecular weight of 300 or less is provided on the support. Such a photosensitive layer can be formed by a method of coating a photosensitive composition containing the above components on a support. Hereinafter, these components will be specifically described.

[(e) Compound having a molecular weight of 300 or less having a sulfur atom and a carboxyl group in the molecule]
In the present invention, the compound having a sulfur atom and a carboxyl group in the molecule and having a molecular weight of 300 or less is preferably a compound represented by the following general formula (I) or general formula (II).

In the general formula (I), R ₁ represents a C1-3 alkylene group, and X ₁ and X ₂ each independently represent an oxygen atom or a sulfur atom. However, at least one of X ₁ and X ₂ is a sulfur atom.

  Of the compounds represented by the general formula (I), compounds containing at least one sulfur atom in the molecule are preferred. More preferred are compounds represented by the following general formulas (Ia) to (Ic).

In the formula, R ₁ has the same meaning as in formula (I).

In the general formula (II), X ₃ represents a single bond or a divalent linking group, Y ₁ represents a monovalent organic group, and Z ₁ represents a monovalent organic group having a carboxyl group. n represents an integer of 0 to 5.

Examples of the divalent linking group represented by X ₃ include a linear or branched, chain or cyclic alkylene group having 1 to 20 carbon atoms, and a linear or branched, chain or cyclic alkenylene group having 2 to 20 carbon atoms. Group, an alkynylene group having 2 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms (monocyclic, heterocyclic), -C (= O) N-, -OC (= O) N-, -NC (= O ) N-, -SC (= O) N-, -C (= S)-, -OC (= S)-, -NC (= S)-, -SC (= S)-, -O-,- C (═O) O—, —C (═O) —, —S—, —SO ₂ —, —SO ₃ —, —SO ₂ N—, —NH—, —NR—, —NAr—, —N = N-, -N (= NH) N- and the like are preferable. Here, R represents alkyl, alkenyl, or alkynyl, and Ar represents aryl (monocyclic or heterocyclic).

  Moreover, the said bivalent coupling group may have a substituent, As an example of the substituent, C1-C20 linear or branched, linear or cyclic alkylene, C2-C20 Linear or branched, linear or cyclic alkenylene, an alkynyl group having 2 to 20 carbon atoms, an arylene having 6 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an alkoxycarbonyloxy group having 2 to 20 carbon atoms, An aryloxycarbonyloxy group having 7 to 20 carbon atoms, a carbamoyloxy group having 1 to 20 carbon atoms, a carbonamido group having 1 to 20 carbon atoms, a sulfonamide group having 1 to 20 carbon atoms, and a carbamoyl group having 1 to 20 carbon atoms , Sulfamoyl group having 0 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, aryloxycarbonyl group having 7 to 20 carbon atoms, 2-2 carbon atoms An alkoxycarbonyl group, an N-acylsulfamoyl group having 1 to 20 carbon atoms, an N-sulfamoylcarbamoyl group having 1 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, and an aryl having 6 to 20 carbon atoms A sulfonyl group, an alkoxycarbonylamino group having 2 to 20 carbon atoms, an aryloxycarbonylamino group having 7 to 20 carbon atoms, an amino group having 0 to 20 carbon atoms, an imino group having 1 to 20 carbon atoms, and a 3 to 20 carbon atoms Ammonio group, carboxyl group, sulfo group, oxy group, mercapto group, C1-C20 alkylsulfinyl group, C6-C20 arylsulfinyl group, C1-C20 alkylthio group, C6-C20 Arylthio group, ureido group having 1 to 20 carbon atoms, heterocyclic group having 2 to 20 carbon atoms, acyl group having 1 to 20 carbon atoms, 0 to 20 carbon atoms Sulfamoylamino group, silyl group having 2 to 20 carbon atoms, hydroxy group, isocyanate group, isocyanide group, halogen atom (eg, fluorine atom, chlorine atom, bromine atom), cyano group, nitro group, onium group, etc. Can be mentioned.

Specific examples of the monovalent organic group Y ₁ include a linear or branched, chain or cyclic alkyl group having 1 to 20 carbon atoms, and a linear or branched, chain or cyclic alkenyl group having 2 to 20 carbon atoms. , An alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an alkoxycarbonyloxy group having 2 to 20 carbon atoms, and an aryloxycarbonyloxy group having 7 to 20 carbon atoms , A carbamoyloxy group having 1 to 20 carbon atoms, a carbonamido group having 1 to 20 carbon atoms, a sulfonamide group having 1 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a sulfamoyl group having 0 to 20 carbon atoms, carbon C1-C20 alkoxy group, C6-C20 aryloxy group, C7-C20 aryloxycarbonyl group, C2-C20 alkoxycarbonyl group, C1-2 N-acylsulfamoyl group, C1-C20 N-sulfamoylcarbamoyl group, C1-C20 alkylsulfonyl group, C6-C20 arylsulfonyl group, C2-C20 alkoxy Carbonylamino group, aryloxycarbonylamino group having 7 to 20 carbon atoms, amino group having 0 to 20 carbon atoms, imino group having 1 to 20 carbon atoms, ammonio group having 3 to 20 carbon atoms, carboxyl group, sulfo group, oxy Group, mercapto group, alkylsulfinyl group having 1 to 20 carbon atoms, arylsulfinyl group having 6 to 20 carbon atoms, alkylthio group having 1 to 20 carbon atoms, arylthio group having 6 to 20 carbon atoms, ureido having 1 to 20 carbon atoms A group having 2 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, a sulfamoylamino group having 0 to 20 carbon atoms, and a group having 2 to 20 carbon atoms A silyl group, a hydroxy group, an isocyanate group, an isocyanide group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a nitro group, an onium group, and the like can be given. These substituents may further have a substituent.

As the monovalent Specific examples of the organic group Z ₁ is alkyl of 2 to 20 carbon atoms having a carboxyl group, an aryl, an aralkyl group.

  Specific examples of the compounds represented by formula (I) and formula (II) are shown below, but are not limited thereto.

These compounds preferably have a molecular weight of 300 or less, more preferably 250 or less.
These compounds are preferably 0.1% by mass or more and 5.0% by mass or less based on the entire photosensitive layer. Preferably they are 0.3 mass% or more and 3.0 mass% or less. When the content is 0.1% by mass or more, highlighting with time can be further improved, and when the content is 5.0% by mass or less, sensitivity can be further increased. Although the mechanism of action of these compounds is not clear, the substrate adhesion effect is achieved by the carboxyl group, and the compound functions as an antioxidant and the photosensitive system is stabilized, so that high sensitivity and stability over time can be obtained. It is thought that it is compatible.

[(A) Addition polymerizable compound having an ethylenically unsaturated double bond]
The addition polymerizable compound having an ethylenically unsaturated double bond used in the present invention has at least one photooxidizable group and an ethylenically unsaturated double bond, or a polyepoxy compound and It is an addition polymerizable compound having an ethylenically unsaturated double bond obtained by reaction with a (meth) acrylate having a hydroxyl group or a carboxyl group.

[Addition polymerizable compound having ethylenically unsaturated double bond obtained by reaction of polyepoxy compound with (meth) acrylate having hydroxyl group or carboxyl group]
As an addition polymerizable compound having an ethylenically unsaturated double bond obtained by the reaction of a polyepoxy compound and a (meth) acrylate having a hydroxyl group or a carboxyl group of the present invention, as an epoxy (meth) acrylate, For example, (meth) acrylic acid or hydroxy such as hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol tri (meth) acrylate, tetramethylolethane tri (meth) acrylate, etc. (Meth) acrylate compounds, (poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) penta Tylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl Aliphatic polyepoxy compounds such as ether, phenol novolac polyepoxy compounds, brominated phenol novolac polyepoxy compounds, (o-, m-, p-) cresol novolac polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds Aromatic polyepoxy compounds such as sorbitan polyglycidyl ether, triglycidyl isocyanurate, triglycidyl tris (2-hydroxy Reaction product of poly epoxy compound heterocyclic polyepoxy compounds chill) isocyanurate.

[Addition polymerizable compound having at least one photooxidizable group and having an ethylenically unsaturated double bond]
The addition polymerizable compound of the present invention having at least one photooxidizable group and having an ethylenically unsaturated double bond includes at least one photooxidizable group in the molecule and, if desired, at least one urethane. Polymeric compounds containing groups are particularly preferred. Suitable photooxidizable groups are in particular amino groups, urea groups, thio groups (which can also be components of heterocyclic rings) and carboxyl groups (in combination with olefinic double bonds). Examples of this type of group include triethanolamino, triphenylamino, thiourea, imidazole, oxazole, thiazole, acetylacetonyl, N-phenylglycine and ascorbic acid groups. Of these, polymerizable compounds having primary, secondary and especially tertiary amino groups are preferred.
Preferred examples of the addition polymerizable compound containing a photooxidizable group include compounds represented by the following general formula (III).

  [Where Q is

Or -S- is represented. R represents an alkyl group, a hydroxyalkyl group or an aryl group. R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group or an alkoxyalkyl group. R ⁷ represents a hydrogen atom, a methyl group or an ethyl group. X ¹ represents a saturated hydrocarbon group having 2 to 12 carbon atoms. X ² represents a (c + 1) -valent saturated hydrocarbon group, and 5 or less methylene groups may be substituted with an oxygen atom. D ¹ and D ² each independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms. E is a saturated hydrocarbon group having 2 to 12 carbon atoms, an alicyclic group having 5 to 7 ring members (which can contain up to 2 N, O or S atoms as ring members if desired), 6 carbon atoms Represents an ˜12 arylene group or a 5- or 6-ring heteroaromatic group. a is 0 or a number from 1 to 4, b is 0 or 1, c is an integer from 1 to 3, m is 2, 3 or 4 depending on the valence of Q, and n is 1 Are integers of ~ m, and all symbols of the same definition can be the same or different from each other.

  The compound represented by the above general formula (III) and its production method and use are described in detail in European Patent No. 287,818 (corresponding to JP-A 63-277653). In the compound of the general formula (III), when one or more R groups or one or more groups of the type listed in square brackets are bonded to the central group Q, these groups are mutually May be different.

Compounds in which all substituents of Q are polymerizable groups, i.e., m is n are generally preferred. In general, a is 0 in no more than one group, preferably not 0 in all groups. Preferably a is 1.
When R is an alkyl group or a hydroxyalkyl group, this group generally has 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms. When R is an aryl group, it may generally be monocyclic or bicyclic, preferably monocyclic, and may be substituted with an alkyl or alkoxy group having up to 5 carbon atoms or a halogen atom.
When R ⁵ and R ⁶ are alkyl group or an alkoxyalkyl group, which may contain 1 to 5 carbon atoms. R ⁷ is preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.
X ¹ is preferably a linear or branched aliphatic or alicyclic group (preferably having 4 to 10 carbon atoms). X ² preferably has 2 to 15 carbon atoms, up to 5 of which may be substituted by oxygen atoms. When these are simple carbon chains, those having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, are generally used. X ² is preferably an alicyclic group having 5 to 10 carbon atoms, and particularly preferably a cyclohexylene group. D ¹ and D ² may be the same or different and together with two nitrogen atoms form a saturated heterocyclic ring having 5 to 10 ring members, preferably 6 ring members.
If E is an alkylene group, E preferably has 2 to 6 carbon atoms and as an arylene group is preferably a phenylene group. A preferred alicyclic group is a cyclohexylene group, and a preferred aromatic heterocyclic product is one having N or S as a hetero atom and 5 or 6 ring members. The value of c is preferably 1.

  As another addition-polymerizable compound containing a photo-oxidizable group, other suitable compounds include compounds represented by the following formula (IV).

[In the formula (IV), Q, R, R ⁵ , R ⁶ , R ⁷ , m and n have the same meaning as in the formula (III), and Q is the following group

  (In the formula, E ′ represents the following formula (V).)

Wherein c has the same meaning as in formula (III); a1 and b1 are integers from 1 to 4. ]
The compounds of the above formula and their production and use are described in detail in EP 316,706 (corresponding to JP-A-1-165613).

Still other suitable compounds of the addition polymerizable compound having a photooxidizable group include the following general formula (
And a compound represented by VI).

[In Formula (VI), Q ¹ is

X ¹ is C _i H _2i or

D ³ is a saturated hydrocarbon group having 4 to 8 carbon atoms (this forms a 5- or 6-membered ring together with the nitrogen atom), and Z is a hydrogen atom or the following formula

I and k are each independently an integer of 1 to 12, n ′ is ¹ , 2 or 3, depending on the valence of Q ¹ , and R ⁷ , X ¹ , X ² , D ¹ , D ² , a and b have the meaning given in the general formula (III), all symbols of the same definition may be identical or different from each other and at least one substitution on the Q group A in the group is 0. ]

Of the compounds of formula (VI), those containing at least one urethane group in addition to the urea group are preferred.
The symbol a in the formula (VI) is preferably 0 or 1. i is preferably a number of 2 to 10.
The polymerizable compound of the formula (VI) can be formed similarly to the compound of the general formula (III). The compound of the formula (VI) and its production process are described in detail in EP 355,387 (corresponding JP-A-2-73813).

  In the present invention, the amount of the (a) addition polymerizable compound used is preferably 10 to 80% by mass, more preferably 20 to 60% by mass of the photosensitive layer.

[(B) Organic linear polymer binder]
For example, when the organic linear polymer binder is a water-soluble organic polymer, water development is possible. Examples of such an organic polymer include addition polymers having a carboxylic acid group in the side chain, such as JP 59-44615, JP-B 54-34327, JP-B 58-12577, JP-B 54-. No. 25957, JP 54-92723, JP 59-53836, JP 59-71048, ie, methacrylic acid copolymer, acrylic acid copolymer, itacon Examples include acid copolymers, crotonic acid copolymers, maleic acid copolymers, and partially esterified maleic acid copolymers.

Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, a product obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group is useful. Among these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition-polymerizable vinyl monomers as required] copolymer and [allyl (meth) acrylate (meth) acrylic acid / as required Other addition polymerizable vinyl monomers] copolymers are preferred. In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble organic polymer. In order to increase the strength of the cured film, alcohol-soluble polyamide, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.
JP-B-7-120040, JP-B-7-120041, JP-B-7-120042, JP-B-8-12424, JP-A-63-287944, JP-A-63-287947, JP-A-1-271741 And polyurethane resins described in JP-A-11-352691 are also useful for the use of the present invention.

These polymer polymers can improve the strength of the cured film by introducing a radical reactive group into the side chain. Functional groups that can undergo addition polymerization reactions, such as unsaturated bond groups, amino groups, and epoxy groups, and functional groups that can become radicals upon light irradiation include mercapto groups, thiol groups, halogen atoms, triazine structures, onium salt structures, etc. Moreover, a carboxyl group, an imide group, etc. are mentioned as a polar group. The functional group capable of undergoing addition polymerization reaction is particularly preferably an ethylenically unsaturated bond group such as an acryl group, a methacryl group, an allyl group, or a styryl group, but also an amino group, a hydroxy group, a phosphonic acid group, a phosphoric acid group, or a carbamoyl group. A functional group selected from an isocyanate group, a ureido group, a ureylene group, a sulfonic acid group, and an ammonio group is also useful.
In order to maintain the developability of the composition, the polymer of the present invention preferably has an appropriate molecular weight and acid value. Specifically, it is preferable to use a high molecular weight polymer having a weight average molecular weight Mw of 5000 to 300,000 and an acid value of 0.2 to 5.0 meq / g.

  These polymer polymers can be mixed in an arbitrary amount in the entire composition. Preferably it is 10 to 90%, More preferably, it is 30 to 80%. The addition polymerizable compound and the organic linear polymer conjugate are preferably in the range of 1/9 to 9/1 by mass ratio. A more preferable range is 2/8 to 8/2, still more preferably 3/7 to 7/3.

[(C) Polymerization initiator]
As the polymerization initiator used in the present invention, various photoinitiators known in patents, literatures, etc., or a combination system (photoinitiation system) of two or more photoinitiators should be appropriately selected and used. Can do.

  For example, a complex initiation system of dye and amine (Japanese Patent Publication No. 44-20189), hexaarylbiimidazoles (Japanese Patent Publication No. 47-2528, Japanese Patent Publication No. 54-155292, Japanese Patent Publication No. 59-140203, Japanese Patent Laid-Open No. Hei. No. 10-36354), cyclic cis-α-dicarbonyl compounds (JP-A 48-84183, etc.), triazine compounds (JP-A 54-151024, etc.), organic peroxides (JP No. 59-1504, JP-A-59-140203, JP-A-59-189340, JP-A-62-174203, JP-B-62-1641, US Pat. No. 4,766,055, etc.), activity Halogen (JP-A 63-258903, JP-A 2-63054, etc.), borate compounds (JP-A 62-143044, JP-A 1-222900) , JP-A-9-188585, JP-A-9-188686, JP-A-9-188710, etc.) and titanocene compounds (JP-A 63-221110, JP-A-4-221958, JP-A-4-219756). No. 6, JP-A-6-295061, JP-A-8-334897, etc.).

In the present invention, a system using a titanocene compound is particularly preferable in view of sensitivity.
Various titanocene compounds can be used. For example, various titanocene compounds described in JP-A-59-152396 and JP-A-61-151197 can be appropriately selected and used. . More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5 , 6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2 , 4,6-trifluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,6-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4 -Di-fluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti- Bis-2, 6 Difluoro-1-yl, di - cyclopentadienyl -Ti- bis-2,6-difluoro-3- (pyrr-1-yl) - can be exemplified 1-yl and the like.

Furthermore, auxiliary agents such as amine compounds and thiol compounds may be added to the polymerization initiator used in the present invention as necessary, and the polymerization initiation ability can be further enhanced by adding these hydrogen donating compounds.
The amount of these polymerization initiators used is preferably 0.05 to 100 parts by weight, more preferably 0.1 to 70 parts by weight, and still more preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the addition polymerizable compound. Part range.

[(D) Sensitizing dye]
The sensitizing dye used in the photosensitive lithographic printing plate of the present invention is not particularly limited, but merocyanine dyes represented by the following general formula (VII), benzopyrans or coumarins represented by the following general formula (VIII), Aromatic ketones represented by the following general formula (IX), anthracene represented by the following general formula (X), styryl dyes represented by the following general formula (XI), and the following general formula (XII) The cyanine type | system | group represented etc. can be mentioned.

(In the formula (VII), A represents an S atom or —N (R ⁶ ) —, R ⁶ represents a monovalent nonmetallic atomic group. Y represents a dye in combination with adjacent A and adjacent carbon atoms. X ¹ and X ² each independently represent a monovalent nonmetallic atomic group, and X ¹ and X ² are bonded to each other to form an acidic nucleus of the dye. (Details of X ¹ and X ² will be described later.)

(In the formula (VIII), = Z represents a carbonyl group, a thiocarbonyl group, an imino group or an alkylidene group represented by the partial structural formula (I ′). X ¹ and X ² are those of the general formula (VII). X ¹ and X ² are synonymous, and R ⁷ to R ¹² each independently represents a monovalent nonmetallic atomic group.)

(In the formula (IX), Ar ₃ represents an aromatic group or a heteroaromatic group which may have a substituent. R ¹³ represents a monovalent non-metallic atomic group, preferably an aromatic group. Or it is a heteroaromatic group, and Ar ₃ and R ¹³ may be bonded to each other to form a ring.)

(In the formula (X), X ³ , X ⁴ and R ¹⁴ to R ²¹ each independently represents a monovalent non-metallic atomic group. X ³ and X ⁴ are electron donating properties whose Hammett's substituent constant is negative. It is preferably a group.)

(In the formula (XI), X ¹ and X ² have the same meanings as in the general formula (VII), and R ²² to R ²⁷ are each independently a monovalent non-metallic atomic group, preferably R ²² To R ²⁶ , at least one is an electron-donating substituent having a negative Hammett substituent constant.)

(In the formula (XII), Z ¹ and Z ² represent a nonmetallic atom group necessary for forming a benzimidazole or naphthimidazole ring, and may be the same or different. R ¹ , R ² , R ³ and R ⁴ represents an optionally substituted alkyl group, X ⁻ represents a counter anion, and n is 0 or 1.)

  Examples of the xanthene dye include rhodamine B, rhodamine 6G, ethyl eosin, alcohol-soluble eosin, pyronin Y, and pyronin B.

Preferable examples of the monovalent nonmetallic atomic group represented by X ¹ to X ⁴ and R ⁶ to R ²⁷ in the general formulas (VII) to (XII) include the following groups.
Hydrogen atom, alkyl group (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, Octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, Cyclopentyl, 2-norbornyl, chloromethyl, bromomethyl, 2-chloroethyl, trifluoromethyl, methoxymethyl, methoxyethoxyethyl, allyloxymethyl, phenoxymethyl, methylthiomethyl, tolylthiomethyl Group, ethylamino 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, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoyl Methyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, Phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatoxy Butyl, benzyl, phenethyl, α-methylbenzyl, 1-methyl-1-phenylethyl, p-methylbenzyl, cinnamyl, allyl, 1-propenylmethyl, 2-butenyl, 2- Methyl allyl group, 2-methylpropenylmethyl group, 2-propynyl group, -Butynyl group, 3-butynyl group, etc.), aryl group (for example, phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxy group) Phenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxy Phenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophene Group, phosphonophenyl group, phosphonatophenyl group, etc.), heteroaryl group (for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine) , Pyrimidine, pyridazine, indolizine, isoindolizine, indoir, indazole, purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, sinoline, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthroline, phthalazine, phenlazazine Phenoxazine, furazane, phenoxazine, etc.), alkenyl groups (eg vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro- 1-ethenyl group, etc.), alkynyl group (for example, ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group, etc.), 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-diaryl Carbamoyloxy group, N-alkyl-N-arylcarbamoylo Si group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkyl Ureido group, N′-arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N -Alkylureido group, N'-alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N -Alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'-diaryl-N-a Lilleureido 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, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl Group, 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, alkyl sulf Inyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N -Alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (-PO ₃ H ₂₎ and its conjugated base group (hereinafter, referred as phosphonato group ), Dialkylphosphono group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphonates Group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as aryl) Phosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugated base group (hereinafter referred to as phosphonatoxy group), dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy group (—OPO ₃ (alkyl) (aryl)), monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group , Alkylphosphonatoki Referred to as group), monoarylphosphono group (-OPO ₃ H (aryl)) and its conjugated base group (hereinafter referred to as aryl phosphite Hona preparative group), a cyano group, a nitro group, etc., and more Of the substituents, a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an alkoxy group, and an acyl group are particularly preferable.
Further, examples of the acidic nucleus of the dye formed by combining X ¹ and X ² with each other include the same ring formed by connecting G ¹ and G ² described later to each other.

  Examples of the basic nucleus of the dye formed together with A adjacent to Y in the general formula (VII) and the adjacent carbon atom include 5-, 6-, and 7-membered nitrogen-containing or sulfur-containing heterocycles. A 5- or 6-membered heterocyclic ring is preferable.

Examples of nitrogen-containing heterocycles include those constituting the basic nucleus in merocyanine dyes described in LGBrooker et al., J. Am. Chem. Soc., 73, 5326-5358 (1951) and references Any of those known as can be suitably used.
Specific examples include thiazoles (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4,5- Di (p-methoxyphenylthiazole), 4- (2-thienyl) thiazole, etc.), benzothiazoles (for example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7- Chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzo Cheer , 6-methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-di Oxymethylenebenzothiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, 6-dimethylaminobenzothiazole, 5-ethoxycarbonylbenzothiazole, etc.), naphthothiazoles (for example, naphtho [1,2] thiazole, naphtho [2 , 1] thiazole, 5-methoxynaphtho [2,1] thiazole, 5-ethoxynaphtho [2,1] thiazole, 8-methoxynaphtho [1,2] thiazole, 7-methoxynaphtho [1,2] thiazole, etc.) , Chianafuteno 7 ′, 6 ′, 4,5-thiazole (for example, 4′-methoxythianaphtheno-7 ′, 6 ′, 4,5-thiazole, etc.), oxazole (for example, 4-methyloxazole, 5-methyloxazole) 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole, 4,5-dimethyloxazole, 5-phenyloxazole, etc.), benzoxazoles (benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole) , 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 6-methoxybenzoxazole, 5-methoxybenzoxazole, 4-ethoxybenzoxazole, 5-chloro Benzoki Sol, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.), naphthoxazoles (eg, naphtho [1,2] oxazole, naphtho [2,1] oxazole, etc.), selenazoles (eg, , 4-methylselenazole, 4-phenylselenazole, etc.), benzoselenazoles (for example, benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, tetrahydrobenzoselena) Sol etc.), naphthoselenazoles (eg naphtho [1,2] selenazole, naphtho [2,1] selenazole etc.), thiazolines (eg thiazoline, 4-methylthiazoline etc.), 2-quinolines (eg Quinoline, 3-methyl Norin, 5-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline, etc.), 4 -Quinolines (eg, quinoline, 6-methoxyquinoline, 7-methylquinoline, 8-methylquinoline, etc.), 1-isoquinolines (eg, isoquinoline, 3,4-dihydroisoquinoline, etc.), 3-isoquinolines (eg, , Isoquinoline, etc.), benzimidazoles (eg, 1,3-diethylbenzimidazole, 1-ethyl-3-phenylbenzimidazole, etc.), 3,3-dialkylindolenins (eg, 3,3-dimethylindolenin, 3,3,5-trimethylindolenine, 3,3,7-tri Methylindolenine etc.), 2-pyridines (eg pyridine, 5-methylpyridine etc.), 4-pyridine (eg pyridine etc.) and the like.

Examples of the sulfur-containing heterocycle include a dithiol partial structure in dyes described in JP-A-3-296759.
Specific examples include benzodithiols (for example, benzodithiol, 5-t-butylbenzodithiol, 5-methylbenzodithiol, etc.), naphthodithiols (for example, naphtho [1,2] dithiol, naphtho [2,1] Dithiols, etc.), dithiols (for example, 4,5-dimethyldithiols, 4-phenyldithiols, 4-methoxycarbonyldithiols, 4,5-dimethoxycarbonylbenzodithiols, 4,5-ditrifluoromethyldithiols, 4 , 5-dicyanodithiol, 4-methoxycarbonylmethyldithiol, 4-carboxymethyldithiol and the like.

  As mentioned above, for the sake of convenience, the description used in the description of the heterocyclic ring has conventionally used the name of the heterocyclic mother skeleton, but when forming the basic skeleton partial structure of the sensitizing dye, for example, in the case of the benzothiazole skeleton It is introduced in the form of an alkylidene type substituent with one degree of unsaturation, such as a 3-substituted-2 (3H) -benzothiazolylidene group.

  Among the sensitizing dyes that can be used in the present invention, a dye more preferable from the viewpoint of high sensitivity is a dye represented by the following general formula (1) having an absorption maximum in a wavelength range of 360 nm to 450 nm.

(In the general formula (1), A represents an aromatic ring or a hetero ring which may have a substituent, and X represents an oxygen atom, a sulfur atom or N- (R ₃ ). R ₁ , R ₂ and R ₃ each independently represents a hydrogen atom or a monovalent nonmetallic atomic group, and A and R ₁ and R ₂ and R ₃ are bonded to each other to form an aliphatic or aromatic ring. May be.)

The general formula (1) will be described in more detail. R ₁ , R ₂ and R ₃ are each independently a hydrogen atom or a monovalent nonmetallic atomic group, preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, substituted or non-substituted It represents a substituted aryl group, a substituted or unsubstituted aromatic heterocyclic residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, and a halogen atom.

Preferable examples of R ₁ , R ₂ and R ₃ will be specifically described. Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group. Of these, 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.

As the substituent of the substituted alkyl group, a monovalent nonmetallic atomic group excluding hydrogen is used, and preferred examples include a halogen atom (—F, —Br, —Cl, —I), a hydroxyl group, an 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-arylcarbamoyloxy group, alkylsulfoxy group, Reelsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N'-alkylureido group, N ', N'-dialkylureido group, N'-arylureido Group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′- Alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'- Aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-ary Luureido 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, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group , 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 , Alkylsul Finyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N -Alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (-PO ₃ H ₂₎ and its conjugated base group (hereinafter, phospho Referred to as bets group), dialkyl phosphono group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )) , Monoalkyl phosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkyl phosphonate group), monoaryl phosphono group (—PO ₃ H (aryl)) and its conjugate base group (Hereinafter referred to as aryl phosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonateoxy group), dialkyl phosphonooxy group (—OPO ₃ (alkyl)) ₂ ), a diarylphosphonooxy group (—OPO ₃ (aryl) ₂ ), an alkylarylphosphonooxy group (—OPO ₃ (alkyl) (aryl)), a monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) )and The conjugated base group (hereinafter referred to as alkyl phosphonophenyl group), monoaryl phosphonooxy group (-OPO ₃ H (aryl)) and its conjugated base group (hereinafter referred to as aryl phosphite Hona preparative group), a cyano group , A nitro group, an aryl group, a heteroaryl group, an alkenyl group, and an alkynyl group.

  Specific examples of the alkyl group in these substituents include the above-described alkyl groups, and specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, and a cumenyl group. , Chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylamino Phenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group Cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl phenyl group, phosphonophenyl phenyl group and the like.

As the preferred heteroaryl group as R ₁ , R ₂ and R ₃ , a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms is used. Examples of particularly preferred heteroaryl groups Is, for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indolizine, indazole, indazole, Purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, sinoline, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthrolin, phthalazine, phenalazine, phenoxazine, flaza And phenoxazine and the like. These may be further benzo-fused and may have a substituent.

Examples of preferable alkenyl groups as R ₁ , R ₂ and R ₃ include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group and the like, and alkynyl Examples of the group include ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like. Examples of G ₁ in the acyl group (G ₁ CO—) include hydrogen and the above alkyl groups and aryl groups. Among these substituents, even more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N— Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfa Yl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphine group Examples include an onato group, a phosphonooxy group, a phosphonateoxy group, an aryl group, and an alkenyl group.

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms.

Specific examples of preferable substituted alkyl groups as R ₁ , R ₂ and R ₃ obtained by combining the substituent and the alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxy Methyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, 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, methoxycarbo Nylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl- N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobu Group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonateoxybutyl 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.

Specific examples of preferred aryl groups as R ₁ , R ₂ and R ₃ include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable. .

Specific examples of preferred substituted aryl groups as R ₁ , R ₂ and R ₃ include those having a monovalent non-metallic atomic group excluding hydrogen as a substituent on the ring-forming carbon atom of the aryl group described above. . Examples of preferred substituents include the aforementioned alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group. Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carbo Cyphenyl 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, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphono Enyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group, 2- Examples thereof include a methylpropenylphenyl group, a 2-propynylphenyl group, a 2-butynylphenyl group, and a 3-butynylphenyl group.

Next, A in the general formula (1) will be described. A represents an aromatic ring or a hetero ring which may have a substituent. Specific examples of the aromatic ring or hetero ring which may have a substituent include R ₁ and R in the general formula (1). similar to those described in ₂ and R ₃ can be exemplified.

  The sensitizing dye represented by the general formula (1) of the present invention includes an acidic nucleus as shown above, an acidic nucleus having an active methylene group, a substituted or unsubstituted aromatic ring or heterocyclic ring. These can be synthesized by referring to Japanese Patent Publication No. 59-28329.

  Preferred specific examples (D1) to (D38) of the compound represented by the general formula (1) are shown below. In addition, an isomer with a double bond connecting an acidic nucleus and a basic nucleus is not limited to either isomer.

  These sensitizing dyes are preferably used in the range of 1.0 to 10.0% by mass of the total components of the photosensitive layer.

  The sensitizing dyes represented by the formulas (VII) to (XII) of the present invention can be easily synthesized by using known synthetic methods and related synthetic methods, for example, the method described in JP-B-59-28329.

[Other ingredients]
The photosensitive layer of the photosensitive lithographic printing plate of the present invention contains the above components (a) to (e) as essential components, but preferably further contains an organic pigment dispersion.
Hereinafter, the organic pigment dispersion preferably contained in the photosensitive layer of the photosensitive lithographic printing plate of the present invention will be described.

  Preferred organic pigments used in the present invention are described below by C.I. Number described in the Color Index (Published by The Society of Dyes and Colorists, Third Edition).

  For example, Pigment Violet 29 (perylene pigment) Pigment Violet 19 (quinacridone pigment), Pigment Violet 1, 3 (basic dye lake pigment) Pigment Blue 60 (slen pigment), Pigment Blue 15, 15: 3. 6 (phthalocyanine pigment) and the like, and β- and / or ε-type phthalocyanine pigments are preferable, among which Pigment Blue 60 and Pigment Blue 15, 15: 3, 15: 6, and the like are particularly preferable.

In the present invention, when the coloring compound constituting the organic pigment dispersion takes a molecular dispersion state (dissolution) in the photosensitive layer instead of a solid dispersion, an adverse effect such as an increase in fog or desensitization occurs. It is preferable to use a pigment that has as little influence as possible.
Next, the general dispersion method of the organic pigment in the present invention will be described, but the present invention is not limited by these descriptions.
Conventionally, these organic pigments are supplied after drying by various methods after synthesis. Usually, it is dried from an aqueous medium and supplied as a powder. However, since water requires a large latent heat of vaporization for drying, a large amount of heat energy is given to dry it to form a powder. Therefore, the pigment usually forms an aggregate (secondary particle) in which primary particles are aggregated.
It is not easy to make organic pigments forming such an aggregate into fine particles and disperse them in the photosensitive layer. Therefore, it is preferable to treat the organic pigment with various resins in advance. Examples of these resins include the aforementioned (b) organic linear polymer binder. Examples of the treatment method include a flushing treatment and a kneading method using a kneader, an extruder, a bead mill, a ball mill, a two or three roll mill, and the like. Among these, a flushing treatment, a kneading method using two or three roll mills, and a bead mill is suitable for fine particle formation.

  The flushing treatment is usually a method of mixing an organic pigment aqueous dispersion and a resin solution dissolved in a solvent immiscible with water, extracting the organic pigment from the aqueous medium into the organic medium, and treating the organic pigment with the resin. . According to this method, since the organic pigment is not dried, aggregation can be prevented and dispersion is facilitated. In kneading with two or three roll mills, the organic pigment and resin or resin solution are mixed, and then the organic pigment and resin are kneaded while applying a high shear (shearing force) to coat the resin on the surface of the organic pigment. In this way, the organic pigment is treated. The organic pigment particles aggregated in this process are dispersed from lower order aggregates to primary particles. The bead mill inserts a stirring shaft (rotating shaft) in which a plurality of disks are attached to an elongated vessel, and stirs the beads in the vessel at high speed. The agglomerated pigment in the pumped mill base is dispersed by the strong shear stress generated between the beads moving at high speed and when the beads collide with the inner wall shaft of the vessel.

  In addition, processed organic pigments previously treated with an acrylic resin, vinyl chloride-vinyl acetate resin, maleic acid resin, ethyl cellulose resin, nitrocellulose resin or the like can also be used conveniently. As the form of the processed organic pigment treated with the above-mentioned various resins, powder, paste, pellet, and paste in which the resin and the organic pigment are uniformly dispersed are preferable. On the other hand, a non-uniform lump in which the resin is gelled is not preferable.

In order to obtain an organic pigment dispersion having a fine particle size distribution, the organic pigment is first flashed or kneaded with a binder resin by a kneader, an extruder, a bead mill, a two or three roll mill. As a preferable kneading method, wet dispersion (primary dispersion) is performed by mixing with other components including an organic pigment and a pigment dispersant. The obtained dispersion is subjected to wet dispersion (secondary dispersion) again using finer beads until the desired particle size distribution is obtained. Alternatively, the wet-dispersed dispersion is separated by centrifugation, or coarse particles are removed by decantation to obtain particles having a desired particle size and size distribution.

  Moreover, a conventionally well-known pigment dispersant and surfactant can be added in order to improve the dispersibility of an organic pigment. As these dispersants, many kinds of compounds are used. For example, phthalocyanine derivatives (commercially available products EFKA-745 (manufactured by Morishita Sangyo)); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid -Based (co) polymer polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho), etc .; polyoxyethylene lauryl ether, polyoxyethylene stearyl Nonionic surfactants such as ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; F-top EF301, E 303, EF352 (manufactured by Shin-Akita Kasei), Megafac F171, F172, F173 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S382, SC-101, SC-102, SC -103, SC-104, SC-105, SC-1068 (manufactured by Asahi Glass) and the like; W004, W005, W017 (manufactured by Yusho) and the like; EFKA-46, EFKA- 47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo), disperse aid 6, disperse aid 8, disperse aid 15, disperse aid 9100 (manufactured by Sannopco) ) Polymer Powders; Solsols 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000 and other Solsperse dispersants (manufactured by Zeneca); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68 , L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka) and Isonet S-20 (Sanyo Kasei).

The amount of the organic pigment used is set to an upper limit so that the polymerization reactivity of the photosensitive layer components and the development processability of the photosensitive lithographic printing plate are not significantly reduced. On the other hand, the lower limit is set so as to obtain a sufficient effect for improving the plate inspection property. These depend on the optical properties of the individual pigments. Usually, it is 0.001-5 g / m < ² >, Preferably it is 0.05-3 g / m < ² >, More preferably, the range of 0.1-2 g / m < ² > is good.

  Furthermore, various known techniques can be applied as preferred usage forms of the organic pigment. In particular, as described in JP-A-8-101498, when a polymer having an aliphatic double bond in the main chain or side chain is present in the dispersion of the pigment, a highly sensitive photosensitive layer can be obtained. it can. Other conventional proposals for using pigments in photopolymerization systems are described in JP-A-10-282647, JP-A-9-230601, and the like.

  In the present invention, in addition to the above components, a small amount of heat is used to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated compound during the production or storage of the photosensitive composition for the photosensitive layer. It is desirable to add a polymerization inhibitor. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t- Butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine cerium salt, N-nitrosophenylhydroxylamine aluminum salt and the like. The addition amount of the thermal polymerization inhibitor is preferably about 0.01% to about 5% with respect to the mass of the entire composition. Also, if necessary, higher fatty acid derivatives such as behenic acid and behenamide may be added to prevent polymerization inhibition by oxygen, and unevenly distributed on the surface of the photosensitive layer in the drying process after coating. Good. The amount of the higher fatty acid derivative added is preferably about 0.5% to about 10% of the total composition.

  When the photosensitive layer is coated on a support described later, the photosensitive layer composition is dissolved in various organic solvents and used. Solvents used here include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, lactic acid There are ethyl and the like. These solvents can be used alone or in combination. And 1-50 mass% is suitable for the density | concentration of the solid content in a coating solution.

A surfactant may be added to the polymerizable photosensitive layer composition in order to improve the coating surface quality.
The coating amount is preferably in the range of about 0.1 g / m ² to about 10 g / m ² in terms of mass after drying. More preferably, it is 0.3-5 g / m < ² >, More preferably, it is 0.5-3 g / m < ² >.

(Support)
The support for the photosensitive lithographic printing plate used in the present invention is not particularly limited as long as it is a dimensionally stable plate-like material, but an aluminum support is preferred.
Aluminum supports include aluminum based on dimensionally stable aluminum and alloys containing aluminum (eg, alloys of aluminum with metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel). Or a plastic film or paper laminated or vapor-deposited with aluminum or an aluminum alloy. Further, a composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in Japanese Patent Publication No. 48-18327 may be used. It is preferable that the aluminum support is appropriately subjected to a substrate surface treatment described later to obtain a hydrophilic support.

(Graining treatment)
Examples of the graining method include mechanical graining, chemical etching, and electrolytic grain as disclosed in JP-A-56-28893. In addition, electrochemical graining method that electrochemically grained in hydrochloric acid or nitric acid electrolyte solution, and a wire brush grain method in which the aluminum surface is scratched with a metal wire, and a ball that makes the aluminum surface grainy with a polishing ball and an abrasive. A mechanical graining method such as a grain method or a brush grain method in which the surface is grained with a nylon brush and an abrasive can be used, and the above graining methods can be used alone or in combination.

Among them, the method of making the surface roughness usefully used in the present invention is an electrochemical method of graining in a hydrochloric acid or nitric acid electrolyte, and a suitable current density is 100 C / dm ² to 4.
The range is 00 C / dm ² . More specifically, in the electrolytic solution containing from 0.1 to 50% hydrochloric acid or nitric acid, the temperature 20 to 100 ° C., for 1 second to 30 minutes, electrolysis at a current density of 100C / dm ² ~400C / dm ² It is preferable to carry out.
The grained aluminum support is chemically etched with acid or alkali. When an acid is used as an etching agent, it takes time to destroy the fine structure, which is disadvantageous when the present invention is applied industrially, but it can be improved by using an alkali as the etching agent.
As the alkali agent suitably used in the present invention, caustic soda, sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, potassium hydroxide, lithium hydroxide and the like are used, and preferred ranges of concentration and temperature are 1 to 50 respectively. %, 20 to 100 ° C., and conditions such that the dissolution amount of Al is 5 to 20 g / m ³ are preferable.

Pickling is performed to remove dirt (smut) remaining on the surface after etching. As the acid used, nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, borohydrofluoric acid and the like are used. In particular, as a method for removing smut after the electrochemical surface roughening treatment, contact with 15 to 65 mass% sulfuric acid at a temperature of 50 to 90 ° C. as described in JP-A-53-12739 is preferable. And the alkali etching method described in Japanese Patent Publication No. 48-28123.
The surface roughness (Ra) of the Al support used particularly effectively in the present invention is 0.3 to 0.7 μm.

(Anodizing treatment)
The aluminum support treated as described above is further anodized.
The anodizing treatment can be performed by a method conventionally used in this field. Specifically, when a direct current or an alternating current is applied to aluminum in an aqueous solution or non-aqueous solution by combining sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, etc. An anodized film can be formed.
The conditions for anodizing treatment vary depending on the electrolyte used, and therefore cannot be determined in general. In general, the concentration of the electrolyte is 1 to 80%, the solution temperature is 5 to 70 ° C., and the current density is 0.5. A range of ˜60 amperes / dm ² , a voltage of 1 to 100 V, and an electrolysis time of 10 to 100 seconds is appropriate.

Among these anodizing treatments, a method for anodizing at a high current density in sulfuric acid and U.S. Pat. No. 3,511,661, particularly described in British Patent 1,412,768. A method of anodizing the described phosphoric acid as an electrolytic bath is preferred.
In the present invention, the anodized film is preferably from ^{1~10g / m 2, 1g / m} 2 plate to easily enter the wound is not more than, 10 g / m ² or more is great power is required for the production , Economically disadvantageous. Preferably, a 1.5~7g / m ^2. More preferably 2-5 g / m ^2.
Furthermore, in the present invention, the aluminum support may be subjected to sealing treatment after graining treatment and anodizing. Such sealing treatment is performed by immersing the substrate in a hot aqueous solution containing hot water and an inorganic salt or an organic salt, and a water vapor bath. The aluminum support may be subjected to a treatment other than a silicate treatment with an alkali metal silicate, for example, a surface treatment such as an immersion treatment in an aqueous solution of potassium fluoride zirconate, phosphate or the like.

In addition to the aluminum support, the following dimensionally stable plate-like material is also preferably used for the support of the photosensitive lithographic printing plate of the present invention. For example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, butyric acid) Cellulose, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), paper or plastic film on which a metal as described above is laminated or vapor-deposited.

Moreover, it is also preferable to perform the surface hydrophilization process according to the support body with respect to these support bodies. Examples of the surface hydrophilization treatment include treatment by chemical reaction such as etching, oxidation, reduction, sol-gel coating, and coating of a specific compound that is adsorbed on the surface of the support.
For example, in the case of an anodized aluminum support, organic compounds having phosphoric acid groups (phosphoric acid, phosphonic acid, phosphinic acid) are particularly preferably used.
By forming the above-mentioned photosensitive layer on the support, the photosensitive lithographic printing plate of the present invention is produced. Before coating the photosensitive layer, an organic or inorganic undercoat layer is formed as necessary. It does not matter if it is provided.

(Oxygen barrier protective layer)
The photosensitive lithographic printing plate of the present invention may have an oxygen-blocking protective layer containing a water-soluble vinyl polymer as a main component on the polymerizable photosensitive layer.
Examples of the water-soluble vinyl polymer contained in the oxygen-blocking protective layer include polyvinyl alcohol and partial esters, ethers, and acetals thereof, or a substantial amount of unsubstituted vinyl alcohol units that make them necessary water-soluble. And a copolymer thereof. Examples of the polyvinyl alcohol include those having a hydrolysis degree of 71 to 100% and a polymerization degree in the range of 300 to 2400. Specifically, Kuraray Co., Ltd. PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HC, PVA -203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E , PVA-224E, PVA-405, PVA-420, PVA-613, L-8 and the like. Examples of the copolymer include 88-100% hydrolyzed polyvinyl acetate chloroacetate or propionate, polyvinyl formal and polyvinyl acetal, and copolymers thereof. Other useful polymers include polyvinylpyrrolidone, gelatin, gum arabic and the like, and these may be used alone or in combination.

A pure water is preferable as a solvent used for applying the oxygen-blocking protective layer, but alcohols such as methanol and ethanol, and ketones such as acetone and methyl ethyl ketone may be mixed with pure water. The concentration of the solid content in the coating solution is suitably 1 to 20% by mass.
The oxygen barrier protective layer may further contain a known additive such as a surfactant for improving the coating property and a water-soluble plasticizer for improving the physical properties of the film.
Examples of the water-soluble plasticizer include propionamide, cyclohexanediol, glycerin, sorbitol and the like. Further, a water-soluble (meth) acrylic polymer or the like may be added.
The coating amount is preferably in the range of about 0.1 g / m ² to about 15 g / m ² in terms of mass after dry drying. More preferably, it is 1.0 g / m ² to about 5.0 g / m ² .

[Plate making process]
As the plate making process of the photosensitive lithographic printing plate of the present invention, the entire surface may be heated before exposure, during exposure, and between exposure and development, if necessary. 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 may occur. Further, for the purpose of improving the image strength and printing durability, it is also effective to carry out whole surface post-heating or whole surface exposure on the developed image. Usually, heating before development is preferably performed under mild conditions of 150 ° C. or less. If the temperature is too high, problems such as covering the non-image area occur. Very strong conditions are used for heating after development. Usually, it is the range of 200-500 degreeC. If the temperature is low, sufficient image strengthening action cannot be obtained. If the temperature is too high, problems such as deterioration of the support and thermal decomposition of the image area occur.

As a method for exposing the photosensitive lithographic printing plate of the present invention, a known method can be used without limitation. As the light source, a laser having a wavelength of 390 to 550 nm is preferable. For example, the following can be used as an available laser light source having a wavelength of 390 to 550 nm.
As gas laser, He—Cd laser (441 nm, 1 mW to 100 mW), as solid laser, combination of Cr: LiSAF and SHG crystal (430 nm, 10 mW), as semiconductor laser system, KNbO 3, ring resonator (430 nm, 30 mW), A combination of a waveguide type wavelength conversion element and AlGaAs and InGaAs semiconductors (380 nm to 450 nm, 5 mW to 100 mW), AlGaInN (350 nm to 450 nm, 5 mW to 30 mW), Ar laser (488 nm), FD-YAG laser (532 nm).

  Among these, an AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 400 to 410 nm, 5 to 30 mW) is preferable in terms of wavelength characteristics and cost.

  The exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like. Moreover, the photosensitive layer component of the photosensitive lithographic printing plate of the present invention can be made soluble in neutral water or weak alkaline water by using a highly water-soluble component. The planographic printing plate can be loaded on a printing press and then subjected to a method such as exposure-development on the press.

  The photosensitive lithographic printing plate of the present invention is usually subjected to image exposure, and then an unexposed portion of the photosensitive layer is removed with a developer to obtain an image. Examples of a preferred developer for use in preparing a lithographic printing plate from these photosensitive lithographic printing plates include those described in Japanese Patent Publication No. 57-7427, such as sodium silicate, silicate Potassium, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. An inorganic alkali agent such as this and an aqueous solution of an organic alkali agent such as monoethanolamine or diethanolamine are suitable. The concentration of the alkali solution is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.

As the inorganic alkaline agent, any substance that gives the above physical property values can be used as appropriate. For example, tribasic sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate Inorganic alkaline agents such as potassium, ammonium, sodium borate, potassium, ammonium, sodium hydroxide, potassium, ammonium, and lithium.
In addition, an organic alkali agent may be supplementarily used for the purpose of finely adjusting the alkali concentration and assisting the solubility of the photosensitive layer. Examples of the organic alkali agent include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, Examples thereof include diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, tetramethylammonium hydroxide and the like.
These alkali agents are used alone or in combination of two or more.

  The pH of the developer used in the present invention is preferably in the range of 10.0 to 12.5. A more preferred pH range is 10.5 to 12.4, and even more preferably 11.0 to 12.3.

  The conductivity of the developer used in the present invention is preferably in the range of 4 to 25 mS / cm, more preferably in the range of 5 to 20 mS / cm.

The developer used in the present invention preferably contains a nonionic surfactant having a polyoxyalkylene ether group. By adding this surfactant, the dissolution of the photosensitive layer in the unexposed area is promoted, and the exposed area is exposed to the exposed area. The permeability of the developer can be reduced.
As the surfactant containing a polyoxyalkylene ether group, one having a structure of the following general formula (XV) is preferably used.

R ³⁰ —O— (R ³¹ —O) _n H (XV)
In the formula, R ³⁰ has an optionally substituted alkyl group having 3 to 15 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 15 carbon atoms, or a substituent. An optionally substituted heteroaromatic cyclic group having 4 to 15 carbon atoms (wherein the substituent is an alkyl group having 1 to 20 carbon atoms, a halogen atom such as Br, Cl, or I, or an aromatic hydrocarbon having 6 to 15 carbon atoms) R ³¹ is a group, an aralkyl group having 7 to 17 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxy-carbonyl group having 2 to 20 carbon atoms, or an acyl group having 2 to 15 carbon atoms. , An optionally substituted alkylene group having 1 to 100 carbon atoms (in addition, examples of the substituent include an alkyl group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 15 carbon atoms). N represents an integer of 1 to 100.

In addition, the part of (R ³¹ —O) _{n in} formula (XV) may be two or three groups as long as it is in the above range. Specific examples include a combination of random or block combinations of ethyleneoxy and propyleneoxy, ethyleneoxy and isopropyloxy, ethyleneoxy and butyleneoxy, ethyleneoxy and isobutylene, and the like. .
In the present invention, the surfactant having a polyoxyalkylene ether group is used alone or in combination, and it is effective to add 1 to 30% by mass, more preferably 2 to 20% by mass in the developer. It is.
Specific examples of the nonionic compound of the general formula (XV) are shown below.

Further, other surfactants described below may be added. Examples of other surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene stearyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like. Polyoxyethylene alkyl allyl ethers, polyoxyethylene alkyl esters such as polyoxyethylene stearate, sorbitan monolaurate, sorbitan monostearate, sorbitan distearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate Monoglyceride alkyl esters such as sorbitan alkyl esters such as glycerol, glycerol monostearate and glycerol monooleate Nonionic surfactants such as alkylbenzenes; alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; alkylnaphthalene sulfonates such as sodium butylnaphthalenesulfonate, sodium pentylnaphthalenesulfonate, sodium hexylnaphthalenesulfonate, sodium octylnaphthalenesulfonate Anionic surfactants such as alkyl sulfates such as sodium lauryl sulfate, alkyl sulfonates such as sodium dodecyl sulfonate, sulfosuccinic acid ester salts such as sodium dilauryl sulfosuccinate; alkyl betaines such as lauryl betaine and stearyl betaine; Amphoteric surfactants such as amino acids can be used, but anionic surfactants such as alkylnaphthalene sulfonates are particularly preferred.
These surfactants can be used alone or in combination. Further, the content of these surfactants in the developer is preferably from 0.1 to 20% by mass in terms of active ingredients.

In addition to the above components, the following components can be used in combination in the developer of the present invention as necessary. For example, benzoic acid, phthalic acid, p-ethylbenzoic acid, pn-propylbenzoic acid, p-isopropylbenzoic acid, pn-butylbenzoic acid, pt-butylbenzoic acid, pt-butylbenzoic acid , P-2-hydroxyethylbenzoic acid, decanoic acid, salicylic acid, 3-hydroxy-2-naphthoic acid and other organic carboxylic acids; isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone Organic solvents such as alcohol; in addition, chelating agents, reducing agents, dyes, pigments, hard water softeners, preservatives, antifoaming agents, and the like.
Further, the developed photosensitive lithographic printing plate is washed with water, a surfactant and the like as described in JP-A Nos. 54-8002, 55-1115045 and 59-58431. And a desensitizing solution containing gum arabic, starch derivatives and the like. These treatments can be used in various combinations for the post-treatment of the photosensitive lithographic printing plate of the present invention.
The lithographic printing plate obtained by such treatment is applied to an offset printing machine and used for printing a large number of sheets.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
[Example 1]
[Example of support production]
(Support 1: Anodized aluminum support)
An aluminum plate made of material 1S having a thickness of 0.30 mm was used with a No. 8 nylon brush and an aqueous suspension of 800 mesh Pamiston, and its surface was grained and washed thoroughly with water. After etching by immersing in 10% sodium hydroxide at 70 ° C. for 60 seconds, washed with running water, neutralized with 20% HNO ₃ and washed with water. This was subjected to an electrolytic surface roughening treatment in a 1% nitric acid aqueous solution with a anodic electricity amount of 300 coulomb / dm ² using a sinusoidal alternating current under the condition of VA = 12.7V. When the surface roughness was measured, it was 0.45 μm (Ra indication). Next, after dipping in 30% H ₂ SO ₄ aqueous solution and desmutting at 55 ° C. for 2 minutes, a cathode was placed on the grained surface in 33 ° C., 20% H ₂ SO ₄ aqueous solution, and the current density was When anodized at 5 A / dm ² for 50 seconds, the thickness was 2.7 g / m ² . Furthermore, the following surface-treatment undercoat liquid composition 1 was applied so that the P amount was about 0.05 g / m ^2, and dried at 100 ° C. for 1 minute.

<Liquid composition 1 for undercoat>
Phenylphosphonic acid 2 parts by weight Methanol 800 parts by weight Water 50 parts by weight

[Examples of photosensitive materials]
On the above-mentioned support, a polymerizable composition having the following composition was applied so that the dry coating mass was 1.5 g / m ² and dried at 90 ° C. to form a photosensitive layer.
Subsequently, an aqueous solution of 6% by mass of polyvinyl alcohol (saponification degree: 98 mol%, polymerization degree: 500) was applied onto the photosensitive layer so that the dry coating mass was 2.5 g / m ^2. It was dried for half and half to obtain a photosensitive lithographic printing plate (photosensitive material) 1.

(Photosensitive layer coating solution 1 (polymerizable composition))
Ethylenically unsaturated bond-containing compound (A) 1.70 parts by mass Linear organic polymer (B) 1.90 parts by mass Sensitizing dye (C) 0.15 parts by mass Photoinitiator (I) 0.30 Part by mass Additive (F) 0.50 part by mass Fluorosurfactant 0.03 part by mass (Megafac F-177: manufactured by Dainippon Ink & Chemicals, Inc.)
Thermal polymerization inhibitor 0.01 parts by mass (N-nitrosohydroxylamine aluminum salt)
ε-phthalocyanine dispersion
(10% 1 methoxy 2-propanol solution) 0.2 parts by mass Methyl ethyl ketone 30.0 parts by mass Propylene glycol monomethyl ether 30.0 parts by mass

  The ethylenically unsaturated bond-containing compound (A), linear organic polymer (B), sensitizing dye (C), photoinitiator (I), additive (F) used in the photosensitive layer coating solution Is shown below.

[Examples 2-3]
Photosensitive lithographic printing plate (photosensitive material) 2 and photosensitive lithographic printing plate (photosensitive plate) (Example 1) except that the photosensitive layer coating solution 1 of Example 1 was replaced with the following photosensitive layer coating solution 2 and photosensitive layer coating solution 3 Photosensitive material 3 was prepared.
(Photosensitive layer coating solution 2 (polymerizable composition))
Ethylenically unsaturated bond-containing compound (A ′) 1.70 parts by mass Linear organic polymer (B ′) 1.90 parts by mass Sensitizing dye (C ′) 0.15 parts by mass Photoinitiator (I ′ ) 0.30 parts by mass Additive (F) 0.50 parts by mass Fluorosurfactant 0.03 parts by mass (Megafac F-177: manufactured by Dainippon Ink & Chemicals, Inc.)
Thermal polymerization inhibitor 0.01 parts by mass (N-nitrosohydroxylamine aluminum salt)
ε-phthalocyanine dispersion (10% 1 methoxy 2-propanol solution) 0.2 parts by mass Auxiliary agent (D ₁ ) 0.10 parts by mass Auxiliary agent (D ₂ ) 0.10 parts by mass Methyl ethyl ketone 30.0 parts by mass Propylene glycol monomethyl Ether 30.0 parts by mass

In addition, the ethylenically unsaturated bond-containing compound (A ′), linear organic polymer (B ′), sensitizing dye (C ′), photoinitiator (I ′), used for the photosensitive layer coating solution 2, The auxiliary agent (D ₁ ) and auxiliary agent (D ₂ ) are shown below.

(Photosensitive layer coating solution 3 (polymerizable composition))
Ethylenically unsaturated bond-containing compound (A ″) 1.70 parts by mass Linear organic polymer (B ″) 1.90 parts by mass Sensitizing dye (C ″) 0.15 parts by mass Photoinitiator (I) 0.30 parts by mass Additive (F) 0.50 parts by mass Auxiliary agent (D ″) 0.10 parts by mass Fluorosurfactant 0.03 parts by mass (Megafac F-177: Dainippon Ink (Chemical Industry Co., Ltd.)
Thermal polymerization inhibitor 0.01 parts by mass (N-nitrosohydroxylamine aluminum salt)
ε-phthalocyanine dispersion (10% 1 methoxy 2-propanol solution)
0.2 parts by mass Methyl ethyl ketone 30.0 parts by mass Propylene glycol monomethyl ether 30.0 parts by mass

  The ethylenically unsaturated bond-containing compound (A ″), linear organic polymer (B ″), sensitizing dye (C ″), auxiliary agent (D ′) used for the photosensitive layer coating solution 3 ') Is shown below.

This photosensitive lithographic printing plate (110 × 40 cm) is 175 lines / inch at 4000 dpi with an exposure of 150 μJ / cm ² using an FD • YAG laser (Luxel Plate Setter P-9600 CTP NEWS manufactured by Fuji Photo Film Co., Ltd.). Under the conditions, a solid image and a 1-99% halftone image (in 1% increments) were scanned and exposed. The plate after the exposure was automatically sent to an automatic processor LP1250PLX connected thereto, heated at 100 ° C. for 10 seconds, the PVA protective layer was washed away with water, and subsequently developed at 28 ° C. for 20 seconds. The developer was prepared by diluting a developer DV-2 manufactured by Fuji Photo Film Co., Ltd. five times with water. The plate after development was washed with a rinse bath and then sent to a gumming bath, and a solution obtained by diluting a gum solution FP-2W manufactured by Fuji Photo Film Co., Ltd. with water twice. The plate after gumming was discharged after drying with hot air. Table 1 shows the results for the 2% dot on each plate and the 2% dot on each plate when exposed to development after 60 days at 60 ° C.

Examples 4-6
Example 4 repeated Example 1, Example 5 repeated Example 2, and Example 6 repeated Example 3 except having changed the additive (F) into the following additive (F ′). The results are shown in Table 1.

Comparative Examples 1-6
In Examples 1 to 3, Examples 1 to 3 were repeated except that the additive (F) was not used. These are referred to as Comparative Examples 1 to 3, respectively. In Examples 1 to 3, Examples 1 to 3 were repeated except that the ethylenically unsaturated bond-containing compound was changed to pentaerythritol tetraacrylate. These are referred to as Comparative Examples 4 to 6, respectively. The results are shown in Table 1.

  As is apparent from Table 1, the photosensitive lithographic printing plate of the present invention has high sensitivity, excellent laser exposure suitability, excellent reproducibility of halftone dots and fine lines, and storage stability.

Examples 7-9
[Examples of photosensitive materials]
On the above-mentioned support, a polymerizable composition having the following composition was applied so that the dry coating mass was 1.5 g / m ² and dried at 90 ° C. to form a photosensitive layer.
Subsequently, an aqueous solution of 6% by mass of polyvinyl alcohol (saponification degree: 98 mol%, polymerization degree: 500) was applied onto the photosensitive layer so that the dry coating mass was 2.5 g / m ^2. It was dried for half and half to obtain a photosensitive lithographic printing plate (photosensitive material).

In Example 7, the sensitizing dye (C) of Example 1 was changed to the sensitizing dye (C ′ ″).
In Example 8, the sensitizing dye (C ′) of Example 2 was changed to the sensitizing dye (C ′ ″).
In Example 9, the sensitizing dye (C ″) of Example 3 was changed to a sensitizing dye (C ′ ″) having the following structure.

[Examples 10 to 12]
Example 10 was repeated with Example 7 except that the additive (F) was changed to the additive (F ′), Example 11 was repeated with Example 8, and Example 12 was repeated with Example 9.

[Comparative Examples 7-12]
In Examples 7 to 9, Examples 7 to 9 were repeated except that the additive (F) was not used. These are referred to as Comparative Examples 7 to 9, respectively. In Examples 10 to 12, Examples 10 to 12 were repeated except that the ethylenically unsaturated bond-containing compound was changed to pentaerythritol tetraacrylate. These are referred to as Comparative Examples 10 to 12, respectively.

[Developer example]
The same developer as in Example 1 was used.

[Evaluation of sensitivity and image reproducibility]
This photosensitive lithographic printing plate (110 × 40 cm) is loaded into a violet semiconductor laser setter Vx9600 (InGaN-based semiconductor laser 405 nm ± 10 nm, light emission / output 30 mW) manufactured by FUJIFILM Electronic Imaging Ltd., resolution is 2400 dpi with an exposure amount of 90 μJ / cm ^2. A solid image and a 1-99% halftone dot image (in 1% increments) were scanned and exposed at 175 lines / inch. The plate after the exposure was automatically sent to an automatic processor LP1250PLX connected thereto, heated at 100 ° C. for 10 seconds, the PVA protective layer was washed away with water, and subsequently developed at 28 ° C. for 20 seconds. The developer was prepared by diluting a developer DV-2 manufactured by Fuji Photo Film Co., Ltd. five times with water. The plate after development was washed with a rinse bath and then sent to a gumming bath, and a solution obtained by diluting a gum solution FP-2W manufactured by Fuji Photo Film Co., Ltd. with water twice. The plate after gumming was discharged after drying with hot air. Table 2 shows the results for the 2% dot on each plate and the 2% dot on each plate when exposed to development after 60 days at 60 ° C.

  As is apparent from Table 2, the photosensitive lithographic printing plate of the present invention has high sensitivity, excellent laser exposure suitability, and excellent reproducibility of halftone dots and fine lines, and storage stability.

  According to the present invention, photosensitive lithographic printing has high sensitivity, good highlighting, excellent reproducibility of halftone dots and fine lines, and can maintain the highlighting without lowering the sensitivity even when the plate is stored for a long time. An image recording material for a plate is provided.

Claims (1)

An image recording material having a photosensitive layer containing the following components (a) to (e) on a support:
(A) An addition polymerizable compound having at least one photooxidizable group and having an ethylenically unsaturated double bond, or a reaction between a polyepoxy compound and a (meth) acrylate having a hydroxyl group or a carboxyl group An addition polymerizable compound having an ethylenically unsaturated double bond,
(B) an organic linear polymer binder,
(C) a polymerization initiator,
(D) a sensitizing dye, and (e) a compound having a molecular weight of 300 or less having a sulfur atom and a carboxyl group in the molecule.