JP2003302750A - Image recording material and lithographic printing plate precursor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image recording material for making a lithographic printing plate having wide development latitude and scuffing resistance and containing a lubricative material free of transfer to rollers, protective paper sheets (inserting paper sheets) and the rear face of a substrate in production and transport. <P>SOLUTION: The image recording material comprises (a) an IR absorber and (b) a polymer to lower a dynamic coefficient of friction to 0.38-0.60, which can undergo image formation upon exposure with infrared laser. A lithographic printing plate precursor has on a support a recording layer comprising (a) an IR absorber, (c) a water-insoluble and alkali-soluble resin and (d) a polymer having a structural unit represented by a specified structure, and having solubility in an alkaline aqueous solution increased upon exposure with infrared laser. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an image recording material and a lithographic printing plate precursor. In particular, the present invention relates to an infrared laser image recording material for so-called direct plate making, which enables direct plate making from a digital signal from a computer or the like, and a lithographic printing plate precursor using the image recording material.

[0002]

2. Description of the Related Art The development of lasers in recent years has been remarkable, and in particular, solid-state lasers having an emission region from near infrared to infrared.
High-power and small-sized semiconductor lasers are easily available. These lasers are very useful as an exposure light source when making a plate directly from digital data of a computer or the like.

The positive type lithographic printing plate precursor for infrared laser has a binder resin soluble in an alkaline aqueous solution and an infrared absorbing dye or the like (light-heat converting substance) which absorbs light to generate heat, and the infrared absorbing dye or the like. However, in the unexposed area (image area), it acts as a dissolution inhibitor that substantially lowers the solubility of the binder resin due to the interaction with the binder resin,
In the exposed area (non-image area), the generated heat weakens the interaction between the infrared absorbing dye and the binder resin and dissolves in an alkali developing solution to form a lithographic printing plate.

However, in such a positive type lithographic printing plate precursor for infrared laser, the unexposed area (image area) is dissolved during development even if the surface condition slightly changes due to contact with the surface during handling. As a result, there is a problem that scratches are left and cause deterioration of printing durability and poor inking property.

Also, in the case of a negative type lithographic printing plate precursor for infrared laser, there is a problem that the scratch resistance of the recording layer is insufficient in the unexposed state before curing.

As means for solving the above problems, for example,
Patent Document 1 (US Pat. No. 6,124,425)
Describes an example of an alkali-soluble resin having an infrared absorbing functional group in its side chain for the purpose of easily achieving film strength (image strength). That is, it is intended to improve the film strength by introducing a partial structure having a photothermal conversion function into the alkali-soluble resin to reduce the components in the material. However, since this alkali-soluble resin is a high molecular weight compound having a molecular weight of 5000 or more, its adhesion to a support becomes great and its solubility in a processing agent at the time of development becomes insufficient. When used as a planographic printing plate material, the solubility of the non-image area is low,
The recording layer to be removed is not sufficiently removed by the development process,
There has been a problem that a non-image area is liable to be left as a residual film, which tends to cause stains.

Further, for example, Patent Document 2 (Japanese Patent Laid-Open No. 2000)
It has been known that the addition of a low molecular weight wax to JP-A-35666) improves surface slipperiness and develops excellent scratch resistance, but since it is a low molecule, a lithographic printing plate precursor is laminated. However, there were problems such as protection paper (interleaving paper), transfer to the back surface of the support, and transfer to the rollers during lithographic printing plate precursor manufacturing, which was an instability factor during manufacturing and transportation. .

Further, for example, Patent Document 3 (European Patent No. 9
No. 50514) and Patent Document 4 (European Patent No. 95).
No. 0517) proposes an example of exhibiting slipperiness with a polysiloxane-based surfactant, but this is also due to concern about dust during development and difficulty in controlling slipperiness such as excessive slippage. It was a cause of instability during manufacturing and transportation.

Further, it is conceivable to provide a protective layer on the recording layer. For example, when a general protective layer using a water-soluble resin is provided, particularly when stored under high humidity,
There is a problem that the protective layer and the support are adhered to each other, which makes it difficult to peel them off, resulting in a decrease in workability.
Productivity was bad. Therefore, there has been a demand for a lithographic printing plate precursor that does not deteriorate workability, does not affect image forming properties, and can suppress scratches on the recording layer.

[0010]

[Patent Document 1] US Pat. No. 6,124,425

[Patent Document 2] Japanese Patent Laid-Open No. 2000-35666

[Patent Document 3] European Patent No. 950514

[Patent Document 4] European Patent No. 950517

[0011]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the above-mentioned problems, that is, it has a wide development latitude and a scratch resistance, and is manufactured and transported. By providing an image recording material for producing a lithographic printing plate containing a roller, a protective paper (interleaving paper), a slippery material without transfer on the back surface of the substrate, and a lithographic printing plate precursor using the image recording material. is there.

[0012]

As a result of intensive studies to achieve the above object, the present inventor has found that the dynamic friction coefficient is 0.3.
The present invention has been completed by finding that the above problems can be solved by using an image recording material containing a polymer which reduces the amount to 8 to 0.60 as a recording layer, and completed the present invention. That is, the present invention is as follows.

1. An image recording material comprising (a) an infrared absorber and (b) a polymer that reduces the dynamic friction coefficient to 0.38 to 0.60 and capable of forming an image by exposure to an infrared laser.

2. On the support, (a) infrared absorber,
A recording layer containing (c) a water-insoluble and alkali-soluble resin, and (d) a polymer having a structural unit represented by the following general formula (1), the solubility of which in an alkaline aqueous solution is increased by exposure to an infrared laser. Original planographic printing plate.

[0015]

[Chemical 2]

(N represents an integer of 4 or more, and m represents 0.6 ≦
It represents m ≦ 20. X represents a skeleton having an alkali-soluble group having a pKa of 12 or less, and R represents an alkyl group or a hydrogen atom. )

According to the above invention, a positive type lithographic printing plate precursor for infrared laser for so-called direct plate making, which can directly make a plate from a digital signal of a computer or the like, is obtained, has a wide development latitude and scratch resistance, and is manufactured, It is possible to provide a lithographic printing plate containing a roller, a protective paper (interleaving paper) at the time of conveyance, and a slippery material without transfer of the back surface of the substrate. Although the mechanism of action of the image recording material of the present invention having the above-mentioned scratch resistance and slipperiness has not been clarified, a polymer that reduces the dynamic friction coefficient to 0.38 to 0.60 is the outermost layer in the image recording material. Uneven distribution, lowering surface energy, and exhibiting appropriate slipperiness, and exhibiting scratch resistance such as scratches, and its high molecular weight makes it easy to transfer to rollers and slip sheets during production and transportation. It is presumed that this is suppressed.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The image recording material of the present invention is characterized by containing a polymer that reduces the dynamic friction coefficient to 0.38 to 0.60, and an infrared absorbing agent. A polymer that reduces the coefficient of kinetic friction to less than 0.38 has too high a slip property, and a lithographic printing plate precursor using the image recording material cannot be stably produced. In addition, during transportation of the planographic printing plate precursor,
It is not preferable because the laminated original plates slip and cause scratches. If the dynamic friction coefficient exceeds 0.60, the effect of improving scratch resistance due to slipperiness cannot be obtained.

The above-mentioned dynamic friction coefficient (dynamic or kinetic c
oefficient of friction) (μk) is standard ASTM
The coefficient of kinetic friction with respect to stainless steel measured by placing the lithographic printing plate precursor such that the surface of the recording layer was in contact with stainless steel in accordance with D1894.

The image recording material of the present invention contains a water-insoluble and alkali-soluble resin or an acid-decomposable compound, and as a positive-type image recording material whose solubility in an alkaline aqueous solution is increased by exposure to infrared laser, a positive-type planographic printing method is used. It can be used for the recording layer of the original plate. The image recording material of the present invention contains a heat-crosslinkable component or a heat-polymerizable component, and is negative-working lithographic printing as a negative-type image recording material that becomes insoluble in a developer by causing crosslinking or polymerization by exposure to infrared laser. It can be used for the recording layer of the original plate. Hereinafter, each component constituting the image recording material of the present invention and the lithographic printing plate precursor using the image recording material of the present invention will be sequentially described.

[Image Recording Material] (Polymer for Reducing Dynamic Friction Coefficient to 0.38 to 0.60) As a polymer that can be used to reduce the dynamic friction coefficient to 0.38 to 0.60 in the present invention, Examples thereof include polymers having a long-chain alkyl group having 4 or more carbon atoms (hereinafter, also simply referred to as long-chain alkyl group), polyphenylene polymers, and polyurethane polymers. Of these, long-chain alkyl group-containing polymers are preferable. Furthermore, the long-chain alkyl group-containing polymer is a polymer obtained by copolymerizing a long-chain alkyl group-containing monomer having 4 or more carbon atoms and at least one kind of monomer (called a long-chain alkyl group-containing copolymer) Is preferred.

The composition mol% of the long-chain alkyl group-containing monomer in the long-chain alkyl group-containing copolymer is preferably in the range of 99 to 60%, and in the range of 97 to 65%, from the viewpoint of improving the slip property. More preferably within,
Most preferably, it is within the range of 95 to 70%.

As the above long-chain alkyl group-containing monomer having 4 or more carbon atoms, a compound having an addition-polymerizable ethylenically unsaturated group in the molecule is preferable, and the solvent solubility and the resistance to the production of the image recording material are preferable. From the viewpoints of scratch resistance improving effect, surface coating property, and small adverse effect on image forming property, etc., acrylate, methacrylate, acrylamide, methacrylamide, styrene, vinyl, vinyl ether having a long-chain alkyl group. It is preferable that the monomer is a maleic acid-based monomer or a fumaric acid-based monomer, and further, long chain alkyl acrylate, long chain alkyl methacrylate, long chain alkyl group-containing vinyl ether or long chain alkyl group-containing styrene. Further, the carbon number n of the long chain alkyl group is more preferably 6 or more, further preferably 8 or more, and most preferably 12 or more and 20 or less.

More specifically, the long chain alkyl group-containing monomer is preferably a monomer represented by the following general formula (2).

[0025]

[Chemical 3]

N represents an integer of 6 to 40. Z represents a divalent linking group. W, W'and W "represent monovalent organic groups.

Specific examples of the divalent linking group represented by Z include:
C1-C20 linear or branched, chain-like or cyclic alkylene group, C2-C20 straight-chain or branched, chain-like or cyclic alkenylene group, C2-C20 alkynylene group, C6 To 20 arylene groups (monocyclic and heterocyclic), -OC (= O)-, -OC (= O) Ar-, -O.
C (= O) O-, -OC (= O) OAr-, -C (=
O) NR -, - C ( = O) NAr -, - SO 2 NR-,
_{-SO 2 NAr -, - O -} , ( alkyleneoxy, polyalkyleneoxy), - OAr- aryleneoxy, polyarylene oxy), - C (= O) O -, - C (=
O) O-Ar-, -C (= O) Ar-, -C (= O)
_{-, - SO 2 O -,} - SO 2 OAr -, - OSO 2 -, -
_{OSO 2 Ar -, - NRSO 2} -, - NArSO 2 -, -
NRC (= O)-, -NArC (= O)-, -NRC
(= O) O-, -NArC (= O) O-, -OC (=
O) NR-, -OC (= O) NAr-, -NAr-,-
^{NR -, - N + RR '} -, - N + RAr -, - N + ArA
r'-, -S-, -SAr-, -ArS-, a heterocyclic group (as a hetero atom, for example, at least one or more of nitrogen, oxygen, sulfur and the like is contained, and is a 3- to 12-membered monocyclic ring,
Condensed ring), -OC (= S)-, -OC (= S) Ar-,
-C (= S) O-, -C (= S) OAr-, -C (=
S) OAr-, -C (= O) S-, -C (= O) SAr
-, -ArC (= O)-, -ArC (= O) NR-,-
ArC (= O) NAr-, -ArC (= O) O-, -A
rC (= O) O-, -ArC (= O) S-, -ArC
(= S) O-, -ArO-, -ArNR- and the like. Here, R and R ′ represent H, a linear or branched, chain or cyclic alkyl group, alkenyl group or alkynyl group, and Ar and Ar ′ represent an aryl group.

The above-mentioned linking groups are the same as the linking groups listed here.
The linking group may be formed by combining more than one kind. As such a linking group, an arylene group having 6 to 20 carbon atoms (monocycle or heterocycle), -C (= O) NR-, -C (=
O) NAr-, -O- (alkyleneoxy, polyalkyleneoxy), -OAr-aryleneoxy, polyaryleneoxy), -C (= O) O-, -C (= O) O-.
Ar-, -C (= O)-, -C (= O) Ar-, -S
-, -SAr-, -ArS-, -ArC (= O)-,-
ArC (= O) O-, -ArC (= O) O-, -ArO
-, -ArNR- and the like are preferable, and an arylene group having 6 to 20 carbon atoms (monocycle or heterocycle), -C (= O) NR-, -C.
(= O) NAr-, -O- (alkyleneoxy, polyalkyleneoxy), -OAr-aryleneoxy, polyaryleneoxy), -C (= O) O-, -C (= O).
O-Ar-, -SAr-, -ArS-, -ArC (=
O)-, -ArC (= O) O-, -ArC (= O) O
-, -ArO-, -ArNR- and the like are more preferable.

The linking group may have a substituent, and examples of the substituent include linear or branched, chain or cyclic alkylene having 1 to 20 carbon atoms, and 2 to 20 carbon atoms.
Linear or branched, chain 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, and 2 to 20 carbon atoms.
Alkoxycarbonyloxy group, aryloxycarbonyloxy group having 7 to 20 carbon atoms, carbamoyloxy group having 1 to 20 carbon atoms, carbonamido group having 1 to 20 carbon atoms, sulfonamide group having 1 to 20 carbon atoms, carbon number 1-2
A carbamoyl group having 0 to 20 carbon atoms, a sulfamoyl group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, and 2 to 20 carbon atoms. Alkoxycarbonyl group, N-acyl sulfamoyl group having 1 to 20 carbon atoms, N-sulfamoylcarbamoyl group having 1 to 20 carbon atoms, alkylsulfonyl group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms
Arylsulfonyl group, C2-20 alkoxycarbonylamino group, C7-20 aryloxycarbonylamino group, C0-20 amino group, C1-20 imino group, C3-3 20 ammonio group, 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, and 6 to carbon atoms 20 arylthio group, C1-20 ureido group, C2-20 heterocyclic group, C1-20 acyl group, C0-20 sulfamoylamino group, C2-20 Silyl group, hydroxy group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, etc.), cyano group, nitro group and the like.

Specific examples of W, W'and W "include, but are not limited to, the following: hydrogen atom, straight or branched chain having 1 to 50 carbon atoms, or chain. Or a cyclic alkyl group (eg, methyl, ethyl,
Propyl, heptafluoropropyl, isopropyl, butyl, t-butyl, t-pentyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, dodecyl, etc.), a straight-chain or branched, chain-like or cyclic alkenyl group having 2 to 50 carbon atoms. (For example, vinyl, 1-methylvinyl, cyclohexen-1-yl, etc.), C2-C50 alkynyl group (eg, ethynyl, 1-propynyl, etc.), C6-C50 aryl group (eg, phenyl, naphthyl). , Anthryl, etc.), an acyloxy group having 1 to 50 carbon atoms (eg, acetoxy, tetradecanoyloxy, benzoyloxy, etc.), an alkoxycarbonyloxy group having 2 to 50 carbon atoms (eg, methoxycarbonyloxy group, 2-methoxyethoxy). Carbonyloxy group, etc.), Chromatography (such as phenoxycarbonyl group) oxy carbonyloxy group, a carbamoyloxy group having 1 to 50 carbon atoms (e.g., N, N
-Dimethylcarbamoyloxy, etc.), a carbonamide group having 1 to 50 carbon atoms (for example, formamide, N-methylacetamide, acetamide, N-methylformamide, benzamide, etc.), a sulfonamide group having 1 to 50 carbon atoms (for example, Methanesulfonamide, dodecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, etc.), a carbamoyl group having 1 to 50 carbon atoms (for example, N-methylcarbamoyl, N, N-diethylcarbamoyl, N-mesylcarbamoyl, etc.), Carbon number 0-5
A sulfamoyl group of 0 (eg, N-butylsulfamoyl, N, N-diethylsulfamoyl, N-methyl-
N- (4-methoxyphenyl) sulfamoyl etc.), an alkoxy group having 1 to 50 carbon atoms (eg, methoxy, propoxy, isopropoxy, octyloxy, t-octyloxy, dodecyloxy, 2- (2,4-di-). t-pentylphenoxy) ethoxy, polyalkyleneoxy, etc.), an aryloxy group having 6 to 50 carbon atoms (eg, phenoxy, 4-methoxyphenoxy, naphthoxy, etc.),
Aryloxycarbonyl group having 7 to 50 carbon atoms (for example, phenoxycarbonyl, naphthoxycarbonyl, etc.)

Alkoxycarbonyl group having 2 to 50 carbon atoms (eg, methoxycarbonyl, t-butoxycarbonyl, etc.), N-acylsulfamoyl group having 1 to 50 carbon atoms (eg, N-tetradecanoylsulfamoyl, N-
Benzoylsulfamoyl etc.), N- having 1 to 50 carbon atoms
Sulfamoylcarbamoyl group (for example, N-methanesulfonylcarbamoyl group), alkylsulfonyl group having 1 to 50 carbon atoms (for example, methanesulfonyl, octylsulfonyl, 2-methoxyethylsulfonyl, 2-hexyldecylsulfonyl, etc.), carbon number 6-50 arylsulfonyl group (for example, benzenesulfonyl, p-toluenesulfonyl, 4-phenylsulfonylphenylsulfonyl, etc.), C2-C50 alkoxycarbonylamino group (for example, ethoxycarbonylamino, etc.), C7- An aryloxycarbonylamino group of 50 (for example, phenoxycarbonylamino, naphthoxycarbonylamino, etc.), an amino group of 0 to 50 carbon atoms (for example, amino, methylamino, diethylamino, diisopropylamino, anilino, Ruhorino etc.), an ammonio group of 3 to 50 carbon atoms (e.g., trimethylammonio group, such as dimethyl benzyl ammonio group), a cyano group, a nitro group,
A carboxyl group, a hydroxy group, a sulfo group, a mercapto group, an alkylsulfinyl group having 1 to 50 carbon atoms (for example, methanesulfinyl, octansulfinyl, etc.),
Arylsulfinyl group having 6 to 50 carbon atoms (eg, benzenesulfinyl, 4-chlorophenylsulfinyl, p-toluenesulfinyl, etc.), alkylthio group having 1 to 50 carbon atoms (eg, methylthio, octylthio,
Cyclohexylthio, etc.), arylthio groups having 6 to 50 carbon atoms (eg, phenylthio, naphthylthio, etc.), ureido groups having 1 to 50 carbon atoms (eg, 3-methylureido, 3,3-dimethylureido, 1,3-diphenyl). Ureido, etc.), a heterocyclic group having 2 to 50 carbon atoms (as a hetero atom, at least one or more of nitrogen, oxygen, sulfur, etc., is a 3- to 12-membered monocyclic or condensed ring, for example, 2- Furyl, 2-pyranyl, 2-pyridyl, 2-
Thienyl, 2-imidazolyl, morpholino, 2-quinolyl, 2-benzimidazolyl, 2-benzothiazolyl,
2-benzoxazolyl, etc.), an acyl group having 1 to 50 carbon atoms (eg, acetyl, benzoyl, trifluoroacetyl, etc.), a sulfamoylamino group having 0 to 50 carbon atoms (eg, N-butylsulfamoyl). Amino, N-phenylsulfamoylamino, etc.), silyl group having 3 to 50 carbon atoms (eg, trimethylsilyl, dimethyl-t-butylsilyl, triphenylsilyl, etc.), azo group, halogen atom (eg, fluorine atom, chlorine atom) , Bromine atom, etc.). The above-mentioned substituents may further have a substituent, and examples of the substituent include the substituents mentioned here.

W, W'and W "may form a ring with each other, and examples of such a ring include an aliphatic ring, an aromatic ring and a heterocycle.

Specific examples of the general formula (2) include the followings, but the invention is not limited thereto. In the specific examples, n represents an integer of 4-40.

[0034]

[Chemical 4]

[0035]

[Chemical 5]

[0036]

[Chemical 6]

[0037]

[Chemical 7]

The copolymer component of the long chain alkyl group-containing monomer is preferably a monomer having an acid group of pKa12 or less from the viewpoint of solubility in an alkali developing solution and sensitivity.

As the monomer having an acid group having a pKa of 12 or less, those having an acidic group described in the following (1) to (6) are preferable in terms of solubility in an alkaline developing solution and sensitivity. (1) phenol group (-Ar-OH) (2) sulfonamide group _{(-SO 2 NH-R) (} 3) active imide group [-SO ₂ NHCOR, -SO ₂ NH
SO ₂ R, -CONHSO ₂ R] (4) carboxylic acid group (-CO ₂ H) (5) sulfonic acid group (-SO ₃ H) (6) phosphoric acid group (-OPO ₃ H ₂₎

In the above (1) to (6), Ar represents a divalent aryl linking group which may have a substituent, and R represents a hydrocarbon group which may have a substituent. .

Examples of the monomer having a phenol group (1) include acrylamide having a phenol group, methacrylamide, acrylic acid ester, methacrylic acid ester, and hydroxystyrene.

Examples of the monomer (2) having a sulfonamide group include compounds having at least one sulfonamide group having the above structure and at least one polymerizable unsaturated group in the molecule. Among them, a low molecular weight compound having an acryloyl group, an allyl group or a vinyloxy group and a sulfonamide group in the molecule is preferable. For example, the following general formula (i)
Compounds represented by (v) to (v) are mentioned.

[0043]

[Chemical 8]

In the above general formulas (i) to (v), X¹And X²
Are each independently -O- or -NR ⁷Represents-. R¹as well as
R^FourAre each independently a hydrogen atom or -CH₃Represents
R², R^Five, R⁹, R¹², And R¹⁶Are independent of each other.
Alkylene having 1 to 12 carbon atoms which may have a substituent
Group, cycloalkylene group, arylene group or aralkyl group
Represents a group. R³, R⁷, And R¹³Each independently, water
Elementary atoms and C 1-12 carbon atoms which may have a substituent
Alkyl group, cycloalkyl group, aryl group or aralkyl group
Represents a radical. Also, R⁶And R¹⁷Are each independently replaced
An alkyl group having 1 to 12 carbon atoms which may have a group,
It represents a chloroalkyl group, an aryl group, or an aralkyl group. R
⁸, R^TenAnd R¹⁴Are each independently a hydrogen atom or -CH₃
Represents R¹¹And R¹⁵Are each independently a single bond or a substitution.
An alkylene group having 1 to 12 carbon atoms which may have a group,
Cycloalkylene group, arylene group or aralkylene group
Represents Y¹And Y²Are each independently a single bond, or-
Represents CO-.

Among the compounds represented by the general formulas (i) to (v), in the image recording material of the present invention, particularly m-aminosulfonylphenyl methacrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- -(P-Aminosulfonylphenyl) acrylamide and the like can be preferably used.

Examples of the above-mentioned (3) monomer having an active imide group include compounds having at least one active imide group represented by the above structural formula and at least one polymerizable unsaturated group in the molecule. Among these, compounds having one or more active imide groups represented by the following structural formulas and one or more polymerizable unsaturated groups in the molecule are preferable.

[0047]

[Chemical 9]

Specifically, N- (p-toluenesulfonyl) methacrylamide, N- (p-toluenesulfonyl) acrylamide and the like can be preferably used.

Examples of the above-mentioned (4) carboxylic acid group-containing monomer include compounds having one or more carboxylic acid groups and one or more polymerizable unsaturated groups in the molecule. Examples of the above-mentioned (5) monomer having a sulfonic acid group include compounds having at least one sulfonic acid group and at least one polymerizable unsaturated group in the molecule. Examples of the above-mentioned (6) monomer having a phosphoric acid group include compounds having at least one phosphoric acid group and at least one polymerizable unsaturated group in the molecule.

Among the above-mentioned monomers having an acid group having a pKa of 12 or less, a monomer having (1) a phenol group, (2) a sulfonamide group, (3) an active imide group or (4) a carboxylic acid is preferable, and particularly ( 1) phenolic group,
The monomer having (2) sulfonamide group or (4) carboxylic acid is most preferable from the viewpoint of ensuring sufficient solubility in an alkaline developing solution, developing latitude and film strength.

Other monomers may be used as a copolymerization component of the long-chain alkyl group-containing monomer and the acid group-containing monomer. Monomers other than such long-chain alkyl group-containing monomers and acid group-containing monomers are preferably contained in the copolymer component in an amount of 30 mol% or less, more preferably 20 mol% or less from the viewpoint of the effect of the present invention. preferable.

The monomers other than the long-chain alkyl group-containing monomer and the acid group-containing monomer include the following (7) to (17)
The compounds listed in can be exemplified.

(7) Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate. (8) Methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, benzyl acrylate,
Acrylate such as 2-chloroethyl acrylate, glycidyl acrylate, N-dimethylaminoethyl acrylate, polyethylene glycol monoacrylate and polypropylene glycol monoalkylate. (9) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, N-
Methacrylates such as dimethylaminoethyl methacrylate, polyethylene glycol monomethacrylate and polypropylene glycol monomethacrylate.

(10) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N -Acrylamide or methacrylamide such as ethyl-N-phenylacrylamide. (11) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether and phenyl vinyl ether. (12) Vinyl acetate, vinyl chloroacetate,
Vinyl esters such as vinyl butyrate and vinyl benzoate.

(13) Styrene, α-methylstyrene,
Styrenes such as methylstyrene and chloromethylstyrene. (14) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone. (15) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene.

(16) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like. (17) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, and N- (p-chlorobenzoyl) methacrylamide.

As the copolymerization method of the above-mentioned monomers, there are conventionally known graft copolymerization method, block copolymerization method,
A random copolymerization method or the like can be used. Further, two or more kinds of copolymerization components of the long chain alkyl group-containing monomer can be mixed and used.

Specific examples of the polymer that reduces the dynamic friction coefficient to 0.38 to 0.60 include the following, but is not limited to these.

[0059]

[Chemical 10]

[0060]

[Chemical 11]

[0061]

[Chemical 12]

[0062]

[Chemical 13]

[0063]

[Chemical 14]

[0064]

[Chemical 15]

The dynamic friction coefficient used in the present invention is 0.38 to
A polymer having a weight average molecular weight of 2,000 or more and a number average molecular weight of 1,000 or more is preferably used as the polymer to be reduced to 0.60. More preferably, the weight average molecular weight in terms of polystyrene is 5,000 to 5,000.
10,000, particularly preferably 5,000 to 2,000
10,000, more preferably 10,000 to 1,000
It is 10,000. Such polymers may be used alone or in combination of two or more.

When the image recording material of the present invention is applied to a lithographic printing plate precursor, when the image recording material of the present invention is applied to the lithographic printing plate precursor, the amount of residual monomer in the polymer for decreasing the dynamic friction coefficient to 0.38 to 0.60 is determined. It is preferably 10% by mass or less, and more preferably 5% by mass or less, in view of problems such as transfer to a protective paper (interleaving paper), a back surface of a substrate, and transfer to a roller during production of a lithographic printing plate precursor.

The amount of the polymer used to reduce the dynamic friction coefficient to 0.38 to 0.60 is preferably 1 to 20% by mass, and more preferably 2 to 10% by mass, based on all the components of the recording layer in which the image recording material is used. % Is more preferable. Within this range,
Good scratch resistance can be obtained without problems of transfer of slipping substances or problems with image formation during manufacturing or transportation.

In the coating liquid for the recording layer of the present invention, a surfactant such as, for example, JP-A-62-1 is used for improving the surface quality of the coating.
Fluorine-based surfactants such as those described in JP-A-70950 and JP-A-2002-72474 can be added. The preferable addition amount is 0.0 of the solid content of the recording layer.
01 to 1.0 mass%, more preferably 0.005
Is 0.5% by mass. When such a fluorosurfactant is used in combination with a polymer that reduces the dynamic friction coefficient to 0.38 to 0.60, the dynamic friction coefficient is reduced to 0.38 to 0.60. The amount of the polymer used is preferably 5 to 30% by mass, and more preferably 5 to 15% by mass, based on the total components of the recording layer in which the image recording material is used.

The polymer that reduces the dynamic friction coefficient to 0.38 to 0.60 may be compatible or phase-separated in the image forming material. The outermost surface of the image forming material containing a polymer that reduces the dynamic friction coefficient to 0.38 to 0.60 may be smooth or may have irregularities. The contact angle of water droplets in the air on the surface of the image forming material containing a polymer that reduces the dynamic friction coefficient to 0.38 to 0.60 is preferably in the range of 60 degrees to 140 degrees. The dynamic friction coefficient is 0.38 to 0.
Polymers reduced to 60 preferably do not crystallize in the imaging element.

The dynamic friction coefficient of the present invention is 0.38 to 0.60.
More preferably, the polymer having a structural unit represented by the following general formula (1) can be used as the polymer having the above structure.

[0071]

[Chemical 16]

N is an integer of 4 or more, and m is 0.6 ≦ m.
Represents ≦ 20. X represents a skeleton having an alkali-soluble group having a pKa of 12 or less, and R represents an alkyl group or a hydrogen atom. In the general formula (1), n is more preferably 8 ≦ n ≦ 30, and particularly preferably 12 ≦ n ≦ 20, from the viewpoints of the effect of improving scratch resistance and the effect on solubility. M in the general formula (1) is 0.6 ≦ m ≦ 1 from the viewpoint of slipperiness.
0 is more preferable.

Suitable examples of the long chain alkyl group-containing monomer capable of forming the long chain alkyl group-containing monomer component in the general formula (1) include the following monomers.

[0074]

[Chemical 17]

X in the general formula (1) has a pKa of 1
It represents a monomer component having 2 or less alkali-soluble groups. Specific examples of the monomer capable of forming X include p described above.
Monomers (1) to (6) having an acid group having a Ka of 12 or less are preferable in terms of solubility and sensitivity in an alkaline developer. Among them, the monomer having the above-mentioned (1) phenol group, (2) sulfonamide group and (3) active imide group (4) carboxylic acid is preferable,
In particular, a monomer having (1) a phenol group, (2) a sulfonamide group or (4) a carboxylic acid is preferable from the viewpoint of ensuring sufficient solubility in an alkaline developing solution, developing latitude and film strength.

Further, as the copolymerization component of the polymer having the structural unit represented by the general formula (1), the above-mentioned (7)-
The copolymerizable monomer listed in (17) is used in the copolymer component 30
It can be used in an amount of not more than mol%, and is preferably not more than 20% from the viewpoint of the effect of the present invention.

Specific examples of the polymer represented by the general formula (1) include, among the specific examples of the polymer whose dynamic friction coefficient is reduced to 0.38 to 0.60, paragraphs [0059] to
Examples include, but are not limited to, the polymers described in paragraph [0061].

[0078]

[Chemical 18]

[0079]

[Chemical 19]

The weight average molecular weight of the polymer represented by the general formula (1), the amount of residual monomer in the polymer, and the amount added in the recording layer are in the case of a polymer which reduces the dynamic friction coefficient to 0.38 to 0.60. It is preferably the same as The compatibility, crystallization, the influence on the smoothness of the outermost surface, and the contact angle of water drops in the air in the image forming material are the same as those in the case of the polymer that reduces the dynamic friction coefficient to 0.38 to 0.60. Preferably there is.

(Infrared Absorbing Agent) As the infrared absorbing agent used in the present invention, any substance which absorbs infrared rays and generates heat can be used without particular limitation of absorption wavelength range, but it is easily available. From the viewpoint of compatibility with output lasers,
An infrared absorbing dye or pigment having an absorption maximum at a wavelength of 700 nm to 1200 nm is preferred.

As the dye, commercially available dyes and known dyes described in documents such as "Dye Handbook" (edited by the Society of Organic Synthetic Chemistry, published in 1970) can be used. Specifically, azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, naphthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, cyanine dyes, squarylium dyes, (thio) pyrylium salts , Metal thiolate complex, indoaniline metal complex dye, oxonol dye, diimonium dye, aminium dye, croconium dye, intermolecular CT dye and the like.

Preferred dyes include, for example, JP-A-5
Cyanine dyes described in JP-A No. 8-125246, JP-A-59-84356, JP-A-60-78787, JP-A-58-173696 and JP-A-58-1.
81690, methine dyes described in JP-A-58-194595, JP-A-58-112793.
JP-A-58-224793, JP-A-59-481
87, JP-A-59-73996, JP-A-60-52.
940, naphthoquinone dyes described in JP-A-60-63744 and the like, JP-A-58-112792.
Examples thereof include squarylium dyes described in Japanese Patent Publication No. JP-A No. 1993-242, and cyanine dyes described in British Patent No. 434,875.

The near-infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferably used, and
Substituted arylbenzo (thio) pyrylium salts described in U.S. Pat. No. 3,881,924, JP-A-57-
142645 (US Pat. No. 4,327,169
Trimethine thiapyrylium salt, JP-A-58-
No. 181051, No. 58-220143, No. 59-4
1363, 59-84248, 59-8424
No. 9, No. 59-146063, No. 59-146061.
Pyrylium compounds described in JP-A No. 59-216146, cyanine dyes described in JP-A-59-216146, pentamethine thiopyrylium salts described in U.S. Pat. No. 4,283,475, and JP-B-5. -13514, 5
The pyrylium compound disclosed in each of the 19702 publications is also preferably used.

Another preferred example of the dye is represented by the formula (I) in US Pat. No. 4,756,993:
The near infrared absorbing dye described as (II) can be mentioned.

Among these dyes, particularly preferred are cyanine dyes, phthalocyanine dyes, oxonol dyes, squarylium dyes, pyrylium salts, thiopyrylium dyes, and nickel thiolate complexes.

Further, the dyes represented by the following general formulas (a) to (f-2) are preferable because they have excellent photothermal conversion efficiency, and the cyanine dye represented by the following general formula (a) is particularly preferable as the photosensitive composition of the present invention. It is most preferable because it gives a high interaction with an alkali-soluble resin, and is excellent in stability and economy when used as a product.

[0088]

[Chemical 20]

In the general formula (a), R ¹ and R ² each independently represent a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Examples of the substituent include an alkoxy group, an aryl group, an amide group, an alkoxycarbonyl group, a hydroxyl group, a sulfo group and a carboxyl group. Y ¹ and Y ² each independently represent oxygen, sulfur, selenium, a dialkylmethylene group or —CH═CH—. Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group, which may have a substituent selected from an alkyl group, an alkoxy group, a halogen atom and an alkoxycarbonyl group, and are adjacent to Y ¹ or Y ² . The aromatic ring may be condensed with two consecutive carbon atoms.

X represents a counter ion necessary for neutralizing the charge, and is not always necessary when the dye cation portion has an anionic substituent. Q represents a polymethine group selected from a trimethine group, a pentamethine group, a heptamethine group, a nonamethine group, or an undecamethine group, and is preferably a pentamethine group, a heptamethine group, or a nonamethine group from the viewpoint of wavelength suitability to infrared rays used for exposure. It is preferable in terms of stability to have a cyclohexene ring or a cyclopentene ring containing three consecutive methine chains on the carbon.

Q is an alkoxy group, an aryloxy group,
Alkylthio group, arylthio group, dialkylamino group, diarylamino group, halogen atom, alkyl group,
It may be substituted with a group selected from an aralkyl group, a cycloalkyl group, an aryl group, an oxy group, an iminium base and a substituent represented by the following general formula (Q1), and a preferable substituent is a chlorine atom or the like. Examples thereof include a halogen atom, a diarylamino group such as a diphenylamino group, and an arylthio group such as a phenylthio group.

[0092]

[Chemical 21]

In the formula, R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, or 6 to 10 carbon atoms.
Represents an aryl group, and Y ³ represents an oxygen atom or a sulfur atom.

Among the cyanine dyes represented by the general formula (a), when exposed to infrared rays having a wavelength of 800 to 840 nm, particularly preferable ones are the following general formulas (a-1) to (a-
The heptamethine cyanine dye represented by 4) can be mentioned.

[0095]

[Chemical formula 22]

In formula (a-1), X ¹ represents a hydrogen atom or a halogen atom. R ¹ and R ² each independently represent a hydrocarbon group having 1 to 12 carbon atoms. The storage stability of the recording layer coating liquid, R ¹ and R ² are preferably a hydrocarbon group having two or more carbon atoms, further, R ¹
And R ² are particularly preferably bonded to each other to form a 5-membered ring or a 6-membered ring.

Ar ¹ and Ar ^{2, which} may be the same or different, each represents an aromatic hydrocarbon group which may have a substituent. Preferred aromatic hydrocarbon groups include a benzene ring and a naphthalene ring. Examples of preferable substituents include a hydrocarbon group having 12 or less carbon atoms, a halogen atom, and an alkoxy group having 12 or less carbon atoms. Y ¹ and Y ² may be the same or different and each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms. R ³ and R ^{4, which} may be the same or different, each represents a hydrocarbon group having 20 or less carbon atoms, which may have a substituent. Preferred substituents include an alkoxy group having 12 or less carbon atoms, a carboxyl group and a sulfo group. R ⁵ ,
R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. From the availability of raw materials, hydrogen atom is preferable. Za ⁻ represents a counter anion necessary for neutralizing the charge, and when any of R ^{1 to} R ⁸ is substituted with an anionic substituent, Za ⁻ is not necessary. Preferred Za ⁻ is
From the storage stability of the recording layer coating liquid, halogen ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, and sulfonate ion, particularly preferably perchlorate ion, tetrafluoroborate ion, hexa Fluorophosphate ion,
And sulfonate ion. The heptamethine dye represented by the above general formula (a-1) can be suitably used for a positive image recording material, and is a so-called interaction-release type positive image recording in combination with an alkali-soluble resin having a phenolic hydroxyl group. It is preferably used as a material.

[0098]

[Chemical formula 23]

In the general formula (a-2), R^lAnd R²Is that
Independently, a hydrogen atom or a hydrocarbon having 1 to 12 carbon atoms
Group, R^lAnd R²And are bonded to each other to form a ring structure
A 5-membered ring or 6-membered ring is preferable as the ring to be formed.
A 5-membered ring is particularly preferable. Ar^lAnd Ar²Is that
Each of which may be the same or different and has a substituent
It also represents an aromatic hydrocarbon group. Preferred aromatic carbonization
Examples of the hydrogen group include a benzene ring and a naphthalene ring.
Be done. In addition, preferred substituents on the aromatic hydrocarbon group
Is a hydrocarbon group having 12 or less carbon atoms, halogen
Atoms, alkoxy groups with 12 or less carbon atoms, alkoxy
Cycarbonyl group, alkylsulfonyl group, halogenated
Examples thereof include an alkyl group, and an electron-withdrawing substituent is particularly preferable.
Good Y ^lAnd Y²Are the same or different
Well, dialkyls with 12 or less sulfur atoms or carbon atoms
Indicates a methylene group. R³And R^FourAre the same or different
A carbon atom which may be substituted or may have a substituent
The number of hydrocarbon groups is 20 or less. As a preferred substituent
Is an alkoxy group having 12 or less carbon atoms,
Examples thereof include a sil group and a sulfo group. R^Five, R⁶, R⁷And R⁸
May be the same or different, and may be a hydrogen atom or
Represents a hydrocarbon group having 12 or less carbon atoms. Input of raw materials
From the viewpoint of hand property, it is preferably a hydrogen atom. R⁹And R
^TenMay be the same or different, and
Aromatic hydrocarbon having 6 to 10 carbon atoms which may be contained
Group, alkyl group having 1 to 8 carbon atoms, hydrogen atom or R⁹
And R^TenAnd may combine with each other to form a ring having the structure below.
Yes.

[0100]

[Chemical formula 24]

Of the above, R ⁹ and R ¹⁰ are most preferably an aromatic hydrocarbon group such as a phenyl group. Further, X ⁻ is the same definition as Za ^{− in the} above general formula (a-1) for the counter anion necessary for neutralizing the charge. The heptamethine dye represented by the general formula (a-2) can be preferably used for an image recording material in which an acid and / or a radical generator such as an onium salt is used in combination, and particularly, a radical generating agent such as a sulfonium salt or an iodonium salt is generated. It is preferably used for a negative type image recording material in which an agent is used in combination.

[0102]

[Chemical 25]

In the formula, R ^{1 to} R ⁸ , Ar ¹ , Ar ² , Y ¹ , and Y ²
And X ⁻ each have the same meaning as in the general formula (a-2). Ar ³ represents a phenyl group, an aromatic hydrocarbon group such as a naphthyl group, or a monocyclic or polycyclic heterosphere group containing at least one of nitrogen, oxygen and sulfur atoms, and a thiazole-based, benzothiazole-based, Naphthothiazole type, thianaphtheno-7 ', 6', 4,5-thiazole type, oxazole type, benzoxazole type, naphthoxazole type, selenazole type, benzoselenazole type, naphthoselenazole type, thiazoline type, 2-quinoline type , 4-quinoline-based, 1-isoquinoline-based, 3-isoquinoline-based, benzimidazole-based, 3,3-dialkylbenzoindolenine-based, 2-pyridine-based, 4-pyridine-based, 3,3-dialkylbenzo [e] indole system,
A heterocyclic group selected from the group consisting of a tetrazole type, a triazole type, a pyrimidine type, and a thiadiazole type is preferable, and particularly preferable heterocyclic groups include those having the following structures.

[0104]

[Chemical formula 26]

[0105]

[Chemical 27]

In the formula, R ^{1 to} R ⁸ , Ar ¹ , Ar ² , Y ¹ and Y ² have the same meanings as in formula (a-2). R ¹¹ and R ¹² may be the same or different and each represents a hydrogen atom, an allyl group, a cyclohexyl group or an alkyl group having 1 to 8 carbon atoms. Z represents an oxygen atom or a sulfur atom.

Specific examples of the cyanine dye represented by the general formula (a) which can be preferably used in the present invention include those shown below and JP-A 2001-1339.
Paragraph Nos. [0017] to [0019] of Japanese Patent Laid-Open No. 69, paragraph [0012] of Japanese Patent Laid-Open No. 2002-40638.
To [0038], paragraphs [0012] to [0023] of JP-A-2002-23360.

[0108]

[Chemical 28]

[0109]

[Chemical 29]

[0110]

[Chemical 30]

[0111]

[Chemical 31]

[0112]

[Chemical 32]

[0113]

[Chemical 33]

[0114]

[Chemical 34]

In the general formula (b), L represents a methine chain having a conjugated carbon atom number of 7 or more, and the methine chain may have a substituent, and the substituents are bonded to each other to form a ring structure. May be. Zb ⁺ represents a counter cation. Preferred counter cations include ammonium, iodonium, sulfonium, phosphonium, pyridinium, alkali metal cations (Ni ⁺ , K ⁺ , Li ⁺ ) and the like. R ^{9 to} R ¹⁴
And R ^{15 to} R ²⁰ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a carbonyl group, a thio group, a sulfonyl group, a sulfinyl group, an oxy group, or an amino group. It represents a selected substituent or a substituent in which two or three of them are combined and may be bonded to each other to form a ring structure. Here, in the general formula (b), L represents a methine chain having a conjugated carbon atom number of 7, and R ^{9 to} R ¹⁴
It is preferable that R ^{15 to} R ²⁰ all represent hydrogen atoms from the viewpoint of easy availability and effects.

Specific examples of the dye represented by the general formula (b) which can be preferably used in the invention include the followings.

[0117]

[Chemical 35]

[0118]

[Chemical 36]

In the general formula (c), Y³And Y^FourIs that
Oxygen atom, sulfur atom, selenium atom, or tellurium atom
Represents M represents a methine chain having a conjugated carbon number of 5 or more. R
^{twenty one}~ R ^{twenty four}And R^{twenty five}~ R²⁸Are the same or different
May be, hydrogen atom, halogen atom, cyano
Group, alkyl group, aryl group, alkenyl group, alkyn
Group, carbonyl group, thio group, sulfonyl group, sulfi group
It represents a nyl group, an oxy group, or an amino group. Also, in the formula Z
a^-Represents a counter anion, and in the general formula (a-1)
Za^-Is synonymous with.

In the present invention, specific examples of the dye represented by formula (c) which can be preferably used include the followings.

[0121]

[Chemical 37]

[0122]

[Chemical 38]

In formula (d), R ^{29 to} R ³² each independently represents a hydrogen atom, an alkyl group or an aryl group. R
³³ and R ³⁴ are each independently an alkyl group, a substituted oxy group,
Alternatively, it represents a halogen atom. n and m each independently represent an integer of 0 to 4. R ²⁹ and R ³⁰ , or R ³¹ and R ³² may be bonded to each other to form a ring, and R ²⁹ and / or R ³⁰ is R ^33, and R ³¹ and / or R ³² is R ³⁴ . They may be bonded to each other to form a ring, and when a plurality of R ³³ or R ³⁴ are present, R ^33's or R ^34's may be bonded to each other to form a ring. X ² and X ³ each independently represent a hydrogen atom, an alkyl group, or an aryl group. Q is a trimethine group or a pentamethine group which may have a substituent, and may form a ring structure with a divalent organic group.
Zc ^- represents a counter anion, Za in the general formula (a-1) ^- synonymous.

In the present invention, specific examples of the dye represented by formula (d) which can be preferably used include the followings.

[0125]

[Chemical Formula 39]

[0126]

[Chemical 40]

In formula (e), R ^{35 to} R ⁵⁰ are each independently a halogen atom, which may have a hydrogen atom or a substituent, a cyano group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, A hydroxyl group, a carbonyl group, a thio group, a sulfonyl group, a sulfinyl group, an oxy group, an amino group, and an onium salt structure are shown. R ³⁶ and R ³⁷ , R ⁴⁰ and R ⁴¹ , R ⁴⁴ and R ^45, and R ⁴⁸ and R ⁴⁹ may be linked to form an aliphatic ring, an aromatic ring or a heterocycle, and the ring is a condensed ring. May have. M represents two hydrogen atoms or a metal atom, a halometal group, or an oxymetal group, and the metal atom contained therein is a group IA, IIA, IIIB, IVB atom, first, second, or group of the periodic table. Examples include transition metal of three cycles and lanthanoid element, and among them, copper, nickel, magnesium,
Iron, zinc, tin, cobalt, aluminum, titanium and vanadium are preferable, and vanadium, nickel, zinc and tin are particularly preferable. These metal atoms may be bonded to oxygen atoms, halogen atoms or the like in order to make the valence appropriate.

In the present invention, specific examples of the dye represented by formula (e) which can be preferably used include the followings.

[0129]

[Chemical 41]

[0130]

[Chemical 42]

In the general formulas (f-1) and (f-2), R ⁵¹
To R ⁵⁸ each independently represent a hydrogen atom or an alkyl group or an aryl group which may have a substituent. X ⁻ has the same meaning as in the general formula (a-2).

Specific examples of the dyes represented by formulas (f-1) and (f-2) which can be preferably used in the present invention include the followings.

[0133]

[Chemical 43]

Infrared absorbing agents other than the above are disclosed in JP-A No.
A dye having a plurality of chromophores described in JP-A-01-242613,
JP-A-2002-97384, a dye in which a chromophore is covalently linked to a polymer compound described in US Pat.No. 6,124,425, an anionic dye described in US Pat. No. 6,248,893, and JP-A-2001-347765. Dyes having a surface-orienting group described in JP-A No. 1994-242242 can be preferably used.

The pigment used as the infrared absorber in the present invention includes commercially available pigments and color indexes.
(CI) Handbook, "Latest Pigment Handbook" (edited by Japan Pigment Technology Association, 1977), "Latest Pigment Application Technology" (CMC Publishing, 1986), "Printing Ink Technology" CMC Publishing,
Pigments described in 1984).

The types of pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments,
Blue pigment, green pigment, fluorescent pigment, metal powder pigment, etc.
Polymer bound dyes may be mentioned. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments,
Perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, dyed lake pigments,
Azine pigment, nitroso pigment, nitro pigment, natural pigment, fluorescent pigment, inorganic pigment, carbon black and the like can be used.
Preferred among these pigments is carbon black.

These pigments may be used without surface treatment or may be used after surface treatment. The surface treatment method includes a method of surface-coating a resin or wax, a method of attaching a surfactant, a method of binding a reactive substance (for example, a silane coupling agent, an epoxy compound, polyisocyanate, etc.) to the pigment surface, etc. Can be considered. The above surface treatment method is "property and application of metal soap" (Koushobo),
It is described in "Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986).

The particle size of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, and particularly preferably 0.1 μm to 1 μm.
It is preferably in the range of. Within this range, good stability of the dispersion in the coating solution for the recording layer and good uniformity of the recording layer can be obtained.

As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production and the like can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill and a pressure kneader. For details, see "Latest Pigment Application Technology" (CMC Publishing, 1
986).

These pigments or dyes are used in an amount of 0.01 to 50% by mass, preferably 0.1 to 10% by mass, based on the total solids constituting the recording layer, and particularly preferably 0.5 in the case of dyes.
10 to 10% by mass, particularly preferably 0.1 to 10 in the case of pigment
It can be added in a mass% ratio. Within this range,
Good sensitivity can be obtained without the possibility of adversely affecting the uniformity of the recording layer or the durability of the recording layer. Also,
The dye or pigment used may be a single compound or 2
A mixture of two or more compounds may be used, and it is also preferable to use dyes or pigments having different absorption wavelengths in combination in order to cope with an exposure device having a plurality of wavelengths.

[Lithographic printing plate precursor] As the lithographic printing plate precursor to which the image recording material of the present invention is applied, there are a positive lithographic printing plate precursor and a negative lithographic printing plate precursor capable of forming an image by infrared laser exposure. Can be mentioned.

(Positive lithographic printing plate precursor) As the positive lithographic printing plate precursor to which the image recording material of the present invention is applied,
(1) Water-insoluble and alkali-soluble resin (hereinafter, appropriately
It is referred to as an alkali-soluble resin) and a substance (dissolution inhibitor) that interacts with the alkali-soluble resin to suppress alkali solubility, and utilizes the fact that the interaction is released by heating to increase alkali solubility. An image forming type positive lithographic printing plate precursor, and (2) containing a compound which is converted into a developing solution (for example, an alkaline aqueous solution) by the action of an acid and an acid generator which generates an acid by heat, and by heating A positive type lithographic printing plate precursor of the type in which an image is formed by utilizing the fact that the solubility of the developer is increased by the action of the acid generated can be mentioned.

Examples of the positive type lithographic printing plate precursor using the above-mentioned (1) alkali-soluble resin and dissolution inhibitor include, for example, US Pat. No. 3,628,953 and US Pat. No. 4,708,925. Description, JP-A-7-28527
5, JP-A-97 / 39,894, JP-A-11-44956, and JP-A-11-2685.
No. 12, and the positive planographic printing plate precursors described in JP-A No. 2001-324808 and the like. But,
Any positive type planographic printing plate precursor may be used as long as an image is formed according to the above principle, and the present invention is not limited thereto.

The positive planographic printing plate precursor of the above (1) to which the image recording material of the present invention is applied is specifically as follows:
On the support, (a) an infrared absorber, (b) a copolymer of a long-chain alkyl-containing monomer and a hydrophilic monomer that reduces the dynamic friction coefficient to a ratio of 0.38 to 0.6, and (c) an alkali-soluble A positive type lithographic printing plate precursor having a recording layer containing a resin can be mentioned. More preferably, the recording layer is
Further, there can be mentioned a positive lithographic printing plate precursor containing (d) a dissolution inhibitor and (e) other known additives which are optionally added.

The above-mentioned alkali-soluble resin is a water-insoluble and alkali-soluble resin, and includes homopolymers containing an acidic group in the main chain and / or side chain in the polymer, copolymers thereof or mixtures thereof. To do. Above all, the following (1)
Those having an acidic group listed in (6) to (6) in the main chain and / or side chain of the polymer are preferable from the viewpoint of solubility in an alkaline developing solution and manifestation of dissolution inhibiting ability.

(1) Phenol group (-Ar-OH) (2) Sulfonamide group (-SO ₂ NH-R) (3) Active imide group [-SO ₂ NHCOR, -SO ₂ N
HSO ₂ R, -CONHSO ₂ R] (4) carboxylic acid group (-CO ₂ H) (5) sulfonic acid group (-SO ₃ H) (6) phosphoric acid group (-OPO ₃ H ₂₎

Among the alkali-soluble resins having an acidic group selected from the above (1) to (6), (1) phenol group, (2) sulfonamide group (3) active imide group, and (4) carboxylic acid group The alkali-soluble resin having (1) a phenol group or (2) a sulfonamide group and (4) a carboxylic acid group is particularly preferable for the alkali-soluble resin having a solubility, a developing latitude and a film strength. It is the most preferable from the point of securing sufficient.

Examples of the alkali-soluble resin having an acidic group selected from the above (1) to (6) include, for example, US Pat. No. 3,628,953 and US Pat. No. 4,708,9.
25, JP-A-7-285275, International Publication No. 97 / 39,894 pamphlet, JP-A-11-
No. 44956, JP-A No. 11-268512,
JP-A-2001-324808, JP-A-7-282
44, JP-A-7-36184, JP-A-51-
No. 34711, JP-A-2-866, etc., phenol resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, copolymer of N- (4-hydroxyphenyl) methacrylamide, hydroquinone monomethacrylate copolymer. , A sulfonylimide-based polymer, a carboxyl group-containing polymer, a phenolic hydroxyl group-containing acrylic resin, a sulfonamide group-containing acrylic resin, and a urethane-based resin.

As a dissolution inhibitor which is optionally used in the recording layer of the positive type lithographic printing plate precursor, there is disclosed JP-A-7-2.
No. 85275, JP-A No. 2002-55446, etc. are thermally decomposable, such as onium salts, o-quinonediazide compounds, aromatic sulfone compounds, and aromatic sulfonic acid ester compounds. A compound capable of suppressing dissolution in a developing solution is preferable. Examples of onium salts include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts and the like.

Among the positive type lithographic printing plate precursors, the positive type lithographic printing plate precursor containing (2) a compound capable of being converted into a developing solution by the action of an acid and an acid generator is described in JP-A-9-17.
1254, JP-A-10-55067, JP-A-10-
The positive planographic printing plate precursors described in JP-A No. 87733, JP-A No. 10-268507 and the like can be mentioned. But,
Any positive type planographic printing plate precursor may be used as long as an image is formed according to the above principle, and the present invention is not limited thereto.

The positive planographic printing plate precursor of (2) above to which the image recording material of the present invention is applied is specifically as follows:
On the support, (a) an infrared absorber, (b) a copolymer of a long-chain alkyl-containing monomer and a hydrophilic monomer that reduces the dynamic friction coefficient to 0.38 to 0.60, and (c) irradiation with actinic rays. A positive lithographic printing plate precursor having a recording layer containing a compound capable of generating an acid (acid generator) and (d) a compound having at least one bond capable of decomposing with an acid (acid decomposable compound) can be mentioned. .

Examples of the acid-decomposable compound include those described in JP-A-48.
-89603, 51-1207714, 53-1
33429, 55-12995, 55-126.
C-O described in each publication of No. 236 and No. 56-17345.
Compounds having a -C bond, JP-A-60-37549,
Compounds having a Si-O-C bond described in JP-A-60-121446, JP-A-60-3625 and JP-A-60-
Other acid-decomposable compounds described in JP-A-10247 can be mentioned, and further, JP-A-62-22224.
No. 6, a compound having a Si—N bond, a carbonic acid ester described in JP-A No. 62-251743, an orthocarbonic acid ester described in JP-A No. 62-209451, Kaisho 62-2808
41, orthotitanate ester,
Orthosilicic acid esters described in JP-A-62-280842, JP-A-63-010153, JP-A-9-171254, JP-A-10-55067 and JP-A-10-55067.
-11156, 10-87733, 10-1
53853, 10-228102, 10-26.
No. 8507, No. 282648, No. 10-282670.
Use of the acetals, ketals and orthocarboxylic acid esters described in European Patent Application Publication No. 0888447Al and compounds having a C—S bond described in JP-A No. 62-244038. You can

Among them, compounds having a C--O--C bond,
Compounds having a Si-O-C bond, orthocarbonates, acetals, ketals and silyl ethers are preferred. Further, a polymer compound having an acetal or ketal moiety in the main chain repeatedly and whose solubility in an alkaline developer is increased by the acid generated is preferably used.

Examples of the acid generator used together with the above acid decomposable compound include onium salts such as iodonium salts, sulfonium salts, phosphonium salts and diazonium salts. Specific examples thereof include compounds described in US Pat. No. 4,708,925 and JP-A-7-20629. Particularly, iodonium salts, sulfonium salts, and diazonium salts having sulfonate ion as a counter ion are preferable. Examples of the diazonium salt include diazonium compounds described in U.S. Pat. No. 3,867,147, diazonium compounds described in U.S. Pat. No. 2,632,703, JP-A-1-102456, and JP-A-1-102457. The diazo resins described in each of the above publications are also preferable. Also, US Pat. No. 5,135,83
The benzyl sulfonates described in US Pat. No. 8, and US Pat. No. 5,200,544 are also preferred. Furthermore, JP-A Nos. 2-100054 and 2-10005.
Active sulfonic acid esters and disulfonyl compounds described in JP-A No. 5 and JP-A No. 9-197671 are also preferable. In addition, haloalkyl-substituted S-triazines described in JP-A-7-271029 are also preferable.

(Negative type lithographic printing plate precursor) As a negative type lithographic printing plate precursor to which the image recording material of the present invention is applied, a radical polymerization reaction is caused by heat and the product becomes insoluble in a developing solution. And a lithographic printing plate precursor utilizing the fact that a product becomes insoluble in a developer by causing a crosslinking reaction (including cationic polymerization) by heat, and the like.

As a lithographic printing plate precursor utilizing a polymerization reaction by heat, for example, JP-A-2001-183825,
JP 2001-337447 A, JP 2002-023 A
360, JP-A-2002-040638, JP-A-200
2-62642, JP-A-2002-62648, JP-A-2002-69109, and the like, and negative type lithographic printing plate precursors of the type that are polymerized by heat generated by infrared laser exposure. In these negative type lithographic printing plate precursors, the radical generator (polymerization initiator) generates ra-6 radical to polymerize the polymerizable compound by heat generation due to exposure, and the product is insolubilized in a developing solution. ing. However, the negative lithographic printing plate precursor to which the image recording material of the present invention is applied may be any negative lithographic printing plate precursor as long as it is an image formed according to the above principle, and is not limited thereto.

As such a negative type lithographic printing plate precursor to which the above image recording material is applied, for example, on a support,
(A) infrared absorber, (b) dynamic friction coefficient of 0.38 to
Copolymer of long-chain alkyl-containing monomer and hydrophilic monomer to reduce to 0.60, (c) radical generator, (d)
Examples thereof include a negative-working lithographic printing plate precursor having a recording layer containing a radically polymerizable compound, and (e) other optional binder polymers and known additives.

The radical generator used in the present invention is a compound which generates radicals by the energy of light, heat or both to initiate and accelerate the polymerization of the compound having a polymerizable unsaturated group. As the radical generator that can be used in the present invention, a known thermal polymerization initiator used in a polymer synthesis reaction by radical polymerization, a compound having a bond with a small bond dissociation energy, a photopolymerization initiator, or the like can be used. Examples of the radical-generating compound preferably used in the present invention include compounds that generate radicals by thermal energy to initiate and accelerate the polymerization of the compound having a polymerizable unsaturated group. The radical generators can be used alone or in combination of two or more.

As such a radical generator, for example, JP-A-8-220758 and JP-A-10-2605 can be used.
36, JP 2001-337447 A, 2002
-023360, etc. Organic halogenated compounds, carbonyl compounds, organic peroxide compounds, azo-based polymerization initiators, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, onium Examples thereof include salt compounds.
As the onium salt, the same one as described in the positive type lithographic printing plate precursor is used, but in such a polymerization system, the onium salt functions not as an acid generator but as an initiator of ionic radical polymerization.

As the radically polymerizable compound used in the present invention, at least one terminal ethylenically unsaturated group (eg, acryloyl group, methacryloyl group, vinyl group, allyl group, etc.) for radical polymerization reaction, preferably 2 Suitable examples are compounds having one or more.
Such a compound group is widely known in the industrial field as a monomer or a cross-linking agent for a photopolymerizable or thermopolymerizable composition, and these can be used in the invention without particular limitation. The chemical form is a monomer, a prepolymer, that is, a dimer, a trimer, an oligomer, a polymer or a copolymer, or a mixture thereof.

Specific examples of the radically polymerizable compound include:
JP-A-8-220758 and JP-A-2001-18382
The same polymerizable compounds as those described in JP-A No. 5, JP-A-2002-62648 and the like can be mentioned.

Examples of the lithographic printing plate precursor utilizing the crosslinking reaction by heat include, for example, US Pat. No. 5,340,699, JP-A-7-20629, and JP-A-7-2710.
29, JP-A-10-111564, JP-A-11-8.
4649, JP-A-11-95419, JP-A-11-
No. 102071, JP-A-11-119428, JP-A-11-216965, and JP-A-11-218903,
JP-A-11-231509, JP-A-11-25485
The negative type lithographic printing plate precursors described in each publication No. 0, WO 98/51544 pamphlet, WO 98/31545 pamphlet and the like can be mentioned. In these negative-working lithographic printing plate precursors, the heat generated by exposure causes the acid generator to generate an acid, and the acid acts as a catalyst to cause a crosslinking reaction of the crosslinking agent, resulting in acid-catalyzed crosslinking of the product. The reaction is used. In order to initiate or accelerate the acid-catalyzed crosslinking reaction, it is also preferable to heat the original plate after the exposure and then develop it. However, the negative type lithographic printing plate precursor to which the image recording material of the present invention is applied may be any negative type lithographic printing plate precursor as long as it is an image formed according to the above principle, and is not limited thereto.

As such a negative type lithographic printing plate precursor to which the above image recording material is applied, for example, on a support,
(A) infrared absorber, (b) dynamic friction coefficient of 0.38 to
Copolymer of long-chain alkyl-containing monomer and hydrophilic monomer to reduce to 0.60, (c) compound capable of generating acid upon irradiation with actinic rays (acid generator), (d) cross-linking agent which reacts with an acid catalyst , And (e) and other negative-working lithographic printing plate precursors having a recording layer containing a binder polymer added as necessary and known additives.

Specific examples of the cross-linking agent are described in JP-A-7-
20629, JP-A-11-102071, JP-A-1
(I) an aromatic compound substituted with an alkoxymethyl group or a hydroxymethyl group, (ii) an N-hydroxymethyl group, an N-alkoxymethyl group or an N-acyloxymethyl group described in JP-A No. 1-254850. And the same compounds such as (iii) epoxy compounds.

Suitable examples of the acid generator used together with the crosslinking agent include the same compounds as the acid generator used in the positive lithographic printing plate precursor described above.

(Support for lithographic printing plate precursor) The support used in the present invention is a dimensionally stable plate-like material,
A well-known support can be preferably used as a support for the printing plate. Examples of such a support include paper and plastics (for example, polyethylene, polypropylene, polystyrene, etc.)
Laminated paper such as aluminum (including aluminum alloy), zinc, iron, copper and other metal plates such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate ,polyethylene terephthalate,
Films of plastics such as polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, and the like, papers or plastic films laminated or vapor-deposited with the metals described above are included, and aluminum plates are particularly preferable. The aluminum plate includes a pure aluminum plate and an aluminum alloy plate. Various types of aluminum alloy can be used,
For example, silicon, copper, manganese, magnesium, chromium,
An alloy of aluminum with a metal such as zinc, lead, bismuth, or nickel is used. These compositions include some iron and titanium, as well as other negligible amounts of impurities.

The support is surface-treated if necessary.
The surface of the support of the photosensitive lithographic printing plate is preferably hydrophilized. Further, in the case of a support having a surface of metal, particularly aluminum, surface treatment such as graining treatment, sodium silicate, potassium fluorozirconate, dipping in an aqueous solution of phosphate, or anodizing treatment Is preferably done. Anodizing treatment is, for example,
Inorganic acids such as phosphoric acid, chromic acid, sulfuric acid, boric acid, or organic acids such as oxalic acid, sulfamic acid, etc. It is carried out by passing an electric current as an anode.

Further, as described in US Pat. No. 2,714,066, an aluminum plate which has been grained and then immersed in an aqueous sodium silicate solution, US Pat. No. 3,181,461. An aluminum plate which has been subjected to anodizing treatment and then immersed in an aqueous solution of an alkali metal silicate as described in 1. is also preferably used. Further, silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective. These hydrophilization treatments are performed to make the surface of the support hydrophilic, in addition to prevent harmful reaction with the photosensitive composition provided thereon and to improve the adhesion to the recording layer. It is given to improve.

Prior to graining the aluminum plate, if necessary, the surface rolling oil may be removed and the surface of the aluminum plate may be pretreated to expose a clean aluminum surface. For the former, solvents such as trichlene and surfactants are used. For the latter, a method using an alkali etching agent such as sodium hydroxide or potassium hydroxide is widely used.

As the graining method, any of mechanical, chemical and electrochemical methods is effective. Mechanical methods include a ball polishing method, a blast polishing method, and a brush polishing method in which a water-dispersed slurry of an abrasive such as pumice is rubbed with a nylon brush. As a chemical method, JP-A-54-31187 is used. A method of immersing in a saturated aqueous solution of an aluminum salt of a mineral acid as described in the publication is suitable, and an electrochemical method is a method of alternating-current electrolysis in an acidic electrolytic solution such as hydrochloric acid, nitric acid or a combination thereof. Is preferred. Among such surface-roughening methods, a surface-roughening method combining mechanical surface-roughening and electrochemical surface-roughening as described in JP-A-55-137993 is particularly suitable for the oil-sensitive image. This is preferable because it has a strong adhesion to the support. In the graining by the above method, the center line surface roughness (Ra) of the surface of the aluminum plate is 0.3 to 1.0 μm.
It is preferably applied in a range such that m.

The grained aluminum plate is washed with water and chemically etched if necessary. The etching treatment liquid is usually selected from an aqueous solution of a base or an acid that dissolves aluminum. In this case, the etched surface must not form a coating different from aluminum derived from the etching solution component. Examples of preferable etching agents include sodium hydroxide, potassium hydroxide, trisodium phosphate, disodium phosphate, tripotassium phosphate, dipotassium phosphate as basic substances; sulfuric acid, persulfuric acid as acidic substances. , Phosphoric acid, hydrochloric acid, and salts thereof, but salts having a lower ionization tendency than aluminum, for example, salts of zinc, chromium, cobalt, nickel, copper, etc. are not preferable because they form an unnecessary film on the etched surface. These etching agents have a dissolution rate of 0.3 or less per minute of immersion time when the concentration of use and temperature are set.
Most preferably, it is carried out at a rate of 40 g / m ² to gram, but higher or lower levels may be used. The etching is performed by immersing the aluminum plate in the above-mentioned etching solution or by coating the aluminum plate with the etching solution.
It is preferable that the treatment is performed in the range of 5 to 10 g / m ² . As the above-mentioned etching agent, it is desirable to use an aqueous solution of a base because of its high etching rate. In this case, smut is generated, and thus desmutting is usually performed. As the acid used for the desmutting treatment, nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, borofluoric acid or the like is used.

The etched aluminum plate is
If necessary, it is washed with water and anodized. The anodic oxidation 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 a non-aqueous solution containing sulfuric acid, phosphorus, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, etc., or a combination of two or more thereof, aluminum is supported. An anodized film can be formed on the body surface.

The treatment conditions for the anodic oxidation cannot be generally determined because they vary depending on the electrolytic solution used, but generally the concentration of the electrolytic solution is 1 to 80% by mass, and the liquid temperature is 5 to 70%.
C, current density 0.5-60 amps / dm ² , voltage 1-10
A range of 0 V and electrolysis time of 30 seconds to 50 minutes is suitable. Among these anodizing treatments, especially British Patent Nos. 1,4
A method for anodizing in sulfuric acid at high current density as described in US Pat. No. 3,511,511
The method of anodic oxidation using phosphoric acid described in Japanese Patent No. 661 as an electrolytic bath is preferable.

The aluminum plate which has been surface-roughened and anodized as described above may be subjected to a hydrophilic treatment if necessary, and a preferable example thereof is US Pat. No. 2,71.
Alkali metal silicates such as those disclosed in US Pat. Nos. 4,066 and 3,181,461, for example, aqueous sodium silicate solutions or potassium fluorozirconate disclosed in JP-B-36-22063. And the treatment with polyvinylphosphonic acid as disclosed in US Pat. No. 4,153,461.

The support may be provided with an organic undercoat layer before coating the recording layer for the purpose of reducing the development residual film thickness of the recording layer. Examples of the organic compound used in such an organic undercoat layer include phosphonic acids having an amino group such as carboxymethyl cellulose, dextrin, gum arabic, and 2-aminoethylphosphonic acid, phenylphosphonic acid which may have a substituent, and naphthyl. Organic phosphonic acids such as phosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, phenylphosphoric acid which may have a substituent, naphthylphosphoric acid, alkylphosphoric acid and glycerophosphoric acid Phosphoric acid, organic phosphinic acids such as phenylphosphinic acid which may have a substituent, naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid, glycine and β
It is selected from amino acids such as alanine and hydrochlorides of amines having a hydroxyl group such as triethanolamine hydrochloride, but two or more kinds may be used in combination.

It is also preferable that the organic undercoat layer contains a compound having an onium group. Compounds having an onium group are disclosed in JP-A Nos. 2000-10292 and 2000-1.
No. 08538 is described in detail.

In addition, at least one compound selected from the group of polymer compounds having a structural unit represented by poly (p-vinylbenzoic acid) or the like in the molecule can be used. More specific examples include a copolymer of p-vinylbenzoic acid and vinylbenzyltriethylammonium salt, and a copolymer of p-vinylbenzoic acid and vinylbenzyltrimethylammonium chloride.

This organic undercoat layer can be provided by the following method. That is, water or methanol, ethanol,
A method in which the above-mentioned organic compound is dissolved in an organic solvent such as methyl ethyl ketone or a mixed solvent thereof is applied onto an aluminum plate and dried, and water or methanol, ethanol, an organic solvent such as methyl ethyl ketone or a mixed solvent thereof. Is a method in which an aluminum plate is immersed in a solution in which the above organic compound is dissolved to adsorb the above organic compound, followed by washing with water or the like and drying to provide an organic undercoat layer. In the former method, a 0.005 to 10 mass% solution of the above organic compound can be applied by various methods. For example, bar coater coating, spin coating,
Any method such as spray coating or curtain coating may be used. In the latter method, the solution concentration is 0.01
-20% by mass, preferably 0.05-5% by mass,
The immersion temperature is 20 to 90 ° C, preferably 25 to 50 ° C, and the immersion time is 0.1 second to 20 minutes, preferably 2 seconds to 1
Minutes.

The solution used for this is adjusted to pH 1 by adjusting the pH with a basic substance such as ammonia, triethylamine or potassium hydroxide, or an acidic substance such as hydrochloric acid or phosphoric acid.
It can also be used in the range of -12.

Further, a compound represented by the following general formula (V) can be added to this solution. General formula (V) (HO) _x -R _5- (COOH) _y However, R ₅ represents an arylene group having 14 or less carbon atoms which may have a substituent, and x and y are independently 1 to 3 Represents the integer.

Specific examples of the compound represented by the general formula (V) include 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, salicylic acid, 1-hydroxy-2-naphthoic acid and 2-hydroxy-1-naphthoic acid. Acid, 2-hydroxy-3-
Examples thereof include naphthoic acid, 2,4-dihydroxybenzoic acid and 10-hydroxy-9-anthracenecarboxylic acid.

The coating amount of the organic undercoat layer after drying is 1 to 10
0 mg / m ² is suitable, and preferably ² to 70 mg / m ^2.
m ² . If the coating amount is less than 2 mg / m ² , sufficient printing durability cannot be obtained. The same applies when the amount is larger than 100 mg / m ² .

A back coat is provided on the back surface of the support, if necessary. As such a back coat, a coating layer composed of a metal oxide obtained by hydrolyzing and polycondensing an organic polymer compound described in JP-A-5-45885 and an organic or inorganic metal compound described in JP-A-6-35174 Is preferably used. Among these coating layers, Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC
Silicon alkoxy compounds such as ₃ H ₇ ) ₄ and Si (OC ₄ H ₉ ) ₄ are particularly preferable because they are inexpensive and easily available, and a metal oxide coating layer obtained from them is excellent in developing solution resistance.

[Plate making and printing] The planographic printing plate precursor of the invention is image-formed by heat. Specifically, direct image-like recording with a thermal recording head, scanning exposure with an infrared laser,
High-intensity flash exposure such as xenon discharge lamp and infrared lamp exposure are used, but wavelength 700-1200n
Exposure with a solid-state high-power infrared laser such as a semiconductor laser or a YAG laser that emits infrared rays of m is suitable.

The exposed planographic printing plate precursor of the invention is subjected to development processing and post-treatment with a finisher or protective gum to give a printing plate. As in the case of the negative type lithographic printing plate precursor utilizing the above acid-catalyzed crosslinking reaction, the plate can be heated before the development treatment, if necessary.

The processing agent used in the development processing and post-processing of the lithographic printing plate precursor according to the invention can be appropriately selected from known processing agents and used. A suitable developer has a pH in the range of 9.0 to 14.0, preferably 1.
The developer is in the range of 2.0 to 13.5. A conventionally known alkaline aqueous solution can be used as the developer. Among the above-mentioned alkaline aqueous solutions, as a particularly suitable developing solution, a solution containing an alkali silicate as a base or an alkali silicate obtained by mixing a silicon compound with a base is known, which is well known in the art. An aqueous solution having a pH of 12 or more, which is called a "silicate developer", and a so-called JP-A-8-305039, which does not contain an alkali silicate but contains a non-reducing sugar (organic compound having a buffering action) and a base. "Non-silicate developer" is mentioned.

When the lithographic printing plate of the present invention is subjected to a burning treatment, it is preferable to use a conventionally known method of using a burning surface-adjusting solution and a burning processor.

The lithographic printing plate obtained by such treatment is applied to an offset printing machine or the like and used for printing a large number of sheets.

[0189]

The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited by these examples.

(Synthesis Example 1: Synthesis of long-chain alkyl group-containing polymer A) 1000 equipped with a condenser and a stirrer
ml, three-necked flask, N, N-dimethylacetamide
22.0g was put and it heated at 70 degreeC. Under nitrogen stream, n-
Dodecyl methacrylate 20.0 g, compound a1.9 below
g, V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.215 g of N, N-dimethylacetamide 22.0 g solution was added dropwise over 2 hours and a half. Furthermore, the reaction was carried out at 70 ° C. for 2 hours. The reaction mixture was cooled to room temperature and poured into 1000 ml of methanol. After decantation, the product was washed with methanol, and the obtained liquid product was dried under reduced pressure to obtain 18.5 g of long-chain alkyl group-containing polymer A. As a result of measuring the weight average molecular weight by gel permeation chromatography (GPC) using polystyrene as a standard substance, it was 30,000.

[0191]

[Chemical 44]

(Synthesis Example 2: Synthesis of long chain alkyl group-containing polymer B) 1000 equipped with a condenser and a stirrer
21.0 g of 1-methoxy-2-propanol was put into the ml three necked flask, and it heated at 70 degreeC. Under a nitrogen stream,
20.0 g of n-dodecyl methacrylate, methacrylic acid
A solution of 0.677 g and V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.215 g in 1-methoxy-2-propanol (21.0 g) was added dropwise over 2 hours and a half. Furthermore, the reaction was carried out at 70 ° C. for 2 hours. The reaction mixture was cooled to room temperature and poured into 1000 ml of methanol. After decantation, the product was washed with methanol, and the obtained liquid product was dried under reduced pressure to obtain 18.2 g of a long-chain alkyl group-containing polymer B.
The weight average molecular weight was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance, and as a result, it was 50,000.

(Synthesis Examples 3 to 9: Synthesis of long-chain alkyl group-containing polymers C to I) In the same manner as in Synthesis Example 1 or Synthesis Example 2, long-chain alkyl group-containing monomers and hydrophilic monomers shown in Table 1 below. Was used to synthesize long-chain alkyl group-containing polymers C to I of the present invention. Furthermore, the molecular weight was measured by GPC. The measured results are shown in Table 1.

[0194]

[Table 1]

(Production of Substrate A) An aluminum plate having a thickness of 0.24 mm (Si: 0.06 mass%, Fe: 0.30 mass%, Cu: 0.014 mass%, Mn: 0.001 mass%, Mg: 0.001% by mass, Zn: 0.001% by mass, Ti: 0.03% by mass, with the balance being Al and aluminum alloy of unavoidable impurities), the following surface treatment was continuously performed. .

While supplying a suspension of a polishing agent (silica sand) having a specific gravity of 1.12 and water as a polishing slurry liquid to the surface of an aluminum plate, mechanical roughening was performed by a rotating roller nylon brush. It was Then, caustic soda concentration 2.6 mass%, aluminum ion concentration 6.5 mass%,
Etching treatment by spraying was performed at a temperature of 70 ° C., an aluminum plate was melted at 6 g / m ² , and washed with water by spraying. Further, desmutting treatment was performed by spraying with a 1% by weight nitric acid aqueous solution (containing 0.5% by weight of aluminum ion) at a temperature of 30 ° C., and washing with water was performed by spraying. Then, electrochemical roughening treatment was continuously performed using an alternating voltage of 60 Hz. The electrolytic solution at this time was 10 g / L nitric acid aqueous solution (aluminum ion was 5 g / L,
It contains ammonium ions in an amount of 0.007 mass%. ) And the temperature was 80 ° C. After washing with water, the aluminum plate was subjected to etching treatment by spraying at a caustic soda concentration of 26% by mass and an aluminum ion concentration of 6.5% by mass at 32 ° C. to dissolve the aluminum plate at 0.20 g / m ² and then washing by spraying with water. Thereafter, desmutting treatment was performed by spraying with a 25% by weight aqueous solution of sulfuric acid having a temperature of 60 ° C. (containing 0.5% by weight of aluminum ion), and washing with water was performed by spraying. Next, an anodizing treatment was performed using the anodizing device of the two-stage power feeding electrolytic treatment method. Sulfuric acid was used as the electrolytic solution supplied to the electrolysis section. Then, washing with water was performed by spraying. Final oxide film amount is 2.7
It was g / m ² . The aluminum support obtained by the anodizing treatment was treated with 1% by mass of sodium silicate No. 3 at a temperature of 30 ° C.
Alkali metal silicate treatment (silicate treatment) was performed by immersing the treatment layer in the aqueous solution for 10 seconds. Then, washing with water was performed by spraying.

On the aluminum support treated with alkali metal silicate obtained as described above, the undercoat liquid having the following composition was applied and dried at 80 ° C. for 15 seconds to form a coating film. The coating amount after drying was 15 mg / m ² .

[0198] (Undercoat)     ・ The following compound 0.3g     ・ Methanol 100g     ・ Water 1g

[0199]

[Chemical formula 45]

(Production of Substrate B) An aluminum plate having the same material as that used for production of the substrate A and having a thickness of 0.24 mm was continuously subjected to the following surface treatment. Electrochemical surface roughening treatment was continuously performed using an alternating voltage of 60 Hz. At this time, the electrolytic solution was a 10 g / L nitric acid aqueous solution (aluminum ion was 5 g / L, ammonium ion was 0.1 g / L).
007 mass% is included. ) And the temperature was 80 ° C. After washing with water
The aluminum plate was subjected to a spray etching treatment at 32 ° C. with a caustic soda concentration of 26% by mass and an aluminum ion concentration of 6.5% by mass to give an aluminum plate of 0.20 g.
/ M ^{2 It was} dissolved and washed with water by spraying. afterwards,
A desmutting treatment by spraying was performed with a 25% by weight sulfuric acid aqueous solution (containing 0.5% by weight of aluminum ion) at a temperature of 60 ° C., and washing with water was performed by spraying.

Then, similarly to the preparation of the substrate A, anodization treatment (oxide film amount 2.7 g / m ² ), silicate treatment and undercoat liquid coating (dry coating amount 15 mg / m ² ) were carried out,
Substrate B was produced.

(Production of Substrate C) JIS A containing 99.5% by mass or more of aluminum and 0.30% by mass of Fe, 0.10% by mass of Si, 0.02% by mass of Ti, and 0.013% by mass of Cu. The molten metal of 1050 alloy was subjected to a cleaning treatment and cast. For the cleaning treatment, degassing treatment was performed to remove unnecessary gas such as hydrogen in the molten metal, and ceramic tube filter treatment was performed. The casting method was a DC casting method. Solidified 500 mm thick ingot 1 from the surface
The surface was ground to 0 mm, and homogenized at 550 ° C. for 10 hours so that the intermetallic compound did not become coarse. Then
Hot rolled at 400 ℃, 500 ℃ in a continuous annealing furnace, 60
After the second intermediate annealing, cold rolling is performed and the plate pressure is 0.30 m.
m rolled aluminum plate. The center line average surface roughness R after cold rolling is controlled by controlling the roughness of the rolling roll.
a was controlled to 0.2 μm. Then, a tension leveler was applied to improve the flatness.

The following surface treatment was applied to this aluminum plate. First, in order to remove the rolling oil on the surface of the aluminum plate, degreasing treatment was performed with a 10 mass% sodium aluminate aqueous solution at 50 ° C. for 30 seconds, neutralization with a 30 mass% sulfuric acid aqueous solution at 50 ° C. for 30 seconds, and smut removal treatment. Next, in order to improve the adhesion between the support and the recording layer and to impart water retention to the non-image rear part, a so-called graining treatment for roughening the surface of the support was performed. An aqueous solution containing 1% by mass of nitric acid and 0.5% by mass of aluminum nitrate was kept at 45 ° C., and while carrying the aluminum web through the aqueous solution, the current density was 20 A / dm ² and the duty ratio was 1: by an indirect power supply cell. Electrolytic graining was performed by applying an electric charge of 240 C / dm ² on the anode side with an alternating waveform of 1. After that, an etching treatment was performed with a 10 mass% sodium aluminate aqueous solution at 50 ° C. for 30 seconds, and a smut removal treatment was performed with a 30 mass% sulfuric acid aqueous solution at 50 ° C. for 30 seconds.

Further, in order to improve abrasion resistance, chemical resistance and water retention, an oxide film was formed on the support by anodic oxidation. 20% by mass aqueous solution of sulfuric acid as an electrolyte at 35 ° C
As described above, an anodized film of 2.5 g / m ² was produced by carrying out electrolytic treatment with a direct current of 14 A / dm ² using an indirect power supply cell while carrying the aluminum web through the electrolyte. Then, in order to secure hydrophilicity as a non-image portion of the printing plate, a silicate treatment was performed. The treatment was carried out by keeping a 1.5% by mass aqueous solution of sodium silicate No. 3 at 70 ° C. so that the contact time of the aluminum web was 15 seconds, and further washing with water. The amount of attached Si was 10 mg / m ² . The Ra (center line surface roughness) of the substrate C completed as described above was 0.25 μm.

Example 1 The following recording layer coating liquid 1 was applied to the obtained substrate B so that the coating amount was 1.0 g / m ^2, and then PERFECT OVEN manufactured by TABAI was used.
Wind Control was set to 7 in PH200, and the recording layer was formed by drying at 140 ° C. for 50 seconds to obtain a lithographic printing plate precursor 1.

[0206] (Recording layer coating liquid 1)   ・ Long-chain alkyl group-containing polymer A 0.02 g   -M, p-cresol novolak (m / p molar ratio = 6/4, weight average molecular weight     3500, containing 0.5% by mass of unreacted cresol) 0.474 g   ・ Specific copolymer 1 (below) 2.37 g   Infrared absorber (IR-1 described in the present specification) 0.155 g   ・ 2-Methoxy-4- (N-phenylamino) benzene     Diazonium hexafluorophosphate 0.03g   ・ Tetrahydrophthalic anhydride 0.19g   6-hydroxy counter ion of ethyl violet     Replaced with -β-naphthalene sulfonate ion 0.05g   ・ Fluorosurfactant (manufactured by Dainippon Ink and Chemicals, Inc.)     Megafac F176PF (solid content 20 mass%)) 0.035g   -P-toluenesulfonic acid 0.008 g   -Bis-p-hydroxyphenyl sulfone 0.063 g   ・ Γ-Butyrolactone 13 g   ・ Methyl ethyl ketone 24g   ・ 1-Methoxy-2-propanol 11 g

Specific copolymer 1: N- (p-aminosulfonylphenyl) methacrylamide / ethyl methacrylate / acrylonitrile (mol% 32/43/25), weight average molecular weight 53,000. Synthesis method: JP-A-11-28
8093.

Example 2 The following recording layer coating liquid 2 was applied to the obtained substrate B so that the dry coating amount was 1.8 g / m ^2, and then dried under the same conditions as in Example 1. A recording layer was formed to obtain a lithographic printing plate precursor 2.

[0209] (Recording layer coating liquid 2)   -Long-chain alkyl group-containing polymer A 0.09 g   ・ Novolak resin ((B) resin) 0.90g   (M / p-cresol (6/4), weight average molecular weight 7,000, unreacted cresol     0.5% by mass)   ・ Ethyl methacrylate / isobutyl methacrylate / methacrylic acid (35/35     / 30 mol%) copolymer 0.10 g   Infrared absorber (IR-1 described in the present specification) 0.1 g   ・ Phthalic anhydride 0.05g   -P-toluenesulfonic acid 0.002 g   6-hydroxy counter ion of ethyl violet     Replaced with -β-naphthalene sulfonate ion 0.02g   Fluorine-based polymer (Defencer F-176 (solid content 20% by mass)       Dainippon Ink and Chemicals Co., Ltd.) 0.015g   Fluorine-based polymer (Defencer MCF-312 (solid content 30% by mass)       Dainippon Ink and Chemicals Co., Ltd.) 0.035g   ・ Methyl ethyl ketone 12g

[Examples 3 to 9] In the coating liquid 1 for recording layer of Example 1, instead of the long chain alkyl group-containing polymer A, combinations of long chain alkyl group containing polymers shown in Table 2 below were used. Lithographic printing plate precursors 3 to 9 were obtained in the same manner as in Example 1 except for the above.

[0211]

[Table 2]

Comparative Example 1 A lithographic printing plate precursor 10 was obtained in the same manner as in Example 1 except that the long-chain alkyl group-containing polymer A was not added to the recording layer coating liquid 1 of Example 1.

[Comparative Example 2] A lithographic plate was prepared in the same manner as in Example 1 except that 0.02 g of n-dodecyl stearate was used in place of the long chain alkyl group-containing polymer in Recording Layer Coating Solution 1 of Example 1. A printing plate precursor 11 was obtained.

[Comparative Example 3] A lithographic printing plate precursor 12 was obtained in the same manner as in Example 2 except that the long-chain alkyl group-containing polymer was not added to the recording layer coating liquid 2 of Example 2.

Example 10 The following recording layer coating liquid 3 was coated on the substrate A so that the dry coating amount was 2.0 g / m ^2, and then PERFECT OVEN P manufactured by Tabai was applied.
After setting Wind Control to 7 on H200 and drying at 130 ° C. for 50 seconds, the coating liquid 4 for the recording layer is applied so that the coating amount becomes 0.40 g / m ^2, and then 1
It was dried at 40 ° C. for 1 minute to obtain a lithographic printing plate precursor 13.

[0216] (Recording layer coating liquid 3) ・ N- (4-aminosulfonylphenyl) methacrylamide /     Acrylonitrile / methyl methacrylate copolymer     (36/34/30: weight average molecular weight 50,000, acid value 2.65) 2.133 g Infrared absorber (IR-1 described in the present specification) 0.134 g * 4,4'-bishydroxyphenyl sulfone 0.126 g ・ Tetrahydrophthalic anhydride 0.190g -P-toluenesulfonic acid 0.008 g ・ 3-Methoxy-4-diazodiphenylamine     Hexafluorophosphate 0.032 g ・ The counter ion of ethyl violet is 6-hydroxy.   -Β-naphthalene sulfonate ion 0.781g ・ Megafuck F176 (manufactured by Dainippon Ink and Chemicals, Inc.)   Coating surface condition improving fluorochemical surfactant (solid content 20% by mass)) 0.035 g ・ Methyl ethyl ketone 25.41 g ・ 1-Methoxy-2-propanol 12.97 g * Γ-butyrolactone 13.18 g

[0217] (Recording layer coating liquid 4) -M, p-cresol novolac (m / p ratio = 6/4, weight average molecular weight     4500, containing 0.8% by mass of unreacted cresol) 0.3479 g Infrared absorber (IR-1 described in the present specification) 0.0192 g ・ Ethyl methacrylate / isobutyl methacrylate / acrylic acid     Copolymer (37/37/26 mol%) 30 mass% MEK solution 0.1403 g -Long-chain alkyl group-containing polymer A 0.034 g ・ Megafuck F176 (20 mass%) (manufactured by Dainippon Ink and Chemicals, Inc.)   Fluorine-based surfactant) 0.022g ・ MegaFac MCF-312 (30 mass%) (manufactured by Dainippon Ink and Chemicals, Inc.)   Fluorine-based surfactant) 0.011g ・ Methyl ethyl ketone 13.07g ・ 1-Methoxy-2-propanol 7.7 g

[Example 11] The recording layer coating liquid 5 was applied to the same substrate as used in Example 10 under the same conditions as the recording layer coating liquid 3 of Example 10 and dried. 10
The recording layer coating solution 6 was applied and dried under the same conditions as the recording layer coating solution 4 above to obtain a lithographic printing plate precursor 14 having a two-layer recording layer.

[0219] (Recording layer coating liquid 5) ・ N- (4-aminosulfonylphenyl) methacrylamide /     Acrylonitrile / methyl methacrylate copolymer     (36/34/30: weight average molecular weight 50,000, acid value 2.65) 2.133 g Infrared absorber (IR-1 described in the present specification) 0.109 g * 4,4'-bishydroxyphenyl sulfone 0.126 g ・ Tetrahydrophthalic anhydride 0.190g -P-toluenesulfonic acid 0.008 g ・ 3-Methoxy-4-diazodiphenylamine     Hexafluorophosphate 0.030 g ・ The counter ion of ethyl violet is 6-hydroxy. 0.100 g of which was changed to -β-naphthalene sulfonate ion ・ Megafuck F176 (manufactured by Dainippon Ink and Chemicals, Inc.)   Fluorine-based surfactant (solid content 20% by mass)) 0.035 g ・ Methyl ethyl ketone 25.38 g ・ 1-Methoxy-2-propanol 13.0 g -Γ-butyrolactone 13.2 g

[0220] (Recording layer coating liquid 6) -M, p-cresol novolac (m / p ratio = 6/4, weight average molecular weight   4500, containing 0.8% by mass of unreacted cresol) 0.3478 g Infrared absorber (IR-1 described in the present specification) 0.0192 g -Long-chain alkyl group-containing polymer A 0.034 g -Used in Example 2 of Japanese Patent Laid-Open No. 2001-398047   Ammonium compound 0.0115g ・ Megafuck F176 (20 mass%) (manufactured by Dainippon Ink and Chemicals, Inc.)   Fluorine-based surfactant) 0.022g ・ Methyl ethyl ketone 13.07g ・ 1-Methoxy-2-propanol 6.79 g

[Examples 12 to 19] In the coating liquid 4 for recording layer of Example 10, the long chain alkyl group-containing polymers shown in Table 2 below were used in place of the long chain alkyl group containing polymer A. Lithographic printing plate precursor 1 as in 10.
5-22 were obtained.

[0222]

[Table 3]

Examples 20 to 27 In the recording layer coating liquid 6 of Example 11, the long chain alkyl group-containing polymers shown in Table 4 below were used in place of the long chain alkyl group containing polymer A Lithographic printing plate precursor 2 as in 12
3 to 30 were obtained.

[0224]

[Table 4]

[Comparative Example 4] Coating liquid 4 for recording layer of Example 10
In the same manner as in Example 2 except that the long-chain alkyl group-containing polymer A was not added in, the lithographic printing plate precursor 3
Got 1.

[Evaluation of lithographic printing plate precursors produced in Examples 1-27 and Comparative Examples 1 to 4] With respect to the lithographic printing plate precursors produced as described above, the coefficient of dynamic friction, scratch resistance, development latitude and transferability were determined. Was evaluated by the following method.

<Measurement of Dynamic Friction Coefficient> The dynamic friction coefficient of the image recording material of the present invention (dynamic or kinetic coefficient of
Friction) (μk) was measured using standard ASTM D18 using the planographic printing plate precursors 1 to 31 of the obtained Examples and Comparative Examples.
The measurement was carried out in the order of 94, with the surface of the lithographic printing plate precursor recording layer in contact with stainless steel. The results are shown in Table 5.
It was shown to.

<Evaluation of Scratch Resistance> The lithographic printing plate precursors 1 to 31 of the obtained Examples and Comparative Examples were used with a rotary ablation tester (manufactured by TOYOSEIKI) and 2
Abrazer felt CS5 was rubbed 15 times under a load of 50 g. After that, Fuji Photo Film Co., Ltd. developer D
Using a PS processor 900H manufactured by Fuji Photo Film Co., Ltd., which was charged with T-1 (diluted 1: 8) and Finisher FP2W manufactured by Fuji Photo Film Co., Ltd. (diluted by 1: 1), a liquid temperature of 30 Development was carried out at a temperature of 12 ° C. for 12 seconds. At this time, the conductivity of the developer is 45 mS / cm.
Met. The scratch resistance was evaluated by visual observation of the optical density of a part rubbed with an ablazer felt and the part not rubbed after development, and a reflection densitometer (Gretag Macbeth D19C).
Was measured according to the following criteria. The evaluation results are shown in Table 5.

(Evaluation Criteria for Scratch Resistance) A: The optical density of the recording layer film in the rubbed portion did not change at all. B: The optical density of the recording layer film in the rubbed portion was slightly observed visually. Item C: The optical density of the recording layer film in the rubbed portion was 2 in the non-rubbed portion.
/ 3 or less

<Evaluation of Development Latitude> The lithographic printing plate precursors 1 to 31 of the prepared Examples and Comparative Examples were manufactured by using Creo's Tr.
Infrared laser beam intensity 9W at endsetter 3244VFS,
The test pattern was drawn in the form of an image under the condition of the drum rotation speed of 150 rpm. Non-silicate developer DT-1 manufactured by Fuji Photo Film Co., Ltd. was diluted with tap water to prepare developers having various electric conductivities. This developing solution was charged into PS processor 900H manufactured by Fuji Photo Film Co., Ltd., and the above exposed lithographic printing plate precursor was developed at a liquid temperature of 30 ° C. and a developing time of 12 seconds. As a finisher liquid, F
P-2W (diluted with tap water at 1: 1) was used.

Under these development conditions, the decrease in optical density of the non-exposed area (image area) of the recording layer of the lithographic printing plate precursor was visually evaluated, and the conductivity of the developer used when the decrease in density was observed was (X) mS. / Cm. Further, under the same developing conditions, the decrease in optical density of the exposed portion (non-image area) of the recording layer of the lithographic printing plate precursor was visually evaluated, and when the decrease in density was observed, the conductivity of the developer used was (Y) mS / cm. In this embodiment, (X)-(Y) is defined as the development latitude. The larger the development latitude value, the less likely it is that a residual film will be formed in the exposed area (non-image area) and the lowering of the density in the unexposed area (image area) will be less likely to occur. Can be said. The evaluation results are shown in Table 6.

<Evaluation of Transferability> The transferability was evaluated by placing chloroprene rubber (90 mm × 90 mm) on the planographic printing plate precursors 1 to 31 of Examples and Comparative Examples, applying a weight of 6 kg, and applying 100 ° C. After heating for 10 minutes, the surface of the chloroprene rubber in contact with the lithographic printing plate precursor recording layer was visually evaluated. The following criteria were used as the evaluation scale. The evaluation results are shown in Table 5. ○: No color change ×: Color change

[0233]

[Table 5]

As is clear from Table 5, the lithographic printing plate precursor obtained from the image-forming material of the present invention had a better development latitude than Comparative Examples 1 to 3 containing no long chain alkyl group-containing polymer. It was found that the residual film is unlikely to occur in the non-image area and the density decrease in the image area is unlikely to occur. Further, it was found that the scratch resistance was excellent as compared with Comparative Examples 1, 3, and 4. Further, it was found that there was no problem of transferability as compared with Comparative Example 2.

[Examples 28 to 30 and Comparative Examples 5 to 7] The following recording layer coating liquid 7 was prepared on the substrate (C), coated using a wire bar, and dried at 115 ° C in a warm air dryer. At 45
A recording layer was formed by drying for 2 seconds to obtain a lithographic printing plate precursor.
The dry coating amount was within the range of 1.2 to 1.3 g / m ² .

[0236] (Recording layer coating liquid 7) ・ Alkali-soluble polymer (Compound name and addition amount are shown in Table 6) Infrared absorber (IR-5 described in the present specification) 0.10 g ・ Radical generator (S-1 below) 0.45 g ・ Radical polymerizable compound (Compound name and addition amount are shown in Table 6) -Long-chain alkyl group-containing polymer (described in Table 6) 0.023 g ・ Victoria Pure Blue Naphthalene Sulfonate 0.04g ・ Fluorosurfactant 0.0 lg (Megafuck F-176, manufactured by Dainippon Ink and Chemicals, Inc. (solid content 20 mass)) ・ P-methoxyphenol 0.001 g ・ Methyl ethyl ketone 9.0 g ・ Methanol 10.0g ・ 1-Methoxy-2-propanol 8.0 g

[0237]

[Table 6]

The structures of the alkali-soluble polymers used in the above Examples and Comparative Examples are shown below.

[0239]

[Chemical formula 46]

Similarly, the structures of the radical generators used in Examples and Comparative Examples are shown below.

[0241]

[Chemical 47]

Similarly, the structures of the radically polymerizable compounds used in Examples and Comparative Examples of the present invention are shown below.

[0243]

[Chemical 48]

Each of the obtained lithographic printing plate precursors was used as a Trendset manufactured by Creo equipped with a water-cooled 40 W infrared semiconductor laser.
Exposure was performed with a ter3244VFS at an output of 6.5 W, an outer surface drum rotation speed of 81 rpm, a plate surface energy of 188 mJ / cm ² , and a resolution of 2,400 dpi.

After exposure, development processing was performed using an automatic processor Stablon 900NP manufactured by Fuji Photo Film Co., Ltd. As the developing solution, the following (D-1) was used as a charging solution and the following (D-2) was used as a replenishing solution. Development bath temperature is 30 ℃, development time is 12
Processed in seconds. At this time, the replenisher was automatically added while adjusting the electric conductivity of the developer in the developing bath of the automatic processor so as to be constant. As the finisher, a 1: 1 water dilution of FN-6 manufactured by Fuji Photo Film Co., Ltd. was used.

[0246] (Developer (D-1)) ・ Potassium hydroxide 3g ・ Potassium bicarbonate 1g ・ Potassium carbonate 2g ・ Sodium sulfite 1g ・ Polyethylene glycol mononaphthyl ether 150g ・ Dibutylnaphthalenesulfonic acid sodium salt 50g ・ Ethylenediamine tetraacetic acid tetrasodium salt 8g ・ Water 785g

[0247] (Development replenisher (D-2)) ・ Potassium hydroxide 6g ・ Potassium carbonate 2g ・ Sodium sulfite 1g ・ Polyethylene glycol mononaphthel ether 150g ・ Dibutylnaphthalenesulfonic acid sodium salt 50g ・ Hydroxyethanediphosphonic acid potassium salt 4g ・ Silicon TSA-731 0.1g   (Manufactured by Toshiba Silicone Co., Ltd.) ・ Water 786.9g

<Evaluation of Printing Durability> Next, printing was performed using a printer Lithrone manufactured by Komori Corporation. At that time, the printing durability was evaluated by visually measuring how many sheets can be printed while maintaining a sufficient ink density. The results are shown in Table 6.

<Evaluation of Scratch Resistance> The lithographic printing plate precursor coated with the recording layer was evaluated for scratch resistance. As equipment, Scruching made by HEIDON
Using TESTER HEIDON-14 and a 0.4 mmR diamond needle as a scratching needle, the surface of the recording layer was scratched at a speed of 400 mm / min while changing the load on the needle. The scratched original plate was subjected to the above-described development treatment, and the magnitude of the load at which the residual film was visually observed was evaluated.
The larger the load, the less likely a residual scratch film will be formed, and the more excellent the scratch resistance will be. The results are shown in Table 6.

As is clear from the results shown in Table 6, the lithographic printing plate precursors of Examples 28 to 30 using the image recording material of the present invention as the recording layer contained Comparative Example 5 containing no long chain alkyl group-containing polymer. It can be seen that compared with No. 7, it has excellent scratch resistance and also has good printing durability. No ablation during exposure was observed in any of the samples.

Examples 31 to 38 Examples except that long chain alkyl group-containing polymers B to I were used as shown in Table 7 in place of the long chain alkyl group containing polymer A used in Example 29 A lithographic printing plate precursor was prepared in the same manner as in 29. These original plates were evaluated in the same manner as in Example 29, and the results are shown in Table 7.

[0252]

[Table 7]

Examples 39 to 40, Comparative Examples 8 to 9 On the aluminum substrate C, the following undercoat layer coating solution was applied and dried in an atmosphere of 80 ° C. for 30 seconds. The dry coating amount was 10 mg / m ² .

[0254] (Coating liquid for undercoat layer) ・ 2-Aminoethylphosphonic acid 0.5 g ・ Methanol 40g ・ Pure water 60g

Thereafter, the recording layer coating liquid 8 shown below was applied onto the support having the undercoat layer formed thereon with a wire bar and dried at 115 ° C. for 45 seconds in a warm air dryer to obtain a lithographic printing plate. I got the original edition. Dry coating amount is 1.2-1.3g
It was within the range of / m ² .

[0256] (Recording layer coating liquid 8) Alkali-soluble polymer (compounds listed in Table 8 and amount listed in Table 8) Infrared absorber (IR-8 described in the present specification) 0.08 g -Radical generator (S-2 above) 0.30 g Radical-polymerizable compound (compounds listed in Table 8 and amount listed in Table 8) -Long-chain alkyl group-containing polymer (described in Table 8) 0.023 g ・ Victoria pure blue naphthalene sulfonic acid 0.04g ・ Fluorosurfactant 0.01g   (Megafuck F-176, manufactured by Dainippon Ink and Chemicals, Inc. (solid content 20 mass)) -N-nitroso-N-phenylhydroxylamine aluminum 0.001 g ・ Methyl ethyl ketone 9.0 g ・ Methanol 10.0g ・ 1-Methoxy-2-propanol 8.0 g

[0257]

[Table 8]

The lithographic printing plate precursor thus obtained was evaluated by comparing it with the one which was not subjected to forced aging after forced aging (storage under forced conditions). Forced aging condition is storage at 60 ° C for 3 days, and 4
It was stored for 3 days at 5 ° C. and a humidity of 75% RH. The exposure was performed under the same conditions as in Examples 28 to 30 and Comparative Examples 5 to 7, and Fuji Photo Film Co., Ltd. automatic processor Stablon 900N was used.
Development processing was performed using P. As the developing solution, both a charging solution and a replenishing solution were DP-8 1: 8 water diluted solutions manufactured by Fuji Photo Film Co., Ltd. The temperature of the developing bath was 30 ° C. and the developing time was 12 seconds. At this time, the replenisher was automatically added while adjusting the electric conductivity of the developer in the developing bath of the automatic processor so as to be constant. As the finisher, a 1: 1 water dilution of FN-6 manufactured by Fuji Photo Film Co., Ltd. was used.

The lithographic printing plate thus obtained was used in Examples 28 to
Printing was performed in the same manner as in No. 30 and Comparative Examples 5 to 7 to evaluate printing durability and stain resistance. The results are also shown in Table 8 above.

From Table 8, it can be seen that the lithographic printing plate precursors of Examples 39 to 40 using the image recording material of the present invention as the recording layer were higher in temperature than Comparative Examples 8 to 9 containing no long chain alkyl group-containing polymer. It can be seen that even after storage in a high humidity environment, printing durability and stain resistance of the non-image area do not deteriorate, and stability with time is excellent.

[Examples 41 to 48] In place of the long chain alkyl group-containing polymer A used in Example 40, long chain alkyl group containing polymers B to I were used as shown in Table 9 A lithographic printing plate precursor was prepared in the same manner as in 40. These original plates were evaluated in the same manner as in Example 40, and the results are shown in Table 9.

[0262]

[Table 9]

Examples 49 to 50, Comparative Examples 10 to 11 The following recording layer coating liquid 9 was applied onto an aluminum substrate C using a wire bar and dried at 115 ° C. for 4 hours in a warm air dryer.
It was dried for 5 seconds to obtain a lithographic printing plate precursor. The dry coating amount was within the range of 1.2 to 1.3 g / m ² .

[0264] (Recording layer coating liquid 9) Alkali-soluble polymer (compounds listed in Table 10 and amounts listed in Table 10) -Infrared absorber (IR-9 described in the present specification) 0.10 g Radical generator (S-1 above) 0.50 g -Long-chain alkyl group-containing polymer (described in Table 10) 0.023 g ・ Victoria Pure Blue Naphthalene Sulfonate 0.04g ・ Fluorosurfactant 0.01g   (Megafuck F-176, manufactured by Dainippon Ink and Chemicals, Inc. (solid content 20 mass)) ・ Methyl ethyl ketone 9.0 g ・ Methanol 10.0g ・ 1-Methoxy-2-propanol 8.0 g

[0265]

[Table 10]

The lithographic printing plate precursor thus obtained was water-cooled 40 W
Trendsetter3 made by Creo equipped with infrared semiconductor laser
At 244VFS, output 9W, outer drum rotation speed 210r
pm, plate energy 100 mJ / cm ² , resolution 24
It was exposed under the condition of 00 dpi.

After exposure, development processing was performed using an automatic processor Stablon 900N manufactured by Fuji Photo Film Co., Ltd. As the developing solution, a 1: 1 water dilution solution of DN-3C manufactured by Fuji Photo Film Co., Ltd. was used for both the charging solution and the replenishing solution. The temperature of the developing bath was 30 ° C. As the finisher, a 1: 1 water dilution of FN-6 manufactured by Fuji Photo Film Co., Ltd. was used.

Next, printing was performed using a SOR-KZ printing machine manufactured by Heidelberg. At this time, the printing durability was evaluated by measuring how many sheets can be printed while maintaining a sufficient ink density. In addition, scratch resistance was evaluated in the same manner as in Examples 28 to 30 and Comparative Examples 5 to 7.

From Table 10, the lithographic printing plate precursors of Examples 49 to 50 using the image recording material of the present invention as the recording layer are
Comparative Examples 10 to 10 containing no long chain alkyl group-containing polymer
It can be seen that, as compared with No. 11, excellent scratch resistance is achieved and excellent printing durability is maintained.

[Examples 51 to 58] In place of the long chain alkyl group-containing polymer A used in Example 49, long chain alkyl group containing polymers B to I were used as shown in Table 11 A lithographic printing plate precursor was prepared in the same manner as in 49. These original plates were evaluated in the same manner as in Example 49, and the results are shown in Table 11.

[0271]

[Table 11]

(Evaluation of transportability of planographic printing plate precursor) Example 2
Thirty sheets of planographic printing plate precursors of No. 8 were stacked, loaded into a plate material supply device, continuously and fully automatically exposed and developed, and discharged to a stocker. Adhesion between lithographic printing plate precursors and defective transport due to the same were not observed during the operation of the device, so that it has good slidability and the transfer of the slip agent to the back surface of the support is also suppressed. I understood. Further, similar results were obtained in the transport evaluation performed using the planographic printing plate precursors of Examples 29 to 34.

As is clear from the above examples, the planographic printing plate precursor using the image recording material of the present invention as the recording layer (planographic printing plate precursor of the present invention) has scratch resistance, printing durability and slipperiness. In addition, the excellent effect that the transfer of the slippery material (material having a reduced friction coefficient) was suppressed was exhibited.

[0274]

EFFECTS OF THE INVENTION According to the present invention, it has good scratch resistance and a wide development latitude, and does not cause a transfer problem to the roller and the protective paper (interleaving paper) or the back surface of the support at the time of production and transportation. By using the image recording material and the image recording material in the recording layer, it is possible to provide an infrared laser lithographic printing plate precursor for direct plate making having the same characteristics.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Tadahiro Soroshi             Fuji-Sha, 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture             Shin Film Co., Ltd. F-term (reference) 2H025 AA04 AA13 AA15 AA18 AB03                       AC08 AD03 CB13 CB14 CB15                       CB17 CB43 CB45 CB51 CC13                       FA10 FA17                 2H096 AA06 BA11 EA04 EA23 GA08                 4J100 AA07P AA15P AB07P AE09P                       AF10P AJ02Q AL03P AL03Q                       AL03S AL04P AL05P AL08P                       AL34P AM02Q AM15R AM17P                       AM19P AM21P AM21R AP01P                       AP01Q AQ08Q AQ11Q AQ12Q                       BA03P BA03R BA04P BA10P                       BA53P BA56Q BA59P BA59R                       BC04P BC43P BC43R BD10Q                       BD12Q CA04 CA05 CA06                       DA28 JA07 JA38

Claims (2)

[Claims] 1. An image containing (a) an infrared absorbent and (b) a polymer that reduces the dynamic friction coefficient to 0.38 to 0.60, and capable of forming an image by exposure to an infrared laser. Recording material. 2. An infrared absorbent (a) on a support,
A recording layer containing (c) a water-insoluble and alkali-soluble resin, and (d) a polymer having a structural unit represented by the following general formula (1), the solubility of which in an alkaline aqueous solution is increased by exposure to an infrared laser. Original planographic printing plate. [Chemical 1] (N represents an integer of 4 or more, m represents 0.6 ≦ m ≦ 20, X represents a skeleton having an alkali-soluble group having a pKa of 12 or less, and R represents an alkyl group or a hydrogen atom.)