JP2009184113A - Original planographic printing plate and planographic printing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an original planographic printing plate that allows image recording using infrared laser beams, can provide a large amount of good printed matter with a practical amount of energy, is excellent in on-machine developability and printing resistance, and particularly includes improved stain resistance, and a planographic printing method using it. <P>SOLUTION: The original planographic printing plate includes on support an image recording layer that can be removed by means of printing ink and/or dampening water, the image recording layer containing a chelating agent. The planographic printing method includes either exposing the original planographic printing plate to an infrared laser beam in such a manner as to create an image, after mounting the plate in a printer, or mounting the plate in the printer after exposing it to an infrared laser beam in such a manner as to create an image, then supplying the printing ink and the dampening water, removing the portion of the image recording layer unexposed to the infrared beam, and performing printing. Preferably, an undercoat layer between the support and the image recording layer preferably contains a polymer having a base-absorbing group, a polymerizable group, and a hydrophilic group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a planographic printing plate precursor and a method for producing the same. Specifically, the present invention relates to a so-called lithographic printing plate precursor capable of direct plate making by scanning an infrared laser based on a digital signal from a computer or the like, and a lithographic printing method using the lithographic printing plate precursor.

In general, a lithographic printing plate comprises an oleophilic image area that receives ink in the printing process and a hydrophilic non-image area that receives dampening water. Lithographic printing utilizes the property that water and oil-based inks repel each other, so that the oleophilic image area of the lithographic printing plate is the ink receiving area and the hydrophilic non-image area is dampened with the water receiving area (ink non-receiving area). As described above, a difference in ink adhesion is caused on the surface of a lithographic printing plate, and after ink is applied only to an image portion, the ink is transferred to a printing medium such as paper and printed.
In order to produce this lithographic printing plate, conventionally, a lithographic printing plate precursor (PS plate) in which an oleophilic photosensitive resin layer (image recording layer) is provided on a hydrophilic support has been widely used. Usually, the lithographic printing plate precursor is exposed through an original image such as a lithographic film, and then the image portion of the image recording layer is left, and the other unnecessary image recording layer is removed with an alkaline developer or organic A lithographic printing plate is obtained by dissolving and removing with a solvent and exposing the surface of the hydrophilic support to form a non-image area.

  In the conventional plate making process of a lithographic printing plate precursor, a step of dissolving and removing an unnecessary image recording layer with a developer or the like is necessary after exposure. However, such additional wet processing is unnecessary or Simplification is cited as one of the issues. In particular, in recent years, disposal of waste liquids discharged with wet processing has become a major concern for the entire industry due to consideration for the global environment, and therefore, the demand for solving the above-mentioned problems has become stronger.

On the other hand, as one simple plate making method, an image recording layer that can remove an unnecessary portion of the image recording layer in a normal printing process is used. A method called on-press development has been proposed in which unnecessary portions are removed to obtain a lithographic printing plate.
As a specific method of on-press development, for example, a method of using a lithographic printing plate precursor having an image recording layer that can be dissolved or dispersed in dampening water, an ink solvent, or an emulsion of dampening water and ink , A method of mechanically removing the image recording layer by contact with rollers or a blanket of a printing press, cohesion of the image recording layer or adhesion between the image recording layer and the support by penetration of dampening water, ink solvent, etc. There is a method in which after the force is weakened, the image recording layer is mechanically removed by contact with rollers or a blanket.
In the present invention, unless otherwise specified, the “development process step” refers to using a device other than a printing press (usually an automatic developing machine) and bringing a liquid (usually an alkaline developer) into contact therewith. Refers to the process of removing the image recording layer of the lithographic printing plate precursor as a non-image part and exposing the surface of the hydrophilic support. “On-press development” refers to a liquid (usually normal) using a printing press. Refers to a method and a process for removing the image recording layer in a portion to be a non-image portion of the lithographic printing plate precursor and exposing the surface of the hydrophilic support by contacting with printing ink and / or fountain solution.

  However, when an image recording layer of a conventional image recording system using ultraviolet rays or visible light is used, the image recording layer does not fix even after exposure. For example, the lithographic plate after exposure until it is mounted on a printing press. It was necessary to take a time-consuming method such as storing the printing plate precursor completely in a light-shielded state or under constant temperature conditions.

  On the other hand, in recent years, digitization technology for electronically processing, storing, and outputting image information by a computer has become widespread, and various new image output methods corresponding to such digitization technology will be put into practical use. It is becoming. Along with this, digitized image information is carried by high-convergence radiation such as laser light, and the lithographic printing plate precursor is scanned and exposed with that light, directly without using a lithographic film. Computer-to-plate technology for manufacturing is attracting attention. Therefore, obtaining a lithographic printing plate precursor adapted to such a technique is one of the important technical issues.

  As described above, in recent years, the simplification, drying, and no processing of plate making operations have become more desirable than ever in terms of consideration for the global environment and adaptation to digitalization. It is coming.

  In recent years, the development of lasers has been remarkable, and in particular, semiconductor lasers and solid-state lasers that emit infrared light with a wavelength of 760 to 1200 nm have become readily available as high-power and small-sized lasers. As a method for producing a lithographic printing plate by scanning exposure, which is easy to incorporate into a laser beam, a method using these high-power lasers as image recording means has become extremely useful.

  In the conventional plate-making method, imagewise exposure is performed on a photosensitive lithographic printing plate precursor at low to medium illuminance, and image recording is performed by image-like physical property change due to a photochemical reaction in an image recording layer. In contrast, in the method using the above-described high-power laser, a large amount of light energy is irradiated to the exposure region in an extremely short time, and the light energy is efficiently converted into heat energy. In the process, a thermal change such as a chemical change, a phase change, a change in form or structure is caused, and the change is used for image recording. Accordingly, image information is input by light energy such as laser light, but image recording is performed in a state in which reaction by heat energy is taken into account in addition to light energy. Usually, such a recording method using heat generated by high power density exposure is called heat mode recording, and changing light energy to heat energy is called photothermal conversion.

  The major advantages of the plate making method using heat mode recording are that the image recording layer is not exposed to light at a normal illuminance level such as indoor lighting, and that fixing of images recorded by high illuminance exposure is not essential. is there. That is, the lithographic printing plate precursor used for heat mode recording is not likely to be exposed to room light before exposure, and image fixing is not essential after exposure. Therefore, for example, if an image recording layer that is insolubilized or solubilized by exposure using a high-power laser is used, and the plate making process in which the exposed image recording layer is imaged to form a lithographic printing plate is performed on-machine development, after exposure Even if it is exposed to ambient light in the room, a printing system is possible in which the image is not affected. Therefore, if heat mode recording is used, it is expected that a lithographic printing plate precursor suitably used for on-press development can be obtained.

As an on-press development type lithographic printing plate precursor for image recording with an infrared laser, for example, Patent Document 1 discloses that an image forming layer in which hydrophobic thermoplastic polymer particles are dispersed in a hydrophilic binder is hydrophilic. A lithographic printing plate precursor provided on a support is described. In this Patent Document 1, the above lithographic printing plate precursor is exposed by an infrared laser, and the hydrophobic thermoplastic polymer particles are coalesced by heat to form an image, which is then mounted on a cylinder of a printing machine and moistened. It is described that it is possible to perform on-press development with water and / or ink.
In this way, the method of forming an image by merging by simple thermal fusion of fine particles shows good on-press developability, but the image strength (adhesion with the support) is extremely weak and the printing durability is insufficient. Had the problem of being.

Patent Documents 2 and 3 describe lithographic printing plate precursors containing microcapsules encapsulating a polymerizable compound on a hydrophilic support.
Furthermore, Patent Document 4 describes a lithographic printing plate precursor in which a photosensitive layer containing an infrared absorber, a radical polymerization initiator, and a polymerizable compound is provided on a support.
The method using the polymerization reaction as described above has a characteristic that the image strength is relatively good because the chemical bond density of the image portion is higher than that of the image portion formed by thermal fusion of the polymer fine particles. It was necessary to provide an undercoat layer in order to achieve both upper developability / press life / stainability.

As an undercoat layer used for this purpose, it is generally known that a water-soluble resin imparted with hydrophilicity is used. An on-press development type lithographic printing plate precursor provided with a layer is described.
However, in the on-press development type lithographic printing plate precursor, even when these undercoat layers are provided, the stain resistance of the non-image area is not yet sufficient, and the on-press developability / press life / stain resistance are not sufficient. there were.

Japanese Patent No. 2938397 JP 2001-277740 A JP 2001-277742 A JP 2002-287334 A Japanese Patent Laid-Open No. 2005-125749

  The present invention has been made in view of the above prior art, and can record an image with an infrared laser, and can obtain a large number of good printed materials with a practical amount of energy. It is an object of the present invention to provide a lithographic printing plate precursor having excellent properties, in particular, improved stain resistance, and a lithographic printing method using the same.

  As a result of intensive studies, the present inventor has found that the above object can be achieved by adding a chelating agent to the image recording layer, and has completed the present invention. That is, the present invention is as follows.

1. A lithographic printing plate precursor comprising an image recording layer which can be removed with a printing ink and / or fountain solution on a support, and the image recording layer containing a chelating agent.
2. 2. The lithographic printing plate precursor as described in 1 above, wherein the chelating agent is a chelating agent having at least two metal-adsorptive groups in one molecule.
3. 3. The flat plate as described in 1 or 2 above, wherein an undercoat layer is provided between the support and the image recording layer, and the undercoat layer contains a polymer having a substrate adsorptive group, a polymerizable group and a hydrophilic group. A printing plate master.
4). The lithographic printing plate precursor as described in any one of 1 to 3 above, wherein the image recording layer contains (A) an infrared absorber, (B) a polymerization initiator, and (C) a polymerizable compound. .
5. The lithographic printing plate precursor as described in any one of 1 to 4 above, wherein the support is an aluminum support.
6). The lithographic printing plate precursor as described in any one of 1 to 5 above, wherein the chelating agent is a compound represented by the following general formula (I) or (II).

In the general formulas (I) and (II), R ₁ , R ₂ , R ₄ , R ₅ , R ₆ and R ₇ are each independently a single bond or a linear alkylene group having 1 to 3 carbon atoms. R ₃ is a divalent organic group, and R ₈ is a trivalent organic group. X is methine (—CH <) or amine (—N <). Y _{1 to} Y ₆ each independently represent a metal adsorbing group, and A represents a hydrogen atom or a hydrophilic group.

7). The lithographic printing plate precursor as described in any one of 1 to 5 above, wherein the chelating agent is at least one compound selected from salicylic acid derivatives and salts thereof.
8). The lithographic printing plate precursor as described in 7 above, wherein the chelating agent is a compound represented by the following general formula (III).

In general formula (III), X represents an oxygen atom or a sulfur atom. M ¹ and M ² are each independently selected from H, Li, Na, K, Rb, Cs, 1 / 2Mg, 1 / 2Ca, 1 / 2Sr, 1 / 2Ba, 1 / 2Zn, and a nitrogen-containing cation. Represents a species. R ¹ , R ² , R ³ , and R ⁴ represent any substituents, and R ¹ and R ² , R ² and R ³ , and R ³ and R ⁴ are bonded to each other to form a cyclic structure. Also good.

9. The chelating agent is 3-sulfophthalic acid, 4-sulfophthalic acid, 2-sulfoterephthalic acid, 4-hydroxyphthalic acid, 5-sulfosalicylic acid, trimellitic acid and propane-1,2,3-tricarboxylic acid or a metal salt thereof. The lithographic printing plate precursor as described in any one of 1 to 8 above, which is at least one selected.
10. The lithographic printing plate precursor as described in any one of 1 to 9 above, wherein the image recording layer further comprises (D) fine polymer particles having a polymerizable reactive group.
11. The lithographic printing plate precursor according to any one of 1 to 10 above, image-wise exposed with an infrared laser after being mounted on a printing machine, or image-wise exposed with an infrared laser and then mounted on a printing machine, Next, a lithographic printing method in which printing ink and fountain solution are supplied to remove an infrared unexposed portion of the image recording layer and printing is performed.

  According to the present invention, it is possible to record an image with an infrared laser, it is possible to obtain a large number of good printed materials with a practical energy amount, excellent on-machine developability and printing durability, and particularly excellent stain resistance. A lithographic printing plate precursor and a lithographic printing method using the same can be provided.

  The lithographic printing plate precursor according to the invention has an image recording layer on a support. The lithographic printing plate precursor according to the invention preferably has an undercoat layer between the support and the image recording layer. Furthermore, it is preferable to have a protective layer on the image recording layer.

(Image recording layer)
The image recording layer of the present invention contains a chelating agent. In addition, the image recording layer of the present invention is an image recording layer containing (A) an infrared absorber, (B) a polymerization initiator, and (C) a polymerizable compound and capable of being recorded by infrared irradiation. preferable.
In such an image recording layer, the exposed portion of the image recording layer is cured by infrared irradiation to form a hydrophobic (lipophilic) region, and the unexposed portion is dampened with water, ink or dampening at the start of printing. It is possible to form an image recording layer that can be quickly removed from the support by the emulsion of water and ink, that is, can be developed on the machine.
Hereinafter, each component of the image recording layer will be described.

<Chelating agent>
The chelating agent used in the image recording layer of the present invention is a compound that forms a complex bond with a metal by two or more functional groups in one molecule. The functional group is preferably a metal adsorbing group. The chelating agent of the present invention preferably contains two or more metal-adsorptive groups in one molecule, and by containing two or more metal-adsorptive groups, especially the metal on the support is exposed. It becomes easier to adsorb in the place where the hydrophilicity is impaired, and the dirtiness is improved. The metal of the support is particularly preferably aluminum, and the metal adsorbing group of the chelating agent is preferably a functional group that adsorbs to aluminum.

The metal adsorbing group of the present invention is preferably an acid group or a cationic group.
The acid group preferably has an acid dissociation constant (pKa) of 7 or less. Examples of acid groups include phenolic hydroxyl groups, —COOH, —SO ₃ H, —OSO ₃ H, —PO ₃ H ₂ , —OPO ₃ H ₂ , and COCH ₂ COCH ₃ . Of these, -COOH is particularly preferred. These acid groups may be acid group salts. Examples of the salt include metal salts and salts of nitrogen-containing cations. The metal salt is preferably a metal salt selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba and Zn. Details of the nitrogen-containing cation will be described later.
The cationic group is preferably an onium group. Examples of the onium group include an ammonium group, a phosphonium group, an arsonium group, a stibonium group, an oxonium group, a sulfonium group, a selenonium group, a stannonium group, and an iodonium group. An ammonium group, a phosphonium group and a sulfonium group are preferred, an ammonium group and a phosphonium group are more preferred, and an ammonium group is most preferred.

  A chelating agent having a carboxyl group (hereinafter, appropriately referred to as “carboxylic acid compound”) has at least one carboxyl group in one molecule, but more preferably has two or more carboxyl groups in one molecule. preferable.

Carboxylic acid compounds having one carboxyl group are not only carboxyl groups but also other metal-adsorbing groups, alcoholic hydroxyl groups, mercapto groups, amino groups, carbonyl groups, etc. It preferably has a coordinating functional group. Specific examples include glycolic acid, thioglycolic acid, lactic acid, β-hydroxypropionic acid, gluconic acid, pyruvic acid, acetoacetic acid, salicylic acid, β-alanine, phenylalanine, N-ethylglycine, and the like.
Specific examples of the carboxylic acid compound having two carboxyl groups include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, phthalic acid, 3 -Sulfophthalic acid, 4-sulfophthalic acid, 2-sulfoterephthalic acid, 3-hydroxyphthalic acid, 4-hydroxyphthalic acid, tartaric acid, malic acid, dipicolinic acid, citric acid and the like.

  Among these, compounds having two or more carboxyl groups and one sulfonic acid group in an aromatic ring such as 3-sulfophthalic acid, 4-sulfophthalic acid, and 2-sulfoterephthalic acid, and aromatic compounds such as 5-sulfosalicylic acid Compounds having a hydroxyl group, carboxyl group, sulfonic acid group in the ring, 4-hydroxyphthalic acid, oxalic acid, tartaric acid, malic acid, and dipicolinic acid are more preferable, and 3-sulfophthalic acid, 4-sulfophthalic acid, and the like are particularly preferable. Sulfophthalic acid, 5-sulfosalicylic acid, and 4-hydroxyphthalic acid.

Moreover, the low molecular organic compound which has 3 or more carboxyl groups which are illustrated by the following specific example, and does not have other functional groups containing elements other than carbon and hydrogen is also preferable as a carboxylic acid compound.
Specific examples thereof include, for example, propane-1,2,3-tricarboxylic acid, butane-1,2,3-tricarboxylic acid, butane-1,2,4-tricarboxylic acid butane-1,2,3,4-. Tetracarboxylic acid, 2-carboxymethylpropane-1,3-dicarboxylic acid, pentane-1,2,3-tricarboxylic acid, pentane-1,2,4-tricarboxylic acid, pentane-1,2,5-tricarboxylic acid, Pentane-1,3,4-tricarboxylic acid, pentane-2,3,4-tricarboxylic acid, pentane-1,2,3,4-tetracarboxylic acid, pentane-1,2,3,5-tetracarboxylic acid, 2-carboxymethylbutane-1,3-dicarboxylic acid, 2-carboxymethylbutane-1,4-dicarboxylic acid, 3-carboxymethylbutane-1,2-dicarboxylic acid, 3-carboxy Boxymethylbutane-1,2,4-tricarboxylic acid, 2,2-dicarboxymethylpropane-1,3-dicarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, hemimellitic acid, trimellit Examples include acid, pyromellitic acid, naphthalene-1,4,5,8-tetracarboxylic acid.
Among these, particularly preferred are those in which 3 or more carboxyl groups are substituted on an alkyl group having 5 or less carbon atoms, and most preferred is propane-1,2,3-tricarboxylic acid.

  In addition, a compound having three or more carboxyl groups such as 2-phosphonobutane-1,2,3-tricarboxylic acid and having another functional group containing a hetero element is also preferable.

  Another preferred example of the chelating agent used in the present invention is a compound represented by the following formula (I) or (II).

In the above formula, R ₁ , R ₂ , R ₄ , R ₅ , R ₆ and R ₇ are each independently a single bond or a linear alkylene group having 1 to 3 carbon atoms. R ₃ is a divalent organic group, preferably a linear or branched alkylene group and an arylene group, preferably having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms. R ₈ is a trivalent organic group, preferably having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms. The organic group may have a substituent, the substituents may be bonded to each other to form a cyclic structure, and the organic chain may have a hetero atom. X is methine (—CH <) or an amine (—N <), preferably an amine. In the case of containing an amine, the hydrophilicity is increased and the effect of improving the soiling property is increased.

Y ₁ to Y ₆ in the formulas (I) and (II) each independently represent a metal adsorbing group. As the metal adsorbing group, an acid group or a cationic group is preferable. Specific examples are the same as the specific examples of the acid group or the cationic group described above for the metal adsorption group of the carboxylic acid compound.

  A in the formulas (I) and (II) represents a hydrogen atom or a hydrophilic group. Examples of hydrophilic groups include hydroxyl group, carboxyl group, carboxylate group, hydroxyethyl group, polyoxyethyl group, hydroxypropyl group, polyoxypropyl group, amino group, aminoethyl group, aminopropyl group, ammonium group, Preferred examples include an amide group, a carboxymethyl group, a sulfonic acid group, and a phosphoric acid group. Of these, a hydroxyl group is most preferred.

In the chelating agent represented by the above formulas (I) and (II), the physical property value CLogP representing the hydrophilicity / hydrophobicity of the portion excluding Y _{1 to} Y ₆ is preferably 3 to -4, 0.5 is more preferable, and −1 to −3 is most preferable. The CLogP value can be calculated using CS ChemDraw. A positive value indicates hydrophobicity, and a negative value indicates hydrophilicity.
Specific examples of the chelating agent represented by the formulas (I) and (II) are shown below, but the present invention is not limited thereto.

  Another preferred example of the chelating agent used in the present invention is a salicylic acid derivative and a salt thereof. The salicylic acid derivative and its salt are preferably compounds represented by the following general formula (III).

In general formula (III), X represents an oxygen atom or a sulfur atom. M ¹ and M ² are each independently selected from H, Li, Na, K, Rb, Cs, 1 / 2Mg, 1 / 2Ca, 1 / 2Sr, 1 / 2Ba, 1 / 2Zn, and a nitrogen-containing cation. Represents a species. Among these, H, Li, Na, K, 1 / 2Zn and nitrogen-containing cations are preferable from the viewpoint of solubility, and H, Li, Na, K and nitrogen-containing cations are more preferable from the viewpoint of reducing environmental burden, and H, Na , K and nitrogen-containing cations are particularly preferred from the viewpoint of production cost.
R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom or an arbitrary substituent, and R ¹ and R ² , R ² and R ³ , and R ³ and R ⁴ are bonded to each other to form a cyclic structure. May be.

In general formula (III), as R ^{1 to} R ⁴ , hydrogen atom, amino group, dialkylamino group, halogen atom, hydroxyl group, alkyl group, nitro group, alkoxy group, aryl group, arylthio group, alkylthio group, formyl Group, —SO ₃ M group (M represents the same group as the above-mentioned M ¹ ), and mercapto group, hydrogen atom, amino group, dialkylamino group, halogen atom, hydroxyl group, alkyl group, nitro group , An alkoxy group, an aryl group, an arylthio group, an alkylthio group, a —SO ₃ M group and a mercapto group, more preferably a hydrogen atom, an amino group, a dialkylamino group, a halogen atom, a hydroxyl group, an alkyl group, a nitro group, an alkoxy group, Aryl group, arylthio group, alkylthio group and —SO ₃ M group are particularly preferred.
Depending on the system to be used, substituents other than amino groups may be preferable as R ^{1 to} R ^{4 from} the viewpoints of solubility, developability, printing durability, minute spot-like stains, and the like.

R ^{1 to} R ⁴ may further have a substituent. The substituent is preferably an alkyl group, a hydroxyl group, a halogen atom, an aryl group, an alkoxy group and an amino group, more preferably an alkyl group, a hydroxyl group, a halogen atom, an aryl group and an alkoxy group, and an alkyl group, a hydroxyl group, a halogen group. Atoms and aryl groups are particularly preferred.
The substituents of R ^{1 to} R ⁴ may be further substituted with the same substituent.

As the chelating agent of the present invention, a salicylic acid structure of the general formula (III) may be a combination of a plurality of so-called bis-type structures with R ^{1 to} R ⁴ groups as linking groups. As the linking group, —S—, an alkylene group, and an alkyleneoxy group are preferable, and among them, —S—, —CH ₂ —, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ —, preferably —S—, —CH ₂ —, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, more preferably —S—, —CH ₂ —, —CH ₂ CH ₂ — is particularly preferred.

As the cyclic structure R ¹ and R ^2, R ² and R ^3, and R ³ and R ⁴ are bonded to each other forming, e.g., an aromatic ring, a cycloalkyl ring include, naphthalene overall inter alia A benzene ring forming a ring is preferred.

When the group represented by R ^{1 to} R ⁴ is alkyl group, methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl, cyclobutyl, n-amyl, i-amyl, sec-amyl, t-amyl, neo-pentyl, cyclopentyl, n-hexyl, i-hexyl, sec-hexyl Group, t-hexyl group, cyclohexyl group, cyclohexylmethyl group, cyclopentyl group, cyclopropylmethyl group, cyclohexylmethyl group, cyclobutylmethyl group, linear or branched heptyl group, cyclopentylethyl group, linear or branched octyl group , A linear or branched nonyl group, and a linear or branched decyl group are preferred, and among them, a methyl group, an ethyl group, -Propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, cyclobutyl group, n-amyl group, i-amyl-group, sec-amyl Group, t-amyl group, neo-pentyl group, cyclopentyl group, n-hexyl group, i-hexyl group, sec-hexyl group, t-hexyl group, cyclohexyl group, cyclohexylmethyl group, linear or branched heptyl group, A cyclopentylethyl group and a linear or branched octyl group are more preferable. Among them, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, sec -Butyl group, t-butyl group, cyclobutyl group, n-amyl group, i-amyl group, sec-amyl group, t-amyl group, neo-pen Particularly preferred are a til group, a cyclopentyl group, an n-hexyl group, an i-hexyl group, a sec-hexyl group, a t-hexyl group, a cyclohexyl group, a cyclohexylmethyl group, and a linear or branched octyl group.

When the group represented by R ^{1 to} R ⁴ is an aryl group, the aryl group is preferably a phenyl group, a naphthyl group, a biphenylenyl group, an acenaphthenyl group, a fluorenyl group, an anthracenyl group, an anthraquinonyl group, or a pyrenyl group, Of these, a phenyl group, a naphthyl group, a biphenylenyl group, an acenaphthenyl group, a fluorenyl group, and an anthracenyl group are more preferable, and among them, a phenyl group, a naphthyl group, a biphenylenyl group, and a fluorenyl group are particularly preferable.

  Specific examples of the compound represented by the general formula (III) are shown below, but the compound represented by the general formula (III) is not limited to the following examples.

  When the chelating agent of the present invention is a nitrogen-containing cation salt of an acid group, the nitrogen-containing cation is not particularly limited as long as it is a quaternary ammonium cation and a cation that is a hydrogen adduct of an amine. As the quaternary ammonium cation, for example, tetramethylammonium cation, tetraethylammonium cation, tetrapropylammonium cation, methyltributylammonium cation, tetrabutylammonium cation, choline-type cation (hydroxyethyltrimethylammonium cation) and the like are preferable. However, tetramethylammonium cation, tetraethylammonium cation, tetrapropylammonium cation, tetrabutylammonium cation and choline-type cation are more preferable. preferable.

  The cations which are hydrogen adducts of amines include triethylamine hydrogen adduct cations, tripropylamine hydrogen adduct cations, tributylamine hydrogen adduct cations, pyridine and pyridine derivative hydrogen adduct cations, and the following nitrogen-containing cations. A hydrogen adduct cation of the compound (the cation here is a cation obtained by protonation of the following nitrogen-containing compound) is preferable.

  Among them, triethylamine hydrogen adduct cation, tripropylamine hydrogen adduct cation, pyridine and pyridine derivative hydrogen adduct cation are more preferable, and triethylamine hydrogen adduct cation and tripropylamine hydrogen adduct cation are particularly preferable. .

When M ¹ and M ^{2 in} the general formula (III) are nitrogen-containing cations, the nitrogen-containing cations may be cationic polymers.
The cationic polymer may have an arbitrary structure, but a polymer including a structural unit having an ammonium structure as a repeating unit is preferable. The ammonium structure here may be a chain (eg, alkylammonium, dialkylammonium, trialkylammonium, tetraalkylammonium) or cyclic (eg, pyridinium, imidazolinium, etc.).
The cationic polymer may be an addition polymer, a polycondensation product, a polyaddition product, or a ring-opening polymer without any particular limitation, but is preferably an addition polymer.

  It is more preferable that the cationic polymer has a repeating unit represented by the following general formula (1).

In general formula (1), R ¹¹ represents a hydrogen atom or a substituent. L ¹ represents a divalent linking group, and R ¹² , R ¹³ and R ¹⁴ each independently represents a hydrogen atom or a substituent.

R ¹¹ will be described. In general formula (1), R ¹¹ represents a hydrogen atom or a substituent. Preferably, it represents a hydrogen atom, an alkyl group, an aryl group, a substituted carbonyl group, a substituted oxy group, a heterocyclic group or a halogen atom, more preferably a hydrogen atom, an alkyl group or a halogen atom, particularly preferably a hydrogen atom or Represents an alkyl group.

As a preferable example of the alkyl group represented by R ¹¹ , a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms can be mentioned. Among these, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms are more preferable. Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group. , Eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group , And 2-norbornyl groups.

The aryl group represented by R ¹¹ preferably represents a substituted or unsubstituted aryl group having 5 to 20 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 12 carbon atoms. The aryl group represented by R ¹¹ may further have a substituent.
Preferred examples include phenyl group, 4-methylphenyl group, 4-methoxyphenyl group, 4-chlorophenyl group, 4- (dimethylamino) group, 1-naphthyl group, 2-naphthyl group, biphenyl group, xylyl group, mesityl group. , Cumenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylamino Phenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, cyanophenyl , Sulfophenyl group, sulfonatophenyl group, phosphonophenyl group, phosphate Hona preparative phenyl group, and the like.

The heterocyclic group represented by R ¹¹ is preferably a 3- to 8-membered ring, more preferably a 3- to 6-membered ring, and particularly preferably a 5- to 6-membered ring. Moreover, as a kind of hetero atom which comprises a heterocyclic ring, it is preferable that a nitrogen atom, an oxygen atom, or a sulfur atom is included. The heterocyclic group represented by R ¹¹ may further have a substituent.
Preferred examples include pyrrole ring group, furan ring group, thiophene ring group, benzopyrrole ring group, benzofuran ring group, benzothiophene ring group, pyrazole ring group, isoxazole ring group, isothiazole ring group, indazole ring group, benzoiso Xazole ring group, benzoisothiazole ring group, imidazole ring group, oxazole ring group, thiazole ring group, benzimidazole ring group, benzoxazole ring group, benzothiazole ring group, pyridine ring group, quinoline ring group, isoquinoline ring group, Pyridazine ring group, pyrimidine ring group, pyrazine ring group, phthalazine ring group, quinazoline ring group, quinoxaline ring group, acylidin ring group, phenanthridine ring group, carbazole ring group, purine ring group, pyran ring group, piperidine ring group, Piperazine ring group, morpholine ring group, indole ring group, indoli Ring group, a chromene ring group, a cinnoline ring group, an acridine ring group, a phenothiazine ring group, a tetrazole ring group, a triazine ring group, and the like.

The substituted carbonyl group represented by R ¹¹ is preferably a group represented by (R ¹⁵ —CO—). R ¹⁵ represents a hydrogen atom or a substituent. Preferred examples of R ¹¹ include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N , N-diarylcarbamoyl group, N-alkyl-N′-arylcarbamoyl group. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Of these, more preferred substituted carbonyl groups include formyl, acyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, N-ary. A rucarbamoyl group is exemplified, and particularly preferred are a formyl group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group.
Preferred examples of R ¹¹ include formyl group, acetyl group, benzoyl group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, allyloxycarbonyl group, dimethylaminophenylethenylcarbonyl group, methoxycarbonylmethoxycarbonyl group, N- Examples thereof include a methylcarbamoyl group, an N-phenylcarbamoyl group, an N, N-diethylcarbamoyl group, and a morpholinocarbonyl group.

The substituted oxy group represented by R ¹¹ is preferably a group represented by (R ¹⁶ O—). R ¹⁶ represents a hydrogen atom or a substituent. Preferred examples of the substituted oxy group include hydroxyl group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N- Examples thereof include a diarylcarbamoyloxy group, an N-alkyl-N-arylcarbamoyloxy group, an alkylsulfoxy group, an arylsulfoxy group, a phosphonooxy group, and a phosphonatoxy group. Examples of the alkyl group and aryl group in these include the alkyl groups, substituted alkyl groups, aryl groups, and substituted aryl groups described above. Specific examples of the acyl group when the substituted oxy group represented by R ¹¹ represents an acyloxy group include the examples when R ¹¹ represents a substituted carbonyl group. Among these substituents, an alkoxy group, an aryloxy group, an acyloxy group, and an arylsulfoxy group are more preferable.
Specific examples of preferred substituted oxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, allyloxy, phenethyloxy, Carboxyethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, allyloxyethoxyethoxy group, Phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group, mesityloxy group, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyl Alkoxy group, bromophenyl group, acetyloxy group, benzoyloxy group, naphthyloxy group, a phenylsulfonyloxy group, a phosphonooxy group, phosphonatoxy group, and the like.

The halogen atom represented by R ¹¹ is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom, a chlorine atom or a bromine atom, and a fluorine atom, a chlorine atom or a bromine atom. It is particularly preferred that

When the group represented by R ¹¹ can be substituted, it may further have a substituent. Any kind of substituent can be selected as long as it is a substitutable group. For example, an alkyl group, aryl group, alkenyl group, alkynyl group, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) ), Hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N , N-Diarylcarbamoyloxy group, N-alkyl-N- Lillecarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N ′ -Dialkylureido group, N'-arylureido group, N ', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl -N-alkylureido group, N'-alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl -N-alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', '- diaryl -N- arylureido group, N'- alkyl -N'- aryl -N- alkylureido group, N'- alkyl -N'- aryl -N- arylureido group,

Alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N -Aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N- di arylcarbamoyl group, N- alkyl -N- arylcarbamoyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (-SO ₃ H) and its conjugated base group (scan Honato group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinaimoyl group, N-arylsulfinamoyl group, N, N-diaryl Sulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N- Diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group,

A phosphono group (—PO ₃ H ₂ ) and its conjugate base group (referred to as a phosphonate group), a dialkylphosphono group (—PO ₃ (alkyl) ₂ ) “alkyl = alkyl group, hereinafter the same”, a diarylphosphono group ( -PO ₃ (aryl) ₂ ) “aryl = aryl group, hereinafter the same”, alkylarylphosphono group (—PO ₃ (alkyl) (aryl)), monoalkylphosphono group (—PO ₃ (alkyl)) and its Conjugated base group (referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonate group), phosphonooxy group (—OPO ₃ H ₂₎ ) and its conjugated base group (referred to as phosphonatooxy group), dialkylphosphono group (-OPO ₃ H (alkyl) _2), diaryl Suhonookishi group _{(-OPO 3 (aryl) 2)} , alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), monoalkyl phosphono group (-OPO ₃ H (alkyl)) and its conjugated base group (Referred to as alkylphosphonatoxy group), monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonatoxy group), cyano group, nitro group, aryl group Alkenyl group, alkynyl group, heterocyclic group, silyl group, and the like.

These groups may be further combined to form a composite substituent. Of these groups, R ¹¹ is particularly preferably a hydrogen atom or a methyl group.

R ¹² , R ¹³ and R ¹⁴ will be described. R ¹² , R ¹³ and R ¹⁴ each independently represents a hydrogen atom or a substituent. Preferably, it represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, more preferably a hydrogen atom or an alkyl group, and particularly preferably an alkyl group.

When R ¹² , R ¹³ and R ¹⁴ represent an alkyl group, preferred examples include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, cyclobutyl group, n-pentyl group, i-pentyl group, sec-pentyl group, t-pentyl group, neo-pentyl group, cyclopentyl group, n-hexyl group, i-hexyl group , Sec-hexyl group, t-hexyl group, cyclohexyl group, cyclohexylmethyl group, cyclopentyl group, cyclopropylmethyl group, cyclohexylmethyl group, cyclobutylmethyl group, linear or branched heptyl group, cyclopentylethyl group, linear or Branched octyl group, linear or branched nonyl group, linear or branched decyl group, dodecyl group, tetradecyl group A syl group, a hexadecyl group, an octadecyl group, an icosyl group, etc. can be mentioned, More preferable examples include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i -Butyl group, sec-butyl group, t-butyl group, cyclobutyl group, n-pentyl group, i-pentyl group, sec-pentyl group, t-pentyl group, neo-pentyl group, cyclopentyl group, n-hexyl group, Examples thereof include i-hexyl group, sec-hexyl group, t-hexyl group, cyclohexyl group, cyclohexylmethyl group, linear or branched heptyl group, cyclopentylethyl group, linear or branched octyl group, and particularly preferable. Examples include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl. I-butyl group, sec-butyl group, t-butyl group, cyclobutyl group, n-pentyl group, i-pentyl group, sec-pentyl group, t-pentyl group, neo-pentyl group, cyclopentyl group, n-hexyl Group, i-hexyl group, sec-hexyl group, t-hexyl group and cyclohexyl group.

The group represented by R ¹² , R ¹³ and R ¹⁴ may have a substituent. Although any substitutable group can be selected as the substituent, preferred examples include trifluoromethyl group, fluoro group, chloro group, bromo group, methoxy group, hydroxyl group, nitro group, vinyl group, dimethyl group. An amino group, an aryl group, a methoxycarbonyl group, an ethoxycarbonyl group, etc. can be mentioned, and more preferred examples include a fluoro group, a chloro group, a bromo group, a methoxy group, a hydroxyl group, a vinyl group, a dimethylamino group, a phenyl group. Methoxycarbonyl group, ethoxycarbonyl group and the like, and particularly preferable examples include fluoro group, chloro group, bromo group, methoxy group, hydroxyl group, vinyl group, phenyl group, methoxycarbonyl group, ethoxycarbonyl group and the like. Can be mentioned. These groups may be further substituted with the same substituent.
Preferred examples of the group represented by R ¹² , R ¹³ and R ¹⁴ having a substituent include a benzyl group, a 4-methylbenzyl group, a 3-methylbenzyl group, a 2-methylbenzyl group, and 4-methoxybenzyl. Group, 3-methoxybenzyl group, 2-methoxybenzyl group, 4-dimethylaminobenzyl group, 3,5-dimethylbenzyl group, 3,4,5-trimethylbenzyl group, 4-phenylbenzyl group, 4-phenoxybenzyl, And so on.
More preferable examples include benzyl group, 4-methylbenzyl group, 3-methylbenzyl group, 2-methylbenzyl group, 4-methoxybenzyl group, 3-methoxybenzyl group, 2-methoxybenzyl group, 4-dimethylaminobenzyl. Group, 3,5-dimethylbenzyl group, and the like.
Particularly preferred examples include benzyl group, 4-methylbenzyl group, 3-methylbenzyl group, 2-methylbenzyl group, 4-methoxybenzyl group, 3-methoxybenzyl group, 2-methoxybenzyl group, 4-dimethylaminobenzyl. Group, and the like.

The groups represented by R ¹² , R ¹³ and R ¹⁴ may be the same or different, or two of the three may be the same, and any combination can be selected. R ¹² , R ¹³ and R ¹⁴ are all preferably alkyl groups having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 8 carbon atoms. R ¹² , R ¹³ and R ¹⁴ may all be the same or different.
In the present invention, examples of preferable combinations of groups represented by R ¹² , R ¹³ and R ¹⁴ include (methyl group, methyl group, and methyl group combination), (methyl group, methyl group, and ethyl group). Group combination), (combination of methyl group, methyl group, and propyl group), (combination of methyl group, methyl group, and isopropyl group), (combination of methyl group, methyl group, and butyl group), (Combination of methyl group, methyl group, and isobutyl group), (combination of methyl group, methyl group, and pentyl group), (combination of methyl group, methyl group, and hexyl group), (methyl group, methyl group) Group and benzyl group) (ethyl group, ethyl group and methyl group combination), (ethyl group, ethyl group and methyl group combination), (ethyl group, ethyl group, And combinations of ethyl groups), (combination of ethyl groups, ethyl groups, and propyl groups), (combination of ethyl groups, ethyl groups, and isopropyl groups), (ethyl groups, ethyl groups, and butyl groups) Combination), (ethyl group, ethyl group, and isobutyl group combination), (ethyl group, ethyl group, and pentyl group combination), (ethyl group, ethyl group, and hexyl group combination), (ethyl A combination of a group, an ethyl group, and a benzyl group).
Examples of further preferred combinations of the groups represented by R ¹² , R ¹³ and R ¹⁴ include (a combination of methyl group, methyl group and methyl group), (a combination of methyl group, methyl group and ethyl group) ), (Combination of methyl, methyl and propyl), (combination of methyl, methyl and isopropyl), (combination of methyl, methyl and butyl), (methyl) , Methyl group and isobutyl group), (combination of methyl group, methyl group and pentyl group), (combination of methyl group, methyl group and hexyl group), (methyl group, methyl group and And a combination of benzyl groups).
Examples of particularly preferred combinations of the groups represented by R ¹² , R ¹³ and R ¹⁴ include (combination of methyl group, methyl group and methyl group), (combination of methyl group, methyl group and ethyl group) ), (Combination of methyl, methyl and propyl), (combination of methyl, methyl and isopropyl), (combination of methyl, methyl and butyl), (methyl) , A combination of methyl group and isobutyl group), (a combination of methyl group, methyl group and pentyl group).

When R ¹² , R ¹³ and R ¹⁴ represent an aryl group or a heterocyclic group, preferred examples of R ¹¹ described above can be given as preferred examples.

L ¹ will be described. L ¹ represents a single bond or a divalent linking group.
When L ¹ is a divalent linking group, 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms , And 0 to 20 sulfur atoms.
More specifically, the following divalent groups or groups formed by appropriately combining these groups can be exemplified.

More preferable examples of the divalent linking group represented by L ¹ include divalent groups represented by the following structural formulas.

  The repeating unit having an ammonium structure of the present invention more preferably has a structure represented by the following general formula (3), (4) or (5).

In the general formula (3), (4) and (5), R ^11, R ^12, R ^13, and R ¹⁴ is, R ¹¹ in the general formula (1) in, R ^12, R ^13, and R ¹⁴ as defined It is. Further, L is the same meaning as L ¹ in the general formula (1).

  As the repeating unit having an ammonium group of the present invention, the cationic polymer is a polycondensate (for example, polyester) in addition to the repeating unit in the case where the cationic polymer represented by the general formula (1) is an addition polymer. Also preferred are those in which an ammonium group is introduced into the side chain of the monomer unit in the case of a polyaddition product (for example, polyurethane) or a ring-opening polymer. When the cationic polymer is polyurethane, a structural unit in which an ammonium group is introduced into the side chain of a diisocyanate or diol-derived structural unit, for example, a diol-derived structural unit having an ammonium group in the side chain may be mentioned as a preferred example. it can.

  The structural unit having an ammonium structure contained in the cationic polymer used in the present invention may be composed of only a single type or a plurality of types.

  The cationic polymer used in the present invention may further contain a copolymer component for the purpose of improving various performances such as image strength as long as the effects of the present invention are not impaired. As a preferable structure of the copolymer component, one represented by the following general formula (2) can be exemplified.

In the general formula (2), R ²¹ represents a hydrogen atom or a substituent. R ²² represents a substituent.
Preferable examples of R ²¹ include the preferable examples of R ¹¹ in the general formula (1). Preferable examples of R ²² include an ester group, an amide group, a cyano group, or an aryl group. Of these, an ester group, an amide group, or a phenyl group which may have a substituent is preferable.
Examples of the substituent of the phenyl group include those listed as the substituents of R ^{12 to} R ^{14 in} the general formula (1), and alkyl groups, aralkyl groups, alkoxy groups, acetoxymethyl groups, and the like. Moreover, the substituent of the phenyl group may further have a substituent.

  Examples of the copolymer component represented by the general formula (2) include acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, N-substituted acrylamides, N-substituted methacrylamides, N, N -2 substituted acrylamides, N, N-2 substituted methacrylamides, styrenes, acrylonitriles, methacrylonitriles and the like. Preferably, acrylic esters, methacrylic esters, acrylamides, methacrylamides, N-substituted acrylamides, N-substituted methacrylamides, N, N-2 substituted acrylamides, N, N-2 substituted methacrylamides And styrenes.

  Specifically, for example, acrylic esters such as alkyl acrylate (the alkyl group preferably has 1 to 20 carbon atoms), (for example, methyl acrylate, ethyl acrylate, propyl acrylate, acrylic acid) Butyl, amyl acrylate, ethyl hexyl acrylate, octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol Monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), aryl acrylate (for example, phenyl acrylate) Methacrylic acid esters (for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl) such as alkyl methacrylate (the alkyl group preferably has 1 to 20 carbon atoms). Methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, Glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl meta Relates, etc.), aryl methacrylates (eg, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.), styrenes such as styrene, alkyl styrene (eg, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl) Styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, etc.), alkoxy styrene (for example, methoxy styrene, 4-methoxy-3-methyl styrene, Dimethoxystyrene), halogen styrene (eg, chlorostyrene, dichlorostyrene, trichlorostyrene) , Tetrachlorostyrene, pentachlorostyrene, promstyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.) , Acrylonitrile, methacrylonitrile acrylic acid, radical polymerizable compounds containing carboxylic acid (acrylic acid, methacrylic acid, itaconic acid, p-carboxylstyrene, and metal salts of these acid groups, ammonium salt compounds, etc.) .

Moreover, it is preferable that the structural unit of General formula (2) has a polyalkyleneoxy group in a structural unit. Examples of polyalkyleneoxy groups include -O- (CH ₂ CH ₂ -O-) _n -R ²³ , -O- (CH (CH ₃ ) CH ₂ -O-) _n -R ²³ , -O- ( A group represented by CH ₂ CH (CH ₃ ) —O—) _n —R ²³ is exemplified. Here, n is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, and particularly preferably 1 to 2. Here, n may be single or a mixture of a plurality of types, and in the case of a mixture, n represents an average value. R ²³ preferably represents a substituent having 1 to 30 carbon atoms, more preferably 1 to 20, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 10 carbon atoms.

Examples of R ²³ include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, cyclobutyl group, n-pentyl group, i-pentyl group, sec-pentyl group, t-pentyl group, neo-pentyl group, cyclopentyl group, n-hexyl group, i-hexyl group, sec-hexyl group, t-hexyl group, cyclohexyl group Cyclohexylmethyl group, cyclopentyl group, cyclopropylmethyl group, cyclohexylmethyl group, cyclobutylmethyl group, linear or branched heptyl group, cyclopentylethyl group, linear or branched octyl group, linear or branched nonyl group, Linear or branched decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosi More preferred examples include methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, sec-butyl, t -Butyl group, cyclobutyl group, n-pentyl group, i-pentyl group, sec-pentyl group, t-pentyl group, neo-pentyl group, cyclopentyl group, n-hexyl group, i-hexyl group, sec-hexyl group, Examples thereof include a t-hexyl group, a cyclohexyl group, a cyclohexylmethyl group, a linear or branched heptyl group, a cyclopentylethyl group, a linear or branched octyl group, and particularly preferable examples include a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, n-hexyl group, linear or branched Octyl group, can be exemplified.

The cationic polymer used in the present invention may further have an ethylenically unsaturated group in the side chain. The ethylenically unsaturated group as used herein represents a known arbitrary group having a substituted or unsubstituted ethylene group, and preferred examples include acryloyl group, methacryloyl group, styryl group, allyl group, vinyl group, acrylonitrile group. Methacrylonitrile group, maleic acid structure, maleimide structure, cinnamic acid structure, and the like.
The ethylenically unsaturated group and the main chain may be bonded via an arbitrary linking group. Preferred examples include a linking group represented by L ¹ in the general formula (1). it can.

In the cationic polymer used in the present invention, the ratio between the structural unit having an ammonium structure and the structural unit represented by the general formula (2) is not particularly limited, but is preferably 1:99 to 99: 1 in molar ratio. More preferably, it is 5: 95-95: 5, More preferably, it is 5: 95-80: 20. Within these ranges, the effects of the present invention that are excellent in inking property and on-press developability while maintaining printing durability are remarkable.
In addition, the structural unit having an ethylenically unsaturated group in the side chain is preferably in a molar ratio of 1:99 to the total of the structural unit having an ammonium structure and the structural unit represented by the general formula (2). The ratio is 50:50, more preferably 1:99 to 30:70, and more preferably 1:99 to 20:80. Within these ranges, the effect of the present invention, which is excellent in inking properties and on-press developability, is remarkable, and it is possible to improve printing durability.

The cationic polymer used in the present invention may further contain other copolymerization components as long as the effects of the present invention can be secured. Other copolymerization components that can be used in the present invention are not particularly limited as long as they are monomers capable of copolymerization of two or more, but crotonic acid, maleic acid, (anhydrous) maleic acid, partially esterified maleic acid , Partially amidated maleic acid, aromatic hydrocarbon rings having vinyl group, heteroaromatic rings having vinyl group (vinyl imidazole, vinyl triazole, vinyl carbazole, vinyl pyrrolidone, etc.), (meth) acrylonitrile, (meta ) Crotonnitrile, various benzoyloxyethylenes, various acetoxyethylenes, vinyl ketones, vinyl ethers and the like.
Although the number of types of monomers to be copolymerized is not particularly limited, 1 to 12 types are preferable, 1 to 8 types are more preferable, and 1 to 5 types are particularly preferable.

  The cationic polymer used in the present invention has a reduced specific viscosity (unit: CSt / g / ml) determined by the following measurement method, preferably in the range of 5 to 120, and in the range of 10 to 110. Are more preferable, and those in the range of 15 to 100 are particularly preferable.

-Measurement method of reduced specific viscosity-
Weigh 3.33 g of 30% polymer solution (1 g as solid content) into a 20 ml volumetric flask and make up with N-methylpyrrolidone. This solution is put in an Ubbelohde reduced viscosity tube (viscosity constant = 0.010 cSt / s), and the time to flow down at 30 ° C. is measured. Time of passage (second) ") was calculated by a conventional method.

  Specific examples of the cationic polymer used in the present invention are shown below, but the cationic polymer used in the present invention is not limited to the following examples, and a coating liquid component for preparing a printing plate precursor and In combination, the structure and the amount added can be changed as appropriate. Moreover, the cationic polymer to be used may be 1 type, and may use 2 or more types together.

  The amount of the chelating agent added to the image recording layer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and most preferably 1 to 10% by mass based on the total solid mass of the image recording layer.

<(A) Infrared absorber>
When forming an image of the lithographic printing plate precursor according to the present invention with a laser that emits infrared rays of 760 to 1200 nm using a light source, it is usually essential to use an infrared absorber. The infrared absorber has a function of converting the absorbed infrared ray into heat and a function of being excited by the infrared ray and transferring electrons / energy to a polymerization initiator (radical generator) described later. The infrared absorber used in the present invention is a dye or pigment having an absorption maximum at a wavelength of 760 to 1200 nm.

As the dye, commercially available dyes and known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specifically, dyes such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes, etc. Is mentioned.
Preferred dyes include, for example, cyanine dyes described in JP-A-58-125246, JP-A-59-84356, JP-A-60-78787, JP-A-58-173696, The methine dyes described in JP-A-58-181690 and JP-A-58-194595, JP-A-58-112793, JP-A-58-224793, JP-A-59-48187, Naphthoquinone dyes described in JP-A-59-73996, JP-A-60-52940, JP-A-60-63744, and the like, squarylium dyes described in JP-A-58-112792, and the like; And cyanine dyes described in British Patent No. 434,875.

In addition, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferably used, and a substituted arylbenzo (thio) described in US Pat. No. 3,881,924 is also suitable. ) Pyrylium salt, trimethine thiapyrylium salt described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, 58-220143, 59- No. 41363, No. 59-84248, No. 59-84249, No. 59-146063, No. 59-146061, and Pyrlium compounds described in JP-A-59-216146. And pentamethine thiopyrylium salts described in US Pat. No. 4,283,475, and Japanese Patent Publication Nos. 5-13514 and 5-19702. Pyrylium compounds shown also preferably used. Another example of a preferable dye is a near-infrared absorbing dye described in US Pat. No. 4,756,993 as formulas (I) and (II).
Other preferable examples of the infrared absorbing dye of the present invention include specific indolenine cyanine dyes described in JP-A-2002-278057 as exemplified below.

  Particularly preferred among these dyes are cyanine dyes, squarylium dyes, pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes. Further, cyanine dyes and indolenine cyanine dyes are preferable, and one particularly preferable example is a cyanine dye represented by the following general formula (i).

In formula (i), X ¹ represents a hydrogen atom, a halogen atom, -NPh _2, X ² -L ¹ or a group shown below. Here, X ² represents an oxygen atom, a nitrogen atom or a sulfur atom, and L ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, an aromatic ring having a hetero atom, or 1 to 1 carbon atom containing a hetero atom. 12 hydrocarbon groups are shown. In addition, a hetero atom here shows a nitrogen atom, a sulfur atom, an oxygen atom, a halogen atom, and a selenium atom. X _a ^- is Z _a which will be described below ^- has the same definition as, R ^a represents a hydrogen atom, an alkyl group, an aryl group, a substituted or unsubstituted amino group, substituted or unsubstituted amino group and a halogen atom.

R ¹ and R ² each independently represents a hydrocarbon group having 1 to 12 carbon atoms. From the storage stability of the recording layer coating solution, R ¹ and R ² are preferably hydrocarbon groups having 2 or more carbon atoms, and R ¹ and R ² are bonded to each other to form a 5-membered ring or It is particularly preferable that a 6-membered ring is formed.

Ar ¹ and Ar ² may be the same or different and each represents an aromatic hydrocarbon group which may have a substituent. Preferred aromatic hydrocarbon groups include a benzene ring and a naphthalene ring. Preferred substituents include a hydrocarbon group having 12 or less carbon atoms, a halogen atom, an alkoxy group having 12 or less carbon atoms, a hydrocarbon group having 12 or less carbon atoms, and 12 carbon atoms. Most preferred are not more than alkoxy groups. 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 may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferable substituents include an alkoxy group having 12 or less carbon atoms, a carboxyl group, and a sulfo group, and an alkoxy group having 12 or less carbon atoms is most preferable. 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, a hydrogen atom is preferred. Z _a ^- represents a counter anion. However, when the cyanine dye represented by formula (i) has an anionic substituent in the structure thereof, Z _a is does not require charge neutralization ^- is not necessary. Preferred Z _a ⁻ is a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, particularly preferably a perchlorate ion, from the storage stability of the recording layer coating solution. , Tetrafluoroborate ions, hexafluorophosphate ions, and aryl sulfonate ions.

Specific examples of cyanine dyes represented by formula (i) that can be suitably used in the present invention include those described in paragraph numbers [0017] to [0019] of JP-A No. 2001-133969. Can do.
Further, other particularly preferable examples include specific indolenine cyanine dyes described in JP-A-2002-278057 described above.

  Examples of the pigment used in the present invention include commercially available pigments and color index (CI) manual, “Latest Pigment Handbook” (edited by Japan Pigment Technology Association, published in 1977), “Latest Pigment Application Technology” (CMC Publishing, 1986), “Printing Ink Technology”, CMC Publishing, 1984) can be used.

  Examples of the pigment include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other polymer-bonded dyes. 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 In addition, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used. Among these pigments, carbon black is preferable.

  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 with a resin or wax, a method of attaching a surfactant, a method of bonding a reactive substance (eg, silane coupling agent, epoxy compound, polyisocyanate, etc.) to the pigment surface, etc. Can be considered. The above-mentioned surface treatment methods are described in “Characteristics and Application of Metal Soap” (Shobobo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 1986). Yes.

  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 in the range of 0.1 μm to 1 μm. Within this range, good stability of the pigment dispersion in the image recording layer coating solution and good uniformity of the image recording layer can be obtained.

  As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production, or 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. Details are described in "Latest Pigment Applied Technology" (CMC Publishing, 1986).

These infrared absorbers may be added to the same layer as the other components, or may be added to another layer provided, but when a negative lithographic printing plate precursor is produced, image recording is performed. The layer is added so that the absorbance at the maximum absorption wavelength in the wavelength range of 760 nm to 1200 nm is in the range of 0.3 to 1.2 by the reflection measurement method. Preferably, it is the range of 0.4-1.1. Within this range, a uniform polymerization reaction in the depth direction of the image recording layer proceeds, and good film strength of the image area and adhesion to the support can be obtained.
The absorbance of the image recording layer can be adjusted by the amount of infrared absorber added to the image recording layer and the thickness of the image recording layer. Absorbance can be measured by a conventional method. As a measuring method, for example, on a reflective support such as aluminum, an image recording layer having a thickness appropriately determined in a range in which the coating amount after drying is necessary as a lithographic printing plate is formed, and the reflection density is set to the optical density. And a method of measuring with a spectrophotometer by a reflection method using an integrating sphere.

<(B) Polymerization initiator>
The polymerization generator used in the present invention is a compound that generates radicals by light, heat, or both, and initiates and accelerates polymerization of a compound having a polymerizable unsaturated group. As the polymerization generator that can be used in the present invention, a known thermal polymerization initiator, a compound having a bond with a small bond dissociation energy, a photopolymerization initiator, or the like can be used, and a radical that is suitably used in the present invention is generated. The compound to be used refers to a compound that initiates and accelerates polymerization of a compound having a polymerizable unsaturated group by generating radicals by thermal energy. As the thermal radical generator according to the present invention, a known polymerization initiator, a compound having a bond with a small bond dissociation energy, or the like can be appropriately selected and used. Moreover, the compound which generate | occur | produces a radical can be used individually or in combination of 2 or more types.

  Examples of the radical generating compound include organic halides, carbonyl compounds, organic peroxides, azo polymerization initiators, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic borate compounds, disulfone compounds, oximes. Examples thereof include ester compounds and onium salt compounds.

  Specific examples of the organic halide include Wakabayashi et al., “Bull Chem. SocJapan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Examined Patent Publication No. 46-4605, 48-36281, JP-A 55-32070, JP-A 60-239736, JP-A 61-169835, JP-A 61-169837, JP-A 62-58241, JP-A 62- No. 212401, JP-A 63-70243, JP-A 63-298339, P. Hut "Journal of Heterocyclic Chemistry" 1 (No 3), (1970) "The compounds described in the brush are mentioned, and in particular, an oxazole compound substituted with a trihalomethyl group and an S-triazine compound.

  More preferably, an s-triazine derivative having at least one mono, di, or trihalogen-substituted methyl group bonded to the s-triazine ring, specifically, for example, 2,4,6-tris (monochloromethyl)- s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl)- s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [ 1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (P-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- ( p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-Fe Ruthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -S-triazine and the like.

  Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy- 2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1- Hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) Acetophenone derivatives such as thioxanthone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, thioxanthone derivatives such as 2,4-diisopropylthioxanthone, p- Examples thereof include benzoic acid ester derivatives such as ethyl dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

  As the azo compound, for example, an azo compound described in JP-A-8-108621 can be used.

  Examples of the organic peroxide include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butyl). Peroxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydro Peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2, -Oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , Dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert- Butyl peroxyoctanoate, tert-butyl peroxylaurate, tersyl carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4 ′ − Tra- (t-hexylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate), carbonyl And di (t-hexylperoxydihydrogen diphthalate).

  Examples of the metallocene compound include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705, Various titanocene compounds described in JP-A-5-83588, such as di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, Di-cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di- -Cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-penta Fluoro-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluoropheny -1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4 , 5,6-pentafluorophen-1-yl, iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109, and the like.

  Examples of the hexaarylbiimidazole compound include JP-B-6-29285, U.S. Pat. Nos. 3,479,185, 4,311,783, and 4,622,286. Various compounds described in the literature, specifically 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) )) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5 '-Tetraphenylbiimidazole, 2, 2' Bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and the like.

  Examples of the organic borate compounds include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188585, JP-A-9-188686, JP-A-9-188710, and JP-A-9-188710. 2000-131837, JP 2002-107916 A, JP 2764769 A, JP 2002-116539 A, and Kunz, Martin “Rad Tech '98. Proceeding April 19-22, 1998, Chicago. "Organic borate salts described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, and organic boron oxosulfonium complexes described in JP-A-6-157623, JP-A-6-175554, JP-A-6-175 53, organoboron iodonium complexes described in JP-A-9-188710, organoboron phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, Specific examples include organoboron transition metal coordination complexes such as JP-A-7-306527 and JP-A-7-292014.

  Examples of the disulfone compound include compounds described in JP-A Nos. 61-166544 and 2003-328465.

  Examples of the oxime ester compound include JCS Perkin II (1979) 1653-1660) JCSPerkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, Examples include compounds described in JP 2000-80068 A, specifically compounds represented by the following structural formulas.

  Examples of the onium salt compound include S.I. I. Schlesinger, Photogr. Sci. Eng. 18, 387 (1974), T .; S. Diazonium salts described in Bal et al, Polymer, 21, 423 (1980), ammonium salts described in US Pat. No. 4,069,055, JP-A-4-365049, etc., US Pat. No. 4,069 , 055 and 4,069,056, phosphonium salts described in European Patent Nos. 104 and 143, U.S. Pat. Nos. 339,049 and 410,201, 2-150848, JP-A-2-296514, iodonium salts, European Patent Nos. 370,693, 390,214, 233,567, 297,443, and 297,442 U.S. Pat. Nos. 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,73 No. 4,444, 2,833,827, German Patent Nos. 2,904,626, 3,604,580, and 3,604,581, the sulfonium salts described in J . V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

In particular, the oxime ester compound, diazonium salt, iodonium salt, and sulfonium salt are preferable from the viewpoint of reactivity and stability. In the present invention, these onium salts function not as acid generators but as ionic radical polymerization initiators.
The onium salt suitably used in the present invention is an onium salt represented by the following general formulas (RI-I) to (RI-III).

In the formula (RI-I), Ar ¹¹ represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents include an alkyl group having 1 to 12 carbon atoms and 1 carbon atom. -12 alkenyl group, C1-C12 alkynyl group, C1-C12 aryl group, C1-C12 alkoxy group, C1-C12 aryloxy group, halogen atom, C1-C12 An alkylamino group, a C1-C12 dialkylamino group, a C1-C12 alkylamide group or arylamide group, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a C1-C12 thioalkyl group, A C1-C12 thioaryl group is mentioned. Z ^11- represents a monovalent anion, which is a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, and is stable. From the above viewpoint, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, and sulfinate ion are preferable.

In the formula (RI-II), Ar ²¹ and Ar ²² each independently represent an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents have 1 to 12 carbon atoms. Alkyl group, alkenyl group having 1 to 12 carbon atoms, alkynyl group having 1 to 12 carbon atoms, aryl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, aryloxy group having 1 to 12 carbon atoms, halogen atom An alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, and 1 carbon atom -12 thioalkyl group and C1-C12 thioaryl group are mentioned. Z ^21- represents a monovalent anion, which is a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, and is stable. From the viewpoint of reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, and carboxylate ions are preferable.

In formula (RI-III), R ³¹ , R ³² and R ³³ each independently represents an aryl group having 20 or less carbon atoms, an alkyl group, an alkenyl group or an alkynyl group which may have 1 to 6 substituents. In view of reactivity and stability, an aryl group is desirable. Preferred substituents are alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 1 to 12 carbon atoms, alkynyl groups having 1 to 12 carbon atoms, aryl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, Aryloxy group having 1 to 12 carbon atoms, halogen atom, alkylamino group having 1 to 12 carbon atoms, dialkylamino group having 1 to 12 carbon atoms, alkylamide group or arylamide group having 1 to 12 carbon atoms, carbonyl group, carboxyl Group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ^31- represents a monovalent anion, which is a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, and is stable. From the viewpoint of reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, and carboxylate ions are preferable. More preferred are the carboxylate ions described in JP-A No. 2001-343742, and particularly preferred are the carboxylate ions described in JP-A No. 2002-148790.
Examples of onium salts that can be suitably used as a polymerization initiator in the present invention will be given below, but the present invention is not limited thereto.

  These polymerization initiators are added in a proportion of 0.1 to 50% by mass, preferably 0.5 to 30% by mass, particularly preferably 1 to 20% by mass, based on the total solid content constituting the image recording layer. Can do. Within this range, good sensitivity and good stain resistance of the non-image area during printing can be obtained. These polymerization initiators may be used alone or in combination of two or more. Moreover, these polymerization initiators may be added to the same layer as other components, or another layer may be provided and added thereto.

<(C) Polymerizable compound>
The polymerizable compound that can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is a compound having at least one terminal ethylenically unsaturated bond, preferably two or more. To be elected. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional compound. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or Also suitable are substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a tosyloxy group with monofunctional or polyfunctional alcohols, amines or thiols. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include, for example, aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. And those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  Further, urethane-based addition polymerizable compounds produced using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples of such compounds are described in, for example, Japanese Patent Publication No. 48-41708. Containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups in the molecule A vinyl urethane compound etc. are mentioned.

^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH (A)
(However, R ⁴ and R ⁵ represent H or CH _3. )

  Further, urethane acrylates as described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56-17654 And urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Depending on the case, it is possible to obtain a photopolymerizable composition excellent in the photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and acrylic acid or methacrylic acid described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. In addition, JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, specific unsaturated compounds described in each gazette, vinylphosphonic acid compounds described in JP-A-2-25493, and the like are also included. Can be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these addition polymerizable compounds, the details of usage, such as the structure, single use or combination, addition amount, etc. can be arbitrarily set according to the performance design of the final lithographic printing plate precursor. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the image area, that is, the cured film, those having three or more functionalities are preferable, and furthermore, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrenic compound, vinyl ether type). A method of adjusting both sensitivity and strength by using a compound) is also effective.
Further, the selection and use method of the addition polymerization compound is also an important factor for the compatibility and dispersibility with other components (for example, binder polymer, initiator, colorant, etc.) in the image recording layer. In some cases, the compatibility can be improved by using a low-purity compound or by using two or more kinds in combination.
The addition polymerizable compound is preferably used in the range of 5 to 80% by mass, more preferably 25 to 75% by mass, with respect to the non-volatile component in the image recording layer. These may be used alone or in combination of two or more. In addition, the use method of the addition polymerizable compound can be arbitrarily selected from the viewpoint of polymerization inhibition with respect to oxygen, resolution, fogging, refractive index change, surface adhesiveness, etc. Depending on the case, a layer configuration and coating method such as undercoating and overcoating can be performed.

<(D) Polymer fine particles having a polymerizable reactive group>
In the present invention, it is preferable to contain (D) polymer fine particles having a polymerizable reactive group in addition to the image recording layer constituting components (A) to (C).
Examples of the polymer fine particles having a polymerizable reactive group used in the image recording layer of the present invention include those obtained by introducing a monomer having an acryloyl group, a methacryloyl group, a vinyl group, or an allyl group into a polymer chain. The introduction of these functional groups into the polymer fine particles may be performed at the time of polymerization, or may be performed using a polymer reaction after the polymerization.

  When introduced at the time of polymerization, it is preferable to subject these monomers having a polymerizable reactive group to a polycondensation reaction such as emulsion polymerization, suspension polymerization, or urethanization. If necessary, a monomer having no polymerizable reactive group may be added as a copolymerization component.

  Specific examples of the monomer having such a functional group include allyl methacrylate, allyl acrylate, vinyl methacrylate, vinyl acrylate, glycidyl methacrylate, glycidyl acrylate, 2-isocyanate ethyl methacrylate, 2-isocyanate ethyl acrylate, 2-aminoethyl methacrylate, 2 -Aminoethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, acrylic acid, methacrylic acid, maleic anhydride, bifunctional acrylate, bifunctional methacrylate and the like can be mentioned, but not limited thereto.

  Examples of the polymer reaction used when the polymerization-reactive functional group is introduced after the polymerization include a polymer reaction described in International Publication No. 96-034316 pamphlet.

  The polymer fine particles having a polymerizable reactive group may be combined with each other by heat. Further, it is particularly preferable that the surface is hydrophilic and is dispersed in water. In order to make the surface of the polymer fine particles hydrophilic, a hydrophilic polymer or oligomer such as polyvinyl alcohol or polyethylene glycol, or a hydrophilic low molecular weight compound may be adsorbed on the surface of the polymer fine particles, but the method is limited to these. It is not something. The average particle diameter of the polymer fine particles is preferably 0.01 to 10 μm, more preferably 0.05 to 2 μm, and most preferably 0.1 to 1 μm. If the average particle size is too large, the resolution will be poor, and if it is too small, the stability over time will be poor.

  Further, the form of the polymer fine particle having a polymerizable reactive group may be a microcapsule or a microgel encapsulating a compound having a polymerizable reactive group without forming a covalent bond with the compound having a polymerizable reactive group. .

  That is, in the present invention, several modes can be used as a method for incorporating the above-mentioned image recording layer constituent components (A) to (C) and other constituent components described later into the image recording layer. One is a molecular dispersion type image recording layer in which the constituent components are dissolved and applied in an appropriate solvent as described in, for example, JP-A-2002-287334. In another embodiment, as described in, for example, JP-A-2001-277740 and JP-A-2001-277742, all or part of the constituent components are encapsulated in microcapsules and contained in the image recording layer. It is a capsule type image recording layer. further. In the microcapsule type image recording layer, the constituent component may be contained outside the microcapsule. Here, it is preferable that the microcapsule-type image recording layer includes a hydrophobic constituent component in the microcapsule and a hydrophilic constituent component outside the microcapsule. In order to obtain better on-press developability, the image recording layer is preferably a microcapsule type image recording layer.

  The microcapsule or microgel in the form of polymer fine particles having a polymerizable reactive group used in the present invention contains a compound having a polymerizable reactive group. As the compound having a polymerizable reactive group, the compounds described in the above-mentioned (C) polymerizable compound can be used without limitation.

  A known method can be applied as a method for microencapsulating the constituent components of the image recording layer. For example, as a method for producing microcapsules, a method using coacervation found in U.S. Pat. Nos. 2,800,547 and 2,800,498, U.S. Pat. No. 3,287,154, JP-B-38-19574, 42-446 by the interfacial polymerization method, US Pat. No. 3,418,250, US Pat. No. 3,660,304 by polymer precipitation method, US Pat. No. 3,796,669, isocyanate polyol A method using a wall material, a method using an isocyanate wall material found in US Pat. No. 3,914,511, and a urea-formaldehyde system found in US Pat. Nos. 4,001,140, 4,087,376 and 4,089,802. Or urea formaldehyde-resorcino A method using a wall forming material, a method using a wall material such as melamine-formaldehyde resin and hydroxycellulose, as shown in US Pat. No. 4,025,445, and Japanese Patent Publication Nos. 36-9163 and 51-9079. In situ method using monomer polymerization, spray drying method found in British Patent No. 930422, US Pat. No. 3,111,407, electrolytic dispersion cooling method seen in British Patent Nos. 952807 and 967074, etc. However, it is not limited to these.

  A preferable microcapsule wall used in the present invention has a three-dimensional cross-linking and has a property of swelling with a solvent. From such a viewpoint, the wall material of the microcapsule is preferably polyurea, polyurethane, polyester, polycarbonate, polyamide, and a mixture thereof, and particularly preferably polyurea and polyurethane. Further, the compound having a polymerizable reactive group may be introduced into the microcapsule wall.

The average particle diameter of the microcapsules is preferably 0.01 to 10 μm, more preferably 0.05 to 2 μm, and particularly preferably 0.1 to 1 μm. If the average particle size is too large, the resolution will be poor, and if it is too small, the stability over time will be poor.
Such microcapsules may be combined with each other by heat or may not be combined.

<Binder polymer>
In the image recording layer of the present invention, a binder polymer can be used in order to improve the film forming property of the image recording layer. Conventionally known binder polymers can be used without limitation, and polymers having film properties are preferred. Examples of such binder polymers include acrylic resins, polyvinyl acetal resins, polyurethane resins, polyurea resins, polyimide resins, polyamide resins, epoxy resins, methacrylic resins, polystyrene resins, novolac phenolic resins, polyester resins, and synthetic rubbers. And natural rubber.
The binder polymer may have crosslinkability in order to improve the film strength of the image area. In order to impart crosslinkability to the binder polymer, a crosslinkable functional group such as an ethylenically unsaturated bond may be introduced into the main chain or side chain of the polymer. The crosslinkable functional group may be introduced by copolymerization.
Examples of the polymer having an ethylenically unsaturated bond in the main chain of the molecule include poly-1,4-butadiene and poly-1,4-isoprene.
An example of a polymer having an ethylenically unsaturated bond in the side chain of the molecule is an ester or amide polymer of acrylic acid or methacrylic acid, wherein the ester or amide residue (-COOR or CONHR R) is ethylene. Examples thereof include polymers having a polymerizable unsaturated bond.

Examples of the residue (the R) having an ethylenically unsaturated _{bond, - (CH 2) n CR} 1 = CR 2 R 3, - (CH 2 O) n CH 2 CR 1 = CR 2 R 3, - _{(CH 2 CH 2 O) n} CH 2 CR 1 = CR 2 R 3, - (CH 2) n NH-CO-O-CH 2 CR 1 = CR 2 R 3, - (CH 2) n -O-CO —CR ¹ ═CR ² R ³ and (CH ₂ CH ₂ O) ₂ —X (wherein R ^{1 to} R ³ are each a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkoxy group) R ¹ and R ² or R ³ may be bonded to each other to form a ring, n represents an integer of 1 to 10. X is a dicyclopentadienyl residue. Represents a group).
Specific examples of the ester _{residue, -CH 2 CH = CH 2,} ( described in JP Kokoku _{7-21633.) - CH 2 CH 2} O-CH 2 CH = CH 2, -CH 2 C _{(CH 3) = CH 2,} -CH 2 CH = CH-C 6 H 5, -CH 2 CH 2 OCOCH = CH-C 6 H 5, -CH 2 CH 2 -NHCOO-CH 2 CH = CH 2 and CH ₂ CH ₂ O—X (wherein X represents a dicyclopentadienyl residue).
Specific examples of the amide residue include —CH ₂ CH═CH ₂ , —CH ₂ CH ₂ —Y (wherein Y represents a cyclohexene residue), —CH ₂ CH ₂ —OCO—CH═CH _2. Is mentioned.

  In the case of a binder polymer having crosslinkability, for example, free radicals (polymerization initiation radicals or growth radicals in the polymerization process of a polymerizable compound) are added to the crosslinkable functional group, and a polymerization chain of a polymerizable compound is formed directly between polymers. Through addition polymerization, a cross-link is formed between the polymer molecules and cured. Alternatively, atoms in the polymer (eg, hydrogen atoms on carbon atoms adjacent to the functional bridging group) are abstracted by free radicals to form polymer radicals that are bonded to each other so that crosslinking between the polymer molecules occurs. Forms and cures.

  The content of the crosslinkable group in the binder polymer (content of unsaturated double bond capable of radical polymerization by iodine titration) is preferably 0.1 to 10.0 mmol, more preferably 1.0, per 1 g of the binder polymer. -7.0 mmol, most preferably 2.0-5.5 mmol. Within this range, good sensitivity and good storage stability can be obtained.

  Further, from the viewpoint of improving the on-press developability of the image recording layer unexposed portion, the binder polymer preferably has high solubility or dispersibility in ink and / or fountain solution. In order to improve the solubility or dispersibility in ink, the binder polymer is preferably lipophilic, and in order to improve the solubility or dispersibility in dampening water, the binder polymer is hydrophilic. Is preferred. For this reason, in the present invention, it is also effective to use a lipophilic binder polymer and a hydrophilic binder polymer in combination.

  Examples of the hydrophilic binder polymer include hydroxyl group, carboxyl group, carboxylate group, hydroxyethyl group, polyoxyethyl group, hydroxypropyl group, polyoxypropyl group, amino group, aminoethyl group, aminopropyl group, and ammonium. Preferred are those having a hydrophilic group such as a group, an amide group, a carboxymethyl group, a sulfonic acid group, and a phosphoric acid group.

  Specific examples include gum arabic, casein, gelatin, starch derivatives, carboxymethylcellulose and its sodium salt, cellulose acetate, sodium alginate, vinyl acetate-maleic acid copolymers, styrene-maleic acid copolymers, polyacrylic acids and their salts, Polymethacrylic acids and their salts, homopolymers and copolymers of hydroxyethyl methacrylate, homopolymers and copolymers of hydroxyethyl acrylate, homopolymers and copolymers of hydroxypropyl methacrylate, homopolymers and copolymers of hydroxypropyl acrylate, homopolymers of hydroxybutyl methacrylate Polymers and copolymers, homopolymers and copolymers of hydroxybutyl acrylate Polyethylene glycols, hydroxypropylene polymers, polyvinyl alcohols, hydrolyzed polyvinyl acetate, polyvinyl formal, polyvinyl butyral, polyvinyl pyrrolidone, acrylamide homopolymers and copolymers having a hydrolysis degree of 60 mol% or more, preferably 80 mol% or more , Homopolymers and polymers of methacrylamide, homopolymers and copolymers of N-methylolacrylamide, polyvinylpyrrolidone, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. Is mentioned.

  The binder polymer preferably has a mass average molar mass of 5000 or more, more preferably 10,000 to 300,000, and a number average molar mass of 1000 or more, preferably 2000 to 250,000. Is more preferable. The polydispersity (mass average molar mass / number average molar mass) is preferably 1.1 to 10.

The binder polymer can be synthesized by a conventionally known method. Examples of the solvent used in the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy. Examples include 2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, and water. These may be used alone or in combination of two or more.
As the radical polymerization initiator used when synthesizing the binder polymer, known compounds such as an azo initiator and a peroxide initiator can be used.

The content of the binder polymer is 5 to 90% by mass, preferably 5 to 80% by mass, and more preferably 10 to 70% by mass with respect to the total solid content of the image recording layer. Within this range, good image area strength and image formability can be obtained.
Further, (C) the polymerizable compound and the binder polymer are preferably used in a mass ratio of 0.5 / 1 to 4/1.

<Surfactant>
In the present invention, it is preferable to use a surfactant in the image recording layer in order to promote on-press developability at the start of printing and to improve the coated surface state. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and fluorosurfactants. Surfactant may be used independently and may be used in combination of 2 or more type.

  The nonionic surfactant used for this invention is not specifically limited, A conventionally well-known thing can be used. For example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol Fatty acid partial esters, propylene glycol mono fatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, Polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N N- bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid ester, trialkylamine oxide, polyethylene glycol, copolymers of polyethylene glycol and polypropylene glycol.

  The anionic surfactant used in the present invention is not particularly limited, and conventionally known anionic surfactants can be used. For example, fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinate esters, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl phenoxy poly Oxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium salt, N-alkyl sulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated beef oil, fatty acid alkyl esters Sulfates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alcohol Ruphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, styrene / maleic anhydride Examples thereof include partial saponification products of polymers, partial saponification products of olefin / maleic anhydride copolymers, and naphthalene sulfonate formalin condensates.

The cationic surfactant used in the present invention is not particularly limited, and conventionally known cationic surfactants can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.
The amphoteric surfactant used in the present invention is not particularly limited, and conventionally known amphoteric surfactants can be used. Examples thereof include carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfuric esters, and imidazolines.

  Of the above surfactants, the term “polyoxyethylene” can be read as “polyoxyalkylene” such as polyoxymethylene, polyoxypropylene, polyoxybutylene, etc. These surfactants can also be used.

  More preferable surfactants include fluorine-based surfactants containing a perfluoroalkyl group in the molecule. Examples of such fluorosurfactants include anionic types such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and perfluoroalkyl phosphates; amphoteric types such as perfluoroalkyl betaines; Cation type such as trimethylammonium salt; perfluoroalkylamine oxide, perfluoroalkylethylene oxide adduct, oligomer containing perfluoroalkyl group and hydrophilic group, oligomer containing perfluoroalkyl group and lipophilic group, perfluoroalkyl Nonionic types such as an oligomer containing a group, a hydrophilic group and a lipophilic group, and a urethane containing a perfluoroalkyl group and a lipophilic group. Moreover, the fluorine-type surfactant described in each gazette of Unexamined-Japanese-Patent No. 62-170950, 62-226143, and 60-168144 is also mentioned suitably.

Surfactant can be used individually or in combination of 2 or more types.
The content of the surfactant is preferably 0.001 to 10% by mass and more preferably 0.01 to 5% by mass with respect to the total solid content of the image recording layer.

<Colorant>
In the present invention, various compounds other than these may be added as necessary. For example, a dye having a large absorption in the visible light region can be used as an image colorant. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (orientated chemistry) Kogyo Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI145170B), Malachite Green (CI42000), Methylene Blue (CI522015), etc., and JP-A-62-2 And dyes described in No. 293247. Also, pigments such as phthalocyanine pigments, azo pigments, carbon black, titanium oxide, etc. can be suitably used.
These colorants are preferably added since it is easy to distinguish an image area from a non-image area after image formation. The addition amount is 0.01 to 10% by mass with respect to the total solid content of the image recording material.

<Bakeout agent>
In the image recording layer of the present invention, a compound that changes color by an acid or a radical can be added to produce a printout image. As such a compound, for example, various dyes such as diphenylmethane, triphenylmethane, thiazine, oxazine, xanthene, anthraquinone, iminoquinone, azo, and azomethine are effectively used.

  Specific examples include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose bengal, methanyl yellow, thymol sulfophthalein, xylenol blue, methyl orange, paramethyl red, Congo Fred, Benzopurpurin 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuchsin, Victoria Pure Blue BOH [manufactured by Hodogaya Chemical Co., Ltd.], Oil Blue # 603 [Orient Chemical Industry Co., Ltd.], Oil Pink # 312 [Made by Orient Chemical Co., Ltd.], Oil Red 5B [Made by Orient Chemical Co., Ltd.], Oil Scarlet # 308 [Orient Gaku Kogyo Co., Ltd.], Oil Red OG [Orient Chemical Co., Ltd.], Oil Red RR [Orient Chemical Co., Ltd.], Oil Green # 502 [Orient Chemical Co., Ltd.], Spiron Red BEH Special [made by Hodogaya Chemical Co., Ltd.], m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p- Diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-pN, N-bis (hydroxyethyl) amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, 1-β-naphthyl-4- - dyes and p of diethylamino phenyl imino-5-pyrazolone, p ', p "- hexamethyl triamnotriphenylmethane (leuco crystal violet), and a leuco dye such as Pergascript Blue SRB (manufactured by Ciba-Geigy).

  In addition to the above, a leuco dye known as a material for thermal paper or pressure-sensitive paper is also suitable. Specific examples include crystal violet lactone, malachite green lactone, benzoylleucomethylene blue, 2- (N-phenyl-N-methylamino) -6- (Np-tolyl-N-ethyl) amino-fluorane, 2-anilino. -3-methyl-6- (N-ethyl-p-toluidino) fluorane, 3,6-dimethoxyfluorane, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) ) -Fluorane, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluorane, 3- (N, N-diethylamino) -6-methyl-7-anilinofluorane, 3 -(N, N-diethylamino) -6-methyl-7-xylidinofluorane, 3- (N, N-diethylamino) -6-methyl-7-chloro Fluorane, 3- (N, N-diethylamino) -6-methoxy-7-aminofluorane, 3- (N, N-diethylamino) -7- (4-chloroanilino) fluorane, 3- (N, N-diethylamino) -7-chlorofluorane, 3- (N, N-diethylamino) -7-benzylaminofluorane, 3- (N, N-diethylamino) -7,8-benzofluorane, 3- (N, N-dibutyl) Amino) -6-methyl-7-anilinofluorane, 3- (N, N-dibutylamino) -6-methyl-7-xylidinofluorane, 3-piperidino-6-methyl-7-anilinofluorane 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3,3-bis (1-n-butyl- -Methylindol-3-yl) phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl- 2-methylindol-3-yl) -4-zaphthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, and the like.

  A suitable addition amount of the dye that changes color by an acid or a radical is 0.01 to 10% by mass with respect to the solid content of the image recording layer.

<Polymerization inhibitor>
In order to prevent unnecessary thermal polymerization of the (C) radical polymerizable compound during production or storage of the image recording layer, it is preferable to add a small amount of a thermal polymerization inhibitor to the image recording layer of the present invention.
Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t- (Butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt are preferred. The addition amount of the thermal polymerization inhibitor is preferably about 0.01 to about 5% by mass with respect to the total solid content of the image recording layer.

<Higher fatty acid derivatives, etc.>
In order to prevent polymerization inhibition by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide is added to the image recording layer of the present invention, and the surface of the image recording layer is dried during the coating process. It may be unevenly distributed. The amount of the higher fatty acid derivative added is preferably about 0.1 to about 10% by mass with respect to the total solid content of the image recording layer.

<Plasticizer>
The image recording layer of the present invention may contain a plasticizer in order to improve the on-press developability.
Examples of the plasticizer include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octyl capryl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diallyl phthalate; Glycol esters such as glycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, triethylene glycol dicaprylate; Phosphate esters such as tricresyl phosphate and triphenyl phosphate Diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dioct Ruazereto, aliphatic dibasic acid esters such as dibutyl maleate; polyglycidyl methacrylate, triethyl citrate, glycerin triacetyl ester, butyl laurate in.
The plasticizer content is preferably about 30% by mass or less based on the total solid content of the image recording layer.

<Inorganic fine particles>
The image recording layer of the present invention may contain inorganic fine particles for the purpose of improving the strength of the cured film in the image area and improving the on-press developability of the non-image area.
As the inorganic fine particles, for example, silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate or a mixture thereof can be preferably mentioned. Even if they are not photothermally convertible, they can be used for strengthening the film, enhancing interfacial adhesion by surface roughening, and the like.
The inorganic fine particles preferably have an average particle size of 5 nm to 10 μm, and more preferably 0.5 μm to 3 μm. Within the above range, it is possible to form a non-image portion having excellent hydrophilicity, which is stably dispersed in the image recording layer, sufficiently retains the film strength of the image recording layer, and hardly causes stains during printing.
The inorganic fine particles as described above can be easily obtained as a commercial product such as a colloidal silica dispersion.
The content of the inorganic fine particles is preferably 40% by mass or less, and more preferably 30% by mass or less, based on the total solid content of the image recording layer.

<Low molecular hydrophilic compound>
The image recording layer of the present invention may contain a hydrophilic low molecular weight compound for improving on-press developability. Examples of hydrophilic low molecular weight compounds include water-soluble organic compounds such as glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol, and ether or ester derivatives thereof, glycerin, Polyhydroxys such as pentaerythritol, organic amines such as triethanolamine and diethanolamine monoethanolamine and salts thereof, organic sulfonic acids such as toluenesulfonic acid and benzenesulfonic acid and salts thereof, organic phosphonic acids such as phenylphosphonic acid and the like Examples thereof include organic carboxylic acids such as salts thereof, tartaric acid, oxalic acid, citric acid, malic acid, lactic acid, gluconic acid and amino acids, and salts thereof.

<Formation of image recording layer>
The image recording layer of the present invention is applied by preparing a coating solution by dispersing or dissolving the necessary components described above in a solvent. Solvents used here include ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxy Examples include ethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, γ-butyllactone, toluene, water, and the like. However, the present invention is not limited to this. These solvents are used alone or in combination. The solid content concentration of the coating solution is preferably 1 to 50% by mass.
The image recording layer of the present invention can be formed by preparing a plurality of coating solutions in which the same or different components are dispersed or dissolved in the same or different solvents, and repeatedly applying and drying a plurality of times.

Further, the coating amount (solid content) of the image recording layer on the support obtained after coating and drying varies depending on the use, but generally 0.3 to 3.0 g / m ² is preferable. Within this range, good sensitivity and good film properties of the image recording layer can be obtained.
Various methods can be used as a coating method. Examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.

(Undercoat layer)
The undercoat layer contributes to improving stain resistance and achieving both on-press developability / press life / stain resistance. Although the well-known undercoat layer compound can be used for the undercoat layer of the present invention, it preferably contains a polymer having the following substrate adsorptive group, polymerizable group, and hydrophilic group.

<Polymer having substrate adsorptive group, polymerizable group, and hydrophilic group>
As the polymer having a substrate adsorptive group, a polymerizable group, and a hydrophilic group, a monomer having an adsorptive group, a monomer having a hydrophilic group, and a monomer having a polymerizable reactive group (crosslinkable group) were copolymerized. A polymer resin can be mentioned.

One of the essential components of the polymer resin is an adsorptive group to the substrate (hydrophilic support surface). The presence or absence of adsorptivity on the surface of the hydrophilic support can be determined by the following method, for example.
A coating night is prepared by dissolving the test compound in a readily soluble solvent, and the coating night is coated and dried on the support so that the coating amount after drying is 30 mg / m ² . Next, the support on which the test compound is applied is sufficiently washed with an easily soluble solvent, and then the residual amount of the test compound that has not been removed by washing is measured to calculate the amount of adsorption of the support. Here, the measurement of the remaining amount may be performed by directly quantifying the amount of the remaining compound or by quantifying the amount of the test compound dissolved in the cleaning liquid. The compound can be quantified by, for example, fluorescent X-ray measurement, reflection spectral absorbance measurement, liquid chromatography measurement and the like. The compound having support adsorptivity is a compound that remains at 1 mg / m ² or more even after the above-described washing treatment.

The adsorptive group on the surface of the hydrophilic support is a substance (for example, metal, metal oxide) or a functional group (for example, hydroxyl group) existing on the surface of the hydrophilic support and a chemical bond (for example, ionic bond, hydrogen). Bond, coordination bond, bond by intermolecular force). The adsorptive group is preferably an acid group or a cationic group.
Specific examples of the acid group and the cationic group are the same as the specific examples of the acid group and the cationic group described in the section of the metal adsorbing group of the chelating agent.

  Particularly preferred examples of the monomer having an adsorptive group include compounds represented by the following formula (U1) or (U2).

In the above formula, R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms. R ¹ , R ² and R ³ are each independently preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. More preferred is a hydrogen atom or methyl. R ² and R ³ are particularly preferably a hydrogen atom. Z is a functional group that adsorbs to the surface of the hydrophilic support.

In the formula (U1), X is an oxygen atom (—O—) or imino (—NH—). X is more preferably an oxygen atom.
In the formula (U1), L is a divalent linking group. L is a divalent aliphatic group (alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group), divalent aromatic group (arylene group, substituted arylene group) or divalent Or an oxygen atom (—O—), a sulfur atom (—S—), an imino (—NH—), a substituted imino (—NR—, R is an aliphatic group or an aromatic group. Or a combination with a heterocyclic group) or carbonyl (—CO—).

  The aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms in the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and most preferably 1 to 10. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.

The number of carbon atoms in the aromatic group is preferably 6 to 20, more preferably 6 to 15, and most preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.
The heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle. The hetero ring may be condensed with other hetero ring, aliphatic ring or aromatic ring. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, oxo (═O), thio (═S), imino (═NH), substituted imino group (═N—R, R is an aliphatic group, aromatic group or hetero group. Ring group), aliphatic group, aromatic group and heterocyclic group.

L is preferably a divalent linking group containing a plurality of polyoxyalkylene structures. The polyoxyalkylene structure is more preferably a polyoxyethylene structure. In other words, L preferably contains — (OCH ₂ CH ₂ ) n— (n is an integer of 2 or more).
In the formula (U2), Y is a carbon atom or a nitrogen atom. When Y is a nitrogen atom and L is connected to Y to form a quaternary pyridinium group, Z is not essential because it exhibits adsorptivity itself, and Z = H may be used. L represents the same divalent linking group or single bond as in formula (U1).

The adsorptive functional group is as described above.
Examples of typical compounds represented by formula (U1) or (U2) are shown below.

  Examples of the hydrophilic group of the undercoat polymer resin that can be used in the present invention include a hydroxyl group, a carboxyl group, a carboxylate group, a hydroxyethyl group, a polyoxyethyl group, a hydroxypropyl group, a polyoxypropyl group, and an amino group. Preferred examples include a group, an aminoethyl group, an aminopropyl group, an ammonium group, an amide group, a carboxymethyl group, a sulfonic acid group, and a phosphoric acid group. Of these, sulfonic acid groups exhibiting high hydrophilicity are preferred. Specific examples of the monomer having a sulfonic acid group include methallyloxybenzene sulfonic acid, allyloxybenzene sulfonic acid, aryl sulfonic acid, vinyl sulfonic acid, p-styrene sulfonic acid, methallyl sulfonic acid, and acrylamide t-butyl sulfonic acid. Examples include 2-acrylamido-2-methylpropanesulfonic acid, sodium salt of (3-acryloyloxypropyl) butylsulfonic acid, and amine salt. Of these, 2-acrylamido-2-methylpropanesulfonic acid sodium salt is preferred in view of hydrophilic performance and handling of synthesis.

  The water-soluble polymer resin for the undercoat layer of the present invention preferably has a polymerizable reactive group. Improvement of adhesion with the image area is obtained by the polymerizable reactive group. In order to make the polymer resin for the undercoat layer crosslinkable, a crosslinkable functional group such as an ethylenically unsaturated bond is introduced into the side chain of the polymer, or the polar substituent of the polymer resin is countercharged. Or a compound having an ethylenically unsaturated bond may be introduced by forming a salt structure.

  Examples of monomers for introducing an ethylenically unsaturated bond into the side chain of the molecule are acrylic acid or methacrylic acid ester or amide monomers, the ester or amide residue (-COOR or CONHR R ) May have a monomer having an ethylenically unsaturated bond.

Examples of the residue (the R) having an ethylenically unsaturated _{bond, - (CH 2) n CR} 1 = CR 2 R 3, - (CH 2 O) n CH 2 CR 1 = CR 2 R 3, - _{(CH 2 CH 2 O) n} CH 2 CR 1 = CR 2 R 3, - (CH 2) n NH-CO-O-CH 2 CR 1 = CR 2 R 3, - (CH 2) n -O-CO —CR ₁ ═CR ₂ R ₃ and (CH ₂ CH ₂ O) ₂ —X (wherein R _{1 to} R ₃ are each a hydrogen atom, a halogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, Represents an alkoxy group or an aryloxy group, and R ₁ and R ₂ or R ₃ may combine with each other to form a ring, n represents an integer of 1 to 10. X represents dicyclopentadienyl. Represents a residue).
Specific examples of the ester _{residue, -CH 2 CH = CH 2,} ( described in JP Kokoku _{7-21633.) - CH 2 CH 2} O-CH 2 CH = CH 2, -CH 2 C (CH ₃ ) ═CH ₂ , —CH ₂ CH═CH—C ₆ H ₅ , —CH ₂ CH ₂ OCOCH═CH—C ₆ H ₅ , —CH ₂ CH ₂ NHCOO—CH ₂ CH═CH ₂ , and CH ₂ CH ₂ O—X (wherein X represents a dicyclopentadienyl residue).
Specific examples of the amide residue include —CH ₂ CH═CH ₂ , —CH ₂ CH ₂ O—Y (wherein Y represents a cyclohexene residue), —CH ₂ CH ₂ OCO—CH═CH _2. Is mentioned.

  The content of the polymerizable reactive group in the polymer resin for the undercoat layer (content of unsaturated double bond capable of radical polymerization by iodine titration) is preferably 0.1 to 10.0 mmol per 1 g of the polymer resin. More preferably, it is 1.0-7.0 mmol, Most preferably, it is 2.0-5.5 mmol. Within this range, both good sensitivity and dirtiness and good storage stability can be obtained.

The polymer resin for the undercoat layer preferably has a mass average molar mass of 5000 or more, more preferably 10,000 to 300,000, and a number average molar mass of 1000 or more is preferable. More preferably, it is ˜250,000. The polydispersity (mass average molar mass / number average molar mass) is preferably 1.1 to 10.
The polymer resin for the undercoat layer may be any of a random polymer, a block polymer, a graft polymer, and the like, but is preferably a random polymer.
The undercoat polymer resin may be used alone or in combination of two or more.

  The undercoat layer of the present invention can contain a secondary or tertiary amine. By these amines, stains (pot-like stains) due to point-like residual films that are likely to occur on a lithographic printing plate precursor after storage are suppressed. Preferable secondary or tertiary amines include the following compounds.

  In the present invention, two or more of these amines may be contained in the undercoat layer. The amount of amine added to the undercoat layer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and most preferably 30 to 70% by mass of the constituent components of the undercoat layer.

  The undercoat layer of the present invention may contain the aforementioned chelating agent for enhancing the dirt performance. A chelating agent may be used independently or may be used in mixture of 2 or more types. The content of the chelating agent is preferably 10 to 90% by mass, more preferably 10 to 80% by mass, and most preferably 30 to 70% by mass based on the total solid mass of the undercoat layer.

The undercoat layer coating solution is obtained by dissolving the above-described undercoat polymer resin and other necessary components in an organic solvent (eg, methanol, ethanol, acetone, methyl ethyl ketone, etc.) and / or water. The undercoat layer coating solution may contain an infrared absorber.
Various known methods can be used as a method of applying the undercoat layer coating solution to the support. Examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.
The coating amount (solid content) of the undercoat layer is preferably from 0.1-100 mg / m ^2, and more preferably 1 to 50 mg / m ^2.

[Protective layer]
In the lithographic printing plate precursor according to the present invention, a protective layer is provided on the image recording layer as necessary in order to prevent the occurrence of scratches in the image recording layer, to block oxygen, and to prevent ablation during high-illuminance laser exposure. Can do.
In the present invention, exposure is usually carried out in the atmosphere, but the protective layer is an image of low molecular weight compounds such as oxygen and basic substances present in the atmosphere that inhibit the image forming reaction caused by exposure in the image recording layer. This prevents the recording layer from being mixed, and prevents the image formation reaction from being hindered by exposure in the air. Therefore, the properties desired for the protective layer are low permeability of low-molecular compounds such as oxygen, furthermore, good transparency of light used for exposure, excellent adhesion with the image recording layer, and It is preferable that it can be easily removed in an on-press development process after exposure.
Various studies have been made on the protective layer having such characteristics, and are described in detail, for example, in US Pat. No. 3,458,311 and JP-B-55-49729.

  Examples of the material used for the protective layer include water-soluble polymer compounds that are relatively excellent in crystallinity. Specific examples include water-soluble polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, acidic celluloses, gelatin, gum arabic, and polyacrylic acid. Among these, when polyvinyl alcohol (PVA) is used as a main component, the best results are obtained for basic characteristics such as oxygen barrier properties and development removability. The polyvinyl alcohol may be partially substituted with an ester, ether or acetal as long as it contains an unsubstituted vinyl alcohol unit for providing the oxygen barrier property and water solubility necessary for the protective layer, and a part of the other You may have a copolymerization component.

  As specific examples of polyvinyl alcohol, those having a hydrolysis degree of 71 to 100 mol% and a polymerization degree of 300 to 2400 are preferably mentioned. Specifically, for example, PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA manufactured by Kuraray Co., Ltd. -HC, PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405 , PVA-420, PVA-613, and L-8.

The components of the protective layer (selection of PVA, use of additives, etc.), coating amount, etc. are appropriately selected in consideration of fogging properties, adhesion, scratch resistance, etc. in addition to oxygen barrier properties and development removability. In general, the higher the hydrolysis rate of PVA (that is, the higher the content of the unsubstituted vinyl alcohol unit in the protective layer), the higher the film thickness, the higher the oxygen barrier property, which is preferable in terms of sensitivity. . Further, in order to prevent unnecessary polymerization reaction during production and storage, unnecessary fogging during image exposure, image line thickening, and the like, it is preferable that the oxygen barrier property is not too high. Accordingly, the oxygen permeability A at 25 ° C. and 1 atm is preferably 0.2 ≦ A ≦ 20 (ml / m ² · day).

  As a preferred embodiment of the protective layer of the present invention, a protective layer containing an inorganic layered compound described in JP-A No. 11-38633 can be exemplified. Good oxygen barrier properties can be obtained by combining the inorganic layered compound and the binder. The inorganic layered compound used in the present invention is a particle having a thin planographic shape, for example,

General formula A (B, C) _2-5 D ₄ O ₁₀ (OH, F, O) ₂

[However, A is any of K, Na, and Ca, B and C are any of Fe (II), Fe (III), Mn, Al, Mg, and V, and D is Si or Al. And mica groups such as natural mica and synthetic mica, talc, teniolite, montmorillonite, saponite, hectorite, zirconium phosphate and the like represented by the formula 3MgO.4SiO.H ₂ O.

In the mica group, examples of natural mica include muscovite, soda mica, phlogopite, biotite and sericite. Synthetic mica includes non-swellable mica such as fluorine phlogopite mica ₃ (AlSi ₃ O ₁₀ ) F ₂ , potassium tetrasilicon mica KMg _2.5 Si ₄ O ₁₀ ) F ₂ , and Na tetrasilicic mica NaMg _2.5 ( Si ₄ O ₁₀ ) F ₂ , Na or Li teniolite (Na, Li) Mg ₂ Li (Si ₄ O ₁₀ ) F ₂ , montmorillonite-based Na or Li hectorite (Na, Li) _1/8 Mg _2/5 Li Examples thereof include swelling mica such as _1/8 (Si ₄ O ₁₀ ) F ₂ . Synthetic smectites are also useful.

  In the present invention, among the inorganic layered compounds, fluorine-based swellable mica, which is a synthetic inorganic layered compound, is particularly useful.

  As the shape of the inorganic layered compound used in the present invention, from the viewpoint of diffusion control, the smaller the thickness, the better. The plane size is as long as it does not hinder the smoothness of the coated surface or the transmittance of actinic rays. Larger is better. Accordingly, the aspect ratio is 20 or more, preferably 100 or more, particularly preferably 200 or more. The aspect ratio is the ratio of the thickness to the major axis of the particle, and can be measured, for example, from a projected view of the particle by a micrograph. The larger the aspect ratio, the greater the effect that can be obtained.

  As for the particle diameter of the inorganic stratiform compound used in the present invention, the average major axis is 0.3 to 20 μm, preferably 0.5 to 10 μm, particularly preferably 1 to 5 μm. The average thickness of the particles is 0.1 μm or less, preferably 0.05 μm or less, particularly preferably 0.01 μm or less. For example, among inorganic layered compounds, the size of the swellable synthetic mica that is a representative compound is about 1 to 50 nm in thickness and about 1 to 20 μm in surface size.

  When the inorganic layered compound particles having such a large aspect ratio are contained in the protective layer, the coating film strength is improved, and the permeation of oxygen and moisture can be effectively prevented. Prevent deterioration.

  The amount contained in the protective layer of the inorganic stratiform compound is preferably 5% by mass to 55% by mass, more preferably 10% by mass to 40% by mass with respect to the total solid content of the protective layer. When the content is 5% by mass or more, an effect on the adhesion resistance is recognized. Even when a plurality of types of inorganic layered compounds are used in combination, the total amount of these inorganic layered compounds is preferably the above-described mass%.

The inorganic stratiform compound used in the protective layer is dispersed, for example, as follows. First, 5 to 10 parts by mass of the swellable layered compound mentioned above as a preferred inorganic layered compound is added to 100 parts by mass of water, and the mixture is thoroughly swelled and swollen, and then dispersed by a disperser.
Examples of the disperser used here include various mills that disperse mechanically by applying a direct force, a high-speed stirring disperser having a large shearing force, and a disperser that provides high-intensity ultrasonic energy. Specifically, ball mill, sand grinder mill, visco mill, colloid mill, homogenizer, tisol bar, polytron, homomixer, homo blender, ketdy mill, jet agitator, capillary emulsifier, liquid siren, electrostrictive ultrasonic generator, An emulsifying device having a Paulman whistle can be used. A dispersion of 5 to 10% by mass of the inorganic stratiform compound dispersed by the above method is highly viscous or gelled and has very good storage stability. When preparing a protective layer coating solution using this dispersion, it is preferably prepared by diluting with water and stirring sufficiently, and then blending with a binder solution.

  As another composition of the protective layer, glycerin, dipropylene glycol and the like can be added in an amount corresponding to several mass% with respect to the water-soluble polymer compound, and flexibility can be imparted. Anionic surfactants such as sodium acid salts; amphoteric surfactants such as alkylaminocarboxylates and alkylaminodicarboxylates; nonionic surfactants such as polyoxyethylene alkylphenyl ethers to the (co) polymer Mass% can be added. The thickness of the protective layer is suitably from 0.1 to 5 μm, particularly preferably from 0.2 to 2 μm.

  In addition, adhesion to the image area, scratch resistance, and the like are extremely important in handling the lithographic printing plate precursor. That is, when a protective layer that is hydrophilic because it contains a water-soluble polymer compound is laminated on the image recording layer when the image recording layer is oleophilic, the protective layer is liable to peel off due to insufficient adhesion, and the peeling occurs. In some parts, defects such as poor film hardening due to inhibition of polymerization by oxygen may occur.

  On the other hand, various proposals have been made to improve the adhesion between the image recording layer and the protective layer. For example, in JP-A-49-70702, a hydrophilic polymer mainly composed of polyvinyl alcohol is mixed with 20 to 60% by mass of an acrylic emulsion, a water-insoluble vinylpyrrolidone-vinyl acetate copolymer, etc. It is described that sufficient adhesion can be obtained by laminating on a recording layer.

  The protective layer coating solution thus prepared is applied onto the image recording layer provided on the support and dried to form a protective layer. The coating solvent can be appropriately selected in relation to the binder, but when a water-soluble polymer is used, it is preferable to use distilled water or purified water. The method for applying the protective layer is not particularly limited, and a known method such as the method described in US Pat. No. 3,458,311 or Japanese Patent Publication No. 55-49729 can be applied. . Specific examples include a blade coating method, an air knife coating method, a gravure coating method, a roll coating coating method, a spray coating method, a dip coating method, and a bar coating method.

The coating amount of the protective layer, the coating amount after drying is preferably in the range of 0.01 to 10 g / m ^2, more preferably in the range of 0.02 to 3 g / m ^2, and most preferably 0. It is in the range of 02 to 1 g / m ² .

  Furthermore, other functions can be imparted to the protective layer. For example, by adding a colorant (for example, a water-soluble dye) that is excellent in the transparency of infrared rays used for exposure and that can efficiently absorb light of other wavelengths, safe light is not caused. Suitability can be improved.

[Support]
The support used for the lithographic printing plate precursor according to the invention is preferably a metal support. For example, a metal plate (eg, aluminum, zinc, copper, etc.), a paper or plastic film on which a metal is laminated or deposited (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate) Polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.). Among these, an aluminum plate that has good dimensional stability and is relatively inexpensive is preferable.

  The aluminum plate is a pure aluminum plate, an alloy plate containing aluminum as a main component and containing a trace amount of different elements, or a plastic laminated on a thin film of aluminum or an aluminum alloy. Examples of foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content of foreign elements in the alloy is preferably 10% by mass or less. In the present invention, a pure aluminum plate is preferable, but completely pure aluminum is difficult to manufacture in terms of refining technology, and therefore may contain a slightly different element. The composition of the aluminum plate is not specified, and a publicly known material can be used as appropriate.

  The thickness of the support is preferably from 0.1 to 0.6 mm, more preferably from 0.15 to 0.4 mm.

  Prior to using the aluminum plate, it is preferable to perform a surface treatment such as roughening treatment or anodizing treatment. By the surface treatment, it is easy to improve hydrophilicity and secure adhesion between the image recording layer and the support. Prior to the roughening treatment of the aluminum plate, a degreasing treatment with a surfactant, an organic solvent, an alkaline aqueous solution or the like for removing rolling oil on the surface is performed as desired.

The surface roughening treatment of the aluminum plate is performed by various methods. For example, mechanical surface roughening treatment, electrochemical surface roughening treatment (surface roughening treatment for dissolving the surface electrochemically), chemical treatment, etc. Surface roughening treatment (roughening treatment that chemically selectively dissolves the surface).
As a method for the mechanical surface roughening treatment, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, or a buff polishing method can be used. Also, a transfer method in which the uneven shape is transferred with a roll provided with unevenness in the aluminum rolling step may be used.
Examples of the electrochemical surface roughening treatment include a method in which an alternating current or a direct current is used in an electrolytic solution containing an acid such as hydrochloric acid or nitric acid. Another example is a method using a mixed acid as described in JP-A-54-63902.

  The surface-roughened aluminum plate is subjected to an alkali etching treatment using an aqueous solution of potassium hydroxide, sodium hydroxide or the like, if necessary, further neutralized, and if desired, wear resistant. In order to increase the anodic oxidation treatment.

As the electrolyte used for the anodizing treatment of the aluminum plate, various electrolytes that form a porous oxide film can be used. In general, sulfuric acid, hydrochloric acid, oxalic acid, chromic acid or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of electrolyte.
The conditions for anodizing treatment vary depending on the electrolyte used and cannot be specified in general. In general, however, the electrolyte concentration is 1 to 80% by mass solution, the liquid temperature is 5 to 70 ° C., and the current density is 5 to 60 A / day. dm ² , voltage 1 to 100 V, and electrolysis time 10 seconds to 5 minutes are preferable. The amount of the anodized film formed is preferably from 1.0 to 5.0 g / m ^2, and more preferably 1.5 to 4.0 g / m ^2. Within this range, good printing durability and good scratch resistance of the non-image area of the lithographic printing plate can be obtained.

  As the support used in the present invention, the substrate having the above-mentioned surface treatment and having an anodized film may be used as it is, but for further improvement in adhesion to the upper layer, hydrophilicity, resistance to contamination, heat insulation and the like. If necessary, an aqueous solution containing an anodized film micropore enlargement treatment, sealing treatment and a hydrophilic compound described in JP 2001-253181 A or JP 2001-322365 A The surface hydrophilization treatment to be immersed can be appropriately selected and performed. Of course, the enlargement process and the sealing process are not limited to those described above, and any conventionally known methods can be performed. For example, as the sealing treatment, in addition to the vapor sealing, a single treatment with fluorinated zirconic acid, a treatment with sodium fluoride, and a vapor sealing with addition of lithium chloride are possible.

  The sealing treatment used in the present invention is not particularly limited, and a conventionally known method can be used. Among them, sealing treatment with an aqueous solution containing an inorganic fluorine compound, sealing treatment with water vapor, and hot water. Sealing treatment is preferred. Each will be described below.

<1> Sealing treatment with an aqueous solution containing an inorganic fluorine compound As the inorganic fluorine compound used for the sealing treatment with an aqueous solution containing an inorganic fluorine compound, a metal fluoride is preferably exemplified.
Specifically, for example, sodium fluoride, potassium fluoride, calcium fluoride, magnesium fluoride, sodium fluoride zirconate, potassium fluoride zirconate, sodium fluoride titanate, potassium fluoride titanate, zircon fluoride Ammonium acid, ammonium fluoride titanate, potassium fluoride titanate, zirconate fluoride, titanate fluoride, hexafluorosilicic acid, nickel fluoride, iron fluoride, phosphor fluoride, ammonium fluoride phosphate It is done. Of these, sodium fluorinated zirconate, sodium fluorinated titanate, fluorinated zirconic acid, and fluorinated titanic acid are preferable.

  The concentration of the inorganic fluorine compound in the aqueous solution is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, from the viewpoint of sufficiently sealing the micropores of the anodized film. Further, in terms of stain resistance, it is preferably 1% by mass or less, and more preferably 0.5% by mass or less.

  It is preferable that the aqueous solution containing the inorganic fluorine compound further contains a phosphate compound. When the phosphate compound is contained, the hydrophilicity of the surface of the anodized film is improved, so that on-machine developability and stain resistance can be improved.

Suitable examples of the phosphate compound include phosphates of metals such as alkali metals and alkaline earth metals.
Specifically, for example, zinc phosphate, aluminum phosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, monoammonium phosphate, monopotassium phosphate, monosodium phosphate, dihydrogen phosphate Potassium, dipotassium hydrogen phosphate, calcium phosphate, sodium ammonium hydrogen phosphate, magnesium hydrogen phosphate, magnesium phosphate, ferrous phosphate, ferric phosphate, sodium dihydrogen phosphate, sodium phosphate, hydrogen phosphate Disodium, lead phosphate, diammonium phosphate, calcium dihydrogen phosphate, lithium phosphate, phosphotungstic acid, phosphotungstic acid, sodium phosphotungstate, ammonium phosphomolybdate, sodium phosphomolybdate, sodium phosphite , Tripolyphosphate Potassium, and sodium pyrophosphate. Of these, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, and dipotassium hydrogen phosphate are preferable.
The combination of the inorganic fluorine compound and the phosphate compound is not particularly limited, but the aqueous solution contains at least sodium zirconate fluoride as the inorganic fluorine compound and contains at least sodium dihydrogen phosphate as the phosphate compound. Is preferred.

  The concentration of the phosphate compound in the aqueous solution is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, from the viewpoint of improving on-press developability and stain resistance. Further, in terms of solubility, it is preferably 20% by mass or less, and more preferably 5% by mass or less.

The ratio of each compound in the aqueous solution is not particularly limited, but the mass ratio of the inorganic fluorine compound and the phosphate compound is preferably 1/200 to 10/1, and preferably 1/30 to 2/1. Is more preferable.
The temperature of the aqueous solution is preferably 20 ° C. or higher, more preferably 40 ° C. or higher, preferably 100 ° C. or lower, more preferably 80 ° C. or lower.
The aqueous solution preferably has a pH of 1 or more, more preferably has a pH of 2 or more, preferably has a pH of 11 or less, and more preferably has a pH of 5 or less.
The method for sealing with an aqueous solution containing an inorganic fluorine compound is not particularly limited, and examples thereof include an immersion method and a spray method. These may be used alone or in combination, or may be used in combination of two or more.
Of these, the dipping method is preferred. When the treatment is performed using the dipping method, the treatment time is preferably 1 second or longer, more preferably 3 seconds or longer, and preferably 100 seconds or shorter, and 20 seconds or shorter. More preferred.

<2> Sealing treatment with water vapor Sealing treatment with water vapor includes, for example, a method in which pressurized or normal pressure water vapor is brought into contact with the anodized film continuously or discontinuously.
The temperature of the water vapor is preferably 80 ° C. or higher, more preferably 95 ° C. or higher, and preferably 105 ° C. or lower.
The water vapor pressure is preferably in the range (1.008 × 10 ^{5 to} 1.043 × 10 ⁵ Pa) from (atmospheric pressure−50 mmAq) to (atmospheric pressure + 300 mmAq).
Further, the time for which the water vapor is contacted is preferably 1 second or longer, more preferably 3 seconds or longer, 100 seconds or shorter, more preferably 20 seconds or shorter.

<3> Sealing treatment with hot water Sealing treatment with water vapor includes, for example, a method in which an aluminum plate on which an anodized film is formed is immersed in hot water.
The hot water may contain an inorganic salt (for example, phosphate) or an organic salt.
The temperature of the hot water is preferably 80 ° C. or higher, more preferably 95 ° C. or higher, and preferably 100 ° C. or lower.
Further, the time of immersion in hot water is preferably 1 second or longer, more preferably 3 seconds or longer, more preferably 100 seconds or shorter, and even more preferably 20 seconds or shorter.

  The hydrophilization treatment is described in US Pat. Nos. 2,714,066, 3,181,461, 3,280,734 and 3,902,734. There are alkali metal silicate methods. In this method, the support is immersed in an aqueous solution such as sodium silicate or electrolytically treated. In addition, the treatment with potassium zirconate fluoride described in JP-B 36-22063, U.S. Pat. Nos. 3,276,868, 4,153,461 and 4,689, And a method of treating with polyvinylphosphonic acid as described in each specification of No.272.

  The support preferably has a center line average roughness of 0.10 to 1.2 μm. Within this range, good adhesion to the image recording layer, good printing durability and good stain resistance can be obtained.

[Back coat layer]
After the surface treatment is performed on the support or after the undercoat layer is formed, a backcoat layer can be provided on the back surface of the support, if necessary.
Examples of the back coat layer include hydrolysis and polycondensation of organic polymer compounds described in JP-A-5-45885, organic metal compounds or inorganic metal compounds described in JP-A-6-35174, and the like. Preferable examples include a coating layer made of a metal oxide. Of these, the use of silicon alkoxy compounds such as Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ ) ₄ , Si (OC ₄ H ₉ ) _4, etc. is inexpensive. It is preferable in that it is easily available.

[Lithographic printing method]
In the lithographic printing method using the lithographic printing plate precursor according to the invention, the lithographic printing plate precursor is imagewise exposed with an infrared laser. Although the infrared laser used for this invention is not specifically limited, The solid laser and semiconductor laser which radiate | emit infrared rays with a wavelength of 760-1200 nm are mentioned suitably. The output of the infrared laser is preferably 100 mW or more. In order to shorten the exposure time, it is preferable to use a multi-beam laser device. The exposure time per pixel is preferably within 20 microseconds. Moreover, it is preferable that irradiation energy amount is 10-300 mJ / cm < ² >.

  In the lithographic printing method of the present invention, the lithographic printing plate precursor is imagewise exposed with an infrared laser and then supplied with oil-based ink and an aqueous component for printing without any development process. Specifically, after exposing the lithographic printing plate precursor with an infrared laser, it is mounted on a printing machine without passing through a development process, and after printing the lithographic printing plate precursor on the printing machine, Examples of the method include printing with exposure using an infrared laser.

  After the lithographic printing plate precursor is imagewise exposed with an infrared laser, the aqueous component and the oil-based ink are supplied and printed without going through a development processing step such as a wet development processing step. In this case, in the exposed portion of the image recording layer, the image recording layer cured by exposure forms an oil-based ink receiving portion having a lipophilic surface. On the other hand, in the unexposed portion, the uncured image recording layer is dissolved or dispersed and removed by the supplied aqueous component and / or oil-based ink, and a hydrophilic surface is exposed at the portion. As a result, the aqueous component adheres to the exposed hydrophilic surface, and the oil-based ink is deposited on the image recording layer in the exposed area, and printing is started. In the case of an untreated lithographic printing plate precursor, the unexposed area is a hydrophilic surface, and the exposed area is converted to an oleophilic surface. Therefore, when an aqueous component and / or oil-based ink is supplied, the unexposed area is water-soluble. The component adheres, and the oil-based ink selectively adheres to the exposed portion, and printing can be performed as it is. Here, an aqueous component or oil-based ink may be supplied first to the plate surface, but in the on-press development type lithographic printing plate precursor of the present invention, the aqueous component is contaminated by the image recording layer in the unexposed area. In order to prevent this, it is preferable to supply oil-based ink first. As the aqueous component and oil-based ink, fountain solution and printing ink for ordinary lithographic printing are used. In this way, the lithographic printing plate precursor is subjected to on-press development on an offset printing machine and used as it is for printing a large number of sheets.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

[Examples 1 to 29 and Comparative Example 1]
1. Production of lithographic printing plate precursors (1) to (29) and (R1)

(1) Preparation of support In order to remove rolling oil on the surface of an aluminum plate (material JIS A 1050) having a thickness of 0.3 mm, degreasing treatment was performed at 50 ° C. for 30 seconds using a 10 mass% sodium aluminate aqueous solution. After that, the aluminum surface was grained using ^three bundle-planted nylon brushes having a bristle diameter of 0.3 mm and a pumice-water suspension (specific gravity 1.1 g / cm ³ ) having a median diameter of 25 μm and washed thoroughly with water. . This plate was etched by being immersed in a 25 mass% sodium hydroxide aqueous solution at 45 ° C for 9 seconds, washed with water, further immersed in 20 mass% nitric acid at 60 ° C for 20 seconds, and washed with water. The etching amount of the grained surface at this time was about 3 g / m ² .

Next, an electrochemical roughening treatment was performed continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a 1% by mass nitric acid aqueous solution (containing 0.5% by mass of aluminum ions) and a liquid temperature of 50 ° C. As an AC power supply waveform, an electrochemical roughening process using a carbon electrode as a counter electrode using a trapezoidal rectangular wave AC having a time TP of 0.8 msec until the current value reaches a peak and a duty ratio of 1: 1. Went. Ferrite was used for the auxiliary anode. The current density was 30 A / dm ² at the peak current value, and 5% of the current flowing from the power source was shunted to the auxiliary anode.
The amount of electricity in the nitric acid electrolysis was 175 C / dm ² when the aluminum plate was the anode. Then, water washing by spraying was performed.

Next, a 0.5% by mass hydrochloric acid aqueous solution (containing 0.5% by mass of aluminum ions) and an electrolytic solution having a liquid temperature of 50 ° C. and nitric acid electrolysis under the condition of an electric quantity of 50 C / dm ² when the aluminum plate is an anode. In the same manner as above, an electrochemical surface roughening treatment was performed, followed by washing with water by spraying.
Next, the plate was provided with a DC anodized film of 2.5 g / m ² at a current density of 15 A / dm ² using 15% by mass sulfuric acid (containing 0.5% by mass of aluminum ions) as an electrolyte, and then washed with water. It dried and produced the support body (1).
Then, in order to ensure the hydrophilic property of a non-image part, the support (1) was subjected to silicate treatment at 70 ° C. for 12 seconds using a 1.5 mass% No. 3 sodium silicate aqueous solution. The adhesion amount of Si was 6 mg / m ² . Then, it washed with water and the support body (2) was obtained. The centerline average roughness (Ra) of this substrate was measured using a needle having a diameter of 2 μm and found to be 0.51 μm.

On the support (2), the following undercoat liquid (1) was applied so that the dry coating amount was 20 mg / m ² to prepare a support used in the following experiments.

<Undercoat liquid (1)>
・ The following undercoat compound (1) 0.18 g
・ DABCO 0.12g
・ Methanol 55.24g
・ Distilled water 6.15g

(2) Formation of image recording layer The above support having an undercoat layer was bar-coated with an image recording layer coating solution (1) having the following composition, and then oven-dried at 100 ° C for 60 seconds to obtain a dry coating amount of 1.0 g / An m ² image recording layer was formed.
The image recording layer coating solution (1) was obtained by mixing and stirring the following photosensitive solution (1) and microgel solution (1) immediately before coating.

<Photosensitive solution (1)>
-Binder polymer (1) [the following structure] 0.240 g
Infrared absorber (1) [the following structure: component (A)] 0.030 g
-Polymerization initiator (1) [the following structure: (B) component] 0.162g
・ Polymerizable compound [component (C)]
Tris (acryloyloxyethyl) isocyanurate (NK ester A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.192 g
・ Tris (2-hydroxyethyl) isocyanurate 0.062g
Benzyl - dimethyl - octylammonium, PF ₆ salt 0.018g
・ 0.055 g of chelating agents listed in Table 1
・ Fluorosurfactant (1) [The following structure] 0.008g
・ Methyl ethyl ketone 1.091g
・ 1-methoxy-2-propanol 8.609g

<Microgel solution (1)>
-Microgel (1) [the following synthesis method] 2.640 g
・ Distilled water 2.425g

(Synthesis of microgel (1))
As oil phase components, trimethylolpropane and xylene diisocyanate adduct (Mitsui Takeda Chemical Co., Ltd., Takenate D-110N) 10 g, pentaerythritol triacrylate (Nippon Kayaku Co., Ltd., SR444) 3.15 g, And 0.1 g of Pionein A-41C (manufactured by Takemoto Yushi Co., Ltd.) was dissolved in 17 g of ethyl acetate. As an aqueous phase component, 40 g of a 4% by mass aqueous solution of PVA-205 was prepared. The oil phase component and the aqueous phase component were mixed and emulsified for 10 minutes at 12,000 rpm using a homogenizer. The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours. The solid content concentration of the microgel solution thus obtained was diluted with distilled water so as to be 15% by mass. The average particle size was 0.2 μm.

(3) Formation of Protective Layer After the protective layer coating solution (1) having the following composition was further bar-coated on the image recording layer, it was oven-dried at 120 ° C. for 60 seconds, and the dry coating amount was 0.15 g / m ^2. The lithographic printing plate precursors (1) to (21) of the present invention and a comparative lithographic printing plate precursor (R1) were obtained.

<Protective layer coating solution (1)>
-1.5 g of inorganic layered compound dispersion (1) prepared as follows
・ Polyvinyl alcohol (Nippon Synthetic Chemical Industry Co., Ltd. CKS50, sulfonic acid modified,
Saponification degree 99 mol% or more, polymerization degree 300) 6% by mass aqueous solution 0.55 g
・ Polyvinyl alcohol (PVA-405 manufactured by Kuraray Co., Ltd., saponification degree: 81.5 mol%,
Polymerization degree 500) 6% by mass aqueous solution 0.03 g
・ Nippon Emulsion Co., Ltd. surfactant (Emalex 710),
1 mass% aqueous solution 8.60g
・ Ion-exchanged water 6.0g

(Preparation of inorganic layered compound dispersion (1))
6.4 g of synthetic mica Somasif ME-100 (manufactured by Coop Chemical Co., Ltd.) was added to 193.6 g of ion-exchanged water, and dispersed using an homogenizer until the average particle size (laser scattering method) became 3 μm. The aspect ratio of the obtained dispersed particles was 100 or more.

2. Exposure and Printing / Evaluation of Planographic Printing Plate Precursor The resulting lithographic printing plate precursor was subjected to an external drum rotation speed of 1000 rpm, a laser output of 70%, and a resolution of 2400 dpi using Fujifilm's Luxel PLASETTER T-6000III equipped with an infrared semiconductor laser. The image was exposed and exposed under the following conditions. The exposed image contained an FM halftone dot of 20 μm.
The exposed lithographic printing plate precursor was attached to a cylinder of a printing machine SOR-M manufactured by Heidelberg without developing. Using fountain solution (IF-102 (manufactured by Fuji Film Co., Ltd.) / Water = 4/96 (volume ratio)) and TRANS-G (N) black ink (manufactured by Dainippon Ink & Chemicals, Inc.) After supplying dampening water and ink, printing was performed at a printing speed of 6,000 sheets per hour. At this time, the number of printing sheets required until the ink was not transferred to the non-image area was evaluated as on-machine developability. At that time, the dirtiness of the non-image area was visually evaluated. In order to confirm the effect of the present invention, the lithographic printing plate precursors (1) to (21) are stored for two days at a temperature of 60 ° C. and a relative humidity of 50% as a forced severe condition before exposure. The stains of the non-image area were also evaluated for those subjected to the process.
When printing was continued and the number of printed sheets was increased, the image recording layer was gradually worn out and the ink receptivity was lowered, so that the ink density in the printing paper was lowered. Printing durability was evaluated by the number of printed sheets when the ink density (reflection density) was reduced by 0.1 from the start of printing. These results are shown in Table 1.

<Chelating Agent Added to Image Recording Layer> [] is ClogP value • Chelating agent (1): Exemplified compound (K-1) [0.945] (Wako Pure Chemical Industries, Ltd.)
Chelating agent (2): Exemplified compound (K-2) [0.614] (manufactured by Tokyo Chemical Industry Co., Ltd.)
Chelating agent (3): Exemplified compound (K-3) [2.207] (manufactured by Kanto Chemical Co., Inc.)
Chelating agent (4): phthalic acid [2.142] (manufactured by Tokyo Chemical Industry Co., Ltd.)
Chelating agent (5): Exemplified compound (K-5) [-0.748] (manufactured by Tokyo Chemical Industry Co., Ltd.)
Chelating agent (6): Exemplified compound (K-6) [-1.98] (manufactured by Tokyo Chemical Industry Co., Ltd.)
Chelating agent (7): Exemplary compound (K-7) [-6.470]
Chelating agent (8): Exemplified compound (K-8) [-1.795] (manufactured by Wako Pure Chemical Industries, Ltd.)
Chelating agent (9): Exemplified compound (K-9) [-2.150] (manufactured by Kirest Co., Ltd.)
Chelating agent (10): Exemplified compound (K-10) [-1.884] (manufactured by Wako Pure Chemical Industries, Ltd.)
Chelating agent (11): Exemplified compound (K-11) [-2.150] (manufactured by Kirest Co., Ltd.)
Chelating agent (12): Exemplified compound (K-12) [-2.274] (manufactured by Kirest Co., Ltd.)
Chelating agent (13): Exemplified compound (K-13) [-2.975] (manufactured by Wako Pure Chemical Industries, Ltd.)
Chelating agent (14): Exemplified compound (K-14) [-1.905] (manufactured by Kirest Co., Ltd.)
-Chelating agent (15): DL-malic acid [-0.759] (manufactured by Wako Pure Chemical Industries, Ltd.)
Chelating agent (16): DL-tartaric acid [-2.113] (manufactured by Wako Pure Chemical Industries, Ltd.)
Chelating agent (17): 4-sulfophthalic acid Chelating agent (18): 4-hydroxyphthalic acid Chelating agent (19): trimellitic acid Chelating agent (20): 5-sulfosalicylic acid (salicylic acid-based exemplary compound ( 69))
Chelating agent (21): Propane-1,2,3-tricarboxylic acid Chelating agent (22): Salicylic acid-based exemplary compound (42)
Chelating agent (23): salicylic acid-based exemplary compound (17)
Chelating agent (24): Salicylic acid-based exemplary compound (20)
Chelating agent (25): salicylic acid-based exemplary compound (22)
Chelating agent (26): salicylic acid type exemplified compound (24)
Chelating agent (27): salicylic acid-based exemplary compound (25)
Chelating agent (28): salicylic acid-based exemplary compound (58)
Chelating agent (29): salicylic acid-based exemplary compound (67)

  As is apparent from the results in Table 1, according to the present invention, excellent on-press developability and printing durability, particularly stain resistance is improved, and many good printed materials can be obtained with a practical energy amount.

Claims (11)

  A lithographic printing plate precursor comprising an image recording layer which can be removed with a printing ink and / or fountain solution on a support, and the image recording layer containing a chelating agent.   The lithographic printing plate precursor as claimed in claim 1, wherein the chelating agent is a chelating agent having at least two metal-adsorptive groups in one molecule.   The undercoat layer is provided between the support and the image recording layer, and the undercoat layer contains a polymer having a substrate adsorptive group, a polymerizable group, and a hydrophilic group. A lithographic printing plate precursor.   The lithographic printing plate according to any one of claims 1 to 3, wherein the image recording layer contains (A) an infrared absorber, (B) a polymerization initiator, and (C) a polymerizable compound. Original edition.   The lithographic printing plate precursor as claimed in any one of claims 1 to 4, wherein the support is an aluminum support. The lithographic printing plate precursor as claimed in any one of claims 1 to 5, wherein the chelating agent is a compound represented by the following general formula (I) or (II).

In the general formulas (I) and (II), R ₁ , R ₂ , R ₄ , R ₅ , R ₆ and R ₇ are each independently a single bond or a linear alkylene group having 1 to 3 carbon atoms. R ₃ is a divalent organic group, and R ₈ is a trivalent organic group. X is methine (—CH <) or amine (—N <). Y _{1 to} Y ₆ each independently represent a metal adsorbing group, and A represents a hydrogen atom or a hydrophilic group.   The lithographic printing plate precursor as claimed in any one of claims 1 to 5, wherein the chelating agent is at least one compound selected from a salicylic acid derivative and a salt thereof. The lithographic printing plate precursor as claimed in claim 7, wherein the chelating agent is a compound represented by the following general formula (III).

In general formula (III), X represents an oxygen atom or a sulfur atom. M ¹ and M ² are each independently selected from H, Li, Na, K, Rb, Cs, 1 / 2Mg, 1 / 2Ca, 1 / 2Sr, 1 / 2Ba, 1 / 2Zn, and a nitrogen-containing cation. Represents a species. R ¹ , R ² , R ³ , and R ⁴ represent any substituents, and R ¹ and R ² , R ² and R ³ , and R ³ and R ⁴ are bonded to each other to form a cyclic structure. Also good.   The chelating agent is 3-sulfophthalic acid, 4-sulfophthalic acid, 2-sulfoterephthalic acid, 4-hydroxyphthalic acid, 5-sulfosalicylic acid, trimellitic acid and propane-1,2,3-tricarboxylic acid or a metal salt thereof. The lithographic printing plate precursor as claimed in any one of claims 1 to 8, wherein the lithographic printing plate precursor is at least one selected.   The lithographic printing plate precursor as claimed in any one of claims 1 to 9, wherein the image recording layer further comprises (D) polymer fine particles having a polymerizable reactive group.   The lithographic printing plate precursor according to any one of claims 1 to 10 is imagewise exposed with an infrared laser after being mounted on a printing press, or is imagewise exposed with an infrared laser and then mounted on a printing press. Then, a lithographic printing method in which printing ink and fountain solution are supplied to remove an infrared unexposed portion of the image recording layer and printing is performed.