JP2010085765A - Lithographic printing plate precursor, and method of manufacturing lithographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lithographic printing plate precursor in which pigment in a non-image area can be thoroughly removed upon development, so that residual color in the non-image area is eliminated to improve plate inspectability, and which can also prevent soiling in printing, with respect to a lithographic printing plate precursor of a simple development processing type with a weakly alkaline to weakly acidic aqueous solution, and to provide a method of manufacturing a lithographic printing plate using the precursor. <P>SOLUTION: The lithographic printing plate precursor can be developed with a developer of pH 2-11 and has, on a support in the following order, an undercoat layer containing a polymer compound having at least (A1) a group which is adsorptive to the support and (A2) a hydrophilic group, and a photosensitive layer containing a pigment which is not adsorbed to the polymer compound. The method of manufacturing a lithographic printing plate includes imagewise exposing the lithographic printing plate precursor with laser, and removing an unexposed area of the photosensitive layer in the presence of a developer of pH 2-11. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a lithographic printing plate precursor that can be developed with an aqueous developer having a pH of 2 to 11, in particular, a lithographic printing plate precursor that provides a lithographic printing plate excellent in dirt and residual color, and the lithographic printing plate precursor. The present invention relates to a lithographic printing plate preparation method using

Conventionally, a lithographic printing plate has a structure in which a photosensitive resin layer is provided on a support having a hydrophilic surface. As a plate-making method, usually, surface exposure (mask exposure) is performed through a lithographic film. The desired printing plate was obtained by removing the non-image area with a high pH developer. However, computer-to-plate that directly exposes the plate without using a lith film by scanning the plate according to digitized image information with highly directional light such as laser light by recent digitization technology. (CTP) technology has been developed, and a photosensitive lithographic printing plate (lithographic printing plate precursor) adapted to this has been developed.
Examples of the lithographic printing plate precursor suitable for exposure with such laser light include a lithographic printing plate precursor using a polymerizable photosensitive layer. By selecting a photopolymerization initiator or a polymerization initiator system (hereinafter also simply referred to as an initiator or an initiator system), the polymerizable photosensitive layer can be easily increased in sensitivity as compared with other conventional photosensitive layers.
As the laser light source, a 405 nm or 830 nm semiconductor laser, an FD-YAG laser, or the like is used. In recent years, CTP systems equipped with a 405 nm semiconductor laser have become widespread from the viewpoint of system cost and handleability.

In the conventional plate making process of a lithographic printing plate precursor, after the exposure as described above, a step of dissolving and removing an unnecessary image recording layer with a developer or the like is necessary. However, such additional wet processing is performed. One of the problems has been to make it unnecessary or simplified. 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 a simple plate making method, a simple development treatment with a weakly alkaline to weakly acidic aqueous solution can be mentioned. For such development processing, an aqueous solution having a pH of 11 or less is usually used. For example, Patent Document 1 contains a hydrophilic support, a radically polymerizable ethylenically unsaturated monomer, a radical polymerization initiator, and an infrared absorbing dye, cured by infrared laser exposure, and 60 mass% or more. A lithographic printing plate precursor comprising an oleophilic heat-sensitive layer that can be developed with an aqueous developer having a pH of 2.0 to 10.0 and containing an aqueous solution is exposed imagewise with an infrared laser, and the heat-sensitive layer is not cured with an aqueous developer. A method for processing a lithographic printing plate precursor consisting of excluding areas is described.

On the other hand, the lithographic printing plate precursor generally contains a plate inspection agent (colorant, dye or pigment) in the image recording layer of the lithographic printing plate precursor in order to make it easy to confirm the image formability.
Among them, as a plate inspection agent to be contained in the image recording layer of a photopolymerization type lithographic printing plate precursor, a pigment is often used because it has an advantage of not inhibiting photopolymerization. In order to increase the dispersibility of the pigment, it is common to coat with a polymer, or to replace the acid group, base, etc. on the pigment surface. However, in a simple development processing type lithographic printing plate precursor using a weakly alkaline to weakly acidic aqueous solution, the pigment in the non-image area cannot be completely removed by development, and a residual color is generated in the non-image area. There was a problem of generating dirt. Incidentally, in the lithographic printing plate precursor using a conventional high pH alkaline developer, the aluminum support surface is slightly dissolved by an alkaline aqueous solution during development, and the undercoat layer is removed by the alkaline aqueous solution. Therefore, no matter what kind of pigment is used, there will be no problem of residual color or stain. Therefore, the problem is a phenomenon peculiar to a lithographic printing plate precursor using a weakly alkaline to weakly acidic developer.
US Patent Application Publication No. 2004/0013968

  The present invention is a simple development processing type lithographic printing plate precursor using a weakly alkaline to weakly acidic aqueous solution, whereby the pigment in the non-image area can be satisfactorily removed by development, and there is no residual color in the non-image area, and the plate inspection is possible. It is an object of the present invention to provide a lithographic printing plate precursor capable of improving printing quality and preventing contamination during printing, and a method for producing a lithographic printing plate using the same.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventor adsorbed to the undercoat layer containing a polymer compound having at least a support-adsorbing group and a hydrophilic group on the support and the polymer compound. The above object is achieved by a lithographic printing plate precursor which has a photosensitive layer containing a non-sensitive pigment in this order and can be developed with a developer having a pH of 2 to 11 and a method for preparing a lithographic printing plate using the same. The present invention has been completed.

The present invention is as follows.
(1) An undercoat layer containing a polymer compound having at least (A1) a support adsorbing group and (A2) a hydrophilic group, and a photosensitive layer containing a pigment that is not adsorbed on the polymer compound on the support. A lithographic printing plate precursor that can be developed with a developer having a pH of 2 to 11 in this order.
(2) The pigment is a pigment dispersed with a pigment dispersant having a pigment adsorbing group, and the hydrophilic group and the pigment adsorbing group satisfy at least one of the following conditions 1 and 2. The lithographic printing plate precursor as described in (1) above.
Condition 1: The hydrophilic group is a neutral group and the pigment adsorbing group is an acidic group, neutral group or basic group. Condition 2: The hydrophilic group is a basic group and the pigment adsorbing group is an acidic group or neutral group. (3) The lithographic printing plate precursor as described in (2) above, wherein the hydrophilic group is selected from functional groups represented by the following general formula:

In the formula, L represents a divalent linking group for linking to the compound nucleus, L ₁ represents a divalent linking group, and R _{1 to} R ₇ are each independently an alkyl group, aryl group, alkenyl. Group, alkynyl group, -OR, -NRR ', -SR, -COR, -COOR, -CONRR', -OCOR, -OCONRR ', -OCOOR, -NRCOR', -NRCOOR ', -NRCONR'R'', —N═R, —SO ₂ R, —SO ₃ R, —SO ₂ NRR ′, hydrogen atom, halogen group, cyano group, nitro group, hydroxyl group or mercapto group (R, R ′, R ″ are each independently Represents an alkyl group, an aryl group, an alkenyl group, an alkynyl group or a hydrogen atom, or each may be bonded to each other to form a ring), and L, L ₁ , R ₁ in the same functional group, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ may be bonded to each other to form a ring. n represents a number representing the average value of repeating units, X ⁻ represents a counter anion, and M ⁺ represents a counter cation.
(4) The lithographic plate as described in (3) above, wherein the hydrophilic group is a functional group selected from the general formulas (N-1) to (N-7) and (B-1) A printing plate master.
(5) The lithographic printing plate precursor as described in (2) above, wherein the pigment adsorption group is selected from functional groups represented by the following general formula:

In the formula, L represents a divalent linking group for linking to the compound nucleus, and R _{11 to} R ₁₈ each independently represents an alkyl group, an aryl group, an alkenyl group, an alkynyl group, —OR, —NRR ′. , -SR, -COR, -COOR, -CONRR ', - OCOR, -OCONRR', - OCOOR, -NRCOR ', - NRCOOR', - NRCONR'R '', - N = R, -SO 2 R, - SO ₃ R, —SO ₂ NRR ′, hydrogen atom, halogen group, cyano group, nitro group, hydroxyl group or mercapto group (R, R ′, R ″ each independently represents an alkyl group, aryl group, alkenyl group, Represents an alkynyl group or a hydrogen atom, or each may be bonded to each other to form a ring). X represents an oxygen atom, a sulfur atom, a selenium atom or NR ₁₉ , Y represents a covalent bond, an oxygen atom, a sulfur atom, NR ₁₉ , CO or SO ₂ , and R ₁₉ has the same meaning as R ₁₁ . L, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ in the same functional group may be bonded to each other to form a ring.
(6) The pigment adsorbing group is the general formula (PA-2), (PA-5), (PN-1), (PN-2), (PB-1), (PB-10), (PB The lithographic printing plate precursor as described in (5) above, which is a functional group selected from -11) and (PB-12).
(7) Any one of the above (1) to (6), wherein the photosensitive layer further contains a radical polymerizable compound, a radical polymerization initiator, a sensitizing dye, a co-sensitizer, and a binder polymer. The lithographic printing plate precursor as described in the paragraph.
(8) The lithographic printing plate precursor as described in any one of (1) to (7) above, which has a protective layer on the photosensitive layer.

(9) An undercoat layer containing a polymer compound having at least (A1) a support adsorbing group and (A2) a hydrophilic group on the support, and a photosensitive layer containing a pigment that is not adsorbed to the polymer compound. A method for preparing a lithographic printing plate, comprising exposing a lithographic printing plate precursor in this order to an image with a laser and then removing a photosensitive layer in a non-exposed portion in the presence of a developer having a pH of 2 to 11.
(10) The pigment is a pigment dispersed with a pigment dispersant having a pigment adsorbing group, and the hydrophilic group and the pigment adsorbing group satisfy at least one of the following conditions 1 and 2. The method for producing a lithographic printing plate as described in (9) above.
Condition 1: The hydrophilic group is a neutral group and the pigment adsorbing group is an acidic group, neutral group or basic group. Condition 2: The hydrophilic group is a basic group and the pigment adsorbing group is an acidic group or neutral group. (11) The method for preparing a lithographic printing plate as described in (10) above, wherein the hydrophilic group is selected from functional groups represented by the following general formula:

In the formula, L represents a divalent linking group for linking to the compound mother nucleus, L ₁ represents a divalent linking group, and R1 to R7 each independently represents an alkyl group, an aryl group, an alkenyl group, Alkynyl group, -OR, -NRR ', -SR, -COR, -COOR, -CONRR', -OCOR, -OCONRR ', -OCOOR, -NRCOR', -NRCOOR ', -NRCONR'R'', -N ═R, —SO ₂ R, —SO ₃ R, —SO ₂ NRR ′, hydrogen atom, halogen group, cyano group, nitro group, hydroxyl group or mercapto group (R, R ′, R ″ are each independently Represents an alkyl group, an aryl group, an alkenyl group, an alkynyl group or a hydrogen atom, or each may be bonded to each other to form a ring), and L, L ₁ , R ₁ , R ₂ in the same functional group _{, R 3, R 4, R} 5, R It may form a ring wherein R ₇ is each other. n represents a number representing the average value of repeating units, X ⁻ represents a counter anion, and M ⁺ represents a counter cation.
(12) The lithographic plate as described in (11) above, wherein the hydrophilic group is a functional group selected from the above general formulas (N-1) to (N-7) and (B-1) A method for preparing a printing plate.
(13) The method for preparing a lithographic printing plate as described in (10) above, wherein the pigment adsorbing group is selected from functional groups represented by the following general formula:

In the formula, L represents a divalent linking group for linking to the compound nucleus, and R _{11 to} R ₁₈ each independently represents an alkyl group, an aryl group, an alkenyl group, an alkynyl group, —OR, —NRR ′. , -SR, -COR, -COOR, -CONRR ', - OCOR, -OCONRR', - OCOOR, -NRCOR ', - NRCOOR', - NRCONR'R '', - N = R, -SO 2 R, - SO ₃ R, —SO ₂ NRR ′, hydrogen atom, halogen group, cyano group, nitro group, hydroxyl group or mercapto group (R, R ′, R ″ each independently represents an alkyl group, aryl group, alkenyl group, Represents an alkynyl group or a hydrogen atom, or each may be bonded to each other to form a ring). X represents an oxygen atom, a sulfur atom, a selenium atom or NR ₁₉ ; Y represents a covalent bond, an oxygen atom, a sulfur atom, NR ₁₉ , CO or SO ₂ ;
R ₁₉ has the same meaning as R ₁₁ . L, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ in the same functional group may be bonded to each other to form a ring.
(14) The pigment adsorbing group has the general formulas (PA-2), (PA-5), (PN-1), (PN-2), (PB-1), (PB-10), (PB -11) The method for producing a lithographic printing plate as described in (13) above, wherein the functional group is selected from (PB-12).
(15) Any one of the above (9) to (14), wherein the photosensitive layer further contains a radical polymerizable compound, a radical polymerization initiator, a sensitizing dye, a co-sensitizer, and a binder polymer. A method for producing a lithographic printing plate as described in the paragraph.
(16) The method for preparing a lithographic printing plate as described in any one of (9) to (15) above, wherein a protective layer is provided on the photosensitive layer.
(17) After the image exposure with the laser, the mixture is heated at a temperature of 70 ° C. or higher, and then the photosensitive layer in the non-exposed area is removed in the presence of a developer having a pH of 2 to 11. The method for producing a lithographic printing plate according to any one of 9) to (16).

  According to the present invention, in a simple development processing type lithographic printing plate precursor using a non-alkaline to weakly acidic aqueous solution, the pigment in the non-image area can be satisfactorily removed by development, and the residual color in the non-image area is eliminated. It is possible to provide a planographic printing plate precursor capable of improving plate properties and preventing smearing during printing, and a method for producing a planographic printing plate using the same.

  According to the study of the present inventor, in the simple development processing type lithographic printing plate precursor, the pigment adsorbing group is formed on the undercoat layer containing at least the polymer compound having (A1) support adsorbing group and (A2) hydrophilic group. It has been found that when a photosensitive layer containing a pigment dispersed by a pigment dispersant using is used, residual colors and stains become prominent under certain conditions. That is, when these pigment adsorbing groups have a lower acidity than the hydrophilic group (A2) in the undercoat layer or a basicity lower than the basicity of the (A2) hydrophilic group in the undercoat layer, The color and dirt were remarkable. This is because the hydrophilicity of the (A2) hydrophilic group in the undercoat layer is stronger than that of the pigment adsorbing group in the pigment dispersant because the adsorptivity to the pigment is higher than the pigment adsorbing group in the pigment dispersant. The dispersant is removed and replaced with the (A2) hydrophilic group in the undercoat layer and adsorbed on the undercoat layer. As a result, the pigment remains on the surface of the undercoat layer even after development [the undercoat layer is (A1) support adsorbing group Therefore, it is presumed that the residual color and stain problem are caused. In the lithographic printing plate precursor according to the invention, (A2) the hydrophilic group in the undercoat layer is used as a neutral group to suppress the adsorption of the pigment, or (A2) the hydrophilic group and the pigment adsorbing group have different properties. Thus, the adsorption to the undercoat layer of the pigment was suppressed, and the above problems could be solved.

  Hereinafter, the lithographic printing plate precursor according to the invention will be described in detail. In the lithographic printing plate precursor according to the invention, an undercoat layer containing a polymer compound having at least (A1) a support-adsorptive group and (A2) a hydrophilic group on the support, and a pigment that does not adsorb to the polymer compound. It is a lithographic printing plate precursor that can be developed with a developer having a pH of 2 to 11 and having photosensitive layers contained in this order.

(Undercoat layer)
The undercoat layer of the lithographic printing plate precursor according to the invention contains at least a polymer compound having at least (A1) a support adsorbing group and (A2) a hydrophilic group (hereinafter sometimes simply referred to as a polymer compound) as an essential component. It can contain and contain arbitrary components, such as surfactant, a polymerization inhibitor, an initiator, a sensitizing dye, a co-sensitizer, as needed.
Below, each component which forms an undercoat layer is demonstrated.

<Polymer compound>
The polymer compound used in the present invention will be described.
The polymer compound used in the present invention is a polymer compound having at least (A1) a support adsorbing group and (A2) a hydrophilic group.

(A1) Support adsorptive group The support adsorptive group used in the present invention can be variously selected depending on the support to be used. For example, an aluminum support that has been conventionally used favorably for a lithographic printing plate precursor In the case of the body, specific support adsorptive groups differ depending on the surface treatment, but phosphoric acid group and its base, phosphonic acid group and its base, ammonium group, siloxane group, β-dicarbonyl group, carboxylic acid group and Examples thereof include functional groups such as bases. Preferred are a phosphoric acid (salt) group, a phosphonic acid (salt) group, an ammonium group, a siloxane group, a β-dicarbonyl group, and a carboxylic acid (salt) group. Support adsorbability can be used in combination.
In the polymer compound used in the present invention, the amount of the support-adsorbing group introduced is preferably 0.01 mmol / g or more and 10 mmol / g or less, more preferably 0.05 mmol / g or more and 5 mmol / g or less. 1 mmol / g or more and 3 mmol / g or less is particularly preferable.

(A2) Hydrophilic group The hydrophilic group used in the present invention can be suitably used as long as it is a functional group generally known as a hydrophilic functional group. It is preferable that
As the neutral functional group, functional groups represented by the following general formulas (N-1) to (N-11) are preferable, and functional groups represented by (N-1) to (N-7) are more preferable. preferable.

In the formula, L represents a divalent linking group for linking to the polymer main chain, and is selected from a carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, silicon atom, hydrogen atom, halogen atom and boron atom. Formed by one or more of the above. L ₁ represents a divalent linking group and is formed of one or more selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, silicon atoms, hydrogen atoms, halogen atoms, and boron atoms. Specific examples of L and L ₁ include divalent linking groups formed by combining the following units, but the present invention is not limited thereto.

R _{1 to} R ₇ are each independently an alkyl group, aryl group, alkenyl group, alkynyl group, —OR, —NRR ′, —SR, —COR, —COOR, —CONRR ′, —OCOR, —OCONRR ′, -OCOOR, -NRCOR ', - NRCOOR' , - NRCONR'R '', - N = R, -SO 2 R, -SO 3 R, -SO 2 NRR ', a hydrogen atom, a halogen group, a cyano group, a nitro group , A hydroxyl group or a mercapto group (R, R ′, R ″ each independently represents an alkyl group, an aryl group, an alkenyl group, an alkynyl group, or a hydrogen atom, or each may be bonded to each other to form a ring. Good).

The alkyl group, aryl group, alkenyl group, and alkynyl group may have a substituent.
Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, Octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, Cyclopentyl, 2-norbornyl, chloromethyl, bromomethyl, 2-chloroethyl, trifluoromethyl, methoxymethyl, methoxyethoxyethyl, allyloxymethyl, phenoxymethyl, methylthiomethyl, tolylthiomethyl Group, ethylaminoethyl group, die Tylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2- Oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoyl group Til group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, Diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatooxybutyl group, benzyl group Phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2- Methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl Etc. is Ageraru.

Specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxy Phenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, Ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, nitrophenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonopheny Group, phosphonatophenyl group and the like.

  Specific examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 1-butenyl group, a cinnamyl group, and a 2-chloro-1-ethenyl group. Specific examples of the alkynyl group include ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like.

R _{1 to} R ₇ include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, —OR, —NRR ′, —SR, —COR, —COOR, —CONRR ′, —OCOR, —OCONRR ′, —OCOOR, -NRCOR ', - NRCOOR', - NRCONR'R '', - N = R, -SO 2 R, -SO 3 R, -SO 2 NRR ', preferably a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, alkynyl groups, -NRR ', - COOR, -CONRR ', - NRCOR ', - NRCOOR', - NRCONR'R '', - N = R, -SO 2 R, -SO 3 R, -SO 2 NRR ', A hydrogen atom is more preferable, an alkyl group and a hydrogen atom are particularly preferable, and an alkyl group having 4 or less carbon atoms and a hydrogen atom are most preferable.

L, L ₁ , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ existing in the same functional group may be bonded to each other to form a ring. .

  n is a number representing the average value of repeating units, and is a value calculated according to the following formula.

For example, when the repeating unit has 2 functional groups of 20 mol, 3 functional groups of 30 mol, 4 functional groups of 30 mol, 5 functional groups of 15 mol, and 6 functional groups of 5 mol, the following calculation According to the equation, n is 3.55.
n = (2 * 20 + 3 * 30 + 4 * 30 + 5 * 15 + 6 * 5) / (20 + 30 + 30 + 15 + 5) = 3.55.
n is preferably a number of 1 to 100, more preferably a number of 2 to 70, and particularly preferably a number of 3 to 60.

Specific examples of the counter anion represented by X ⁻ include a halogen anion, a sulfate anion, a nitrate anion, a phosphate anion, a carboxylic acid (acetic acid, benzoic acid, butyric acid, trifluoroacetic acid, etc.) anion, and a sulfonic acid (methanesulfonic acid). , Butanesulfonic acid, toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, etc.) anion, sulfate amide anion (cyclohexylamide sulfate anion, etc.), BF ₄ ⁻ , PF ₆ ⁻ , tetraarylborate anion (tetraphenylborate, tetrakis) Pentafluorophenylborate), imide anion (such as saccharin anion), phosphate monoester anion, phosphate diester anion, phosphonic acid (methylphosphonic acid, phenylphosphonic acid, etc.) anion, etc. The invention is not limited to these examples. The counter anion represented by X ⁻ includes halogen anion, sulfate anion, nitrate anion, phosphate anion, carboxylate anion, sulfonate anion, sulfate amide anion, BF ₄ ⁻ , PF ₆ ⁻ , tetraarylborate anion, and imide. Anions are preferred, halogen anions, sulfate anions, nitrate anions, phosphate anions, carboxylate anions, sulfonate anions and sulfate amide anions are more preferred, and halogen anions, sulfate anions, nitrate anions and sulfonate anions are particularly preferred.

Specific examples of the counter cation represented by M ⁺ include alkali metal cations, alkaline earth metal cations, 3A group metal cations, 4A group metal cations, 5A group metal cations, 6A group metal cations, 7A group metal cations, 8 Group metal cation, Group 1B metal cation, Group 2B metal cation, Group 3B metal cation, Group 4B metal cation, ammonium cation (tetramethylammonium, tetraethylammonium, tetrabutylammonium, etc.), phosphonium cation (tetraphenylphosphonium, triphenylmethyl) Phosphonium, etc.), sulfonium cations (triphenylsulfonium, trischlorophenylsulfonium, etc.), iodonium cations (diphenyliodonium, etc.), pyridinium cations (N-methylpyridinium, etc.) Etc.), azinium cations (O-methylazinium and the like), diazonium cations and the like, but the present invention is not limited thereto. Examples of the counter cation represented by M ⁺ include alkali metal cations, alkaline earth metal cations, group 3A metal cations, group 4A metal cations, group 5A metal cations, group 6A metal cations, group 7A metal cations, and group 8 metal cations. 1B group metal cation, 2B group metal cation, 3B group metal cation, 4B group metal cation, ammonium cation and phosphonium cation are preferable, alkali metal cation, alkaline earth metal cation and ammonium cation are more preferable, alkali metal cation, total An ammonium cation having 16 or less carbon atoms is particularly preferred. Neutral functional groups can be used in combination.

  As a basic functional group, the amino group represented by the following general formula (B-1) is preferable.

In the formula, each of R ₁ and R ₂ independently represents an alkyl group, an aryl group, an alkenyl group, an alkynyl group, —OR, —NRR ′, —SR, —COR, —COOR, —CONRR ′, —OCOR, — OCONRR ′, —OCOOR, —NRCOR ′, —NRCOOR ′, —NRCONR′R ″, —N═R, —SO ₂ R, —SO ₃ R, —SO ₂ NRR ′, hydrogen atom, halogen group, cyano group , A nitro group, a hydroxyl group or a mercapto group (R, R ′, R ″ each independently represents an alkyl group, an aryl group, an alkenyl group, an alkynyl group, or a hydrogen atom, or they are bonded to each other to form a ring. May be). The alkyl group, aryl group, alkenyl group, and alkynyl group may have a substituent. Specific examples of the alkyl group, aryl group, alkenyl group and alkynyl group are as described above. Further, R ₁ and R ₂ may form a ring. R ₁ and R ₂ are preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, —NRR ′, —N═R, or a heterocyclic group having 10 or less carbon atoms, a hydrogen atom or 8 carbon atoms. The following alkyl groups, —NRR ′, —N═R, alkenyl groups and alkynyl groups are more preferred, and hydrogen atoms and alkyl groups and alkenyl groups having 6 or less carbon atoms are particularly preferred. Basic functional groups can be used in combination.

In the polymer compound used in the present invention, the introduction amount of the hydrophilic group is preferably 0.01 mmol / g or more and 10 mmol / g or less, and 0.05 mmol / g or more and 7.5 mmol.
1 / g or less is more preferable, and 0.1 mmol / g or more and 5 mmol / g or less is particularly preferable.

(Other functional groups)
The polymer compound used in the present invention preferably has a functional group capable of interacting with the photosensitive layer in addition to the above (A1) support adsorbing group and (A2) hydrophilic group. Examples of the functional group capable of interacting with the photosensitive layer include (A3) an ethylenically unsaturated double bond group, (A4) a hydrogen bond forming group, and (A5) a hydrophobic group. Hereinafter, these functional groups will be described.

(A3) Ethylenically unsaturated double bond group The ethylenically unsaturated double bond group used in the polymer compound of the present invention is a group containing an ethylenically unsaturated double bond that causes a polymerization reaction by a radical. Any of them can be suitably used, but the functional groups represented by the following general formulas (c1) to (c3) are particularly preferable.

In the general formula (c1), R ^{1 to} R ³ each independently represents a hydrogen atom or a monovalent organic group.
R ¹ preferably includes a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom, a methyl group, and a —CH ₂ Q group are preferable because of high radical reactivity.
Q is a halogen atom, cyano group, —OR ¹⁴ group, —OCOR ¹⁴ group, —OCONR ¹⁴ R ₁₅ group, —OCOOR ¹⁴ group, —OSO ₂ R ¹⁴ group, —OPO (OR ¹⁴ ) (OR ¹⁵ ) group. , -OPOR ¹⁴ (OR ¹⁵ ) group, -NR ¹⁴ R ¹⁵ group, -NR ¹⁴ COR ¹⁵ group, -NR ¹⁴ COOR ¹⁵ group, -NR ¹⁴ CONR ¹⁵ R ¹⁶ group, -NR ¹⁴ SO ₂ R ¹⁵ group,- _{^{N (SO 2 R 14) (}} SO 2 R 15) ^{group, -N (COR 14) (COR} 15) groups, ^{-SR 14} groups, -SOR ¹⁴ _group, -SO ^{2 R 14} _group, -SO ^{3 R 14} groups , —SO ₂ NR ¹⁴ R ¹⁵ group, —PO (OR ¹⁴ ) (OR ¹⁵ ) group, halogen atom, cyano group, —OR ¹⁴ group, —OCOR ¹⁴ group, —OCONR ¹⁴ R ¹⁵ group. , —OCOOR ¹⁴ group, —NR ¹⁴ R ¹⁵ group, —NR ¹⁴ COR ¹⁵ group, —NR ¹⁴ COOR ¹⁵ group, —NR ¹⁴ CONR ¹⁵ R ¹⁶ group, and —SR ¹⁴ group are particularly preferable.
Here, R ^{14 to} R ¹⁶ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkynyl which may have a substituent. Represents an alkenyl group which may have a group or a substituent.

R ² and R ³ are preferably each independently a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or an alkyl group which may have a substituent. An aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, a substituent An arylamino group that may have, an alkylsulfonyl group that may have a substituent, an arylsulfonyl group that may have a substituent, and the like, among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, An alkyl group which may have a substituent and an aryl group which may have a substituent are more preferable because of high radical reactivity.

X represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —, and R ¹² represents a hydrogen atom or a monovalent organic group. Here, examples of the monovalent organic group for R ¹² include an alkyl group which may have a substituent. Among these, as R ¹² , a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.
Here, examples of the substituent that can be introduced include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, an alkylamino group, an arylamino group, a carboxyl group, an alkoxycarbonyl group, A sulfo group, a nitro group, a cyano group, an amide group, an alkylsulfonyl group, an arylsulfonyl group and the like can be mentioned.

In the general formula (c2), R ^{4 to} R ⁸ each independently represents a hydrogen atom or a monovalent organic group.
R ^{4 to} R ⁸ are preferably a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, An aryl group that may have a substituent, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylamino group that may have a substituent, and a substituent. An arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like. Among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, a substituent An alkyl group which may have a group and an aryl group which may have a substituent are more preferable. Examples of the substituent that can be introduced are the same as those described in formula (c1).
Y represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —. R ¹² has the same meaning as R ^{12 in} formula (c1), and preferred examples thereof are also the same.

In General Formula (c3), R ^{9 to} R ¹¹ each independently represent a hydrogen atom or a monovalent organic group.
The monovalent organic group for R ⁹ is preferably an alkyl group which may have a substituent. Among these, as R ⁹ , a hydrogen atom or a methyl group is preferable because of high radical reactivity.
R ¹⁰ and R ¹¹ preferably each independently have a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or a substituent. An alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent , An arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like. Among them, a hydrogen atom, a carboxyl group, An alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are more preferable because of high radical reactivity. Here, as a substituent which can be introduce | transduced, the thing similar to what is described in general formula (c1) is illustrated.

Z represents an oxygen atom, a sulfur atom, —N (R ¹³ ) —, or an optionally substituted phenylene group. Examples of R ¹³ include an alkyl group which may have a substituent. Among them, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.
When the ethylenically unsaturated double bond group is contained in the polymer compound, it may contain only one kind, may contain two or more kinds, or contains two or more kinds. May be.
The amount of the ethylenically unsaturated double bond group introduced in the polymer compound used in the present invention is preferably 0.01 mmol / g or more and 10 mmol / g or less, more preferably 0.05 mmol / g or more and 5 mmol / g or less. 0.1 mmol / g or more and 3 mmol / g or less is particularly preferable.

(A4) Hydrogen bond-forming group The hydrogen bond-forming group used in the present invention can be appropriately selected depending on the components contained in the photosensitive layer, but-[(CR11R12) nO] m-R13 (R11 and R12 are independent of each other). Represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, or an alkynyl group, and R13 represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkylacyl group, an arylacyl group, an alkylaminoacyl group, an arylaminoacyl group. Group, an alkylsulfone group, an arylsulfone group, n and m each independently represents a natural number), an alkylene oxide group represented by -NR11R12 (wherein R11 and R12 are the same as those described above) A hydrogen-accepting group such as a group, a carbonyl group represented by -CO-, a nitrogen-containing heterocyclic group having a structure of -N = structure, or a carboxyl represented by -COOH Group, a hydroxyl group represented by -OH, a functional group containing a nitrogen atom having a hydrogen atom represented by -NH-, thiol group represented by -SH, a sulfonic acid group represented by -SO ₃ H, - A phosphoric acid group represented by OPO (OR11) (OH) (R11 is as defined above), a phosphonic acid group represented by -PO (OR11) (OH) (R11 is as defined above), etc. Examples include a hydrogen donating group. Preferred as the hydrogen bond-forming group are an alkylene oxide group, an amino group, a carbonyl group, a nitrogen-containing heterocyclic group having a -N = structure, a carboxylic acid group, a hydroxyl group, and a nitrogen atom having a hydrogen atom represented by -NH-. And a functional group containing a nitrogen atom having a hydrogen atom represented by an alkylene oxide group, an amino group, a carbonyl group, a carboxylic acid group, a hydroxyl group, or —NH— is more preferable.

A hydrogen bond forming group may contain only 1 type in a high molecular compound, and may contain 2 or more types. When two different types of hydrogen bond-forming groups are used, it is preferable to use hydrogen accepting groups or hydrogen donating groups in combination.
In the polymer compound used in the present invention, the amount of hydrogen bonding group introduced is preferably 0.01 mmol / g or more and 10 mmol / g or less, more preferably 0.05 mmol / g or more and 5 mmol / g or less, and 0.1 mmol. / G or more and 3 mmol / g or less is particularly preferable.

(A5) Hydrophobic group Examples of the hydrophobic group used in the present invention include an alkyl group, aryl group, alkenyl group, and alkynyl group having 8 or more carbon atoms. Among them, an alkyl group and an aryl group having 8 or more carbon atoms are preferable, an alkyl group and an aryl group having 10 or more carbon atoms are more preferable, and an alkyl group and an aryl group having 12 or more carbon atoms are particularly preferable.
A hydrophobic group may contain only 1 type in a high molecular compound, and may contain 2 or more types.
The amount of the hydrophobic group introduced in the polymer compound used in the present invention is preferably 0.01 mmol / g or more and 20 mmol / g or less, more preferably 0.05 mmol / g or more and 15 mmol / g or less, and 0.1 mmol / g or less. g to 10 mmol / g is particularly preferable.

  The mass average molecular weight of the polymer compound used in the present invention is preferably from 5,000 to 500,000, more preferably from 10,000 to 250,000, and particularly preferably from 20,000 to 150,000. Within this range, good stain resistance and printing durability can be obtained.

  The polymer compound used in the present invention can be produced according to a conventional method by appropriately combining monomers having functional groups such as the above-mentioned support-adsorbing group and hydrophilic group.

  Specific examples of the polymer compound used in the present invention are shown below. The present invention is not limited to these.

The mass average molecular weights of the polymer compounds P-1 to P-19 are shown below.
P-1: 80,000 P-2: 100,000 P-3: 50,000 P-4: 110,000 P-5: 110,000 P-6: 90,000 P-7: 80,000 P-9: 100,000 P- 11: 100,000 P-12: 90,000 P-13: 90,000 P-14: 100,000 P-15: 80,000 P-16: 70,000 P-17: 60,000 P-18: 70,000 P-19: 80,000

  The content of the polymer compound used in the undercoat layer of the present invention is preferably 50% by mass or more and 100% by mass or less, more preferably 60% by mass or more and 100% by mass or less, and 70% by mass with respect to the total solid content of the undercoat layer. More than 100 mass% is especially preferable.

<Surfactant>
The undercoat layer used in the lithographic printing plate precursor according to the invention may contain a surfactant in order to improve coatability. As the surfactant contained in the undercoat layer, a surfactant used in the photosensitive layer described later can be suitably used.
The content of the surfactant used in the undercoat layer of the present invention is preferably 5% by mass or less, more preferably 0.001% by mass to 3% by mass, and more preferably 0.005% by mass with respect to the total solid content of the undercoat layer. Above 1% by mass is particularly preferred.

<Polymerization inhibitor>
The undercoat layer used in the lithographic printing plate precursor according to the invention may contain a polymerization inhibitor in order to improve the stability of the lithographic printing plate precursor. As the polymerization inhibitor contained in the undercoat layer, a polymerization inhibitor used in the photosensitive layer described later can be preferably used.
The content of the polymerization inhibitor used in the undercoat layer of the present invention is preferably 5% by mass or less, more preferably 0.001% by mass to 4% by mass, and more preferably 0.005% by mass with respect to the total solid content of the undercoat layer. Above 3% by mass is particularly preferable.

<Initiator>
The undercoat layer used in the lithographic printing plate precursor according to the invention may contain an initiator in order to improve the sensitivity of the lithographic printing plate precursor. As the initiator contained in the undercoat layer, a radical polymerization initiator used in the photosensitive layer described later can be preferably used.
The content of the initiator used in the undercoat layer of the present invention is preferably 5% by mass or less, more preferably 0.001% by mass or more and 4% by mass or less, and more preferably 0.005% by mass or more with respect to the total solid content of the undercoat layer. Less than 3% by weight is particularly preferred.

<Sensitizing dye>
The undercoat layer used in the lithographic printing plate precursor according to the invention may contain a sensitizing dye in order to improve the sensitivity of the lithographic printing plate precursor. As the sensitizing dye contained in the undercoat layer, a sensitizing dye used in the photosensitive layer described later can be suitably used.
The content of the sensitizing dye used in the undercoat layer of the present invention is preferably 5% by mass or less, more preferably 0.001% by mass to 4% by mass, and more preferably 0.005% by mass with respect to the total solid content of the undercoat layer. More than 3% by mass is particularly preferable.

<Co-sensitizer>
The undercoat layer used in the lithographic printing plate precursor according to the invention may contain a co-sensitizer in order to improve the sensitivity of the lithographic printing plate precursor. As the co-sensitizer contained in the undercoat layer, a co-sensitizer used in the photosensitive layer described later can be suitably used.
The content of the co-sensitizer used in the undercoat layer of the present invention is preferably 5% by mass or less, more preferably 0.001% by mass to 4% by mass, and more preferably 0.005% by mass with respect to the total solid content of the undercoat layer. % Or more and less than 3% by mass is particularly preferable.

<Formation of undercoat layer>
The undercoat layer of the present invention is formed by preparing or applying 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. A solvent is used individually or in mixture. The solid content concentration of the coating solution is preferably 0.05 to 50% by mass, more preferably 0.1 to 25% by mass.

The undercoat 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 repeating a plurality of coating and drying steps.
The coating amount (solid content) of the undercoat layer on the support obtained after coating and drying varies depending on the use, but is generally preferably 0.001 to 0.5 g / m ² , and preferably 0.003 to 0.25 g / m ² is more preferable, and 0.005 to 0.1 g / m ² is particularly preferable. Within this range, good sensitivity, stain resistance and printing durability can be obtained.
Various methods can be used as the coating method. Examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.

(Photosensitive layer)
The photosensitive layer of the lithographic printing plate precursor according to the invention is a photosensitive layer in which an unexposed portion can be removed in the presence of a developer having a pH of 2 to 11, and does not adsorb to the polymer compound of the undercoat layer as an essential component. Contains pigments. As a preferred embodiment, a radical polymerizable compound, a radical polymerization initiator, a sensitizing dye, a co-sensitizer, and a binder polymer are added to the photosensitive layer. Moreover, the photosensitive layer can contain a coloring agent and other arbitrary components as needed.
Control of the developing speed of the unexposed part of the photosensitive layer and the penetration speed of the developer into the photosensitive layer after curing can be performed by a conventional method in addition to the method using a binder polymer. Addition of a hydrophilic compound is useful for improving the speed, and addition of a hydrophobic compound is useful for suppressing the penetration of the developer into the exposed area.

In the lithographic printing plate precursor according to the invention, a protective layer (also referred to as an overcoat layer) may be further provided on the photosensitive layer in order to perform exposure in the air. The protective layer prevents exposure of low molecular weight compounds such as oxygen and basic substances present in the atmosphere that hinder the image formation reaction caused by exposure in the photosensitive layer to allow exposure in the atmosphere. To do.
Below, each component which comprises the photosensitive layer of the lithographic printing plate precursor concerning this invention is demonstrated.

<Pigment>
As the pigment used in the present invention, any pigment that does not adsorb to the polymer compound of the undercoat layer can be suitably used. However, at least (a) a functional group (pigment adsorbing group) adsorbed on the pigment and (b It is preferably a pigment dispersed with a compound having a functional group (dispersing group) imparting organic solvent dispersibility (hereinafter also referred to as a pigment dispersant). The pigment dispersant is preferably a compound comprising at least (a) a unit having a pigment adsorbing group and (b) a unit having a dispersing group.
The unit having a functional group (pigment adsorbing group or dispersing group) in the pigment dispersant used in the present invention is a unit composed of a low molecular compound (molecular weight of 1000 or less) containing a functional group. Examples of the low molecular weight compound include a monomer having a functional group, and the functional group and the polymerizable double bond group are bonded directly or via a connecting chain. The connecting chain may be arbitrary, and is usually formed of one or more selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, silicon atoms, hydrogen atoms, halogen atoms, and boron atoms.

The (b) dispersing group used in the present invention is a group that imparts organic solvent dispersibility to the pigment, and any functional group can be suitably used as long as it has such a function. (B) Specific examples of the dispersing group include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, -OR, -NRR ', -SR, -COR, -COOR, -CONRR', -OCOR, -OCONRR ', -OCOOR, -NRCOR ', - NRCOOR' , - NRCONR'R '', - N = R, -SO 2 R, -SO 3 R, -SO 2 NRR ', a hydrogen atom, a halogen group, a cyano group, a nitro group A hydroxyl group and a mercapto group (R, R ′ and R ″ each independently represents an alkyl group, an aryl group, an alkenyl group, an alkynyl group or a hydrogen atom, or they are bonded to each other to form a ring. You may do it.)

Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, Octadecyl group, eicosyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group, Examples thereof include linear, branched, or cyclic alkyl groups having 30 or less carbon atoms such as a cyclohexyl group, 1-adamantyl group, and 2-norbornyl group.
Specific examples of the alkenyl group include a vinyl group, 1-propenyl group, 1-butenyl group, 1-methyl-1-propenyl group, 1-cyclopentenyl group, 1-cyclohexenyl group and the like having 30 or less carbon atoms. A linear, branched, or cyclic alkenyl group is mentioned.
Specific examples of the alkynyl group include alkynyl groups having 30 or less carbon atoms such as ethynyl group, 1-propynyl group, 1-butynyl group, 1-octynyl group and the like.

  Specific examples of the aryl group include those in which 1 to 4 benzene rings form a condensed ring, and those in which a benzene ring and an unsaturated five-membered ring form a condensed ring. Specific examples include Examples thereof include aryl groups having 30 or less carbon atoms, such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, a fluorenyl group, and a pyrenyl group. In addition, a heteroaryl group containing at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom can also be mentioned. Specific examples of the heteroaryl group include pyrrole, furan, thiophene, pyrazole, imidazole. , Triazole, oxazole, isoxazole, oxadiazole, thiazole, thiadiazole, indole, carbazole, benzofuran, dibenzofuran, thianaphthene, dibenzothiophene, indazolebenzimidazole, anthranyl, benzisoxazole, benzoxazole, benzothiazole, purine, pyridine, pyridazine , Pyrimidine, pyrazine, triazine, quinoline, acridine, isoquinoline, phthalazine, quinazoline, quinoxaline, naphthyridine, phenanthroli Include groups derived from heterocyclic pteridine and the like.

One or more of the above alkyl groups, aryl groups, alkenyl groups, and alkynyl groups may be substituted with any substituent. Examples of the substituent include monovalent non-metallic atomic groups excluding hydrogen, halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups. , 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-aryl Amino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyl Oxy, alkylsulfoxy, arylsulfoxy, acylthio Group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N '-Diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl-N-arylureido Group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group, N′-aryl-N-arylureido Group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-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 and its conjugate base 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, alkylsulfinyl Group, Arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group, alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N— Dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N -Dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N-acylsulfamoyl group and its conjugate base group, N- alkylsulfonylsulfamoyl group (-SO ₂ NHSO ₂ ( lkyl)) and its conjugated base group, N- aryl sulfonylsulfamoyl group _{(-SO 2 NHSO 2 (aryl)} ) and its conjugated base group, N- alkylsulfonylcarbamoyl group (-CONHSO ₂ (alkyl)) and its conjugate Base group, N-arylsulfonylcarbamoyl group (—CONHSO ₂ (aryl)) and its conjugate base group, alkoxysilyl group (—Si (Oalkyl) ₃ ), aryloxysilyl group (—Si (Oaryl) ₃ ), hydroxysilyl Group (—Si (OH) ₃ ) and its conjugate base group, phosphono group (—PO ₃ H ₂ ) and its conjugate base group, dialkylphosphono group (—PO ₃ (alkyl) ₂ ), diarylphosphono group (— PO ₃ (aryl) _2), alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )) Monoalkyl phosphono group (-PO ₃ H (alkyl)) and its conjugated base group, monoaryl phosphono group (-PO ₃ H (aryl)) and its conjugated base group, a phosphonooxy group (-OPO ₃ H ₂₎ and Its conjugated base group, dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy group (—OPO ₃ (alkyl) (aryl) )), Monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group, monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group, cyano group, nitro group , Aryl group, alkyl group, alkenyl group and alkynyl group.

  The dispersing group of the pigment dispersant used in the pigment of the present invention is preferably a functional group having a hydrocarbon (alkyl, aryl, alkenyl, alkynyl) group having 6 or more carbon atoms, or a polyalkylene oxide group, and having 9 or more carbon atoms. Of these, a functional group having a hydrocarbon group and a polyalkylene oxide group are more preferred. Only one type of dispersing group may be used, or two or more types may be used in combination. The dispersing group is preferably present at 0.05 mmol or more, more preferably 0.1 mmol or more, per 1 g of pigment dispersant.

As the functional group (a) adsorbed on the pigment used in the present invention, various functional groups can be selected depending on the type of pigment. When the pigment surface is substituted with an acidic functional group, a basic functional group such as an amino group or anilino group is preferred. When the pigment surface is substituted with a basic functional group, a carboxyl group, a phosphoric acid group, or a phosphonic acid group Acidic functional groups such as sulfonic acid groups and sulfuric acid groups are preferred. Moreover, when a pigment contains a metal, the functional group coordinated to these metals and the functional group which has a structure similar to a pigment, and adsorb | sucks by pi-pi interaction etc. are mentioned. Among these functional groups, the adsorption amount of the functional group on the pigment is more preferably 0.01 mmol / g or more. The adsorption amount with respect to the pigment mentioned here is a value obtained by the following method.
That is, a low molecular weight compound having a functional group (molecular weight of 1000 or less) is dissolved in a suitable solvent to prepare solution 1, 1 g of the pigment used in solution 1 is added, and the mixture is stirred at room temperature for 4 hours and filtered through a filter. 2 is prepared. In this method, the low molecular weight compound having the functional group contained in Solution 1 and Solution 2 is quantified by HPLC, and the amount of the low molecular weight compound adsorbed on 1 g of pigment is determined from the decrease amount.

Among the pigment adsorbing groups, the pigment adsorbing group used in the present invention particularly preferably satisfies either of the following conditions 1 and 2.
Condition 1: The hydrophilic functional group is a neutral group and the pigment adsorbing group is an acidic group, a neutral group, and a basic group. Condition 2: The hydrophilic functional group is a basic group and the pigment adsorbing group is an acidic group. Neutral group

  As the pigment adsorbing group used in the present invention, any functional group as described above is preferably used, but the acidic group is represented by the following general formulas (PA-1) to (PA-5). Are preferred. Of these, the functional groups represented by (PA-2) and (PA-5) are particularly preferable.

In the formula, L represents a divalent linking group for linking to the compound mother nucleus, and is selected from a carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, silicon atom, hydrogen atom, halogen atom and boron atom. Or more than one kind. Specific examples of L include specific examples of the divalent linking group described for the hydrophilic group in the polymer compound.
As the basic group, functional groups represented by the following general formulas (PB-1) to (PB-12) are preferable. Among these, the functional groups represented by (PB-1), (PB-10), (PB-11), and (PB-12) are particularly preferable.

In the formula, each of R _{11 to} R ₁₈ independently represents an alkyl group, an aryl group, an alkenyl group, an alkynyl group, —OR, —NRR ′, —SR, —COR, —COOR, —CONRR ′, —OCOR, — OCONRR ′, —OCOOR, —NRCOR ′, —NRCOOR ′, —NRCONR′R ″, —N═R, —SO ₂ R, —SO ₃ R, —SO ₂ NRR ′, hydrogen atom, halogen group, cyano group , A nitro group, a hydroxyl group or a mercapto group (R, R ′, R ″ each independently represents an alkyl group, an aryl group, an alkenyl group, an alkynyl group, or a hydrogen atom, or they are bonded to each other to form a ring. May be). The alkyl group, aryl group, alkenyl group, and alkynyl group may have a substituent. Specific examples of R _{11 to} R ₁₈ include the specific examples of R _{1 to} R ₇ described for the hydrophilic group in the above-described polymer compound. R _{11 to} R ₁₈ include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, —OR, —NRR ′, —SR, —COOR, —CONRR ′, —OCOR, —OCONRR ′, —NRCOR ′, and —NRCOOR. ', -NRCONR'R'', a hydrogen atom or a halogen group is preferable, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, -OR, -NRR', -COOR, -CONRR ', -OCOR, -NRCOR', A hydrogen atom and a halogen group are more preferable, and an alkyl group, an aryl group, an alkenyl group, an alkynyl group, —OR, —NRR ′, a hydrogen atom, and a halogen group are particularly preferable.
L represents a divalent linking group for linking to the compound mother nucleus, one kind selected from a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a hydrogen atom, a halogen atom and a boron atom. It is formed by the above. Specific examples of L include specific examples of L in the acidic group.

X represents an oxygen atom, a sulfur atom, a selenium atom or NR ₁₉ , and R ₁₉ has the same definition as R ₁₁ . X is preferably an oxygen atom, a sulfur atom, or NR ₁₉ , and particularly preferably an oxygen atom or NR ₁₉ .
Y represents a covalent bond, an oxygen atom, a sulfur atom, NR ₁₉ , CO or SO ₂ , and R ₁₉ has the same definition as R ₁₁ . Y is preferably a covalent bond, an oxygen atom, NR ₁₉ , or CO, and more preferably a covalent bond, an oxygen atom, or CO.

Further, L, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ in the same functional group may be bonded to each other to form a ring. That is, L in the formula (PB-1)
And R ₁₁ , L and R ₁₁ and R ₁₂ in Formula (PB-2), L and R ₁₁ in Formula (PB-3), L and R ₁₁ and R ₁₂ in Formula (PB-4), Formula (PB− L and _{R 11} and _{R 12} in 5), equation (PB-6) in the L and _{R 11} and _{R 12} and _{R 13,} formula (PB-7 L and _{R 11} in) and _{R 12} and _{R 13,} formula (PB L and _{R 11} and _{R 12} and _{R 13} in -8), L and _{R 11} and _{R 12} and _{R 13} in formula (PB-9), and L and X and _{RR 11} and _{R 12} in formula (PB-10) R ₁₃ and _{R 14,} formula (PB-11) in the L, Y and _{R 11} and _{R 12} and _{R 13} and _{R 14} and _{R 15} and _{R 16} and _{R 17} and _{R 18,} and L in formula (PB-12) A ring may be formed by any two of R ₁₁ and R ₁₂ .

  As the neutral group, functional groups represented by the following general formulas (PN-1) and (PN-2) are preferable.

In the formula, R ₁₁ and R ₁₂ are each independently an alkyl group, aryl group, alkenyl group, alkynyl group, —OR, —NRR ′, —SR, —COR, —COOR, —CONRR ′, —OCOR, — OCONRR ′, —OCOOR, —NRCOR ′, —NRCOOR ′, —NRCONR′R ″, —N═R, —SO ₂ R, —SO ₃ R, —SO ₂ NRR ′, hydrogen atom, halogen group, cyano group , A nitro group, a hydroxyl group or a mercapto group (R, R ′, R ″ each independently represents an alkyl group, an aryl group, an alkenyl group, an alkynyl group, or a hydrogen atom, or they are bonded to each other to form a ring. May be). The alkyl group, aryl group, alkenyl group, and alkynyl group may have a substituent. Specific examples of the alkyl group, aryl group, alkenyl group, and alkynyl group are the same as in the case of R _{11 to} R ₁₈ described above. R ₁₁ and R ₁₂ are preferably an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a hydrogen atom, a halogen group, —OR, —NRR ′, and —SR, and an alkyl group, an aryl group, an alkenyl group, an alkynyl group, A hydrogen atom, —OR, and —NRR ′ are more preferable, and an alkyl group, an aryl group, a hydrogen atom, —OR, and —NRR ′ are particularly preferable.

L represents a divalent linking group for linking to the compound mother nucleus, one kind selected from a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a hydrogen atom, a halogen atom and a boron atom. It is formed by the above. Specific examples of L are the same as those of L in the acidic group.
A ring may be formed by any two of L, R ₁₁ and R ₁₂ .

  Only one type of pigment adsorbing group may be used, or two or more types may be used in combination. The pigment adsorbing group is preferably present in an amount of 0.05 mmol or more per gram of pigment dispersant, and more preferably 0.1 mmol or more.

  Specific examples of the pigment dispersant used in the present invention are described below. The present invention is not limited to these.

  In the present invention, the combination of the hydrophilic group used in the undercoat layer polymer compound and the pigment adsorbing group used in the pigment dispersant of the photosensitive layer pigment is important. When the hydrophilic group used in the undercoat layer polymer compound is a neutral group, an acidic group, a basic group, or a neutral group can be used as the pigment adsorption group. When the hydrophilic group used in the undercoat layer polymer compound is a basic group, an acidic group or a neutral group can be used as the pigment adsorption group.

The mass average molecular weight of the pigment dispersant used in the present invention is preferably from 1,000 to 1,000,000, more preferably from 2,000 to 500,000, and even more preferably from 5,000 to 200,000.
The amount of the pigment dispersant added is preferably 10 to 200% by mass, more preferably 30 to 100% by mass, based on the pigment.

As the pigment used in the present invention (hereinafter also referred to as the pigment of the present invention), conventionally known pigments including commercially available pigments can be suitably used. For example, those described in the revised new edition Handbook for Pigments (edited by the Japan Pigment Technology Association) (Seibundo Shinkosha), the Color Index Handbook, and the like. Examples of the pigment include black pigments, yellow pigments, red pigments, brown pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, and metal powder pigments. Specifically, for example, inorganic pigments (titanium dioxide, carbon black, graphite, zinc oxide, Prussian blue, cadmium sulfide, iron oxide and lead, zinc, barium and calcium chromates) and organic pigments (azo-based, thioindigo) , Anthraquinone, anthanthrone, and triphendioxazine pigments, vat dye pigments, phthalocyanine pigments and derivatives thereof, quinacridone pigments, and the like. Among these, it is preferable to add a pigment having substantially no absorption in the absorption wavelength region of the sensitizing dye corresponding to the laser used for image exposure, and specifically, a pigment using an integrating sphere at the laser wavelength. It is preferable that the reflection absorption is 0.05 or less.

  In addition, when using an argon laser, SHG-YAG laser or violet laser, which is currently mainstream in a photopolymerization type lithographic printing plate precursor, pigment absorption in the above photosensitive wavelength region and visible image property after development From the viewpoint, it is preferable to use a purple pigment or a blue pigment. Examples of such a pigment include cobalt blue, cerulean blue, alkaline blue lake, phonatone blue 6G, Victoria blue lake, metal-free phthalocyanine blue, and phthalocyanine blue first. Examples include Sky Blue, Indanthrene Blue, Indigo, Dioxane Violet, Isoviolanthrone Violet, Indanthrone Blue, Indanthrone BC. Of these, phthalocyanine blue and dioxane violet are more preferable.

The pigment of the present invention may be used after being subjected to surface treatment or may be used without being subjected to surface treatment. As a surface treatment method, for example, a treatment with a resin, wax, surfactant, other coupling agent, or the like as described in JP-A-3-69949 may be performed.
The average particle size of the pigment of the present invention in the photosensitive layer is preferably 0.05 μm or more and 1.5 μm or less, and more preferably 0.1 μm or more and 1.0 μm or less. By setting it in the above range, printing durability is improved, and no soiling occurs on the support. However, if the particle size is smaller than 0.05 μm, it does not contribute to the improvement of the printing durability, but also clogs the surface of the support to which hydrophilicity has been applied, which may cause background staining, which is not preferable. On the other hand, if the particle size is larger than 1.5 μm, it sometimes becomes larger than the dry film thickness of the photosensitive layer, and the effects of the present invention may not be effectively achieved.

Examples of the method for measuring the average particle size of the pigment of the present invention include measurement with a transmission electron microscope. In the present invention, the primary average particle diameter of the pigment is defined as 0.1 mg of a pigment dispersion solution after dispersing the pigment in a single solvent on 200 mesh with a hydrophilized carbon support film and applied by a spin coater. The average particle size of the dried sample, and the particle size in the layer is a sample prepared by applying and drying a photosensitive solution with a solid content of 10% at 95 ° C. on a PET film so as to be 3 g / m ^2. After coating and drying and curing a room temperature curable epoxy resin on the surface of the glass, an ultra-thin piece (section thickness: 150 nm) was produced by a microtome, and the average of pigment aggregates observed on a 200 mesh with a carbon support film subjected to hydrophilic treatment Refers to particle size. The measurement at this time was performed using a transmission electron microscope (JEM-2000FX manufactured by JEOL Ltd.), and the measurement conditions were an acceleration voltage: 200 kV.

  In the pigment of the present invention, the ratio between the primary average particle diameter of the pigment and the pigment particle diameter in the photosensitive layer is preferably 1: 1 or more and 1:15 or less. The above ratio means that the average particle diameter of the pigment in the photosensitive layer is preferably as close as possible to the primary average particle diameter, and the pigment is finely, uniformly and stably dispersed in the photosensitive layer. Has been. If the above ratio exceeds 1:15, the pigment is enlarged, which is not preferable.

Examples of the method for setting the particle size of the pigment of the present invention in the photosensitive layer to 0.05 μm or more and 1.5 μm or less include, for example, dispersing the pigment in a single solvent and forming the solvent with the solvent. The method used as the main solvent of the solution for the above. An organic solvent is indispensable as a solvent used in the dispersion of the pigment, and these solvents are preferably used as a single solvent as described above from the viewpoint of dispersion stability. Preferred organic solvents include alcohol solvents such as methanol, ethanol, propanol, isopropanol and 1-methoxy-2-propanol, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, and esters such as ethyl acetate, butyl acetate and γ-butyrolactone. Solvents, ether solvents such as tetrahydrofuran, 1,3-dioxolane, diisopropyl ether, hydrocarbon solvents such as toluene, hexane, xylene, amide solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, chloroform, A halogen-based solvent such as carbon chloride and an existing solvent such as dimethyl sulfoxide can be used, but a ketone-based organic solvent having a solubility parameter value (SP value) in the range of 9 to 10.5 is preferable. And cyclohexanone (9.9), methyl ethyl ketone (MEK) (9.3), cyclopentanone (10.4), methylcyclohexanone (9.3) and the like. Among these, methyl ethyl ketone and cyclohexanone are the most preferred. It is.

When the pigment is dispersed, the use of the organic solvent as a solvent greatly affects the dispersion stability when the pigment dispersion is added to the photosensitive layer composition. In addition, the use of a solvent as a main solvent of a solution dissolved in a solvent for forming a photosensitive layer also contributes greatly to dispersion stability.
In this way, the pigment of the present invention dispersed in an organic solvent can have an average particle size in the photosensitive layer of 0.05 to 1.5 μm and is very fine, uniformly and stably dispersed. A dispersion of the pigment particles thus prepared can be prepared.
When dispersing, it is common to add a pigment and a pigment dispersant in the above-mentioned solvent so as to have a concentration of 10 to 30% by mass and disperse with a paint shaker or the like, but other known dispersion methods are also suitable. Can be used for
The content of the pigment dispersed by the pigment dispersant in the photosensitive layer is not particularly limited, but is preferably 0.01 to 20% by mass, more preferably 0.05 to 15% by mass, and still more preferably, It is 0.1-10 mass%.

<Radically polymerizable compound>
The radically polymerizable compound (hereinafter also referred to as a polymerizable compound) used in the photosensitive layer in the invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has at least one terminal ethylenically unsaturated bond. It is selected from compounds having, preferably two or more. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. The polymerizable compound has a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a copolymer thereof, or a mixture thereof. Examples of monomers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, preferably unsaturated carboxylic acids. An ester of an acid and an aliphatic polyhydric alcohol compound and an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound are 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 monofunctional or polyfunctional 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 In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. 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, isocyanuric acid ethylene oxide (EO) Examples include modified triacrylates and polyester acrylate oligomers.

  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 Sorbitol tetritaconate, etc. 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 aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59- Those having an aromatic skeleton described in JP-A No. 5241 and JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are also preferably used.
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 No. 54-21726.

  Further, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinylurethane compound 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 Etc.

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

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in Japanese Patent No. 17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable. 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 (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. In addition, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and vinylphosphonic acid-based compounds described in JP-A-2-25493 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, photocurable monomers and oligomers described on pages 300 to 308 (1984) can also be used.

About the polymerizable compound, 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 portion, that is, the cured film, those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether type). A method of adjusting both sensitivity and strength by using a compound) is also effective.
In addition, the compatibility and dispersibility with other components in the photosensitive layer (for example, binder polymer, polymerization initiator, colorant, etc.), the selection and use method of the polymerizable compound is an important factor. In some cases, the compatibility can be improved by using a low-purity compound or by using two or more kinds in combination. In addition, a specific structure may be selected for the purpose of improving adhesion to a support or a protective layer described later. In addition, the usage of the polymerizable compound can be arbitrarily selected from the viewpoint of polymerization inhibition with respect to oxygen, resolution, fogging, refractive index change, surface adhesiveness, etc. The layer construction and coating method such as undercoating and overcoating can be considered.

The polymerizable compound is preferably used in the range of 5 to 75% by mass, more preferably 25 to 70% by mass, and particularly preferably 30 to 60% by mass with respect to the total solid content of the photosensitive layer.

<Radical polymerization initiator>
The radical polymerization initiator used in the photosensitive layer of the present invention (hereinafter also referred to as a polymerization initiator or an initiator compound) is subjected to actions such as electron transfer, energy transfer, and heat generation caused by the electronic excitation state of the sensitizing dye, A compound that undergoes a chemical change to produce at least one selected from radicals, acids and bases. Hereinafter, radicals, acids, and bases generated in this way are simply referred to as active species. When the initiator compound is not present or when only the initiator compound is used alone, practically sufficient sensitivity cannot be obtained. As one mode in which a sensitizing dye and an initiator compound are used in combination, they can be used as a single compound by an appropriate chemical method (such as linking a sensitizing dye and an initiator compound through a chemical bond). It is.

  Usually, many of these initiator compounds are considered to generate active species through the initial chemical processes represented by the following (1) to (3). (1) Reductive decomposition of the initiator compound based on the electron transfer reaction from the electronically excited state of the sensitizing dye to the initiator compound, (2) Electron transfer from the initiator compound to the electronically excited state of the sensitizing dye (3) decomposition of the initiator compound from the electronically excited state based on energy transfer from the electronically excited state of the sensitizing dye to the initiator compound. In many cases, it is unclear as to which type of (1) to (3) each initiator compound belongs, but in the present invention, it is very high when combined with any of these types of initiator compounds. A sensitizing effect is obtained.

As the initiator compound in the present invention, those known among those skilled in the art can be used without limitation. Specifically, for example, trihalomethyl compounds, carbonyl compounds, organic peroxides, azo compounds, azide compounds, metallocene compounds, Examples include hexaarylbiimidazole compounds, organic boron compounds, disulfone compounds, oxime ester compounds, onium salt compounds, and iron arene complexes. Among these, at least one selected from hexaarylbiimidazole compounds, onium salt compounds, trihalomethyl compounds, and metallocene compounds is preferable, and hexaarylbiimidazole compounds are particularly preferable.
Two or more polymerization initiators may be used in combination as appropriate.

Examples of hexaarylbiimidazole compounds include lophine dimers described in JP-B-45-37377 and JP-B-44-86516, such as 2,2'-bis (o-chlorophenyl) -4,4 ', 5. , 5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2, 2'-bis (o, o'-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,4', 5,5 ' -Te Raphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-trifluorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and the like.
The hexaarylbiimidazole compound is particularly preferably used in combination with a sensitizing dye having a maximum absorption at 350 to 450 nm.

Onium salts that are preferably used in the present invention (in the present invention, function as ionic polymerization initiators, not as acid generators) are represented by the following general formulas (RI-I) to (RI-II).
An onium salt represented by I).

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 a carbon number. C2-C12 alkenyl group, C2-C12 alkynyl group, C6-C12 aryl group, C1-C12 alkoxy group, C6-C12 aryloxy group, halogen atom, C1-C1 12 alkylamino groups, C2-C12 dialkylamino groups, C2-C12 alkylamide groups or arylamide groups, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, C1-C12 thioalkyl groups And a thioaryl group having 6 to 12 carbon atoms. Z ₁₁ ^- represents a monovalent anion, specifically a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, a sulfate ion Can be mentioned. Of these, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion and sulfinate ion are preferable from the viewpoint of stability.

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 include 1 to 12 alkyl groups, alkenyl groups having 2 to 12 carbon atoms, alkynyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryloxy groups having 6 to 12 carbon atoms, Halogen atom, C1-C12 alkylamino group, C2-C12 dialkylamino group, C2-C12 alkylamide group or arylamide group, carbonyl group, carboxyl group, cyano group, sulfonyl group, carbon Examples thereof include a thioalkyl group having 1 to 12 carbon atoms and a thioaryl group having 6 to 12 carbon atoms. Z ₂₁ ⁻ represents a monovalent anion. Specific examples include halogen ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, thiosulfonate ions, sulfate ions, and carboxylate ions. Among these, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, and carboxylate ion are preferable from the viewpoint of stability and reactivity.

In the formula (RI-III), R ₃₁ , R ₃₂ and R ₃₃ are each independently an aryl group, alkyl group, alkenyl group or alkynyl having 20 or less carbon atoms, which may have 1 to 6 substituents. Represents a group. Among them, an aryl group is preferable from the viewpoint of reactivity and stability. Examples of the substituent include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, Aryloxy group having 6 to 12 carbon atoms, halogen atom, alkylamino group having 1 to 12 carbon atoms, dialkylamino group having 2 to 12 carbon atoms, alkylamide group or arylamide group having 2 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 6 to 12 carbon atoms. Z ₃₁ ^- represents a monovalent anion. Specific examples include halogen ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, thiosulfonate ions, sulfate ions, and carboxylate ions. Of these, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, and carboxylate ion are preferable from the viewpoints of stability and reactivity. 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.
The onium salt is particularly preferably used in combination with an infrared absorber having a maximum absorption in a wavelength range of 750 to 1400 nm.

  Other polymerization initiators include JP-A-2007-171406, JP-A-2007-206216, JP-A-2007-206217, JP-A-2007-225701, JP-A-2007-225702, JP-A-2007-316582, The polymerization initiators described in JP-A-2007-328243 can be preferably used.

The polymerization initiator in the present invention is suitably used alone or in combination of two or more.
The amount of the polymerization initiator used in the photosensitive layer in the present invention is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, based on the total solid content of the photosensitive layer. More preferably, it is 1.0 mass%-10 mass%.

<Sensitizing dye>
The photosensitive layer of the present invention has a sensitizing dye, for example, a sensitizing dye having a maximum absorption in the wavelength range of 350 to 450 nm, a sensitizing dye having a maximum absorption in the wavelength range of 500 to 600 nm, and a wavelength range of 750 to 1400 nm. By adding an infrared absorber having a maximum absorption, a highly sensitive lithographic printing plate precursor corresponding to a 405 nm violet laser, a 532 nm green laser, and a 803 nm IR laser, which are usually used in the industry, is provided. be able to.
First, a sensitizing dye having a maximum absorption in the wavelength region of 350 to 450 nm will be described. Examples of such a sensitizing dye include merocyanine dyes, benzopyrans, coumarins, aromatic ketones, anthracenes, and the like.

  Of the sensitizing dyes having an absorption maximum in a wavelength range of 360 nm to 450 nm, a dye more preferable from the viewpoint of high sensitivity is a dye represented by the following general formula (IX).

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

General formula (IX) will be described in more detail. R ₁ , R ₂ and R ₃ are each independently a monovalent nonmetallic atomic group, preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group. Represents a substituted or unsubstituted aromatic heterocyclic residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, or a halogen atom.

Next, A in the general formula (IX) represents an aromatic ring group or a heterocyclic group which may have a substituent, and specific examples of the aromatic ring or heterocyclic ring which may have a substituent include The same thing as the substituted or unsubstituted aryl group described by R < ₁ >, R < ₂ > and R < ₃ > in general formula (IX), a substituted or unsubstituted aromatic heterocyclic residue is mentioned.

  Specific examples of such a sensitizing dye include the compounds described in JP-A-2007-58170, [0047] to [0053].

  Furthermore, sensitizing dyes represented by the following general formulas (V) to (VII) can also be used.

In formula (V), R ^{1 to} R ¹⁴ each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a cyano group or a halogen atom. However, at least one of R ^{1 to} R ¹⁰ represents an alkoxy group having 2 or more carbon atoms.
In the formula (VI), R ^{15 to} R ³² each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a cyano group, or a halogen atom. However, at least one of R ^{15 to} R ²⁴ represents an alkoxy group having 2 or more carbon atoms.

In formula (VII), R ¹ , R ² and R ³ each independently represents a halogen atom, an alkyl group, an aryl group, an aralkyl group, an —NR ⁴ R ⁵ group or an —OR ⁶ group, and R ⁴ , R ⁵ And R ⁶ each independently represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and k, m and n each represents an integer of 0 to 5.

JP-A-2007-171406, JP-A-2007-206216, JP-A-2007-206217, JP-A-2007-225701, JP-A-2007-225702, JP-A-2007-316582, JP-A-2007-328243 The sensitizing dyes described in each of the above publications can also be preferably used.
The preferable addition amount of the sensitizing dye having the maximum absorption in the wavelength range of 350 to 450 nm is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts per 100 parts by mass of the total solid content of the photosensitive layer. It is in the range of 0.2 to 10 parts by weight, most preferably 0.2 to 10 parts by weight.

Subsequently, a sensitizing dye having a maximum absorption in a wavelength range of 750 to 1400 nm that is preferably used in the present invention will be described in detail.
Such a sensitizing dye includes an infrared absorber, and is highly sensitive to infrared laser irradiation (exposure) and is in an electronically excited state. Electron transfer, energy transfer, and heat generation (photothermal conversion function) associated with the electronically excited state. It is estimated that these act on the polymerization initiator coexisting in the photosensitive layer to cause a chemical change in the polymerization initiator to generate radicals. In any case, the addition of a sensitizing dye having a maximum absorption at 750 to 1400 nm is particularly suitable for plate making directly drawn with an infrared laser beam having a wavelength of 750 to 1400 nm, and the conventional lithographic printing plate precursor Compared with this, high image forming properties can be exhibited.

  The infrared absorber is preferably a dye or pigment having an absorption maximum at a wavelength of 750 nm to 1400 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.
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 preferred, and particularly preferred examples include cyanine dyes represented by the following general formula (a).

In formula (a), 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 N, S, O, a halogen atom, and Se. 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 photosensitive 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. Moreover, as a preferable substituent, a C12 or less hydrocarbon group, a halogen atom, and a C12 or less alkoxy group are mentioned. 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. Preferred substituents include alkoxy groups having 12 or less carbon atoms, carboxyl groups, and sulfo groups. 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. In addition, Za ^-
Represents a counter anion. However, when the cyanine dye represented by formula (a) has an anionic substituent in its structure and does not require charge neutralization, Za ^- is not necessary. Preferred Za ⁻ is a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, particularly preferably a perchlorate ion, a hexagonal salt, in view of storage stability of the photosensitive layer coating solution. Fluorophosphate ions and aryl sulfonate ions. In addition, the thing which does not contain a halogen ion as a counter ion is especially preferable.

  Specific examples of the cyanine dye represented by formula (a) that can be suitably used include those described in paragraph numbers [0017] to [0019] of JP-A No. 2001-133969.

  Further, other particularly preferable examples include specific indolenine cyanine dyes described in JP-A-2002-278057.

  Examples of pigments include commercially available pigment and color index (CI) manuals, “Latest Pigment Handbook” (edited by the Japan Pigment Technology Association, published in 1977), “Latest Pigment Applied Technology” (published by CMC, published in 1986), “Printing” The pigments described in "Ink Technology", published by 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 Applications of Metal Soap” (Yokoshobo), “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 preferred particle size range, excellent dispersion stability of the pigment in the photosensitive layer can be obtained, and a uniform photosensitive 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).

  The infrared absorber may be added to the same layer as other components, or another layer may be provided and added thereto.

  From the viewpoint of uniformity in the photosensitive layer and durability of the photosensitive layer, the infrared absorbent is 0.01 to 50% by mass, preferably 0.1 to 10% by mass, based on the total solid content constituting the photosensitive layer. In the case of, it is particularly preferably 0.5 to 10% by mass, and in the case of a pigment, particularly preferably 0.1 to 10% by mass.

<Co-sensitizer>
In the photosensitive layer of the present invention, a known compound called a chain transfer agent or a co-sensitizer having an action such as further improving sensitivity or suppressing polymerization inhibition by oxygen may be added.

  Examples of such compounds include amines such as MR Sander et al., “Journal of Polymer Society”, Vol. 10, page 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, JP-A-59-138205, JP-A-60-84305, JP-A-62-18537, JP-A-64-33104, Research Disclosure 33825, and the like. In particular, N, N-dialkylaniline derivatives such as triethanolamine, N-phenylglycine, N-phenylaspartic acid, and p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline, etc. Is mentioned.

As another example of acting as a chain transfer agent, for example, a group of compounds having SH, PH, SiH, GeH in the molecule is used. These can donate hydrogen to low-activity radical species to generate radicals, or can be oxidized and then deprotonated to generate radicals.
In the photosensitive layer of the present invention, in particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.) Can be preferably used as a chain transfer agent.
Especially, the thiol compound represented by the following general formula (I) is used especially suitably. By using this thiol compound as a chain transfer agent, the problem of odor and sensitivity reduction due to evaporation from the photosensitive layer and diffusion to other layers are avoided, and it has excellent storage stability and high sensitivity and high printing durability. A lithographic printing plate precursor is obtained.

  In general formula (I), R represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and A has a carbon atom together with an N = CN moiety. It represents an atomic group that forms a 5-membered or 6-membered heterocycle, and A may further have a substituent.

  More preferably, those represented by the following general formula (IA) or general formula (IB) are used.

  In general formulas (IA) and (IB), R represents a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent, and X represents a hydrogen atom, a halogen atom, It represents an alkoxyl group that may have a substituent, an alkyl group that may have a substituent, or an aryl group that may have a substituent.

  Specific examples of the compound represented by formula (I) are shown below, but the present invention is not limited to these.

  The amount of the chain transfer agent such as a thiol compound used is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, based on the total solid content of the photosensitive layer. More preferably, it is 1.0-10 mass%.

<Binder polymer>
The binder polymer used in the photosensitive layer of the present invention is a polymer that functions as a film-forming agent for the photosensitive layer, and preferably contains a linear organic polymer. As such a linear organic polymer, known ones can be used.
Examples of the binder polymer are preferably polymers selected from acrylic resins, polyvinyl acetal resins, polyurethane resins, polyamide resins, epoxy resins, methacrylic resins, styrene resins, and polyester resins. Of these, acrylic resins and polyurethane resins are preferable. Here, the “acrylic resin” refers to an acrylic polymer having an acrylic acid derivative as a (co) polymerization component. “Polyurethane resin” refers to a polymer produced by a condensation reaction of a compound having two isocyanate groups and a compound having two or more hydroxyl groups.

Further, the binder polymer can be cross-linked 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 or may be introduced by a polymer reaction.

Here, the crosslinkable group is a group that crosslinks the binder polymer in the process of radical polymerization reaction that occurs in the photosensitive layer when the lithographic printing plate precursor is exposed. Although it will not specifically limit if it is a group of such a function, For example, an ethylenically unsaturated bond group, an amino group, an epoxy group etc. are mentioned as a functional group which can be addition-polymerized. Moreover, the functional group which can become a radical by light irradiation may be sufficient, and as such a crosslinkable group, a thiol group, a halogen group, an onium salt structure etc. are mentioned, for example. Especially, an ethylenically unsaturated bond group is preferable and the functional group represented by the following general formula (1)-(3) is especially preferable.

In the general formula (1), R ^{1 to} R ³ each independently represents a hydrogen atom or a monovalent organic group. R ¹ preferably includes a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom and a methyl group are preferable because of high radical reactivity. R ² and R ³ are each independently a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an optionally substituted alkyl group, or a substituted group. An aryl group that may have a group, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylamino group that may have a substituent, and a substituent An arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like. Among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, a substituent An alkyl group which may have a substituent and an aryl group which may have a substituent are preferable because of high radical reactivity.

X represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —, and R ¹² represents a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group for R ¹² include an alkyl group which may have a substituent. Among these, as R ¹² , a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group is preferable because of high radical reactivity.

  Examples of substituents that can be introduced include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, halogen atoms, amino groups, alkylamino groups, arylamino groups, carboxyl groups, alkoxycarbonyl groups, sulfo groups, A nitro group, a cyano group, an amide group, an alkylsulfonyl group, an arylsulfonyl group and the like can be mentioned.

In the general formula (2), R ^{4 to} R ⁸ each independently represents a hydrogen atom or a monovalent organic group. R ^{4 to} R ⁸ are preferably a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or an alkyl group which may have a substituent. An aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, a substituent An arylamino group that may have, an alkylsulfonyl group that may have a substituent, an arylsulfonyl group that may have a substituent, and the like, among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, An alkyl group which may have a substituent and an aryl group which may have a substituent are preferable.

Examples of the substituent that can be introduced are the same as those in the general formula (1). Y represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —. R ¹² has the same meaning as R ^{12 in} formula (1), and preferred examples thereof are also the same.

In General formula (3), R < ⁹ > -R < ¹¹ > represents a hydrogen atom or monovalent organic group each independently. R ⁹ is preferably a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom or a methyl group is preferable because of high radical reactivity. R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or an alkyl which may have a substituent. Group, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, substituent An arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, etc., among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group An alkyl group which may have a substituent and an aryl group which may have a substituent are preferable because of high radical reactivity.

Examples of the substituent that can be introduced are the same as those in the general formula (1). Z represents an oxygen atom, a sulfur atom, —N (R ¹² ) — or a phenylene group which may have a substituent. R ¹² has the same meaning as R ^{12 in} formula (1), and preferred examples thereof are also the same.
Among these, (meth) acrylic acid copolymers having a crosslinkable group in the side chain and polyurethane are more preferable.

  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.

  The binder polymer to be used is appropriately selected according to the mode of the development treatment so that the non-image portion of the photosensitive layer can be satisfactorily removed in the plate making process of the lithographic printing plate precursor. Details are given below.

(D-1) Alkali-soluble binder polymer In an embodiment in which the development treatment is performed using an alkali developer, the binder polymer needs to be dissolved in the alkali developer, and therefore an organic polymer compound that is soluble in alkaline water is preferred. used.
In order to be soluble in alkaline water, the binder polymer preferably has an alkali-soluble group. The alkali-soluble group is preferably an acid group, and examples thereof include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a hydroxyl group. Among these, a binder polymer having a carboxyl group is particularly preferable from the viewpoint of achieving both film properties, counter-printing properties, and developability.
Furthermore, the alkali-soluble binder polymer can be cross-linked as described above 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 or may be introduced by a polymer reaction.

The alkali-soluble binder polymer preferably has a mass average molecular weight of 5,000 or more, more preferably 10,000 to 300,000, and a number average molecular weight of 1,000 or more, preferably 2000 to 250,000. Is more preferable. The polydispersity (mass average molecular weight / number average molecular weight) is preferably 1.1 to 10.
The alkali-soluble binder polymer may be any of a random polymer, a block polymer, a graft polymer and the like, but is preferably a random polymer.
The alkali-soluble binder polymer may be used alone or in combination of two or more.
The content of the alkali-soluble binder polymer is usually 5 to 90% by mass, preferably 10 to 70% by mass, and more preferably 10 to 60% by mass with respect to the total solid content of the photosensitive layer. Within this range, good image area strength and image formability can be obtained.

(D-2) Binder polymer having a hydrophilic group As the binder polymer of the photosensitive layer of the present invention, a binder polymer having a hydrophilic group may be used in order to improve developability to a developer. In particular, when an acidic to weakly alkaline developer is used, this binder polymer is preferably used.
The hydrophilic group is selected from monovalent or divalent or higher hydrophilic groups, for example, an alkyleneoxy group such as hydroxy group, sulfonic acid group, carboxylic acid group, phosphoric acid group, ethyleneoxy group, propyleneoxy group, Primary amino group, secondary amino group, tertiary amino group, salt obtained by neutralizing amino group with acid, quaternary ammonium group, sulfonium group, iodonium group, phosphonium group, amide group, ether group, or carvone Salts obtained by neutralizing acid groups such as acids, sulfonic acids, and phosphoric acids are preferred. In particular, primary amino groups, secondary amino groups, tertiary amino groups, salts obtained by neutralizing amino groups with acids, fourth salts Secondary ammonium group, amide group, hydroxy group, —CH ₂ CH ₂ O—repeating unit, —CH ₂ CH ₂ NH—repeating unit are preferred, and tertiary amino group, acid group neutralized with amino group-containing compound A A salt formed by neutralization of the amino group with an acid, a quaternary ammonium group is most preferred.

The hydrophilic group-containing binder polymer is preferably a copolymer, and the proportion of the copolymer component having a hydrophilic group as described above in the total copolymer components of the copolymer is 1 to 70 from the viewpoint of developability. % Is preferred. In consideration of compatibility between developability and printing durability, 1 to 50% is more preferable, and 1 to 30% is particularly preferable.
The skeleton of the hydrophilic group-containing binder polymer is preferably a polymer selected from acrylic resins, polyvinyl acetal resins, polyvinyl alcohol resins, polyurethane resins, polyamide resins, epoxy resins, methacrylic resins, styrene resins, and polyester resins. Of these, acrylic resins, methacrylic resins, vinyl copolymers such as styrene resins, and polyurethane resins are particularly preferable.

The hydrophilic group-containing binder polymer used in the present invention preferably has a crosslinkable group as described above. The content of the crosslinkable group in the hydrophilic group-containing binder polymer (content of unsaturated double bond capable of radical polymerization by iodine titration) is preferably 0.01 to 10.0 mmol per 1 g of the hydrophilic group-containing binder polymer. More preferably, it is 0.05-5.0 mmol, Most preferably, it is 0.1-2.0 mmol.
Further, from the viewpoint of improving printing durability, the crosslinkable group is desirably in the vicinity of the hydrophilic group, and the hydrophilic group and the crosslinkable group may be on the same polymer unit.

  The hydrophilic group-containing binder polymer used in the present invention includes an alkyl (meth) acrylate or an aralkyl ester in addition to the unit having the hydrophilic group, the unit having a crosslinkable group, the unit having a hydrophilic group and a crosslinkable group. It is preferable to have these units. The alkyl group of the (meth) acrylic acid alkyl ester is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group. Examples of (meth) acrylic acid aralkyl esters include benzyl (meth) acrylate.

The hydrophilic group-containing binder polymer preferably has a mass average molecular weight of 5,000 or more, more preferably 10,000 to 300,000, and a number average molecular weight of 1,000 or more, preferably 2000 to 250,000. More preferably. The polydispersity (mass average molecular weight / number average molecular weight) is preferably 1.1 to 10.
The hydrophilic group-containing binder polymer may be any of a random polymer, a block polymer, a graft polymer, and the like.
The hydrophilic group-containing binder polymer may be used alone or in combination of two or more. The content of the hydrophilic group-containing binder polymer is preferably from 5 to 75 mass%, more preferably from 10 to 70 mass%, based on the total solid content of the photosensitive layer, from the viewpoint of good image area strength and image formation. More preferably, the content is 10 to 60% by mass.

  The total content of the polymerizable compound and the binder polymer is preferably 80% by mass or less based on the total solid content of the photosensitive layer. If it exceeds 80% by mass, the sensitivity and developability may be lowered. More preferably, it is 35-75 mass%.

Specific examples of the hydrophilic group-containing binder polymer used in the present invention are shown below, but the present invention is not limited thereto.
The molecular weight of each binder polymer is a mass average molecular weight (Mw) measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

<Microcapsule>
In the present invention, as a method for causing the photosensitive layer to contain the above-described photosensitive layer constituents and other constituents described later, for example, as described in JP-A Nos. 2001-277740 and 2001-277742, A part of the components can be encapsulated in microcapsules and added to the photosensitive layer. In that case, each component can be contained in any ratio in and out of the microcapsule.

  As a method for microencapsulating the photosensitive layer constituent components, known methods can be applied. 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. Moreover, you may introduce | transduce into the microcapsule wall the compound which has crosslinkable functional groups, such as an ethylenically unsaturated bond which can be introduce | transduced into said binder polymer.

  The average particle size of the microcapsules is preferably 0.01 to 3.0 μm. 0.05-2.0 micrometers is further more preferable, and 0.10-1.0 micrometer is especially preferable. Within this range, good resolution and stability over time can be obtained.

<Other photosensitive layer components>
The photosensitive layer of the present invention can further contain various additives as required. Additives include surfactants for promoting developability and improving the surface of the coating, hydrophilic polymers for improving developability and dispersion stability of microcapsules, and visual and non-image areas visible A colorant and a print-out agent, a polymerization inhibitor for preventing unnecessary thermal polymerization of radically polymerizable compounds during production or storage of the photosensitive layer, a higher fat derivative for preventing polymerization inhibition by oxygen, Examples include inorganic fine particles for improving the strength of the cured film in the image area, hydrophilic low molecular weight compounds for improving developability, co-sensitizers and chain transfer agents for improving sensitivity, and plasticizers for improving plasticity. . Any of these additives can be used, for example, JP 2007-171406, JP 2007-206216, JP 2007-206217, JP 2007-225701, JP 2007-225702. The compounds described in JP-A-2007-316582 and JP-A-2007-328243 can be used.

<Formation of photosensitive layer>
The photosensitive layer of the present invention is formed by preparing or applying 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 photosensitive 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.

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

[Protective layer]
In the lithographic printing plate precursor according to the invention, a protective layer (oxygen blocking layer) is preferably provided on the photosensitive layer in order to block diffusion and penetration of oxygen that hinders the polymerization reaction during exposure. The protective layer used in the present invention has an oxygen permeability A at 25 ° C. and 1 atm of 1.0 ≦ A ≦ 20 (mL / m ² · d
ay). When the oxygen permeability A is extremely low at less than 1.0 (mL / m ² · day), unnecessary polymerization reaction occurs at the time of production and raw storage, and unnecessary fogging and image streaking occur during image exposure. The problem that fatness arises arises. Conversely, when the oxygen permeability A is ^{20 (mL / m 2 · day} ) Beyond decrease in sensitivity may be incurred. The oxygen permeability A is more preferably 1.5 ≦ A ≦ 12 (mL / m ² · day), and further preferably 2.0 ≦ A ≦ 10.
The range is 0 (mL / m ² · day). In addition to the oxygen permeability described above, the properties desired for the protective layer are that the transmission of light used for exposure is not substantially inhibited, the adhesiveness with the photosensitive layer is excellent, and the development process after exposure It is desirable that it can be easily removed. The device concerning such a protective layer has been conventionally made, and is described in detail in US Pat. No. 3,458,311 and JP-B-55-49729.

  As the binder for the protective layer, for example, a water-soluble polymer compound having relatively excellent crystallinity is preferably used. Specifically, polyvinyl alcohol, vinyl alcohol / vinyl phthalate copolymer, vinyl acetate / vinyl alcohol / Water-soluble polymers such as vinyl phthalate copolymer, vinyl acetate / crotonic acid copolymer, polyvinyl pyrrolidone, acidic celluloses, gelatin, gum arabic, polyacrylic acid, polyacrylamide, etc., may be used alone or in combination Can be used. Of these, the use of polyvinyl alcohol as the main component gives the best results in terms of basic properties such as oxygen barrier properties and development removability.

  The polyvinyl alcohol used for the protective layer may be partially substituted with an ester, an ether, and an acetal as long as it contains an unsubstituted vinyl alcohol unit for having necessary oxygen barrier properties and water solubility. Similarly, some of them may have other copolymer components. Specific examples of the polyvinyl alcohol include those having a hydrolysis degree of 71 to 100 mol% and a polymerization repeating unit in the range of 300 to 2400. Specifically, Kuraray Co., Ltd. PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HC, PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA- 420, PVA-613, L-8 and the like, and these can be used alone or in combination. In a preferred embodiment, the content of polyvinyl alcohol in the protective layer is 20 to 95% by mass, and more preferably 30 to 90% by mass.

  Moreover, well-known modified polyvinyl alcohol can also be used preferably. For example, various hydrophilic modification sites such as anion modification sites modified with anions such as carboxyl groups and sulfo groups, cation modification sites modified with cations such as amino groups and ammonium groups, silanol modification sites, and thiol modification sites are randomly selected. Polyvinyl alcohol having various degrees of polymerization, the anion-modified site, the cation-modified site, the silanol-modified site, the thiol-modified site, the alkoxyl-modified site, the sulfide-modified site, and the ester modification of vinyl alcohol and various organic acids. Examples thereof include polyvinyl alcohol having various polymerization degrees having various modified sites such as a site, an ester-modified site of the anion-modified site and alcohols, an epoxy-modified site, and the like.

  As a component used by mixing with polyvinyl alcohol, polyvinyl pyrrolidone or a modified product thereof is preferable from the viewpoint of oxygen barrier properties and development removability, and the content in the protective layer is 3.5 to 80% by mass, preferably 10 to 60%. It is 15 mass%, More preferably, it is 15-30 mass%.

  Components of the protective layer (selection of PVA, use of additives), coating amount, and the like are selected in consideration of fogging, adhesion, and scratch resistance in addition to oxygen barrier properties and development removability. In general, the higher the hydrolysis rate of the PVA used (the higher the content of the unsubstituted vinyl alcohol unit in the protective layer), the thicker the film thickness, the higher the oxygen barrier property, which is advantageous in terms of sensitivity. The molecular weight of the binder such as polyvinyl alcohol (PVA) can be in the range of 2000 to 10 million, preferably in the range of 20,000 to 3 million.

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 binder to give flexibility, and sodium alkyl sulfate, sodium alkyl sulfonate, etc. Anionic surfactants; amphoteric surfactants such as alkylaminocarboxylates and alkylaminodicarboxylates; nonionic surfactants such as polyoxyethylene alkylphenyl ethers can be added in an amount of several mass% with respect to the binder.

  In addition, adhesion to the photosensitive layer and scratch resistance are extremely important in handling the plate. That is, when a hydrophilic layer made of a water-soluble polymer is laminated on an oleophilic photosensitive layer, film peeling due to insufficient adhesion tends to occur, and the peeled part causes defects such as poor film hardening due to inhibition of oxygen polymerization. On the other hand, various proposals have been made to improve the adhesion between these two layers. For example, in U.S. Patent Application No. 292,501 and U.S. Patent Application No. 44,563, an acrylic emulsion or a water-insoluble vinyl pyrrolidone-vinyl acetate copolymer is contained in a hydrophilic polymer mainly composed of polyvinyl alcohol. It is described that sufficient adhesiveness can be obtained by mixing 20 to 60% by mass and laminating on a photosensitive layer. Any of these known techniques can be applied to the protective layer in the present invention. Such a coating method for the protective layer is described in detail in, for example, US Pat. No. 3,458,311 and Japanese Patent Publication No. 55-49729.

Furthermore, the protective layer in the lithographic printing plate precursor according to the invention preferably contains an inorganic stratiform compound for the purpose of improving oxygen barrier properties and photosensitive layer surface protection.
Here, the inorganic layered compound is a particle having a thin flat plate shape. For example, the following general formula A (B, C) _2-5 D ₄ O ₁₀ (OH, F, O) ₂
[However, A is any one 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 present invention, among the inorganic layered compounds described above, fluorine-based swellable synthetic mica that is a synthetic inorganic layered compound is particularly useful.
The aspect ratio of the inorganic layered compound of the present invention is preferably 20 or more, more preferably 100 or more, and 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 particles of inorganic layered compounds having a large aspect ratio are contained in the protective layer in this way, the coating film strength is improved and oxygen and moisture permeation can be effectively prevented. Deterioration is prevented, and even when stored for a long time under high-humidity conditions, the storage stability of the planographic printing plate precursor does not deteriorate due to changes in humidity, and the storage stability is excellent.

  It is preferable that content of the inorganic stratiform compound in a protective layer is 5/1-1/100 by mass ratio with respect to the quantity of the binder used for a protective layer. 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 ratio.

  The dispersion method of the inorganic stratiform compound used for the protective layer is disclosed in JP 2007-171406, JP 2007-206216, JP 2007-206217, JP 2007-225701, JP 2007-225702, JP 2007. -316582, JP-A-2007-328243, etc. are used.

The coating amount of the protective layer is preferably 0.05 to 10 g / m ^{2 in} terms of the coating amount after drying. When the inorganic layered compound is contained, 0.1 to 0.5 g / The range of m ² is more preferable, and in the case where no inorganic layered compound is contained, the range of 0.5 to 5 g / m ² is more preferable.

[Support]
As the support for the lithographic printing plate precursor according to the invention, any material can be used as long as the surface is hydrophilic. However, a dimensionally stable plate-like material is preferable. For example, paper, plastic (for example, polyethylene, polypropylene, Paper laminated with polystyrene, etc., and also metals such as aluminum (including aluminum alloys), zinc, copper, etc. or alloys thereof (eg silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, A plate of an alloy with nickel), and further, for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose butyrate acetate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc. Plastic fi Beam, the above described metal or alloys having laminated or vapor-deposited paper or plastic films. Of these supports, the aluminum plate is particularly preferred because it is dimensionally remarkably stable and inexpensive. Further, a composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in Japanese Patent Publication No. 48-18327 is also preferable. Usually, the thickness is about 0.05 mm to 1 mm.

Further, in the case of a support having a surface of metal, particularly aluminum, surface treatment such as graining treatment described later, immersion treatment in an aqueous solution of sodium silicate, potassium fluoride zirconate, phosphate or the like, or bipolar oxidation treatment, etc. It is preferable that
<Graining process>
Examples of the graining method include mechanical graining, chemical etching, and electrolytic grain as disclosed in JP-A-56-28893. Furthermore, electrochemical graining method that electrochemically grains in hydrochloric acid or nitric acid electrolyte solution, and wire brush grain method that scratches aluminum surface with metal wire, and ball grain method that graines aluminum surface with polishing ball and abrasive. Further, a mechanical graining method such as a brush grain method in which the surface is grained with a nylon brush and an abrasive can be used, and the above graining methods can be used alone or in combination.
Among them, the method of making the surface roughness usefully used in the present invention is an electrochemical method of graining chemically in hydrochloric acid or nitric acid electrolyte, and a suitable current density is 100 C / dm ^{2 to} 400 C / dm. The range is ² . More specifically, in an electrolyte containing 0.1 to 50% hydrochloric acid or nitric acid, the temperature is 20 to 100 ° C., the time is 1 second to 30 minutes, and the current density is 100 C / dm ² to.
Electrolysis is preferably performed under the condition of 400 C / dm ² .

The grained aluminum support is chemically etched with acid or alkali. When an acid is used as an etching agent, it takes time to destroy the fine structure, which is disadvantageous when the present invention is applied industrially, but it can be improved by using an alkali as the etching agent.
Examples of the alkali agent suitably used in the present invention include caustic soda, sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, potassium hydroxide, lithium hydroxide and the like. The conditions are 50%, 20 to 100 ° C., and the amount of aluminum dissolved is 5 to 20 g / m ³ .
After etching, pickling is performed to remove dirt (smut) remaining on the surface. Examples of the acid used include nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, and borohydrofluoric acid. In particular, as a method for removing smut after the electrochemical surface roughening treatment, contact with 15 to 65 mass% sulfuric acid at a temperature of 50 to 90 ° C. as described in JP-A-53-12739 is preferable. And an alkali etching method described in Japanese Patent Publication No. 48-28123.
In addition, the surface roughness (Ra) of the aluminum support preferable in the present invention is 0.3 to 0.7 μm.

<Anodizing treatment>
The aluminum support treated as described above may be further anodized.
The anodizing treatment can be performed by a method conventionally performed in this technical field.
Specifically, sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzene sulfonic acid, etc., or a combination of two or more of these, and when direct current or alternating current is applied to aluminum in an aqueous solution or non-aqueous solution, aluminum is supported. An anodized film can be formed on the body surface.
The conditions of the anodizing treatment cannot be determined unconditionally because they vary depending on the electrolytic solution used. In general, the concentration of the electrolytic solution is 1 to 80%, the liquid temperature is 5 to 70 ° C., the current density is 0.00. 5-60 amps / dm ^2, a voltage of from 1 to 100 V, is suitably electrolysis time of 10 to 100 seconds.
Among these anodizing treatments, a method for anodizing at a high current density in sulfuric acid described in British Patent 1,412,768, and US Pat. No. 3,511,661, in particular. A method of anodizing phosphoric acid described in the book as an electrolytic bath is preferred.
In the present invention, the anodized film is preferably from ^{1~10g / m 2, 1g / m} 2 less than the plate to easily enter the wound to be, requires significant power production exceeds 10 g / m ² It is economically disadvantageous. Preferably, it is 1.5-7 g / m < ² >, More preferably, it is 2
˜5 g / m ² .

  Furthermore, in the present invention, the support may be subjected to a sealing treatment after graining treatment and anodizing. Such sealing treatment is performed by immersing the substrate in a hot aqueous solution containing hot water and an inorganic salt or an organic salt, a steam bath, or the like. The support used in the present invention may be subjected to a surface treatment such as a treatment other than a silicate treatment with an alkali metal silicate, for example, an immersion treatment in an aqueous solution of potassium fluorinated zirconate or phosphate.

[Back coat layer]
After the surface treatment is performed on the support or after the undercoat layer is formed, a back coat can be provided on the back surface of the support, if necessary.
Examples of the back coat include hydrolysis and polycondensation of organic polymer compounds described in JP-A-5-45885, organometallic compounds or inorganic metal compounds described in JP-A-6-35174. A coating layer made of a metal oxide obtained in this manner is preferred. Among them, it is inexpensive to use a silicon alkoxy compound such as Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ ) ₄ , Si (OC ₄ H ₉ ) _4. It is preferable in terms of easy availability.

[Preparation method of lithographic printing plate]
Next, a method for preparing a lithographic printing plate using the lithographic printing plate precursor according to the present invention will be described in detail. The method for producing a lithographic printing plate of the present invention basically comprises a step of exposing a lithographic printing plate precursor with a laser (exposure step), and removing a photosensitive layer in an unexposed area in the presence of a developer having a pH of 2 to 11. Process (developing process). If necessary, a step of exposing and / or heating the lithographic printing plate precursor between the exposure step and the development step and / or after the development step may be provided. Further, a drying step (including natural drying) may be provided after the developing step.

<Exposure>
Image exposure of a lithographic printing plate precursor is performed by a laser beam scanning method using digital data. A preferable example of the light source wavelength used for image exposure is 350 nm to 450 nm.

Specifically, as a gas laser, an Ar ion laser (364 nm, 351 nm, 10 mW to 1 W), a Kr ion laser (356 nm, 351 nm, 10 mW to 1 W), a He—Cd laser (441 nm, 325 nm, 1 mW to 100 mW), a solid-state laser Nd: YAG (YVO ₄ ) and SHG crystal × 2 combinations (355 nm, 5 mW to 1 W), Cr: LiSAF and SHG crystal combination (430 nm, 10 mW), and a semiconductor laser system using a KNbO ₃ ring resonator ( 430 nm, 30 mW), a combination of waveguide type wavelength conversion element and AlGaAs, InGaAs semiconductor (380 nm to 450 nm, 5 mW to 100 mW), a combination of waveguide type wavelength conversion element, AlGaInP, AlGaAs semiconductor (300 nm to 350 nm, 5 mW) ˜100 mW), AlGaInN (350 nm to 450 nm, 5 mW to 30 mW), and N ₂ laser (337 nm, pulse 0.1 to 10 mJ) and XeF (351 nm, pulse 10 to 250 mJ) as pulse lasers. In particular, an AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 400 to 410 nm, 5 to 30 mW) is preferable in terms of wavelength characteristics and cost.

  Other preferred examples of the light source wavelength used for image exposure include 750 nm to 1400 nm. Specifically, a solid laser and a semiconductor laser are preferably used. The laser output is preferably 100 mW or more, and a multi-beam laser device is preferably used to shorten the exposure time. The exposure time per pixel is preferably within 20 μsec. The energy applied to the planographic printing plate precursor is preferably 10 to 300 mJ / cm <2>. If the exposure energy is too low, the photosensitive layer is not sufficiently cured. If the exposure energy is too high, the photosensitive layer may be laser ablated and the image may be damaged.

In the image exposure according to the present invention, the light beams of the light sources can be overlapped for exposure. Overlap means that the sub-scanning pitch width is smaller than the beam diameter. The overlap is, for example, when the beam diameter is expressed by the full width at half maximum (FWHM) of the beam intensity.
M / sub-scanning pitch width (overlap coefficient) can be expressed quantitatively. In the present invention, the overlap coefficient is preferably 0.1 or more.

  Regarding the lithographic printing plate precursor exposure apparatus of the scanning exposure method, the exposure mechanism may be any of an inner drum method, an outer drum method, and a flat bed method, and a light source that can oscillate continuously is preferably used. .

<Development>
After the lithographic printing plate precursor according to the invention is image-exposed, the photosensitive layer in the non-exposed area can be removed with a developer to form an image. In the present invention, a developer having a pH of 2 to 11 that is milder than the conventionally used strong alkali developer is used. A particularly preferred pH is 3 to 10.5, and more preferably 4 to 10.5.
The developer used in the present invention preferably contains a surfactant. The surfactant used may contain any of anionic, nonionic, cationic, and amphoteric.

  It does not specifically limit as an anionic surfactant, A conventionally well-known thing can be used. For example, fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinates, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl phenoxy polyoxyethylene Propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium, N-alkyl sulfosuccinic acid monoamide disodium salts, petroleum sulfonates, sulfated castor oil, sulfated beef oil, Fatty acid alkyl ester sulfate ester salt, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, fatty acid monoglyceride sulfate ester, polyoxy Tylene alkylphenyl ether sulfate ester salt, polyoxyethylene styryl phenyl ether sulfate ester salt, alkyl phosphate ester salt, polyoxyethylene alkyl ether phosphate ester salt, polyoxyethylene alkylphenyl ether phosphate ester salt, styrene-maleic anhydride copolymer And olefin-maleic anhydride copolymer partial saponification products, naphthalene sulfonate formalin condensates, aromatic sulfonates, aromatic substituted polyoxyethylene sulfonates, and the like. Among these, dialkyl sulfosuccinates, alkyl sulfate esters and alkyl naphthalene sulfonates are particularly preferably used.

  The cationic surfactant 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 nonionic surfactant is not particularly limited, and a conventionally known nonionic surfactant can be used. For example, polyethylene glycol type higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, polyethylene glycol adducts of aromatic compounds, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, higher alkylamine ethylene oxide additions Products, fatty acid amide ethylene oxide adducts, oil and fat ethylene oxide adducts, polypropylene glycol ethylene oxide adducts, dimethylsiloxane-ethylene oxide block copolymers, dimethylsiloxane- (propylene oxide-ethylene oxide) block copolymers, and polyhydric alcohol types Glycerol fatty acid ester, pentaerythritol fatty acid ester, sorbitol and sol Tan fatty acid esters, fatty acid esters of sucrose, alkyl ethers of polyhydric alcohols, fatty acid amides of alkanolamines.

  In the present invention, a polyethylene glycol-type higher alcohol ethylene oxide adduct, a polyethylene glycol adduct of an aromatic compound, an ethylene oxide adduct of sorbitol and / or sorbitan fatty acid ester, a polypropylene glycol ethylene oxide adduct, and dimethylsiloxane-ethylene oxide More preferred are block copolymers, dimethylsiloxane- (propylene oxide-ethylene oxide) block copolymers, and fatty acid esters of polyhydric alcohols.

  Further, from the viewpoint of stable solubility or turbidity in water, the nonionic surfactant preferably has an HLB (Hydrophile-Lipophile Balance) value of 6 or more, more preferably 8 or more. Further, acetylene glycol-based and acetylene alcohol-based oxyethylene adducts, fluorine-based and silicon-based surfactants can be used in the same manner.

  As is well known in the field of surfactants, amphoteric surfactants are compounds having an anionic site and a cationic site in the same molecule, and are amphoteric interfaces such as amino acids, betaines, and amine oxides. An active agent is included. As the amphoteric surfactant used in the developer used in the present invention, a compound represented by the following formula <1> and a compound represented by the following formula <2> are preferable.

In formula <1>, R8 represents an alkyl group, R9 and R10 each represent a hydrogen atom or an alkyl group, R11 represents an alkylene group, and A represents a carboxylate ion or a sulfonate ion.
In formula <2>, R18, R19 and R20 each represent a hydrogen atom or an alkyl group. However, not all of R18, R19 and R20 are hydrogen atoms.

In the above formula <1>, the alkyl group represented by R8, R9 or R10 and the alkylene group represented by R11 may be linear or branched, and may have a linking group in the chain. Moreover, it may further have a substituent. As the linking group, those containing a hetero atom such as an ester bond, an amide bond, or an ether bond are preferable. Moreover, as a substituent, a hydroxyl group, an ethylene oxide group, a phenyl group, an amide group, a halogen atom, etc. are preferable.
In the compound represented by the formula <1>, when the total carbon number is increased, the hydrophobic portion is increased and it is difficult to dissolve in an aqueous developer. In this case, it is improved by adding a solubilizing agent such as an organic solvent such as alcohol, but when the total carbon number becomes too large, the surfactant cannot be dissolved within the proper mixing range. There is a case. Therefore, the total number of carbon atoms of R8 to R11 is preferably 8 to 25, and more preferably 11 to 21.

In the above formula <2>, the alkyl group represented by R18, R19 or R20 may be linear or branched, may have a linking group in the chain, and further has a substituent. You may do it. As the linking group, those containing a hetero atom such as an ester bond, an amide bond, or an ether bond are preferable. Moreover, as a substituent, a hydroxyl group, an ethylene oxide group, a phenyl group, an amide group, a halogen atom, etc. are preferable.
In the compound represented by the formula <2>, when the total carbon number is increased, the hydrophobic portion is increased and it is difficult to dissolve in an aqueous developer. In this case, it is improved by adding a solubilizing agent such as an organic solvent such as alcohol, but when the total carbon number becomes too large, the surfactant cannot be dissolved within the proper mixing range. There is a case. Therefore, the total number of carbon atoms of R18 to R20 is preferably 8 to 22, and more preferably 10 to 20.

  The total carbon number of the amphoteric surfactant may be affected by the properties of the material used for the photosensitive layer, particularly the binder polymer. When a binder polymer having a high hydrophilicity is used, those having a relatively small total carbon number are preferable, and when the binder polymer used has a low hydrophilicity, a polymer having a large total carbon number tends to be preferable.

  Although the preferable specific example of the amphoteric surfactant used for a developing solution is shown below, this invention is not limited to these.

  Surfactants can be used alone or in combination. The content of the surfactant in the developer is preferably from 0.01 to 10% by mass, more preferably from 0.01 to 5% by mass.

The developer used in the present invention may further contain a pH buffer.
As the pH buffering agent of the present invention, any buffering agent that exhibits a buffering action at pH 2 to 11 can be used without particular limitation. In the present invention, an alkaline buffer is preferably used.For example, (a) carbonate ion and hydrogen carbonate ion, (b) borate ion, (c) water-soluble amine compound and ion of the amine compound, and combinations thereof Etc. By using such a buffering agent, the pH buffering effect is exerted in the developer, and even if the developer is used for a long period of time, fluctuations in pH can be suppressed, and development deterioration due to pH fluctuations, development debris generation, etc. are suppressed. it can. Particularly preferred is a combination of carbonate ions and bicarbonate ions.

(a) In order to allow carbonate ions and hydrogen carbonate ions to be present in the developer, carbonate and bicarbonate may be added to the developer, and the pH is adjusted after adding carbonate or bicarbonate. Thus, carbonate ions and hydrogen carbonate ions may be generated. The carbonate and bicarbonate are not particularly limited, but are preferably alkali metal salts. Examples of the alkali metal include lithium, sodium, and potassium, and sodium is particularly preferable. Alkali metals may be used alone or in combination of two or more.

(b) To make borate ions present in the developer, after adding boric acid or borate to the developer, the pH is adjusted using an alkali or an alkali and an acid. To generate an appropriate amount of borate ions.
The boric acid or borate used here is not particularly limited, and examples of boric acid include orthoboric acid, metaboric acid, and tetraboric acid. Among them, orthoboric acid and tetraboric acid are preferable. Examples of borates include alkali metal salts or alkaline earth metal salts, such as orthoborate, diborate, metaborate, tetraborate, pentaborate, and octaborate. Of these, orthoborate and tetraborate, particularly alkali metal tetraborate are preferred. Preferred tetraborate salts include sodium tetraborate, potassium tetraborate, and lithium tetraborate. Among them, sodium tetraborate is preferable. Two or more borates may be used in combination.
As the boric acid or borate used in the present invention, orthoboric acid, tetraboric acid or sodium tetraborate is particularly preferable. Boric acid and borates may be used in combination with the developer.

(c) Water-soluble amine compound ions can be generated in an aqueous solution of a water-soluble amine compound, and an alkali or acid may be further added to the aqueous solution of the water-soluble amine compound. It can be made to contain in the aqueous solution by adding the compound which becomes.
The water-soluble amine compound is not particularly limited, but a water-soluble amine compound having a group that promotes water solubility is preferable. Examples of groups that promote water solubility include carboxylic acid groups, sulfonic acid groups, sulfinic acid groups, phosphonic acid groups, and hydroxyl groups. The water-soluble amine compound may have a plurality of these groups.
When the water solubility of the amine compound is promoted by a carboxylic acid group, a sulfonic acid group, a sulfinic acid group, or a phosphonic acid group, the water-soluble amine compound corresponds to an amino acid. The amino acid is in an equilibrium state in an aqueous solution, and when the acid group is, for example, a carboxylic acid group, the equilibrium state is expressed as follows. The amino acid in the present invention refers to the following B state, and the amino acid ion means the C state. As the counter ion in the C state, sodium ion and potassium ion are preferable.

Specific examples of water-soluble amine compounds having a carboxylic acid group, a sulfonic acid group, and a sulfinic acid group include glycine, iminodiacetic acid, lysine, threonine, serine, aspartic acid, parahydroxyphenylglycine, dihydroxyethylglycine, alanine, and anthranyl. acid,
Examples include amino acids such as tryptophan, sulfamic acid, cyclohexylsulfamic acid, fatty acid amine sulfonic acids such as taurine, and fatty acid amine sulfinic acids such as aminoethanesulfinic acid. Of these, glycine and iminodiacetic acid are preferred.

  Specific examples of water-soluble amine compounds having a phosphonic acid group (including a phosphinic acid group) include 2-aminoethylphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, 1-amino-1-phenylmethane-1, Examples include 1-diphosphonic acid, 1-dimethylaminoethane-1,1-diphosphonic acid, and ethylenediaminopentamethylenephosphonic acid. 2-aminoethylphosphonic acid is particularly preferable.

  A water-soluble amine compound having a hydroxyl group as a group that promotes water solubility means an alkylamine having a hydroxyl group on an alkyl group (the following state B), and these ions mean an ammonium ion of an amino group (described below). State A).

  Specific examples of the water-soluble amine compound having a hydroxyl group include monoethanolamine, diethanolamine, trimethanolamine, triethanolamine, tripropanolamine, and triisopropanolamine. Of these, triethanolamine and diethanolamine are preferred. As the counter ion of ammonium ion, chloro ion is preferable.

  Examples of the alkali that can be used for adjusting the pH include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate, and organic alkali. Agents, combinations thereof, and the like can be used. As the acid, an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid can be used.

When using a pH buffer, the pH of the developer is preferably in the range of 8.5 to 10.8. If the pH is 8.5 or more, the developability of the non-image area can be improved. On the other hand, if the pH is 10.8 or less, it is difficult to be influenced by carbon dioxide in the air, and the influence of carbon dioxide A reduction in processing capacity can be suppressed. More preferably, it is in the range of pH 8.8 to 10.2, particularly preferably in the range of pH 9.0 to 10.0.
Further, for the purpose of assisting the fine adjustment of the alkali concentration and the dissolution of the non-image area photosensitive layer, an alkali agent such as an organic alkali agent may be supplementarily used together. Examples of the organic alkali agent include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, Examples thereof include diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, tetramethylammonium hydroxide and the like. These auxiliary alkaline agents are used alone or in combination of two or more.

  When (a) a combination of carbonate ions and bicarbonate ions is employed as the pH buffer, the total amount of carbonate ions and bicarbonate ions is preferably 0.05 to 5 mol / L with respect to the total mass of the aqueous solution, 0.1 ˜2 mol / L is more preferable, and 0.2 to 1 mol / L is particularly preferable. If the total amount is 0.05 mol / L or more, developability and processing capacity do not decrease, and if it is 5 mol / L or less, it becomes difficult to form precipitates and crystals, and further, during processing of the waste liquid of the developing solution, during neutralization It becomes difficult to gel and does not interfere with waste liquid treatment.

  When (b) borate ions are employed as the pH buffering agent, the total amount of borate ions is preferably 0.05 to 5 mol / L, more preferably 0.1 to 2 mol / L, based on the total mass of the aqueous solution. 0.2-1 mol / L is particularly preferable. When the total amount of borate is 0.05 mol / L or more, developability and processing ability are not deteriorated. On the other hand, when it is 5 mol / L or less, it is difficult to form precipitates and crystals, and further, during processing of waste liquid of the developer. It becomes difficult to gel during neutralization and does not interfere with waste liquid treatment.

  When (c) a water-soluble amine compound and an ion of the amine compound are employed as a pH buffer, the total amount of the water-soluble amine compound and the ion of the amine compound is 0.01 to 1 mol based on the total mass of the aqueous solution. / L is preferable, 0.03 to 0.7 mol / L is more preferable, and 0.05 to 0.5 mol / L is particularly preferable. When the total amount of the water-soluble amine compound and the ions of the amine compound is within this range, developability and processing ability are not deteriorated, while waste liquid treatment is easy.

  In addition to the above components, the developer used in the present invention may contain a wetting agent, preservative, chelate compound, antifoaming agent, organic solvent, inorganic acid, inorganic salt, water-soluble resin, and the like.

  As the wetting agent, ethylene glycol, propylene glycol, triethylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, diglycerin and the like are preferably used. The wetting agent may be used alone or in combination of two or more. Generally, the wetting agent is used in an amount of 0.1 to 5% by weight based on the total weight of the developer.

  Preservatives include phenol or derivatives thereof, formalin, imidazole derivatives, sodium dehydroacetate, 4-isothiazolin-3-one derivatives, benzoisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, benztriazole derivatives Amiding anidine derivatives, quaternary ammonium salts, derivatives such as pyridine, quinoline, guanidine, diazine, triazole derivatives, oxazole, oxazine derivatives, nitrobromoalcohol-based 2-bromo-2-nitropropane-1,3diol, 1, 1-dibromo-1-nitro-2-ethanol, 1,1-dibromo-1-nitro-2-propanol and the like can be preferably used. It is preferable to use two or more kinds of preservatives in combination so as to be effective against various molds and sterilization. The addition amount of the preservative is an amount that exhibits a stable effect on bacteria, fungi, yeast, and the like, and varies depending on the type of bacteria, fungi, yeast, but 0.01 to 4 relative to the developer. A range of mass% is preferred.

  Examples of the chelate compound include ethylenediaminetetraacetic acid, potassium salt thereof, sodium salt thereof; diethylenetriaminepentaacetic acid, potassium salt thereof, sodium salt thereof; triethylenetetraminehexaacetic acid, potassium salt thereof, sodium salt thereof, hydroxyethylethylenediaminetriacetic acid Nitrilotriacetic acid, sodium salt; 1-hydroxyethane-1,1-diphosphonic acid, potassium salt, sodium salt; aminotri (methylenephosphonic acid), potassium salt, sodium salt And organic phosphonic acids and phosphonoalkanetricarboxylic acids. Organic amine salts are also effective in place of the sodium and potassium salts of the chelating agents. A chelating agent is selected that is stably present in the treatment liquid composition and does not impair the printability. The addition amount is preferably 0.001 to 1% by mass with respect to the developer.

  As the antifoaming agent, a general silicon-based self-emulsifying type, emulsifying type, nonionic HLB 5 or less compound can be used. Silicon antifoaming agents are preferred. Among them, emulsification dispersion type and solubilization can be used. The content of the antifoaming agent is preferably in the range of 0.001 to 1.0 mass% with respect to the developer.

  Examples of the organic solvent include aliphatic hydrocarbons (hexane, heptane, “Isopar E, H, G” (produced by Esso Chemical Co., Ltd.) or gasoline, kerosene, etc.), aromatic hydrocarbons (toluene, xylene, etc.) ) Or halogenated hydrocarbons (methylene dichloride, ethylene dichloride, trichrene, monochlorobenzene, etc.) and polar solvents.

  Polar solvents include alcohols (methanol, ethanol, propanol, isopropanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, etc.) , (Acetone, methyl ethyl ketone, ethyl butyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, methyl lactate, butyl lactate, ethylene glycol monobutyl acetate, propylene Glycol monomethyl ether acetate, diethylene glycol acetate, diethyl phthalate, butyl levulinate, etc.) and others (triethyl phosphate, tricresyl phosphate, N-phenylethanolamine, N-phenyldiethanolamine, etc.).

  When the organic solvent is insoluble in water, it can be used after being solubilized in water using a surfactant or the like. When the developer contains an organic solvent, the concentration of the solvent is preferably less than 40% by mass from the viewpoint of safety and flammability.

  Examples of inorganic acids and inorganic salts include phosphoric acid, metaphosphoric acid, primary ammonium phosphate, secondary ammonium phosphate, primary sodium phosphate, secondary sodium phosphate, primary potassium phosphate, secondary potassium phosphate, Examples include sodium tripolyphosphate, potassium pyrophosphate, sodium hexametaphosphate, magnesium nitrate, sodium nitrate, potassium nitrate, ammonium nitrate, sodium sulfate, potassium sulfate, ammonium sulfate, sodium sulfite, ammonium sulfite, sodium hydrogen sulfate, nickel sulfate and the like. The content of the inorganic salt is preferably 0.01 to 0.5% by mass based on the total mass of the developer.

  Examples of water-soluble resins include soybean polysaccharides, modified starches, gum arabic, dextrin, fibrin derivatives (eg, carboxymethylcellulose, carboxyethylcellulose, methylcellulose, etc.) and modified products thereof, pullulan, polyvinyl alcohol and derivatives thereof, polyvinylpyrrolidone, polyacrylamide And acrylamide copolymer, vinyl methyl ether / maleic anhydride copolymer, vinyl acetate / maleic anhydride copolymer, styrene / maleic anhydride copolymer, and the like. A preferable acid value of the water-soluble resin is 0 to 3.0 meq / g.

  As the soybean polysaccharide, conventionally known ones can be used. For example, as a commercial product, there is Soya Five (manufactured by Fuji Oil Co., Ltd.), and various grades can be used. What can be preferably used is one in which the viscosity of a 10% by mass aqueous solution is in the range of 10 to 100 mPa / sec.

  Examples of modified starch include those represented by the following general formula (III). Any starch such as corn, potato, tapioca, rice, wheat, etc. can be used as the starch used in the production of the modified starch. The starch can be modified by a method of decomposing within 5 to 30 glucose residues per molecule with an acid or an enzyme, and further adding oxypropylene in an alkali.

  In formula (III), the degree of etherification (degree of substitution) is in the range of 0.05 to 1.2 per glucose unit, n represents an integer of 3 to 30, and m represents an integer of 1 to 3.

  Examples of modified starch and derivatives thereof include roasted starch such as British gum, enzyme-modified dextrins such as enzyme dextrin and shardinger dextrin, oxidized starch shown in solubilized starch, modified pregelatinized starch and unmodified pregelatinized starch Alpha starch, phosphate starch, fat starch, sulfate starch, nitrate starch, xanthate starch, carbamic acid starch and other esterified starch, carboxyalkyl starch, hydroxyalkyl starch, sulfoalkyl starch, cyanoethyl starch, allyl starch, benzyl starch , Etherified starch such as carbamylethyl starch and dialkylamino starch, methylol cross-linked starch, hydroxyalkyl cross-linked starch, phosphate cross-linked starch, dicarboxylic acid cross-linked starch and other cross-linked starch, starch polyacrylamide copolymer, starch polyacrylic acid co Polymer, starch polyvinyl acetate copolymer, starch polyacrylonitrile copolymer, chaotic starch polyacrylic ester copolymer, chaotic starch vinyl polymer copolymer, starch polystyrene maleic acid copolymer, starch polyethylene oxide copolymer Examples thereof include starch graft polymers such as coalescence and starch polypropylene copolymer.

Among the water-soluble resins, preferred are soy polysaccharides, modified starches, gum arabic, dextrin, carboxymethyl cellulose, polyvinyl alcohol and the like.
Two or more water-soluble resins can be used in combination. The content of the water-soluble resin in the developer is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass.

  The temperature of the developer is usually 60 ° C. or less, preferably about 15 to 40 ° C. In the developing process using an automatic developing machine, the developing solution may be fatigued depending on the amount of processing, and thus the processing capability may be restored by using a replenishing solution or a fresh developing solution.

  The development process can be preferably carried out by an automatic processor equipped with a rubbing member. Examples of the automatic processing machine include an automatic processing machine described in JP-A-2-220061 and JP-A-60-59351, which performs a rubbing process while conveying a lithographic printing plate precursor after image exposure, or on a cylinder. Examples thereof include an automatic processor described in US Pat. Nos. 5,148,746, 5,568,768 and British Patent 2,297,719, which rub the lithographic printing plate precursor after image exposure while rotating a cylinder. Among these, an automatic processor using a rotating brush roll as the rubbing member is particularly preferable.

The rotating brush roll used in the present invention can be appropriately selected in consideration of the difficulty of scratching the image area and the stiffness of the support of the lithographic printing plate precursor. As the rotating brush roll, a known one formed by planting a brush material on a plastic or metal roll can be used. For example, a metal or plastic groove mold material in which brush materials are implanted in a row, as described in JP-A-58-159533, JP-A-3-1-1534, or JP-A-62-167253 A brush roll can be used in which the core is radially wound around a plastic or metal roll with no gap.
Examples of brush materials include plastic fibers (for example, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides such as nylon 6.6 and nylon 6.10, and polyacryls such as polyacrylonitrile and poly (meth) acrylate). , Polyolefin synthetic fibers such as polypropylene and polystyrene). For example, fibers having a hair diameter of 20 to 400 μm and a hair length of 5 to 30 mm can be preferably used.
The outer diameter of the rotating brush roll is preferably 30 to 200 mm, and the peripheral speed at the tip of the brush rubbing the plate surface is preferably 0.1 to 5 m / sec. It is preferable to use a plurality of rotating brush rolls.

  The rotating direction of the rotating brush roll may be the same or opposite to the transport direction of the lithographic printing plate precursor. However, when two or more rotating brush rolls are used, at least one rotating brush roll is used. It is preferred that the rotating brush rolls rotate in the same direction and at least one rotating brush roll rotates in the opposite direction. This further ensures the removal of the photosensitive layer in the non-image area. It is also effective to swing the rotating brush roll in the direction of the rotation axis of the brush roll.

After the development step is performed, the developer may be dried by natural drying, but it is preferable to provide a drying step with warm air or the like.
In the method for preparing a lithographic printing plate according to the present invention, the entire surface may be heated between exposure and development, if necessary. By such heating, an image forming reaction in the image recording layer is promoted, and advantages such as improvement in sensitivity and printing durability and stabilization of sensitivity may occur.

The heating conditions can be appropriately set within the range where these effects are present. Examples of the heating means include a conventional convection oven, an IR irradiation device, an IR laser, a microwave device, a Wisconsin oven, and the like. For example, it can be carried out by holding the plate surface temperature in the range of 70 to 150 ° C. for 1 second to 5 minutes. Preferably, the temperature is 80 ° C to 140 ° C for 5 to 1 minute, more preferably 90 ° C to 130 ° C for 10 to 30 seconds. This range is preferable in that the above effect can be obtained efficiently and there is no adverse effect such as deformation of the printing plate due to heat.
The heat treatment means used for the heat treatment is preferably connected to the plate setter used in the exposure process and the developing device used in the development process so as to be automatically continuously processed. Specifically, there is a plate making line in which a plate setter and a developing device are coupled by a conveying means such as a conveyor. A heat treatment unit may be provided between the plate setter and the developing device, and the heating unit and the developing device may be integrated.

When the lithographic printing plate precursor to be used is easily affected by ambient light in the working environment, the plate making line is preferably shielded from light by a filter or a cover.
Further, the entire surface of the printing plate after development may be exposed with an actinic ray such as ultraviolet light to accelerate the curing of the image area. Examples of the light source for the entire surface exposure include a carbon arc lamp, a mercury lamp, a gallium lamp, a metal halide lamp, a xenon lamp, a tungsten lamp, and various laser lights. In order to obtain sufficient printing durability, the exposure dose is preferably at least 10 mJ / cm ² or more, more preferably 100 mJ / cm ² or more.
Heating may be performed simultaneously with the entire surface exposure, and further improvement in printing durability is recognized by heating. Examples of the heating device include a conventional convection oven, an IR irradiation device, an IR laser, a microwave device, a Wisconsin oven, and the like. At this time, the plate surface temperature is preferably 30 ° C to 150 ° C, more preferably 35 ° C to 130 ° C, and still more preferably 40 ° C to 120 ° C. Specifically, the method described in JP 2000-89478 A can be used.
Further, for the purpose of improving printing durability, the developed printing plate can be heated under very strong conditions. The heating temperature is usually in the range of 200 to 500 ° C. If the temperature is low, sufficient image strengthening action cannot be obtained, and if it is too high, problems such as deterioration of the support and thermal decomposition of the image area may occur.
The lithographic printing plate thus obtained is loaded on an offset printing machine and used for printing a large number of sheets.

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

[Examples 1 to 19 and Comparative Examples 1 to 4]
[Production of organic pigment dispersion]
<Organic pigment dispersions (1) to (6)>
An organic pigment composition having the following composition was stirred to obtain a coarse dispersion. The obtained coarse dispersion was dispersed with a sand mill filled with 0.8 mmφ glass beads at a peripheral speed of 15 m / sec for 30 minutes to obtain organic pigment dispersions (1) to (6).

Propylene glycol monomethyl ether acetate 17.5 parts by mass Cyclohexanone 17.5 parts by mass Methoxypropanol 40.0 parts by mass Pigment dispersant described in Table A 10.0 parts by mass Cyan pigment (No. 700-10-FGCY blue manufactured by Toyo Ink) 15.0 parts by mass

<Organic pigment dispersions (7) to (10)>
An organic pigment composition having the following composition was stirred to obtain a coarse dispersion. The obtained coarse dispersion was dispersed with a sand mill filled with 0.8 mmφ glass beads for 30 minutes at a peripheral speed of 15 m / sec to obtain organic pigment dispersions (7) to (10).

Propylene glycol monomethyl ether acetate 17.5 parts by mass Cyclohexanone 17.5 parts by mass Methoxypropanol 40.0 parts by mass Pigment dispersant described in Table A 10.0 parts by mass Cyan pigment (Ciba Irgalite Blue GLVO) 15.0 parts by mass

[Preparation of Aluminum Support 1]
In order to remove rolling oil on the surface of an aluminum plate (material: JIS A1050) having a thickness of 0.3 mm, a degreasing treatment was performed at 50 ° C. for 30 seconds using a 10 mass% sodium aluminate aqueous solution, and then the hair diameter was adjusted to 0. The aluminum surface was grained using ^three 3 mm bundled nylon brushes and a pumice-water suspension (specific gravity 1.1 g / cm ³ ) having a median diameter of 25 μm and washed well 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 a 20 mass% nitric acid aqueous solution at 60 ° C for 20 seconds, and washed with water. At this time, the etching amount of the grained surface 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. The AC power source waveform is electrochemical roughening treatment using a trapezoidal rectangular wave alternating current with a time ratio TP of 0.8 msec until the current value reaches a peak from zero, a duty ratio of 1: 1, and a trapezoidal rectangular wave alternating current. 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 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. 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 a 15 mass% sulfuric acid aqueous solution (containing 0.5 mass% of aluminum ions) as an electrolyte, then washed with water and dried. .
The centerline average roughness (Ra) of the aluminum support 1 thus obtained was measured using a needle having a diameter of 2 μm and found to be 0.51 μm.
Further, the following undercoat liquid (1) was bar-coated and then oven-dried at 80 ° C. for 10 seconds to prepare a support having an undercoat layer having a dry coating amount of 10 mg / m ² .

<Undercoat liquid (1)>
・ Polymer compounds described in Table A 0.017 g
・ Methanol 9.00 g
・ Water 1.00g

[Preparation of planographic printing plate precursors (1) to (23)]
A photosensitive layer coating solution 1 having the following composition was bar coated on the support provided with the above undercoat layer, and then oven-dried at 70 ° C. for 60 seconds to form a photosensitive layer having a dry coating amount of 1.1 g / m ^2. Then, a protective layer coating solution 1 having the following composition was coated thereon using a bar so that the dry coating amount was 0.75 g / m ^2, and then dried at 125 ° C. for 70 seconds to be a planographic printing plate precursor (1) to (23) were obtained.

<Photosensitive layer coating solution 1>
-The following binder polymer (1) (mass average molecular weight: 80,000, acid value 0 meq / g)
0.54g
・ Polymerizable compound 0.40g
Isocyanuric acid EO-modified triacrylate (manufactured by Toa Gosei Co., Ltd., Aronix M-315)
・ Polymerizable compound Ethoxylated trimethylolpropane triacrylate 0.08 g
(Nippon Kayaku Co., Ltd., SR9035, EO addition mole number 15, molecular weight 1000)
・ The following sensitizing dye (1) 0.06 g
・ The following polymerization initiator (1) 0.18 g
・ The following co-sensitizer (1) 0.07 g
・ 0.40 g of organic pigment dispersion described in Table A
・ Thermal polymerization inhibitor 0.01g
N-nitrosophenylhydroxylamine aluminum salt-The following fluorosurfactant (1) (mass average molecular weight: 11,000) 0.001 g
・ Polyoxyethylene-polyoxypropylene condensate 0.04g
(Asahi Denka Kogyo Co., Ltd., Pluronic L44)
・ 3.5 g of 1-methoxy-2-propanol
・ Methyl ethyl ketone 8.0g

<Protective layer coating solution 1>
Polyvinyl alcohol (saponification degree 98 mol%, polymerization degree 500) 40 g
Polyvinylpyrrolidone (mass average molecular weight: 50,000) 5 g
Poly (vinyl pyrrolidone / vinyl acetate (1/1)) (mass average molecular weight: 70,000) 0.5 g
Surfactant (Emalex 710, manufactured by Nippon Emulsion Co., Ltd.) 0.5g
950g of water

(1) Exposure, development and printing For each of the above lithographic printing plate precursors (1) to (23), using a 405 nm semiconductor laser with an output of 100 mW, a 50% halftone dot image was obtained with a plate exposure amount of 300 μJ / cm ² and 100 lpi. The imagewise exposure was performed under the conditions of:
Thereafter, using the developer (1) having the following composition, development processing was carried out with an automatic developing processor having a structure as shown in FIG. 1 to prepare a lithographic printing plate. The automatic developing processor is an automatic processor having two rotating brush rolls. As the rotating brush roll, the first brush roll is made of polybutylene terephthalate fiber (hair diameter: 200 μm, hair length: 17 mm). Using a brush roll having an outer diameter of 90 mm in which is implanted, 200 revolutions per minute in the same direction as the conveying direction (peripheral speed of the brush tip: 0.94 m / sec), the second brush roll is made of polybutylene terephthalate Using a brush roll having an outer diameter of 60 mm in which fibers (hair diameter: 200 μm, hair length: 17 mm) were implanted, it was rotated 200 times per minute in the direction opposite to the conveying direction (peripheral speed of the brush tip: 0.63 m / sec). . The planographic printing plate precursor was transported at a transport speed of 100 cm / min.

  The developer was showered from the spray pipe with a circulation pump and supplied to the plate surface. The tank capacity of the developer was 10 liters.

  On the other hand, each of the lithographic printing plate precursors (1) to (23) was forcibly stored by being left in an oven at 60 ° C. for 3 days, and thereafter the same development treatment was performed to prepare a lithographic printing plate.

Developer (1)
・ Water 100.00g
・ Benzyl alcohol 1.00g
・ Polyoxyethylene naphthyl ether (oxyethylene average number n = 13) 1.00 g
・ Dioctylsulfosuccinate sodium salt 0.50 g
・ Arabic gum 1.00g
・ Ethylene glycol 0.50g
・ Primary ammonium phosphate 0.05g
・ Citric acid 0.05g
・ Ethylenediaminetetraacetate tetrasodium salt 0.05g
Adjust the pH of the developer to 7.0 using phosphoric acid and sodium hydroxide

  The obtained lithographic printing plate was attached to a printing machine SOR-M manufactured by Heidelberg, and dampening water (EU-3 (Eth Liquid manufactured by Fuji Film Co., Ltd.) / Water / isopropyl alcohol = 1/89/10 (capacity ratio). )) And TRANS-G (N) black ink (manufactured by Dainippon Ink & Chemicals, Inc.), printing was performed at a printing speed of 6000 sheets per hour.

(2) Evaluation A lithographic plate produced from a lithographic printing plate precursor that has been forcibly stored using a lithographic printing plate produced from a lithographic printing plate precursor that is not subjected to forced storage. Using the printing plate, the residual color and stain resistance were evaluated as follows. The results are shown in Table A. In Tables A to D below, the structure of the undercoat layer polymer compound PC used in the comparative examples is shown below.

<Colorability>
The cyan density of the photosensitive layer in the lithographic printing plate precursor before exposure was measured with a Macbeth densitometer, and the colorability was evaluated based on the density. The larger the number, the higher the colorability.
<Remaining color>
The cyan density of the non-image portion of the obtained lithographic printing plate was measured with a Macbeth densitometer, and the residual color was evaluated based on the density. The smaller the number, the better the residual color.
<Dirty>
When 500 sheets were printed under the above printing conditions, the ink stain generated in the non-image area was visually confirmed. The evaluation was made on a 10-point scale with 10 points when a non-image area having no stain was obtained, and 1 point when the ink was almost adhered and dirty.
<Print durability>
Printing was performed under the above printing conditions, and printing durability was evaluated by the number of printed sheets when the ink density (reflection density) on the printing paper was reduced by 0.1 from the start of printing.

  As is clear from the results in Table A, the lithographic printing plate precursor of the present invention has a residual color in a non-image area while maintaining printing durability despite development with a neutral developer having a pH of 7. A lithographic printing plate excellent in dirt during printing can be produced. It can also be seen that these characteristics are maintained well even when the lithographic printing plate precursor is forcibly stored.

[Examples 20 to 23 and Comparative Examples 5 to 6]
[Preparation of planographic printing plate precursors (24) to (29)]
The lithographic printing plate precursors (24) to (29) were prepared in the same manner as the lithographic printing plate precursors (1) to (23) except that the photosensitive layer coating solution 1 was changed to the following photosensitive layer coating solution 2. .

<Photosensitive layer coating solution 2>
・ The following binder polymer (4) (mass average molecular weight: 70,000) 0.54 g
-0.48 g of the following polymerizable compound (2)
-0.06 g of the above sensitizing dye (1)
・ The above polymerization initiator (1) 0.18 g
・ Cosensitizer (1) 0.07g
・ 0.40 g of organic pigment dispersions listed in Table B
・ Thermal polymerization inhibitor 0.01g
N-nitrosophenylhydroxylamine aluminum salt-Fluorosurfactant (1) 0.001 g
・ Polyoxyethylene-polyoxypropylene condensate 0.04g
(Asahi Denka Kogyo Co., Ltd., Pluronic L44)
・ 3.5 g of 1-methoxy-2-propanol
・ Methyl ethyl ketone 8.0g

Each lithographic printing plate precursor (24) to (29) was subjected to imagewise exposure using a 405 nm semiconductor laser with an output of 100 mW and a halftone dot image of 50% plate surface exposure of 80 μJ / cm ² and 100 lpi. After that, the lithographic printing plate precursor was placed in an oven within 30 seconds, and hot air was blown to heat the entire surface of the lithographic printing plate precursor, which was kept at 110 ° C. for 15 seconds. Then, within 30 seconds, a lithographic printing plate was prepared by developing in the same manner as in Example 1 except that the developer (1) was changed to the following developer (2). Evaluation was performed in the same manner as in Example 1. The results are shown in Table B.

Developer (2)
・ Water 100.00g
・ N-lauryldimethylbetaine 10.00g
(Takemoto Yushi Co., Ltd .; Pionein C157K)
・ Polystyrenesulfonic acid 1.00g
・ Primary ammonium phosphate 0.05g
・ Citric acid 0.05g
・ Ethylenediaminetetraacetate tetrasodium salt 0.05g
Adjust the pH of the developer to 4.5 with phosphoric acid

  As is clear from the results in Table B, the lithographic printing plate precursor according to the present invention has the remaining in the non-image area while maintaining the printing durability despite the development treatment with a weakly acidic developer having a pH of 4.5. A lithographic printing plate excellent in color and stain during printing can be produced. It can also be seen that these characteristics are maintained well even when the lithographic printing plate precursor is forcibly stored.

[Examples 24-27 and Comparative Examples 7-8]
[Preparation of planographic printing plate precursors (30) to (35)]
The lithographic printing plate precursors (1) to (23) were changed except that the photosensitive layer coating solution 1 was changed to the photosensitive layer coating solution 3 having the following composition and the protective layer coating solution 1 was changed to the protective layer coating solution 2 having the following composition. Lithographic printing plate precursors (30) to (35) were prepared in the same manner as the preparation.

<Photosensitive layer coating solution 3>
・ The following binder polymer (3) (mass average molecular weight: 50,000) 0.54 g
・ 0.48 g of the above polymerizable compound (2)
-0.06 g of the above sensitizing dye (1)
・ The above polymerization initiator (1) 0.18 g
・ Cosensitizer (1) 0.07g
・ 0.40 g of organic pigment dispersions listed in Table 3
・ Thermal polymerization inhibitor 0.01g
N-nitrosophenylhydroxylamine aluminum salt-The above water-soluble fluorosurfactant (1) 0.001 g
・ Polyoxyethylene-polyoxypropylene condensate 0.04g
(Asahi Denka Kogyo Co., Ltd., Pluronic L44)
・ 3.5 g of 1-methoxy-2-propanol
・ Methyl ethyl ketone 8.0g

Binder polymer (3)

<Protective layer coating solution>
・ The following mica dispersion (1) 13.0 g
Polyvinyl alcohol (saponification degree 98 mol%, polymerization degree 500) 1.3 g
-Sodium 2-ethylhexyl sulfosuccinate 0.2g
・ Poly (vinyl pyrrolidone / vinyl acetate = 1/1) mass average molecular weight: 70,000 g
・ Surfactant (Emalex 710, manufactured by Nippon Emulsion Co., Ltd.) 0.05g
・ 133g of water

(Mica dispersion (1))
To 368 g of water, 32 g of synthetic mica (“Somasif ME-100”: manufactured by Co-op Chemical Co., Ltd., aspect ratio: 1000 or more) is added and dispersed using an homogenizer until the average particle size (laser scattering method) becomes 0.5 μm. A mica dispersion (1) was obtained.

  Each lithographic printing plate precursor (30) to (35) was exposed, heated and developed in the same manner as in Example 20 except that the developer (1) was changed to the developer (3) shown below to obtain a lithographic printing plate. This was prepared and evaluated in the same manner as in Example 20. The results are shown in Table C.

Developer (3)
・ Water 100.00g
・ Benzyl alcohol 1.00g
・ Polyoxyethylene naphthyl ether (oxyethylene average number n = 13) 1.00 g
・ Dioctylsulfosuccinate sodium salt 0.50 g
・ Arabic gum 1.00g
・ Ethylene glycol 0.50g
・ Primary ammonium phosphate 0.05g
・ Citric acid 0.05g
・ Sodium carbonate 1.40g
・ Sodium bicarbonate 0.59g
Adjust the pH of the developer to 9.8 using phosphoric acid and sodium hydroxide

  As is clear from the results in Table C, the lithographic printing plate precursor according to the present invention has the remaining in the non-image area while maintaining the printing durability despite the development with a weak alkaline developer having a pH of 9.8. A lithographic printing plate excellent in color and dirt during printing can be produced. It can also be seen that these characteristics are maintained well when the lithographic printing plate precursor is forcibly stored.

[Examples 28 to 31 and Comparative Examples 9 to 10]
[Preparation of planographic printing plate precursors (36) to (41)]

[Preparation of aluminum support 2]
Using an aluminum plate (material: JIS A1050) having a thickness of 0.3 mm, the following steps (a) to (k) were performed in this order for surface treatment.

(A) Mechanical surface roughening treatment While supplying a suspension of abrasive (silica sand) having a specific gravity of 1.12. Roughening was performed. The average particle size of the abrasive was 8 μm, and the maximum particle size was 50 μm. The material of the nylon brush was 6 · 10 nylon, the hair length was 50 mm, and the hair diameter was 0.3 mm. The nylon brush was planted so as to be dense by making a hole in a stainless steel tube having a diameter of 300 mm. Three rotating brushes were used. The distance between the two support rollers (Φ200 mm) at the bottom of the brush was 300 mm. The brush roller was pressed until the load of the drive motor for rotating the brush became 7 kW plus with respect to the load before the brush roller was pressed against the aluminum plate. The rotating direction of the brush was the same as the moving direction of the aluminum plate. The rotation speed of the brush was 200 rpm.

(B) Alkaline etching treatment An aluminum plate was sprayed with an aqueous NaOH solution at a temperature of 70 ° C. (concentration: 26 mass%, aluminum ion concentration: 6.5 mass%) to dissolve the aluminum plate by 6 g / m ² . Thereafter, washing with water was performed using well water.

(C) Desmutting treatment The desmutting treatment was performed by spraying with a 1% by mass aqueous solution of nitric acid at a temperature of 30 ° C. (containing 0.5% by mass of aluminum ions), and then washed with water by spraying. The nitric acid aqueous solution used for the desmut was the waste liquid from the process of electrochemical surface roughening using alternating current in the nitric acid aqueous solution.

(D) Electrochemical roughening treatment An electrochemical roughening treatment was carried out continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a 10.5 g / liter aqueous solution of nitric acid (containing 5 g / liter of aluminum ions) at a temperature of 50 ° C. The AC power supply waveform has an electrochemical surface roughening treatment using a carbon electrode as a counter electrode using a trapezoidal rectangular wave alternating current with a time TP of 0.8 ms until the current value reaches a peak from zero, a DUTY ratio of 1: 1. went. Ferrite was used for the auxiliary anode. The electrolytic cell used was a radial cell type. The current density was 30 A / dm ² at the peak current value, and the amount of electricity was 220 C / dm ² in terms of the total amount of electricity when the aluminum plate was the anode. 5% of the current flowing from the power source was shunted to the auxiliary anode. Thereafter, washing with water was performed using well water.

(E) Alkaline etching treatment The aluminum plate was sprayed with an aqueous solution of caustic soda concentration of 26% by mass and aluminum ion concentration of 6.5% by mass at 32 ° C. to dissolve the aluminum plate by 0.20 g / m ^2, and the previous AC The smut component mainly composed of aluminum hydroxide generated when electrochemical surface roughening was removed using the slag, and the edge portion of the generated pit was melted to smooth the edge portion. Thereafter, washing with water was performed using well water.

(F) Desmut treatment Desmut treatment by spraying was performed with a 15% by weight aqueous solution of nitric acid at a temperature of 30 ° C. (including 4.5% by weight of aluminum ions), and then washed with water using well water. The nitric acid aqueous solution used for the desmut was the waste liquid from the process of electrochemical surface roughening using alternating current in the nitric acid aqueous solution.

(G) Electrochemical surface roughening treatment An electrochemical surface roughening treatment was performed continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a hydrochloric acid 7.5 g / liter aqueous solution (containing 5 g / liter of aluminum ions) at a temperature of 35 ° C. The AC power supply waveform was a rectangular wave, and an electrochemical surface roughening treatment was performed using a carbon electrode as a counter electrode. Ferrite was used for the auxiliary anode. The electrolytic cell used was a radial cell type. The current density was 25 A / dm ² at the peak current value, and the amount of electricity was 50 C / dm ² in terms of the total amount of electricity when the aluminum plate was the anode. Thereafter, washing with water was performed using well water.

(H) Alkaline etching treatment The aluminum plate was sprayed with an aqueous solution of caustic soda concentration of 26% by mass and aluminum ion concentration of 6.5% by mass at 32 ° C. to dissolve the aluminum plate at 0.10 g / m ^2, and the previous AC The smut component mainly composed of aluminum hydroxide generated when the electrochemical surface roughening treatment was performed was removed, and the edge portion of the generated pit was melted to smooth the edge portion. Thereafter, washing with water was performed using well water.
(I) Desmut treatment A desmut treatment by spraying was performed with a 25% by mass aqueous solution of sulfuric acid at a temperature of 60 ° C. (containing 0.5% by mass of aluminum ions), and then water washing by spraying was performed using well water.
(J) Anodizing treatment Anodizing treatment was performed using sulfuric acid as an electrolytic solution. The sulfuric acid concentration of the electrolytic solution was 170 g / liter (containing 0.5 mass% of aluminum ions), and the temperature was 43 ° C. Thereafter, washing with water was performed using well water. The current density was about 30A / dm ^2. The final oxide film amount was 2.7 g / m ² .

(K) Alkali metal silicate treatment The alkali metal silicate treatment (silicate treatment) was performed by immersing the aluminum plate in a treatment tank of 1 mass% aqueous solution of sodium silicate No. 3 at a temperature of 30 ° C. for 10 seconds. . Then, the aluminum support body 2 was produced by performing the water washing by the spray using well water. The amount of silicate adhered was 3.6 mg / m ² .

(Formation of the lower layer)
On the surface of the aluminum support 2, an undercoat layer coating solution having the following composition was applied so that the dry coating amount was 10 mg / m ^2, and dried at 100 ° C. for 1 minute to form a lower layer.

<Undercoat layer coating solution>
・ High molecular compounds listed in Table D 1 g
・ Methanol 1000g

(Formation of photosensitive layer)
Subsequently, a photosensitive layer coating solution 4 having the following composition was applied by a bar and then oven-dried at 70 ° C. for 60 seconds to form a photosensitive layer having a dry coating amount of 1.0 g / m ² .

<Photosensitive layer coating solution 4>
・ The following binder polymer (2) (mass average molecular weight: 80,000) 0.50 g
・ Polymerizable compound 1.15 g
Isocyanuric acid EO-modified triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester M-315)
・ The following polymerization initiator (1) 0.20 g
・ The following infrared absorber (1) 0.05 g
・ The following microcapsule liquid (1) 2.00 g
-The following fluorosurfactant (1) (mass average molecular weight: 11,000) 0.05 g
-0.40 g of the organic pigment dispersion Nord listed in Table D
・ 1-Methoxy-2-propanol 18.00g

<Microcapsule solution (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, The following infrared absorber (2) 0.35 g and Pionein A-41C (manufactured by Takemoto Yushi Co., Ltd.) 0.1 g were 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 12000 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 40 ° C. for 3 hours. The microcapsule solution (1) was prepared by diluting the solid content concentration of the microcapsule solution thus obtained with distilled water so as to be 20% by mass. The average particle size was 0.3 μm.

(Formation of protective layer)
The protective layer coating solution 2 is applied onto the photosensitive layer so that the dry coating mass is 0.5 g / m ² , dried at 100 ° C. for 1 minute to provide a protective layer, and the planographic printing plate precursor (36) to (41) was produced.

  Each lithographic printing plate precursor (36) to (41) was subjected to a 50% flat screen image under the conditions of output 9W, outer drum rotation speed 210rpm, resolution 2400dpi using a Creo Trendsetter 3244VX equipped with a water-cooled 40W infrared semiconductor laser. After the exposure, development processing was performed in the same manner as in Example 1 to prepare a lithographic printing plate, and evaluation was performed in the same manner as in Example 1. The results are shown in Table D.

  As is clear from the results in Table D, even when the exposure light source is changed, the lithographic printing plate precursor of the present invention maintains printing durability despite the development treatment with a neutral developer having a pH of 7. A lithographic printing plate excellent in the residual color in the non-image area and the stain during printing can be produced. It can also be seen that these characteristics are maintained well even when the lithographic printing plate precursor is forcibly stored.

It is explanatory drawing which shows the structure of an automatic developing processor.

Explanation of symbols

61 Rotating Brush Roll 62 Receiving Roll 63 Conveying Roll 64 Conveying Guide Plate 65 Spray Pipe 66 Pipe Line 67 Filter 68 Plate Feeding Plate 69 Discharge Plate 70 Developer Tank 71 Circulation Pump 72 Planographic Printing Plate Master

Claims (17)

  On the support, at least (A1) an undercoat layer containing a polymer compound having a support adsorbing group and (A2) a hydrophilic group, and a photosensitive layer containing a pigment not adsorbing to the polymer compound are provided in this order. A lithographic printing plate precursor that can be developed with a developer having a pH of 2 to 11. The pigment is a pigment dispersed with a pigment dispersant having a pigment adsorbing group, and the hydrophilic group and the pigment adsorbing group satisfy at least one of the following conditions 1 and 2. Item 2. The lithographic printing plate precursor as described in Item 1.
Condition 1: The hydrophilic group is a neutral group and the pigment adsorbing group is an acidic group, neutral group or basic group. Condition 2: The hydrophilic group is a basic group and the pigment adsorbing group is an acidic group or neutral group. Is The lithographic printing plate precursor as claimed in claim 2, wherein the hydrophilic group is selected from functional groups represented by the following general formula.
In the formula, L represents a divalent linking group for linking to the compound nucleus, L ₁ represents a divalent linking group, and R _{1 to} R ₇ are each independently an alkyl group, aryl group, alkenyl. Group, alkynyl group, -OR, -NRR ', -SR, -COR, -COOR, -CONRR', -OCOR, -OCONRR ', -OCOOR, -NRCOR', -NRCOOR ', -NRCONR'R'', —N═R, —SO ₂ R, —SO ₃ R, —SO ₂ NRR ′, hydrogen atom, halogen group, cyano group, nitro group, hydroxyl group or mercapto group (R, R ′, R ″ are each independently Represents an alkyl group, an aryl group, an alkenyl group, an alkynyl group or a hydrogen atom, or each may be bonded to each other to form a ring), and L, L ₁ , R ₁ in the same functional group, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ may be bonded to each other to form a ring. n represents a number representing the average value of repeating units, X ⁻ represents a counter anion, and M ⁺ represents a counter cation.   The lithographic printing plate precursor as claimed in claim 3, wherein the hydrophilic group is a functional group selected from the general formulas (N-1) to (N-7) and (B-1). The lithographic printing plate precursor as claimed in claim 2, wherein the pigment adsorbing group is selected from functional groups represented by the following general formula.
In the formula, L represents a divalent linking group for linking to the compound nucleus, and R _{11 to} R ₁₈ each independently represents an alkyl group, an aryl group, an alkenyl group, an alkynyl group, —OR, —NRR ′. , -SR, -COR, -COOR, -CONRR ', - OCOR, -OCONRR', - OCOOR, -NRCOR ', - NRCOOR', - NRCONR'R '', - N = R, -SO 2 R, - SO ₃ R, —SO ₂ NRR ′, hydrogen atom, halogen group, cyano group, nitro group, hydroxyl group or mercapto group (R, R ′, R ″ each independently represents an alkyl group, aryl group, alkenyl group, Represents an alkynyl group or a hydrogen atom, or each may be bonded to each other to form a ring). X represents an oxygen atom, a sulfur atom, a selenium atom or NR ₁₉ , Y represents a covalent bond, an oxygen atom, a sulfur atom, NR ₁₉ , CO or SO ₂ , and R ₁₉ has the same meaning as R ₁₁ . L, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ in the same functional group may be bonded to each other to form a ring.   The pigment adsorbing group is the general formula (PA-2), (PA-5), (PN-1), (PN-2), (PB-1), (PB-10), (PB-11). The lithographic printing plate precursor as claimed in claim 5, wherein the lithographic printing plate precursor is a functional group selected from (PB-12).   The lithographic printing according to any one of claims 1 to 6, wherein the photosensitive layer further contains a radical polymerizable compound, a radical polymerization initiator, a sensitizing dye, a co-sensitizer, and a binder polymer. Version original edition. The lithographic printing plate precursor as claimed in any one of claims 1 to 7, further comprising a protective layer on the photosensitive layer.   On the support, at least (A1) an undercoat layer containing a polymer compound having a support adsorbing group and (A2) a hydrophilic group, and a photosensitive layer containing a pigment not adsorbing to the polymer compound are provided in this order. A method for preparing a lithographic printing plate, comprising exposing a lithographic printing plate precursor with a laser and then removing a photosensitive layer in an unexposed area in the presence of a developer having a pH of 2 to 11. The pigment is a pigment dispersed with a pigment dispersant having a pigment adsorbing group, and the hydrophilic group and the pigment adsorbing group satisfy at least one of the following conditions 1 and 2. Item 10. A method for producing a lithographic printing plate according to Item 9.
Condition 1: The hydrophilic group is a neutral group and the pigment adsorbing group is an acidic group, neutral group or basic group. Condition 2: The hydrophilic group is a basic group and the pigment adsorbing group is an acidic group or neutral group. Is The method for preparing a lithographic printing plate according to claim 10, wherein the hydrophilic group is selected from functional groups represented by the following general formula.
In the formula, L represents a divalent linking group for linking to the compound mother nucleus, L ₁ represents a divalent linking group, and R1 to R7 each independently represents an alkyl group, an aryl group, an alkenyl group, Alkynyl group, -OR, -NRR ', -SR, -COR, -COOR, -CONRR', -OCOR, -OCONRR ', -OCOOR, -NRCOR', -NRCOOR ', -NRCONR'R'', -N ═R, —SO ₂ R, —SO ₃ R, —SO ₂ NRR ′, hydrogen atom, halogen group, cyano group, nitro group, hydroxyl group or mercapto group (R, R ′, R ″ are each independently Represents an alkyl group, an aryl group, an alkenyl group, an alkynyl group or a hydrogen atom, or each may be bonded to each other to form a ring), and L, L ₁ , R ₁ , R ₂ in the same functional group _{, R 3, R 4, R} 5, R It may form a ring wherein R ₇ is each other. n represents a number representing the average value of repeating units, X ⁻ represents a counter anion, and M ⁺ represents a counter cation.   The lithographic printing plate according to claim 11, wherein the hydrophilic group is a functional group selected from the general formulas (N-1) to (N-7) and (B-1). Method. The method for preparing a lithographic printing plate according to claim 10, wherein the pigment adsorbing group is selected from functional groups represented by the following general formula.
In the formula, L represents a divalent linking group for linking to the compound nucleus, and R _{11 to} R ₁₈ each independently represents an alkyl group, an aryl group, an alkenyl group, an alkynyl group, —OR, —NRR ′. , -SR, -COR, -COOR, -CONRR ', - OCOR, -OCONRR', - OCOOR, -NRCOR ', - NRCOOR', - NRCONR'R '', - N = R, -SO 2 R, - SO ₃ R, —SO ₂ NRR ′, hydrogen atom, halogen group, cyano group, nitro group, hydroxyl group or mercapto group (R, R ′, R ″ each independently represents an alkyl group, aryl group, alkenyl group, Represents an alkynyl group or a hydrogen atom, or each may be bonded to each other to form a ring). X represents an oxygen atom, a sulfur atom, a selenium atom or NR ₁₉ , Y represents a covalent bond, an oxygen atom, a sulfur atom, NR ₁₉ , CO or SO ₂ , and R ₁₉ has the same meaning as R ₁₁ . L, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ in the same functional group may be bonded to each other to form a ring.   The pigment adsorbing group is the general formula (PA-2), (PA-5), (PN-1), (PN-2), (PB-1), (PB-10), (PB-11). The method for preparing a lithographic printing plate according to claim 13, wherein the functional group is selected from (PB-12).   The lithographic printing according to any one of claims 9 to 14, wherein the photosensitive layer further contains a radical polymerizable compound, a radical polymerization initiator, a sensitizing dye, a co-sensitizer, and a binder polymer. Plate making method.   The method for producing a lithographic printing plate according to claim 9, further comprising a protective layer on the photosensitive layer.   The photosensitive layer in the non-exposed area is removed in the presence of a developer having a pH of 2 to 11 after image exposure with the laser and heating at a temperature of 70 ° C or higher. A method for producing a lithographic printing plate according to any one of the above.