JP2008250228A - Planographic printing plate precursor and platemaking method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a planographic printing plate precursor showing high sensitivity and high plate wear in which developing property and contamination property in a non-image part are improved, and to provide a method for making a planographic printing plate using the precursor. <P>SOLUTION: The planographic printing plate precursor has a support and a photosensitive layer, characterized in that the photosensitive layer contains (A) a polymerizable compound having a specified cyclic structure, (B) a polymerization initiator, (D) a sensitizing dye having a maximum absorption in a wavelength region from 350 to 450 nm, and (E) a binder polymer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a lithographic printing plate precursor and a plate making method using the same.

In general, a lithographic printing plate has a surface composed of an oleophilic image portion and a hydrophilic non-image portion. In lithographic printing, dampening water and oil-based ink are alternately applied to the plate surface, and the hydrophilic non-image area is dampened with a dampening water receiving area (ink non-receiving area) by utilizing the property that water and oil repel each other. ), After the ink is received only in the oleophilic image area, the ink is transferred to a printing medium such as paper and printed.
In order to produce this lithographic printing plate, a lithographic printing plate precursor (PS plate) in which an oleophilic photosensitive layer (image recording layer) is provided on a hydrophilic support has been widely used. Normally, after exposing a lithographic printing plate precursor through an original image such as a lithographic film, the photosensitive layer to be an image portion is left, and other unnecessary photosensitive layers are dissolved with an alkaline developer or an organic solvent. The lithographic printing plate is obtained by carrying out plate making by a method of exposing the surface of the hydrophilic support to form a non-image portion by removing it.

  In the conventional plate-making process of a lithographic printing plate precursor, a step of dissolving and removing unnecessary photosensitive layers with a developer or the like is necessary after exposure, but simplifies such additional wet processing. Is listed as one of the issues. As one of simplification, it is desired that development can be performed with an aqueous solution close to neutrality or simple water.

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

  From the background as described above, it is now more strongly desired than ever to adapt both the simplification of the plate making operation and the digitization.

  On the other hand, for example, in Patent Document 1, in an image forming layer of a lithographic printing plate precursor having an image forming layer containing a hydrophobic precursor, a hydrophilic resin, and a photothermal conversion agent on a hydrophilic support. In addition to the on-press development, it is further described that by using a compound having an ethylene oxide chain, it can be used for printing after being subjected to exposure, liquid development processing using water or a suitable aqueous solution as a developer. Yes.

  Patent Document 2 contains (i) a hydrophilic support, and (ii) a radical polymerizable ethylenically unsaturated monomer, a radical polymerization initiator and an infrared absorbing dye, and is cured by infrared laser exposure. Moreover, a lithographic printing plate precursor comprising an oleophilic heat-sensitive layer containing 60% by mass or more of water and developable with an aqueous developer having a pH of 2.0 to 10.0 is prepared and exposed imagewise with an infrared laser. A processing method for a lithographic printing plate precursor comprising removing an uncured region of the heat-sensitive layer with an aqueous developer is described.

Further, Patent Document 3 discloses that an ethylenically unsaturated layer is formed on a photosensitive layer or other layer containing a polymerization initiator, a polymerizable compound, a binder polymer that is soluble or swells in water or an aqueous alkali solution, and is present on a support. By containing a binder polymer having a functional group that binds and interacts with the surface of the support, a lithographic printing plate precursor having high sensitivity, high printing durability and excellent non-image area stainability can be obtained under the conditions of using an alkaline developer. It is described. In addition, after image exposure of a lithographic printing plate precursor having a photosensitive layer on a support, a recording surface of the lithographic printing plate precursor in the presence of a developer having a pH of 2 to 10 in a development processing section provided with a rubbing member There is known a method for preparing a lithographic printing plate including a development step in which a photosensitive layer in an unexposed portion is removed by rubbing with a rubbing member (see Patent Documents 4 and 5). Also known is a method for preparing a printing plate comprising a step of removing a non-exposed portion with a gum solution after a photopolymerization layer is provided on a hydrophilic support and exposed (see Patent Document 6).

Moreover, as a photosensitive composition containing the polymeric compound which has a highly polar functional group, the composition (refer patent document 7) containing a specific highly polar functional group, a urethane group, and a heterocyclic group are included. A radiation curable composition containing a (meth) acrylate having a highly polar functional group (see Patent Document 8) is known. However, these inventions are silent about compositions that require development.
Further, a (meth) acrylate monomer having a specific structure having a cyclic carbonate group and a photosensitive recording material for an offset printing plate using the monomer are known (see Patent Document 9).
JP 2002-365789 A US Patent Application Publication No. 2004/0013968 JP 2006-78999 A JP 2006-39468 A JP 2006-106700 A International Publication No. 05/111727 Pamphlet JP-T-2004-514759 JP 2005-526169 A JP-T-9-501654

However, it has been difficult to improve all the developability, stain resistance, sensitivity, and printing durability in lithographic printing plate precursor applications using any of the above techniques. An object of the present invention is to provide a lithographic printing plate precursor having improved developability and stain resistance in non-image areas and exhibiting high sensitivity and high printing durability, and a method for producing a lithographic printing plate using the same. is there.

The above-mentioned subject is achieved by the following composition. That is, the present invention is as follows.
1. A lithographic printing plate precursor having a support and a photosensitive layer, wherein the photosensitive layer has (A) at least one polymerizable compound represented by any one of the following formulas (I) to (III): A lithographic printing plate precursor comprising (B) a polymerization initiator, (D) a sensitizing dye having a maximum absorption in a wavelength region of 350 to 450 nm, and (E) a binder polymer.

In the formula, X, X ₁ , X ₂ , X ₃ , Y, Y ₁ , Y ₂ and Z each independently represent O, S or NR ₇ , and X ₄ represents OR ₇ , SR ₇ , N ( R ₈ ) (R ₉ ) or an alkyl group is represented. V ₁ and V ₂ each independently represents O, S, NR ₇ , or C (R ₅ ) (R ₆ ). L ₃ represents an atomic group that combines with Y and Z to form a ring structure, L ₄ represents an atomic group that combines with Y ₁ and V ₁ to form a ring structure, and L ₅ represents Y ₂ and V ₂ Represents an atomic group that forms a ring structure by bonding with. R _{5 to} R ₉ each independently represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group.
Further, the formula (I), wherein the at least one polymerizable group via any position of R ₇ or L ₃ of R _7, wherein Z in R _7, Y in X is connected. Formula (II), _R 7 in in _{X 1, X R} 7 in _{2, Y 1} in _R 7, _R in _{V 1} 5, _R 6 in the _{V 1, R 7} in _{V 1} or At least one polymerizable group is linked via any position of L ₄ . Formula _{(III), R 7, R} 7 in _{X 4, X 4} in _R 8, _{X 4} in _R 9, alkyl in _{X 4} in _{X 3, R} 7, _{V 2} in in _{Y 2} at least one via any position of _{R 7} or _{L 5} of _R 5, _{V R} 6, _{V 2} of ₂ polymerizable groups is linked.

2. 2. The lithographic printing plate precursor as described in 1 above, wherein (A) is a polymerizable compound having at least one structure selected from a 5- or 6-membered cyclic carbonate and a cyclic urethane structure.
3. 3. The lithographic printing plate precursor as described in 1 or 2 above, wherein the photosensitive layer contains a polymerizable compound (C) other than the (A).
4). 4. The lithographic printing plate precursor as described in any one of 1 to 3 above, wherein an undercoat layer is provided between the support and the photosensitive layer.
5. The lithographic printing plate precursor as described in any one of 1 to 4 above, further comprising a protective layer on the photosensitive layer.
6). The lithographic printing plate precursor as described in any one of 1 to 5 above, which can be developed with a developer having a pH of 2 to 10.
7). The lithographic printing plate precursor as described in any one of 1 to 6 above is exposed using an exposure apparatus equipped with a light source having an oscillation wavelength in the range of 350 to 450 nm, and then exposed to unexposed portions in the presence of a developer. A method for preparing a lithographic printing plate, comprising removing the layer.

  According to the present invention, it is possible to provide a lithographic printing plate precursor having improved developability and stain resistance in non-image areas and having high sensitivity and high printing durability, and a method for producing a lithographic printing plate using the same.

[Lithographic printing plate precursor]
(Photosensitive layer)
The photosensitive layer of the lithographic printing plate precursor according to the invention comprises (A) a polymerizable compound having at least one structure selected from the following formulas (I) to (III), (B) a polymerization initiator, (D) It contains a sensitizing dye having a maximum absorption in a wavelength region of 350 to 450 nm, and (E) a binder polymer.

<(A) Polymerizable compound having at least one structure represented by any one of formulas (I) to (III)>
Hereinafter, the polymerizable compound having at least one structure represented by any one of (A) Formula (I) to Formula (III) is also referred to as a specific polymerizable compound.

In the formula, X, X ₁ , X ₂ , X ₃ , Y, Y ₁ , Y ₂ and Z each independently represent O, S or NR ₇ , and X ₄ represents OR ₇ , SR ₇ , N ( R ₈ ) (R ₉ ) or an alkyl group is represented.
V ₁ and V ₂ each independently represents O, S, NR ₇ , or C (R ₅ ) (R ₆ ).
L ₃ represents an atomic group that combines with Y and Z to form a ring structure, L ₄ represents an atomic group that combines with Y ₁ and V ₁ to form a ring structure, and L ₅ represents Y ₂ and V ₂ Represents an atomic group that forms a ring structure by bonding with. R _{5 to} R ₉ each independently represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group.
Further, the formula (I), wherein the at least one polymerizable group via any position of R ₇ or L ₃ of R _7, wherein Z in R _7, Y in X is connected. Formula (II), _R 7 in in _{X 1, X R} 7 in _{2, Y 1} in _R 7, _R in _{V 1} 5, _R 6 in the _{V 1, R 7} in _{V 1} or At least one polymerizable group is linked via any position of L ₄ . Formula _{(III), R 7, R} 7 in _{X 4, X 4} in _R 8, _{X 4} in _R 9, alkyl in _{X 4} in _{X 3, R} 7, _{V 2} in in _{Y 2} at least one via any position of _{R 7} or _{L 5} of _R 5, _{V R} 6, _{V 2} of ₂ polymerizable groups is linked. In addition, at least one polymerizable group is linked via any position of the above L _{3 to} L ₅ and any one of R _{5 to} R ₉ .

Here, the structure selected from the formulas (I) to (III) means a residue in which at least one hydrogen atom is eliminated from the compounds represented by the formulas (I) to (III), In formulas (I) to (III), the hydrogen atom is removed at any position of L _{3 to} L ₅ and any one of R _{5 to} R ₉ . The polymerizable group is an ethylenically unsaturated group capable of addition polymerization, and is preferably a terminal ethylenically unsaturated group.

  By using such a specific polymerizable compound (A), a lithographic printing plate precursor having good developability and stain resistance in non-image areas, good curing characteristics, high sensitivity and high printing durability is obtained. be able to.

Below, the preferable aspect of (A) specific polymeric compound of this invention is described.
In the formula (I), X is preferably O or S, and at least one of Y and Z is preferably O.
L _{3 to} L _{5 in} Formula (I) to Formula (III) are alkylene, —O—, —S—, —N (R ₅ ) —, —CO—, —SO—, —SO ₂ —, or these A combination thereof, alkylene, —O—, —S—, —N (R ₅ ) —, or a combination thereof is more preferable, and alkylene is more preferable.

A ring structure formed by combining L _{3 of} formula (I) with Y and Z, a ring structure formed by combining L _{4 of} formula (II) with Y ₁ and V ₁ , and L _{5 of} formula (III) The ring structure formed by bonding with Y ₂ and V ₂ is preferably a 5-membered ring or a 6-membered ring.

  As formula (I), a 5-membered or 6-membered cyclic carbonate, a 5-membered or 6-membered cyclic urethane, a 5-membered or 6-membered cyclic thiourethane, a 5-membered or 6-membered cyclic urea A 5-membered or 6-membered cyclic thiourea is preferred, a 5-membered or 6-membered cyclic carbonate, a 5-membered or 6-membered cyclic urethane, a 5-membered or 6-membered cyclic thiourea is more preferred, More preferred are 5-membered or 6-membered cyclic carbonates, 5-membered or 6-membered cyclic urethanes.

  As the formula (II), a 5-membered or 6-membered cyclic sulfate, a 5-membered or 6-membered cyclic sulfonate, a 5-membered or 6-membered cyclic sulfonamide is preferred, and a 5-membered or 6-membered cyclic sulfonamide is preferred. A membered cyclic sulfonic acid ester, a 5-membered ring or a 6-membered cyclic sulfonamide is more preferable.

  As formula (III), a 5- or 6-membered cyclic phosphate ester, a 5- or 6-membered cyclic phosphate amide, a 5- or 6-membered cyclic phosphonate ester, a 5-membered ring or 6 A membered cyclic phosphonic acid amide is preferable, and a 5-membered or 6-membered cyclic phosphonic acid ester is more preferable, and a 5-membered or 6-membered cyclic phosphonic acid amide is more preferable.

As the specific polymerizable compound (A) of the present invention, a compound having at least one 5-membered or 6-membered cyclic carbonate structure, or 5-membered or 6-membered cyclic urethane structure is preferable.
100-5000 are preferable and, as for the molecular weight of (A) specific polymeric compound of this invention, 500-3000 are especially preferable.

  More specific examples of the specific polymerizable compound (A) of the present invention include compounds represented by the formula (IV) or the formula (V).

In the formula, M ₁ represents a monovalent residue in which one hydrogen atom is eliminated from formula (I), formula (II), or formula (III). M ₂ represents a (n3 + 1) -valent residue from which (n3 + 1) hydrogen atoms have been eliminated from formula (I), formula (II) or formula (III).
R ₁ and R ₂ each independently represents a hydrogen atom or an alkyl group, R ₃ represents a hydrogen atom, an alkyl group, COOR ₄ or CONR ₅ R ₆ , and R ₄ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, A represents an (n1 + n2) -valent organic group, D represents an n4-valent organic group, and L ₁ And L ₂ each independently represents a divalent linking group.
n1 and n2 represent the integer of 1-10. More preferably, n1 is an integer of 2 or more. n3 and n4 are each an integer that is 1 or more and satisfies 1 ≦ (n3 × n4) ≦ 10. More preferably, (n3 × n4) is 2 or more.

-L ₂ -M ₁ in formula (IV) means that the structure represented by formula (I), formula (II) or formula (III) is bonded to L ₂ in formula (IV). . (..., -L _1- ) _n3 in the formula (V)
—M ₂ —L ₂ — represents that the structure represented by formula (I), formula (II) or formula (III) is bonded to L ₁ or L _{2 in} formula (V). means.

Among the above, R ₁ and R ₂ are more preferably hydrogen atoms. R ₃ is a hydrogen atom, a methyl _{group, COOCH 3, COOCH 2 CH 3} , CONHCH 3, CONHCH 2 CH 3, CONH 2, CON (CH 3) 2 or _{CON (CH 2 CH 3),} 2 is more preferable.
L ₁ is _{-CO 2 -L 4 -, - CON} (R 5) -L 4 -, - phenylene _{-L 4 -, - CH 2 -O} -L 4 -, or _-CH 2 -C (= O) - L ₄ - is more preferable. Here, L ₄ is a divalent linking group composed of alkylene, —O—, —S—, —N (R ₅ ) —, —CO—, —SO—, —SO ₂ —, or a combination thereof. is there.
L ₂ is preferably a group consisting of alkylene, —O—, —S—, —N (R ₅ ) —, —SO—, —SO ₂ —, or a combination thereof, alkylene, —S—, — More preferred is a group consisting of N (R ₅ ) —, —CO—, —SO—, —SO ₂ —, or a combination thereof.

A and D are more preferably those in which a hydrocarbon group having 1 to 30 carbon atoms is a (n1 + n2) -valent or n4-valent residue, respectively. The carbon atom at an arbitrary position of the hydrocarbon group may be replaced with a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom, or —CO—, —SO— or —SO ₂ —. In addition, a halogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, —COOR ₄ , —CONR ₅ R ₆ , —OCOR ₄ , —N (R ₅ ) COR Substituents such as ₄ may be substituted.

  The specific polymerizable compound (A) of the present invention may be used alone or in combination of a plurality of compounds. For example, the number of carbon-carbon double bonds, that is, the value of n1 in the case of formula (IV) and the value of (n3 × n4) in the case of formula (V) may be used in combination. Good.

  Specific examples of the specific polymerizable compound (A) are shown below.

<Synthesis of Specific Polymerizable Compound (A-1)>
Glycerol 1,2-carbonate 11.81 g (0.1 mol), tetrahydrofuran 100 ml, dibutyltin dilaurate (IV) 0.063 g (0.0001 mol), benzoquinone 0.011 g (0.0001 mol) were added to a 300 ml three-necked flask, and nitrogen was added. The mixture was stirred while replacing with gas. Thereafter, 23.92 g (0.1 mol) of Karenz BEI manufactured by Showa Denko KK was added dropwise over 1 hour. After stirring for 2 hours at 60 ° C. after completion of the dropping,
Allowed to cool to room temperature. Thereafter, the solvent was distilled off under reduced pressure to obtain 35.02 g (yield 98%) of the specific polymerizable compound (A-1).

<Synthesis of Specific Polymerizable Compound (A-64)>
(1) Synthesis of intermediate (1) In a 100 ml three-necked flask, 12.11 g (0.1 mol) of 2-amino-2-hydroxymethyl-1,3-propanediol, 14.18 g (0.12 mol) of diethyl carbonate, sodium 0.5 ml of methoxide (28 mass% methanol solution) was added, and the mixture was heated to reflux for 3 hours. Thereafter, the mixture was allowed to cool to room temperature, and excess diethyl carbonate was distilled off under reduced pressure. 20 ml of methanol was added to the taken-out solid and washed with stirring, followed by suction filtration and air drying to obtain 12.06 g (yield 82%) of intermediate (1).

(2) Synthesis of A-64 Intermediate (1) 7.36 g (0.05 mol), tetrahydrofuran 50 ml, dibutyltin dilaurate (IV) 0.03 g (0.00005 mol), benzoquinone 0.005 g (0) 0.0005 mol) was added and stirred while replacing nitrogen gas. Thereafter, 15.52 g (0.1 mol) of Karenz MOI manufactured by Showa Denko KK was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 60 ° C. for 2 hours, and then allowed to cool to room temperature. Thereafter, the solvent was distilled off under reduced pressure to obtain 21.96 g (yield 96%) of the specific polymerizable compound (A-64).

<Synthesis of Specific Polymerizable Compound (A-67)>
In the synthesis of the intermediate (1), 1,3-bis [tris (hydroxymethyl) -methylamino] propane was used instead of 2-amino-2-hydroxymethyl-1,3-propanediol, (2) can be synthesized. In the synthesis of (A-64), the specific polymerizable compound (A-67-3) can be synthesized by using the intermediate (2) instead of the intermediate (1).

<Synthesis of Specific Polymerizable Compound (A-44)>
(1) Synthesis of intermediate (3) To a 300 ml three-necked flask, 6.11 g (0.1 mol) of 2-aminoethanol, 50 ml of tetrahydrofuran and 12.14 g (0.12 mol) of triethylamine were added, and the resulting mixture was purged with nitrogen gas and stirred. Cooled to 0 ° C. Thereafter, a solution of 16.30 g (0.1 mol) of 2-chloro-1-ethanesulfonyl chloride in 100 ml of tetrahydrofuran was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours and further triethylamine 12.1.
4 g (0.12 mol) was added and the mixture was heated to reflux for 3 hours and then allowed to cool to room temperature. After the reaction solution was filtered, chloroform and a saturated aqueous sodium chloride solution were added for liquid separation, and the chloroform layer was dehydrated by adding magnesium sulfate. After filtering magnesium sulfate and concentrating the solvent with an evaporator, purification was performed by silica gel column chromatography to obtain 4.63 g (yield 28%) of intermediate (3).

(2) Synthesis of A-44 In a 300 ml three-necked flask, 6.68 g (0.025 mol) of 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 50 ml of tetrahydrofuran, 0.063 g of dibutyltin dilaurate (IV) ( 0.0001 mol) and 0.011 g (0.0001 mol) of benzoquinone were added and stirred while replacing with nitrogen gas. Thereafter, 6.51 g (0.05 mol) of 2-hydroxyethyl methacrylate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was further stirred for 2 hours, and then a solution of 4.13 g of the intermediate (3) in 30 ml of tetrahydrofuran was added dropwise over 30 minutes. After completion of dropping, the mixture was stirred at 60 ° C. for 1 hour, and then allowed to cool to room temperature. Thereafter, the solvent was distilled off under reduced pressure to obtain 16.63 g (yield 24%) of the specific polymerizable compound (A-44).

<Synthesis of Specific Polymerizable Compound (A-45)>
(1) Synthesis of Intermediate (4) 6.21 g (0.1 mol) of ethylene glycol, 11.13 g (0.11 mol) of triethylamine and 100 ml of tetrahydrofuran were added to a 300 ml three-necked flask and stirred while substituting nitrogen gas. Thereafter, a solution of 16.74 g (0.1 mol) of chloromethylphosphonic dichloride in 50 ml of tetrahydrofuran was added dropwise over 1 hour. After stirring for 2 hours after the completion of dropping, the reaction solution was filtered, and 9.84 g (0.12 mol) of sodium acetate was further added, followed by heating under reflux for 2 hours. Thereafter, the mixture was allowed to cool to room temperature, the salt was filtered, and 20 ml of 5N aqueous sodium hydroxide solution was added and stirred for 2 hours. Thereafter, ethyl acetate and a saturated aqueous sodium chloride solution were added to carry out a liquid separation operation, and the ethyl acetate layer was dehydrated by adding magnesium sulfate. After filtering magnesium sulfate and concentrating the solvent with an evaporator, purification was performed by silica gel column chromatography to obtain 4.83 g (yield 35%) of intermediate (4).

(2) Synthesis of A-45 In the synthesis of the specific polymerizable compound (A-44), by using the intermediate (4) instead of the intermediate (3), the specific polymerizable compound (A-45) Can be synthesized.

  (A) The amount of the specific polymerizable compound added to the photosensitive layer is preferably 1 to 70% by mass, more preferably 3 to 65% by mass, and particularly preferably 5 to 55% by mass with respect to the total solid content of the photosensitive layer. % Range. Within this range, the effects of the present invention, such as improved developability and improved stain resistance of the non-image area, higher sensitivity, and higher printing durability can be obtained.

<(C) Polymerizable compound>
In the photosensitive layer in the present invention, a polymerizable compound (C) other than the above-mentioned specific polymerizable compound (A) can be used in combination as long as the effects of the present invention are not impaired. The polymerizable compound used in combination is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or copolymers thereof, or mixtures 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 a monofunctional or polyfunctional compound. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or Also suitable are substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a tosyloxy group with monofunctional or polyfunctional alcohols, amines or thiols. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

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

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

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

  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, and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like are also included. Can be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these polymerizable compounds, the details of usage such as the structure, single use or combination, addition amount, etc. can be arbitrarily set according to the performance design of the final lithographic printing plate precursor. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the image area, that is, the cured film, those having three or more functionalities are preferable, and furthermore, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrenic compound, vinyl ether type). A method of adjusting both sensitivity and strength by using a compound) is also effective.
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 method 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 content of the polymerizable compound in the photosensitive layer is (A) the total amount of the polymerizable compound (C) used in combination with the specific polymerizable compound, and preferably 5 to 75% by mass with respect to the total solid content of the photosensitive layer. More preferably, it is 25-70 mass%, Most preferably, it is the range of 30-60 mass%.

<(B) Polymerization initiator>
The polymerization initiator used in the present invention is a compound that initiates and accelerates the polymerization of a compound having a polymerizable unsaturated group by generating radicals by light or thermal energy. As such a radical generator, a known polymerization initiator or a compound having a bond having a small bond dissociation energy can be appropriately selected and used.

  Examples of the compounds that generate radicals include organic halogen compounds, carbonyl compounds, organic peroxides, azo polymerization initiators, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boron compounds, disulfone compounds, and oximes. Examples thereof include ester compounds and onium salt compounds.

  Specific examples of the organic halogen compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP 48-36281, JP 53-133428, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62- 58241, JP-A 62-212401, JP-A 63-70243, JP-A 63-298339, Phutt, “Journal of Heterocyclic Chemistry”, 1 (No. 3) (1970). Of these, oxazole compounds substituted with a trihalomethyl group and S-triazine compounds are preferred.

  More preferable examples include s-triazine derivatives in which at least one mono, di, or trihalogen-substituted methyl group is bonded to the s-triazine ring, and oxadiazole derivatives in which the oxadiazole ring is bonded. Specifically, for example, 2,4,6-tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [1- (P-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- ( -Methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p- Tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenylthio-4,6-bis ( Trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris ( Tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) Etc. -s- triazine and the following compounds.

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

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

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

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

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

Examples of the organic boron compound include, for example, JP-A-62-143044, JP-A-62-1050242, JP-A-9-188865, JP-A-9-188686, and JP-A-9-1.
88710, JP 2000-131837, JP 2002-107916, JP 2764769, JP 2002-116539, and Kunz, Martin “Rad Tech '98. Proceeding April 19-22. , 1998, Chicago ", etc., organoboron sulfonium complexes or organoboron oxosulfonium complexes described in JP-A-6-157623, JP-A-6-175564, and JP-A-6-175561. Complexes, organoboron iodonium complexes described in JP-A-6-175554, JP-A-6-175553, organoboron phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP 7-128785 Publication, Hei 7-140589, JP-A No. 7-306527, JP-organic boron transition metal coordination complexes such as JP-A-7-292014 and the like.

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

  Examples of the oxime ester compound described in JCS Perkin II (1979) 1653-1660), JCSPerkin II (1979) 156-162, Journal of PHotopolymer Science and Technology (1995) 202-232, and JP-A No. 2000-66385. And compounds described in JP 2000-80068 A. Specific examples include compounds represented by the following structural formula.

  Examples of the onium salt compound include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Diazonium salts described in Bal et al, Polymer, 21, 423 (1980), ammonium salts described in US Pat. No. 4,069,055, JP-A-4-365049, etc., US Pat. No. 4,069 , 055, 4,069,056, phosphonium salts described in European Patent Nos. 104,143, US Pat. Nos. 339,049, 410,201, JP -150848, JP-A-2-296514, iodonium salts, European Patent Nos. 370,693, 390,214, 233,567, 297,443, and 297 442, U.S. Pat. Nos. 4,933,377, 161,811, 410,201, 339,049, 4,760,013 No. 4,734,444, No. 2,833,827, German Patent No. 2,904,626, No. 3,604,580, No. 3,604,581 Or a sulfonium salt described in J. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

In the present invention, these onium salts function not as acid generators but as ionic radical polymerization initiators.
The onium salts preferably used in the present invention 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. 1-12 alkenyl group, C1-C12 alkynyl group, C1-C12 aryl group, C1-C12 alkoxy group, C1-C12 aryloxy group, halogen atom, C1-C1 12 alkylamino groups, C1-C12 dialkylamino groups, C1-C12 alkylamide groups or arylamide groups, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, C1-C12 thioalkyl groups And a thioaryl group having 1 to 12 carbon atoms. Z ₁₁ ⁻ represents a monovalent anion, specifically, halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion,
Examples thereof include sulfinate ion, thiosulfonate ion, and sulfate ion. 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 1 carbon atoms. 12 alkyl groups, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, Halogen atom, C1-C12 alkylamino group, C1-C12 dialkylamino group, C1-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 1 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, and sulfate 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 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, Aryloxy group having 1 to 12 carbon atoms, halogen atom, alkylamino group having 1 to 12 carbon atoms, dialkylamino group having 1 to 12 carbon atoms, alkylamide group or arylamide group having 1 to 12 carbon atoms, carbonyl group, carboxyl Group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₃₁ ^- represents a monovalent anion. Specific examples include halogen ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, thiosulfonate ions, and sulfate 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 polymerization initiator is not limited to the above, but particularly from the viewpoint of reactivity and stability, a triazine-based initiator, an organic halogen compound, an oxime ester compound, a metallocene compound, a hexaarylbiimidazole compound, an organic boron compound, a diazonium salt. More preferred are iodonium salts and sulfonium salts.

These polymerization initiators may be used alone or in combination of two or more. Moreover, these polymerization initiators may be added to the same layer as other components, or another layer may be provided and added thereto. These polymerization initiators are preferably from 0.1 to 50% by mass, more preferably from 0.5 to 30% by mass, particularly preferably from 0.8 to 20% by mass, based on the total solid content constituting the photosensitive layer. Can be added.

<(D) Sensitizing dye having maximum absorption in the wavelength range of 350 to 450 nm>
The photosensitive layer of the present invention contains a sensitizing dye having a maximum absorption in a wavelength range of 350 to 450 nm corresponding to the wavelength of the exposure light source. Examples of such a sensitizing dye include merocyanine dyes represented by the following general formula (VI), benzopyrans and coumarins represented by the following general formula (VII), and fragrances represented by the following general formula (VIII). And anthracenes represented by the following general formula (IX).

(In the formula, A represents an S atom or NR ₆ , R ₆ represents a monovalent non-metallic atomic group, Y represents a basic nucleus of a dye in cooperation with an adjacent A and an adjacent carbon atom. A non-metallic atomic group, X ₁ and X ₂ each independently represent a monovalent non-metallic atomic group, and X ₁ and X ₂ may combine with each other to form an acidic nucleus of the dye.)

(In the formula, = Z represents a carbonyl group, a thiocarbonyl group, an imino group or an alkylidene group represented by the partial structural formula (1 ′), and X ₁ and X ₂ have the same meaning as in the general formula (VI)). R _{7 to} R ₁₂ each independently represents a monovalent nonmetallic atomic group.)

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

(In the formula, X ₃ , X ₄ and R _{14 to} R ₂₁ each independently represent a monovalent non-metallic atomic group, and more preferable X ₃ and X ₄ are electron donating groups having a negative Hammett's substituent constant. .)

In the general formulas (VI) to (IX), preferred examples of the monovalent nonmetallic atomic group represented by X ₁ to X ₄ and R ₆ to R ₂₁ include a hydrogen atom, an alkyl group (for example, a methyl group, Ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group , S-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, 2-norbornyl group, chloromethyl group , Bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxy Tyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl Group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chloro Phenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl Ru-N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoyl group Propyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphine group Onatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, syn Mil group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc.), aryl group (for example, , Phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, Acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, Noxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group, phosphonatophenyl group, etc.), heteroaryl group (for example, thiophene, thiathrene) , Furan, pyran, isobenzofuran, chromene, xanthene,
Phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indoyl, indazole, purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, cinolin, pteridine, carbazole, carboline Phenanthrin, acridine, perimidine, phenanthroline, phthalazine, phenazazine, phenoxazine, furazane, phenoxazine, etc.), alkenyl groups (eg vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1 -Ethenyl group, etc.), alkynyl group (for example, ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group, etc.), halogen atom (-F, -Br, -Cl, I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino Group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, Ureido group, N'-a Killureido 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, Lucoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl- N-aryloxycarbonylamino group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N- di arylcarbamoyl group, N- alkyl -N- arylcarbamoyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (-SO ₃ H) and its conjugated base group (hereinafter, sulfonato ), 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-diarylsulfa Moyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonate group), dialkyl phosphono group (—PO ₃ (alkyl) ₂ ), diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphine Amino group (-PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (-PO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkyl phosphonophenyl group), monoaryl phosphono group ( -PO ₃ H (aryl)) and its conjugated base group (hereinafter referred to as aryl phosphonophenyl group), phosphonooxy group (-OPO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonophenyl group) , Dialkyl phosphonooxy group (—OPO ₃ (alkyl) ₂ ), diaryl phosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylaryl phosphonooxy group (—OPO ₃ (alkyl) (aryl)), mono An alkylphosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonatooxy); Called Shiki)
A monoarylphosphonooxy group (—OPO ₃ H (aryl)) and a conjugate base group thereof (hereinafter referred to as an arylphosphonatooxy group), a cyano group, a nitro group, and the like. Among the above substituents, Particularly preferred are a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an alkoxy group, and an acyl group.

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

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

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

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

  Of the sensitizing dyes having an absorption maximum in the wavelength range of 350 nm to 450 nm, a dye more preferable from the viewpoint of high sensitivity is a dye represented by the following general formula (X).

(In the general formula (X), 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 represent a monovalent nonmetallic atomic group, and A and R ₁ and R ₂ and R ₃ are bonded to each other to form an aliphatic or aromatic ring. May be good.)

General formula (X) 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.

Preferable examples of R ₁ , R ₂ and R ₃ will be specifically described. Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group. Among these, straight chain having 1 to 12 carbon atoms, branched chain having 3 to 12 carbon atoms,
In addition, a cyclic alkyl group having 5 to 10 carbon atoms is more preferable.

As the substituent of the substituted alkyl group, a monovalent nonmetallic atomic group excluding hydrogen is used, and preferred examples include a halogen atom (—F, —Br, —Cl, —I), a hydroxyl group, an alkoxy group, Aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, Reelsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N'-alkylureido group, N ', N'-dialkylureido group, N'-arylureido Group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′- Alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'- Aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-ary Luureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl- N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, acyl group, carboxyl group, alkoxycarbonyl Group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl Group, Arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkyls Rufinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkyl Sulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (-PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonato group , Dialkyl phosphono group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono Group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphine group). A phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as a phosphonatooxy group), a dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), a diarylphosphine Fonookishi group _{(-OPO 3 (aryl) 2)} , alkylaryl phosphonooxy group (-OPO ₃ (alkyl (Aryl)), monoalkyl phosphonooxy group (-OPO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkyl phosphonophenyl group), monoaryl phosphonooxy group (-OPO ₃ H (aryl )) And conjugated base groups thereof (hereinafter referred to as arylphosphonatooxy groups), cyano groups, nitro groups, aryl groups, heteroaryl groups, alkenyl groups, and alkynyl groups.

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

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

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

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

Specific examples of preferable substituted alkyl groups as R ₁ , R ₂ and R ₃ obtained by combining the substituent and the alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxy Methyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N -Cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbo Nylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl- N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobu Group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonateoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p -Methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc. Can be mentioned.

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

Specific examples of preferred substituted aryl groups as R ₁ , R _2, and R ₃ include those having a monovalent non-metallic atomic group excluding hydrogen as a substituent on the ring-forming carbon atom of the aforementioned aryl group. . Examples of preferred substituents include the alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group. Preferred examples of such a substituted aryl group include a biphenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a chlorophenyl group, a bromophenyl group, a fluorophenyl group, a chloromethylphenyl group, and a trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carbo Cyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphono Enyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatephenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group Group, 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, and the like.

Next, A in the general formula (X) will be described. A represents an aromatic ring group or a heterocyclic group which may have a substituent. Specific examples of the aromatic ring or heterocyclic ring which may have a substituent include R ₁ in the general formula (X). , R ₂ and R ₃ are the same.

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

  Preferred specific examples (D1) to (D75) of the compound represented by the general formula (X) are shown below. In addition, an isomer with a double bond connecting an acidic nucleus and a basic nucleus is not limited to either isomer.

Details of the usage such as which structure of these sensitizing dyes are used, whether they are used alone or in combination of two or more, and the addition amount can be appropriately set according to the performance design of the lithographic printing plate precursor.
For example, the compatibility with the photosensitive layer can be increased by using two or more sensitizing dyes in combination. In selecting the sensitizing dye, in addition to the photosensitivity, the molar extinction coefficient at the emission wavelength of the light source used is an important factor. By using a dye having a large molar extinction coefficient, the amount of the dye added can be made relatively small, which is economical and advantageous from the viewpoint of film physical properties of the photosensitive layer when used in a lithographic printing plate precursor. is there. The photosensitivity and resolution of the photosensitive layer and the physical properties of the exposed film are greatly affected by the absorbance at the light source wavelength, and thus the addition amount of the sensitizing dye is appropriately selected in consideration of these.

  However, for example, for the purpose of curing a thick film having a thickness of 5 μm or more, the degree of curing may be increased by lower absorbance. When used as a lithographic printing plate precursor used in a relatively thin film thickness, the addition amount of the sensitizing dye is such that the absorbance of the photosensitive layer of the present invention is in the range of 0.1 to 1.5, preferably from 0.25. It is preferable to set so as to be in the range of 1. Usually, the amount is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and most preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive layer.

<(E) Binder polymer>
A binder polymer is used in the photosensitive layer of the present invention. The binder polymer used in the present invention is a polymer that functions as a film-forming agent for the photosensitive layer, and preferably contains a linear organic polymer. Any such “linear organic polymer” may be used.
As an example of such a binder polymer, a polymer selected from acrylic resins, polyvinyl acetal resins, polyurethane resins, polyamide resins, epoxy resins, methacrylic resins, styrene resins, and polyester resins is preferable. Of these, acrylic resins and polyurethane resins are preferable.

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 polymer binder 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 monovalent organic group, and R ¹ is preferably 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 which may have a group, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which 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. Here, examples of R ¹² include an alkyl group which may have a substituent. Among them, 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 (2), R ⁴ to R ⁸ is each independently a monovalent organic group, R ⁴
To R ⁸ is 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 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, 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 The alkyl group which may have and the 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 general formula (1), and preferred examples are also the same.

In the general formula (3), 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 has high radical reactivity. preferable. 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 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, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, etc. are mentioned, 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.

Here, examples of the substituent that can be introduced are the same as those in the general formula (1). Further, Z is an oxygen atom, a sulfur atom, -N (R ¹³⁾ -, or a phenylene group which may have a substituent. 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.
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.

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

(E-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, so that the organic polymer is soluble or swellable in alkali water. Polymers are preferably used. In particular, when an alkali developer having a pH of 10 or more is used, an alkali-soluble binder is preferably used.
In order to be soluble in alkaline water, it preferably has an alkali-soluble group. The alkali solubility is preferably an acid group, and examples thereof include a carboxyl group, a sulfo 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 from 5 to 90% by mass, preferably from 10 to 70% by mass, more preferably from 10 to 60% by mass, based on the total solid content of the photosensitive layer. . Within this range, good image area strength and image formability can be obtained.

(E-2) Binder polymer having an acid value of 0.3 meq / g or less In an embodiment in which the development process in the plate making process is performed using a developer having a pH of 2 to 10, a binder having an acid value of 0.3 meq / g or less. A polymer is preferably used.
As the hydrophobic binder polymer having an acid value of 0.3 meq / g or less used in the photosensitive layer of the present invention, a water-insoluble polymer is preferably used. Furthermore, the thing which does not contain acid groups, such as a carboxyl group, a sulfo group, and a phosphate group substantially, is preferable. The acid value of the binder polymer is the acid content per gram of polymer expressed as a chemical equivalent number. The acid value of the binder polymer is preferably 0.1 meq / g or less.
That is, the hydrophobic binder polymer used in the present invention is preferably insoluble in water and an aqueous solution having a pH of 10 or more. The solubility of the hydrophobic binder polymer in water and an aqueous solution having a pH of 10 or more is preferably 0.5% by mass or less, and more preferably 0.1% by mass or less. By using such a hydrophobic binder polymer, the film strength, water resistance and wall-thickness of the photosensitive layer are improved, and printing durability is improved.

As the hydrophobic binder polymer, as long as the performance of the lithographic printing plate of the present invention is not impaired, a conventionally known one can be used without limitation within the above range, and a linear organic polymer having a film property is preferable.
As an example of such a hydrophobic binder polymer, a polymer selected from acrylic resin, polyvinyl acetal resin, polyurethane resin, polyamide resin, epoxy resin, methacrylic resin, styrene resin, and polyester resin is preferable. Especially, an acrylic resin is preferable and a (meth) acrylic acid ester copolymer is preferable. More specifically, an alkyl (meth) acrylate or an aralkyl ester and an ester residue (—COOR) of (meth) acrylate ester may have a —CH ₂ CH ₂ O— unit or a —CH ₂ CH ₂ NH— unit as R. A copolymer with a (meth) acrylic acid ester containing is particularly preferred. The preferable alkyl group of the said (meth) acrylic-acid alkylester is a C1-C5 alkyl group, and a methyl group is more preferable. Preferable (meth) acrylic acid aralkyl esters include benzyl (meth) acrylate.

Further, the hydrophobic 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.

In addition, the binder polymer is preferably hydrophilic from the viewpoint of improving developability with respect to an aqueous solution, and it is important that the binder polymer is compatible with the polymerizable compound contained in the photosensitive layer from the viewpoint of improving printing durability. Yes, ie lipophilic. From such a viewpoint, in the present invention, it is also effective to copolymerize a hydrophilic group and a lipophilic group in a hydrophobic binder polymer in order to improve developability and printing durability. Examples of the hydrophilic group include a hydroxyl group, a carboxylate group, a hydroxyethyl group, an ethyleneoxy group, a hydroxypropyl group, a polyoxyethyl group, a polyoxypropyl group, an amino group, an aminoethyl group, an aminopropyl group, and an ammonium group. And those having a hydrophilic group such as an amide group or a carboxymethyl group.

The hydrophobic 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 hydrophobic 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 hydrophobic binder polymer may be used alone or in combination of two or more.
The content of the hydrophobic 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.

<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 water-insoluble 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. These will be described below.

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

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

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

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

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

  More preferable surfactants include fluorine-based surfactants containing a perfluoroalkyl group in the molecule. Examples of such fluorosurfactants include anionic types such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and perfluoroalkyl phosphates; amphoteric types such as perfluoroalkyl betaines; Cation type such as trimethylammonium salt; perfluoroalkylamine oxide, perfluoroalkylethylene oxide adduct, oligomer containing perfluoroalkyl group and hydrophilic group, oligomer containing perfluoroalkyl group and lipophilic group, perfluoroalkyl Nonionic types such as an oligomer containing a group, a hydrophilic group and a lipophilic group, and a urethane containing a perfluoroalkyl group and a lipophilic group. Also preferred are the fluorosurfactants described in JP-A-62-170950, JP-A-62-226143 and JP-A-60-168144.

Among the surfactants, anionic surfactants and cationic surfactants are preferable from the viewpoint of developability.
The content of the surfactant is preferably 0.001 to 10% by mass and more preferably 0.01 to 7% by mass with respect to the total solid content of the photosensitive layer.

<Hydrophilic polymer>
In the present invention, a hydrophilic polymer can be contained in order to improve the developability and the dispersion stability of the microcapsules.
Examples of the hydrophilic polymer include hydroxyl group, carboxyl group, carboxylate group, hydroxyethyl group, polyoxyethyl group, hydroxypropyl group, polyoxypropyl group, amino group, aminoethyl group, aminopropyl group, ammonium group, Those having a hydrophilic group such as an amide group, a carboxymethyl group, a sulfo group, and a phosphoric acid group are preferred.

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

The hydrophilic polymer preferably has a mass average molecular weight of 5000 or more, more preferably 10,000 to 300,000. The hydrophilic polymer may be any of a random polymer, a block polymer, a graft polymer, and the like.
The content of the hydrophilic polymer in the photosensitive layer is preferably 20% by mass or less, more preferably 10% by mass or less, based on the total solid content of the photosensitive layer.

<Colorant>
In the present invention, a dye having a large absorption in the visible light region can be used as an image colorant. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (orientated chemistry) Kogyo Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI145170B), Malachite Green (CI42000), Methylene Blue (CI522015), etc. And dyes described in Japanese Patent No. 293247. Also, pigments such as phthalocyanine pigments, azo pigments, carbon black, titanium oxide, etc. can be suitably used.

  These colorants are preferably added since it is easy to distinguish an image area from a non-image area after image formation. The amount added is preferably 0.01 to 10% by mass with respect to the total solid content of the image recording material.

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

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

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

  A suitable addition amount of the dye that changes color by acid or radical is 0.01 to 15% by mass relative to the solid content of the photosensitive layer.

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

<Higher fatty acid derivatives, etc.>
In order to prevent polymerization inhibition by oxygen, a higher fatty acid derivative such as behenic acid or behenamide is added to the photosensitive layer of the present invention so that it is unevenly distributed on the surface of the photosensitive layer during the drying process after coating. May be. The amount of the higher fatty acid derivative added is preferably from about 0.1 to about 10% by mass based on the total solid content of the photosensitive layer.

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

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

The content of the inorganic fine particles is preferably 20% by mass or less, and more preferably 10% by mass or less, based on the total solid content of the photosensitive layer.
<Low molecular hydrophilic compound>
The photosensitive layer of the present invention can contain a hydrophilic low molecular weight compound for improving developability. Examples of the hydrophilic low-molecular compound include water-soluble organic compounds such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and the like, and ether or ester derivatives thereof, glycerin, Polyhydroxys such as pentaerythritol, organic amines such as triethanolamine and diethanolamine monoethanolamine and salts thereof, organic sulfonic acids such as toluenesulfonic acid and benzenesulfonic acid and salts thereof, organic phosphonic acids such as phenylphosphonic acid and the like Its salts, tartaric acid, oxalic acid, citric acid, malic acid, lactic acid, gluconic acid, organic carboxylic acids such as amino acids and their salts, and fourth such as tetraethylammonium chloride Ammonium salts.

<Chain transfer agent>
The photosensitive layer of the present invention can contain a chain transfer agent. Chain transfer agents contribute to sensitivity and storage stability. As the compound that acts as a chain transfer agent, for example, a compound group having SH, PH, SiH, and 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 (XI) 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 (XI), R represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and A represents a 5-membered ring having a carbon atom together with an N = CN moiety. Alternatively, it represents an atomic group that forms a 6-membered heterocycle, and A may further have a substituent.

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

  In general formulas (XIA) and (XIB), R represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and X represents a halogen atom, an alkoxyl group or a substituent. The alkyl group which may have or the aryl group which may have a substituent is represented.

  Although the specific example of a compound represented by general formula (XI) below is shown, this invention is not limited to these.

  The amount of these chain transfer agents such as thiol compounds 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%.

<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 coating, the photosensitive layer coating amount on the support obtained after drying (solid content) may be varied according to the intended purpose, generally 0.3 to 3.0 g / m ² is preferred. Within this range, good sensitivity and good film properties of the photosensitive layer can be obtained.
Various methods can be used as a coating method. Examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.

(Protective layer)
In the lithographic printing plate precursor according to the invention, a protective layer (oxygen blocking layer) is 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 preferably has an oxygen permeability A at 25 ° C. and 1 atm of 1.0 ≦ A ≦ 20 (mL / m ² · day). 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 exceeds 20 (mL / m ² · day) and is too high, the sensitivity is lowered. The oxygen permeability A is more preferably in the range of 1.5 ≦ A ≦ 12 (mL / m ² · day), more preferably 2.0 ≦ A ≦ 10.0 (mL / m ² · day). In addition to the oxygen permeability described above, the properties desired for the protective layer further do not substantially inhibit the transmission of light used for exposure, have excellent adhesion to the photosensitive layer, and are easy in the development process after exposure. It is desirable that it can be 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 a material that can be used 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 are used. Examples include water-soluble polymers such as alcohol / vinyl phthalate copolymer, vinyl acetate / crotonic acid copolymer, polyvinyl pyrrolidone, acidic celluloses, gelatin, gum arabic, polyacrylic acid, and polyacrylamide. Or they can be mixed. 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 polyvinyl alcohol include those that are hydrolyzed by 71 to 100 mol% and have a polymerization repeating unit in the range of 300 to 2400. Specifically, PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HC made by Kuraray Co., Ltd. , 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 (co) polymer 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 (co) polymer to provide flexibility. Anionic surfactants such as sodium acid salts; amphoteric surfactants such as alkylaminocarboxylates and alkylaminodicarboxylates; nonionic surfactants such as polyoxyethylene alkylphenyl ethers to the (co) polymer Mass% can be added.

  In addition, adhesion to the image area 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 mica group, natural mica includes muscovite, soda mica, phlogopite, biotite, and sericite. Synthetic mica includes non-swellable mica such as fluorine phlogopite mica ₃ (AlSi ₃ O ₁₀ ) F ₂ , potassium tetrasilicon mica KMg _2.5 Si ₄ O ₁₀ ) F ₂ , and Na tetrasilicic mica NaMg _2.5 ( _{Si 4 O 10) F 2,} Na or Li teniolite _{(Na, Li) Mg 2 Li} (Si 4 O 10) F 2, montmorillonite based Na or Li hectorite _{(Na, Li) 1/8 Mg 2} /5 Li Examples thereof include swelling mica such as _1/8 (Si ₄ O ₁₀ ) F ₂ . Synthetic smectites are also useful.

In the present invention, among the inorganic layered compounds, fluorine-based swellable mica, which is a synthetic inorganic layered compound, is particularly useful. That is, this swellable synthetic mica and swellable viscosity minerals such as montmorillonite, saponite, hectorite, bentonite, etc. have a laminated structure composed of unit crystal lattice layers with a thickness of about 10-15A, Atomic substitution is significantly greater than other viscous minerals. As a result, the lattice layer is deficient in positive charges, and cations such as Na ⁺ , Ca ²⁺ and Mg ²⁺ are adsorbed between the layers in order to compensate for this. The cations present between these layers are called exchangeable cations and exchange with various cations. In particular, when the cation between the layers is Li ⁺ or Na ⁺ , the bond between the layered crystal lattices is weak because the ionic radius is small, and the layer swells greatly with water. If shear is applied in this state, it will easily cleave and form a stable sol in water. Bentonite and swellable synthetic mica have this tendency and are useful in the present invention, and swellable synthetic mica is particularly preferably used.

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

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

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

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

  In addition to the inorganic layered compound, known additives such as a surfactant for improving the coating property and a water-soluble plasticizer for improving the physical properties of the film can be added to the protective layer coating solution. Examples of the water-soluble plasticizer include propionamide, cyclohexanediol, glycerin, sorbitol and the like. A water-soluble (meth) acrylic polymer can also be added. Furthermore, known additives for improving the adhesion to the photosensitive layer and the temporal stability of the coating solution may be added to the coating solution.

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

The coating amount of the protective layer is preferably in the range of 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 when the inorganic layered compound is not contained, the range of 0.5 to 5 g / m ² is more preferable.

(Support)
The support used for the lithographic printing plate precursor according to the invention is not particularly limited as long as it is a dimensionally stable plate-like hydrophilic support. For example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate) Cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), and paper or plastic films on which the above-mentioned metals are laminated or deposited. Preferable supports include a polyester film and an aluminum plate. Among these, an aluminum plate that has good dimensional stability and is relatively inexpensive is preferable.

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

  The thickness of the support is preferably 0.1 to 0.6 mm, more preferably 0.15 to 0.4 mm, and still more preferably 0.2 to 0.3 mm.

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

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

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

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

  As the support used in the present invention, the substrate having the above-mentioned surface treatment and having an anodized film may be used as it is, but for further improvement in adhesion to the upper layer, hydrophilicity, resistance to contamination, heat insulation and the like. If necessary, it contains a micropore enlargement treatment, a micropore sealing treatment, and a hydrophilic compound described in Japanese Patent Application Laid-Open Nos. 2001-253181 and 2001-322365. A surface hydrophilization treatment immersed in an aqueous solution can be selected as appropriate. Of course, these enlargement processing and sealing processing are not limited to those described above, and any conventionally known method can be performed.

Sealing treatment includes vapor sealing, single treatment with zirconic fluoride, treatment with an aqueous solution containing an inorganic fluorine compound such as treatment with sodium fluoride, vapor sealing with addition of lithium chloride, sealing with hot water. Hole processing is also possible.
Of these, sealing treatment with an aqueous solution containing an inorganic fluorine compound, sealing treatment with water vapor, and sealing treatment with hot water are preferable.

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

  When using a support with insufficient surface hydrophilicity such as a polyester film as the support of the present invention, it is desirable to apply a hydrophilic layer to make the surface hydrophilic. As the hydrophilic layer, at least one element selected from beryllium, magnesium, aluminum, silicon, titanium, boron, germanium, tin, zirconium, iron, vanadium, antimony, and a transition metal described in JP-A-2001-199175 A hydrophilic layer formed by coating a coating solution containing a colloid of oxide or hydroxide, or organic hydrophilicity obtained by crosslinking or pseudo-crosslinking an organic hydrophilic polymer described in JP-A-2002-79772 A hydrophilic layer having a hydrophilic matrix, a hydrophilic layer having an inorganic hydrophilic matrix obtained by sol-gel conversion comprising hydrolysis, condensation reaction of polyalkoxysilane, titanate, zirconate or aluminate, or a metal oxide A hydrophilic layer made of an inorganic thin film having a surface is preferred. Arbitrariness. Among these, a hydrophilic layer formed by applying a coating solution containing a silicon oxide or a hydroxide colloid is preferable.

  Moreover, when using a polyester film etc. as a support body of this invention, it is preferable to provide an antistatic layer in the hydrophilic layer side of a support body, the opposite side, or both sides. In the case where the antistatic layer is provided between the support and the hydrophilic layer, it also contributes to improving the adhesion with the hydrophilic layer. As the antistatic layer, a polymer layer in which metal oxide fine particles or a matting agent are dispersed as described in JP-A-2002-79772 can be used.

The support preferably has a center line average roughness of 0.10 to 1.2 μm. Within this range, good adhesion to the photosensitive layer, good printing durability and good stain resistance can be obtained.
The color density of the support is preferably 0.15 to 0.65 as the reflection density value. Within this range, good image formability by preventing halation during image exposure and good plate inspection after development can be obtained.

(Undercoat layer)
In the lithographic printing plate precursor according to the invention, it is preferable to provide an undercoat layer of a compound containing a polymerizable group on a support. When an undercoat layer is used, the photosensitive layer is provided on the undercoat layer. The undercoat layer reinforces the adhesion between the support and the photosensitive layer in the exposed area, and easily peels the photosensitive layer from the support in the unexposed area, thereby improving developability.
As the undercoat layer, specifically, a silane coupling agent having an addition-polymerizable ethylenic double bond reactive group described in JP-A-10-282679, JP-A-2-304441. The phosphorus compound etc. which have the ethylenic double bond reactive group of description are mentioned suitably. Copolymer having (1) a repeating unit having at least one ethylenically unsaturated bond and (2) a repeating unit having at least one functional group that interacts with the support surface described in JP-A-2006-078999 Also preferred are copolymers and (3) copolymers having repeating units containing at least one hydrophilic group. Particularly preferred compounds include compounds having a polymerizable group such as a methacryl group and an allyl group and a support-adsorbing group such as a phosphate group and a phosphate ester. A compound having a hydrophilicity-imparting group such as a sulfo group or an ethylene oxide group in addition to the polymerizable group and the support-adsorbing group can also be mentioned as a suitable compound.
The coating amount (solid content) of the undercoat layer is preferably from 0.1-100 mg / m ^2, and more preferably 1 to 30 mg / m ^2.

(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 an organic polymer compound described in JP-A-5-45885, an organometallic compound or an inorganic metal compound described in JP-A-6-35174. A coating layer made of a metal oxide obtained in this way is preferred. Of these, the use of silicon alkoxy compounds such as Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ ) ₄ , Si (OC ₄ H ₉ ) _4, etc. is inexpensive. It is preferable in that it is easily available.

[Preparation of lithographic printing plate (plate making)]
After the lithographic printing plate precursor according to the present invention is image-exposed, the protective layer and the unexposed photosensitive layer are removed with a developer to prepare a lithographic printing plate.

The developer suitably used in the present invention is classified into two types: (1) one having a pH of 10 or more and (2) one having an aqueous solution having a pH of 2 to 10.
As described above, when the developer (1) is used, an alkali-soluble binder polymer is preferably used as the binder polymer used in the photosensitive layer, and when the developer (2) is used, the above acid is used. It is preferable to use a binder polymer having a value of 0.3 meq / g or less.

A developer having a pH of 10 or more that is preferably used in the present invention will be described.
Developers with a pH of 10 or higher are sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic phosphorus. Aqueous solutions of inorganic alkali agents such as ammonium acid, sodium metasilicate, sodium bicarbonate, aqueous ammonia and organic alkali agents such as monoethanolamine or diethanolamine are suitable. It is added so that the concentration of such an alkaline solution is 0.1 to 10% by mass, preferably 0.5 to 5% by mass.
Such an alkaline aqueous solution can contain a small amount of an organic solvent such as a surfactant, benzyl alcohol, 2-phenoxyethanol, or 2-butoxyethanol as necessary. Examples thereof include those described in US Pat. Nos. 3,375,171 and 3,615,480.
The developer having a pH of 10 or more preferably has a pH in the range of 10 to 14 and more preferably has a pH in the range of 11 to 13 from the viewpoint of both handleability and developability.

  Another developer preferably used in the present invention is an aqueous solution having a pH of 2 to 10. For example, water alone or an aqueous solution containing water as a main component (containing 60% by mass or more of water) is preferable. In particular, an aqueous solution having the same composition as that of a generally known fountain solution, a surfactant (anionic, nonionic, An aqueous solution containing a cationic system or the like, or an aqueous solution containing a water-soluble polymer compound is preferable. In particular, an aqueous solution containing both a surfactant and a water-soluble polymer compound is preferable. The pH of the developer is more preferably from 3 to 8, more preferably from 4 to 6.9.

The components that can be contained in each of the two types of developers are described in detail below.

Examples of the anionic surfactant used in the developer of the present invention include fatty acid salts, abietic acid salts, hydroxyalkane sulfonic acid salts, alkane sulfonic acid salts, dialkyl sulfosuccinic acid salts, linear alkyl benzene sulfonic acid salts, and branched alkyl benzene sulfonic acid. Acid salts, alkylnaphthalene sulfonates, alkylphenoxy 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 tallow oil, sulfate esters of fatty acid alkyl esters, alkyl sulfate esters, polyoxyethylene alkyl ether sulfate esters, Fatty acid monoglyceride sulfates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates Saponification product of styrene-maleic anhydride copolymer, saponification product of olefin-maleic anhydride copolymer, naphthalene sulfonate formalin condensate, and the like. Among these, dialkyl sulfosuccinates, alkyl sulfate esters and alkyl naphthalene sulfonates are particularly preferably used.

  The cationic surfactant used in the developer of the present invention is not particularly limited, and conventionally known ones can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.

Nonionic surfactants used in the developer of the present invention include polyethylene glycol type higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, fatty acid ethylene oxide adduct, polyhydric alcohol fatty acid ester ethylene oxide adduct, higher Alkylamine ethylene oxide adducts, 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, etc. , Fatty acid ester of glycerol of polyhydric alcohol type, fatty acid ester of pentaerythritol, sorbitol and Fatty acid esters of Rubitan, fatty acid esters of sucrose, alkyl ethers of polyhydric alcohols, fatty acid amides of alkanolamines.
These nonionic surfactants may be used alone or in combination of two or more. In the present invention, ethylene oxide adduct of sorbitol and / or sorbitan fatty acid ester, polypropylene glycol ethylene oxide adduct, dimethylsiloxane-ethylene oxide block copolymer, dimethylsiloxane- (propylene oxide-ethylene oxide) block copolymer, polyhydric alcohol Fatty acid esters are more preferred.

Further, from the viewpoint of stable solubility or turbidity in water, the nonionic surfactant used in the developer of the present invention preferably has an HLB (Hydrophile-Lipophile Balance) value of 6 or more, and 8 or more. It is more preferable that Furthermore, the ratio of the nonionic surfactant contained in the developer is preferably 0.01 to 10% by mass, and more preferably 0.01 to 5% by mass.
Also, acetylene glycol-based and acetylene alcohol-based oxyethylene adducts, fluorine-based and silicon-based surfactants can be used in the same manner.
As the surfactant used in the developer of the present invention, a nonionic surfactant is particularly suitable from the viewpoint of foam suppression.

  Examples of the water-soluble polymer compound used in the developer of the present invention include soybean polysaccharide, modified starch, gum arabic, dextrin, fibrin derivatives (eg, carboxymethylcellulose, carboxyethylcellulose, methylcellulose, etc.) and modified products thereof, pullulan. , Polyvinyl alcohol and its derivatives, polyvinyl pyrrolidone, polyacrylamide and acrylamide copolymer, vinyl methyl ether / maleic anhydride copolymer, vinyl acetate / maleic anhydride copolymer, styrene / maleic anhydride copolymer, etc. It is done.

  A well-known thing can be used for the said soybean polysaccharide, for example, there exists a brand name Soya Five (made by Fuji Oil Co., Ltd.) as a commercial item, and the thing of 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.

  As the modified starch, known ones can be used. Starch such as corn, potato, tapioca, rice, wheat is decomposed with acid or enzyme in the range of 5 to 30 glucose residues per molecule, and further in an alkali. It can be made by a method of adding oxypropylene or the like.

  Two or more water-soluble polymer compounds can be used in combination. The content of the water-soluble polymer compound in the developer is preferably from 0.1 to 20% by mass, and more preferably from 0.5 to 10% by mass.

  Further, the developer of the present invention may contain an organic solvent. Examples of the organic solvent that can be contained include aliphatic hydrocarbons (hexane, heptane, “Isopar E, H, G” (manufactured by Esso Chemical Co., Ltd.) or gasoline, kerosene, etc.), and aromatic hydrocarbons (toluene). , Xylene, etc.), halogenated hydrocarbons (methylene dichloride, ethylene dichloride, tricrene, 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.).

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

  In addition to the above, the developer of the present invention may contain a preservative, a chelate compound, an antifoaming agent, an organic acid, an inorganic acid, an inorganic salt, and the like.

  Preservatives include phenol or derivatives thereof, formalin, imidazole derivatives, sodium dehydroacetate, 4-isothiazolin-3-one derivatives, benzisothiazolin-3-one, benztriazole derivatives, amiding anidine derivatives, quaternary ammonium salts, pyridine, Derivatives such as quinoline and 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.

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.

As the antifoaming agent, a general silicon-based self-emulsifying type, emulsifying type, or nonionic surfactant having a HLB of 5 or less can be used. Silicon antifoaming agents are preferred.
Among them, emulsification dispersion type and solubilization can be used.

  Examples of organic acids include citric acid, acetic acid, succinic acid, malonic acid, salicylic acid, caprylic acid, tartaric acid, malic acid, lactic acid, levulinic acid, p-toluenesulfonic acid, xylenesulfonic acid, phytic acid, and organic phosphonic acid. . The organic acid can also be used in the form of its alkali metal salt or ammonium salt.

  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 developer described above can be used as a developer and developer replenisher for the exposed lithographic printing plate precursor, and is preferably applied to an automatic processor described later. When developing using an automatic processor, the developing solution becomes fatigued according to the amount of processing, so the processing capability may be restored using a replenisher or a fresh developer. This replenishing method is also preferably applied to the lithographic printing plate making method of the present invention.

  The development treatment with an aqueous solution having a pH of 2 to 10 in the present invention can be preferably carried out by an automatic processor equipped with a developer supply means and a rubbing member. As an automatic processor, for example, an automatic processor described in JP-A-2-220061 and JP-A-60-59351, which performs a rubbing process while transporting a lithographic printing plate precursor after image recording, or 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 recording set thereon 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 that can be preferably 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, as described in Japanese Patent Application Laid-Open No. 58-159533, Japanese Patent Application Laid-Open No. 3-100554, or Japanese Utility Model Publication No. 62-167253, metal or plastic in which brush materials are implanted in rows. A brush roll in which the groove mold material is radially wound around a plastic or metal roll as a core without any gap can be used.
The brush material includes plastic fibers (for example, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides such as nylon 6.6 and nylon 6.10, polyacrylonitrile, poly (meth) acrylate, etc. Acrylic and polyolefin synthetic fibers such as polypropylene and polystyrene) can be used. For example, the fiber has a hair diameter of 20 to 400 μm and a hair length of 5 to 30 mm. Can be used.
Furthermore, 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.
Moreover, it is preferable to use two or more rotating brush rolls.

  The rotating direction of the rotating brush roll used in the present invention may be the same or opposite to the conveying direction of the planographic printing plate precursor of the present invention. Thus, when two or more rotating brush rolls are used, it is preferable that at least one rotating brush roll rotates in the same direction and at least one rotating brush roll rotates in the opposite direction. Thereby, the removal of the unexposed portion of the photosensitive layer is further ensured. Furthermore, it is also effective to swing the rotating brush roll in the direction of the rotation axis of the brush roll.

  Although the temperature of the developer can be used at any temperature, it is preferably 10 ° C to 50 ° C.

  In the present invention, the lithographic printing plate after the rubbing treatment can be optionally washed with water, dried and desensitized. In the desensitizing treatment, a known desensitizing solution can be used.

  In addition, as the plate-making process of the lithographic printing plate from the lithographic printing plate precursor according to the present invention, the entire surface may be heated before exposure, during exposure, and between exposure and development, if necessary. By such heating, the image forming reaction in the photosensitive layer is promoted, and advantages such as improvement in sensitivity and printing durability and stabilization of sensitivity may occur. Further, for the purpose of improving the image strength and printing durability, it is also effective to subject the developed image to full post heating or full exposure. Usually, heating before development is preferably performed under mild conditions of 150 ° C. or less. If the temperature is too high, problems such as covering the unexposed area occur. Very strong conditions are used for heating after development. Usually, it is the range of 200-500 degreeC. If the temperature is low, sufficient image strengthening action cannot be obtained. If the temperature is too high, problems such as deterioration of the support and thermal decomposition of the image area occur.

The planographic printing plate obtained by the above processing is loaded on an offset printing machine and used for printing a large number of sheets.
As plate cleaners used for removing stains on printing plates, conventionally known plate cleaners for PS plates are used. For example, CL-1, CL-2, CP, CN-4, CN, CG -1, PC-1, SR, IC (manufactured by FUJIFILM Corporation) and the like.

Prior to the above development processing, the lithographic printing plate precursor is exposed through a transparent original image having a line image, a halftone dot image or the like, or imagewise exposed by laser beam scanning or the like using digital data.
A desirable wavelength of the light source is 350 nm to 450 nm, and specifically, an InGaN semiconductor laser is suitable. The exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like.
Other exposure light beams that can be used in the present invention include ultra-high pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet laser lamps, fluorescent lamps. A lamp, a tungsten lamp, sunlight, etc. can also be used.

As available laser light sources of 350 nm to 450 nm, the following can be used.
As a gas laser, an Ar ion laser (364 nm, 351 nm, 10 mW to 1 W), 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), and a solid laser as 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), as a semiconductor laser system, KNbO ₃ ring resonator (430 nm, 30 mW), Combination of waveguide type wavelength conversion element and AlGaAs, InGaAs semiconductor (380 nm to 450 nm, 5 mW to 100 mW),
Combination of waveguide type wavelength conversion element and AlGaInP, AlGaAs semiconductor (300 nm to 350 nm, 5 mW to 100 mW), AlGaInN (350 nm to 450 nm, 5 mW to 30 mW), and N ₂ laser (337 nm, pulse 0.1 to 0.1) as pulse laser 10 mJ), XeF (351 nm, pulse 10-250 mJ). 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.

Further, as the lithographic printing plate exposure apparatus of the scanning exposure method, there are an inner drum method, an outer drum method, and a flat bed method as an exposure mechanism, and a light source that can continuously oscillate among the light sources can be preferably used. . Practically, the following exposure apparatus is particularly preferable in terms of the relationship between the photosensitive material sensitivity and the plate making time.
・ Single beam to triple beam exposure equipment that uses one or more gas lasers or solid-state laser light sources so that it becomes a semiconductor laser with a total output of 20 mW or more with an internal drum system. ・ A total output of 20 mW or more with a flat bed system. Multi-beam (1 to 10) exposure equipment that uses one or more semiconductor lasers, gas lasers, or solid-state lasers • Use one or more semiconductor lasers, gas lasers, or solid-state lasers to achieve a total output of 20 mW or more with the external drum system Multi-beam (1 to 9) exposure apparatus ・ Multi-beam (10 or more) exposure apparatus using one or more semiconductor lasers or solid-state lasers so that the total output is 20 mW or more by the external drum method In general, laser sensitive drawing type lithographic printing plates generally use photosensitive material sensitivity X (J / c Equation (eq 1) is established among m ² ), exposure area S (cm ² ) of the light-sensitive material, power q (W) of one laser light source, n number of lasers, and total exposure time t (s).

  X · S = n · q · t (eq 1)

i) In the case of the internal drum (single beam) system, the laser rotation speed f (radians / s), the sub-scanning length Lx (cm) of the photosensitive material, the resolution Z (dots / cm), and the total exposure time t (s) In general, equation (eq 2) holds.

  f · Z · t = Lx (eq 2)

ii) External drum (multi-beam) system Drum rotation speed F (radians / s), photosensitive material sub-scanning length Lx (cm), resolution Z (dots / cm), total exposure time t (s), number of beams In general, formula (eq 3) is established during (n).

  F.Z.n.t = Lx (eq 3)

iii) Flat head (multi-beam) system Polygon mirror rotation speed H (radians / s), photosensitive material sub-scanning length Lx (cm), resolution Z (dots / cm), total exposure time t (s), Equation (eq 4) is generally established between the number of beams (n).

  F.Z.n.t = Lx (eq 4)

Resolution (2560 dpi) required for the actual printing plate, plate size (A1 / B1, sub-scan length 42 inch), exposure conditions of about 20 sheets / hour and photosensitive characteristics of the planographic printing plate precursor of the present invention (photosensitive wavelength, By substituting (sensitivity: about 0.1 mJ / cm ² ) into the above formula, it is understood that a combination with a multi-beam exposure method using a laser having a total output of 20 mW or more is particularly preferable in the planographic printing plate precursor of the present invention. it can. Further, by combining operability, cost, etc., a combination with an external drum type semiconductor laser multi-beam (10 or more) exposure apparatus is most preferable.

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

[Examples 1 to 5 and Comparative Example 1]
(1) Production of support 1
In order to remove rolling oil on the surface of an aluminum plate (material 1050) 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 0.3 mm. The aluminum surface was grained using three bundle-planted nylon brushes and a pumice-water suspension (specific gravity 1.1 g / cm ³ ) having a median diameter of 25 μm and washed thoroughly with water. This plate was etched by being immersed in a 25 mass% sodium hydroxide aqueous solution at 45 ° C for 9 seconds, washed with water, further immersed in a 20 mass% nitric acid aqueous solution at 60 ° C for 20 seconds, and washed with water. The etching amount of the grained surface at this time was about 3 g / m ² .

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

Next, a 0.5% by mass hydrochloric acid aqueous solution (containing 0.5% by mass of aluminum ions) and an electrolytic solution having a liquid temperature of 50 ° C. and nitric acid electrolysis under the condition of an electric quantity of 50 C / dm ² when the aluminum plate is an anode In the same manner as above, an electrochemical surface roughening treatment was performed, followed by washing with water by spraying. 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% by mass sulfuric acid aqueous solution (containing 0.5% by mass of aluminum ions) as an electrolyte, then washed with water and dried. .
The centerline average roughness Ra (JIS B0601) of the surface of the support 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)>
・ Undercoat compound (1) 0.017 g
・ Methanol 9.00 g
・ Water 1.00g

(2) Preparation of lithographic printing plate precursors (1) to (5) and comparative lithographic printing plate precursor (1) Photosensitive layer coating liquids (1) to (1) having the following composition were formed on the support provided with the undercoat layer. 5) and a comparative photosensitive layer coating solution were bar coated 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. The coating liquid (1) was applied using a bar so that the dry coating amount was 0.75 g / m ^2, and then dried at 125 ° C. for 70 seconds, and the planographic printing plate precursors (1) to (5) and comparison A lithographic printing plate precursor (1) was obtained.

<Photosensitive layer coating solutions (1) to (5) and comparative photosensitive layer coating solution (1)>
・ Binder polymer (described in Table 8) 0.54 g
Specific polymerizable compound (described in Table 8) 0.20 g
・ Polymerizable compound (2-1) 0.20 g
・ The following sensitizing dye (1) 0.06 g
・ The following polymerization initiator (1) 0.18 g
・ The following chain transfer agent (1) 0.07 g
-Ε-phthalocyanine pigment dispersion (1) 0.40 g
・ Thermal polymerization inhibitor 0.01g
(N-nitrosophenylhydroxylamine aluminum salt)
-0.001 g of the following water-soluble fluorosurfactant (1)
・ Polyoxyethylene-polyoxypropylene condensate 0.04g
(Asahi Denka Kogyo Co., Ltd., Pluronic L44)
・ Tetraethylammonium chloride 0.01g
・ 3.5 g of 1-methoxy-2-propanol
・ Methyl ethyl ketone 8.0g

Binder (3): Polyvinyl alcohol (saponification degree 55%)
Binder (4): Polyvinyl butyral
(Butyral ratio 65 mol%, acetate ratio <1 mol%)
Binder (5): Methacrylic acid / Methyl methacrylate copolymer (Molar ratio 30/70)
Polymerizable compound (2-1): Reaction product of 2,2,4-trimethyl-hexamethylene diisocyanate / 2-hydroxyethyl methacrylate (molar ratio 1/2) ε-phthalocyanine pigment dispersion (1):
[Pigment: 15 parts by mass, Dispersant: 10 parts by mass of binder (1),
Solvent: 15 parts by mass of cyclohexanone, 20 parts by mass of methoxypropyl acetate,
1-methoxy-2-propanol 40 parts by mass]

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

(3) Preparation and evaluation of lithographic printing plate 3-1) Exposure, development and printing 405 nm semiconductor laser with an output of 100 mW for each of the lithographic printing plate precursors (1) to (5) and the comparative lithographic printing plate precursor (1) Was used to perform imagewise exposure with different energy densities.
Thereafter, the developing solution (1) having the following composition was used, and development processing was carried out with an automatic developing processor having a structure shown in FIG. The pH of the developer was 4.6. The automatic processor is an automatic processor having two rotating brush rolls. As the rotating brush roll, the first brush roll and the polybutylene terephthalate fiber (hair diameter 200 μm, hair length 17 mm). Using a brush roll with an outer diameter of 90 mm implanted with 200 mm / min in the same direction as the conveying direction (peripheral speed 0.94 m / sec at the tip of the brush), 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 planted, 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.

Developer (1)
・ Water 100g
・ Sodium alkylnaphthalenesulfonate 5g
(Perox NB-L manufactured by Kao Corporation)
・ 1g gum arabic
・ Primary ammonium phosphate 0.05g
・ 2-hydroxypropyl starch 1g
・ Citric acid 0.05g
・ Ethylenediaminetetraacetate tetrasodium salt 0.05g

  Next, the developed lithographic printing plate is attached to a printing machine SOR-M manufactured by Heidelberg, and dampening water (EU-3 (an etchant manufactured by FUJIFILM Corporation) / water / isopropyl alcohol = 1/89/10 ( Volume ratio)) and TRANS-G (N) black ink (manufactured by Dainippon Ink & Chemicals, Inc.) were used for printing at a printing speed of 6000 sheets per hour.

3-2) Evaluation With respect to the lithographic printing plate precursor, the developability, sensitivity, stain resistance, and printing durability of the lithographic printing plate were evaluated as follows. The results are shown in Table 8.

<Developability>
The lithographic printing plate precursor was exposed and developed as described above, the non-image area of the obtained lithographic printing plate was visually confirmed, and the presence or absence of the remaining photosensitive layer was evaluated according to the following criteria.
◎: No residual film △: Slightly residual film ×: There is residual film

<Sensitivity>
After 100 sheets were printed as described above and it was confirmed that a printed matter having no ink stains in the non-image area was obtained, 500 sheets were printed continuously. In the total 600th printed matter, the exposure amount with no unevenness in the ink density in the image area was measured as sensitivity. Sensitivity evaluation is represented by the relative sensitivity defined as follows using Comparative Example 1 as a reference (1.0). The larger the relative sensitivity value, the higher the sensitivity and the better the performance.
Relative sensitivity = (sensitivity of comparative example 1 / sensitivities of examples 1 to 5)

<Stain and printing durability>
When printing was performed as described above, as the number of printed sheets increased, the image area was gradually worn out and the ink receptivity was lowered, so that the ink density in the printing paper was lowered. The number of printed sheets when the ink density (reflection density) was reduced by 0.1 from the start of printing was determined. At this time, the presence or absence of dirt on the non-image area was visually evaluated. The numerical values shown in Table 8 below are relative values of Examples 1 to 5 when the number of printed sheets is 100 in Comparative Example 1 when the ink density (reflection density) is reduced by 0.1 from the start of printing. It is.

(Evaluation of dirtiness)
◎: No dirt is seen at all ○: Little dirt is seen △: Slight dirt is seen ×: The dirt is clearly seen

[Examples 6 and 7 and Comparative Example 2]
A lithographic printing plate precursor (6) was produced in the same manner as in Example 1 except that the photosensitive solution coating formulation (1) was changed to the photosensitive layer coating solution (6).
A lithographic printing plate precursor (7) was produced in the same manner as in Example 6 except that the binder (2) in the photosensitive solution coating formulation (6) was replaced with the binder (5).
A comparative lithographic printing plate precursor (2) is produced in the same manner as in Example 6 except that the specific polymerizable compound (A-64) in the photosensitive solution coating formulation (6) is replaced with the comparative polymerizable compound (1). did.

<Photosensitive layer coating solution (6)>
・ Binder (2) 0.54g
-Specific polymerizable compound (A-64) 0.20 g
・ Polymerizable compound (2-1) 0.20 g
Sensitizing dye (1) 0.06g
・ Polymerization initiator (1) 0.18 g
・ Chain transfer agent (1) 0.07g
-Ε-phthalocyanine pigment dispersion (1) 0.40 g
・ Thermal polymerization inhibitor 0.01g
(N-nitrosophenylhydroxylamine aluminum salt)
・ Water-soluble fluorosurfactant (1) 0.001g
・ Polyoxyethylene-polyoxypropylene condensate 0.04g
(Asahi Denka Kogyo Co., Ltd., Pluronic L44)
・ Tetraethylammonium chloride 0.01g
・ 3.5 g of 1-methoxy-2-propanol
・ Methyl ethyl ketone 8.0g

  The lithographic printing plate precursors (6) and (7) and the comparative lithographic printing plate precursor (2) thus obtained were changed except that the developer (1) was replaced with the following alkaline developer (2). In the same manner as in Example 1, exposure, development and printing were evaluated. Table 9 shows the evaluation results.

Developer (2)
・ Potassium hydroxide 0.15g
・ Polyoxyethylene naphthyl ether (n = 13) 5.0 g
・ Ethylenediaminetetraacetate tetrasodium salt 0.1 g
・ Water 94.75g

It is a figure for demonstrating the structure of an automatic processor.

Explanation of symbols

1: rotating brush roll 2: receiving roll 3: transport roll 4: transport guide plate 5: spray pipe 6: pipeline 7: filter 8: plate supply table 9: plate discharge table 10: developer tank 11: circulation pump 12: plate

Claims (7)

A lithographic printing plate precursor having a support and a photosensitive layer, wherein the photosensitive layer has (A) at least one polymerizable compound represented by any one of the following formulas (I) to (III): A lithographic printing plate precursor comprising (B) a polymerization initiator, (D) a sensitizing dye having a maximum absorption in a wavelength region of 350 to 450 nm, and (E) a binder polymer.
In the formula, X, X ₁ , X ₂ , X ₃ , Y, Y ₁ , Y ₂ and Z each independently represent O, S or NR ₇ , and X ₄ represents OR ₇ , SR ₇ , N ( R ₈ ) (R ₉ ) or an alkyl group is represented. V ₁ and V ₂ each independently represents O, S, NR ₇ , or C (R ₅ ) (R ₆ ). L ₃ represents an atomic group that combines with Y and Z to form a ring structure, L ₄ represents an atomic group that combines with Y ₁ and V ₁ to form a ring structure, and L ₅ represents Y ₂ and V ₂ Represents an atomic group that forms a ring structure by bonding with. R _{5 to} R ₉ each independently represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group.
Further, the formula (I), wherein the at least one polymerizable group via any position of R ₇ or L ₃ of R _7, wherein Z in R _7, Y in X is connected. Formula (II), _R 7 in in _{X 1, X R} 7 in _{2, Y 1} in _R 7, _R in _{V 1} 5, _R 6 in the _{V 1, R 7} in _{V 1} or At least one polymerizable group is linked via any position of L ₄ . Formula _{(III), R 7, R} 7 in _{X 4, X 4} in _R 8, _{X 4} in _R 9, alkyl in _{X 4} in _{X 3, R} 7, _{V 2} in in _{Y 2} at least one via any position of _{R 7} or _{L 5} of _R 5, _{V R} 6, _{V 2} of ₂ polymerizable groups is linked.   The lithographic printing plate precursor as claimed in claim 1, wherein (A) is a polymerizable compound having at least one structure selected from a 5-membered or 6-membered cyclic carbonate and a cyclic urethane structure.   The lithographic printing plate precursor as claimed in claim 1 or 2, wherein the photosensitive layer further comprises a polymerizable compound (C) other than the (A).   The lithographic printing plate precursor as claimed in any one of claims 1 to 3, further comprising an undercoat layer between the support and the photosensitive layer.   The lithographic printing plate precursor as claimed in claim 1, further comprising a protective layer on the photosensitive layer.   The lithographic printing plate precursor as claimed in any one of claims 1 to 5, which can be developed with a developer having a pH of 2 to 10.   The lithographic printing plate precursor according to any one of claims 1 to 6 is exposed using an exposure apparatus equipped with a light source having an oscillation wavelength in the range of 350 to 450 nm, and then exposed to an unexposed portion in the presence of a developer. A method for preparing a lithographic printing plate, comprising removing the photosensitive layer.