JP4466821B2 - Polymerizable composition and planographic printing plate precursor - Google Patents

Description

  The present invention relates to a negative polymerizable composition and a lithographic printing plate precursor, and more particularly to a negative polymerizable composition and a lithographic printing plate precursor that can be written with high sensitivity by an infrared laser.

  Conventionally, as a lithographic printing plate precursor, a PS plate having a configuration in which a lipophilic photosensitive resin layer is provided on a hydrophilic support is widely used. As the plate making method, mask exposure (typically through a lithographic film) After the surface exposure), the desired printing plate was obtained by dissolving and removing the non-image area. In recent years, digitization techniques that electronically process, store, and output image information using a computer have become widespread. Various new image output methods corresponding to such digitization techniques have come into practical use. As a result, computer-to-plate (CTP) technology that scans highly directional light such as laser light according to digitized image information and directly manufactures printing plates without going through a lithographic film is eagerly desired. Therefore, obtaining a lithographic printing plate precursor adapted to this is an important technical issue.

  As such a lithographic printing plate precursor capable of scanning exposure, an oleophilic photosensitive resin layer containing a photosensitive compound capable of generating active species such as radicals and bronzed acids by laser exposure on a hydrophilic support (hereinafter referred to as “lithographic printing plate precursor”) , Which is also referred to as a photosensitive layer) has been proposed and is already on the market. This lithographic printing plate precursor is laser-scanned based on digital information to generate active species, which causes physical or chemical changes in the photosensitive layer to insolubilize it, followed by development processing, thereby developing a negative lithographic printing plate Can be obtained. In particular, a photopolymerization type photosensitive layer containing a photopolymerization initiator excellent in photosensitive speed on a hydrophilic support, an addition-polymerizable ethylenically unsaturated compound, and a binder polymer soluble in an alkali developer, and necessary A lithographic printing plate precursor provided with an oxygen-blocking protective layer in accordance with the printing plate having desirable printing performance due to advantages such as excellent productivity, simple development processing, and good resolution and inking properties. It can be.

Conventionally, as the binder polymer constituting the photosensitive layer, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer Organic polymer polymers that can be developed with alkali have been used (see, for example, Patent Documents 1 to 8). However, in a conventional lithographic printing plate precursor provided with a photosensitive layer containing such a binder polymer, the developer is insufficiently cured due to insufficient curing in the image portion that should have been cured. As a result, the photosensitive layer was damaged and the printing durability was lowered. In order to suppress the penetration of the developing solution into the image area, the developability of the non-image area is usually sacrificed. It was a very difficult problem to achieve both high developability and compatibility.
JP 59-44615 Japanese Patent Publication No.54-34327 Japanese Examined Patent Publication No. 58-12777 Japanese Patent Publication No.54-25957 JP 54-92723 A JP 59-53836 A JP 59-71048 A Japanese Patent Laid-Open No. 2002-40652

  Accordingly, the object of the present invention is to solve the above-mentioned problem of coexistence of the suppression of the developer penetration of the image area and the high developability of the non-image area, and to provide a lithographic printing plate precursor excellent in printing durability and image formability and its It is to provide a polymerizable composition suitable for the photosensitive layer, particularly a lithographic printing plate precursor suitable for drawing with a laser beam and a polymerizable composition suitable for the photosensitive layer.

As a result of intensive studies to achieve the above object, the present inventors have used a photosensitive layer made of a polymerizable composition containing a specific binder polymer and / or contain the polymerizable composition and contain an alkali. The inventors have found that the above object can be achieved by using a photosensitive layer in which the developing speed with respect to the developing solution and the permeation speed of the alkali developing solution are in a desired range, and the present invention has been achieved.

That is, the polymerizable composition of the present invention binds to a binder polymer having a repeating unit represented by the following general formula (I), an infrared absorber (provided that the unit includes a structure having a skeleton having absorption at 700 to 1200 nm). A dye having an ester group selected from the group consisting of a methyl ester group, an aryl ester group, a benzyl ester group, and an allyl ester group, soluble in an organic solvent and an alkaline aqueous solution, and absorbing at 700 to 1200 nm And a polymerization initiator and a polymerizable compound.

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents alkylene, substituted alkylene, arylene, or substituted arylene, or two or more selected from these are linked by an amide bond or an ester bond. And represents a linking group having 2 to 82 atoms and no aliphatic cyclic structure, wherein A represents an oxygen atom or —NR ³ —, and R ³ represents a hydrogen atom or Represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 1 to 5.)

In the polymerizable composition of the present invention, in the binder polymer having the repeating unit represented by the general formula (I), the number of atoms constituting the main skeleton of the linking group represented by R ² is 1 to 30. It is more preferable that the linking group represented by R ² has an alkylene structure, or more preferably has a structure in which the alkylene structure is linked via an ester bond.

Further, the planographic printing BanHara plate of the present invention, on a support, is characterized in that it comprises a photosensitive layer containing a polymerizable composition of the invention described above.

Further, in a lithographic printing BanHara plate of the present invention, on a support, wherein the polymerizable composition of the invention described above, the developing speed of unexposed portions in an alkali developing solution pH10~13.5 is 80nm It is preferable to provide a photosensitive layer having a permeation rate of 100 nF / sec or less at the exposed portion of the alkali developer at / sec or more.
Here, the development speed of the unexposed area with respect to an alkaline developer having a pH of 10 to 13.5 is a value obtained by dividing the film thickness (nm) of the photosensitive layer by the time (sec) required for development. The penetration rate of the liquid at the exposed portion is a value indicating the rate of change in capacitance (nF) when the photosensitive layer is formed on a conductive support and immersed in a developer.

Although the operation of the present invention is not clear, it is presumed as follows.
And the polymerizable composition of the present invention, used Oite the lithographic printing BanHara plate of the present invention, the binder polymer having a repeating unit represented by the formula (I), diffusive and alkaline response in a developer ( It is excellent in solubility in an aqueous alkali solution, and even in a slight acid content (that is, when the acid value is not sufficient), the solubility in a developer is excellent. Thereby, the polymerizable composition containing such a binder polymer and the photosensitive layer of the lithographic printing plate precursor can maintain high developability while suppressing developer penetration damage due to the acid content. I think that the.
Moreover, sensitive optical layer of the lithographic printing plate precursor of the present invention, the developing speed of unexposed portions in an alkali developing solution, for a penetration rate of the exposed portions of the alkaline developer, in the case shown in the above range, In the exposed area, the surface is sufficiently hardened to form a high-strength image area, suppressing the penetration of the alkaline developer, and in the unexposed area, the dissolution rate in the alkaline developer is fast. It is. For this reason, it is estimated that it is excellent in the coexistence of the developing solution permeation suppression capability of an image part, and the development performance of a non-image part. In order to control the developing speed of the unexposed area of the photosensitive layer with respect to the alkaline developer and the penetration speed of the alkaline developer in the exposed area within the above range, the photosensitive layer is represented by the general formula (I). that Ru using a binder polymer having a repeating unit.

According to the planographic printing BanHara plate of the present invention contains a binder polymer having a repeating structure represented by the general formula (I), by providing a photosensitive layer containing a polymerizable composition of the present invention, very high Printing durability and excellent image forming properties can be obtained.
Further, the planographic printing BanHara plate of the present invention, an effect that due to the physical properties of the photosensitive layer, excellent printing durability and image forming properties.
Furthermore, the lithographic printing plate precursor of the present invention is suitable for scanning exposure by a laser beam is capable of writing at a high speed, both high productivity.

The present invention will be described below.
<Polymerizable composition>
The polymerizable composition of the present invention is bonded to a binder polymer having a repeating unit represented by the general formula (I) and an infrared absorbing dye (however, a unit having a structure having a skeleton having absorption at 700 to 1200 nm). A dye having an ester group selected from the group consisting of a methyl ester group, an aryl ester group, a benzyl ester group, and an allyl ester group, soluble in an organic solvent and an alkaline aqueous solution, and having an absorption at 700 to 1200 nm Except)) , containing a polymerization initiator and a polymerizable compound.
Such a polymerizable composition has a mechanism in which a polymerization initiator is decomposed by heat to generate a radical, and the polymerizable compound causes a polymerization reaction by the generated radical. Furthermore, the polymerizable composition of the present invention, which contains the infrared ray absorbing agent, when exposed by a laser beam having a wavelength of 300～1,200Nm, only the exposed portion is generated heat, polymerization The reaction proceeds and hardens. This polymerizable composition can be applied to various uses utilizing these mechanisms, for example, a photosensitive layer of a lithographic printing plate precursor that can be directly drawn by an infrared laser, an image recording material, or It is also suitable as a high-sensitivity optical modeling material, and can be applied to hologram materials by utilizing the change in refractive index accompanying polymerization, and to the production of electronic materials such as photoresists. Among these, it is particularly suitable as a photosensitive layer of a lithographic printing plate precursor that can be directly drawn with an infrared laser or the like.
The polymerizable composition of the present invention will be described in detail with reference to a lithographic printing plate precursor that is the most suitable application.

<Lithographic printing plate precursor>
Lithographic printing BanHara plate of the present invention, on a support, is characterized in that it comprises a photosensitive layer containing a polymerizable composition of the invention described above.
The photosensitive layer of the lithographic printing BanHara plate of the present invention, the developing speed of unexposed portions in an alkali developing solution pH10~13.5 is 80 nm / sec or more, and the permeation rate of the exposed portions of the alkaline developer Is preferably a photosensitive layer of 100 nF / sec or less.

(Photosensitive layer)
First, the photosensitive layer of the lithographic printing plate precursor according to the invention will be described in detail.
The photosensitive layer in the present invention comprises a binder polymer having a repeating unit represented by the general formula (I), an infrared absorber (however, a methyl ester group bonded to a unit having a structure having a skeleton having absorption at 700 to 1200 nm. A dye having an ester group selected from the group consisting of an aryl ester group, a benzyl ester group, and an allyl ester group, soluble in an organic solvent and an aqueous alkali solution, and having an absorption at 700 to 1200 nm. , Containing a polymerization initiator and a polymerizable compound. Further, the photosensitive layer may have a development rate of 80 nm / sec or more in an unexposed portion with respect to a developer having a pH of 10 to 13.5 and a penetration rate of the alkaline developer in an exposed portion of 100 nF / sec or less. preferable.
Hereinafter, each component constituting the photosensitive layer in the invention will be described.

[Binder polymer]
(Binder polymer contained in the photosensitive layer in the first embodiment of the planographic printing plate precursor of the invention)
The binder polymer contained in the photosensitive optical layer of the lithographic printing plate precursor of the present invention has a repeating unit represented by the general formula (I). Hereinafter, the binder polymer having the repeating unit represented by the general formula (I) is appropriately referred to as a specific binder polymer and will be described in detail.
First, R ¹ in the general formula (I) represents a hydrogen atom or a methyl group, and a methyl group is particularly preferable.

The linking group represented by R ² in the general formula (I) has a structure in which alkylene, substituted alkylene, arylene, or substituted arylene, or two or more selected from these are linked by an amide bond or an ester bond. , the number of the atoms is 2 to 82, preferably 2 to 50, more preferably Ri 2-30 der, and no aliphatic cyclic structure. The number of atoms shown here refers to the number of atoms including the substituent when the linking group has a substituent.
More specifically, the number of atoms constituting the main skeleton of the linking group represented by R ² is preferably 1-30, more preferably 3-25, and 4-20. More preferred is 5-10. The “main skeleton of the linking group” in the present invention refers to an atom or an atomic group used only for linking A and the terminal COOH in the general formula (I), and particularly when there are a plurality of linking paths. Refers to an atom or atomic group that constitutes a path with the least number of atoms used. Therefore, when a linking group has a ring structure, the number of atoms to be included differs depending on the linking site (for example, o-, m-, p-, etc.).

Below, the structure of the specific binder polymer of the present invention, the number of atoms constituting the main skeleton of the linking group represented by R ² in the structure, and the calculation method thereof are also described.

The linking group represented by R ² in the general formula (I) has a structure in which alkylene, substituted alkylene, arylene, or substituted arylene, or two or more selected from these are linked by an amide bond or an ester bond. , A linking group having 2 to 82 atoms and having no aliphatic cyclic structure.
Examples of the linking group having a chain structure include ethylene and propylene. A structure in which these alkylenes are linked via an ester bond can also be exemplified as a preferable example.

Most preferably, the linking group represented by R ² is one having 5 to 10 atoms constituting the main skeleton of the linking group, and is structurally a chain structure having an ester bond in the structure. also preferably it has a.

The linking group represented by R ² may have a substituent, and examples of the substituent that can be introduced include monovalent nonmetallic atomic groups other than hydrogen (provided that an aliphatic cyclic structure is included). does not include those with.), a halogen atom (-F, -Br, -Cl, -I), a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, an alkylthio group, an arylthio group, an alkyl dithio group, aryl dithio 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-diarylcarbamoyl group Si group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′- Alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N -Arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N -Arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N Alkylureido group, N ′, N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, Alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N -Aryloxycarbonylamino group, formyl group, acyl group, carboxyl group and its conjugate base group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-ary Rucarbamoyl group, N, N-diarylcarba Moyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group, alkoxysulfonyl group, aryloxysulfonyl Group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfina Moyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfur A famoyl group, an N-acylsulfamoyl group and Conjugate base group, N- alkylsulfonylsulfamoyl group _{(-SO 2 NHSO 2 (alkyl)} ) and its conjugated base group, N- aryl sulfonylsulfamoyl group _{(-SO 2 NHSO 2 (aryl)} ) and its conjugate Base group, N-alkylsulfonylcarbamoyl group (—CONHSO ₂ (alkyl)) and its conjugate base group, N-arylsulfonylcarbamoyl group (—CONHSO ₂ (aryl)) and its conjugate base group, alkoxysilyl group (—Si ( Oalkyl) _3), aryloxy silyl group (-Si (Oaryl) _3), hydroxy silyl group (-Si (OH) ₃₎ and its conjugated base group, a phosphono group (-PO ₃ H ₂₎ and its conjugated base group, dialkylphosphono group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group (-PO ₃ (ar l) _2), alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono group (-PO ₃ H (alkyl)) and its conjugated base group, monoaryl phosphono group (-PO ₃ H (aryl)) and its conjugate base group, phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group, dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (—OPO) ₃ (aryl) ₂ ), an alkylarylphosphonooxy group (—OPO ₃ (alkyl) (aryl)), a monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group, monoarylphosphono An oxy group (—OPO ₃ H (aryl)) and its conjugate base group, a cyano group, a nitro group, a dialkylboryl group (—B (alkyl) ₂ ), diarylboryl group (-B (aryl) ₂ ), alkylarylboryl group (-B (alkyl) (aryl)), dihydroxyboryl group (-B (OH) ₂ ) and its conjugate base group, alkylhydroxyl Examples thereof include a boryl group (—B (alkyl) (OH)) and its conjugate base group, an arylhydroxyboryl group (—B (aryl) (OH)) and its conjugate base group, an aryl group, an alkenyl group, and an alkynyl group.

  Here, although depending on the design of the photosensitive layer, a substituent having a hydrogen atom capable of hydrogen bonding, or particularly a substituent having an acid dissociation constant (pKa) smaller than that of carboxylic acid lowers printing durability. It is not preferable because it is in a tendency. On the other hand, hydrophobic substituents such as halogen atoms, hydrocarbon groups (alkyl groups, aryl groups, alkenyl groups, alkynyl groups), alkoxy groups, aryloxy groups and the like are more preferable because they tend to improve printing durability. When the cyclic structure is a monocyclic aliphatic hydrocarbon having 6 or less members such as cyclopentane or cyclohexane, it preferably has such a hydrophobic substituent. If possible, these substituents may be bonded to each other or with a substituted hydrocarbon group to form a ring, and the substituent may be further substituted.

R ³ in the case where A in the general formula (I) is NR ³ — represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R ³ include an alkyl group, an aryl group, an alkenyl group, and an alkynyl group.
Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, sec-butyl, 1 carbon number such as tert-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, 2-norbornyl group Up to 10 linear, branched or cyclic alkyl groups.
Specific examples of the aryl group include a phenyl group, a naphthyl group, and an indenyl group. In addition, a heteroaryl group having up to 10 carbon atoms containing one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom can also be used. Specifically, for example, a furyl group, a thienyl group, A pyrrolyl group, a pyridyl group, a quinolyl group, etc. are mentioned.
Specific examples of the alkenyl group include those having 2 to 10 carbon atoms such as vinyl group, 1-propenyl group, 1-butenyl group, 1-methyl-1-propenyl group, 1-cyclopentenyl group, 1-cyclohexenyl group and the like. A linear, branched, or cyclic alkenyl group is mentioned.
Specific examples of the alkynyl group include alkynyl groups having 2 to 10 carbon atoms such as ethynyl group, 1-propynyl group, 1-butynyl group, and 1-octynyl group.
Here, the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R ³ may further have a substituent, and examples of the substituent that can be introduced include the substituent that R ² can introduce. Same as listed. The number of carbon atoms of R ³ is 1 to 10 including the carbon number of the substituent.

  A in the general formula (I) is preferably an oxygen atom or —NH— because synthesis is easy.

  N in the general formula (I) represents an integer of 1 to 5, and is preferably 1 in terms of printing durability.

  Although the preferable specific example of the repeating unit represented by general formula (I) is shown below, this invention is not limited to these.

  One type of repeating unit represented by the general formula (I) may be contained in the binder polymer, or two or more types may be contained. The specific binder polymer in the present invention may be a polymer composed of only the repeating unit represented by the general formula (I), but is usually used as a copolymer in combination with other copolymerization components. The total content of the repeating unit represented by the general formula (I) in the copolymer is appropriately determined depending on the structure, the design of the photosensitive layer, etc., but preferably 1 to 99 mol% with respect to the total molar amount of the polymer component. More preferably, it is contained in the range of 5 to 40 mol%, more preferably 5 to 20 mol%.

As a copolymerization component in the case of using as a copolymer, a conventionally well-known thing can be used without a restriction | limiting, if it is a monomer which can be radically polymerized. Specific examples include monomers described in “Polymer Data Handbook—Basic Edition” (Edition of Polymer Society, Bafukan, 1986). One type of such copolymerization component may be used, or two or more types may be used in combination.
Moreover, as a preferable copolymerization component, the unit which has a radically polymerizable group, and the unit which has an amide group are mentioned. Below, the unit which has a radically polymerizable group and the unit which has an amide group which are preferable as a copolymerization component with the repeating unit represented by general formula (I) are demonstrated.

The radical polymerizable group preferable as a copolymerization component with the repeating unit represented by the general formula (I) is not particularly limited as long as it can be polymerized by a radical, but an α-substituted methylacryl group [—OC ( ═O) —C (—CH ₂ Z) ═CH ₂ , Z = hydrocarbon group starting from a hetero atom], acrylic group, methacryl group, allyl group, and styryl group.
More specifically, it is preferably a radical polymerizable group having a structure represented by the following general formulas (A) to (C).

In general formulas (A) to (C), R ^{4 to} R ¹⁴ each independently represents a hydrogen atom or a monovalent substituent. X and Y each independently represent an oxygen atom, a sulfur atom, or —N—R ¹⁵ , and Z represents an oxygen atom, a sulfur atom, —N—R ^15, or a phenylene group. Here, R ¹⁵ represents a hydrogen atom or a monovalent organic group.

In the general formula (A), R ^{4 to} R ⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ⁴ is a hydrogen atom or an alkyl which may have a substituent. An organic group such as a group can be mentioned, and specifically, a hydrogen atom, a methyl group, a methylalkoxy group, and a methyl ester group are preferable. R ⁵ and R ⁶ may each independently have a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or a substituent. Alkyl group, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, substituted An arylamino group that may have a group, an alkylsulfonyl group that may have a substituent, an arylsulfonyl group that may have a substituent, and the like, among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group An alkyl group which may have a substituent and an aryl group which may have a substituent are preferable.
Here, examples of the substituent that can be introduced into these groups include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropyloxycarbonyl group, a methyl group, an ethyl group, and a phenyl group.
X represents an oxygen atom, a sulfur atom, or —N—R ¹⁵ , where R ¹⁵ includes an alkyl group which may have a substituent.

In the general formula (B), R ^{7 to} R ¹¹ each independently represents a hydrogen atom or a monovalent substituent. Specific examples thereof include a hydrogen atom, a halogen atom, an amino group, and a dialkylamino. Group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent An aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, a substituent An arylsulfonyl group which may have a group, etc. are mentioned, among others, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent Preferred.
Here, as a substituent which can be introduced into these groups, those exemplified as the substituent which can be introduced in the general formula (A) are exemplified.
Y represents an oxygen atom, a sulfur atom, or —N—R ¹⁵ . Examples of R ¹⁵ include the same as those in general formula (A).

In the general formula (C), R ^{12 to} R ¹⁴ each independently represents a hydrogen atom or a monovalent substituent. Specific examples thereof include a hydrogen atom, a halogen atom, an amino group, and a dialkylamino. Group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent An aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, a substituent An arylsulfonyl group which may have a group, etc. are mentioned, among others, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent Is preferred.
Here, as a substituent which can be introduced into these groups, those exemplified as the substituent which can be introduced in the general formula (A) are exemplified.
Z represents an oxygen atom, a sulfur atom, —N—R ¹⁵ or a phenylene group. Examples of R ¹⁵ include the same as those in general formula (A).

  The polymer having a radical polymerizable group having a structure represented by the general formula (A) according to the present invention can be produced by at least one of synthesis methods (1) and (2) shown below.

-Synthesis method (1)-
After synthesizing a polymer compound by polymerizing one or more radically polymerizable compounds represented by the following general formula (D), a proton is extracted using a base, and Z ¹ is eliminated to obtain a desired compound. A method for obtaining a polymer compound.

In the general formula (D), R ⁴ ~R ⁶ have the same meanings as R ⁴ to R ⁶ in the general formula (A). Z ¹ represents an anionic leaving group. Q represents an oxygen atom, —NH—, or NR ¹⁷ — (wherein R ¹⁷ represents an alkyl group which may have a substituent). R ¹⁶ includes a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom, a methyl group, a methylalkoxy group or a methyl ester group is preferable. A represents a divalent organic linking group.

  Examples of the radically polymerizable compound represented by the general formula (D) include the following compounds, but are not limited thereto.

These radically polymerizable compounds represented by the general formula (D) can be easily obtained as a commercial product or by a synthesis method shown in Synthesis Examples described later.
A polymer compound was synthesized by polymerizing by one ordinary radical polymerization method using one or more of these radical polymerizable compounds represented by the general formula (D) and other radical polymerizable compounds as required. Thereafter, a desired amount of a base is dropped into a polymer solution under a cooling or heating condition to perform a reaction, and if necessary, neutralization treatment with an acid is performed to represent the general formula (A). Groups can be introduced. A generally known suspension polymerization method or solution polymerization method can be applied to the production of the polymer compound.
Here, as a base to be used, either an inorganic compound (inorganic base) or an organic compound (organic base) may be used. Preferred inorganic bases include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate and the like, and organic bases include sodium methoxide, sodium ethoxide, potassium tert-butoxide. And metal amine alkoxides, triethylamine, pyridine, and organic amine compounds such as diisopropylethylamine.

-Synthesis method (2)-
After synthesizing a trunk polymer compound (polymer compound constituting the main chain) by using at least one radical polymerizable compound having a functional group, the side chain functional group of the trunk polymer compound and the following general formula A method of obtaining a desired polymer compound by reacting a compound having a structure represented by (E).

R ⁴ to R in the general formula (E) ⁶ has the same meaning as R ⁴ to R ⁶ in the general formula (A).

Examples of the functional group of the radical polymerizable compound having a functional group used for the synthesis of the trunk polymer compound in the synthesis method (2) include a hydroxyl group, a carboxyl group, a carboxylic acid halide group, a carboxylic acid anhydride group, an amino group, Examples include halogenated alkyl groups, isocyanate groups, and epoxy groups. Specific examples of the radical polymerizable compound having such a functional group include 2-hydroxylethyl acrylate, 2-hydroxylethyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, acrylic acid, methacrylic acid, acrylic acid chloride, methacrylic acid. Examples include acid chloride, methacrylic anhydride, N, N-dimethyl-2-aminoethyl methacrylate, 2-chloroethyl methacrylate, 2-isocyanate ethyl methacrylate, glycidyl acrylate, and grindyl methacrylate.
After synthesizing one or more kinds of radically polymerizable compounds having such functional groups and copolymerizing with other radically polymerizable compounds as necessary to synthesize a trunk polymer compound, the above general formula (E) A desired polymer compound can be obtained by reacting a compound having the group represented.
Here, as an example of the compound having a group represented by the general formula (E), the compounds mentioned as specific examples of the radical polymerizable compound having such a functional group are mentioned.

  The polymer having a radical polymerizable group having a structure represented by the general formula (B) according to the present invention can be produced by at least one of synthesis methods (3) and (4) shown below.

-Synthesis method (3)-
One or more radically polymerizable compounds having an unsaturated group represented by the general formula (B) and an ethylenically unsaturated group further rich in addition polymerization than the unsaturated group, and further if necessary A method of polymerizing another radical polymerizable compound to obtain a polymer compound. This method uses a compound having a plurality of ethylenically unsaturated groups having different addition polymerization properties in one molecule, for example, a compound such as allyl methacrylate.

  Examples of the radical polymerizable compound having an ethylenically unsaturated group rich in addition polymerization than the unsaturated group represented by the general formula (B) include allyl acrylate, allyl methacrylate, 2-allyloxyethyl acrylate, 2 Examples include -allyloxyethyl methacrylate, propargyl acrylate, propargyl methacrylate, N-allyl acrylate, N-allyl methacrylate, N, N-diallyl acrylate, N, N-diallyl methacrylamide, allyl acrylamide, and allyl methacrylamide.

-Synthesis method (4)-
After synthesizing one or more radically polymerizable compounds having a functional group to synthesize a polymer compound, a side chain functional group and a compound having a structure represented by the following general formula (F) are reacted to form a general formula (B The method of introduce | transducing group represented by this.

R < ⁷ > -R < ¹¹ > in general formula (F) is synonymous with R < ⁷ > -R < ¹¹ > in the said general formula (B).

Specific examples of the radical polymerizable compound having a functional group in the synthesis method (4) include specific examples of the radical polymerizable compound having a functional group shown in the synthesis method (2).
Examples of the compound having the structure represented by the general formula (F) include allyl alcohol, allylamine, diallylamine, 2-allyloxyethyl alcohol, 2-chloro-1-butene, and allyl isocyanate.

  The polymer having a radical polymerizable group having a structure represented by the general formula (C) according to the present invention can be produced by at least one of synthesis methods (5) and (6) shown below.

-Synthesis method (5)-
One or more radically polymerizable compounds having an unsaturated group represented by the general formula (C) and an ethylenically unsaturated group further rich in addition polymerization than the unsaturated group, and further if necessary A method of obtaining a polymer compound by copolymerizing with another radical polymerizable compound.

  Examples of the radical polymerizable compound having an ethylenically unsaturated group richer in addition polymerization than the unsaturated group represented by the general formula (C) include vinyl acrylate, vinyl methacrylate, 2-phenylvinyl acrylate, 2- Examples include phenyl vinyl methacrylate, 1-propenyl acrylate, 1-propenyl methacrylate, vinyl acrylamide, vinyl methacrylamide and the like.

-Synthesis method (6)-
A method in which one or more radically polymerizable compounds having a functional group are polymerized to synthesize a polymer compound, and then introduced by reacting a side chain functional group with a compound having a structure represented by the general formula (G).

R < ¹² > -R < ¹⁴ > in general formula (G) is synonymous with R < ¹² > -R < ¹⁴ > in the said general formula (C).

Specific examples of the radical polymerizable compound having a functional group in the synthesis method (6) include specific examples of the radical polymerizable compound having a functional group shown in the synthesis method (2).
Examples of the compound having the structure represented by the general formula (G) include 2-hydroxyethyl monovinyl ether, 4-hydroxybutyl monovinyl ether, diethylene glycol monovinyl ether, 4-chloromethylstyrene, and the like.

  As mentioned above, although the synthesis method (1)-(6) of the polymer which has a radically polymerizable group of the structure represented by the said general formula (A)-(C) based on this invention was demonstrated, using this synthesis method In order to synthesize the specific binder polymer of the present invention, when the radically polymerizable compound is polymerized in each of the synthesis methods (1) to (6), the radically polymerizable compound and the general formula (I) are represented. This is achieved by copolymerizing the units with a predetermined ratio.

Among these radical polymerizable groups, a radical polymerizable group having a structure represented by the general formulas (A) and (B) is preferable. Among them, particularly preferred is a radically polymerizable group having a structure represented by the general formula (A), and R ⁴ is a hydrogen atom or a methyl group, and X is an oxygen atom or a nitrogen atom. preferable.
Specific preferred examples of the repeating unit having a radically polymerizable group having a structure represented by the general formulas (A) to (C) are shown below, but are not limited thereto.

  Next, an amide group preferable as a copolymerization component with the repeating unit represented by formula (I) will be described. Such an amide group is preferably an amide group having a structure represented by the following general formula (1).

In general formula (1), R ¹⁸ and R ¹⁹ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, or a substituent, each of which may have a substituent. It represents a sulfonyl group, and R ¹⁸ and R ¹⁹ may be bonded to each other to form an alicyclic structure.

Preferable examples of R ¹⁸ and R ¹⁹ will be described in detail. Examples of the alkyl group represented by R ¹⁸ and R ¹⁹ include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, ethyl group, and ethyl group. 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, Examples thereof include s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group. . Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

As a substituent of the substituted alkyl group represented by R ¹⁸ and R ¹⁹ , a group composed of a monovalent non-metallic atomic group excluding a hydrogen atom is used. Preferred examples include halogen atoms (—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-dialkyl Carbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamo Ruoxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkyl Ureido group, N′-arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N -Alkylureido group, N'-alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N -Alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'-diaryl- N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N -Alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group (R ⁰¹ CO—), 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-arylcarbamo Group, alkylsulfinyl group, arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, (referred to as a sulfonato group) sulfo group (-SO ₃ H) and its conjugated base group, alkoxy sulfonyl group, aryloxy sulfonyl group, sulfinamoyl group N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, Sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group Phosphono group (—PO ₃ H ₂ ) and its conjugate base group (phospho A dialkylphosphono group (—PO ₃ (alkyl) ₂ ; alkyl = alkyl group, hereinafter the same), a diarylphosphono group (—PO ₃ (aryl) ₂ ; aryl = aryl group, the same hereinafter), An alkylarylphosphono group (—PO ₃ (alkyl) (aryl)), a monoalkylphosphono group (—PO ₃ (alkyl)) and its conjugate base group (referred to as an alkylphosphonato group), a monoarylphosphono group ( -PO ₃ referred to as H (aryl)) and its conjugated base group (aryl phosphite Hona preparative group), referred to as phosphonooxy group (-OPO ₃ H ₂₎ and its conjugated base group (phosphonatooxy group), dialkylphosphono group (- _{OPO 3 H (alkyl) 2)} , diaryl phosphono group _{(-OPO 3 (aryl) 2)} , alkylaryl phosphonooxymethyl (-OPO ₃ (alkyl) (aryl)), (referred to as alkylphosphonato group) monoalkyl phosphono group (-OPO ₃ H (alkyl)) and its conjugated base group, monoarylphosphono group (- OPO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonatoxy group), cyano group, nitro group, aryl group, alkenyl group, alkynyl group, heterocyclic group, silyl group and the like.

  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, cyanophene Group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group, and a phosphate Hona preparative phenyl group.

Examples of the alkenyl group in these substituents include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group, and the like. Examples of alkynyl groups Includes an ethynyl group, a 1-propynyl group, a 1-butynyl group, a trimethylsilylethynyl group, and the like.
Furthermore, in these substituents, R ⁰¹ in the acyl group (R ⁰¹ CO-), a hydrogen atom, and the above-described alkyl group, and an aryl group.

  Among these substituents, more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N -Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group Group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfa group Moyl group, N-arylsulfur Amoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonato group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono group, arylphospho Examples thereof include a nato group, a phosphonooxy group, a phosphonatooxy group, an aryl group, and an alkenyl group. In addition, examples of the heterocyclic group include a pyridyl group and a piperidinyl group. Examples of the silyl group include a trimethylsilyl group.

  On the other hand, examples of the alkylene group constituting 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. Preferred examples include linear alkylene groups having 1 to 12 carbon atoms, branched alkylene groups having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms. Preferable specific examples of the substituted alkyl group obtained by combining such an alkylene group and a substituent include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, isopropoxymethyl. Group, butoxymethyl group, s-butoxybutyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, pyridylmethyl group, tetramethylpiperidinylmethyl group, N-acetyl Tetramethylpiperidinylmethyl group, trimethylsilylmethyl group, methoxyethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxye Group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, Chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group , Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphono Enyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl Group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1- Examples thereof include a propenylmethyl group, a 2-butenyl group, a 2-methylallyl group, a 2-methylpropenylmethyl group, a 2-propynyl group, a 2-butynyl group, and a 3-butynyl group.

Next, examples of the aryl group as R ¹⁸ and R ¹⁹ 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.

As the substituted aryl group represented by R ¹⁸ and R ¹⁹ , those having a group consisting of a monovalent nonmetallic atomic group excluding a hydrogen atom as a substituent on the ring-forming carbon atom of the aryl group described above are used. It is done. Examples of preferred substituents include the aforementioned alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group. Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, cal Xiphenyl 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, diphenylphosphonophenyl Methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, A 2-methylpropenylphenyl group, a 2-propynylphenyl group, a 2-butynylphenyl group, a 3-butynylphenyl group, and the like can be given.

An alkenyl group represented by R ¹⁸ and R ¹⁹ , a substituted alkenyl group, an alkynyl group, and a substituted alkynyl group (—C (R ⁰² ) ═C (R ⁰³ ) (R ⁰⁴ ), and —C≡C (R ⁰⁵ As for)), R ⁰² , R ⁰³ , R ⁰⁴ , and R ⁰⁵ may be groups having a monovalent nonmetallic atomic group. Preferable examples of R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ include a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group and a substituted aryl group. Specific examples thereof include those shown as the above-mentioned examples. More preferable groups of R ⁰² , R ⁰³ , R ⁰⁴ , and R ⁰⁵ include a hydrogen atom, a halogen atom, and a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. Preferable specific examples of the alkenyl group, substituted alkenyl group, alkynyl group and substituted alkynyl group represented by R ¹⁸ and R ¹⁹ include a vinyl group, 1-propenyl group, 1-butenyl group, 1-pentenyl group, 1-hexenyl group, 1-octenyl group, 1-methyl-1-propenyl group, 2-methyl-1-propenyl group, 2-methyl-1-butenyl group, 2-phenyl-1-ethenyl group, 2-chloro- Examples include 1-ethenyl group, ethynyl group, 1-propynyl group, 1-butynyl group, and phenylethynyl group.

Examples of the heterocyclic group represented by R ¹⁸ and R ¹⁹ include the pyridyl group exemplified as the substituent of the substituted alkyl group.

As the substituted sulfonyl group (R ⁰¹¹ —SO ₂ —) represented by R ¹⁸ and R ¹⁹ , those in which R ⁰¹¹ is a group consisting of a monovalent nonmetallic atomic group can be used. More preferable examples include an alkylsulfonyl group and an arylsulfonyl group. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Specific examples of such a substituted sulfonyl group include a butylsulfonyl group, a phenylsulfonyl group, a chlorophenylsulfonyl group, and the like.

In addition, examples of the ring formed by bonding R ¹⁸ and R ¹⁹ in the general formula (1) include morpholine, piperazine, pyrrolidine, pyrrole, indoline and the like. These may be further substituted with a substituent as described above. Among them, the case where an alicyclic ring is formed is preferable.

In the general formula (1), R ¹⁸ and R ¹⁹ are preferably an alkyl group, an alkenyl group, an aryl group, or a substituted sulfonyl group. It is also preferred when R ¹⁸ and R ¹⁹ form an alicyclic ring.

  Specific examples preferable as the monomer or repeating unit having an amide group having a structure represented by the general formula (1) are shown below, but the invention is not limited thereto.

  As the specific binder polymer used for the photosensitive layer in the first aspect of the lithographic printing plate precursor according to the invention, the unit represented by the general formula (I) and the unit having a radical polymerizable group described above, or More preferably, it is a copolymer comprising a unit having an amide group, and further has a unit represented by the general formula (I), a unit having a radical polymerizable group, and an amide group. It is particularly preferable that the copolymer is composed of three units.

  The molecular weight of the specific binder polymer in the present invention is appropriately determined from the viewpoint of image formability and printing durability. Usually, when the molecular weight increases, the printing durability is excellent, but the image formability tends to deteriorate. On the other hand, if it is low, the image forming property is improved, but the printing durability is lowered. The molecular weight is preferably in the range of 2,000 to 1,000,000, more preferably 5,000 to 500,000, and still more preferably 10,000 to 300,000.

  The content of the radical polymerizable group in the specific binder polymer (content of unsaturated double bond capable of radical polymerization by iodometric titration) is preferably 0.00 per gram of the binder polymer from the viewpoint of sensitivity and storage stability. It is 1-10.0 mmol, More preferably, it is 1.0-8.0 mmol, Most preferably, it is 2.0-7.0 mmol.

  Further, the content of alkali-soluble groups in the specific binder polymer (acid value by neutralization titration) is preferably 0.1 to 3.0 mmol, more preferably 1 g of binder polymer from the viewpoint of developability and printing durability. Is 0.2 to 2.0 mmol, most preferably 0.3 to 1.5 mmol.

  The glass transition point (Tg) of such a specific binder polymer is preferably in the range of 70 to 300 ° C, more preferably 80 to 250 ° C, and most preferably 90 to 200 ° C, from the viewpoint of storage stability and sensitivity. It is.

  In addition, the binder polymer used in the photosensitive layer in the first aspect of the lithographic printing plate precursor according to the invention may be a specific binder polymer alone, or may be used in combination with one or more other binder polymers. May be. The binder polymer used in combination is used in the range of 1 to 60% by mass, preferably 1 to 40% by mass, and more preferably 1 to 20% by mass with respect to the total mass of the binder polymer component. As the binder polymer that can be used in combination, a conventionally known binder polymer can be used without limitation, and specifically, an acrylic main chain binder, a urethane binder, or the like often used in the industry is preferably used.

  The total amount of the specific binder polymer in the photosensitive layer and the binder polymer that may be used in combination can be determined as appropriate, but is usually 10 to 90% by mass, preferably based on the total mass of the nonvolatile components in the photosensitive layer. Is in the range of 20-80% by weight, more preferably 30-70% by weight.

(Binder polymer contained in the photosensitive layer in the second embodiment of the planographic printing plate precursor of the invention)
As the binder polymer contained in the photosensitive layer in the second aspect of the lithographic printing plate precursor according to the invention, when the photosensitive layer is formed together with an infrared absorber, a polymerization initiator and a polymerizable compound, the photosensitive layer has a pH of 10 to 13. If the development rate of the unexposed portion with respect to the alkaline developer of .5 is 80 nm / sec or more and the penetration rate of the alkaline developer in the exposed portion can be controlled to be 100 nF / sec or less, Things can be used without restriction.
Such a lithographic printing plate of the present invention can be used as a binder polymer that can easily control the developing speed of an unexposed portion with respect to an alkali developer and the penetration speed of an alkali developer in an exposed portion within a desired range. It is preferable to use the specific binder polymer used for the photosensitive layer in the first aspect of the original plate, and among the specific binder polymer, more preferably, the unit represented by the general formula (I) and the radical polymerizable property described above. A unit having a group or a unit having an amide group, and more preferably, a unit represented by the general formula (I), and a unit having a radical polymerizable group described above. , A copolymer having three units: an amide group-containing unit.

Moreover, the binder polymer used for the photosensitive layer in the second aspect of the lithographic printing plate precursor according to the invention may be a single binder polymer, or may be used in combination of two or more types as a mixture. Also good.
The total amount (content) of the binder polymer in the photosensitive layer in the second aspect of the lithographic printing plate precursor according to the invention can be determined as appropriate, but is usually based on the total mass of nonvolatile components in the photosensitive layer. It is 10-90 mass%, Preferably it is 20-80 mass%, More preferably, it is the range of 30-70 mass%.

Here, a preferred embodiment of the planographic printing BanHara version definitive photosensitive layer binder polymer for use in the present invention are shown below, but the invention is not limited thereto. In addition, the binder polymer which shows a specific example here is a specific binder polymer in this invention.

[Other essential components constituting the photosensitive layer]
The photosensitive layer in the lithographic printing plate of the present invention contains, as essential components, the above-described binder polymer, infrared absorber, polymerization initiator, and polymerizable compound (also referred to as addition polymerizable compound) as a thermopolymerizable negative type. It is a photosensitive layer. Such a heat-polymerizable negative photosensitive layer has a mechanism in which a polymerization initiator is decomposed by heat to generate radicals, and a polymerizable compound causes a polymerization reaction by the generated radicals. Furthermore, the lithographic printing plate precursor according to the present invention is particularly suitable for plate making by direct drawing with a laser beam having a wavelength of 300 to 1,200 nm, and has higher printing durability and image than the conventional lithographic printing plate precursor. Expresses formability.

  Below, an infrared absorber, a polymerization initiator, and a polymerizable compound, which are essential components constituting the photosensitive layer other than the binder polymer, will be described.

[Infrared absorber]
When the lithographic printing plate precursor according to the present invention is image-formed with a light source of a laser emitting infrared rays of 760 to 1,200 nm, it is usually essential to use an infrared absorber. The infrared absorber has a function of converting absorbed infrared rays into heat. With the heat generated at this time, a polymerization initiator (radical generator) described later is thermally decomposed to generate radicals. The infrared absorber used in the present invention is a dye or pigment having an absorption maximum at a wavelength of 760 nm to 1200 nm. Provided that the organic solvent has an ester group selected from the group consisting of a methyl ester group, an aryl ester group, a benzyl ester group, and an allyl ester group bonded to a unit including a structure having a skeleton having absorption at 700 to 1200 nm. In addition, a dye that is soluble in an alkaline aqueous solution and has absorption at 700 to 1200 nm is excluded from the infrared absorbent used in the present invention.

As the dye, commercially available dyes and known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specifically, dyes such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes, etc. Is mentioned.
Preferred dyes include, for example, cyanine dyes described in JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, and the like. Methine dyes described in JP-A-58-173696, JP-A-58-181690, JP-A-58-194595, JP-A-58-112793, JP-A-58-224793, JP-A-59- 48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744, etc., naphthoquinone dyes, JP-A-58-112792, etc. And cyanine dyes described in British Patent 434,875.

Also, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is preferably used, and a substituted arylbenzo (thio) pyrylium salt described in US Pat. No. 3,881,924, Trimethine thiapyrylium salts described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, 58-220143, 59-41363, 59-84248 Nos. 59-84249, 59-146063, 59-146061, pyranlium compounds, cyanine dyes described in JP-A-59-216146, US Pat. No. 4,283,475 The pentamethine thiopyrylium salts described above and the pyrylium compounds disclosed in Japanese Patent Publication Nos. 5-13514 and 5-19702 are also preferably used. . Moreover, as another example preferable as a dye, the near-infrared absorptive dye described as the formula (I) and (II) in US Patent 4,756,993 can be mentioned.
Other preferred examples of the infrared absorbing dye of the present invention include specific indolenine cyanine dyes described in Japanese Patent Application Nos. 2001-6326 and 2001-237840 as exemplified below.

  Particularly preferred among these dyes are cyanine dyes, squarylium dyes, pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes. Further, cyanine dyes and indolenine cyanine dyes are preferred, and particularly preferred examples include cyanine dyes represented by the following general formulas (a) to (e).

In formula (a), X ¹ represents a hydrogen atom, a halogen atom, -NPh ^_2, -X ₂ -L ¹ or a group shown below. Here, X ² represents an oxygen atom, a nitrogen atom, or a sulfur atom, and L ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, an aromatic ring having a hetero atom, or 1 to 1 carbon atom containing a hetero atom. 12 hydrocarbon groups are shown. In addition, a hetero atom here shows N, S, O, a halogen atom, and Se. Xa ^- the Za described later ^- is defined as for, R ^a represents a hydrogen atom, an alkyl group, an aryl group, a substituted or unsubstituted amino group, substituted or unsubstituted amino group and a halogen atom.

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

Ar ¹ and Ar ² may be the same or different and each represents an aromatic hydrocarbon group which may have a substituent. Preferred aromatic hydrocarbon groups include a benzene ring and a naphthalene ring. Moreover, as a preferable substituent, a C12 or less hydrocarbon group, a halogen atom, and a C12 or less alkoxy group are mentioned. Y ¹ and Y ² may be the same or different and each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms. R ³ and R ⁴ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferred substituents include alkoxy groups having 12 or less carbon atoms, carboxyl groups, and sulfo groups. R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. From the availability of raw materials, a hydrogen atom is preferred. Za ⁻ represents a counter anion. However, when the cyanine dye represented by formula (a) has an anionic substituent in its structure and does not require charge neutralization, Za ^- is not necessary. Preferred Za ⁻ is a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, particularly preferably a perchlorate ion, a hexagonal salt, in view of storage stability of the photosensitive layer coating solution. Fluorophosphate ions and aryl sulfonate ions.

  Specific examples of the cyanine dye represented by formula (a) that can be suitably used in the present invention include those exemplified below, and paragraph numbers [0017] to [0017] of Japanese Patent Application No. 11-310623. [0019], paragraphs [0012] to [0038] of Japanese Patent Application No. 2000-224031, and paragraphs [0012] to [0023] of Japanese Patent Application No. 2000-2111147. .

In the general formula (b), L represents a methine chain having 7 or more conjugated carbon atoms, the methine chain may have a substituent, and the substituents are bonded to each other to form a ring structure. Also good. Zb ⁺ represents a counter cation. Preferred counter cations include ammonium, iodonium, sulfonium, phosphonium, pyridinium, alkali metal cations (Na ⁺ , K ⁺ , Li ⁺ ) and the like. R ^{9 to} R ¹⁴ and R ^{15 to} R ²⁰ are each independently a hydrogen atom or halogen atom, cyano group, alkyl group, aryl group, alkenyl group, alkynyl group, carbonyl group, thio group, sulfonyl group, sulfinyl group, oxy group Or a substituent selected from amino groups, or a combination of two or three of these, and may be bonded to each other to form a ring structure. Here, in the general formula (b), those in which L represents a methine chain having 7 conjugated carbon atoms and those in which R ^{9 to} R ¹⁴ and R ^{15 to} R ²⁰ all represent hydrogen atoms are easily available. From the viewpoint of the effect.

  Specific examples of the dye represented by formula (b) that can be suitably used in the present invention include those exemplified below.

In the general formula (c), Y ³ and Y ⁴ each represent an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom. M represents a methine chain having 5 or more conjugated carbon atoms. R ^{21 to} R ²⁴ and R ^{25 to} R ²⁸ may be the same or different, and are each a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a carbonyl group, a thiol group, Represents a group, a sulfonyl group, a sulfinyl group, an oxy group, or an amino group. Further, wherein Za ^- include a counter anion, Za in the general formula (a) ^- it is synonymous.

  In the present invention, specific examples of the dye represented by formula (c) that can be suitably used include those exemplified below.

In the general formula (d), R ²⁹ to R ³¹ each independently represent a hydrogen atom, an alkyl group, or an aryl group. R ³³ and R ³⁴ each independently represents an alkyl group, a substituted oxy group, or a halogen atom. n and m each independently represents an integer of 0 to 4. R ²⁹ and R ³⁰ , or R ³¹ and R ³² may be bonded to each other to form a ring, and R ²⁹ and / or R ³⁰ is R ³³ and R ³¹ and / or R ³² is R ³⁴ taken together, may form a ring, further, when R ³³ or R ³⁴ there are a plurality, R ³³ or between R ³⁴ each other may be bonded to each other to form a ring. X ² and X ³ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and at least one of X ² and X ³ represents a hydrogen atom or an alkyl group. Q is a trimethine group or a pentamethine group which may have a substituent, and may form a ring structure together with a divalent organic group. Zc ⁻ represents a counter anion and has the same meaning as Za ⁻ in the general formula (a).

  In the present invention, specific examples of the dye represented by the general formula (d) that can be suitably used include those exemplified below.

In the general formula (e), R ^{35 to} R ⁵⁰ are each independently a hydrogen atom, halogen atom, cyano group, alkyl group, aryl group, alkenyl group, alkynyl group, hydroxyl group, carbonyl group, thio group, sulfonyl group, When a sulfinyl group, an oxy group, an amino group, or an onium salt structure is shown and a substituent can be introduced into these groups, it may have a substituent. M represents two hydrogen atoms or metal atoms, a halometal group, and an oxymetal group, and the metal atoms contained therein are IA, IIA, IIIB, IVB group atoms of the periodic table, first, second, second Three-period transition metals and lanthanoid elements can be mentioned, among which copper, magnesium, iron, zinc, cobalt, aluminum, titanium, and vanadium are preferable.

  In the present invention, specific examples of the dye represented by formula (e) that can be suitably used include those exemplified below.

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

  Examples of the pigment include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments In addition, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used. Among these pigments, carbon black is preferable.

  These pigments may be used without surface treatment, or may be used after surface treatment. The surface treatment method includes a method of surface coating with a resin or wax, a method of attaching a surfactant, a method of bonding a reactive substance (eg, silane coupling agent, epoxy compound, polyisocyanate, etc.) to the pigment surface, etc. Can be considered. The above-mentioned surface treatment methods are described in “Characteristics and Applications of Metal Soap” (Yokoshobo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 1986). Yes.

  The particle diameter of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, particularly from the viewpoint of the stability in the coating solution and the uniformity of the photosensitive layer. It is preferably in the range of 0.1 μm to 1 μm.

  As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production, or the like can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. Details are described in "Latest Pigment Applied Technology" (CMC Publishing, 1986).

These infrared absorbers may be added to the same layer as other components, or may be added to another layer. However, from the viewpoint of the strength of the image area, the negative lithographic printing plate precursor Is added so that the absorbance at the maximum absorption wavelength in the wavelength range of 760 nm to 1200 nm of the photosensitive layer is in the range of 0.5 to 1.2 by the reflection measurement method. Preferably, it is the range of 0.6-1.15.
The absorbance of the photosensitive layer can be adjusted by the amount of infrared absorber added to the photosensitive layer and the thickness of the photosensitive layer. The absorbance can be measured by a conventional method. As a measuring method, for example, on a reflective support such as aluminum, a photosensitive layer having a thickness appropriately determined in a range where the coating amount after drying is necessary as a lithographic printing plate is formed, and the reflection density is measured by an optical densitometer. And a method of measuring with a spectrophotometer by a reflection method using an integrating sphere.

  Moreover, these infrared absorbers are 0.01-50 mass% with respect to the total solid which comprises a photosensitive layer from the viewpoint of the uniformity in a photosensitive layer, or the durability of a photosensitive layer, Preferably it is 0.1-0.1%. In the case of 10% by mass, particularly in the case of a dye, 0.5 to 10% by mass, and particularly in the case of a pigment, 0.1 to 10% by mass can be added.

[Polymerization initiator]
As the polymerization initiator used in the present invention for initiating and advancing the curing reaction of the polymerizable compound described later, a thermal decomposition type radical generator that decomposes by heat to generate radicals is useful. Such radical generators are used in combination with the above-mentioned infrared absorbers, and when the infrared laser is irradiated, the infrared absorbers generate heat and generate radicals by the heat. Recording is possible by combining these. It becomes.
Examples of the radical generator include onium salts, triazine compounds having a trihalomethyl group, peroxides, azo polymerization initiators, azide compounds, quinonediazides, oxime ester compounds, triaryl monoalkylborate compounds, etc. Or an oxime ester compound has high sensitivity and is preferable. Below, the onium salt which can be used suitably as a polymerization initiator in this invention is demonstrated. Preferred onium salts include iodonium salts, diazonium salts, and sulfonium salts. In the present invention, these onium salts function not as acid generators but as radical polymerization initiators. The onium salt suitably used in the present invention is an onium salt represented by the following general formulas (III) to (V).

In general formula (III), Ar ¹¹ and Ar ¹² each independently represent an aryl group having 20 or less carbon atoms, which may have a substituent. Preferred substituents when this aryl group has a substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or a carbon atom having 12 or less carbon atoms. An aryloxy group is mentioned. Z ¹¹⁻ represents a counter ion selected from the group consisting of a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, a carboxylate ion, and a sulfonate ion, preferably a perchlorate ion, Hexafluorophosphate ions, carboxylate ions, and aryl sulfonate ions.

In the general formula (IV), Ar ²¹ represents an aryl group having 20 or less carbon atoms which may have a substituent. Preferred examples of the substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an aryloxy group having 12 or less carbon atoms, and 12 or less carbon atoms. Examples thereof include an alkylamino group, a dialkylamino group having 12 or less carbon atoms, an arylamino group having 12 or less carbon atoms, or a diarylamino group having 12 or less carbon atoms. Z ^21- represents a counter ion having the same ^meaning as Z ^11- .

In the general formula (V), R ³¹ , R ³² and R ³³ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferable substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an aryloxy group having 12 or less carbon atoms. Z ^31- represents a counter ion having the same ^meaning as Z ^11- .

  In the present invention, specific examples of onium salts that can be suitably used as a polymerization initiator (radical generator) include those described in JP-A-2001-133696. In the present invention, onium salts represented by general formula (III) ([OI-1] to [OI-10]) and onium salts represented by general formula (IV) ([ON] which can be suitably used in the present invention are shown below. -1] to [ON-5]), and specific examples of the onium salts ([OS-1] to [OS-7]) represented by the general formula (V), are not limited thereto. .

  The polymerization initiator used in the present invention preferably has a maximum absorption wavelength of 400 nm or less, and more preferably 360 nm or less. By making the absorption wavelength in the ultraviolet region in this way, the lithographic printing plate precursor can be handled under white light.

Other preferable polymerization initiators include specific aromatic sulfonium salts described in Japanese Patent Application No. 2000-266797, Japanese Patent Application No. 2001-177150, Japanese Patent Application No. 2000-160323, and Japanese Patent Application No. 2000-184603. The typical compound is illustrated below.
In addition, typical compounds of other preferable polymerization initiators that can be applied to the present invention are exemplified below.

  Moreover, the oxime ester compound which can be used suitably as a polymerization initiator in this invention is demonstrated below. Preferred oxime ester compounds include the following general formula (i).

  In general formula (i), X represents a carbonyl group, a sulfone group, or a sulfoxide group, and Y represents a cyclic or chain alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkynyl group, or an aryl group having 6 to 18 carbon atoms. An aryl group is an aromatic hydrocarbon compound such as a benzene ring, naphthalene ring, anthracene ring, phenanthrene group, pyrene group, triphenylene group, and a heterocyclic ring is a nitrogen atom, sulfur atom, oxygen atom For example, a pyrrole group, a furan group, a thiophene group, a selenophenone group, a pyrazole group, an imidazole group, a triazole group, a tetrazole group, an oxazole group, a thiazole group, an indole group, Benzofuran group, benzimidazole group, benzoxazole group, benzothiazole group, pyridine group, Rimijin group, a pyrazine group, a triazine group, a quinoline group, a carbazole group, an acridine group, a phenoxazine, and a compound such as phenothiazine. These substituents represented by Y are halogen atoms, hydroxyl groups, nitrile groups, nitro groups, carboxyl groups, aldehyde groups, alkyl groups, thiol groups, aryl groups or alkenyl groups, alkynyl groups, ether groups, ester groups, ureas. Group, amino group, amide group, sulfide group, disulfide group, sulfoxide group, sulfo group, sulfone group, hydrazine group, carbonyl group, imino group, halogen atom, hydroxyl group, nitrile group, nitro group, carboxyl group, carbonyl group, urethane It can be substituted by a compound containing a group, an alkyl group, a thiol group, an aryl group, a phosphoroso group, a phospho group, or a carbonyl ether group.

  Z in the general formula (i) is synonymous with Y or is a nitrile group, a halogen atom, a hydrogen atom or an amino group, and these Z compounds are a halogen atom, a hydroxyl group, a nitrile group, a nitro group, a carboxyl group, an aldehyde group. , Alkyl group, thiol group, aryl group or alkenyl group, alkynyl group, ether group, ester group, urea group, amino group, amide group, sulfide group, disulfide group, sulfoxide group, sulfo group, sulfone group, hydrazine group, carbonyl Substitutable with compounds containing groups, imino groups, halogen atoms, hydroxyl groups, nitrile groups, nitro groups, carboxyl groups, carbonyl groups, urethane groups, alkyl groups, thiol groups, aryl groups, phosphoroso groups, phospho groups, carbonyl ether groups It is.

  W in the general formula (i) represents a divalent organic group, and represents a methylene group, a carbonyl group, a sulfoxide group, a sulfone group, or an imino group. The methylene group and imino group are an alkyl group, an aryl group, an ester group, and a nitrile. It can be substituted by a compound containing a group, a carbonyl ether group, a sulfo group, a sulfo ether group, an ether group or the like. n represents an integer of 0 or 1.

V in the general formula (i) is a cyclic or chain alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkynyl group, an aryl group having 6 to 18 carbon atoms, an alkoxy group, or an aryloxy group. Aromatic hydrocarbon compounds such as benzene ring, naphthalene ring, anthracene ring, phenanthrene group, pyrene group, triphenylene group, pyrrole group, furan group, thiophene group, selenophene group, pyrazole group, imidazole group, triazole group, tetrazole group, oxazole Group, thiazole group, indole group, benzofuran group, benzimidazole group, benzoxazole group, benzothiazole group, pyridine group, pyrimidine group, pyrazine group, triazine group, quinoline group, carbazole group, acridine group, phenoxazine, phenothiazine, etc. Heteroatom containing Aromatic compounds and the like. These V compounds are halogen atoms, hydroxyl groups, nitrile groups, nitro groups, carboxyl groups, aldehyde groups, alkyl groups, thiol groups, aryl groups or alkenyl groups, alkynyl groups, ether groups, ester groups, urea groups, amino groups, amides. Group, sulfide group, disulfide group, sulfoxide group, sulfo group, sulfone group, hydrazine group, carbonyl group, imino group, halogen atom, hydroxyl group, nitrile group, nitro group, carboxyl group, carbonyl group, urethane group, alkyl group, thiol It can be substituted by a compound containing a group, an aryl group, a phosphoroso group, a phospho group or a carbonyl ether group.
V and Z may be bonded to each other to form a ring.

As the oxime ester compound represented by the general formula (i), from the viewpoint of sensitivity, X is carbonyl, Y is an aryl group or benzoyl group, Z group is an alkyl group or aryl group, W is a carbonyl group, V Is preferably an aryl group. More preferably, the aryl group of V has a thioether substituent.
Note that the structure of the N—O bond in the general formula (i) may be E-form or Z-form.

  Other oxime ester compounds that can be suitably used in the present invention include Progress in Organic Coatings, 13 (1985) 123-150; C. S Perkin II (1979) 1653-1660; Journal of Photopolymer Science and Technology (1995) 205-232; C. S Perkin II (1979) 156-162; JP-A 2000-66385; JP-A 2000-80068.

  Although the specific example of the oxime ester compound which can be used suitably for this invention is shown below, it is not limited to this.

  These polymerization initiators are 0.1 to 50% by mass, preferably 0.5 to 30% by mass, based on the total solid content constituting the photosensitive layer, from the viewpoint of sensitivity and contamination of non-image areas that occur during printing. Particularly preferably, it can be added at a ratio of 1 to 20% by mass. 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.

[Polymerizable compound]
The addition polymerizable compound having at least one ethylenically unsaturated double bond used in the heat-polymerizable negative photosensitive layer in the invention is a compound having at least one ethylenically unsaturated bond, preferably two or more. Chosen from. 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, that is, dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

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

  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-46-27926, JP-B-51-47334, JP-A-57-196231, JP-A-59-5240, JP-A-59-5241. Those having an aromatic skeleton described in 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-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 vinylurethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following formula (2) to a polyisocyanate compound having two or more isocyanate groups. Etc.

^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH (2)
(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, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, by using 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, 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. Further, 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 can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

  About these addition polymerizable compounds, the details of usage, such as the structure, single use or combination, addition amount, etc. can be arbitrarily set according to the performance design of the final lithographic printing plate precursor. For example, it is selected from the following viewpoints. From the viewpoint of photosensitive speed, a structure having a high 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, styrene compound, vinyl ether). It is also effective to adjust both photosensitivity and strength by using a compound of the type). A compound having a large molecular weight or a compound having high hydrophobicity is excellent in photosensitive speed and film strength, but is not preferable in terms of development speed and precipitation in a developer. In addition, the selection and use method of the addition polymerization compound is also an important factor for the compatibility and dispersibility with other components in the photosensitive layer (for example, binder polymer, initiator, colorant, etc.). 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 the adhesion of the support or the overcoat layer described later. As for the compounding ratio of the addition polymerizable compound in the photosensitive layer, a larger amount is advantageous in terms of sensitivity, but if it is too much, undesirable phase separation occurs or a problem in the production process due to the adhesiveness of the photosensitive layer For example, problems such as transfer of photosensitive layer components and manufacturing defects due to adhesion, and precipitation from the developer may occur. From these viewpoints, the addition polymerizable compound is preferably used in the range of 5 to 80% by mass, and more preferably 25 to 75% by mass with respect to the nonvolatile component in the photosensitive layer. These may be used alone or in combination of two or more. In addition, the use method of the addition polymerizable compound can be arbitrarily selected from the viewpoint of polymerization inhibition with respect to oxygen, resolution, fogging property, refractive index change, surface adhesiveness, etc. Depending on the case, a layer configuration and coating method such as undercoating and overcoating can be performed.

[Other ingredients]
In addition to the above essential components, the photosensitive layer of the lithographic printing plate precursor according to the invention may further contain other components suitable for its use and production method. Hereinafter, preferred additives will be exemplified.

(Polymerization inhibitor)
In the photosensitive layer of the lithographic printing plate precursor according to the present invention, a small amount of heat is used to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated double bond compound during the production or storage of the photosensitive layer. It is desirable to add a polymerization inhibitor. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like. The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the nonvolatile components in the entire composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and it may be unevenly distributed on the surface of the photosensitive layer in the course of drying after coating. . The addition amount of the higher fatty acid derivative is preferably about 0.5% by mass to about 10% by mass with respect to the nonvolatile components in the entire composition.

(Coloring agent)
A dye or a pigment may be added to the photosensitive layer of the lithographic printing plate precursor according to the invention for the purpose of coloring. Thereby, so-called plate inspection properties such as visibility after plate making and suitability for an image density measuring machine as a printing plate can be improved. As the colorant, many dyes cause a decrease in the sensitivity of the photopolymerization type photosensitive layer. Therefore, it is particularly preferable to use a pigment as the colorant. Specific examples include pigments such as phthalocyanine pigments, azo pigments, carbon black and titanium oxide, and dyes such as ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. The addition amount of the dye and the pigment is preferably about 0.5% by mass to about 5% by mass with respect to the nonvolatile components in the whole composition.

(Other additives)
Furthermore, in order to improve the physical properties of the cured film, known additives such as inorganic fillers, other plasticizers, and a sensitizer capable of improving the ink inking property on the surface of the photosensitive layer may be added.
Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, and addition polymerization with binder polymer. Generally, it can be added in a range of 10% by mass or less based on the total mass with the compound.
Further, for the purpose of improving the film strength (printing durability), which will be described later, a UV initiator, a thermal crosslinking agent, or the like can be added to enhance the effect of heating and exposure after development.

Such a photosensitive layer is formed by dissolving a photosensitive layer component in various organic solvents and coating the coating solution on a support or an intermediate layer described later.
Solvents used here include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, lactic acid There are ethyl and the like. These solvents can be used alone or in combination. The solid content in the coating solution is suitably 2 to 50% by mass.

The coating amount of the photosensitive layer mainly affects the sensitivity of the photosensitive layer, the developability, the strength of the exposed film, and the printing durability, and is preferably selected as appropriate according to the application. When the coating amount is too small, the printing durability is not sufficient. On the other hand, if the amount is too large, the sensitivity is lowered, it takes time for exposure, and a longer time is required for development processing, which is not preferable. For the lithographic printing plate precursor for scanning exposure which is the main object of the present invention, the coating amount is suitably in the range of about 0.1 g / m ² to about 10 g / m ² in terms of the mass after drying. More preferably from 0.5 to 5 g / m ^2.

[Physical properties of the photosensitive layer definitive in lithographic printing BanHara plate of the present invention]
Photosensitive layer definitive in the lithographic printing plate precursor of the present invention, the developing speed of unexposed portions in an alkali developing solution pH10~13.5 is 80 nm / sec or more, and the permeation rate of the exposed portions of the alkaline developer 100nF / Sec or less is preferable . Below, the measuring method of the "development speed of the unexposed part with respect to the alkali developing solution" and the "penetration speed of the alkaline developer in the exposed part" in the present invention will be described.

[Measurement of development speed of unexposed area with alkaline developer]
Here, the developing speed of the unexposed portion with respect to the alkaline developer in the photosensitive layer is a value obtained by dividing the film thickness (nm) of the photosensitive layer by the time (sec) required for development.
As a method for measuring the developing speed in the present invention, as shown in FIG. 1, a non-exposed photosensitive layer provided on an aluminum support was fixed at a constant alkaline developer (30 ° C. in the range of pH 10 to 13.5). ) And the dissolution behavior of the photosensitive layer was investigated with a DRM interference wave measuring device. FIG. 1 shows a schematic diagram of a DRM interference wave measuring apparatus for measuring the dissolution behavior of a photosensitive layer. In the present invention, a change in film thickness was detected by interference using light of 640 nm. When the development behavior is non-swelling development from the surface of the photosensitive layer, the film thickness gradually decreases with respect to the development time, and an interference wave corresponding to the thickness can be obtained. Further, in the case of swelling dissolution (film removal dissolution), the film thickness changes due to the penetration of the developer, so that a clean interference wave cannot be obtained.

The measurement is continued under these conditions, and the development speed is expressed by the following equation from the time until the photosensitive layer is completely removed and the film thickness becomes 0 (development completion time) (sec) and the film thickness (nm) of the photosensitive layer. It can ask for. It is determined that the higher the developing speed, the easier the film is removed by the developer and the developability is better.
Development speed (of unexposed area) = [film thickness of photosensitive layer (nm) / recording completion time (sec)]

[Penetration rate of exposed alkaline developer solution]
Further, the permeation speed of the alkaline developer at the exposed portion is a value indicating the change rate of the capacitance (nF) when the photosensitive layer is formed on a conductive support and immersed in the developer. .
As shown in FIG. 2, the method for measuring the capacitance, which is a measure of permeability in the present invention, is as follows. On an aluminum support in a constant alkaline developer (28 ° C.) in the range of pH 10 to 13.5. Exposure is carried out at a predetermined exposure amount, and a hardened photosensitive layer (indicated as a recording layer in FIG. 2) is immersed as one electrode, a conductive wire is connected to an aluminum support, and a normal electrode is connected to the other The method of applying a voltage using it is mentioned. After the voltage is applied, the developer permeates the interface between the support and the photosensitive layer as the immersion time elapses, and the capacitance changes.

From the time (sec) required until this change in capacitance becomes constant and the saturation value (nF) of the capacitance of the photosensitive layer, it can be obtained by the following equation. It is determined that the smaller the permeation rate, the lower the permeability of the developer.
Developer penetration rate (of exposed area) =
[Saturation value of capacitance of photosensitive layer (nF) /
Time required for capacitance change to become constant (sec)]

Preferred physical properties of the photosensitive layer definitive in lithographic printing BanHara plate of the present invention, the developing speed of unexposed portions in an alkali developing solution of pH10~13.5 by the measurement is a 80 to 400 nm / sec, the same alkali The penetration rate of the developer at the exposed portion is more preferably 90 nF / sec or less. Further, the development speed of the unexposed area with respect to the alkaline developer having a pH of 10 to 13.5 by the above measurement is 90 to 200 nm / sec, and the penetration speed of the similar alkaline developer in the exposed area is 80 nF / sec or less. More preferably. The upper limit value of the development speed or the lower limit value of the permeation speed is not particularly limited, but is preferably controlled in consideration of the balance between the two.
Control of the developing speed of the unexposed part of the photosensitive layer and the penetration speed of the alkali developer with respect to the cured photosensitive layer (exposed part of the photosensitive layer) can be performed by a conventional method. Addition of a hydrophilic compound is useful for improving the developing speed of the unexposed area, and means for adding a hydrophobic compound is useful for suppressing penetration of the developer in the exposed area.
By using the specific binder polymer according to the present invention, the development speed of the unexposed part of the photosensitive layer and the penetration speed of the developer in the exposed part can be easily adjusted to the above preferable range. .

[Support]
As the support for the lithographic printing plate precursor according to the invention, a conventionally known hydrophilic support for use in a lithographic printing plate precursor can be used without limitation.
The support used is preferably a dimensionally stable plate, for example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc). , Copper, etc.), plastic films (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), Paper or plastic film, etc. on which such metals are laminated or vapor-deposited are included. Appropriately known physical and chemical treatments are applied to these surfaces for the purpose of imparting hydrophilicity and improving strength as necessary. You may give it.

  In particular, preferred supports include paper, polyester film or aluminum plate, among which dimensional stability is good, relatively inexpensive, and a surface with excellent hydrophilicity and strength is provided by surface treatment as required. An aluminum plate that can be formed is more preferable. A composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in Japanese Patent Publication No. 48-18327 is also preferable.

An aluminum plate is a metal plate mainly composed of dimensionally stable aluminum. In addition to a pure aluminum plate, an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements, or aluminum (alloy) is laminated. Or it is chosen from the vapor-deposited plastic film or paper. In the following description, the above-mentioned support made of aluminum or an aluminum alloy is generically used as an aluminum support. Examples of the foreign element contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content of the foreign element in the alloy is 10% by mass or less. In the present invention, a pure aluminum plate is suitable, but since completely pure aluminum is difficult to manufacture in the refining technique, it may contain a slightly different element. Thus, the composition of the aluminum plate applied to the present invention is not specified, and it is a conventionally known material such as JIS A 1050, JIS A 1100, JIS A 3103, JIS A 3005, etc. Can be used as appropriate.
Moreover, the thickness of the aluminum support body used for this invention is about 0.1 mm-about 0.6 mm. This thickness can be appropriately changed depending on the size of the printing press, the size of the printing plate, and the user's desire. The aluminum support may be subjected to a support surface treatment described later as necessary. Of course, it may not be applied.

(Roughening treatment)
Examples of the surface roughening method include mechanical surface roughening, chemical etching, and electrolytic grain as disclosed in JP-A-56-28893. Furthermore, the electrochemical surface roughening method in which the surface is electrochemically roughened in hydrochloric acid or nitric acid electrolyte solution, the aluminum surface is scratched with a metal wire, the wire brush grain method, the surface of the aluminum is polished with a polishing ball and an abrasive. A mechanical graining method such as a pole grain method, a brush grain method in which the surface is roughened with a nylon brush and an abrasive, can be used, and the above roughening methods can be used alone or in combination. Among them, a method usefully used for roughening is an electrochemical method in which roughening is performed chemically in hydrochloric acid or nitric acid electrolyte, and a suitable amount of electricity at the time of anode is 50 C / dm ^{2 to} 400 C / dm ² . It is a range. More specifically, in the electrolytic solution containing from 0.1 to 50% hydrochloric acid or nitric acid, the temperature 20 to 80 ° C., for 1 second to 30 minutes, alternating at a current density of 100C / dm ² ~400C / dm ² It is preferable to perform direct current electrolysis.

  The aluminum support thus roughened may be chemically etched with acid or alkali. Etching agents suitably used are caustic soda, sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, potassium hydroxide, lithium hydroxide, and the like. Preferred ranges of concentration and temperature are 1 to 50% and 20%, respectively. ~ 100 ° C. Pickling is performed to remove dirt (smut) remaining on the surface after etching. As the acid used, nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, borohydrofluoric acid and the like are used. In particular, as a method for removing smut after the electrochemical surface roughening treatment, contact with 15 to 65 mass% sulfuric acid at a temperature of 50 to 90 ° C. as described in JP-A-53-12739 is preferable. And the alkali etching method described in Japanese Patent Publication No. 48-28123. After the treatment as described above, the method condition is not particularly limited as long as the center line average roughness Ra of the treatment surface is preferably 0.2 to 0.5 μm.

(Anodizing treatment)
The aluminum support treated as described above is preferably anodized after that.
In the anodizing treatment, sulfuric acid, phosphoric acid, oxalic acid, or an aqueous solution of boric acid / sodium borate is used alone or in combination as a main component of the electrolytic bath. In this case, the electrolyte solution may of course contain at least components normally contained in at least an Al alloy plate, an electrode, tap water, groundwater and the like. Further, the second and third components may be added. Here, the second and third components are, for example, metal ions such as Na, K, Mg, Li, Ca, Ti, Al, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn, and ammonium ions. Examples include cations, nitrate ions, carbonate ions, chloride ions, phosphate ions, fluorine ions, sulfite ions, titanate ions, silicate ions, borate ions and the like, and the concentration is 0 to 10,000 ppm. May be included. There are no particular limitations on the conditions of the anodizing treatment, but the treatment is preferably carried out by direct current or alternating current electrolysis at a current density of 0.1 to 40 A / m ² at 30 to 500 g / liter, a treatment liquid temperature of 10 to 70 ° C. . The thickness of the formed anodic oxide film is in the range of 0.5 to 1.5 μm. Preferably it is the range of 0.5-1.0 micrometer. The support prepared by the above treatment is treated so that the pore diameter of the micropores existing in the anodized film is in the range of 5 to 10 nm and the pore density is in the range of 8 × 10 ¹⁵ to 2 × 10 ¹⁶ pieces / m ^2. It is preferred that the conditions are selected.

As the hydrophilization treatment of the support surface, widely known methods can be applied. As a particularly preferable treatment, a hydrophilic treatment with silicate or polyvinylphosphonic acid is performed. A film | membrane is formed by 2-40 mg / m < ² > as Si or P element amount, More preferably, it is 4-30 mg / m < ² >. The coating amount can be measured by fluorescent X-ray analysis.

  The hydrophilization treatment is carried out by applying an anodized film to an aqueous solution containing 1 to 30% by mass, preferably 2 to 15% by mass of alkali metal silicate or polyvinylphosphonic acid, and having a pH of 10 to 13 at 25 ° C. This is carried out by immersing the aluminum support on which is formed, for example, at 15 to 80 ° C. for 0.5 to 120 seconds.

  As the alkali metal silicate used for the hydrophilization treatment, sodium silicate, potassium silicate, lithium silicate, or the like is used. Examples of the hydroxide used for increasing the pH of the aqueous alkali metal silicate solution include sodium hydroxide, potassium hydroxide, and lithium hydroxide. In addition, you may mix | blend alkaline-earth metal salt or Group IVB metal salt with said process liquid. Alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate, and barium nitrate, and water-soluble substances such as sulfate, hydrochloride, phosphate, acetate, oxalate, and borate. Salt. Group IVB metal salts include titanium tetrachloride, titanium trichloride, potassium fluoride titanium, potassium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride, zirconium dioxide, zirconium oxychloride, zirconium tetrachloride, etc. Can be mentioned.

  Alkaline earth metal salts or Group IVB metal salts can be used alone or in combination of two or more. A preferable range of these metal salts is 0.01 to 10% by mass, and a more preferable range is 0.05 to 5.0% by mass. Silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective. A surface obtained by combining a support subjected to electrolytic grain as disclosed in JP-B-46-27481, JP-A-52-58602, and JP-A-52-30503 with the above-described anodizing treatment and hydrophilization treatment. Processing is also useful.

[Middle layer]
The lithographic printing plate precursor according to the invention may be provided with an intermediate layer (also referred to as an undercoat layer) for the purpose of improving the adhesion between the photosensitive layer and the support and the stain resistance. Specific examples of such an intermediate layer include JP-B-50-7481, JP-A-54-72104, JP-A-59-101651, JP-A-60-149491, JP-A-60-232998, JP-A-3-56177, JP-A-4-282737, JP-A-5-16558, JP-A-5-246171, JP-A-7-159983, JP-A-7-314937, JP-A-8-202025, Special Kaihei 8-320551, JP 9-34104, JP 9-236911, JP 9-269593, JP 10-69092, JP 10-115931, JP 10-161317, JP 10-260536, JP-A-10-282682, JP-A-11-84684, Japanese Patent Application No. 8-225335, Japanese Patent Application No. 8-270098, Japanese Patent Application No. 9-195863, Japanese Patent Application No. 9-195864, Japanese Patent Application No. 9-89646, Japanese Patent Application No. 9-106068, Japanese Patent Application No. 9-183834, Japanese Patent Application No. 9-264411, Japanese Patent Application No. 9 -127232, Japanese Patent Application No. 9-245419, Japanese Patent Application No. 10-127602, Japanese Patent Application No. 10-170202, Japanese Patent Application No. 11-36377, Japanese Patent Application No. 11-165661, Japanese Patent Application No. 11-284091 No., Japanese Patent Application No. 2000-14697, and the like.

[Protective layer]
As in the present invention, a lithographic printing plate precursor having a heat-polymerizable negative photosensitive layer is usually exposed in the air. Therefore, a protective layer (also called an overcoat layer) is further formed on the photosensitive layer. .) Is preferably provided. The protective layer prevents exposure of low molecular weight compounds such as oxygen and basic substances present in the atmosphere that hinder the image formation reaction caused by exposure in the photosensitive layer to allow exposure in the atmosphere. To do. Therefore, the properties desired for such a protective layer are low permeability of low-molecular compounds such as oxygen, and further, transmission of light used for exposure is not substantially inhibited, and adhesion to the photosensitive layer is excellent. And it is desirable that it can be easily removed in the development process after exposure. Such a device relating to the protective layer has been conventionally devised and is described in detail in US Pat. No. 3,458,311 and Japanese Patent Publication No. 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, polyvinyl pyrrolidone, acidic celluloses, gelatin, gum arabic, Water-soluble polymers such as acrylic acid are known, but among these, using 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 having a hydrolysis rate of 71 to 100% and a molecular weight in the range of 300 to 2400.
Specifically, Kuraray Co., Ltd. PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HC, PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA- 420, PVA-613, L-8 and the like.

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. However, when the oxygen barrier property is extremely increased, there arises a problem that unnecessary polymerization reaction occurs during production and raw storage, and unnecessary fogging and image line thickening occur during image exposure. 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 adhesive force is likely 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, U.S. Patent Application No. 292,501 and U.S. Patent Application No. 44,563 disclose an acrylic emulsion or a water-insoluble vinylpyrrolidone-vinyl acetate copolymer 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 the like and laminating on the photosensitive layer.
Any of these known techniques can be applied to the protective layer in the present invention. Such a coating method of the protective layer is described in detail in, for example, US Pat. No. 3,458,311 and JP-B-55-49729.

[Plate making]
In order to make the lithographic printing plate precursor according to the present invention, at least exposure and development processes are performed.
As a light source for exposing the negative planographic printing plate precursor of the present invention, a known light source can be used without limitation. The wavelength of a desirable light source is 300 nm to 1200 nm, and specifically, it is preferable to use various lasers as the light source, and among them, an infrared laser having a wavelength of 780 nm to 1200 nm is preferably used.
The exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like.

  In addition, as other exposure beams for the lithographic printing plate precursor according to the present invention, ultrahigh 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, tungsten lamps, sunlight, etc. can also be used.

  The lithographic printing plate precursor according to the invention is developed after being exposed. As the developer used for such development processing, an alkaline aqueous solution having a pH of 14 or less is particularly preferred, and an alkaline aqueous solution having a pH of 8 to 12 containing an anionic surfactant is more preferably used. For example, tribasic sodium phosphate, potassium, ammonium, dibasic sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, ammonium, sodium borate, Examples include inorganic alkali agents such as potassium, ammonium, sodium hydroxide, ammonium, potassium and lithium. Moreover, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine, and pyridine are also used. These alkali agents are used alone or in combination of two or more.

In the development processing of the lithographic printing plate precursor according to the invention, 1 to 20% by mass of an anionic surfactant is added to the developer, and more preferably 3 to 10% by mass. If the amount is too small, the developability deteriorates. If the amount is too large, the strength such as the abrasion resistance of the image deteriorates. Anionic surfactants include, for example, sodium salt of lauryl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate, such as sodium salt of isopropyl naphthalene sulfonic acid, sodium salt of isobutyl naphthalene sulfonic acid, polyoxy Higher carbon number such as sodium salt of ethylene glycol mononaphthyl ether sulfate ester, sodium salt of dodecylbenzene sulfonic acid, alkylaryl sulfonate such as sodium salt of metanitrobenzene sulfonic acid, secondary sodium alkyl sulfate, etc. Aliphatic alcohol phosphates such as alcohol sulfates, sodium salts of cetyl alcohol phosphates, eg C _{17 H 33 CON (CH 3)} CH 2 CH 2 SO 3 sulfonates of alkylamides such as Na, for example, sodium sulfosuccinate dioctyl ester, sulfonate of dibasic aliphatic esters such as sodium sulfosuccinate dihexyl ester Salts are included.

  If necessary, an organic solvent mixed with water such as benzyl alcohol may be added to the developer. As the organic solvent, those having a solubility in water of about 10% by mass or less are suitable, and preferably selected from those having 5% by mass or less. For example, 1-phenylethanol, 2-phenylethanol, 3-phenylpropanol, 1,4-phenylbutanol, 2,2-phenylbutanol, 1,2-phenoxyethanol, 2-benzyloxyethanol, o-methoxybenzyl alcohol, m Examples include -methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 4-methylcyclohexanol, and 3-methylcyclohexanol. The content of the organic solvent is preferably 1 to 5% by mass with respect to the total mass of the developer at the time of use. The amount used is closely related to the amount of surfactant used, and it is preferable to increase the amount of anionic surfactant as the amount of organic solvent increases. This is because if the amount of the organic solvent is large and the amount of the anionic surfactant is small, the organic solvent is not dissolved, and therefore it is impossible to expect good developability.

Furthermore, additives such as an antifoaming agent and a hard water softening agent can be further contained as necessary. Examples of the hard water softener include Na ₂ P ₂ O ₇ , Na ₅ P ₃ O ₃ , Na ₃ P ₃ O ₉ , Na ₂ O ₄ P (NaO ₃ P) PO ₃ Na ₂ , Calgon (sodium polymetaphosphate) Such as polyphosphates, aminopolycarboxylic acids (eg, ethylenediaminetetraacetic acid, its potassium salt, its sodium salt; diethylenetriaminepentaacetic acid, its potassium salt, its sodium salt; triethylenetetraminehexaacetic acid, its potassium salt, its sodium salt Hydroxyethylethylenediaminetriacetic acid, its potassium salt, its sodium salt; nitrilotriacetic acid, its potassium salt, its sodium salt; 1,2-diaminocyclohexanetetraacetic acid, its potassium salt, its sodium salt; 1,3-diamino-2 -Propanol tetraacetic acid, its potassium salt, Sodium salt), other polycarboxylic acids (eg 2-phosphonobutanetricarboxylic acid-1,2,4, potassium salt thereof, sodium salt thereof; 2-phosphonobutanone tricarboxylic acid-2,3,4, Potassium salt, sodium salt thereof, etc., organic phosphonic acids (eg, 1-phosphonoethanetricarboxylic acid-1,2,2, potassium salt, sodium salt thereof; 1-hydroxyethane-1,1-diphosphonic acid, Potassium salt, sodium salt thereof; aminotri (methylenephosphonic acid), potassium salt thereof, sodium salt thereof and the like. The optimum amount of such a hard water softener varies depending on the hardness of the hard water used and the amount used, but is generally 0.01 to 5% by weight, more preferably in the developer at the time of use. It is made to contain in 0.01-0.5 mass%.

  Furthermore, when the lithographic printing plate precursor is developed using an automatic developing machine, the developing solution becomes fatigued according to the processing amount, so that the processing ability is restored by using a replenishing solution or a fresh developing solution. May be. In this case, it is preferable to replenish by the method described in US Pat. No. 4,882,246. Developers described in JP-A-50-26601, 58-54341, JP-B-56-39464, 56-42860, and 57-7427 are also preferable.

  The lithographic printing plate precursor thus developed is subjected to washing water, surface activity as described in JP-A Nos. 54-8002, 55-11545, 59-58431, and the like. It may be post-treated with a rinsing liquid containing an agent, a desensitizing liquid containing gum arabic, starch derivatives, and the like. These treatments can be used in various combinations for the post-treatment of the lithographic printing plate precursor according to the invention.

As the plate-making process of the lithographic printing plate precursor according to the 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 from the viewpoint of occurrence of an undesired curing reaction. Also, very strong conditions can be used for heating after development. Usually, the heating temperature is in the range of 200 to 500 ° C. from the viewpoint of image strengthening action and thermal decomposition of the image area.

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.
Note that the stain on the planographic printing plate subjected to printing can be removed by a plate cleaner. As plate cleaners used for removing stains on the plate during printing, 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 (made by Fuji Photo Film Co., Ltd.), etc. are mentioned.

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

[Synthesis Example 1: Synthesis of Binder Polymer (P-1) of Polymer Type (T-1)]
M-1 (17.1 g) having the following structure, PC-1M (6.1 g) having the following structure, M-3 (4.0) having the following structure, M-4 (2.8 g) having the following structure, and 2, A solution of 2′-azobis (2-methylbutyronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) (0.21 g) in dimethylacetamide (35 g) was added in dimethylacetamide (35 g) at 75 ° C. in a nitrogen stream. Added dropwise over 5 hours. After completion of dropping, the mixture was further stirred at 75 ° C. for 2 hours. After allowing to cool, this solution was poured into vigorously stirred water (2 L) and stirred for 1 hour. The precipitated white solid was filtered off and dried to obtain a binder polymer precursor.
Subsequently, this precursor (21 g), 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (free radical) (0.2 g), and tert-butanol (10 g) Dissolved in dimethylacetamide (120 g), acidified the solution with hydrochloric acid at 0 ° C. and stirred for 30 minutes at 0 ° C. The solution was then poured into vigorously stirred water (2 L) and stirred for 1 hour. The precipitated white solid was filtered off and dried to obtain a polymer polymer (T-1) binder polymer (P-1) shown in Table 1. The binder polymer (P-1) is a polymer outside the range of the specific binder polymer.
When this binder polymer (P-1) was measured by the gel permeation chromatography method, the weight average molecular weight was 121,000 in polystyrene conversion, and the acid value was 0.81 meq / g. Furthermore, the obtained binder polymer (P-1) was identified by NMR and IR spectra.

  Here, the structure of the polymer type (T-1) obtained in Synthesis Example 1 and the structures of the raw material monomers (PC-1M), (M-1), (M-3), and (M-4) are shown below. Shown in

[Synthesis Example 2: Synthesis of Binder Polymer (P-11) of Polymer Type (T-2)]
M-1 (20 g) of the following structure, M-2 (24 g) of the following structure, PC-2M (5.5 g) of the following structure, and dimethyl-2,2′-azobis (2-methylpropionate) ( A solution of Wako Pure Chemical Industries, Ltd. (0.21 g) in dimethylacetamide (58 g) was added dropwise into dimethylacetamide (58 g) at 75 ° C. in a nitrogen stream over 2.5 hours. After completion of dropping, the mixture was further stirred at 75 ° C. for 2 hours. After allowing to cool, this solution was poured into vigorously stirred water (3 L) and stirred for 1 hour. The precipitated white solid was filtered off and dried to obtain a binder polymer precursor.
Subsequently, this precursor (48 g), 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (free radical) (0.15 g), and tert-butanol (17 g). It was dissolved in dimethylacetamide (274 g), and 1,8-diazabicyclo [5.4.0] -7-undecene (62.8 g) was added dropwise at 0 ° C. over 2 hours, followed by stirring at room temperature for 24 hours. The solution was then acidified with hydrochloric acid at 0 ° C. and stirred for 30 minutes at 0 ° C. The solution was then poured into vigorously stirred water (3 L) and stirred for 1 hour. The precipitated white solid was filtered and dried to obtain a polymer polymer (T-2) binder polymer (P-11) shown in Table 1.
When this binder polymer (P-11) was measured by the gel permeation chromatography method, the weight average molecular weight was 101,000 in polystyrene conversion, and the acid value was 0.62 meq / g. Furthermore, the obtained binder polymer (P-11) was identified by NMR and IR spectra.

  Here, the structure of the polymer type (T-2) obtained in Synthesis Example 2 and the structures of the raw material monomers (PC-2M), (M-1), and (M-2) are shown below.

[Synthesis Example 3: Synthesis of Binder Polymer (P-23)]
1-methoxy-2-propanol (300 ml) was placed in a 1000 ml three-necked flask equipped with a condenser and a stirrer and heated to 70 ° C. Under a nitrogen stream, CL-1 (allyl methacrylate) (115 g) having the following structure, PC-2M (30 g) having the following structure, Am-5 (N-isopropylacrylamide) having the following structure (29 g), and V-65 (sum) A 1-methoxy-2-propanol (300 ml) solution of Kogyo Pharmaceutical Co., Ltd. (2.3 g) was added dropwise over 2 hours and a half.
Furthermore, it was made to react at 70 degreeC for 2 hours. Next, the reaction solution was poured into water to precipitate a copolymer. This was collected by filtration, washed and dried to obtain a binder polymer (P-23) shown in Table 2.
As a result of measuring the weight average molecular weight of this binder polymer (P-23) by gel permeation chromatography (GPC) using polystyrene as a standard substance, it was 130,000.

  Here, the structures of the raw material monomers (PC-2M), (CL-1), and (Am-5) used in Synthesis Example 3 are shown below.

In the same manner as in Synthesis Example 1, the raw material monomers were appropriately changed to obtain binder polymers (P-2) to (P- 4 ) shown in Table 1 below (in Table 1, those of polymer type (T-1)) The repeating unit represented by the general formula (I) in the formula corresponds to the repeating unit derived from the raw material monomer PC-1M.). Moreover, it carried out similarly to the synthesis example 2, and changed the raw material monomer suitably, and obtained binder polymer (P- 8)-(P-9) and (P-11)-(P-13) of following Table 1. It was. Further, in the same manner as in Synthesis Example 3, the raw material monomers are appropriately changed, and the binder polymers (P-2 1 ) to (P-22), (P-24) , (P-26) (P-27) and (P-29) to (P-31) were obtained.
Moreover, in Synthesis Example 2, the polymer type (T-2) was replaced with the polymer type (T-3) or (T-4) having the following structure, and the raw material monomer was appropriately changed in the same manner. Binder polymers (P-15) , (P-17) and (P-19) shown in Table 1 below were obtained.
The binder polymers (P- 2) to (P-4) , (P-7) to (P-9), (P-11) to (P-13), and (P-15) used in this example. , (P-17), (P-19), (p-21) to (P-24), (P-26) to (P-27), (P-29) to (P-31) are It is a specific binder polymer in the present invention.

Here, the repeating units (PC- 2) to (P-6), (PC-10), (PC-12) to (PC-14) represented by the general formula (I) described in Table 1 and Table 2 ) Is shown below. PC- 2M to ~ P-6M, PC-10M, PC-12M to PC-14M are replaced with the raw material monomers (methacryloyl) of the units PC-2 to P-6, PC-10, PC-12 to PC-14. Body).

  Moreover, the structure of the raw material monomers (CL-1)-(CL-5) which have the radically polymerizable group of Table 2 is shown below.

  (Am-1) to (Am-3), (Am-5) to (Am-8), (Am-12), (Am-16), and (Am-23) described in Table 2 above. These raw material monomers are those listed as specific examples of the monomer having an amide group represented by the general formula (1).

[Examples 1 to 11 and Comparative Examples 1 to 4]
A lithographic printing plate precursor was prepared according to the following procedure, and printing performance was evaluated. Table 3 shows the types of binder polymer, polymerization initiator and infrared absorber constituting the photosensitive layer, and the evaluation results of the printing performance.

[Create support]
A molten metal of JIS A 1050 alloy containing 99.5% or more of aluminum and Fe 0.30%, Si 0.10%, Ti 0.02% and Cu 0.013% was subjected to cleaning treatment and cast. In the cleaning process, a degassing process was performed to remove unnecessary gases such as hydrogen in the molten metal, and a ceramic tube filter process was performed. The casting method was a DC casting method. The solidified 500 mm thick ingot was chamfered 10 mm from the surface and homogenized at 550 ° C. for 10 hours so as not to coarsen the intermetallic compound.
Next, after hot rolling at 400 ° C. and intermediate annealing at 500 ° C. for 60 seconds in a continuous annealing furnace, cold rolling was performed to obtain an aluminum rolled plate having a plate thickness of 0.30 mm. By controlling the roughness of the rolling roll, the centerline average surface roughness Ra after cold rolling was controlled to 0.2 μm. Then, it applied to the tension leveler in order to improve planarity.

Next, the surface treatment for making a lithographic printing plate support was performed.
First, in order to remove the rolling oil on the surface of the aluminum plate, degreasing treatment was carried out with a 10% sodium aluminate aqueous solution at 50 ° C. for 30 seconds, and neutralization and smut removal treatment were carried out with a 30% sulfuric acid aqueous solution at 50 ° C. for 30 seconds.
Next, in order to improve the adhesion between the support and the photosensitive layer and to provide water retention to the non-image area, a so-called graining treatment was performed to roughen the surface of the support. While maintaining an aqueous solution containing 1% nitric acid and 0.5% aluminum nitrate at 45 ° C. and flowing an aluminum web through the aqueous solution, an alternating waveform with a current density of 20 A / dm ² and a duty ratio of 1: 1 by an indirect power supply cell Then, electrolytic graining was performed by giving an anode side electric quantity of 240 C / dm ² . Thereafter, etching treatment was performed with a 10% sodium aluminate aqueous solution at 50 ° C. for 30 seconds, and neutralization and smut removal treatment were performed with a 30% sulfuric acid aqueous solution at 50 ° C. for 30 seconds.

Furthermore, in order to improve wear resistance, chemical resistance and water retention, an oxide film was formed on the support by anodic oxidation. An anodized film of 2.5 g / m ² by using a 20% sulfuric acid aqueous solution as an electrolyte at 35 ° C. and carrying out an electrolytic treatment with a direct current of 14 A / dm ² by an indirect power feeding cell while carrying an aluminum web into the electrolyte. It was created.
Thereafter, silicate treatment was performed in order to increase the hydrophilicity in the non-image area of the printing plate. In the treatment, a 1.5% aqueous solution of sodium silicate 3 was kept at 70 ° C. so that the contact time of the aluminum web was 15 seconds, and further washed with water. The adhesion amount of Si was 10 mg / m ² .
The Ra (center line surface roughness) of the aluminum support produced as described above was 0.25 μm.

[Coating photosensitive layer]
On such an aluminum support, the following photosensitive layer coating solution was applied with a wire bar, and dried at 125 ° C. for 27 seconds with a hot air dryer to form a photosensitive layer. The coating amount after drying was 1.2 g / m ² .

(Photosensitive layer coating solution)
・ Polymerizable compound (dipentaerythritol hexaacrylate) 2.0 g
・ Binder polymer 2.0g
(Described in Table 3, the specific binder polymer over, and
Comparative binder polymers (P-32) to (P-35) having the following structure)
Infrared absorber (compound described in Table 3) 0.08 g
・ Polymerization initiator (compound described in Table 3) 0.3 g
・ Fluorine nonionic surfactant 0.01g
(Dai Nippon Ink Chemical Co., Ltd., MegaFuck F-176)
・ Victoria Pure Blue Naphthalenesulfonate 0.04g
・ Methyl ethyl ketone 9.0g
・ Propylene glycol monomethyl ether 8.0g
・ Methanol 10.0g

[Exposure of planographic printing plate precursor]
The lithographic printing plate precursor obtained as described above was subjected to the conditions of 9 W output, 210 rpm external drum rotation speed, 100 mJ / cm ² plate surface energy, and 2400 dpi resolution on a Trendsetter 3244VFS manufactured by Creo equipped with a water-cooled 40 W infrared semiconductor laser. Exposed.

[Development / plate making]
After exposure, an automatic processor Stablon 900N manufactured by Fuji Photo Film Co., Ltd. was developed with a developer D-1 having the following composition and a 1: 1 water dilution solution development of FN-6 manufactured by Finisher Fuji Photo Film Co., Ltd. Each was charged and developed / plate-making at 30 ° C. to obtain a lithographic printing plate.

(Developer D-1)
・ 95g of pure water
-5g of a compound having the structure of the following formula (3)
・ KOH 0.06g
・ 0.2g potassium carbonate
-Compound having the structure of the following formula (4) 0.2 g

[Image area printing durability test]
A Lislon manufactured by Komori Corporation was used as a printing machine, and Graph G (N) manufactured by Dainippon Ink Co., Ltd. was used as an ink. The printed matter in the solid image area was observed, and the printing durability of the image area was examined based on the number of images where the image started to fade. The larger the number, the better the image area printing durability. The evaluation results are shown in Table 3.

[Forced dot printing test]
A Lithlon manufactured by Komori Corporation was used as a printing machine, and Graph G (N) manufactured by Dainippon Ink was used as an ink. On the 5,000th sheet from the start of printing, PS plate cleaner CL-2 manufactured by Fuji Photo Film Co., Ltd. was soaked in a printing sponge, the halftone dots were wiped off, and the ink on the printing plate was washed. Thereafter, 10,000 sheets were printed, and the presence or absence of halftone dots in the printed matter was visually observed. The evaluation results are shown in Table 3.

  Here, the structures of infrared absorbers (IR-1) to (IR-3) described in Table 3 and the structures of polymerization initiators (OI-1) to (OI-11) are shown below.

Moreover, the structure of comparative binder polymer (P-32)-(P-35) as described in Table 3 is shown below.
The comparative binder polymer (P-32) is the same as in Synthesis Example 1, and the comparative binder polymers (P-33) to (P-35) are the same as in Synthesis Example 2 as appropriate. It was synthesized by replacing the raw material monomers.

[Examples 12 to 22 , Comparative Examples 5 to 8]
Oite to Example 1, the other of the photosensitive layer was formed, a protective layer as shown below on the photosensitive layer the amount of the polymerizable compound and the binder polymer in the photosensitive layer coating solution as 1.5g together Produced a planographic printing plate precursor in the same manner as in Example 1 . Printing performance was evaluated in the same manner as in Example 1 except that the lithographic printing plate precursors obtained in Examples 12 to 22 and Comparative Examples 5 to 8 were developed using a developer D-2 having the following composition.
Table 4 shows the types of binder polymer, polymerization initiator and infrared absorber constituting the photosensitive layer, and the evaluation results of the printing performance.

[Coating of protective layer]
On the formed photosensitive layer, a 3% by weight aqueous solution of polyvinyl alcohol (saponification degree 98 mol%, polymerization degree 550) was applied so that the dry coating weight was 2 g / m ² and dried at 100 ° C. for 2 minutes. did.

(Developer D-2)
・ Potassium hydroxide 6g
・ Potassium carbonate 2g
・ Sodium sulfite 1g
・ Polyethylene glycol mononaphthel ether 150g
・ Dibutyl naphthalenesulfonic acid sodium salt 50g
・ Hydroxyethanediphosphonic acid potassium salt 4g
・ Silicon TSA-731 (Toshiba Silicone Co., Ltd.) 0.1g
・ Water 786.9g

[Examples 23 to 34 , Comparative Examples 9 to 12]
Oite to Example 1, on an aluminum support, an undercoat layer is provided as shown below, further to the photosensitive layer coating solution, as a binder polymer, described in Table 5, the binder polymer (P-11), (P-15), (P-17), (P-21) to (P-24), (P-26) to (P-27), (P-29) to (P-31), comparison A lithographic printing plate precursor was prepared in the same manner as in Example 1 except that binder polymers (P-34) to (P-37) were used. Printing performance was evaluated in the same manner as in Example 1 except that the lithographic printing plate precursors obtained in Examples 23 to 34 and Comparative Examples 9 to 12 were developed using the developer D-2 having the above composition.
Table 5 shows the evaluation results of the binder polymer, polymerization initiator, and infrared absorber constituting the photosensitive layer, and the printing performance.

[Coating undercoat layer]
On an aluminum support used Oite in Example 1, an undercoat layer coating solution having the following dry coating weight. The coating is 10 mg / m ^2, and dried for 30 seconds at 90 ° C..
(Undercoat layer coating solution)
・ 0.5g 2-aminoethylsulfonic acid
・ Methanol 40g

Here, the structures of the comparative binder polymers (P-36) and (P-37) shown in Table 5 are shown below.
The comparative binder polymers (P-36) and (P-37) were synthesized by appropriately replacing the raw material monomers in the same manner as in Synthesis Example 3 above.

[Examples 35 to 48 , Comparative Examples 13 to 16]
The photosensitive layer coating solution in Example 1, as a binder polymer, described in Table 6, the binder polymer (P-11), (P -15), (P-17), (P-19), (P- 2 1) to (P-24), (P-26) to (P-27), (P-29) to (P-31), comparative binder polymers (P-34) to (P-37) having the above structure A lithographic printing plate precursor was prepared in the same manner as in Example 1 except that a photosensitive layer was formed using the above method and a protective layer was provided on the photosensitive layer in the same manner as in Example 12 . The printing performance of the planographic printing plate precursors obtained in Examples 35 to 48 and Comparative Examples 13 to 16 was evaluated in the same manner as in Example 1 .
Table 6 shows the results of evaluation of the binder polymer, polymerization initiator, infrared absorber, and printing performance constituting the photosensitive layer.

According to the said Tables 3-6, Examples 1-1 provided with the photosensitive layer which consists of a polymeric composition (polymerizable composition of this invention) containing the binder polymer which has a repeating unit represented by general formula (I). The lithographic printing plate precursor No. 48 has a development rate of 80 nm / sec or more in the unexposed portion of the photosensitive layer and a permeation rate of 100 nF / sec or less in the exposed portion of the alkaline developer. Regardless, it was clear that a lithographic printing plate having very good printing durability was obtained. Further, the lithographic printing plate precursors of Examples 1 to 48 have such a photosensitive layer that exhibits the development speed of the unexposed area with respect to the alkaline developer and the penetration speed of the alkaline developer at the exposed area. It is easily assumed that the image forming property is excellent.
On the other hand, the lithographic printing plate precursors in Comparative Examples 1 to 16 do not contain a binder polymer having a repeating unit represented by the general formula (I), and the development rate of the unexposed portion of the photosensitive layer is 80 nm / sec or more, In addition, since it has a photosensitive layer in which the permeation rate at the exposed portion of the alkali developer does not become 100 nF / sec or less, the obtained lithographic printing plate has printing durability compared to the lithographic printing plates of Examples 1 to 48. In particular, halftone dot skipping was observed in the lithographic printing plates of Comparative Examples 1, 4, 5, 9, 10, 13 and 14.

It is a schematic block diagram which shows an example of the DRM interference wave measuring apparatus for measuring the dissolution behavior of a photosensitive layer. It is a schematic block diagram which shows an example of the measuring method of the electrostatic capacitance used in evaluating the permeability to the photosensitive layer of a developing solution.

Claims (4)

Binder polymer having a repeating unit represented by the following general formula (I), infrared absorber (however, a methyl ester group, aryl ester group, benzyl ester bonded to a unit containing a structure having a skeleton having absorption at 700 to 1200 nm And a dye having an ester group selected from the group consisting of a group and an allyl ester group, soluble in an organic solvent and an alkaline aqueous solution, and having absorption at 700 to 1200 nm.) , Polymerization initiator and polymerizability A polymerizable composition comprising a compound.

(In general formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents alkylene, substituted alkylene, arylene, or substituted arylene, or two or more selected from these are linked by an amide bond or an ester bond. And represents a linking group having 2 to 82 atoms and no aliphatic cyclic structure, A represents an oxygen atom or —NR ³ —, and R ³ represents a hydrogen atom or carbon. Represents a monovalent hydrocarbon group of formulas 1 to 10. n represents an integer of 1 to 5.) ^{2. The} binder polymer having a repeating unit represented by the general formula (I), wherein the number of atoms constituting the main skeleton of the linking group represented by R2 is 1-30. The polymerizable composition as described.   A lithographic printing plate precursor comprising a photosensitive layer containing the polymerizable composition according to claim 1 or 2 on a support.   A developing composition comprising the polymerizable composition according to claim 1 or 2 on a support, wherein a developing speed of an unexposed portion with respect to an alkaline developer having a pH of 10 to 13.5 is 80 nm / sec or more, and the alkaline developer A lithographic printing plate precursor comprising a photosensitive layer having a permeation rate of 100 nF / sec or less at an exposed portion of