JP5444831B2 - Planographic printing plate precursor - Google Patents

Abstract

The present invention provides a lithographic printing plate precursor that exhibits an excellent antiscumming performance while exhibiting an excellent printing durability and that can also achieve an excellent on-press developability. The lithographic printing plate precursor is a lithographic printing plate precursor that has an image recording layer on an aluminum support, wherein the image recording layer contains from 0.01 to 10 mass% of a compound represented by the following general formula (I) (in the formula, R 1 represents a C 2-10 organic Substituent and R 2 to R 7 each independently represent a hydrogen atom or a C 1-10 organic Substituent).

Description

  The present invention relates to a lithographic printing plate precursor, and more particularly to a lithographic printing plate precursor containing an image recording layer containing a specific cyclic amide compound. More specifically, the present invention relates to a lithographic printing plate precursor that achieves both high printing durability and antifouling properties.

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

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

Furthermore, in the conventional plate making process of a lithographic printing plate precursor, a step of dissolving and removing an unnecessary image recording layer with a developer or the like is necessary after exposure, but such additional wet processing is unnecessary. Simplification or simplification is also cited as one of the problems. In particular, in recent years, disposal of waste liquid discharged with wet processing has become a major concern for the entire industry due to consideration of the global environment, and the demand for solving the above-mentioned problems has become stronger.
On the other hand, as one simple plate making method, an image recording layer that can remove an unnecessary portion of the image recording layer in a normal printing process is used. A method called on-press development has been proposed in which unnecessary portions are removed to obtain a lithographic printing plate.
As a specific method of on-press development, for example, a method of using a lithographic printing plate precursor having an image recording layer that can be dissolved or dispersed in an fountain solution, an ink solvent, or an emulsion of a fountain solution and an ink. , Method of mechanically removing the image recording layer by contact with rollers or blankets of a printing press, cohesion of the image recording layer or adhesion between the image recording layer and the support by penetration of dampening water, ink solvent, etc. There is a method in which after the force is weakened, the image recording layer is mechanically removed by contact with rollers or a blanket.

  In the present invention, unless otherwise specified, the “development process step” means that a device other than a printing press (usually an automatic developing machine) is used, and a liquid (usually containing an alkaline developer and a surfactant). This refers to the process of removing the image recording layer of the unexposed portion of the lithographic printing plate precursor by contacting the developer and an aqueous solution containing a hydrophilic polymer, and exposing the surface of the hydrophilic support. "The surface of the hydrophilic support is removed by removing the image recording layer of the lithographic printing plate precursor by contacting a liquid (usually printing ink and / or fountain solution) with a printing machine. Refers to methods and processes for exposing

In the above-described simplification, drying, or no processing of the plate-making work, the image recording layer after exposure is not fixed by the development processing, and thus has photosensitivity and may be covered before printing. Therefore, an image recording layer and a light source that can be handled in a bright room or under a yellow light are preferably used.
As such a laser light source, a solid-state laser such as a semiconductor laser and a YAG laser that emits infrared light having a wavelength of 760 to 1200 nm is extremely useful because a high-power and small-sized laser can be obtained at low cost. . A UV laser can also be used.
Various additives for imparting antifouling properties to such a lithographic printing plate precursor have been proposed (see, for example, Patent Document 1). However, it is difficult to achieve both printing durability and antifouling properties. In particular, as described in, for example, Patent Document 2, when using a specific binder and imparting printing durability with UV ink, it is an issue to achieve both printing durability and antifouling properties. Yes.

JP-A-2005-41206 JP 2008-247000 A

  An object of the present invention is to provide a lithographic printing plate precursor that can exhibit good printing durability, can exhibit good antifouling properties, and can achieve good on-press developability.

As a result of studying various image recording layer compositions, the present inventors have found that a lithographic printing plate precursor having an image recording layer containing a specific cyclic amide compound can be stored for a long time under severe conditions. The present inventors have found an unexpected effect that has sufficient printing durability and good anti-staining properties, and also good on-press developability, and has reached the present invention. In particular, it has been found that the above-mentioned effect is obtained when a specific polymer that has high printing durability against UV ink is used in the image recording layer.
Accordingly, the present invention provides a lithographic printing plate precursor having an image recording layer on an aluminum support, the image recording layer containing 0.01 to 10% by mass of a compound represented by the following general formula (I). A lithographic printing plate precursor characterized by the above.

（式中、Ｒ¹は炭素数２〜１０の有機置換基を表し、Ｒ²〜Ｒ⁷はそれぞれ独立に水素原子、又は炭素数１〜１０の有機置換基を表す。）

(In the formula, R ¹ represents an organic substituent having 2 to 10 carbon atoms, and R ^{2 to} R ⁷ each independently represents a hydrogen atom or an organic substituent having 1 to 10 carbon atoms.)

The lithographic printing plate precursor according to the invention may be a negative lithographic printing plate precursor, and the image recording layer may further contain a polymerization initiator and a polymerizable compound. Moreover, a photothermal conversion substance can be contained.
In another embodiment, the lithographic printing plate precursor according to the present invention has an image-exposed portion of the image-recording layer that becomes a non-image portion after development. The image-recording layer is insoluble in water and soluble in an alkaline aqueous solution. A positive planographic printing plate precursor containing a polymer compound can be obtained. As the polymer compound that is insoluble in water and soluble in an alkaline aqueous solution, a novolak resin is preferable, and the image recording layer can contain a photothermal conversion substance.
As an embodiment of the image recording layer in the present invention, there is an embodiment containing a polymer compound containing at least one structure selected from a sulfonamide group, a maleimide group, and a urea structure.
The lithographic printing plate precursor according to the present invention can have an intermediate layer. Therefore, the present invention further includes an intermediate layer and the above-mentioned image recording layer in this order on an aluminum support. It is directed to the original edition.

  According to the lithographic printing plate precursor of the present invention, it is possible to provide a lithographic printing plate that can achieve both good printing durability and antifouling properties. The lithographic printing plate precursor of the present invention also provides a lithographic printing plate capable of achieving good antifouling properties while maintaining good printing durability after plate making even when stored for a long time under severe conditions. it can. The lithographic printing plate precursor according to the invention can exhibit excellent on-press developability, and the on-press developability does not deteriorate even if the lithographic printing plate precursor is stored for a long period of time. The lithographic printing plate precursor according to the invention has high temporal stability.

The lithographic printing plate precursor of the present invention can be used for both negative lithographic printing plate precursors by radical polymerization and positive lithographic printing plate precursors in which the exposed portion becomes a non-image portion after development. The lithographic printing plate precursor of the present invention can also be used for both a lithographic printing plate precursor that has undergone a development treatment step and an on-press development type lithographic printing plate precursor that is directly developed and printed on a printing press.
The lithographic printing plate precursor according to the invention is preferably used for a negative type lithographic printing plate precursor by radical polymerization, and particularly preferably used for a negative on-press development type lithographic printing plate by radical polymerization.

（式中、Ｒ¹は炭素数２〜１０の有機置換基を表し、Ｒ²〜Ｒ⁷はそれぞれ独立に水素原子、又は炭素数１〜１０の有機置換基を表す。）
一般式（Ｉ）において、Ｒ¹は炭素数２〜１０の置換基を表し、窒素原子に置換可能な基であれば任意のものを選択できるが、好ましくは、炭素数２〜１０のアルキル基、炭素数２〜１０のアルケニル基、炭素数２〜１０のアルキニル基又は炭素数６〜１０のアリール基である。 <Compound of general formula (I)>
The content of the compound of the following general formula (I) in the image recording layer of the lithographic printing plate precursor according to the invention is 0.01 to 10% by mass. The content is preferably 0.05 to 7% by mass, more preferably 0.08 to 5% by mass, and particularly preferably 0.10 to 3% by mass.

(In the formula, R ¹ represents an organic substituent having 2 to 10 carbon atoms, and R ^{2 to} R ⁷ each independently represents a hydrogen atom or an organic substituent having 1 to 10 carbon atoms.)
In the general formula (I), R ¹ represents a substituent having 2 to 10 carbon atoms, and any group can be selected as long as it is a group that can be substituted with a nitrogen atom, but preferably an alkyl group having 2 to 10 carbon atoms. , An alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

The alkyl group represented by R ¹ is a linear, branched or cyclic alkyl group having 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 4 carbon atoms. The alkyl group represented by R ¹ may be unsubstituted or may have a substituent.
When the alkyl group represented by R ¹ is unsubstituted, specific examples thereof include an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and an isopropyl group. , Isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and the like.
When R ¹ has a substituent (that is, a substituted alkyl group), the alkyl part of the substituted alkyl group is any one of the above-described hydrogen atoms on the alkyl group having 2 to 10 carbon atoms. A divalent organic residue can be exemplified, and a preferable range of the number of carbon atoms is the same as that of the alkyl group.

Examples of the substituent that can be introduced into the alkyl group represented by R ¹ include monovalent substituents composed of nonmetallic atoms exemplified below. Preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups, arylthio groups, amino groups, N-alkylamino groups, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy 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-arylurei group Group, N, N-diaryl ureido group, N'- alkyl -N- alkylureido group, N'- alkyl -N- arylureido group,

Alkoxycarbonylamino group, aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group Group, N, N-diarylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (referred to as sulfonate group), alkoxysulfonyl group, Aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinaimoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, sulfa Yl group, N- alkylsulfamoyl group, N, N- dialkylsulfamoyl group, N- aryl sulfamoyl group,

  Cyano group, nitro group, aryl group (for example, phenyl group, naphthyl group, tolyl group, mesityl group, cumenyl group, chlorophenyl group, hydroxyphenyl group, methoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylaminophenyl Group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, phenoxycarbonylphenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group, phosphonatophenyl group, etc.) Alkenyl group, alkynyl group, heterocyclic group, silyl group, hydroxyalkoxy group, alkoxyalkoxy group and the like.

  Preferred examples of the substituted alkyl group include methoxymethyl group, methoxycarbonylmethyl group, isopropoxymethyl group, butoxymethyl group, s-butoxybutyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, acetyl group. Oxymethyl, methylthiomethyl, tolylthiomethyl, pyridylmethyl, trimethylsilylmethyl, methoxyethyl, ethylaminoethyl, diethylaminopropyl, morpholinopropyl, acetyloxymethyl, benzoyloxymethyl, N- Cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxyl Propyl group, a methoxycarbonylethyl group, allyloxycarbonyl butyl group, chlorophenoxy carbonyl methyl group,

  Carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl Group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, phosphonobutyl group, diethylphosphonobutyl group, methylphosphonobutyl group, methylphosphonatobutyl group, phosphonooxypropyl group, phospho Examples include natooxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, p-methylbenzyl group and the like.

Examples of the alkenyl group represented by R ¹ include linear, branched or cyclic alkenyl groups having 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and particularly preferably 2 to 4 carbon atoms. The alkenyl group represented by R ¹ may be unsubstituted or may further have a substituent.
When the alkenyl group represented by R ¹ is unsubstituted, specific examples thereof include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl 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, allyl group, 2-butenyl group, 2-methylallyl group, 2-methyl-3-butenyl group , 3-methyl-2-butenyl group and the like.

When the alkenyl group represented by R ¹ has a substituent (that is, when it is a substituted alkenyl group), the alkenyl part of the substituted alkenyl group includes any of the hydrogen atoms on the alkenyl group having 2 to 10 carbon atoms described above. The divalent organic residue can be exemplified by removing one of them, and the preferable range of the number of carbon atoms is the same as that of the alkenyl group.
Examples of the substituent that can be introduced into the alkenyl group represented by R ¹ include the substituents described in the above description of the substituted alkyl group.

Examples of the alkynyl group represented by R ¹ include linear, branched or cyclic alkynyl groups having 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and particularly preferably 2 to 4 carbon atoms. The alkynyl group represented by R ¹ may be unsubstituted or may further have a substituent.
When the alkynyl group represented by R ¹ is unsubstituted, specific examples thereof include a 2-propynyl group, a 2-butynyl group, and a 3-butynyl group.
When the alkynyl group represented by R ¹ has a substituent (that is, when it is a substituted alkynyl group), the alkynyl part of the substituted alkynyl group includes any of the hydrogen atoms on the alkynyl group having 2 to 10 carbon atoms described above. The divalent organic residue can be exemplified by removing one of them, and the preferable range of the number of carbon atoms is the same as that of the alkynyl group.
Examples of the substituent that can be introduced into the alkynyl group represented by R ¹ include the substituents described in the description of the substituted alkyl group.

The aryl group represented by R ¹ is an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, preferably 6 to 9 carbon atoms, and particularly preferably 6 to 8 carbon atoms. Examples of such aryl groups include phenyl, methylphenyl, methoxyphenyl, dimethylphenyl, chlorophenyl and the like.
When the aryl group represented by R ¹ has a substituent (that is, when it is a substituted aryl group), the aryl part of the substituted aryl group includes any of the above-described hydrogen atoms on the aryl group having 6 to 10 carbon atoms. The divalent organic residue can be exemplified by removing one of these, and the preferable range of the number of carbon atoms is the same as that of the aryl group.
Examples of the substituent that can be introduced into the aryl group represented by R ¹ include the substituents described in the above description of the substituted alkyl group. Further, a benzene ring or a hetero ring may be further condensed to the benzene ring to form a condensed ring. Specific examples include a phenyl group and a naphthyl group.

R ¹ is preferably an alkyl group, and more specifically, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like are preferable, and an ethyl group, a propyl group, and a butyl group are particularly preferable. .

R ^{2 to} R ⁷ each independently represents a hydrogen atom or an organic substituent having 1 to 10 carbon atoms. When R ^{2 to} R ⁷ represent a substituent, any group can be selected as long as the group can be substituted on a carbon atom.
Examples of the organic substituent represented by R ^{2 to} R ⁷ include alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 1 to 10 carbon atoms, alkynyl groups having 1 to 10 carbon atoms, and 6 to 10 carbon atoms. Aryl group, C1-C10 heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diaryl Amino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group Group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, Raid group, N-alkylureido group, N, N-dialkylureido group, N-arylureido group, N, N-diarylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-aryl Ureido group,

Alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N , N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N -Alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, sulfamoyl group, N-a Kill sulfamoyl group, N, N- dialkylsulfamoyl group, N- aryl sulfamoyl group, N, N- diaryl sulfamoyl group, N- alkyl -N- arylsulfamoyl group, and the like.
R ^{2 to} R ⁷ may be bonded to each other to form a ring.

R ^{2 to} R ⁷ are preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom or a carbon atom. A C 1-4 alkyl group (for example, methyl group, ethyl group, propyl group, butyl group, etc.).

In the general formula (I), a particularly preferable combination of R ¹ and R ^{2 to} R ⁷ is when R ¹ is an ethyl group, a propyl group, or a butyl group, and R ^{2 to} R ⁷ are all hydrogen atoms. is there.
Most preferably, R ¹ is an ethyl group and R ^{2 to} R ⁷ are all hydrogen atoms. Although the preferable example of a compound represented by general formula (I) below is shown, this invention is not limited to these.

（n)は分岐していない直鎖状の基を意味する。

(N) means an unbranched linear group.

  The content of the compound of the above general formula (I) in the image recording layer is determined by extracting a predetermined area of the prepared lithographic printing plate precursor with an appropriate solvent, for example with methanol, and using the extract as a sample for gas chromatography. Measured by performing the method, the content in a predetermined area is obtained. This is divided by the weight of the image recording layer of a predetermined area to determine the content (%). The content of the compound of the general formula (I) in the image recording layer can be adjusted by adjusting the amount of the compound in the image recording layer coating solution and the drying time of the coating solution.

Hereinafter, other components in the image recording layer of the present invention will be described in detail.
<Image recording layer of radically polymerizable negative lithographic printing plate precursor>
A photopolymerizable photosensitive composition (hereinafter referred to as “photopolymerizable composition”) used as an image recording layer of a negative lithographic printing plate precursor by radical polymerization is a polymerizable compound, specifically, addition polymerization is possible. It contains an ethylenically unsaturated bond-containing compound (hereinafter simply referred to as “ethylenically unsaturated bond-containing compound”) and a polymerization initiator as essential components, and if necessary, a polymer compound as a binder, a colorant, Contains various compounds such as plasticizers and thermal polymerization inhibitors.
[Compound containing ethylenically unsaturated bond]
The ethylenically unsaturated bond-containing compound contained in the photopolymerizable composition is such that, when the photopolymerizable composition is irradiated with actinic rays, it undergoes addition polymerization by the action of the photopolymerization initiator, crosslinks and cures. It is a compound having an ethylenically unsaturated bond. The ethylenically unsaturated bond-containing compound can be arbitrarily selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more, such as monomers, prepolymers (ie, dimers). Trimers and oligomers), mixtures thereof, and copolymers thereof. Examples of monomers include ester-based radical polymerizable compounds of unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid) and aliphatic polyhydric alcohol compounds, unsaturated carboxylic acids. Examples thereof include amide radical polymerizable compounds of an acid and an aliphatic polyvalent amine compound. A urethane radical polymerizable compound is also suitable.

[Polymerization initiator]
As the polymerization initiator contained in the photopolymerizable composition, various polymerization initiators or a combination system (photoinitiation system) of two or more polymerization initiators may be appropriately selected and used depending on the wavelength of the light source used. For example, an initiation system shown in JP-A-2001-22079 [0021] to [0023] is preferable. Further, onium salts can be preferably used, and preferable specific examples include those described in paragraph numbers [0030] to [0033] of JP-A No. 2001-133969.
[Other ingredients]
The polymer compound contained in the photopolymerizable composition not only functions as a film-forming agent for the photopolymerizable composition but also needs to dissolve the photosensitive layer in an alkali developer, so that it is soluble or swelled in alkaline water. What is sex is used. As the polymer compound, those shown in the publications [0036] to [0063] are useful. In particular, a polymer compound containing an ethylenically unsaturated bond in the side chain is preferable.
In addition, it is also preferable to add the additive (for example, surfactant for improving applicability | paintability) shown by the same gazette [0079]-[0088] to a photopolymerizable composition.
[Other layers]
Further, it is preferable to provide an oxygen-blocking protective layer on the photosensitive layer in order to prevent the oxygen polymerization inhibiting action. Examples of the polymer contained in the oxygen barrier protective layer include polyvinyl alcohol or a copolymer thereof. Further, it is preferable to provide an intermediate layer or an adhesive layer as disclosed in JP-A-2001-228608 [0124] to [0165] as the lower layer of the photopolymer type photosensitive layer.

<Radically polymerizable image recording layer sensitive to infrared laser>
A polymerizable negative image recording layer sensitive to an infrared laser comprises: (A) a photothermal conversion substance, (B) a polymerization initiator, (C) an ethylenically unsaturated bond-containing compound, and (D) a polymer compound as a binder if necessary. Containing.
The infrared rays absorbed by the infrared absorbent, which is a photothermal conversion substance, are converted into heat, and the generated heat decomposes a polymerization initiator such as an onium salt to generate radicals. The ethylenically unsaturated bond-containing compound is selected from compounds having a terminal ethylenically unsaturated bond, and a polymerization reaction is caused in a chain by the generated radicals to be cured.
(A) As an infrared absorber which is a photothermal conversion substance, for example, a photothermal conversion substance described later contained in the above-described thermal positive type heat-sensitive layer can be mentioned. Examples thereof include those described in paragraph Nos. [0017] to [0019] of JP-A-133969.
For (B) a polymerization initiator, (C) an ethylenically unsaturated bond-containing compound, and if necessary, (D) a polymer compound as a binder, those described in detail in the publications [0036] to [0060] are used. it can. As other additives, it is also preferable to add an additive (for example, a surfactant for improving coating properties) shown in the publications [0061] to [0068].

<Radically polymerizable image recording layer for on-press development>
In the radically polymerizable image recording layer that is sensitive to the infrared laser, there is an image recording layer that is developed on a printing machine with dampening water and ink. In the polymerizable image recording layer of this system, it is necessary to use a specific (C) polymerizable compound, (D) a polymer compound as a binder, and, if necessary, a hydrophobized precursor.

[Polymerizable compound]
Modified with isocyanuric acid ethylene oxide such as tris (acryloyloxyethyl) isocyanurate and bis (acryloyloxyethyl) hydroxyethyl isocyanurate because of its excellent balance of hydrophilicity involved in on-press development and polymerization ability involved in printing durability Acrylates are particularly preferred.
The radical polymerizable compound is preferably used in the range of 5 to 80% by mass, more preferably 25 to 75% by mass, based on the total solid content of the image recording layer.

[Polymer compound as binder]
The polymer compound as the binder preferably has a hydrophilic group. The hydrophilic group contributes to imparting on-press developability to the image recording layer. In particular, the coexistence of the crosslinkable group and the hydrophilic group makes it possible to achieve both printing durability and developability.
As the hydrophilic group, for example, an alkylene oxide structure having 1 to 100 alkylene oxide units having 2 or 3 carbon atoms is preferable. An alkylene oxide structure having 2 to 12 is particularly preferable, and an alkylene oxide structure having 2 to 8 is most preferable. In order to impart a hydrophilic group to the binder polymer, a monomer having a hydrophilic group may be copolymerized.
Among them, suitable polymer compounds include a crosslinkable functional group for improving the film strength of the image area as described in JP-A-2008-195018 in the main chain or side chain, preferably in the side chain. What you are doing. Crosslinking is formed between the polymer molecules by the crosslinkable group, and curing is accelerated.

The crosslinkable functional group is preferably an ethylenically unsaturated group such as a (meth) acryl group, a vinyl group or an allyl group, or an epoxy group, and these groups can be introduced into the polymer by polymer reaction or copolymerization. . For example, a reaction between an acrylic polymer or polyurethane having a carboxy group in the side chain and polyurethane and glycidyl methacrylate, or a reaction between a polymer having an epoxy group and an ethylenically unsaturated group-containing carboxylic acid such as methacrylic acid can be used.
The content of the crosslinkable group in the binder polymer is preferably 0.1 to 10.0 mmol, more preferably 1.0 to 7.0 mmol, and most preferably 2.0 to 5.5 mmol per 1 g of the binder polymer. .
In particular, the binder polymer is preferably a polymer having film properties, and is preferably an acrylic resin, a polyvinyl acetal resin, or a polyurethane resin.
In addition, it is preferable that mass average molar mass (Mw) is 2000 or more, as for a binder polymer, it is more preferable that it is 5000 or more, and it is more preferable that it is 10,000-300,000.

The content of the binder polymer is 5 to 90% by mass, preferably 5 to 80% by mass, and more preferably 10 to 70% by mass with respect to the total solid content of the image recording layer. Within this range, good image area strength and image formability can be obtained.
Moreover, it is preferable to use (C) a polymeric compound and (D) binder polymer in the quantity used as 0.4 / 1-1.8 / 1 by mass ratio. More preferably, it is 0.7 / 1 to 1.5 / 1. Within this range, the effect of improving the on-press developability or gum developability is remarkably exhibited while maintaining the printing durability, which is the effect of the present invention.

[Hydrophobic precursor]
In order to improve the on-press developability, a hydrophobized precursor can be used in the image recording layer. The hydrophobized precursor means fine particles capable of converting the image recording layer to hydrophobic when heat is applied. The fine particles are preferably at least one particle selected from hydrophobic thermoplastic polymer fine particles, heat-reactive polymer fine particles, microcapsules enclosing a hydrophobic compound, and microgel (crosslinked polymer fine particles). Among these, polymer fine particles and microgels having a polymerizable group are preferable.

Hydrophobic thermoplastic polymer fine particles include Research Disclosure No. 1 of January 1992. 33303, hydrophobic thermoplastic polymer fine particles described in JP-A-9-123387, JP-A-9-131850, JP-A-9-171249, JP-A-9-171250 and European Patent No. 931647 are suitable. Can be cited as
Specific examples of polymers constituting such polymer fine particles include ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, vinyl carbazole, and polyalkylene structures. Mention may be made of homopolymers or copolymers of monomers such as acrylates or methacrylates or mixtures thereof. Among them, more preferred are polystyrene and polymethyl methacrylate.

The average particle diameter of the hydrophobic thermoplastic polymer fine particles is preferably 0.01 to 2.0 μm.
Examples of the heat-reactive polymer fine particles include polymer fine particles having a heat-reactive group, and these form a hydrophobized region by crosslinking due to a heat reaction and a functional group change at that time.
The heat-reactive group in the polymer fine particle having a heat-reactive group may be any functional group that performs a reaction as long as a chemical bond is formed, but an ethylenically unsaturated group that performs a radical polymerization reaction (for example, Acryloyl group, methacryloyl group, vinyl group, allyl group, etc.), cationic polymerizable group (for example, vinyl group, vinyloxy group, etc.), isocyanate group that performs addition reaction or its block, epoxy group, vinyloxy group, and these reactions Functional group having an active hydrogen atom as a partner (for example, amino group, hydroxy group, carboxy group, etc.), carboxy group for performing a condensation reaction, hydroxy group or amino group as a reaction partner, an acid anhydride for performing a ring-opening addition reaction In addition, an amino group or a hydroxy group which is a reaction partner can be preferably mentioned.

As the microcapsule, for example, as described in JP-A Nos. 2001-277740 and 2001-277742, all or a part of the constituent components of the image recording layer are encapsulated in the microcapsule. The constituent components of the image recording layer can also be contained outside the microcapsules. Furthermore, the image recording layer containing microcapsules is preferably a mode in which hydrophobic constituent components are encapsulated in microcapsules and hydrophilic constituent components are contained outside the microcapsules.
The aspect containing a crosslinked resin particle, ie, a microgel, may be sufficient. This microgel can contain a part of the constituents of the image recording layer in and / or on the surface thereof. In particular, the microgel is a reactive microgel having (C) a radical polymerizable compound on the surface thereof. Is particularly preferable from the viewpoint of image formation sensitivity and printing durability.
As a method for microencapsulating or microgelling the constituent components of the image recording layer, known methods can be applied.
The average particle size of the microcapsules or microgel is preferably 0.01 to 3.0 μm. 0.05-2.0 micrometers is further more preferable, and 0.10-1.0 micrometer is especially preferable. Within this range, good resolution and stability over time can be obtained.
The content of the hydrophobizing precursor is preferably in the range of 5 to 90% by mass in terms of the solid content concentration of the image recording layer.

  Other components include a sensitizer, a combination of a development accelerator other than the present invention, a surfactant, a colorant, a bake-out agent, a polymerization inhibitor, a higher fatty acid derivative, a plasticizer, inorganic fine particles, an inorganic layered compound, and the like. Can be added. Specifically, compounds and addition amounts described in paragraph numbers [0114] to [0159] of JP-A-2008-284817 are preferable.

<Positive image recording layer>
The positive type image recording layer is an image recording layer in which an image exposed portion is developed, and contains an alkali-soluble polymer compound and a photothermal conversion substance.
[Alkali-soluble polymer compound]
The alkali-soluble polymer compound includes a homopolymer containing an acidic group in the polymer, a copolymer thereof, and a mixture thereof, and particularly preferably has a phenolic hydroxy group (—Ar—OH). And novolak resin. Specifically, for example, phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p- and m- / p-mixed). Any may be used) Novolak resins such as mixed formaldehyde resins; pyrogallol acetone resins are preferred. More specifically, the polymers shown in [0023] to [0042] of JP-A No. 2001-305722 are preferably used.
In the present invention, the image recording layer preferably has 50% by mass or more of novolak resin.

[Photothermal conversion material]
The photothermal conversion substance converts exposure energy into heat and can efficiently cancel the interaction of the exposed area of the heat sensitive layer. From the viewpoint of recording sensitivity, a pigment or dye having a light absorption region in the infrared region with a wavelength of 700 to 1200 nm is preferable. As a dye. Specifically, 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 (for example, A dye such as a nickel thiolate complex) can be used. Among these, cyanine dyes are preferable, and examples thereof include cyanine dyes represented by general formula (I) in JP-A No. 2001-305722. In the thermal positive type composition, it is preferable to add a compound such as a sensitivity adjusting agent, a baking agent, a dye, etc., and a surfactant for improving the coating property, similar to those described for the conventional positive type. Specifically, the compounds shown in [0053] to [0059] of JP-A No. 2001-305722 are preferable.

The thermal positive type heat-sensitive layer may be a single layer or a two-layer structure as described in JP-A-11-218914.
An undercoat layer is preferably provided between the thermal positive type heat-sensitive layer and the support. Examples of the component contained in the undercoat layer include various organic compounds described in JP-A-2001-305722, [0068].
A thermal positive type heat-sensitive lithographic printing plate precursor provided with a heat-sensitive composition containing these alkali-soluble polymer compound and a photothermal conversion substance on a support is imagewise exposed using an infrared laser, and then an alkaline developer. Developed with Examples of the developer include Japanese Patent Publication No. 57-7427, Japanese Patent No. 3086354, Japanese Patent Application Laid-Open No. 11-216962, Japanese Patent Application Laid-Open No. 2001-51406, Japanese Patent Application Laid-Open No. 2001-174981, and Japanese Patent Application Laid-Open No. 2002-72501. As a preferred example, a developing solution described in Japanese Patent Publication No. JP-A No. 2004-259561 can be given.

<Polymer compound having specific structural group>
The image recording layer containing the compound represented by the general formula (I) according to the present invention, in particular, when a polymer compound containing at least one structure selected from a sulfonamide group, a maleimide group and a urea structure is used. In particular, printing durability and stain resistance when UV ink is used can be satisfactorily achieved.
That is, specific structural groups such as sulfonamide groups, maleimide groups, and urea structures are generally considered to have high cohesiveness and high film properties and high printing durability. On the other hand, the developability deteriorates due to the high cohesiveness. By adding the compound of the above general formula (I) to such a binder, the above-mentioned compound having hydrogen bonding properties is present between the polymers, the developability is improved, and the antifouling property is enhanced. Furthermore, the compound represented by the general formula (I) hardly participates in the decrease in printing durability, and causes very little deterioration in printing durability particularly in UV ink.
As the polymer compound having a specific structural group that can be used in the image recording layer in the present invention, for example, a resin having the following groups (1) to (3) in the main chain and / or side chain of the polymer is suitable. It is mentioned in.

(1) Sulfonamide group (—SO ₂ NH—R)
(2) Maleimide group (3) Urea structure (-NR-C (= O) -NR-)
In said (1)-(3), R represents the hydrocarbon group which may have a hydrogen atom or a substituent.
Among the polymers selected from the above (1) to (3), (1) a sulfonamide group is most preferable from the viewpoint of sufficiently securing the film strength.

(1) As an alkali-soluble resin having a sulfonamide group, for example, a polymer composed of a minimum constituent unit derived from a compound having a sulfonamide group as a main constituent can be mentioned.
Examples of the compound as described above include compounds having at least one sulfonamide group in which at least one hydrogen atom is bonded to a nitrogen atom and one or more polymerizable unsaturated groups in the molecule. Among them, a low molecular compound having an acryloyl group, an allyl group, or a vinyloxy group and a substituted or monosubstituted aminosulfonyl group or a substituted sulfonylimino group in the molecule is preferable. For example, the following general formula (i) to general formula ( and a compound represented by v).

In the general formulas (i) to (v), X ¹ and X ² each independently represent —O— or —NR ⁷ . R ¹ and R ⁴ each independently represents a hydrogen atom or —CH ₃ . R ² , R ⁵ , R ⁹ , R ¹² , and R ¹⁶ each independently represent an optionally substituted alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, an arylene group, or an aralkylene group. . R ³ , R ⁷ and R ¹³ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. R ⁶ and R ¹⁷ each independently represents a C 1-12 alkyl group, cycloalkyl group, aryl group or aralkyl group which may have a substituent. R ⁸ , R ¹⁰ and R ¹⁴ each independently represent a hydrogen atom or —CH ₃ . R ¹¹ and R ¹⁵ each independently represent a C 1-12 alkylene group, cycloalkylene group, arylene group or aralkylene group which may have a single bond or a substituent. Y ¹ and Y ² each independently represent a single bond or CO.

  Among the compounds represented by the general formula (i) to the general formula (v), examples of the alkali-soluble resin that can be used in the present invention include m-aminosulfonylphenyl methacrylate and N- (p-aminosulfonylphenyl) methacrylamide. N- (p-aminosulfonylphenyl) acrylamide and the like can be preferably used.

(2) As a polymer which has a maleimide group, the polymer comprised by using as a main structural component the minimum structural unit derived from the compound which has a maleimide group can be mentioned, for example. Examples of such compounds include compounds each having one or more maleimide groups represented by the following structural formula in the molecule.

一般式（１）において、Ｒ₁は任意の置換基を表す。Ｒ₁は、好ましくは、水素；非置換若しくは任意に置換された（Ｃ₆−Ｃ₁₂）アリール；非置換若しくは任意に置換された（Ｃ₁−Ｃ₁₂）アルキル；非置換若しくは任意に置換された（Ｃ₃−Ｃ₁₀）シクロアルキル；非置換若しくは任意に置換されたアリールスルホンアミド基；または非置換若しくは任意に置換されたスルホンアミド基である。前記各基における任意の置換基としては、ハロゲン、アルキル、−ＮＯ₂及び−ＯＨから選択される一つ以上の置換基が好ましい。特に好ましくは、Ｒ₁は、水素、フェニル、シクロヘキシル、またはヒドロキシフェニルである。
また、一般式（１）において、Ｒ₂、Ｒ₃も同様に、任意の置換基を表すが、好ましくは、Ｒ₂及びＲ₃は、独立に、水素、ハロゲン、（Ｃ₁−Ｃ₄）アルキル、及びフェニルからなる群より選択される。特に好ましくは、Ｒ₂及びＲ₃は、両者とも水素である。

In the general formula (1), R ₁ represents an arbitrary substituent. R ₁ is preferably hydrogen; unsubstituted or optionally substituted (C ₆ -C ₁₂ ) aryl; unsubstituted or optionally substituted (C ₁ -C ₁₂ ) alkyl; unsubstituted or optionally substituted (C ₃ -C ₁₀ ) cycloalkyl; an unsubstituted or optionally substituted arylsulfonamido group; or an unsubstituted or optionally substituted sulfonamido group. The optional substituent in each group is preferably one or more substituents selected from halogen, alkyl, —NO ₂ and —OH. Particularly preferably R ₁ is hydrogen, phenyl, cyclohexyl or hydroxyphenyl.
In the general formula (1), R ₂ and R ₃ also represent an arbitrary substituent. Preferably, R ₂ and R ₃ are independently hydrogen, halogen, (C ₁ -C ₄ ) Selected from the group consisting of alkyl and phenyl. Particularly preferably, R ₂ and R ₃ are both hydrogen.

式中、Ｒ¹及びＲ²はそれぞれ水素原子、ハロゲン原子、アルキル基、アリール基、又はカルボキシル基、もしくはその塩を表し、Ｒ³は水素原子、ハロゲン原子、アルキル基またはアリール基を表し、Ｘは２価の連結基を表し、Ｙは置換基を有してもよい２価の芳香族基を表す。 (3) Examples of the polymer having a urea structure include polymers having the following structure as a repeating unit.

In the formula, R ¹ and R ² each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a carboxyl group, or a salt thereof; R ³ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group; Represents a divalent linking group, and Y represents a divalent aromatic group which may have a substituent.

As a specific example, it has a repeating unit derived from the following monomers.
1- (N ′-(4-hydroxyphenyl) ureido) methyl acrylate, 1- (N ′-(3-hydroxyphenyl) ureido) methyl acrylate, 1- (N ′-(2-hydroxyphenyl) ureido) methyl acrylate 2- (N ′-(4-hydroxyphenyl) ureido) ethyl acrylate, 4- (N ′-(4-hydroxyphenyl) ureido) butyl acrylate, 1- (N ′-(4-hydroxyphenyl) ureido) methyl Methacrylate, 1- (N ′-(3-hydroxyphenyl) ureido) methyl methacrylate, 1- (N ′-(2-hydroxyphenyl) ureido) methyl methacrylate, 2- (N ′-(4-hydroxyphenyl) ureido) Ethyl methacrylate, 4- (N ′-(4-hydroxyphenyl) ureido) butyl methacrylate Relate, 4- (N ′-(3-hydroxyphenyl) ureido) butyl methacrylate, 4- (N ′-(2-hydroxyphenyl) ureido) butyl methacrylate, 4- (N ′-(3-hydroxy-4-methyl) Phenyl) ureido) butyl methacrylate, 4- (N ′-(2-hydroxy-5-methylphenyl) ureido) butyl methacrylate, 4- (N ′-(5-hydroxynaphthyl) ureido) butyl methacrylate, 2- (N ′) -(4-sulfamoylphenyl) ureido) ethyl acrylate, 2- (N '-(4-sulfamoylphenyl) ureido) ethyl methacrylate, 2- (N'-(2-hydroxy-5-sulfamoylphenyl) And methacrylate derivatives such as ureido) ethyl methacrylate.

The minimum structural unit having a group selected from the above (1) to (3) is not particularly limited to one kind, and the minimum structural unit having two or more minimum structural units having the same group or different groups. What copolymerized 2 or more types can also be used.
The polymer compound preferably contains 10 mol% or more of repeating units having the specific structural group as described above, and more preferably contains 20 mol% or more. If it is less than 10 mol%, the printing durability in UV ink tends not to be sufficiently improved.

The monomer which brings about the repeating unit which has said specific structural group can be copolymerized with the monomer raised to the following (m1)-(m12), for example.
(M1) Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate.
(M2) Alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, and glycidyl acrylate.
(M3) Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, and glycidyl methacrylate.
(M4) Acrylamide, methacrylamide, N-methylol acrylamide, N-ethyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N-phenyl acrylamide, N-nitrophenyl acrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide.
(M5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.

(M6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(M7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene.
(M8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(M9) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene.
(M10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(M11) Unsaturated imides such as N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(M12) Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride and itaconic acid.

When developing with dampening water and ink on a printing press, that is, when developing on press, 1 to 100 alkylene oxide units having 2 or 3 carbon atoms as a hydrophilic group in a polymer binder having a specific structural group The acrylate or methacrylate having an alkylene oxide structure is preferably copolymerized. Such an alkylene oxide structure is particularly preferably an alkylene oxide structure having 2 to 12, and most preferably an alkylene oxide structure having 2 to 8. In order to impart a hydrophilic group to the polymer binder, a monomer having a hydrophilic group may be copolymerized.
Specific examples of the polymer binder having a specific structural group include the following structures.

As the repeating unit of the above polymer, a polymerizable monomer having a sulfonamide group, such as m-aminosulfonylphenyl methacrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) acrylamide, etc. Homopolymers or copolymers are preferred.
The polymer binder preferably has a weight average molecular weight of 2,000 or more and a number average molecular weight of 500 or more. More preferably, the weight average molecular weight is 5,000 to 300,000, the number average molecular weight is 800 to 250,000, and the dispersity (weight average molecular weight / number average molecular weight) is 1.1 to 10. .

  The addition amount of the binder polymer in the image recording layer is suitably 10 to 80% by mass, preferably 20 to 70% by mass, particularly preferably 25 to 60% by mass in the total solid content of the image recording layer.

<Formation of image recording layer>
The image recording layer in the present invention includes, for example, a compound represented by the general formula (I) of the present invention as described in paragraphs [0142] to [0143] of JP-A-2008-195018, and a necessary component. In accordance with the above, each of the above components is dispersed or dissolved in a known solvent to prepare a coating solution, which is applied by a known method such as bar coater coating on a support on which an intermediate layer may be coated and dried. It is formed.
The image recording layer coating solution in the present invention preferably contains an organic solvent having a boiling point at 1 atm of 50 ° C. to 130 ° C. from the viewpoints of handleability, coating suitability, and drying properties. Preferred examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, 1-propanol, 2-propanol, butanol, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 1-methoxy-2-propanol, 1-methoxy. -2-propan-2-yl acetate, 2-methoxyethanol, 2-ethoxyethanol and the like. Among these, methyl ethyl ketone, methanol, ethanol, and 1-methoxy-2-propanol are preferable. These solvents may be used alone or as a mixture.
The image recording layer coating amount (solid content) on the support obtained after coating and drying varies depending on the application, but is generally preferably 0.3 to 3.0 g / m ² . Within this range, good sensitivity and good film characteristics of the image recording layer can be obtained.

<Intermediate layer>
The lithographic printing plate precursor according to the invention may have an intermediate layer between the support and the image recording layer. The intermediate layer preferably contains a polymer compound, and the polymer compound further preferably contains a repeating unit having at least one functional group capable of adsorbing to an aluminum support.
As the polymer compound for the intermediate layer, a compound having at least one of a hydrophilic group, a crosslinkable group, and a hydrophobic group in addition to the aluminum support adsorptive functional group is preferable. The polymer compound for the intermediate layer is more preferably a polymer compound obtained by copolymerizing a monomer having an aluminum support adsorptive group and a monomer having a hydrophilic group, and in the case of a radical polymerization negative type, A polymer compound obtained by copolymerizing a monomer having a support-adsorbing group, a monomer having a hydrophilic group, and a monomer having a crosslinkable group is particularly preferable.
Examples of the intermediate layer compound include a silane coupling agent having an addition polymerizable ethylenic double bond reactive group described in JP-A-10-282679, and JP-A-2-304441. A phosphorus compound having an ethylenic double bond reactive group is also preferably used.

The adsorptivity of the compound to the surface of the aluminum support can be determined, for example, by the following method.
A coating solution is prepared by dissolving the test compound in a readily soluble solvent, and the coating night is coated and dried on the support so that the coating amount after drying is 30 mg / m ² . Next, after the support coated with the test compound is sufficiently washed with an easily soluble solvent, the residual amount of the test compound that has not been removed by washing is measured to calculate the support adsorption amount. Here, the measurement of the remaining amount may be performed by directly quantifying the amount of the remaining compound or by quantifying the amount of the test compound dissolved in the cleaning liquid. The compound can be quantified by, for example, fluorescent X-ray measurement, reflection spectral absorbance measurement, liquid chromatography measurement and the like. In the present invention, the compound having an aluminum support adsorptivity is a compound that remains at 1 mg / m ² or more even when the above washing treatment is performed.

The adsorptive group on the surface of the aluminum support can interact with a substance (eg, aluminum, aluminum oxide, silicate, etc.) existing on the surface of the aluminum support (eg, ionic bond, hydrogen bond, coordination bond, molecule). It is a functional group that can cause (bonding by interstitial force). As the adsorptive group, an acid group or a cationic group is preferable.
Examples of acid groups include phenolic hydroxyl groups, carboxyl groups (—CO ₂ H), sulfonic acid groups (—SO ₃ H), sulfate ester groups (—OSO ₃ H), phosphonic acid groups (—PO ₃ H ₂ ). , Phosphate group (—OPO ₃ H ₂ ), —CONHSO ₂ —, —SO ₂ NHSO ₂ —, —C═O—CH ₂ —C═O— and the like. The acid group preferably has an acid dissociation constant (pKa) of 10 or less, more preferably 8 or less, and particularly preferably 6 or less.
The acid group is more preferably a carboxyl group, a phosphonic acid group, a phosphate ester group, or —C═O—CH ₂ —C═O—, and particularly preferably a phosphonic acid group or a phosphate ester group. It is. These groups may be used alone or in combination of two or more, and may have a counter ion.

  The cationic group is preferably an onium group or an N-oxide group. Examples of the onium group include an ammonium group, a phosphonium group, an arsonium group, a stibonium group, an oxonium group, a sulfonium group, a selenonium group, a stannonium group, and an iodonium group. Among these, an ammonium group, a phosphonium group, and a sulfonium group are preferable, an ammonium group and a phosphonium group are more preferable, and an ammonium group is most preferable. Particularly preferred as the cationic group is an ammonium group or an N-oxide group. These groups may be used alone or in combination of two or more, and may have a counter ion.

The polymer compound for the intermediate layer preferably further has a hydrophilic group. Preferred examples of the hydrophilic group include a hydroxy group, a carboxy group, a hydroxyalkyl group (hydroxyethyl group, hydroxypropyl group, etc.), a polyoxyalkylene group (polyoxyethyl group, polyoxypropyl group, alkylpolyoxyethyl group, Alkyl polyoxypropyl group), amino group, ammonium group, amide group, sulfonamido group, sulfonic acid group, phosphoric acid group, phosphonic acid group, and salts thereof.
More preferably, a hydroxy group, a carboxy group, a hydroxyalkyl group (hydroxyethyl group, hydroxypropyl group, etc.), a polyoxyalkylene group (polyoxyethyl group, polyoxypropyl group, alkylpolyoxyethyl group, alkylpolyoxypropyl group) ), Amide group, sulfonamido group, sulfonic acid group, phosphoric acid group, phosphonic acid group, and salts thereof.
Particularly preferred are polyoxyalkylene groups (polyoxyethyl group, polyoxypropyl group, alkylpolyoxyethyl group, alkylpolyoxypropyl group), sulfonic acid groups, and salts thereof.

  Preferred examples of the monomer having a polyoxyalkylene group include methacrylic acid (2- (2-hydroxyethoxy) ethyl), acrylic acid (2- (2-hydroxyethoxy) ethyl), methacrylic acid (2- (2- (2- ( 2-hydroxyethoxy) ethoxy) ethyl), acrylic acid (2- (2- (2-hydroxyethoxy) ethoxy) ethyl), methacrylic acid (2- (2- (2- (2-hydroxyethoxy) ethoxy) ethoxy) Ethyl), acrylic acid (2- (2- (2- (2-hydroxyethoxy) ethoxy) ethoxy) ethyl), methacrylic acid (2- (2-methoxyethoxy) ethyl), acrylic acid (2- (2-methoxy) Ethoxy) ethyl), methacrylic acid (2- (2- (2-methoxyethoxy) ethoxy) ethyl), acrylic acid (2- (2- 2-methoxyethoxy) ethoxy) ethyl), methacrylic acid (2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) ethyl), acrylic acid (2- (2- (2- (2-methoxyethoxy)) ) Ethoxy) ethoxy) ethyl), methacrylic acid (2- (2-methoxyethoxy) ethyl), methacrylic acid (2- (2-hydroxypropoxy) propyl), acrylic acid (2- (2-hydroxypropoxy) propyl), Methacrylic acid (2- (2- (2-hydroxypropoxy) propoxy) propyl), acrylic acid (2- (2- (2-hydroxypropoxy) propoxy) propyl), methacrylic acid (2- (2- (2- (2- ( 2-hydroxypropoxy) propoxy) propoxy) propyl), acrylic acid (2- (2- (2- (2-hydroxypropyl)) Poxy) propoxy) propoxy) propyl), methacrylic acid (2- (2-methoxypropoxy) propyl), acrylic acid (2- (2-methoxypropoxy) propyl), methacrylic acid (2- (2- (2-methoxypropoxy)) ) Propoxy) propyl), acrylic acid (2- (2- (2-methoxypropoxy) propoxy) propyl), methacrylic acid (2- (2- (2- (2-methoxypropoxy) propoxy) propoxy) propyl), acrylic Examples include acid (2- (2- (2- (2-methoxypropoxy) propoxy) propoxy) propyl), methacrylic acid (2- (2-methoxypropoxy) propyl), and the like.

  Preferred examples of the monomer having a sulfonic acid group include methallyloyloxybenzenesulfonic acid, acryloyloxybenzenesulfonic acid, allylsulfonic acid, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, methallylsulfonic acid, 2-acrylamide-2. -Methylpropanesulfonic acid, (3-acryloyloxypropyl) butylsulfonic acid, and salts thereof. More preferred are vinyl sulfonic acid, 4-vinylbenzene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and salts thereof.

  Particularly preferred as the monomer having a hydrophilic group is 2-acrylamido-2-methylpropanesulfonic acid and a salt thereof.

  The intermediate layer polymer compound used in the radically polymerizable negative lithographic printing plate precursor according to the invention preferably further has a crosslinkable group. The crosslinkable group can improve the adhesion with the image area. In order to give the polymer compound for the intermediate layer a crosslinkability, a crosslinkable functional group such as an ethylenically unsaturated bond is introduced into the side chain of the polymer, or the polar substituent of the polymer resin is countercharged. It can introduce | transduce by forming a salt structure with the compound which has the substituent which has, and an ethylenically unsaturated bond.

Examples of the polymer compound having an ethylenically unsaturated bond in the side chain of the molecule include an ester or amide polymer of acrylic acid or methacrylic acid, and an ester or amide residue (R of -COOR or -CONHR ) Is a polymer compound having an ethylenically unsaturated bond.
Examples of the residue (the R) having an ethylenically unsaturated _{bond, - (CH 2) n CR} 1 = CR 2 R 3, - (CH 2 O) n CH 2 CR 1 = CR 2 R 3, - _{(CH 2 CH 2 O) n} CH 2 CR 1 = CR 2 R 3, - (CH 2) n NH-CO-O-CH 2 CR 1 = CR 2 R 3, - (CH 2) n -O-CO —CR ¹ ═CR ² R ³ and — (CH ₂ CH ₂ O) ₂ —X (wherein R ^{1 to} R ³ are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group. Represents an alkoxy group or an aryloxy group, and R ¹ and R ² or R ³ may combine with each other to form a ring, n represents an integer of 1 to 10. X represents dicyclopentadi An enyl residue).
Specific examples of the ester _{residue, -CH 2 CH = CH 2,} ( described in JP Kokoku _{7-21633.) - CH 2 CH 2} O-CH 2 CH = CH 2, -CH 2 C _{(CH 3) = CH 2,} -CH 2 CH = CH-C 6 H 5, -CH 2 CH 2 OCOCH = CH-C 6 H 5, -CH 2 CH 2 NHCOO-CH 2 CH = CH 2 , and - CH ₂ CH ₂ O—X (wherein X represents a dicyclopentadienyl residue).
Specific examples of the amide residue include —CH ₂ CH═CH ₂ , —CH ₂ CH ₂ O—Y (wherein Y represents a cyclohexene residue), —CH ₂ CH ₂ OCO—CH═CH _2. Is mentioned.
As the monomer having a crosslinkable group of the polymer resin for the intermediate layer, an ester or amide of acrylic acid or methacrylic acid having the crosslinkable group is preferable.

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

The intermediate layer polymer compound preferably has a weight average molecular weight of 5000 or more, more preferably 10,000 to 300,000, and a number average molecular weight of 1000 or more, preferably 2000 to 250,000. It is more preferable that The dispersity (weight average molecular weight / number average molecular weight) is preferably 1.1 to 10.
The intermediate layer polymer compound may be any of a random polymer, a block polymer, a graft polymer, and the like, but is preferably a random polymer.
The intermediate layer compounds may be used alone or in combination of two or more.
The content of the intermediate layer compound in the intermediate layer coating solution is preferably 0.01 to 50% by mass, more preferably 0.1 to 40% by mass, and particularly preferably 0.5 to 30% by mass. It is.

Although the example of the high molecular compound for intermediate | middle layers is shown below, this invention is not limited to these.

Various known methods can be used as a method of applying the intermediate layer coating solution to the support. Examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.
The coating amount (solid content) of the intermediate layer is preferably from 0.1-100 mg / m ^2, and more preferably 1 to 30 mg / m ^2.

<Support>
As the support used in the lithographic printing plate precursor according to the invention, a known support is used. Of these, an aluminum plate that has been roughened and anodized by a known method is preferred.
In addition, the above aluminum plate is optionally subjected to micropore enlargement treatment or sealing treatment of an anodized film described in JP-A Nos. 2001-253181 and 2001-322365, and US Pat. 714,066, 3,181,461, 3,280,734 and 3,902,734, or alkali metal silicates as described in U.S. Pat. Surface hydrophilization treatment with polyvinylphosphonic acid or the like as described in each specification of 3,276,868, 4,153,461 and 4,689,272 is appropriately performed and performed. be able to.
The support preferably has a center line average roughness of 0.10 to 1.2 μm.

  If necessary, the support used in the present invention has an organic polymer compound described in JP-A-5-45885 and a silicon alkoxy compound described in JP-A-5-45885 on the back surface. A backcoat layer can be provided.

<Protective layer>
In the lithographic printing plate precursor according to the invention, a protective layer (overcoat layer) is preferably provided on the image recording layer. In addition to the function of suppressing the image formation inhibition reaction by blocking oxygen, the protective layer has a function of preventing scratches in the image recording layer and preventing ablation during high-illuminance laser exposure.
The protective layer having such characteristics is described in, for example, US Pat. No. 3,458,311 and Japanese Patent Publication No. 55-49729. As the low oxygen permeability polymer used for the protective layer, either a water-soluble polymer or a water-insoluble polymer can be appropriately selected and used. Specific examples include polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble cellulose derivatives, poly (meth) acrylonitrile, and the like.

Further, in order to enhance the oxygen barrier property, the protective layer preferably contains an inorganic layered compound such as natural mica and synthetic mica as described in JP-A-2005-119273.
Further, the protective layer may contain known additives such as a plasticizer for imparting flexibility, a surfactant for improving coating properties, and inorganic fine particles for controlling surface slipperiness. Further, the protective layer can contain the sensitizer described in the description of the image recording layer. In particular, when an inorganic layered compound is contained, it is preferable to use modified polyvinyl alcohol, particularly sulfonic acid-modified polyvinyl alcohol, in order to disperse the inorganic layered compound.

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

<Plate making-Image formation>
As the light source used for imagewise exposure to the lithographic printing plate precursor, a laser is preferable. The laser used in the present invention is not particularly limited, but ultraviolet rays, argon lasers, ultraviolet lasers, semiconductor lasers such as solid lasers and semiconductor lasers that irradiate infrared rays having a wavelength of 760 to 1200 nm, high-pressure mercury lamps that emit light of 250 to 420 nm, etc. Etc. are preferable.
Regarding the infrared laser, the output is preferably 100 mW or more, the exposure time per pixel is preferably within 20 microseconds, and the irradiation energy amount is preferably 10 to 300 mJ / cm ² . In a semiconductor laser that emits light of 250 to 420 nm, the output is preferably 0.1 mW or more. In any laser, it is preferable to use a multi-beam laser device in order to shorten the exposure time.
These are imagewise exposed and then developed with a developer. Preferred developers include alkali agents, organic solvents, surfactants, hard water softeners, reducing agents, organic carboxylic acids, inorganic salts, antifoaming agents, and various other types known in the art as necessary. An aqueous solution containing an additive is used. Particularly preferred examples include developers described in JP-B-58-54341, JP-A-8-248643, JP-A-2002-91015, and JP-A-8-171214.

When performing on-press development, the exposed lithographic printing plate precursor is mounted on a plate cylinder of a printing press. In the case of a printing press equipped with a laser exposure device, the lithographic printing plate precursor may be imagewise exposed after being mounted on the plate cylinder of the printing press.
After the lithographic printing plate precursor is exposed imagewise with an infrared laser or the like, printing is performed by supplying printing ink and fountain solution without going through a development process such as a wet development process, and the like in the exposed part of the image recording layer The image recording layer cured by exposure forms a printing ink receiving portion having an oleophilic surface. On the other hand, in the unexposed area, the uncured image recording layer is removed by dissolution or dispersion by the supplied dampening water and / or printing ink, and a hydrophilic surface is exposed in that area. As a result, the fountain solution adheres to the exposed hydrophilic surface, and the printing ink is deposited on the image recording layer in the exposed area and printing is started.

Here, dampening water or printing ink may be supplied to the printing plate first, but the dampening water is prevented from being contaminated by the components of the image recording layer from which the dampening water has been removed. It is preferable to supply printing ink. As the fountain solution and printing ink, normal lithographic fountain solution and printing ink are used.
In this way, the lithographic printing plate precursor is subjected to on-press development on an offset printing machine and used as it is for printing a large number of sheets.

  Note that the lithographic printing plate precursor according to the present invention may be made in a form through a development process such as a wet development process, in which case the development process is performed between the exposure process and the printing process. I do. The development processing method to be applied is not particularly limited, and can be appropriately determined depending on the type of the image forming layer.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
[Examples 1 to 16 and Comparative Examples 1 to 4]
1. Preparation of lithographic printing plate precursor (1) Preparation of support (1) In order to remove rolling oil on the surface of an aluminum plate (material JIS A 1050) having a thickness of 0.3 mm, a 10 mass% sodium aluminate aqueous solution was used. After degreasing treatment at 30 ° C. for 30 seconds, the aluminum surface was sanded using ^three bundled nylon brushes with a bristle diameter of 0.3 mm and a pumice-water suspension (specific gravity 1.1 g / cm ³ ) with a median diameter of 25 μm. Conspicuous and washed well with water. This plate was etched by being immersed in a 25 mass% sodium hydroxide aqueous solution at 45 ° C for 9 seconds, washed with water, further immersed in 20 mass% nitric acid at 60 ° C for 20 seconds, and washed with water. The etching amount of the grained surface at this time was about 3 g / m ² .

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

Next, a 0.5% by mass hydrochloric acid aqueous solution (containing 0.5% by mass of aluminum ions) and an electrolytic solution having a liquid temperature of 50 ° C. and nitric acid electrolysis under the condition of an electric quantity of 50 C / dm ² when the aluminum plate is an anode. In the same manner as above, an electrochemical surface roughening treatment was performed, followed by washing with water by spraying.
Next, after a direct current anodized film of 2.5 g / m ² to the plate 15 wt% sulfuric acid (containing 0.5 mass% of aluminum ion) at a current density of 15A / dm ² as the electrolytic solution, washing with water, Dried.
Then, in order to ensure the hydrophilic property of a non-image part, the silicate process was performed for 12 second at 70 degreeC using 2.5 mass% 3 sodium silicate aqueous solution. The adhesion amount of Si was 10 mg / m ² . Then, it washed with water and the support body (1) was obtained. The centerline average roughness (Ra) of this substrate was measured using a needle having a diameter of 2 μm and found to be 0.51 μm.

(2) Formation of Intermediate Layer Next, the following intermediate layer coating solution was applied on the support so that the dry coating amount was 28 mg / m ² to provide an intermediate layer.
<Coating liquid for intermediate layer>
-0.18 g of the following intermediate layer (undercoat layer) compound (1)
・ Hydroxyethyliminodiacetic acid 0.10g
・ Methanol 55.24g
・ Water 6.15g

(3) Formation of image recording layer An image recording layer coating solution having the following composition was bar-coated on the intermediate layer formed as described above, followed by oven drying at 100 ° C., and a dry coating amount of 1.0 g / m. ^Two image recording layers were formed. In the following composition, the amount (content) of the general formula (I) shown in Table 1 is based on the mass of the image recording layer of the finished lithographic printing plate precursor.
By adjusting the drying time, the amount (content ratio) of the compound of the general formula (I) or the comparative compound in the image recording layer was adjusted.
The image recording layer coating solution was obtained by mixing and stirring the following photosensitive solution (1) and microgel solution (1) immediately before coating.
<Photosensitive solution (1)>
Compound of general formula (I) or comparative compound (type and amount described in Table 1 below)
-High molecular compound (1) [following structure] 0.108g
-High molecular compound having a specific structural group (see Table 1) 0.054 g
(Selected from specific examples (1) to (20) of the polymer compound having the above-mentioned specific structural group)
Infrared absorber (1) [the following structure] 0.030 g
-Radical polymerization initiator (1) [the following structure] 0.162 g
Polymerizable compound tris (acryloyloxyethyl) isocyanurate (NK ester A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.192 g
・ Low molecular weight hydrophilic compound Tris (2-hydroxyethyl) isocyanurate 0.062g
・ Low molecular weight hydrophilic compound (1) [the following structure] 0.050 g
-Sensitizing agent Phosphonium compound (1) [the following structure] 0.055 g
・ Sensitizer Benzyl-dimethyl-octylammonium ・ PF ₆ salt 0.018g
・ Trimethylglycine 0.01g
・ Fluorosurfactant (1) [The following structure] 0.008g
・ Methyl ethyl ketone 1.091g
・ 1-methoxy-2-propanol 8.609g

<Microgel solution (1)>
・ Microgel (1) 2.640 g
・ Distilled water 2.425g

The above-described polymer compound (1), infrared absorber (1), radical polymerization initiator (1), phosphonium compound (1), low molecular weight hydrophilic compound (1), and fluorine-based surfactant (1) The structures of the comparative compounds C-1 and C-2 are as shown below.
Polymer compound (1)

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

(Quantification of compound of general formula (I) or comparative compound)
The prepared lithographic printing plate precursor 100 cm ² was extracted with methanol, the compound in the image recording layer was quantified by gas chromatography, and the content in the image recording layer was expressed in mass%.
(Gas chromatography measurement conditions)
The lithographic printing plate material 10cm * 10cm is immersed in special grade methanol and stirred at room temperature for 3 hours to extract the photosensitive layer components. 1 μL of the obtained sample solution is injected into the GC and quantified by the absolute calibration curve method.
GC conditions Equipment Agilent 6890 (Agilent Technologies)
Column DB-17MS 30m * 0.25mmID film thickness 0.25μm (manufactured by J & W Scientific)
Oven temperature 50 ° C (5 minutes hold) → Temperature rise at 10 ° C / minute → 280 ° C (2 minutes hold)
Inlet temperature 280 ℃
Split 10
Carrier gas He = 1mL / min
Detector FID
Detector temperature 300 ° C

(4) Formation of protective layer (1) On the image recording layer formed as described above, a protective layer coating solution (1) having the following composition was further bar-coated, followed by oven drying at 120 ° C for 60 seconds. A protective layer (1) having a dry coating amount of 0.15 g / m ² was formed.
<Coating liquid for protective layer (1)>
・ Inorganic layered compound dispersion (1) 1.5 g
-Polyvinyl alcohol (Nippon Synthetic Chemical Industry Co., Ltd. CKS50, sulfonic acid modification,
Saponification degree 99 mol% or more, polymerization degree 300) 6% by mass aqueous solution 0.55 g
・ Polyvinyl alcohol (PVA-405 manufactured by Kuraray Co., Ltd.)
Degree of saponification 81.5 mol% degree of polymerization 500) 6% by weight aqueous solution 0.03 g
・ Nippon Emulsion Co., Ltd. surfactant (Emalex 710) 1 mass% aqueous solution 8.60 g
・ Ion-exchanged water 6.0g

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

2. Evaluation of lithographic printing plate precursor The obtained lithographic printing plate precursor was exposed under the conditions of an external drum rotation speed of 1000 rpm, a laser output of 70%, and a resolution of 2400 dpi using Fujifilm's Luxel PLASETTER T-6000III equipped with an infrared semiconductor laser. did. The exposure image included a solid image and a 50% halftone dot chart of a 20 μm dot FM screen.
The obtained exposed original plate was attached to a plate cylinder of a printing machine LITHRONE 26 manufactured by Komori Corporation without developing. Equality-2 (manufactured by FUJIFILM Corporation) / tap water = 2/98 (volume ratio) dampening water and Values-G (N) black ink (manufactured by Dainippon Ink & Chemicals, Inc.) After dampening water and ink were supplied by the standard automatic printing start method of LITHRONE 26 and developed on the machine, 100 sheets were printed on Tokuhishi Art (76.5 kg) paper at a printing speed of 10,000 sheets per hour.

(A) On-press developability Printing was performed as described above, and it was necessary until the on-press development on the printing press of the unexposed portion of the image recording layer was completed and the ink was not transferred to the non-image portion. The number of print sheets was measured as on-press developability. The smaller the number, the better the on-press developability.
(B) On-machine developability after time The obtained lithographic printing plate precursor was left in a constant temperature and humidity chamber set at 45 ° C. and a relative humidity of 75% for 3 days, then exposed and printed in the same manner as described above. The on-press developability was determined.
It can be determined that the aging stability is better as the number is closer to the on-press development number when the forced aging is not performed in the above (A).

(C) Normal printing durability Printing was continued after the above-described evaluation of on-press developability. As the number of printed sheets was increased, the image recording layer was gradually worn out, so that the ink density on the printed material decreased. Printing durability was evaluated using the number of printed copies when the value measured by the Gretag densitometer for the 50% halftone dot area ratio of the FM screen in the printed material was 5% lower than the measured value for the 100th printed sheet. .

(D) Antifouling property after elapse of time The obtained lithographic printing plate precursor was left in a constant temperature and humidity chamber set at 45 ° C. and a relative humidity of 75% for 3 days, and then exposed in the same manner as described above. (C) The anti-staining property of the non-image area was evaluated in three stages.
The case where the antifouling property has no practical problem is indicated by ◯, the case where the antifouling property is problematic depending on the conditions is indicated by Δ, and the case where the antifouling property is poor and which is practically problematic is indicated by ×.
(E) UV ink printing durability The obtained exposed original plate was attached to a cylinder of a Dia IF-2 printing machine manufactured by Mitsubishi Heavy Industries, Ltd. without developing. After supplying fountain solution and ink using IF102 2% aqueous solution of fountain solution (Fuji Film) and Best Cure UV-BF-WRO standard black ink (T & K TOKA), printing 10,000 sheets per hour Printing was performed at speed.
In the evaluation of printing durability, the number of sheets in which the image density of the obtained printed matter was reduced by 5% from the start of printing was judged to be finished.
(F) Antifouling property after UV ink aging The obtained lithographic printing plate precursor was left in a constant temperature and humidity chamber set at 45 ° C. and a relative humidity of 75% for 3 days, and then exposed in the same manner as above ( Printing was performed under the conditions of E), and the anti-staining property of the non-image area was evaluated in three stages.
With respect to the antifouling property, “◯” indicates that there is no problem in practical use, “Δ” indicates that the antifouling property is problematic depending on conditions, and “x” indicates that the antifouling property is poor and causes practical problems.

上記の結果より、本発明の平版印刷版原版が、経時後の機上現像性、耐刷性、及び汚れ防止性の点で優れたものであることが判る。
なお、実施例１４においては、特定構造基を有する高分子化合物を含有しないため、高分子化合物（１）の添加量を0.162ｇとした。
使用した特定構造基を有する高分子化合物の分子量は、（１）：Mw=55000、（７）：Mw=53000、及び（20）：Mw=55000である。

From the above results, it can be seen that the lithographic printing plate precursor of the present invention is excellent in terms of on-press development property, printing durability and antifouling properties after aging.
In Example 14, since the polymer compound having a specific structural group was not contained, the amount of polymer compound (1) added was 0.162 g.
The molecular weight of the polymer compound having the specific structural group used is (1): Mw = 55000, (7): Mw = 53000, and (20): Mw = 55000.

[Examples 17 to 23 and Comparative Examples 5 to 8]
<Thermal negative planographic printing plate precursor>
JP-A-2001-264991 except that the compound of general formula (I) or the comparative compound (type and amount shown in Table 2) was added to the image forming layer of Example 1 of JP-A-2001-264991. A lithographic printing plate precursor (Examples 17 to 23, Comparative Examples 5 to 8) was prepared in the same manner as in Example 1 of the publication, and the remaining color of non-image areas, adhesion and printing durability were evaluated. . The amount (content) of the general formula (I) shown in the table is based on the mass of the image recording layer of the finished lithographic printing plate precursor.
Moreover, the antifouling property after aging was evaluated as follows.
<Stain prevention after time>
The lithographic printing plate precursor was left in a constant temperature and humidity chamber set at 45 ° C. and a relative humidity of 75% for 4 days, then exposed and printed in the same manner as described above, and the anti-staining property of the non-image area was evaluated in three stages. did. After developing whether there is a residual color in the unexposed area, when the lithographic printing plate precursor is mounted on a Heidel printer SOR-M and printed 50 sheets, it is visually confirmed whether there is ink stains in the unexposed area, Evaluation was performed as follows.
Antifouling property after aging: .largecircle .: no problem in practical use, x: practical problem. Table 2 shows the results.
It can be seen that the lithographic printing plate precursor having an image recording layer containing the compound of the general formula (I) according to the present invention has particularly high printing durability and is excellent in terms of balance with antifouling properties.

非画像部の残色：○…実用上問題がないもの、△…条件によっては問題となるもの
密着性：○…実用上問題がないもの、△…条件によっては問題となるもの

Residual color of non-image part: ○: No problem in practical use, Δ: Problem in some conditions Adhesion: ○: No problem in practical use, Δ: Problems in some conditions

[Examples 24 to 30 and Comparative Examples 9 to 12]
<Thermal negative type, simplified development lithographic printing plate precursor>
Lithographic printing was carried out in exactly the same manner except that the compound of the general formula (I) or the comparative compound (type and amount described in Table 3) was added to the image forming layer of Example 1 of JP-A-2007-316598. Plate original plates (Examples 24 to 30 and Comparative Examples 9 to 12) were prepared, and developability (presence or absence of remaining film in non-image areas) and printing durability by the method described in Examples of Japanese Patent Application Laid-Open No. 2007-316598. Was evaluated. The amount (content) of the general formula (I) shown in the table is based on the mass of the image recording layer of the finished lithographic printing plate precursor.
In addition, as for the anti-stain property after aging, after being left in a constant temperature and humidity chamber set at 45 ° C. and a relative humidity of 75% for 4 days, printing is performed under the conditions described in JP-A-2007-316598 [0338], The adhesion of the ink to the non-image area of the printed material was evaluated and determined as follows.
Antifouling property after aging: .largecircle .: no problem in practical use, .DELTA .: problematic depending on conditions. The lithographic printing plate precursor having an image recording layer according to the present invention has high printing durability, is excellent in balance with developability, and is excellent in stain resistance after aging. I understand.

現像性 ○：残膜なし △：わずかに残膜

Developability ○: No remaining film △: Slightly remaining film

[Examples 31 to 39 and Comparative Examples 13 to 15]
<Thermal positive lithographic printing plate precursor>
Si: 0.06 mass%, Fe: 0.30 mass%, Cu: 0.014 mass%, Mn: 0.001 mass%, Mg: 0.001 mass%, Zn: 0.001 mass%, Ti: Containing 0.03% by mass, the balance is prepared using Al and an inevitable impurity aluminum alloy, and after performing the molten metal treatment and filtration, an ingot having a thickness of 500 mm and a width of 1200 mm is obtained by a DC casting method. Created. After the surface was shaved with a chamfering machine with an average thickness of 10 mm, it was kept soaked at 550 ° C. for about 5 hours, and when the temperature dropped to 400 ° C., rolling with a thickness of 2.7 mm using a hot rolling mill A board was used. Further, after heat treatment was performed at 500 ° C. using a continuous annealing machine, an aluminum plate having a thickness of 0.24 mm was finished by cold rolling. After making this aluminum plate 1030 mm in width, the following surface treatment was continuously performed.

(A) Mechanical surface roughening treatment While a suspension of abrasive (silica sand) having a specific gravity of 1.12 and water is supplied to the surface of the aluminum plate as a polishing slurry liquid, it is mechanically rotated by a roller nylon brush. Roughening was performed. The average particle size of the abrasive was 8 μm, and the maximum particle size was 50 μm. The material of the nylon brush was 6 · 10 nylon, the hair length was 50 mm, and the hair diameter was 0.3 mm. The nylon brush was planted so as to be dense by making a hole in a stainless steel tube having a diameter of 300 mm. Three rotating brushes were used. The distance between the two support rollers (φ200 mm) at the bottom of the brush was 300 mm. The brush roller was pressed until the load of the drive motor for rotating the brush became 7 kW plus with respect to the load before the brush roller was pressed against the aluminum plate. The rotating direction of the brush was the same as the moving direction of the aluminum plate. The rotation speed of the brush was 200 rpm.

(B) Etching treatment with alkali agent The aluminum plate after the mechanical roughening treatment obtained above is subjected to etching treatment by spraying at caustic soda concentration 2.6 mass%, aluminum ion concentration 6.5 mass%, and temperature 70 ° C. The aluminum plate was dissolved at 6 g / m ² . Then, water washing by spraying was performed.
(C) Desmutting treatment The desmutting treatment was performed by spraying with a 1% by mass aqueous solution of nitric acid at a temperature of 30 ° C. (containing 0.5% by mass of aluminum ions), and then washed with water by spraying. The nitric acid aqueous solution used for the desmut was the waste liquid from the step of electrochemical surface roughening using alternating current in nitric acid aqueous solution.

(D) Electrochemical roughening treatment An electrochemical roughening treatment was carried out continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a nitric acid 10 g / liter aqueous solution (containing 5 g / liter of aluminum ions and 0.007 mass% of ammonium ions) at a temperature of 80 ° C. The current density was 30 A / dm ² at the peak current value, and the amount of electricity was 130 C / dm ² in terms of the total amount of electricity when the aluminum plate was the anode. 5% of the current flowing from the power source was shunted to the auxiliary anode. Then, water washing by spraying was performed.

(E) Alkali etching treatment The aluminum plate was sprayed at a caustic soda concentration of 26% by mass and an aluminum ion concentration of 6.5% by mass at 32 ° C. to dissolve the aluminum plate by 0.20 g / m ² , The smut component mainly composed of aluminum hydroxide generated when electrochemical surface roughening was used was removed, and the edge portion of the generated pit was melted to smooth the edge portion. Then, water washing by spraying was performed.
(F) Desmutting treatment A desmutting treatment by spraying was performed with a 25% by weight aqueous solution of sulfuric acid having a temperature of 60 ° C. (containing 0.5% by weight of aluminum ions), followed by washing with water by spraying.

(G) Anodizing treatment Anodizing device of two-stage feeding electrolytic treatment method (first and second electrolytic section length 6 m each, first and second feeding section length 3 m each, first and second feeding electrode length 2.4 m each) Anodizing was performed using this. Sulfuric acid was used as the electrolytic solution supplied to the first and second electrolysis units. All electrolytes had a sulfuric acid concentration of 170 g / liter (containing 0.5 mass% of aluminum ions) and a temperature of 43 ° C. Then, water washing by spraying was performed. The final oxide film amount was 2.7 g / m ² .

(H) Alkali metal silicate treatment An aluminum support obtained by anodizing treatment was immersed in a treatment layer of a 1% by weight aqueous solution of sodium silicate No. 3 at a temperature of 30 ° C. for 10 seconds to immerse the alkali metal silica. Acid salt treatment (silicate treatment) was performed. Then, water washing by spraying was performed.

(I) Formation of undercoat layer On the aluminum support after the alkali metal silicate treatment obtained as described above, an undercoat solution having the following composition was applied and dried at 80 ° C for 15 seconds.
<Undercoat liquid composition>
・ The following polymer compound 0.3 g
・ Methanol 100 g
・ Water 1 g

j) Formation of image recording layer (lower layer and upper layer) Next, the coating amount after drying the lower layer coating solution having the following composition on the lithographic printing plate support provided with the undercoat layer becomes 0.85 g / m ^2. After coating, the TARFAI PERFECT OVEN PH200 was used with a Wind Control set to 7, and dried at 140 ° C. for 50 seconds. Then, after apply | coating the coating liquid for upper layers of the following composition so that an application quantity might be set to 0.15 g / m < ² >, it dried at 120 degreeC and obtained the heat-sensitive lithographic printing plate. The amount of the compound of general formula (I) or the comparative compound was adjusted by adjusting the drying time.

・４，４'−ビスヒドロキシフェニルスルホン ０．０６３ｇ
・テトラヒドロ無水フタル酸 ０．１９０ｇ
・ｐ−トルエンスルホン酸 ０．００８ｇ
・２−メトキシ−４−（Ｎ−フェニルアミノ）
ベンゼンジアゾニウムヘキサフルオロホスフェート ０．０３ｇ
・エチルバイオレットの対イオンを
６−ヒドロキシ−β−ナフタレンスルホンに変えたもの ０．０５ｇ
・フッ素系界面活性剤
（メガファックＦ−１７６、大日本インキ化学工業社製） ０．０３５ｇ
・メチルエチルケトン ２６．６ｇ
・１−メトキシ−２−プロパノール １３．６ｇ
・γ−ブチロラクトン １３．８ｇ <Coating liquid for lower layer>
Compound of general formula (I) or comparative compound (type and amount described in Table 4)
Polymer binder N- (p-aminosulfonylphenyl) methacrylamide / acrylonitrile / methyl methacrylate copolymer (monomer ratio = 36/34/30, weight average molecular weight 50,000) 1.896 g having a specific structure
M, p-cresol novolak (m / p ratio = 6/4, weight average molecular weight 4,500,
0.237 g containing 0.8% by mass of unreacted cresol)
-Cyanine dye A represented by the following structural formula 0.109 g

・ 4,4'-bishydroxyphenylsulfone 0.063g
・ Tetrahydrophthalic anhydride 0.190g
・ 0.008 g of p-toluenesulfonic acid
2-methoxy-4- (N-phenylamino)
Benzenediazonium hexafluorophosphate 0.03g
-Ethyl violet counter ion changed to 6-hydroxy-β-naphthalene sulfone 0.05 g
・ Fluorosurfactant (Megafac F-176, manufactured by Dainippon Ink & Chemicals, Inc.) 0.035g
・ Methyl ethyl ketone 26.6g
1-methoxy-2-propanol 13.6 g
・ Γ-Butyrolactone 13.8g

<Upper layer coating solution>
M, p-cresol novolak (m / p ratio = 6/4, weight average molecular weight 4,500,
0.237 g containing 0.8% by mass of unreacted cresol)
-Cyanine dye A represented by the above structural formula 0.047 g
・ Dodecyl stearate 0.060g
・ 3-Methoxy-4-diazodiphenylamine hexafluorophosphate
0.030g
・ Fluorine-based surfactant (Megafac F-176, manufactured by Dainippon Ink & Chemicals, Inc.) 0.110 g
Fluorosurfactant (Defenser MCF-312 (solid content 30% by mass), manufactured by Dainippon Ink & Chemicals, Inc.)
0.120g
・ Methyl ethyl ketone 15.1g
-1-methoxy-2-propanol 7.7g

Using GEOS-G (N) (manufactured by Dainippon Ink, Inc.) as normal ink and Best Cure UV-BF-WRO standard black ink (manufactured by T & K TOKA) as UV ink, stain resistance and printing durability are as follows: It was evaluated as follows.
(Dirty (non-image area remaining color))
After developing whether there is a residual color in the unexposed area, when the lithographic printing plate precursor is mounted on a Heidel printer SOR-M and printed 50 sheets, it is visually confirmed whether there is ink stains in the unexposed area, Evaluation was performed as follows.
◯: No ink stains (Triangle | delta): It becomes a problem depending on conditions.

(Evaluation of printing durability)
As a printing machine, a printing machine SOR-M manufactured by Heidel was used to print on high-quality paper. The solid image portion of the obtained printed matter was observed, and the number of images where the image portion to which ink originally adhered began to fade was counted. The larger the number, the better the printing durability.

^*一般式（Ｉ）の化合物又は比較化合物の含有率は、画像記録層下層の質量に対する含有率である。
(A)^** Ｎ−（ｐ−アミノスルホニルフェニル）メタクリルアミドを２−（Ｎ'−（４−スルファモイルフェニル）ウレイド）エチルメタクリレートに置き換えたポリマーバインダー
(B)^*** Ｎ−（ｐ−アミノスルホニルフェニル）メタクリルアミドをＮ−（４−スルファモイルフェニル）マレイミドに置き換えたポリマーバインダー

^* The content of the compound of the general formula (I) or the comparative compound is a content relative to the mass of the lower layer of the image recording layer.
(A) ^** Polymer binder in which N- (p-aminosulfonylphenyl) methacrylamide is replaced with 2- (N ′-(4-sulfamoylphenyl) ureido) ethyl methacrylate
(B) ^*** Polymer binder obtained by replacing N- (p-aminosulfonylphenyl) methacrylamide with N- (4-sulfamoylphenyl) maleimide

  As can be seen from the above results, the lithographic printing plate precursor according to the present invention can provide a lithographic printing plate capable of satisfying both good printing durability and antifouling properties, and in particular, compatibility between printing durability and antifouling properties. In the printing with UV ink, which is difficult to achieve, it is possible to achieve both. The lithographic printing plate precursor of the present invention can also provide a lithographic printing plate that can achieve good antifouling properties after plate making even when stored for a long time under severe conditions. Moreover, according to the planographic printing plate precursor of the present invention, excellent on-press developability can be exhibited, and on-press developability does not deteriorate even after storage over time.

Claims (4)

On an aluminum support, a lithographic printing plate precursor of the negative type having an image recording layer, the image recording layer, the compound represented by the following general formula (I) containing 0.01 to 10 wt%, The negative lithographic printing plate precursor further comprising a polymerization initiator and a polymerizable compound .

(In the formula, R ¹ represents an organic substituent having 2 to 10 carbon atoms, and R ^{2 to} R ⁷ each independently represents a hydrogen atom or an organic substituent having 1 to 10 carbon atoms.) The negative lithographic printing plate precursor according to claim 1 , wherein the image recording layer further contains a photothermal conversion substance. The negative lithographic printing plate precursor according to claim 1 or 2 , wherein the image recording layer contains a polymer compound having at least one structure selected from a sulfonamide group, a maleimide group, and a urea structure. The negative planographic printing plate precursor according to any one of claims 1 to 3 , further comprising an intermediate layer and an image recording layer in this order on an aluminum support.