JP2010284963A - Plate surface treatment agent for lithographic printing plate and method for treating lithographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a plate surface treatment agent for a lithographic printing plate superior in fouling prevention of a non-image section, and to provide a method for treating a lithographic printing plate. <P>SOLUTION: The plate surface treatment agent for a lithographic printing plate includes a vinyl copolymer containing: a monomer unit having at least one group selected from the group consisting of a phosphonic acid group, a phosphoric acid group, a carboxylic acid group, and a salt of these groups; and a monomer unit having at least one group or structure selected from the group consisting of a sulfonic acid group, a salt thereof, an amide group, and a betaine structure. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a lithographic printing plate surface treatment agent and a lithographic printing plate processing method.

Conventionally, a lithographic printing plate has a structure in which a photosensitive resin layer is provided on a support having a hydrophilic surface. As a plate-making method, usually, surface exposure (mask exposure) is performed through a lithographic film. The desired printing plate was obtained by removing the non-image area with a developer. However, computer-to-plate that directly exposes the plate without using a lith film by scanning the plate according to digitized image information with highly directional light such as laser light by recent digitization technology. (CTP) technology has been developed, and a photosensitive lithographic printing plate (lithographic printing plate precursor) adapted to this has been developed.
Examples of the lithographic printing plate precursor suitable for exposure with such laser light include a lithographic printing plate precursor using a polymerizable photosensitive layer. By selecting a photopolymerization initiator or a polymerization initiator system (hereinafter also simply referred to as an initiator or an initiator system), the polymerizable photosensitive layer can be easily increased in sensitivity as compared with other conventional photosensitive layers.
As the laser light source, a 405 nm or 830 nm semiconductor laser, an FD-YAG laser, or the like is used. In recent years, CTP systems equipped with a 405 nm or 803 nm semiconductor laser have become widespread from the viewpoints of system cost and handleability.

When making a lithographic printing plate, a plate surface treating agent (so-called gum solution) is applied in the final step in order to protect the non-image area and the image area. This process is called gumming.
As the plate surface treating agent, for example, Patent Documents 1 to 3 are known.
Patent Document 1 discloses a photosensitive lithographic printing plate having a photopolymerizable photosensitive layer containing an ethylenic double bond-containing compound, a photopolymerization initiator, and a polymer binder on an aluminum plate support. A photosensitive lithographic printing plate characterized by being exposed and developed with a developer substantially free of silicate, and then subjected to plate surface treatment at 40 ° C. to 90 ° C. with a plate surface protective agent containing a phosphonic acid compound. A processing method is disclosed.
Patent Document 2 discloses a photosensitive lithographic printing plate having a photopolymerizable photosensitive layer containing a polymerizable ethylenic double bond-containing compound, a photopolymerization initiator, and a polymer binder on an aluminum plate support. After image exposure and development processing, (A) a plate surface protective agent containing a phosphonic acid compound having a molecular weight of less than 2000 and (B) a phosphonic acid compound having a molecular weight of 2000 or more is then heated at 50 ° C. to 200 ° C. A method for processing a photosensitive lithographic printing plate characterized by the above is disclosed.
In Patent Document 3, the surface treatment or development treatment of the aluminum support is performed with a surface treatment agent or a development treatment agent that substantially does not contain silicic acid or a salt thereof, and in the step after the development treatment, A processing method for a lithographic printing plate is disclosed, wherein the processing is performed with a plate surface treating agent containing a compound having a phosphoric acid or phosphonic acid group in the molecule and having no film property itself.

  Further, as a printing chemical used for fountain solution or the like, Patent Document 4 discloses a printing chemical containing a water-soluble polymer having an adsorptive group and a sulfonic acid group that can be adsorbed on the surface of a lithographic printing plate support. ing.

JP 2006-11413 A Japanese Patent Laid-Open No. 2005-114892 JP 2007-45114 A JP 2007-38483 A

  An object of the present invention is to provide a lithographic printing plate surface treatment agent having excellent anti-staining properties for non-image areas and a lithographic printing plate processing method.

The above-described problems of the present invention have been solved by the means described in <1> or <12> below. It is described below together with <2> to <11>, <13> and <14> which are preferred embodiments.
<1> A group comprising a monomer unit having at least one group selected from the group consisting of a phosphonic acid group, a phosphoric acid group, a carboxylic acid group and salts thereof, and a sulfonic acid group, a salt thereof, an amide group and a betaine structure A lithographic printing plate surface treatment agent comprising a vinyl copolymer having a monomer unit having at least one group or structure selected from
<2> The group in which the monomer unit having at least one group selected from the group consisting of the phosphonic acid group, phosphoric acid group, carboxylic acid group and salts thereof consists of a phosphonic acid group, phosphoric acid group and salts thereof The plate surface treating agent for a lithographic printing plate according to the above <1>, which is a monomer unit having at least one group selected from
<3> The monomer unit having at least one group or structure selected from the group consisting of the sulfonic acid group and its salt, amide group and betaine structure is selected from the group consisting of the sulfonic acid group and its salt and betaine structure. A lithographic printing plate treating agent according to <1> or <2>, which is a monomer unit having at least one group or structure;
<4> The above <1>, wherein the monomer unit having at least one group or structure selected from the group consisting of the sulfonic acid group and a salt thereof, an amide group, and a betaine structure is a monomer unit having at least one betaine structure. A plate surface treating agent for a lithographic printing plate according to any one of to <3>,
<5> A monomer unit having at least one group or structure selected from the group consisting of the sulfonic acid group and its salt, amide group and betaine structure, and having at least one sulfonic acid group and / or salt thereof The plate surface treating agent for a lithographic printing plate according to any one of the above <1> to <3>,
<6> In the copolymer, the copolymer has a content ratio of a monomer unit having at least one group selected from the group consisting of a phosphonic acid group, a phosphoric acid group, a carboxylic acid group, and a salt thereof. The plate surface treating agent for a lithographic printing plate according to any one of the above <1> to <5>, which is 2 to 70 mol% based on all monomer units,
<7> In the copolymer, the content ratio of monomer units having at least one group or structure selected from the group consisting of a sulfonic acid group and a salt thereof, an amide group, and a betaine structure is the total content of the copolymer. The plate surface treating agent for a lithographic printing plate according to any one of the above <1> to <6>, which is 30 to 98 mol% with respect to the monomer unit,
<8> The plate surface treatment agent for a lithographic printing plate according to any one of <1> to <7>, wherein the content of the copolymer is 0.005 to 10% by weight,
<9> The lithographic printing plate surface treatment agent according to any one of the above <1> to <8>, further comprising a water-soluble polymer compound different from the vinyl copolymer.
<10> The water-soluble polymer compound is gum arabic, a fibrous derivative and a modified product thereof, polyvinyl alcohol and a derivative thereof, polyvinyl pyrrolidone, a vinyl methyl ether / maleic anhydride copolymer, and a vinyl acetate / maleic anhydride copolymer. A water-soluble polymer selected from the group consisting of a polymer, a styrene / maleic anhydride copolymer, a water-soluble soybean polysaccharide, starch, a starch derivative, pullulan and a pullulan derivative, gelatin, and hemicellulose extracted from soybean A lithographic printing plate surface treatment agent as described in <9> above,
<11> The lithographic printing plate according to <9> or <10>, wherein the content of the water-soluble polymer compound is 0.1 to 25% by weight based on the total weight of the lithographic printing plate surface treatment agent. Plate surface treatment agent,
<12> A plate surface using the plate surface treating agent for a lithographic printing plate according to any one of <1> to <11>, and a step of image exposure of the lithographic printing plate precursor, a step of developing with a developer, and A processing method of a lithographic printing plate including a processing step,
<13> The processing method of a lithographic printing plate as described in <12> above, wherein the lithographic printing plate precursor has a support subjected to electrochemical surface roughening treatment with an aqueous hydrochloric acid solution,
<14> The processing method of a lithographic printing plate as described in <12> or <13> above, wherein the lithographic printing plate precursor has a photosensitive layer containing a sensitizing dye, a polymerization initiator and a binder polymer.

  ADVANTAGE OF THE INVENTION According to this invention, the plate surface treating agent for lithographic printing plates excellent in the antifouling property of a non-image part and the processing method of a lithographic printing plate could be provided.

It is a side view which shows the concept of the process of the brush graining used for the machine roughening process in preparation of an aluminum support body. It is a graph which shows an example of the alternating waveform current waveform figure used for the electrochemical roughening process in preparation of an aluminum support body.

  Hereinafter, the plate surface treating agent for a lithographic printing plate and the processing method of the lithographic printing plate of the present invention will be described in detail.

(Plate treatment for lithographic printing plates)
The plate surface treating agent for lithographic printing plates of the present invention (hereinafter also referred to simply as “plate surface treating agent”, also referred to as “plate surface protecting agent” or “finisher”) is a phosphonic acid group, phosphoric acid group, carboxylic acid group. And a monomer unit having at least one group selected from the group consisting of these salts (hereinafter also referred to as “acidic monomer unit”), a sulfonic acid group and its salt, an amide group, and a betaine structure. Containing a vinyl copolymer (hereinafter also referred to as “specific copolymer”) having at least one monomer unit having at least one group or structure (hereinafter also referred to as “hydrophilic monomer unit”). Features.

(Specific copolymer)
The plate surface treating agent for a lithographic printing plate of the present invention contains a vinyl copolymer (specific copolymer) having an acidic monomer unit and a hydrophilic monomer unit.

The acidic monomer unit includes a phosphonic acid group (—PO (OH) ₂ ), a phosphoric acid group (—OPO (OH) ₂ ), a carboxylic acid group (—COOH) and a salt thereof (—PO (OH) (OM)). , —PO (OM) ₂ , —OPO (OH) (OM), —OPO (OM) ₂ , —COOM (where M represents a counter cation other than proton (H ⁺ )). The monomer unit having at least one group, preferably a monomer unit having at least one group selected from the group consisting of a phosphonic acid group, a phosphoric acid group and salts thereof.
As described above, the phosphonic acid group, phosphoric acid group and carboxylic acid group in the acidic monomer unit may form a salt, and the counter cation other than the proton is not particularly limited, and is inorganic such as a metal cation. It may be a cation, an organic cation such as a tetraalkylammonium ion, or a polymer cation. The counter cation may be a monovalent counter cation or a divalent or higher counter cation.

  The acidic monomer unit is preferably a monomer unit represented by the following formulas (U-1) to (U-3), and is a monomer unit represented by the following formula (U-1) or (U-2). It is more preferable that

（式（Ｕ−１）〜（Ｕ−３）中、Ｒ¹は、水素原子又はアルキル基を表し、Ａ¹は、単結合又は（ｎ＋１）価の有機基を表し、Ｘ¹及びＸ²はそれぞれ独立に、水素原子又はプロトン以外の対カチオンを表し、ｎは１以上の整数を表す。）

(In formulas (U-1) to (U-3), R ¹ represents a hydrogen atom or an alkyl group, A ¹ represents a single bond or an (n + 1) -valent organic group, and X ¹ and X ² represent Each independently represents a counter cation other than a hydrogen atom or a proton, and n represents an integer of 1 or more.)

R ¹ represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom or a methyl group.
The counter cation other than protons in X ¹ and X ² is not particularly limited, and may be an inorganic cation such as a metal cation or an organic cation such as a tetraalkylammonium ion, or a polymer cation. It may be. The counter cation may be a monovalent counter cation or a divalent or higher counter cation.
The n represents an integer of 1 or more, preferably an integer of 1 to 5, preferably 1 or 2, and particularly preferably 1.

The (n + 1) valent organic group in A ¹ is preferably a group formed of at least one element selected from the group consisting of carbon, hydrogen, oxygen and nitrogen, and consists of carbon, hydrogen and oxygen. It is more preferably a group formed from at least one element selected from the group, a group obtained by removing (n + 1) hydrogen atoms from a hydrocarbon, or m from a hydrocarbon (where m is 1 or more) More preferably a group in which two or more groups selected from the group consisting of an ester bond and an ether bond are combined.

  The acidic monomer unit is more preferably a monomer unit represented by the following formula (U-4) or (U-5).

（式（Ｕ−４）及び（Ｕ−５）中、Ｒ¹は、水素原子又はアルキル基を表し、Ａ²は、二価の有機基を表し、Ｘ¹及びＸ²はそれぞれ独立に、水素原子又はプロトン以外の対カチオンを表す。）

(In formulas (U-4) and (U-5), R ¹ represents a hydrogen atom or an alkyl group, A ² represents a divalent organic group, and X ¹ and X ² each independently represent hydrogen. (Represents a counter cation other than an atom or a proton.)

R ^1, X ¹ and X ² in Formula (U-4) and (U-5) has the same meaning as R ^1, X ¹ and X ² in the formula (U-1) ~ (U -3), preferred The range is the same.
The divalent organic group in A ² of the formula (U-5) is preferably a group formed from at least one element selected from the group consisting of carbon, hydrogen, and oxygen, an alkylene group, or More preferably a group in which two or more groups selected from the group consisting of an alkylene group, an ester bond and an ether bond are combined, and an alkylene group or a group in which two or more groups are combined with an alkylene group and an ether bond. It is more preferable that it is an alkylene group or a polyalkyleneoxy group. In addition, the phosphorus atom side terminal of the polyalkyleneoxy group may be a carbon atom or an oxygen atom. The alkylene group and polyalkyleneoxy group may be linear or branched.
In the monomer unit represented by the formula (U-5), the terminal group of the monomer unit is a phosphonic acid group or a salt thereof depending on whether the terminal of A ² is a carbon atom or an oxygen atom. In some cases, it may be a phosphate group or a salt thereof.
Further, (U-4) and (U-5) carbon atoms of A ² in is preferably 2 to 60, more preferably from 2 to 20, more preferably 2 to 10.

  Specific examples of the acidic monomer unit are preferably monomer units represented by the following (A-1) to (A-6). Moreover, the monomer unit in which the phosphonic acid group of the monomer unit represented by the following (A-1)-(A-6), the phosphoric acid group, or the carboxylic acid group forms the salt can also be illustrated preferably. In the present invention, the hydrocarbon chain of the compound or its partial structure may be described by a simplified structural formula in which symbols for carbon (C) and hydrogen (H) are omitted.

The specific copolymer that can be used in the present invention may have only one type of acidic monomer unit or may have two or more types of acidic monomer units.
The content ratio of acidic monomer units in the specific copolymer that can be used in the present invention is preferably 2 to 80 mol%, and preferably 2 to 70 mol%, based on all monomer units of the specific copolymer. More preferably, it is more preferably 5 to 50 mol%, and particularly preferably 10 to 40 mol%.

The hydrophilic monomer unit includes a sulfonic acid group (—SO ₃ H) and a salt thereof (—SO ₃ M (where M represents a counter cation other than proton (H ⁺ ))), an amide group (—CONR— (Wherein R represents a hydrogen atom or an organic group)) and a monomer unit having at least one group or structure selected from the group consisting of betaine structures.
The betaine structure is a structure having both a cation structure and an anion structure in one monomer unit, and the charge is neutralized in the same monomer unit.
The cation structure in the betaine structure is not particularly limited, but is preferably a quaternary nitrogen cation.
The anionic structure in the betaine structure is not particularly ^{_{limited, -COO -, -SO 3 -,}} -PO 3 2-, and / or, -PO ₃ H ^- is preferably, -COO ^-, and More preferably, it is —SO ₃ ^— .
The amide group may be —CONR— or —NRCO— in the monomer unit. R represents a hydrogen atom or an organic group, preferably a hydrogen atom or a monovalent hydrocarbon group, more preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.
The hydrophilic monomer unit is preferably a monomer unit having at least one group or structure selected from the group consisting of a sulfonic acid group and a salt thereof and a betaine structure.

  The hydrophilic monomer unit is preferably a monomer unit represented by the following formulas (U-6) to (U-8), and a monomer represented by the following formula (U-7) or (U-8) More preferably it is a unit.

（式（Ｕ−６）〜（Ｕ−８）中、Ｒ¹は、水素原子又はアルキル基を表し、Ｒ²及びＲ³はそれぞれ独立に、水素原子又は一価の炭化水素基を表し、Ａ³は、単結合又は（ｎ＋１）価の有機基を表し、Ａ⁴は、（ｎ＋１）価の有機基を表し、Ａ⁵はそれぞれ独立に、二価の有機基を表し、Ｘ¹はそれぞれ独立に、水素原子又はプロトン以外の対カチオンを表し、ｎは１以上の整数を表す。）

(In the formulas (U-6) to (U-8), R ¹ represents a hydrogen atom or an alkyl group, R ² and R ³ each independently represents a hydrogen atom or a monovalent hydrocarbon group, ³ represents a single bond or an (n + 1) -valent organic group, A ⁴ represents an (n + 1) -valent organic group, A ⁵ independently represents a divalent organic group, and X ¹ represents each independently Represents a counter cation other than a hydrogen atom or a proton, and n represents an integer of 1 or more.)

R ^1, X ¹ and n in Formula (U-6) ~ (U -8) have the same meanings as R ^1, X ¹ and n in the formula (U-1) ~ (U -3), preferable range It is the same.
The (n + 1) -valent organic group in A ³ of the formula (U-6) is preferably a group formed from at least one element selected from the group consisting of carbon, hydrogen, oxygen and nitrogen. A group obtained by removing (n + 1) hydrogen atoms from a hydrocarbon, or a group obtained by removing m hydrogen atoms from a hydrocarbon (where m represents an integer of 1 or more), an ester bond, an amide bond, and an ether A group obtained by combining two or more groups selected from the group consisting of a bond is more preferable.
The (n + 1) -valent organic group in A ⁴ of the formulas (U-7) and (U-8) is a group formed from at least one element selected from the group consisting of carbon, hydrogen, oxygen, and nitrogen And more preferably a group formed from at least one element selected from the group consisting of carbon, hydrogen and oxygen, a group obtained by removing (n + 1) hydrogen atoms from a hydrocarbon, or And a group obtained by combining two or more groups selected from the group consisting of an ester bond and a group obtained by removing m hydrogen atoms (however, m represents an integer of 1 or more) from a hydrocarbon. .
The divalent organic group in A ⁵ in the formulas (U-7) and (U-8) is a group formed from at least one element selected from the group consisting of carbon, hydrogen, and oxygen. Preferably, it is an alkylene group. The alkylene group may be linear or branched.
R ² and R ³ are each independently of the formula (U-7) and (U-8), represents a hydrogen atom or a monovalent hydrocarbon group, preferably a monovalent hydrocarbon group, the number of carbon atoms It is more preferably an alkyl group of 1 to 8, and further preferably a methyl group.

  The hydrophilic monomer unit is more preferably a monomer unit represented by the following formulas (U-9) to (U-12).

（式（Ｕ−９）〜（Ｕ−１２）中、Ｒ¹は、水素原子又はアルキル基を表し、Ｒ²及びＲ³はそれぞれ独立に、水素原子又は一価の炭化水素基を表し、Ａ⁶、Ａ⁷及びＡ⁸はそれぞれ独立に、二価の有機基を表し、Ｘ¹はそれぞれ独立に、水素原子又はプロトン以外の対カチオンを表す。）

(In formulas (U-9) to (U-12), R ¹ represents a hydrogen atom or an alkyl group, R ² and R ³ each independently represents a hydrogen atom or a monovalent hydrocarbon group, ⁶ , A ⁷ and A ⁸ each independently represent a divalent organic group, and X ¹ each independently represents a hydrogen atom or a counter cation other than a proton.)

R ¹ and X ¹ in Formula (U-9) ~ (U -12) has the same meaning as R ¹ and X ¹ in Formula (U-1) ~ (U -3), and preferred ranges are also the same.
R ² and R ³ in the formula (U-9) ~ (U -12) , the formula (U-7) and (U-8) have the same meanings as R ² and R ³ in the preferred range is also the same .
A ⁶ in the formulas (U-9) and (U-10) represents a divalent organic group, and is preferably a linear or branched alkylene group, and is a linear or branched alkylene group having 2 to 20 carbon atoms. More preferably, it is more preferably a linear or branched alkylene group having 2 to 10 carbon atoms.
A ⁷ in the formulas (U-11) and (U-12) represents a divalent organic group, preferably a linear or branched alkylene group, and is a linear or branched alkylene group having 2 to 20 carbon atoms. More preferably, it is more preferably a linear or branched alkylene group having 2 to 10 carbon atoms.
A ⁸ in the formulas (U-11) and (U-12) represents a divalent organic group, preferably a linear or branched alkylene group, and is a linear or branched alkylene group having 1 to 10 carbon atoms. More preferably, it is more preferably a linear or branched alkylene group having 1 to 4 carbon atoms.

  Specific examples of the hydrophilic monomer unit are preferably monomer units represented by the following (H-1) to (H-8). Moreover, the monomer unit which the sulfonic acid group of the monomer unit represented by the following (H-1)-(H-4) forms the salt can also be illustrated preferably.

The specific copolymer that can be used in the present invention may have only one type of hydrophilic monomer unit or may have two or more types of hydrophilic monomer units.
The content ratio of the hydrophilic monomer units in the specific copolymer that can be used in the present invention is preferably 30 to 98 mol%, and preferably 40 to 90 mol%, based on all monomer units of the specific copolymer. More preferably, it is more preferably 50 to 90 mol%.

Moreover, the specific copolymer which can be used for this invention may have another monomer unit other than an acidic monomer unit and a hydrophilic monomer unit.
There is no restriction | limiting in particular as another monomer unit, What is necessary is just a monomer unit obtained by copolymerizing a well-known monomer.
Moreover, as another monomer unit, the monomer unit which has a hydroxyl group and / or a polyalkyleneoxy group can illustrate preferably.
The content ratio of other monomer units in the specific copolymer that can be used in the present invention is preferably 40 mol% or less, and preferably 30 mol%, based on all monomer units of the specific copolymer. More preferably, it is still more preferably 20 mol% or less.

The specific copolymer is a vinyl copolymer.
The vinyl copolymer is, for example, a monomer having an ethylenically unsaturated bond such as acrylates, methacrylates, styrenes, aromatic vinyl compounds, aliphatic vinyl compounds, allyl compounds, acrylic acid, methacrylic acid and the like. It is a copolymer obtained by copolymerizing two or more monomers.
The specific copolymer may be any copolymer such as a random copolymer, a block copolymer, or a graft copolymer, but is preferably a random copolymer.
The acidic monomer unit, the hydrophilic monomer unit, and the other monomer unit are monomer units obtained from a monomer having an ethylenically unsaturated bond.

The plate surface treating agent of the present invention may contain one specific copolymer alone or two or more kinds.
The content of the specific copolymer in the plate surface treating agent of the present invention is preferably 0.005 to 10% by weight, more preferably 0.01 to 5% by weight, and 0.1 to 3% by weight. More preferably. If it is within the above range, the anti-staining effect of the non-image area and the halftone image area can be obtained.
The weight average molecular weight of the specific copolymer is preferably 5,000 or more, more preferably 10,000 or more, and preferably 1,000,000 or less, and 500,000 or less. More preferably.
The number average molecular weight of the specific copolymer is preferably 1,000 or more, more preferably 2,000 or more, and preferably 500,000 or less, and 300,000 or less. It is more preferable.
The polydispersity (weight average molecular weight / number average molecular weight) of the specific copolymer is preferably 1.1 to 10.

In the plate surface treating agent of the present invention, in addition to the above compound, a water-soluble polymer compound other than the specific copolymer, an inorganic acid, an inorganic acid salt, an organic acid, an organic acid salt, other than the above compound Surfactants, organic solvents, nitrates, sulfates, chelating agents, preservatives, antifoaming agents and the like can be included.
Various components are described below.

To the plate surface treating agent of the present invention, it is preferable to add a water-soluble polymer compound other than the specific copolymer having film-forming properties in order to maintain hydrophilicity and protect the plate surface from scratches. The specific copolymer may be water-soluble or not water-soluble, but is preferably water-soluble.
Examples of water-soluble polymer compounds other than the specific copolymer include gum arabic, fiber derivatives (eg, carboxymethylcellulose, carboxyethylcellulose, methylcellulose, hydroxypropylcellulose, methylpropylcellulose, etc.) and modified products thereof, polyvinyl alcohol And derivatives thereof, polyvinylpyrrolidone, polyacrylamide, vinyl methyl ether / maleic anhydride copolymer, vinyl acetate / maleic anhydride copolymer, styrene / maleic anhydride copolymer, starch derivatives (eg, dextrin, maltodextrin, Enzymatic degradation dextrin, hydroxypropylated starch, hydroxypropylated starch enzymatic degradation dextrin, carboxydimethylated starch, phosphorylated starch, cyclodextrin), pullulan and pullulan Conductor, and the like.
Other starch derivatives that can be used as water-soluble polymer compounds include roasted starch such as British gum, enzyme-modified dextrins such as enzyme dextrin and shardinger dextrin, oxidized starch shown in solubilized starch, and modified starch. Pregelatinized starch such as alpha starch and non-modified pregelatinized starch, phosphate starch, fat starch, sulfate starch, nitrate starch, xanthate starch and starch starch such as carbamic acid starch, carboxyalkyl starch, hydroxyalkyl starch, sulfo Alkyl starch, cyanoethyl starch, allyl starch, benzyl starch, carbamylethyl starch, dialkylamino starch and other etherified starches, methylol crosslinked starch, hydroxyalkyl crosslinked starch, phosphoric acid crosslinked starch, dicarboxylic acid crosslinked starch, etc. Amide copolymer, starch polyacrylic acid copolymer, starch polyvinyl acetate copolymer, starch polyacrylonitrile copolymer, chaotic starch polyacrylic acid ester copolymer, chaotic starch vinyl polymer copolymer, starch polystyrene Examples thereof include starch graft polymers such as maleic acid copolymer, starch polyethylene oxide copolymer, and starch polypropylene copolymer.
Examples of natural polymer compounds that can be used as water-soluble polymer compounds include water-soluble soybean polysaccharides, starch, gelatin, hemicellulose extracted from soybeans, potato starch, potato starch, tapioca starch, wheat starch and corn starch. Starch, Carrageenan, Laminaran, Sea Saumannan, Funari, Irish Moss, Agar, Algae, etc. , Plant mucous substances such as benzoin gum, homopolysaccharides such as dextran, glucan and levan, and microbial mucilages such as hetropolysaccharides such as succinoglucan and santangum, glue, gelatin, casein and Proteins such as collagen is preferable.
Among them, gum arabic, starch derivatives such as dextrin and hydroxypropyl starch, carboxymethyl cellulose, soybean polysaccharide and the like can be preferably used.
The content of the water-soluble polymer compound other than the specific copolymer is preferably 0.1 to 25.0% by weight, and more preferably 0.3 to 20.0% by weight.

In general, the plate surface treating agent of the present invention is more advantageously used in the acidic range of pH 2 to 6. In order to achieve such a pH, it is preferable to add and adjust a pH adjusting agent such as a mineral acid, an organic acid, or a salt thereof in the plate surface treatment agent.
Examples of the pH adjuster include nitric acid, sulfuric acid, phosphoric acid, metaphosphoric acid, and polyphosphoric acid as mineral acids. Examples of the organic acid include acetic acid, succinic acid, citric acid, malic acid, malonic acid, tartaric acid, p-toluenesulfonic acid, lactic acid, repric acid, phytic acid, and organic phosphonic acid. Preferred salts include disodium hydrogen phosphate, dipotassium hydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium dihydrogen phosphate, potassium pyrophosphate, sodium hexametaphosphate, sodium tripolyphosphate, sodium nitrate , Potassium nitrate, ammonium nitrate, sodium sulfate and the like.
A pH adjuster may be used individually by 1 type, or may use 2 or more types together. The addition amount is preferably 0.01 to 3.0% by weight.

The plate surface treating agent of the present invention preferably further contains a surfactant.
Examples of the surfactant include an anionic surfactant and / or a nonionic surfactant.
Anionic surfactants include fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinates, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, alkyl naphthalene sulfonates, Alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium, N-alkylsulfosuccinic acid monoamide disodium salts, petroleum sulfonates, sulfated castor oil, Sulfated tallow oil, sulfates of fatty acid alkyl esters, alkyl sulfates, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates Salts, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, styrene-anhydrous Examples thereof include partially saponified products of maleic acid copolymers, partially saponified products of olefin-maleic anhydride copolymers, and naphthalene sulfonate formalin condensates.
Among these, dialkyl sulfosuccinates, alkyl sulfate esters, and alkyl naphthalene sulfonates are particularly preferably used.

Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, glycerin fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol mono fatty acid esters, Sugar fatty acid partial ester, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene castor oil ether, polyoxyethylene sorbitol fatty acid partial ester, polyethylene glycol fatty acid ester, polyglycerin fatty acid partial ester, polyoxyethylene glycerin fatty acid partial ester , Fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamine, tri Ethanolamine fatty acid esters, such as trialkylamine oxides.
Among these, polyoxyethylene alkyl ethers, polyoxyethylene-polyoxypropylene block copolymers, polyoxyethylene castor oil ether, and the like are preferably used.
Acetylene glycol-based and acetylene alcohol-based oxyethylene adducts, fluorine-based, silicon-based anions, and nonionic surfactants can also be used in the same manner.

These surfactants can be used in combination of two or more. For example, a combination of two or more different anionic surfactants or a combination of an anionic surfactant and a nonionic surfactant is preferable. These compounds are preferably selected and used in consideration of environmental effects.
The amount of the surfactant used is not particularly limited, but is preferably 0.01 to 20% by weight in the plate surface treating agent.

It is preferable to add an organic solvent having a boiling point of 130 ° C. or higher to the plate surface treating agent of the present invention in order to protect the oil sensitivity of the image area. This type of organic solvent, on the other hand, functions to remove the trace amount of remaining photosensitive film adhering to the non-image area hydrophilic layer and to increase the hydrophilicity of the non-image area.
Specific examples of the organic solvent having a boiling point of 130 ° C. or higher include alcohols such as n-hexanol, 2-ethylbutanol, n-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethylhexanol, 3, 5 , 5-trimethylhexanol, nonanol, n-decanol, undecanol, n-dodecanol, trimethylnonyl alcohol, tetradecanol, cyclohexanol, benzyl alcohol, tetrahydrofurfuryl alcohol and the like.
Examples of ketones include methyl-n-amyl ketone, methyl-n-hexyl ketone, ethyl-n-butyl ketone, di-n-propyl ketone, diacetone alcohol, and cyclohexanone.
Examples of the esters include n-amyl acetate, isoamyl acetate, methyl isoamyl acetate, methoxybutyl acetate, benzyl acetate, ethyl lactate, butyl lactate, n-amyl lactate, methyl benzoate, ethyl benzoate, and benzyl benzoate. Phthalic acids such as benzoates, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dinonyl phthalate, didecyl phthalate, dilauryl phthalate, butyl benzyl phthalate Aliphatic dibasic esters such as diesters, dioctyl adipate, butyl glycol adipate, dioctyl azelate, dibutyl sebacate, di (2-ethylhexyl) sebacate, dioctyl sebacate, epoxidized trig such as epoxidized soybean oil Celite ethers, tricresyl phosphate, trioctyl phosphate, phosphate esters such as tris chloroethyl phosphate, and the like.
Examples of amides include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone and the like.

Polyhydric alcohols and their derivatives include ethylene glycol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol butyl ether, ethylene glycol dibutyl ether, ethylene glycol isoamyl ether, ethylene glycol monophenyl ether, ethylene glycol monophenyl Ether acetate, ethylene glycol benzyl ether, ethylene glycol monohexyl ether, methoxyethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether Ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol, propylene glycol, dipropylene glycol, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 1 -Butoxyethoxypropanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, butylene glycol, hexylene glycol, octylene glycol, glycerin, diglycerin , It may be mentioned trimethylolpropane, glycerol monoacetate, glycerol triacetates.
Examples of the hydrocarbon system include aromatics, aliphatic compounds, squalane and the like of petroleum fractions having a boiling point of 160 ° C. or higher.
Conditions for selecting an organic solvent having a boiling point of 130 ° C. or higher include its environmental safety, particularly odor. These solvents may be used alone or in combination of two or more.
The amount of the organic solvent having a boiling point of 130 ° C. or higher is preferably 0.1 to 5.0% by weight, and more preferably 0.3 to 3.0% by weight in the plate surface treating agent.
In the plate surface treating agent of the present invention, these organic solvents may be solubilized with a surfactant to be a solution type, or emulsified and dispersed as an oil phase to be an emulsified type.

The plate surface treating agent of the present invention may contain nitrate or sulfate.
Examples of nitrates and sulfates that can be included in the plate surface treating agent include magnesium nitrate, sodium nitrate, potassium nitrate, ammonium nitrate, sodium sulfate, potassium sulfate, ammonium sulfate, sodium hydrogen sulfate, nickel sulfate, and the like.
The amount of these used is preferably 0.05 to 1.0% by weight in the plate surface treating agent.

Usually, the plate surface treatment agent is often marketed as a concentrated solution, and is used after being diluted by adding tap water, well water or the like at the time of use. Since calcium ions contained in the diluted tap water and well water adversely affect printing and may cause the printed matter to be easily stained, the plate surface treatment agent of the present invention is used to eliminate this drawback. It is preferable to contain a chelate compound.
Preferable chelate compounds include, for example, Na ₂ P ₂ O ₇ , Na ₅ P ₃ O ₃ , Na ₃ P ₃ O ₉ , Na ₂ O ₄ P (NaO ₃ P) PO ₃ Na ₂ , calgon (sodium polymetaphosphate) Such as polyphosphate, ethylenediaminetetraacetic acid, its potassium salt, its sodium salt; dihydroxyethylglycine, its potassium salt, its sodium salt; hydroxyiminodiacetic acid, its potassium salt, its sodium salt; glycol ether diamine tetraacetic acid, its Potassium salt, sodium salt thereof; diethylenetriaminepentaacetic acid, potassium salt thereof, sodium salt thereof; triethylenetetramine hexaacetic acid, potassium salt thereof, sodium salt thereof, hydroxyethylethylenediaminetriacetic acid, potassium salt thereof, sodium salt thereof; -Diaminosi Rhohexanetetraacetic acid, its potassium salt, its sodium salt; aminopolycarboxylic acids such as 1,3-diamino-2-propanoltetraacetic acid, its potassium salt, its sodium salt, nitrilotriacetic acid, its potassium salt, its sodium 1-hydroxyethane-1,1-diphosphonic acid, its potassium salt, its sodium salt; aminotri (methylenephosphonic acid), its potassium salt, its sodium salt; ethyleneaziminetetra (methylenephosphonic acid), its potassium salt , Its sodium salt; diethylenetriaminepenta (methylenephosphonic acid), its potassium salt, its sodium salt; organic phosphonic acids such as hexamethylenediaminetetra (methylenephosphonic acid), its potassium salt, its sodium salt, etc., or 2-phospho Butanetricarboxylic acid-1,2,4, potassium salt thereof, sodium salt thereof; 2 monophosphonobutanone tricarboxylic acid-2,3,4, potassium salt thereof, sodium salt thereof; 1-phosphonoethanetricarboxylic acid-1, Examples include phosphonoalkanetricarboxylic acids such as 2, 2, its potassium salt, its sodium salt and the like.
An organic amine salt is also effective in place of the sodium salt or potassium salt of the chelate compound.
These chelate compounds are selected so that they are stably present in the plate surface treating agent composition and do not impair the printability.
The addition amount of the chelate compound is preferably 0.001 to 1.0% by weight with respect to the plate surface treating agent at the time of use.

A preservative, an antifoaming agent, etc. can be further added to the plate surface treating agent of the present invention.
Examples of preservatives include phenol or derivatives thereof, formalin, imidazole derivatives, sodium dehydroacetate, 4-isothiazolin-3-one derivatives, benzisothiazolin-3-one, benztriazole derivatives, amiding anidine derivatives, quaternary ammonium salts, pyridine , Derivatives of quinoline, guanidine, etc., diazine, triazole derivatives, oxazole, oxazine derivatives, 2-bromo-2-nitropropane-1,3-diol of nitrobromoalcohol, 1,1-dibromo-1-nitro-2- Examples include ethanol, 1,1-dibromo-1-nitro-2-propanol, and omadins.
A preferable addition amount of the preservative is an amount that stably exerts an effect on bacteria, fungi, yeast, and the like, and varies depending on the type of bacteria, fungi, yeast, etc. The range of ˜4.0% by weight is preferable, and two or more kinds of preservatives are preferably used in combination so as to be effective against various molds and sterilization.
In addition, as the antifoaming agent, a general silicone-based self-emulsifying type, emulsifying type, surfactant nonionic HLB (Hydrophile-Lipophile Balance) value of 5 or less can be used. Silicone defoamers are preferred. Among them, an emulsified dispersion type and a solubilized type can be used. The content of the antifoaming agent is preferably 0.001 to 1.0% by weight in the plate surface treating agent.

The balance of the plate surface protective agent of the present invention is preferably water.
When the plate surface protective agent of the present invention is prepared as a solution type or an emulsification type, it can be prepared according to a conventional method. For example, for emulsification dispersion, prepare the aqueous phase at a temperature of 40 ° C ± 5 ° C, stir at high speed, slowly drop the prepared oil phase into the aqueous phase, stir well, and then prepare the emulsion through a pressure homogenizer. Can do.

  The plate surface treating agent of the present invention can be used for either a positive lithographic printing plate precursor or a negative lithographic printing plate precursor, and can be used for making a lithographic printing plate from various lithographic printing plate precursors. Further, the development method of the lithographic printing plate precursor may be a thermal method or a photopolymer method.

<Negative photosensitive layer>
The lithographic printing plate precursor that can be used in the present invention is not particularly limited, and contains (A) a sensitizing dye, (B) a polymerization initiator, (C) a polymerizable compound, and (D) a binder polymer. A lithographic printing plate precursor having a negative type (negative type) photosensitive layer (hereinafter also referred to as “image forming layer” or “recording layer”) is preferable.

(A) Sensitizing dye The photosensitive layer in the lithographic printing plate precursor that can be used in the invention preferably contains a sensitizing dye.
There is no restriction | limiting in particular as a sensitizing dye which can be used for this invention, A well-known sensitizing dye can be used.
For example, by adding a sensitizing dye having a maximum absorption at 300 to 450 nm, a sensitizing dye having a maximum absorption at 500 to 600 nm, and a sensitizing dye (infrared absorber) having a maximum absorption at 750 to 1,400 nm. , A high-sensitivity lithographic printing plate precursor corresponding to a 405 nm violet laser, a 532 nm green laser, and a 830 nm IR laser, which are usually used in the industry, can be provided.

  The sensitizing dye having a maximum absorption at 750 to 1,400 nm that is preferably used in the present invention will be described in detail. In the present invention, the “sensitizing dye having maximum absorption at 750 to 1,400 nm” is also referred to as “infrared absorber”. The infrared absorber is preferably a dye or pigment having an absorption maximum at a wavelength of 750 to 1,400 nm.

As the dye, commercially available dyes and known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used.
Specifically, dyes such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes, etc. Is mentioned. Particularly preferred among these dyes are cyanine dyes, squarylium dyes, pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes. Further, cyanine dyes and indolenine cyanine dyes are preferred, and particularly preferred examples include cyanine dyes represented by the following formula (a).

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

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

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

These infrared absorbers may be added to the same layer as other components, or another layer may be provided and added thereto.
The content of these infrared absorbers in the photosensitive layer is 0.01 to 50% by weight with respect to the total solid content constituting the photosensitive layer, from the viewpoint of uniformity in the photosensitive layer and durability of the photosensitive layer. It is preferably 0.1 to 10% by weight, more preferably 0.5 to 10% by weight.

  Other infrared absorbers include paragraphs 0012 to 0038 of JP-A No. 2002-40638, paragraphs 0144 to 0174 of JP-A No. 2004-250158, paragraphs 0219 to 0249 of JP-A No. 2005-47947, and JP-A No. 2005-91617. Paragraphs 0231 to 0260, paragraphs 0219 to 0249 of JP-A-2005-91618, paragraphs 0195 to 0224 of JP-A-2005-134893, paragraphs 0144 to 0173 of JP-A-2005-250158, paragraphs of JP-A-2005-250438 0192 to 0201, paragraphs 0241 to 0273 of JP-A-2005-257949, paragraphs 0235 to 0268 of JP-A-2005-298567, paragraphs 0243 to 0276 of JP-A-2005-300650, paragraph 0177 of JP-A-2005-300817 018 JP-A-2006-267289, paragraphs 0215-0224, JP-A-2007-17948, paragraphs 0107-0124, JP-A-2007-47742, paragraphs 0275-0304, JP-A-2007-248863, paragraphs 0188-0206, JP 2007-249036, paragraphs 0114 to 0125, JP 2007-249037, paragraphs 0115 to 0123, JP 2008-242093, paragraphs 0115 to 0145, and JP 2008-249851, paragraphs 0040 to 0061 Those described can be preferably used.

Next, a sensitizing dye having a maximum absorption in the wavelength region of 350 to 450 nm will be described.
Examples of such a sensitizing dye include merocyanine dyes, benzopyrans, coumarins, aromatic ketones, anthracenes, and the like.

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

（式（IX）中、Ａは置換基を有してもよい芳香族環基又はヘテロ環基を表し、Ｘは酸素原子、硫黄原子又はＮＲ₃を表す。Ｒ₁、Ｒ₂及びＲ₃は、それぞれ独立に、一価の非金属原子団を表し、ＡとＲ₁及びＲ₂とＲ₃はそれぞれ互いに結合して、脂肪族性又は芳香族性の環を形成してもよい。）

(In the formula (IX), A represents an aromatic ring group or a heterocyclic group which may have a substituent, X represents an oxygen atom, a sulfur atom or NR _3. R ₁ , R ₂ and R ₃ represent Each independently represents a monovalent non-metallic atomic group, and A and R ₁ and R ₂ and R ₃ may be bonded to each other to form an aliphatic or aromatic ring.)

R _1, R ₂ and R ₃ independently denote a monovalent non-metallic atomic group, preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, It represents a substituted or unsubstituted aromatic heterocyclic residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, or a halogen atom.

Next, A in the formula (IX) represents an aromatic ring group or a heterocyclic group which may have a substituent. Specific examples of the aromatic ring or heterocyclic ring which may have a substituent include The thing similar to what was described by R < ₁ >, R < ₂ > and R < ₃ > in Formula (IX) is mentioned.

  As specific examples of such a sensitizing dye, compounds described in paragraphs 0047 to 0053 of JP-A-2007-58170 are preferably used.

  Further, paragraphs 0168-0218 of JP-A-2005-47947, paragraphs 0180-0230 of JP-A-2005-91617, paragraphs 0168 of JP-A-2005-91618) to 0218, paragraphs 0144 to 0194 of JP-A-2005-134893. JP-A-2005-250158, paragraphs 0192 to 0242, JP-A-2005-250438, paragraphs 0202 to 0250, JP-A-2005-257949, paragraphs 0190 to 240, JP-A-2005-298567, paragraphs 0184 to 0234, JP 2005-300650, paragraphs 0192 to 0242, JP 2005-300817, paragraphs 0170 to 0176, JP 2006-267289, paragraphs 0225 to 0273, JP 2007-17948, paragraphs 0058 to 0084, JP 2007 -47 No. 42, paragraphs 0230 to 0274, JP 2007-248863, paragraphs 0207 to 0246, JP 2007-249036, paragraphs 0076 to 0113, JP 2007-249037, paragraphs 0078 to 0114, and JP 2007-171406. Paragraphs 0033-0038, paragraphs 0023-0059 of JP 2007-206216, paragraphs 0016-0043 of JP 2007-225701, paragraphs 0037-0049 of JP 2007-316582, paragraphs of JP 2007-328243. The sensitizing dyes described in JP-A Nos. 0026 to 0115 and paragraphs 0067 to 0114 of JP-A-2008-242903 can also be preferably used.

(B) Polymerization initiator The photosensitive layer in the lithographic printing plate precursor that can be used in the invention preferably contains a polymerization initiator (hereinafter also referred to as “initiator compound”).

As the initiator compound in the present invention, those known to those skilled in the art can be used without limitation. Specifically, for example, trihalomethyl compounds, carbonyl compounds, organic peroxides, azo compounds, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boron compounds, disulfone compounds, oxime ester compounds, onium salt compounds, An iron arene complex is mentioned.
Among these, at least one selected from the group consisting of hexaarylbiimidazole compounds, onium salts, trihalomethyl compounds and metallocene compounds is preferable, and at least one selected from the group consisting of hexaarylbiimidazole compounds and onium salts. Particularly preferred is a seed.
Two or more of the above polymerization initiators can be used in combination as appropriate.

Examples of hexaarylbiimidazole compounds include lophine dimers described in JP-B Nos. 45-37377 and 44-86516, such as 2,2′-bis (o-chlorophenyl) -4,4 ′, 5. , 5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2, 2′-bis (o, o′-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5 ′ -Tetraphenylbiimidazole 2,2′-bis (o-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole.
The hexaarylbiimidazole compound is particularly preferably used in combination with a sensitizing dye having a maximum absorption at 300 to 450 nm.

  The onium salt suitably used in the present invention is an onium salt represented by the following formulas (RI-I) to (RI-III).

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

In formula (RI-II), Ar ₂₁ and Ar ₂₂ each independently represent an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents include 1 to 1 carbon atoms. 12 alkyl groups, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, Halogen atom, C1-C12 alkylamino group, C1-C12 dialkylamino group, C1-C12 alkylamide group or arylamide group, carbonyl group, carboxyl group, cyano group, sulfonyl group, carbon Examples thereof include a thioalkyl group having 1 to 12 carbon atoms and a thioaryl group having 1 to 12 carbon atoms.
Z ₂₁ ⁻ represents a monovalent anion. Specific examples include halide ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, thiosulfonate ions, and sulfate ions. Among these, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, and carboxylate ion are preferable from the viewpoint of stability and reactivity.

In the formula (RI-III), R ₃₁ , R ₃₂ and R ₃₃ are each independently an aryl group, alkyl group, alkenyl group or alkynyl group having 20 or less carbon atoms which may have 1 to 6 substituents. Represents. Among them, an aryl group is preferable from the viewpoint of reactivity and stability. Examples of the substituent include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, Aryloxy group having 1 to 12 carbon atoms, halogen atom, alkylamino group having 1 to 12 carbon atoms, dialkylamino group having 1 to 12 carbon atoms, alkylamide group or arylamide group having 1 to 12 carbon atoms, carbonyl group, carboxyl Group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms.
Z ₃₁ ^- represents a monovalent anion. Specific examples include halide ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, thiosulfonate ions, and sulfate ions. Of these, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, and carboxylate ion are preferable from the viewpoints of stability and reactivity. More preferred are the carboxylate ions described in JP-A No. 2001-343742, and particularly preferred are the carboxylate ions described in JP-A No. 2002-148790.

  Examples of other polymerization initiators include paragraphs 0065 to 0124 of JP-A No. 2004-317652, paragraphs 0202 to 0264 of JP-A No. 2005-47947, paragraphs 0091 to 0164 of JP-A No. 2005-91618, and JP-A No. 2005-134893. Paragraphs 0031 to 0104, paragraphs 0103 to 0140 of JP-A-2005-250158, paragraphs 0115 to 0189 of 2005-300650, paragraphs 0120 to 0209 of JP-A 2006-267289, paragraphs 0051 to JP-A 2007-17948 0054, paragraphs 0190 to 0227 of JP 2007-47742, paragraphs 0111 to 0185 of JP 2007-248863, paragraphs 0037 to 0062 of JP 2007-249036, paragraphs 0038 to 0063 of JP 2007-249037, Special Paragraphs 0039 to 0047 of 2007-171406, Paragraphs 0060 to 0115 of JP-A-2007-206216, Paragraphs 0071 to 0126 of JP-A-2007-206217, Paragraphs 0050 to 0059 of JP-A-2007-316582, JP-A-2008- Those described in JP-A-242093, 0042 to 0066, and JP-A-2008-276167, paragraphs 0016 to 0054 can be preferably used.

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

(C) Polymerizable compound The photosensitive layer in the lithographic printing plate precursor that can be used in the invention preferably contains a polymerizable compound.
The polymerizable compound that can be used in the photosensitive layer in the present invention is a compound having at least one ethylenically unsaturated bond, and is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. It is. Such a compound group is widely known in the industrial field, and in the present invention, these compounds can be used without any particular limitation.
Examples of monomers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, preferably unsaturated carboxylic acids. An ester of an acid and an alcohol compound and an amide of an unsaturated carboxylic acid and an amine compound are used.
In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional compound. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or A substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

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

  Examples of amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

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

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in Japanese Patent No. 17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Depending on the case, it is possible to obtain a photopolymerizable composition excellent in the photosensitive speed.

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

The polymerizable compounds in the photosensitive layer may be used alone or in combination of two or more.
The content of the polymerizable compound in the photosensitive layer is preferably 5 to 75% by weight, more preferably 25 to 70% by weight, and more preferably 30 to 60% by weight with respect to the total solid content of the photosensitive layer. More preferably.

(D) Binder polymer The photosensitive layer in the lithographic printing plate precursor that can be used in the present invention preferably contains a binder polymer.
The chemical structure of the binder polymer that can be used in the present invention is not particularly limited, but is preferably an organic polymer having an acid group from the viewpoint of solubility in an alkaline processing liquid, that is, developability, and particularly a carboxylic acid or a salt thereof. The organic polymer to contain is more preferable.
Examples of the binder polymer that can be used in the present invention include carboxylic acid-containing alkaline water-soluble or swellable organic polymers. Examples of such organic polymers include addition polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957. , JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, methacrylic acid copolymer, acrylic acid copolymer, itacon Acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and the like are useful. As the binder polymer, a copolymer containing a monomer unit derived from a (meth) acrylic acid ester containing a carboxylic acid (salt) group is preferable.
Also useful are acidic cellulose derivatives having a carboxylic acid group in the side chain, and those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxy group. Further, Japanese Patent Publication No. 7-120040, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Application Laid-Open No. 63-287944, Japanese Patent Application Laid-Open No. 63-287947, Japanese Patent Application Laid-Open No. Polyurethane resins described in JP-A Nos. 271741 and 11-352691 are also useful as alkaline water-soluble or swellable binders. As the binder polymer that can be used in the present invention, an acrylic resin, a methacrylic resin, or a urethane resin is preferably used.

  An example of a material suitable as a binder polymer that can be used in the present invention is a copolymer having (a) a monomer unit containing a carboxylic acid group (including a salt thereof) and (b) a monomer unit imparting radical crosslinkability. It is a polymer.

(A) Although it does not specifically limit as a monomer unit containing a carboxylic acid group, The structure of Paragraph 0059-0075 of Unexamined-Japanese-Patent No. 2002-40652 and Unexamined-Japanese-Patent No. 2005-300650 is used preferably.
(B) Although it does not specifically limit as a monomer unit which provides radical crosslinkability, The structure as described in Paragraph 0041-0053 of Unexamined-Japanese-Patent No. 2007-248863 is used preferably.

The binder polymer that can be used in the present invention includes a monomer unit derived from an ethylenically unsaturated compound that does not include (a) a monomer unit containing a carboxylic acid group and (b) a monomer unit imparting radical crosslinkability. You may have as a polymerization component.
As such a monomer unit, a monomer unit derived from (meth) acrylic acid ester or (meth) acrylic acid amide is preferable. In particular, a monomer unit derived from an amide group (meth) acrylic acid amide described in paragraphs 0061 to 0084 of JP-A-2007-272134 is preferably used. The content of this monomer is preferably 5 to 50 units, more preferably 5 to 35 units, even more preferably 5 to 25 units, when the total number of monomer units is 100. .

  In the photosensitive layer according to the invention, a urethane resin having a crosslinkable group in the side chain can be used as the binder polymer in addition to the addition polymer having the above-mentioned combination of monomer units. Here, the crosslinkable group is a group capable of crosslinking the binder polymer by a chemical reaction occurring in the image forming layer when the lithographic printing plate precursor is exposed. The chemical structure is not particularly limited as long as it has such a function. For example, an ethylenically unsaturated group is preferable as a functional group capable of addition polymerization. Moreover, the functional group described in Paragraphs 0130 to 0139 of Unexamined-Japanese-Patent No. 2007-17948 can be illustrated.

  The polyurethane resin having a crosslinkable group in the side chain particularly preferably used in the present invention comprises (i) a diisocyanate compound, (ii) a diol compound having a carboxyl group, (iii) a diisocyanate compound having a crosslinkable group, and If present, it can be obtained by polyaddition reaction of (iv) a diol compound having no carboxyl group and (v) a compound having an amino group.

  Examples of the compounds (i), (ii) and (iii) include formulas (4) to (10) and specific examples described in paragraphs 0142 to 0167 of JP-A No. 2007-17948. The compound of (iv) includes the general formula (A ′), formulas (a) to (e), formulas (11) to (22) and specific examples described in paragraphs 0180 to 0225 of JP-A No. 2007-17948. Compounds. Examples of the compound (v) include Formula (31) and Formula (32) described in paragraphs 0227 to 0230 of JP-A No. 2007-17948 and specific compounds. In addition to the above polyurethane resin, a polyurethane resin obtained by introducing a crosslinkable group into a polyurethane having a carboxyl group as described in JP-A-2003-270775 by a polymer reaction can also be exemplified.

  In order to maintain the developability of the photosensitive layer, the binder polymer used preferably has an appropriate molecular weight, more preferably a weight average molecular weight of 5,000 to 300,000, and 20,000 to More preferably, it is 150,000.

  These binder polymers can be contained in an arbitrary amount in the photosensitive layer, but the content of the binder polymer in the photosensitive layer is preferably 10 to 90% by weight, and 30 to 80% by weight. More preferably.

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

<Acid cross-linked layer>
As one of the thermal negative type image recording layers, an acid cross-linked image recording layer (acid cross-linked layer) is also preferably exemplified. The acid-crosslinking layer comprises a photothermal conversion substance, a thermal acid generator, a compound that crosslinks with an acid that is a curable compound (crosslinking agent), and an alkali-soluble polymer compound that can react with the crosslinking agent in the presence of an acid. contains. In the acid cross-linking layer, infrared light absorbed by the photothermal conversion substance is converted into heat, the heat acid generator is decomposed by this heat to generate an acid, and the generated acid reacts with the cross-linking agent and the alkali-soluble polymer compound. And harden. Specifically, for example, photosensitive layers described in JP-A-7-306528, JP-A-8-276558, JP-A-10-123701, and JP-A-10-203037 are preferably used.

<Positive photosensitive layer>
A positive type (positive type) photosensitive composition contains an alkali-soluble polymer compound and a photothermal conversion substance. In the positive-type image recording layer, the photothermal conversion substance converts light energy such as an infrared laser into heat, and the heat efficiently releases the interaction that reduces the alkali solubility of the alkali-soluble polymer compound. Specifically, JP-A-11-218914, JP-A-2001-215893, JP-A-2001-305722, JP-A-2002-311570, JP-A-2002-3233769, JP-A-2007-122003, JP-A-2008. JP-A-64778, JP-A-2008-64959, JP-A-2008-76516, JP-A-2008-76996, JP-A-2008-197566, JP-A-2008-209774, JP-A-2008-224991, JP-A-2008-. The photosensitive layer described in each publication of No. 233496 is preferably used.

<Formation of photosensitive layer>
The photosensitive layer in the lithographic printing plate precursor that can be used in the present invention can be formed by preparing or applying a coating solution by dispersing or dissolving the necessary components described above in a solvent. As the solvent used here, compounds described in paragraph 0159 of JP-A-2007-249037 are preferably used, and these solvents are used alone or in combination.
The solid content concentration of the coating solution is preferably 1 to 50% by weight.
Moreover, although the photosensitive layer coating amount (solid content) on the support obtained after coating and drying varies depending on the application, it is preferably 0.3 to 3.0 g / m ² . Within the above range, good sensitivity and good film properties of the photosensitive layer can be obtained.

<Protective layer>
The lithographic printing plate precursor that can be used in the present invention comprises a protective layer on the image recording layer, if necessary, for preventing the occurrence of scratches in the image recording layer, blocking oxygen, and preventing ablation during high-illumination laser exposure. May be provided.
In the present invention, the exposure is usually performed in the atmosphere, but the protective layer is an image of low molecular weight compounds such as oxygen and basic substances present in the atmosphere that inhibit the image forming reaction caused by exposure in the image recording layer. This prevents the recording layer from being mixed, and prevents the image formation reaction from being hindered by exposure in the air. Therefore, the properties desired for the protective layer are low permeability of low molecular compounds such as oxygen, furthermore, good transparency of light used for exposure, excellent adhesion with the image recording layer, and It is preferable that it can be easily removed in an on-press development process after exposure. Various studies have been made on the protective layer having such characteristics, and are described in detail, for example, in US Pat. No. 3,458,311 and JP-B-55-49729.
Moreover, as a protective layer, the protective layer described in Paragraph 0200-0261 of Unexamined-Japanese-Patent No. 2008-15503 and Unexamined-Japanese-Patent No. 2008-139813 can be used suitably.

<Support>
The support that can be used for the lithographic printing plate precursor is not particularly limited as long as it is a dimensionally stable plate-like support, but is preferably a hydrophilic support, and more preferably an aluminum plate. .
For example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate) Cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), paper or plastic film on which the metal is laminated or deposited. A preferable support includes a polyester film and an aluminum plate. Among them, an aluminum plate that has good dimensional stability and is relatively inexpensive is preferable.
Specific examples of the aluminum support and the treatment method include preferably the aluminum support and the treatment method described in JP-A-2005-88300.

Further, in the present invention, high-strength aluminum can be preferably used, and specifically, those described in JP-A-2008-291305 can be suitably used.
The support that can be used for the lithographic printing plate precursor is preferably subjected to a surface roughening treatment.
For the roughening treatment of the support, methods described in JP-A-2005-88300 and the like can be referred to.
Further, the support that can be used for the lithographic printing plate precursor is preferably a support that has been subjected to an electrochemical surface roughening treatment with an aqueous hydrochloric acid solution. More preferably, the support is subjected to a roughening treatment and an electrochemical roughening treatment with an aqueous hydrochloric acid solution. In the case of the above embodiment, when the plate surface treating agent of the present invention is used, the anti-staining property of the non-image area is more excellent.
The average opening diameter of the small pits in the support subjected to electrochemical surface roughening with an aqueous hydrochloric acid solution is preferably 0.05 to 0.8 μm, more preferably 0.1 to 0.6 μm. The average opening diameter of the small pits is calculated by the measurement method described in paragraphs 0029 to 0036 of JP-A-2006-272745.

<Undercoat layer>
The lithographic printing plate precursor according to the invention may be provided with an undercoat layer (also referred to as “intermediate layer”) for the purpose of improving the adhesion between the photosensitive layer and the support and the stain resistance.
Specific examples of such an undercoat layer (intermediate layer) include JP-B-50-7481, JP-A-54-72104, JP-A-59-101651, JP-A-60-149491, and JP-A-60. -232998, JP-A-3-56177, JP-A-4-282737, JP-A-5-16558, JP-A-5-246171, JP-A-7-159983, JP-A-7-314937, JP-A-8-. 202025, JP-A-8-320551, JP-A-9-34104, JP-A-9-236911, JP-A-9-269593, JP-A-10-69092, JP-A-10-115931, JP-A-10-161317 JP-A-10-260536, JP-A-10-282682, JP-A-11-84684, JP-A-11-38635, JP-A-11-38 29, JP-A-10-282645, JP-A-10-301262, JP-A-11-24277, JP-A-11-109641, JP-A-10-319600, JP-A-11-327152, JP-A-2000-10292 And JP-A-2000-235254, JP-A-2000-352824, and JP-A-2001-209170.

In the lithographic printing plate precursor, it is preferable to provide an undercoat layer of a compound containing a polymerizable group on a support. The undercoat layer using a compound containing a polymerizable group enhances the adhesion between the support and the photosensitive layer in the exposed area, and easily peels off the photosensitive layer from the support in the unexposed area. Therefore, developability is improved.
As an undercoat layer using a compound containing a polymerizable group, specifically, a silane cup having an addition-polymerizable ethylenic double bond reactive group described in JP-A-10-282679. Preferable examples include a ring agent and a phosphorus compound having an ethylenic double bond reactive group described in JP-A-2-304441. Particularly preferable compounds include compounds having a polymerizable group such as a methacryl group or an allyl group and a support adsorbing group such as a sulfonic acid group, a phosphoric acid group, or a phosphoric acid ester. A compound having a hydrophilicity-imparting group such as an ethylene oxide group in addition to the polymerizable group and the support-adsorbing group can also be exemplified as a suitable compound.

  The undercoat layer preferably also contains a resin having a phosphate group and / or a phosphonic acid group. In particular, it preferably has a resin having a phosphonic acid group, and an undercoat layer formed by treatment with the polyvinylphosphonic acid mentioned in the hydrophilization treatment of the support is preferably used. In particular, a resin having the following structure is preferably used. In addition, the ratio of each monomer unit described in the following chemical structural formula is a molar ratio.

The coating amount (solid content) of the undercoat layer is preferably 0.1-100 mg / m ^2, more preferably 1 to 30 mg / m ^2.

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

[Processing for planographic printing plates]
The processing method of the lithographic printing plate of the present invention is not particularly limited as long as it is a method using the lithographic printing plate surface treatment agent of the present invention, but the step of image exposure of the lithographic printing plate precursor (hereinafter referred to as “exposure step”). ), A step of developing with a processing solution (hereinafter also referred to as “developing step”), and a step of performing plate surface treatment using the lithographic printing plate surface treatment agent of the present invention (hereinafter referred to as “plate surface treatment”). It is preferable that the method includes a step.

<Exposure process and development process>
The processing method of the lithographic printing plate of the present invention is not particularly limited as long as it is a method using the lithographic printing plate surface treatment agent of the present invention, but the step of image-exposing the lithographic printing plate precursor and a developer It is preferable to include a step of developing.
Here, the development processing means that an unexposed portion of the photosensitive layer is removed with a developer to form an image corresponding to the exposed portion.

  In the present invention, in the plate making process for producing a lithographic printing plate from a lithographic printing plate precursor, the entire surface of the lithographic printing plate precursor may be heated before exposure, during exposure, and between exposure and development, as necessary. . By such heating, an image forming reaction in the image forming layer is promoted, and the advantages of improved sensitivity, improved printing durability, and stabilized sensitivity are obtained. Further, for the purpose of improving the image strength and printing durability, it is also effective to post-heat the image obtained by development or to expose the entire surface. Usually, heating before development is preferably performed under mild conditions of 150 ° C. or less. Stronger conditions are used for heating after development. A temperature range of 200-500 ° C is preferred.

As the lithographic printing plate precursor that can be used in the processing method of the lithographic printing plate of the present invention, those described above can be suitably used.
The lithographic printing plate precursor that can be used in the present invention is preferably a lithographic printing plate precursor that can be recorded with a laser such as a visible light laser or an infrared laser. Thermal recording with an ultraviolet lamp or a thermal head is also possible.
The exposure light source that can be used in the present invention can be appropriately selected according to the mode of the photosensitive layer, but a visible light laser having a wavelength of 350 nm to 450 nm, a solid-state laser and a semiconductor laser emitting infrared light having a wavelength of 760 nm to 1,200 nm. It is preferable that the lithographic printing plate precursor is image-exposed.

  The lithographic printing plate precursor that can be used in the present invention is preferably developed with water or an alkaline aqueous solution after exposure.

As a developer and a replenisher for a lithographic printing plate precursor, a conventionally known alkaline aqueous solution can be used.
For example, sodium silicate, potassium, tribasic sodium phosphate, potassium, ammonium, dibasic sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium Examples include inorganic alkali salts such as ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium, and lithium.
Moreover, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine, and pyridine can also be used.
These alkaline agents can be used alone or in combination of two or more.
The pH of the developer or replenisher is preferably 14 or less, more preferably 8 to 13, and still more preferably 11 to 13.

  Furthermore, when developing using an automatic developing machine, the developer in the developing tank can be developed for a long time by adding an aqueous solution (replenisher) that is the same as the developer or higher in alkali strength than the developer. It is known that a large amount of a lithographic printing plate precursor can be processed without changing the liquid. This replenishment method is also preferably applied in the present invention.

Various surfactants, organic solvents, and the like can be added to the developer and the replenisher as necessary for the purpose of promoting and suppressing developability, dispersing development residue, and improving the ink affinity of the printing plate image area.
Examples of the surfactant include anionic, cationic, nonionic and amphoteric surfactants.
Preferred organic solvents include benzyl alcohol. Further, addition of polyethylene glycol or a derivative thereof, or polypropylene glycol or a derivative thereof is also preferable. In addition, non-reducing sugars such as arabit, sorbit and mannitol can be added.

  Further, in the developer and replenisher, if necessary, inorganic salt-based reducing agents such as hydroquinone, resorcin, sodium sulfite or sodium bisulfite, potassium salt, organic carboxylic acid, antifoaming agent, water softener Can also be added.

<Plate surface treatment process>
The processing method of a lithographic printing plate of the present invention includes a step of performing a plate surface treatment using the lithographic printing plate surface treatment agent of the present invention.
Although the usage aspect of the plate surface treating agent of this invention is not restrict | limited in particular, when an automatic gum applicator etc. are used, it can apply | coat uniformly and is preferable.
The treatment with the plate surface treating agent of the present invention can be carried out immediately after the development step by anhydrous washing, or after the development treatment (including washing step, washing with circulating water or a small amount of applied washing with water) or containing a surfactant. It can also be performed after the treatment with the rinse solution.

The plate surface treatment with the plate surface treating agent of the present invention is also suitably performed using an automatic developing machine. This automatic processor generally comprises a developing unit and a post-processing unit, and includes a device for transporting a lithographic printing plate precursor, each processing solution tank and a spray device, and transports the exposed lithographic printing plate precursor horizontally. However, each processing liquid pumped up by the pump is sprayed from the spray nozzle to develop and post-process. In addition, a method of immersing and transporting in a processing liquid tank filled with the processing liquid by a guide roll in the liquid and developing processing, or supplying a small amount of rinsing water after development to the plate surface and rinsing the waste water A method of reusing as a diluting water for a developer stock solution is also known.
In such automatic processing, each processing solution can be processed while being replenished with each replenisher according to the processing amount, operating time, and the like. In addition, a so-called disposable processing method in which processing is performed with a substantially unused processing solution can also be applied. The planographic printing plate obtained by such processing is loaded on an offset printing machine and used for printing a large number of sheets.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to these examples.
In the following description, “parts” means “parts by weight” unless otherwise specified.

(Examples 1-17 and Comparative Examples 1-4)
<Production of support>
The following aluminum plates were used.
S-1 to S-5: Aluminum plate having a thickness of 0.30 mm (Si: 0.09 wt%, Fe: 0.30 wt%, Cu: 0.013 wt%, Mn: 0.001 wt%, Mg : 0.001% by weight, Zn: 0.001% by weight, Ti: 0.027% by weight, the balance being Al and inevitable impurities aluminum alloy)
S-6: 0.30 mm thick aluminum plate (Si: 0.09 wt%, Fe: 0.30 wt%, Cu: 0.013 wt%, Mn: 0.001 wt%, Mg: 0.08 (Wt%, Zn: 0.001 wt%, Ti: 0.027 wt%, the balance being Al and an inevitable impurity aluminum alloy)
<Surface treatment>
In the surface treatment, the following various treatments (a) to (k) were continuously performed. In addition, after each process and water washing, the liquid was drained with the nip roller.

(A) Mechanical surface roughening treatment While supplying a suspension of a polishing agent (pumice) having a specific gravity of 1.12 and water as a polishing slurry liquid to the surface of the aluminum plate, mechanical roughening is performed by a rotating nylon brush. Surface treatment was performed. In FIG. 1, 21 is an aluminum plate, 22 and 24 are roller brushes, 23 is a polishing slurry, and 25, 26, 27 and 28 are support rollers. The average particle size of the abrasive was 30 μm, and the maximum particle size was 100 μm. The material of the nylon brush was 6 · 10 nylon, the hair length was 45 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) Alkali etching treatment The aluminum plate obtained above was subjected to an etching treatment by spraying using an aqueous solution having a caustic soda concentration of 2.6% by weight, an aluminum ion concentration of 6.5% by weight, and a temperature of 70 ° C. / M ² dissolved. Then, water washing by spraying was performed.

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

(D) Electrochemical roughening treatment An electrochemical roughening treatment was carried out continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a 10.5 g / L aqueous solution of nitric acid (containing 5 g / L of aluminum ions and 0.007% by weight of ammonium ions) at a liquid temperature of 50 ° C. The AC power supply waveform is the waveform shown in FIG. 2, the time TP until the current value reaches the peak from zero is 0.8 msec, the duty ratio is 1: 1, a trapezoidal rectangular wave AC is used with the carbon electrode as the counter electrode An electrochemical roughening treatment was performed. Ferrite was used for the auxiliary anode.
The current density was 30 A / dm ² at the peak current value, and the amount of electricity was 220 C / dm ² in terms of the total amount of electricity when the aluminum plate was the anode. 5% of the current flowing from the power source was shunted to the auxiliary anode. Then, water washing by spraying was performed.

(E) Alkali etching treatment An aluminum plate was subjected to an etching treatment by spraying at 32 ° C. using an aqueous solution having a caustic soda concentration of 26% by weight and an aluminum ion concentration of 6.5% by weight, and the aluminum plate was dissolved at 0.50 g / m ² . Removes the smut component mainly composed of aluminum hydroxide generated when electrochemical surface roughening treatment was performed using alternating current in the previous stage, and also melted the edge part of the generated pit to smooth the edge part. did. Then, water washing by spraying was performed.

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

(G) 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 hydrochloric acid 5.0 g / L aqueous solution (containing 5 g / L of aluminum ions) at a temperature of 35 ° C. The waveform of the AC power supply is electrochemically roughened with a carbon electrode as the counter electrode using a trapezoidal trapezoidal wave alternating current with a time TP of 0.8 msec until the current value reaches a peak from zero, a duty ratio of 1: 1. Processed. Ferrite was used for the auxiliary anode.
The current density was 25 A / dm ² at the peak current value, and the amount of electricity was 50 C / dm ² in terms of the total amount of electricity when the aluminum plate was the anode. Then, water washing by spraying was performed.

(H) Alkali etching treatment The aluminum plate was subjected to etching treatment at 32 ° C. using an aqueous solution having a caustic soda concentration of 26% by weight and an aluminum ion concentration of 6.5% by weight to dissolve the aluminum plate by 0.10 g / m ² . Removes the smut component mainly composed of aluminum hydroxide that was generated when electrochemical roughening treatment was performed using the alternating current of the previous stage, and also melted the edge part of the generated pit to smooth the edge part. did. Then, water washing by spraying was performed.

(I) 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), and then washing with water by spraying was performed.

(J) Anodizing treatment Anodizing treatment is carried out using an anodizing apparatus (first and second electrolysis section length 6 m, first and second feeding section length 3 m each, first and second feeding electrode section length 2.4 m each). went. Sulfuric acid was used as the electrolytic solution supplied to the first and second electrolysis units. All electrolytes had a sulfuric acid concentration of 50 g / L (containing 0.5% by weight of aluminum ions) and a temperature of 20 ° C. Then, water washing by spraying was performed.

(K) Alkali metal silicate treatment An aluminum support obtained by anodizing treatment was immersed in a treatment tank of a 1 wt% aqueous solution of sodium silicate No. 3 at a temperature of 30 ° C for 10 seconds. Acid salt treatment (silicate treatment) was performed. Thereafter, washing with water using well water was performed to obtain a support subjected to a surface silicate hydrophilization treatment.

The aluminum plate on which all the steps (a) to (k) were carried out was the support S-1, the aluminum plate dissolution amount in the step (e) was 2.0 g / m ^2, and the electrolyte in the step (g) was hydrochloric acid 4 An aluminum plate having a current density of 17 A / dm ² and an electric quantity of 40 C / dm ² in a 0.0 g / L aqueous solution is the support S-2, and the dissolution amount of the aluminum plate in the step (e) is 2.0 g / m ^2. And (g) an aluminum plate having a current density of 17 A / dm ² and an electric quantity of 40 C / dm ² , the support S-3, the steps (a), (e) to (g) are omitted. The dissolution amount of the aluminum plate in step (b) is 5 g / m ² , the nitric acid aqueous solution temperature in step (c) is 37 ° C., the nitric acid aqueous solution in step (d) is 10.0 g / L, the liquid temperature is 37 ° C., and the current density is 35A / dm ^2, the amount of electricity 250C / dm ^2, the sodium hydroxide concentration of step (h) 26 wt% The aluminum ion concentration of 7.5 wt%, 35 ° C. The temperature of the aluminum plate dissolved amount 0.2 g / m ^2, and then an aluminum plate support S-4, is omitted above (a) ~ (d) Step (E) The caustic soda concentration in the step (e) is 27% by weight and the temperature is 70 ° C., the aluminum plate dissolution amount is 1.0 g / m ² , the alternating voltage in the step (g) is 50 Hz, and the electrolytic solution is hydrochloric acid 14.0 g / An aluminum plate having an aqueous solution of L, a temperature of 30 ° C., a current density of 75 A / dm ² , an amount of electricity of 450 C / dm ² , and a temperature of step (h) of 35 ° C. was designated as Support S-5.

  When the center line average roughness (Ra indication according to JIS B0601) of each support was measured using a needle having a diameter of 2 μm, the supports S-1 to S-3, S-5 and S-6 were 0.50 μm. The support S-4 was 0.30 μm.

Then coated on the aluminum support Undercoat layer coating liquid dry coating amount of (A) was subjected to the above surface treated to be 10 mg / m ^2, and dried.
<Undercoat layer coating solution (A)>
・ Polyvinylphosphonic acid 0.017 weight part ・ Methanol 9.00 weight part ・ Water 1.00 weight part

<Formation of photosensitive layer>
The following coating solution (A) for the photosensitive layer was prepared and applied on the undercoat layer formed as described above using a wire bar. Examples 1 to 9 and 15 to 22, and Comparative Examples 1 and 2 and The lithographic printing plate precursor used in 5-7 was prepared. Drying was performed at 125 ° C. for 34 seconds using a warm air dryer. The coating amount after drying was 1.4 g / m ² .

<Coating solution for photosensitive layer (A)>
Infrared absorber (IR-1) 0.038 parts by weight Polymerization initiator A (S-1) 0.061 parts by weight Polymerization initiator B (I-1) 0.094 parts by weight Mercapto compound (E- 1) 0.015 part by weight / ethylenically unsaturated compound (M-1) 0.425 part by weight (trade name: A-BPE-4, Shin-Nakamura Chemical Co., Ltd.)
-Binder polymer A (B-1) (weight average molecular weight: 110,000) 0.311 parts by weight-Binder polymer B (B-2) (weight average molecular weight: 100,000) 0.250 parts by weight-Binder polymer C (B -3) (weight average molecular weight: 120,000) 0.062 parts by weight, additive (T-1) 0.079 parts by weight, polymerization inhibitor (Q-1) 0.0012 parts by weight, ethyl violet (EV-1) ) 0.021 parts by weight · Fluorosurfactant 0.0081 parts by weight (Megafac F-780-F Dainippon Ink & Chemicals, Inc., methyl isobutyl ketone (MIBK) 30% by weight solution)
-Methyl ethyl ketone 5.886 parts by weight-Methanol 2.733 parts by weight-1-methoxy-2-propanol 5.886 parts by weight

  In addition, the infrared absorber (IR-1), the polymerization initiator A (S-1), the polymerization initiator B (I-1), and the mercapto compound (E-1) used for the photosensitive layer coating solution (A). ), Ethylenically unsaturated compound (M-1), binder polymer A (B-1), binder polymer B (B-2), binder polymer C (B-3), additive (T-1), polymerization prohibited The structures of the agent (Q-1) and ethyl violet (EV-1) are shown below. In the following, Me represents a methyl group, and the ratio of each monomer unit of the binder polymers A to C below is a molar ratio.

<Formation of lower protective layer>
On the formed photosensitive layer, synthetic mica (Somasif MEB-3L, 3.2% aqueous dispersion, manufactured by Coop Chemical Co., Ltd.), polyvinyl alcohol (Goselan CKS-50, saponification degree 99 mol%, polymerization degree 300) , Sulfonic acid-modified polyvinyl alcohol, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), surfactant A (manufactured by Nippon Emulsion Co., Ltd., Emalex 710), and surfactant B (Adeka Pluronic P-84: Co., Ltd.) A mixed solution of ADEKA) was applied with a wire bar and dried at 125 ° C. for 30 seconds using a hot air dryer.
The content ratio of synthetic mica (solid content) / polyvinyl alcohol / surfactant A / surfactant B in this mixed aqueous solution (coating liquid for forming the lower protective layer) was 7.5 / 89/2 / 1.5. (Weight%), and the coating amount (coating amount after drying) was 0.5 g / m ² .

<Formation of upper protective layer>
On the lower protective layer, an organic filler (Art Pearl J-7P, manufactured by Negami Industrial Co., Ltd.), synthetic mica (Somasif MEB-3L, 3.2% aqueous dispersion, manufactured by Coop Chemical Co., Ltd.), polyvinyl alcohol ( L-3266: Saponification degree 87 mol%, polymerization degree 300, sulfonic acid-modified polyvinyl alcohol, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), thickener (Serogen FS-B, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Then, a mixed aqueous solution of the surfactant (Emulex 710, manufactured by Nippon Emulsion Co., Ltd.) is applied with a wire bar and dried at 125 ° C. for 30 seconds with a hot air dryer. It was.
The content ratio of the organic filler / synthetic mica (solid content) / polyvinyl alcohol / thickener / surfactant in the mixed aqueous solution (upper protective layer forming coating solution) is 3.2 / 2.0 / 80. It was 5 / 11.5 / 2.8 (% by weight), and the coating amount (the coating amount after drying) was 1.76 g / m ² .

<Formation of back coat layer>
A back coat layer similar to that in Example 1 of JP-A-6-35174 was provided on the side of the planographic printing plate precursor A opposite to the side on which the photosensitive layer and protective layer were provided.

<Plate making method>
The obtained lithographic printing plate precursor was processed in the order of steps of exposure, development, and drying.
Light source (setter) used for exposure: Image-like exposure was performed with an infrared semiconductor laser (Trendsetter 3244VX manufactured by Creo) equipped with a water-cooled 40W infrared semiconductor laser, with an output of 9 W, an outer drum rotation speed of 210 rpm, and a resolution of 2,400 dpi. It was. As the exposure image, an image in which drawn thin lines having a width of 5 to 100 μm (interval of 5 μm) are arranged as an image for evaluating drawn fine lines. For printing durability evaluation, an image capable of solid printing durability evaluation was used.
After the exposure, a heat treatment and a water washing treatment were performed, and a development treatment was performed using a 1: 4 water dilution solution of a developer HN-D (former product name: DH-N) manufactured by FUJIFILM Corporation. The pH of the developer was 12, and the temperature of the developer bath was 30 ° C.
The developer was showered from the spray pipe with a circulation pump and supplied to the printing plate. The tank capacity of the developer was 10 liters. After development, a water washing treatment was performed to remove the developer adhering to the plate surface.

  After the development and washing treatment, image portion protection was carried out using the following plate surface treating agent A by Fujifilm Corporation automatic developing machine LP1310News.

<Plate surface treatment agent A>
・ 746.8 parts by weight of water ・ Hydroxypropylated starch (manufactured by Nissho Chemical Co., Ltd.) 197.6 parts by weight ・ Risogam (manufactured by IRANEX) 33.4 parts by weight ・ Gum arabic (weight average amount: 200,000) 61 4 parts by weight, ethylenediaminetetraacetate disodium salt 2.5 parts by weight, Lapisol A-80 (manufactured by NOF Corporation) 2.7 parts by weight, phosphoric acid (85%) 6.1 parts by weight, primary phosphorus Ammonium acid 1.7 parts by weight Sodium hydroxide 1.7 parts by weight Eleminol MON2 (manufactured by Sanyo Chemical Co., Ltd.) 7.5 parts by weight Propylene glycol 11.1 parts by weight Pionein D-1420 (Takemoto Yushi Co., Ltd.) ) 9.6 parts by weight · benzyl alcohol 18.4 parts by weight · 7.0 parts by weight of the specific copolymer listed in Table 1

[Evaluation]
<Non-image area dirt prevention evaluation (stop dirt prevention evaluation)>
The lithographic printing plate precursor was forcibly aged at 60 ° C./2 days, then exposed and developed by the plate making method described above, and treated with the plate surface treating agent A to obtain a lithographic printing plate. Apply this to a printing press (2N-600, manufactured by Tohama Seiki Co., Ltd.), and use renewal paper, ink (Soybee Red manufactured by The Inktec Co., Ltd.), and dampening water (Alky manufactured by Toyo Ink Manufacturing Co., Ltd.). Was printed. When 50,000 sheets of printing paper used for this printing were printed, the printing machine was temporarily stopped, left for 3 hours, and then restarted to print 200 sheets. The number of sheets until the ink completely disappeared from the non-image area was evaluated. It can be said that the smaller the number of sheets, the less the loss paper from the re-start of printing, and the better.

  The evaluation results of the planographic printing plates obtained in Examples 1 to 17 and Comparative Examples 1 to 4 are shown in Table 1 below.

  The structures of P-1 to P-9, P-3-2, P-3-3, and PN-1 described in Table 1 and Table 2 described later are shown below. In addition, ratio of each monomer unit described in Table 1, Table 2, and the following chemical structural formula is molar ratio.

  From Table 1, it can be seen that the occurrence of smudges in the non-image area after resuming printing is improved by the plate surface treating agent of the present invention and the processing method of the lithographic printing plate of the present invention.

(Examples 18 to 34 and Comparative Examples 5 to 8)
In the formation of the undercoat layer, the following undercoat layer coating solution (B) was used, and the undercoat layer coating solution (B) was applied onto the support so that the coating amount after drying was 1.5 mg / m ^2. Preparation of lithographic printing plate precursors of Examples 18 to 34 and Comparative Examples 5 to 8 and lithographic printing in the same manner as in Examples 1 to 17 and Comparative Examples 1 to 4 except that they were dried Plate making and evaluation of the obtained lithographic printing plate were performed, respectively. The results are shown in Table 2.
<Undercoat layer coating solution (B)>
-0.3 parts by weight of the following polymer-60.0 parts by weight of pure water-939.7 parts by weight of methanol

  From Table 2, it can be seen that the occurrence of smearing in the non-image area after resuming printing is improved by the plate surface treating agent of the present invention and the processing method of the lithographic printing plate of the present invention.

(Examples 35-39 and Comparative Examples 9 and 10)
<Formation of photosensitive layer>
The photosensitive layer coating solution (B) having the following composition was bar-coated on the support and then oven-dried at 90 ° C. for 60 seconds to be used in Examples 35 to 39 and Comparative Examples 9 and 10. An original plate B was prepared. The dry coating amount was 1.3 g / m ² .

<Photosensitive layer coating solution (B)>
-The following binder polymer (1) (weight average molecular weight: 80,000) 0.34 parts by weight-The following polymerizable compound (1) 0.68 parts by weight (PLEX6661-O, manufactured by Evonik Degussa Japan Co., Ltd.)
The following sensitizing dye (1) 0.06 part by weight The following polymerization initiator (1) 0.18 part by weight The following chain transfer agent (1) 0.02 part by weight A dispersion of ε-phthalocyanine pigment 0.40 Parts by weight (pigments: 15 parts by weight, dispersant (allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio 83/17): 10 parts by weight, cyclohexanone: 15 parts by weight)
・ 0.01 parts by weight of thermal polymerization inhibitor (N-nitrosophenylhydroxylamine aluminum salt)
-The following fluorosurfactant (1) (weight average molecular weight: 11,000) 0.001 part by weight-Polyoxyethylene-polyoxypropylene condensate 0.02 part by weight (manufactured by ADEKA, Pluronic L44)
-Yellow pigment dispersion 0.04 parts by weight (Yellow pigment Novoperm Yellow H2G (manufactured by Clariant): 15 parts by weight, dispersant (allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio 83/17)): 10 Parts by weight, cyclohexanone: 15 parts by weight)
-1-methoxy-2-propanol 3.5 parts by weight-Methyl ethyl ketone 8.0 parts by weight

<Formation of protective layer 1>
On the photosensitive layer, a protective layer coating solution (B) having the following composition was applied using a bar so that the dry coating amount was 1.0 g / m ^2, and then dried at 125 ° C. for 70 seconds. A protective layer was formed to obtain a lithographic printing plate precursor.

<Protective layer coating solution (B)>
-0.6 part by weight of the following mica dispersion (B)-0.8 part by weight of sulfonic acid-modified polyvinyl alcohol (Goselan CKS-50, manufactured by Nippon Synthetic Chemical Co., Ltd., degree of saponification: 99 mol%, average degree of polymerization: 300, degree of modification: about 0.4 mol%)
・ Poly (vinyl pyrrolidone / vinyl acetate (1/1)) (molecular weight 70,000)
0.001 part by weight / surfactant (Emalex 710, manufactured by Nippon Emulsion Co., Ltd.) 0.002 part by weight / water 13 part by weight

(Preparation of mica dispersion (B))
32 parts by weight of synthetic mica (Somasif ME-100, manufactured by Co-op Chemical Co., Ltd., aspect ratio: 1,000 or more) was added to 368 parts by weight of water, and the average particle size (laser scattering method) was 0. Dispersion was carried out until the thickness became 5 μm to obtain a mica dispersion (B).

(1) Exposure, Development, and Printing Image exposure was performed on the obtained lithographic printing plate precursor using a violet semiconductor laser plate setter Vx9600 manufactured by FUJIFILM Electronic Imaging Ltd (equipped with InGaN semiconductor laser 405 nm ± 10 nm emission / output 30 mW). As the exposure image, an image in which drawn thin lines having a width of 5 to 100 μm (interval of 5 μm) are arranged as an image for evaluating drawn fine lines. For printing durability evaluation, an image capable of solid printing durability evaluation was used. Image drawing is a resolution 2,400 dpi, was performed imagewise exposure in a plate surface exposure amount 0.05 mJ / cm ^2.
Next, after preheating at 110 ° C. for 30 seconds with an automatic developing machine IP850HD manufactured by G & J, Inc., a solution (pH 12) obtained by diluting the developer DV-2 manufactured by Fuji Film Co., Ltd. 1: 4 was used. Development was carried out at 25 ° C. for 28 seconds, followed by washing with water. The plate surface treatment was performed by changing the additive of the plate surface treatment agent A to the additives shown in Table 3 below.
In addition, forced aging was performed at 60 ° C./2 days in the same manner as in Example 1, and the above-described exposure / development / plate surface treatment was performed, and evaluation of prevention of stop contamination was performed. The evaluation results are shown in Table 3.

  From Table 3, it can be seen that the occurrence of smudges in the non-image area after the resumption of printing is improved by the plate surface treating agent of the present invention and the processing method of the lithographic printing plate of the present invention.

(Examples 40 to 44 and Comparative Examples 11 and 12)
In the formation of the undercoat layer, the following intermediate layer coating solution was used, and the intermediate layer coating solution was applied onto the support using a bar coater so that the coating amount after drying was 10 mg / m ² , and then 80 ° C. In the same manner as in Examples 35 to 39 and Comparative Examples 9 and 10, except for drying for 20 seconds, preparation of planographic printing plate precursors of Examples 40 to 44 and Comparative Examples 11 and 12 The plate making of the lithographic printing plate and the evaluation of the obtained lithographic printing plate were each performed. The results are shown in Table 4.
<Coating liquid for intermediate layer>
・ 100 parts by weight of the following sol liquid 900 parts by weight of methanol

-Sol solution-
-Phosmer PE (Unichemical Co., Ltd.) 5 parts by weight-Methanol 45 parts by weight-Water 10 parts by weight-85% by weight phosphoric acid 5 parts by weight-Tetraethoxysilane 20 parts by weight-3-Methacryloxypropyltrimethoxysilane 15 Parts by weight

  From Table 4, it can be seen that the occurrence of smudges in the non-image area after the resumption of printing is improved by the plate surface treating agent of the present invention and the processing method of the lithographic printing plate of the present invention.

(Example 45 and Comparative Example 13)
The following undercoat coating solution (C) was applied to the support S-1 and dried at 80 ° C. for 15 seconds to provide an undercoat layer. The dry coating amount of the undercoat layer was 15 mg / m ² .

<Undercoat coating liquid (C)>
-Polymer compound represented by the following formula (I) 0.3 parts by weight-Methanol 100 parts by weight-Water 1 part by weight The ratio of each monomer unit of the following polymer compound is a molar ratio.

[Formation of photosensitive layer]
After coating the photosensitive layer coating solution C-1 having the following composition on a support provided with an undercoat layer with a wire bar, the coating amount is 0.85 g / m ² by drying in a drying oven at 150 ° C. for 50 seconds. And a lower layer was provided.
Moreover, after providing a lower layer, the coating liquid C-2 for photosensitive layers of the following composition was apply | coated with the wire bar. Photosensitive lithographic printing in which the component of the coating solution C-2 for photosensitive layer is the upper layer so that the coating amount of the lower layer and the upper layer is 1.1 g / m ² after drying at 140 ° C. for 60 seconds. I got the original version.

<Composition of photosensitive layer coating solution C-1>
N- (4-aminosulfonylphenyl) methacrylamide / acrylonitrile / methyl methacrylate (molar ratio 36/34/30, weight average molecular weight 50,000) 1.920 parts by weight m, p-cresol novolak (m / p Ratio = 6/4, weight average molecular weight 4000) 0.213 parts by weight Cyanine dye A represented by the following formula (A) 0.032 parts by weight p-toluenesulfonic acid 0.008 parts by weight Tetrahydrophthalic anhydride 0.19 parts by weight-Bis-p-hydroxyphenylsulfone 0.126 parts by weight 2-methoxy-4- (N-phenylamino) benzenediazonium-hexafluorophosphate 0.032 parts by weight-Victoria pure blue BOH counter anion 0.078 parts by weight of a dye made from 1-naphthalenesulfonic acid anion Activator (Megafac F-780, manufactured by Dainippon Ink and Chemicals, Inc.) 0.02 parts by weight. Γ-butyrolactone 13.18 parts by weight methyl ethyl ketone 25.41 parts by weight 1-methoxy-2-propanol 97 parts by weight

<Composition of photosensitive layer coating solution C-2>
Phenol / m, p-cresol novolak (phenol / m / p ratio = 5/3/2, weight average molecular weight 4,000) 0.274 parts by weight Cyanine dye A represented by the above formula (A) 0. 029 parts by weight-30% by weight methyl ethyl ketone solution of a polymer represented by the following formula (B) 0.14 parts by weight-Quaternary ammonium salt represented by the following formula (C) 0.004 parts by weight-the following formula (D 0.065 parts by weight of fluorine surfactant (Megafac F-780, manufactured by Dainippon Ink and Chemicals, Inc.) 0.004 parts by weight of fluorosurfactant (Megafac F) -782, manufactured by Dainippon Ink & Chemicals, Inc.) 0.020 parts by weight · Methyl ethyl ketone 10.39 parts by weight · 1-methoxy-2-propanol 20.98 parts by weight

<Exposure, development and printing>
The resulting lithographic printing plate precursor was subjected to imagewise exposure under the conditions of a beam intensity of 7.0 W and a drum rotation speed of 250 rpm using an exposure machine TrendSetter VX manufactured by CREO.
Next, development processing was performed with an automatic developing machine LP-1310H2 manufactured by FUJIFILM Corporation. As a developing solution, a solution obtained by diluting a developing solution DT-2R manufactured by Fuji Film Co., Ltd. 1: 6.5 (conductivity 50 mS / cm) is used. Processed. The plate surface treatment was performed by changing the additive of the plate surface treatment agent A to the additives shown in Table 5 below.
In addition, forced aging was performed at 60 ° C./2 days in the same manner as in Example 1, and the above-described exposure / development / plate surface treatment was performed, and evaluation of prevention of stop contamination was performed. The evaluation results are shown in Table 5.

  From Table 5, it can be seen that the occurrence of smudges in the non-image area after resuming printing is improved by the plate surface treating agent of the present invention and the processing method of the lithographic printing plate of the present invention.

(Examples 46-52 and Comparative Example 14)
The lithographic plates of Examples 46 to 52 and Comparative Example 14 are the same as the methods described in Examples 18 to 34 and Comparative Examples 5 to 8 except that the specific copolymers are changed to those shown in Table 6. Preparation of a printing plate precursor, plate making of a lithographic printing plate, and evaluation of the obtained lithographic printing plate were performed. The results are shown in Table 6.

  In addition, the specific copolymer P-10 described in Table 6 is a compound having the structure shown below, and each of the monomer units having a composition ratio (molar ratio) described in Table 6 was used. .

  From Table 6, it can be seen that the occurrence of smudges in the non-image area after the resumption of printing is improved by the plate surface treating agent of the present invention and the processing method of the lithographic printing plate of the present invention.

21: Aluminum plate 22, 24: Roller brush 23: Polishing slurry liquid 25, 26, 27, 28: Support roller

Claims (14)

A monomer unit having at least one group selected from the group consisting of a phosphonic acid group, a phosphoric acid group, a carboxylic acid group, and salts thereof, and a sulfonic acid group, a salt thereof, an amide group, and a betaine structure. A plate surface treating agent for a lithographic printing plate comprising a vinyl copolymer having at least one monomer unit having a group or structure.   The monomer unit having at least one group selected from the group consisting of the phosphonic acid group, phosphoric acid group, carboxylic acid group and salts thereof is selected from the group consisting of phosphonic acid groups, phosphoric acid groups and salts thereof. The plate surface treating agent for a lithographic printing plate according to claim 1, which is a monomer unit having at least one group.   The monomer unit having at least one group or structure selected from the group consisting of the sulfonic acid group and its salt, amide group and betaine structure is at least one selected from the group consisting of the sulfonic acid group and its salt and betaine structure The plate surface treating agent for a lithographic printing plate according to claim 1, which is a monomer unit having one group or structure.   The monomer unit having at least one group or structure selected from the group consisting of the sulfonic acid group and a salt thereof, an amide group, and a betaine structure is a monomer unit having at least one betaine structure. The plate surface treating agent for lithographic printing plates according to any one of the above.   The monomer unit having at least one group or structure selected from the group consisting of the sulfonic acid group and a salt thereof, an amide group and a betaine structure is a monomer unit having at least one sulfonic acid group and / or a salt thereof. Item 4. The plate surface treatment agent for a lithographic printing plate according to any one of Items 1 to 3.   In the copolymer, the content ratio of monomer units having at least one group selected from the group consisting of a phosphonic acid group, a phosphoric acid group, a carboxylic acid group, and a salt thereof is the total monomer unit that the copolymer has. The plate surface treating agent for a lithographic printing plate according to any one of claims 1 to 5, wherein the amount is 2 to 70 mol%.   In the copolymer, the content ratio of the monomer unit having at least one group or structure selected from the group consisting of a sulfonic acid group and a salt thereof, an amide group and a betaine structure is the total monomer unit of the copolymer. The plate surface treating agent for a lithographic printing plate according to any one of claims 1 to 6, which is 30 to 98 mol%.   Content of the said copolymer is 0.005 to 10 weight%, The plate surface treating agent for lithographic printing plates as described in any one of Claims 1-7.   The plate surface treating agent for a lithographic printing plate according to any one of claims 1 to 8, further comprising a water-soluble polymer compound different from the vinyl copolymer.   The water-soluble polymer compound is gum arabic, a fibrous derivative and a modified product thereof, polyvinyl alcohol and a derivative thereof, polyvinyl pyrrolidone, vinyl methyl ether / maleic anhydride copolymer, vinyl acetate / maleic anhydride copolymer, styrene. A water-soluble polymer compound selected from the group consisting of: / maleic anhydride copolymer, water-soluble soybean polysaccharide, starch, starch derivative, pullulan and pullulan derivative, gelatin, and hemicellulose extracted from soybean The plate surface treating agent for lithographic printing plates according to 9,   The plate surface treating agent for a lithographic printing plate according to claim 9 or 10, wherein the content of the water-soluble polymer compound is 0.1 to 25% by weight based on the total weight of the plate surface treating agent for a lithographic printing plate. A step of image exposure of the lithographic printing plate precursor,
Developing with a developer, and
A method for processing a lithographic printing plate, comprising a step of performing a plate surface treatment using the lithographic printing plate surface treatment agent according to any one of claims 1 to 11.   The method for processing a lithographic printing plate according to claim 12, wherein the lithographic printing plate precursor has a support subjected to an electrochemical surface roughening treatment with an aqueous hydrochloric acid solution.   The lithographic printing plate processing method according to claim 12 or 13, wherein the lithographic printing plate precursor has a photosensitive layer containing a sensitizing dye, a polymerization initiator, and a binder polymer.

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