JP2003251954A - Finishing gum liquid for making planographic printing plate and manufacturing method for planographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a means capable of imparting sufficient printing durability (capacity enabling the printing of many sheets) to a planographic printing plate, even if curing reaction is not advanced sufficiently at the time of exposure in the case of plate making using a negative image forming material as the original plate for the planographic printing plate. <P>SOLUTION: A polymerizable finishing liquid for making the planographic printing plate contains a compound having at least one group selected from an amino group and imino group, both of which can be added to an ethylenic unsaturated double bond by Michael addition, in its molecule. The negative image forming material is obtained by providing an image recording layer containing a polymerizable compound having at least one ethylenic unsaturated double bond on a support and imagewise exposed and developed. Thereafter, plate surface treatment is performed using the finishing gum solution to make the planographic printing plate. In the plate making method, the finishing gum solution contains at least one compound having at least the amino group and the imino group in its molecule capable of being added to the ethylenic unsaturated double bond of the polymerizable compound by Michael addition. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a finishing gum solution for lithographic printing plate making and a method for making a lithographic printing plate, and more particularly, a finishing gum solution containing a compound capable of Michael addition to an ethylenically unsaturated double bond. And a method for making a lithographic printing plate using the finishing gum solution.

[0002]

2. Description of the Related Art Conventionally, a photosensitive lithographic printing plate which has been widely used as a lithographic printing plate precursor uses an aluminum plate as a support and has a photodegradable or photocurable photosensitive layer provided thereon. It is a thing. These photosensitive layers are solubilized in the developing solution by the actinic rays, and the latter are insoluble in the developing solution. Therefore, when this is developed, only the developer-soluble portion of the photosensitive layer is removed and the surface of the support is exposed. Since the surface of the aluminum support is hydrophilic, the portion (non-image area) where the surface of the support is exposed by development holds water and repels the oil-based ink. On the other hand, the area (image area) where the photosensitive layer has not been removed by the development is lipophilic and thus repels water and accepts ink.

Among the above-mentioned lithographic printing plate precursors, a so-called negative type image forming material in which the photosensitive layer is insolubilized by an actinic ray is a so-called negative type image forming material. Is more likely to decrease,
Can print only a small number of prints. Therefore, it is important to sufficiently cure the exposed portion in order to print many sheets. On the other hand, in recent years, digital data of a computer or the like is directly drawn on a printing plate by laser light or the like (Computer to Plate: hereinafter, abbreviated as CTP as appropriate)
Is the mainstream. At this time, it is desired that the image can be drawn at the highest possible speed. In that case, what is required of the negative image-forming material is to impart a sufficiently curable performance with a minimum of energy.

In order to solve such problems, it has been proposed to increase the sensitivity of the photosensitive composition and increase the film strength, but as a harmful effect, problems such as deterioration of storage stability are likely to occur. Especially, for example, wavelengths from 760 nm to 1200
Solid-state lasers and semiconductor lasers that emit nm infrared rays are
It is useful because it has a higher output than other wavelength regions,
In the case of so-called heat curing reaction, heat is difficult to reach the photosensitive layer / aluminum support interface, and the reaction is stopped by curing only the photosensitive layer surface. However, when it is necessary to print a large number of sheets, it is necessary to increase the film strength by performing heat treatment or the like after development. It is also effective to reduce the damage during development processing, but in that case,
The problem is that the developability of the unexposed area also deteriorates, leading to poor reproducibility of stains and shadow areas.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to provide a plate for a lithographic printing plate in which a negative image-forming material is used as a lithographic printing plate precursor even when the curing reaction does not proceed sufficiently during exposure. It is an object of the present invention to provide a means capable of imparting excellent printing durability (ability to print a large number of sheets).

[0006]

The inventors of the present invention have conducted extensive studies in order to achieve the above object, and as a result, by imparting a curing accelerating function to a processing solution used for post-processing after development, It has been found that even when the curing reaction does not proceed sufficiently, the post-treatment promotes curing and the surface of the support in the non-image area is sufficiently hydrophilic. The image recording layer of the negative image-forming material is generally cured by an active ray such as ultraviolet ray, visible ray or infrared ray through a radical addition polymerization reaction to form an image portion. In the image recording layer, a polymerizable compound is usually used,
The compound is selected from compounds having an ethylenically unsaturated double bond. Therefore, the present invention is characterized by containing a compound having at least one group selected from an amino group and an imino group capable of Michael addition to an ethylenically unsaturated double bond in a molecule, for a polymerizable lithographic printing plate precursor It is a finishing gum solution. The present invention further provides a finishing gum after image-exposing and developing a negative image-forming material comprising an image-recording layer containing a polymerizable compound having at least one ethylenically unsaturated double bond on a support. A plate making method of a lithographic printing plate comprising a plate surface treatment with a liquid, wherein the finishing gum liquid is a group selected from an amino group and an imino group capable of Michael addition to the ethylenically unsaturated double bond of the polymerizable compound. A plate-making method of a lithographic printing plate, comprising a compound having at least one in the molecule. Michael addition is generally α, β-
It refers to a reaction in which a compound having a high nucleophilicity with respect to an unsaturated compound, such as amine, imine, active methylene and the like, is nucleophilically added. The finishing gum solution as used herein means a processing solution containing a water-soluble resin for the purpose of desensitizing the plate surface. Further, unless otherwise specified, the finishing gum solution and the finishing gum replenishing solution are collectively referred to as a finishing gum solution.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION A group selected from an amino group (-NH ₂ ) and an imino group (-NH-) capable of Michael addition to an ethylenically unsaturated double bond, which is used in the finishing gum solution of the present invention (hereinafter , Also called Michael-addable group)
The compound having at least one in the molecule may be an acid addition salt thereof or a hydrate thereof. The above compound preferably has two or more groups capable of Michael addition in the molecule.

Examples of the above compounds include those represented by the following formula (I). (In the formula, R ₁ and R ₂ each represent a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group, and X ₁ and X ₂ each represent a divalent organic group. Represents, and a represents 0 or an integer of 1 to 300. When a is 2 or more, X ₂ may be the same or different.) R ₁ and R ₂ are, for example, a hydrogen atom or a C 1-20. Represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, etc., which may be linear or branched, and these groups may have a substituent, and examples of the substituent include a hydroxyl group, an amino group and a halogen atom. And so on. X ₁ and X ₂ are, for example, a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group, —O—, —S—, —S—S -, -OC (O)
It represents a group selected from —, —C (O) O—, —C (O) —, and the substituent includes a hydroxyl group, an amino group, a halogen atom and the like. Divalent aliphatic hydrocarbon group may be saturated or unsaturated, for example, -C _b H _2b - (wherein, b is 1
Represents an integer of 20, may be linear or branched, a part of a methylene group (-CH ₂ -) is -O -, - S -, - S-S
-, -OC (O)-, -C (O) O-, -C (O)-
May be substituted, and the hydrogen atom may be substituted with a hydroxyl group, an amino group, a halogen atom, or the like. )and so on.

Further specific examples of the above compounds include those represented by the following formula (II). (In the formula, R ₃ and R ₄ each represent a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group, and Y ₁ , Y ₂ and Y ₃ each represent a single bond or Represents a divalent organic group, Cy ₁ and Cy ₂ each represent a monocyclic or condensed polycyclic alicyclic or aromatic hydrocarbon group or heterocyclic group which may have a substituent, and c is 0 Or an integer of 1 to 200, d is an integer of 0 or 1, and when c is 2 or more, Y ₂ may be the same or different, and Cy ₂ may be the same or different.) R ₃ and R ₄ represents, for example, a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, or the like, and a substituent Examples thereof include a hydroxyl group, an amino group and a halogen atom. Y ₁ , Y ₂ and Y ₃
Is a single bond or, for example, a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a divalent aromatic hydrocarbon group, -O-, -S-, -S. -S-, -O-
It represents a group selected from C (O)-, -C (O) O-, -C (O)-and the like, and examples of the substituent include a hydroxyl group, an amino group and a halogen atom. Divalent aliphatic hydrocarbon group may be saturated or unsaturated, for example, -C _f H _2f - (wherein,
f represents an integer of 1 to 20, and may be linear or branched,
Some of the methylene group (-CH ₂ -) is -O -, - S -, -
S-S-, -O-C (O)-, -C (O) O-, -C
It may be substituted with (O)-, -NH-, or the like, and the hydrogen atom may be substituted with a hydroxyl group, an amino group, a halogen atom, or the like. )and so on. Cy ₁ and Cy ₂ represent, for example, a cycloalkylene group which may have a substituent, or an arylene group such as a phenylene group and a naphthylene group, and as the substituent, an alkyl group, a hydroxyl group, an amino group, N-
Examples thereof include an alkylamino group, an aminoalkyl group and a halogen atom.

Further examples of the above compounds include compounds having a ring structure containing an imino group (-NH-) which is a Michael-addable group. For example, there is a compound represented by the following formula (III). (In the formula, Y ₄ represents a single bond or a divalent organic group, and Z ₁ , Z
₂ , Z ₃ and Z ₄ each represent a single bond or an optionally substituted divalent aliphatic hydrocarbon group, Z ₁ and Z ₂ do not simultaneously form a single bond, and Z ₃ and Z ₄ And are not a single bond at the same time. ) Y < ₄ > is a single bond or, for example, an optionally substituted divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, -O-,
-S-, -SS-, -OC (O)-, -C (O) O
It represents a group selected from —, —C (O) — and the like, and examples of the substituent include a hydroxyl group, an amino group and a halogen atom. Divalent aliphatic hydrocarbon group may be saturated or unsaturated, for example, -C _g H _2g - (wherein, g represents an integer of 1 to 20, may be linear or branched, a part of the methylene groups (-
CH ₂ —) is —O—, —S—, —S—S—, —O—C
It may be substituted with (O)-, -C (O) O-, -C (O)-, -NH- and the like, and the hydrogen atom may be substituted with a hydroxyl group, an amino group, a halogen atom and the like. . )and so on. When Z ₁ , Z ₂ , Z ₃ , and Z ₄ are divalent aliphatic hydrocarbon groups, for example, —C _h H _2h — (in the formula, h represents an integer of 1 to 6, and even a straight chain or a branched chain) However, some methylene groups (—CH ₂ —) may be —O—, —S—, —S—S—, —O.
-C (O)-, -C (O) O-, -C (O)-, -NH
It may be substituted with — or the like, and the hydrogen atom may be substituted with a hydroxyl group, an amino group, a halogen atom or the like. )
Represents

In addition, there is a compound represented by the following formula (IV). (In the formula, R ₅ represents a hydrogen atom or —Y ₅ —NH ₂ (Y ₅ is a single bond or a divalent alkylene group having 1 to 20 carbon atoms), and W may be substituted. 1 carbon atom
Represents a divalent aliphatic hydrocarbon group of 10 to 10, and p is 1 to 10
When p is 2 or more, R ₅ may be the same or different, and W may be the same or different. ) Divalent aliphatic hydrocarbon group W may be saturated or unsaturated, for example, -C _i H _2i - (In the formula, i represents an integer of 1 to 10, may be linear or branched, partially Methylene group (-
CH ₂ —) is —O—, —S—, —S—S—, —O—C
It may be substituted with (O)-, -C (O) O-, -C (O)-, -NH- and the like, and the hydrogen atom may be substituted with a hydroxyl group, an amino group, a halogen atom and the like. . ) Represents.

Specific examples of the compound having at least one Michael-addable group used in the present invention are as follows:
The following compounds may be mentioned.

[0013]

[Chemical 1]

[0014]

[Chemical 2]

[0015]

[Chemical 3]

[0016]

[Chemical 4]

[0017]

[Chemical 5]

As described above, in the present invention, from a compound having a low molecular weight as a compound having at least one Michael-addable group in a molecule to a high molecular compound such as polyalkylene polyamine and polyarylene amine such as polyethyleneimine, a finishing gum. Can be included in the liquid. The weight average molecular weight is suitably up to about 100,000. The finishing gum solution of the present invention,
The compound having at least one Michael-addable group in the molecule may be used alone or in combination of two or more. The amount of the compound having at least one Michael-addable group in the molecule is appropriately 0.1 to 10% by mass based on the total mass of the finishing gum solution,
More preferably, it is 1 to 5 mass%. This content is 10
If the content exceeds 0.1% by weight, stains and ink receptivity, which are the original functions of the finishing gum solution, may be impaired, whereas if the content is less than 0.1% by weight, curing will not proceed sufficiently.

The finishing gum solution is generally advantageously used in a pH range of 3 to 12, which is lower than that of the developing solution. In order to adjust the pH to 3 to 12, a mineral acid, an organic acid, an inorganic salt or the like is generally added to the finishing gum solution to adjust the pH. The addition amount is 0.01 to 2 mass%. Examples of the mineral acid include nitric acid, sulfuric acid, phosphoric acid and metaphosphoric acid. Examples of the organic acid include acetic acid, oxalic acid, malonic acid, p-toluenesulfonic acid, levulinic acid, phytic acid, organic phosphonic acid, and amino acids such as glycine, α-alanine and β-alanine. Examples of the inorganic salt include magnesium nitrate, monobasic sodium phosphate, dibasic sodium phosphate, nickel sulfate, sodium hexametaphosphate and sodium tripolyphosphate. You may use together at least 1 type, or 2 or more types, such as a mineral acid, an organic acid, or an inorganic salt.

The finishing gum solution of the present invention contains a desensitizing agent, a surfactant, an antiseptic agent, in addition to the above pH adjusting agent.
An antifungal agent, a lipophilic substance, a wetting agent, a chelating agent, a defoaming agent and the like can be contained. Basically, gum arabic is often used as a desensitizing agent, and an aqueous solution of about 15 to 20% of gum arabic is often used as the finishing gum solution. In addition to gum arabic, various water-soluble resins are used as desensitizing agents. For example, dextrin,
Stellabic, tractane, alginates, polyacrylates, hydroxyethylcellulose, polyvinylpyrrolidone, polyacrylamide, methylcellulose, hydroxypropylcellulose, hydroxymethylcellulose, carboxyalkylcellulose salts, water-soluble polysaccharides extracted from soybean okara are preferred, and also , Pullulan or pullulan derivatives and polyvinyl alcohol are also preferred.

Further, as modified starch derivatives, roasted starch such as British gum, enzyme modified dextrins such as enzyme dextrin and Schardinger dextrin, oxidized starch shown in solubilized starch, modified pregelatinized starch and non-modified pregelatinized starch. Esterified starches such as alpha starch, starch phosphate, fatty starch, starch sulfate, nitrate starch, xanthate starch and carbamic acid starch, carboxyalkyl starch, hydroxyalkyl starch, sulfoalkyl starch, cyanoethyl starch, allyl starch, benzyl starch. , Carbamylethyl starch, etherified starch such as dialkylamino starch, methylol crosslinked starch, hydroxyalkyl crosslinked starch, phosphoric acid crosslinked starch, dicarboxylic acid crosslinked starch and other crosslinked starch, starch polyacryloamide copolymer, starch polyacryl starch Acid copolymer, starch-polyvinyl acetate copolymer, starch polyacrylonitrile copolymer, cationic starch polyacrylic acid ester copolymer,

A chaotic starch vinyl polymer copolymer,
Starch graft polymers such as starch polystyrene maleic acid copolymer, starch polyethylene oxide copolymer and starch polypropylene copolymer are preferred. Further, as the natural polymer compound, those obtained from algae such as starch, potato starch, tapioca starch, starches such as wheat starch and corn starch, carrageenan, laminaran, sea soup mannan, wisteria, Irish moss, agar and sodium alginate. , Mallow, mannan, quince seed, pectin, tragacanth gum, karaya gum,
Plant mucilages such as xanthine gum, guar bingham, locust bingham, carob gum, benzoin gum,
Homopolysaccharides such as dextran, glucan and levan, and microbial mucilages such as hetropolysaccharides such as succinoglucan and suntan gum, proteins such as glue, gelatin, casein and collagen are preferable. These water-soluble resins can be used in a combination of two or more, and are preferably 5 to 40% by mass, more preferably 10% by mass in the finishing gum solution.
It can be contained in the range of up to 30% by mass.

Examples of the surfactant contained in the finishing gum solution include anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants. As the anionic surfactant, fatty acid salts, abietic acid salts, hydroxyalkanesulfonic acid salts, alkanesulfonic acid salts, α-olefinsulfonic acid salts,
Dialkyl sulfosuccinates, alkyl diphenyl ether disulfonates, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, alkylnaphthalene sulfonates, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-
Methyl-N-oleyl taurine sodium, N-alkyl sulfosuccinic acid monoamide disodium salt,

Petroleum sulfonates, sulfated castor oil, sulfated beef tallow oil, fatty acid alkyl ester sulfate ester salts, alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts, fatty acid monoglyceride sulfate ester salts, polyoxyethylene alkyl Phenyl ether sulfate ester salts, polyoxyethylene styryl phenyl ether sulfate ester salts, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphate ester salts, polyoxyethylene alkylphenyl ether phosphate ester salts, styrene-maleic anhydride copolymer part Examples thereof include saponified products, partially saponified products of olefin-maleic anhydride copolymers, and naphthalenesulfonate formalin condensates. Among these, dialkyl sulfosuccinates, alkyl sulfate ester salts and alkylnaphthalene sulfonates and α-
Olefin sulfonates and alkyl diphenyl ether disulfonates are particularly preferably used. As the cationic surfactant, alkylamine salts, quaternary ammonium salts and the like are used.

As the amphoteric surfactant, alkyl carboxy betaines, alkyl imidazolines, alkyl amino carboxylic acids and the like are used. Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, sorbitan fatty acid partial esters. , Pentaerythritol fatty acid partial ester, propylene glycol mono fatty acid ester, sucrose fatty acid partial ester, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene sorbitol fatty acid partial ester, polyethylene glycol fatty acid ester, polyglycerin fatty acid partial ester ,

Polyoxyethylenated castor oils, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, tris Examples thereof include alkylamine oxide, polypropylene glycol having a molecular weight of 200 to 5,000, trimethylolpropane, glycerin or sorbitol adduct of polyoxyethylene or polyoxypropylene, and acetylene glycol. Further, fluorine-based or silicon-based nonionic surfactants can be used as well. Two or more of these surfactants can be used in combination. The amount used is not particularly limited, but a preferable range is 0.01 to 20% by mass, preferably 0.05 to 10% by mass, based on the total weight of the finishing gum solution.

As the preservative, known substances used in the fields of fiber, wood processing, food, medicine, cosmetics, agricultural chemicals and the like can be used. For example, quaternary ammonium salt, monohydric phenol derivative, dihydric phenol derivative, polyhydric phenol derivative, imidazole derivative, pyrazolopyrimidine derivative, monohydric naphthol, carbonates, sulfone derivative, organotin compound, cyclopentane derivative, phenyl derivative , Phenol ether derivative, phenol ester derivative, hydroxylamine derivative, nitrile derivative, naphthalene, pyrrole derivative, quinoline derivative,
Benzothiazole derivatives, secondary amines, 1,3,5 triazine derivatives, thiadiazole derivatives, anilide derivatives, pyrrole derivatives, halogen derivatives, dihydric alcohol derivatives, dithiols, cyanic acid derivatives, thiocarbamic acid derivatives, diamine derivatives, iso Thiazole derivative,
Monohydric alcohol, saturated aldehyde, unsaturated monocarboxylic acid, saturated ether, unsaturated ether,

Lactones, amino acid derivatives, hydantoins, cyanuric acid derivatives, guanidine derivatives, pyridine derivatives, saturated monocarboxylic acids, benzenecarboxylic acid derivatives, hydroxycarboxylic acid derivatives, biphenyl, hydroxamic acid derivatives, aromatic alcohols, halogenophenol derivatives, Benzenecarboxylic acid derivative, mercaptocarboxylic acid derivative, quaternary ammonium salt derivative, triphenylmethane derivative, hinokitiol, furan derivative, benzofuran derivative, acridine derivative, isoquinoline derivative, arsine derivative, thiocarbamic acid derivative, phosphate ester, halogenobenzene Derivative, quinone derivative,
Benzenesulfonic acid derivative, monoamine derivative, organic phosphate ester, piperazine derivative, phenazine derivative,
Known preservatives among pyrimidine derivatives, thiophanate derivatives, imidazoline derivatives, isoxazole derivatives, ammonium salt derivatives and the like can be used.

Particularly preferred preservatives are pyridinethiol-1-oxide salts, salicylic acid and salts thereof,
1,3,5-Trishydroxyethylhexahydro-S
-Triazine, 1,3,5-trishydroxymethylhexahydro-S-triazine, 1,2-benzisothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-bromo- 2-nitro-1,
3-propanediol may be mentioned. The preferable addition amount is an amount that exerts a stable effect on bacteria, molds, yeasts, etc., and varies depending on the types of bacteria, molds, yeasts, but is 0.01 for the finishing gum solution at the time of use.
The range of 4 to 4% by mass is preferable, and it is preferable to use two or more kinds of preservatives together so as to be effective against various molds and bacteria.

The finishing gum solution may contain a lipophilic substance. Preferred lipophilic substances include
For example, organic carboxylic acids having 5 to 25 carbon atoms such as oleic acid, lanolinic acid, valeric acid, nonylic acid, capric acid, myristic acid, palmitic acid, and castor oil are included. These lipophilic substances can be used alone or in combination of two or more. The lipophilic substance contained in the finishing gum liquid is 0.0 with respect to the total mass.
05-10% by mass, more preferably 0.05-5% by mass
Is the range.

In addition, glycerin, ethylene glycol, triethylene glycol and the like can be added as a wetting agent to the finishing gum solution, if necessary. The preferable amount of these wetting agents used is 0.1 to 5% by mass.
Is.

A chelating compound may be added to the finishing gum solution. Usually, the finishing gum solution is usually marketed as a concentrated solution, and when used, it is diluted with tap water, well water or the like before use. Calcium ions contained in this diluted tap water or well water may adversely affect the printing and cause the printed matter to be easily soiled. Therefore, a chelate compound may be added to eliminate the above-mentioned drawbacks. . Preferred chelate compounds include, for example, ethylenediaminetetraacetic acid, its potassium salt, its sodium salt; diethylenetriaminepentaacetic acid, its potassium salt, its sodium salt; triethylenetetraminehexaacetic acid, its potassium salt, its sodium salt,
Hydroxyethylethylenediaminetriacetic acid, its potassium salt, its sodium salt; Nitrilotriacetic acid, its sodium salt; 1-Hydroxyethane-1,1-diphosphonic acid, its potassium salt, its sodium salt; Aminotri (methylenephosphonic acid), its potassium Examples thereof include organic phosphonic acids such as salts and sodium salts thereof, or phosphonoalkane tricarboxylic acids. Organic amine salts are also effective in place of the sodium and potassium salts of the above chelating agents. As these chelating agents, those which are stably present in the finishing gum solution composition and which do not impair the printability are selected. An appropriate amount of addition is 0.001 to 1.0 mass% with respect to the finishing gum solution at the time of use.

An antifoaming agent may be added to the finishing gum solution, and a silicone antifoaming agent is particularly preferable.
Among them, both the emulsified dispersion type and the solubilized type can be used. Preferably, the range of 0.001 to 1.0 mass% with respect to the finishing gum solution at the time of use is optimum.

The remaining component of the finishing gum solution is water. It is advantageous in terms of transportation that the finishing gum solution is a concentrated solution having a water content smaller than that at the time of use and is diluted with water at the time of use. In this case, the degree of enrichment should be such that each component does not separate or precipitate. The finishing gum solution may be prepared as an emulsion dispersion type, an organic solvent is used as the oil phase,
It may be solubilized with the aid of a solubilizer. Further, a solidified finishing gum agent obtained by removing water by a spray drying method or the like or mixing solid raw materials is also a preferable embodiment.

The finishing gum solution of the present invention described above can be applied to the plate making of a polymerizable lithographic printing plate, and more specifically, at least one ethylenically unsaturated double bond is provided on a support. It can be preferably used for making a lithographic printing plate from a negative image-forming material provided with an image recording layer containing a polymerizable compound having Accordingly, here, further, a negative image-forming material provided with an image recording layer containing a polymerizable compound having at least one ethylenically unsaturated double bond on a support is subjected to image exposure and development, and thereafter,
A method of making a planographic printing plate including a plate surface treatment with the above finishing gum solution is touched. As an example of a negative image-forming material to which the finishing gum solution of the present invention can be applied, mainly near-infrared or infrared rays are absorbed and converted into heat, and radical polymerization is generated by radical generation by the heat. Examples include so-called infrared curable image-forming materials that start, and so-called ultraviolet-visible photopolymerizable photosensitive lithographic printing plates that generate radical species by absorbed light energy. These image forming materials will be described below.

I. Infrared curable image forming material The infrared curable image forming material contains (A) a radical generator, (B) a radical polymerizable compound, (C) an infrared absorbing agent, and (D) a binder polymer on a support. An image recording layer is provided. Such an image-forming material undergoes imagewise exposure with an infrared laser to photothermally convert the infrared absorbing agent (C) in the exposed area, and the generated heat decomposes the radical generating agent (A) to generate radicals. And (B) a radically polymerizable compound,
The image recording layer containing (D) the binder polymer is cured to form an image portion. Then, by developing with an alkaline developer, the uncured unexposed recording layer is removed,
A non-image portion is formed.

Each constituent component of the image recording layer will be sequentially described. [(A) Radical Generator] The radical generator is used in combination with the infrared absorber (C), and refers to a compound that generates a radical when irradiated with an infrared laser. Examples of the radical generator include onium salts, S-triazines having a trihalomethyl group, peroxides, azo-based polymerization initiators, azide compounds and borate salts. Onium salts are preferred because they have high sensitivity. Examples of onium salts include iodonium salts, diazonium salts, and sulfonium salts.
In the present invention, these onium salts function not as an acid generator but as an initiator of radical polymerization. The onium salt preferably used is an onium salt represented by the following general formulas (1) to (3).

[0038]

In the formula (1), Ar ¹¹ and Ar ¹² each independently represent an aryl group having 20 or less carbon atoms which may have a substituent. When the aryl group has a substituent, preferable substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an alkyl group having 12 or less carbon atoms. An aryloxy group is mentioned. Z ^11- represents a counter ion such as a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a carboxylate ion, a hexafluorophosphate ion, and a sulfonate ion,
Preferred are perchlorate ion, carboxylate ion, and arylsulfonate ion.

In the formula (2), Ar ²¹ represents an aryl group having 20 or less carbon atoms which may have a substituent. Preferred substituents include halogen atoms, nitro groups, alkyl groups having 12 or less carbon atoms, alkoxy groups having 12 or less carbon atoms, aryloxy groups having 12 or less carbon atoms, and those having 12 or less carbon atoms. Alkylamino group, dialkylamino group having 12 or less carbon atoms, 1 carbon atom
Examples thereof include an arylamino group having 2 or less or a diarylamino group having 12 or less carbon atoms. Z ^{21 -} is Z ^11-
Represents a counter ion having the same meaning as.

In the formula (3), R ³¹ , R ³² and R ^{33, which} may be the same or different, each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferred substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an aryloxy group having 12 or less carbon atoms. Z ^31- represents a counter ion having the same ^meaning as Z ^11- .

Specific examples of onium salts that can be preferably used are shown below, but the present invention is not limited thereto.

[0043]

[0044]

[0045]

[0046]

[0047]

The radical generator has a maximum absorption wavelength of 400.
It is preferably not more than nm, more preferably not more than 360 nm. By thus setting the absorption wavelength in the ultraviolet region, the image forming material can be handled under a white light.

These radical generators are contained in an amount of 0.1 to 50% by mass, preferably 0.5 to 30% by mass, particularly preferably 1 to 20% by mass, based on the total solid content of the coating liquid for the image recording layer. It can be added to the coating liquid for the image recording layer. If the amount added is less than 0.1% by mass, the sensitivity will be low, and if it exceeds 50% by mass, stains will occur on the non-image area during printing. These radical generators may be used alone or in combination of two or more. Further, these radical generators may be added to the same layer as other components,
Another layer may be provided and added to it.

[(B) Radical Polymerizable Compound] The radical polymerizable compound used in the present invention is a radical polymerizable compound having at least one ethylenically unsaturated double bond, and has a terminal ethylenically unsaturated bond. At least 1
, Preferably two or more compounds. Such compounds are widely known in the industrial field, and they can be used in the invention without any particular limitation. These have a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof. Examples of the monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and their esters and amides. As the ester, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound and an amide of an unsaturated carboxylic acid and an aliphatic polyhydric amine compound are used. Further, unsaturated carboxylic acid esters having a nucleophilic substituent such as a hydroxyl group, an amino group, and a mercapto group, monofunctional or polyfunctional isocyanates with amides, addition reaction products with epoxies, monofunctional or polyfunctional, or A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines and thiols, and halogens. A substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving group such as a group or a tosyloxy group with a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
Further, as another example, it is possible to use a compound group in which unsaturated phosphonic acid, styrene or the like is substituted for the above unsaturated carboxylic acid.

Specific examples of the radically polymerizable compound which is an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate and 1,3-butane. Diol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1 , 4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, penta Risuri toll triacrylate,
Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate,
There are sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer and the like.

Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3- Methacryloxy-2-hi Rokishipuropokishi) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

As the itaconic acid ester, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate,
1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate and the like. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Examples of other esters include, for example, Japanese Examined Patent Publication No. 46-27926 and Japanese Examined Patent Publication No. 51-47334.
JP-A-57-196231, aliphatic alcohol-based esters described in JP-A-57-196231, JP-A-59-5240,
Those having an aromatic skeleton described in JP-A-59-5241 and JP-A-2-226149, JP-A-1-16
Those containing an amino group described in Japanese Patent No. 5613 are also preferably used.

Specific examples of the amide monomer of an aliphatic polyvalent amine compound and an unsaturated carboxylic acid include methylenebis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, 1,6- Hexamethylene bis-methacrylamide,
Examples include diethylenetriamine tris acrylamide, xylylene bis acrylamide, and xylylene bis methacrylamide.

Examples of other preferable amide-based monomers include those having a cyclohexylene structure described in JP-B-54-21726.

Further, urethane-based addition-polymerizable compounds produced by addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, Japanese Examined Patent Publication No.
In a molecule obtained by adding a vinyl monomer having a hydroxyl group represented by the following general formula (4) to a polyisocyanate compound having two or more isocyanate groups in one molecule described in JP-A-8-41708. Examples thereof include vinyl urethane compounds having two or more polymerizable vinyl groups. Formula _{(4) CH 2 = C (} R 41) COOCH 2 CH (R 42) OH ( provided that, R ⁴¹ and R ⁴² represent H or CH _3.)

Further, urethane acrylates as described in JP-A-51-37193, JP-B-2-32293 and JP-B-2-16765, and JP-B-58-
49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62
The urethane compounds having an ethylene oxide skeleton described in JP-B-39417 and JP-B-62-39418 are also suitable.

Further, radically polymerizable compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909 and JP-A-1-105238, may be used. good.

Another example is JP-A-48-641.
No. 83, Japanese Patent Publication No. 49-43191, Japanese Patent Publication No. 52-30
Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in Japanese Patent No. 490 and each publication can be given. Also,
JP-B-46-43946, JP-B1-40337,
Specific unsaturated compounds described in JP-B-1-40336,
The vinylphosphonic acid compounds described in JP-A-2-25493 can also be used. In some cases, the structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Japan Adhesive Association magazine vol.20, No.7, pages 300-308 (1984)
Those introduced as photo-curable monomers and oligomers can also be used.

Regarding these radically polymerizable compounds,
The details of the method of use, such as what kind of structure is used, whether it is used alone or in combination, and how much is added, can be arbitrarily set according to the performance design of the final recording material. For example, it is selected from the following viewpoints. From the viewpoint of sensitivity, a structure having a large content of unsaturated groups per molecule is preferable, and in many cases, bifunctional or more is preferable. Further, in order to increase the strength of the image area, that is, the cured film, a compound having a trifunctional or higher functionality is preferable, and further, a compound having different functional numbers and different polymerizable groups (for example, an acrylic ester compound, a methacrylic ester compound Compounds, styrenic compounds, etc.) are used in combination to control both photosensitivity and strength. Large molecular weight compounds and highly hydrophobic compounds have excellent sensitivity and film strength, but
It may not be preferable in terms of development speed and precipitation in a developing solution. In addition, compatibility and dispersibility with other components in the image recording layer (for example, binder polymer, initiator, colorant, etc.) are important factors in selecting and using the radical polymerization compound. In some cases, the compatibility may be improved by using a low-purity compound or using two or more compounds in combination. In addition, a specific structure may be selected for the purpose of improving the adhesiveness of the support, the overcoat layer and the like. Regarding the blending ratio of the radical-polymerizable compound in the image recording layer, the larger the amount, the more advantageous in terms of sensitivity. However, if the amount is too large, undesired phase separation may occur or the adhesiveness of the image recording layer may affect the production process. May occur (for example, transfer of recording layer components, manufacturing failure due to adhesion), or precipitation from a developing solution. From these viewpoints, in many cases, the preferable compounding ratio of the radically polymerizable compound is 5 to 80% by mass, preferably 20 to 75% by mass based on all the components of the composition. These may be used alone or in combination of two or more. In addition, the method of using the radically polymerizable compound, the degree of inhibition of polymerization with respect to oxygen, resolution, fogging, refractive index change, surface tackiness, etc., an appropriate structure, formulation, and addition amount can be arbitrarily selected. Depending on the case, a layer constitution / coating method such as undercoating or topcoating may be performed.

[(C) Infrared Absorber] Since an infrared ray curable image forming material records an image using infrared rays, especially by an infrared laser, it is essential to include an infrared absorber in the image recording layer. The infrared absorber has a function of converting the absorbed infrared rays into heat. The heat generated at this time decomposes the radical generator to generate radicals. The infrared absorbent used in the present invention has a wavelength of 760n.
It is a dye or pigment having an absorption maximum from m to 1200 nm.

As the dyes, commercially available dyes and known dyes described in documents such as "Dye Handbook" (edited by the Society of Synthetic Organic Chemistry, published in 1970) can be used. Specific examples thereof include those described in paragraphs [0050] to [0051] of JP-A No. 10-39509. Azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes. , Phthalocyanine dye, carbonium dye, quinone imine dye,
Examples include dyes such as methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, and metal thiolate complexes.

Preferred dyes are, for example, JP-A-5
Cyanine dyes described in JP-A No. 8-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, and JP-A-58-1736.
96, JP-A-58-181690, JP-A-58-1
Methine dyes described in Japanese Patent Application No. 94595, JP-A-Sho 5
8-112793, JP-A-58-224793, JP-A-59-48187, JP-A-59-73996,
Naphthoquinone dyes described in JP-A-60-52940, JP-A-60-63744 and the like, JP-A-58-1
Squarylium dyes described in No. 12792,
Examples thereof include cyanine dyes described in British Patent 434,875.

The near infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferably used, and the substituted arylbenzo (thio) described in US Pat. No. 3,881,924 is also used. Pyrylium salt, JP-A-57-142645
Trimethine thiapyrylium salt described in U.S. Pat. No. 4,327,169, JP-A Nos. 58-181051, 58-220143, 59-41363 and 59-11363.
-84248, 59-84249, 59-14
Nos. 6063 and 59-146061, pyranium compounds described in JP-A-59-216146, pentamethine thiopyrylium salts described in U.S. Pat. No. 4,283,475, and the like. Fair 5-13
The pyrylium compounds disclosed in Nos. 514 and 5-19702 are also preferably used.

Another preferred example of the dye is represented by the formula (I) in US Pat. No. 4,756,993:
The near infrared absorbing dye described as (II) can be mentioned.

Among these dyes, particularly preferred are cyanine dyes, squarylium dyes, pyrylium salts and nickel thiolate complexes. Further, a cyanine dye is preferable, and a cyanine dye represented by the following general formula (5) is most preferable.

[0068]

X in the general formula (5)¹Is a halogen atom,
X²-L¹Or NL²L³Indicates. Where X²Is oxygen source
Child or sulfur atom, L¹Has 1 to 1 carbon atoms
2 represents a hydrocarbon group, L²And L³Each independently charcoal
A hydrocarbon group having 1 to 12 elementary atoms is shown. R¹And R
²Are each independently a hydrocarbon having 1 to 12 carbon atoms.
Indicates a group. From the storage stability of the recording layer coating liquid, R¹and
R²Is a hydrocarbon group having 2 or more carbon atoms
Preferably, further, R¹And R²And are bonded to each other
Alternatively, it is particularly preferable to form a 6-membered ring. Ar
¹, Ar²Can be the same or different,
The aromatic hydrocarbon group which may have a substituent is shown.
Y¹, Y²Can be the same or different,
Yellow or dialkylmethylene having 12 or less carbon atoms
Group. R ³, R^FourAre the same or different
20 carbon atoms, which may or may not have a substituent
The following hydrocarbon groups are shown. The preferred substituent is charcoal.
An alkoxy group having 12 or less elementary atoms, a carboxyl group,
Examples thereof include a sulfo group. R^Five, R⁶, R⁷And R⁸Is that
They may be the same or different, and each may be a hydrogen atom or charcoal.
A hydrocarbon group having 12 or less elementary atoms is shown. Raw material availability
Therefore, it is preferably a hydrogen atom. Also, Z^1-Is a
Indicates Nion. However, R¹~ R⁸A sulfo group
Z is replaced by Z^1-Is not necessary. Preferred Z
^1-Is a halogen ion because of the storage stability of the recording layer coating solution.
Ion, perchlorate ion, tetrafluoroborate ion,
Hexafluorophosphate ion, and sulfone
Acid ion, particularly preferably perchlorate ion,
Lifluoromethylsulfonate ion, and Aryls
Rufonate ion.

Specific examples of the cyanine dye represented by formula (5) which can be preferably used are shown below, but the invention is not limited thereto.

[0071]

[0072]

[0073]

[0074]

As the pigment to be used, commercially available pigment and color index (CI) handbook, "Latest pigment handbook" (edited by Japan Pigment Technology Association, 1977), "Latest Pigment Application Technology" (CMC Publishing, 1986), "Printing Ink Technology", CMC Publishing Co., Ltd., 1984).

The types of pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments,
Blue pigment, green pigment, fluorescent pigment, metal powder pigment, etc.
Polymer bound dyes may be mentioned. Details of these pigments are described in paragraph No. [005 of JP-A-10-39509.
2] to [0054], which are also applicable to the present invention. Preferred among these pigments is carbon black.

The content of the above-mentioned dye or pigment in the image recording layer is preferably 0.01 to 50% by mass, more preferably 0.1 to 10% by mass based on the total solid content of the image recording layer. Preferably, in the case of a dye, 0.5 to
10% by mass is most preferable, and in the case of a pigment, 1.0 to
Most preferred is 10% by weight. If the content is less than 0.01% by mass, the sensitivity may be lowered, and if it exceeds 50% by mass, stains may occur on the non-image area in the lithographic printing plate precursor.

[(D) Binder Polymer] It is preferable to add a binder polymer to the image recording layer from the viewpoint of improving the film property. It is preferable to use a linear organic polymer as the binder. Any of these "linear organic polymers" may be used. A linear organic polymer that is soluble or swellable in water or weak alkaline water is preferably selected to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film forming agent for forming an image recording layer but also as a developer such as water, weak alkaline water or an organic solvent developer. For example, water development becomes possible by using a water-soluble organic polymer. As such a linear organic polymer, a radical polymer having a carboxylic acid group in its side chain, for example, JP-A-59-44615,
JP-B-54-34327, JP-B-58-12577
Japanese Patent Publication No. 54-25957, JP-A-54-9272.
3, JP-A-59-53836, JP-A-59-710.
No. 48, that is, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer,
Examples include crotonic acid copolymers, maleic acid copolymers and partially esterified maleic acid copolymers. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in its side chain. In addition to these, it is useful to add a cyclic acid anhydride to a polymer having a hydroxyl group.

Among these, a (meth) acrylic resin having a benzyl group or an allyl group and a carboxyl group in its side chain is particularly preferable because it has an excellent balance of film strength, sensitivity and developability. Especially in these [benzyl (meta)
Acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomer] copolymer and [allyl (meth) acrylate (meth) acrylic acid / optionally other addition-polymerizable vinyl monomer] copolymer Coalescence is preferred.

Further, Japanese Patent Publications 7-120040, 7-120041, 7-120042, 8-124424, 63-287944, 63-287947, Kaihei 1-271741
The urethane-based binder polymer containing an acid group described in JP-A No. 11-352691, etc. is very excellent in strength and is advantageous in terms of printing durability and low exposure suitability.

In addition to these, polyvinylpyrrolidone and polyethylene oxide are useful as the water-soluble linear organic polymer. Further, alcohol-soluble polyamide, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. are also useful for increasing the strength of the cured film.

The weight average molecular weight of the polymer used in the present invention is preferably 5,000 or more, more preferably 10,000 to 300,000, and the number average molecular weight is preferably 1,000 or more, further preferably Is in the range of 2000 to 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably 1.1 to 10.

These polymers are random polymers,
It may be either a block polymer or a graft polymer, but a random polymer is preferable.

The binder polymers used in the present invention may be used alone or as a mixture. These polymers are added to the image recording layer in a proportion of 20 to 95% by mass, preferably 30 to 90% by mass, based on the total solid content of the coating liquid for the image recording layer. If the addition amount is less than 20% by mass, the strength of the image area will be insufficient when an image is formed. The addition amount is 9
If it exceeds 5% by mass, no image is formed. The mass ratio of the compound having a radically polymerizable ethylenically unsaturated double bond and the linear organic polymer is preferably 1/9 to 7/3.

[Other Components] If desired, various compounds other than the above may be added to the image recording layer. For example, a dye having a large absorption in the visible light region can be used as a colorant for images. In particular,
Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black B
Y, Oil Black BS, Oil Black T-505
(All manufactured by Orient Chemical Industries, Ltd.), Victoria Pure Blue, Crystal Violet (CI4255)
5), methyl violet (CI42535), ethyl violet, rhodamine B (CI145170B),
Malachite green (CI42000), methylene blue (CI52015), etc., and JP-A-62-29324.
The dyes described in No. 7 can be mentioned. Further, pigments such as phthalocyanine pigments, azo pigments, and titanium oxide can also be preferably used. It is preferable to add these colorants because the image area and the non-image area can be easily distinguished after the image formation. The addition amount is 0.01 to 10% by mass based on the total solid content of the coating liquid for the image recording layer.

Further, it is desirable to add a small amount of a thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of the compound having an ethylenically unsaturated double bond capable of radical polymerization during the preparation or storage of the coating solution. . Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol,
Di-t-butyl-p-cresol, pyrogallol, t-
Butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2 '
-Methylenebis (4-methyl-6-t-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt and the like. The addition amount of the thermal polymerization inhibitor is preferably about 0.01 mass% to about 5 mass% with respect to the mass of the entire composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide or an alcohol such as 1-docosanol may be added to lower the friction coefficient of the image recording layer and prevent scratches. It may be unevenly distributed on the surface of the image recording layer during the drying process. The amount of the higher fatty acid derivative added is preferably about 0.1% by mass to about 10% by mass of the total composition.

Further, in the coating liquid for the image recording layer, in order to extend the stability of the treatment against the developing conditions, it is disclosed in JP-A-62-25
1740 and nonionic surfactants described in JP-A-3-208514, JP-A-59-12104.
No. 4, and an amphoteric surfactant as described in JP-A-4-13149 can be added.

Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride and polyoxyethylene nonylphenyl ether. Specific examples of the amphoteric surfactant include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, N-tetradecyl-N, N-. Betaine type (for example,
Examples of the brand name include Amogen K, manufactured by Daiichi Kogyo Co., Ltd. The ratio of the nonionic surfactant and the amphoteric surfactant in the coating liquid for the image recording layer is 0.05 to 15% by mass.
Is preferable, and more preferably 0.1 to 5 mass%.

If necessary, a plasticizer is added to the coating liquid for the image recording layer in order to impart flexibility to the coating film. For example, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate and the like are used.

In order to produce an image-forming material, the above-mentioned components required for the image-recording layer coating solution are usually dissolved in a solvent and coated on a suitable support. As the solvent used here, ethylene dichloride, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol,
1-methoxy-3-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate,
Dimethoxyethane, methyl lactate, ethyl lactate, N, N-
Dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyrolactone,
Toluene, water, etc. may be mentioned, but the invention is not limited thereto. These solvents are used alone or as a mixture. The concentration of the above components (total solids including additives) in the solvent is preferably 1 to 50% by mass.

The coating amount (solid content) of the image recording layer on the support obtained after coating and drying varies depending on the use,
As for the lithographic printing plate precursor, it is generally 0.5 to 5.0.
g / m ² is preferred. Various methods can be used for coating, and examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating. As the coating amount decreases,
Although the apparent sensitivity is high, the film properties of the image recording layer that functions as an image recording are deteriorated.

(Oxygen-shielding protective layer) An oxygen-shielding protective layer containing a water-soluble vinyl polymer as a main component may be provided on the image recording layer of the infrared curable image forming material. Examples of the water-soluble vinyl polymer contained in the oxygen barrier protective layer include polyvinyl alcohol, and partial esters, ethers, and acetals thereof, or a substantial amount of an unsubstituted vinyl alcohol unit such that they have the necessary water solubility. And its copolymers containing Polyvinyl alcohol is 71 to 100% hydrolyzed and has a degree of polymerization of 3
The thing of the range of 00-2400 is mentioned. Specifically, PVA-105, PVA-11 manufactured by Kuraray Co., Ltd.
0, PVA-117, PVA-117H, PVA-12
0, PVA-124, PVA-124H, PVA-C
S, PVA-CST, PVA-HC, PVA-203,
PVA-204, PVA-205, PVA-210, P
VA-217, PVA-220, PVA-224, PV
A-217EE, PVA-220, PVA-224, P
VA-217EE, PVA-217E, PVA-220
E, PVA-224E, PVA-405, PVA-42
0, PVA-613, L-8 and the like. Examples of the above-mentioned copolymers include polyvinyl acetate chloroacetate or propionate which is 88 to 100% hydrolyzed, polyvinyl formal and polyvinyl acetal, and copolymers thereof. Other useful polymers include polyvinylpyrrolidone, gelatin and gum arabic, which may be used alone or in combination.

Pure water is preferably used as a solvent for coating the oxygen-blocking protective layer, but alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone may be mixed with pure water. The concentration of the solid content in the coating solution is preferably 1 to 20% by weight.
Known additives such as a surfactant for improving the coating property and a water-soluble plasticizer for improving the physical properties of the film may be added to the oxygen barrier protective layer. Examples of the water-soluble plasticizer include propionamide, cyclohexanediol, glycerin, sorbitol and the like. Also, a water-soluble (meth) acrylic polymer or the like may be added. The coating amount is about 0.1 g / dry weight.
A range of m ² to about 15 g / m ² is suitable. More preferably, it is 1.0 g / m ² to about 5.0 g / m ² .

II. Ultraviolet-Visible Light Polymerization Type Photosensitive Lithographic Printing Plate The image recording layer (hereinafter, also referred to as photosensitive layer) of the ultraviolet-visible light polymerization type photosensitive lithographic printing plate comprises (a) a polymerizable compound and (b) a binder. Including a polymer and (c) a photopolymerization initiator system, various compounds such as a colorant, a plasticizer, and a thermal polymerization inhibitor may be added, if necessary. [(A) Polymerizable compound] As the (a) polymerizable compound contained in the photosensitive layer, those described as the radical polymerizable compound as a component of the image recording layer of the infrared curable image forming material can be used. . The amount of the polymerizable compound used is 5 to 70% by mass, preferably 10 to 50% by mass relative to all the components of the composition.
It is% by mass.

[(B) Binder Polymer] As the binder polymer, it is preferable to use a high molecular polymer which is soluble or swellable in alkaline water. As such a high molecular polymer, those described as the components of the image recording layer of the above infrared curable image forming material can be used. By introducing a radical reactive group into the side chain of these high molecular weight polymers, the strength of the cured film can be improved. The functional group capable of addition polymerization reaction is an ethylenically unsaturated bond group, an amino group, an epoxy group or the like, and the functional group capable of becoming a radical by light irradiation is a mercapto group, a thiol group, a halogen atom, a triazine structure, an onium salt. Examples of the structure include a polar group such as a carboxyl group and an imide group. The functional group capable of undergoing the addition polymerization reaction is particularly preferably an ethylenically unsaturated bond group such as an acrylic group, a methacrylic group, an allyl group and a styryl group, but also an amino group, a hydroxy group, a phosphonic acid group, a phosphoric acid group, a carbamoyl group. A functional group selected from an isocyanate group, an ureido group, a ureylene group, a sulfonic acid group and an ammonio group is also useful. In order to maintain the developability of the composition, the high molecular weight polymer preferably has an appropriate molecular weight and acid value. Since it is developed with the above-mentioned developing solution, it has a weight average molecular weight of 5,000 to 300,000 and an acid value of 0.2 to 5.0 meq / g.
It is preferable to use the high molecular weight polymer.

These organic high molecular weight polymers can be mixed in arbitrary amounts in the entire composition. However, if it exceeds 90% by mass, favorable results are not obtained in terms of the strength of the formed image. It is preferably 10 to 90% by mass, more preferably 30 to 80% by mass. Further, the photopolymerizable ethylenically unsaturated compound and the organic high molecular weight polymer are preferably in a mass ratio of 1/9 to 9/1. A more preferable range is 2/8 to 8/2, and further more preferable is 3/7.
~ 7/3.

[(C) Photopolymerization Initiator System] The photopolymerization initiator contained in the photosensitive layer may be various photoinitiators known in patents, literatures, etc., or two or more kinds depending on the wavelength of the light source used. The combined use system (photoinitiator system) of the above photoinitiator can be appropriately selected and used. The photopolymerization initiator system also includes a combination of a light absorber and a radical generator suitable for the wavelength of the light source used.

Examples of the initiator showing sensitivity in the ultraviolet region include acetophenone type, benzoin type, benzophenone type and thioxanthene type initiators. Further, as an initiator having sensitivity in the visible light region, a combination of organic peroxide and chlorophyll, a combination of organic peroxide and eosin G, a combination of organic peroxide and riboflavin, an organic peroxide Combination with methylene blue, combination of organic peroxide and (thio) pyrylium salt, combination of organic peroxide and merocyanine, combination of organic peroxide and quinoline, combination of organic peroxide and styrylquinone, organic Combination of peroxide and (thio) xanthene dye, combination of organic peroxide and riboflavin tetrabutyrate, organic peroxide and (keto)
Combination with coumarin type dye, combination with organic peroxide, N-phenylglycine and thioxanthene type dye, combination with diphenyliodonium salt and merocyanine dye, combination with diphenyliodonium salt and rhodamine derivative polymer, diphenyliodonium salt Combination with ketocoumarin dye, combination with diphenyliodonium salt and tetraphenylporphyrin dye, combination with diphenyliodonium salt and tetrabenzoporphyrin, combination with diphenyliodonium salt and spiropyran,

Combination of diphenyliodonium salt, N-phenylglycine and thioxanthene dye, combination of diphenyliodonium salt, N-phenylglycine and merocyanine dye, cyanine dye, alkyl borate of cyanine dye, rhodamine dye Dye alkyl borate, methylene blue dye alkyl borate, iron arene complex, iron arene complex and ketocoumarin dye combination, iron arene complex and thioxanthene dye combination, titanocene, titanocene and merocyanine dye combination Combination, bisimidazole and arylidene aryl ketone, bisimidazole and ketocoumarin-based dye, N-phenylglycine and ketocoumarin-based dye, N-phenylglycine and (thio) xanthene-based dye Combined, tris (trichloromethyl) -
s-triazine derivative, tris (trichloromethyl) -s
A combination of a triazine derivative and a merocyanine dye,
Combination of tris (trichloromethyl) -s-triazine derivative and ketocoumarin dye, combination of tris (trichloromethyl) -s-triazine derivative and thiopyrylium salt, tris (trichloromethyl) -s-triazine derivative and thioxanthene dye , A combination of aminobenzoic acid ester and riboflavin tetrabutyrate,
A combination of 2-mercaptobenzimidazole and a thiopyrylium salt may, for example, be mentioned. Further, the initiator having sensitivity to near infrared light is, for example, a borate salt of a near infrared absorbing cationic dye, a combination of a near infrared absorbing cationic dye and a borate salt, a near infrared absorbing cationic dye and a triazine compound. A combination and the like can be mentioned.

Various photoinitiating systems have been proposed when a visible light of 400 nm or more, an Ar laser, a second harmonic of a semiconductor laser, or an SHG-YAG laser is used as a light source. For example, US Pat. No. 2,850. , 445, for example, rose bengal, eosin, erythrosine and the like, or a combination of a dye and an initiator, for example, a complex initiation system of a dye and an amine (Japanese Patent Publication No. 44-20189). No.), a system in which a hexaarylbiimidazole, a radical generator and a dye are used in combination (Japanese Patent Publication No. 45-37377), a system of hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (Japanese Patent Publication No. 47-2528, Japanese Patent Laid-Open Publication No. Sho 25-2528). 54-155292),
System of cyclic cis-α-dicarbonyl compound and dye (JP-A-48-84183), system of cyclic triazine and merocyanine dye (JP-A-54-151024), system of 3-ketocoumarin and activator (JP-A-54-1024). No. 52-112681, JP-A-58-15503), biimidazole, styrene derivatives, and thiol systems (JP-A-59-140203).
No.), a system of organic peroxide and dye (JP-A-59-1504).
JP-A-59-140203, JP-A-59-189
340, JP-A-62-174203, JP-B-62-
1641, U.S. Pat. No. 4,766,055), a system of a dye and an active halogen compound (JP-A-63-258903,
JP-A-2-63054), dye-borate compound systems (JP-A-62-143044, JP-A-62-15)
No. 0242, JP-A-64-13140, JP-A-64-
13141, JP-A-64-13142, JP-A-64
-13143, JP-A 64-13144, JP-A-6
No. 4-17048, JP-A 1-229003, JP-A 1-298348, JP-A 1-138204, etc.), a system containing a dye having a rhodanine ring and a radical generator (JP-A-2-179643, JP-A-2-19643). -244050
No.), a system of a titanocene and a 3-ketocoumarin dye (JP-A-63-221110), a system in which a titanocene and a xanthene dye, and an addition-polymerizable ethylenically unsaturated compound containing an amino group or a urethane group are combined (JP-A-H04-43104).
-221958, JP-A-4-219756), a system of titanocene and a specific merocyanine dye (JP-A-6-29).
No. 5061), a system of a dye having a titanocene and a benzopyran ring (JP-A-8-334897), and the like.

A system using a titanocene compound is particularly preferable because of its excellent sensitivity. As the titanocene compound, various compounds can be used. For example, various titanocene compounds described in JP-A-59-152396 and JP-A-61-151197 can be appropriately selected and used. . More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5 , 6-Pentafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2 , 4,6-Trifluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,6-di-fluorophen-1-yl, di-cyclopentadienyl-Ti
-Bis-2,4-di-fluorophen-1-yl, di-
Methylcyclopentadienyl-Ti-bis-2,3
4,5,6-Tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-cyclopentadienyl-
Ti-bis-2,6-difluoro-3- (pyr-1-yl) -phen-1-yl and the like can be mentioned.

If necessary, an auxiliary agent such as an amine compound or a thiol compound may be added to the photopolymerization initiator system, and the photopolymerization initiation ability can be further enhanced by adding these hydrogen donating compounds. . The total amount of these photopolymerization initiator systems (laser light absorbing dye, photopolymerization initiator, sensitization aid, etc.) used is 0.05 to 100 parts by weight, preferably 0 to 100 parts by weight of the polymerizable compound. 1 ~
70 parts by mass, and more preferably 0.2 to 50 parts by mass can be used.

[Other Components] In addition to the above basic components, unnecessary thermal polymerization of ethylenically unsaturated compounds polymerizable during production or storage of the photosensitive composition for the photosensitive layer In order to prevent this, it is desirable to add a small amount of a thermal polymerization inhibitor. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol and di-t.
-Butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-
Methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol),
N-nitrosophenyl hydroxylamine primary cerium salt, N-nitrosophenyl hydroxylamine aluminum salt, etc. are mentioned. The addition amount of the thermal polymerization inhibitor is preferably about 0.01 to about 5 mass% with respect to the mass of the entire composition. Further, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be unevenly distributed on the surface of the photosensitive layer during the drying process after coating. Good. The amount of the higher fatty acid derivative added is preferably about 0.5 to about 10 mass% of the total composition.

Further, a colorant may be added for the purpose of coloring the photosensitive layer. As the colorant, for example, a phthalocyanine-based pigment (CI Pigment Blue 1
5: 3.15: 4, 15: 6, etc.), azo pigments, carbon black, pigments such as titanium oxide, ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. The addition amount of the dye and pigment is preferably about 0.5 to about 20% by mass of the total solid content of the photosensitive layer. In addition, additives such as an inorganic filler and a plasticizer such as dioctyl phthalate, dimethyl phthalate and tricresyl phosphate may be added to improve the physical properties of the cured film. The addition amount of these is 10% of the total solid content of the photosensitive layer.
It is preferably not more than mass%.

When the photosensitive layer is coated on a support described below, the photosensitive layer composition is dissolved in various organic solvents before use. The solvent used here is acetone,
Methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl Ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether,
Propylene glycol monomethyl ether acetate,
Propylene glycol monoethyl ether acetate,
There are 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, ethyl lactate and the like. These solvents can be used alone or as a mixture. And the concentration of the solid content in the coating solution is appropriately 1 to 50% by weight.

A surfactant may be added to the composition for photopolymerizable photosensitive layer in order to improve the quality of the coated surface. The coating amount (solid content) of the photosensitive layer on the support obtained after coating and drying the photosensitive layer composition is about 0.1 g / m ² to about 10 g /
A range of m ² is suitable. More preferably 0.3-5 g
/ M ² . More preferably, it is 0.5 to 3 g / m ² .

[Acid Value of Photosensitive Layer] The acid value of the photosensitive layer means the photosensitive composition coated on the support of the photosensitive lithographic printing plate (an overcoat layer coated on the photosensitive layer, for example, , And does not include oxygen barrier layer) pKa contained per 1 g of layer
Equivalent amount of acid of 9 or less. Although it can be experimentally determined by directly titrating the photosensitive layer with an aqueous sodium hydroxide solution, it can also be determined by calculation from the content of the compound having an acid group having a pKa of 9 or less in the photosensitive composition. Specifically, as a method of changing the acid value of the photosensitive layer, the content ratio of the cross-linking agent monomer which is a component of the photosensitive layer / the binder polymer (linear polymer) having an acid group and the low acid value binder polymer having a small number of acid groups can be used. It can be used. The low acid value binder polymer preferably has an acid value of 1.5 meq / g or less. It is more preferably 1.2 meq / g or less. The photosensitive layer acid value of the photosensitive layer is preferably 1.0 meq / g or less. It is more effective to apply to a lithographic printing plate having a photosensitive layer having an acid value of 0.20 to 0.60 meq / g. From the viewpoint of image forming property, 0.30 is more preferable.
It has a photosensitive layer of 0.50 meq / g.

(Oxygen-shielding protective layer) The ultraviolet-visible light-polymerizable photosensitive lithographic printing plate has an oxygen-shielding protective layer containing a water-soluble vinyl polymer as a main component on the photopolymerizable photosensitive layer. May be. Examples of the water-soluble vinyl polymer contained in the oxygen barrier protective layer include polyvinyl alcohol, and partial esters, ethers, and acetals thereof, or a substantial amount of an unsubstituted vinyl alcohol unit such that they have the necessary water solubility. And its copolymers containing Examples of polyvinyl alcohol include those that are 71 to 100% hydrolyzed and have a degree of polymerization of 300 to 2400. Specifically, PVA-1 manufactured by Kuraray Co., Ltd.
05, PVA-110, PVA-117, PVA-11
7H, PVA-120, PVA-124, PVA-12
4H, PVA-CS, PVA-CST, PVA-HC,
PVA-203, PVA-204, PVA-205, P
VA-210, PVA-217, PVA-220, PV
A-224, PVA-217EE, PVA-220, P
VA-224, PVA-217EE, PVA-217
E, PVA-220E, PVA-224E, PVA-4
05, PVA-420, PVA-613, L-8 and the like. Examples of the above-mentioned copolymers include polyvinyl acetate chloroacetate or propionate which is 88 to 100% hydrolyzed, polyvinyl formal and polyvinyl acetal, and copolymers thereof. Other useful polymers include polyvinylpyrrolidone, gelatin and gum arabic, which may be used alone or in combination.

Pure water is preferably used as the solvent for coating the oxygen barrier protective layer, but alcohols such as methanol and ethanol, and ketones such as acetone and methyl ethyl ketone may be mixed with pure water. The concentration of the solid content in the coating solution is preferably 1 to 20% by weight.
Known additives such as a surfactant for improving the coating property and a water-soluble plasticizer for improving the physical properties of the film may be added to the oxygen barrier protective layer. Examples of the water-soluble plasticizer include propionamide, cyclohexanediol, glycerin, sorbitol and the like. Also, a water-soluble (meth) acrylic polymer or the like may be added. The coating amount is about 0.1 g / dry weight.
A range of m ² to about 15 g / m ² is suitable. More preferably, it is 1.0 g / m ² to about 5.0 g / m ² .

(Support) As a support to which the image recording layer or the photosensitive layer of the negative-type image forming material described above can be applied, a dimensionally stable plate-like material is suitable, 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.),
Examples thereof include paper or plastic film on which the above metal is laminated or vapor deposited. A preferable support includes a polyester film or an aluminum plate.

As the support used for the image forming material,
It is preferable to use an aluminum plate that is lightweight and has excellent surface treatment properties, workability, and corrosion resistance. The aluminum material used for this purpose includes aluminum and aluminum-containing alloys such as JIS 1050 material and JIS 110.
0 material, JIS 1070 material, Al-Mg alloy, Al-
It is selected from Mn-based alloys, Al-Mn-Mg-based alloys, Al-Zr-based alloys, Al-Mg-Si-based alloys, etc., or plastic films or papers on which aluminum or aluminum alloys are laminated or vapor-deposited. Further, a composite sheet in which an aluminum sheet is bonded onto a polyethylene terephthalate film as described in JP-B-48-18327 may be used.

The surface of the aluminum plate may be subjected to surface treatment such as roughening treatment, and an image recording layer or a photosensitive layer may be applied to obtain a lithographic printing plate precursor. The surface roughening treatment includes mechanical surface roughening, chemical surface roughening, and electrochemical surface roughening, either alone or in combination. In addition, it is also preferable to perform anodizing treatment for ensuring the scratch resistance of the surface and treatment for increasing the hydrophilicity.

The surface treatment of the support will be described below. Prior to roughening the aluminum plate, if necessary, for example, a surfactant for removing rolling oil on the surface,
Degreasing treatment with an organic solvent or an alkaline aqueous solution may be performed. In the case of alkali, a treatment such as neutralization and smut removal with an acidic solution may be performed next.

Next, in order to improve the adhesion between the support and the image recording layer and to impart water retention to the non-image area, a so-called graining treatment for roughening the surface of the support is performed. As a concrete means of this graining method, there is a mechanical graining method such as sandblasting, and there is a chemical graining method in which the surface is roughened with an etching agent composed of an alkali, an acid or a mixture thereof. . In addition, an electrochemical graining method, a method of roughening the surface by adhering a granular material to a support material with an adhesive or a method having its effect, or a continuous band or roll having fine unevenness is used as a support. A known method such as a surface-roughening method in which unevenness is transferred by pressure bonding to a material can be applied.

A plurality of such surface-roughening methods may be carried out in combination, and the order, the number of repetitions, etc. can be arbitrarily selected. Since smut is generated on the surface of the support obtained by the above-mentioned roughening treatment, that is, graining treatment, appropriate treatment such as washing with water or alkali etching should be performed to remove the smut. Are generally preferred.

In the case of an aluminum support, after the above-mentioned pretreatment, an oxide film is usually formed on the support by anodic oxidation in order to improve abrasion resistance, chemical resistance and water retention. Let As the electrolyte used for the anodizing treatment of the aluminum plate, any one can be used as long as it forms a porous oxide film, and generally, sulfuric acid, phosphoric acid, oxalic acid, hydrochloric acid, nitric acid, boric acid, chromic acid, Sulfamic acid, benzenesulfonic acid, or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of electrolyte. The treatment conditions for anodic oxidation cannot be unconditionally specified because they vary depending on the electrolyte used, but generally, the electrolyte concentration is 1 to 80% solution, the liquid temperature is 5 to 70 ° C., and the current density is 5 to 60 A / dm ^2. , Voltage 1
It is suitable if the electrolysis time is -100 V and the electrolysis time is 10 seconds-5 minutes. The amount of the anodized film is suitably 1.0 g / m ² or more, but more preferably in the range of 2.0 to 6.0 g / m ^2. If the anodic oxide film is less than 1.0 g / m ² , printing durability is insufficient, or the non-image area of the lithographic printing plate is easily scratched, and ink adheres to the scratched portion during printing. "Scratch stains" easily occur.

After the anodizing treatment, the surface of the aluminum may be sealed. Such sealing treatment is performed by immersing the substrate in hot water and a hot aqueous solution containing an inorganic salt or an organic salt, a steam bath, or the like. Further, the aluminum support may be subjected to a hydrophilization treatment such as a silicate treatment with an alkali metal silicate or a dipping treatment with an aqueous solution of potassium fluorozirconate, phosphate or the like.

An intermediate layer may be provided to enhance the adhesion between the support and the image recording layer or the photosensitive layer. In order to improve the adhesiveness, a diazo resin, a phosphonic acid or phosphoric acid compound, or an aluminum compound such as an aluminum alkoxide is used in the intermediate layer.
You may use the organic silicone compound etc. which are used for the adhesive layer provided on the aluminum substrate described in Japanese Patent No. 139. The thickness of the intermediate layer is arbitrary, and it must be a thickness that allows a uniform bond forming reaction with the upper image recording layer when exposed. Usually about 1-100 mg dry solid
/ Application rate of m ² is good, 5 to 40 mg / m ² is particularly favorable. After the surface of the support is subjected to the above treatment or undercoating, a back coat is provided on the back surface of the support, if necessary. As such a back coat, a coating layer composed of a metal oxide obtained by hydrolyzing and polycondensing an organic polymer compound described in JP-A-5-45885 and an organic or inorganic metal compound described in JP-A-6-35174. It is preferably used.

A preferable characteristic of the support for a lithographic printing plate is a center line average roughness of 0.10 to 1.2 μm. When the thickness is less than 0.10 μm, the adhesion to the image recording layer is deteriorated and the printing durability is remarkably deteriorated. If it is larger than 1.2 μm, the stain resistance during printing will deteriorate. Further, the color density of the support is 0.15 as the reflection density value.
If it is 0.65 and is whiter than 0.15, halation during image exposure is too strong to hinder image formation, and if it is blacker than 0.65, the image is difficult to see in the plate inspection work after development, The plate inspection property is remarkably poor.

[Plate-making process] The negative image-forming material can be produced as described above. The infrared curable image forming material can be recorded with an infrared laser. Also, thermal recording with an ultraviolet lamp or a thermal head is possible. In the present invention, the wavelength is from 760 nm to 1
Image exposure is preferably carried out by a solid-state laser emitting a 200 nm infrared ray and a semiconductor laser. The laser output is preferably 100 mW or more, and it is preferable to use a multi-beam laser device in order to shorten the exposure time. The exposure time per pixel is preferably within 20 μsec. The energy applied to the image forming material is preferably 10 to 300 mJ / cm ² .

As a method for exposing the ultraviolet-visible light-polymerizable photosensitive lithographic printing plate, known methods can be used without limitation. A laser is preferable as the light source, and for example, 350 to 450.
The following can be used as available laser light sources with a wavelength of nm. As a gas laser, Ar ion laser (364 nm, 351 nm, 10 mW to 1 W),
Kr ion laser (356nm, 351nm, 10mW ~ 1
W), He-Cd laser (441nm, 325nm, 1mW
〜100mW), Nd: YAG (Y
VO4) and SHG crystal x 2 times combination (355mm,
5 mW to 1 W), a combination of Cr: LiSAF and SHG crystals (430 nm, 10 mW), as a semiconductor laser system,
Combination of KNbO ₃ , ring resonator (430 nm, 30 mW), waveguide type wavelength conversion element and AlGaAs, InGaAs semiconductor (380 nm-450 nm, 5 mW-100 m)
W), waveguide type wavelength conversion element and AlGaInP, AlGa
As semiconductor combination (300nm-350nm, 5mW-
100 mW), AlGaInN (350 nm to 450 nm, 5
mW to 30 mW), N ₂ laser (337 nm, pulse 0.1 to 10 mJ) as pulse laser, XeF
(351 nm, pulse 10 to 250 mJ) Al especially in this
A GaInN semiconductor laser (commercially available InGaN semiconductor laser 400 to 410 nm, 5 to 30 mW) is suitable in terms of wavelength characteristics and cost.

Other available light sources of 450 nm to 700 nm include Ar + laser- (488 nm) and YAG.
-SHG laser (532 nm), He-Ne laser (633 nm), He-Cd laser, red semiconductor laser (650-690 nm), and 700 nm-120
A semiconductor laser (800
~ 850 nm), Nd-YAG laser (1064 nm)
Can be suitably used.

In addition, ultra-high pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, ultraviolet laser lamps (ArF excimer laser, KrF excimer laser, etc.), and electron as radiation Rays, X-rays, ion beams, far infrared rays and the like can be used, but the above-mentioned laser light source of 350 nm or more is particularly preferable in terms of low cost.

In the plate-making process for the negative image-forming material, the entire surface may be heated before exposure, during exposure, or between exposure and development, if necessary. By such heating,
The image forming reaction in the photosensitive layer is promoted, and advantages such as improvement in sensitivity and printing durability and stabilization of sensitivity may occur. further,
For the purpose of improving the image strength and printing durability, it is also effective to subject the image after development to the entire surface post-heating or the entire surface exposure. Usually, heating before development is preferably carried out under mild conditions of 150 ° C. or lower. For example, it is preferable to perform the heating in the range of 80 to 150 ° C. for 10 seconds to 5 minutes. If the temperature is too high, the non-image area may be fogged.
Very strong conditions are used for heating after development. Usually 2
It is in the range of 00 to 500 ° C. When the temperature is low, sufficient image strengthening effect cannot be obtained, and when it is too high, deterioration of the support,
This causes problems such as thermal decomposition of the image area.

Further, the exposure mechanism may be any of an inner drum system, an outer drum system, a flat bed system and the like. After exposure, a pre-development water washing treatment may be performed. An alkaline aqueous solution having a pH range of 9 to 14 is used as a developing solution and a developing replenishing solution used in the developing process. Alkali compounds used in the developer include alkali metal hydroxides, alkali earth metal hydroxides, silicates, alkali metal carbonates and hydrogen carbonates, ammonium carbonates and hydrogen carbonates,
Examples thereof include organic bases such as amines. In addition, various surfactants (nonionic, cationic, anionic)
It is also useful to include. The developed image-forming material is used as a lithographic printing plate after optionally post-treatment with washing water and further with the finishing gum solution of the present invention.

In recent years, automatic developing machines for printing plates have been widely used in the plate making / printing industry in order to rationalize and standardize the plate making work. This automatic developing machine is generally composed of a developing section and a post-processing section, and is composed of a device for conveying a printing plate material, each processing liquid tank, and a spray device. Each of the processing liquids pumped up is sprayed from a spray nozzle for development processing. Further, recently, a method has also been known in which a printing plate material is dipped and conveyed by a submerged guide roll or the like in a treatment liquid tank filled with the treatment liquid for treatment. In such automatic processing,
It is possible to carry out the processing while supplementing the replenishing solution to each processing solution according to the processing amount, operating time and the like. Also, electrical conductivity and pH
Can be detected by a sensor and automatically replenished. Further, a so-called disposable processing method of processing with a substantially unused processing liquid can be applied. The plate making method of the present invention is
Such an automatic processor can be adopted and implemented.

[0127]

The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited thereto. The indication of "%" means% by mass.

Examples 1 to 4 and Comparative Examples 1 and 2 [Preparation of Support] Aluminum web having a thickness of 0.30 mm (material 1050)
Was washed with trichlorethylene for degreasing, and then the surface was grained with a nylon brush and 400 mesh pumicetone-water suspension, and thoroughly washed with water. This aluminum web was immersed in a 25% sodium hydroxide aqueous solution (45 ° C.) for 9 seconds, etched and washed with water, and then further immersed in a 2% HNO ₃ aqueous solution for 20 seconds and washed with water. At this time, the etching amount of the grained surface was about 3 g / m ² . Next, 7% sulfuric acid was used as the electrolyte solution, and a DC anodic oxide coating of 3 g / m ² was provided on the aluminum web at a current density of 15 A / dm ² . After that, a silicate treatment was performed in order to secure hydrophilicity as a non-image portion of the printing plate. The treatment was carried out by keeping a 1.5% aqueous solution of sodium silicate No. 3 at 70 ° C. so that the contact time of the aluminum web was 15 seconds, and further washing with water. The amount of attached Si was 10 mg / m ² .

[Undercoating] Next, the following undercoating liquid was applied to this aluminum support with a wire bar and dried at 90 ° C for 30 seconds using a warm air dryer. The coated amount after drying was 80 mg / m ² . <Undercoat liquid> -Alkyl acetoacetate aluminum diisopropylate 1.0 g (Kawaken Fine Chemicals Co., Ltd. aluminum chelate M) -Methanol 100 g-Ion exchange water 10 g

[Formation of image-recording layer] The following coating solution for image-recording layer was applied onto the support having the undercoat layer formed thereon with a wire bar and dried at 120 ° C. for 45 seconds with a hot air dryer to form an image. A recording layer was formed to obtain a lithographic printing plate precursor [P-1] used in Examples 1 to 4 and Comparative Examples 1 and 2. The coating amount after drying was 2.0 g / m ² . The polymer (PB-1) used in the following composition was prepared by synthesizing a copolymer of methacrylic acid, acrylamide and benzyl methacrylate, and then in the presence of 3-chloro-2-hydroxypropyl methacrylate, a base and potassium iodide. It was synthesized by reacting with. The composition molar ratio is 15:30:
It was 15:40 and the weight average molecular weight was 100,000.

[0130] <Coating liquid for image recording layer [P-1]> -Onium salt [OS-7] 0.25 g -Polymerizable compound [RM-1] 0.60 g ・ Infrared absorber [IR-13] 0.06 g -Polymer [PB-1] 1.40 g ・ Victoria Pure Blue Naphthalene Sulfonate 0.04g ・ 1-Docosanol 0.01g ・ Polymerization inhibitor 0.005g     (Irganox 1010, manufactured by Ciba Specialty Chemicals Co., Ltd.) ・ Fluorosurfactant 0.03g   (Megafuck KF309, manufactured by Dainippon Ink and Chemicals, Inc.) ・ Methyl ethyl ketone 10g ・ Γ-Butyrolactone 5 g ・ Methanol 7g ・ 1-Methoxy-3-propanol 5 g

The structural formulas of the compounds used in the coating liquid for the image recording layer are shown below.

[0132]

[Preparation and plate making of finishing gum solution]
Plate material supply device (SA-L8000), exposure device (Lux)
el T-9000CTP), conveyor (T-9000)
Conveyor), automatic processor (LP-1310)
H), a stocker (ST-1160) Fuji Photo Film Co., Ltd. CTP output system was used. DV-2 (Fuji Photo Film Co., Ltd.)
(Manufactured by Mitsui Chemicals Co., Ltd.): Water = 1: 4 diluted developer was charged and kept at 30 ° C. Tap water was added to the second bath of the automatic processor.
In the third bath, various finishing gum solutions 1 to 4 (Examples 1 to 4) and comparative finishing gum solutions 1 and 2 (Comparative Examples 1 and 2) having the compositions shown below were charged and subjected to a plate-making treatment.

[0134] [Finishing gum liquid 1]   Piperazine 2.0%   Gum arabic 1.6%   Enzyme-modified potato starch 8.8%   Phosphorylated waxy corn starch starch 0.80%   Dioctyl sulfosuccinate sodium salt 0.10%   Citric acid 0.14%   α-alanine 0.11%   EDTA-tetrasodium salt 0.10%   Dodecyl diphenyl ether disulfonic acid 2Na salt 0.18%   Ethylene glycol 0.72%   Benzyl alcohol 0.87%   Sodium dehydroacetate 0.04%   Emulsion type antifoaming agent 0.01%   Add water to make 100

[0135] [Finishing gum liquid 2]   Polyethyleneimine (molecular weight 10,000) 2.0%   Gum arabic 1.6%   Enzyme-modified potato starch 8.8%   Phosphorylated waxy corn starch starch 0.80%   Dioctyl sulfosuccinate sodium salt 0.10%   Citric acid 0.14%   α-alanine 0.11%   EDTA-tetrasodium salt 0.10%   Dodecyl diphenyl ether disulfonic acid 2Na salt 0.18%   Ethylene glycol 0.72%   Benzyl alcohol 0.87%   Sodium dehydroacetate 0.04%   Emulsion type antifoaming agent 0.01%   Add water to make 100%

[0136] [Finishing gum liquid 3]   Piperazine 2.0%   Enzyme-modified potato starch 10.4%   Phosphorylated waxy corn starch starch 0.80%   Dioctyl sulfosuccinate sodium salt 0.10%   Citric acid 0.14%   α-alanine 0.11%   EDTA-tetrasodium salt 0.10%   Dodecyl diphenyl ether disulfonic acid 2Na salt 0.18%   Ethylene glycol 0.72%   Benzyl alcohol 0.87%   Sodium dehydroacetate 0.04%   Emulsion type antifoaming agent 0.01%   Add water to make 100%

[0137] [Finishing gum liquid 4]   4,4-trimethylene dipiperidine 2.0%   Enzyme-modified potato starch 10.4%   Phosphorylated waxy corn starch starch 0.80%   Dioctyl sulfosuccinate sodium salt 0.10%   Citric acid 0.14%   α-alanine 0.11%   EDTA-tetrasodium salt 0.10%   Dodecyl diphenyl ether disulfonic acid 2Na salt 0.18%   Ethylene glycol 0.72%   Benzyl alcohol 0.87%   Sodium dehydroacetate 0.04%   Emulsion type antifoaming agent 0.01%   Add water to make 100%

[0138] [Comparative finishing gum solution 1]   Gum arabic 1.6%   Enzyme-modified potato starch 8.8%   Phosphorylated waxy corn starch starch 0.80%   Dioctyl sulfosuccinate sodium salt 0.10%   Citric acid 0.14%   α-alanine 0.11%   EDTA-tetrasodium salt 0.10%   Dodecyl diphenyl ether disulfonic acid 2Na salt 0.18%   Ethylene glycol 0.72%   Benzyl alcohol 0.87%   Sodium dehydroacetate 0.04%   Emulsion type antifoaming agent 0.01%   Add water to make 100%

[0139] [Comparative finishing gum solution 2]   Enzyme-modified potato starch 10.4%   Phosphorylated waxy corn starch starch 0.80%   Dioctyl sulfosuccinate sodium salt 0.10%   Citric acid 0.14%   α-alanine 0.11%   EDTA-tetrasodium salt 0.10%   Dodecyl diphenyl ether disulfonic acid 2Na salt 0.18%   Ethylene glycol 0.72%   Benzyl alcohol 0.87%   Sodium dehydroacetate 0.04%   Emulsion type antifoaming agent 0.01%   Add water to make 100%

[0140]

[Examples 5 to 8 and Comparative Examples 3 and 4] [Preparation of support] An aluminum plate having a thickness of 0.30 mm and made of a material 1S was prepared by using a No. 8 nylon brush and an 800 mesh pumicetone water suspension. After being grained, it was thoroughly washed with water.
It was immersed in 10% sodium hydroxide at 70 ° C. for 60 seconds for etching, washed with running water, neutralized with 20% HNO ₃ and washed with water. This was subjected to 30 V in a 1% nitric acid aqueous solution using a sinusoidal alternating current under the condition of V _A = 12.7V.
The electrolytic surface-roughening treatment was performed with an electric quantity at the time of the anode of 0 coulomb / dm ² . When the surface roughness was measured, it was 0.45 μm.
(Ra display). Continued 30% H ₂ SO ₄
After soaking in an aqueous solution and desmutting at 55 ° C for 2 minutes,
When a cathode was placed on the grained surface in a 20% H ₂ SO ₄ aqueous solution at 33 ° C. and anodized at a current density of 5 A / dm ² for 50 seconds, the thickness was 2.7 g / m ² . . This was used as a support.

[Formation of image-recording layer] An image-recording layer coating solution [P-2] having the following composition was coated on the above support so that the dry coating weight was 1.5 g / m ^2, and the temperature was 100 ° C. It was dried for 1 minute to form an image recording layer. Then, polyvinyl alcohol (saponification degree: 98 mol%,
A 3% by weight aqueous solution having a degree of polymerization of 500) was applied so that the dry coating weight was 2.5 g / m ^2, and dried at 120 ° C. for 3 minutes, and used for Examples 5-8 and Comparative Examples 3 and 4. A printing plate precursor [P-2] was obtained.

[0142] <Image recording layer coating liquid [P-2]>   1.7 parts by weight of ethylenically unsaturated bond-containing compound (A-1)   1.9 parts by weight of linear organic polymer (B-2)   Sensitizer (C-1) 0.15 parts by weight   Photoinitiator (D-1) 0.30 parts by weight   Additive (S-1) 0.50 parts by weight   Fluorine-based surfactant 0.03 parts by weight   (Megafuck F-177: manufactured by Dainippon Ink and Chemicals, Inc.)   Thermal polymerization inhibitor 0.01 parts by weight   (N-nitrosohydroxylamine aluminum salt)   ε-type copper phthalocyanine dispersion 0.2 parts by weight   Methyl ethyl ketone 30.0 parts by weight   Propylene glycol monomethyl ether 30.0 parts by weight

Ethylenically unsaturated bond-containing compound (A-1), linear organic polymer (B-2), sensitizer (C-1), photoinitiator used in the coating solution for image recording layer. (D-
1) and the additive (S-1) are shown below.

[0144]

[Chemical 6]

[Plate-making] DV-2 was placed in the developing tank of an automatic developing machine (LP-850P2) manufactured by Fuji Photo Film Co., Ltd.
(Manufactured by Fuji Photo Film Co., Ltd.): water = 1: 4 diluted developer) was charged and kept at 30 ° C. Tap water was charged in the second bath of the automatic processor, and the finishing gum solutions 1 to 4 having the compositions shown above were used in the third bath (Examples 5 to 8).
And Comparative finishing gum solutions 1 and 2 (Comparative Examples 3 and 4), respectively. The lithographic printing plate precursor [P-2] was exposed to 40 μm / cm ² (standard exposure condition) with a 405 nm, 30 mW violet LD (inner drum type experimental machine).
Scanning exposure was carried out at 00 dpi under the condition of 175 lines / inch, and then the above-mentioned automatic developing machine was used for processing.

(Evaluation of printing durability and print stain resistance) Various lithographic printing plates obtained by the plate making in the above-mentioned Examples and Comparative Examples were manufactured by Man Roland Co., Ltd. R201 type printing machine and manufactured by Dainippon Ink and Chemicals GEOS. Print using G ink (N),
The number of printed sheets in which 2% halftone dots or solid portions caused the plate jump was evaluated and used as an index of printing durability. Print stain resistance is Mitsubishi Heavy Industries Diamond IF2 type printing machine, Dainippon Ink and Chemicals GEOS
Printing was performed using G red (S), and the ink stain on the non-image area was visually evaluated. The results are shown in Table 1 below.

[0147]

[Table 1]

[0148]

According to the plate making method of the lithographic printing plate of the present invention, by performing the plate surface treatment with a specific finishing gum solution, the strength of the image area can be increased and the printing durability can be improved. The hydrophilicity can be sufficiently retained on the surface of the support in the image area, the print stain resistance is not deteriorated, and an excellent lithographic printing plate can be provided.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AB03 AC01 AC08 AD01 BC32                       BC42 BC51 CA01 CA18 CA23                       CA26 CA28 CA48 CA50 CB13                       CB14 CB43 CC20 FA03 FA17                       FA28                 2H096 AA07 BA05 BA16 BA20 EA02                       EA04 GA08 HA02 JA04                 2H114 AA04 AA22 AA23 AA27 BA01                       DA41 DA53 EA03 EA06 EA08                       GA01 GA22

Claims (2)

[Claims] 1. A polymerizable lithographic printing plate precursor comprising a compound having in the molecule at least one group selected from an amino group and an imino group capable of Michael addition to an ethylenically unsaturated double bond. Finishing gum solution. 2. A negative-type image-forming material comprising a support and an image-recording layer containing at least one polymerizable compound having an ethylenically unsaturated double bond is image-exposed and developed, and then the finishing gum is formed. A plate making method of a lithographic printing plate comprising a plate surface treatment with a liquid, wherein the finishing gum liquid is a group selected from an amino group and an imino group capable of Michael addition to the ethylenically unsaturated double bond of the polymerizable compound. A method for making a lithographic printing plate, comprising a compound having at least one in the molecule.