WO2010004778A1 - Developing solution for lithographic printing plate material, and lithographic printing plate material - Google Patents

Abstract

Disclosed is a lithographic printing plate material which is highly sensitive, does not cause the sludge generation even when the material is subjected to the image developing treatment at a low pH value, and does not cause staining on a nonimage area. Also disclosed is a developing solution for a lithographic printing plate material. The developing solution for a lithographic printing plate material is used for the development of a lithographic printing plate material comprising a hydrophilic resin, and is characterized by comprising cyclodextrin or a derivative thereof.

Description

Developer for lithographic printing plate material and lithographic printing plate material

The present invention relates to a lithographic printing plate material used in a so-called computer-to-plate (hereinafter referred to as “CTP”) system and a developer for the lithographic printing plate material. The present invention relates to a lithographic printing plate material suitable for exposure with a laser beam of ˜450 nm and a developer for the lithographic printing plate material.

In recent years, digitization technology that electronically processes, stores, and outputs image information using a computer has become widespread, and in printing plate preparation technology for offset printing, directivity is determined according to digitized image information. A so-called CTP system that scans directly on a lithographic printing plate material by scanning with a high laser beam has been developed, and its practical application is progressing.

Of these, in the field of printing requiring relatively high printing durability, it is known to use a negative lithographic printing plate material having a polymerization type photosensitive layer containing a polymerizable compound (for example, (See Patent Documents 1 and 2.)

Light sources such as Ar laser (488 nm) and YD-YAG (532 nm) are known as light sources used for the polymerization type photosensitive layer, but the output is not sufficiently high in plate making using these light sources. Therefore, it is insufficient to increase the productivity of the plate making process, and the workability is insufficient from the viewpoint of the use of the safelight.

On the other hand, in recent years, lasers capable of continuous transmission within the range of high-power and small-sized shortwave light (wavelength: 350 to 450 nm) have become readily available.

In order to improve the above-described productivity and safelight properties, printing plate materials suitable for these short-wave lasers have been developed. For example, a printing plate material containing biimidazole in the photosensitive layer is known. Further, as a photopolymerizable composition having high sensitivity and low sublimation, for example, a hexagon containing an aryl group having a substituent such as an alkyl group. A photopolymerizable composition containing an arylbiimidazole compound is known (see, for example, Patent Documents 3 and 4).

However, these printing plate materials still have problems such as insufficient sensitivity and proper development.

On the other hand, the photopolymerization type lithographic printing plate material is usually subjected to image exposure and heat treatment as necessary, followed by washing with water for removing the oxygen blocking layer, and dissolution removal of unexposed portions (non-image portions). A lithographic printing plate is obtained by performing a development process, a water washing process, and a finisher gum process for making the non-image area hydrophilic. When preparing a lithographic printing plate from this lithographic printing plate material, in order to completely remove the unexposed photosensitive layer of the photosensitive layer, that is, to perform development, it is usually a pH of 12.5 or more as an aqueous alkaline developer. It was common to be used in.

However, in recent years, processing with an alkaline developer having a lower pH has been desired from the viewpoint of workability, safety, environmental suitability, and the like. However, such a relatively low pH developer basically has poor dissolving power of the photosensitive layer, and therefore has problems such as insufficient development and contamination of non-image areas.

Further, a planographic printing plate material containing cyclodextrin or a derivative thereof (Patent Document 5), and an example of impregnating the planographic printing material before development (Patent Document 6) are known. However, it did not solve the above problem.
JP-A-1-105238 JP-A-2-127404 JP 2001-194882 A JP 2004-137152 A JP-A-8-248625 JP 7-225470 A

The present invention has been made in view of the above problems, and an object of the present invention is to provide lithographic printing that prevents sludge from occurring even in a development process with high sensitivity and low pH, and does not cause stains in non-image areas. The object is to provide a plate material and a developer for a lithographic printing plate material.

The above object of the present invention is achieved by the following configuration.

1. A developer for a lithographic printing plate material, which is used for developing a lithographic printing plate material containing a hydrophilic resin and contains cyclodextrin or a derivative thereof.

2. 2. The developer for a lithographic printing plate material according to 1, wherein the cyclodextrin is α-cyclodextrin, β-cyclodextrin, or γ-cyclodextrin.

3. The developer for a lithographic printing plate material according to 1 or 2, wherein the developer is an aqueous solution containing a water-soluble resin and a surfactant and having a pH of 3.0 to 9.0.

4. 4. The lithographic printing plate material having a photosensitive layer containing a spectral sensitizer, a polymerization initiator, a polymerizable monomer, and a polymer binder on a support, the developer according to any one of 1 to 3 A lithographic printing plate material characterized by being developed using.

5. 5. The lithographic printing plate material according to 4, wherein the polymerization initiator is hexaarylbisimidazole.

6. 6. The lithographic printing plate material according to 4 or 5, wherein the lithographic printing plate material is exposed and recorded with image information by a laser light source having an emission wavelength in the range of 350 nm to 450 nm.

According to the present invention, there is provided a lithographic printing plate material that prevents sludge from being generated even in a high-sensitivity and low-pH development process and that does not cause stains in non-image areas, and a developer for the lithographic printing plate material. can do.

Hereinafter, the best mode for carrying out the present invention will be described, but the present invention is not limited thereto.

The developer of the present invention is used for developing a lithographic printing plate material containing a hydrophilic resin, and contains cyclodextrin or a derivative thereof.

The lithographic printing plate material of the present invention is a lithographic printing plate material having a photosensitive layer containing a spectral sensitizer, a polymerization initiator, a polymerizable monomer, and a polymer binder on a support. Development processing is performed using a developer.

In the present invention, in particular, the developer of the present invention is used for the development of a lithographic printing plate material containing a hydrophilic resin. By containing cyclodextrin or a derivative thereof, development at high sensitivity and low pH is performed. The processing also improves the developability, prevents the generation of sludge, and provides a lithographic printing plate material that does not cause stains in non-image areas. Moreover, the developing solution for lithographic printing plate materials can be provided. Although the mechanism of action of the present invention is not clear, particularly in a low pH developer, the polymerization initiator hexaarylbisimidazole is one of the causes of sludge generation, and the addition of cyclodextrin to it causes sludge generation due to the inclusion effect. Presumed to be suppressed.

Hereinafter, the present invention and its components will be described in detail.

<Developer>
The developer of the present invention is used for developing an unexposed portion (non-image portion) of a lithographic printing plate material containing a hydrophilic resin after exposing and recording image information with a laser light source. It is characterized by containing a derivative.

(Cyclodextrin or its derivatives)
The developer of the present invention contains cyclodextrin or a derivative thereof.

Examples of the cyclodextrin and derivatives thereof in the present invention include compounds represented by the following general formula (I) or (II) and branched cyclodextrins.

In the general formula (I), R ₁ , R ₂ and R ₃ represent a hydrogen atom, an alkyl group or a substituted alkyl group, and each may be the same or different. n is an integer of 4 to 10.

R ₁ , R ₂ and R ₃ are preferably a hydrogen atom, a hydroxyethyl group or a hydroxypropyl group, and more preferably a substituted alkyl group content in one molecule is 15 to 50%.

In the general formula (II), R is a hydrogen atom, —R ₂ —CO ₂ H, —R ₂ —SO ₃ H, —R ₂ —NH ₂ or —N— (R ₃ ) ₂ , R ₂ is carbon Represents a linear or branched alkylene group having 1 to 5 carbon atoms, and R ₃ represents a linear or branched alkyl group having 1 to 5 carbon atoms.

Specific examples of the cyclodextrin in the present invention include α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin and derivatives thereof. Preferred are α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin.

Examples of cyclodextrin production are described in “Junal of the American Chemical Society”, Volume 71, page 354, 1949, “Cheimish Berichte”, Volume 90, page 2561, 1949, Volume 90, page 2561, 1957. Of course, the present invention is not limited to these.

The branched cyclodextrin used in the present invention is a product obtained by adding or binding a known cyclodextrin to a water-soluble substance such as glucose, maltose, cellobiose, lactose, sucrose, galactose, glucosamine, or other water-soluble substances such as disaccharides or disaccharides. Preferably, maltosylcyclodextrin in which maltose is bound to cyclodextrin (the number of binding molecules of maltose may be one molecule, two molecules, or three molecules) or glucosylcyclodextrin in which glucose is bound to cyclodextrin (The number of binding molecules of glucose may be 1 molecule, 2 molecules, 3 molecules, etc.).

Specific methods for synthesizing these branched cyclodextrins include, for example, Starch Chemistry, Vol. 33, No. 2, 119-126 (1986), 127-132 (1986), Starch Chemistry, Vol. 30, Vol. 2, pp. 231 to 239 (1983), etc., and can be synthesized with reference to these known methods. For example, maltosyl cyclodextrin uses cyclodextrin and maltose as raw materials, isoamylase and pullulanase. It can be produced by a method of binding maltose to cyclodextrin using an enzyme such as Glucosylcyclodextrin can be produced by the same method.

In the present invention, examples of the branched cyclodextrin preferably used include the following specific exemplified compounds.
[Exemplary compound]
D-1 α-cyclodextrin with one molecule of maltose D-2 β-cyclodextrin with one molecule of maltose D-3 γ-cyclodextrin with one molecule of maltose D-4 α- with two molecules of maltose bonded Cyclodextrin D-5 β-cyclodextrin D-6 with two molecules of maltose bound γ-cyclodextrin D-7 with two molecules of maltose bound α-cyclodextrin D-8 with three molecules of maltose bound three molecules of maltose β-cyclodextrin D-9 γ-cyclodextrin D-10 with 3 molecules of maltose bound α-cyclodextrin D-11 with 1 molecule of glucose β-cyclodextrin D-12 1 molecule of glucose bound with 1 molecule of glucose Bound γ-cyclodextrin D-13 guru Α-Cyclodextrin D-14 with two molecules of course β-Cyclodextrin D-15 with two molecules of glucose γ-Cyclodextrin D-16 with two molecules of glucose α-Cyclodextrin D with three molecules of glucose -17 β-cyclodextrin with 3 molecules of glucose D-18 γ-cyclodextrin with 3 molecules of glucose For the structure of these branched cyclodextrins, HPLC, NMR, TLC (thin layer chromatography), INEPT method (Insensitive method) Although various studies have been made with measurement methods such as "nuclei enhanced by polarization transfer", it has not yet been determined even with the current chemical technology, and is in the stage of a presumed structure. However, the fact that each monosaccharide or disaccharide is bound to cyclodextrin is an error in the above measurement method. Therefore, in the present invention, when a monosaccharide or disaccharide multimolecule is bound to cyclodextrin, for example, as shown in the figure below, when each is linked to each glucose of cyclodextrin, It includes both those bound linearly to a single glucose.

In these branched cyclodextrins, since the ring structure of the existing cyclodextrins is maintained as it is, the same inclusion activity as that of the existing cyclodextrins is exhibited, and highly water-soluble maltose or glucose is added to the water. It is characterized by drastic improvement in solubility.

The branched cyclodextrin used in the present invention can also be obtained as a commercial product. For example, maltosyl cyclodextrin is commercially available as Isoelite (registered trademark) manufactured by Shimizu Minato Sugar Co., Ltd.

The content of cyclodextrin or a derivative thereof in the present invention is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, based on the developer.

The developer of the present invention preferably further contains a water-soluble resin and a surfactant.

Examples of water-soluble resins include gum arabic, fiber derivatives (for example, carboxymethyl cellulose, carboxyethyl cellulose, methyl cellulose, etc.) and modified products thereof, polyvinyl alcohol and derivatives thereof, polyvinyl pyrrolidone, polyacrylamide and copolymers thereof, vinyl methyl ether / Examples thereof include a maleic anhydride copolymer, a vinyl acetate / maleic anhydride copolymer, and a styrene / maleic anhydride copolymer. The content of these water-soluble resins is suitably 0.1 to 50% by mass, more preferably 0.5 to 3.0% by mass in the composition.

Also, examples of the surfactant include an anionic surfactant and a nonionic surfactant. For example, anionic surfactants include fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinates, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, alkyl naphthalene sulfones. Acid salts, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, polyoxyethylene aryl ether sulfonates, polyoxyethylene naphthyl ether sulfonates, N-methyl-N-oleyl taurine sodium salts N-alkylsulfosuccinic acid monoamide disodium salts, petroleum sulfonates, nitrated castor oil, sulfated beef tallow oil, sulfate esters of fatty acid alkyl esters, Rualkyl nitrates, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ethers Phosphoric acid ester salts, polyoxyethylene alkylphenyl ether phosphoric acid ester salts, partially saponified products of styrene-maleic anhydride copolymer, partially saponified products of olefin-maleic anhydride copolymer, naphthalene sulfonate formalin condensates Etc. Among these, dialkyl sulfosuccinates, alkyl sulfate esters, and alkyl naphthalene sulfonates are particularly preferably used.

Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene aryl ethers, polyoxyethylene naphthyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene polyoxy Propylene alkyl ether, glycerin fatty acid partial ester, sorbitan fatty acid partial ester, 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 moiety Esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, polyoxyethylenation Bran oils, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, trialkylamine oxides, etc. It is done. Of these, polyoxyethylene alkylphenyl ethers, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene-polyoxypropylene block polymers and the like are preferably used. Fluorine-based and silicon-based anions and nonionic surfactants can also be used.

Examples of preferable surfactants include surfactants added to the lithographic printing plate surface protective agents described in JP-A Nos. 2004-167903, 2004-230650, and 2005-43393. .

These surfactants can be used in combination of two or more. For example, two or more different from each other can be used in combination. For example, a combination of two or more different anionic surfactants or a combination of an anionic surfactant and a nonionic surfactant is preferable. The amount of the surfactant used is not particularly limited, but is preferably 0.01 to 20% by mass of the post-treatment liquid.

The pH of the developer of the present invention can be used in the range of 3.0 to 9.0. When used in the acidic range of pH 3 to 6, it is adjusted by adding a mineral acid, organic acid or inorganic salt to the aqueous solution. The addition amount is preferably 0.01 to 2% by mass. Examples of mineral acids include nitric acid, sulfuric acid, phosphoric acid, and metaphosphoric acid.

Examples of organic acids include citric acid, acetic acid, succinic acid, malonic acid, p-toluenesulfonic acid, tartaric acid, malic acid, lactic acid, levulinic acid, phytic acid, and organic phosphonic acid.

Further examples of inorganic salts include magnesium nitrate, primary sodium phosphate, secondary sodium phosphate, nickel sulfate, sodium hexamethanoate, sodium tripolyphosphate, and the like. You may use together at least 1 sort (s) or 2 or more types, such as a mineral acid, an organic acid, or an inorganic salt.

When used in the basic region pH 8 to 9, it can be adjusted to the pH by adding a water-soluble organic base or inorganic base. A water-soluble organic base is preferable, and examples include triethanolamine, diethanolamine, and ethanolamine.

Further, a preservative, an antifoaming agent and the like can be added to the developer of the present invention.

For example, as a preservative, phenol or a derivative thereof, o-phenylphenol, p-chlorometacresol, hydroxybenzoic acid alkyl ester, formalin, imidazole derivative, sodium dehydroacetate, 4-isothiazolin-3-one derivative, benzoisothiazoline-3- ON, benztriazole derivatives, amiding anidine derivatives, quaternary ammonium salts, derivatives of pyridine, quinoline, guanidine, diazine, triazole derivatives, oxazole, oxazine derivatives and the like. A preferable addition amount is an amount that exerts a stable effect on bacteria, molds, yeasts, etc., and varies depending on the type of bacteria, molds, yeasts, but 0.01% with respect to the plate surface protective agent at the time of use. The range of ˜4% by mass is preferable, and two or more kinds of preservatives are preferably used in combination so as to be effective against various molds and sterilization. As the antifoaming agent, a silicon antifoaming agent is preferable. Among them, emulsification dispersion type and solubilization can be used. The range of 0.01 to 1.0% by mass is optimal.

Further, a chelate compound may be added. Preferred chelate compounds include, for example, ethylenediaminetetraacetic acid, potassium salt thereof, sodium salt thereof; diethylenetriaminepentaacetic acid, potassium salt thereof, sodium salt thereof; triethylenetetraminehexaacetic acid, sodium salt thereof; ethylenediamine disuccinic acid, potassium salt thereof. Triethylenetetramine hexaacetic acid, potassium salt thereof, sodium salt thereof, hydroxyethylethylenediaminetriacetic acid, potassium salt thereof, sodium salt thereof: nitrilotriacetic acid, sodium salt thereof; 1-hydroxyethane-1,1-diphosphone Acids, potassium salts, sodium salts; organic phosphonic acids or phosphonoalkanetricarboxylic acids such as aminotri (methylenephosphonic acid), potassium salts, sodium salts, etc. It can be mentioned.

An organic amine salt is also effective in place of the sodium salt and potassium salt of the chelating agent. These chelating agents are selected so that they exist stably in the developer composition and do not impair the printability. The addition amount is suitably 0.001 to 1.0% by mass.

In addition to the above components, a sensitizer can be added if necessary. For example, hydrocarbons such as turpentine oil, xylene, toluene, low heptane, solvent naphtha, kerosene, mineral spirit, petroleum fraction having a boiling point of about 120 ° C to about 250 ° C, such as dibutyl phthalate, dihebutyl phthalate, di-n-octyl Phthalic acid diester agents such as phthalate, di (2-ethylhexyl) phthalate, dinonyl phthalate, didecyl phthalate, dilauryl phthalate, butyl benzyl phthalate, such as dioctyl adipate, butyl glycol adipate, dioctyl azelate, dibutyl sebacate, di ( 2-ethylhexyl) aliphatic dibasic acid esters such as sebacate and dioctyl sebacate, epoxidized triglycerides such as epoxidized soybean oil, such as tricresyl phosphate, trioctylfolate Feto, phosphoric acid esters such as tris chloroethyl phosphate, for example, freezing point, such as benzoic acid esters of benzyl benzoate and at 15 ℃ below boiling point at one atmosphere include 300 ° C. or more plasticizers.

In addition, caproic acid, enanthic acid, caprylic acid, helargonic acid, capric acid, undecyl acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachic acid, behenic acid, lignoserine Saturated fatty acids such as acid, serotic acid, heptacosanoic acid, montanic acid, melicinic acid, lactelic acid and isovaleric acid, acrylic acid, crotonic acid, isocrotonic acid, undecylenic acid, oleic acid, elaidic acid, celetic acid, nillic acid, buteticidin Examples also include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, propiolic acid, stearolic acid, sardine acid, talylic acid and licanoic acid. More preferred are fatty acids which are liquid at 50 ° C., more preferred are those having 5 to 25 carbon atoms, and most preferred are those having 8 to 21 carbon atoms. These sensitizers can be used alone or in combination of two or more. A preferable range of the amount used is 0.01 to 10% by mass, and a more preferable range is 0.05 to 5% by mass.

(Hydrophilic resin)
The image forming layer of the lithographic printing plate material in which the developer of the present invention is used for development contains a hydrophilic resin as a polymer binder.

Examples of the hydrophilic resin include those similar to the hydrophilic resin contained as a polymer binder in the photosensitive layer of the lithographic printing plate material of the present invention described later.

<Lithographic printing plate material>
The lithographic printing plate material of the present invention is a lithographic printing plate material having a photosensitive layer containing a spectral sensitizer, a polymerization initiator, a polymerizable monomer, and a polymer binder on a support. It is characterized by being developed using

(Polymerization initiator)
The lithographic printing plate material of the present invention contains a polymerization initiator in the photosensitive layer.

The polymerization initiator according to the present invention is capable of initiating polymerization of a polymerizable ethylenic double bond-containing compound by image exposure. In the present invention, the photosensitive layer has a hexaarylbisimidazole compound as a polymerization initiator. It is preferable to contain.

The process for the preparation of hexaarylbiimidazole (HABI, triaryl-imidazole dimer) compounds used in the present invention is described in DE 1,470,154 and those in photopolymerizable compositions Is described in EP 24,629, EP 107,792, US 4,410,621, EP 215,453 and DE 3,211,312.

Preferred derivatives are, for example, 2,4,5,2 ′, 4 ′, 5′-hexaphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenylbiimidazole. Imidazole, 2,2'-bis (2-bromophenyl) -4,5,4 ', 5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,5,4' , 5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetrakis (3-methoxyphenyl) biimidazole, 2,2'-bis (2- Chlorophenyl) -4,5,4 ', 5'-tetrakis (3,4,5-trimethoxyphenyl) -biimidazole, 2,5,2', 5'-tetrakis (2-chlorophenyl) -4,4 ' -Bis (3,4-di Toxiphenyl) biimidazole, 2,2'-bis (2,6-dichlorophenyl) -4,5,4 ', 5'-tetraphenylbiimidazole, 2,2'-bis (2-nitrophenyl) -4, 5,4 ', 5'-tetraphenylbiimidazole, 2,2'-di-o-tolyl-4,5,4', 5'-tetraphenylbiimidazole, 2,2'-bis (2-ethoxyphenyl) ) -4,5,4 ', 5'-tetraphenylbiimidazole and 2,2'-bis (2,6-difluorophenyl) -4,5,4', 5'-tetraphenylbiimidazole.

In the present invention, in addition to hexaarylbiimidazole, other kinds of polymerization initiators can be used in combination as a polymerization initiator. For example, titanocene compounds, monoalkyltriaryl borate compounds, iron arene complex compounds, and polyhalogen compounds are preferably used.

Examples of the titanocene compound include compounds described in JP-A-63-41483 and JP-A-2-291. More preferred specific examples include bis (cyclopentadienyl) -Ti-di-chloride. Bis (cyclopentadienyl) -Ti-bis-phenyl, bis (cyclopentadienyl) -Ti-bis-2,3,4,5,6-pentafluorophenyl, bis (cyclopentadienyl) -Ti -Bis-2,3,5,6-tetrafluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,4,6-trifluorophenyl, bis (cyclopentadienyl) -Ti-bis-2 , 6-Difluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,4-difluorophenyl, bis (methylcyclopentadienyl) -Ti- -2,3,4,5,6-pentafluorophenyl, bis (methylcyclopentadienyl) -Ti-bis-2,3,5,6-tetrafluorophenyl, bis (methylcyclopentadienyl)- Ti-bis-2,6-difluorophenyl (IRGACURE727L: manufactured by Ciba Japan), bis (cyclopentadienyl) -bis (2,6-difluoro-3- (py-1-yl) phenyl) titanium (IRGACURE784) : Ciba Japan), bis (cyclopentadienyl) -bis (2,4,6-trifluoro-3- (pyridin-1-yl) phenyl) titanium bis (cyclopentadienyl) -bis (2 , 4,6-trifluoro-3- (2-5-dimethylpy-1-yl) phenyl) titanium and the like.

Examples of the monoalkyl triaryl borate compound include compounds described in JP-A-62-1050242 and JP-A-62-143044, and more preferable specific examples include tetra-n-butylammonium.n- Butyl-trinaphthalen-1-yl-borate, tetra-n-butylammonium / n-butyl-triphenyl-borate, tetra-n-butylammonium / n-butyl-tri- (4-tert-butylphenyl) -borate Tetra-n-butylammonium · n-hexyl-tri- (3-chloro-4-methylphenyl) -borate, tetra-n-butylammonium · n-hexyl-tri- (3-fluorophenyl) -borate, etc. Can be mentioned.

Examples of the iron arene complex compound include compounds described in JP-A-59-219307, and more preferable specific examples include η-benzene- (η-cyclopentadienyl) iron hexafluorophosphate, η- Cumene- (η-cyclopentadienyl) iron hexafluorophosphate, η-fluorene- (η-cyclopentadienyl) iron hexafluorophosphate, η-naphthalene- (η-cyclopentadienyl) iron hexafluorophosphate, η -Xylene- (η-cyclopentadienyl) iron hexafluorophosphate, η-benzene- (η-cyclopentadienyl) iron tetrafluoroborate, and the like.

As the polyhalogen compound, a compound having a trihalogenmethyl group, a dihalogenmethyl group or a dihalomethylene group is preferably used, and in particular, a halogen compound represented by the following general formula (PIH1) and the above group is substituted with an oxadiazole ring. A compound is preferably used.

Among these, a halogen compound represented by the following general formula (PIH2) is particularly preferably used.

Formula (PIH1) R ₁ —CY ₂ — (C═O) —R ₂
In the formula, R ₁ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an iminosulfonyl group, or a cyano group. R ₂ represents a monovalent substituent. R ₁ and R ₂ may be bonded to form a ring. Y ₂ represents a halogen atom.

Formula (PIH2) CY ₃ — (C═O) —XR ₃
In the formula, R ₃ represents a monovalent substituent. X represents —O— or —NR ₄ —. R ₄ represents a hydrogen atom or an alkyl group. R ₃ and R ₄ may be bonded to form a ring. Y ₃ represents a halogen atom. Among these, those having a polyhalogenacetylamide group are particularly preferably used.

A compound in which a polyhalogenmethyl group is substituted with an oxadiazole ring is also preferably used. Furthermore, oxadiazole compounds described in JP-A Nos. 5-34904, 45875, and 8-240909 are also preferably used.

The biimidazole compound is a derivative of biimidazole, and examples thereof include compounds described in JP-A No. 2003-295426.

Other optional polymerization initiators can be used in combination. For example, J. et al. Carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo, diazo compounds, halogen compounds, and photoreductive dyes as described in Chapter 5 of “Light Sensitive Systems” by J. Kosar Etc. More specific compounds are disclosed in British Patent 1,459,563.

That is, as the polymerization initiator that can be used in combination, the following can be used.

Benzoin derivatives such as benzoin methyl ether, benzoin-i-propyl ether, α, α-dimethoxy-α-phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-bis (dimethyl) Benzophenone derivatives such as amino) benzophenone; thioxanthone derivatives such as 2-chlorothioxanthone and 2-i-propylthioxanthone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; N-methylacridone, N-butylacridone and the like Acridone derivatives: α, α-diethoxyacetophenone, benzyl, fluorenone, xanthone, uranyl compounds, JP-B-59-1281, JP-A-69-1621 and JP-A-60-60104 Triazine derivatives; organic peroxides described in JP-A-59-1504 and JP-A-61-243807; JP-B-43-23684, JP-A-44-6413, JP-A-44-6413, JP-A-47-1604 and the United States Diazonium compounds described in Japanese Patent No. 3,567,453; organic azide compounds described in US Pat. Nos. 2,848,328, 2,852,379 and 2,940,853; Japanese Patent Publication No. 36-22062b, O-quinonediazides described in JP-A-37-13109, JP-A-38-18015 and JP-A-45-9610; JP-B-55-39162, JP-A-59-14023 and “Macromolecules”, Vol. 10, Various onium compounds described on page 1307 (1977); compounds described in JP-A-59-142205 Compound: described in JP-A-1-54440, European Patents 109,851, 126,712, and “Journal of Imaging Science (J. Imag. Sci.)”, Vol. 30, 174 (1986) Metal allene complexes; (oxo) sulfonium organoboron complexes described in Japanese Patent Application Nos. 4-56831 and 4-89535; “Coordination Chemistry Review”, 84, 85-277 (1988) And transition metal complexes containing a transition metal such as ruthenium described in JP-A-2-182701; 2,4,5-triarylimidazole dimer described in JP-A-3-209477; carbon tetrabromide, JP Organohalogen compounds described in 59-107344 Etc..

The content of the polymerization initiator according to the present invention (total amount of the polymerization initiator) is preferably 0.1% by mass to 20% by mass, and preferably 0.5% by mass to 15%, relative to the polymerizable ethylenically unsaturated bond-containing compound. Mass% is particularly preferred.

(Co-initiator)
The lithographic printing plate material of the present invention can contain a mercapto compound as a coinitiator in the photosensitive layer.

Here, the “co-initiator” refers to a compound having a function of promoting a polymerization reaction that proceeds with the reaction of the polymerization initiator described above.

The image forming layer according to the present invention preferably contains a mercapto compound from the viewpoint of sensitivity and sensitivity fluctuation prevention.

The mercapto compound is a compound having a mercapto group. For example, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercapto-4-methyl-5-acetylthiazole, 2-mercapto-4 -Methylthiazole, 1-methyl-2-mercaptoimidazole, 2-mercapto-4,5-dimethylthiazole, 2-mercapto-5-acetylthiazole, 1-methyl-2-mercaptobenzimidazole, 1-methyl-2-mercapto Examples include -4-methyl-5-acetylimidazole, 2-mercaptooxazole, 2-mercaptobenzoxazole, and 2-mercapto-2-imidazoline.

More specifically, the mercapto compound used as a coinitiator is preferably a compound represented by the following general formulas (1) to (6).

[X represents an oxygen atom, —NR ₁ — or selenium, R ₁ represents an alkyl group which may have a substituent, or an aryl group which may have a substituent, and Y represents N═C—X It represents an atomic group that forms a 5-membered heterocycle with the moiety, and Y may further have a substituent. ]

[R ₁ represents an alkyl group that may have a substituent, or an aryl group that may have a substituent, and R ₂ represents a hydrogen atom, an alkyl group that may have a substituent, or a substituent. Represents an aryl group which may have ]

[R ₂ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. ]

[R ₁ represents an alkyl group which may have a substituent or an aryl group which may have a substituent. ]

[R ₂ and R ₃ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. ]

[R ₁ represents an alkyl group which may have a substituent or an aryl group which may have a substituent. R ₄ to R _{7 each} represents a hydrogen atom, a halogen atom, an alkoxyl group, a dialkylamino group, an alkyl group that may have a substituent, or an aryl group that may have a substituent. ]
In the general formulas (1) to (6), X represents an oxygen atom, —NR ₁ —, or selenium, Y represents an atomic group that forms a 5-membered heterocycle with the N═C—X moiety, You may have a substituent.

R ₁ to R ₃ represent an alkyl group which may have a substituent or an aryl group which may have a substituent.

R ₄ to R ₇ represent a hydrogen atom, a halogen atom, an alkoxyl group, a dialkylamino group, an alkyl group which may have a substituent, or an aryl group which may have a substituent.

The alkyl group which may have the above substituent is not particularly limited, but is methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group. N-pentyl group, n-hexyl group, cyclohexyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group and other linear, branched and cyclic alkyl groups, and those having any substituents on them As mentioned. The substituents that can be substituted on these alkyl groups are not particularly limited, and examples thereof include alkyl groups, alkoxy groups, alkylamino groups, dialkylamino groups, halogens, aryl groups, and aralkyl groups.

Preferred examples include methyl group, ethyl group, n-butyl group, t-butyl group, methoxymethyl group, methoxyethyl group, benzyl group, chloromethyl group and the like.

Examples of the aryl group that may have the above-described substituent include a phenyl group, a naphthyl group, and those having an arbitrary substituent. The substituent that can be substituted on the aryl group is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an alkylamino group, a dialkylamino group, a halogen, an aryl group, and an aralkyl group.

Preferred examples include phenyl group, tolyl group, methoxyphenyl group, chlorophenyl group, t-butylphenyl group, dialkylaminophenyl group and the like.

Hereinafter, specific examples of the compounds represented by the above general formulas (1) to (6) will be given, but the present invention is not limited thereto.

The amount of the compounds represented by the general formulas (1) to (6) is preferably 0.01 to 20% by mass, more preferably 0.01 to 15% by mass with respect to the total solid content of the photosensitive layer. %. More preferably, it is 0.05 to 10% by mass, and more preferably 0.1 to 3% by mass.

In the present invention, various co-initiators conventionally known in the technical field according to the present invention, for example, co-initiators disclosed in JP-A-8-254821 and JP-A-2005-062482 are used in combination. You can also.

(Polymerizable monomer)
The lithographic printing plate material of the present invention contains a polymerizable monomer in the photosensitive layer.

The polymerizable monomer is a compound (monomer) that can be polymerized by the product of the reaction of the polymerization initiator by image exposure. As the polymerizable monomer according to the present invention, a wide range of compounds that can start a polymerization reaction triggered by a reaction with a radical species generated from the polymerization initiator according to the present invention can be used.

As the polymerizable monomer according to the present invention, an ethylenically unsaturated bond-containing compound that is preferably used is a polymerizable compound, which is generally used for general radical polymerizable monomers and ultraviolet curable resins. Polyfunctional monomers and polyfunctional oligomers having a plurality of addition-polymerizable ethylenic double bonds in the molecule to be used.

The polymerizable monomer according to the present invention is not limited, but preferred examples thereof include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryl. Monofunctional acrylates such as oxyethyl acrylate, tetrahydrofurfuryloxyhexanolide acrylate, ε-caprolactone adduct of 1,3-dioxane alcohol, 1,3-dioxolane acrylate, or methacrylates of these acrylates, Methacrylic acid, itaconic acid, crotonic acid, maleic acid ester instead of itaconate, crotonate, maleate, eg ethyl Glycol diacrylate, triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcinol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, dipentylate of hydroxypivalate neopentyl glycol A diacrylate of neopentyl glycol adipate, a diacrylate of an ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1 , 3-dioxane diacrylate, tricyclodecane dimethylol acrylate, ε- of tricyclodecane dimethylol acrylate Prolactone adducts, bifunctional acrylic esters such as diacrylate of diglycidyl ether of 1,6-hexanediol, or methacrylic acid, itaconic acid, crotonic acid in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate Maleic esters, such as trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexa Acrylate, ε-caprolactone adduct of dipentaerythritol hexaacrylate, pyro Polyfunctional acrylic acid ester such as roll triacrylate, propionic acid / dipentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, or these acrylates with methacrylate, itaconate, Mention may be made of methacrylic acid, itaconic acid, crotonic acid, maleic acid ester, etc. instead of crotonate and maleate.

Also, prepolymers can be used in the same manner as described above. Examples of the prepolymer include compounds as described below, and a prepolymer obtained by introducing acrylic acid or methacrylic acid into an oligomer having an appropriate molecular weight and imparting photopolymerizability can be preferably used. These prepolymers may be used singly or in combination of two or more, and may be used by mixing with the above-mentioned monomers and / or oligomers.

Examples of prepolymers include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumaric acid, glutaric acid, pimelic acid, Polybasic acids such as sebacic acid, dodecanoic acid, tetrahydrophthalic acid, and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, trimethylol Polyester in which (meth) acrylic acid is introduced into polyester obtained by the combination of polyhydric alcohols such as propane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol Acrylates such as bisphenol A, epichlorohydrin, (meth) acrylic acid, and epoxy acrylates in which (meth) acrylic acid is introduced into an epoxy resin such as phenol novolac, epichlorohydrin, (meth) acrylic acid, such as ethylene glycol adipine Acid / tolylene diisocyanate / 2-hydroxyethyl acrylate, polyethylene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate, hydroxyethyl phthalyl methacrylate / xylene diisocyanate, 1,2-polybutadiene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate , Trimethylolpropane, propylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate As described above, urethane acrylates in which (meth) acrylic acid is introduced into a urethane resin, for example, silicone resin acrylates such as polysiloxane acrylate, polysiloxane diisocyanate, 2-hydroxyethyl acrylate, and other oil-modified alkyd resins (meth) Examples thereof include prepolymers such as alkyd-modified acrylates and spirane resin acrylates introduced with acryloyl groups.

The photosensitive layer according to the present invention includes a phosphazene monomer, triethylene glycol, isocyanuric acid EO (ethylene oxide) modified diacrylate, isocyanuric acid EO modified triacrylate, dimethylol tricyclodecane diacrylate, trimethylolpropane benzoic acid benzoic acid. Addition-polymerizable oligomers and prepolymers having monomers such as esters, alkylene glycol type acrylic acid-modified, urethane-modified acrylates, and structural units formed from the monomers can be contained.

Furthermore, examples of the ethylenic monomer that can be used in combination with the present invention include phosphate ester compounds containing at least one (meth) acryloyl group. The compound is not particularly limited as long as it is a compound in which at least part of the hydroxyl group of phosphoric acid is esterified and has a (meth) acryloyl group.

In addition, JP-A Nos. 58-212994, 61-6649, 62-46688, 62-48589, 62-173295, 62-187092, 63- 67189, JP-A-1-244891, and the like. Furthermore, “11290 Chemical Products”, Chemical Industry Daily, p. 286-p. 294, “UV / EB Curing Handbook (raw material)”, Kobunshi Publishing Co., p. The compounds described in 11 to 65 can also be suitably used in the present invention. Of these, compounds having two or more acrylic groups or methacryl groups in the molecule are preferred in the present invention, and those having a molecular weight of 10,000 or less, more preferably 5,000 or less are preferred.

In addition, it is preferable to use an addition-polymerizable ethylenic double bond-containing compound containing a tertiary amino group in the molecule, which is a tertiary amine monomer, in the photosensitive layer according to the present invention. Although there is no particular limitation on the structure, a tertiary amine compound having a hydroxyl group modified with glycidyl methacrylate, methacrylic acid chloride, acrylic acid chloride or the like is preferably used. Specifically, polymerizable compounds described in JP-A-1-165613, JP-A-1-203413, and JP-A-1-197213 are preferably used.

Furthermore, in the present invention, a tertiary amine monomer, a polyhydric alcohol containing a tertiary amino group in the molecule, a diisocyanate compound, and a compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule are used. It is preferred to use a reaction product.

Examples of the polyhydric alcohol having a tertiary amino group in the molecule include triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-tert-butyldiethanolamine, N, N-di (hydroxyethyl) aniline, N, N, N ′, N′-tetra-2-hydroxypropylethylenediamine, p-tolyldiethanolamine, N, N, N ′, N′-tetra-2-hydroxyethylethylenediamine, N, N-bis (2-hydroxypropyl) aniline, allyldiethanolamine, 3- (dimethylamino) -1,2-propanediol, 3-diethylamino-1,2-propanediol, N, N-di (n-propyl) Amino-2,3-propanediol, N, N- (An iso-propyl) amino-2,3-propanediol, 3- (N-methyl--N- benzylamino) -1,2-propane diol, and the like, but is not limited thereto.

Diisocyanate compounds include butane-1,4-diisocyanate, hexane-1,6-diisocyanate, 2-methylpentane-1,5-diisocyanate, octane-1,8-diisocyanate, 1,3-diisocyanate methyl-cyclohexanone 2,2,4-trimethylhexane-1,6-diisocyanate, isophorone diisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene- Examples include 2,5-diisocyanate, tolylene-2,6-diisocyanate, 1,3-di (isocyanatomethyl) benzene, 1,3-bis (1-isocyanato-1-methylethyl) benzene, and the like. In Not a constant.

Examples of the compound containing a hydroxyl group and an addition polymerizable ethylenic double bond in the molecule include 2-hydroxyethyl methacrylate (MH-1), 2-hydroxyethyl acrylate (MH-2), 4-hydroxybutyl. Examples include acrylate (MH-4), 2-hydroxypropylene-1,3-dimethacrylate (MH-7), 2-hydroxypropylene-1-methacrylate-3-acrylate (MH-8), and the like.

Specific examples of polyhydric alcohol containing a tertiary amino group in the molecule, a diisocyanate compound, and a compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule are as follows. As a reaction product. These reactions can be carried out in the same manner as a method for synthesizing urethane acrylate by a reaction of a normal diol compound, diisocyanate compound, and hydroxyl group-containing acrylate compound.

M-1: Reaction product of triethanolamine (1 mol), hexane-1,6-diisocyanate (3 mol), 2-hydroxyethyl methacrylate (3 mol) M-2: Triethanolamine (1 mol), isophorone Reaction product of diisocyanate (3 mol) and 2-hydroxyethyl acrylate (3 mol) M-3: Nn-butyldiethanolamine (1 mol), 1,3-bis (1-isocyanato-1-methylethyl) Reaction product of benzene (2 mol) and 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) M-4: Nn-butyldiethanolamine (1 mol), 1,3-di (isocyanatomethyl) ) Reaction of benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) Product M-5: Reaction product of N-methyldiethanolamine (1 mol), tolylene-2,4-diisocyanate (2 mol), 2-hydroxypropylene-1,3-dimethacrylate (2 mol) Acrylates or alkyl acrylates described in JP-A-1-105238 and JP-A-2-127404 can be used.

In the present invention, among the polymerizable monomers, it is particularly preferable to use a polymerizable compound having a hydroxyl group in the molecule in order to solve the above-mentioned problem according to the present invention.

As the polymerizable compound having a hydroxyl group in the molecule that can be used in the present invention, a compound represented by the following general formula (PMOH) is preferable.

[Wherein, R ₁ represents a hydrogen atom or a methyl group, and X ₁ represents —CH ₂ —CR ₂ R ₃ —CH ₂ —, — (CH ₂ —CH (OR ₄ ) —CH ₂ —O) _m − CH ₂ —CH (OR ₅ ) CH ₂ —, — (CH (R ₆ ) CH ₂ O) _n —CH (R ₆ ) CH ₂ —, —CO—X ₂ —CO— or —X ₂ — is represented. R ₂ and R ₃ each independently represents a hydrogen atom, an alkyl group, or a substituted alkyl group. R ₄ , R ₅ and R ₆ each independently represents a hydrogen atom or an alkyl group. X ₂ represents an arylene group, an alkylene group, or a cycloalkylene group. m and n represent an integer of 1 to 20. ]
Preferable alkyl groups of R ₂ to R ₆ in the general formula (PMOH) include, for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group and the like. Of these, an alkyl group having 1 to 10 carbon atoms is preferable. Particularly preferred are alkyl groups having 1 to 5; however, R ₂ and R ₃ are particularly preferably alkyl groups having 1 to 4 carbon atoms, and R ₄ to R ₆ are particularly preferably methyl groups.

Substituents of substituted alkyl include aryl groups (eg, phenyl group, naphthyl group, etc.), alkoxyl groups (eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, etc.), alkoxycarbonyl groups ( For example, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, etc.), amide group (for example, Methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group), amino group ( For example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), halogen atom (eg, fluorine atom, chlorine) Atom, bromine atom, etc.).

Among these substituents, an aryl group, an amino group, an amide group, an alkoxycarbonyl group, and a hydroxyl group are preferable.

Examples of the alkylene group for X ₂ include an ethylene group, trimethylene group, tetramethylene group, propylene group, ethylethylene group, pentamethylene group, hexamethylene group, and 2,2,4-trimethylhexamethylene group.

Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group.

Examples of the arylene group include a phenylene group and a naphthylene group.

Specific examples of the compound represented by the general formula (PMOH) according to the present invention are given below, but the present invention is not limited thereto.

(Spectral sensitizer)
The photosensitive layer according to the present invention preferably contains a spectral sensitizer having a maximum absorption wavelength of 350 to 450 nm as a spectral sensitizer.

Examples of the spectral sensitizer include cyanine, merocyanine, porphyrin, spiro compound, ferrocene, fluorene, fulgide, imidazole, perylene, phenazine, phenothiazine, acridine, acridone, azo compound, diphenylmethane, triphenylmethane, triphenylamine, coumarin. Derivatives, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, ketoalcohol borate complexes, and the like.

Examples of the coumarin derivative include B-1 to B-22 coumarin derivatives of JP-A-8-129258, D-1 to D-32 coumarin derivatives of JP-A-2003-21901, and JP-A-2002. No. 1-363206 of coumarin derivatives, JP-A No. 2002-363207 No. 1 to 40 coumarin derivatives, JP-A No. 2002-363208 No. 1 to 34 coumarin derivatives, JP-A No. 2002-363209 Examples thereof include 1 to 56 coumarin derivatives and can be preferably used.

Other preferable dyes that can be used include, for example, JP-A No. 2000-98605, JP-A No. 2000-147663, JP-A No. 2000-206690, JP-A No. 2000-258910, JP-A No. 2000-309724, and JP-A No. 2001. And spectral sensitizers described in JP-A-042525, JP-A No. 2002-202598, and JP-A No. 2000-221790.

(Polymer binder)
The photosensitive layer contains a polymer binder. The polymer binder according to the present invention can carry the components contained in the photosensitive layer on a support.

(Hydrophilic resin)
The lithographic printing plate material of the present invention is developed with the developer of the present invention, and contains a hydrophilic resin as a polymer binder in the photosensitive layer. Examples of hydrophilic resins include acrylic polymers, polyvinyl butyral resins, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, polyvinyl butyral resins, polyvinyl formal resins, shellacs, and other natural resins. Can be used. Two or more of these may be used in combination.

Preferably, a vinyl copolymer obtained by copolymerization of an acrylic monomer is preferable. Further, the copolymer composition of the polymer binder may be a copolymer of (a) polyalkylene glycol methacrylic acid ester or acrylic acid ester, (b) methacrylic acid alkyl ester, or acrylic acid alkyl ester. preferable.

(A) Polyalkylene glycol methacrylic acid ester or acrylic acid ester includes polyethylene glycol monomethacrylic acid ester, polyethylene glycol monoacrylic acid ester, polyethylene glycol monomethacrylic acid ester monoalkyl ether, polyethylene glycol Examples thereof include monoacrylic acid ester monoalkyl ether, polypropylene glycol monomethacrylic acid ester, polypropylene glycol monoacrylic acid ester, polypropylene glycol monomethacrylic acid ester monoalkyl ether, and polypropylene glycol monoacrylic acid ester monoalkyl ether. These are commercially available from manufacturers such as Shin-Nakamura Chemical Co., Ltd.

(B) Specific examples of alkyl methacrylates and alkyl esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, Nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, acrylic acid In addition to unsubstituted alkyl esters such as nonyl, decyl acrylate, undecyl acrylate and dodecyl acrylate, cyclic alkyl ethers such as cyclohexyl methacrylate and cyclohexyl acrylate Tellurium, benzyl methacrylate, 2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate, benzyl acrylate, 2-chloroethyl acrylate, N, N-dimethylaminoethyl acrylate, glycidyl acrylate, etc. Also included are substituted alkyl esters.

Furthermore, in the polymer binder, the monomers described in the following (1) to (15) can be used as copolymerization monomers.

(1) Monomers having an aromatic hydroxyl group, such as o- (or p-, m-) hydroxystyrene, o- (or p-, m-) hydroxyphenyl acrylate and the like.

(2) Monomers having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxypentyl Methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether and the like.

(3) A monomer having an aminosulfonyl group, such as m- (or p-) aminosulfonylphenyl methacrylate, m- (or p-) aminosulfonylphenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- ( p-aminosulfonylphenyl) acrylamide and the like.

(4) Monomers having a sulfonamide group, such as N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide and the like.

(5) Acrylamide or methacrylamides such as acrylamide, methacrylamide, N-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N- (4-nitrophenyl) acrylamide, N-ethyl-N -Phenylacrylamide, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide and the like.

(6) Monomers containing fluorinated alkyl groups such as trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl methacrylate, N -Butyl-N- (2-acryloxyethyl) heptadecafluorooctylsulfonamide and the like.

(7) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether and the like.

(8) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate and the like.

(9) Styrenes such as styrene, methyl styrene, chloromethyl styrene and the like.

(10) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

(11) Olefins such as ethylene, propylene, i-butylene, butadiene, isoprene and the like.

(12) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine and the like.

(13) Monomers having a cyano group, such as acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, o- (or m-, p-) cyanostyrene.

(14) A monomer having an amino group, such as N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, polybutadiene urethane acrylate, N, N-dimethylaminopropyl acrylamide, N , N-dimethylacrylamide, acryloylmorpholine, Ni-propylacrylamide, N, N-diethylacrylamide and the like.

(15) Specific examples of the carboxyl group-containing monomer include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like. In addition, carboxylic acids such as phthalic acid and 2-hydroxymethacrylate half ester are also preferred.

Further, other monomers that can be copolymerized with these monomers may be copolymerized.

Furthermore, the polymer binder is preferably a vinyl polymer having a polymerizable double bond. For example, an unsaturated bond-containing vinyl copolymer obtained by addition-reacting a compound having a (meth) acryloyl group and an epoxy group in the molecule to a carboxyl group present in the molecule of the vinyl copolymer. Is also preferred as a polymer binder.

Specific examples of the compound containing both an unsaturated bond and an epoxy group in the molecule include glycidyl acrylate, glycidyl methacrylate, and an epoxy group-containing unsaturated compound described in JP-A No. 11-271969. In addition, an unsaturated bond-containing vinyl copolymer obtained by adding a compound having a (meth) acryloyl group and an isocyanate group in the molecule to a hydroxyl group present in the molecule of the vinyl polymer is also high. Preferred as a molecular binder. Compounds having both an unsaturated bond and an isocyanate group in the molecule include vinyl isocyanate, (meth) acrylic isocyanate, 2- (meth) acryloyloxyethyl isocyanate, m- or p-isopropenyl-α, α'-dimethylbenzyl. Isocyanates are preferred, and examples include (meth) acrylic isocyanate and 2- (meth) acryloyloxyethyl isocyanate.

The content of the polymer binder in the photosensitive layer is preferably in the range of 10 to 90% by weight, more preferably in the range of 15 to 70% by weight, and the use in the range of 20 to 50% by weight from the viewpoint of sensitivity. Particularly preferred.

In the lithographic printing plate material of the present invention, in order to solve the problems according to the present invention, it is particularly preferable that the photosensitive layer contains a homopolymer or copolymer of N-vinylpyrrolidone among the polymer binders. Is preferred.

When a copolymer of N-vinylpyrrolidone is used, the monomer to be copolymerized is not particularly limited, but vinyl acetate can be preferably used.

(Various additives)
In the photosensitive layer according to the present invention, in addition to the above-mentioned various components, in order to prevent unnecessary polymerization of the polymerizable ethylenic double bond monomer during the production or storage of the lithographic printing plate material, It is desirable to add an agent.

Suitable 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-nitrosophenylhydroxylamine cerium salt, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5 -Methylbenzyl) -4-methylphenyl acrylate and the like.

The addition amount of the polymerization inhibitor is preferably about 0.01% to about 5% with respect to the mass of the total solid content of the photosensitive layer. If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition due to oxygen, or they may be unevenly distributed on the surface of the photosensitive layer during the drying process after coating. . The amount of higher fatty acid derivative added is preferably about 0.5% to about 10% of the total composition.

In addition, a colorant can also be used, and as the colorant, conventionally known ones can be suitably used, including commercially available ones. Examples include those described in the revised new edition “Pigment Handbook”, edited by Japan Pigment Technology Association (Seikodo Shinkosha), Color Index Handbook, and the like.

Examples of pigments include black pigments, yellow pigments, red pigments, brown pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, and metal powder pigments. Specifically, inorganic pigments (titanium dioxide, carbon black, graphite, zinc oxide, Prussian blue, cadmium sulfide, iron oxide, and lead, zinc, barium and calcium chromates) and organic pigments (azo-based, thioindigo) , Anthraquinone, anthanthrone, and triphendioxazine pigments, vat dye pigments, phthalocyanine pigments and derivatives thereof, quinacridone pigments, and the like.

Among these, it is preferable to select and use a pigment having substantially no absorption in the absorption wavelength region of the spectral sensitizing dye corresponding to the exposure laser to be used. In this case, an integrating sphere at the laser wavelength to be used is used. It is preferable that the reflection absorption of the used pigment is 0.05 or less. The addition amount of the pigment is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the solid content of the composition.

From the viewpoints of pigment absorption in the above-mentioned photosensitive wavelength region and visible image properties after development, it is preferable to use a violet pigment or a blue pigment. Such as, for example, cobalt blue, cerulean blue, alkali blue lake, phonatone blue 6G, Victoria blue lake, metal free phthalocyanine blue, phthalocyanine blue first sky blue, indanthrene blue, indico, dioxane violet, iso Violanthrone Violet, Indanthrone Blue, Indanthrone BC and the like can be mentioned. Among these, phthalocyanine blue and dioxane violet are more preferable.

Further, the photosensitive layer can contain a surfactant as a coating property improving agent as long as the performance of the present invention is not impaired. Of these, fluorine-based surfactants are preferred.

In order to improve the physical properties of the cured film, additives such as inorganic fillers and plasticizers such as dioctyl phthalate, dimethyl phthalate and tricresyl phosphate may be added. These addition amounts are preferably 10% or less of the total solid content.

Examples of the solvent used in preparing the photosensitive layer coating solution for the photosensitive layer according to the present invention include, for example, alcohol: polyhydric alcohol derivatives such as sec-butanol, isobutanol, n-hexanol, benzyl alcohol, Diethylene glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, ethers: propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ketones, aldehydes: diacetone alcohol, cyclohexanone Preferred examples include methylcyclohexanone and esters: ethyl lactate, butyl lactate, diethyl oxalate, methyl benzoate and the like.

Although the photosensitive layer coating solution has been described above, the photosensitive layer according to the present invention is constituted by coating on a support using this.

In the photosensitive layer according to the present invention, the weight on the support is preferably from 0.1 g / m ² to 10 g / m ² , and particularly preferably from 0.5 g / m ² to 5 g / m ² .

(Oxygen barrier layer)
On the upper side of the photosensitive layer according to the present invention, it is preferable to provide an oxygen blocking layer having oxygen blocking and other protective functions as required.

The oxygen barrier layer preferably has high solubility in a developer (which is generally an aqueous alkali solution) described later, and for this reason, the present invention is characterized by containing polyvinyl alcohol. Polyvinyl alcohol has an effect of suppressing the permeation of oxygen. In addition, it is preferable to use together polyvinyl pyrrolidone which has the effect of ensuring adhesiveness with the adjacent photosensitive layer.

In addition to the above two polymers, polysaccharides, polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, gum arabic, sucrose octaacetate, ammonium alginate, sodium alginate as required Water-soluble polymers such as polyvinylamine, polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid, and water-soluble polyamide can also be used in combination.

When an oxygen blocking layer is provided on the planographic printing plate material of the present invention, the peel force between the photosensitive layer and the oxygen blocking layer is preferably 35 mN / mm or more, more preferably 50 mN / mm or more, and even more preferably 75 mN / mm or more. It is. Preferred examples of the composition of the oxygen barrier layer include those described in JP-A-10-10742.

Peeling force is measured by applying an adhesive tape with a predetermined width on the oxygen barrier layer and peeling it with the oxygen barrier layer at an angle of 90 degrees with respect to the plane of the lithographic printing plate material. Can be obtained.

The oxygen barrier layer can further contain a surfactant, a matting agent and the like as required. The oxygen barrier layer composition is dissolved in a suitable solvent, applied onto the photosensitive layer and dried to form an oxygen barrier layer. The main component of the coating solvent is particularly preferably water or alcohols such as methanol, ethanol and i-propanol.

When the oxygen barrier layer is provided, the thickness is preferably 0.1 to 5.0 μm, particularly preferably 0.5 to 3.0 μm.

(Support)
The support according to the present invention is a plate or film capable of carrying a photosensitive layer, and preferably has a hydrophilic surface on the side where the photosensitive layer is provided.

Examples of the support according to the present invention include a metal plate such as aluminum, stainless steel, chromium and nickel, or a laminate obtained by laminating or vapor-depositing the above metal thin film on a plastic film such as a polyester film, a polyethylene film and a polypropylene film. .

Also, a surface of a polyester film, vinyl chloride film, nylon film or the like that has been subjected to a hydrophilic treatment can be used, but an aluminum support is preferably used.

In the case of an aluminum support, pure aluminum or an aluminum alloy is used.

Various aluminum alloys can be used as the support, and for example, alloys of metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, iron, and aluminum are used. . Further, the aluminum support having a roughened surface is used for water retention.

When using an aluminum support, it is preferable to perform a degreasing treatment to remove the rolling oil on the surface prior to roughening (graining treatment). As the degreasing treatment, a degreasing treatment using a solvent such as trichlene or thinner, an emulsion degreasing treatment using an emulsion such as kesilon or triethanol, or the like is used. In addition, an alkaline aqueous solution such as caustic soda can be used for the degreasing treatment. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, dirt and oxide film that cannot be removed only by the degreasing treatment can be removed. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, smut is generated on the surface of the support. In this case, it is immersed in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof, It is preferable to perform the treatment. Examples of the roughening method include a mechanical method and a method of etching by electrolysis.

The mechanical surface roughening method used is not particularly limited, but a brush polishing method and a honing polishing method are preferable.

The electrochemical roughening method is not particularly limited, but a method of electrochemical roughening in an acidic electrolyte is preferable.

After the surface is roughened by the electrochemical surface roughening method, it is preferably immersed in an acid or alkali aqueous solution in order to remove aluminum scraps on the surface. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an alkaline aqueous solution.

The amount of aluminum dissolved on the surface is preferably 0.5 to 5 g / m ² . In addition, it is preferable that after the immersion treatment with an alkaline aqueous solution, neutralization treatment is performed by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.

The mechanical surface roughening method and the electrochemical surface roughening method may each be used alone for roughing, or the mechanical surface roughening method followed by the electrochemical surface roughening method. You may roughen.

Anodizing treatment can be performed after the roughening treatment. There is no restriction | limiting in particular in the method of the anodizing process which can be used in this invention, A well-known method can be used. By performing the anodizing treatment, an oxide film is formed on the support.

The anodized support may be subjected to a sealing treatment as necessary. These sealing treatments can be performed using known methods such as hot water treatment, boiling water treatment, water vapor treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment, and ammonium acetate treatment.

Furthermore, after performing these treatments, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having sulfonic acid groups in the side chain, polyacrylic acid, water-soluble metal salts (for example, zinc borate) or Also suitable are those coated with a yellow dye, amine salt or the like. Further, a sol-gel treated substrate having a functional group capable of causing an addition reaction by a radical as disclosed in JP-A-5-304358 is also preferably used.

(Application)
The photosensitive layer coating solution can be applied onto a support by a conventionally known method and dried to prepare a lithographic printing plate material.

Examples of coating methods for the coating liquid include air doctor coater method, blade coater method, wire bar method, knife coater method, dip coater method, reverse roll coater method, gravure coater method, cast coating method, curtain coater method and extrusion coater method. Can be mentioned.

The drying temperature of the photosensitive layer is preferably in the range of 60 to 160 ° C., more preferably 80 to 140 ° C., and particularly preferably 90 to 120 ° C.

<Image exposure>
As a light source for recording an image on the lithographic printing plate material of the present invention, it is preferable to use a laser beam having an emission wavelength of 350 to 450 nm.

As a light source for exposing the lithographic printing plate material of the present invention, for example, a He—Cd laser (441 nm), a combination of Cr: LiSAF and SHG crystal (430 nm) as a solid state laser, KNbO ₃ as a semiconductor laser system, a ring resonator (430 nm), AlGaInN (350 nm to 450 nm), AlGaInN semiconductor laser (commercially available InGaN semiconductor laser 400 to 410 nm), and the like.

In the case of laser exposure, light can be narrowed down in the form of a beam and scanning exposure according to image data is possible, so that it is suitable for direct writing without using a mask material.

Further, when a laser is used as a light source, it is easy to reduce the exposure area to a very small size, and high-resolution image formation is possible.

Laser scanning methods include cylindrical outer surface scanning, cylindrical inner surface scanning, and planar scanning. In the cylindrical outer surface scanning, laser exposure is performed while rotating a drum around which the recording material is wound, and the rotation of the drum is set as main scanning, and the movement of laser light is set as sub scanning. In cylindrical inner surface scanning, a recording material is fixed to the inner surface of a drum, a laser beam is irradiated from the inside, and a main scanning is performed in the circumferential direction by rotating a part or all of the optical system. Sub scanning is performed in the axial direction by linearly moving all of them in parallel with the drum axis. In planar scanning, main scanning of laser light is performed by combining a polygon mirror or galvanometer mirror and an fθ lens, and sub scanning is performed by moving a recording medium. Cylindrical outer surface scanning and cylindrical inner surface scanning are easier to increase the accuracy of the optical system and are suitable for high-density recording.

<Automatic processor>
An unexposed portion of the lithographic printing plate material of the present invention is an aqueous solution containing the developer of the present invention, preferably a water-soluble resin and a surfactant and having a pH of 3.0 to 9.0 at a temperature of 25 ° C., It is advantageous to use an automatic developing machine used for developing a general lithographic printing plate material. The automatic processor is preferably provided with a heat treatment apparatus for performing a heat treatment after removing the unexposed portion after inserting the exposed lithographic printing plate material. The heat treatment apparatus is one that performs heat treatment with radiant heat such as a ceramic heater, or one that performs heat treatment with warm air heated by a ceramic heater or the like, and the temperature of the plate surface is set to an arbitrary temperature within a range of 80 ° C to 160 ° C. Those that can be adjusted are preferable. Further, it can have a water washing portion for removing part of the oxygen blocking layer and the photosensitive layer after the heat treatment. Examples of the washing unit include those equipped with a shower nozzle that supplies washing water to the plate surface, and those that immerse the plate in a washing tank filled with washing water. Those provided with a mechanism for rubbing the plate surface with a roller-like brush are also preferred.

In the step of removing the unexposed portion with the developer of the present invention, a developing bath of an automatic processor used for developing a general lithographic printing plate material can be used. The developing bath preferably has a mechanism capable of adjusting the aqueous solution to a constant temperature. It is preferable that the temperature adjustment can be arbitrarily set within a range of 20 to 35 ° C. Further, a mechanism for automatically replenishing the required amount of the aqueous solution is provided. Preferably, the aqueous solution in excess of a certain amount is provided with a mechanism for discharging, preferably a mechanism for detecting plate passing. Preferably, a mechanism for estimating the processing area of the plate based on the detection of the plate is provided, preferably replenishment of the replenisher to be replenished based on the detection of the plate and / or the estimation of the processing area A mechanism for controlling the amount and / or replenishment timing is provided, preferably a mechanism for controlling the temperature of the aqueous solution is provided, and preferably a mechanism for detecting the pH and / or conductivity of the aqueous solution is provided. Preferably, a mechanism for controlling the replenishment amount and / or replenishment timing of the replenisher and / or water to be replenished based on the pH and / or conductivity of the aqueous solution is provided.

Hereinafter, although an example is given and the present invention is explained in detail, the mode of the present invention is not limited to this. In the examples, “parts” represents “parts by mass” unless otherwise specified.

Example 1
<Production of support>
Using a JIS A 1050 aluminum plate having a thickness of 0.30 mm and a width of 1030 mm, the treatment was continuously performed as follows.

(A) The aluminum plate was subjected to an etching process by spraying at a caustic soda concentration of 2.6 mass%, an aluminum ion concentration of 6.5 mass%, and a temperature of 70 ° C. to dissolve 0.3 g / m ^{2 of the} aluminum plate. Thereafter, washing with water was performed by spraying.

(B) A desmut treatment was performed by spraying with a 1% by mass aqueous solution of nitric acid at a temperature of 30 ° C. (including 0.5% by mass of aluminum ions), and then washed with water by spraying.

(C) An electrochemical surface roughening treatment was continuously performed using an alternating voltage of 60 Hz. The electrolytic solution at this time contains 1.1% by mass of hydrochloric acid, 0.5% by mass of aluminum ions, and 0.5% by mass of acetic acid. The temperature was 21 ° C. The AC power source was subjected to electrochemical surface roughening treatment using a sine wave alternating current having a time TP of 2 msec until the current value reached a peak from zero, using a carbon electrode as a counter electrode. The current density was an effective value of 50 A / dm ² , and the energization amount was 900 C / dm ² . Then, water washing by spraying was performed.

(D) A desmut treatment was performed for 10 seconds with a phosphoric acid concentration 20 mass% aqueous solution (containing 0.5 mass% of aluminum ions) at a temperature of 60 ° C., and then washed with water by spraying.

(E) An anodizing apparatus of an existing two-stage feed electrolytic treatment method (first and second electrolysis unit length 6 m, first feed unit length 3 m, second feed unit length 3 m, first and second feed electrode lengths 2.4 m each ) Was used to perform anodization at a sulfuric acid concentration of 170 g / liter (containing 0.5 mass% of aluminum ions) at a temperature of 38 ° C. Thereafter, washing with water was performed by spraying.

At this time, in the anodizing device, the current from the power source flows to the first power supply electrode provided in the first power supply unit, flows to the plate-like aluminum via the electrolytic solution, An oxide film is formed on the surface, passes through the electrolytic electrode provided in the first power feeding portion, and returns to the power source.

On the other hand, the current from the power source flows to the second power feeding electrode provided in the second power feeding portion, similarly flows to the plate-like aluminum via the electrolytic solution, and an oxide film is formed on the surface of the plate-like aluminum by the second electrolysis portion. Although the amount of electricity fed from the power source to the first feeding unit and the amount of electricity fed from the power source to the second feeding unit are the same, the feeding current density on the oxide film surface in the second feeding unit is about It was 25 A / dm ² . In the 2nd electric power feeding part, it came to feed from the oxide-film surface of 1.35 g / m < ² >. The final oxide film amount was 2.7 g / m ² . Furthermore, after spray water washing, it was immersed in 0.4 mass% polyvinylphosphonic acid solution for 30 seconds, and was hydrophilized. The temperature was 85 ° C. Thereafter, it was washed with spray water and dried with an infrared heater. At this time, the center line average roughness (Ra) of the surface was 0.65 μm.

<< Preparation of lithographic printing plate material >>
On the above support, a photopolymerizable photosensitive layer coating solution having the following composition was coated with a wire bar so that the dried solution was 1.5 g / m ² , and dried at 95 ° C. for 1.5 minutes. Got.

Further, on the photopolymerization photosensitive layer coating sample, an oxygen barrier layer coating solution having the following composition was coated with a wire bar so that the drying rate became 2.0 g / m ² and dried at 65 ° C. for 3 minutes. Planographic printing plate material samples 1 to 3 having an oxygen blocking layer were prepared (having photosensitive layers 1 to 3 having different polymerization initiators).

(Photopolymerizable photosensitive layer coating solution)
Ethylene double bond-containing monomer (NK Oligo U-4HA: Shin-Nakamura Chemical Co., Ltd.)
5.0 parts ethylenic double bond-containing monomer (NK Ester 3G: Shin-Nakamura Chemical Co., Ltd.)
25.0 parts Ethylenic double bond-containing monomer (Denacol Acrylate DA314: Nagase ChemteX Corporation) 25.0 parts N-carboxymethylacridone 4.0 parts Polymerization initiator (type described in Table 1 ) 3.0 parts 2-mercaptobenzothiazole 0.3 part N-vinylpyrrolidone / vinyl acetate copolymer VA64 (BASF) 10.0 parts Poly (N-vinylpyrrolidone) Rubytec K30 (BASF) 10. 0 parts Acetylene-based surfactant (Surfinol 465; manufactured by Air Products) 0.5 parts Phthalocyanine pigment dispersion MHI # 454 (manufactured by Oguni Dye) 3.0 parts Water 450 parts Ethanol 450 parts (Oxygen barrier coating solution) )
Polyvinyl alcohol (GL-05: manufactured by Nippon Synthetic Chemical Co., Ltd.) 90 parts Poly (N-vinylpyrrolidone) Rubitec K30 (manufactured by BASF) 5 parts Polyethyleneimine (Lupazole WF: manufactured by BASF) 5 parts Surfactant (Surfinol 465) : Nissin Chemical Industry Co., Ltd.) 0.5 parts Water 900 parts << Exposure and development >>
Using the above lithographic printing plate material, a plate setter (NewsCTP: manufactured by ECRM) having a light source of 405 nm and 60 mW (exposure pattern used 100% image area and 175 LPI 50% square dots), 2540 dpi (Dpi represents the number of dots per 2.54 cm), and exposure (exposure energy was 50 μj / cm ² ) was performed.

Next, the developer is of the type shown in Table 2 in a CTP automatic developing machine equipped with a preheating section set at 105 ° C., a pre-water washing section for removing the oxygen blocking layer, and a developing section (filled with the developer described below). The lithographic printing plate was obtained by carrying out development processing as described above.

(Developer)
Developers 1 to 9 were prepared as shown in Table 1 using the materials shown in Table 1 in the masses shown in Table 1.

"printing"
The lithographic printing plate produced above is coated with a printing machine (DAIYA1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.), printing ink (soybean oil ink “Naturalis 100” manufactured by Dainippon Ink & Chemicals, Inc.) and wet Printing was performed using shimizu (Tokyo liquid, H liquid SG-51 concentration 1.5% by mass).

(Ink stain on non-image area)
In the above printing, spotted ink stains within 100 cm ² in the non-image area of the printed matter after 500 m ² were visually observed and evaluated according to the following criteria.

◎: Ink smudge is not recognized in non-image area ○: Ink smudge is hardly recognized in non-image area △: Ink smudge is slightly recognized in non-image area, but can be used as printed matter ×: Non-image area Ink smear is recognized and cannot be used as printed matter (sludge generation prevention)
After the above 300 m ² development processing, the sludge generation state in the development part was visually observed and evaluated according to the following rank, which was used as an index for preventing sludge generation.

◎: Almost no sludge sludge is generated in the container. ○: Slight sludge is slightly generated in the container, but it does not adhere to the developed plate material and there is no substantial problem. △: Sludge in the container. Occurrence of sludge and cleaning with a sponge or brush is required for cleaning the inside of the container. ×: Gel sludge sludge is generated in the container, and the fluidity of the container tank is deteriorated due to gelation. Table 2 shows the results of defects in the liquid feed pump and the stirring screw.

From Table 2, it can be seen that in the case of the present invention, the ink smudge prevention property of the non-image area at the time of printing is excellent, and the sludge generation prevention property in the developer is excellent when a large number of lithographic printing plate materials are processed. .

Example 2
In Example 1, a planographic printing material 4 having a photosensitive layer 4 in which 1 part by mass of α-cyclodextrin was added to the photosensitive layer 1 of the planographic printing plate material sample 1 was prepared.

"sensitivity"
A 100% solid image was output while changing the exposure energy of the laser of the platesetter. Next, according to the above image forming method, the density of each energy of the image developed with the developer shown in the table was measured with a densitometer [D196: manufactured by GRETAG].

Sensitivity is the exposure energy at which the density starts to drop from the saturated solid density of the photosensitive material. It calculated | required by converting the energy amount used as saturated solid density x0.9.

The results are shown below.

According to the present invention, it is possible to provide a lithographic printing plate material and a lithographic printing plate material developer that can prevent sludge from being generated even in a high-sensitivity and low-pH development process and that does not cause stains in non-image areas.

Claims (6)

1. A developer for a lithographic printing plate material, which is used for development of a lithographic printing plate material containing a hydrophilic resin and contains cyclodextrin or a derivative thereof.
2. 2. The developer for a lithographic printing plate material according to claim 1, wherein the cyclodextrin is α-cyclodextrin, β-cyclodextrin or γ-cyclodextrin.
3. 3. The lithographic printing plate as claimed in claim 1, wherein the developer is an aqueous solution containing a water-soluble resin and a surfactant and having a pH of 3.0 to 9.0. Developer for materials.
4. 4. The lithographic printing plate material having a photosensitive layer containing a spectral sensitizer, a polymerization initiator, a polymerizable monomer, and a polymer binder on a support, and any one of claims 1 to 3 A lithographic printing plate material, which is developed using the developer described in the above item.
5. The lithographic printing plate material according to claim 4, wherein the polymerization initiator is hexaarylbisimidazole.
6. 6. The lithographic printing plate material according to claim 4 or 5, wherein the lithographic printing plate material is exposed and recorded with image information by a laser light source having an emission wavelength in the range of 350 nm to 450 nm.