JP2009109617A - Method for manufacturing positive planographic printing plate material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a positive planographic printing plate material for providing high productivity without producing scratches in an image forming layer. <P>SOLUTION: The method for manufacturing a positive planographic printing plate includes steps of applying and drying an image forming layer on an aluminum support in a roll state and having a roughened surface, cutting the support into sheets and stacking, and is characterized in that: a slip sheet is placed between the planographic printing plate materials cut into sheets; the coefficient of static friction (μ1) between the surface of the slip sheet and the image forming layer of the planographic printing plate material is higher by 0.05 to 0.3 than the coefficient of dynamic friction (μ2) between the back surface of the slip sheet and the back face of the aluminum support of the plate material; and the planographic printing plate materials (cut into sheets with a slip sheet placed between the plate materials) are mounted on an inclined mount. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a lithographic printing plate material having a positive type image forming layer used in a so-called computer-to-plate (hereinafter referred to as “CTP”) system. The present invention relates to a method for producing a positive planographic printing plate material capable of realizing high productivity without causing scratches on a forming surface.

  As a lithographic printing plate material using a positive composition in which an exposed portion is solubilized in a developer upon irradiation with actinic light, an image forming layer containing a thermal acid generator and an acid-decomposable compound (“photosensitive An image forming material having a layer is also known. For example, a technique containing a compound having an orthocarboxylic acid or carboxylic acid amide acetal group (for example, see Patent Document 1), a technique containing a compound having an acetal in the main chain (for example, see Patent Document 2), and A technique containing a compound having a silyl ether group (see, for example, Patent Document 3) is disclosed in Patent Document.

  As another example, there is also a technique for forming an image by containing a resin containing a phenolic hydroxyl group and a photothermal conversion agent, and increasing the alkali solubility of the resin containing the phenolic hydroxyl group by heat generated in an exposed area. Are known.

  In recent years, with the digitization of plate making data, a so-called CTP system that modulates digital data directly into a laser signal and exposes a lithographic printing plate material has become widespread. In recent years, the development of lasers has been remarkable. In particular, solid-state lasers and semiconductor lasers having a light emitting region from near infrared to infrared can be easily obtained with high output and small size. These lasers are very useful as an exposure light source when directly making a plate from digital data such as a computer.

  By adding a near-infrared absorber as a photothermal conversion agent to the positive photosensitive material described above, the alkali solubility of the exposed area is increased by the heat generated by the infrared absorber, and the near-infrared ray is formed by forming an image. A composition having sensitivity to laser can be obtained, and a lithographic printing plate material using this technique has been put into practical use (for example, see Patent Documents 4 and 5).

  Positive type lithographic printing plate materials have a problem in that if the pressure is applied to the image forming surface before development or the surface is scratched due to the principle of image formation, the portion becomes apparent as a deep scratch by the development process. There was a thing. In particular, when the production speed is increased, the pressure applied to the image forming layer on the line is increased, which is disadvantageous for the generation of scratches.

  In order to prevent scratches during manufacturing or handling, a device for increasing the mechanical strength of the image forming layer has also been proposed. In that case, however, the image forming sensitivity is greatly deteriorated and the productivity during plate making is remarkably increased. It is lowered and is not practical.

Positive type lithographic printing plate materials, in principle, have insufficient functions to suppress dissolution of the image forming layer immediately after production (immediately after coating and drying), and are easily damaged by weak impacts. The lithographic printing plate material required extremely careful handling.
US Pat. No. 3,779,779 JP-A-53-133429 JP-A-60-37549 JP 2000-3031 A Japanese Patent Laid-Open No. 10-55067

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for producing a positive lithographic printing plate material that can achieve high productivity without causing scratches on the image forming layer. There is.

  The above object of the present invention can be achieved by the following constitution.

  1. After the image forming layer is applied and dried to a roughened roll-shaped aluminum support, it is cut into sheets in a method for producing a positive-type planographic printing plate material having a process of cutting and stacking into sheets. A slip sheet is placed between each of the lithographic printing plate materials, and a static friction coefficient (μ1) between the surface of the slip sheet and the image forming layer of the lithographic printing plate material is such that the back surface of the slip sheet and the The lithographic printing plate material is 0.05 to 0.3 larger than the dynamic friction coefficient (μ2) of the lithographic printing plate material with the back surface of the aluminum support, and the lithographic printing plate material is placed on a tilted base (each lithographic plate cut into sheets) A method for producing a positive planographic printing plate material, wherein a slip sheet is installed between the printing plate materials).

  2. The static friction coefficient (μ1) between the surface of the slip sheet and the image forming layer of the lithographic printing plate material is 0.4 to 0.8, and the back surface of the slip sheet and the back surface of the aluminum support of the lithographic printing plate material 2. The method for producing a positive planographic printing plate material according to 1, wherein the coefficient of dynamic friction (μ2) is in the range of 0.3 to 0.6.

  3. The burrs on the front end surface in the moving direction of the lithographic printing plate material cut into a sheet are in the range of 0 to 50 μm on the image forming layer side, or 0 to −50 μm on the back side. A method for producing a positive planographic printing plate material as described in 1 above.

  4). The positive lithographic printing plate according to any one of 1 to 3, wherein the image forming layer contains a resin having a phenolic hydroxyl group and a dye that absorbs infrared rays and converts it into heat. Material manufacturing method.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the positive type lithographic printing plate material which can obtain high productivity, without generating a damage | wound in an image forming layer can be provided.

  Hereinafter, although the best mode for carrying out the present invention will be described, the present invention is not limited to these.

  The method for producing a positive planographic printing plate material according to the present invention comprises a step of cutting and stacking into a sheet after an image forming layer is applied and dried on a roughened aluminum support in a roll shape. In the method for producing a lithographic printing plate material of a mold, a slip sheet is installed between each lithographic printing plate material cut into sheets, and the surface of the slip sheet and the image forming layer of the lithographic printing plate material The static friction coefficient (μ1) is 0.05 to 0.3 than the dynamic friction coefficient (μ2) between the back surface of the slip sheet and the back surface of the aluminum support of the lithographic printing plate material, and the lithographic printing plate material is inclined. It is characterized in that it is stacked on a pedestal (with a slip sheet installed between each lithographic printing plate material cut into sheets).

  The present invention will be described in detail below.

<< 1. Support
As the support (roughened roll-shaped aluminum support) that can be used for the lithographic printing plate material according to the present invention, an aluminum plate is preferably used. In this case, a pure aluminum plate, an aluminum alloy plate, or the like is used. It doesn't matter.

  Various aluminum alloys can be used as the support, such as alloys of aluminum and metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, iron, etc. Aluminum plates manufactured by various rolling methods can be used. In addition, a recycled aluminum plate obtained by rolling recycled aluminum ingots such as scrap materials and recycled materials that are becoming popular in recent years can also be used.

  The support that can be used for the lithographic printing plate material of the present invention is preferably subjected to a degreasing treatment in order to remove 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, the substrate is immersed in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof and desmutted. 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 roughening method used is not particularly limited, but a brush polishing method and a honing polishing method are preferable. The roughening by the brush polishing method is, for example, by rotating a rotating brush using a bristle having a diameter of 0.2 to 0.8 mm, and for example, volcanic ash particles having a particle size of 10 to 100 μm on water. While supplying the uniformly dispersed slurry, the brush can be pressed. The roughening by honing polishing is performed by, for example, uniformly dispersing volcanic ash particles having a particle size of 10 to 100 μm in water, injecting pressure from a nozzle, and causing the surface to collide obliquely with the support surface. Can do. Further, for example, abrasive particles having a particle size of 10 to 100 μm are applied to the support surface so as to be present at a density of 2.5 × 10 ³ to 10 × 10 ³ particles / cm ² at intervals of 100 to 200 μm. Roughening can also be performed by laminating the sheets and applying a pressure to transfer the rough surface pattern of the sheet.

After the surface is roughened by the mechanical surface roughening method, it is preferable to immerse in an aqueous solution of acid or alkali in order to remove the abrasive that has digged into the surface of the support, formed aluminum scraps, and the like. 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 aqueous alkali solution such as sodium hydroxide. The dissolution amount of aluminum in the support surface, 0.5 to 5 g / m ² is preferred. After the immersion treatment with an alkaline aqueous solution, it is preferable to carry out a neutralization treatment by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.

The electrochemical surface roughening method is not particularly limited, but a method of electrochemical surface roughening in an acidic electrolyte is preferable. As the acidic electrolytic solution, an acidic electrolytic solution usually used in an electrochemical surface roughening method can be used, but a hydrochloric acid-based or nitric acid-based electrolytic solution is preferably used. As the electrochemical surface roughening method, for example, methods described in Japanese Patent Publication No. 48-28123, British Patent No. 896,563 and Japanese Patent Laid-Open No. 53-67507 can be used. This roughening method can be generally performed by applying a voltage in the range of 1 to 50 volts, but is preferably selected from the range of 10 to 30 volts. Current density may be in the range of 10 to 200 A / dm ^2, preferably selected from the range of 50 to 150 A / dm ^2. The quantity of electricity, may be in the range of 5000 C / dm ^2, preferably selected from the range of 100~2000c / dm ^2. The temperature at which the roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C.

When electrochemical surface roughening is performed using a nitric acid-based electrolyte as the electrolyte, it can be generally performed by applying a voltage in the range of 1 to 50 volts, but is selected from the range of 10 to 30 volts. Is preferred. Current density may be in the range of 10 to 200 A / dm ^2, preferably selected from the range of 20 to 100 A / dm ^2. The quantity of electricity, may be in the range of 5000 C / dm ^2, preferably selected from the range of 100~2000c / dm ^2. The temperature at which the electrochemical roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C. The concentration of nitric acid in the electrolytic solution is preferably 0.1 to 5% by mass. If necessary, nitrates, chlorides, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, and the like can be added to the electrolytic solution.

When a hydrochloric acid-based electrolyte is used as the electrolyte, it can be generally applied by applying a voltage in the range of 1 to 50 volts, but is preferably selected from the range of 2 to 30 volts. Current density may be in the range of 10 to 200 A / dm ^2, preferably selected from the range of 50 to 150 A / dm ^2. The quantity of electricity, may be in the range of 5000 C / dm ^2, preferably 100~2000c / dm ^2, and more and more preferably selected from the range of 200~1000c / dm ^2. The temperature at which the electrochemical roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C. The concentration of hydrochloric acid in the electrolytic solution is preferably 0.1 to 5% by mass. If necessary, nitrates, chlorides, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, and the like can be added to the electrolytic solution.

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 dissolution amount of aluminum in the support surface, 0.5 to 5 g / m ² is preferred. 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 roughening, or the mechanical surface roughening treatment method followed by the electrochemical surface roughening method may be used for roughening. You may face it.

Following the roughening treatment, an anodic oxidation treatment can be performed. 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. For the anodizing treatment, a method of electrolyzing an aqueous solution containing sulfuric acid and / or phosphoric acid at a concentration of 10 to 50% as an electrolytic solution at a current density of 1 to 10 A / dm ² is preferably used. The method of electrolyzing at high current density in sulfuric acid described in Japanese Patent No. 1,412,768, the method of electrolyzing using phosphoric acid described in Japanese Patent No. 3,511,661, chromic acid, Examples thereof include a method using a solution containing one or more acids, malonic acids and the like. The formed anodic oxidation coating amount is suitably 1 to 50 mg / dm ² , preferably 10 to 40 mg / dm ² . The anodized coating amount is obtained by, for example, immersing an aluminum plate in a chromic phosphate solution (85% phosphoric acid solution: 35 ml, prepared by dissolving 20 g of chromium (IV) oxide in 1 L of water) to dissolve the oxide film, It is obtained from mass change measurement before and after dissolution of the coating on the plate.

  The anodized support may be sealed 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, in this invention, after performing these processes, the process which coat | covers a support body surface with polyvinylphosphonic acid can be performed. The coating treatment is not limited to a coating method, a spray method, a dip method, or the like, but a dip method is suitable for making the equipment inexpensive.

  In the case of a dip type, it is preferable to treat polyvinylphosphonic acid with a 0.01 to 35% aqueous solution, and a 0.1 to 5% aqueous solution is particularly preferable. The treatment temperature is preferably 20 ° C. or higher and 90 ° C. or lower, and more preferably 40 ° C. or higher and 80 ° C. or lower. If it is lower than 20 ° C., printing stains are bad, and if it is higher than 90 ° C., printing durability is deteriorated.

  The treatment time is preferably 10 to 180 seconds. After the treatment, it is preferable to perform a squeegee treatment or a water washing treatment in order to remove the excessively laminated polyvinylphosphonic acid. Furthermore, it is preferable to perform a drying process. As a drying temperature, 20-95 degreeC is preferable.

The applied amount of polyvinylphosphonic acid on the surface of the aluminum support is preferably 3 to ²⁰ mg / m2. Particularly, 4 to 15 mg / m ² is preferable. If it is less than 3 mg / m ² , printing stains in the non-image area will occur, and if it exceeds 20 mg, the printing durability will deteriorate.

  Various concentrations of polyvinylphosphonic acid aqueous solution concentration, treatment temperature, and treatment time can be combined to obtain a desired coating amount.

  The surface phosphorus atom concentration (atm%) in a state where the surface of the aluminum support is coated with polyvinyl sulfonic acid is preferably 3 to 15 atm%. Especially preferably, it is 5-9 atm%.

  The thickness of the hydrophilic support is preferably from 100 to 350 μm, more preferably from 150 to 300 μm. The surface roughness (Ra) on which the photosensitive layer of the hydrophilic support is applied is preferably from 0.30 to 0.70 [mu] m, more preferably from 0.35 to 0.60 [mu] m.

<< 2. Image forming layer >>
(Resin having a phenolic hydroxyl group)
The image forming layer of the lithographic printing plate material according to the present invention preferably contains a resin having a phenolic hydroxyl group.

  Examples of the resin having a phenolic hydroxyl group that can be used in the present invention include novolak resins obtained by condensing phenols with aldehydes. Phenols include phenol, m-cresol, p-cresol, m- / p-mixed cresol, phenol and cresol (any of m-, p-, or m- / p-mixed), pyrogallol, phenol group Acrylamide, methacrylamide, acrylic acid ester, methacrylic acid ester, hydroxystyrene, etc. having In addition, substituted phenols such as isopropylphenol, t-butylphenol, t-amylphenol, hexylphenol, cyclohexylphenol, 3-methyl-4-chloro-6-t-butylphenol, isopropylcresol, t-butylcresol, and t-amylresole. Is mentioned. Preferably, t-butylphenol and t-butylcresol can also be used. On the other hand, examples of aldehydes include aliphatic and aromatic aldehydes such as formaldehyde, acetaldehyde, acrolein, and crotonaldehyde. Preferred is formaldehyde or acetaldehyde, and most preferred is formaldehyde.

  Among the above combinations, preferably phenol-formaldehyde, m-cresol-formaldehyde, p-cresol-formaldehyde, m- / p-mixed cresol-formaldehyde, phenol / cresol (m-, p-, o-, m- / Any of p-mixing, m- / o-mixing and o- / p-mixing.) Mixed-formaldehyde. Particularly preferred is cresol (m-, p-mixed) -formaldehyde.

  These novolak resins preferably have a weight average molecular weight of 1,000 or more and a number average molecular weight of 200 or more. More preferably, the weight average molecular weight is 1500 to 300,000, the number average molecular weight is 300 to 250,000, and the dispersity (weight average molecular weight / number average molecular weight) is 1.1 to 10. Particularly preferably, the weight average molecular weight is 8000 to 15,000, the number average molecular weight is 1,000 to 10,000, and the dispersity (weight average molecular weight / number average molecular weight) is 1.1 to 5. . Furthermore, it is preferable that the component having a weight average molecular weight of 500 or less is 0.01 to 5% by mass of the whole. By setting it as the above range, the film strength, alkali solubility, chemical solubility, interaction property with the photothermal conversion substance, etc. of the novolak resin can be appropriately adjusted, and the effects of the present invention can be easily obtained. In addition, the weight average molecular weight in this invention employ | adopts the value of polystyrene conversion calculated | required by the gel permeation chromatograph (GPC) method which uses the monodispersed polystyrene of novolak resin as a standard.

  Examples of the method for producing the novolak resin according to the present invention include phenols and substituted phenols as described in “New Experimental Chemistry Course [19] Polymer Chemistry [I]” (1993, Maruzen Publishing), Item 300. (For example, xylenol, cresols, etc.) are reacted with an aqueous formaldehyde solution in a solvent using an acid as a catalyst to dehydrate and condense phenol, the o-position or p-position of the substituted phenol component, and formaldehyde. After dissolving the novolak resin thus obtained in an organic polar solvent, an appropriate amount of a nonpolar solvent is added and left for several hours, whereby the novolak resin solution is separated into two layers. By concentrating only the lower layer of the separated solution, a novolak resin with a concentrated molecular weight can be produced.

  Examples of the organic polar solvent used include acetone, methyl alcohol, and ethyl alcohol. Examples of the nonpolar solvent include hexane and petroleum ether. In addition to the production method described above, for example, as described in JP-T-2001-506294, a novolak resin is dissolved in a water-soluble organic polar solvent, and then water is added to form a precipitate. A novolak resin fraction can also be obtained. Further, in order to obtain a novolak resin having a low degree of dispersion, it is possible to use a method in which a novolak resin obtained by dehydration condensation of phenol derivatives is dissolved in an organic polar solvent and then applied to a silica gel for molecular weight fractionation.

  The dehydration condensation between the o-position or p-position of the phenol and the substituted phenol component and formaldehyde gives a concentration of 60 to 90% by mass, preferably 70 to 80% by mass as the total mass of the phenol and the substituted phenol component. In the solvent solution, the molar ratio of formaldehyde to the total number of moles of phenol and substituted phenol components is 0.2 to 2.0, preferably 0.4 to 1.4, particularly preferably 0.6 to 1.2. In addition, the acid catalyst has a molar ratio with respect to the total number of moles of phenol and substituted phenol components of 0.01 to 0.1, preferably 0.02 to 0.05. It can be performed by adding under temperature conditions and stirring for several hours while maintaining the temperature range. In addition, it is preferable that reaction temperature is the range of 70 to 150 degreeC, and it is more preferable that it is the range of 90 to 140 degreeC.

  Examples of the solvent used include water, acetic acid, methanol, ethanol, 2-propanol, 2-methoxyethanol, ethylpropionate, ethoxyethylpropionate, 4-methyl-2-pentanone, dioxane, xylene, benzene and the like. Is mentioned. Examples of the acid catalyst include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, phosphoric acid, oxalic acid, tartaric acid, citric acid, zinc acetate, manganese acetate, cobalt acetate, magnesium methylsulfonate, aluminum chloride, and zinc oxide. Can be mentioned. The residual monomer and dimer of the synthesized phenol resin are preferably removed by distillation.

  Here, a general method for adjusting the molecular weight distribution has been described, but the method for adjusting the novolak resin having physical properties suitable for the present invention is not limited thereto, and for example, the molecular weight distribution can be obtained by using a special acid catalyst or solvent. Needless to say, a known method such as preparing the above can be appropriately applied.

  The novolak resin according to the present invention may be used alone or in combination of two or more. By combining two or more kinds, it is possible to effectively use different characteristics such as film strength, alkali solubility, solubility in chemicals, and interaction with a photothermal conversion substance, which is preferable. When two or more kinds of novolak resins are used in combination in the image recording layer, it is preferable to combine those having as much difference as possible, such as weight average molecular weight and m / p ratio. For example, the difference in weight average molecular weight is preferably 1000 or more, and more preferably 2000 or more. The m / p ratio preferably has a difference of 0.2 or more, more preferably 0.3 or more.

  The addition amount of the resin having a phenolic hydroxyl group with respect to the total solid content in the photosensitive layer (image recording layer) in the lithographic printing plate material of the present invention is 30 to 99% by mass from the viewpoint of chemical resistance and printing durability. It is preferably 45 to 95% by mass, and most preferably in the range of 60 to 90% by mass.

  In the present invention, a resin having a phenolic hydroxyl group can be used alone or in combination of two or more. From the viewpoint of the object effect of the present invention, the resin having a phenolic hydroxyl group is mainly composed of a novolac resin. A resin is preferred.

(Alkali-soluble acrylic resin)
The image forming layer of the lithographic printing plate material according to the present invention can contain an alkali-soluble acrylic resin.

  The alkali-soluble acrylic resin that can be used in the present invention is preferably a copolymer containing the following structural units. Other structural units that can be suitably used include, for example, acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, maleic Examples include acid imides and lactones.

Specific examples of acrylates that can be used include methyl acrylate, ethyl acrylate, (n- or i-) propyl acrylate, (n-, i-, sec- or t-) butyl acrylate, amyl acrylate, 2 -Ethylhexyl acrylate, dodecyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-hydroxypentyl acrylate, cyclohexyl acrylate, allyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl Acrylate, methoxybenzyl acrylate, chlorobenzyl acrylate, 2- (p-hydroxyphenyl) ethyl acetate Rate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, chlorophenyl acrylate, sulfamoyl phenyl acrylate, and the like.

  Specific examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, (n- or i-) propyl methacrylate, (n-, i-, sec- or t-) butyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate, Dodecyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 5-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, methoxybenzyl methacrylate, chloro Benzyl methacrylate, 2- (p-hydroxyphenyl) ethyl methacrylate Rate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, chlorophenyl methacrylate, sulfamoylphenyl methacrylate and the like.

  Specific examples of acrylamides include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-benzylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, and N-tolylacrylamide. N- (p-hydroxyphenyl) acrylamide, N- (sulfamoylphenyl) acrylamide, N- (phenylsulfonyl) acrylamide, N- (tolylsulfonyl) acrylamide, N, N-dimethylacrylamide, N-methyl-N- Examples include phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N- (p-toluenesulfonyl) acrylamide and the like.

  Specific examples of methacrylamides include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-butylmethacrylamide, N-benzylmethacrylamide, N-hydroxyethylmethacrylamide, N -Phenylmethacrylamide, N-tolylmethacrylamide, N- (p-hydroxyphenyl) methacrylamide, N- (sulfamoylphenyl) methacrylamide, N- (phenylsulfonyl) methacrylamide, N- (tolylsulfonyl) methacrylamide N, N-dimethylmethacrylamide, N-methyl-N-phenylmethacrylamide, N- (p-toluenesulfonyl) methacrylamide, N-hydroxyethyl-N-methylmethacrylamide and the like.

  Specific examples of lactones include pantoyl lactone (meth) acrylate, α- (meth) acryloyl-γ-butyrolactone, and β- (meth) acryloyl-γ-butyrolactone.

  Specific examples of maleic imides include hydroxyphenylmaleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide and the like.

  Specific examples of vinyl esters include vinyl acetate, vinyl butyrate, vinyl benzoate and the like.

  Specific examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, propyl styrene, cyclohexyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, methoxy styrene, dimethoxy styrene. Chlorostyrene, dichlorostyrene, bromostyrene, iodostyrene, fluorostyrene, carboxystyrene and the like.

  Specific examples of acrylonitriles include acrylonitrile and methacrylonitrile.

  Among these monomers, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, acrylic acid, methacrylic acid, acrylonitriles, maleic imides having 20 or less carbon atoms are particularly preferably used. is there.

  The molecular weight of the copolymer using these is preferably 2000 or more in terms of weight average molecular weight (Mw), more preferably in the range of 50,000 to 100,000, and particularly preferably in the range of 10,000 to 50,000. By making it into the above range, the film strength, alkali solubility, solubility in chemicals, etc. can be adjusted, and the effects of the present invention can be easily obtained. On the other hand, the polymerization form of the alkali-soluble acrylic resin that can be used in the present invention may be a random polymer, a block polymer, a graft polymer, or the like. However, the hydrophilic group and hydrophobicity can be controlled in that the solubility of the developer can be controlled. The block polymer is preferably a block polymer capable of phase separation.

  The alkali-soluble acrylic resin that can be used in the present invention may be used alone or in combination of two or more.

(Infrared absorbing dye)
The image forming layer of the lithographic printing plate material according to the present invention preferably contains a dye that absorbs infrared rays and converts it into heat. A dye having a function of absorbing near-infrared rays of 750 to 1100 nm and converting it into heat (also referred to as infrared absorbing dye) has a light absorption range of 700 or more, preferably 750 to 1100 nm, and has this wavelength. Various pigments or dyes that absorb light in the region and generate heat can be used.

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

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

  The particle size of the pigment is preferably in the range of 0.1 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, and particularly preferably in the range of 0.1 μm to 1 μm. When the particle diameter of the pigment is less than 0.01 μm, it is not preferable from the viewpoint of stability of the dispersion in the photosensitive layer coating solution, and when it exceeds 10 μm, it is not preferable from the viewpoint of uniformity of the photosensitive layer. As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production, or the like can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. Details are described in "Latest Pigment Applied Technology" (CMC Publishing, 1986).

  The pigment is added in a proportion of 0.01 to 10% by mass, preferably 0.1 to 5% by mass, based on the total solid content constituting the photosensitive layer, from the viewpoints of sensitivity, uniformity of the photosensitive layer and durability. Can do.

(dye)
As the dye, commercially available dyes and known dyes described in the literature (for example, “Dye Handbook” edited by Organic Synthetic Chemical Society, published in 1970) can be used. Specific examples include azo dyes, metal complex azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, and cyanine dyes. In the present invention, among these pigments or dyes, those that absorb infrared light or near infrared light are particularly preferred because they are suitable for use in lasers that emit infrared light or near infrared light.

  Examples of dyes that absorb such infrared light or near-infrared light are, for example, JP-A-58-125246, JP-A-59-84356, JP-A-59-20.2829, JP-A-60-. Cyanine dyes described in JP-A-78787, methine dyes described in JP-A-58-173696, JP-A-58-181690, JP-A-58-194595, etc., JP-A-58-112793 JP, 58-224793, JP 59-48187, JP 59-73996, JP 60-52940, JP 60. Naphthoquinone dyes described in No. 63744, etc., squarylium dyes described in JP-A No. 58-112792, etc., cyanine dyes described in British Patent No. 434,875, and the like. Further, near-infrared absorption sensitizers described in US Pat. No. 5,156,938 are also preferably used as dyes, and substituted arylbenzo (thio) pyrylium described in US Pat. No. 3,881,924. Salts, trimethine thiapyrylium salts described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, 58-220143, 59-41363, 59 -84248, 59-84249, 59-146063, 59-146061, pyrylium compounds described in JP-A-59-216146, cyanine dyes, U.S. Pat. No. 4,283,475 The pentamethine thiopyrylium salt described in No. 5, JP-B-5-13514, and the pyrium compound disclosed in JP-A-5-1970.2, polight III-178, Epolight III-130, Epolight III-125 and the like are particularly preferably used.

  Particularly preferred among these dyes are cyanine dyes, phthalocyanine dyes, oxonol dyes, squarylium dyes, pyrylium salts, thiopyrylium dyes, and nickel thiolate complexes. Furthermore, the cyanine dye represented by the following general formula (a) gives high interaction with the alkali-soluble resin when used in the lithographic printing plate material of the present invention, and is excellent in stability and economy. Most preferred.

In general formula (a), X ¹ represents a hydrogen atom, a halogen atom, —NPh ₂ , X ² -L ¹ or a group shown below. Here, X ² represents an oxygen atom or a sulfur atom, and L ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, an aromatic ring having a hetero atom, or a carbon atom having 1 to 12 carbon atoms including a hetero atom. Indicates a hydrogen group. In addition, a hetero atom here shows N, S, O, a halogen atom, and Se.

In the above formula, Xa ^- has Za described later ^- is defined as for, Ra represents a hydrogen atom, an alkyl group, ant - represents a group, a substituted or unsubstituted amino group, substituted or unsubstituted amino group and a halogen atom . R ¹ and R ² each independently represents a hydrocarbon group having 1 to 12 carbon atoms. From the storage stability of the recording layer coating solution, R ¹ and R ² are preferably hydrocarbon groups having 2 or more carbon atoms, and R ¹ and R ² are bonded to each other to form a 5-membered ring or It is particularly preferable that a 6-membered ring is formed.

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

 Specific examples of the cyanine dye represented by formula (a) that can be preferably used in the present invention include those exemplified below, and paragraph numbers [0017] to [0019] of JP-A No. 2001-133969. And those described in paragraph numbers [0012] to [0038] of JP-A No. 2002-40638 and paragraph numbers [0012] to [0023] of JP-A No. 2002-23360.

  The infrared absorbing dye according to the present invention is from 0.1 to 30% by mass, preferably from 0.1 to 10% by mass, based on the total solid content constituting the photosensitive layer, from the viewpoints of sensitivity, chemical resistance and printing durability. %, Particularly preferably 0.1 to 5% by mass.

  Preferred specific examples of the infrared absorbing dye according to the present invention are shown below.

(Acid-decomposable compound)
The image forming layer of the lithographic printing plate material according to the present invention can contain an acid-decomposable compound.

  The acid-decomposable compound used in the present invention is a compound having at least one bond that can be decomposed by an acid (hereinafter referred to as “acid-decomposable compound according to the present invention”). 48-89003, 51-120714, 53-133429, 55-12995, 55-126236, 56-17345 and the C—O—C bond described in the specification. Compounds having Si—O—C bonds described in the specifications of JP-A-60-37549 and JP-A-60-112446, JP-A-60-3625, JP-A-60-10247 Other acid-decomposable compounds described in the specification. Furthermore, compounds having a Si—N bond described in the specification of JP-A-62-222246, carbonate esters described in the specification of JP-A-62-251743, and JP-A-62-2 In the ortho carbonate ester described in the specification of 20.9451, the ortho titanate ester described in the specification of JP-A-62-280841, in the specification of JP-A-62-280842 Orthosilicates described, acetals and ketals described in the specification of JP-A 63-10153, C—S bonds described in the specification of JP-A 62-244038 A compound or the like can be used.

  Of the above, JP-A-53-133429, JP-A-56-17345, JP-A-60-121446, JP-A-60-37549 and JP-A-62-20.9451, JP-A-63-10153 Compounds having C—O—C bonds, Si—O—C bonds, orthocarbonates, acetals, ketals and silyl ethers described in the document are preferred.

  Among them, an organic polymerization compound having a repeating acetal or ketal moiety in the main chain described in JP-A-53-133429, and whose solubility in a developer is increased by the action of an acid, and JP-A The compounds described in JP-A 63-10153 are particularly preferred.

  Preferred examples of the acid-decomposable compound according to the present invention include acid-decomposable compounds represented by the following general formula (ADC-1).

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and may be bonded to each other to form a ring)
More preferred is an acid-decomposable compound represented by the following general formula (ADC-2).

(Wherein R ₅ and R ₆ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and may be bonded to each other to form a ring. R ₇ represents an alkylene group. Represents a cycloalkylene group or an arylene group, and n and m are integers of 1 or more.)
The content of the acid-decomposable compound according to the present invention is preferably 0.5 to 30% by mass, particularly preferably 1 to 20% by mass, based on the total solid content of the composition forming the image forming layer. The acid-decomposable compound of the present invention may be used alone or in combination of two or more.

  Preferred specific examples of the acid-decomposable compound are shown below.

(Thermal acid generator)
The image forming layer of the lithographic printing plate material according to the present invention may contain a thermal acid generator.

  Examples of the thermal acid generator used in the present invention include known onium salts such as ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, and organic halogen compounds. In particular, trihaloalkyl compounds and diazonium salt compounds are preferably used in that high sensitivity can be obtained. Moreover, you may use together the compound which generate | occur | produces an acid with two or more types of heat as needed.

  As the trihaloalkyl compound, for example, trihalomethyl-s-triazine compounds, oxadiazole compounds, tribromomethylsulfonyl compounds and the like described in US Pat. No. 4,239,850 are preferable.

  In the present invention, an organic halogen compound is preferable as a thermal acid generator from the viewpoints of sensitivity in image formation by infrared exposure and storage stability of a lithographic printing plate material. As the organic halogen compound, triazines having a halogen-substituted alkyl group and oxadiazoles having a halogen-substituted alkyl group are preferable, and s-triazines having a halogen-substituted alkyl group are particularly preferable. Specific examples of oxadiazoles having a halogen-substituted alkyl group include JP 54-74728, JP 55-24113, JP 55-77742, JP 60-3626 and JP 60-3626. Examples include 2-halomethyl-1,3,4-oxadiazole compounds described in JP-A-60-138539. Preferred examples of the 2-halomethyl-1,3,4-oxadiazole acid generator are given below.

  As the s-triazines having a halogen-substituted alkyl group, compounds represented by the following general formula (TZN) are preferable.

  In the general formula (TZN), R represents an alkyl group, a halogen-substituted alkyl group, a phenyl vinylene group or an aryl group (for example, a phenyl group or a naphthyl group) which may be substituted with an alkoxy group, or a substituted product thereof, and X represents Represents a halogen atom.

  Examples of the s-triazine acid generator represented by the general formula (TZN) are shown below.

  The addition amount of the compound that generates an acid by heat is preferably in the range of 0.1 to 10% by mass, particularly preferably in the range of 0.3 to 5% by mass with respect to the solid content of the photosensitive layer. Preferably, the amount of the compound that generates an acid by heat is 0.01% by mass or more, so that generation of sufficient acid necessary for decomposing the compound that decomposes by the acid can be expected. It is preferable in terms of storage stability and safe light property.

(Additive)
In addition to the copolymer, various additives can be added to the composition constituting the image forming layer of the present invention as required. For example, a substance that is thermally decomposable, such as an onium salt, an o-quinonediazide compound, an aromatic sulfone compound, and an aromatic sulfonic acid ester compound, and that substantially reduces the solubility of the alkaline water-soluble polymer compound without being decomposed. Use in combination is preferable in terms of improving the dissolution inhibition of the image area in the developer. Examples of onium salts include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, and arsonium salts. In the present invention, a diazonium salt is particularly preferable. Particularly suitable diazonium salts include those described in JP-A-5-158230.

  Suitable quinonediazides include o-quinonediazide compounds. The o-quinonediazide compound used in the present invention is a compound having at least one o-quinonediazide group, which increases alkali solubility by thermal decomposition, and compounds having various structures can be used. That is, o-quinonediazide helps the solubility of the sensitive material system by both the effect of losing the ability to suppress the dissolution of the binder due to thermal decomposition and the change of o-quinonediazide itself into an alkali-soluble substance. Examples of the o-quinonediazide compound used in the present invention include J. The compounds described in “Light-Sensitive Systems” (John Wiley &Amp; Sons. Inc.) pp. 339 to 352 can be used, but they have been reacted with various aromatic polyhydroxy compounds or aromatic amino compounds. O-quinonediazide sulfonic acid esters or sulfonic acid amides are preferred. Further, benzoquinone (1,2) -diazide sulfonic acid chloride or naphthoquinone- (1,2) -diazide-5-sulfonic acid chloride and pyrogallol-acetone resin as described in JP-B-43-28403. Esters of benzoquinone- (1,2) -diazide sulfonic acid chloride or naphthoquinone- (1,2) -diazide- described in US Pat. Nos. 3,046,120 and 3,188,210 Esters of 5-sulfonic acid chloride and phenol-formaldehyde resin are also preferably used.

  Further, an ester of naphthoquinone- (1,2) -diazido-4-sulfonic acid chloride and phenol formaldehyde resin or cresol-formaldehyde resin, naphthoquinone- (1,2) -diazido-4-sulfonic acid chloride and pyrogallol-acetone resin Similarly, the esters are also preferably used.

  The addition amount of the o-quinonediazide compound is preferably in the range of 1 to 50% by mass, more preferably 5 to 30% by mass, and particularly preferably 10 to 30% by mass with respect to the total solid content of the printing plate material. These compounds can be used alone, but may be used as a mixture of several kinds.

  The counter ion of the onium salt includes tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 5-sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol-5-sulfone Examples include acid, 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, and paratoluenesulfonic acid. Of these, particularly preferred are alkyl aromatic sulfonic acids such as hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid and 2,5-dimethylbenzenesulfonic acid.

  The amount of additives other than the o-quinonediazide compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, and particularly preferably 10 to 30% by mass.

  Further, for the purpose of further improving sensitivity, cyclic acid anhydrides, phenols, and organic acids can be used in combination. Examples of cyclic acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endooxy-Δ4-tetrahydrophthalic anhydride described in US Pat. No. 4,115,128, Tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used. As phenols, bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4 ', 4 ″ -Trihydroxytriphenylmethane, 4,4 ′, 3 ″, 4 ″ -tetrahydroxy-3,5,3 ′, 5′-tetramethyltriphenylmethane and the like. There are sulfonic acids, sulfinic acids, alkylsulfuric acids, phosphonic acids, phosphoric esters, carboxylic acids and the like, which are described in, for example, Kokai 60-88942 and JP-A-2-96755. p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethylsulfuric acid , Phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 4-cyclohexene-1 , 2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, ascorbic acid, etc. The proportion of the cyclic acid anhydrides, phenols and organic acids in the (A) layer constituting material is 0. 0.05 to 20% by mass is preferable, more preferably 0.1 to 15% by mass, and particularly preferably 0.1 to 10% by mass.

  In the present invention, a fatty acid having a large carbon number called a wax or a derivative thereof can be added to the image forming layer in order to improve the stability before development. C6-C32 alkyl group or alkenyl group (for example, linear alkyl group such as n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, 14-methylpentadecyl group, branched alkyl group such as 16-methylheptadecyl group, 1-hexenyl group, 1-heptenyl group, 1-octenyl group, alkenyl group such as 2-methyl-1-heptenyl group) Fatty acids, fatty acid esters, and the like are preferable, and among them, those having an alkyl group or alkenyl group having 25 or less carbon atoms are preferable from the viewpoint of solubility in a coating solvent. Specific examples of compounds that can be used include enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, Nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, mellicic acid, lacteric acid, undecylenic acid, oleic acid, elaidic acid, cetoleic acid, erucic acid, brassic acid and the like can be mentioned. Examples of fatty acid esters include methyl esters, ethyl esters, propyl esters, butyl esters, dodecyl esters, phenyl esters, and naphthyl esters of these fatty acids. Examples of the thio fatty acid ester include methyl thioester, ethyl thioester, propyl thioester, butyl thioester, and benzyl thioester of these fatty acids. Examples of fatty acid amides include amides, methyl amides, and ethyl amides of these fatty acids.

  Each of these compounds may be used alone or in combination of two or more, and is 0.02 to 10% by mass, preferably 0.2 to 10% by mass, particularly preferably in the total solid content of the printing plate material. It is used in an addition amount of 2 to 10% by mass.

  Further, in the image forming layer constituting material, a nonionic surfactant as described in JP-A-62-251740 and JP-A-3-208514 is used in order to broaden the stability of the processing with respect to the developing conditions. , Amphoteric surfactants as described in JP-A-59-121044 and JP-A-4-13149 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, polyoxyethylene nonylphenyl ether and the like. Specific examples of the double-sided activator include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N-betaine. Type (for example, trade name “Amorgen K” manufactured by Daiichi Kogyo Co., Ltd.). The proportion of the nonionic surfactant and the amphoteric surfactant in the image forming layer constituting material is preferably 0.05 to 15% by mass, more preferably 0.1 to 5% by mass.

  In the image forming layer constituting material in the present invention, a printing-out agent for obtaining a visible image immediately after heating by exposure, or a dye or pigment as an image coloring agent can be added. Typical examples of the printing-out agent include a combination of a compound that releases an acid by heating by exposure (photoacid releasing agent) and an organic dye that can form a salt. Specifically, combinations of o-naphthoquinonediazide-4-sulfonic acid halides and salt-forming organic dyes described in JP-A-50-36209 and JP-A-53-8128, No. -36223, 54-74728, 60-3626, 61-143748, 61-151644 and 63-58440, and trihalomethyl compounds and salt-forming organic dyes Can be mentioned. Such trihalomethyl compounds include oxazole-based compounds and triazine-based compounds, both of which have excellent temporal stability and give clear printout images.

  As the image colorant, other dyes can be used in addition to the above-mentioned salt-forming organic dyes. Examples of suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (oriental chemical industry) Manufactured by Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI145170B), Malachite Green (CI42000), Methylene Blue (CI522015), and the like. The dyes described in JP-A-62-293247 are particularly preferred. These dyes can be added in an amount of 0.01 to 10% by mass, preferably 0.1 to 3% by mass, based on the total solid content of the image forming layer constituting material.

  Further, a plasticizer can be added to the image forming layer constituting material, if necessary, in order to impart flexibility of the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid These oligomers and polymers are used. Furthermore, long chain fatty acid esters, long chain fatty acid amides, and the like may be added to improve film strength.

  In the layer constituting material in the present invention, a surfactant for improving the coating property, for example, a fluorosurfactant described in JP-A-62-170950 can be added. A preferable addition amount is 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass of the total layer constituting material.

(Coating solvent)
The image forming layer of the lithographic printing plate material according to the present invention can be usually formed by dissolving the above-described components in a solvent and coating and drying on the above-mentioned hydrophilic support. As the solvent used here, the following coating solvents can be used. These solvents are used alone or in combination.

  For example, n-propanol, isopropyl alcohol, n-butanol, sec-butanol, isobutanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 2-ethyl-1-butanol 1-pentanol, 2-pentanol, 3-pentanol, n-hexanol, 2-hexanol, cyclohexanol, methylcyclohexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 4-methyl 2-pentanol, 2-hexyl alcohol, benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,5-pentane glycol, dimethyltriglycol, fluoro Furyl alcohol, hexylene glycol, hexyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, butylphenyl ether, ethylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono Propyl ether, propylene glycol monobutyl ether, propylene glycol phenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, methyl carbitol, ethyl Carbitol, ethyl carbitol acetate Butyl carbitol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol dimethyl ether, diacetone alcohol, acetophenone, cyclohexanone, methylcyclohexanone, acetonyl acetone, isophorone, methyl lactate, ethyl lactate, butyl lactate, propylene carbonate , Phenyl acetate, acetic acid-sec-butyl, cyclohexyl acetate, diethyl oxalate, methyl benzoate, ethyl benzoate, γ-butyllactone, 3-methoxy-1-butanol, 4-methoxy-1-butanol, 3-ethoxy- 1-butanol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-ethyl-1-pentanol, 4-ethoxy-1-pentanol, 5-methoxy-1-hex Nord, 3-hydroxy-2-butanone, 4-hydroxy-2-butanone, 4-hydroxy-2-pentanone, 5-hydroxy-2-pentanone, 4-hydroxy-3-pentanone, 6-hydroxy-2-pentanone, Examples include 4-hydroxy-3-pentanone, 6-hydroxy-2-hexanone, 3-methyl-3-hydroxy-2-pentanone, methyl cellosolve (MC), and ethyl cellosolve (EC).

<< 3. Application drying >>
The prepared coating composition for the image forming layer (image forming layer coating solution) can be coated on 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 image forming layer is preferably in the range of 60 to 160 ° C, more preferably in the range of 80 to 140 ° C, and particularly preferably in the range of 90 to 120 ° C. Further, an infrared radiation device can be installed in the drying device to improve the drying efficiency.

(aging)
In the production method of the present invention, after the photosensitive layer is coated on the support and dried, an aging treatment may be performed to stabilize the performance. The aging treatment may be performed continuously with the drying zone or may be performed separately.

<< 4. Cutting and loading >>
In the method for producing a lithographic printing plate material of the present invention, after the image forming layer is applied and dried on the roughened roll-shaped aluminum support as described above, the lithographic printing plate material is A slip sheet is installed between the lithographic printing plate materials cut into leaves, and a static friction coefficient (μ1) between the surface of the slip sheet and the image forming layer of the planographic printing plate material is It is 0.05 to 3.0 larger than the dynamic friction coefficient (μ2) between the back surface and the back surface of the aluminum support of the lithographic printing plate material, and the lithographic printing plate material is cut on a tilted pedestal (sheet-fed) In addition, a slip sheet is installed between the planographic printing plate materials).

In the present invention,
Coefficient of static friction (μ1) between the surface of the slip sheet and the image forming layer of the planographic printing plate material,
Coefficient of dynamic friction (μ2) between the back surface of the slip sheet and the back surface of the aluminum support of the lithographic printing plate material,
Is measured as follows.

<Measurement of friction coefficient>
The lithographic printing plate material sample that was cut and loaded was measured using a friction coefficient measuring device (made by Shinto Kagaku Co., Ltd., HEIDON 14FW) compliant with ASTM D1894 at a moving speed of 152 mm / min (image formation) The static friction coefficient (μ1) of the layer surface) and the interleaf paper surface, and the dynamic friction coefficient (μ2) of the lithographic printing plate material back surface (aluminum surface) and interleaf paper back surface are measured.

  The figure which illustrates the manufacturing method (the method of cutting and loading a planographic printing plate material) of the present invention about the manufacturing method of the planographic printing plate material of the present invention (method of cutting and stacking the planographic printing plate material) 1 will be used for explanation.

  In FIG. 1, the lithographic printing plate material coated and dried as described above flows from the left in FIG. The slip sheet 4 fed out overlaps the surface (surface on the image forming layer side) 2 of the planographic printing plate material so as to overlap the surface of the slip sheet. After being attached well by the charging device 5 for attaching the interleaving paper and the planographic printing plate material, the paper is cut to a predetermined size by a cross cutter (cutting section) 6 and then loaded on a loading table 8 by a conveyor 7. The The loading table 8 is inclined at the receiving table and moves up and down according to the loading amount. The loaded lithographic printing plate materials are alternately stacked with slip sheets. The slip sheet is preferably the same width as the planographic printing plate material or slightly smaller.

  The present invention is characterized in that the lithographic printing plate material cut into sheets is deposited on a stacking portion inclined with respect to the flow direction. By adopting such a tilting structure for the loading table, it is possible to minimize the contact between the plates during loading. The angle of the loading table is appropriately set according to the plate thickness, plate size, and line speed, but is usually set in the range of 5 to 45 degrees.

  It is preferable that the loading table is set so that the position of the loading surface is adjusted in accordance with the loading amount, and the cut lithographic printing plate material is dropped on the loading surface with a minimum vertical movement during loading.

  By using such a stacking method, it is possible to prevent the occurrence of scratches caused by the plates rubbing at the time of stacking even in a highly productive line.

(Control of friction coefficient)
In the present invention, the static friction coefficient (μ1) between the surface of the slip sheet and the image forming layer of the lithographic printing plate material is 0 than the dynamic friction coefficient (μ2) between the back surface of the slip sheet and the back surface of the planographic printing aluminum support. .05 or larger is required.

  By adjusting the following conditions, by satisfying the above conditions, the slip sheet position may shift when loaded, or scratches caused by slippage between the planographic printing plate material surface and the slip sheet surface may occur during subsequent handling. Can be prevented.

(1) Surface roughness of interleaf paper (2) Lubricant component amount in image forming layer (3) Charge amount when interleaving interleaf paper with lithographic printing plate material (control of burr direction)
FIG. 2 shows a preferred example of cutting a lithographic printing plate material. As shown in FIG. 2, by configuring the trailing end of the planographic printing plate material in the conveying direction to be cut with a blade surface, the front of the planographic printing plate material in the plate traveling direction is an upper burr and the rear end of the plate is a lower burr. Thus, the burrs of the upper plate do not come into contact with the lower plate surface during loading, and the generation of scratches can be prevented.

<< 5. exposure"
The image recording material produced as described above is preferably used as a lithographic printing plate material, and is usually subjected to image exposure and development treatment and used as a lithographic printing plate.

  As the light source of the light beam used for image exposure, a light source having an emission wavelength in the near infrared to infrared region is preferable, and a solid laser or a semiconductor laser is particularly preferable. Image exposure uses a commercially available CTP setter, and after exposure with an infrared laser (830 nm) based on digitally converted data, an image is formed on the surface of the aluminum plate support by processing such as development. Can be provided as a lithographic printing plate.

  The exposure apparatus used in the plate making method is not particularly limited as long as it is a laser beam method, and any of a cylindrical outer surface (outer drum) scanning method, a cylindrical inner surface (inner drum) scanning method, and a flat (flat bed) scanning method may be used. However, in order to increase productivity by low-illumination long-time exposure, an outer drum type that is easy to be multi-beamed is preferably used, and an outer drum type exposure apparatus including a GLV modulation element is particularly preferable.

The laser beam pixel residence time means the time for which the laser beam passes one pixel (one dot), that is, the exposure time per pixel. The laser beam pixel residence time is set to 2.0 to 20 μsec, preferably 2.5 to 15 μsec. The laser beam applied amount of time the laser beam passes through the 1 pixel is preferably 10 to 300 mJ / cm ^2, more preferably 30~180mJ / cm ^2.

  In the exposure process, it is preferable to use a laser exposure recording apparatus equipped with a GLV modulation element to make a multi-channel in order to improve the productivity of the lithographic printing plate. As the GLV modulation element, one that can divide the laser beam into 200 channels or more is preferable, and one that can divide the laser beam into 500 channels or more is more preferable. The laser beam diameter is preferably 15 μm or less, more preferably 10 μm or less. The laser output is preferably 10 to 100 W, more preferably 20 to 80 W. The drum rotation speed is preferably 20 to 300 rpm, more preferably 30 to 200 rpm.

<< 6. developing"
The developer and replenisher that can be applied to the lithographic printing plate material according to the present invention have a pH in the range of 9.0 to 14.0, preferably in the range of 12.0 to 13.5. A known alkaline aqueous solution can be used as the developer (hereinafter referred to as a developer including a replenisher). For example, sodium hydroxide, ammonium, potassium and lithium are preferably used as the base. These alkali agents are used alone or in combination of two or more. Other examples include potassium silicate, sodium silicate, lithium silicate, ammonium silicate, potassium metasilicate, sodium metasilicate, lithium metasilicate, ammonium metasilicate, tripotassium phosphate, trisodium phosphate, trilithium phosphate, triammonium phosphate, phosphoric acid. Dipotassium, disodium phosphate, dilithium phosphate, diammonium phosphate, potassium carbonate, sodium carbonate, lithium carbonate, ammonium carbonate, potassium bicarbonate, sodium bicarbonate, lithium bicarbonate, ammonium bicarbonate, potassium borate, sodium borate, boric acid Lithium, ammonium borate and the like can be mentioned and may be added in the form of a preformed salt. Again, sodium hydroxide, ammonium, potassium and lithium can be added to the pH adjustment. Moreover, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine, and pyridine are also used in combination. Most preferred are potassium silicate and sodium silicate. The concentration of silicate is ₂ to 4% by mass in terms of SiO ₂ concentration. Further, the molar ratio of SiO ₂ to alkali metal M (SiO ₂ / M) is more preferably in the range of 0.25 to ₂ .

  The developer referred to in the present invention is not only an unused solution used at the start of development, but also replenished to correct the activity of the solution that decreases due to processing of the infrared laser-sensitive lithographic printing plate material. The liquid is replenished and the liquid whose activity is maintained (so-called running liquid) is included.

  Various surfactants and organic solvents can be added to the developer and the replenisher as necessary for the purpose of promoting developability, dispersing development residue, and improving ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Preferred examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, sorbitan Fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol mono fatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, poly Glycerin fatty acid partial esters, polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial esters, polyoxy Ethylene-polyoxypropylene block copolymer, ethylenediamine polyoxyethylene-polyoxypropylene block copolymer adduct, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamine, Nonionic surfactants such as triethanolamine fatty acid esters and trialkylamine oxides, fatty acid salts, abietic acid salts, hydroxyalkane sulfonic acid salts, alkane sulfonic acid salts, dialkyl sulfosuccinic acid ester salts, linear alkylbenzene sulfonic acid salts Branched alkylbenzene sulfonates, alkyl naphthalene sulfonates, alkyl diphenyl ether sulfonates, alkylphenoxy polyoxyethylene propyl sulfonates, Oxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium salt, N-alkyl sulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated beef oil, sulfate esters of fatty acid alkyl esters, alkyl sulfates Ester salts, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkyl phenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ether phosphorus Acid ester salts, polyoxyethylene alkylphenyl ether phosphate ester salts, partially saponified styrene / maleic anhydride copolymers, olefins / anhydrides Partially saponified products of maleic acid copolymer, anionic surfactants such as naphthalenesulfonate formalin condensates, alkylamine salts, quaternary ammonium salts such as tetrabutylammonium bromide, polyoxyethylene alkylamine salts, polyethylene Examples include cationic surfactants such as polyamine derivatives, and amphoteric surfactants such as carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfuric esters, and imidazolines. Among the surfactants described above, polyoxyethylene can be read as polyoxyalkylene such as polyoxymethylene, polyoxypropylene, and polyoxybutylene, and these surfactants are also included. . A more preferred surfactant is a fluorosurfactant containing a perfluoroalkyl group in the molecule. Examples of such fluorosurfactants include perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, anionic types such as perfluoroalkyl phosphate esters, amphoteric types such as perfluoroalkyl betaines, and perfluoroalkyls. Cation type and perfluoroalkylamine oxide such as trimethylammonium salt, perfluoroalkylethylene oxide adduct, perfluoroalkyl group and hydrophilic group-containing oligomer, perfluoroalkyl group and lipophilic group-containing oligomer, perfluoroalkyl group, hydrophilic Nonionic types such as group- and lipophilic group-containing oligomers, perfluoroalkyl groups and lipophilic group-containing urethanes. Said surfactant can be used individually or in combination of 2 or more types, and is added in 0.001-10 mass% in a developing solution, More preferably, it is added in 0.01-5 mass%.

  Various development stabilizers can be used in the developer and the replenisher as necessary. Preferred examples thereof include polyethylene glycol adducts of sugar alcohols described in JP-A-6-282079, tetraalkylammonium salts such as tetrabutylammonium hydroxide, phosphonium salts such as tetrabutylphosphonium bromide, and iodonium such as diphenyliodonium chloride. Examples include salts. Further, anionic surfactants or amphoteric surfactants described in JP-A-50-51324, water-soluble cationic polymers described in JP-A-55-95946, and JP-A-56-142528 are described. There are water-soluble amphoteric polyelectrolytes that have been described. Furthermore, an organic boron compound to which an alkylene glycol is added as described in JP-A-59-84241, a polyoxyethylene / polyoxypropylene block polymerization type water-soluble surfactant as described in JP-A-60-111246, An alkylenediamine compound substituted with polyoxyethylene / polyoxypropylene disclosed in JP-A-60-129750, a polyethylene glycol having a mass average molecular weight of 300 or more described in JP-A-61-215554, and a cation described in JP-A-63-175858 And a water-soluble ethylene oxide addition compound obtained by adding 4 mol or more of ethylene oxide to an acid or alcohol disclosed in JP-A-2-39157, a water-soluble polyalkylene compound, and the like.

  If necessary, an organic solvent can be used for the developer and the development replenisher. As the organic solvent that can be used in the present invention, those having a solubility in water of about 10% by mass or less are suitable, and preferably selected from those having 5% by mass or less. For example, 1-phenylethanol, 2-phenylethanol, 3-phenyl-1-propanol, 4-phenyl-1-butanol, 4-phenyl-2-butanol, 2-phenyl-1-butanol, 2-phenoxyethanol, 2- Benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol and 4-methylcyclohexanol, N-phenylethanol Examples include amines and N-phenyldiethanolamine. However, the content of the organic solvent is 0.1 to 5% by mass with respect to the total mass of the used liquid, but it is preferable that the content is not substantially included, and it is particularly preferable that it is not included at all. Here, “substantially not contained” means 1% by mass or less.

  If necessary, an organic carboxylic acid can be further added to the developer and the replenisher. Preferred organic carboxylic acids are aliphatic carboxylic acids and aromatic carboxylic acids having 6 to 20 carbon atoms. Specific examples of the aliphatic carboxylic acid include caproic acid, enanthylic acid, caprylic acid, lauric acid, myristic acid, palmitic acid and stearic acid, and particularly preferred are alkanoic acids having 8 to 12 carbon atoms. . Further, it may be an unsaturated fatty acid having a double bond in the carbon chain or a branched carbon chain. The aromatic carboxylic acid is a compound in which a carboxyl group is substituted on a benzene ring, naphthalene ring, anthracene ring, etc., specifically, o-chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid, p -Hydroxybenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3 , 5-dihydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-naphthoic acid, 2-naphthoic acid, etc. Hydroxynaphthoic acid is particularly effective. The aliphatic and aromatic carboxylic acids are preferably used as sodium salts, potassium salts or ammonium salts in order to enhance water solubility. The content of the organic carboxylic acid in the developer used in the present invention is not particularly limited, but if it is less than 0.1% by mass, the effect is not sufficient, and if it is 10% by mass or more, the effect cannot be further improved. In addition, dissolution may be hindered when other additives are used in combination. Therefore, the preferable addition amount is 0.1 to 10% by mass, more preferably 0.5 to 4% by mass with respect to the developing solution at the time of use.

  In addition to the above, the following additives can be added to the developer and replenisher, such as NaCl, KCl, KBr, etc. described in JP-A-58-75152. Amphoteric, such as a complex salt, a complex such as [Co (NH3)] 6Cl3 described in JP-A-59-121336, and a copolymer of vinylbenzyltrimethylammonium chloride and sodium acrylate described in JP-A-56-142258 Examples thereof include polymer electrolytes, organometallic surfactants containing Si, Ti and the like described in JP-A-59-75255, organoboron compounds described in JP-A-59-84241, and the like.

The developer and replenisher may further contain a preservative, a colorant, a thickener, an antifoaming agent, a hard water softening agent, and the like as necessary. Examples of the antifoaming agent include mineral oil, vegetable oil, alcohol, surfactant, silicone and the like described in JP-A-2-244143. Examples of the water softener include polyphosphoric acid and its sodium salt, potassium salt and ammonium salt, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, 1,2-diaminocyclohexane. Aminopolycarboxylic acids such as tetraacetic acid and 1,3-diamino-2-propanoltetraacetic acid and their sodium, potassium and ammonium salts, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta ( Methylenephosphonic acid), triethylenetetramine hexa (methylenephosphonic acid), hydroxyethylethylenediaminetri (methylenephosphonic acid) and 1-hydro Shietan 1,1-diphosphonic acid and their sodium salts, potassium salts and ammonium salts. The optimum value of such a hard water softening agent varies depending on its chelating power, the hardness of the hard water used and the amount of hard water. % By mass, more preferably in the range of 0.01 to 0.5% by mass. If the addition amount is less than this range, the intended purpose is not sufficiently achieved. If the addition amount is more than this range, adverse effects on the image area such as color loss will occur. The remaining component of the developer and replenisher is water.

  In addition, it is advantageous in terms of transportation that the developer and the replenisher are concentrated solutions having a water content less than that in use and are diluted with water during use. The degree of concentration in this case is suitably such that each component does not separate or precipitate, but it is preferable to add a solubilizer if necessary. As the solubilizer, so-called hydrotropes such as toluene sulfonic acid, xylene sulfonic acid and alkali metal salts thereof described in JP-A-6-32081 are preferably used.

  In preparing a lithographic printing plate, it is preferable to use an automatic processor. The automatic processor used in the present invention is preferably provided with a mechanism for automatically replenishing a replenisher with a required amount in a developing bath, and preferably provided with a mechanism for discharging a developer exceeding a certain amount, Preferably, a mechanism for automatically replenishing a required amount of water to the developing bath is provided, preferably a mechanism for detecting plate passing is provided, and preferably the processing area of the plate based on detection of plate passing A mechanism for controlling the replenishment amount and / or replenishment timing of the replenisher and / or water to be replenished preferably based on detection of the plate and / or estimation of the processing area is provided. A mechanism for controlling the temperature of the developer, preferably a mechanism for detecting the pH and / or conductivity of the developer, preferably a pH and / or developer. Or electric Mechanism for controlling the replenishment amount and / or replenishment timing of replenishment solution and / or water tries to refill the original is given in degrees.

  The automatic processor may have a pretreatment unit that immerses the plate in the pretreatment liquid before the development step. The pretreatment unit is preferably provided with a mechanism for spraying the pretreatment liquid onto the plate surface, and preferably provided with a mechanism for controlling the temperature of the pretreatment liquid to an arbitrary temperature of 25 ° C to 55 ° C. Preferably, a mechanism for rubbing the plate surface with a roller-like brush is provided. Moreover, water etc. are used as this pretreatment liquid.

  Infrared laser heat-sensitive lithographic printing plate material developed with the developer having the above composition is rinse water containing rinse water, surfactant, etc., finisher or protective gum mainly composed of gum arabic or starch derivatives, etc. After-treatment with liquid. In the post-treatment of the infrared laser heat-sensitive lithographic printing plate material according to the present invention, these treatments can be used in various combinations, for example, after development-washing-rinsing solution containing a surfactant or development- Washing with a water-finisher solution is preferable because there is little fatigue of the rinsing liquid or the finisher liquid. Furthermore, a multi-stage countercurrent process using a rinse liquid or a finisher liquid is also a preferred embodiment. These post-processing are generally performed using an automatic developing machine including a developing unit and a post-processing unit. As the post-treatment liquid, a method of spraying from a spray nozzle or a method of immersing and conveying in a treatment tank filled with the treatment liquid is used. A method is also known in which a certain amount of a small amount of washing water is supplied to the plate surface after the development to wash it, and the waste solution is reused as dilution water for the developer stock solution. In such automatic processing, processing can be performed while each replenisher is replenished with each replenisher according to the processing amount, operating time, and the like. In addition, a so-called disposable treatment method in which treatment is performed with a substantially unused post-treatment liquid is also applicable. The infrared laser heat-sensitive lithographic printing plate material obtained by such treatment is applied to an offset printing machine and used for printing a large number of sheets.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.
In addition, unless otherwise indicated, "part" in an Example shows a "mass part".

Example 1
<Production of support>
An aluminum plate (material 1050, tempered H16) having a thickness of 0.3 mm was immersed in a 5% by mass aqueous sodium hydroxide solution maintained at 65 ° C., degreased for 1 minute, and then washed with water. This degreased aluminum plate was neutralized by dipping in a 10% by mass sulfuric acid aqueous solution maintained at 25 ° C. for 1 minute, and then washed with water. Next, this aluminum plate was subjected to an electrolytic surface roughening treatment for 20 seconds in an alternating current having a hydrochloric acid concentration of 11 g / L, 25 ° C., a frequency of 50 Hz, and 50 A / dm ² . After electrolytic surface roughening, it was washed with water, desmutted for 10 seconds in a 1% by mass aqueous sodium hydroxide solution maintained at 50 ° C., washed with water, and in 30% by mass sulfuric acid maintained at 50 ° C. The mixture was neutralized for 30 seconds and washed with water. Next, anodization was performed for 30 seconds in a 30% by mass sulfuric acid solution under the conditions of 25 ° C., current density of 30 A / dm ² , and voltage of 25 V, and washed with deionized water. Further, a 0.44 mass% polyvinylphosphonic acid aqueous solution was dipped at 75 ° C. for 30 seconds, then washed with deionized water and dried with cold air at 25 ° C. to obtain a hydrophilically treated support. It was. The center line average roughness (Ra) of the surface of this support was 0.50 μm.

<< Preparation of lithographic printing plate material >>
On the support, an image forming layer coating solution (A), (B), (C) or (D) comprising the following composition is dried to a dry film thickness of 2.0 g / m ² using a wire bar. Applied. The coating solvent was dried by holding it in a far-infrared heater at 125 ° C. for 20 seconds and then in a hot air circulation dryer at 115 ° C. for 60 seconds to dry the lithographic printing plate materials 1-4, 1 ′, 2 ′, 2 ″ Was prepared as shown in Table 1.

<Image forming layer coating solution (A)>
60 parts by mass of novolak resin (* 1) * 1: co-condensation compound of o-, p-mixed cresol and formaldehyde, weight average molecular weight 3100, weight average molecular weight 9800, molar ratio of o-, p-cresol is 40: 60, ratio of weight average molecular weight of 500 or less is 1.8%
Acrylic resin 1 (* 2) 23 parts by mass * 2: Ternary copolymer compound with N- (p-hydroxyphenyl) maleimide, acrylonitrile, methyl methacrylate (weight average molecular weight 35000, molar ratio 20:70:10)
Polyethylene glycol (PEG # 4000 (manufactured by NOF Corporation)) 2 parts by mass Sorbitan laurate 1 part by mass Phthalic anhydride 3 parts by mass Acid-decomposable compound (acid-decomposable compound A of the exemplified compound) 2 parts by mass Acid generator (exemplary) Compound (12)) 1 part by weight Infrared absorbing dye A (below) 2 parts by weight Visible dye (OIL BLUE 613 manufactured by Orient Chemical Industries) 2 parts by weight Acetone 150 parts by weight Methyl ethyl ketone 100 parts by weight Propylene glycol monomethyl ether 500 parts by weight Cyclohexanone 150 parts by mass γ-butyrolactone 100 parts by mass

<Image forming layer coating solution (B)>
The following was further added to the image forming layer coating solution (A).

Fluoroalkyl group-containing oligomer (Omnova's Polyfox 6520)
0.03 part by mass <Image forming layer coating solution (C)>
The following was further added to the image forming layer coating solution (A).

Fluoroalkyl group-containing oligomer (Omnova's Polyfox 6520)
0.1 parts by mass <Image forming layer coating solution (D)>
The following was further added to the image forming layer coating solution (A).

Fluoroalkyl group-containing oligomer (Omnova's Polyfox 6520)
0.5 parts by mass <Image forming layer coating solution (A ′)>
The following was further added to the image forming layer coating solution (A).

Fluoroalkyl group-containing oligomer (Omnova's Polyfox 6520)
0.05 parts by mass <Image forming layer coating solution (B ′)>
About the image formation layer coating liquid (A), the amount of the following composition among the compositions was changed as follows.

Novolac resin (* 1) 61 parts by mass Polyethylene glycol (PEG # 4000 (manufactured by NOF Corporation)) 1 part by mass <Image forming layer coating solution (B ″)>
About the image formation layer coating liquid (A), the amount of the following composition among the compositions was changed as follows.

Novolak resin 62 parts by mass Polyethylene glycol (PEG # 4000) 0.5 part by mass Sorbitan laurate 0.5 part by mass The obtained lithographic printing plate material (cut to 1,140 mm × 850 mm) was used as shown in “ Using the method of cutting and stacking a lithographic printing plate material ”(however, the cutting part of the cross cutter (cutting part) 6 in FIG. 1 was changed to the cutting blade 22 shown in FIG. 2) 100 sheets were produced by overlaying with interleaving paper in an atmosphere of 23 ° C and 50% RH at the line speed and the loading platform angle, and the sheets were stacked and heat-treated in an atmosphere of 55 ° C for 30 hours, and then cut and loaded The lithographic printing plate material samples 101 to 126 thus prepared were prepared as shown in Table 1.

As the interleaving paper, # 25 White MG Medical (basis weight: 40 g / m ² ) manufactured by Shimney USA was used.

"Evaluation methods"
<Measurement of friction coefficient>
About the lithographic printing plate material sample cut and stacked, the coefficient of static friction (μ1) between the surface of the lithographic printing plate material (image forming layer surface) and the surface of the interleaf paper is measured at a moving speed of 152 mm / min using a friction coefficient measuring device conforming to ASTM D1894. ), And the dynamic friction coefficient (μ2) of the lithographic printing plate material back surface (aluminum surface) and interleaf back surface.

<Cutting burr amount (first burr amount)>
As the cutting burr amount, with respect to the top burr amount, the generated front burr amount was measured for the lithographic printing plate material sample cut and stacked, and the maximum burr amount is shown in Table 1 as the top burr amount. The amount of head burr was changed with the cross cutter unit reversed in the front-rear direction. The leading burr amount is shown in Table 1 as a leading burr amount in which the burr ahead in the plate traveling direction (lead burr amount) in FIG.

<Evaluation of the number of scratches>
The number of scratches generated was determined by using an automatic developing machine (manufactured by Raptor 85 Thermal GLUNZ & JENSEN) for each of 100 lithographic printing plate material samples that were cut and stacked, and using an undeveloping solution below. After developing at 30 ° C./30 seconds, the number of scratches (250 μm or more) that can be visually discriminated on the plate surface is measured and converted per sheet.

<Developer>
A Potassium silicate (40% aqueous solution) 87.8 g, manufactured by Nippon Kagaku Co., Ltd.
Caustic potash (50% aqueous solution) 61.1 g, manufactured by Toho Chemical Co., Ltd.
1.4 g of Trilon M Liquid (40% aqueous solution) BASF
896.0 g of pure water
The results are also shown in Table 1.

  *: The leading burr amount on the image forming layer side is represented by +, and the leading burr amount on the back side is represented by-.

  **: The slip sheet was misaligned during deposition.

  As can be seen from Table 1, in the case of the present invention, it is understood that high productivity can be obtained without causing scratches on the image forming layer.

  According to the present invention, it can be seen that it is possible to provide a method for producing a positive planographic printing plate material capable of obtaining high productivity without causing scratches on the image forming layer.

It is a figure which shows an example of the manufacturing method (The method of cutting and loading a lithographic printing plate material) of the lithographic printing plate material of this invention. It is a figure which shows a preferable example of the cutting of a lithographic printing plate material.

Explanation of symbols

1 Interleaving paper 2 Planographic printing plate surface (image forming layer side)
3 Back side of lithographic printing plate material (aluminum side)
4 Rolled out interleaving paper 5 Charging device (attaches interleaving paper and planographic printing plate material)
6 Cross cutter (cutting part)
7 Conveyor 8 Loading platform (The receiving platform is tilted and moves up and down according to the loading capacity)
9 Stacked planographic printing plate material and slip sheet 10 Overlap of planographic printing plate material and slip sheet (the slip sheet is the same width or slightly smaller than the planographic printing plate material)
21 Pressing roll 22 Cutting blade

Claims (4)

After the image forming layer is applied and dried to a roughened roll-shaped aluminum support, it is cut into sheets in a method for producing a positive-type planographic printing plate material having a process of cutting and stacking into sheets. A slip sheet is placed between each of the lithographic printing plate materials, and a static friction coefficient (μ1) between the surface of the slip sheet and the image forming layer of the lithographic printing plate material is such that the back surface of the slip sheet and the The lithographic printing plate material is 0.05 to 0.3 larger than the dynamic friction coefficient (μ2) of the lithographic printing plate material with the back surface of the aluminum support, and the lithographic printing plate material is placed on a tilted base (each lithographic plate cut into sheets) A method for producing a positive planographic printing plate material, wherein a slip sheet is installed between the printing plate materials). The static friction coefficient (μ1) between the surface of the slip sheet and the image forming layer of the lithographic printing plate material is 0.4 to 0.8, and the back surface of the slip sheet and the back surface of the aluminum support of the lithographic printing plate material The method of producing a positive planographic printing plate material according to claim 1, wherein the coefficient of dynamic friction (μ2) is in the range of 0.3 to 0.6. 2. The burr on the front end face in the moving direction of the lithographic printing plate material cut into a sheet is in the range of 0 to 50 μm on the image forming layer side, or 0 to −50 μm on the back side. Or a method of producing a positive planographic printing plate material described in 2. The positive lithographic plate according to any one of claims 1 to 3, wherein the image forming layer contains a resin having a phenolic hydroxyl group and a dye that absorbs infrared rays and converts the infrared rays into heat. A method for producing a printing plate material.

Images