JP2009274260A - Aging method of positive type lithographic printing plate material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aging method of a positive type lithographic printing plate material by which a stable performance is obtained by preventing occurrence of scratches even if an aging processing is performed after vibration is applied to an integrated body, when aging the positive type lithographic printing plate material made into an integrated body with an interleaf between. <P>SOLUTION: In the aging method of the positive type lithographic printing plate material, an integrated body is formed having a rectangular shape in which the positive type lithographic printing plate material with interleaves held in-between is stacked, the material having an image forming layer containing an infrared ray absorbing compound on an aluminum support, and then, the integrated body is covered with a coating member for aging. In four corners in perpendicular direction of the integrated body, a position controlling member is arranged from above the coating member, with the integrated body fixed in the periphery with at least one tightening belt from above the position controlling member to perform the aging processing, which is the characteristic of the aging method of the positive type lithographic printing plate material. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for aging a positive planographic printing plate material having an image layer containing an infrared absorbing compound on an aluminum support.

  Printing using a lithographic printing plate such as a conventional PS plate is a lithographic printing plate material (lithographic printing plate material) in which a negative or positive support is produced from an original image and a photosensitive layer is provided on an aluminum grained support through a film. A printing plate precursor) is exposed to an image, and developed with an alkaline developer to produce a lithographic printing plate, which is attached to a printing machine and printed.

  In recent plate making methods for lithographic printing plates such as PS plates, the conventional plate making method using close contact exposure using film, advanced digitization of information, development of high output laser to record it and Development of accompanying sensitizers progressed in parallel, and as a result, computer-to-plate (CTP) (Computer to Plate) development, in which a plate printing plate was exposed and developed directly without passing through a film original, was rapidly developed. Progress is being made in the structural reforms of plate making. Along with such technological advancement, automation of the plate making process has been promoted rapidly for the purpose of improving the efficiency of plate making work.

  The exposure in CTP has been performed with a laser, and the time has been shortened among them. As such an exposure method, a method using a heat mode laser is becoming mainstream. However, in this method, since image formation is performed by heat-like exposure to heat-like images or by sublimation of substances, the scattered matter accumulates and the light source or printing plate of the exposure machine accumulates. There are problems such as quality.

  As a countermeasure for these, for example, in JP-A-8-207003, JP-A-9-123387, JP-A-9-123388, and JP-A-9-131850, a photosensitive layer containing thermoplastic resin particles in a hydrophilic binder is disclosed. Development of a heat-conversion positive photosensitive lithographic printing plate material in which a lithographic printing plate is converted into image-like light by laser exposure and the thermoplastic resin particles coalesce with the heat to form an image. It was. The heat conversion type positive photosensitive lithographic printing plate material is exposed to a laser to form an image, and then the lithographic printing plate is placed on a printing cylinder and rotated in a dampening water to make the image ink-receptive and the background portion is hydrophilic. The ink is not receptive and can be printed.

  The greatest feature of the heat conversion type positive photosensitive lithographic printing plate material is that the alkali solubility of the photosensitive layer is increased by the heat itself generated by laser light irradiation, and when the alkali solubility of the photosensitive layer increases, It does not cause chemical changes. Further, if an ultraviolet (UV) non-photosensitive material is used as a dissolution inhibitor or other additive, there is an advantage that the photosensitive layer becomes non-photosensitive to UV and can be operated even under a white light.

  When a positive image is to be formed by laser exposure, the photosensitivity becomes a problem because the time during which laser light is irradiated to one point of the photosensitive layer is extremely short. In particular, when the chemical characteristics of the entire surface irradiated with laser light are not uniform, the alkali solubility of the photosensitive layer is not constant depending on the location, and image formation becomes unstable.

  In order to cope with these problems, it is known to perform a so-called aging process, in which a photosensitive layer is formed and then heat-treated to make the chemical characteristics uniform. For example, a positive photosensitive printing plate having a photosensitive layer obtained by applying a photosensitive composition containing a photothermal conversion substance having an absorption region in a wavelength range of 600 nm to 1300 nm and an alkali-soluble resin on a substrate is used as a photosensitive layer. After forming the sheet, a method for producing a positive photosensitive printing plate is known in which an interleaving paper is overlaid, the outer periphery thereof is covered with a heat insulating material, and kept under heating in that state (see Patent Document 1). .

  Also, the thickness of the lithographic printing plate interleaf is adhered to the surface of the image forming surface of the lithographic printing plate, cut to stack 1000 sheets to form an aggregate, and then the paper and the surface are laminated with aluminum-deposited polyethylene. A method is known in which a side face is covered with a 100 μm polyethylene sheet, placed in a heat treatment chamber at a temperature of 60 ° C., treated for 32 hours and aged to produce a lithographic printing plate (see Patent Document 2).

  The methods described in Patent Documents 1 and 2 are excellent because the heat can be transferred to the entire assembly, so that stable aging can be achieved and the performance is stable. However, the method has the following disadvantages. understood. In the methods described in Patent Document 1 and Patent Document 2, there is no problem when the sheet is cut and formed into an aggregate and then does not move to perform heat treatment. However, when the heat treatment (aging process) chamber is separated, transportation work is involved. . At this time, it has been found that the accumulated body causes a scratch on the misaligned image forming surface due to vibration accompanying the carrying work. In particular, when the place to cut and the heat treatment (aging process) chamber are separated, it has been found that the generation of scratches increases as the moving distance becomes longer.

In such a situation, when the positive lithographic printing plate material that has been cut and sandwiched with the interleaving paper is subjected to aging treatment, vibration is given to the accumulated body (for example, the place to be aged from the loading place) Development of a positive lithographic printing plate material aging treatment method that prevents the occurrence of scratches even when an aging treatment is carried out after the vibration of the lithographic printing plate material has been desired.
JP 2001-133965 A Japanese Patent Laid-Open No. 2003-320764

  The present invention has been made in view of the above situation, and its purpose is to cut and vibrate the stack when a positive planographic printing plate material that is a stack with a slip sheet sandwiched therebetween is aged. An object of the present invention is to provide a method for aging a positive lithographic printing plate material that prevents the occurrence of scratches even if the aging process is applied after the application and provides stable performance.

  The above object of the present invention has been achieved by the following constitution.

  1. A positive lithographic printing plate material having an image forming layer containing an infrared absorbing compound on an aluminum support is formed into a stack having a rectangular parallelepiped shape sandwiched between interleaf sheets, and the stack is covered with a covering member and aged. In the aging method of a positive planographic printing plate material, a position restricting member is disposed from above the covering member at four corners in the vertical direction of the accumulation body, and the periphery of the accumulation body is disposed above the position restriction member. A method for aging a positive planographic printing plate material, comprising fixing by at least one fastening belt and performing an aging treatment.

  2. 2. The positive mold according to 1 above, wherein the integrated body is placed on a vibration isolating member having an area of 10% to 150% with respect to the area of the bottom surface of the positive planographic printing plate material. Aging method for lithographic printing plate materials.

  3. 3. The method for aging a positive planographic printing plate material according to 1 or 2, wherein the vibration-absorbing member has a vibration absorption capacity of 10 ° C. to 40 ° C. and a vibration frequency of 30 Hz to 100 Hz.

  4). The area of the side surface of the aggregate covered with the position restricting member is 5% to 40% with respect to the area of the side surface of the aggregate before being covered with the position restricting member. 4. The aging method for a positive planographic printing plate material according to any one of 3 above.

  5). The area of the side surface of the integrated body covered with the fastening belt is 5% to 25% with respect to the area of the side surface of the integrated body before being covered with the fastening belt. 5. A method for aging a positive planographic printing plate material according to any one of 4 above.

  6). 6. The method for aging a positive lithographic printing plate material according to any one of 1 to 5 above, comprising microcapsule particles on the surface of the slip sheet that contacts the image-forming layer side.

  7. 7. The aging method for a positive planographic printing plate material according to any one of 1 to 6, wherein the aging treatment is performed at a temperature of 50 ° C. to 100 ° C. for 8 hours to 100 hours.

  A planographic printing plate that prevents the generation of scratches even if the aging process is performed by moving from the stacking place to the aging process place when the lithographic printing plate material that has been cut and laminated with the interleaving paper sandwiched We were able to provide a material aging treatment method.

  Embodiments of the present invention will be described with reference to FIGS. 1 to 6, but the present invention is not limited thereto.

  FIG. 1 is a schematic view showing an example of the configuration of a positive planographic printing plate material.

  In the figure, reference numeral 1 denotes a positive planographic printing plate material having a structure provided separately from the image forming layer 103 and the hydrophilic layer 102. The lithographic printing plate material 1 includes an aluminum support 101, a hydrophilic layer 102 that develops a non-image part by sequentially applying energy onto the aluminum support 101, and an image that develops an image part by applying energy. The layer structure includes a formation layer 103 and a protective layer 104. A lithographic printing plate material in which a hydrophilic layer has the function of an image forming layer and the hydrophilic layer and the image forming layer are the same layer is also known. In this case, an image is formed at a location where energy is applied, and the location where energy is not applied becomes hydrophilic and is removed in the process of producing a lithographic printing plate. The image forming layer 103 is mainly composed of an alkaline water-soluble resin and preferably contains a photopolymerization initiator, and is formed by applying and drying an image forming layer forming coating solution using an organic solvent. The protective layer 104 preferably contains a water-soluble polymer compound, and is formed by applying and drying a protective layer-forming coating solution using an organic solvent.

  An intermediate layer may be provided between the aluminum support and the hydrophilic layer in order to improve the adhesion of the hydrophilic layer. Further, an intermediate layer may be provided between the hydrophilic layer and the image forming layer in order to improve adhesion. Moreover, you may provide a back surface layer in the back side of an aluminum support body.

  The thickness of the hydrophilic layer is preferably 0.5 μm to 10 μm in consideration of film strength, printing durability, printing stain, and the like. The thickness of the image forming layer is preferably 0.2 μm to 5 μm in consideration of printing durability, developability and the like. The thickness of the protective layer is preferably 1 μm to 3 μm in consideration of oxygen barrier properties, protection of the image forming layer, removability of the protective layer, and the like. The thickness of the back layer is preferably 0.2 μm to 5 μm in consideration of the holding power of the mat material, the registerability, and the like.

  It is preferable to provide an antistatic layer on the side of the aluminum support on which the hydrophilic layer is provided, on the opposite side, or on both sides. In the case where the antistatic layer is provided between the aluminum support and the hydrophilic layer, it also contributes to improving the adhesion with the hydrophilic layer.

  FIG. 2 is a schematic diagram of a production process for producing a positive planographic printing plate material.

  In the figure, 2 indicates a manufacturing process. The manufacturing apparatus 2 includes an aluminum support supply process 201, a first coating process 202, a first drying process 203, a second coating process 204, a second drying process 205, a slip sheet overlaying process 206, and a cutting process 207. And an aging preparation step 208 and an aging treatment step 209.

  From the aluminum support supply step 201, the grain-like treatment wound around the winding core 201a is performed, and the strip-shaped aluminum support 201c is fed out from the roll-shaped aluminum support 201b coated with polyvinyl alcohol and formed with a hydrophilic layer. .

  The first coating step 202 was applied to the coating liquid container 202a, the pickup roll 202c for coating the coating liquid 202b for forming an image forming layer on the strip-shaped aluminum support 201c, and the strip-shaped aluminum support 201c excessively. A coating apparatus 202e having a bar 202d for scraping off the coating liquid is used. A coating film for forming an image forming layer is formed on the belt-like aluminum support 201c by the coating device 202e. This figure shows a case where a so-called bar coating device is used, but the type of the coating device is not particularly limited. For example, a dip coating device, a roller coating device, a fountain coating device, a gravure coating device, a blade coating device, a slide coating device. Examples thereof include an apparatus and an extrusion coating apparatus. It is possible to select and use as appropriate according to the coating liquid to be used.

  In the first drying step 203, a drying device 203a is used. In the drying device 203a, the amount of solvent in the coating film for the image forming layer formed on the strip-shaped aluminum support 201c is adjusted as necessary to dry, and an image forming layer is formed. The inside of the drying apparatus 203a may be partitioned in order to remove the solvent step by step. The solvent is preferably recovered for environmental protection and solvent reuse. There is no particular limitation on the drying method in the drying apparatus 203a, and examples include hot air drying, far infrared drying, combined use of hot air drying and far infrared drying, etc., but considering drying efficiency, process shortening, and process compactness. It is preferable to perform far infrared drying.

The drying conditions are set according to the solvent used and the amount of the coating solution, but the time from application to the residual solvent amount of 100 mg / m ² or less is homogeneous as the constituent components in the coating film for the image forming layer move. Image forming layer coating, the fine structure formed during the anodic oxidation of the aluminum support, the components of the image forming layer enter more than necessary, and the photosensitive layer is not easily removed. In view of uniform drying of the coating film, it is preferable to carry out under conditions that are 10 seconds or less. Preferably, it is 5 seconds or less and 2 seconds or more. The drying temperature of the image forming layer is preferably in the range of 60 ° C to 160 ° C, more preferably in the range of 80 ° C to 140 ° C, and particularly preferably in the range of 90 ° C to 120 ° C. As the far-infrared heater used as the far-infrared drying apparatus, a panel-shaped, tubular, or lamp-shaped one is used, and a panel-shaped ceramic far-infrared heater is preferable from the viewpoint of uniformly drying the entire drying surface.

  The second coating step 204 includes a coating liquid container 204a, a pickup roll 204c for coating the protective layer forming coating liquid 204b on the image forming layer formed on the band-shaped aluminum support 201c, and an excessive image. A coating device 204e having a bar 204d for scraping off the coating solution coated on the forming layer is used. A coating film for forming a protective layer is formed on the image forming layer formed in the first drying step 203 by the coating device 204e. This figure shows a case where a so-called bar coating device is used, but the type of the coating device is not particularly limited. For example, a dip coating device, a roller coating device, a fountain coating device, a gravure coating device, a blade coating device, a slide coating device. Examples thereof include an apparatus and an extrusion coating apparatus. It is possible to select and use as appropriate according to the coating liquid to be used.

  The second drying step 205 uses a drying device 205a. The protective layer is formed by adjusting and drying the amount of the solvent in the protective layer-forming coating film as necessary using the drying device 205a. The drying process may be partitioned in the drying apparatus 205a in order to remove the solvent step by step. At this stage, a strip-shaped planographic printing plate material before aging is produced.

  As a drying condition in the second drying step 205, a drying apparatus (not shown) using far infrared rays as a drying means is used, and the temperature during drying is in the image forming layer with respect to the drying temperature of the image forming layer. 15 ° C. to 50 ° C. in consideration of leaching of the alkaline water-soluble resin contained in the protective layer, removal of the protective layer, quality stability of the finished lithographic printing plate material, residual amount of solvent in the protective layer, etc. A low temperature is preferable.

  The surface temperature of the protective layer during drying is kept at 45 ° C. to 70 ° C. in consideration of downsizing production equipment, productivity, quality stability of the image forming layer, and the time is 20 seconds to 90 seconds. It is preferable to dry.

  In the slip sheet superimposing step 206, a slip sheet feeder (not shown) is used to protect and stack the strip-shaped aluminum support 201c (hereinafter referred to as strip-shaped positive planographic printing plate material) on which a protective layer is formed. This is a step of stacking an interleaf paper 206a on the protective layer for preventing sticking between the protective layer and the back surface of the belt-like positive planographic printing plate material. The interleaving interleaving step is preferably 40% RH to 80% RH in consideration of aging processability, performance stabilization, prevention of sticking, and the like. The temperature is preferably 15 ° C to 30 ° C.

  As shown in this figure, the interleaving paper can be overlapped on a protective layer while feeding the interleaving paper rolled in advance, or it can be cut on a positive lithographic printing plate material that has been cut in advance. Although there is a method of combining the interleaving sheets, a method of continuously cutting the interleaving sheets after production is preferably used from the viewpoint of production efficiency. When the positive planographic printing plate material and the slip sheet are combined, a method of charging the slip sheet and improving the adhesion to the plate is also preferably used.

  The cutting process 207 uses a cutting device 207a and a collection device 207b. In the cutting device 207a, the interleaf paper 206a is cut to a required size while being stacked on the protective layer, and is collected by the collecting device 207b. The method of collecting is not particularly limited, and for example, it may be manually stacked on the collection table 207c or automatically stacked on the collection table 207c. When stacking on the collection table 207c, the collection table 207c is placed on an apparatus having a vertical movement function, and the height of the uppermost positive planographic printing plate material on the collection table 207c and the collection apparatus 207b. Are preferably always equal. Reference numeral 301 denotes a positive-type planographic printing plate material that has been cut into a single-wafer state. The positive-type planographic printing plate material is a stack 3 that is stacked on the collection table 207c and has a rectangular parallelepiped shape.

  Since the cutting device 207a differs in the cutting method depending on the width of the produced positive planographic printing plate material and the required size of the positive planographic printing plate material, the type of the cutting device 207a provided also differs. In order to obtain a plurality of positive lithographic printing plate materials from a wide positive lithographic printing plate material, for example, there is a method of cutting in the vertical direction as the first stage and cutting in the horizontal direction in the second stage. . In this case, two units, a vertical cutting device (slitter) and a horizontal cutting device are required. Further, when obtaining a single sheet size positive type lithographic printing plate material, only the cutting device for the horizontal direction is used. This figure shows the case of obtaining a single-size sheet-type positive planographic printing plate material. The temperature and humidity in the cutting step 207 are preferably the same as those in the slip-sheet superimposing step 206.

  The aging preparation step 208 uses a coating device (not shown) and a position regulating member fixing device (not shown). After covering the integrated body 3 with a covering member by a covering device (not shown), a position restricting member is arranged on the four corners in the vertical direction from above the covering member, and the periphery of the integrated body is positioned above the position restricting member. It is fixed with at least one fastening belt by a fixing device (not shown). Thereafter, it is conveyed to an aging process step 209. Note that the temperature and humidity in the aging preparation step 208 are preferably the same as those in the slip sheet overlapping step 206. The aging preparation step 208 may be arranged continuously with the cutting step 207. A specific form of the aggregate 3 prepared in the aging preparation step 208 will be described with reference to FIGS.

  In the aging treatment step 209, an aging treatment chamber 209a capable of temperature control is used. The aggregate 3 prepared in the aging preparation step 208 is subjected to an aging process in an aging process chamber 209a, and a positive planographic printing plate material is produced. The present invention relates to an aging treatment method for this positive planographic printing plate material assembly.

  The aging treatment conditions cannot be uniquely defined because the conditions vary depending on the type of the positive planographic printing plate material, but it is generally said that heating at 50 ° C. or more for 12 hours or more is preferred. There is no particular limitation on the method of heating the aging treatment chamber 209a to 50 ° C. or higher. For example, heated air may be used, and a method of irradiating infrared rays may be used. However, it is preferable not to blow air of 50 ° C. or higher directly on the accumulation body, but to dispose a temperature distribution by providing an air agitator inside the aging treatment chamber 209a.

  FIG. 3 is an enlarged schematic view of a portion indicated by P in FIG.

  The stacked body 3 is in a state in which an interleaf paper 206 a is sandwiched between the sheet-like positive lithographic printing plate material 301 and the sheet-like positive lithographic printing plate material 301. Note that the stack 3 is stacked with the image forming layer facing upward. The number of sheets is preferably 500 to 2000 in consideration of aging stability, workability, durability and stability of the loading platform.

  The material of the interleaf is not particularly limited, for example, paper, chemical fiber paper, non-woven fabric, plastic sheet or film, or laminate sheet or film having a resin layer on one or both sides of paper, positive type Examples include those containing microcapsule particles on the surface of the lithographic printing plate material that contacts the image forming layer side. Among these, particularly preferable slip sheets include slip sheets in which microcapsule particles are contained on the surface of the positive lithographic printing plate material that contacts the image forming layer side. Hereinafter, a description will be given with respect to a slip sheet in which microcapsule particles are contained on the surface of the positive planographic printing plate material on the side in contact with the image forming layer side.

  Having the microcapsule particles on the surface means that the microcapsule particles are present in a region from the outermost surface of the slip sheet to a position having a depth of 20 μm inside the slip sheet. Examples of the method for causing the microcapsule particles to exist in this region include a method of providing a layer containing the microcapsule particles and a method of attaching the microcapsule particles by powder coating or the like. Among these, a method of providing a layer containing microcapsule particles is preferably used.

  The average particle size of the microcapsule particles contained on the surface is preferably 0.1 μm to 30.0 μm, more preferably 0.5 μm to 20 μm, further preferably 2.0 μm to 10 μm, from the viewpoint of scratch resistance and ease of handling of the laminate. 0.0 μm is particularly preferable.

  The average particle size is a number average value obtained by measuring the particle size of 100 microcapsule particles. The particle diameter refers to an average value of the maximum diameter and the minimum diameter of the projected view observed with an electron microscope.

The amount of the microcapsule particles present on the surface of the interleaving paper is preferably 10 ⁸ particles / m ² to 10 ¹¹ particles / m ² .

  The degree of dispersion of the microcapsule particles present on the surface of the interleaving paper is preferably within 90%, particularly preferably within 15%, more preferably within 10%, from the viewpoint of scratch resistance and interleaving properties of the interleaving paper. Preferably there is.

  The degree of dispersion is the measurement of the particle size of 100 microcapsule particles, and the standard deviation and average particle size are determined from the measured particle size and the number thereof, and expressed as (standard deviation / average particle size) × 100. Indicates the value to be processed.

  As a means for reducing the particle size distribution of the microcapsules, it can be appropriately adjusted according to the method of filtering with a filter or the like after preparing the microcapsules described later, the temperature and time during synthesis, the type of active agent and the amount added during synthesis, etc. it can.

Mass per unit area of the stack becomes ^{500kg / m 2 ~2000kg / m 2} , but a state of high stress to the integrated body is applied, this time, when the microcapsule particles are present on the surface of the slip sheet, the photosensitive layer On the other hand, since a fine concavo-convex structure can be formed on the surface, the buffering and protecting action is preferable because it is effective in suppressing the occurrence of film rubbing and scratches due to external force and impact during handling.

  The microcapsule particle is a particle having a microcapsule wall and enclosing a substance in the microcapsule wall. Examples of the material constituting the wall include hydrophilic polymer compounds such as gelatin, gum arabic and hydroxycellulose, urea-formaldehyde or urea formaldehyde-resorcinol compounds, isocyanate polyol compounds, melamine-formaldehyde resins and the like. In addition, as the material to be included, a high boiling point organic solvent, an organic substance dissolved in the high boiling point organic solvent, or the like is preferably used.

  The form of the microcapsule particles may be a core-shell structure in which the substance to be encapsulated is completely separated from the microcapsule wall, or may be a form in which the substance is mixed and contained in the microcapsule wall.

  In the present invention, from the viewpoint of scratch resistance, it is preferable to have a core-shell structure, and the microcapsule particles are particularly preferably soft particles.

  As a method for producing the microcapsule particles, a known method can be applied. For example, as a method for producing microcapsules, US Pat. No. 2,800,547, US Pat. No. 2,800,498, a method using coacervation, US Pat. No. 3,287,154, Japanese Patent Publication No. 38-19574, A method based on an interfacial polymerization method found in US Pat. No. 42-446, a method based on polymer precipitation found in US Pat. Nos. 3,418,250 and 3,660,304, and an isocyanate found in US Pat. No. 3,796,669. Methods using polyol wall materials, methods using isocyanate wall materials found in US Pat. No. 3,914,511, ureas found in US Pat. Nos. 4,001,140, 4,087,376 and 4,089,802 -Formaldehyde or urea formaldehyde A method using a resorcinol-based wall forming material, a method using a wall material such as melamine-formaldehyde resin and hydroxycellulose, as shown in US Pat. No. 4,025,445, and Japanese Patent Publication Nos. 36-9163 and 51-9079. In situ method by monomer polymerization, spray drying method found in British Patent No. 930422, US Pat. No. 3,111,407, electrolytic dispersion cooling found in British Patent Nos. 952807 and 967074 There are laws, but it is not limited to these. Among these, as a particularly preferable method, a microencapsulation method by a coacervation method using gelatin, gum arabic or the like is preferable.

  As a method for producing microcapsule particles, an interfacial polymerization method, an in situ polymerization method, or a microbial microencapsulation method is preferably used. The emulsifier used for the in situ polymerization method encapsulation is preferably a polymer electrolyte. Specifically, styrene-maleic anhydride copolymer, styrene-benzyl methacrylate-maleic anhydride copolymer, α-alkylstyrene-maleic anhydride copolymer, nuclear monoalkyl-substituted styrene-maleic anhydride copolymer, Nuclear dialkyl-substituted styrene-maleic anhydride copolymer, styrene-maleic anhydride monoalkyl ester copolymer, ethylene-maleic anhydride copolymer, polystyrene sulfonic acid, polyacrylic acid, acrylic acid-acrylic acid ester copolymer An aqueous solution such as, or a mixed aqueous solution thereof is used.

  As the emulsifier used for interfacial polymerization encapsulation, an aqueous solution such as polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, various types of starch (such as wheat, potato, corn), or a mixed aqueous solution thereof may be used in addition to the above-mentioned in situ encapsulation. . In addition, a known substance having nonionic, cationic or amphoteric interfacial activity may be added to such an extent that does not cause a problem in the encapsulation process, and it may be used in combination.

  As microcapsule particles, for example, those encapsulating organic substances such as those described below can be preferably used. This is presumably because the following organic substances are dissolved and encapsulated in a high-boiling solvent, so that the microcapsules have an appropriate elasticity and thus have a buffering and protecting action against the pressure applied to the laminate.

  Examples of organic substances include crystal violet lactone, 3-3 bis (P-dimethylaminophenyl) phthalide, and 3- (P-dimethylaminophenyl) -3- (2-methylindol-3-yl) -6-dimethyl. Triallylmethanephthalide series such as aminophthalide and acyl derivatives of benzoyl, anisoyl, bivaloyl, etc. of methylene blue; 3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-7-dibenzylaminofluor There are xanthenephthalide-based compounds such as orane.

  Examples of high-boiling solvents that dissolve organic substances as described above include alkylnaphthalenes represented by diisopropylnaphthalene, diallylalkanes represented by 1-phenyl-1-xylylethane, alkylbiphenyls represented by isopropylbiphenyl, and others. Aromatic hydrocarbons such as triallyldimethanes, alkylbenzenes, benzylnaphthalenes, diallylalkylenes, allylindanes; carboxylic acid ester compounds represented by dibutyl phthalate, dioctyl maleate, etc .; tricresyl phosphate A vegetable oil such as castor oil, soybean oil, cottonseed oil, or a modified oil thereof; a natural product high-boiling fraction (comprising aliphatic hydrocarbons) such as mineral oil, and the like.

  As the material of the interleaving paper, NBKP (coniferous bleached kraft pulp), LBKP (hardwood bleached kraft pulp), NBSP (coniferous sulfite pulp), LBSP (hardwood bleached sulfite pulp), GP (crushed wood pulp), TMP (thermomechanical pulp) Waste paper and the like can be mentioned, and in use, they can be mixed and used at a ratio according to the purpose.

  In addition to the above surface sizing agents, fillers such as kaolin, talc, calcium carbonate and titanium oxide that are usually used in papermaking, dyes, fixing agents, wet paper strength enhancers, dry paper strength enhancers, etc. It can be included. In particular, paper that does not use synthetic pulp can be manufactured at low cost because the material cost is low. Specifically, the bleached kraft pulp is beaten, and the sizing agent is added to the paper stock diluted to a concentration of 4% by weight so that the base paper weight is 0.1% by weight and the paper strength agent is 0.2% by weight. Further, it is a paper made using a paper stock to which aluminum sulfate is added until the pH reaches 5.0.

  In the papermaking method for interleaving paper, a paper machine known in the paper industry such as a long paper machine, a twin-wire paper machine, a combination paper machine, a round paper machine, and a Yankee paper machine can be used as the paper machine.

The basis weight of the interleaving paper is 9 g / m ^{2 to} 60 g / m ² , preferably 35 g / m ^{2 to} 50 g / m in consideration of the stress buffering protection effect of the interleaving paper, interleaving paper transportability in the exposure machine, and handling properties. ² is preferred. The basis weight indicates a value measured according to JIS P8124.

  In consideration of the thickness of the interleaf paper, the total amount in the product form unit, the transportability, the handleability, etc., 42 μm to 80 μm is preferable, and 45 μm to 65 μm is particularly preferable. The thickness indicates a value measured according to JIS P 8118-1998.

The density of the slip ^sheet, preferably ^{0.3g / m 2 ~1.5g / m 2} , particularly preferably ^{0.4g / m 2 ~1.0g / m 2} .

  The moisture content of the interleaving paper is preferably 1% by mass to 10% by mass in consideration of aging stability, adhesion between interleaving papers and the plate surface, and the like. The moisture content is a value measured with a paper moisture meter Moistrex MX8000-T80 manufactured by Infrared Engineering Co., Ltd. under a measurement environment of 23 ° C. and 50% RH.

  The smoothness of the interleaving paper is preferably a different value on the surface side containing the microcapsule particles and on the opposite side. The side of the surface containing the microcapsule particles is preferably 10 to 100 seconds, preferably 15 to 50 seconds, according to the Beck smoothness measuring method defined in JIS8119. On the other hand, the other side is 0.5 seconds to 30 seconds, preferably 2 seconds to 10 seconds, according to the Beck smoothness measuring method specified in JIS8119. Thus, by making the smoothness different between the surface containing the microcapsule particles and the opposite side, the stress buffering protection effect on the image forming layer of the slip sheet is more effective.

  The air permeation resistance is preferably 60 seconds to 120 seconds in consideration of the suction property of the interleaf removal mechanism in the exposure machine. The value of the air resistance is a value measured according to JIS P 8117.

  As a method of providing a layer containing microcapsule particles on the surface of the slip paper, in addition to size press, gait coater, film transfer coater, various coaters such as rod coater, air knife coater, curtain coater contain microcapsules. The coating method is a coating method. From the viewpoint of cost, it is desirable to attach it with a size press, a gait coater, a film transfer coater or the like installed in the paper machine and to perform surface treatment on-machine.

  As the coating liquid containing microcapsule particles, a solution obtained by dissolving or dispersing microcapsule particles in water together with a latex binder, a water-soluble binder, and a protective agent can be used as necessary. A binder / protective agent having a concentration of 10 to 60% by mass is preferably used.

  The mixing ratio of the microcapsule / binder / protectant is generally 5 parts by mass or more, preferably 10 parts by mass to 70 parts by mass, more preferably 30 parts by mass with respect to 100 parts by mass of the microcapsules. The proportion of the binder and the protective agent is preferably 50 parts by mass to 200 parts by mass with respect to 100 parts by mass of the binder.

  Specific examples of the latex binder include styrene-butadiene copolymer latex, acrylonitrile-butadiene copolymer latex, vinyl acetate, acrylic latex and the like, and alkali thickening latexes thereof.

  As the water-soluble binder, generally known water-soluble polymer compounds as shown below can be used. For example, gelatin, albumin, casein, starch, pregelatinized starch, oxidized starch, etherified starch, esterified starch, sodium alginate, arabic gum, carboxymethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polyacrylamide, ethylene-maleic anhydride Examples thereof include natural, synthetic or semi-synthetic polymer compounds such as copolymers, isobutylene-maleic anhydride copolymers, styrene-maleic anhydride copolymers, methyl vinyl ether-maleic anhydride copolymers, and methylcellulose. These can also be mixed and used.

  As the capsule protective agent (stilt), wheat starch granules, corn starch granules, pea starch granules, various plastic pigments, pulp powders and the like are preferable, and the size (average diameter) is preferably in the range of 1 μm to 100 μm. Especially preferably, the range of 5 micrometers-30 micrometers is preferable. When a white pigment is added to the microcapsule-containing layer, for example, calcium carbonate, aluminum hydroxide, zinc oxide, titanium oxide, kaolin, talc and the like can be used.

  FIG. 4 is a schematic view showing an example of a positive planographic printing plate material assembly prepared in the aging preparation step shown in FIG. FIG. 4A is a schematic perspective view showing an example of a positive planographic printing plate material assembly prepared in the aging preparation step shown in FIG. FIG. 4B is a schematic front view of the positive planographic printing plate material assembly shown in FIG.

  In the figure, reference numeral 4 denotes a covering member that covers the assembly 3. By covering with a covering member, during the aging process, a uniform supply of moisture from the interleaving paper to the positive type lithographic printing plate material and a uniform transfer of heat are made, and a uniform aging of the positive type lithographic printing plate material is possible It has become. The place covered with the covering member 4 may be the side surface around the aggregate 3 or the whole aggregate 3, but the side surface around the aggregate 3 is preferable in consideration of workability and aging effects.

  Reference numerals 302 a to 302 d denote four corners of the integrated body 3. Reference numeral 303 a denotes a position restricting member disposed at a corner 302 a in the vertical direction of the stack 3. Reference numeral 303 b denotes a position restricting member disposed at a corner 302 b in the vertical direction of the stack 3. Reference numeral 303 c denotes a position restricting member disposed at a corner 302 c in the vertical direction of the stack 3. Reference numeral 303 d denotes a position restricting member disposed at a corner 302 d in the vertical direction of the stack 3. The position restricting members 303a to 303d are preferably disposed from above the covering member 4 from the viewpoint of improving the adhesion of the covering member 4 to the periphery of the assembly 3. As the position restricting members 303a to 303d, it is preferable to use equilateral L-shaped angles. The material used for the position restricting members 303a to 303d is not particularly limited as long as it has a strength that can prevent displacement of the integrated body 3, and examples thereof include metals (for example, iron, aluminum, and the like), resins, and the like.

  O indicates the width of one side of the position restricting member 303a, and the other three position restricting members 303b to 303d preferably have the same width. The width O of the side surface of the aggregate covered with the four position regulating members 303a to 303d is 5% to 40% in consideration of heat transfer inhibition in an aging environment, stability of the aggregate, and the like. It is preferable to set as described above.

  304 a and 304 b are provided from above the position restricting members 303 a to 303 d around the stack 3 in order to fix the position restricting members 303 a to 303 d disposed at the four corners 302 a to 302 d in the vertical direction of the stack 3. The tightening belt is shown. The number of the fastening belts is preferably determined by the height of the integrated body 3, and at least one is required. This figure shows the case where two fastening belts are used.

  The material used for the tightening belt is not particularly limited as long as it has strength to suppress the movement of the position restricting members 303a to 303d by the pressure applied to the position restricting members 303a to 303d as the integrated body 3 moves, and examples thereof include metals and resins. It is done.

  P indicates the width of the fastening belt 304a. The width P may be set so that the area of the side surface of the assembly covered with the fastening belt 304a is 5% to 15% in consideration of the stability of the position restricting member and the assembly, heat conductivity, and the like. preferable. When a plurality of tightening belts are used, it is preferable that the width of the tightening belt is equally divided so that the area of the side surface of the assembly to be coated is 5% to 25%.

  By fixing the placement restricting members 303a to 303d with the fastening belt 304a (304b), the movement of the sheet-like positive planographic printing plate material 201h in the integrated body 3 can be restricted, and the occurrence of scratches. Can be prevented.

  Reference numeral 5 denotes a carriage for transporting the integrated body 3, and casters 501 are provided at four corners of the bottom to give a degree of freedom to the direction of movement of the carriage.

  Reference numeral 6 denotes a vibration isolating member disposed between the cart 5 and the collection table 207c. By using the vibration isolating member 6, for example, the vibration when moving the carriage to the aging treatment chamber 209 a (see FIG. 2) is absorbed, and the sheet-like positive type lithographic printing plate material 301 is accumulated in the assembly 3. This is preferable because the movement can be restricted. The vibration isolator 6 can be used as necessary.

  The area of the vibration isolating member is preferably 10% to 150% with respect to the area of the positive planographic printing plate material in consideration of heat transfer, adhesion, weighted uniformity and the like.

  The vibration absorbing capacity of the vibration isolating member 6 is preferably 10 ° C. to 40 ° C. and the vibration frequency is 30 Hz to 100 Hz in consideration of vibration load, collision, loading / unloading load, etc. during work.

The positive planographic printing plate material assembly when performing the aging treatment shown in this figure can be produced by the following method.
1. When collecting the sheet-like positive planographic printing plate material cut together with the interleaf paper 206a in the cutting step 207 of the manufacturing step 2 shown in FIG. It is placed on the carriage 5 through the vibration member 6. Then, after covering the surrounding surface of the accumulation body 3 with a covering member, the placement regulating members 303a to 303d are arranged at four corners in the vertical direction of the accumulation body 3 and fixed with a fastening belt to perform an aging process. A positive lithographic printing plate material assembly is produced as it is performed. The place covered with the covering member and the place where the placement restricting members 303a to 303d are disposed and fixed with the fastening belt are preferably near the cutting step 207 from the viewpoint of preventing the displacement of the accumulated body.
2. When the sheet-like positive planographic printing plate material cut together with the interleaf paper 206a in the cutting step 207 of the manufacturing step 2 shown in FIG. 2 is collected, the carriage 5 on which the collection stand 207c is placed via the vibration isolating member 6 is used. prepare. The carriage 5 is placed on a device having a vertical movement function, and a stacked assembly is produced so that the height of the uppermost planographic printing plate material on the collection table 207c and the collection device 207b are always equal. Thereafter, the carriage 5 is removed from the device having the up-and-down movement function, the side surfaces around the integrated body 3 are covered with a covering member, and the placement regulating members 303 a to 303 d are arranged at the four corners in the vertical direction of the integrated body 3. The positive lithographic printing plate material assembly when the aging treatment is performed by installing and fixing with a fastening belt is produced. The place covered with the covering member and the place where the placement restricting members 303a to 303d are disposed and fixed with the fastening belt are preferably near the cutting step 207 from the viewpoint of preventing the displacement of the accumulated body.

  FIG. 5 is a schematic sectional view taken along the line AA ′ of FIG.

  In the figure, Q indicates the thickness of the vibration isolation member 6. The thickness Q is preferably 10 mm to 50 mm in consideration of workability, stability of the integrated body, maintaining the flatness of the plate surface, and the like. There is no particular limitation on the vibration-proof member. For example, chloroprene rubber (CR), ethylene-propylene rubber (EP-DM), styrene-butadiene rubber (SBR), nitrile rubber (NBR), natural rubber (NR), urethane, neoprene , Silicon and the like, and can be selected and used from among commercially available products.

The covering member 4 is not particularly limited as long as it has a low water vapor permeability and adheres closely. Water vapor permeability of the covering member 4, aging stability, particularly considering the water retention and the like on the side surface of the stack, ^7g / m 2 / 24hr or less well, and more preferably, less preferably ^2g / m ² / 24hr . The water vapor transmission rate is a water vapor transmission rate measured by a measurement method described in JIS K7129-1992.

  As the material used for the covering member 4, various materials described in the new development of functional packaging materials (Toray Research Center, Inc.) can be used. For example, polyethylene resin, polypropylene resin, polyethylene terephthalate system Examples thereof include resins, polyamide resins, ethylene-vinyl alcohol copolymer resins, ethylene-vinyl acetate copolymer resins, acrylonitrile-butadiene copolymer resins, cellophane resins, vinylon resins, and vinylidene chloride resins. Resins such as polypropylene resins and nylon resins may be stretched and further coated with a vinylidene chloride resin. In addition, a polyethylene resin having a low density or a high density can be used.

  Among the above polymer materials, nylon (Ny), nylon (KNy) coated with vinylidene chloride (PVDC), unstretched polypropylene (CPP), stretched polypropylene (OPP), polypropylene coated with PVDC (KOP), polyethylene Use of terephthalate (PET), PVDC-coated cellophane (KPT), polyethylene-vinyl alcohol copolymer (Eval), low density polyethylene (LDPE), high density polyethylene HDPE, linear low density polyethylene (LLDPE) preferable. Of these thermoplastic films, a multilayer film made by coextrusion with a different type of film, a multilayer film made by laminating at different stretching angles, and the like can be used.

  In addition, a polymer material bonded to an aluminum foil on these thermoplastic films and a polymer material having a deposited layer on which an inorganic compound is deposited can also be used. Thin film handbooks p879-p901 (Japan Society for the Promotion of Science), vacuum technology handbooks p502-p509, p612, p810 (Nikkan Kogyo Shimbun), vacuum handbook revised editions p132-p134 (ULVAC Japan Vacuum Technology KK) Inorganic membranes as described in (1).

Examples of the inorganic film include a metal vapor-deposited film and an inorganic oxide vapor-deposited film. The metal deposited film, for example _{ZrN, SiC, TiC, Si 3} N 4, a single crystal Si, ZrN, PSG, amorphous Si, W, aluminum and the like, and particularly preferred metal vapor deposition film include, for example, aluminum .

For example, SiO _x (x: 1 or 2), Cr ₂ O ₃ , Ta ₂ O ₃ , AI ₂ O ₃ or the like is used as the inorganic oxide vapor deposition film. Among these, preferable inorganic oxide vapor deposition films include SiO _x (x: 1 or 2) and AI ₂ O ₃ in view of the strength of the vapor deposition film.

  When the side surface of the aggregate is covered with these covering members, it is preferable that the sheet-like positive planographic printing plate material is closely adhered so that the temperature rises uniformly. The thickness of the covering member 4 is preferably 10 μm to 100 μm, more preferably 20 μm to 80 μm, in consideration of handleability and adhesion to the side surface of the aggregate. After covering the side surface of the aggregate with the covering member 301, it is desirable to stop the end of the covering member 4 with a tape or the like.

  FIG. 6 is a schematic perspective view showing another example of the positive-type planographic printing plate material assembly prepared in the aging preparation step shown in FIG. The reference numerals in the figure are the same as those in FIG.

A positive planographic printing plate material assembly when performing the aging process shown in FIG. The only difference from the positive lithographic printing plate material assembly when performing the aging treatment shown in FIG. 4 is that the assembly 3 is directly placed on the vibration isolating member 6, and the others are the same. is there. The positive planographic printing plate material assembly when performing the aging treatment shown in this figure can be produced by the following method.
1. When the sheet-like positive planographic printing plate material cut together with the interleaf paper 206a in the cutting process 207 of the manufacturing process 2 shown in FIG. 2 is collected, it is placed on the vibration isolating member 6 placed on the collection table 207c. After forming the stacked assembly 3, it is placed on the carriage 5. The subsequent process is the same as the method 1 for producing a positive planographic printing plate material assembly when performing the aging process shown in FIG.
2. When the sheet-like positive planographic printing plate material cut together with the interleaf paper 206a in the cutting process 207 of the manufacturing process 2 shown in FIG. 2 is collected, the carriage 5 on which the collection base 207c on which the vibration isolating member 6 is placed is placed. Prepare. The cart 5 is mounted on a device having a function of moving up and down, and a stacked assembly is produced so that the height of the uppermost planographic printing plate material on the collection table 207c and the height of the collection device 207b are always equal. The subsequent process is the same as the method 1 for producing a positive planographic printing plate material assembly when performing the aging process shown in FIG.

A positive planographic printing plate material assembly when performing the aging treatment shown in (b) will be described. The difference from the positive planographic printing plate material assembly when performing the aging process shown in FIG. 4 is that the assembly 3 is directly mounted on the carriage 5 without using the collection table 207c. It is only mounted on the member 5, and others are the same. The positive planographic printing plate material assembly when performing the aging treatment shown in this figure can be produced by the following method.
1. When collecting the sheet-like positive planographic printing plate material cut together with the interleaf paper 206a in the cutting step 207 of the manufacturing step 2 shown in FIG. 2, the carriage 5 on which the vibration isolating member 6 is placed is prepared. The carriage 5 is placed on a device having a vertical movement function, and a stacked assembly is produced so that the height of the uppermost planographic printing plate material on the collection table 207c and the collection device 207b are always equal. The subsequent process is the same as the method 1 for producing a positive planographic printing plate material assembly when performing the aging process shown in FIG.

A positive planographic printing plate material assembly when performing the aging treatment shown in (c) will be described. The difference from the positive lithographic printing plate material assembly when performing the aging treatment shown in FIG. 4 is that the assembly 3 is directly mounted on the vibration isolation member 6 and the vibration isolation member 6 is integrated. It is arranged only at the four corners of the body 3 and the others are the same. The positive planographic printing plate material assembly when performing the aging treatment shown in this figure can be produced by the following method.
1. When the sheet-like positive lithographic printing plate material cut together with the interleaf paper 206a in the cutting step 207 of the manufacturing process 2 shown in FIG. 2 is collected, four corners of the sheet-like positive lithographic printing plate material are placed. Then, sheet-like positive planographic printing plate materials are stacked on the vibration isolating member 6 placed on the collection table 207c to form the stacked body 3 and then placed on the carriage 5. The subsequent process is the same as the method 1 for producing a positive planographic printing plate material assembly when performing the aging process shown in FIG.
2. When the sheet-like positive lithographic printing plate material cut together with the interleaf paper 206a in the cutting step 207 of the manufacturing process 2 shown in FIG. 2 is collected, four corners of the sheet-like positive lithographic printing plate material are placed. A cart 5 on which a recovery table 207c on which a vibration isolating member 6 is mounted is mounted. The cart 5 is placed on a device having a function of moving up and down, and stacked so that the surface of the uppermost planographic printing plate material on the collecting table 207c and the collecting device 207b are always equal in height. . The subsequent process is the same as the method 1 for producing a positive planographic printing plate material assembly when performing the aging process shown in FIG.

  In the form shown in FIGS. 4 to 6, the aging process can be performed at the set temperature and time by entering the aging process chamber 209 a shown in FIG. 2.

The following effects can be obtained by placing in an aging treatment chamber in the form shown in FIGS. 4 to 6 and performing an aging treatment at a set temperature and time.
1) It is possible to prevent vibration caused by loading and unloading of the aggregates into the aging treatment chamber, and deviation of the aggregates caused by handling, and aging treatment can be performed while preventing generation of scratches. The quality of positive lithographic printing plate materials can be improved.
2) Since the generation of scratches can be prevented, the yield can be improved and the production efficiency can be improved.
3) Efficient production became possible with little yield loss.
4) Reduction of working time for aging was achieved.

  Next, a positive planographic printing plate material related to the aging method of the present invention will be described.

(Aluminum support)
Examples of the aluminum support include a pure aluminum plate or an aluminum alloy plate. Various aluminum alloys can be used, for example, alloys of aluminum with metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, iron, etc. The aluminum plate manufactured by the method 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 aluminum support preferably has a roughened surface. Prior to roughening (graining treatment), it is preferable to perform a degreasing treatment in order to remove the rolling oil on the surface. 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. An alkaline aqueous solution such as caustic soda can also 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.

  Next, a roughening process is performed. Examples of the roughening method include a mechanical method and a method of etching by electrolysis. In the present invention, AC electrolytic surface roughening treatment in an electrolyte mainly composed of hydrochloric acid is preferable, but prior to that, mechanical surface roughening treatment and electrolytic surface roughening treatment mainly composed of nitric acid may be performed.

The mechanical roughening method 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, rotating a rotating brush using brush hair having a diameter of 0.2 mm to 0.8 mm, and, for example, volcanic ash particles having a particle diameter of 10 μm 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 μm to 100 μm in water, injecting pressure from a nozzle, and causing the surface to collide obliquely with the support surface. I can do it. Further, for example, on the substrate surface, the abrasive particles having a particle diameter of 10 to 100 [mu] m, at intervals of 100 m to 200 m, 2.5 × 10 ³ cells ^/ cm 2 to 10.0 × 10 ³ cells / cm ² density It is also possible to perform roughening by laminating the coated sheets so as to exist and transferring the rough surface pattern of the sheet by applying pressure.

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 amount of aluminum dissolved on the surface is preferably 0.5 to 5.0 g / m ² . 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 electrolytic surface roughening treatment mainly composed of nitric acid 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. The current density can be in the range of 10 A / dm ^{2 to} 200 A / dm ² , but is preferably selected from the range of 20 A / dm ^{2 to} 100 A / dm ² . The quantity of electricity can be used range of 5000 C / dm ^2, preferably selected from the range of ^{100C / dm 2 ~2000C / dm 2} . The temperature at which the electrochemical surface roughening method is performed can be in the range of 10 ° C to 50 ° C, but is preferably selected from the range of 15 ° C to 45 ° C. The concentration of nitric acid in the electrolytic solution is preferably 0.1% by mass to 5.0% by mass. If necessary, nitrate, chloride, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, aluminum ions, etc. can be added to the electrolytic solution.

After the electrolytic surface-roughening treatment mainly composed of nitric acid, 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 plate ^{surface, 0.5g / m 2 ~5.0g / 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.

In the AC electrolytic surface roughening treatment in an electrolytic solution mainly composed of hydrochloric acid, the hydrochloric acid concentration is 5 g / l to 20 g / l, preferably 6 g / l to 15 g / l. The current density was ^{15A / dm 2 ~120A / dm 2} , preferably from ^{20A / dm 2 ~90A / dm 2} . The quantity of electricity was ^{400C / dm 2 ~2000C / dm 2} , and preferably ^{500C / dm 2 ~1200C / dm 2} . The frequency is preferably in the range of 40 Hz to 150 Hz. The temperature of the electrolytic solution can be in the range of 10 ° C to 50 ° C, but is preferably selected from the range of 15 ° C to 45 ° C. If necessary, nitrate, chloride, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, aluminum ions, etc. can be added to the electrolytic solution.

After the electrolytic surface roughening treatment is performed in the above-described electrolytic solution mainly composed of hydrochloric acid, it is preferably immersed in an aqueous solution of acid or alkali 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 plate ^{surface, 0.5g / m 2 ~2.0g / 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 arithmetic average roughness (Ra) of the surface of the resulting aluminum support on the photosensitive layer side is preferably 0.4 μm to 0.6 μm, and is controlled by a combination of hydrochloric acid concentration, current density, and electric quantity in the roughening treatment. I can do it.

Following the roughening treatment, an anodizing treatment is performed to form an anodized film. The anodizing method is preferably carried out using sulfuric acid or an electrolytic solution mainly composed of sulfuric acid as the electrolytic solution. The concentration of sulfuric acid is preferably 5% by mass to 50% by mass, and particularly preferably 10% by mass to 35% by mass. The temperature is preferably 10 ° C to 50 ° C. The treatment voltage is preferably 18V or more, and more preferably 20V or more. The current density is preferably 1 A / dm ^{2 to} 30 A / dm ² . Quantity of electricity 200C ^/ dm ² ~600C ^/ dm 2 is preferred.

Coated amount of the formed anodization film is ^{preferably 2g / m 2 ~6g / m 2} , preferably ^{3g / m 2 ~5g / m 2} . The anodic oxidation coating amount is obtained by, for example, immersing an aluminum plate in a chromic phosphate solution (produced by dissolving 85% phosphoric acid solution: 35 ml, chromium oxide (IV): 20 g in 1 L of water), dissolving the oxide coating, It is calculated | required from the mass change measurement etc. before and after melt | dissolution of the coating. Although the anodized film micropores is created, the density of the micropores is preferably from 400 pieces / [mu] m ² to 700 pieces / [mu] m ^2, more preferably 400 pieces / [mu] m ² to 600 pieces / [mu] m ^2.

  The anodized support may be sealed as necessary. These sealing treatments can be performed using a known method such as hot water treatment, boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment, ammonium acetate treatment.

<Hydrophilic treatment>
From the viewpoint of chemical resistance and sensitivity, it is preferable to perform a hydrophilic treatment after the roughening treatment and the anodizing treatment. Hydrophilization treatment is not particularly limited, but water-soluble resins such as phosphonic acids having amino groups such as polyvinylphosphonic acid, polyvinyl alcohol and derivatives thereof, carboxymethylcellulose, dextrin, gum arabic, 2-aminoethylphosphonic acid, sulfonic acid Polymers and copolymers having a group in the side chain, polyacrylic acid, a water-soluble metal salt (for example, zinc borate), a yellow dye, an amine salt or the like can be used.

  Furthermore, a sol-gel treated substrate in which a functional group capable of causing an addition reaction by a radical as disclosed in JP-A-5-304358 is covalently used. It is preferable to perform a hydrophilic treatment with an aqueous solution containing polyvinylphosphonic acid.

  The 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 the dip type, it is preferable to treat polyvinylphosphonic acid with an aqueous solution of 0.05% to 3.00%. The treatment temperature is preferably 20 ° C. to 90 ° C., and the treatment time is preferably 10 seconds to 180 seconds. After the treatment, it is preferable to perform a squeegee treatment or a water washing treatment in order to remove excessively laminated polyvinylphosphonic acid. Furthermore, it is preferable to perform a drying process.

  As drying temperature, 40 to 180 degreeC is preferable, More preferably, it is 50 to 150 degreeC. The drying treatment is preferable because the adhesion to the lower layer and the function as a heat insulating layer are improved, and the chemical resistance and sensitivity are improved.

  The film thickness of the hydrophilic treatment layer is preferably 0.002 μ to 0.100 μ, more preferably 0.005 μ to 0.050 μ from the viewpoints of adhesiveness, heat insulation, and sensitivity.

(Image forming layer)
The image forming layer contains an alkali-soluble resin and a photothermal conversion compound and can form a positive image by image exposure. An embodiment in which the image forming layer further contains an acid generator and an acid-decomposable compound is a preferred embodiment.

(Alkali-soluble resin)
The alkali-soluble resin is a resin that dissolves in an aqueous potassium hydroxide solution having a pH of 13 at 25 g / l or more at 25 ° C. As the alkali-soluble resin, a novolak resin, an acrylic resin, or an acetal resin is preferably used from the viewpoint of ink inking property, alkali solubility, and the like. The alkali-soluble resin may have a single structure, or two or more kinds may be combined.

(Novolac resin)
The novolak resin is synthesized by condensing various 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 Examples thereof include acrylamide, methacrylamide, acrylic acid ester, methacrylic acid ester, and hydroxystyrene.

  Substituted phenols such as isopropylphenol, t-butylphenol, t-amylphenol, hexylphenol, cyclohexylphenol, 3-methyl-4-chloro-6-t-butylphenol, isopropylcresol, t-butylcresol, 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 1,500 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 2,000 to 10,000, the number average molecular weight is 500 to 10,000, and the dispersity (weight average molecular weight / number average molecular weight) is 1.1 to 5. . By setting it within the above range, the film strength, alkali solubility, chemical solubility, interaction with the photothermal conversion substance, etc. of the novolak resin can be appropriately adjusted, and the effect of uniformity of image reproduction can be easily obtained. The weight average molecular weight of the novolak resin can be adjusted in the upper layer and the lower layer. Since the upper layer is required to have chemical resistance, film strength, etc., the relatively high weight average molecular weight is preferably 2,000 to 10,000. As the weight average molecular weight, a value in terms of polystyrene determined by a gel permeation chromatography (GPC) method using a monodisperse polystyrene of a novolak resin as a standard is adopted.

  As a method for producing a novolak resin, for example, as described in “New Experimental Chemistry Course [19] Polymer Chemistry [I]” (1993, Maruzen Publishing), Item 300, phenol and substituted phenols (for example, xylenol) , Cresols and the like) in a solvent using an acid as a catalyst and an aqueous formaldehyde solution, phenol, the o-position or p-position of the substituted phenol component, and formaldehyde are dehydrated and condensed. 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 novolac resin is dissolved in a water-soluble organic polar solvent, and then water is added to form a precipitate. A novolac 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 makes the total mass of the phenol and the substituted phenol component 60 to 90% by mass, preferably 70 to 80% by mass. 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 carried out 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.

  A novolac resin may be used independently and may use 2 or more types together. 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 is preferably 30% by mass to 99% by mass, and 45% by mass to 95% by mass with respect to the solid content of the upper layer from the viewpoint of chemical resistance and printing durability. More preferably, it is most preferably in the range of 60% by mass to 90% by mass.

(acrylic resin)
The acrylic resin 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 thereof include structural units introduced from known monomers such as 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 acrylate DOO, 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 DOO, 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 maleimide, 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.

  The polymerization form of the acrylic resin may be any of random polymer, block polymer, graft polymer, etc., but it should be a block polymer capable of phase separation of hydrophilic group and hydrophobic group in that the solubility of developer can be controlled. Is preferred. The acrylic resin to be used may be used independently or may be used in mixture of 2 or more types.

(Acetal resin)
The polyvinyl acetal resin can be synthesized by a method in which polyvinyl alcohol is acetalized with an aldehyde and the remaining hydroxy group is reacted with an acid anhydride. Examples of the aldehyde used herein include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, pentylaldehyde, hexylaldehyde, glyoxylic acid, N, N-dimethylformamide di-n-butyl acetal, bromoacetaldehyde, chloroacetaldehyde, 3-hydroxy- Examples include, but are not limited to, n-butyraldehyde, 3-methoxy-n-butyraldehyde, 3- (dimethylamino) -2,2-dimethylpropionaldehyde, cyanoacetaldehyde, and the like.

  As the acetal resin, a polyvinyl acetal resin is preferably used. The acid content of the polyvinyl acetal resin is preferably in the range of 0.5 meq / g to 5.0 meq / g (that is, 84 to 280 in terms of mg of KOH) in terms of sensitivity and development latitude. / G to 3.0 meq / g is more preferable.

  The molecular weight of the polyvinyl acetal resin is preferably about 5000 to 400000, more preferably about 20000 to 300000, as a weight average molecular weight measured by gel permeation chromatography. By adjusting to the above range, film strength, alkali solubility, chemical solubility, etc. can be adjusted, and a positive lithographic material having high sensitivity and excellent image reproduction uniformity can be easily obtained.

  In addition, these polyvinyl acetal resins may be used independently or may be used in mixture of 2 or more types. Acetalization of polyvinyl alcohol can be carried out according to a known method, for example, US Pat. No. 4,665,124, US Pat. No. 4,940,646, US Pat. No. 5,169,898, US Pat. No. 5,700,609, It is described in U.S. Pat. No. 5,792,823, U.S. Pat. No. 09328519, and the like.

  The image forming layer may have a plurality of layers. In this case, for example, in the case of having two layers of the lower layer and the upper layer of the image forming layer, the alkali-soluble resin used for the lower layer is preferably mainly an acrylic resin or an acetal resin in terms of alkali solubility, etc. As the alkali-soluble resin used in the ink, a novolak resin is preferable from the viewpoint of ink inking property.

(Infrared absorbing compound)
The infrared absorbing compound has a light absorption region in the infrared region of 700 nm or more, preferably 750 to 1200 nm, and expresses light / heat conversion ability in light in this wavelength range. 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), “Printing” The pigments described in "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 pigment particle size is preferably in the range of 0.01 μm to 10.00 μm, more preferably in the range of 0.05 μm to 1.00 μm, and particularly preferably in the range of 0.1 μm to 1.0 μm. preferable.

  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).

  From the viewpoint of sensitivity, uniformity of the photosensitive layer and durability, the pigment is 0.01% by mass to 10.00% by mass, preferably 0.10% by mass to 5.0%, based on the total solid content constituting the photosensitive layer. It can be added at a rate of mass%.

(dye)
As the dye, commercially available dyes and known dyes described in literature (for example, “Dye Handbook” edited by the Society of Synthetic Organic Chemistry, 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 include, for example, JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, and JP-A-60. Cyanine dyes described in JP-A-78787 etc., methine dyes described in JP-A-58-173696, JP-A-58-181690, JP-A-58-194595, etc. JP-A-58-112793, JP-A-58-224793, JP-A-59-48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744, etc. Naphthoquinone dyes described, squarylium dyes described in JP-A-58-112792, etc., cyanine dyes described in British Patent 434,875, etc. You can gel. Further, near infrared absorption sensitizers described in US Pat. No. 5,156,938 are also preferably used as dyes, and substituted dyes described in US Pat. No. 3,881,924 are also used. Arylbenzo (thio) pyrylium salt, trimethine thiapyrylium salt described in JP-A No. 57-142645 (US Pat. No. 4,327,169), JP-A No. 58-181051 and No. 58-220143 JP, 59-41363, 59-84248, 59-84249, 59-146063, 59-146061, pyrylium compounds described in JP 59 -216146, the cyanine dye described in U.S. Pat. No. 4,283,475, the pentamethine thiopyrylium salt, and the like Publication, pyrylium compounds disclosed in JP same 5-19702, Epolight 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. Examples of the cyanine dye include paragraph numbers [0017] to [0019] of JP-A No. 2001-133969, paragraph numbers [0012] to [0038] of JP-A No. 2002-40638, and paragraphs of JP-A No. 2002-23360. Nos. [0012] to [0023] can be mentioned.

  From the viewpoint of sensitivity, chemical resistance and printing durability, the infrared absorbing dye is 0.01% by mass to 30.00% by mass, preferably 0.1% by mass to 10% by mass with respect to the total solid content constituting the image forming layer. 0.000% by mass, particularly preferably 0.1% by mass to 5.00% by mass can be added.

(Acid generator)
The acid generator is a compound capable of generating an acid upon image exposure, and includes various known compounds and mixtures. Such as diazonium, phosphonium, sulfonium, and iodonium of _{^{BF 4 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 - , an organic halogen containing compound, ortho-quinone - diazide sulfonyl chloride, and organometallic / organic Halogen compounds can also be used as the acid generator in the present invention. Further, compounds that generate photosulfonic acid by photolysis, such as iminosulfonates described in JP-A-4-365048, etc., disulfone compounds described in JP-A-61-166544, JP-A-50 -36209 (U.S. Pat. No. 3,969,118), o-naphthoquinonediazide-4-sulfonic acid halide, JP-A-55-62444 (UK Patent No. 2038801), or JP-B 1-1935 O-Naphthoquinonediazide compounds described in 1). Examples of other acid generators include sulfonic acid alkyl esters such as cyclohexyl citrate, p-acetaminobenzene sulfonic acid cyclohexyl ester, p-bromobenzene sulfonic acid cyclohexyl ester, and alkyl sulfonic acid esters.

  Examples of the above-mentioned compounds forming hydrohalic acid include U.S. Pat. Nos. 3,515,552, 3,536,489 and 3,779,778, and West Germany. Examples thereof include those described in Japanese Patent Publication No. 2,243,621, and also compounds that generate an acid by photolysis described in, for example, West German Patent Publication No. 2,610,842. Can be used. Further, o-naphthoquinonediazide-4-sulfonic acid halogenide described in JP-A-50-36209 can be used.

  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-A-54-74728, JP-A-55-24113, JP-A-55-77742, and JP-A-60-3626. And 2-halomethyl-1,3,4-oxadiazole compounds described in JP-A-60-138539.

  As other acid generators, for example, a polymerization initiator described in JP-A-2005-70211, a compound capable of generating radicals described in JP-A-2002-537419, JP-A-2001-175006, Polymerization initiators described in JP-A-2002-278057 and JP-A-2003-5363 can be used, and onium salts described in JP-A-2003-76010 have two or more cation moieties in one molecule. JP-A-2001-133966, N-nitrosamine compounds, JP-A-2001-343742, compounds generating radicals by heat, JP-A-2002-6482, compounds generating acids or radicals by heat, Borate compounds disclosed in Japanese Patent Application Laid-Open No. 2002-116539 and heat disclosed in Japanese Patent Application Laid-Open No. 2002-148790. Compound that generates acid or radical, photo or thermal polymerization initiator having polymerizable unsaturated group described in JP-A No. 2002-207293, onium having a divalent or higher anion as a counter ion in JP-A No. 2002-268217 A compound such as a salt, a specific structure sulfonyl sulfone compound disclosed in JP-A No. 2002-328465, or a compound capable of generating a radical by heat disclosed in JP-A No. 2002-341519 can be used as necessary.

  The acid generator may be a polymer having a group capable of generating an acid. It is preferable to use the acid generator as a polymer type because the effects of the alkali-soluble resin and the acid generator can function with one material. For example, by adding an acid-generating group to the above-mentioned acrylic resin, two or more effects such as chemical resistance, sensitivity due to the acid generator, and development latitude of the acrylic resin can be exhibited. The polymer type acid generator is not particularly limited as long as it is a polymer having a group capable of generating an acid. A combined use of a polymer type acid generator and a low molecular type acid generator is a preferred form in order to achieve both effects of the present invention. Specific examples of the compound include compounds shown in Table 1 described in paragraph No. 0046 of JP-A No. 2003-91054.

  The content of these acid generators is usually 0.1% by mass to 30.0% by mass, more preferably 1% by mass with respect to the total solid content of the image forming layer in terms of sensitivity, development latitude, and safelight properties. % To 15% by mass. One acid generator may be used, or two or more acid generators may be mixed and used.

(Acid-decomposable compound)
An acid-decomposable compound is a compound that can be decomposed by an acid generated by an acid generator by image exposure. Specific examples of the acid-decomposable compound include JP-A-48-89003, 51-120714, 53-133429, 55-12995, 55-126236, and 56. Compounds having a C—O—C bond described in JP-A-17345, compounds having a Si—O—C bond described in JP-A Nos. 60-37549 and 60-112446, Other acid-decomposable compounds described in JP-A-60-3625 and JP-A-60-10247 may be mentioned.

  Further, compounds having Si-N bonds described in JP-A-62-222246, carbonates described in JP-A-62-251743, and compounds described in JP-A-62-220951. Ortho-carbonates, ortho-titanates described in JP-A-62-280841, ortho-silicates described in JP-A-62-280842, JP-A-2000-221676 Acetals and ketals, compounds having a C—S bond described in JP-A-62-244038, phenolphthalein, cresolphthalein, and phenolsulfophthalein described in JP-A-2005-91802 And compounds protected with heat or acid-decomposable groups.

  Among these, compounds having at least one acetal or ketal group are preferred from the viewpoint of reaction efficiency with an acid, that is, sensitivity and development latitude.

Also in terms of sensitivity and developability of the _{balance, - (CH 2 CH 2 O} ) n- group (n is an integer of 2 to 5) include compounds having the. Among these compounds, compounds having an ethyleneoxy group chain number n of 3 or 4 are preferred. Specific examples of the compound having the — (CH ₂ CH ₂ O) n— group include condensation production of dimethoxycyclohexane, benzaldehyde and substituted derivatives thereof and any of diethylene glycol, triethylene glycol, tetraethylene glycol and pentaethylene glycol. Things.

  The content of the acid-decomposable compound is preferably 5% by mass to 70% by mass, particularly preferably 10% by mass to 50% by mass, based on the total solid content of the composition forming the image forming layer. An acid-decomposable compound may be used alone or in combination of two or more.

  The weight average molecular weight Mw measured by polystyrene conversion of gel permeation chromatography (GPC) of the acid-decomposable compound is preferably 500 to 30000, more preferably 1000 to 10000.

(Visible paint)
The image forming layer preferably contains a colorant as a visible image agent. Examples of the colorant include oil-soluble dyes and basic dyes including salt-forming organic dyes.

  Particularly preferred are those which change color tone by reacting with free radicals or acids. “Color tone changes” includes both a change from colorless to colored color tone and a change from colored to colorless or different colored tone. Preferred dyes are those that change color tone by forming a salt with an acid.

  For example, Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.), Oil Blue # 603 (Orient Chemical Industry Co., Ltd.), Patent Pure Blue (Sumitomo Sangoku Chemical Co., Ltd.), Crystal Violet, Brilliant Green, Ethyl Violet, Methyl Violet, Methyl Triphenylmethane series represented by green, erythrosin B, pacific fuchsin, malachite green, oil red, m-cresol purple, rhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, cyano-p-diethylaminophenylacetanilide, etc. , Diphenylmethane-based, oxazine-based, xanthene-based, iminonaphthoquinone-based, azomethine-based or anthraquinone-based pigments that change from colored to colorless or different colored tones And the like to.

  On the other hand, examples of the color changing agent that changes from colorless to colored include leuco dyes and, for example, triphenylamine, diphenylamine, o-chloroaniline, 1,2,3-triphenylguanidine, naphthylamine, diaminodiphenylmethane, p, p'-bis. -Dimethylaminodiphenylamine, 1,2-dianilinoethylene, p, p ', p "-tris-dimethylaminotriphenylmethane, p, p'-bis-dimethylaminodiphenylmethylimine, p, p', p"- Primary or secondary typified by triamino-o-methyltriphenylmethane, p, p'-bis-dimethylaminodiphenyl-4-anilinononaphthylmethane, p, p ', p "-triaminotriphenylmethane These compounds can be used alone or in combination of two or more. It can be used. In addition, particularly preferred dyes are Victoria Pure Blue BOH, an Oil Blue # 603.

  As the upper colorant, it is preferable to use a dye having an absorption maximum wavelength of less than 800 nm, particularly less than 600 nm. When the acid generator is used for the lower layer according to the above aspect, the upper colorant is preferable because transmission of light having a wavelength of visible light is suppressed and safelight properties are improved. An acid generator that can be used in the lower layer is also preferable because it can be used and printed even if the safelight property is not good.

  These dyes are added to the printing plate material in a proportion of 0.01% by mass to 10.00% by mass, preferably 0.1% by mass to 3.0% by mass, based on the total solid content of the upper layer or the lower layer. I can do it.

(Development accelerator)
The image forming layer may contain a compound having a low molecular weight acidic group as a development accelerator for the purpose of improving the solubility as required. Examples of the acidic group include acidic groups having a pKa value of 7 to 11, such as a thiol group, a phenolic hydroxyl group, a sulfonamide group, and an active methylene group. The addition amount is preferably 0.05% by mass to 5% by mass, more preferably 0.1% by mass to 3% by mass with respect to the lower layer.

(Development inhibitor)
The image forming layer may contain various dissolution inhibitors for the purpose of adjusting solubility. As the dissolution inhibitor, a disulfone compound or a sulfone compound as disclosed in JP-A-11-119418 is preferably used, and as a specific example, it is preferable to use 4,4′-bishydroxyphenylsulfone. The addition amount is preferably 0.05% by mass to 20.00% by mass, more preferably 0.5% by mass to 10.0% by mass with respect to each layer.

  Further, a development inhibitor can be contained for the purpose of enhancing dissolution inhibiting ability. As a development inhibitor, it forms an interaction with the alkali-soluble resin, substantially reduces the solubility of the alkali-soluble resin in the developer in the unexposed area, and weakens the interaction in the exposed area. Any quaternary ammonium salt, polyethylene glycol compound, or the like is preferably used as long as it can be soluble in the developer.

  Although it does not specifically limit as a quaternary ammonium salt, A tetraalkyl ammonium salt, a trialkyl aryl ammonium salt, a dialkyl diaryl ammonium salt, an alkyl triaryl ammonium salt, a tetraaryl ammonium salt, a cyclic ammonium salt, and a bicyclic ammonium salt are mentioned. .

  The addition amount of the quaternary ammonium salt is preferably 0.1% by mass to 50.0% by mass with respect to the total solid content of the upper layer from the viewpoint of the development inhibiting effect and film forming property, and is preferably 1% by mass to 30% by mass. % Is more preferable.

(Sensitivity improver)
The image forming layer may contain cyclic acid anhydrides, phenols, and organic acids for the purpose of improving sensitivity. 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.

  Furthermore, examples of organic acids include sulfonic acids, sulfinic acids, alkyl sulfates, phosphonic acids, phosphoric esters, and carboxylic acids described in JP-A-60-88942 and JP-A-2-96755. Specifically, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, p-toluenesulfinic acid, ethylsulfuric acid, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid 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. Can be mentioned. The proportion of the cyclic acid anhydride, phenols and organic acids in the composition is preferably 0.05% by mass to 20% by mass, more preferably 0.1% by mass to 15% by mass, and particularly preferably 0%. 1% by mass to 10% by mass.

  Also, alcohol compounds in which at least one trifluoromethyl group described in JP-A-2005-99298 is substituted at the α-position can be used. This compound has the effect of improving the solubility in an alkali developer by improving the acidity of the α-position hydroxyl group due to the electron-withdrawing effect of the trifluoromethyl group.

(Surfactant)
In the present invention, the image forming layer coating solution is disclosed in Japanese Patent Application Laid-Open No. 62-251740 and Japanese Patent Application Laid-Open No. 3-208514 in order to improve the coating property and to increase the stability of the processing with respect to the development conditions. Nonionic surfactants as described in JP-A-59-121044 and amphoteric surfactants as described in JP-A-4-13149, described in EP950517 Such siloxane compounds, fluorine-containing monomer copolymers such as those described in JP-A Nos. 62-170950, 11-288093 and 2003-57820 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 amphoteric activators 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.).

  As the siloxane compound, a block copolymer of dimethylsiloxane and polyalkylene oxide is preferable. Specific examples include DBE-224, DBE-621, DBE-712, DBP-732, DBP-534, manufactured by Chisso Corporation. And polyalkylene oxide-modified silicones such as Tego Glide 100 manufactured by Tego, Germany.

  The proportion of the nonionic surfactant and amphoteric surfactant in the total solid content of the lower layer or upper layer is preferably 0.01% by mass to 15% by mass, more preferably 0.1% by mass to 5% by mass, and further Preferably it is 0.05 mass%-0.5 mass%.

(Coating solution for image forming layer)
As the solvent used in the image forming layer coating solution, the following coating solvents can be used. These solvents are used alone or in combination.

(Coating solvent)
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, acetate-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-hexano 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).

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” represents “parts by mass” unless otherwise specified.

Example 1
<Preparation of aluminum support>
A strip-shaped aluminum plate having a thickness of 0.3 mm, a width of 1200 mm, and a length of 4000 m was immersed in a 5% aqueous sodium hydroxide solution maintained at 65 ° C., degreased for 1 minute, and then washed with water. This degreased strip-shaped aluminum plate was immersed in a 10% aqueous sulfuric acid solution maintained at 25 ° C. for 1 minute for neutralization, and then washed with water. Then the strip-shaped aluminum plate, hydrochloric acid concentration 11g / L, 25 ° C., a frequency 50 Hz, for 20 seconds electrolytic graining treatment in alternating current of 50A / dm ² was carried out. After electrolytic surface roughening, it was washed with water, desmutted for 10 seconds in a 1% aqueous sodium hydroxide solution kept at 50 ° C., washed with water, and then washed in 30% sulfuric acid kept at 50 ° C. for 30 seconds. The neutralization process was performed and it washed with water. Next, anodization was performed for 30 seconds in a 30% 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% polyvinyl phosphonic 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 hydrophilized aluminum support. It was. The centerline average roughness (Ra) of the surface of the band-shaped aluminum support was 0.50 μm. The center line average roughness (Ra) is a value measured according to JISB0601-1994.

(Preparation of slip paper)
A commercially available non-carbon paper “N40” manufactured by Mitsubishi Paper Industries NCR (domestic) was prepared.

<Preparation of positive planographic printing plate material>
The positive photosensitive composition which consists of the following composition was apply | coated so that it might become a dry film thickness of 2.0 g / m < ² > using the wire bar on the prepared aluminum support body using the manufacturing process shown by FIG. . The coating solution was dried by holding in a far-infrared heater at 125 ° C. for 20 seconds, then in a warm air circulating dryer at 115 ° C. for 60 seconds, and then the prepared slip sheet was cut on the image forming layer side. The sheet was cut into a size of 1200 mm × 900 mm using a machine, and 1500 sheets were stacked on a collection table to form an integrated body as shown in FIG. The interleaving paper was adjusted so that the blue color surface side overlapped the image forming layer. The collection table was placed on a transport cart having casters at the four corners of the bottom. The temperature was controlled at 23 ° C. and the humidity was 50% RH in the process of overlapping the slip sheets and the cutting process. The integrated body is a rectangular parallelepiped having a height of 1300 mm, a width of 12100 mm, and a length of 900 mm, and the area of one side surface on the long side is 156 × 10 ⁴ mm ² and the area of one side surface on the short side is 117 × 10 ⁴ mm ^2. It was.

(Preparation of positive photosensitive composition)
Novolak resin (* 1) 60 parts * 1: Cocondensation compound of phenol and m-, p-mixed cresol and formaldehyde (Mn = 500, Mw = 2500, molar ratio of phenol, m-cresol and P-cresol is 20:48:32 respectively)
Acrylic resin 1 (* 2)
* 2: N- (p-hydroxyphenyl) maleimide, terpolymer of acrylonitrile and methyl methacrylate (Mw = 12000, molar ratio 50:40:10)
24.7 parts Acrylic resin 2 (* 3)
* 3: Copolymerized compound of p-hydroxyphenyl methacrylate and tert-butoxycarbonylated-p-hydroxyphenyl methacrylate (Mw = 30000, molar ratio 60:40) 2 parts Polyethylene glycol (PEG # 4000) 2 parts Sorbitan laurate 1 part Phthalic anhydride 3 parts Acid-decomposable compound (Compound A below) 2 parts Acid generator (2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine) 1 part Infrared absorbing dye (Compound B below) 2 parts Visible dye (OIL BLUE 613, manufactured by Orient Chemical Industry Co., Ltd.) 2 parts Fluorine compound (Compound C below) 0.3 part The solid content concentration was adjusted to 15% with a solvent having the following composition.

γ-butyrolactone 7 parts Methyl ethyl ketone 30 parts Propylene glycol monomethyl ether 40 parts Cyclohexanone 13 parts Acetone 10 parts

(Preparation before aging process)
As shown in FIG. 4 in the aging preparation step, the assembly obtained in the manufacturing process shown in FIG. 2 was covered four times with the prepared coating member, and the end portion was stopped with an adhesive tape. Thereafter, position regulating members are attached to the four corners in the vertical direction of the assembly, and two locations are fixed with fastening belts. 1-1. The area of the side surface of the integrated body covered with the position regulating member was 25%, and the area of the side surface of the integrated body covered with the fastening belt was 10%. The temperature and humidity in the aging preparation process were the same as in the cutting process.

The covering member was used width 800 mm, thickness 70 [mu] m, water vapor permeability of 1.5g ^/ m 2 ^/ 24hr oriented polypropylene (OPP) resin. As the position regulating member, an equal side L-shaped angle made of aluminum having a thickness of 4 mm and a side length of 1800 mm was used. The fastening belt made of polypropylene resin having a width of 100 mm was used. In addition, as a comparative integrated body, all of them were manufactured under the same conditions except that the position restricting members were not provided at the four corners in the vertical direction. 1-2.

(Aging process)
The prepared aggregate No. 1-1, 1-2 placed on a transport vehicle, subjected to vibration treatment with a vibration tester under the conditions shown in Table 1, and then treated at a temperature of 55 ° C. for 80 hours to produce a positive planographic printing plate material. No. 101-107. As a vibration tester, a large vibration tester AST-120H manufactured by Mitutoyo Corporation was used.

Evaluation Each sample No. Table 1 shows the results of evaluations of sensitivity, image reproduction uniformity (alkali-soluble in-plane uniformity), and scratches according to the following evaluation ranks.

Sensitivity Three samples from the top, three from the middle, and three from the bottom of each sample were taken out, and drum rotation using a commercially available CTP setter (PTR-4300 manufactured by Dainippon Screen Mfg. Co., Ltd.) equipped with a semiconductor laser head. 50% halftone image exposure corresponding to 175 lines was performed at a resolution of 2400 dpi (dpi represents the number of dots per 2.54 cm) while changing the laser output to several thousand rpm and 40 to 100%.

  The exposed sample was developed at 30 ° C. for 30 seconds using an automatic developing machine (manufactured by Raptor 85 Thermal GLUNZ & JENSEN) and a developer having the following composition. The obtained image was measured with ccDot (manufactured by X-Rite), and the exposure energy value for outputting a 50% halftone dot was taken as the sensitivity. The smaller the value, the higher the sensitivity.

<Developer>
A 40% by weight aqueous solution of potassium silicate (containing 26.5% by weight SiO ₂ , 13.5% by weight K ₂ O) 87.8 parts 50% by weight aqueous potassium hydroxide 61.1 parts Surfactant (TrilonM (BASF) 40% solution) 1.4 parts water 896 parts (uniformity of image reproduction (in-plane uniformity of alkali solubility))
Three pieces from the top, three from the middle, and three from the bottom of the prepared corner sample were extracted, and left unexposed at 32 ° C. with an automatic processor (Raptor 85 Thermal GLUNZ & JENSEN) charged with the developer. Development is performed for 35 seconds, and the cyan density is measured with an X-Rite 520 densitometer from the edge of the plate after development to the center, and the fluctuation range of density is calculated by the following formula, thereby obtaining an index of image reproduction uniformity. did. The smaller the numerical value, the better the in-plane uniformity and the better the image reproduction uniformity.

Density fluctuation range = (Maximum density value-Minimum density value)
(Scratch)
Three sheets from the top, three from the middle, and three from the bottom of the assembly were taken out and developed at 32 ° C. for 35 seconds with an automatic processor (Raptor 85 Thermal GLUNZ & JENSEN) charged with the developer without exposure. The degree of image defects was ranked by visual sensory evaluation. ○ to ◎ are practical levels.

Evaluation rank of scratches ◎: No image defects, uniform coating surface ○: There are several scratches of 200 μm or less at the plate edge, but there is no actual damage Δ: Scratches of 1 mm or less are at the plate edge There are dozens of spots in the plate, and the appearance is not good. ×: Several scratches are also generated in the center of the plate and can be recognized as image defects. XX: Innumerable scratches are generated in the entire plate and it cannot be put into practical use.

  Sample No. 1 was prepared by positioning position regulating members from the top of the covering member at four corners in the vertical direction of the aggregate whose peripheral side surfaces were covered with the covering member, and fixing with two tightening belts. Nos. 101 to 104 showed the results of excellent sensitivity and uniformity of image reproduction even when vibration was applied and no scratch was generated. Sample No. 1 was prepared by covering the surrounding side surface with a covering member. 105-107, the sensitivity is the sample No. of the present invention. Although the same performance as 101 to 104 was shown, it was confirmed that the uniformity of image reproduction deteriorates and the generation of scratches increases as the vibration increases. The effectiveness of the present invention was confirmed.

Example 2
<Preparation of support>
The same belt-like aluminum support as in Example 1 was prepared.

(Preparation of slip paper)
The same slip sheet as in Example 1 was prepared.

<Preparation of positive planographic printing plate material>
<Preparation of aggregate before aging treatment>
Using the manufacturing process shown in FIG. 2, the same image forming layer and protective layer as in Example 1 are formed on the belt-like aluminum support prepared in the same manner as in Example 1, and then the prepared slip sheet is overlaid. In addition, a positive planographic printing plate material cut to 1200 mm × 900 mm in the same manner as in Example 1 is placed on a transport carriage having casters at the four corners of the bottom as shown in Table 2. A pre-aging assembly was prepared under the same conditions as in Example 1 except that the plate was placed on a collection base placed on a vibration-proof member whose area relative to the area of the bottom surface of the printing plate material was changed. 2-1 to 2-7. In addition, the area of the bottom face of the aggregate was 10.8 × 10 ⁵ mm ² . The vibration-proof member used was a flick mat B type manufactured by Fukae Co., Ltd. (thickness 10 mm, hardness 40 °, vibration absorption ability 10 ° C. to 40 ° C., vibration frequency 30 Hz to 100 Hz). The vibration-proof member is disposed at a position where the center of the vibration-proof member matches the center of the positive planographic printing plate material.

(Aging process)
The prepared aggregate No. With 2-1 to 2-7 mounted on a transport vehicle under the same conditions as in Example 1, after vibration treatment with a vibration tester for 120 minutes at an amplitude of 40 Hz, treatment was carried out at a temperature of 55 ° C. for 80 hours to produce positive lithographic printing A plate material was prepared and sample no. 201-207. The same vibration tester as that used in Example 1 was used.

Evaluation The produced sample No. 201 to 207, the sensitivity, image reproduction uniformity (alkali solubility in-plane uniformity), and scratches were evaluated by the same method as in Example 1, and the results of evaluation according to the same evaluation rank as in Example 1 are shown. It is shown in 2.

  Sample No. 201 has an area of 10% to 150% with respect to the area of the bottom surface of the positive planographic printing plate material. Sample No. prepared on In 202 to 206, the vibration-damping member is disposed, and the occurrence of scratches due to vibration is further reduced. Sample No. 207 increases the cost of the vibration isolating member even if the area of the vibration isolating member is increased. It was confirmed that it was not different from 202-206. The effectiveness of the present invention was confirmed.

Example 3
(Preparation of positive planographic printing plate materials)
<Preparation of support>
The same belt-like aluminum support as in Example 1 was prepared.

(Preparation of slip paper)
The same slip sheet as in Example 1 was prepared.

<Preparation of aggregate before aging treatment>
Using the manufacturing process shown in FIG. 2, the same image forming layer and protective layer as in Example 1 are formed on a band-shaped aluminum support prepared in the same manner as in Example 1, and then the same method as in Example 1. The positive lithographic printing plate material cut into 1500 mm × 1000 mm was stacked on a collection table to form an integrated body. Thereafter, the side surface around the prepared assembly was coated with the same coating member as in Example 1 in the same manner. Thereafter, equilateral L-shaped angle-regulating members having different side lengths are arranged at four corners in the vertical direction of the integrated body, and fixed by the same fastening belt as in the first embodiment. By changing the length of one side of the angle, an integrated body in which the area of the side surface of the integrated body covered with the position regulating member was changed as shown in Table 4 was prepared. 3-1 to 3-6. The position regulating member was made of stainless steel having a thickness of 5 mm. The area of the side surface of the aggregate before attaching the position regulating member was 48 × 10 ⁵ mm ² .

(Aging process)
The prepared aggregate No. Samples 3-1 to 3-6 were placed on a transport vehicle and subjected to vibration treatment with a vibration tester at an amplitude of 40 Hz for 120 minutes and then treated at a temperature of 55 ° C. for 80 hours to produce a positive planographic printing plate material. No. 301 to 306. The same vibration tester as that used in Example 1 was used.

Evaluation The produced sample No. In Tables 301 to 306, sensitivity, image reproduction uniformity (alkali-soluble in-plane uniformity), and scratches were evaluated by the same method as in Example 1, and the evaluation results according to the same evaluation rank as in Example 1 are shown. 3 shows.

  Sample Nos. Produced by setting the area of the side surface of the aggregate covered with the position regulating member to 5% to 40% with respect to the area of the side surface of the aggregate before being covered with the position regulating member Nos. 302 to 305 were confirmed to be effective in sensitivity, uniformity of image reproduction, and prevention of occurrence of scratches, and the effectiveness of the present invention was confirmed.

Example 4
(Preparation of positive planographic printing plate materials)
<Preparation of support>
The same belt-like aluminum support as in Example 1 was prepared.

(Preparation of slip paper)
The same slip sheet as in Example 1 was prepared.

<Preparation of aggregate before aging treatment>
Using the manufacturing process shown in FIG. 2, the same image forming layer and protective layer as in Example 1 are formed on a band-shaped aluminum support prepared in the same manner as in Example 1, and then the same method as in Example 1. A positive planographic printing plate material cut to 500 mm × 1000 mm was stacked on a collection table to form an integrated body. Thereafter, the side surface around the prepared assembly was coated with the same coating member as in Example 1 in the same manner. Thereafter, the same position restriction members as those of the first embodiment are arranged at the four corners in the vertical direction of the accumulation body, and the side surface of the accumulation body covered with the fastening belt that changes the width of the fastening belt and fixes the position restriction member. An assembly having the area changed as shown in Table 5 was prepared, and sample No. 4-1 to 4-6. The fastening belt was made of nylon having a thickness of 10 mm. The area of the side surface of the assembly before the position regulating member was disposed and the fastening belt was attached was 48 × 10 ⁵ mm ² .

(Aging process)
The prepared aggregate No. 4-1 to 4-6 are placed on a transport vehicle, subjected to vibration treatment for 120 minutes with a vibration tester, and then treated at a temperature of 55 ° C. for 80 hours to produce a positive lithographic printing plate material. . 401 to 406. The same vibration tester as that used in Example 1 was used.

Evaluation The produced sample No. In Tables 401 to 406, sensitivity, image reproducibility uniformity (alkali solubility in-plane uniformity), and scratches were evaluated in the same manner as in Example 1 and evaluated according to the same evaluation rank as in Example 1. 4 shows.

  Sample No. 2 produced with the area of the side surface of the aggregate covered with the clamping belt being 5% to 25% with respect to the area of the side surface of the aggregate before being covered with the clamping belt. Nos. 402 to 405 were confirmed to be effective in sensitivity, uniformity of image reproduction, and prevention of scratching, and the effectiveness of the present invention was confirmed.

Example 5
(Production of aggregate)
The integrated body No. 1 produced in Example 1 was used. The same assembly as 1-1 was prepared.

(Aging process)
With the prepared assembly mounted on a transport vehicle, the vibration tester was vibrated for 120 minutes under the conditions shown in Table 1, with an amplitude of 40 Hz, and then treated with an aging treatment as shown in Table 5 to produce a positive planographic printing plate material. Sample No. 501-513. The same vibration tester as in Example 1 was used.

Evaluation The produced sample No. Table 501 to 513 shows the results of evaluating sensitivity, uniformity of image reproduction (in-plane uniformity of alkali solubility), and scratches by the same method as in Example 1 and according to the same evaluation rank as in Example 1. As shown in FIG.

  The aging treatment was performed at a temperature of 50 ° C. to 100 ° C. under the conditions of 8 to 100 hours. Each of 502 to 512 was confirmed to be effective in sensitivity, uniformity of image reproduction, and prevention of scratching, and it was confirmed that performance sufficient to withstand practical use was obtained even under a short aging time. . The effectiveness of the present invention was confirmed.

It is the schematic which shows an example of a structure of positive type lithographic printing plate material. It is a schematic diagram of the manufacturing process which manufactures a positive type lithographic printing plate material. FIG. 3 is an enlarged schematic view of a portion indicated by P in FIG. 2. FIG. 3 is a schematic diagram showing an example of a positive planographic printing plate material assembly prepared in the aging preparation step shown in FIG. 2. It is a schematic sectional drawing in alignment with AA 'of FIG. FIG. 4 is a schematic perspective view showing another example of a positive planographic printing plate material assembly prepared in the aging preparation step shown in FIG. 2.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1,301 Positive type lithographic printing plate material 101 Aluminum support body 102 Hydrophilic layer 103 Image forming layer 104 Protective layer 2 Manufacturing process 201 Aluminum support body supply process 202 First coating process 203 First drying process 204 Second coating process 205 Second 2 Drying process 206 Interleaving paper stacking process 206a Interleaving paper 207 Cutting process 207c Collection table 208 Aging preparation process 209 Aging process process 209a Aging process chamber 3 Stacked body 301 Sheet-fed positive planographic printing plate material 302a to 302d Square 303a to 303d Position regulating member 304a, 304b Clamping belt 4 Cover member 5 Carriage 6 Vibration isolating member

Claims (7)

A positive lithographic printing plate material having an image forming layer containing an infrared absorbing compound on an aluminum support is formed into a stack having a rectangular parallelepiped shape sandwiched between interleaf sheets, and the stack is covered with a covering member and aged. In the aging method of a positive planographic printing plate material, a position restricting member is disposed from above the covering member at four corners in the vertical direction of the accumulation body, and the periphery of the accumulation body is disposed above the position restriction member. A method for aging a positive planographic printing plate material, comprising fixing by at least one fastening belt and performing an aging treatment. 2. The positive electrode according to claim 1, wherein the integrated body is placed on a vibration isolating member having an area of 10% to 150% with respect to an area of a bottom surface of the positive planographic printing plate material. Aging method for mold lithographic printing plate materials. The method for aging a positive planographic printing plate material according to claim 1 or 2, wherein the vibration-absorbing member has a vibration absorption capacity of 10 to 40 ° C and a vibration frequency of 30 to 100 Hz. The area of the side surface of the aggregate covered with the position regulating member is 5% to 40% with respect to the area of the side surface of the aggregate before being covered with the position regulating member. The method for aging a positive planographic printing plate material according to any one of 1 to 3. The area of the side surface of the aggregate covered with the clamping belt is 5% to 25% with respect to the area of the side surface of the aggregate before being covered with the clamping belt. A method for aging a positive planographic printing plate material according to any one of -4. The aging method of a positive planographic printing plate material according to any one of claims 1 to 5, further comprising microcapsule particles on a surface of the slip sheet that contacts the image-forming layer side. The aging method for a positive planographic printing plate material according to any one of claims 1 to 6, wherein the aging treatment is performed at a temperature of 50C to 100C for 8 hours to 100 hours.

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