JP2005088406A - Printing plate fixing sheet, plate setting method and printing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a printing plate fixing sheet by which printing positional stability at the time of printing, a picture quality and resistance to plate wear are increased, a plate setting method and a printing method. <P>SOLUTION: At least one sheet of this printing plate fixing sheet is used for printing by being inserted between a printing plate material having at least a hydrophilic layer, an image forming functional layer and a back coating layer on a polyester support, and the plate cylinder of a printing machine. In this case, the moisture change rate at 23°C and 80%RH of the printing plate fixing sheet is 0.01 to 0.08%. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a printing plate fixing sheet, a printing method, and a printing method, and more particularly to a printing plate fixing sheet, a printing method, and a printing method that have improved printing position stability, image quality, and printing durability during printing.

  With the digitization of print data, there is a need for CTP (computer to plate) technology that is inexpensive, easy to handle, and has the same printability as the PS plate.

  As a support used for a printing plate used for CTP, from the viewpoint of printability, a material having excellent hydrophilicity, water retention, and adhesion to a photosensitive layer is required. From such a viewpoint, usually, A roughened aluminum plate called the graining surface was used, but recently, printing plate technology using a polyester film support is known to be convenient for handling and carrying the printing plate. (For example, see Patent Documents 1 to 3).

  In the printing plate using these polyester supports, there is a problem that there is distortion due to elongation at the time of printing, and in order to improve these, a method of interposing a printing plate fixing sheet between the printing plate and the printing press plate cylinder Is known (see, for example, Patent Document 4).

However, these techniques have a problem that the printing plate moves on the printing press plate cylinder from the start of printing and the length of the printed matter fluctuates, so-called printing position stability deteriorates. In addition, there is a problem that the printing performance of the obtained printed matter, in particular, the printing image quality is deteriorated.
JP-A-5-257287 JP 2000-258899 A JP 2002-79773 A Japanese Patent Laid-Open No. 10-193828

  An object of the present invention is to provide a printing plate fixing sheet, a printing method, and a printing method with improved printing position stability, image quality, and printing durability during printing.

The above object of the present invention is achieved by the following configurations.
(Claim 1)
At least one printing plate fixing sheet used for printing by interposing between a printing plate material having at least a hydrophilic layer, an image forming functional layer and a backing layer on a polyester support and a printing drum A printing plate fixing sheet, wherein the wet change rate at 23 ° C. and 80% RH is 0.01 to 0.08%.
(Claim 2)
The printing plate fixing sheet according to claim 1, wherein the printing plate fixing sheet is made of a plastic base material having a thickness distribution of 10% or less.
(Claim 3)
In a plate-hanging method in which a printing plate fixing sheet is interposed between a printing plate material having at least a hydrophilic layer, an image forming functional layer and a backing layer on a polyester support, and a plate cylinder of a printing machine, the printing plate fixing sheet A printing method characterized in that the wet change rate at 23 ° C. and 80% RH is 0.01 to 0.08%.
(Claim 4)
4. The method according to claim 3, wherein the printing plate fixing sheet comprises a plastic substrate having a thickness distribution of 10% or less.
(Claim 5)
In a printing method in which a printing plate fixing sheet is interposed between a printing plate material having at least a hydrophilic layer, an image forming functional layer and a backing layer on a polyester support and a printing drum, the printing plate is fixed. The printing method, wherein the wet change rate at 23 ° C. and 80% RH of the sheet is 0.01 to 0.08%.
(Claim 6)
After forming an image of a printing plate material having at least a hydrophilic layer, an image forming functional layer, and a backing layer on a polyester support using a laser, the printing plate material and the printing plate are not subjected to wet development. In a printing method in which a printing plate fixing sheet is interposed between cylinders and attached to a printing press to print on printing paper, the wet change rate at 23 ° C. and 80% RH of the printing plate fixing sheet is 0.01-0. A printing method characterized in that the printing method is 08%.

  According to the present invention, it is possible to provide a printing plate fixing sheet, a plate-hanging method, and a printing method with improved printing position stability, image quality, and printing durability during printing.

  As a result of diligent research, the present inventor (1) performs printing by interposing between a printing plate material having at least a hydrophilic layer, an image forming functional layer and a backing layer on a polyester support and a printing drum. At least one printing plate fixing sheet used in the printing plate fixing sheet having a wet change rate at 23 ° C. and 80% RH of 0.01 to 0.08%, (2) at least hydrophilic on the polyester support In a printing method in which a printing plate fixing sheet is interposed between a printing plate material having a layer, an image forming functional layer and a backing layer, and a plate cylinder of a printing machine, the printing plate fixing sheet is wetted at 23 ° C. and 80% RH (3) printing plate material having at least a hydrophilic layer, an image-forming functional layer and a backing layer on a polyester support, and a plate cylinder of a printing press During the printing plate (4) A printing method in which printing is performed with a sheet interposed, the wet plate change rate at 23 ° C. and 80% RH of the printing plate fixing sheet is 0.01 to 0.08%. After forming an image of a printing plate material having at least a hydrophilic layer, an image forming functional layer, and a backing layer on a polyester support using a laser, the printing plate material and the printing plate are not subjected to wet development. In a printing method in which a printing plate fixing sheet is interposed between cylinders and attached to a printing press to print on printing paper, the wet change rate at 23 ° C. and 80% RH of the printing plate fixing sheet is 0.01-0. It has been found that the above object can be achieved by a printing method of 08%.

  Moreover, in order to express the effect of this invention more, it is preferable to consist of a plastic base material whose thickness distribution of the base material of a printing plate fixing sheet is 10% or less.

[Moisture change rate]
The present invention is characterized in that the rate of change in wetness of the printing plate fixing sheet at 23 ° C. and 80% RH is 0.01 to 0.08%. The wet change rate is a value measured by the following method.

<Measurement of wet change rate at 23 ° C. and 80% RH>
The printing plate fixing sheet is cut into a 12 cm width × 30 cm length and conditioned at 23 ° C. and 45% RH for 4 hours or more, then two holes are formed at 25 cm intervals, and the distance between the holes is measured using a pin gauge (this length) Let L ₀ ). After that, after adjusting the humidity for 48 hours under the conditions of 23 ° C. and 80% RH (relative humidity), the distance between the holes is measured again using a pin gauge (this length is defined as L ₁ ). The wet change rate is obtained based on the following formula.

Wet change rate (%) = | L ₀ −L ₁ | / L ₀ × 100
In the printing plate fixing sheet, the range of the wet change rate of the present invention is achieved by appropriately selecting and combining a plurality of technical means shown below.

(1) As a base material of the printing plate fixing sheet, a plastic film base material having an elastic modulus at 120 ° C. (E120) of 1000 to 6000 N / mm ² is used.
(2) The thickness distribution of the substrate of the printing plate fixing sheet is 10% or less.
(3) The moisture content of the base material of the printing plate fixing sheet is 0.5% by mass or less.
(4) containing particles having an average particle diameter of 1 to 100 μm in the surface layer of the printing plate fixing sheet,
(5) Disperse the particles in a binder resin and apply, or after forming a binder resin film on the surface, push the particles.
(6) At least one layer containing a polyvinylidene chloride resin is provided on at least one surface of the substrate of the printing plate fixing sheet.

  Each technical means will be described below.

(1) A plastic film substrate having an elastic modulus (E120) at 120 ° C. of 1000 to 6000 N / mm ² is used as the substrate of the printing plate fixing sheet.

<Plastic film base>
(Constituent material of base material)
The constituent material of the plastic film substrate according to the present invention is preferably a plastic film, and examples thereof include polyethylene terephthalate, polyethylene naphthalate, polyimide, polyamide, polycarbonate, polysulfone, polyphenylene oxide, and cellulose esters.

The base material according to the present invention preferably has an elastic modulus (E120) at 120 ° C. of 100 to 600 kg / mm ² from the viewpoint of imparting the above-mentioned handling suitability to the printing plate fixing sheet of the present invention, and more preferably. Is 120 to 500 kg / mm ² . Specifically, polyethylene naphthalate (E120 = 410 kg / mm ² ), polyethylene terephthalate (E120 = 150 kg / mm ² ), polybutylene naphthalate (E120 = 160 kg / mm ² ), polycarbonate (E120 = 170 kg / mm ² ), Syndiotactic polystyrene (E120 = 220 kg / mm ² ), polyetherimide (E120 = 190 kg / mm ² ), polyarylate (E120 = 170 kg / mm ² ), polysulfone (E120 = 180 kg / mm ² ), polyethersulfone ( E120 = 170 kg / mm ² ) and the like. These may be used singly or may be laminated or mixed. Among them, particularly preferable plastic films include polyethylene naphthalate and polyethylene terephthalate.

  Here, the elastic modulus is obtained by using a tensile tester to obtain the slope of the stress with respect to the strain amount in a region where the strain indicated by the standard line of the sample conforming to JIS C2318 and the corresponding stress have a linear relationship. It is a thing. This is a value called Young's modulus, and in the present invention, the Young's modulus is defined as an elastic modulus.

  (2) The thickness distribution of the base material of the printing plate fixing sheet is set to 10% or less.

  Furthermore, the base material according to the present invention preferably has an average film thickness in the range of 50 to 300 μm, more preferably from 50 to 300 μm, from the viewpoint of improving handling suitability when the printing plate fixing sheet is installed in a printing press. The range is 200 μm.

  The thickness distribution of the substrate according to the present invention (a value obtained by dividing the difference between the maximum value and the minimum value by the average thickness and expressed as a percentage) is preferably 10% or less, more preferably 8 as described above. % Or less, particularly preferably 6% or less.

  Here, the method for measuring the thickness distribution of the base material is that the base material cut into a square having a side of 60 cm is vertically and horizontally drawn at intervals of 10 cm, the thickness of these 25 points is measured, the average value and the maximum value are measured. Find the value and minimum value.

  In order to adjust the thickness distribution of the substrate according to the present invention to the above range, there are methods of adjusting the film forming conditions appropriately or adjusting with a smooth roller while reheating after film formation. It is preferable to manufacture by a film forming process.

  As a film forming means for the base plate of the printing plate fixing sheet, a thermoplastic resin is melted between a melting point (Tm) and Tm + 50 ° C., filtered through a sintered filter, and then extruded from a T-die, and a glass transition temperature ( Tg) An unstretched sheet is formed on a casting drum whose temperature is adjusted to −50 ° C. to Tg. At this time, in order to make the thickness distribution within the above range, it is preferable to use an electrostatic application method or the like.

  The unstretched sheet is longitudinally stretched 2 to 4 times between Tg and Tg + 50 ° C. Further, as another method for adjusting the thickness distribution within the above range, it is preferable to perform multi-stage stretching in the longitudinal stretching. At this time, it is preferable to adjust the temperature of the post-stage stretching to be higher in the range of 1 to 30 ° C than that of the pre-stage stretching, and it is more preferable to perform the stretching while adjusting the temperature to be higher in the range of 2 to 15 ° C.

  The magnification of the former drawing is preferably 0.25 to 0.7 times, more preferably 0.3 to 0.5 times the magnification of the latter drawing. Thereafter, the film is held in the temperature range of Tg-30 ° C to Tg for 5 to 60 seconds, more preferably 10 to 40 seconds, and then stretched 2.5 to 5 times between Tg and Tg + 50 ° C in the transverse direction. Is preferred.

  Thereafter, heat fixation is performed in a state of being gripped with a chuck at (Tm-50 ° C) to (Tm-5 ° C) for 5 to 120 seconds. At this time, it is also preferable to narrow the chuck interval by 0 to 10% in the width direction (thermal relaxation). After cooling this, a method such as obtaining a multiaxially stretched film after winding a knurling of 10 to 100 μm at the end (also referred to as providing a knurling height) is preferable.

  In order for the base material which concerns on this invention to improve adhesiveness with an application layer, you may perform an easily bonding process and undercoat layer application | coating to an application surface.

  In addition, as the substrate according to the present invention, a plastic film substrate is used, but a material such as a plastic film and a metal plate (for example, iron, stainless steel, aluminum, etc.) or paper coated with polyethylene (also referred to as a composite substrate). ) Can be used as appropriate. These composite substrates may be bonded together before forming the coating layer, may be bonded after forming the coating layer, or may be bonded immediately before being attached to the printing press.

  (3) The water content of the base material of the printing plate fixing sheet is 0.5% by mass or less.

  In the present invention, the moisture content of the base material of the printing plate fixing sheet is D ′ represented by the following formula.

D ′ (mass%) = (w ′ / W ′) × 100
(W ′ is the mass of the base plate of the printing plate fixing sheet that is in a humidity adjustment equilibrium under an atmosphere of 25 ° C. and 60% RH, and w ′ is a humidity adjustment equilibrium under an atmosphere of 25 ° C. and 60% RH. (It represents the moisture content of the base material of the printing plate fixing sheet.)
The moisture content of the substrate of the printing plate fixing sheet is preferably 0.5% by mass or less, more preferably 0.01 to 0.5% by mass, and particularly preferably 0.01 to 0.3% by mass. %.

  As means for controlling the moisture content of the base material of the printing plate fixing sheet to 0.5% by mass or less, (a) a coating liquid of a necessary layer is applied to the base material of the printing plate fixing sheet, or a resin film is used. The base material is heat-treated at 100 ° C. or more immediately before forming, (b) controlling the relative humidity in the step of applying a coating liquid of a necessary constituent layer to the base material of the printing plate fixing sheet, or forming a resin film, (C) Apply the coating liquid of the necessary constituent layers to the base of the printing plate fixing sheet, or heat-treat the base at 100 ° C. or higher before forming the resin film, cover with a moisture-proof sheet, store, and open For example, it may be applied immediately afterwards or a resin film may be formed. Two or more of these may be combined.

  (4) The surface layer of the printing plate fixing sheet contains particles having an average particle diameter of 1 μm to 100 μm.

  (5) The above particles are dispersed in a binder resin and applied, or after forming a binder resin film on the surface, the particles are pushed in.

  In the present invention, the surface of the printing plate fixing sheet refers to a surface in contact with the backing layer side of the printing plate material when the printing plate fixing sheet is wound around the plate cylinder of a printing press.

  The particles used are preferably particles having a particle diameter of 1 to 100 μm. The average particle diameter is more preferably 1 to 80 μm, and particularly preferably the average particle diameter is 1 to 50 μm. The material of the particles is not particularly limited, and is a particle made of an inorganic material, an organic material, an organic-inorganic composite material, or the like. Particles having a hardness higher than that of the back surface of the lithographic printing plate support are preferably used.

Examples of the inorganic particles include metal powders, metal oxides, metal nitrides, metal hydroxides, metal sulfides, metal carbides, and composite metal compounds thereof, preferably glass, SiO ₂ , TiO ₂ , These are oxides such as ZnO, Fe ₂ O ₃ , ZrO ₂ and SnO ₂ and sulfides such as ZnS and CuS.

  Examples of the organic particles include synthetic resin particles, natural polymer particles, and the like, and preferably acrylic resin, polyethylene, polypropylene, polyethylene oxide, polypropylene oxide, polyethyleneimine, polystyrene, polyurethane, polyurea, polyester, polyamide, polyimide, carboxy. Methyl cellulose, gelatin, starch, chitin, chitosan and the like are preferable, and synthetic resin particles such as acrylic resin, polyethylene, polypropylene and polystyrene are more preferable.

Examples of the organic / inorganic composite particles include at least two kinds of composites of the above-described inorganic particles and materials forming the organic particles. Preferably, glass, SiO ₂ , TiO ₂ , ZnO, Fe ₂ O _{3 are used.} Oxides such as ZrO ₂ and SnO ₂ and / or sulfides such as ZnS and CuS and acrylic resins, polyethylene, polypropylene, polyethylene oxide, polypropylene oxide, polyethyleneimine, polystyrene, polyurethane, polyurea, polyester, polyamide, polyimide, carboxy Complexes such as methylcellulose, gelatin, starch, chitin, chitosan, and the like, more preferably oxides such as SiO ₂ , TiO ₂ , ZnO, Fe ₂ O ₃ , ZrO ₂ , SnO ₂ and hydrogen-bonding functional groups Acrylic resin, polyethylene oxide, Examples thereof include composites such as polypropylene oxide, polyethyleneimine, polyurethane, polyurea, polyester, polyamide, polyimide, carboxymethylcellulose, gelatin, starch, chitin, and chitosan.

  In the present invention, as a binder resin for dispersing and binding such particles, generally used organic resins (lipophilic resins, water-soluble resins, etc.), organic resin emulsions, inorganic resins, organic-inorganic hybrid resins, All of natural, semi-synthetic and synthetic resins can be used, and can be cured and used as necessary.

  Examples of lipophilic organic resins include acrylic resins (polymethyl methacrylate, polymethyl acrylate, polyethyl methacrylate, various alkyl, aralkyl or aryl acrylate copolymers, various alkyl, aralkyl or aryl methacrylate copolymers, etc.), alkyds Examples thereof include resins (melamine resins, phenol resins, etc.), polystyrene resins, polyvinyl acetate resins, epoxy resins, polyalkylene resins (polyethylene, polypropylene, etc.), polyester resins, polyurethane resins and the like.

  Examples of water-soluble organic resins include cellulose, cellulose derivatives (cellulose esters; cellulose nitrate, cellulose sulfate, cellulose acetate, cellulose propionate, cellulose succinate, cellulose butyrate, cellulose acetate succinate, cellulose acetate butyrate, cellulose acetate phthalate, etc. , Cellulose ethers; methylcellulose, ethylcellulose, cyanoethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, ethylhydroxyethylcellulose, hydroxypropylmethylcellulose, carboxymethylhydroxyethylcellulose, etc.), starch, starch derivatives (oxidized starch, esterified starches; Estes such as nitric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, butyric acid, succinic acid , Etherified starches; methylated, ethylated, cyanoethylated, hydroxyalkylated, carboxymethylated etherified products), alginic acid, pectin, carrageenan, tamarind gum, natural gums (gum arabic, guar gum, locust) Bean gum, tragacanth gum, xanthan gum, etc.), pullulan, dextran, casein, gelatin, chitin, chitosan, polyvinyl alcohol, polyalkylene glycol (polyethylene glycol, polypropylene glycol, (ethylene / propylene glycol) copolymer, etc.), allyl alcohol copolymer Polymer, copolymer of acrylic acid, methacrylic acid, polyamino acid, polyamide (polymer or copolymer of N-substituted acrylamide or methacrylamide [as N-substituent For example, methyl, ethyl, propyl, isopropyl, butyl, phenyl, monomethylol, 2-hydroxyethyl, 3-hydroxypropyl, 1,1-bis (hydroxymethyl) ethyl, 2,3,4,5,6-pentahydroxy Pentyl group etc.), polyamine (polyethyleneimine, polyallylamine, polyvinylamine etc.), polyurea (urea resin etc.) and the like.

  Organic resin emulsions include acrylic resin (polymethyl methacrylate, polymethyl acrylate, polyethyl methacrylate, various alkyl, aralkyl or aryl acrylate copolymers, various alkyl, aralkyl or aryl methacrylate copolymers, etc.) emulsion, alkyd Examples thereof include resin (melamine resin, phenol resin, etc.) emulsion, styrene resin emulsion, vinyl acetate resin emulsion, epoxy resin emulsion, alkylene resin (polyethylene, polypropylene, etc.) emulsion, ester resin emulsion, urethane resin emulsion, and the like.

  Examples of the inorganic resin include a bond-containing resin in which metal atoms are connected through oxygen atoms or nitrogen atoms (hereinafter also referred to as metal-containing resin). The metal-containing resin indicates a polymer mainly containing a bond composed of “oxygen atom (nitrogen atom) -metal atom-oxygen atom (nitrogen atom)”.

  Among the metal-containing resins, the resin having an oxygen atom-metal atom-oxygen atom bond is preferably a polymer obtained by hydrolysis polycondensation of a metal compound represented by the following general formula (I). Here, hydrolysis polycondensation is a reaction in which a reactive group repeats hydrolysis and condensation under acidic or basic conditions and polymerizes.

Formula (I) (R ₀ ) _n M (Y) _xn
(In the general formula (I), R ₀ represents a hydrogen atom, a hydrocarbon group or a heterocyclic group, Y represents a reactive group, M represents a trivalent to hexavalent metal, and x represents the valence of the metal M. And n represents 0, 1, 2, 3 or 4, provided that xn is 2 or more.)
Next, the metal compound represented by the general formula (I) will be described in detail. R ₀ in the general formula (I) is preferably a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted {for example, methyl group, ethyl group, propyl group, butyl group, pentyl Group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, etc .; these groups can be substituted by halogen atom (chlorine atom, fluorine atom, bromine atom), hydroxy group, thiol group Carboxy group, sulfo group, cyano group, epoxy group, -OR 'group (R' is a hydrocarbon group such as methyl group, ethyl group, propyl group, butyl group, hexyl group, heptyl group, octyl group, decyl group. , Propenyl group, butenyl group, hexenyl group, octenyl group, 2-hydroxyethyl group, 3-chloropropyl group, 2-cyanoethyl group, N, N-dimethylaminoethyl group 2-bromoethyl group, 2- (2-methoxyethyl) oxyethyl group, 2-methoxycarbonylethyl group, 3-carboxypropyl group, benzyl group, etc.), -OCOR 'group, -COOR' group, -COR 'group , —N (R ″) (R ″) (R ″ represents the same content as a hydrogen atom or R ′, and each may be the same or different), —NHCONHR ′ group, —NHCOOR ′ group, —Si (R ′) ₃ group, —CONHR ″ group, —NHCOR ′ group and the like can be mentioned. A plurality of these substituents may be substituted in the alkyl group)},
C2-C12 linear or branched alkenyl group which may be substituted (for example, vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, octenyl group, decenyl group, dodecenyl group, etc. Examples of the group that can be substituted with the group include those having the same contents as the group that can be substituted with the alkyl group, and may be substituted plurally, and an aralkyl group that may be substituted with 7 to 14 carbon atoms. (For example, a benzyl group, a phenethyl group, a 3-phenylpropyl group, a naphthylmethyl group, a 2-naphthylethyl group, etc .; the group that can be substituted with these groups is the same as the group that can be substituted with the alkyl group. And may be substituted in plural, alicyclic groups having 5 to 10 carbon atoms which may be substituted (for example, cyclopentyl group, cyclohexyl group, 2 Examples of the group that can be substituted by these groups such as cyclohexylethyl group, 2-cyclopentylethyl group, norbornyl group, adamantyl group, and the like include those having the same content as the substituent of the alkyl group. Or an aryl group having 6 to 12 carbon atoms which may be substituted (for example, a phenyl group or a naphthyl group, examples of the substituent include those having the same content as the group which can be substituted with the alkyl group, and multiple substitutions) May be)
Or a heterocyclic group which may be condensed with at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom (for example, a pyran ring, a furan ring, a thiophene ring, a morpholine ring, a pyrrole as a heterocyclic ring) Ring, thiazole ring, oxazole ring, pyridine ring, piperidine ring, pyrrolidone ring, benzothiazole ring, benzoxazole ring, quinoline ring, tetrahydrofuran ring, etc., which may contain a substituent. And those having the same contents as the substituents therein may be used, and a plurality of substituents may be substituted).

The reactive group Y is preferably a hydroxy group, a halogen atom (representing a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), an —OR ₁ group, an —OCOR ₂ group, —CH (COR ₃ ) (COR ₄ ). Represents a group, —CH (COR ₃ ) (COOR ₄ ) group or —N (R ₅ ) (R ₆ ) group.

In the —OR ₁ group, R ₁ is an optionally substituted aliphatic group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, Nonyl, decyl, propenyl, butenyl, heptenyl, hexenyl, octenyl, decenyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-methoxyethyl, 2- (methoxyethyloxy) ethyl Group, 2- (N, N-diethylamino) ethyl group, 2-methoxypropyl group, 2-cyanoethyl group, 3-methyloxypropyl group, 2-chloroethyl group, cyclohexyl group, cyclopentyl group, cyclooctyl group, chlorocyclohexyl group , Methoxycyclohexyl group, benzyl group, phenethyl group, dimethoxybenzyl group, methyl base Benzyl group, bromobenzyl group, etc.).

In the —OCOR ₂ group, R ₂ preferably represents the same content as R _1, and preferably an aliphatic group or an aromatic group having 6 to 12 carbon atoms which may be substituted (the aromatic group includes the above R 0 The same as those exemplified for the aryl group in the middle).

In the —CH (COR ₃ ) (COR ₄ ) group and —CH (COR ₃ ) (COOR ₄ ) group, R ₃ is an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group). Etc.) or an aryl group (for example, phenyl group, tolyl group, xylyl group, etc.), R ₄ is an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, A hexyl group, etc.), an aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, phenylpropyl group, methylbenzyl group, methoxybenzyl group, carboxybenzyl group, chlorobenzyl group, etc.) or aryl group (for example, phenyl) Group, tolyl group, xylyl group, mesityl group, methoxyphenyl group, chlorophenyl group, carboxyphenyl group, diethoxyphenyl group, etc.) The

In the —N (R ₅ ) (R ₆ ) group, R ₅ and R ₆ may be the same or different from each other, and each is preferably a hydrogen atom or an optionally substituted aliphatic group having 1 to 10 carbon atoms. (e.g., include those of the same contents as R ₁ -OR ₁ group of the) representative of. More preferably, the total number of carbon atoms of R ₅ and R ₆ is 12 or less.

  The metal M is preferably a transition metal, a rare earth metal, or a group III to V group metal. More preferably, Al, Si, Sn, Ge, Ti, Zr, etc. are mentioned, More preferably, Al, Si, Ti, Zr, etc. are mentioned. Si is particularly preferable.

  Specific examples of the metal compound represented by the general formula (I) include the following, but are not limited thereto.

Methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltrit-butoxysilane, ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane, ethyltriethoxysilane, Ethyltriisopropoxysilane, ethyltrit-butoxysilane, n-propyltrichlorosilane, n-propyltribromosilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltriisopropoxysilane, n-propyl Tri-t-butoxysilane, n-hexyltrichlorosilane, n-hexyltribromosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltriiso Lopoxysilane, n-hexyltri-t-butoxysilane, n-decyltrichlorosilane, n-decyltribromosilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-decyltriisopropoxysilane, n-decyltrit- Butoxysilane, n-octadecyltrichlorosilane, n-octadecyltribromosilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n-octadecyltri-t-butoxysilane, phenyltrichlorosilane , Phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltri-t-butoxysilane,
Tetrachlorosilane, tetrabromosilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane, dimethyldichlorosilane, dimethyldibromosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyl Dichlorosilane, diphenyldibromosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldibromosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, triethoxyhydrosilane, tribromohydrosilane, tri Methoxyhydrosilane, isopropoxyhydrosilane, tri-t-butoxyhydrosilane, vinyltrichlorosilane, vinyltribro Silane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltrit-butoxysilane, trifluoropropyltrichlorosilane, trifluoropropyltribromosilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane , Trifluoropropyltriisopropoxysilane, trifluoropropyltri-t-butoxysilane,
γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxy Silane, γ-glycidoxypropyltri-t-butoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxy Propyltriisopropoxysilane, γ-methacryloxypropyltri-t-butoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopro Lutriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltri-t-butoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ- Mercaptopropyltriethoxysilane, γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltri-t-butoxine run, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Triethoxysilane,
Ti (OR) ₄ (R is methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc.), TiCl ₄ , Zn (OR) ₂ , Zn (CH ₃ COCHCOCH ₃ ) ₂ , Sn (OR) ₄ , Sn (CH ₃ COCHCOCH ₃ ) ₄ , Sn (OCOR) ₄ , SnCl ₄ , Zr (OR) ₄ , Zr (CH ₃ COCHCOCH ₃ ) ₄ , Al (OR) ₃ . The above metal compounds are used alone or in combination to produce a metal-containing resin.

  Examples of the metal-containing resin having a nitrogen atom-metal atom-nitrogen atom bond include polysilazane.

  In the present invention, it is further preferable to use a composite of the metal-containing resin and an organic polymer containing a group capable of forming a hydrogen bond with the resin as the binder resin. The composite of a metal-containing resin and an organic polymer is used to mean including a sol-like substance and a gel-like substance.

  The organic polymer contains a group capable of forming a hydrogen bond with the metal-containing resin (hereinafter also referred to as a specific bonding group). The specific linking group preferably includes at least one bond selected from an amide bond (including a carboxylic acid amide bond and a sulfonamide bond), a urethane bond and a ureido bond, and a hydroxyl group.

The organic polymer includes a repeating unit component containing the specific bonding group of the present invention in the main chain and / or side chain of the polymer. Preferably, as a repeating unit _{component, -N (R 11) CO -} , - N (R 11) SO 2 -, - NHCONH- and at least one binding polymer selected from -NHCOO- main chain and / or Examples include a component present in the side chain and / or a component containing an —OH group. R ₁₁ in the amide bond represents a hydrogen atom or an organic residue, and examples of the organic residue include those having the same contents as the hydrocarbon group and the heterocyclic group in R ₀ in the general formula (I). .

Examples of the polymer containing the specific bonding group of the present invention in the polymer main chain include an amide resin having —N (R ₁₁ ) CO— bond or —N (R ₁₁ ) SO ₂ — bond, and a ureido having —NHCONH— bond. Resin, urethane resin containing -NHCOO- bond is mentioned.

  Diamines and dicarboxylic acids or disulfonic acids used for the production of amide resins, diisocyanates used for ureido resins, and diols used for urethane resins include, for example, “Polymer Data Handbook-Basics” "Chapter I Co., Ltd. published by Baifu Shuku (1986), Shinzo Yamashita, Tosuke Kaneko" Crosslinking Agent Handbook "published by Taiseisha (1981), etc. can be used.

  As other compounds that can be used, compounds described in paragraphs (0048) to (0057) of JP-A-2002-19322 can be preferably used.

  On the other hand, the hydroxyl group-containing organic polymer may be any of a natural water-soluble polymer, a semi-synthetic water-soluble polymer, and a synthetic polymer. I "published by Asakura Shoten (1960), published by the Management Development Center," Water-soluble polymer and water-dispersible resin general technical data collection ", published by the Management Development Center (1981), Shinji Nagatomo" New water-soluble polymer " Applications and Markets "published by CMC (1988)," Development of Functional Cellulose "(CMC) (1985), and the like.

  For example, natural and semi-synthetic polymers include cellulose, cellulose derivatives (cellulose esters; cellulose nitrate, cellulose sulfate, cellulose acetate, cellulose propionate, cellulose succinate, cellulose butyrate, cellulose acetate succinate, cellulose acetate butyrate, Cellulose acetate phthalate, etc., cellulose ethers; methyl cellulose, ethyl cellulose, cyanoethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl hydroxyethyl cellulose, etc.), starch, starch derivatives (oxidized starch, Esterified starches: nitric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, butyric acid, co Esters such as succinic acid, etherified starches; derivatives such as methylated, ethylated, cyanoethylated, hydroxyalkylated, carboxymethylated), alginic acid, pectin, carrageenan, tamarind gum, natural gums (gum arabic, Guar gum, locust bean gum, tragacanth gum, xanthan gum), pullulan, dextran, casein, gelatin, chitin, chitosan and the like.

  Examples of the synthetic polymer include polyvinyl alcohol, polyalkylene glycol (polyethylene glycol, polypropylene glycol, (ethylene glycol / propylene glycol) copolymer, etc.), allyl alcohol copolymer, an acrylate ester containing at least one hydroxyl group, or Methacrylic acid ester polymer or copolymer (for example, 2-hydroxyethyl group, 3-hydroxypropyl group, 2,3-dihydroxypropyl group, 3-hydroxy-2-hydroxymethyl-2-methylpropyl as ester substituents) Group, 3-hydroxy-2,2-di (hydroxymethyl) propyl group, polyoxyethylene group, polyoxypropylene group, etc.), acrylamide or methacrylamide N-substituted polymer or copolymer (N- Examples of the substituent include a monomethylol group, 2-hydroxyethyl group, 3-hydroxypropyl group, 1,1-bis (hydroxymethyl) ethyl group, 2,3,4,5,6-pentahydroxypentyl group, etc. ) And the like. However, the synthetic polymer is not particularly limited as long as it contains at least one hydroxyl group in the side chain substituent of the repeating unit.

The mass average molecular weight of the organic polymer used in the present invention is preferably 10 ³ to 10 ⁶ , more preferably 5 × 10 ³ to 4 × 10 ⁵ .

  In the composite of the metal-containing resin and the organic polymer according to the present invention, the ratio of the metal-containing resin and the organic polymer can be selected within a wide range, but the mass ratio of the metal-containing resin / organic polymer is 10/90 to 90/10, More preferably, it is 20/80 to 80/20.

  For example, in the case of a metal-containing resin produced by hydrolysis polycondensation of the metal compound, the binder resin containing the complex is formed by hydrogen bonding between the hydroxyl group and the specific bonding group in the organic polymer. A uniform organic / inorganic hybrid is formed and becomes microscopically homogeneous without phase separation. When the hydrocarbon group is present in the metal-containing resin, it is presumed that the affinity with the organic polymer is further improved due to the hydrocarbon group. Since the composite has both organic and inorganic characteristics, it has a strong interaction with both inorganic and organic particles, and the binder resin strongly adsorbs to the particles. In addition, this composite is excellent in film formability.

  A complex of a metal-containing resin and an organic polymer is produced by hydrolytic polycondensation of the metal compound and mixing with the organic polymer, or hydrolytic polycondensation of the metal compound in the presence of the organic polymer. Manufactured by. Preferably, an organic / inorganic polymer composite can be obtained by hydrolytic polycondensation of the metal compound by a sol-gel method in the presence of an organic polymer. In the produced organic-inorganic polymer composite, the organic polymer is uniformly dispersed in a gel matrix (that is, a three-dimensional fine network structure of inorganic metal oxide) formed by hydrolytic polycondensation of a metal compound.

  The sol-gel method as the preferable method can be performed using a conventionally known sol-gel method. Specifically, “Thin-gel coating technology by sol-gel method”, Technical Information Association (published) (1995), Yoshio Sakuhana “Science of sol-gel method”, Agne Jofusha (published) (1988), Satoshi Hirashima, “Functional Thin Film Formation Technology by the Latest Sol-Gel Method”, General Technology Center (published) (1992), etc.

  The solvent used is appropriately selected from water, organic solvents and the like. Examples of the organic solvent include alcohols (methanol, ethanol, propyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.), ethers (tetrahydrofuran, Ethylene glycol dimethyl ether, propylene glycol dimethyl ether, tetrahydropyran, etc.), ketones (acetone, methyl ethyl ketone, acetylacetone, etc.), esters (methyl acetate, ethylene glycol monomethyl monoacetate, etc.), amides (formamide, N-methylformamide, pyrrolidone) , N-methylpyrrolidone, etc.). The solvent may be used alone or in combination of two or more.

  Furthermore, when using the said composite_body | complex, in order to accelerate | stimulate the hydrolysis and polycondensation reaction of the said metal compound shown by general formula (I), it is preferable to use together an acidic catalyst or a basic catalyst. As the catalyst, an acid or a basic compound is used as it is or dissolved in a solvent such as water or alcohol (hereinafter referred to as an acidic catalyst and a basic catalyst, respectively). The concentration at that time is not particularly limited, but when the concentration is high, the hydrolysis and polycondensation rates tend to increase. However, when a basic catalyst with a high concentration is used, a precipitate may be generated in the sol solution. Therefore, the concentration of the basic catalyst is preferably 1 mol / L (concentration in aqueous solution) or less.

  The type of the acidic catalyst or the basic catalyst is not particularly limited, but when it is necessary to use a catalyst having a high concentration, a catalyst composed of an element that hardly remains in the catalyst crystal grains after sintering is preferable. Specifically, examples of the acidic catalyst include hydrogen halides such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acids such as formic acid and acetic acid, and R of the structural formula RCOOH. Examples of basic catalysts such as substituted carboxylic acids substituted with other elements or substituents, sulfonic acids such as benzenesulfonic acid, and the like include ammoniacal bases such as aqueous ammonia and amines such as ethylamine and aniline.

  The binder resin is generally used in a proportion of 8 to 50 parts by mass, preferably 10 to 30 parts by mass with respect to 100 parts by mass of the particles. Within this range, the effects of the present invention are effectively exhibited.

  Moreover, you may add a crosslinking agent. As a crosslinking agent, the compound normally used as a crosslinking agent can be mentioned. Specifically, it is described in Shinzo Yamashita, Tosuke Kaneko “Cross-linking agent handbook” published by Taiseisha (1981), “Polymer Data Handbook, Fundamentals” edited by Polymer Society of Japan (1986), etc. Can be used.

  For example, ammonium chloride, metal ions, organic peroxides, polyisocyanate compounds (for example, toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylenephenyl isocyanate, hexamethylene diisocyanate, isophorone Diisocyanates, polymer polyisocyanates, etc.), polyol compounds (eg, 1,4-butanediol, polyoxypropylene glycol, polyoxyethylene glycol, 1,1,1-trimethylolpropane, etc.), polyamine compounds (For example, ethylenediamine, γ-hydroxypropylated ethylenediamine, phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.), polyepoxy Compounds and epoxy resins (for example, “New Epoxy Resin” edited by Hiroshi Kakiuchi published in Shoshado, 1985), “Epoxy Resins” published by Kuniyuki Hashimoto, published by Nikkan Kogyo Shimbun (1969), melamine resins (for example, , Ichiro Miwa, Hideo Matsunaga, “Yulia Melamine Resin”, Nikkan Kogyo Shimbun (1969), etc.), poly (meth) acrylate compounds (for example, Nobu Okawara, Takeo Saegusa, Toshinobu Higashimura) “Oligomer” Kodansha (published in 1976), Eizo Omori “Functional acrylic resin” Techno system (published in 1985), etc.).

  In the present invention, an overcoat layer may be further provided on the surface to which the matting agent is added. The overcoat layer is made of a film-forming resin, and the same materials as those described for the binder resin for forming the surface to which the matting agent is added are used. Preferably, the surface to which the matting agent containing the hydrophilic binder resin is added has a hydrophilic overcoat layer and the uneven surface containing the hydrophobic binder resin so that the adhesion to the surface to which the matting agent is added is good. A hydrophobic overcoat layer is used.

  The overcoat layer can be obtained by coating the coating liquid containing the film-forming resin and the solvent on the surface to which the matting agent has been added, using a conventionally known coating method, drying, and forming a film. As the solvent, the above-mentioned solvents can be used as appropriate. Examples of the coating method include coater coating (air doctor, blade, rod, squeeze, gravure, etc.), spray coating (air spray, electrostatic spray, etc.) and the like.

  A conventionally known method is used to fix the printing plate fixing sheet of the present invention to the plate cylinder. For example, a method of applying an adhesive or pressure sensitive adhesive such as spray glue or double-sided tape to the back surface of the support of the printing plate fixing sheet, or a claw portion provided with the front and rear ends of the printing plate fixing sheet on the plate cylinder Examples include a locking method. Moreover, the method which combined these can also be used.

  (6) At least one layer containing a polyvinylidene chloride resin is provided on at least one surface of the substrate of the printing plate fixing sheet.

(Polyvinylidene chloride resin)
As the polyvinylidene chloride resin according to the present invention, a copolymer is preferably used, and the amount of the polymerization component of the vinylidene chloride monomer in the repeating unit of the copolymer is 70 to 99.9% by mass. More preferably, it is 85-99 mass%, Most preferably, it is 90-99 mass%.

  Examples of copolymer components other than the vinylidene chloride monomer in the copolymer include methacrylic acid, acrylic acid, itaconic acid, citraconic acid and esters thereof, acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, methyl methacrylate, Examples thereof include glycidyl methacrylate, 2-hydroxyethyl methacrylate, vinyl acetate, acrylamide, and styrene.

  The mass average molecular weight of these copolymers is preferably in the range of 5000 to 100,000, more preferably 8000 to 80,000, and particularly preferably in the range of 10,000 to 45,000. Here, the mass average molecular weight can be measured by a commercially available GPC (gel permeation chromatography) apparatus.

  The arrangement of the monomer units of these copolymers is not limited, and any of random, block and the like may be used.

  When the polyvinylidene chloride resin is an aqueous dispersion, it may be a latex of polymer particles having a uniform structure or a latex of polymer particles having a so-called core-shell structure having different compositions in the core and shell portions. Specific examples of the vinylidene chloride copolymer include the following. However, the numerical value indicating the copolymerization ratio is a mass ratio, and Mw represents a mass average molecular weight.

(A) Latex (Mw = 42000) of vinylidene chloride / methyl acrylate / acrylic acid (90: 9: 1)
(B) Latex (Mw = 40000) of vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / methacrylic acid (87: 4: 4: 4: 1)
(C) Latex (Mw = 38000) of vinylidene chloride / methyl methacrylate / glycidyl methacrylate / methacrylic acid (90: 6: 2: 2)
(D) Latex (Mw = 44000) of vinylidene chloride / ethyl methacrylate / 2-hydroxyethyl methacrylate / acrylic acid (90: 8: 1.5: 0.5)
(E) Core-shell type latex (core part 90% by mass, shell part 10% by mass)
Core part: vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid (93: 3: 3: 0.9: 0.1)
Shell part: vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid (88: 3: 3: 3: 3) (Mw = 38000)
(F) Core-shell type latex (core part 70% by mass, shell part 30% by mass)
Core part: vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / methacrylic acid (92.5: 3: 3: 1: 0.5)
Shell part: vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / methacrylic acid (90: 3: 3: 1: 3) (Mw = 20000)
The polyvinylidene chloride resin according to the present invention may be contained in a constituent layer on any surface of the base of the printing plate fixing sheet, but is preferably contained in the undercoat layer. The undercoat layer may be a single layer or a plurality of layers. The thickness of these layers is preferably provided at a film thickness in the range of 0.5 to 10 μm on at least one side of the substrate, and more preferably on both sides of the substrate in the range of 0.8 to 5 μm. It is to provide a layer, and it is particularly preferably 1.0 to 3 μm on both sides.

  The printing plate material according to the present invention will be described.

[Polyester film support]
The polyester used for the support in the present invention is not particularly limited, but is mainly composed of a dicarboxylic acid component and a diol component, for example, polyethylene terephthalate (hereinafter sometimes referred to as PET for short). And polyesters such as polyethylene naphthalate (hereinafter sometimes abbreviated as PEN). Preferably, PET or a copolymer or blended polyester having a mass ratio of constituents in the whole polyester as a main constituent component of PET or a portion comprising PET is 50% by mass or more.

  PET is polymerized with terephthalic acid and ethylene glycol, and PEN polymerized with naphthalenedicarboxylic acid and ethylene glycol as constituent components. A dicarboxylic acid or diol constituting PET or PEN may be polymerized by mixing another suitable one kind or two or more kinds of third components. As a suitable third component, a divalent ester-forming functional group may be used. Examples of the dicarboxylic acid having a group include the following. Terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenylether dicarboxylic acid, diphenylethanedicarboxylic acid, cyclohexanedicarboxylic acid, diphenyldicarboxylic acid, diphenylthioether dicarboxylic acid Examples thereof include acid, diphenyl ketone dicarboxylic acid, and phenylindane dicarboxylic acid. Examples of glycols include propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, and bis (4- Hydroxyphenyl) sulfone, bisphenol full orange hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol and the like. As the third component, a polyfunctional carboxylic acid or a polyhydric alcohol can also be mixed, but these can be mixed in an amount of about 0.001 to 5% by mass with respect to all the polyester components.

  In the present invention, the intrinsic viscosity of the polyester is preferably 0.5 to 0.8. Moreover, you may mix and use what has a different intrinsic viscosity.

  The polymerization method of the polyester is not particularly limited, and can be produced according to a conventionally known polyester polymerization method. For example, a direct ester is obtained by directly esterifying a dicarboxylic acid component with a diol component, diesterifying one hydroxyl group of the diol to a dicarboxylic acid, and heating the other diol under reduced pressure to distill off the excess diol. In addition, a dialkyl ester (for example, dimethyl ester) is used as a dicarboxylic acid component, and this is subjected to a transesterification reaction with the diol component to distill alkyl alcohol (for example, methanol) to convert one hydroxyl group of the diol to a dicarboxylic acid. A transesterification method can be used in which polymerization is carried out by esterifying the excess diol component by heating and distilling it off under reduced pressure.

As the catalyst, a transesterification catalyst, a polymerization reaction catalyst, and a heat stabilizer used for synthesis of a normal polyester can be used. For example, examples of transesterification catalysts include Ca (OAc) ₂ .H ₂ O, Zn (OAc) ₂ .2H ₂ O, Mn (OAc) ₂ .4H ₂ O, Mg (OAc) ₂ .4H ₂ O, and the like. Examples of the polymerization catalyst include Sb ₂ O ₃ and GeO ₂ . Examples of the heat stabilizer include phosphoric acid, phosphorous acid, PO (OH) (CH ₃ ) ₃ , PO (OC ₆ H ₅ ) ₃ , P (OC ₆ H ₅ ) _{3 and the} like. In addition, anti-coloring agent, crystal nucleating agent, slip agent, stabilizer, anti-blocking agent, UV absorber, viscosity modifier, clearing agent, antistatic agent, pH adjuster, dye, pigment, etc. May be added.

  The film thickness of the polyester film support used in the present invention is preferably in the range of 80 to 300 μm, more preferably 120 to 200 μm. If the thickness is less than 80 μm, the support as a support is weak and is not suitable for printing. On the other hand, if the thickness exceeds 300 μm, the film is too thick and inconvenient to handle.

(Method for producing support)
The support according to the present invention is preferably subjected to a film forming treatment as described below.

  As a film forming means for the support, a thermoplastic resin is melted at a melting point (Tm) to Tm + 50 ° C., filtered through a sintered filter, and then extruded from a T-die to obtain a glass transition temperature (Tg) -50. An unstretched sheet is formed on a casting drum whose temperature is adjusted to from C to Tg. At this time, in order to make the thickness distribution within the above range, it is preferable to use an electrostatic application method or the like. The unstretched sheet is longitudinally stretched 2 to 4 times between Tg and Tg + 50 ° C. Further, as another method for adjusting the thickness distribution within the above range, it is preferable to perform multi-stage stretching in the longitudinal stretching. At this time, it is preferable to adjust the temperature of the subsequent stretching higher than the first stretching in the range of 1 to 30 ° C., and more preferably, the stretching is performed while adjusting the temperature higher in the range of 2 to 15 ° C.

  The magnification of the former drawing is preferably 0.25 to 0.7 times, more preferably 0.3 to 0.5 times the magnification of the latter drawing. Thereafter, the film is held in the temperature range of Tg-30 ° C to Tg for 5 to 60 seconds, more preferably 10 to 40 seconds, and then stretched 2.5 to 5 times between Tg and Tg + 50 ° C in the transverse direction. Is preferred. Thereafter, heat fixing is performed in a state of being gripped by the chuck for 5 to 120 seconds at (Tm-50 ° C) to (Tm-5 ° C). At this time, it is also preferable to narrow the chuck interval by 0 to 10% in the width direction (thermal relaxation). After cooling this, a method such as obtaining a multiaxially stretched film after winding a knurling of 10 to 100 μm at the end (also referred to as providing a knurling height) is preferable.

(Heat treatment of support)
In the present invention, it is preferable to heat-treat the polyester film after stretching and heat setting in order to stabilize the dimensions during printing and prevent color misregistration during color printing. The heat treatment according to the present invention is preferably accomplished by the following means after cooling and winding after completion of heat setting and then unwinding in a separate step. As a heat treatment method according to the present invention, the film is conveyed by a conveyance method in which both ends of a film such as a tenter are gripped by pins or clips, a roll conveyance method by a plurality of roll groups, an air conveyance in which air is blown to the film and floated. A method (a method in which heated air is blown from one or both sides of a film surface from a plurality of slits), a method of using radiant heat by an infrared heater, a method of contacting a plurality of heated rolls, etc., alone or in combination, and a heat treatment method, Further, it is preferable to hang the film by its own weight and use a conveying method such as winding alone or a combination of a plurality of methods below.

  The tension of the heat treatment can be adjusted by adjusting the torque of the take-up roll and / or the delivery roll, and / or by installing a dancer roll in the process and adjusting the load applied to the dancer roll. When changing the tension during the heat treatment and / or cooling after the heat treatment, a desired tension state may be set by installing dancer rolls before and after these processes and / or in the processes and adjusting their loads. . Further, it is possible to effectively change the conveyance tension by vibration by reducing the span between the heat treatment rolls.

  In the heat treatment according to the present invention, it is desirable to make the conveying tension as low as possible and lengthen the heat treatment time in order to reduce the dimensional change without hindering the progress of heat shrinkage. As the processing temperature, a temperature range of Tg + 50 to Tg + 150 ° C. of the polyester film is preferable, and in that temperature range, the transport tension is preferably 5 Pa to 1 MPa, more preferably 5 Pa to 500 kPa, still more preferably 5 Pa to 200 kPa, and the processing time. Is preferably 30 seconds to 30 minutes, more preferably 30 seconds to 15 minutes. By using the above temperature range, conveyance tension range, and processing time, the flatness of the support does not deteriorate due to a partial difference in thermal shrinkage of the support during heat treatment, and fine scratches due to friction with the transfer roll, etc. Etc. can also be suppressed.

  In the present invention, the heat treatment is preferably performed at least once in order to obtain a desired dimensional change rate, and can be performed twice or more as necessary.

  In the present invention, after the heat-treated polyester film is cooled from a temperature near Tg to room temperature, it is wound up, and in order to prevent deterioration of flatness due to cooling at this time, at least −5 until the temperature is lowered to room temperature across Tg. It is preferable to cool at a rate of at least ° C / second.

  In the present invention, the heat treatment is preferably performed after coating the above-described undercoat layer. For example, it is preferable to apply an undercoat layer in-line between extrusion, heat setting and cooling, and then winding it once, followed by heat treatment in a separate step. Moreover, after winding up after heat setting, you may heat-process in the state which hold | maintained the undercoated polyester film support continuously, after apply | coating and drying undercoat in another process. Further, after applying and drying various functional layers such as a back layer, a conductive layer, a slippery layer, and an undercoat layer, the same heat treatment as described above may be performed.

(Easy adhesion treatment to support, undercoat coating)
The support according to the present invention is preferably subjected to easy adhesion treatment or undercoat layer coating on the coated surface in order to improve the adhesion to the coated layer. Examples of the easy adhesion treatment include corona discharge treatment, flame treatment, plasma treatment, and ultraviolet irradiation treatment.

  As the undercoat layer, a layer containing gelatin, latex or vinylidene chloride resin is preferably provided on the support. Further, the conductive polymer-containing layer described in paragraph Nos. (0031) to (0073) of JP-A-7-20596 and the metal oxide-containing layer described in paragraph Nos. (0074) to (0081) of JP-A-7-20596 It is preferable to provide such a conductive layer. The conductive layer may be coated on either side as long as it is on the polyester film support, but it is preferably coated on the opposite side of the image forming functional layer with respect to the support. When this conductive layer is provided, the chargeability is improved, the adhesion of dust and the like is reduced, and white-out failures during printing are greatly reduced.

  Further, as the support according to the present invention, a polyester film support is used, but a material such as a polyester film and a metal plate (for example, iron, stainless steel, aluminum) or paper coated with polyethylene (also referred to as a composite base material). ) May be used as appropriate. These composite substrates may be bonded together before forming the coating layer, may be bonded after forming the coating layer, or may be bonded immediately before being attached to the printing press.

(Fine particles)
Moreover, it is preferable to add 0.01-1000 ppm of microparticles | fine-particles of 0.01-10 micrometers to said support body for handling property improvement.

  Here, the fine particles may be either organic or inorganic. Examples of inorganic substances include silica described in Swiss Patent No. 330,158 and the like, glass powder described in French Patent No. 1,296,995, and British Patent No. 1,173,181. Alkaline earth metals or carbonates such as cadmium and zinc described in the book can be used. Examples of organic substances include starch described in US Pat. No. 2,322,037 and the like, starch derivatives described in Belgian Patent 625,451 and British Patent 981,198, and the like. No. 44-3643, etc., polyvinyl alcohol described in Swiss Patent No. 330,158 etc., polymethacrylate, US Pat. No. 3,079,257, etc., polyacrylonitrile, US Patent Organic fine particles such as polycarbonates described in US Pat. No. 3,022,169 can be used. The shape of the fine particles may be either regular or irregular.

  The printing plate material in the present invention has a layer capable of forming a printable image on a polyester support after exposure or after exposure and development. Preferably, a lithographic printing plate using a silver salt diffusion transfer method as described in JP-A-4-261539, or JP-A-8-507727 or JP-A-Hei Hei 8 recorded by thermal laser recording or thermal head recording. This is a printing plate material of an ablation type as described in JP-A-6-186750 and a development type and thermal fusion transfer type on a thermal fusion image layer as described in JP-A-9-123387. Among them, the so-called processless CTP printing plates that do not require a developer treatment with special chemicals, such as ablation type, thermal fusion image layer on-machine development type, and thermal fusion transfer type printing plate materials, are burdens on the global environment. Is preferable because of the reduction. More preferably, a printing plate material having an image-forming functional layer containing heat-fusible fine particles or heat-fusible fine particles on a polyester film support is preferable.

(Image forming functional layer)
The image forming functional layer according to the present invention preferably contains heat-fusible and / or heat-fusible fine particles.

(Hot-melting fine particles)
The heat-meltable fine particles used in the present invention are fine particles formed of a material that has a low viscosity when melted, and is generally classified as a wax, among thermoplastic materials. The physical properties are preferably a softening point of 40 to 120 ° C. and a melting point of 60 to 150 ° C., more preferably a softening point of 40 to 100 ° C. and a melting point of 60 to 120 ° C. When the melting point is less than 60 ° C., storage stability is a problem, and when the melting point is higher than 150 ° C., ink deposition sensitivity is lowered.

  Examples of usable materials include paraffin, polyolefin, polyethylene wax, microcrystalline wax, and fatty acid wax. These have a molecular weight of about 800 to 10,000, and in order to facilitate emulsification, these waxes can be oxidized to introduce polar groups such as a hydroxyl group, an ester group, a carboxyl group, an aldehyde group, and a peroxide group. Furthermore, in order to lower the softening point and improve workability, these waxes include, for example, stearamide, linolenic amide, lauryl amide, myristamide, hardened bovine fatty acid amide, palmitoamide, oleic acid amide, rice sugar fatty acid amide, It is also possible to add coconut fatty acid amides or methylolated products of these fatty acid amides, methylene bisstellaramide, ethylene bisstellaramide and the like. Coumarone-indene resin, rosin-modified phenol resin, terpene-modified phenol resin, xylene resin, ketone resin, acrylic resin, ionomer, and copolymers of these resins can also be used.

  Among these, it is preferable to contain any of polyethylene, microcrystalline, fatty acid ester, and fatty acid. Since these materials have a relatively low melting point and a low melt viscosity, high-sensitivity image formation can be performed. Further, since these materials have lubricity, damage when a shearing force is applied to the surface of the printing plate material is reduced, and resistance to printing stains due to scratches or the like is improved.

  The heat-meltable fine particles are preferably dispersible in water, and the average particle diameter is preferably 0.01 to 10 μm, more preferably 0.05 to 3 μm. When the average particle size is smaller than 0.01 μm, when the coating solution for the layer containing the heat-meltable fine particles is applied onto the hydrophilic layer having a porous structure described later, the heat-meltable fine particles are converted into the hydrophilic layer. In the fine pores of the film, or into the gaps between the fine irregularities on the surface of the hydrophilic layer, the on-press development becomes insufficient, and there is a concern about soiling. When the average particle size of the heat-meltable fine particles is larger than 10 μm, the resolution is lowered.

  Moreover, the composition of the inside and the surface layer of the heat-meltable fine particles may be continuously changed, or may be coated with a different material. As a coating method, a known microcapsule formation method, a sol-gel method, or the like can be used.

  As content of the heat-meltable microparticles | fine-particles in a structural layer, 1-90 mass% of the whole layer is preferable, and 5-80 mass% is more preferable.

(Heat-fusion fine particles)
Examples of the heat-fusible fine particles according to the present invention include thermoplastic hydrophobic polymer fine particles, and there is no specific upper limit for the softening temperature of the thermoplastic hydrophobic high-polymer fine particles, but the temperature is high. It is preferably lower than the decomposition temperature of the polymer fine particles. The mass average molecular weight (Mw) of the polymer is preferably in the range of 10,000 to 1,000,000.

  Specific examples of the polymer constituting the thermoplastic hydrophobic polymer fine particles include, for example, diene (co) polymers such as polypropylene, polybutadiene, polyisoprene, and ethylene-butadiene copolymer, and styrene-butadiene. Synthetic rubbers such as copolymer, methyl methacrylate-butadiene copolymer, acrylonitrile-butadiene copolymer, polymethyl methacrylate, methyl methacrylate- (2-ethylhexyl acrylate) copolymer, methyl methacrylate-methacrylic acid copolymer, Methyl acrylate- (N-methylolacrylamide) copolymer, (meth) acrylic acid ester such as polyacrylonitrile, (meth) acrylic acid (co) polymer, polyvinyl acetate, vinyl acetate-vinyl propionate copolymer, acetic acid Vinyl-ethylene copolymer Vinyl ester (co) polymer of the polymer such as, vinyl acetate - (2-ethylhexyl acrylate) copolymers, polyvinyl chloride, polyvinylidene chloride, polystyrene and copolymers thereof. Of these, (meth) acrylic acid esters, (meth) acrylic acid (co) polymers, vinyl ester (co) polymers, polystyrene, and synthetic rubbers are preferably used.

  The thermoplastic hydrophobic polymer fine particles may be made of a polymer polymer polymerized by any known method such as emulsion polymerization, suspension polymerization, solution polymerization, and gas phase polymerization. As a method for making a polymer polymer polymerized by a solution polymerization method or a gas phase polymerization method into a fine particle, a solution is sprayed in an inert gas in an organic solvent of the polymer polymer and dried to make a fine particle, Examples include a method in which a high molecular polymer is dissolved in an organic solvent immiscible with water, this solution is dispersed in water or an aqueous medium, and the organic solvent is distilled off to form fine particles. Further, in any method, the heat-meltable fine particles and the heat-fusible fine particles may be used as a dispersant or a stabilizer, for example, when polymerized or finely divided, for example, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, polyethylene A surfactant such as glycol or a water-soluble resin such as polyvinyl alcohol may be used. Further, triethylamine, triethanolamine or the like may be contained.

  The heat-fusible fine particles are preferably dispersible in water, and the average particle diameter is preferably 0.01 to 10 μm, more preferably 0.1 to 3 μm. When the average particle diameter is smaller than 0.01 μm, when the coating solution for the layer containing the heat-fusible fine particles is applied on the porous hydrophilic layer described later, the heat-fusible fine particles are in the hydrophilic layer. In the fine pores of the film, or into the gaps between the fine irregularities on the surface of the hydrophilic layer, the on-press development becomes insufficient, and there is a concern about soiling. When the average particle size of the heat-fusible fine particles is larger than 10 μm, the resolution is lowered.

  Further, the heat-fusible fine particles may be continuously changed in composition between the inside and the surface layer, or may be coated with different materials. As a coating method, a known microcapsule formation method, a sol-gel method, or the like can be used.

  The content of the heat-fusible fine particles in the constituent layer is preferably 1 to 90% by mass, more preferably 5 to 80% by mass of the entire layer.

  It is also a preferred embodiment that the image forming functional layer according to the present invention contains a photothermal conversion material described later.

The dry coating mass of the image forming functional layer is preferably 0.10 to 1.50 g / m ² , more preferably 0.15 to 1.00 g / m ² .

[Hydrophilic layer]
The printing plate material used in the present invention has an image forming functional layer and has at least one hydrophilic layer between the support and the image forming functional layer. The hydrophilic layer provided between the support and the image forming functional layer according to the invention will be described. The hydrophilic layer is defined as a layer having a low affinity for ink and a high affinity for water when the printing plate material is used as a printing plate.

  In the printing plate material, it is preferable that at least one of the hydrophilic layers provided on the support has a porous structure. In order to form the hydrophilic layer having the porous structure, materials for forming the hydrophilic matrix described below are preferably used.

(Metal oxide)
As a material for forming the hydrophilic matrix, a metal oxide is preferable. The metal oxide preferably contains fine metal oxide particles, and examples thereof include colloidal silica, alumina sol, titania sol, and other metal oxide sols. The form of the metal oxide fine particles may be spherical, needle-like, feather-like, or any other form. The average particle diameter is preferably in the range of 3 to 100 nm, and several kinds of metal oxides having different average particle diameters are used. Fine particles can be used in combination. Further, the surface of the particles may be subjected to a surface treatment.

  The metal oxide fine particles can be used as a binder by utilizing the film forming property. The decrease in hydrophilicity is less than when an organic binder is used, and it is suitable for use in a hydrophilic layer.

(Colloidal silica)
Among these, colloidal silica can be particularly preferably used. Colloidal silica has the advantage of high film-forming properties even under relatively low temperature drying conditions, and can provide good strength. The colloidal silica preferably includes necklace-like colloidal silica, which will be described later, and fine particle colloidal silica having an average particle size of 20 nm or less, and the colloidal silica preferably exhibits alkalinity as a colloidal solution.

  Necklace-shaped colloidal silica is a general term for an aqueous dispersion of spherical silica whose primary particle diameter is of the order of nm, and spherical colloidal silica having a primary particle diameter of 10 to 50 nm bonded to a length of 50 to 400 nm. It means colloidal silica in the form of “pearl necklace”.

  The pearl necklace shape (that is, a pearl necklace shape) means that the image in a state in which the silica particles of colloidal silica are connected and linked has a shape like a pearl necklace.

  The bond between the silica particles constituting the necklace-shaped colloidal silica is presumed to be —Si—O—Si— in which —SiOH groups present on the surface of the silica particles are dehydrated. Specific examples of the colloidal silica in the form of necklace include “Snowtex-PS” series manufactured by Nissan Chemical Industries, Ltd., and the product name is “Snowtex-PS-S” (average particle diameter in the connected state is 110 ")," Snowtex-PS-M (average particle size in the connected state is about 120 nm) "and" Snowtex-PS-L (average particle size in the connected state is about 170 nm) " Acidic products corresponding to the above are "Snowtex-PS-SO", "Snowtex-PS-MO" and "Snowtex-PS-LO".

  By adding necklace-like colloidal silica, it becomes possible to maintain the strength while ensuring the porosity of the layer, and it can be preferably used as a porous material for the hydrophilic layer matrix. Among these, when “Snowtex PS-S”, “Snowtex PS-M”, and “Snowtex PS-L”, which are alkaline, are used, the strength of the hydrophilic layer is improved and the number of printed sheets is large. However, it is particularly preferable because the occurrence of soiling is suppressed.

  In addition, it is known that colloidal silica has a stronger binding force as the particle size is smaller. In the present invention, it is preferable to use colloidal silica having an average particle size of 20 nm or less, more preferably 3 to 15 nm. It is.

  As described above, among the colloidal silica, an alkaline one is particularly preferable because it has an effect of suppressing the occurrence of soiling. Examples of the alkaline colloidal silica having an average particle diameter in this range include, for example, “Snowtex-20 (particle diameter 10-20 nm)”, “Snowtex-30 (particle diameter 10-20 nm)” manufactured by Nissan Chemical Co., Ltd. “Snowtex-40 (particle diameter 10-20 nm)”, “Snowtex-N (particle diameter 10-20 nm)”, “Snowtex-S (particle diameter 8-11 nm)”, “Snowtex-XS (particle diameter) 4-6 nm) ".

  Colloidal silica having an average particle size of 20 nm or less is particularly preferable because it can be further improved in strength while maintaining the porosity of the layer to be formed, when used in combination with the aforementioned necklace-shaped colloidal silica.

  The ratio of colloidal silica / necklace-like colloidal silica having an average particle size of 20 nm or less is preferably in the range of 95/5 to 5/95, more preferably in the range of 70/30 to 20/80, and 60/40. A range of ˜30 / 70 is more preferred.

(Porous metal oxide particles)
In the present invention, porous metal oxide particles having a particle size of less than 1 μm can be contained as a porous material having a hydrophilic layer matrix structure. As the porous metal oxide particles, the following porous silica, porous aluminosilicate particles, or zeolite particles can be preferably used.

(Porous silica, porous silica, porous aluminosilicate particles)
The porous silica particles are generally produced by a wet method or a dry method. In the wet method, the gel obtained by neutralizing the aqueous silicate solution can be obtained by drying and pulverizing, or by pulverizing the precipitate deposited by neutralization. In the dry method, silicon tetrachloride is burned together with hydrogen and oxygen to obtain silica. These particles can be controlled in their porosity and particle size by adjusting the production conditions. As the porous silica particles, those obtained from a wet gel are particularly preferable.

  The porous aluminosilicate particles are produced, for example, by the method described in JP-A-10-71764. That is, amorphous composite particles synthesized by hydrolysis using aluminum alkoxide and silicon alkoxide as main components. The ratio of alumina to silica in the particles can be synthesized in the range of 1: 4 to 4: 1. Moreover, what was manufactured as composite particle | grains of 3 or more components by adding the alkoxide of another metal at the time of manufacture can be used for this invention. These composite particles can also control the porosity and particle size by adjusting the production conditions.

  The porosity of the particles is preferably 0.5 ml / g or more in terms of pore volume, more preferably 0.8 ml / g or more, and further preferably 1.0 to 2.5 ml / g. preferable. The pore volume is closely related to the water retention of the coating film. The larger the pore volume, the better the water retention, the less likely to get dirty during printing, and the greater the water volume latitude, but more than 2.5 ml / g When it becomes large, the particles themselves become very brittle, so that the durability of the coating film is lowered. Conversely, if the pore volume is less than 0.5 ml / g, the printing performance may be slightly insufficient.

(Measurement method of pore volume)
Here, the pore volume is measured by using Autosorb-1 (manufactured by Cantachrome) and assuming that the voids of the powder are filled with nitrogen by nitrogen adsorption measurement using a constant volume method. Thus, the relative pressure is calculated from the nitrogen adsorption amount at 0.998.

(Zeolite particles)
Zeolite is a crystalline aluminosilicate and is a porous body having regular three-dimensional network voids having a pore diameter of 0.3 to 1 nm. The general formula combining natural and synthetic zeolite is expressed as follows:

(M ₁ , (M ₂ ) _0.5 ) _m (Al _m Si _n O ₂ ) _{(m + n)} · xH ₂ O
Here, M ₁ and M ₂ are exchangeable cations, and M ₁ is Li ⁺ , Na ⁺ , K ⁺ , Tl ⁺ , Me ₄ N ⁺ (TMA), Et ₄ N ⁺ (TEA), Pr _4. N ⁺ (TPA), C ₇ H ₁₅ N ²⁺ , C ₈ H ₁₆ N ^{+ and the} like, and M ₂ is Ca ²⁺ , Mg ²⁺ , Ba ²⁺ , Sr ²⁺ , C ₈ H ₁₈ N ₂ ^{2. +} Etc. Further, n ≧ m, and the value of m / n, that is, the Al / Si ratio is 1 or less. The higher the Al / Si ratio, the greater the amount of exchangeable cations, and thus the higher the polarity and therefore the higher the hydrophilicity. A preferable Al / Si ratio is 0.4 to 1.0, and more preferably 0.8 to 1.0. x represents an integer.

The zeolite particles used in the present invention are preferably synthetic zeolite having a stable Al / Si ratio and a relatively sharp particle size distribution. For example, zeolite A: Na ₁₂ (Al ₁₂ Si ₁₂ O ₄₈ ). 27H ₂ O; Al / Si ratio 1.0, zeolite X: Na ₈₆ (Al ₈₆ Si ₁₀₆ O ₃₈₄ ) · 264H ₂ O; Al / Si ratio 0.811, zeolite Y: Na ₅₆ (Al ₅₆ Si ₁₃₆ O ₃₈₄ 250H ₂ O; Al / Si ratio 0.412 and the like.

  By containing highly hydrophilic porous particles having an Al / Si ratio of 0.4 to 1.0, the hydrophilicity of the hydrophilic layer itself is greatly improved, it is difficult to get dirty during printing, and the water latitude is widened. Also, fingerprint marks are greatly improved. When the Al / Si ratio is less than 0.4, the hydrophilicity is insufficient, and the effect of improving the performance becomes small.

  Moreover, the hydrophilic layer matrix structure which comprises a hydrophilic layer can contain a layered clay mineral particle. Examples of the layered mineral particles include kaolinite, halloysite, talc, smectite (montmorillonite, beidellite, hectorite, sabonite, etc.), clay minerals such as vermiculite, mica (mica), chlorite, hydrotalcite, layered polysilicic acid. Examples thereof include salts (kanemite, macatite, ialite, magadiite, kenyaite, etc.). In particular, the higher the charge density of the unit layer (unit layer), the higher the polarity and the higher the hydrophilicity. The charge density is preferably 0.25 or more, more preferably 0.6 or more. Examples of the layered mineral having such a charge density include smectite (charge density 0.25 to 0.6; negative charge), vermiculite (charge density 0.6 to 0.9; negative charge) and the like. In particular, synthetic fluoromica is preferable because it can be obtained with stable quality such as particle size. Further, among the synthetic fluorine mica, those that are swellable are preferable, and those that are free swell are more preferable.

  Also used are intercalation compounds of the above-mentioned layered minerals (pillar crystals, etc.), those subjected to ion exchange treatment, and those subjected to surface treatment (silane coupling treatment, compounding treatment with organic binder, etc.) can do.

  As the size of the flat lamellar mineral particles, the average particle diameter (maximum length of the particles) is less than 1 μm in the state of being contained in the layer (including the case where the swelling process and the dispersion peeling process have been performed). The aspect ratio is preferably 50 or more. When the particle size is in the above range, the continuity and flexibility in the planar direction, which are the characteristics of the thin layered particles, are imparted to the coating film, and it is difficult for cracks to occur, and a tough coating film can be obtained in a dry state. Moreover, in the coating liquid containing many particulate matters, sedimentation of particulate matter can be suppressed by the thickening effect of the layered clay mineral. When the particle diameter is larger than the above range, the coating film may be non-uniform, and the strength may be locally reduced. Further, when the aspect ratio is not more than the above range, the number of tabular grains with respect to the addition amount is reduced, the viscosity is insufficient, and the effect of suppressing the sedimentation of the particulate matter is reduced.

  The content of the layered mineral particles is preferably 0.1 to 30% by mass, and more preferably 1 to 10% by mass based on the entire layer. In particular, swellable synthetic fluorinated mica and smectite are preferable because they are effective even when added in a small amount. The layered mineral particles may be added as a powder to the coating solution, but in order to obtain a good degree of dispersion even with a simple preparation method (no need for a dispersion step such as media dispersion), the layered mineral particles are used alone. It is preferable to prepare the gel swollen in water and add it to the coating solution.

A silicate aqueous solution can also be used as the other additive material in the hydrophilic layer matrix constituting the hydrophilic layer. Alkali metal silicates such as silicate Na, silicate K, and silicate Li are preferred, and the SiO ₂ / M ₂ O ratio is in a range where the pH of the entire coating solution does not exceed 13 when silicate is added. It is preferable to select such that the inorganic particles are not dissolved.

  Further, an inorganic polymer or an organic-inorganic hybrid polymer using a metal alkoxide by a so-called sol-gel method can also be used. The formation of an inorganic polymer or an organic-inorganic hybrid polymer by the sol-gel method is described in, for example, “Application of the sol-gel method” (Sakuo Sakuo / Agne Jofusha) or in this book Known methods described in the cited documents can be used.

  In the present invention, a water-soluble resin may be contained. Examples of the water-soluble resin include polysaccharides, polyethylene oxide, polypropylene oxide, polyvinyl alcohol, polyethylene glycol (PEG), polyvinyl ether, styrene-butadiene copolymer, conjugated diene polymer latex of methyl methacrylate-butadiene copolymer. Examples thereof include resins such as acrylic polymer latex, vinyl polymer latex, polyacrylamide, and polyvinylpyrrolidone. As the water-soluble resin used in the present invention, it is preferable to use a polysaccharide.

  As the polysaccharide, starches, celluloses, polyuronic acid, pullulan, and the like can be used, but cellulose derivatives such as methyl cellulose salt, carboxymethyl cellulose salt, hydroxyethyl cellulose salt are particularly preferable, and sodium salt and ammonium salt of carboxymethyl cellulose are preferable. More preferred. This is because an effect of forming the surface shape of the hydrophilic layer in a preferable state can be obtained by including the polysaccharide in the hydrophilic layer.

  The surface of the hydrophilic layer preferably has a concavo-convex structure with a pitch of 0.1 to 20 μm like the aluminum grain of the PS plate, and this concavo-convex improves water retention and image area retention. Such a concavo-convex structure can be formed by adding an appropriate amount of a filler having an appropriate particle size to the hydrophilic layer matrix. However, the above-mentioned alkaline colloidal silica and the above-mentioned water-soluble solution are added to the hydrophilic layer coating solution. It is preferable that a structure having better printability can be obtained by forming a phase separation when the hydrophilic polysaccharide is applied and dried.

  The shape of the concavo-convex structure (pitch, surface roughness, etc.) is determined depending on the type and addition amount of alkaline colloidal silica, the type and addition amount of water-soluble polysaccharides, the type and addition amount of other additives, the solid content concentration of the coating liquid, and the wetness. It is possible to appropriately control the film thickness, drying conditions, and the like.

  In the present invention, the water-soluble resin added to the hydrophilic matrix structure part is preferably present in a state where at least a part thereof is water-soluble and can be eluted in water. This is because even if it is a water-soluble material, when it is cross-linked by a cross-linking agent or the like and becomes insoluble in water, its hydrophilicity is lowered and printability may be deteriorated. Further, it may further contain a cationic resin. Examples of the cationic resin include polyalkylene polyamines such as polyethylene amine and polypropylene polyamine or derivatives thereof, tertiary amino groups and quaternary ammonium groups. Examples thereof include acrylic resin and diacrylamine. The cationic resin may be added in the form of fine particles, and examples thereof include a cationic microgel described in JP-A-6-161101.

  In addition, the coating liquid used for coating the hydrophilic layer can contain a water-soluble surfactant for the purpose of improving the coatability, and a Si-based or F-based surfactant can be added. Although it can be used, it is particularly preferable to use a surfactant containing Si element because there is no fear of causing printing stains. The content of the surfactant is preferably 0.01 to 3% by mass, more preferably 0.03 to 1% by mass, based on the entire hydrophilic layer (solid content as the coating solution).

  Further, the hydrophilic layer can contain a phosphate. In the present invention, since the hydrophilic layer coating solution is preferably alkaline, the phosphate is preferably added as trisodium phosphate or disodium hydrogen phosphate. By adding phosphate, the effect of improving the mesh opening at the time of printing can be obtained. The addition amount of phosphate is preferably 0.1 to 5% by mass, and more preferably 0.5 to 2% by mass as an effective amount excluding hydrate.

  Moreover, the photothermal conversion raw material mentioned later can also be contained. As the photothermal conversion material, in the case of a particulate material, the particle size is preferably less than 1 μm.

(Inorganic particles with a particle size of 1 μm or more or particles coated with an inorganic material)
As the inorganic particles that can be used in the present invention, for example, known metal oxide particles such as silica, alumina, titania, zirconia, etc. can be used, but in order to suppress sedimentation in the coating solution, it is porous. Preferably, metal oxide particles are used. As the porous metal oxide particles, the aforementioned porous silica particles and porous aluminosilicate particles can be preferably used.

  Examples of the particles coated with an inorganic material include particles in which organic particles such as polymethyl methacrylate and polystyrene are used as a core material, and the particles are coated with inorganic particles having a particle diameter smaller than that of the core material particles. The particle size of the inorganic particles is preferably about 1/10 to 1/100 of the core particles. In addition, as the inorganic particles, known metal oxide particles such as silica, alumina, titania, zirconia can be used. As the coating method, various known methods can be used, but the core material particles and the coating material particles are collided at high speed in the air like a hybridizer to cause the coating material particles to bite into the surface of the core material particles. A dry coating method of fixing and coating can be preferably used.

  Moreover, the particle | grains which carried out the metal plating of the core material of an organic particle can also be used. Examples of such particles include “Micropearl AU” manufactured by Sekisui Chemical Co., Ltd., in which resin particles are plated with gold.

  The particle size is preferably 1 to 10 μm, more preferably 1.5 to 8 μm, and particularly preferably 2 to 6 μm.

  In this invention, it is preferable that it is 1-50 mass% of the whole hydrophilic layer as an addition amount of particle | grains with a particle size of 1 micrometer or more, and it is more preferable that it is 5-40 mass%. The hydrophilic layer as a whole preferably has a low content ratio of materials containing carbon such as organic resin and carbon black in order to improve hydrophilicity, and the total of these materials is preferably less than 9% by mass. More preferably, it is less than 5 mass%.

[Hydrophilic overcoat layer]
In the present invention, it is preferable to have a hydrophilic overcoat layer as an upper layer of the image forming functional layer in order to prevent scratches during handling. The hydrophilic overcoat layer may be a layer immediately above the image forming functional layer, or an intermediate layer may be provided between the image forming functional layer and the hydrophilic overcoat layer. The hydrophilic overcoat layer is preferably removable on a printing press.

  In the present invention, the hydrophilic overcoat layer preferably contains a water-soluble resin or a water-swellable resin partially crosslinked with a water-soluble resin. As such a water-soluble resin, those contained in the image forming functional layer are used.

  In this invention, a hydrophilic overcoat layer can contain the photothermal conversion raw material mentioned later.

  In order to prevent damage when the printing plate of the present invention is mounted on a laser recording device or a printing machine, it is preferable that the matting agent having an average particle size of 1 μm or more and less than 20 μm is contained in the overcoat layer in the present invention.

  Preferred matting agents include inorganic fine particles having a new Mohs hardness of 5 or more and organic matting agents. Examples of inorganic fine particles having a new Mohs hardness of 5 or more include metal oxide particles (silica, alumina, titania, zirconia, iron oxide, chromium oxide, etc.), metal carbide particles (silicon carbide, etc.), boron nitride particles, diamond particles, and the like. Can be mentioned. Examples of the organic matting agent include starch described in US Pat. No. 2,322,037 and the like, starch derivatives described in BE625,451 and GB981,198, and the like, and Japanese Patent Publication No. 44-3643. Polyvinyl alcohol described in U.S. Pat. No. 3,022,169, polystyrene or polymethacrylate described in CH 330,158, etc., polyacrylonitrile described in U.S. Pat. No. 3,079,257, etc. Examples include polycarbonates described in the specification and the like.

The addition amount of these matting agents is preferably 0.1 g or more and less than 10 g per 1 m ² .

  In addition, a nonionic surfactant can be mainly added to the overcoat layer in the case of aqueous solution coating for the purpose of ensuring the uniformity of coating. Specific examples of such nonionic surfactants include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, polyoxyethylene nonylphenyl ether, polyoxyethylene dodecyl ether and the like. . The proportion of the nonionic surfactant in the overcoat layer in the total solid is preferably 0.05 to 5 mass%, more preferably 1 to 3 mass%.

In the present invention, a dry coated amount of the overcoat layer is preferably from 0.05 to 1.5 g / m ^2, more preferred range is 0.1~0.7g / m ^2. Within this range, it is possible to satisfactorily prevent stains, prevent scratches, prevent fingerprint marks, and reduce the generation of ablation residue without impairing the removability of the overcoat layer on the printing press.

[Photothermal conversion material]
The image forming functional layer, the hydrophilic layer, the hydrophilic overcoat layer and the other layers provided in the present invention preferably contain a photothermal conversion material.

  As the photothermal conversion material, an infrared absorbing dye or pigment can be added.

(Infrared absorbing dye)
Common infrared absorbing dyes such as cyanine dyes, croconium dyes, polymethine dyes, azurenium dyes, squalium dyes, thiopyrylium dyes, naphthoquinone dyes, anthraquinone dyes, organic compounds such as phthalocyanine dyes and naphthalocyanine dyes , Azo, thioamide, dithiol, and indoaniline organometallic complexes. Specifically, JP-A-63-139191, JP-A-64-33547, JP-A-1-160683, JP-A-1-280750, JP-A-1-293342, JP-A-2-2074, Kaihei 3-26593, JP-A-3-30991, JP-A-3-34891, JP-A-3-36093, JP-A-3-36094, JP-A-3-36095, JP-A-3-42281, JP-A-3-42281 And compounds described in JP-A-3-97589, JP-A-3-103476, JP-A-7-43851, JP-A-7-102179, JP-A-2001-117201, and the like. These can be used alone or in combination of two or more.

  Examples of the pigment include carbon, graphite, metal, metal oxide and the like.

  As carbon, furnace black or acetylene black is particularly preferable. The particle size (d50) is preferably 100 nm or less, and more preferably 50 nm or less.

  As the graphite, fine particles having a particle size of 0.5 μm or less, preferably 100 nm or less, more preferably 50 nm or less can be used.

  As the metal, any metal can be used as long as the particle diameter is 0.5 μm or less, preferably 100 nm or less, more preferably 50 nm or less. The shape may be any shape such as a spherical shape, a piece shape, or a needle shape. Colloidal metal fine particles (Ag, Au, etc.) are particularly preferable.

As the metal oxide, a material that is black in the visible light region, or a material that has conductivity or is a semiconductor can be used. Examples of the material exhibiting black color in the visible light region include black iron oxide (Fe ₃ O ₄ ) and black mixed metal oxides containing two or more of the aforementioned metals. The metal oxide is a black complex metal oxide composed of two or more kinds of metal oxides. Specifically, it is a composite metal oxide composed of two or more metals selected from Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sb, and Ba. These are disclosed by methods disclosed in JP-A-8-27393, JP-A-9-25126, JP-A-9-237570, JP-A-9-241529, JP-A-10-231441, and the like. Can be manufactured. The composite metal oxide that can be used in the present invention is particularly preferably a Cu-Cr-Mn-based or Cu-Fe-Mn-based composite metal oxide. In the case of a Cu—Cr—Mn system, it is preferable to perform the treatment disclosed in JP-A-8-27393 in order to reduce the elution of hexavalent chromium. These composite metal oxides are colored with respect to the amount added, that is, they have good photothermal conversion efficiency. These composite metal oxides preferably have an average primary particle size of 1 μm or less, and more preferably have an average primary particle size in the range of 0.01 to 0.5 μm. When the average primary particle diameter is 1 μm or less, the photothermal conversion ability with respect to the addition amount becomes better, and when the average primary particle diameter is within the range of 0.01 to 0.5 μm, the photothermal conversion ability with respect to the addition amount is obtained. Better. However, the photothermal conversion ability with respect to the addition amount is greatly affected by the degree of dispersion of the particles, and the better the dispersion, the better. Therefore, it is preferable to disperse these composite metal oxide particles by a known method before adding them to the layer coating solution to prepare a dispersion (paste). An average primary particle size of less than 0.01 is not preferable because dispersion becomes difficult. A dispersing agent can be appropriately used for the dispersion. The addition amount of the dispersant is preferably 0.01 to 5% by mass, and more preferably 0.1 to 2% by mass with respect to the composite metal oxide particles. Although the kind of dispersing agent is not specifically limited, it is preferable to use Si type surfactant containing Si element.

Examples of the material that has a conductivity or is a semiconductor include SnO ₂ (ATO) doped with Sb, In ₂ O ₃ (ITO) to which Sn is added, TiO ₂ , TiO ₂ with reduced TiO ₂ (TiO ₂ ) And titanium oxynitride, generally titanium black). Further, it is also possible to use those obtained by coating the core _{(BaSO 4, TiO 2, 9Al} 2 O 3 · 2B 2 O, K 2 O · nTiO 2 , etc.) in these metal oxides. These particle sizes are 0.5 μm or less, preferably 100 nm or less, and more preferably 50 nm or less.

  A particularly preferable embodiment of the photothermal conversion material is that the infrared absorbing dye and the metal oxide are black complex metal oxides composed of two or more metal oxides.

  As addition amount of these photothermal conversion raw materials, it is 0.1-50 mass% with respect to each layer, 1-30 mass% is preferable, and 3-25 mass% is more preferable.

[Give visibility]
Usually, in the printing industry, there is an operation of plate inspection for inspecting whether an image is correctly formed before printing a printing plate on which an image is formed on a printing material. In order to perform plate inspection, it is preferable that the image formed before printing is visible on the plate surface, that is, the visual image quality is good. Since the printing plate material of the present invention is a processless printing plate material that can be printed without development processing, it is preferable that the optical density of the exposed or unexposed portion is changed by light or heat by exposure.

  As a method preferably used in the present invention, a method containing a cyanine-based infrared absorbing dye whose optical density changes by exposure, a method using a photoacid generator and a compound which changes color by the acid, and a color development such as a leuco dye And a method of using a combination of an agent and a developer.

  In the present invention, the photoacid generator means a compound that generates a Lewis acid or a Bronsted acid upon exposure.

  Specific examples of the photoacid generator include diazo compounds, orthoquinonediazide compounds, polyhalogen compounds, onium salt compounds and the like. A compound in which these structures are incorporated into a polymer can also be used.

Examples of diazo compounds include diazonium salts disclosed in US Pat. No. 2,063,631 and US Pat. No. 2,667,415, and organic compounds containing reactive carbonyl groups such as aldols and acetals. Diphenylamine-p-diazonium salt, which is a reaction product with a binder, and a formaldehyde condensation product, and these water-soluble diazonium salt compounds are converted to BF ₄ ⁻ , by the method disclosed in JP-A-54-98613. PF ₆ ^- halogenated Lewis acid salt was replaced with an anionic component such as, allyl diazonium salt compounds and the like.

  As the orthoquinonediazide compound, a compound having at least one orthoquinonediazide group in one molecule, 1,2-naphthoquinone-2-diazide-5-sulfonic acid-ethyl ester, 1,2-naphthoquinone-2-diazide-5 -Sulfonic acid-isobutyl ester, 1,2-naphthoquinone-2-diazide-5-sulfonic acid-phenyl ester, 1,2-naphthoquinone-2-diazido-5-sulfonic acid-α-naphthyl ester, 1,2-naphthoquinone -2-diazido-5-sulfonic acid-benzyl ester, 1,2-naphthoquinone-2-diazido-4-sulfonic acid-phenyl ester, 1,2-naphthoquinone-2-diazido-4-sulfonic acid-ethylamide, 1, 2-Naphthoquinone-2-diazide-4-sulfonic acid-fe Ruamido, and the like.

  Examples of polyhalogen compounds include acetophenones containing polyhalogen such as tribromoacetophenone, trichloroacetophenone, o-nitro-tribromoacetophenone, p-nitro-tribromoacetophenone, m-nitro-tribromoacetophenone, m-bromo-tribromo. Acetophenone, p-bromo-tribromoacetophenone, etc., and sulfoxides containing polyhalogen such as bis (tribromomethyl) sulfoxide, dibromomethyl-tribromomethyl sulfoxide, tribromomethyl-phenyl sulfoxide, etc. Also, sulfones containing polyhalogen such as bis (tribromomethyl) sulfone, trichloromethyl-phenylsulfone, tribromomethyl-phenylsulfone, trichloromethyl p-chlorophenylsulfone, tribromomethyl-p-nitrophenylsulfone 2-trichloromethylbenzothiazole sulfone, 2,4-dichlorophenyl-trichloromethylsulfone, and other pyrone compounds containing polyhalogens, triazine compounds, oxadiazole compounds, etc. Can be mentioned.

Examples of onium salt compounds and other photoacid generators include S.I. P. Papas, et al. , Polym. Photochem. , 5,1, onium salt compounds described P104～115 (1984), also the coloring material, 66 (2), have been introduced in _{p104~115 (1993), Ph 2 I} + / SbF 6- , etc. Photoacid generators typified by diallyliodonium salt compounds, triallylsulfonium salt compounds, triallyl selenonium salt compounds, dialkylphenacylsulfonium salt compounds, dialkyl-4-phenacylsulfonium salt compounds, α- Hydroxymethylbenzoin sulfonate, N-hydroxyiminosulfonate, α-sulfonyloxyketone, β-sulfonyloxyketone, iron-arene complex compound (benzene-cyclopentadienyl-iron (II) hexafluorophosphate Etc.), o-nitrobenzylsilyl ether compound, benzoin Shireto, tri (nitrobenzyl) phosphate, and the like.

  In addition, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts, organic halogen compounds, o-nitrobenzyl derivatives, iminosulfonates, disulfone compounds, and the like can be given.

  More specifically, for example, compounds represented by the formulas T-1 to T-15 described in Chemical Formulas 7 to 9 of JP-A-9-244226 can be given.

  Among these, more preferable are s-triazine compounds having two or more trihalomethyl groups, and particularly preferable is tris (trichloromethyl) -s-triazine. Content of these photo-acid generators is 0.01-40 mass% with respect to the total solid of printing plate material, Preferably it is 0.1-30 mass%.

  In the present invention, various compounds such as diphenylmethane, triphenylmethane, thiazine, oxazine, xanthene, anthraquinone, iminoquinone, azo, and azomethine are effectively used as the compound that changes color by acid. .

  Specific examples include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose bengal, methanyl yellow, thymol sulfophthalein, xylenol blue, methyl orange, paramethyl red, Congo Fred, Benzopurpurin 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachide Green, Parafuchsin, Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.), Oil Blue # 603 (Orient Chemical Industries) ), Oil pink # 312 (manufactured by Orient Chemical Industries), oil red 5B (manufactured by Orient Chemical Industries), oil scarlet # 308 (manufactured by Orient Chemical Industries), Il Red OG (manufactured by Orient Chemical Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Co., Ltd.), Oil Green # 502 (manufactured by Orient Chemical Co., Ltd.), Spiron Red BEH Special (manufactured by Hodogaya Chemical Co., Ltd.), m-cresol purple, cresol red , Rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carbostearylamino-4-p-dihydrooxyethyl Amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone, etc. It is.

  Moreover, an organic dye of arylamines can be used as a compound that develops color with an acid. Suitable arylamines for this purpose include so-called leuco dyes in addition to simple arylamines such as primary and secondary aromatic amines. Examples of these include the following.

  Diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, diphenyl-p-phenylenediamine, p-toluidine, 4,4'-biphenyldiamine, o-chloroaniline, o-bromoaniline, 4-chloro-o-phenylenediamine O-bromo-N, N-dimethylaniline, 1,2,3-triphenylguanidine, naphthylamine, diaminodiphenylmethane, aniline, 2,5-dichloroaniline, N-methyldiphenylamine, o-toluidine, p, p'- Tetramethyldiaminodiphenylmethane, N, N-dimethyl-p-phenylenediamine, 1,2-dianilinoethylene, p, p ', p "hexamethyltriaminotriphenylmethane (leuco crystal violet), p, p'-tetra Methyldiamino Riphenylmethane, p, p′-tetramethyldiaminodiphenylmethylimine, p, p ′, p ″ -triamino-o-methyltriphenylmethane, p, p ′, p ″ -triaminotriphenylcarbinol, p, p'-tetramethylaminodiphenyl-4-anilinonaphthylmethane, p, p ', p "-triaminophenylmethane, p, p', p" -hexapropyltriaminotriphenylmethane, and the like.

  In the present invention, as the developer, any acidic substance used as an electron acceptor in a heat-sensitive recording material can be used. For example, an inorganic acid such as acidic clay kaolin or zeolite, an aromatic carboxylic acid, an anhydride thereof or the like Examples include metal salts, organic sulfonic acids, other organic acids, phenolic compounds, methylolated products of the phenolic compounds, organic developers such as salts or complexes of the phenolic compounds, Methylolated products and salts of phenolic compounds (including complex salts unless otherwise specified) are preferred.

  Among these developers, specific examples of organic developers include phenol, 4-phenylphenol, 4-hydroxyacetophenone, 2,2'-dihydroxydiphenyl, and 2,2'-methylenebis (4-chlorophenol). 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-isopropylidenediphenol (also known as bisphenol A), 4,4'-isopropylidenebis (2-chlorophenol), 4 , 4'-isopropylidenebis (2-methylphenol), 4,4'ethylenebis (2-methylphenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol), 1,1- Bis (4-hydroxyphenyl) -cyclohexane, 2,2'-bis (4-hydroxyphenyl) -n-heptane, 4,4'- Phenolic compounds such as chloridylidenebis (2-isopropylphenol) and 4,4′-sulfonyldiphenol, methylolated products of the phenolic compounds, salicylic acid anilides of the phenolic compounds, novolac-type phenolic resins, p- Examples include benzyl hydroxybenzoate.

  In the present invention, as the color former used together with the developer, a leuco dye such as triphenylmethanelactone type can be used.

  Examples of such leuco dyes include crystal violet lactone, 3-diethylamino-7-chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluorane, and 2- (N-phenyl-N-methylamino). -6- (Np-tolyl-N-ethyl) aminofluorane, malachite green lactone, 3,3-bis (1-ethyl-2-methyldol-3-yl) phthalide, 3-diethylamino-6-methyl -7-anilinofluorane, 2-anilino-3-methyl-6- (N-ethyl-p-toluidino) fluorane, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilino Fluorane, 3-piperidino-6-methyl-7-anilinofluorane and the like can be mentioned.

  The color former and the developer are usually used in a range where the mass ratio of the developer / color developer is 0.1 / 1 to 5/1. Among them, the mass ratio is preferably 0.5 / 1 to 3 /. A range of 1 is preferred.

[Backcoat layer]
In the present invention, it is preferable to have at least one backing layer on the opposite side of the image forming functional layer of the support in order to handle and prevent physical property changes during storage. A preferable backing layer is an undercoat layer, a hydrophilic binder-containing layer or a hydrophobic binder-containing layer, and the binder-containing layer may be coated on the undercoat layer.

  As the undercoat layer, the above-described undercoat layer of the support is preferable.

  The hydrophilic binder is not particularly limited as long as it is hydrophilic. Polyvinyl alcohol (PVA), which is a resin having a hydroxyl group as a hydrophilic structural unit, a cellulose resin (methyl cellulose (MC), ethyl cellulose (EC), Hydroxyethylcellulose (HEC), carboxymethylcellulose (CMC), etc.), chitins, and starch; polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol (PEG) and polyvinyl ether (PVE) which are resins having an ether bond And polyacrylamide (PAAM) and polyvinylpyrrolidone (PVP) which are resins having an amide group or an amide bond. In addition, polyacrylic acid salt having a carboxyl group as a dissociable group, maleic acid resin, alginate and gelatins; polystyrene sulfonate having a sulfone group; amino group, imino group, tertiary amine and quaternary ammonium salt Examples thereof include polyallylamine (PAA), polyethyleneimine (PEI), epoxidized polyamide (EPAm), polyvinylpyridine, and gelatins.

  The hydrophobic binder is not particularly limited as long as it is hydrophobic as a binder. For example, polymers derived from α, β-ethylenically unsaturated compounds such as polyvinyl chloride, post-chlorinated polyvinyl chloride, and vinyl chloride are used. Copolymers of vinylidene chloride, copolymers of vinyl chloride and vinyl acetate, polyvinyl acetate and partially hydrolyzed polyvinyl acetate, starting from polyvinyl alcohol, and only a portion of the repeating vinyl alcohol units react with the aldehyde. And polyvinyl acetals, preferably polyvinyl butyral, copolymers of acrylonitrile and acrylamide, polyacrylates, polymethacrylates, polystyrene and polyethylene or mixtures thereof.

  Further, the hydrophobic binder is obtained from an aqueous dispersion resin (polymer latex) described in paragraphs (0033) to (0038) of JP-A No. 2002-258469 if the finished printing plate material surface is hydrophobic. May be good.

  In addition, in order to prevent color misregistration in color printing due to ease of attachment to the plate cylinder of the printing press and misregistration of the printing plate during printing, the average grain is formed on the outermost surface layer of the constituent layers in the present invention. It is preferable to contain a matting agent having a diameter of 1 μm or more and less than 20 μm.

  Preferred matting agents include inorganic fine particles having a new Mohs hardness of 5 or more and organic matting agents. Examples of inorganic fine particles having a new Mohs hardness of 5 or more include metal oxide particles (silica, alumina, titania, zirconia, iron oxide, chromium oxide, etc.), metal carbide particles (silicon carbide, etc.), boron nitride particles, diamond particles, and the like. Can be mentioned. Examples of the organic matting agent include starch described in USP 2,322,037, etc., starch derivatives described in BEP 625,451 and GBP981,198, and Japanese Patent Publication No. 44-3643. Polyvinyl alcohol, polystyrene or polymethacrylate described in CHP 330,158, etc., polyacrylonitrile described in USP 3,079,257, etc., polycarbonate described in USP 3,022,169, etc. can give.

The addition amount of these matting agents is preferably 0.1 g or more and less than 10 g per 1 m ² .

  In the present invention, the surface roughness of the opposite surface of the image forming layer is 0.1 μm or more and less than 2 μm by adjusting the particle size of the matting agent, the addition amount, and the amount of the binder. It is preferable that If the thickness is less than 0.1 μm, there is a concern that the transportability of the printing plate material may cause a problem due to a high friction coefficient, or there may be a problem in mounting the printing plate material to the printing machine. On the other hand, when the printing plate material is wound on a roll during production of the printing plate material or the like, or when the printing plate material is fixed on the plate cylinder, The printing plate material surface partially protrudes when pushed up from the side, and the printing pressure is concentrated on that portion, so there is a concern that printing durability may be deteriorated.

  Furthermore, the laser recording apparatus or the processless printing machine has a sensor for controlling the conveyance of the printing plate inside the apparatus, and in order to perform these controls without delay, Preferably contains a dye and a pigment. As the dye and the pigment, an infrared absorbing dye and a black pigment such as carbon black used for the above-described photothermal conversion material are preferably used. Further, the constituent layer can contain a known surfactant.

[Packaging materials]
The printing plate material produced as described above is packaged for storage until it is exposed to the later-described exposure after cutting to a desired size. In order to withstand long-term storage, the packaging material is preferably packaged with a packaging material having an oxygen permeability of 50 ml / atm · m ² · 30 ° C. · day or less as described in JP-A-2000-206653. Further, as another preferred embodiment, it is preferably packaged with a packaging material having a moisture permeability of 10 g / atm · m ² · 25 ° C. · day or less as described in JP-A-2000-206653.

〔exposure〕
The present invention also provides a printing method including a step of removing a non-image portion of an image forming layer on a printing machine after an image is formed on a printing plate material using a thermal head or a thermal laser.

  Since image formation of the printing plate material according to the present invention can be performed by heat, it is possible to form an image with a thermal head such as that used in a thermal printer. In particular, image formation can be performed by exposure with a thermal laser. preferable.

  Regarding exposure, more specifically, scanning exposure using a laser that emits light in the infrared and / or near infrared region, that is, emits light in the wavelength range of 700 to 1500 nm is preferable. A gas laser may be used as the laser, but it is particularly preferable to use a semiconductor laser that emits light in the near infrared region.

  As an apparatus suitable for scanning exposure, any apparatus may be used as long as it can form an image on the surface of a printing plate material in accordance with an image signal from a computer using the semiconductor laser.

In general,
(1) A method of exposing the entire surface of the printing plate material by performing two-dimensional scanning using one or a plurality of laser beams on the printing plate material held by the plate-like holding mechanism,
(2) The circumferential direction of the cylinder (main scanning direction) using one or a plurality of laser beams from the inside of the cylinder to the printing plate material held along the cylindrical surface inside the fixed cylindrical holding mechanism ), Scanning the entire surface of the printing plate material by moving it in a direction perpendicular to the circumferential direction (sub-scanning direction),
(3) A printing plate material held on the surface of a cylindrical drum that rotates about an axis as a rotating body is rotated in the circumferential direction (main scanning direction) by rotating the drum using one or a plurality of laser beams from the outside of the cylinder. ) And moving in the direction perpendicular to the circumferential direction (sub-scanning direction) to expose the entire surface of the printing plate material.

  In the present invention, the scanning exposure method (3) is particularly preferable, and the exposure method (3) is used particularly in an apparatus that performs exposure on a printing apparatus.

  The printing plate material on which an image has been formed in this way can be printed without performing development processing. The printing plate material after image formation is directly attached to the plate cylinder of the printing press, or the image forming is performed after the printing plate material is attached to the plate cylinder of the printing press, and the water supply roller and / or ink supply is performed while rotating the plate cylinder. The non-image portion of the image forming layer can be removed by bringing the roller into contact with the printing plate material.

  In the printing plate material according to the present invention, the image forming layer non-image part removing step can be performed by a normal printing sequence using a PS plate, and therefore it is necessary to extend the working time by so-called on-press development processing. This is effective in reducing costs.

  Furthermore, the printing method of the present invention preferably includes a step of drying the surface of the printing plate material after the image formation until the surface of the printing plate material and the water supply roller or the ink supply roller contact on the printing press. . In the printing method of the present invention, it is considered that the image intensity gradually improves immediately after image formation. In the general external drum method (method (3) described above) for a thermal laser, it generally takes about 3 minutes from the start to the end of exposure, so that the image intensity differs between the exposure start portion and the end portion at the end of exposure. There are concerns. By providing a drying step, the difference in image intensity can be reduced to a level that does not cause a problem.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

Example 1
[Preparation of printing plate fixing sheet]
<< Preparation of printing plate fixing sheet U-1 >>
(Substrate 1: Aluminum metal substrate)
An aluminum plate (material 1050, tempered H16) having a thickness of 0.20 mm was immersed in a 1% by mass sodium hydroxide aqueous solution at 50 ° C., dissolved so that the dissolved amount became 2 g / m ² , and washed with water. Then, it was immersed in a 0.1 mass% hydrochloric acid aqueous solution at 25 ° C. for 30 seconds, neutralized, and then washed with water. The thickness distribution of the obtained base material was 20%. The obtained metal substrate was designated as a printing plate fixing sheet U-1.

<< Preparation of printing plate fixing sheet U-2 >>
(Substrate 2: Polyethylene terephthalate substrate)
Using terephthalic acid and ethylene glycol, PET having an intrinsic viscosity of 0.66 (measured in phenol / tetrachloroethane = 6/4 (mass ratio) at 25 ° C.) was obtained according to a conventional method. After pelletizing this, it is dried at 130 ° C. for 4 hours, melted at 300 ° C., extruded from a T-die, rapidly cooled on a cooling drum at 50 ° C. and heat-fixed so that the average film thickness becomes 190 μm. A stretched film was prepared. This was stretched 1.1 times at a stretching temperature of 102 ° C. in the former stage stretching and 2.6 times in the latter stage stretching at 110 ° C. Subsequently, the film was stretched 1.8 times at 120 ° C. with a tenter. Then, after heat setting at 240 ° C. for 20 seconds, the film was relaxed by 4% in the lateral direction at the same temperature. Thereafter, the chuck portion of the tenter was slit, knurled at both ends, cooled to 40 ° C. and wound up at 83.3 N / m. The width (film forming width) of the polyethylene terephthalate film thus obtained was 2.5 m. The thickness distribution of the obtained base material was 12%.

Gelatin was added to water on the surface of the obtained base material 2 and dissolved by heating. After coating with a wire bar to 4 g / m ² , cooling and setting, drying was performed at 30 ° C. for 1 minute, and printing plate fixing sheet U -2 was obtained. The smooth star value was measured and found to be 1.5 kPa.

<< Preparation of printing plate fixing sheet U-3 >>
(Substrate 3: Polyethylene terephthalate substrate)
Using terephthalic acid and ethylene glycol, PET having an intrinsic viscosity of 0.66 (measured in phenol / tetrachloroethane = 6/4 (mass ratio) at 25 ° C.) was obtained according to a conventional method. After pelletizing this, it is dried at 130 ° C. for 4 hours, melted at 300 ° C., extruded from a T-die, rapidly cooled on a cooling drum at 50 ° C., and not yet thick enough to have an average film thickness of 350 μm after heat setting. A stretched film was prepared. The stretching temperature was longitudinally stretched 1.5 times at 102 ° C. for the first-stage stretching and 4.0-fold at 110 ° C. for the second-stage stretching. Subsequently, it was transversely stretched 5.0 times at 120 ° C. with a tenter. Thereafter, the film was heat-fixed at 240 ° C. for 20 seconds and relaxed by 4% in the lateral direction at the same temperature. Thereafter, the chuck portion of the tenter was slit, knurled at both ends, cooled to 40 ° C. and wound up at 83.3 N / m. The width (film forming width) of the polyethylene terephthalate film thus obtained was 2.5 m. The thickness distribution of the obtained base material was 12%.

Gelatin was added to water on the surface of the obtained base material 3 and dissolved by heating. After coating with a wire bar to 2 g / m ² , cooling and setting, drying was performed at 30 ° C. for 1 minute, and printing plate fixing sheet U -3 was obtained. The smooth star value was measured and found to be 1.5 kPa.

<< Preparation of printing plate fixing sheet U-4 >>
(Substrate 4: Polyethylene terephthalate substrate)
Using terephthalic acid and ethylene glycol, PET having an intrinsic viscosity of 0.66 (measured in phenol / tetrachloroethane = 6/4 (mass ratio) at 25 ° C.) was obtained according to a conventional method. After pelletizing this, it is dried at 130 ° C. for 4 hours, melted at 300 ° C., extruded from a T-die, rapidly cooled on a cooling drum at 50 ° C., and not yet thick enough to have an average film thickness of 90 μm after heat setting. A stretched film was prepared. The former drawing was stretched 1.3 times at 102 ° C and the latter drawing was 2.6 times stretched at 110 ° C. Then, it was stretched 4.5 times at 120 ° C. with a tenter. Thereafter, the film was heat-fixed at 240 ° C. for 20 seconds and relaxed by 4% in the lateral direction at the same temperature. Thereafter, the chuck portion of the tenter was slit, knurled at both ends, cooled to 40 ° C. and wound up at 47.04 N / m. The width (film forming width) of the polyethylene terephthalate film thus obtained was 2.5 m. The thickness distribution of the obtained base material was 3%.

On both sides of the polyethylene terephthalate film obtained above, a corona discharge treatment of 8 W / m ² · min is applied, and then the following conductive layer and intermediate layer are sequentially applied on one side and dried at 180 ° C. for 4 minutes, On these layers, the following undercoat coating liquid c-1 was applied so as to have a dry film thickness of 0.8 μm and dried at 180 ° C. for 4 minutes. The opposite surface was coated in the same manner and dried to prepare a subbed substrate 4. The surface electrical resistance at 25 ° C. and 25% RH after coating was 10 ⁹ Ω.

《Conductive layer》
Julimer ET-410 (Nippon Pure Chemicals Co., Ltd., Tg = 52 ° C.) 38 mg / m ²
SnO ₂ / Sb (9/1 mass ratio, average particle diameter 0.25 μm) 120 mg / m ²
Matting agent (polymethyl methacrylate, average particle size 5 μm) 7 mg / m ²
Denacor EX-614B (manufactured by Nagase Kasei Kogyo Co., Ltd.) 13 mg / m ²
《Middle layer》
Julimer ET-410 (Nippon Pure Chemicals Co., Ltd., Tg = 52 ° C.) 38 mg / m ²
<< Undercoat coating liquid c-1 >>
Polyvinylidene chloride polymer latex (core part 90% by mass, shell part 10% by mass, core-shell type latex)
Core part: vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 93: 3: 3: 0.9: 0.1 (mass%)
Shell part: vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 88: 3: 3: 3: 3 (mass%), mass average molecular weight 38000
3000 parts by weight 2,4-dichloro-6-hydroxy-s-triazine 23 parts by weight Matting agent (polystyrene, average particle size 2.4 μm) 1.5 parts by weight 5 g of polyvinyl alcohol PVA405 (manufactured by Kuraray Co., Ltd.) The mixture was added to 50 g with stirring, and stirred as it was for 30 minutes. To this solution, add 3 g of tetramethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), stir for 30 minutes, add 1 ml of concentrated hydrochloric acid, stir for 2 hours, and add glass particles with an average particle size of 2 μm. The mixture was placed in a paint shaker (manufactured by Toyo Seiki Co., Ltd.) and dispersed for 15 minutes, and then the glass beads were separated by filtration to obtain a dispersion. This dispersion was applied to the surface of the subbed substrate 4 obtained above with a wire bar so as to be 4 g / m ² , dried at 110 ° C. for 3 minutes, and the printing plate fixing sheet U-2 was obtained. Obtained. The smooth star value was measured and found to be 30 kPa.

<Measurement of wet change rate>
The printing plate fixing sheet is cut into a 12 cm width × 30 cm length and conditioned at 23 ° C. and 45% RH for 4 hours or more, then two holes are formed at 25 cm intervals, and the distance between the holes is measured using a pin gauge (this length) Let L ₀ ). Thereafter, the humidity is adjusted for 48 hours under the condition of 23 ° C. and 80% RH (relative humidity), and the length is measured again using a pin gauge (this length is defined as L ₁ ). The wet change rate is obtained based on the following formula.

Wet change rate (%) = (100 × | L ₀ −L ₁ | / L ₀ )
<< Production of polyethylene terephthalate support for printing plate material >>
(Production of support)
Using terephthalic acid and ethylene glycol, polyethylene terephthalate having an intrinsic viscosity of 0.66 dl / g (measured at 25 ° C. in phenol / tetrachloroethane = 6/4 (mass ratio)) was obtained according to a conventional method. This is pelletized, dried at 130 ° C. for 4 hours, melted at 300 ° C., extruded from a T-die, rapidly cooled on a cooling drum at 50 ° C., and not yet thick enough to have an average film thickness of 175 μm after heat setting. A stretched film was prepared. With respect to the drawing temperature, the first drawing was stretched 1.3 times at 102 ° C. and the second drawing was longitudinally stretched 2.6 times at 110 ° C. Next, it was stretched 4.5 times at 120 ° C. with a tenter. Thereafter, the film was heat-fixed at 240 ° C. for 20 seconds and relaxed by 4% in the lateral direction at the same temperature. Thereafter, the chuck portion of the tenter was slit, knurled at both ends, cooled to 40 ° C., and wound at 47.1 N / m. A biaxially stretched polyethylene terephthalate film having a thickness of 190 μm was thus obtained. The glass transition temperature (Tg) of this biaxially stretched polyethylene terephthalate film was 79 ° C. The obtained polyethylene terephthalate film had a width (film formation width) of 2.5 m. The thickness distribution of the obtained support was 3%.

《Preparation of underdrawn support》
A corona discharge treatment of 8 W / m ² · min is applied to both surfaces of the support film obtained above, and then the following undercoat coating solution a is applied to one surface so as to have a dry film thickness of 0.8 μm. After the coating, the undercoating liquid b was applied so as to have a dry film thickness of 0.1 μm while performing a corona discharge treatment (8 W / m ² · min) and dried at 180 ° C. for 4 minutes (undercoating surface A). . Further, after coating the following undercoat coating liquid c-1 on the opposite surface so as to have a dry film thickness of 0.8 μm, the undercoating liquid d-1 is applied while performing a corona discharge treatment (8 W / m ² · min). It apply | coated so that it might become a dry film thickness of 1.0 micrometer, and it dried at 180 degreeC for 4 minutes, respectively (undercoating surface B). Subsequently, the surface of each undercoat layer was subjected to plasma treatment under the following plasma treatment conditions.

<< Undercoat coating liquid a >>
Styrene / glycidyl methacrylate / butyl acrylate = 60: 39: 1 ternary copolymer latex (Tg = 75 ° C.) 6.3 mass% (solid content basis)
Styrene / Glycidyl methacrylate / Butyl acrylate = 20: 40: 40 ternary copolymer latex 1.6% by mass
Anionic surfactant S-1 0.1% by mass
92.0% by weight of water
<< Undercoat coating liquid b >>
Gelatin 1% by mass
Anionic surfactant S-1 0.05% by mass
Hardener H-1 0.02 mass%
Matting agent (silica, average particle size 3.5 μm) 0.02% by mass
Antifungal agent F-1 0.01% by mass
98.9% by weight of water

<< Undercoat coating liquid c-1 >>
Styrene / glycidyl methacrylate / butyl acrylate = 20: 40: 40 terpolymer latex 0.4% by mass (based on solid content)
Styrene / glycidyl methacrylate / butyl acrylate / acetoacetoxyethyl methacrylate = 39: 40: 20: 1 quaternary copolymer latex 7.6% by mass
Anionic surfactant S-1 0.1% by mass
91.9% by weight of water
<< Undercoat coating liquid d-1 >>
Component d-11 / component d-12 / component d-13 = 66: 31: 1 conductive composition
6.4% by mass
Hardener H-2 0.7% by mass
Anionic surfactant S-1 0.07 mass%
Matting agent (silica, average particle size 3.5 μm) 0.03% by mass
Water 93.4% by mass
Component d-11: Anionic polymer compound comprising a copolymer of sodium styrenesulfonate / maleic acid = 50: 50 Component d-12: Three component system comprising styrene / glycidyl methacrylate / butyl acrylate = 40: 40: 20 Copolymer latex Component d-13: high molecular weight activator comprising styrene / sodium isoprenesulfonate = 80: 20

<< Plasma treatment conditions >>
Using a batch type atmospheric pressure plasma processing apparatus (EC-I-H-340, manufactured by EC Chemical Co., Ltd.), the high frequency output is 4.5 kW, the frequency is 5 kHz, the processing time is 5 seconds, and the gas conditions are argon, Plasma treatment was performed at a volume ratio of nitrogen and hydrogen of 90% and 5%, respectively.

《Heat treatment conditions》
The support after slitting to a width of 1.25 m was subjected to low tension heat treatment at 180 ° C. for 1 minute at a tension of 2 hPa.

<Preparation of printing plate material>
Using a wire bar on the undercoating surface B of the undercoated support body using the coating liquid for the undercoat layer shown in Table 1 (preparation method is shown below), the drying amount is 4 g / m ^2. And dried at 100 ° C. for 1 minute. The smooth star value was measured and found to be 65 kPa.

(Preparation of coating solution for backing layer)
Each material shown in Table 1 was sufficiently stirred and mixed using a homogenizer, and then mixed and filtered with the composition shown in Table 1 to prepare a coating solution for hydrophilic layer 1. In addition, the detail of each raw material is as having described in Table 1, and the numerical value in a table | surface represents the mass of the solid content per 1 m < ² >. A solution diluted and dispersed with pure water was used as a coating solution.

Further, the coating solution for hydrophilic layer 1 shown in Table 2 (preparation method is shown below) and the coating solution for hydrophilic layer 2 shown in Table 3 (preparation method is shown below) It applied on the drawing surface A using the wire bar. Each was applied to each dry coating weight of 2.5 g / m ^2, becomes 0.6 g / m ² using a Wayaba on subbed support hydrophilic layer 1, in the order of hydrophilic layer 2, After drying at 120 ° C. for 3 minutes, a heat treatment was performed at 60 ° C. for 24 hours. Then, the image forming functional layer coating solution shown in Table 3 was applied using a wire bar so that the dry weight was 0.6 g / m ² and dried at 50 ° C. for 3 minutes to prepare a printing plate material. Thereafter, each printing plate material was subjected to a seasoning treatment at 50 ° C. for 72 hours.

[Preparation of coating solution for hydrophilic layer 1]
Each material described in Table 2 was sufficiently stirred and mixed using a homogenizer, and then mixed and filtered with the composition described in Table 2 to prepare a coating solution for hydrophilic layer 1. In addition, the detail of each raw material is as having described in Table 2, and the numerical value in a table | surface represents the mass part of solid content amount. A solution diluted and dispersed with pure water was used as a coating solution.

[Preparation of coating solution for hydrophilic layer 2]
Each material shown in Table 3 was sufficiently stirred and mixed using a homogenizer, and then mixed and filtered with the composition shown in Table 3 to prepare a coating solution for hydrophilic layer 2. In addition, the detail of each raw material is as having described in Table 3, and the numerical value in a table | surface represents the mass part of solid content. A solution diluted and dispersed with pure water was used as a coating solution.

<Preparation of coating solution for image forming functional layer>
(Preparation of image forming functional layer coating solution)
Table 4 shows the details of the material of the image forming functional layer coating solution. In addition, the detail of each raw material is as having described in Table 4, and the numerical value in a table | surface represents the mass part of the amount of solid content. A solution diluted and dispersed with pure water was used as a coating solution.

<< Preparation of printing plate sample >>
The printing plate material prepared above was cut into a length of 73 m and a length of 32 m, and wound around a core made of cardboard with a diameter of 7.5 cm to prepare a printing plate sample in a roll shape. Furthermore, the printing plate sample was wound with a packaging material of 150 cm × 2 m made of a material of Al ₂ O ₃ PET (12 μm) / Ny (15 μm) / CPP (70 μm). The produced packaged printing plate sample was heated for 7 days at 50 ° C. and 60% RH as forced deterioration conditions. The oxygen permeability of the packaging material was 1.7 ml / atm · m ² · 30 ° C · day, and the moisture permeability was 1.8 g / atm · m ² · 25 ° C · day.

<Evaluation of printing plate samples>
(A) Image formation by infrared laser method A printing plate sample was cut according to the exposure size, and then wound and fixed on an exposure drum. For the exposure, a laser beam having a wavelength of 830 nm and a spot diameter of about 18 μm is used, and the exposure energy is changed stepwise from 50 to 100 mJ / cm ² every 50 mJ, and 2,400 dpi (dpi is a dot per 2.54 cm) An image was formed with 175 lines, and an image-formed printing plate sample was prepared.

(B) Evaluation of various properties as a printing plate << Printing method >>
Using Lithrone 26P manufactured by Komori Corporation as a printing apparatus, the obtained printing plate fixing sheet was cut into a predetermined size and adhered to the plate cylinder. Using a coated paper, a 2% by weight solution of Astro Mark 3 (manufactured by Nikken Chemical Laboratories) as fountain solution, and Toyo King Hi-Echo M Red made by Toyo Ink Co., Ltd. And printed. The printing start sequence was the PS printing sequence, and no special on-press development operation was performed. When the plate surface was observed after printing, the non-image area was removed from the printing plate sample according to the printing method of the present invention.

<Evaluation of printing position stability>
Before printing, scratches with a width of 50 μm were attached to the plate surface at two locations of 50 cm apart. Printing was performed after preparing four of them. However, the ink was printed using Toyo King High Echo M yellow, M indigo, M red, and M black inks manufactured by Toyo Ink. After confirming that the three colors of the ten-character image were not shifted on the 100th sheet, 2,000 sheets were continuously printed. It was measured with a loupe how much the misalignment of each color of the ten characters occurred on the printed paper surface at the end of printing 2,000 sheets. The lower the value, the better.

<Evaluation of image quality>
After printing 5,000 sheets, the quality of the 2% halftone dot image was visually observed with a 100 × magnifier to evaluate the rank. Rank 5 is a high-quality halftone dot with no fringes, and the rank was lowered as quality deteriorated. Below rank 3, the image quality is unusable.

<Evaluation of printing durability>
The number of printed sheets in which more than half of the dots in the 3% halftone image were missing was obtained (printing was performed up to 20,000 sheets). The higher the number of prints, the better.

  Table 5 shows the results obtained as described above.

  From Table 5, it is clear that the printing method of the present invention has excellent printing position stability, good image quality, and excellent printing durability compared to the comparative printing method.

Example 2
<Preparation of printing plate material>
In the same manner as the printing plate material prepared in Example 1, a backing layer was applied on the undercoat surface B, and a hydrophilic layer 1, a hydrophilic layer 2 and an image forming functional layer were applied on the undercoat surface A. . Next, an overcoat layer coating solution having the following composition is applied on the image forming functional layer using a wire bar so that the drying weight is 0.4 g / m ^2, and dried at 50 ° C. for 3 minutes. The material was made. The printing plate material was subjected to seasoning at 50 ° C. for 24 hours, and then conditioned at 23 ° C. and 20% relative humidity for 24 hours.

[Overcoat layer coating solution]
98% hydrolyzed polyvinyl acetate (mass average molecular weight 200,000) 15 parts by weight hexamethylene diisocyanate 1 part by weight Matting agent (amorphous silica, average particle size 2 μm) 2 parts by weight water 82 parts by weight The printing plate prepared above As in Example 1, the material was cut into a length of 73 cm and a length of 32 m and wound around a core made of cardboard with a diameter of 7.5 cm to prepare a roll-shaped printing plate sample. Furthermore, the printing plate sample was wound with a packaging material of 150 cm × 2 m made of a material of Al ₂ O ₃ PET (12 μm) / Ny (15 μm) / CPP (70 μm). The produced packaged printing plate sample was heated for 7 days at 50 ° C. and 60% RH as forced deterioration conditions. The oxygen permeability of the packaging material was 1.7 ml / atm · m ² · 30 ° C · day, and the moisture permeability was 1.8 g / atm · m ² · 25 ° C · day.

  An image was formed in the same manner as in Example 1 to prepare a printing plate sample. Printing was performed under the same conditions as in Example 1, and the same evaluation as in Example 1 was performed. In the evaluation of printing durability, the number of printed sheets with fading on the solid portion was determined (printing was performed up to 30,000 sheets).

  Table 6 shows the results obtained as described above.

  From Table 6, it is clear that the printing method using the printing plate sample provided with the overcoat layer has excellent printing position stability, good image quality, and excellent printing durability.

Example 3
An antistatic layer (gelatin 0.8 g / m ² ) containing conductive carbon is provided on one side (back side) of the support of the printing plate material produced in Example 1, and a silica powder (average particle size of 4 μm) is formed thereon. Fuji Silysia chemical Co., Ltd. SY378) was backing layer containing 0.2 g / m ² (the gelatin 2 g / m ²⁾ provided. Next, the surface (surface) on the opposite side of the support is subjected to corona discharge machining, and then an undercoat layer (gelatin 3.5 g / m ² ) containing carbon black and silica powder having an average particle size of 4 μm (SY378, manufactured by Fuji Silysia Chemical Ltd.) On the undercoat layer, two layers of a high-sensitivity silver chloride emulsion (containing 0.8 g / m ^{2 of} gelatin) sensitized in red were simultaneously applied and dried so as to give 1.0 g / m ² as silver nitrate. Further, after heating at 40 ° C. for 7 days, a coating solution containing physical development nuclei described in Example 2 of JP-A No. 53-21602 (No. 3 copolymer of acrylamide and vinylimidazole as a polymer) And a developing agent containing hydroquinone at a ratio of 0.8 g / m ² ) and a P-2 polymer described in JP-A-8-21614 added with 5 mg / m ² of a physical development nucleus layer The liquid was applied and dried to prepare a lithographic printing plate material for scanning exposure.

The lithographic printing plate material produced above was cut into a length of 73 m and a length of 32 m in the same manner as in Example 1 and wound around a core made of cardboard having a diameter of 7.5 cm to produce a lithographic printing plate sample in the form of a roll. . Furthermore, the lithographic printing plate sample was wound with a 150 cm × 2 m packaging material made of Al ₂ O ₃ PET (12 μm) / Ny (15 μm) / CPP (70 μm) material. The packaged lithographic printing plate sample thus produced was heated for 7 days at 50 ° C. and 60% RH as forced deterioration conditions. The oxygen permeability of the packaging material was 1.7 ml / atm · m ² · 30 ° C · day, and the moisture permeability was 1.8 g / atm · m ² · 25 ° C · day. Two lots of printing plate samples derived from the support 1 were prepared.

  Using these lithographic printing plate samples as a scanning exposure apparatus (image setter), helium neon laser manufactured by Mitsubishi Paper Industries Co., Ltd. and SDP-Eco 1630II equipped with a developing processor, 1,200 dpi (dpi is 2.54 cm) A lithographic printing plate sample having an image formed by scanning exposure and development processing at 175 lines was prepared. The developing solution used was a developing solution SLM-EAC and a stabilizing solution SLM-EST manufactured by Mitsubishi Paper Industries Co., Ltd.

  The imaged lithographic printing plate sample was printed under the same conditions as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 7.

  From Table 7, compared with the printing method using the comparative printing plate fixing sheet, the printing method using the printing plate fixing sheet of the present invention has excellent printing position stability, good image quality, and printing durability. It is clear that it is excellent.

Claims (6)

At least one printing plate fixing sheet used for printing by interposing between a printing plate material having at least a hydrophilic layer, an image forming functional layer and a backing layer on a polyester support and a printing drum A printing plate fixing sheet, wherein the wet change rate at 23 ° C. and 80% RH is 0.01 to 0.08%. The printing plate fixing sheet according to claim 1, wherein the printing plate fixing sheet is made of a plastic base material having a thickness distribution of 10% or less. In a plate-hanging method in which a printing plate fixing sheet is interposed between a printing plate material having at least a hydrophilic layer, an image forming functional layer and a backing layer on a polyester support, and a plate cylinder of a printing machine, the printing plate fixing sheet A printing method characterized in that the wet change rate at 23 ° C. and 80% RH is 0.01 to 0.08%. 4. The method according to claim 3, wherein the printing plate fixing sheet comprises a plastic substrate having a thickness distribution of 10% or less. In a printing method in which a printing plate fixing sheet is interposed between a printing plate material having at least a hydrophilic layer, an image forming functional layer and a backing layer on a polyester support and a printing drum, the printing plate is fixed. The printing method, wherein the wet change rate at 23 ° C. and 80% RH of the sheet is 0.01 to 0.08%. After forming an image of a printing plate material having at least a hydrophilic layer, an image forming functional layer, and a backing layer on a polyester support using a laser, the printing plate material and the printing plate are not subjected to wet development. In a printing method in which a printing plate fixing sheet is interposed between cylinders and attached to a printing press to print on printing paper, the wet change rate at 23 ° C. and 80% RH of the printing plate fixing sheet is 0.01-0. A printing method characterized in that the printing method is 08%.