JP2005305852A - Lithographic printing plate material, lithographic printing plate and printing method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lithographic printing plate material, which develops no coating trouble and has favorable on press developing properties. <P>SOLUTION: In the lithographic printing plate material, which is formed by providing an undercoating layer, a hydrophilic layer and an image forming layer in the order named on a plastic support and is wound in a roll, the annexed amount of a hardening agent to be added to a coating liquid for forming the undercoating layer is set to be at least 0.5×10<SP>-4</SP>mol and below 25×10<SP>-4</SP>mol to 1g of gelatin. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a lithographic printing plate material, and relates to a lithographic printing plate material having an undercoat layer having high film strength, a lithographic printing plate, and a printing method using the same.

  Along with the digitization of print data, CTP (computer to plate) that is inexpensive and easy to handle and has printability equivalent to that of the PS plate is required. In particular, in recent years, there is an increasing expectation for a so-called processless plate that does not require a development process using a special agent and can be applied to a printing press having a direct imaging (DI) function.

  As the structure of the processless plate, it is possible to use the same aluminum grain as the PS plate, but from the viewpoints of freedom of layer structure and cost reduction, various types of processes using coated and formed hydrophilic layers. Wrestles have been proposed.

  As such a processless, at present, it is substantially provided only for DI printing press applications, and a processless plate having sufficient performance as a general-purpose printing plate material is not provided.

  The processless plate is mainly a so-called thermal type that forms an image by infrared laser exposure, but the thermal type can be roughly divided into two types.

  One type of thermal type printing plate material is an ablation type, for example, by laminating two layers having different affinity for dampening water or ink used for printing on a substrate, The surface-side layer is ablated by laser exposure and completely removed. However, this type of printing plate material has a problem that the cost of the apparatus is greatly increased because it is necessary to attach a mechanism for completely removing the scattered material on the ablated surface side to the exposure apparatus. In addition, since the energy required for exposure is relatively high, it is necessary to reduce the beam linear velocity during exposure (for example, to reduce the rotation speed of the exposure drum), which may reduce image formation productivity.

  Another type of thermal type printing plate material is an on-press development type. In this type, for example, two layers having different affinity for dampening water or ink used for printing are laminated on a substrate, and the adhesion between the surface side layer and the layer below it is improved by laser exposure. It is made to change and a part with weak adhesive force is removed on a printing machine. Various methods such as contact with a dampening water supply roller, dissolution or swelling by application of dampening water, contact with an ink roller, peeling by ink tack, contact with a blanket cylinder, etc. are used to remove a weakly adhesive part. Can be used.

  As such, a lithographic printing plate is known in which a layer containing a photothermal conversion agent, a layer containing a material that melts by heat, and a layer containing inorganic fine particles are sequentially laminated (for example, Patent Document 1). reference.).

Further, from the viewpoint of plate material cost, a printing plate material using a plastic support wound in a roll shape as a product form is preferable. When a plastic support is used, it is preferable that the hydrophilic layer is formed by coating as printing plate performance, and an aqueous coating solution is more preferable in consideration of printing suitability. Since it is difficult to apply a water-based hydrophilic layer directly to a plastic support, a method of applying an undercoat layer to a plastic support and applying a hydrophilic layer thereon has been adopted. However, when the hydrophilic layer is applied by a contact coating method such as a wire bar, if the film strength of the undercoat layer is weak, the wire bar is scraped off by the wire bar and appears as a coating failure, and the on-press developability of that part decreases and printing Appears as a stain on the printed material.
Japanese Patent Laid-Open No. 2001-138852

  An object of the present invention is to provide a lithographic printing plate material which is free from coating failure and has good on-press developability.

  The above problem could be solved by the following configuration.

(Claim 1)
In a lithographic printing plate material that is provided with an undercoat layer, a hydrophilic layer, and an image forming layer in this order on a plastic support and is rolled into a roll, a dura is added to the coating solution that forms the undercoat layer. A lithographic printing plate material, wherein the additive is added in an amount of 0.5 × 10 ⁻⁴ mol or more and less than 25 × 10 ⁻⁴ mol to 1 g of gelatin.

(Claim 2)
2. The lithographic printing plate material according to claim 1, wherein the undercoat layer has a two-layer structure.

(Claim 3)
The lithographic printing plate according to claim 2, wherein a photothermal conversion agent for converting near-infrared rays into heat is contained in at least one of the hydrophilic layer and the image forming layer provided in the rolled lithographic printing plate material. material.

(Claim 4)
The lithographic printing plate material according to any one of claims 1 to 3, wherein the hydrophilic layer is formed by a coating step and has a two-layer structure.

(Claim 5)
The lithographic printing plate material according to any one of claims 1 to 4, wherein a back coating layer is provided on the back surface of the image forming layer application surface.

(Claim 6)
An image is formed on the lithographic printing plate material according to any one of claims 1 to 5 using a thermal head or a thermal laser.

(Claim 7)
The lithographic printing plate material according to any one of claims 1 to 5, wherein the lithographic printing plate material is laser-exposed based on image information, is attached to a printing press without being subjected to a wet development process, and is printed by on-press development. Printing method.

  By including a specific amount of hardener with respect to gelatin in the coating solution for forming the undercoat layer, it becomes possible to form an undercoat layer having a high scratch strength, and a hydrophilic layer formed thereon, The image forming layer can be formed without any coating failure, and a lithographic printing plate having good performance can be provided.

  Hereinafter, embodiments of the present invention will be described in detail.

<Support>
Examples of the constituent material of the plastic film support according to the present invention include polyethylene terephthalate, polyethylene naphthalate, polyimide, polyamide, polycarbonate, polysulfone, polyphenylene oxide, and cellulose esters.

Support according to the present invention, the handling aptitude in terms of imparting the printing plate material, it is preferable that the elastic modulus at 120 ° C. (E120) is ^{1kN / mm 2 ~6kN / mm 2} , more preferably 1, ² kN / mm ² to ⁵ kN / mm ² . Specifically, polyethylene naphthalate (E120 = 4 kN / mm ² ), polyethylene terephthalate (E120 = 1.5 kN / mm ² ), polybutylene naphthalate (E120 = 1.6 kN / mm ² ), polycarbonate (E120 = 1. 7kN / mm ^2), syndiotactic polystyrene ^{(E120 = 2.2kN / mm 2)} , polyetherimide ^{(E120 = 1.9kN / mm 2)} , polyarylate ^{(E120 = 1.7kN / mm 2)} , polysulfone ( E120 = 1.8 kN / mm ² ), polyethersulfone (E120 = 1.7 kN / 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.

  Furthermore, the support according to the present invention has an average film thickness from the viewpoint of improving handling suitability when the printing plate material is installed in a printing machine in order for the printing plate material of the present invention to exhibit the effects described in the present invention. Is in the range of 50 μm to 500 μm, and the thickness distribution is preferably 10% or less.

  The average film thickness of the support is preferably in the range of 110 μm to 500 μm as described above, more preferably in the range of 120 μm to 400 μm, and particularly preferably in the range of 125 μm to 300 μm.

  The thickness distribution of the support 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 support is as follows. The support cut out into a square having a side of 60 cm is drawn in a grid pattern at intervals of 10 cm vertically and horizontally, the thickness of these 36 points is measured, and the average value and maximum value are measured. Find the value and minimum value.

(Method for producing support)
In order to adjust the average film thickness and thickness distribution of the support according to the present invention to the above range, there is a method of adjusting the film forming conditions appropriately or adjusting with a smooth roller while reheating after film formation, In this invention, it is preferable to manufacture by the film forming process 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 post-stage stretching to be higher in the range of 1 ° C. to 30 ° C. than the pre-stage stretching, and it is more preferable to perform the stretching while adjusting the temperature in the range of 2 ° C. to 15 ° C.

  The ratio of the former drawing is preferably 0.25 to 0.7 times the magnification of the latter drawing, and more preferably 0.3 to 0.5. After this, hold for 5 seconds to 60 seconds, more preferably 10 seconds to 40 seconds in the temperature range of Tg-30 ° C to Tg, and then laterally increase between 2.5 times and 5 times between Tg and Tg + 50 ° C. It is preferable to stretch.

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

(Fine particles)
Moreover, it is preferable to add 0.01 ppm-10 micrometers microparticles | fine-particles to said support body 1 ppm-1000 ppm for a handleability 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.

<Polyvinylidene chloride resin>
As one aspect for obtaining the effects described in the present invention, the printing plate material of the present invention is the one surface of the support in which the support is the plastic film described above and has an image forming functional layer. Is an embodiment having at least one layer containing a 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%.

  As copolymerization components other than the vinylidene chloride monomer in the copolymer, 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 weight 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 weight 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 weight 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 portion; 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 portion; vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: methacrylic acid (90: 3: 3: 1: 3) (Mw = 20000)
(Contained layer of polyvinylidene chloride resin)
The polyvinylidene chloride resin according to the present invention may be any of an undercoat layer, a hydrophilic layer described later, an image forming functional layer, and other layers as long as the image forming functional layer is coated on the support. Although it may be contained in this layer, it 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 thickness of 0.5 to 10 μm on at least one side of the support, and more preferably, a layer having a thickness of 0.8 to 5 μm is provided on both sides of the support. Particularly preferably, the thickness is 1.0 to 3 μm on both sides.

(Moisture content of support)
In the present invention, the moisture content of the support is D ′ represented by the following formula.

D ′ (mass%) = (w ′ / W ′) × 100
In the formula, W ′ is the mass of the support in a humidity-controlled equilibrium under an atmosphere of 25 ° C. and 60% RH, and w ′ is the moisture content of the support in a humidity-controlled equilibrium under an atmosphere of 25 ° C. and 60% RH. Represents.

  The water content of the support is preferably 0.5% by mass or less, more preferably 0.01 to 0.5% by mass, and particularly preferably 0.3% by mass or less.

  Means for controlling the moisture content of the support to 0.5% by mass or less are as follows: (1) The support is heat-treated at 100 ° C. or higher immediately before the application liquid for the image forming functional layer and other layers is applied (2 ) Control the relative humidity in the step of applying the coating liquid for the image forming functional layer and other layers. (3) Heat the support at 100 ° C. or higher before applying the coating liquid for the image forming functional layer and other layers. And covering with a moisture-proof sheet, storing, and applying immediately after opening. Two or more of these may be combined.

(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.

  In the present invention, it is necessary to provide a layer containing gelatin or latex on the support as an undercoat layer on the image forming functional layer side, and it may be either a single layer or multiple layers. More preferably, it is a configuration. Of the two-layer structure, the layer (lower layer) closer to the plastic support is preferably a latex-containing layer from the viewpoint of adhesion to the plastic support, and further closer to the hydrophilic layer. The (upper layer) is preferably a layer containing gelatin from the viewpoint of adhesion to the hydrophilic layer.

  After applying the undercoat layer, a hydrophilic layer is applied. However, in coating methods such as wire bar coating and gravure coating where the coating coater is in direct contact with the support, the undercoat layer must be cured. It is necessary to add a hardener that hardens gelatin. In the present invention, any hardener that satisfies the effects of the present invention can be used, but typical hardeners include vinyl, vinylsulfone, epoxy, peptide, melamine, and formalin. Aldehyde-based, triazine-based, etc. Among them, vinyl-based and epoxy-based are preferable.

The Keep present invention, the content of hardening agent is 0.5 × 10 ^-4 mol or more with respect to gelatin 1g, should be less than 25 × 10 ^-4 mol, preferably 0.5 × 10 ^-4 mol or more and less than 20 × 10 ⁻⁴ mol, more preferably 0.5 × 10 ⁻⁴ mol or more and less than 10 × 10 ⁻⁴ mol.

When the hardener content is less than 0.5 × 10 ⁻⁴ mol per 1 g of gelatin, the undercoat layer is not sufficiently hardened, and the undercoat layer is scraped off with a wire bar or the like when the hydrophilic layer is applied. And shavings appear as a coating failure. On the other hand, if the content is 25 × 10 ⁻⁴ mol or more, the film is hardened too much and the coating film of the hydrophilic layer is cracked, the printing performance is deteriorated, especially the on-press developability is lowered, and the printing waste paper is not printed. Increase.

  In addition, the undercoat layer may be a conductive polymer-containing layer described in paragraphs [0031] to [0073] of JP-A-7-20596 or a metal oxide described in paragraphs [0074] to [0081] of JP-A-7-20596. It is preferable to provide a conductive layer such as a material-containing layer. The conductive layer may be coated on either side as long as it is on the plastic 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 spots failure during printing is greatly reduced.

  In addition, a plastic film support is used as the support according to the present invention, and a material such as a plastic film and a metal plate (eg, 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.

<Stiffness>
Since the printing plate material of the present invention is composed of a plastic support, it preferably has a stiffness in the range of 0.5 to 5N. If it is less than 0.5 N, the printing plate material is not elastic, and if it exceeds 5 N, the printing plate material is too strong, and in any case, it is difficult to handle the printing plate material and attach the printing plate to the plate cylinder.

  In the present invention, the stiffness can be measured using a commercially available film stiffness tester (for example, “Stiffness Tester UT-100-230” or “Stiffness Tester UT-200GR” manufactured by Toyo Seiki Seisakusho Co., Ltd.). Specifically, both ends on the long side of a 20 cm × 10 cm sample placed on a flat table are brought close to the table, 5 cm on both ends are fixed to the table, and the center is bent 1 cm above the table. Assume that the evaluation is based on the force when the top is pushed down by 3 mm with a needle.

<Hydrophilic layer>
Examples of the material used for the hydrophilic layer of the printing plate material of the present invention include the following.

  The material forming the hydrophilic matrix is preferably a metal oxide, more preferably metal oxide fine particles.

  Examples include colloidal silica, alumina sol, titania sol, and other metal oxide sols. The metal oxide may be in the form of a sphere, feather, or the like, and the average particle size is 3 to 100 nm. However, several kinds of metal oxide fine particles having different average particle diameters can be used in combination. Further, the surface of the particles may be subjected to a surface treatment.

  The metal oxide 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.

  Among the above, colloidal silica can be preferably used in the present invention. 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 a necklace-shaped colloidal silica, which will be described later, and a 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.

  The necklace-like colloidal silica used in the present invention is a general term for the water dispersion diameter of spherical silica whose primary particle diameter is on the order of nm.

  The necklace-shaped colloidal silica used in the present invention means “pearl necklace-shaped” colloidal silica in which spherical colloidal silica having a primary particle diameter of 10 to 50 nm is bonded to a length of 50 to 400 nm.

  A pearl necklace shape (that is, a pearl necklace shape) means that an image in a state in which silica particles of colloidal silica are joined together and connected is shaped 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. As product names, “Snowtex-PS-S (average particle size in a connected state is about 110 nm)”, “Snowtex-PS-M (average particle size in a connected state is about 120 nm)” and “Snowtex- PS-L (the average particle size of the linked state is about 170 nm) ", and acidic products corresponding to these 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, alkaline “Snowtex-PS-S”, “Snowtex-PS-M” and “Snowtex-PS-L” improve the strength of the hydrophilic layer and increase the number of printed sheets. Even in this case, the occurrence of soiling is suppressed, which is particularly preferable.

  Further, it is known that the colloidal silica has a stronger binding force as the particle diameter is smaller. In the present invention, it is preferable to use colloidal silica having an average particle diameter of 20 nm or less, and more preferably 3 to 15 nm. . Further, as described above, it is particularly preferable to use alkaline colloidal silica because the alkaline substance has a high effect of suppressing the occurrence of soiling in the colloidal silica.

  Examples of alkaline colloidal silica having an average particle size within this range include “Snowtex-20 (particle diameter 10-20 nm)”, “Snowtex-30 (particle diameter 10-20 nm)”, “Snowtex” manufactured by Nissan Chemical. -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 porous property of the layer when used in combination with the aforementioned necklace-like colloidal silica.

  The ratio of colloidal silica / necklace-shaped colloidal silica having an average particle diameter of 20 nm or less is preferably 95/5 to 5/95, more preferably 70/30 to 20/80, and still more preferably 60/40 to 30/70.

  As the porous material of the hydrophilic layer matrix of the present invention, porous metal oxide particles having a particle size of less than 1 μm can be contained. As the porous metal oxide particles, porous silica, porous aluminosilicate particles, or zeolite particles described later can be preferably used.

  The porous silica particles are generally produced by a wet method or a dry method. In the wet method, it can be obtained by drying and pulverizing a gel obtained by neutralizing an aqueous silicate solution, or by pulverizing a precipitate deposited after neutralization. In the dry method, silicon tetrachloride is burned together with hydrogen and oxygen to obtain silica.

  These particles can be controlled in porosity and particle size by adjusting production conditions. The porous silica particles are particularly preferably those obtained from a wet gel.

  The porous aluminosilicate particles are produced, for example, by the method described in JP-A-10-71764. That is, it is an amorphous composite particle 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. In addition, particles produced by adding other metal alkoxides at the time of production as composite particles of three or more components can be used in the present 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 or less. 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 and the less smudged during printing, and the greater the water volume latitude, but greater than 2.5 ml / g. Then, since the particles themselves become very brittle, the durability of the coating film decreases. When the pore volume is less than 0.5 ml / g, the printing performance may be slightly insufficient.

  Zeolite can also be used as the porous material of the present invention. 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:

(M1, M2 _1/2 ) _m (Al _m Si _n O _{2 (m + n)} ) · xH ₂ O
Here, M1 and M2 are exchangeable cations, and M1 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 M2 is Ca ²⁺ , Mg ²⁺ , Ba ²⁺ , Sr ²⁺ , C ₈ H ₁₈ N ₂ ^{2+ and the} like. . 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. In addition, the dirt on the fingerprint marks is 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 of the printing plate material of the present invention can contain layered clay mineral particles. The layered mineral particles include kaolinite, halloysite, talc, smectite (montmorillonite, beidellite, hectorite, sabonite, etc.), clay minerals such as vermiculite, mica (mica), chlorite, hydrotalcite, layered polysilicate ( Kanemite, macatite, ialite, magadiite, kenyaite, etc.). Among them, it is considered that 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. 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. On the other hand, 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 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 that the gel swollen in water is prepared and then added to the coating solution.

A silicate aqueous solution can also be used as another additive material in the hydrophilic layer matrix of the present invention. 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 / Published by Agne Jofusha) or cited in this book. Known methods described in the published literature can be used.

  Moreover, you may contain water-soluble resin. Examples of water-soluble resins 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, acrylic Examples thereof include resins such as polymer polymer latex, vinyl polymer latex, polyacrylamide, and polyvinylpyrrolidone. However, it is preferable to use a polysaccharide as the water-soluble resin used in the present invention.

  As polysaccharides, starches, celluloses, polyuronic acids, pullulans and the like can be used, but cellulose derivatives such as methyl cellulose salts, carboxymethyl cellulose salts, hydroxyethyl cellulose salts are particularly preferable, and sodium salts and ammonium salts 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 (such as pitch and surface roughness) is the type and amount of alkaline colloidal silica, the type and amount of water-soluble polysaccharides, the type and amount of other additives, the solid content concentration of the coating solution, and the wet film. The thickness and drying conditions can be appropriately controlled.

  The water-soluble resin added to the hydrophilic matrix in the present invention 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, and acrylic having a tertiary amino group or a quaternary ammonium group. Examples thereof include resins and diacrylamine. The cationic resin may be added in the form of fine particles. Examples thereof include a cationic microgel described in JP-A-6-161101.

  The hydrophilic layer coating solution of the present invention may contain a water-soluble surfactant for the purpose of improving coating properties. A surfactant such as Si-based or F-based can be used, but 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).

  In addition, the hydrophilic layer of the present invention 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.

  In this invention, it is preferable to contain the particle | grains coat | covered with the inorganic particle or particle | grains with a particle size of 1 micrometer or more.

Porous, non-porous, organic resin particles, and inorganic fine particles may be used. As inorganic fillers, silica, alumina, zirconia, titania, carbon black, graphite, TiO ₂ , BaSO ₄ , ZnS, MgCO ₃ , CaCO _{3, ZnO, CaO, WS 2} , MoS 2, MgO, SnO 2, Al 2 O 3, α-Fe 2 O 3, α-FeOOH, SiC, CeO 2, BN, SiN, MoC, BC, WC, titanium carbide Corundum, artificial diamond, garnet, garnet, silica, triboli, diatomaceous earth, dolomite, etc., organic fillers include polyethylene fine particles, fluororesin particles, guanamine resin particles, acrylic resin particles, silicon resin particles, melamine resin particles, etc. I can list them. Examples of the inorganic filler include particles obtained by coating a core of organic particles such as PMMA, polystyrene, and melamine with inorganic particles that are smaller than the core particles. The particle size of the inorganic particles is preferably about 1/10 to 1/100 of the core particles. As the inorganic particles, similarly 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.

  In the present invention, any filler that satisfies the scope of the present invention can exert its effect without any particular limitation. In particular, in order to suppress sedimentation in the coating solution, porous silica particles, porous aluminosilicate particles, etc. It is preferable to use a porous inorganic filler or a porous inorganic filler.

The particle size is preferably 1 to 12 μm, more preferably 1.5 to 8 μm, and further preferably 2 to 6 μm. When the particle diameter exceeds 12 μm, there is a concern that the resolution of image formation is reduced and the blanket stain is deteriorated. The amount of particles having a particle size of 1 μm or more is preferably 1 to 50% by mass, more preferably 5 to 40% by mass based on the entire hydrophilic layer.
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%.

  As a form of the present invention, a lower layer may be provided. When a lower layer is provided, the same material as the hydrophilic layer can be used as the material used for the lower layer.

  However, the lower layer is less advantageous in that it is porous, and the nonporous material improves the coating strength, so the content of the porous material of the hydrophilic matrix is higher than that of the hydrophilic layer. Is preferably less, more preferably not contained.

  The addition amount of the particles having a particle size of 1 μm or more is preferably 1 to 50% by mass, more preferably 5 to 40% by mass based on the entire lower layer.

  Similarly to the hydrophilic layer as the entire lower layer, a low content ratio of materials containing carbon such as organic resin and carbon black is preferable for improving hydrophilicity, and the total of these materials is less than 9% by mass. It is preferable that it is less than 5% by mass.

<Image forming functional layer>
The image forming functional layer containing the heat-fusible and / or heat-fusible fine particles of the present invention can contain the following materials.
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 ° C. or higher and 120 ° C. or lower, a melting point of 60 ° C. or higher and 150 ° C. or lower, more preferably a softening point of 40 ° C. or higher and 100 ° C. or lower, and a melting point of 60 ° C. or higher and 120 ° C. or lower. When the melting point is less than 60 ° C., storage stability is a problem, and when the melting point is higher than 300 ° C., ink deposition sensitivity is lowered.

  Usable materials include paraffin, polyolefin, polyethylene wax, microcrystalline wax, fatty acid wax and the like. These have a molecular weight of about 800 to 10,000. In order to facilitate emulsification, these waxes can be oxidized to introduce polar groups such as hydroxyl groups, ester groups, carboxyl groups, aldehyde groups, and peroxide groups. Furthermore, in order to lower the softening point and improve the workability, these waxes are stearamide, linolenamide, laurylamide, myristamide, hardened beef fatty acid amide, palmitoamide, oleic acid amide, rice sugar fatty acid amide, coconut fatty acid amide. Alternatively, methylolated products of these fatty acid amides, methylene bisstellaramide, ethylene bisstellaramide, and the like can be added. 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, fatty acid amide, and fatty acid. Since these materials have a relatively low melting point and a low melt viscosity, high-sensitivity image formation can be performed. In addition, 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 size is preferably 0.01 to 10 μm, more preferably 0.1 to 3 μm. When the average particle size is smaller than 0.1 μm, when the coating solution for the layer containing the heat-meltable fine particles is applied onto the porous hydrophilic layer described later, the heat-meltable fine particles are not removed from the pores of the hydrophilic layer. It becomes easy to enter inside or into the gaps between fine irregularities on the surface of the hydrophilic layer, and the on-press development becomes insufficient, which may cause scumming. When the average particle size of the heat-meltable fine particles is larger than 10 μm, the resolution is lowered.

  Further, the composition of the heat-meltable fine particles may vary continuously between the inside and the surface layer, 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 layer, 1-90 mass% of the whole layer is preferable, and 5-80 mass% is more preferable.

  Examples of the heat-fusible fine particles used in 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-molecular polymer particles, but the temperature is high. It is preferably lower than the decomposition temperature of the molecular polymer fine particles. The weight 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 polymer particles include, for example, diene (co) polymers such as polypropylene, polybutadiene, polyisoprene and ethylene-butadiene copolymer, styrene-butadiene copolymer, Synthetic rubbers such as 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, vinyl acetate-ethylene copolymer Vinyl etc. of polymers Ester (co) polymer, 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 polymer polymer fine particles may be composed of a polymer polymer polymerized by any known method such as emulsion polymerization, suspension polymerization, solution polymerization, and gas phase polymerization. As a method of microparticulating a polymer polymer polymerized by a solution polymerization method or a gas phase polymerization method, a method of spraying a solution in an organic solvent of the polymer polymer into an inert gas and drying to form particles, Examples thereof include a method in which a high molecular weight polymer is dissolved in a water-immiscible organic solvent, this solution is dispersed in water or an aqueous medium, and the organic solvent is distilled off to form fine particles. In any of the methods, a surfactant, such as sodium lauryl sulfate, sodium dodecylbenzenesulfonate, polyethylene glycol, or a water-soluble resin, such as polyvinyl alcohol, is used as a dispersant or stabilizer in polymerization or micronization as necessary. May be used.

  The thermoplastic 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 size is smaller than 0.01 μm, when the coating liquid for the layer containing the heat-meltable fine particles is applied onto the porous hydrophilic layer described later, the heat-meltable fine particles are not removed from the pores of the hydrophilic layer. It becomes easy to enter inside or into the gaps between fine irregularities on the surface of the hydrophilic layer, and the on-press development becomes insufficient, which may cause scumming. When the average particle size of the heat-meltable fine particles is larger than 10 μm, the resolution is lowered.

  The thermoplastic 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. As content of the thermoplastic fine particle in a layer, 1-90 mass% of the whole layer is preferable, and 5-80 mass% is more preferable.

  The image-forming functional layer containing the heat-fusible and / or heat-fusible fine particles used in the present invention can further contain a water-soluble material. By including the water-soluble material, when the image forming functional layer in the unexposed area is removed using dampening water or ink on the printing press, the removability can be improved.

  As the water-soluble material, the water-soluble resins mentioned as materials that can be contained in the hydrophilic layer can also be used. However, as the image forming functional layer of the present invention, it is preferable to use saccharides, particularly oligosaccharides. Is preferred.

  Since the oligosaccharide dissolves quickly in water, the image forming functional layer in the unexposed area on the printing device can be removed very quickly, and the normal PS plate printing operation can be performed without being aware of the special removal operation. Can be removed by printing in the same manner as in the above, and printing waste paper does not increase. In addition, the oligosaccharide can maintain good printability of the hydrophilic layer without concern for lowering the hydrophilicity of the hydrophilic layer. An oligosaccharide is a crystalline substance that is soluble in water and generally has a sweet taste, and is obtained by dehydrating and condensing several monosaccharides by glycosidic bonds. Oligosaccharide is a kind of o-glycoside with sugar as aglycone, so it is easily hydrolyzed with acid to produce monosaccharide, and disaccharide, trisaccharide, tetrasaccharide, pentasaccharide, etc. depending on the number of molecules of monosaccharide produced are categorized. The oligosaccharide in the present invention refers to those from disaccharide to decasaccharide.

  These oligosaccharides are roughly classified into reducing oligosaccharides and non-reducing oligosaccharides depending on the presence or absence of a reducing group, and are composed of homooligosaccharides composed of a single monosaccharide and two or more types of monosaccharides. It is also classified as a hetero-oligosaccharide. Oligosaccharides exist naturally as free or glycosides and can also be obtained by partial hydrolysis of polysaccharides with acids or enzymes. Various oligosaccharides are also generated by glycosyl transfer by other enzymes. Oligosaccharides often exist as hydrates in a normal atmosphere. Moreover, the melting point differs between hydrate and anhydride.

  In the present invention, it is preferable to coat and form a saccharide-containing layer with an aqueous solution. Therefore, when the oligosaccharide is formed from an aqueous solution, if the oligosaccharide present in the layer is an oligosaccharide that forms a hydrate, its melting point. Is considered to be the melting point of the hydrate. Thus, since it has a relatively low melting point, the oligosaccharide also melts in the temperature range in which the hot melt fine particles melt or in the temperature range in which the hot melt fine particles fuse, and the porous hydrophilic layer of the hot melt fine particles It does not hinder image formation such as melt penetration into the film and fusion of heat-fused fine particles.

  Among oligosaccharides, trehalose is commercially available in a relatively high purity state at a low cost, and despite its high solubility in water, its hygroscopicity is very low, and on-press developability and The storage stability is very good.

  In addition, when oligosaccharide hydrate is melted by heat to remove water of hydration and then solidified (for a short time after solidification), it becomes an anhydrous crystal, but trehalose has a melting point of anhydride higher than that of hydrate. It is characteristic that it is higher than 100 ° C. This means that the exposed portion is melted by infrared exposure and immediately after re-solidification, the exposed portion is in a state of being difficult to melt at a high melting point, and is effective in causing image defects during exposure such as banding.

  In order to achieve the object of the present invention, trehalose is particularly preferable among oligosaccharides.

  As content of the oligosaccharide in a layer, 1-90 mass% of the whole layer is preferable, and 10-80 mass% is more preferable.

  Image formation of the printing plate material of one embodiment of the present invention can be performed by heat, but it is particularly preferable to perform image formation by exposure with an infrared laser.

  More specifically, the exposure relating to the present invention is preferably scanning exposure using a laser emitting light in the infrared and / or near infrared region, that is, emitting light in the wavelength range of 700 to 1500 nm. 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 according to the present invention, any apparatus can 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. Good.

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.

  In the printing plate material of the present invention, an image can also be formed by applying an oleophilic material directly to the hydrophilic layer surface in an image-like manner.

  As one of methods for imparting an oleophilic material to the image, a method using a known thermal transfer method can be mentioned. Specifically, there is a method in which a heat transfer type printer is used to image-transfer the heat-meltable ink from the ink ribbon having the heat-meltable ink layer to the hydrophilic layer surface with a thermal head.

  Also, using a digital proof device of an infrared laser heat-melt transfer method, a printing plate material is wound on an exposure drum with a hydrophilic layer on the outside, and an ink sheet further having a heat-meltable ink layer is printed on the ink sheet. There can also be mentioned a method in which the surface is wound in contact with the hydrophilic layer, imagewise exposure is performed with an infrared laser, and the heat-meltable ink is imagewise transferred onto the surface of the hydrophilic layer. In this case, the photothermal conversion material may be contained in the hydrophilic layer, in any layer on the ink sheet side, or in both.

  After forming an image with a heat-meltable ink on the hydrophilic layer, the printing plate material can be heated to further strengthen the adhesion between the hydrophilic layer and the image. When the hydrophilic layer contains a photothermal conversion material, this heat treatment can also be performed using infrared laser irradiation or flash exposure using a known xenon lamp or the like.

  Another method is a method using a known ink jet method. As the ink to be used, the oil-based ink disclosed in Japanese Patent No. 2995075, the hot melt ink disclosed in Japanese Patent Laid-Open No. 10-24550, and the Japanese Patent Laid-Open No. 10-157053 are disclosed. An oil-based ink in which solid and hydrophobic resin particles are dispersed at normal temperature, or a water-based ink in which solid and hydrophobic thermoplastic resin particles are dispersed at normal temperature can be used. As an aspect of the present invention, A radiation curable ink can be preferably used.

  The radiation curable ink used in the present invention is composed of at least a polymerizable compound. In addition, a coloring material can be added for the purpose of obtaining visible image quality. As the color material, a color material that can be dissolved or dispersed in the main component of the polymerizable compound, that is, various dyes and pigments can be used.

  When adding a pigment, since the dispersibility has a great influence on the degree of coloration, the pigment is appropriately dispersed. For the dispersion of the pigment, a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, a paint shaker, or the like can be used. It is also possible to add a dispersant when dispersing the pigment. As the dispersant, it is preferable to use a polymer dispersant. Examples of the polymer dispersant include Solsperse series manufactured by Zeneca. Moreover, it is also possible to use a synergist according to various pigments as a dispersion aid. These dispersants and dispersion aids are preferably added in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the pigment. Although the dispersion medium is a solvent or a polymerizable compound, the radiation curable ink used in the present invention is preferably solventless because it reacts and cures immediately after ink landing. If the solvent remains in the cured image, the solvent resistance deteriorates and the VOC of the remaining solvent arises. Therefore, it is preferable in view of dispersibility that the dispersion medium is not a solvent but a polymerizable compound, and among them, a monomer having the lowest viscosity is selected.

  For the dispersion, it is preferable that the average particle diameter is 0.08 to 0.5 μm, and the pigment, the dispersant, and the dispersion medium are selected so that the maximum particle diameter is 0.3 to 10 μm, preferably 0.3 to 3 μm. Set dispersion conditions and filtration conditions. By controlling the particle size, clogging of the head nozzle can be suppressed, and ink storage stability, ink transparency, and curing sensitivity can be maintained.

  The colorant is preferably added in an amount of 0.1% to 10% by weight of the total ink.

  The radiation polymerizable compound is a radical polymerizable compound such as light described in JP-A-7-159983, JP-B-7-31399, JP-A-8-224982, and JP-A-10-863. Photo-curing materials using a polymerizable composition and cationic polymerization-based photo-curing resins are known, and recently, photo-cation polymerization-based photo-curing resins that have been sensitized to a long wavelength region longer than visible light. Are also disclosed in, for example, JP-A-6-43633 and JP-A-8-324137.

  The radical polymerizable compound is a compound having an ethylenically unsaturated bond capable of radical polymerization, and may be any compound as long as it has at least one ethylenically unsaturated bond capable of radical polymerization in the molecule. , Oligomers, polymers and the like having a chemical form. Only one kind of radically polymerizable compound may be used, or two or more kinds thereof may be used in combination at an arbitrary ratio in order to improve desired properties. A polyfunctional compound having two or more functional groups is more preferable than a monofunctional compound. More preferably, two or more polyfunctional compounds are used in combination for controlling performance such as reactivity and physical properties.

  Examples of compounds having an ethylenically unsaturated bond capable of radical polymerization include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and their salts, esters, urethanes, amides. And radically polymerizable compounds such as unsaturated monomers, acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated urethanes. Specifically, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis (4-acryloxypolyethoxyphenyl) propane, neopentyl glycol Diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaery Acrylic acid derivatives such as lithol tetraacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate, N-methylol acrylamide, diacetone acrylamide, epoxy acrylate, methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate , Lauryl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylol Methacryl derivatives such as tan trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, and other derivatives of allyl compounds such as allyl glycidyl ether, diallyl phthalate, triallyl trimellitate More specifically, Yamashita Junzo, “Crosslinker Handbook”, (1981 Taiseisha); Kato Kiyomi, “UV / EB Curing Handbook (Materials)” (1985, Polymer Publication) ); Rad-Tech Study Group, “Application and Market of UV / EB Curing Technology”, p. 79, (1989, CMC); Eiichiro Takiyama, “Polyester Resin Handbook”, (1988, Nikkan Kogyo Shimbun) Commercially available products described in the above, or radically polymerizable or crosslinkable monomers known in the industry Oligomers and polymers can be used. The amount of the radical polymerizable compound added is preferably 1 to 97% by mass, more preferably 30 to 95% by mass.

  Cationic polymerization type photo-curing resin includes monomers that are polymerized by cationic polymerization (mainly epoxy type), epoxy-type UV curable prepolymer, prepolymer containing two or more epoxy groups in one molecule. Etc. Examples of such prepolymers include alicyclic polyepoxides, polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, and polyglycidyls of aromatic polyols. Examples include ethers, hydrogenated compounds of polyglycidyl ethers of aromatic polyols, urethane polyepoxy compounds, and epoxidized polybutadienes. One of these prepolymers can be used alone, or two or more thereof can be mixed and used.

  In the present invention, (meth) acrylic monomers or prepolymers, epoxy monomers or prepolymers, urethane monomers or prepolymers are preferably used as the polymerizable compound, and the following compounds are more preferable.

  2-ethylhexyl-diglycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxybutyl acrylate, hydroxypivalate neopentyl glycol diacrylate, 2-acryloyloxyethyl phthalate, methoxy-polyethylene glycol acrylate, tetramethylol Methane triacrylate, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, dimethylol tricyclodecane diacrylate, ethoxylated phenyl acrylate, 2-acryloyloxyethyl succinic acid, nonylphenol EO adduct acrylate, modified glycerin triacrylate Bisphenol A diglycidyl ether acrylic acid adduct, modified bisphenol A diacrylate, phenoxy-polyethylene Glycol acrylate, 2-acryloyloxyethyl hexahydrophthalic acid, bisphenol A PO adduct diacrylate, bisphenol A EO adduct diacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate tolylene diisocyanate urethane prepolymer, lactone Modified towable acrylate, butoxyethyl acrylate, propylene glycol diglycidyl ether acrylic acid adduct, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, 2-hydroxyethyl acrylate, methoxydipropylene glycol acrylate, ditrimethylolpropane tetraacrylate, penta Erythritol triacrylate hexamethylene Isocyanate urethane prepolymer, stearyl acrylate, isoamyl acrylate, isomyristyl acrylate, can be mentioned iso-stearyl acrylate.

  These acrylate compounds have lower skin irritation and sensitization (rash) than the polymerizable compounds conventionally used in UV curable inks, can relatively reduce viscosity, and provide stable ink ejection properties. Further, the polymerization sensitivity and the adhesion to the recording medium are also good. 20-95 mass% of the said compound group is used, Preferably it is 50-95 mass%, More preferably, 70-95 mass% is used.

  The monomers listed in the above-mentioned polymerizable compounds are low in sensitization even with low molecular weight, and have high reactivity, low viscosity, and excellent permeability and adhesion to the hydrophilic layer. .

  Furthermore, in order to further improve sensitivity, bleeding, and adhesion to the hydrophilic layer, it is sensitivity to use the above-mentioned monoacrylate together with a polyfunctional acrylate monomer or polyfunctional acrylate oligomer having a molecular weight of 400 or more, preferably 500 or more. From the viewpoint of improving adhesion. While maintaining safety, the sensitivity, bleeding, and adhesion to the recording medium can be further improved. As the oligomer, an epoxy acrylate oligomer and a urethane acrylate oligomer are particularly preferable.

  It is preferable to use a monoacrylate selected from the above compound group in combination with a polyfunctional acrylate monomer or polyfunctional acrylate oligomer, because the film can have flexibility and the film strength can be increased while improving adhesion. As monoacrylates, stearyl acrylate, isoamyl acrylate, isomistyl acrylate, and isostearyl acrylate have high sensitivity, low shrinkage, and can suppress strength reduction due to internal stress in the image area. This is preferable in terms of cost reduction.

  Although methacrylate has better skin irritation than acrylate, sensitization is generally not different from acrylate and is not suitable because it is less sensitive than acrylate, but it has high reactivity and good sensitization. If it is, it can be used suitably. Among the above compounds, alkoxy acrylate has low sensitivity and causes problems such as bleeding, odor, and irradiation light source. Therefore, it is preferable to keep the amount below 70 parts by mass and use other acrylates in combination.

  If necessary, other components can be added to the ink used in the present invention.

  When an electron beam, X-ray, or the like is used as irradiation light, an initiator is not necessary. However, when UV light, visible light, or infrared light is used as a radiation source, a radical polymerization initiator or initiator corresponding to each wavelength is used. Add auxiliaries and sensitizing dyes. These amounts require 1-10 parts by weight of the total ink. Various known compounds can be used as the initiator, but the initiator is selected from those that dissolve in the polymerizable compound. Specific examples of the initiator include xanthone or thiooxanthone series, benzophenone series, quinone series, and phosphine oxide series.

  Moreover, in order to improve preservability, 200-20000 ppm of polymerization inhibitors can be added. The ink of the present invention is preferably heated and reduced in viscosity in the range of 40 to 80 ° C. and ejected. Therefore, it is preferable to add a polymerization inhibitor in order to prevent head clogging due to thermal polymerization.

  In addition to this, surfactants, leveling additives, matting agents, polyester resins, polyurethane resins, vinyl resins, acrylic resins, rubber resins, and waxes are added to adjust film properties as necessary. I can do it. In order to improve adhesion to recording media such as olefin and PET, it is preferable to include a tackifier that does not inhibit polymerization. Specifically, high molecular weight adhesive polymers (esters of (meth) acrylic acid and alcohols having an alkyl group having 1 to 20 carbon atoms, described in JP-A-2001-49200 5-6p, (meta ) A copolymer of acrylic acid and an ester of an alicyclic alcohol having 3 to 14 carbon atoms, an ester of (meth) acrylic acid and an aromatic alcohol having 6 to 14 carbon atoms), or a polymerizable unsaturated bond A low molecular weight tackifying resin having

  In order to improve the adhesion with the hydrophilic layer, it is also effective to add a trace amount of organic solvent. In this case, it is effective to add in a range that does not cause the problem of solvent resistance and VOC, and the amount is 0.1 to 5%, preferably 0.1 to 3%.

  In addition, as a means for preventing a decrease in sensitivity due to the light-shielding effect due to the ink color material, it is possible to combine a cationically polymerizable monomer having a long initiator lifetime with an initiator to obtain a radical-cation hybrid curable ink.

  The composition ratio of the ink is determined so that the temperature at the time of ejection is preferably 7 to 30 mPa · s, more preferably 7 to 20 mPa · s in consideration of ejection properties. The ink viscosity at 25 ° C. is preferably 35 to 500 mPa · s, more preferably 35 to 200 mPa · s. By increasing the viscosity at room temperature, it is possible to prevent ink from penetrating into porous recording media, to reduce uncured monomers and to reduce odor, and to suppress dot bleeding at the time of landing, improving image quality. Is done. If it is less than 35 mPa · s, the effect of preventing bleeding is small. If it is higher than 500 mPa · s, a problem occurs in the delivery of the ink liquid.

  The surface tension is preferably 200 to 300 μN / cm, more preferably 230 to 280 μN / cm. If it is less than 200 μN / cm, there is concern in terms of bleeding and penetration, and if it exceeds 300 μN / cm, there is concern in terms of wettability.

<Photothermal conversion agent>
The hydrophilic layer, the lower layer, and the image forming layer of the present invention achieve high sensitivity by containing the following photothermal conversion material.

  In the present invention, the following metal oxide can be added to the hydrophilic layer as a photothermal conversion material.

  A material that exhibits black color in the visible light region, or a material that has conductivity or is a semiconductor can be used.

Examples of the former include black iron oxide (Fe ₃ O ₄ ) and black composite metal oxides containing two or more of the aforementioned metals.

Examples of the latter include SnO ₂ doped with Sb (ATO), In ₂ O ₃ doped with Sn (ITO), TiO ₂ , TiO ₂ with reduced TiO ₂ (titanium oxynitride, generally titanium black), etc. Is mentioned. Further, it can also be used those obtained by coating the core material _{(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.

  Among these photothermal conversion materials, black composite metal oxides containing two or more metals are more preferable materials.

  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 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-8-273393 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 separately 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.

  The addition amount of these composite metal oxides is 20% or more and less than 40%, more preferably 25% or more and less than 39%, more preferably 25% or more and less than 30%, based on the total solid content of the hydrophilic layer. Range. When the addition amount is less than 20%, sufficient sensitivity cannot be obtained, and when it is 40% or more, ablation residue due to ablation occurs.

  In the present invention, the following infrared absorbing dye can be added as a photothermal conversion material to the hydrophilic layer and the image forming layer.

  General 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-based, thioamide-based, dithiol-based, and indoaniline-based 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 Examples thereof include compounds described in JP-A-3-97589, JP-A-3-103476, and the like. These can be used alone or in combination of two or more.

  The addition amount of these infrared absorbing dyes is 0.1% or more and less than 10%, more preferably 0.3% or more and less than 7%, more preferably 0.5%, based on the total solid content of the image forming layer. The range is less than 6%. If the addition amount deviates from this, as described above, if the addition amount is less than 0.1%, sufficient sensitivity cannot be obtained, and if it is 10% or more, ablation residue due to ablation occurs.

<Back coating layer>
In the present invention, it is preferable to have at least one component 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. Preferred constituent layers are 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), Hydroxyethyl cellulose (HEC), carboxymethyl cellulose (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, polyacrylates, maleic resins, alginates and gelatins having carboxyl groups as dissociable groups; polystyrene sulfonates having sulfone groups; amino groups, imino groups, tertiary amines and quaternary ammonium salts 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.

  The hydrophobic binder may be obtained from an aqueous dispersion resin (polymer latex) described in paragraphs 0033 to 0038 of JP-A No. 2002-258469 as long as the finished printing plate material surface is hydrophobic. .

In the present invention, it is necessary to contain a matting agent in the back coating layer in order to prevent the color misalignment in color printing due to the ease of attachment to the printing press and the misalignment of the printing plate during printing. The matting agent to be contained may be used regardless of porous, nonporous, organic resin particles, and inorganic fine particles. Examples of the inorganic matting agent include silica, alumina, zirconia, titania, carbon black, graphite, TiO ₂ , BaSO ₄ , ZnS, MgCO ₃ , CaCO ₃ , ZnO, CaO, WS ₂ , MoS ₂ , MgO, SnO ₂ , Al ₂ O ₃ , α-Fe ₂ O ₃ , α-FeOOH, SiC, CeO ₂ , BN, SiN, MoC, BC, WC, titanium carbide, corundum, artificial diamond, garnet, garnet, silica, triboli, diatomaceous earth, dolomite, etc. As organic matting agents, polyethylene fine particles, fluororesin particles, guanamine resin particles, acrylic resin particles, silicone resin Examples thereof include particles and melamine resin particles. Examples of the inorganic clothing matting agent include particles in which a core agent of organic particles such as PMMA, polystyrene, and melamine is coated with inorganic particles that are smaller than the core agent particles. The particle size of the inorganic particles is preferably about 1/10 to 1/100 of the core particles. As the inorganic particles, similarly 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.

  In the present invention, the mat agent satisfying the scope of the present invention can exert the effect without any particular limitation. However, particularly in the case of a product form wound in a roll shape, the back coating layer mat agent is an image forming layer. In order to suppress scratches on the surface, it is preferable to use organic resin particles.

  The average particle size of the matting agent in the present invention can be obtained by calculating an equivalent circle light from the projected area using an electron microscope.

  The particle size is preferably 1 to 12 μm, more preferably 1.5 to 8 μm, and even more preferably 2 to 7 μm. When the particle diameter exceeds 12 μm, scratches on the image forming layer are likely to occur, and conversely, with 1 μm particles, plate lifting occurs on the plate cylinder.

The addition amount of the matting agent is preferably 0.2 to 30% by mass, and more preferably 1 to 10% by mass based on the entire back coating layer.
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 may contain a known surfactant.

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

(Production of support)
Using terephthalic acid and ethylene glycol, polyethylene terephthalate having IV (inherent viscosity) = 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》
Both surfaces of the support film obtained above are subjected to a corona discharge treatment of 8 W / m ² · min, and then the undercoat coating solution a shown in Table 1 below is applied on one surface to a dry film thickness of 0.8 μm. In this way, the amount of the hardening agent described in Table 2 below was changed while performing corona discharge treatment (8 W / m ² · min) after coating (level 1 to 8). And dried at 180 ° C. for 4 minutes (undercoating surface A). In addition, the undercoat coating solution c shown in Table 3 below is applied to the opposite surface so that the dry film thickness becomes 0.8 μm, and then the undercoat application in Table 4 below is performed while performing corona discharge treatment (8 W / m ² · min). The liquid d was applied to a dry film thickness of 1.0 μm and dried at 180 ° C. for 4 minutes (undercoating surface B). Subsequently, the surface of each undercoat layer was subjected to plasma treatment under the following plasma treatment conditions. After the plasma treatment, plastic substrates 001 to 008 which had been sublimated were obtained.

Component d-11;
An anionic polymer compound comprising a copolymer of sodium styrenesulfonate / maleic acid = 50/50 component d-12;
Three-component copolymer latex composed of styrene / glycidyl methacrylate / butyl acrylate = 40/40/20 component d-13;
Polymeric 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.

  Preparation of back coating layer

  The composition shown in Table 5 was sufficiently stirred and mixed using a homogenizer, and then filtered to prepare a back coating layer coating solution.

<Application of back coating layer>
The coating liquid of the back coating layer is applied to the undercoated sample 001 to 008 on the support undercoating surface B side using the wire bar # 6, and a drying zone set at 100 ° C. having a length of 15 m is transported at a speed of 15 m. Per minute. The amount of the back coating layer was 2.0 g / m ² .

  <Preparation of lower hydrophilic layer coating solution>

  The composition shown in Table 6 was sufficiently stirred and mixed using a homogenizer, and then filtered to prepare a lower hydrophilic layer coating solution.

  <Preparation of coating solution for upper hydrophilic layer>

  The composition shown in Table 7 was sufficiently stirred and mixed using a homogenizer and then filtered to prepare an upper hydrophilic layer coating solution.

<Application of lower layer and upper hydrophilic layer>
Each lower hydrophilic layer coating solution was applied to the back surface (undercoat coating surface A) of the support on which the above-mentioned backcoat layer had been applied, using wire bar # 5, and was set to 15 ° C. and set to 100 ° C. The drying zone was passed at a conveyance speed of 15 m / min. Subsequently, the upper hydrophilic layer coating solution was applied using wire bar # 3 and passed through a drying zone set at 100 ° C. having a length of 30 m at a conveyance speed of 15 m / min. The amount of each of the lower layer and the hydrophilic layer was 3.0 g / m ² and 0.55 g / m ² . The sample after coating was aged at 60 ° C. for 1 day. The applicability of the lower hydrophilic layer will be described later.

<Preparation of coating solution for image forming layer>
An image layer having the composition shown in Table 8 below was applied on the upper hydrophilic layer prepared above using wire bar # 5, and a drying zone set at 70 ° C. having a length of 30 m was transported at a conveyance speed of 15 m / min. It was passed at a speed to form an image forming layer. The amount of the image forming layer applied was 0.5 g / m ² . The sample after application was aged at 50 ° C. for 2 days.

  The lithographic printing plate material was cut to a width of 660 mm and wound around a paper core having an outer diameter of 76 mm by 30 m to obtain roll-shaped lithographic printing plate materials 011 to 018.

<Printing method>
Printing device: DAIYAF-1 manufactured by Mitsubishi Heavy Industries, Ltd., coated paper, dampening solution astromark 3 (manufactured by Nikken Chemical Research Co., Ltd.), 2% by mass, and two types of inks were prepared and evaluated for printing. Went.
(1): Toyo King High Echo M Red (manufactured by Toyo Ink)
(2): TM HiEcho SOY1 (soy oil ink manufactured by Toyo Ink)
<Evaluation of applicability>
The scratches due to the wire bar when the lower hydrophilic layer was applied to the underdrawn sample were evaluated.

Rank 5: flaw by wire bar or no good Rank 4: No. 3 flaw by wire bar is observed one when the coating was seen 1.0 m ^2: wire when coated material was observed 1.0 m ² Two to five scratches are observed by the bar. Rank 2: Scratches are observed at all pitches of the protruding portion of the wire bar. Rank 1: All the undercoat layer is scraped off by the wire bar.

  Rank 3 or higher is a practically acceptable level, and if it falls below rank 3, printing performance is affected.

<Evaluation of printing (waste paper)>
Good S / N ratio at the time of printing (the non-image portion is free of background stain, that is, the non-image portion of the image forming layer is removed on the printing machine, and the density of the image portion is within an appropriate range. In particular, the number of printed sheets until a printed matter having a development defect due to scratches on the image layer due to the mat material of the backcoat layer was obtained was evaluated. The smaller the number of waste paper, the better. There are practical problems with 40 sheets or more.

<Evaluation of printing durability>
The printing end point was determined at the stage when either a 3% dot missing in the image or a decrease in the density of the solid portion was confirmed, and the number of sheets was determined.

  As can be seen from Table 9, the lithographic printing plate material of the present invention can be stably produced and has excellent printing performance.

Claims (7)

In a lithographic printing plate material that is provided with an undercoat layer, a hydrophilic layer, and an image forming layer in this order on a plastic support and is rolled into a roll, a dura is added to the coating solution that forms the undercoat layer. A lithographic printing plate material, wherein the additive is added in an amount of 0.5 × 10 ⁻⁴ mol or more and less than 25 × 10 ⁻⁴ mol to 1 g of gelatin. 2. The lithographic printing plate material according to claim 1, wherein the undercoat layer has a two-layer structure. The lithographic printing plate according to claim 2, wherein a photothermal conversion agent for converting near infrared rays into heat is contained in at least one of the hydrophilic layer and the image forming layer provided on the roll-shaped lithographic printing plate material. material. The lithographic printing plate material according to any one of claims 1 to 3, wherein the hydrophilic layer is formed by a coating step and has a two-layer structure. The lithographic printing plate material according to any one of claims 1 to 4, wherein a back coating layer is provided on the back surface of the image forming layer application surface. An image is formed on the lithographic printing plate material according to any one of claims 1 to 5 using a thermal head or a thermal laser. The lithographic printing plate material according to any one of claims 1 to 5, wherein the lithographic printing plate material is laser-exposed based on image information, attached to a printing press without being subjected to a wet development process, and printed by on-press development. Printing method.