JP5281445B2 - Photosensitive lithographic printing plate material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a negative photosensitive lithographic printing plate material, relating to a photosensitive lithographic printing plate material for performing water development, in which sludge and development unevenness are improved when a developing process is continued by using a process device, and excellent contamination preventing property, ink deposition property and uniformity of ink deposition are obtained. <P>SOLUTION: The photosensitive lithographic printing plate material includes a hydrophilic layer and a photopolymerizable photosensitive layer containing a water-soluble polymer layered in this order on a support, wherein at least one layer on the support contains a defoaming agent. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a water-developable photosensitive lithographic printing plate material in which a photopolymerizable photosensitive layer including a hydrophilic layer and a water-soluble polymer is provided in this order on a support, and in particular, contains essentially no chemicals. The present invention relates to a negative photosensitive lithographic printing plate material that improves the occurrence of sludge and development unevenness when developed with water, and is excellent in stain resistance, ink transportability and ink transport uniformity.

  In recent years, computer-to-plate (CTP) technology has been developed to output directly on a printing plate without outputting it on film based on digital data produced on a computer, and various types equipped with various lasers as output machines. Plate setters and photosensitive lithographic printing plate materials that match these are being actively developed. Important issues or requests that have been raised with the spread of the CTP method include various points related to development processing. In conventional CTP, a photosensitive lithographic printing plate material is exposed to a laser image, and then a non-image portion is eluted with an alkaline developer, and is subjected to printing through a water washing and gumming process. Alkaline developer is harmful to the human body, and its care and management are required for its handling and storage. Furthermore, the purchase cost and the cost associated with waste liquid treatment place a great burden on the user. In addition, the pH, temperature, etc. must be carefully managed as the liquidity of the alkaline developer. Handling is complicated and it is always difficult to obtain reproducible results in the plate making process.

  There has been proposed a photosensitive lithographic printing plate material that avoids the use of such an alkaline developer and can be developed with water. For example, as shown in JP-A-2008-265297 (Patent Document 1), JP-A-2008-230205, JP-A-2008-238506, JP-A-2008-250195, etc., a support having a hydrophilic surface A photosensitive lithographic printing plate material has been proposed in which a photopolymerizable photosensitive layer that can be developed with water is provided thereon.

  In these water-developable photosensitive lithographic printing plate materials, the development process may be diverted from the automatic development processing apparatus used in the case of using an alkali developer widely used in the past. There are many cases in which a process of entering the water washing section through and then discharging through drying is taken. That is, development is carried out with water, but the processing step itself is essentially the same as a conventional processing step using an alkaline developer.

  Various problems have arisen when water is used for development instead of an alkaline developer. Various solutions have been made in the alkaline developer to stabilize the processing, and it is possible to select an alkali component, a surfactant, etc. so as to uniformly dissolve and disperse the components such as the photosensitive layer to be eluted. In practice, the mechanical configuration and processing conditions of an automatic development processing apparatus are optimized in accordance with alkali development conditions.

  On the other hand, the development processing intended by the present invention is aimed at performing processing with water that is neutral or essentially free of chemicals having a pH in the range of 4 to 9 without using an alkaline developer. Yes. This eliminates the need for strict control of pH and liquid temperature when using an alkaline developer, and facilitates management as processing conditions, but on the other hand, the photopolymerization that is eluted. The components from the photosensitive lithographic printing plate material such as the photosensitive photosensitive layer are difficult to be uniformly dispersed in water, and problems such as smudges during printing due to the generation of sludge and processing unevenness, and poor ink loading have emerged.

  A particularly serious problem is that the water stored in the tank of the water development part when the development process is continued using the processing apparatus is no longer substantially free from the initial chemical, It is an aqueous solution having a complicated composition in which various chemical components derived from the photosensitive layer components are dissolved and dispersed and accumulated. Accordingly, when the processing is continued, there is a problem that the water developability gradually changes as sludge accumulates, and development unevenness, uneven ink loading failure, and printing stains are particularly noticeable.

  Problems associated with similar processing have also occurred with respect to conventional photosensitive lithographic printing plate materials using an alkali developer. For example, JP-A-11-218934 (Patent Document 2) and JP-A-2001-125282 are disclosed. As in the example described in (Patent Document 3), the former discloses a method of adding a nonionic surfactant to the washing water, or the latter discloses a method of adding various antifoaming agents to the washing water. . However, when these are added to washing water, the solubility in water and the defoaming effect itself are not sufficient, and a stable processing level that can be satisfied when a photosensitive lithographic printing plate is processed continuously is reached. It wasn't possible. Further, in order to obtain a sufficient defoaming effect with such washing water, a larger amount of washing water replenishment is required, which is not economical.

  Japanese Patent Application Laid-Open No. 2005-107304 (Patent Document 4) lists problems such as development unevenness related to processing in a processing system using an alkali developer in a photosensitive lithographic printing plate material using silver halide. Yes. In this case, an anti-foaming agent dispersed in oil using a binder such as gelatin is used, and this is added to any layer constituting the photosensitive lithographic printing plate. Although it works effectively in the presence of an alkaline developer, it has been found that in water development, the oil phase-separates in the developing tank and causes processing unevenness.

  Furthermore, for example, a method of adding various antifoaming agents to an alkali developer as seen in JP-A-7-225483 and JP-A-2003-107743 (Patent Document 5) has been conventionally performed, Effective in preventing processing unevenness and contamination in the automatic developing device by suppressing the generation of bubbles in the developer, but in the case of water development, the solubility of various antifoaming agents in water is low. In some cases, it may cause uneven processing and soiling.

JP 2008-265297 A JP-A-11-218934 JP 2001-125282 A JP-A-2005-107304 JP 2003-107743 A

  For photosensitive lithographic printing plate materials that are developed with water, improve the occurrence of sludge and unevenness of development when processing is continued using a processing unit, stain resistance, ink transportability, and uniformity of ink transport The present invention provides a negative photosensitive lithographic printing plate material excellent in performance.

In a photosensitive lithographic printing plate material in which a photopolymerizable photosensitive layer including a hydrophilic layer and a water-soluble polymer is provided in this order on a support, at least one layer on the support is a silicone-based antifoaming agent and a fluorine-based antifoaming agent The photosensitive lithographic printing plate material comprising an antifoaming agent selected from an acetylene alcohol-based antifoaming agent and an acetylene glycol-based antifoaming agent solves the problems relating to the present invention.

  Negative photosensitive lithographic printing that is water-developable and improves the generation of sludge and development unevenness when processing is continued using a processing device, and is excellent in stain resistance, ink transportability and ink transport uniformity. Plate material can be provided.

  An antifoaming agent initially contained in at least one layer on a support with respect to a water-developable photosensitive lithographic printing plate material in which a photopolymerizable photosensitive layer including a hydrophilic layer and a water-soluble polymer is provided in this order on the support Will be described.

Examples of the antifoaming agent used in the present invention, shea recone defoamers, fluorine-based defoaming agents, acetylene alcohol-based antifoaming agents include acetylene glycol-based anti-foaming agent.

  Silicone antifoaming agents are classified according to their shape or properties, and are classified into oil types, emulsion types, self-emulsifying types, solution types, powder types, and compound types. The oil type is used with silicone oil alone, and the solution type is a type obtained by diluting it with an organic solvent. The compound type is a type in which fine powder silica or the like is blended with silicone oil. The emulsion type is a type in which silicone oil is emulsified with a nonionic surfactant or the like. The self-emulsifying type is a modified type silicone oil in which an alkyleneoxy group or the like is introduced into the structure of the silicone oil. The powder mold is formed by adsorbing silicone oil onto an oil-absorbing powder. Of these, the self-emulsifying type and emulsion type silicone antifoaming agents can be preferably used because they are easily emulsified in a water developer and stably dispersed.

  When silicone antifoaming agents are classified according to structure, there are various types having a molecular weight such as a linear type or a branched type having a polydimethylsiloxane structure. In addition, there are alkyleneoxy-modified types in which an alkyleneoxy group such as a polyethylene oxide chain or a polypropylene oxide chain of various molecular weights is substituted as a substituent at the side chain or terminal of the polymer chain with respect to this polydimethylsiloxane structure.

  Examples of commercially available products of various types of silicone antifoaming agents as described above include self-emulsifying antifoaming agents such as YSA6406 and YSA780 available from Momentive Performance Materials Japan GK, TSA730, etc. Emulsion type antifoaming agent. Alternatively, self-emulsifying antifoaming agents such as KS-530 and KS-538 available from Shin-Etsu Chemical Co., Ltd. and other antifoaming agents can be mentioned. Various grades of antifoaming agents are available from Toray Dow Corning Co., Ltd. under the name of FS Antifoam. Among the silicone-based antifoaming agents obtained from these, the most suitable material is selected from the physical properties such as solubility in water and organic solvents and viscosity.

  Examples of the fluorine-based antifoaming agent include an anionic antifoaming agent composed of a salt of an organic acid having a perfluoroalkyl group such as perfluoroalkylsulfonic acid and perfluoroalkylcarboxylic acid with an ammonium or alkali metal, and a perfluoroalkyl group. And cationic non-foaming agents such as quaternary ammonium halides, and nonionic defoaming agents such as perfluoroalkyl alcohols, perfluoroalkyl esters, perfluoroalkyl ethylene oxide adducts, and perfluoroalkyl amine oxides.

  Examples of the acetylene alcohol-based antifoaming agent include unsaturated alcohols having an acetylene bond (carbon-carbon triple bond) in the molecule, and acetylene glycol-based antifoaming agents include those having an acetylene bond in the molecule. Saturated glycol is mentioned, also called alkyne diol.

  The feature of using the antifoaming agent in the present invention is that the ink-foaming of the image area is remarkable at the time of printing by including the antifoaming agent in any layer constituting the photosensitive lithographic printing plate material that can be developed with water. The characteristics to be improved are shown in In the present invention, as described later, a photosensitive lithographic printing plate material using a photopolymerizable photosensitive layer containing a water-soluble polymer is used, but the photopolymerizable photosensitive layer is cured by exposure, followed by water development treatment, The cured photosensitive layer is formed on the hydrophilic layer on the support. Printing can be performed by placing ink on the cured portion at the time of printing. However, a water-soluble polymer contained in the photopolymerizable photosensitive layer, which will be described later, is added with a water-soluble polymer such as a sulfonate group. In some cases, the ink does not have sufficient affinity for the ink that is oleophilic. There was a case where it was generated in a large amount or a sufficient printed matter density was not reached. However, it has been found that adding various antifoaming agents relating to the present invention having moderate lipophilicity to the photosensitive lithographic printing plate material significantly improves the ink transfer in the image area. One.

  Further, in a processing apparatus that performs water development, an antifoaming agent is also used for developing unevenness caused by sludge generation or bubble generation due to various chemical substances derived from a photosensitive layer or the like accumulated in a water developing tank. The lithographic printing plate material is adequately eluted to cover the surface of the lithographic printing plate material being processed to eliminate development unevenness, and also to improve the ink loading, thereby eliminating the unevenness of ink loading during printing. The effect is demonstrated. In addition, it is characterized in that dirt during printing can also be avoided by avoiding sludge surface adhesion. Such an effect is apparent in the examples described later.

  In the present invention, one or more of the various antifoaming agents described above can be used in appropriate combination. Using the various antifoaming agents as described above, in the present invention, a water-developable photosensitive lithographic printing in which a photopolymerizable photosensitive layer including a hydrophilic layer and a water-soluble polymer is provided in this order on a support. As for the plate material, it is used in at least one layer on the support. Of the layers that can be applied, the case where the hydrophilic layer is first applied will be described.

  The hydrophilic layer used in the present invention will be described. The hydrophilic layer of the present invention preferably contains colloidal silica. The colloidal silica referred to herein is various in a spherical shape, a needle shape, an irregular shape, or a necklace shape in which spherical particles are connected, preferably having an average particle diameter of 5 to 200 nm measured by a light scattering particle size distribution analyzer. A silica sol having a shape and a particle diameter and stably dispersed in water is preferably used. As such materials, various colloidal silicas are provided, for example, under the name of Snowtex from Nissan Chemical Industries, Ltd., and as a spherical silica sol, Snowtex XS (particle diameter 4 to 6 nm), Snowtex S (particle diameter 8) To 11 nm), Snowtex 20 (particle size 10 to 20 nm), Snowtex XL (particle size 40 to 60 nm), Snowtex YL (particle size 50 to 80 nm), Snowtex ZL (particle size 70 to 100 nm), Snowtex As an acidic type silica sol from which MP-2040 (particle diameter 200 nm) and sodium salt on the surface are removed, SNOWTEX OXS, OS and the like can be preferably used. Examples of the needle-like or amorphous silica sol include Snowtex UP, OUP, and Fine Cataloid F-120 available from Catalyst Kasei Kogyo Co., Ltd. Examples of the necklace-shaped silica sol include Snowtex PS-S (particle diameter 80 to 120 nm), PS-M (particle diameter 80 to 150 nm), and PS-SO and PS-MO which are acidic types thereof. Among these, a necklace-like silica sol is particularly preferable, and it has an effect of improving adhesiveness with a photocurable photosensitive layer, which will be described later, improving printing durability, and preventing the occurrence of scumming, and can be used very preferably. .

  As such colloidal silica preferably contained in the hydrophilic layer according to the present invention, each type of colloidal silica may be used alone, or different types of colloidal silica may be mixed and used in various proportions. In particular, by using the above-mentioned necklace-like silica and spherical colloidal silica of various particle diameters in combination with this, to increase the coating strength of the hydrophilic layer and to prevent scumming of non-image areas under printing conditions An effective and preferred system is obtained.

  Regarding the dry solid content coating amount of the hydrophilic layer, there is a preferable range, and it is preferable to form a dry mass on the support in the range of 0.5 g to 20 g per square meter. Stain is likely to occur, and if it is applied in excess of 20 g per square meter, the coating film may be easily cracked. The most preferred range is from 1 g to 10 g per square meter. The hydrophilic layer is coated and dried on the support using various known coating methods.

  In addition to the colloidal silica, other inorganic fine particles can be added to the hydrophilic layer. As porous silica fine particles having a particle size of μm, for example, various grades of silicia obtained from Fuji Silysia Chemical Co., Ltd., crystalline aluminosilicate known as zeolite, smectite (montmorillonite etc.) as layered clay mineral fine particles, Examples include talc. When these porous silica fine particles, zeolite, or layered clay mineral fine particles are added and used, there is a preferred ratio to colloidal silica, which is 1 to 10 parts by mass with respect to 100 parts by mass of colloidal silica. If the addition amount is less than this, the effect is hardly recognized, and if it is added in an amount exceeding 10 parts by mass, the smoothness of the coating film may be impaired and the image quality may be deteriorated.

  In the present invention, the hydrophilic layer preferably contains a water-soluble polymer and a crosslinking agent. The water-soluble polymer is preferably one that forms a system that maintains a uniform dispersed state without causing aggregation of the colloidal silica when mixed with the above-mentioned various colloidal silicas. However, it is most preferable that colloidal silica and the water-soluble polymer do not cause phase separation, form a uniform film, and form a system that does not cause a porous structure. In order to realize this, it is preferable that the coating material composed only of colloidal silica and the water-soluble polymer is transparent in appearance or slightly turbid and semi-transparent. It is not preferable in the invention. Further, the surface shape is preferably uniform, and a combination of colloidal silica and a water-soluble polymer that causes roughening is not preferable. It is essential that the water-soluble polymer functions to prevent the formation of a porous structure by colloidal silica and to prevent the ingress of ink during printing by filling the gaps between particles. Water-soluble polymers can be used.

  Examples of water-soluble polymers that can be used in the present invention include polyacrylamide, polyvinyl pyrrolidone, polyvinyl alcohol, modified starch, and modified cellulose. Furthermore, the most preferable water-soluble polymer includes a polymer represented by the following general formula I.

  In the above formula, X represents mass% of the repeating unit in the copolymer composition, and represents any numerical value from 1 to 40. The repeating unit A represents a repeating unit having a group selected from a carboxyl group, an amino group, a hydroxyl group, and an acetoacetoxy group as a reactive group. The repeating unit B represents a repeating unit having a hydrophilic group necessary for making the copolymer water-soluble.

  The water-soluble polymer represented by the above general formula I contains a reactive group in the molecule for allowing a crosslinking reaction to proceed efficiently with a crosslinking agent described later. As the reactive group, a carboxyl group, An amino group, a hydroxyl group, and an acetoacetoxy group. In order to obtain a water-soluble polymer having such a reactive group in the molecule, it is preferable to incorporate various monomers having a reactive group in a copolymerized form. Examples of the monomer corresponding to the repeating unit A represented by the general formula I include acrylic acid, methacrylic acid, 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, itaconic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid, maleic acid. Carboxyl group-containing monomers such as acid monoalkyl esters, fumaric acid monoalkyl esters, 4-carboxystyrene, acrylamide-N-glycolic acid and their salts, allylamine, diallylamine, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate 2-diethylaminoethyl acrylate, 2-diethylaminoethyl methacrylate, 3-dimethylaminopropyl acrylamide, 3-dimethylaminopropyl methacrylamide, 4-aminostyrene Amino group-containing monomers such as 4-aminomethylstyrene, N, N-dimethyl-N- (4-vinylbenzyl) amine, N, N-diethyl-N- (4-vinylbenzyl) amine, 4-vinylpyridine, 2 Nitrogen-containing heterocycle-containing monomers such as vinylpyridine and N-vinylimidazole, (meth) acrylamides such as N-methylolacrylamide and 4-hydroxyphenylacrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxy Examples thereof include hydroxyalkyl (meth) acrylates such as propyl acrylate, 2-hydroxypropyl methacrylate, and glycerol monomethacrylate, and acetoacetoxyethyl methacrylate, but are not limited to these examples.

  In the above general formula I, the ratio X in the copolymer of the repeating unit A is in the range of 1 to 40, and if it is less than this range, the water resistance cannot be exhibited even if the crosslinking reaction proceeds. If it exceeds the range, the effect of introduction of the repeating unit B for imparting water solubility described below is weakened, and the affinity of the hydrophilic layer for water may decrease.

  Further, as the monomer for giving the repeating unit B in the general formula I, vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, 2-acrylamide- Sulfo group-containing monomers such as 2-methylpropane sulfonic acid and salts thereof, phosphate group-containing monomers such as vinylphosphonic acid and salts thereof, dimethyldiallylammonium chloride, acrylic acid 2- (trimethylammonium chloride) ethyl ester, methacryl Acid 2- (trimethylammonium chloride) ethyl ester, acrylic acid 2- (triethylammonium chloride) ethyl ester, methacrylic acid 2- (triethylammonium chloride) ethyl ester Quaternary ammonium salts such as (3-acrylamidopropyl) trimethylammonium chloride, N, N, N-trimethyl-N- (4-vinylbenzyl) ammonium chloride, acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N -Alkyleneoxy such as (meth) acrylamides such as dimethylmethacrylamide, N, N-diethylacrylamide, N-isopropylmethacrylamide, methacrylic acid methoxydiethylene glycol monoester, methacrylic acid methoxypolyethylene glycol monoester, methacrylic acid polypropylene glycol monoester Examples thereof include, but are not limited to, group-containing (meth) acrylates, N-vinylpyrrolidone, N-vinylcaprolactam and the like. These water-soluble monomers may be used alone to constitute the repeating unit A, or any two or more kinds may be used. Examples of preferred water-soluble polymers according to the present invention are shown below.

  When such a water-soluble polymer is used, there is a preferred ratio of colloidal silica, and the mass ratio of the water-soluble polymer and colloidal silica is preferably in the range of 1: 1 to 1: 3. When the water-soluble polymer is contained in the hydrophilic layer in a ratio exceeding 1: 1 of colloidal silica, the adhesiveness with the photocurable photosensitive layer described later may be reduced, and the printing durability may be reduced during printing. . Further, when the water-soluble polymer is less than 1: 3 in the ratio of colloidal silica, the adhesion to the photocurable photosensitive layer is good and the printing durability is sufficient, but the photosensitive layer component is in the gap between the colloidal silica particles. Adsorption of water tends to generate a residual film and may easily cause background contamination. Even during printing, background stains may be a problem depending on printing conditions. The water-soluble polymer is preferably cross-linked and water-resistant by a cross-linking agent to be described later. If the cross-linking agent is not added, if the water-soluble polymer is contained in the above range, the water resistance of the hydrophilic layer is inferior, May peel during printing.

  It is preferable to include a cross-linking agent for adding to the hydrophilic layer according to the present invention to cross-link the water-soluble polymer. Examples of the crosslinking agent used for such purposes include various known compounds. Specific examples include epoxy compounds, aziridine compounds, oxazoline compounds, isocyanate compounds and derivatives thereof, aldehyde compounds such as formalin, methylol compounds, and hydrazide compounds. Hereinafter, specific examples of such crosslinking agents will be described with chemical formulas. Among these, an epoxy compound is a particularly preferable example.

  As the epoxy compound, a compound having two or more epoxy groups in the molecule and water-soluble is preferably used. These epoxy compounds are relatively stable in water under neutral to weakly acidic conditions, and when a coating liquid for forming a hydrophilic layer is prepared, the coating liquid has a long life and is extremely advantageous in continuous production. . Examples of preferred epoxy compounds are shown below.

  In order for the crosslinking reaction to proceed efficiently between the epoxy compound as described above and the water-soluble polymer, a carboxyl group or an amino group is particularly preferable as the reactive group contained in the water-soluble polymer.

  Examples of preferred compounds as aziridine compounds are shown below. In order for the crosslinking reaction to proceed efficiently between the aziridine compound and the water-soluble polymer, a carboxyl group is particularly preferable as the reactive group contained in the water-soluble polymer.

  As the oxazoline compound, a compound containing two or more groups represented by the following general formula as substituents in the molecule is preferable, and as various commercially available compounds, for example, various grades provided by Nippon Shokubai Co., Ltd. under the trade name Epocross These compounds are preferably used. In order for the crosslinking reaction to proceed efficiently between the oxazoline compound and the water-soluble polymer, a carboxyl group is particularly preferred as the reactive group contained in the water-soluble polymer.

  As the isocyanate compound, a compound that is stable in water is preferable, and a so-called self-emulsifiable isocyanate compound or a blocked isocyanate compound is preferably used. Examples of the self-emulsifying isocyanate compound include Japanese Patent Publication No. 55-7472 (U.S. Pat. No. 3,996,154) and Japanese Patent Laid-Open No. 5-222150 (U.S. Pat. No. 5,252,696). ), Self-emulsifiable isocyanate as described in JP-A-9-71720, JP-A-9-328654, JP-A-10-60073, and the like. Specifically, for example, a polyisocyanate having an isocyanurate structure of a cyclic trimer skeleton formed from an aliphatic or alicyclic diisocyanate in a molecule, or a polyisocyanate having a burette structure, a urethane structure or the like in the molecule. A highly preferred example is a polyisocyanate compound having a structure obtained by adding a polyethylene glycol or the like having one terminal etherification to only one part of the polyisocyanate group as a base polyisocyanate. A method for synthesizing an isocyanate compound having such a structure is described in the above specification. Specific examples of such isocyanate compounds are commercially available as polyisocyanates based on cyclic trimerization starting from hexamethylene diisocyanate and the like as base polyisocyanates. For example, Duranate WB40 or WX1741 from Asahi Kasei Corporation. And so on. The blocked isocyanate compound is blocked with bisulfite, alcohols, lactams, oximes, active methylenes, etc. as seen in, for example, JP-A-4-184335 and JP-A-6-175252. Blocked isocyanate is preferably used. In order for the crosslinking reaction to proceed efficiently between the isocyanate compound and the water-soluble polymer, the reactive group contained in the water-soluble polymer is particularly preferably a hydroxyl group or an amino group.

  Examples of aldehyde compounds such as formalin and methylol compounds include formalin, glyoxal, and various N-methylol compounds as shown below. In order for the crosslinking reaction to proceed efficiently between such a compound and the water-soluble polymer, the reactive group contained in the water-soluble polymer is particularly preferably a hydroxyl group or an amino group.

  Examples of compounds that can be preferably used as hydrazide compounds are shown below. In order for the crosslinking reaction to proceed efficiently between the hydrazide compound and the water-soluble polymer, an active methylene group such as an acetoacetoxy group is particularly preferable as the reactive group contained in the water-soluble polymer. .

  There is a preferred range for the ratio of the various cross-linking agents and the water-soluble polymer as described above. The crosslinking agent is preferably used in the range of 1 to 40 parts by mass with respect to 100 parts by mass of the water-soluble polymer, and if it is less than 1 part by mass, the crosslinking water resistance is insufficient and the hydrophilic layer is peeled off during printing. There is a case. On the other hand, when it is used in excess of 40 parts by mass, the affinity of the hydrophilic layer for water decreases, which may cause printing stains.

  When the various antifoaming agents described above in the present invention are included in the hydrophilic layer, there is a preferable range for the amount of addition. As mentioned earlier, there is a preferred range for the dry solids coating amount of the hydrophilic layer, with a dry mass on the support ranging from 0.5 g to 20 g per square meter, the most preferred range being 1 g per square meter. Therefore, in the preferable dry solid mass of such a hydrophilic layer, the preferable dry solid mass included in the antifoaming agent is in the range of 0.01 g to 0.1 g per square meter. . If it is less than this, the effect of the present invention may not be recognized, and when added exceeding this range, the antifoaming agent phase-separates in the hydrophilic layer and a uniform layer is not formed, and the printed matter is uniform. The image may not be printed. However, when the antifoaming agent is contained in another layer other than the hydrophilic layer constituting the photosensitive lithographic printing plate material in the present invention, it may be used below the above amount. In that case, when the amount of the antifoaming agent contained in all the layers constituting the photosensitive lithographic printing plate material is in the range of 0.01 to 0.1 g per square meter in dry solid mass as described above. Is most preferred.

  In the present invention, the various antifoaming agents described above are preferably contained in the photopolymerizable photosensitive layer constituting the photosensitive lithographic printing plate material that can be developed with water. Most preferred is that sludge that clumps and floats is reduced and that the sludge is uniformly dispersed. Next, the photopolymerizable photosensitive layer that can be developed with water according to the present invention will be described.

  The photocurable photosensitive layer that can be developed with water according to the present invention contains a water-soluble polymer as a binder. As such a water-soluble polymer, any polymer which is essentially water-soluble can be used. Examples thereof include polyacrylamide, polyvinyl pyrrolidone, poly (vinyl pyrrolidone-vinyl acetate) copolymer, polyvinyl alcohol. Modified starch, modified cellulose and the like can be used. Furthermore, the polymer etc. which are shown by the above-mentioned general formula I can also be used.

  The water-soluble polymer contained in the photocurable photosensitive layer in the invention is particularly preferably a water-soluble polymer having a polymerizable double bond group in the side chain. In this case, the polymerizable double bond group introduced into the side chain is preferably a vinyl double bond group such as an acryloyl group, a methacryloyl group, or a styryl group, or an allyl group. Examples of specific methods for introducing these polymerizable double bond groups into the water-soluble polymer side chain include, for example, the method disclosed in JP-A No. 2003-215801, or the method described in the examples described later. It is done.

  In order to exhibit good solubility in water as the water-soluble polymer, the side chain in the polymer preferably contains an acidic group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. These acidic groups are particularly preferably neutralized with an arbitrary base. Among these, a water-soluble polymer having a sulfonate group in the side chain exhibits the best water solubility, and a photopolymerizable photosensitive layer using the water-soluble polymer is particularly preferable because of good water developability.

  More preferable examples of the water-soluble polymer include water-soluble polymers having both a sulfonate group and a phenyl group having a vinyl group bonded via a linking group containing a hetero ring in the side chain. The phenyl group to which a vinyl group is bonded via a linking group containing a heterocycle has a group represented by the following general formula II in the side chain.

In the formula, Z represents a linking group having a heterocycle, and R ₁ , R ₂ and R ₃ are a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, a nitro group, a cyano group, an amide group, an amino group, an alkyl group, An aryl group, an alkoxy group, an aryloxy group, and the like, and these groups may be substituted with an alkyl group, an amino group, an aryl group, an alkenyl group, a carboxy group, a sulfo group, a hydroxy group, and the like. R ₄ represents a group or an atom capable of substituting for a hydrogen atom. n represents 0 or 1, m represents an integer of 0 to 4, and k represents an integer of 1 to 4. Examples of the heterocyclic group include pyrrole ring, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, isoxazole ring, oxazole ring, oxadiazole ring, isothiazole ring, thiazole ring, thiadiazole ring, thiatriazole ring, indole ring. , Indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzthiazole ring, benzselenazole ring, benzothiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, quinoline ring, quinoxaline ring, etc. A nitrogen-containing heterocyclic ring, a furan ring, a thiophene ring, and the like, and a substituent may be bonded to these heterocyclic rings. Examples of the group represented by the general formula II are shown below, but are not limited to these examples.

Among the groups represented by the general formula II, preferred ones exist. That is, it is preferable that R ₁ and R ₂ are hydrogen atoms and R ₃ is a hydrogen atom or a lower alkyl group having 4 or less carbon atoms (methyl group, ethyl group, etc.). Further, the linking group is preferably a linking group containing a thiadiazole ring, and k is preferably 1 or 2.

  The sulfonic acid group contained in the side chain in the polymer composition is a sulfonic acid group bonded to the main chain through a linking group as shown in the following general formula III. Neutralized salts are preferred.

In the general formula III, the linking group L represents any atom or group that connects the main chain and the sulfonic acid group, and is preferably a group consisting of a combination of —COO— group, —CONH— group and alkylene group, arylene group, and the like. . Examples of the base B ⁺ that forms a salt with a sulfonic acid group include inorganic bases such as sodium hydroxide, potassium hydroxide, and lithium hydroxide, various amines, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, choline, and the like. A quaternary ammonium base is preferably used.

  In the present invention, the water-soluble polymer contained in the photopolymerizable photosensitive layer is characterized by having a hydrophilic group for imparting water solubility such as a sulfonic acid group because it can be developed with water. There is a preferred range for the ratio of the sulfonic acid group in the water-soluble polymer composition to the phenyl group to which a vinyl group is bonded via a heterocycle. The repeating unit having a sulfonic acid group is preferably in the range of 40% by mass to 90% by mass in the water-soluble polymer composition. When the content is less than this, the polymer becomes insoluble in water, and the developability in water development decreases. There is a case. Moreover, when it exceeds 90 mass%, sufficient printing durability may not be obtained.

  There is a more preferred base as a base for neutralizing the sulfonic acid group. It is a tertiary amine having a hydroxyl group, and specific examples include dimethylaminoethanol, diethylaminoethanol, triethanolamine, n-butyldiethanolamine, and t-butyldiethanolamine. By using a water-soluble polymer in which the sulfonic acid group is neutralized using these bases, the water developability of the polymer becomes extremely good, which is extremely preferable for preventing the occurrence of background stains.

  There is a preferred range for the molecular weight of the water-soluble polymer, and the weight average molecular weight is preferably in the range of 5000 to 500,000. If the molecular weight is less than this, the printing durability may be insufficient, and it exceeds 500,000. With the molecular weight, the viscosity of the coating liquid at the time of coating becomes too high, and uniform coating may be difficult. The most preferred molecular weight range is between tens of thousands and 200,000.

  In the water-soluble polymer composition having both the sulfonate group and a phenyl group having a vinyl group bonded via a linking group containing a hetero ring in the side chain, the sulfonate group and vinyl may be used depending on the purpose. Various repeating units can be introduced in addition to the repeating unit having a group. For example, as hydrophilic monomers, acrylic acid, methacrylic acid, 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, itaconic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid, maleic acid monoalkyl ester, fumaric acid monoalkyl Carboxyl group-containing monomers such as esters, 4-carboxystyrene, acrylamide-N-glycolic acid and salts thereof, phosphate group-containing monomers such as vinylphosphonic acid and salts thereof, allylamine, diallylamine, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-diethylaminoethyl acrylate, 2-diethylaminoethyl methacrylate, 3-dimethylaminopropylacrylamide, 3-dimethylaminopropyl methacrylate Amino group-containing monomers such as amide, 4-aminostyrene, 4-aminomethylstyrene, N, N-dimethyl-N- (4-vinylbenzyl) amine, N, N-diethyl-N- (4-vinylbenzyl) amine And nitrogen-containing heterocycle-containing monomers such as quaternary ammonium salts, 4-vinylpyridine, 2-vinylpyridine, N-vinylimidazole, and N-vinylcarbazole, and quaternary ammonium salts thereof, acrylamide, methacrylamide, N, (Meth) acrylamides such as N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N-isopropylmethacrylamide, diacetoneacrylamide, N-methylolacrylamide, 4-hydroxyphenylacrylamide, 2- Hydroxy Hydroxyalkyl (meth) acrylates such as til acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, glycerol monomethacrylate, methacrylic acid methoxydiethylene glycol monoester, methacrylic acid methoxypolyethylene glycol monoester, methacrylic acid Examples include, but are not limited to, alkyleneoxy group-containing (meth) acrylates such as acid polypropylene glycol monoester, N-vinylpyrrolidone, and N-vinylcaprolactam. These water-soluble monomers may be used alone or in combination of any two or more.

  Alternatively, as a hydrophobic monomer, styrene derivatives such as styrene, 4-methylstyrene, 4-hydroxystyrene, 4-acetoxystyrene, 4-chloromethylstyrene, 4-methoxystyrene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate , N-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, alkyl (meth) acrylates such as dodecyl methacrylate, aryl (meth) acrylates such as phenyl methacrylate, benzyl methacrylate, or arylalkyl (meth) acrylates , Acrylonitrile, methacrylonitrile, phenylmaleimide, hydroxyphenylmaleimide, vinyl acetate, chloro Vinyl esters such as vinyl acid vinyl, vinyl propionate, vinyl butyrate, vinyl stearate, vinyl benzoate, vinyl ethers such as methyl vinyl ether, butyl vinyl ether, etc., acryloylmorpholine, tetrahydrofurfuryl methacrylate, vinyl chloride, vinylidene chloride, allyl Examples include various monomers such as alcohol, vinyltrimethoxysilane, glycidyl methacrylate, and the like. As a water-soluble polymer in the present invention, a copolymer comprising any combination of these and a sulfonate group and a phenyl group having a vinyl group bonded via a linking group containing a hetero ring in a repeating unit at the same time. Can be used. When such a sulfonate group and a repeating unit other than a phenyl group to which a vinyl group is bonded via a linking group containing a heterocyclic ring are contained in the polymer, the proportion in the water-soluble polymer is 50% by mass. It is preferable to keep it below%, and if it is introduced at a rate exceeding this, it may hinder the stain resistance aimed at by the present invention.

  Examples of preferred water-soluble polymers in the present invention are shown below, but are not limited to these examples. In the formula, the number represents the mass% of each repeating unit in the polymer. With respect to the method for synthesizing these water-soluble polymers, for example, they are easily synthesized by a method similar to the synthesis example described in JP-A No. 2003-215801.

  The photopolymerizable photosensitive layer according to the present invention preferably contains a photopolymerization initiator in addition to the water-soluble polymer. As a photoinitiator used for this invention, arbitrary compounds can be used if it is a compound which can generate | occur | produce a radical by irradiation of light or an electron beam.

  Examples of photopolymerization initiators that can be used in the present invention include (a) aromatic ketones, (b) aromatic onium salt compounds, (c) organic peroxides, (d) hexaarylbiimidazole compounds, e) ketoxime ester compounds, (f) azinium compounds, (g) active ester compounds, (h) metallocene compounds, (i) trihaloalkyl-substituted compounds, and (j) organoboron compounds.

  (A) Preferred examples of aromatic ketones include compounds having a benzophenone skeleton or a thioxanthone skeleton described in “RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY” JPFOUASSIER, JFRABEK (1993), P. 77 to P. 177. Α-thiobenzophenone compounds described in JP-B-47-6416, benzoin ether compounds described in JP-B-47-3981, α-substituted benzoin compounds described in JP-B-47-22326, and JP-B-47. Benzoin derivatives described in JP-A-236364, aroylphosphonic acid esters described in JP-A-57-30704, dialkoxybenzophenones described in JP-B-60-26483, JP-B-60-26403, Benzoin ethers described in JP-A No. 62-81345 and JP-A No. 2-211452 P-di (dimethylaminobenzoyl) benzene described in JP-A-61-194062, a thio-substituted aromatic ketone described in JP-A-61-194062, an acylphosphine sulfide described in JP-B-2-9597, and JP-B-2-9596 Examples thereof include acylphosphines described in JP-A No. 63-61950, thioxanthones described in JP-B No. 63-61950, and coumarins described in JP-B No. 59-42864.

  (B) Examples of aromatic onium salts include N, P, As, Sb, Bi, O, S, Se, Te, or I aromatic onium salts. Examples of such aromatic onium salts include compounds exemplified in Japanese Patent Publication No. 52-14277, Japanese Patent Publication No. 52-14278, Japanese Patent Publication No. 52-14279, and the like.

  (C) Examples of organic peroxides include almost all organic compounds having one or more oxygen-oxygen bonds in the molecule. For example, 3,3 ′, 4,4′-tetra (tert-butyl) Peroxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (tert-amylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (tert-hexylperoxycarbonyl) benzophenone, 3, 3 ', 4,4'-tetra (tert-octylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (cumylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra ( p-Isopropylcumylperoxycarbonyl) benzophenone, di-tert-butyldiperoxyisophthalate, etc. Tel systems are preferred.

  (D) Examples of hexaarylbiimidazole include lophine dimers described in JP-B Nos. 45-37377 and 44-86516, such as 2,2′-bis (o-chlorophenyl) -4,4. ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o, p -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (m-methoxyphenyl) biimidazole 2,2'-bis (o, o'-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,4', 5 , 5 ' Tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-trifluoromethylphenyl) -4, Examples include 4 ', 5,5'-tetraphenylbiimidazole.

  (E) Examples of ketoxime esters include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentane- 3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p-toluenesulfonyloxyiminobutan-2-one, 2- And ethoxycarbonyloxyimino-1-phenylpropan-1-one.

  Examples of (f) azinium salt compounds include JP-A-63-138345, JP-A-63-142345, JP-A-63-142346, JP-A-63-143537, JP-B-46. The compound group which has NO bond as described in -42363 gazette etc. can be mentioned.

  (G) Examples of active ester compounds include imide sulfonate compounds described in JP-B-62-2623, etc., and active sulfonates described in JP-B-63-14340, JP-A-59-174831, etc. be able to.

  (H) Examples of metallocene compounds include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, and JP-A-2-4705. And titanocene compounds described in JP-A-1-304453 and iron-arene complexes described in JP-A-1-152109. Specific titanocene compounds include, for example, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3. , 4,5,6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti -Bis-2,4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2, 4-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-T -Bis-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluoro-3- (pyr-1-yl) -phen-1-yl, etc. Can do.

  (I) Specific examples of the trihaloalkyl-substituted compound include compounds having at least one trihaloalkyl group such as a trichloromethyl group and a tribromomethyl group in the molecule. US Pat. No. 3,954,475 Specification, U.S. Pat. No. 3,987,037, U.S. Pat. No. 4,189,323, JP-A-61-151644, JP-A-63-298339, JP-A-4-69661 And trihalomethyl-s-triazine compounds described in JP-A-11-153859, JP-A-54-74728, JP-A-55-77742, JP-A-60-138539, 2-Trihalomethyl-1,3 described in JP-A-61-143748, JP-A-4-362644, JP-A-11-84649, etc. 4- oxadiazole derivatives. Moreover, the trihaloalkyl sulfonyl compound as described in Unexamined-Japanese-Patent No. 2001-290271 etc. which this trihaloalkyl group couple | bonded with the aromatic ring or the nitrogen-containing heterocyclic ring through the sulfonyl group is mentioned.

  (J) Examples of the organic boron salt compound include JP-A-8-217813, JP-A-9-106242, JP-A-9-18885, JP-A-9-188686, JP-A-9-188710. Organoboron ammonium compounds described in JP-A-6-175561, JP-A-6-175564, JP-A-6-157623, and the like. Organoboron iodonium compounds described in JP-A-6-175553, JP-A-6-175554, etc., Organoboron phosphonium compounds described in JP-A-9-188710, JP-A-6-348011, JP-A-7- 128785, JP-A-7-140589, JP-A-7-292 14 JP, organic boron transition metal coordination complex compound described in JP-A-7-306527 Patent Publication, and the like. Examples of the counter anion described in JP-A-62-143044 and JP-A-5-194619 include cationic dyes containing an organic boron anion.

  When the photocurable photosensitive layer of the present invention is adapted for exposure to blue-violet light in the wavelength range of 400 to 430 nm, (d) hexaarylbiimidazole, (h) metallocene compound, (i) trihaloalkyl Substituted compounds and (j) organic boron salt compounds are particularly preferred.

  In addition, when the photocurable photosensitive layer of the present invention is adapted to exposure with near infrared to infrared light in a wavelength range of 750 to 1100 nm, (i) a trihaloalkyl-substituted compound and (j) an organic boron salt compound are particularly preferred. preferable.

  The above photopolymerization initiators may be used alone or in any combination of two or more. In particular, it is preferable to use a combination of (i) a trihaloalkyl-substituted compound and (j) an organic boron salt compound because the sensitivity is greatly improved. The content of the photopolymerization initiator in the photocurable photosensitive layer is preferably 1 to 100% by mass, more preferably 1 to 40% by mass, based on the polymer.

  As the photopolymerization initiator related to the present invention, an organic boron salt is particularly preferably used. More preferably, an organic boron salt and a trihaloalkyl-substituted compound (for example, an s-triazine compound, an oxadiazole derivative, or a trihaloalkylsulfonyl compound as a trihaloalkyl-substituted nitrogen-containing heterocyclic compound) are used in combination.

  The organic boron anion constituting the organic boron salt is represented by the following general formula IV.

In the formula, each of R ₅ , R ₆ , R ₇ and R ₈ may be the same or different, and represents an alkyl group, aryl group, aralkyl group, alkenyl group, alkynyl group, cycloalkyl group or heterocyclic group. Represent. Of these, it is particularly preferred that one of R ₅ , R ₆ , R ₇ and R ₈ is an alkyl group and the other substituent is an aryl group.

  In the above-mentioned organoboron anion, a cation that forms a salt is simultaneously present. Examples of the cation in this case include alkali metal ions, onium ions, and cationic sensitizing dyes. Onium salts include ammonium, sulfonium, iodonium and phosphonium compounds. When a salt of an alkali metal ion or onium compound and an organic boron anion is used, photosensitivity in the wavelength range of light absorbed by the dye is imparted by adding a sensitizing dye separately. Further, when an organic boron anion is contained as a counter anion of the cationic sensitizing dye, photosensitivity is imparted according to the absorption wavelength of the sensitizing dye. However, in the latter case, it is preferable to further contain an organic boron anion as a counter anion of the alkali metal or onium salt.

  The organic boron salt used in the present invention is a salt containing the organic boron anion represented by the general formula IV shown above, and alkali metal ions and onium compounds are preferably used as cations forming the salt. Particularly preferable examples of the onium salt with an organic boron anion include ammonium salts such as tetraalkylammonium salts, sulfonium salts such as triarylsulfonium salts, and phosphonium salts such as triarylalkylphosphonium salts. Examples of particularly preferred organic boron salts are shown below.

  In the present invention, a trihaloalkyl-substituted compound can be used as a photopolymerization initiator that can be used with an organic boron salt to realize higher sensitivity and higher contrast. Specifically, the trihaloalkyl-substituted compound is a compound having at least one trihaloalkyl group such as a trichloromethyl group or a tribromomethyl group in the molecule. As a preferable example, the trihaloalkyl group is a nitrogen-containing complex. Examples of the compound bonded to the ring group include s-triazine derivatives and oxadiazole derivatives, or trihaloalkylsulfonyl compounds in which the trihaloalkyl group is bonded to an aromatic ring or a nitrogen-containing heterocycle via a sulfonyl group. .

  Particularly preferred examples of trihaloalkyl-substituted nitrogen-containing heterocyclic compounds and trihaloalkylsulfonyl compounds are shown below.

  In the photopolymerizable photosensitive layer according to the present invention, the light wavelength region has light absorption in the wavelength region of 400 to 430 nm or 750 to 1100 nm, and the above-mentioned photopolymerization initiator is sensitized at these wavelengths. It is preferable that the compound to be contained is also contained. As compounds that increase the sensitivity in the wavelength region of 400 to 430 nm, cyanine dyes, coumarin compounds described in JP-A-7-271284, JP-A-8-29973, etc., JP-A-9-230913, Carbazole compounds described in JP-A No. 2001-42524 and the like, carbomerocyanine dyes described in JP-A-8-262715, JP-A-8-272096, JP-A-9-328505, and the like, JP-A-4-194857, JP-A-6-295061, JP-A-7-84863, JP-A-8-220755, JP-A-9-80750, JP-A-9-236913, etc. Aminobenzylidene ketone dyes, JP-A-4-184344, JP-A-6-301208, Pyromethine dyes described in Kaihei 7-225474, JP-A-7-5585, JP-A-7-281434, JP-A-8-6245, etc., and JP-A-9-80751 Styryl dyes or (thio) pyrylium compounds. Of these, cyanine dyes, coumarin compounds or (thio) pyrylium compounds are preferred. Examples of cyanine dyes that can be preferably used are shown below.

  Examples of preferred coumarin compounds that can be used to increase the sensitivity in the wavelength range of 400 to 430 nm are shown below.

  Examples of preferred (thio) pyrylium compounds that can be used to increase the sensitivity in the wavelength region of 400 to 430 nm are shown below.

  As sensitizing dyes in the wavelength range of 750 to 1100 nm, cyanine dyes, porphyrins, spiro compounds, ferrocene, fluorene, fulgide, imidazole, perylene, phenazine, phenothiazine, polyenes, azo compounds, diphenylmethane, triphenylmethane, polymethine acridine, Examples include coumarin, ketocoumarin, quinacridone, indigo, styryl, squarylium compounds, (thio) pyrylium compounds, European Patent No. 568,993, US Patent No. 4,508,811, US Patent The compounds described in US Pat. No. 5,227,227 can also be used.

  Examples of preferred sensitizing dyes corresponding to near infrared light in the wavelength range of 750 to 1100 nm are shown below.

  With respect to the present invention, various polyfunctional monomers can also be contained in the photopolymerizable photosensitive layer. Examples of such polyfunctional monomers include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tetraethylene glycol diacrylate, trisacryloyloxyethyl isocyanurate, tripropylene glycol. Polyfunctional (acrylic) monomers such as diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, or various polymers incorporating acryloyl group or methacryloyl group, polyester (meth) acrylate, urethane (meta ) Acrylates, epoxy (meth) acrylates and the like are used in the same manner.

  In addition, as an element constituting the photopolymerizable photosensitive layer, various kinds of dyes and pigments are added for the purpose of enhancing image visibility, and inorganic fine particles or organic fine particles are used for the purpose of preventing blocking of the photosensitive composition. It is also preferably carried out.

  A polymerization inhibitor is preferably added to the photopolymerizable photosensitive layer in order to prevent a curing reaction in the dark due to thermal polymerization for long-term storage. As the polymerization inhibitor preferably used for such purposes, various known phenol compounds can be used.

  Regarding the dry solid content coating amount of the photopolymerizable photosensitive layer itself when used as a photosensitive lithographic printing plate material, the dry solid content coating amount in the range of 0.3 g to 10 g per square meter on the dry weight on the hydrophilic layer. It is preferable that the thickness is in the range of 0.5 g to 3 g in order to exhibit good resolution and greatly improve printing durability. The photocurable photosensitive layer is prepared by preparing a solution in which the above-described various elements are mixed, and is applied and dried on the hydrophilic layer using various known coating methods.

  When various antifoaming agents described above in the present invention are included in the photopolymerizable photosensitive layer, there is a preferable range for the amount of addition. As described above, there is a preferred range regarding the dry solid content coating amount of the photopolymerizable photosensitive layer, the dry mass on the support is in the range of 0.3 g to 10 g per square meter, and the most preferred range is 0.00 per square meter. Since it is in the range of 5 g to 3 g, in the preferable dry solid mass of such a photopolymerizable photosensitive layer, the preferable dry solid mass contained in the antifoaming agent is 0.01 g to 0.1 g per square meter. It is a range. If it is less than this, the effect of the present invention may not be recognized, and when added over this range, the antifoaming agent phase-separates in the photopolymerizable photosensitive layer and a uniform layer is not formed in the printed matter. A uniform image may not be printed. However, when the antifoaming agent is contained in another layer other than the photopolymerizable photosensitive layer constituting the photosensitive lithographic printing plate material in the present invention, it may be used below the above amount. In that case, when the amount of the antifoaming agent contained in all the layers constituting the photosensitive lithographic printing plate material is in the range of 0.01 to 0.1 g per square meter in dry solid mass as described above. Is most preferred.

  In the water-developable photosensitive lithographic printing plate of the present invention, it is also preferable to further provide a protective layer on the photopolymerizable photosensitive layer. The protective layer prevents exposure of low molecular weight compounds such as oxygen and basic substances present in the atmosphere that hinder the image formation reaction caused by exposure in the photosensitive layer to further improve exposure sensitivity in the atmosphere. It has a favorable effect of improving. Furthermore, an effect of preventing the photosensitive layer surface from scratches is also expected. Therefore, the properties desired for such a protective layer are low permeability of low molecular weight compounds such as oxygen and excellent mechanical strength, and further, transmission of light used for exposure is not substantially inhibited, and adhesion to the photosensitive layer. It is desirable that it is excellent in that it can be easily removed in the development process after exposure. In the water-developable photosensitive lithographic printing plate material of the present invention, it is possible to simultaneously remove such an unexposed portion of the protective layer and the photocurable photosensitive layer in the course of water development. It is a feature that it is not necessary to provide a removal process. Furthermore, since the polymer contained in the photo-curable photosensitive layer as described above is water-soluble, it absorbs moisture in the atmosphere and causes blocking, and may cause problems such as sensitivity change during storage. However, it is possible to solve such problems of blocking and sensitivity change by providing a protective layer on the photocurable photosensitive layer. In addition, particularly when recording is performed using a blue-violet semiconductor laser having a wavelength range of 400 to 430 nm, since the laser output is generally lower than that of a near-infrared semiconductor laser, the photosensitive layer is particularly sensitive. Is required. In such a case, since the sensitivity is further increased by providing a protective layer, it can be particularly preferably applied.

  Such a device relating to the protective layer has been conventionally devised, and is described in detail in US Pat. No. 3,458,311 and JP-A-55-49729. As a material that can be used for the protective layer, for example, a water-soluble polymer compound having relatively excellent crystallinity is preferably used. Specifically, polyvinyl alcohol, polyvinyl pyrrolidone, acidic celluloses, gelatin, gum arabic, and polyacrylic are used. Water-soluble polymers such as acids are known, and among these, using polyvinyl alcohol as a main component gives the best results in terms of basic properties such as oxygen barrier properties and development removability. The polyvinyl alcohol used for the protective layer may be partially substituted with an ester, an ether, and an acetal as long as it contains an unsubstituted vinyl alcohol unit for having necessary oxygen barrier properties and water solubility. Similarly, some of them may have other copolymer components. There is a preferred range for the dry solid content applied when applying such a protective layer, and it is formed on the photopolymerizable photosensitive layer with a dry solid content of 0.1 g to 10 g per square meter in dry mass. In particular, the range of 0.2 g to 2 g is preferable. The protective layer is coated and dried on the photopolymerizable photosensitive layer using various known coating methods.

  When the various antifoaming agents described above in the present invention are included in the protective layer, there is a preferable range for the amount of addition. As noted above, there is a preferred range for the dry solids coverage of the protective layer, with a dry mass on the support ranging from 0.1 g to 10 g per square meter, the most preferred range being from 0.2 g to 2 g per square meter. Therefore, in the preferred dry solid mass of such a protective layer, the preferred dry solid mass contained in the antifoaming agent is in the range of 0.01 g to 0.1 g per square meter. If the amount is less than this range, the effect of the present invention may not be recognized. If the amount exceeds this range, the antifoaming agent phase-separates in the protective layer and a uniform layer is not formed, and image exposure and subsequent water are not formed. A uniform image may not be formed during development. However, when the antifoaming agent is also contained in another layer other than the protective layer constituting the photosensitive lithographic printing plate material in the present invention, it may be used below the above amount. In that case, the amount of the antifoaming agent contained in all the layers constituting the photosensitive lithographic printing plate material is in the range of 0.01 g to 0.1 g per square meter in dry solid content as described above. The case is most preferred.

  In the water-developable photosensitive lithographic printing plate material of the present invention, other layers may be provided on the support in addition to the hydrophilic layer, photopolymerizable photosensitive layer and protective layer described above. For example, a back coat layer may be provided on the side opposite to the side on which the photopolymerizable photosensitive layer is provided. In this case, the backcoat layer may contain various components depending on the purpose required. For example, it may be a layer containing inorganic fine particles such as titanium oxide and silica particles together with gelatin, polyvinyl alcohol and other various binder polymers. Even in this case, the anti-foaming agent is contained in the back coat layer, and when it is not contained in the other layers constituting the photosensitive lithographic printing plate material as before, the amount added is dry. Most preferred is a range of 0.01 g to 0.1 g per square meter in solids mass.

  Alternatively, in the photosensitive lithographic printing plate material capable of being developed with water in the present invention, an undercoat layer may be provided between the hydrophilic layer and the support. In this case, the undercoat layer may include various components depending on the purpose required. For example, it may be a layer containing inorganic fine particles such as titanium oxide and silica particles together with gelatin, polyvinyl alcohol and other various binder polymers. Also in this case, when the undercoat layer contains the antifoaming agent and is not contained in the other layers constituting the photosensitive lithographic printing plate material as before, the amount added is dry. Most preferred is a range of 0.01 g to 0.1 g per square meter in solids mass.

  Examples of the support used in the present invention include various plastic films and aluminum plates. Typical examples of the plastic film support include polyethylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, polystyrene, polyvinyl acetal, polycarbonate, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, and cellulose nitrate. In particular, polyethylene terephthalate and polyethylene naphthalate are preferably used. These films are preferably subjected to hydrophilic treatment on the surface before providing the hydrophilic layer, and examples of such hydrophilic treatment include corona discharge treatment, flame treatment, plasma treatment, and ultraviolet irradiation treatment. . An undercoat layer may be provided on the base material in order to enhance the adhesion to the hydrophilic layer provided on the base material as a further hydrophilic treatment. As the undercoat layer, a layer containing a hydrophilic resin as a main component is effective. Examples of hydrophilic resins include gelatin, gelatin derivatives (for example, phthalated gelatin), hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, ethyl hydroxyethyl cellulose, polyvinyl pyrrolidone, polyethylene oxide, xanthan, cationic hydroxyethyl cellulose, polyvinyl alcohol, A water-soluble resin such as polyacrylamide is preferred. Particularly preferred are gelatin and polyvinyl alcohol. By forming the film support and the hydrophilic layer through such an undercoat layer, printing durability under long run printing conditions over a large number of copies is preferably used.

  When an aluminum plate is used as the support, it is preferable to use the hydrophilic layer formed on the surface of a normal aluminum plate. Alternatively, for the purpose of further improving the adhesiveness with the hydrophilic layer, it is also preferable to use an aluminum plate that has been roughened and has an anodized film. Furthermore, an aluminum plate whose surface is silicate-treated can also be preferably used. Alternatively, as a special case, when using an aluminum plate that has been roughened and provided with an anodized film, and further using an aluminum plate that has been subjected to silicate treatment by a known method, the silicate treatment is performed. Since the layer made of the applied anodized film functions as a hydrophilic layer, even when it is used without further providing the hydrophilic layer on the surface, it can exhibit excellent printability without soiling. It can be preferably used.

  In the present invention, it is preferable to use an antifoaming agent and various anionic surfactants in combination. Examples of the anionic surfactant that can be used include higher fatty acid salts such as sodium laurate, sodium stearate, and sodium oleate, alkyl sulfates such as sodium dioctyl sulfosuccinate, sodium lauryl sulfate, and sodium stearyl sulfate, and octyl alcohol sulfate. Higher alcohol sulfates such as sodium ester, sodium lauryl alcohol sulfate, ammonium lauryl alcohol sulfate, aliphatic alcohol sulfates such as sodium acetyl alcohol sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, butylnaphthalene Alkyl naphthalene sulfonates such as sodium sulfonate and sodium isopropyl naphthalene sulfonate Alkyl diphenyl ether disulfonates such as sodium alkyl diphenyl ether disulfonate, alkyl phosphate esters such as sodium lauryl phosphate and sodium stearyl phosphate, polyethylene oxide adduct of sodium lauryl ether sulfate, polyethylene oxide adduct of ammonium lauryl ether sulfate, lauryl ether sulfate Polyethylene oxide adducts of alkyl ether sulfates such as polyethylene oxide adduct of triethanolamine, polyethylene oxide adducts of alkyl phenyl ether sulfates such as polyethylene oxide adduct of sodium nonylphenyl ether sulfate, sodium lauryl ether phosphate Polyethylene of alkyl ether phosphates such as polyethylene oxide adducts Oxide adducts, polyethylene oxide adducts of alkyl phenyl ether phosphate salts of polyethylene oxide adducts of nonyl phenyl ether sodium phosphate and the like. Among these, alkyl naphthalene sulfonates and alkyl sulfates are particularly preferably used together with an antifoaming agent because the developability with water is particularly remarkably improved.

  In the present invention, the use of an anionic surfactant in combination with the antifoaming agent described above significantly improves the developability with water. In particular, when the processing is continued using a processing apparatus, even if the water in the water developing tank is gradually contaminated, the effect of maintaining good developability by using an anionic surfactant is recognized. It is done. However, when an anionic surfactant is used alone, a large amount of bubbles are generated in the water developing tank, so that development unevenness due to the bubbles may occur.

  In the present invention, when an anionic surfactant is used together with an antifoaming agent, there is a preferable range for the amount contained in an arbitrary layer constituting the photosensitive lithographic printing plate material. The preferred amount to be included of the anionic surfactant is in the range of 0.01 to 1 g per square meter in dry solids mass. When used beyond this range, the photosensitive lithographic printing plate material stored in the atmosphere absorbs moisture, and the uppermost layer exhibits tackiness, which may cause problems such as blocking. .

  In order to use the photosensitive lithographic printing plate material having the photocurable photosensitive layer and the hydrophilic layer formed on the support as described above as a printing plate, contact exposure or laser scanning exposure is performed thereon. Since the exposed portion is cross-linked and the solubility in water is reduced, pattern formation is performed by elution of the unexposed portion with water.

  In the present invention, it is most preferable that the water used for water development has a pH in the range of 4 to 9 and does not substantially contain chemicals. However, in accordance with the water developability of the photosensitive lithographic printing plate material, various inorganic and organic ionic compounds may be contained in pure water at a concentration of 1% by mass or less, such as sodium, potassium, calcium, magnesium ions, etc. The water contained may be sufficient. Alternatively, various surfactants known in water may be contained at a concentration of 1% by mass or less. Further, water may contain various alcohols such as methanol, ethanol, propanol, isopropanol, ethylene glycol, propylene glycol, methoxyethanol, and polyethylene glycol at a concentration of 1% by mass or less. Alternatively, it is also possible to preferably use various commercially available gum solutions at a concentration of 1% by mass or less during water development for the purpose of protecting the plate surface from fingerprint stains. Even in the case where these chemicals such as various inorganic and organic ionic compounds, various surfactants, solvents or gum solutions are contained in pure water alone or in combination, they are used in water development related to the present invention. For water, chemicals are preferably used at a concentration of 3% by mass or less in terms of mass% concentration.

  Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to these examples. In addition, the number of parts and percentage in an Example are based on mass.

(Synthesis Example 1) Synthesis Example of Water-Soluble Polymer Having Polymerizable Double Bond Group in Side Chain 50 parts of allyl methacrylate and 40 parts of acrylamide-2-methylpropanesulfonic acid are added to 300 parts of ethanol, and 50 parts of distilled water And 27 parts of dimethylaminoethanol was added and dissolved. It heated at 70 degreeC and superposed | polymerized by adding 2 parts of azobisisobutyronitrile (AIBN) as a polymerization initiator in nitrogen atmosphere. The mixture was heated and stirred at 70 ° C. for 6 hours to obtain a polymer solution having the following structure.

(Synthesis example 2) Synthesis example of water-soluble polymer (SP-8) having a polymerizable double bond group in the side chain According to the synthesis example described in JP-A-2001-290271, p-chloromethylstyrene (AGC) A compound (hereinafter referred to as M-1) having the following structure was obtained from CMS-14) manufactured by Seimi Chemical Co., Ltd. and bismuthiol.

  In a 1 liter flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 350 parts of ethanol and 50 parts of distilled water were added, and 80 parts of M-1 was added thereto, and acrylamide-2-methyl was further added. 120 parts of propanesulfonic acid and 80 parts of dimethylaminoethanol were added and the whole was heated to 70 ° C. and dissolved in a nitrogen atmosphere. Two parts of AIBN was added as a polymerization initiator to initiate polymerization, and the mixture was stirred with heating at 70 ° C. for 12 hours. The whole was cooled to 50 ° C., 1 part of cuperone (N-nitrosophenylhydroxylamine ammonium salt) was added as a polymerization inhibitor, and 46 parts of p-chloromethylstyrene was further added, followed by stirring at this temperature for 5 hours. . Thereafter, the mixture was cooled to room temperature, and the deposited precipitate was separated by decantation, thoroughly washed with methanol, and dried. A white polymer was obtained with a yield of 80%. Analysis of the product by GPC has a weight average molecular weight of about 120,000, and as a result of structural analysis by proton NMR, the presence of a polymerizable double bond was confirmed and found to be consistent with the structure shown by SP-8 as the structure. .

(Examples 1 to 8 and Comparative Examples 1 and 2 of photosensitive lithographic printing plate materials)
Using a polyester film having a thickness of 175 μm and referring to the hydrophilic layer described in JP 2008-250195 A on this, the following hydrophilic layer coating liquid formulation is used and the dry mass is 1 Application was performed using a wire bar so as to be 3 g per square meter. In the hydrophilic layer coating formulation, the types of antifoaming agents and anionic surfactants and the amounts added were prepared as shown in Table 1 below, and samples of Examples 1 to 8 and Comparative Examples 1 and 2 were prepared. went. Drying was performed by heating for 20 minutes with a dryer at 80 ° C. The sample was further heated in a dryer at 40 ° C. for 3 days, and then fed to the subsequent application of the photopolymerizable photosensitive layer.

(Hydrophilic layer coating formulation)
Antifoaming agent (Table 1) X part anionic surfactant (Table 1) Y part polyacrylamide-acrylic acid (80/20) copolymer 10% aqueous solution 10 parts Colloidal silica (Nissan Chemical Industry Co., Ltd. Snowtex) PS-S)
(20% concentration) 10 parts Epoxy cross-linking agent (Nagase Sangyo Co., Ltd. Denacol EX-512) Stock solution 0.2 parts Distilled water 10 parts

  Using the polyester film having the hydrophilic layer prepared above, the photopolymerizable photosensitive layer is applied on the upper part of the hydrophilic layer using the photopolymerizable photosensitive layer formulation 1 shown below using a wire bar. It was. The numerical value shown in the formula 1 represents the mass applied per square meter. Drying was performed by heating for 10 minutes in a dryer at 80 ° C.

(Photopolymerizable photosensitive layer formulation 1)
Water-soluble polymer (SP-8) 1g
Photopolymerization initiator (BC-6) 0.1g
Photoinitiator (T-4) 0.05g
Sensitizing dye (S-36) 0.03g
Phthalocyanine blue (coloring pigment) 0.02g
4g of distilled water
Dioxane 5g
1g of ethanol

(Exposure test)
The photosensitive lithographic printing plate material produced as described above was subjected to an exposure test as follows. For the exposure, PT-R4000 (Dainippon Screen Mfg. Co., Ltd.) equipped with a laser having a wavelength of 830 nm was used. In order to perform drawing using this apparatus, the above-described photosensitive lithographic printing plate material was laminated on a 0.24 mm aluminum plate using a cellophane tape so that the photopolymerizable photosensitive layer was on the surface. The exposure energy was set to 120 mJ / cm ² on the plate surface, and drawing was performed at a drum rotation speed of 1000 rpm. As a test image, a halftone dot pattern showing a halftone dot area ratio from 1% to 97% corresponding to 2400 dpi and 175 lines and a thin line of 10 to 100 μm were output. As for the exposure sensitivity, a control wedge (manufactured by Fuji Film Co., Ltd.) having a step wedge with a density difference of 0.15 is attached to the surface of the photosensitive lithographic printing plate material, and after laser exposure, a water development process described later is performed to develop it. Evaluation was performed by the number of steps in the later step. With respect to the exposure sensitivity evaluated in this way, no difference was observed for all the samples prepared in Examples 1 to 8 and Comparative Examples 1 and 2.

(Water development test)
Using each photosensitive lithographic printing plate on which drawing was performed as described above, an automatic developing device PD-912-M (manufactured by Dainippon Screen Mfg. Co., Ltd.) for an aluminum printing plate (PS plate) was used as an automatic development processing device. Development processing was performed. Pure water adjusted to 30 ° C. was introduced into the developing tank, and the developing time was set to 12 seconds. In order to carry out processing using this apparatus, the above-mentioned photosensitive lithographic printing plate material was laminated on a 0.24 mm aluminum plate using a cellophane tape so that the photosensitive layer was on the surface and passed through an automatic developing apparatus. The photosensitive lithographic printing plate material was adjusted so that the photopolymerizable photosensitive layer in most non-image areas was removed by rubbing the surface of the photosensitive lithographic printing plate material weakly with a Molton roll. After rubbing development with a Molton roll, excess water on the surface of the photosensitive lithographic printing plate material was squeezed out by two squeezing rolls at the outlet of the developing tank. Subsequently, the surface was shower-washed in a water rinsing tank, and finally dried with warm air. In this development processing process, as water developability evaluation, (A) presence or absence of sludge floating in the water development tank, (B) presence or absence of sludge adhesion to the surface of the processed photosensitive lithographic printing plate, (C) treatment Three evaluation items, ie, the presence or absence of development unevenness of the finished photosensitive lithographic printing plate, were evaluated. The evaluation was conducted by continuously passing each of the samples of Examples and Comparative Examples through an A3 size 100-plate automatic developing apparatus. The replenishment of water into the developing tank was not performed throughout the processing. For the evaluation item (A), the case where the floating of the aggregated sludge is marked is X, the case where the sludge is generated but not easily redispersed and settled is set as △, and the state where the sludge is not generated is uniformly dispersed. ○. For the evaluation item (B), the case where sludge adhesion was observed on the treated photosensitive lithographic printing plate surface was evaluated as x, and the case where adhesion was not observed was evaluated as ◯. For the evaluation item (C), a halftone dot image or the like was visually observed, and a case where development unevenness was recognized instead of a homogeneous image was rated as x, and a case where it was not recognized was marked as ◯. The results are summarized in Table 2.

(Print test)
Evaluation of stain resistance was made by Heidelberg TOK (trademark of Haidelberg's offset printing machine) for printing machines, FINE INK New Champion Purple S (made by DIC Corporation) for ink, and Eu-3 (Fuji Film Co., Ltd.) for dampening water. The scum of the sample printed on 10,000 sheets was evaluated using a 0.5% aqueous solution of PS) fountain solution for PS plate). In the evaluation of soiling, the case where the soiling was clearly stained was evaluated as x, the case where the front end portion of the printed material was thin and slightly soiled was evaluated as Δ, and the case where no soiling was observed was evaluated as ○. At the same time, the number of printed sheets is counted from the start of printing, and the number of printed sheets is evaluated by the number of printed sheets until the density of the printed matter is stabilized. The case of not more than one sheet was marked with ◯, the case of not less than 51 sheets and not more than 100 sheets was indicated by Δ, and the case of not less than 101 sheets was indicated by ×. Further, as an evaluation of ink-carrying uniformity, the printed matter at the halftone dot portion was visually evaluated, and a case where the density of the halftone dot portion was uniform and no unevenness was observed was evaluated as ◯, and a case where the unevenness was slightly uneven was evaluated as x. The results are summarized in Table 3.

(Example 9 of photosensitive lithographic printing plate material)
Synthesis Example 1 using the polyester film having the hydrophilic layer prepared in Example 1 above and replacing SP-8 as a water-soluble polymer in the photopolymerizable photosensitive layer formulation 1 on the hydrophilic layer. A photopolymerizable photosensitive layer was coated in the same manner except that the water-soluble polymer obtained in 1 was used to prepare a photosensitive lithographic printing plate material 9. When an exposure test was performed in the same manner as in Example 1, the sensitivity was about ½ compared to Example 1. The exposure energy is set to 240 mJ / cm ² on the printing plate, drawing is performed at a drum rotation speed of 500 rpm, the test image is exposed in the same manner as in Example 1, and the water development treatment test and the printing test are performed in the same manner. did. As a result, good results similar to Example 1 were obtained for all the evaluated items.

(Examples 10 and 11 of photosensitive lithographic printing plate material)
On the hydrophilic layer prepared using the hydrophilic layer coating liquid formulation that does not use the antifoaming agent prepared in the previous Comparative Examples 1 and 2, in the photopolymerizable photosensitive layer formulation 1, KS-508 ( Example 10 of each photosensitive lithographic printing plate material by forming a photopolymerizable photosensitive layer using a photosensitive layer formulation to which 0.05 g of a self-emulsifying silicone-based antifoaming agent manufactured by Shin-Etsu Chemical Co., Ltd. was added. And 11 were produced. When the exposure and water development treatment tests were carried out in the same manner as in the previous example, in Example 10, a result of Δ for evaluation item (A), ○ for (B) and (C) was obtained. In Example 11, the evaluation results (A), (B), and (C) were all good. Further, a printing test was carried out, and good results were obtained in which all of the stain evaluation, the ink transfer speed and the ink transfer uniformity evaluation were ○ or more, and in Example 11, the ink transfer speed was ◎.

(Examples 12 and 13 and Comparative Examples 3 and 4 of photosensitive lithographic printing plate material)
A photopolymerizable photosensitive layer is provided using the following photopolymerizable photosensitive layer formulation 2 on the hydrophilic layer prepared using the hydrophilic layer coating solution formulation that does not use the antifoaming agent prepared in the previous Comparative Example 1. It was. The numerical value shown in the formula 2 represents the mass applied per square meter. In Formula 2, a sample prepared by adding 0.05 g of KS-508 as an antifoaming agent was set as Example 12, 0.05 g of antifoaming agent KS-508, and an anionic surfactant PELEX OT-P. A sample to which 0.02 g was added was designated as Example 13. Further, as Comparative Example 3, a sample in which neither an antifoaming agent nor an anionic surfactant was added was prepared, and as Comparative Example 4, a sample in which an antifoaming agent was not added but 0.02 g of anionic surfactant OT-P was added. Was made. The application amount of each photocurable photosensitive layer was applied using a wire bar so that the following application amount was obtained. Drying was performed by heating for 10 minutes in a dryer at 80 ° C.

(Photopolymerizable photosensitive layer formulation 2)
Antifoaming agent (KS-508) 0.05 g or none Anionic surfactant (OT-P) 0.02 g or none Water-soluble polymer (SP-8) 1 g
Photopolymerization initiator (BC-6) 0.1g
Photopolymerization initiator (T-8) 0.05g
Sensitizing dye (S-11) 0.03 g
Phthalocyanine blue (coloring pigment) 0.02g
4g of distilled water
Dioxane 5g
1g of ethanol

  Furthermore, using a polyvinyl bar (PVA-105 manufactured by Kuraray Co., Ltd.) as a protective layer on each photocurable photosensitive layer, a wire bar is used so that the dry coating weight is 2.0 g per square meter. Then, Examples 12 and 13 and Comparative Examples 3 and 4 of the photosensitive lithographic printing plate material were prepared.

(Exposure test)
The photosensitive lithographic printing plate material produced as described above was subjected to an exposure test as follows. For exposure, a CTP image setter VIPLAS (Mitsubishi Paper Co., Ltd.) equipped with a semiconductor laser having a light wavelength of 405 nm is used, and the exposure energy on the printing plate is set to 100 μJ / cm ² using this apparatus. Drawing was performed by a scanning exposure method. As a test image, a halftone dot pattern showing a halftone dot area ratio from 1% to 97% corresponding to 2400 dpi and 175 lines and a thin line of 10 to 100 μm were output. As for the exposure sensitivity, a control wedge (manufactured by Fuji Film Co., Ltd.) having a step wedge with a density difference of 0.15 is laminated on the surface of the photosensitive lithographic printing plate material, and after laser exposure, the water development described in the previous embodiment Evaluation was performed by performing exactly the same processing as the processing, and determining the number of steps after development. With respect to the exposure sensitivity evaluated in this way, no difference was observed for all samples prepared in Examples 12 and 13 and Comparative Examples 3 and 4.

  Using each photosensitive lithographic printing plate on which the above drawing was performed, a water development treatment test and a printing test were conducted in the same manner as in the previous examples. The results are summarized in Table 4 and Table 5, respectively.

(Examples 14 and 15 of photosensitive lithographic printing plate material)
Both the antifoaming agent and the anionic surfactant in the photopolymerizable photosensitive layer formulation 2 on the hydrophilic layer prepared using the hydrophilic layer coating solution formulation not using the antifoaming agent prepared in the previous Comparative Example 1 A photopolymerizable photosensitive layer was prepared in the same manner as in Comparative Example 3 above using a photopolymerizable photosensitive layer formulation not added together. Using a coating liquid of the following protective layer coating liquid formulation containing polyvinyl alcohol (PVA-105 manufactured by Kuraray Co., Ltd.) as a protective layer on this layer, a wire is applied so that the dry coating weight is 2.0 g per square meter. Examples 14 and 15 of photosensitive lithographic printing plate materials were prepared by coating using a bar. In Example 14, only the antifoaming agent was included in the protective layer, and in Example 15, a sample was prepared that included both the antifoaming agent and the anionic surfactant in the protective layer.

(Protective layer coating formulation)
Polyvinyl alcohol (Kuraray Co., Ltd. PVA-105) 10% aqueous solution 10 parts Defoamer (KS-508) 0.05 part Anionic surfactant (OT-P) 0.02 part or none

  When the exposure and water development treatment tests were carried out in the same manner as in Examples 12 and 13, the results of Example 14 were Δ for evaluation item (A), and ○ for (B) and (C). In Example 15, the result which is (circle) in all the evaluation items (A), (B), (C) was obtained. Further, a printing test was conducted, and good results were obtained in which all of the stain evaluation, the ink transfer speed, and the ink transfer uniformity evaluation were ○ or more, and in Example 15, the ink transfer speed was ◎.

  In a CTP printing plate using a scanning exposure apparatus that uses a laser that emits light in the near infrared region (750 to 1100 nm) or a laser that emits light in the wavelength region of 400 to 430 nm, processing is performed using an automatic development processor. In this case, a system capable of long-term processing without scumming or uneven ink transfer failure is provided. A water-developable plastic film-based printing plate or aluminum-based printing plate making system is provided. Furthermore, a production system suitable for forming a printed wiring board production resist, a color filter, a phosphor pattern, and the like is provided.

Claims (2)

In a photosensitive lithographic printing plate material in which a photopolymerizable photosensitive layer including a hydrophilic layer and a water-soluble polymer is provided in this order on a support, at least one layer on the support is a silicone-based antifoaming agent and a fluorine-based antifoaming agent A photosensitive lithographic printing plate material comprising an antifoaming agent selected from acetylene alcohol defoaming agent and acetylene glycol defoaming agent .   The photosensitive lithographic printing plate material according to claim 1, wherein at least one layer on the support further contains an anionic surfactant.