PHOTOSENSITIVE LITHOGRAPHIC PRINTING PLATE

Abstract: A photosensitive lithographic printing plate is provided. The printing plate contains a supporting substrate and a photosensitive layer carried on the substrate. The photo­ sensitive layer contains a polymer having an acid number of not more than 200, an addition polymerizable compound having at least one ethylenically unsaturated double bond, an organic peroxide and a compound absorbind visible light.

Description: Photosensitive Lithographic Printing Plate The present invention relates to a photosensitive lithographic printing plate, and more particularly to a photosensitive lithographic printing plate having extremely high sensitivity so that a printing image can be formed by the laser plate making process and the thus formed image can be developed by a weakly alkaline aqueous solution. In the field of lithographic printing, so-called PS plates, i.e. presensitized plates prepared by using diazo type photosensitive materials, have been widely used. However, the conventional presensitized plates are low in photosensitivity and sensible mainly by the near-ultraviolet light rays. It has been proposed recently that the process efficiency can be greatly improved by exposing a green or immaculate printing plate with laser or other focused light directly without any intermediate masking by a high speed scanning controlled by a computer. However, this conspicuous proposal has not yet been used practically for the attendant problems that scanning exposure of the conventional photosensitive lithographic plate requires large output ultaviolet laser. leading to increase in investment for the equipment including a large scale optical system with increase in consumed electrical power in addition to reduction in lifetime of the laser generating system. A primary object of this invention is to provide a photosensitive lithographic printing plate having extremely high sensitivity to a wide wavelength range including the visible light range. Another object of this invention is to provide a photosensitive lithographic printing plate which has extremely high sensitivity particularly to the output lines of visible laser lights and does not show the reciprocity low failure even when exposed to a high illumination light for extremely short time during the high speed scanning exposure process. A further object of this invention is to provide a photosensitive lithographic printing plate which may be easily developed by the use of an ordinary aqueous developing solution to form an image including printing areas on which a printing ink can be coated or spread in a satisfactory condition. The above and other objects and advantages of the invention will become apparent from the following detailed description thereof. A photosensitive lithographic printing plate, provided in accordance with the invention, comprises a supporting substrate and a photosensitive layer carried on the supporting substrate, the photosensitive layer containing a polymer (a) having an acid number of not more than 200, an addition polymerizable compound (b) having at least one ethylenically unsaturated double bond, an organic peroxide (c) and a compound (d) absorbing visible light. The present invention will now be described in detail hereinbelow. The photosensitive lithographic printing plate of the invention comprises a supporting substrate and a photosensitive layer carried on the supporting substrate. The photosensitive layer includes a polymer (a) having an acid number of not more than 200, an addition polymerizable compound (b) having at least one ethylenically unsaturated double bond per molecule, an organic peroxide (c) and a compound (d) absorbing visible light. Any of vinyl system polymers of addition polymerization product and polycondensation polymers of polyester system, polyurethane system and polyaminde system may be used as the the polymer (a) having an acid number of not more than 200 as far as they have weight average molecular weight of about 10,000 to 500,000. Preferable examples of such polymers are copolymers of (meth)acrylic acid, (meth)acrylates, maleic acid, fumaric acid, maleates, fumarates, ethylene glycol, styrene and vinyl chlorides; specific examples being copolymers of methyl methacrylate/ethyl acrylate/benzyl methacrylate/ methacrylic acid, copolymers of methyl methacrylatejbutyl methacrylate/methacrylic acid, coplymers of styrene/maleic acid/dimethyl maleate/vinyl chloride, copolymers of tetrahydrophthalic anhydride/fumaric acid/diethylene glycol, and copolymers of methyl methacrylate/ethyl acrylate/butyl methacrylate/methacrylic acid If the acid value of the polymer (a) is more than 200, the solubility of the photosensitive layer becomes excessively hi#gh so that the printing area is apt to be rinsed away by a weak alkaline aqueous solution used as the developing solution-in the development step after the printing plate has been exposed to light. Examples of the addition polymerizable compound (b) having at least one ethylenically unsaturated double bond, used in the present invention, include unsaturated acids, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, phthalic acid, phthalic anhydride and fumaric acid; esters of unsaturated acids, such as methyl (meth)arylate, ethyl (meth)acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, hydroxyethyl (meth)acrylate, dimethyl maleate, diethyl maleate, dimethyl fumarate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethyleneglycol di(meth)acrylate and propyleneglycol di(meth)acrylate; vinyl compounds such as styrene, acrylamide, acrylonitrile, N-vinylpyrrolidone and vinyl acetate; and various other compounds such as unsaturated polyesters, unsaturated polyethers, unsaturated polyurethanes and (meth)acrylate compounds having epoxide groups. The organic peroxide (c) used in the present invention includes a polyperoxy ester containing a benzophenone group and represented by the following general formul (I) of: EMI5.1 wherein R1 and R1' each represents the same or different group and stands for a tertiary alkyl group having 4 to 8 carbon atoms or a tertiary aralkyl group having 9 to 12 carbon atoms, and R2 and R21 each represents the same or different atom or group and stands for a hydrogen atom, a tertiary alkoxy group having 4 to 8 carbon atoms or a tertiary aralkyloxy group having 9 to 12 carbon atoms. Specific examples of the polyperoxy ester containing a benzophenone group, which may be used in the photosensitive layer of the invention are 3,3',4,4'-tetra-(t-butylperoxycarbonyl)benzophenone, 3,3' '4' 4 '-tetra-( t-amylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra-(t-hexylperoxycarbonyl)benzophenone, 3,3',4'4'-tetra-(t-octylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra-(t-cumylperoxycarbonyl)benzophenone, 3,3',4'4'-tetra-(p-isopropylcunylperoxycarbonyl)benzophenone Aromatic peroxides may also be conveniently used in the photosensitive layer of the invention, specific examples being benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, toluoyl peroxide, t-butyl peroxybenzoate, di-t-butyl diperoxyisophthalate, 2, 5-dimethyl-2 '5- di ( benzoylperoxy ) hexane. The compound (d) absorbing visible light used in the invention includes a pyrylium salt compound which is represented by the following general formula (11) of: EMI6.1 wherein R4, R5 and R6 each represents the same or different atom or group and stands for a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an ethylenyl group, a styryl group, an alkoxy group, a phenyl group, a naphtyl group, an alkylphenyl group, an alkoxyphenyl group, a hydroxyphenyl group, a halophenyl group, a nitrophenyl group, an aminophenyl group, a nitro group, an amino group or a hydroxyl group, X stands for an oxygen atom or a sulfur atom, and Y stands for an anionic functional group. As will be seen from the foregoing that the pyrylium salt compounds which may be used in the invention include pyrylium salts represented by the formula (II) wherein X is oxygen, and thiopyrylium salts represented by the formula (II) wherein X is sulfur, the anionic functional groups represented by Y in the formula (II) include, for example, perchlorate, fluoroborate, chloroaluminate, chloropherate, sulfuracetate, methosulfate, fluoroantimonate, thiocyanate, etc. Specific examples of the pyrylium salt compounds which may be used as the compound (d) in the invention are: 2,4,6-triphenylthiopyrylium fluoroborate, 2,4,6-triphenylthiopyrylium fluoroantimonate, 2,4,6-triphenylpyrylium perchlorate, 4-( 4-methoxyphenyl)-2, 6-diphenylpyrylium perchlorate, 2, 6-bis (4-methoxyphenyl)-4-phenylpyrylium perchlorate, 4-(4-butoxyphenyl)-2,6-diphenylpyrylium perchlorate, 4-(4-amyloxyphenyl)-2,6-bis(4-ethylphenyl)pyrylium perchlorate, 2,4, 6-triphenylpyrylium fluoroborate, 4-(4-butoxyphenyl)-2,6-di(4-methoxyphenyl)thiopyrylium fluoroborate, 2,4,6-triphenylthiopyrylium perchlorate, 4- ( 4-methoxyphenyl) -2, 6-diphenylthiopyrylium perchlorate, 6-(4-ethoxyphenyl)-2 -2 ,4-diphenylthiopyrylium perchlorate, 2,4,6-tri(4-methoxyphenyl)thiopyrylium perchlorate, 4-(4-methoxyphenyl)-2,6-diphenylpyrylium fluoroborate, 2, 6-bis (4 -methoxyphenyl) -4-phenylpyrylium fluoroborate, 4-(4-amyloxyphenyl)-2,6-bis(4-ethylphenyl)thiopyrylium perchlorate, 2,4 , 6-triphenylthiopyrylium fluoroborate, 2,4 ,6-triphenylthiopyrylium sulfate, 4-C 4-methoxyphenyl) -2, 6-diphenylthiopyrylium fluoroborate, 2-(4-amyloxyphenyl)-4,6-diphenylthiopyrylium fluoroborate, 4-(4-amyloxyphenyl)-2,6-bis(4-methoxyphenyl)thiopyrylium perchlorate, 4-(4-methoxyphenyl)-2,6-bis(4-ethylphenyl)thiopyrylium perchlorate, 4-( 2, 4-dichlorophenyl) -2 ,6-diphenylpyrylium perchlorate, 2-(3,4-dichlorophenyl)-4-(4-methoxyphenyl)-6-phenylpyrylium perchlorate, 4-(4-amyloxyphenyl)-2,6-bis(4-ethylphenyl)pyrylium perchlorate, a,6-bis(4-ethylphenyl)-4-(4-methoxyphenyl)pyrylium fluoroborate, 6-(3,4-diethoxystyryl)-2,4-diphenylpyrylium perchlorate, 6-(4-dimethylamino-B-ethylstyryl)-2 , 4-diphenylpyrylium fluoroborate, 6-( 4-dimethylaminostyryl) -2, 4-diphenylpyrylium perchlorate, 6-(ss-methyl-4-dimethylaminostyryl)-2,4-diphenylpyrylium fluoroborate, 6-(B,B-bis(4-dimethylaminophenyl)vinylene)-2,4-diphenyl- pyrylium fluoroborate, 4-( 4-dimethylaminophenyl) -2, 6-diphenylpyrylium perchlorate, 2,6-bis(4-ethylphenyl)-4-methoxyphenylthiopyrylium fluoroborate, 2-amino-4,6-bis(4-methoxy-ss-ethylstyryl)thiopyrylium fluoroborate, and 4-(4-dimethylaminostyryl)-6-(13, B-bis(4-dimethylamino- phenyl )vinylene) thiopyrylium perchlorate. The dyes A to D having the defined structures as set forth below may also be used as the compound (d) absorbing visible light in the photosensitive layer in the present invention: A: Cyanine System Dyes Represented by the Following Structural Formulae (1) to (3) EMI10.1 wherein R1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkoxy group or a dialkylamino group, R2 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group, X is a halogen atom, n is an integer of 1, 2 or 3, and Y is a group represented by EMI10.2 EMI10.3 wherein R1 and Rz each represents the same or diferent atom or group and stands for a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group, X stands for a halogen atom, and EMI10.4 stands for EMI11.1 wherein R1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group or an alkoxy group, R2 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group, X is a halogen atom, n is an integer of 1,2 or 3, and Y is a group represented by EMI11.2 Merocyanine System Dyes Represented by the Following Structural Formulae (1) to (3) EMI11.3 wherein R1 and RZ each is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n is an integer of l, 2 or 3, and X is a group represented by EMI12.1 EMI12.2 wherein Rl, Rz and R3 each represents the same or different atom or group and stands for a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group. EMI13.1 wherein Rl, R2 and R3 each represents the same or different atom or group and stands for a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group, and X is a hydrogen atom or an alkali metal element. C: Xanthene System Dyes Represented by the Following Structural Formulae (1) and (2) EMI13.2 wherein X is an hydrogen atom or an alkali metal element, and Y is a hydrogen atom or a halogen atom. EMI14.1 wherein Rl, R2, R3 and R4 each represents the same or different atom or group and stands for a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group, X is a halogen atom, and Y is a hydrogen atom or an alkali metal element. D: Thiazole System Dyes Represented by the Following Structural Formulae (l) and (2) EMI14.2 wherein R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkoxy group, a nitro group or an amino group, and X is an amino group or a phenylamino group. EMI14.3 wherein Rl, R2, R3 and R4 each represents the same or different atom or group and stands for a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group, R5 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, aryl group or sulfonic group, and X is a halogen atom or a hydroxyl group. The photosensitive lithographic printing plate of the invention may be prepared by coating a supporting substrate with a photosensitive layer containing the aforementioned polymer (a) having an acid number of not more than 200, the aforementioned addition polymerizable compound (b) having at least one ethylenically unsaturated double bond, the aforementioned organic peroxide (c) and the aforementioned compound (d) absorbing visible light. In a preferable composition, each of the aforementioned components are mixed in a ratio such that 100 parts by weight of the component (a) is mixed with 10 to 200 parts by weight of the component (b), 0.1 to 10 parts by weight of the component (c) and 0.1 to 10 parts by weight of the component (d). The photosensitive composition may be dissolved in a solvent for dissolving all of the components, such as methyl cellosolve, ethyl cellosolve, methy ethyl ketone, isopropyl alcohol, butyl acetate, toluene, xylene, or butanol to form a uniform solution, which is coated over the supporting substrate through a bar coating, roller coating or spin coating method to form a coating layer having a thickness of from 0.1 to 10 microns followed by drying. Materials used for the supporting substrate include thin plates of metals, such as aluminum and zinc, sheets of plastics materials, such as polyvinyl chloride and polyethylene terephthalate, and paper. When the thus prepared photosensitive lithographic printing plate of the invention is exposed to light, the photosensitive layer being sensitive to light rays having widely spread wavelengths ranging from the ultraviolet range to the visible light range, the portions irradiated by the light ray are changed to be insoluble to a solvent within an extremely short exposure time so that the printing areas may be left on the supporting substrate by developing with the use of an aquesous weak alkali solution after the selective exposure. Since the photosensitive composition used in the photosensitive lithographic printing plate of the invention has an extremely high sensitivity even to a visible light laser, such as the Ar laser, the printing plate of the invention is adapted to form an image by a high speed scanning exposure with a visible light laser of low output. The thus formed latent image may be easily developed by the use of an ordinary aqueous developing solution, and the printing areas left after the developing step may be well applied with a printing ink to form a clear printed image. The present invention will be described more in detail hereinafter with reference to some Examples and Comparative Examples. Incidentally, parts and % are based on weight unless otherwise indicated. Example 1 An surface of an aluminum plate was coarsened by sand blasting and then oxidized by anodic oxidation. A solution of a photosensitive composition prepared by the following formulation was coated over the pretreated aluminum plate using a whirler, and then dried at 600C for 5 minutes to form a coating having a thickness of 2 microns. Formulation of the photosensitive Composition Solution: Acrylic Polymer* (Acid Number: 98) 100 parts Pentaerythritol Triacrylate 60 parts Di-t-butyldiperoxy Isophthalate 3 parts 4-(4-butoxyphenyl)-2,6-di(4-methoxyphenyl) 3 parts thiopyrylium Fluoroborate Hydroquinone 1 part Ethyl Cellosolve 900 parts *Note: The used acrylic polymer was a copolymer of methyl methacrylate (MM), ethyl acrylate (EA), benzyl methacrylate (BM) and methacrylic acid (MA) mixed in a ratio of MM/EA/BM/MA = 30/25/30/15 and having a weight average molecular weight of 100,000. The thus prepared photosensitive lithographic printing plate was exposed to a scanning exposure of a light ray having a wavelength of 488nm and generated as an Ar laser of an output of 10 mW, the laser light ray being focused to form a spot light of 25 microns in diameter, at a scanning rate of 5.1 mlsec. After the scanning exposure, the plate was subjected to a development step effected by using a 3% aqueous solution of sodium metasilicate for one minute to obtain a lithographic printing plate having clear printing areas which are left as the result of exposure by the laser light ray. An emulsion type printing ink was applied on the printing plate to reveal that the ink was spread uniformly in fully satisfactory condition. Example 2 Generally in accordance with the procedures as described in Example l except that 2,6-bis(4-methoxyphenyl)4-phenylpyrylium perchlorate was used as the compound for absorbing visible light, a photosensitive lithographic printing plate was prepared and exposed to a similar Ar laser followed by development to obtain a lithographic printing plate. The resultant printing plate had clear printing areas comparable with those of the printing plate of Example 1, and the ink was spread uniformly in fully satisfactory condition on the printing areas. Example 3 A photosensitive lithographic printing plate was prepared, similarly as in Example 1, while using a photosensitive composition having the following formulation. Acrylic Polymer* (Acid Number: 130) 100 parts Trimethylolpropane Triacrylate 50 parts 3,3' ,4,4'-tetra(t-butylperoxycarbonyl)benzo- 2 parts phenone Cyanine System Dye* 3 parts Hydroquinone Monomethyl Ether 0.5 part Methyl Cellosolve 800 parts *Note 1: The acrylic polymer used was a copolymer of methyl methacrylate (MM), butyl methacrylate (BM) and methacrylic acid (MA) prepared from a mixture of MM/BM/MA = 50/30/20 and having a weight average molecular weight of 70,000 *Note 2: The cyanine system dye used was the one represented by the following structural formula of: EMI19.1 The thus prepared photosensitive lithographic printing plate was exposed to a scanning exposure of a light ray having a wavelength of 488 nm and generated as an Ar laser of an output of 20 mW, the laser light ray being focused to form a spot light of 30 microns in diameter, at a scanning rate of 9.5 m/sec. After the scanning exposure, the plate was subjected to a development step effected by using a 3% aqueous solution of sodium carbonate for 30 seconds to obtain a lithographic printing plate having clear printing areas which are left as the result of exposure by the laser light ray. An emulsion type printing ink was applied on the printing plate to reveal that the ink was spread uniformly in fully satisfactory condition. Example 4 A photosensitive lithographic printing plate was prepared, similarly as in Example 1, while using a photosensitive composition having the following formulation. Vinyl System Polymer* (Acid Number: 145) 100 parts Tetramethylolmethane Tetraacrylate 65 parts t-Butylperoxy Benzoate 3 parts Merocyanine System Dye* 2 parts Hydroquinone 1 part *Note 1: The vinyl system polymer used was a copolymer of styrene (S), maleic acid (MaA), dimethyl maleate (DMa) and vinyl chloride (VC) prepared from a mixture of S/MaA/DMa/VC = 40/15/25/20 and having a weight average molecular weight of 85,000 *Note 2: The merocyanine system dye used was the one represented by the following structural formula of: EMI21.1 The thus prepared photosensitive lithographic printing plate was exposed to a scanning exposure of a light ray having a wavelength of 488 nm and generated as an Ar laser of an output of 25 mW, the laser light ray being focused to form a spot light of 25 microns in diameter, at a scanning rate of 8.8 m/sec. After the scanning exposure, the plate was subjected to a development step effected by using a 3 aqueous solution of sodium metasilicate for one minute to obtain a lithographic printing plate having clear printing areas which are Left as the result of exposure by the laser light ray. An emulsion type printing ink was applied on the printing plate to reveal that the ink was spread uniformly in fully satisfactory condition. Example 5 A photosensitive lithographic printing plate was prepared, similarly as in Example 1, while using a photosensitive composition having the following formulation. Polyester system Polymer* (Acid Number: 85) 100 parts Pentaerythritol Triacrylate 75 parts 2,5-Dimethyl-2,5-di(benzoyloxy)hexane 4 parts Xanthene System Dye* 2 parts Hydroquinone 0.5 part Methyl Isobutyl Ketone 400 parts Methyl Cellosolve 400 parts *Note 1: The polyester system polymer used was a coplymer of tetrahydrophthalic anhydride (THP), fumaric acid (FA) and diethylene glycol (DG) prepared by polycondensation of a mixture of THP/FA/DG = 12/37/51 and having a weight average molecular weight of 20,000 *Note 2: The xanthene system dye used was the one represented by the following structural formula of: EMI22.1 The thus prepared photosensitive lithographic printing plate was exposed to a scanning exposure of an Ar laser, similarly to Example 2, to obtain a lithographic printing plate. An emulsion type printing ink was applied on the printing plate to reveal that the ink was spread uniformly in fully satisfactory condition. Example 6 A photosensitive lithographic printing plate was prepared, similarly as in Example 1, while using a photosensitive composition having the following formulation. Acrylic Polymer* (Acid Number: 65) 100 parts Pentaerythritol Triacrylate 80 parts 3,3',4,4'-Tetra(t-butylperoxycarbonyl) 5 parts benzophenone Thiazole System Dye* 4 parts Hydroquinone 0.5 part Ethyl Cellosolve 700 parts *Note 1: The acrylic polymer used was a copolymer of methyl methacrylate (MM), ethyl acrylate (EA), butyl methacrylate (BM) and methacrylic acid (MA) prepared from a mixture of MM/EA/BM/MA = 30/20/30/10 and having a weight average molecular weight of 10,000 *Note 2: The thiazole system dye used was the one represented by the following structural formula of: EMI23.1 The thus prepared photosensitive lithographic printing plate was exposed to a scanning exposure of an Ar+ laser, similarly to Example 1, to obtain a lithographic printing plate. An emulsion type printing ink was applied on the printing plate to reveal that the ink was spread uniformly in fully satisfactory condition. Comparative Examples 1 to 6 The compositions similar to the compositions of Examples 1 to 6 except that the compounds for absorbing visible light were excluded from respective formulations were not sensitive to the Ar laser having a wavelength of 488 nm to leave no images. Comparative Examples 7 to 12 The compositions similar to the compositions of Examples 1 to 6 except that the organic peroxides were excluded from respective formulations were not sensitive to the Ar laser having a wavelength of 488 nm to leave no images even after scanning with that laser beam. Comparative Examples 13 and 14 Two commercially available PS plates (presentized plates) were scanned by the Ar -laser (Wavelength: 488 nm) ray to be exposed. However, those commercially available PS plates were not sensitive to the laser ray to leave no image thereon. Examples 7 to 14 Generally in accordance with the procedures as described in Example 1, solutions of photosensitive compositions having the following formulation were prepared. Acrylic Polymer (the same polymer as used in 100 parts Example 6) Pentaerythritol Triacrylate 70 parts 3,3',4,4'-tetra(t-butylperoxycarbonyl) 5 parts benzophenone Visible Light Absorbing Compound 5 parts Hydroquinone 1 part Ethyl Cellosolve 800 parts In respective Examples, the following compounds were used as the visible light absorbing compounds: Example 7: 4-( 4-butoxyphenyl)-2, 6-diphenylthiopyrylium fluoroborate Example 8: 4-( 4-butoxyphenyl) -2, 6-di( 4-methoxyphenyl- pyrylium fluoroborate Example 9: A cyanine system dye represented by the following structural formula A(2) of: EMI25.1 The formula No. A(2) corresponds to that shown in the detailed description hereinabove. The same applies to Examples' 10 to 14. Example 10: A cyanine system dye represented by the following structural formula A(3) of: EMI25.2 Example 11: A merocyanine system dye represented by the following structural formula B(2) of: EMI26.1 Example 12: A merocyanine system dye represented by the following structural formula B(3) of: EMI26.2 Example 13: A xanthene system dye represented by the following structural formula C( 2 ) of: EMI26.3 Example 14: A thiazole system dye represented by the following structural formula D(2) of: EMI26.4 Tests were conducted similarly as in Example 1, while using the photosensitive compositions set forth above, similar satisfactory results were obtained.

Claims: CLAIMS 1. A photosensitive lithographic printing plate, comprising a supporting substrate and a photosensitive layer carried on said supporting substrate, said photosensitive layer containing a polymer (a) having an acid number of not more than 200, an addition polymerizable compound (b) having at least one ethylenically unsaturated double bond, an organic peroxide (c) and a compound (d) absorbing visible light. 2. A photosensitive lithographic printing plate according to claim 1, wherein said polymer (a) having an acid number of not more than 200 is a polymer having a weight average molecular weight of from 10,000 to 500,000 and selected from the group consisting of vinyl system addition polymerization polymers, polyester system condensation polymers, polyurethane system condensation polymers, polyamide system condensation polymers and mixtures thereof. 3. A photosensitive lithographic printing plate according to claim 1 or 2, wherein said polymer (a) is a copolymer copolymerized with a monomer selected from the group consisting of acrylic acid, methacrylic acid, acrylates, methacrylates, maleic acid, fumaric acid, maleates, fumarates, ethylene glycol, styrene, vinyl chloride and mixtures thereof. 4. A photosensitive lithographic printing plate according to claim 3, wherein said copolymer is selected from the group consisting of copolymers of methyl methacrylate/ethyl acrylate/benzyl methacrylate/methacrylic acid, copolymers of methyl methacrylate/butyl methacrylate/ methacrylic acid, copolymers of styrene/maleic acid/dimethyl maleate/vinyl chloride, copolymers of tetrahydrophthalic anhydride/fumaric acid/diethylene glycol, copolymers of methyl methacrylate/ethyl acr#ylate/butyl methacrylate/ methacrylic acid and mixtures thereof. 5. A photosensitive lithographic printing plate according to any of the claims 1 to 4, wherein said addition polymerizable compound (b) having at least one ethylenically unsaturated double bond is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid and anhydride thereof, phthalic acid and anhydride thereof, fumaric acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, dimethyl maleate, diethyl maleate, dimethyl fumarate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethyleneglycol diacrylate, ethyleneglycol dimethacrylate, propyleneglycol diacrylate, propyleneglycol dimethacrylate, styrene, acrylamide, acrylonitrile, N-vinyl pyrrolidone, vinyl acetate, unsaturated polyesters, unsaturated polyethers, unsaturated polyurethanes, acrylate compounds having epoxide groups, methacrylate compounds having epoxide groups, and mixtures thereof. 6. A photosensitive lithographic printing plate according to any of the claims 1 to 5, wherein said organic peroxide (c) is 2 polyperoxy ester containing a benzophenone group and represented by the following general formula (I) of: EMI30.1 wherein R1 and R1' each represents the same or different group and stands for a tertiary alkyl group having 4 to 8 carbon atoms or a tertiary aralkyl group having 9 to 12 carbon atoms, and R2 and R21 each represents the same or different atom or group and stands for a hydrogen atom, a tertiary alkoxy group having 4 to 8 carbon atoms or a tertiary aralkyloxy group having 9 to 12 carbon atoms. 7. A photosensitive lithographic printing plate according to claim 6, wherein said polyperoxy ester containing a benzophenone group is selected from the group consisting of 3,3'4,4'-tetra-(t-butylperoxycarbonyl)benzophenone, 3,3'4,4'-tetra-(t-amylperoxycarbonyl)benzophenone, 3,3'4,4'-tetra-(t-hexylperoxycarbonyl)benzophenone, 3,3'4,4'-tetra-(t-octylperoxycarbonyl)benzophenone, 3,3'4,4'-tetra-(cumylperoxycarbonyl)benzophenone, 3,3'4,4'-tetra-(p-isopropylcumylperoxycarbonyl)benzophenone and mixtures thereof. 8. A photosensitive lithographic printing plate according to any of the claims 1 to 5, wherein said organic peroxide (c) is an aromatic peroxide selected from the group consisting of benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, toluoyl peroxide, tertiarybutylperoxy benzoate, ditertiarybutyldiperoxy isophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)- hexane and mixtures thereof, 9. A photosensitive lithographic printing plate according to any of the claims 1 to 8, wherein said compound (d) absorbing visible light is a pyrylium salt compound represented by the following general formula (II) of: EMI31.1 wherein R4, R5 and R6 each represents the same or different atom or group and stands for a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an ethylenyl group, a styryl group, an alkoxy group, a phenyl group, a naphtyl group, an alkylphenyl group, an alkoxyphenyl group, a hydroxyphenyl group, a halophenyl group, a nitrophenyl group, an aminophenyl group, a nitro group, an amino group or a hydroxyl group, X stands for an oxygen atom or a sulfur atom, and Y stands for an anionic functional group. 10 A photosensitive lithographic printing plate according to claim 9, wherein said pyrylium salt compound is slected from the group consisting of: 2,4,6-triphenylthiopyrylium fluoroborate, 4-(4-methoxyphenyl)-2,6-diphenylpyrylium perchlorate, 2, 6-bis ( 4-methoxyphenyl) -4-phenylpyrylium perchlorate, 4-(4-butoxyphenyl)-2,6-diphenylpyrylium perchlorate, 2,4,6-triphenylpyrilium fluoroborate, 4-( 4-butoxyphenyl) -2, 6-di( 4-methoxyphenyl) thiopyrylium fluoroborate, - 2,4, 6-triphenylthiopyrylium perchlorate, 4-(4-methoxyphenyl)-2,6-diphenylthiopyrylium perchlorate, 4-(4-methoxyphenyl)-2,6-diphenylpyrylium fluoroborate, 2, 6-bis ( 4-methoxyphenyl) -4-phenylpyrylium fluoroborate, 2,4, 6-triphenylthiopyrylium fluoroborate, 4-(4-methoxyphenyl)-2,6-diphenylthiopyrylium fluoroborate, 4-(4-amyloxyphenyl)-2,6-bis(4-methoxyphenyl)thiopyrylium perchlorate, 6-(4-dimethylamino-ss-ethylstyryl)-2,4-diphenylpyrylium fluoroborate, 4-( 4-dimethylaminophenyl) -2, 6-diphenylpyrylium perchlorate, and mixtures thereof. 11. A photosensitive lithographic printing plate according to any of the claims 1 to 8, wherein said compound (d) absorbing visible light is selected from the group consisting of cycanine system dyes, merocyanine system dyes, xanthene system dyes, thiazole system dyes and mixtures thereof. 12. A photosensitive lithographic printing plate according to any of the claims 1 to 11, wherein said photosensitive layer contains 100 parts by weight of said polymer (a) having an acid number of not more than 200, 20'to 200 parts by weight of said addition polymerizable compound (b) having at least one ethylenically unsaturated double bond, 0.1 to 10 parts by weight of said organic peroxide (c) and 0.1 to 10 parts by weight of said compound (d) absorbing visible light. 13. A photosensitive lithographic printing plate according to any of the claims 1 to 12, wherein said photosensitive layer has a thickness of from 0.1 to 10 microns. 14. A photosensitive lithographic printing plate according to any of the claims 1 to 13, wherein said supporting substrate is made of a material selected from the group consisting of metals, plastics, paper and combinations thereof.

Inventors: FUJII, KENICHI, GOTO, YOSHITAKA, HAYASHI, AKIO, YAMADA, EIICHI
Applicants: NIPPON OIL AND FATS COMPANY, LIMITED
Application year: 1986
Main classification: G03C1
IPC codes: G03F7