EP1407894B1 - Précurseur photosensible de plaque d'impression lithographique - Google Patents

Précurseur photosensible de plaque d'impression lithographique Download PDF

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Publication number
EP1407894B1
EP1407894B1 EP03022901A EP03022901A EP1407894B1 EP 1407894 B1 EP1407894 B1 EP 1407894B1 EP 03022901 A EP03022901 A EP 03022901A EP 03022901 A EP03022901 A EP 03022901A EP 1407894 B1 EP1407894 B1 EP 1407894B1
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EP
European Patent Office
Prior art keywords
group
acid
printing plate
lithographic printing
plate precursor
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EP03022901A
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German (de)
English (en)
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EP1407894A3 (fr
EP1407894A2 (fr
Inventor
Shunichi c/o Fuji Photo Film. Ltd Kondo
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Fujifilm Corp
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Fujifilm Corp
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • B41C1/1016—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N1/00—Printing plates or foils; Materials therefor
    • B41N1/04—Printing plates or foils; Materials therefor metallic
    • B41N1/08—Printing plates or foils; Materials therefor metallic for lithographic printing
    • B41N1/083—Printing plates or foils; Materials therefor metallic for lithographic printing made of aluminium or aluminium alloys or having such surface layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/02—Cover layers; Protective layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/04—Intermediate layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/14—Location, type or constituents of the non-imaging layers in lithographic printing formes characterised by macromolecular organic compounds, e.g. binder, adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/04—Negative working, i.e. the non-exposed (non-imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/06—Developable by an alkaline solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers

Definitions

  • the present invention relates to a photosensitive lithographic printing plate precursor comprising an aluminum support having provided thereon a photopolymerizable photosensitive layer. More particularly, it relates to a photosensitive lithographic printing plate precursor in which the developing property of the non-image area is improved and the adhesion of photosensitive layer to support is increased and thus both resistance to stain and press life at the printing are fulfilled.
  • the background stain increases with getting a storage period longer after the production of lithographic printing plate precursor, and it becomes severe in the case of storage under high temperature and high humidity conditions. Since in the photopolymerizable photosensitive layer, a radical is generated upon light and a chain reaction polymerization occurs to form an image, it is difficult that the photosensitive lithographic printing plate precursor having such a photopolymerizable photosensitive layer has a good storage stability. Therefore, it has been desired to develop a photosensitive lithographic printing plate precursor, which withstands preservation for a long period of time, particularly preservation under high temperature and high humidity conditions and provides printings free from background stain.
  • a photosensitive lithographic printing plate precursor comprising an anodized aluminum support having an undercoat layer comprising polyvinyl sulfonic acid on the surface of the support and a photosensitive layer containing a diazo compound provided on the undercoat layer (described in West German Patent 1,621,478 ), a photosensitive lithographic printing plate precursor comprising an aluminum support having an undercoat layer comprising polyacrylic acid, etc.
  • a photosensitive lithographic printing plate precursor comprising an aluminum support having an undercoat layer comprising polyacrylamide on the surface of the support and a photosensitive layer provided on the undercoat layer (described in U.S.
  • Patent 3,511,661 a photosensitive lithographic printing plate precursor comprising a photosensitive layer containing a diazo compound and an organic polymer carrier, wherein a polymer organic acid is added to the photosensitive layer in order to improve the preservation stability and to prevent the occurrence of background stain ( JP-A-56-107238 ) (the term "JP-A” as used herein means an "unexamined published Japanese patent application”).
  • JP-A as used herein means an "unexamined published Japanese patent application”
  • a photosensitive adduct containing a combination of a diazo resin having plural side chain diazonium groups with a sulfonated polymer having plural sulfonate groups (for example, sulfonated polyurethane or sulfonated polyester) is described in JP-A-57-5042 .
  • a sulfonated polymer having plural sulfonate groups for example, sulfonated polyurethane or sulfonated polyester
  • an intermediate layer containing a polymer including a repeating unit of a monomer having sulfonic acid as a method for restraining the occurrence of background stain due to preservation of a photosensitive lithographic printing plate precursor having a photosensitive layer containing a diazo compound and a polymerizable composition for a long period of time (for example, refer to Patent Document 1).
  • the improvement in preservation stability according to the above technique is highly achieved in a photopolymerization system of low sensitivity, the effect is insufficient in a high-sensitive photopolymerization system, for example, a CTP system, which is exposed with a laser light source.
  • Such methods of providing the undercoat layer containing a compound having a high solubility in a developing solution or adding such a compound to a photopolymerizable photosensitive layer exhibits a large damage in the exposed area due to the development and causes frequently deterioration of performances, for example, press life, although they are effective for the improvement in background stain.
  • a developing solution for a photosensitive lithographic printing plate precursor having a photopolymerizable photosensitive layer on an aluminum support there is proposed an aqueous solution of a silicate, phosphate, carbonate or hydroxide of alkali metal, etc. or an organic amine compound, etc.
  • a developing solution having a high pH of 12 or more and containing an alkali salt of silicic acid and an amphoteric surface active agent is described in JP-A-8-248643 and a developing solution having a pH of 12 or below and containing an alkali salt of silicic acid with the specified ratio of SiO 2 /M 2 O (wherein M represents an alkali metal) is described in JP-A-11-65129 .
  • the former developing solution has a problem in that the image area tends to be damaged upon the development with the developing solution having such a high pH in addition to the problem of handling.
  • the latter developing solution has a problem in that the silicate may be gelled and insolubilized upon a slight decrease in pH of the developing solution during the development.
  • a developing solution containing no alkali salt of salicic acid a developing solution comprising an alkali agent, a complexing agent, an anionic surface active agent, an emulsifying agent and an n-alkanoic acid is described in JP-A-61-109052 and a developing solution comprising an alkali agent, a complexing agent, an anionic surface active agent, an amyl alcohol and an N-alkoxyamine is described in West German Patent 1,984,605 .
  • these developing solutions damage severely the image area due to the high pH thereof and the organic solvent contained therein and thus, it is difficult to obtain printing performances, for example, press life.
  • a developing solution having a relatively low pH (pH of 12 or below) and containing no alkali salt of salicic acid a developing solution comprising an aqueous potassium hydroxide solution containing an anionic surface active agent is described in JP-A-2000-81711 and a developing solution comprising an aqueous solution of alkali metal carbonate having a pH of from 8.5 to 11.5 is described in JP-A-11-65126 .
  • a plate-making method is described in JP-A-2003-21908 , wherein a lithographic printing plate precursor having an intermediate layer containing a polymer compound including a constituting component having an acid group and a constituting component having an onium salt is provided and is processed with a developing solution having a pH of from 11.0 to 12.7 and containing an inorganic alkali salt and a nonionic surface active agent having a polyoxyalkylene ether group.
  • This method is practical because it strikes a relatively good balance between the developing property in the unexposed area and the film strength in the exposed area.
  • the method has limitations on attempting to further improve the resistance to stain and press life and thus, further development of a more effective intermediate layer has been desired.
  • EP 1 223 196 describes planographic printing plate precursors where a resin interlayer is placed between a negative image-recording material for heat-mode exposure and a support.
  • This resin interlayer comprises an alkali-soluble polymer substance which dissolves in an alkali developer solution.
  • EP 1 199 603 relates to a positive photosensitive composition used in manufacturing lithographic printing plates which comprises an alkali-soluble resin, a compound capable of generating an acid upon exposure to radiation and a compound having acid-decomposable groups.
  • Patent Document 1 JP-A-59-101651
  • an object of the invention is to provide a photosensitive lithographic printing plate precursor comprising a support having provided thereon a photopolymerizable photosensitive layer, which has a high preservation stability and is prevented from the occurrence of background stain by conducting imagewise exposure, development and printing even after the preservation under high temperature and high humidity conditions for a long period of time after the production thereof.
  • Another object of the present invention is to provide a photosensitive lithographic printing plate precursor, which exhibits a small damage in the exposed area upon the development, maintains a firm adhesion between the surface of support and the photopolymerizable photosensitive layer and exhibits a high press life.
  • the invention includes the following photosensitive lithographic printing plate precursors.
  • the constituting component capable of reacting with an alkali developing solution to increase the dissolution rate in the alkali developing solution of the copolymer included in the intermediate layer of the photosensitive lithographic printing plate precursor of the invention in the unexposed area where the alkali developing solution easily penetrates into the photosensitive layer to contact with the intermediate layer, an acid is generated by the reaction, for example, hydrolysis so that the unexposed area has a property in that the solubility thereof is remarkably increased.
  • the exposed area where the contact with the alkali developing solution is restrained due to the photocured photosensitive layer having less permeability of the alkali developing solution exhibits hydrophobicity.
  • the I/O value means a ratio of inorganicity/organicity of a compound and is known that it corresponds to many physical properties as described in Yoshio Koda, Yuuki Gainenzu-Kisso to Oyo-, Sankyo Shuppan Publishers (May 10, 1984 ).
  • a primary scale of the important physical property, for example, solubility to an alkali developing solution in the invention is hydrophilicity and a relation between the hydrophilicity and the I/O value is also described.
  • solubility to an alkali developing solution in the invention is hydrophilicity and a relation between the hydrophilicity and the I/O value is also described.
  • the I/O value is large, that is, when the inorganicity is large, the hydrophilicity is high.
  • the I/O value is small, the oleophilicity is high.
  • a relation between the I/O value and a solubility parameter is described, and there is also described that the correlation therebetween arises under certain conditions.
  • the I/O value is determined by calculating an inorganicity value and an organicity value from a structural formula of a compound and obtaining a ratio of these values.
  • the organicity value is primarily calculated by a number of carbon atoms.
  • the inorganicity value is calculated by using a value of a functional group calculated by taking influence of a hydroxy group as 100.
  • the photosensitive lithographic printing plate precursor of the invention has a feature in that the intermediate layer thereof comprises a polymer compound including a constituting component having an acid group and a constituting component capable of reacting with an alkali developing solution to increase the dissolution rate in the alkali developing solution.
  • the polymer compound includes, for example, a polymer compound obtained by polymerization of a monomer component having an acid group and a monomer component capable of reacting with an alkali developing solution to increase the dissolution rate in the alkali developing solution.
  • the acid group is preferably an acid group having an acid dissociation constant (pKa) of not more than 7, more preferably -COOH, -SO 3 H, -OSO 3 H, -PO 3 H 2 , -OPO 3 H 2 , -CONHSO 2 -, -SO 2 NHSO 2 -, and particularly preferably -COOH.
  • a polymer compound wherein the main chain structure thereof comprises a vinyl polymer, for example, an acrylic resin, a methacrylic resin or a polystyrene, a urethane resin, a polyester or a polyamide is preferred.
  • a polymer wherein the constituting component having an acid group is a polymerizable compound represented by formula (1) or (2) shown below is particularly preferred.
  • A represents a divalent connecting group
  • B represents an aromatic group or a substituted aromatic group
  • D and E each independently represent a divalent connecting group
  • G represents a trivalent connecting group
  • X and X' each independently represent an acid group having pKa of not more than 7 or an alkali metal salt or an ammonium salt thereof
  • R 1 represents a hydrogen atom, an alkyl group or a halogen atom
  • a, b, d and e each independently represent 0 or 1
  • t represents an integer of from 1 to 3.
  • A represents -COO- or -CONH-
  • B represents a phenylene group or a substituted phenylene group in which the substituent is a hydroxy group, a halogen atom or an alkyl group
  • D and E each independently represent an alkylene group or a divalent connecting group represented by a molecular formula of C n H 2n O, C n H 2n S or C n H 2n+1 N
  • G represents a trivalent connecting group represented by a molecular formula of C n H 2n-1 , C n H 2n-1 O, C n H 2n-1 S or C n H 2n N in which n represents an integer of from 1 to 12
  • X and X' each independently represent a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, a sulfuric acid monoester group or a phosphoric acid monoester group
  • R 1 represents a
  • Acrylic acid methacrylic acid, crotonic acid, isocrotonic acid, itaconic acid, maleic acid, maleic anhydride,
  • the constituting component capable of reacting with an alkali developing solution to increase the dissolution rate in the alkali developing solution is described below.
  • the constituting component is a constituting component obtained by copolymerization of a monomer having a functional group capable of generating an acid, for example, a carboxylic acid or a sulfonic acid upon a reaction with alkali, for example, a hydrolysis reaction or a ring-opening reaction.
  • the monomer includes those having the structure shown below.
  • the monomer has an acetal group, a lactone ring, an oxycarboxy group or the like.
  • the monomer used should not be construed as being limited to the specific examples.
  • the polymer according to the invention may contain at least one monomer selected from polymerizable monomers set forth in items (1) to (13) described below as a copolymerization component.
  • the polymer used in the invention contains not less than 20% by mole, preferably not more than 40% by mole of the constituting component having an acid group and not less than 5% by mole, preferably not less than 20% by mole of the constituting component capable of reacting with an alkali developing solution to increase the dissolution rate in the alkali developing solution (the constituting component having a lactone ring or an ester structure).
  • the amount of the constituting component having an acid group included is not less than 20% by mole, the dissolution and removal at the alkali development is more accelerated.
  • the amount of the constituting component capable of reacting with an alkali developing solution to increase the dissolution rate in the alkali developing solution included is not less than 5% by mole, the adhesion is more improved by a synergistic effect with the acid group.
  • the constituting components having an acid group may be used individually or in combination of two or more thereof.
  • the constituting component capable of reacting with an alkali developing solution to increase the dissolution rate in the alkali developing solution may also be used individually or in combination of two or more thereof.
  • two or more polymers according to the invention, which are different in the constituting component, composition ratio or molecular weight may be used as a mixture.
  • composition ratio in the polymer structure is indicated by mole percent.
  • the polymer for use in the intermediate layer of the photosensitive lithographic printing plate precursor according to the invention can be ordinarily prepared using a radical chain polymerization method (refer to F. W. Billmeyer, Textbook of Polymer Science, 3rd Edition, A Wiley-Interscience Publication (1984 )).
  • a number average molecular weight (Mn) which is calculated from an integral intensity ratio of a terminal group to a side-chain functional group measured by NMR, is in a range of from 300 to 5,000, preferably from 500 to 4,800, still more preferably from 800 to 4,500.
  • Mn number average molecular weight
  • the adhesion to the support becomes week, resulting in the degradation of press life.
  • the number average molecular weight exceeding 5,000 is also disadvantageous, because the adhesion to the support becomes too strong so that sufficient removal of residue of the photopolymerizable photosensitive layer in the unexposed area cannot be achieved and further, the degradation of deleting property occurs.
  • a content of the unreacted monomer included in the polymer may be over a wide range, it is preferably not more than 20% by weight, more preferably not more than 10% by weight.
  • the polymer having the above-described molecular weight can be obtained by controlling amounts of a polymerization initiator and a chain transfer agent in the copolymerization of corresponding monomers.
  • chain transfer agent as used herein means a substance capable of transfer an active point of reaction upon a chain transfer reaction in the polymerization reaction. The ease of occurrence of the transfer reaction is represented by a chain transfer constant Cs.
  • the chain transfer constant Cs x 10 4 (at 60°C) of a chain transfer agent used in the invention is preferably not less than 0.01, more preferably not less than 0.1, and particularly preferably not less than 1.
  • the polymerization initiator a peroxide, an azo compound or a redox initiator conventionally used in a radical polymerization is employed as it is. Of these polymerization initiators, the azo compound is particularly preferred.
  • chain transfer agent examples include a halogen compound, for example, carbon tetrachloride or carbon tetrabromide, an alcohol, for example, isopropyl alcohol or isobutyl alcohol, an olefin, for example, 2-methyl-1-butene or 2,4-diphenyl-4-methyl-1-pentene, and a sulfur-containing compound, for example, ethanethiol, butanethiol, dodecanethiol, mercaptoethanol, mercaptopropanol, methyl mercaptopropionate, ethyl mercaptopropionate, mercaptopropionic acid, thioglycolic acid, ethyldisulfide, sec-butyldisulfide, 2-hydroxyethyldisulfide, thiosalicylic acid, thiophenol, thiocresol, benzylmercaptan or phenethylmercaptan, but
  • More preferable examples thereof includes ethanethiol, butanethiol, dodecanethiol, mercaptoethanol, mercaptopropanol, methyl mercaptopropionate, ethyl mercaptopropionate, mercaptopropionic acid, thioglycolic acid, ethyldisulfide, sec-butyldisulfide, 2-hydroxyethyldisulfide, thiosalicylic acid, thiophenol, thiocresol, benzylmercaptan or phenethylmercaptan, and particularly preferable examples thereof includes ethanethiol, butanethiol, dodecanethiol, mercaptoethanol, mercaptopropanol, methyl mercaptopropionate, ethyl mercaptopropionate, mercaptopropionic acid, thioglycolic acid, ethyldisulf
  • the intermediate layer containing the polymer compound according to the invention is provided by means of various methods on an aluminum support optionally subjected to a hydrophilization treatment as described hereinafter.
  • the intermediate layer can be provided according to the following methods.
  • the method include a method of coating a solution containing the polymer compound of the invention dissolved in an organic solvent, for example, methanol, ethanol or methyl ethyl ketone, a mixed solvent thereof or a mixed solvent of the organic solvent with water on the aluminum support and drying to provide the intermediate layer, and a method of immersing the aluminum support in a solution containing the polymer compound of the invention dissolved in an organic solvent, for example, methanol, ethanol or methyl ethyl ketone, a mixed solvent thereof or a mixed solvent of the organic solvent with water, washing with water or cleaning with air and drying to provide the intermediate layer.
  • an organic solvent for example, methanol, ethanol or methyl ethyl ketone, a mixed solvent thereof or a mixed solvent of the organic solvent with water on the aluminum support and drying to provide the intermediate layer
  • the solution having the total solid concentration of from 0.005 to 10% by weight is coated by various methods.
  • any of a bar coater coating, a spin coating, a spray coating and a curtain coating may be employed.
  • the total solid concentration of the solution is from 0.005 to 20% by weight, preferably from 0.01 to 10% by weight
  • an immersion temperature is from 0 to 70°C, preferably from 5 to 60°C
  • an immersion time is from 0.1 second to 5 minutes, preferably from 0.5 to 120 seconds.
  • the solution may be used by controlling a pH preferably in a range of from 0 to 12, more preferably from 0 to 6 using a basic substance, for example, ammonia, triethylamine or potassium hydroxide, an inorganic acid, for example, hydrochloric acid, phosphoric acid, sulfuric acid or nitric acid, a variety of organic acidic substances, for instance, an organic sulfonic acid, for example, nitrobenzenesulfonic acid or naphthalenesulfonic acid, an organic phophonic acid, for example, phenylphophonic acid, an organic carboxylic acid, for example, benzoic acid, fumaric acid or malic acid, or an organic chloride, for example, naphthalenesulfonyl chloride or benzenesulfonyl chloride.
  • a substance absorbing an ultraviolet ray, visible ray or infrared light may be added to improve tone reproducibility of the photosensitive lithographic printing plate precursor.
  • a coverage after drying of the compound constituting the intermediate layer according to the invention is suitably from 1 to 100 mg/m 2 , preferably from 2 to 70 mg/m 2 , in total. When the coverage is less than 1 mg/m 2 , the sufficient effects of the intermediate layer cannot be obtained. When the coverage is more than 100 mg/m 2 , the sufficient effects of the intermediate layer also cannot be obtained.
  • the photosensitive composition of photopolymerization type (hereinafter also referred to as a photopolymerizable composition or a photosensitive composition), which constitutes the photopolymerizable photosensitive layer of the photosensitive lithographic printing plate precursor according to the invention, contains as the essential components, an addition-polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator and a polymer binder.
  • an addition-polymerizable compound having an ethylenically unsaturated bond ethylenically unsaturated bond
  • a photopolymerization initiator ethylenically unsaturated bond
  • a polymer binder ethylenically unsaturated bond
  • Various compounds for example, a coloring agent, a plasticizer or a thermal polymerization inhibitor are also used together in the photosensitive composition, if desired.
  • the compound having an ethylenically unsaturated bond is a compound having an ethylenically unsaturated bond capable of conducting addition-polymerization upon the function of a photopolymerization initiator when the photopolymerizable composition is irradiated with an active ray, thereby causing crosslinking or hardening.
  • the compound having an addition-polymerizable ethylenically unsaturated bond can be appropriately selected from compounds having at least one terminal ethylenically unsaturated bond, preferably compounds having two or more terminal ethylenically unsaturated bonds.
  • Examples of the compound include a compound having the chemical form of a monomer, a prepolymer such as a dimer, a trimer or an oligomer, a mixture thereof and a copolymer thereof.
  • Examples of the monomer include an ester of an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid or maleic acid) with an aliphatic polyhydric alcohol compound and an amide of an unsaturated carboxylic acid with an aliphatic polyvalent amine compound.
  • an ester of an unsaturated carboxylic acid for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid or maleic acid
  • monomer of the ester of an unsaturated carboxylic acid with an aliphatic polyhydric alcohol compound include an acrylic acid ester, e.g., ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri(acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol pent
  • monomer of the amide of an unsaturated carboxylic acid with an aliphatic polyvalent amine compound include methylene bisacrylamide, methylene bismethacrylamide, 1,6-hexamethylene bisacrylamide, 1,6-hexamethylene bismethacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide and xylylene bismethacrylamide.
  • Such a compound include a vinyl urethane compound having at least two polymerizable vinyl groups in the molecule thereof obtained by subjecting addition of a vinyl monomer having a hydroxy group represented by formula (A) shown below to a polyisocyanate compound having at least two isocyanato groups in the molecule thereof as described in JP-B-48-41708 (the term "JP-B” as used herein means an "examined Japanese patent publication”).
  • CH 2 C(R)COOCH 2 CH(R')OH (A) wherein R and R', which may be the same or different, each represent a hydrogen atom or a methyl group.
  • examples thereof include urethane acrylates as described in JP-A-51-37193 and JP-B-2-32293 , polyfunctional acrylates or methacrylates, for example, a polyester acrylate or a epoxy acrylate obtained by reacting an epoxy resin with (meth)acrylic acid as described in JP-A-48-64183 , JP-B-49-43191 and JP-B-52-30490 is employed. Further, photocurable monomers and oligomers as described in Nippon Setchaku Kyoukaishi, Vol. 20, No. 7, pages 300 to 308 (1984) are employed.
  • the compound having an ethylenically unsaturated bond is used in an amount of from 5 to 80% by weight, preferably from 30 to 70% by weight, based on the whole composition of the photopolymerizable photosensitive layer.
  • the photopolymerization initiator incorporated into the photopolymerizable photosensitive layer of the photosensitive lithographic printing plate precursor according to the invention can be appropriately selected from various kinds of known photopolymerization initiators described in patents and literature depending on a wavelength of light source to be used.
  • a combination system of two or more photopolymerization initiators (photo-initiator system) is also used. Specific examples thereof are set forth below, but the invention should not be construed as being limited thereto.
  • Patent 2,850,445 for example, Rose Bengale, Eosine or erythrosine, and a combination system comprising a dye and an initiator, for example, a composite initiator system comprising a dye and an amine as described in JP-B-44-20189 , a combination of a hexaarylbiimidazole, a radical generator and a dye as described in JP-B-45-37377 , a combination of a hexaarylbiimidazole and a p-dialkylaminobenzylidene kotone as described in JP-B-47-2528 and JP-A-54-155292 , a combination of a cyclic cis- ⁇ -dicarbonyl compound and a dye as described in JP-A-48-84183 , a combination of a cyclic triazine and a merocyanine dye as described in JP-A-54-151024 , a combination of a 3-
  • Patent 4,766,055 a combination of a dye and an active halogen compound as described in JP-A-63-258903 and JP-A-2-63054 , a combination of a dye and a borate compound as described in JP-A-62-143044 , JP-A-62-150242 , JP-A-64-13140 , JP-A-64-13141 , JP-A-64-13142 , JP-A-64-13143 , JP-A-64-13144 , JP-A-64-17048 , JP-A-1-229003 , JP-A-1-298348 and JP-A-1-138204 , a combination of a dye having a rhodanine ring and a radical generator as described in JP-A-2-179643 and JP-A-2-244050 , a combination of a titanocene and a 3-ketocoumarin dye as described in JP-A-63-221110 , a combination of
  • a photo-initiator system having high sensitivity to a wavelength of not more than 450 nm sensitive to such a laser has been developed.
  • a photo-initiator system can also be used in the present invention.
  • a combination of a cationic dye and a borate as described in JP-A-11-84647 a combination of a merocyanine dye and a titanocene as described in JP-A-2000-147763 and a combination of a carbazole dye and a titanocene as described in JP-A-2001-42524 are illustrated.
  • the system comprising a titanocene compound is particularly preferred, since it is excellent in sensitivity.
  • titanocene compounds can be used and, for example, they are appropriately selected from those described in JP-A-59-152396 and JP-A-61-151197 .
  • Specific examples thereof include dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bisphenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, dicyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, dicyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2
  • Dyes preferably used in combination with the titanocene compound include cyanine dyes, merocyanine dyes, xanthene dyes, ketocoumarin dyes and benzopyran dyes.
  • Examples of the cyanine dye preferably include those represented by the formula shown below, but the invention should not be construed as being limited thereto.
  • Z 1 and Z 2 which may be the same or different, each represent a non-metallic atomic group necessary for forming a benzimidazole or naphthimidazole ring;
  • R 11 , R 12 , R 13 and R 14 each represent an alkyl group which may be substituted;
  • X - represents a counter anion; and
  • n represents 0 or 1.
  • Examples of the merocyanine dye preferably include those represented by the formula shown below, but the invention should not be construed as being limited thereto.
  • Z 3 and Z 4 each represent a non-metallic atomic group necessary for forming a 5-membered or 6-membered nitrogen-containing heterocyclic ring conventionally used in a cyanine dye
  • R 15 and R 16 each represent an alkyl group
  • Q 1 and Q 2 each represent a non-metallic atomic group necessary for forming a 4-thiazolidinone ring, a 5-thiazolidinone ring, a 4-imidazolidinone ring, a 4-oxazolidinone ring, 5-oxazolidinone ring, a 5-imidazolidinone ring or a 4'-dithiolane ring
  • L 1 , L 2 , L 3 , L 4 and L 5 each represent a methine group
  • m represents 1 or 2
  • i and h each represent 0 or 1
  • 1
  • R 17 and R 18 each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an alkoxycarbonyl group, an aryl group, a substituted aryl group or an aralkyl group;
  • Z 6 represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, a nitrogen atom substituted with an alkyl group or an aryl group or a carbon atom substituted with two alkyl groups;
  • Z 5 represents a non-metallic atomic group necessary for forming a nitrogen-containing 5-membered heterocyclic ring;
  • B 1 represents a substituted phenyl group, an unsubstituted or substituted multinuclear aromatic ring or an unsubstituted or substituted heteroaromatic ring;
  • B 2 represents a
  • xanthene dye examples include Rhodamine B, Rhodamine 6G, Ethyl Eosin, alcohol-soluble eosin, Pyronin Y and Pyronin B.
  • ketocoumarin dye preferably include those represented by the formula shown below, but the invention should not be construed as being limited thereto.
  • R 19 , R 20 and R 21 each represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group
  • R 22 and R 23 each represent an alkyl group, provided that at least one of R 22 and R 23 represents an alkyl group having from 4 to 16 carbon atoms
  • R 24 represents a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, a cyano group, a carboxy group or a group of an ester derivative or amido derivative thereof
  • R 25 represents a heterocyclic residue-CO-R 26 having the total number of carbon atoms of from 3 to 17 (wherein R 26 represents an alkoxy group or a group shown below) ; or R 20 and R 21 or R 22 and R 23 may be combined with each other to form a ring.
  • ketocoumarin dye Specific examples are set forth below.
  • R 27 to R 29 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a hydroxy group, an alkoxy group or an amino group, or R 27 to R 29 may be combined with a carbon atom to form a ring composed of non-metallic atoms together with the carbon atoms;
  • R 31 represents a hydrogen atom, an alkyl group, an aryl group, a heteroaromatic group, a cyano group, an alkoxy group, a carboxy group or an alkenyl group;
  • R 32 represents any one of the groups defined for R 31 or -Z 9 -R 31 (wherein Z 9 represents a carbonyl group, a sulfonyl group, a sulfinyl group or an arylenedicarbonyl group, or R 31 and R 32 may be
  • a photo-initiating function is more improved by adding a hydrogen-donating compound, for example, a thiol compound, e.g., 2-mercaptobenzothiazole, 2-mercaptobenzimidazole or 2-mercaptobenzoxazole, or an amine compound, e.g., N-phenylglycine or an N,N-dialkylamino aromatic alkyl ester to the photopolymerization initiators described above, if desired.
  • a hydrogen-donating compound for example, a thiol compound, e.g., 2-mercaptobenzothiazole, 2-mercaptobenzimidazole or 2-mercaptobenzoxazole
  • an amine compound e.g., N-phenylglycine or an N,N-dialkylamino aromatic alkyl ester
  • the amount of photopolymerization initiator (system) used is from 0.05 to 100 parts by weight, preferably from 0.1 to 70 parts by weight, and more preferably from 0.2 to 50 parts by weight, per 100 parts by weight of the ethylenically unsaturated bond-containing compound.
  • the polymer binder for use in the photopolymerizable photosensitive layer of the photosensitive lithographic printing plate precursor according to the present invention not only acts as a film-forming agent of the photosensitive layer but also must be soluble in an alkali developing solution.
  • an organic polymer soluble or swellable in an aqueous alkali solution is ordinarily employed as the polymer binder.
  • the use of a water-soluble organic polymer as the organic polymer makes the lithographic printing plate precursor water-developable.
  • Examples of such an organic polymer include an addition polymer having a carboxylic acid group in the side chain thereof, for example, polymers described in JP-A-59-44615 , JP-B-54-34327 , JP-B-58-12577 , JP-B-54-25957 , JP-A-54-92723 , JP-A-59-53836 and JP-A-59-71048 , that is, a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer and a partially esterified maleic acid copolymer.
  • An acidic cellulose derivative having a carboxylic acid group in its side chain is also used.
  • a polymer obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxy group is useful.
  • a copolymer of benzyl (meth)acrylate, (meth)acrylic acid and if desired, other addition-polymerizable vinyl monomer and a copolymer of allyl (meth)acrylate, (meth)acrylic acid and if desired, other addition-polymerizable vinyl monomer are particularly preferably used.
  • polyvinyl pyrrolidone and polyethylene oxide are useful as the water-soluble organic polymer.
  • an alcohol-soluble polyamide and a polyether of 2,2-bis-(4-hydroxyphenyl)propane with epichlorohydrin are also useful.
  • Polyurethane resins as described in JP-B-7-120040 , JP-B-7-120041 , JP-B-7-120042 , JP-B-8-12424 , JP-A-63-287944 , JP-A-63-287947 , JP-A-1-271741 and JP-A-11-352691 are also useful in the invention.
  • a radical reactive group By introducing a radical reactive group into the side chain of the organic polymer, the strength of a cured film formed therefrom can be increased.
  • a group having an ethylenically unsaturated bond, an amino group or an epoxy group is illustrated as an addition-polymerizable functional group
  • a mercapto group, a thiol group, a halogen atom, a triazine structure or an onium salt structure is illustrated as a functional group capable of forming a radical upon irradiation with light
  • a carboxy group or an imido group is illustrated as a polar group.
  • the group having an ethylenically unsaturated bond for example, an acryl group, a methacryl group, an allyl group or a styryl group is particularly preferred.
  • a functional group selected from an amino group, a hydroxy group, a phosphonic acid group, a phosphoric acid group, a carbamoyl group, an isocyanato group, a ureido group, a ureylene group, a sulfonic acid group and an ammonio group is also useful.
  • the polymer binder for use in the invention has an appropriate molecular weight and acid value. Specifically, the polymer binder having a weight average molecular weight of from 5,000 to 300,000 and an acid value of from 20 to 200 is effectively used.
  • the polymer binder can be mixed in an appropriate amount in the entire composition for the photosensitive layer. When the amount of polymer binder exceeds 90% by weight, it may be difficult to obtain preferred results in view of the strength of image formed.
  • the amount is preferably from 10 to 90% by weight, more preferably from 30 to 80% by weight of the composition for the photosensitive layer.
  • a ratio of the photopolymerizable ethylenically unsaturated bond-containing compound to the organic polymer binder is in a range of from 1/9 to 9/1 by weight.
  • the range is more preferably from 2/8 to 8/2 by weight, and still more preferably from 3/7 to 7/3 by weight.
  • thermopolymerization inhibitor in addition to the fundamental components described above to the photosensitive composition for the photosensitive layer in order to prevent undesirable thermal polymerization of the photopolymerizable ethylenically unsaturated bond-forming compound during the production and storage of the photosensitive composition in the invention.
  • thermal polymerization inhibitor examples include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-metyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine primary cerium salt and N-nitrosophenylhydroxylamine aluminum salt.
  • the amount of the thermal polymerization inhibitor added is preferably from about 0. 01 to about 5% by weight based on the total photosensitive composition.
  • a higher fatty acid or a derivative thereof for example, behenic acid or behenic amide may be added to the photosensitive composition and localized on the surface of the photopolymerizable photosensitive layer during a drying process after coating in order to prevent polymerization inhibition due to oxygen, if desired.
  • the amount of higher fatty acid or derivative thereof added is preferably from about 0. 5 to about 10% by weight based on the total photosensitive composition.
  • a coloring agent may further be added for the purpose of coloring the photopolymerizable photosensitive layer.
  • the coloring agent include a pigment, for example, a phthalocyanine pigment, e.g., C. I. Pigment Blue 15:3, 15:4 or 15:6, an azo pigment, carbon black or titanium oxide, and a dye, for example, Ethyl Violet, Crystal Violet, an azo dye, an anthraquinone dye or a cyanine dye.
  • the amount of the coloring agent added is preferably from about 0. 5 to about 20% by weight based on the total photosensitive composition.
  • an additive for example, an inorganic filler or a plasticizer, e.g., dioctyl phthalate, dimethyl phthalate or tricresyl phosphate may be added in order to improve physical properties of the cured film.
  • the amount of such an additive added is preferably not more than 10% by weight based on the total photosensitive composition.
  • composition for the photopolymerizable photosensitive layer of the photosensitive lithographic printing plate precursor according to the invention is dissolved in an organic solvent and coated on the intermediate layer described hereinbefore.
  • solvents can be used and examples thereof include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol,
  • a surface active agent may be added to the photopolymerizable composition for the photopolymerizable photosensitive layer of the photosensitive lithographic printing plate precursor according to the invention in order to improve surface properties of coating.
  • a coverage after drying of the photopolymerizable photosensitive layer is preferably in a range of from about 0.1 to about 10 g/m 2 , more preferably from 0.3 to 5 g/m 2 , and still more preferably from 0.5 to 3 g/m 2 .
  • an oxygen-isolating protective layer is ordinarily provided in order to prevent from a polymerization inhibiting function of oxygen.
  • a water-soluble vinyl polymer which is incorporated into the oxygen-isolating protective layer, includes polyvinyl alcohol and a copolymer thereof containing a substantial amount of unsubstituted vinyl alcohol unit sufficient for imparting the desired solubility in water, for example, a partial ester, ether or acetal of polyvinyl alcohol.
  • Polyvinyl alcohol having a hydrolysis rate of from 71 to 100% and a polymerization degree of from 300 to 2,400 is used.
  • polyvinyl alcohol examples include PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HG, PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA-420, PVA-631 and L-8 manufactured by Kuraray Co., Ltd.
  • copolymer examples include polyvinyl acetate, polyvinyl chloroacetate, polyvinyl propionate, polyvinyl formal and polyvinyl acetal each having the hydrolysis ratio of from 80 to 100% and a copolymer thereof.
  • Other useful polymers include polyvinyl pyrrolidone, gelatin and gum arabic.
  • the water-soluble polymers may be used individually or as a mixture of two or more thereof.
  • a solvent, which is used for coating the oxygen-isolating protective layer in the photosensitive lithographic printing plate precursor according to the invention is preferably pure water, however, an alcohol, e.g., methanol or ethanol or a ketone, e.g., acetone or methyl ethyl ketone may be used together with pure water.
  • the concentration of the solid content in the coating solution is suitably from 1 to 20% by weight.
  • known additives for example, a surface active agent for improving coating properties or a water-soluble plasticizer for improving physical properties of the film may be further added.
  • water-soluble plasticizer examples include propionamide, cyclohexanediol, glycerol and sorbitol.
  • a water-soluble (meth)acrylic polymer may also be used.
  • a coverage after drying of the oxygen-isolating protective layer is preferably in a range of from about 0.1 to about 15 g/m 2 , and more preferably from 1.0 to about 5.0 g/m 2 .
  • the aluminum support of photosensitive lithographic printing plate precursor according to the invention is described below.
  • the aluminum support for use in the invention which is dimensionally stable, includes an aluminum or aluminum alloy (for example, alloy of aluminum with silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth or nickel) plate, and a plastic film or paper laminated or deposited with aluminum or aluminum alloy.
  • the thickness of support is ordinarily from about 0.05 to about 1 mm.
  • a composite sheet as described in JP-A-48-18327 is also used.
  • an aluminum support for use in the invention has a surface roughness of 0.2 to 0.55 ⁇ m.
  • a method for the graining treatment used includes a mechanical graining method, a chemical graining method and an electrolytic graining method as described in JP-A-56-28893 .
  • an electrochemical graining method wherein surface graining is electrochemically conducted in an electrolytic solution of hydrochloric acid or nitric acid
  • a mechanical graining method for example, a wire brush graining method wherein a surface of aluminum plate is scratching with a wire brush, a ball graining method wherein a surface of aluminum plate is grained with abrasive balls and an abrasive or a brush graining method wherein a surface of aluminum plate is grained with a nylon brush and an abrasive may also be employed.
  • the graining methods may be used individually or in combination of two or more thereof.
  • an electrochemical graining method wherein surface graining is electrochemically conducted in an electrolytic solution of hydrochloric acid or nitric acid is preferably used.
  • the current density suitable for use is in a range of from 100 to 400 C/dm 2 . More specifically, it is preferred to perform electrolysis in an electrolytic solution containing from 0.1 to 50% of hydrochloric acid or nitric acid under the conditions of a temperature of from 20 to 100°C, a period of from one second to 30 minutes and a current density of from 100 to 400 C/dm 2 .
  • the aluminum support subjected to the surface graining treatment is then chemically etched with an acid or an alkali.
  • the method of using an acid as an etching agent takes time for destroying fine structures and thus, it is disadvantageous to industrially apply the method to the invention.
  • Such disadvantage can be overcome by using an alkali as the etching agent.
  • the alkali agent preferably used in the invention include sodium hydroxide, sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, potassium hydroxide and lithium hydroxide. Preferred ranges of concentration and temperature are form 1 to 50% and 20 to 100°C, respectively.
  • the alkali etching is preferably performed so that a dissolution amount of aluminum is in a range of from 5 to 20 g/m 3 .
  • the support is subjected to washing with an acid for removing smut remaining on the surface of support.
  • the acid for use in the acid-washing step include nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid and borofluoric acid.
  • a method of bringing the aluminum support into contact with a 15 to 65% by weight aqueous solution of sulfuric acid having a temperature of from 50 to 90°C as described in JP-A-53-12739 and a method of performing alkali etching as described in JP-B-48-28123 are particularly preferred.
  • the aluminum support thus-treated is then subjected to anodizing treatment.
  • the anodizing treatment can be conducted in a manner conventionally used in the field of art. Specifically, it is performed by applying a direct current or alternating current to the aluminum support in an aqueous solution or non-aqueous solution containing sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, or a combination of two or more thereof to form an anodic oxide layer on the surface of aluminum support.
  • the conditions of anodizing treatment cannot be determined generally, since they are widely varied depending on an electrolytic solution to be used.
  • a concentration of the electrolytic solution is in a range of from 1 to 80%
  • a temperature of the electrolytic solution is in a range of from 5 to 70°C
  • a current density is in a range of from 0.5 to 60 A/dm 2
  • a voltage is in a range of from 1 to 100 V
  • a period of electrolysis is in a range of from 10 to 100 seconds.
  • the thickness of anodic oxide layer is preferably from 1 to 10 g/m 2 .
  • the thickness is less than 1 g/m 2 , the printing plate prepared is liable to be injured, and on the other hand, when the thickness is more than 10 g/m 2 , a large quantity of electric power is necessary and thus economically disadvantageous.
  • the thickness of anodic oxide layer is more preferably from 1.5 to 7 g/m 2 , and still more preferably from 2 to 5 g/m 2 .
  • the aluminum support may further be subjected to sealing treatment of the anodic oxide layer after the graining treatment and anodizing treatment.
  • the sealing treatment is performed by immersing the aluminum support in hot water or a hot aqueous solution containing an inorganic salt or an organic salt, or transporting the aluminum support in a water vapor bath.
  • the aluminum support may be subjected to surface treatment, for example, silicate treatment with an alkali metal silicate or immersion in an aqueous solution of potassium fluorozirconate or a phosphate.
  • the intermediate layer, the photopolymerizable photosensitive layer comprising the photopolymerizable composition and preferably the oxygen-isolating protective layer are coated in this order to prepare the photosensitive lithographic printing plate precursor according to the invention.
  • the photosensitive lithographic printing plate precursor of the invention is exposed imagewise and then developed with a developing solution.
  • a developing solution for use in the plate-making method of the photosensitive lithographic printing plate precursor of the invention is not particularly restricted and, for example, a developing solution containing an inorganic alkali salt and a surface active agent and having a pH of from 11.0 to 12.7 is preferably used.
  • the inorganic alkali salt is appropriately selected and examples thereof include an inorganic alkali agent, for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide, lithium hydroxide, sodium silicate, potassium silicate, ammonium silicate, lithium silicate, tertiary sodium phosphate, tertiary potassium phosphate, tertiary ammonium phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, ammonium hydrogencarbonate, sodium borate, potassium borate and ammonium borate.
  • the inorganic alkali salts may be used individually or in combination of two or more thereof.
  • developing property can be easily adjusted by appropriately controlling the mixing ratio of silicon oxide (SiO 2 ) to alkali oxide (M 2 O wherein M represents an alkali metal or an ammonium group), each of which are components of the silicate, and the concentration thereof.
  • SiO 2 silicon oxide
  • M alkali oxide
  • concentration thereof aqueous solutions containing the silicate, that having the mixing ratio of silicon oxide (SiO 2 ) to alkali oxide (M 2 O) (a molar ratio of SiO 2 /M 2 O) of from 0.5 to 3.0 is preferred and that having the mixing ratio of silicon oxide (SiO 2 ) to alkali oxide (M 2 O) of from 1.0 to 2.0 is more preferred.
  • the concentration of silicate is preferably from 1 to 10% by weight, more preferably from 3 to 8% by weight, and most preferably from 4 to 7% by weight based on the alkali aqueous solution.
  • concentration is less than 1% by weight, the developing property and processing capacity tend to decrease in some cases.
  • concentration exceeds 10% by weight, precipitation and crystallization tend to occur and the exhausted solution tends to gelate at the time of neutralization to cause a problem during the treatment of waste solution in some cases.
  • an organic alkali agent may be auxiliarily used together with the inorganic alkali agent.
  • the organic alkali agent include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine and tetramethylammonium hydroxide.
  • the organic alkali agents may be used individually or in combination of two or more thereof.
  • the surface active agent is appropriately selected to use.
  • the surface active agent include a nonionic surface active agent having a polyoxyalkylene ether group, a nonionic surface active agent, for example, a polyoxyethylene alkyl ester, e.g., polyoxyethylene stearate, a sorbitan alkyl ester, e.g., sorbitan monolaurate, sorbitan monostearate, sorbitan distearate, sorbitan monooleate, sorbitan sesquioleate or sorbitan trioleate, or a mono glyceride alkyl ester, e.g., glycerol monostearate or glycerol monooleate; an anionic surface active agent, for example, an alkylbenzenesulfonate, e.g., sodium dodecylbenzenesulfonate, an alkylnaphthalenesulfonate, e.g., sodium but
  • nonionic surface active agent having a polyoxyalkylene ether group a compound having a structure represented by formula (I) shown below is preferably used.
  • R 40 represents an alkyl group having from 3 to 15 carbon atoms, which may be substituted, an aromatic hydrocarbon group having from 6 to 15 carbon atoms, which may be substituted or an aromatic heterocyclic group having from 4 to 15 carbon atoms, which may be substituted, wherein the substituent includes an alkyl group having from 1 to 20 carbon atoms, a halogen atom (for example, bromine, chlorine or iodine), an aromatic hydrocarbon group having from 6 to 15 carbon atoms, an aralkyl group having from 7 to 17 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms, an alkoxycarbonyl group having from 2 to 20 carbon atoms and an acyl group having from 2 to 15 carbon atoms;
  • R 41 represents an alkylene group having from 1 to 100 carbon atoms, which may be substituted, wherein the substituent includes an alkyl group having from 1 to 20 carbon atoms and an aromatic hydrocarbon group having from 6 to 15 carbon atoms;
  • aromatic hydrocarbon group examples include a phenyl group, a tolyl group, a naphthyl group, an anthryl group, a biphenyl group and a phenanthryl group
  • aromatic heterocyclic group examples include a furyl group, a thienyl group, an oxazolyl group, an imidazolyl group, a pyranyl group, a pyridinyl group, an acrysinyl group, a benzofuranyl group, a benzothienyl group, a benzopyranyl group, a benzoxazolyl group and a benzimidazolyl group.
  • the part of (R 41 -O) p in formula (I) may comprise two or three kinds of groups as far as R 41 and p are in the above-defined scope. Specifically, it may form a random or block chain comprising, for example, a combination of an ethyleneoxy group and a propyleneoxy group, a combination of an ethyleneoxy group and an isopropyleneoxy group, a combination of an ethyleneoxy group and butyleneoxy group or a combination of an ethyleneoxy group and isobutyleneoxy group.
  • the nonionic surface active agents having a polyoxyalkylene ether group may be used individually or as a mixture of two or more thereof.
  • An amount of the nonionic surface active agent having a polyoxyalkylene ether group effectively added is from 1 to 30% by weight, preferably from 2 to 20% by weight in the developing solution.
  • the amount added is too small, the developing property degrades, and on the other hand, when it is too large, the damage upon development in the exposed area increases, resulting in decrease of press life of a printing plate.
  • nonionic surface active agent having a polyoxyalkylene ether group represented by formula (I) examples include a polyoxyethylene alkyl ether, e.g., polyoxyethylene lauryl ether, polyoxyethylene cetyl ether or polyoxyethylene stearyl ether, a polyoxyethylene aryl ether, e.g., polyoxyethylene phenyl ether or polyoxyethylene naphthyl ether, and a polyoxyethylene alkylaryl ether, e.g., polyoxyethylene methylphenyl ether, polyoxyethylene octylphenyl ether or polyoxyethylene nonylphenyl ether.
  • a polyoxyethylene alkyl ether e.g., polyoxyethylene lauryl ether, polyoxyethylene cetyl ether or polyoxyethylene stearyl ether
  • a polyoxyethylene aryl ether e.g., polyoxyethylene phenyl ether or polyoxyethylene naphthyl ether
  • the surface active agents may be used individually or in combination of two or more thereof.
  • a content of the surface active agent in the developing solution is preferably from 0.1 to 20% by weight in terms of solid content.
  • the pH of developing solution used for the photosensitive lithographic printing plate precursor of the invention is ordinarily from 11.0 to 12.7 and preferably from 11.5 to 12.5.
  • the pH of developing solution is lower than 11.0, images are hardly formed.
  • the pH of developing solution exceeds 12.7, the problem in that damage upon development in the exposed area increases tends to occur.
  • the electric conductivity of developing solution is ordinarily from 3 to 30 mS/cm.
  • the electric conductivity is preferably in a range of from 5 to 20 mS/cm.
  • the photosensitive lithographic printing plate precursor according to the invention is exposed imagewise with a conventionally known active ray, for example, a carbon arc lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a halogen lamp, a helium-cadmium laser, an argon ion laser, an FD-YAG laser, a helium-neon laser or a semiconductor laser (350 to 600 nm), and then subjected to development processing to form images on the aluminum support.
  • a conventionally known active ray for example, a carbon arc lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a halogen lamp, a helium-cadmium laser, an argon ion laser, an FD-YAG laser, a helium-neon laser or a semiconductor laser (
  • the lithographic printing plate precursor may be subjected to a heating process at a temperature of from 50 to 150°C for a period of from one second to 5 minutes for the purpose of increasing the curing rate of photopolymerizable photosensitive layer.
  • the photosensitive lithographic printing plate precursor according to the invention ordinarily has an overcoat layer having the oxygen-isolating property as described above on the photopolymerizable photosensitive layer.
  • an overcoat layer having the oxygen-isolating property as described above on the photopolymerizable photosensitive layer.
  • an antiseptics as described in JP-A-10-10754 or an organic solvent as described in JP-A-8-278636 may be incorporated.
  • the development of photosensitive lithographic printing plate precursor according to the invention with the developing solution described above is carried out at a temperature of from about 0 to about 60°C, preferably from about 15 to about 40°C in a conventional manner, for example, that the imagewise exposed photosensitive lithographic printing plate precursor is immersed in the developing solution and rubbed with a brush.
  • the processing ability of the developing solution may be recovered using a replenisher or a fresh developing solution, since the developing solution becomes exhausted with increase in the processing amount.
  • the photosensitive lithographic printing plate precursor thus-processed is subjected to post-treatment with washing water, a rinsing solution containing a surface active agent or a desensitizing solution containing gum arabic or a starch derivative as described, for example, in JP-A-54-8002 , JP-A-55-115045 and JP-A-59-58431 .
  • These processes may be used in various combinations for the post-treatment of photosensitive lithographic printing plate precursor according to the invention.
  • a printing plate obtained by the development processing described above can be increased its press life using a post-exposure treatment by a method as described in JP-A-2000-89478 or a heat treatment, for example, burning.
  • the lithographic printing plate obtained by the processes described above is mounted on an offset printing machine to perform printing, whereby a large number of prints are obtained.
  • An aluminum plate of IS having a thickness of 0.30 mm was subjected to surface graining using a nylon brush of No. 8 and an aqueous suspension of pumice stone of 800 mesh and washed thoroughly with water.
  • the plate was etched by immersing in a 10% aqueous sodium hydroxide solution at 70°C for 60 seconds, washed with running water, and washed with a 20% aqueous nitric acid solution for neutralization, followed by washing with water.
  • the plate was then subjected to electrolytic surface roughening treatment in a 1% aqueous nitric acid solution using an alternating waveform current of sign wave under the condition of V A of 12.7 V in an amount of electricity of 300 C/dm 2 at anode.
  • the surface roughness of the plate measured was 0.45 ⁇ m (in Ra) (measurement device: Surfcom (TM) manufactured by Tokyo Seimitu Co., Ltd.; diameter of a contact stylus tip: 2 micrometer). Subsequently, the plate was immersed in a 30% aqueous sulfuric acid solution at 55°C for 2 minutes to conduct desmutting and then subjected to anodic oxidation in a 20% aqueous sulfuric acid solution at 33°C at a current density of 5 A/dm 2 for 50 seconds while an cathode was arranged on the side of the roughened surface of the plate to form an anodic oxide layer having a thickness of 2.7 g/m 2 .
  • a high-sensitive photopolymerizable composition P-1 shown below was coated so as to have a dry coating weight of 1.5 g/m 2 , and dried at 100°C for one minute to form a photopolymerizable photosensitive layer.
  • A1 1.5 parts by weight Linear organic high molecular polymer (polymer binder) (B1) 2.0 parts by weight Sensitizer (C1) 0.15 parts by weight Photopolymerization initiator (D1) 0.2 parts by weight Dispersion of ⁇ -phthalocyanine (F1) 0.02 parts by weight Fluorine-containing nonionic surface active agent (Megafac (TM) F177 manufactured by Dai-Nippon Ink & Chemicals, Inc.) 0.03 parts by weight Methyl ethyl ketone 9.0 parts by weight Propylene glycol monomethyl ether acetate 7.5 parts by weight Toluene 11.0 parts by weight
  • a photosensitive lithographic printing plate precursor On the photopolymerizable photosensitive layer was coated a 3% by weight aqueous solution of polyvinyl alcohol (saponification degree: 98% by mole, polymerization degree: 500) so as to have a dry coating weight of 2.5 g/m 2 , and dried at 120°C for 3 minutes to form an oxygen-isolating protective layer, whereby a photosensitive lithographic printing plate precursor was prepared.
  • the photosensitive lithographic printing plate precursor was allowed to stand under forced aging conditions (50°C and 80%RH) for 5 days.
  • the photosensitive lithographic printing plate precursors before and after the forced aging were subjected to scanning exposure of solid image and dot images of from 1 to 99% (every 1%) using an FD-YAG laser (Plate Jet 4 manufactured by CSI Co., Ltd.) in an exposure amount of 100 ⁇ J/cm 2 at 4,000 dpi under condition of 175 lines/inch, and then subjected to standard processing using an automatic developing machine (LP-850P2 manufactured by Fuji Photo Film Co., Ltd.) provided with Developing Solution 1 shown below and a finishing gum solution (FP-2W manufactured by Fuji Photo Film Co., Ltd.).
  • the condition of pre-heating was such that a temperature of the plate surface reached was 100°C.
  • a temperature of the developing solution was 30°C and a period of immersion in the developing solution was about 15 seconds.
  • Developing Solution 1 had the composition shown below and the pH thereof was 11.5 at 25°C and the electric conductivity thereof was 5 mS/cm.
  • Lithographic printing plate precursors were prepared in the same manner as in Example 1 except for changing Polymer No. 1 used in Example 1 to the copolymer for intermediate layer shown in Table 2 below, respectively.
  • the plate-making was conducted using each of the photosensitive lithographic printing plate precursors before and after the forced aging in the same manner as in Example 1.
  • Lithographic printing plate precursors were prepared in the same manner as in Example 1 except for changing the dry coating weight of the intermediate layer to 5m g/m 2 , 15m g/m 2 and 20m g/m 2 , respectively, and the plate-making was conducted in the same manner as in Example 1.
  • Lithographic printing plate precursors were prepared in the same manner as in Example 1 except for changing Linear organic high molecular polymer B1 used in Photopolymerizable Composition P-1 of Example 1 to B2 to B6 described below for Photopolymerizable Compositions P-2 to P-6, respectively, and the plate-making was conducted in the same manner as in Example 1.
  • a lithographic printing plate precursor was prepared in the same manner as in Example 15 except for changing Compound having ethylenically unsaturated bond A1 used in Photopolymerizable Composition P-6 of Example 15 to Compound having ethylenically unsaturated bond A2 described below for Photopolymerizable Composition P-7, and the plate-making was conducted in the same manner as in Example 15.
  • a surface of aluminum plate of JIS A1050 having a thickness of 0.24 mm was subjected to graining using a nylon brush and an aqueous suspension of pumice stone of 400 mesh and washed thoroughly with water.
  • the plate was etched by immersing in a 10% aqueous sodium hydroxide solution at 70°C for 60 seconds, washed with running water, and washed with a 20% aqueous nitric acid solution for neutralization, followed by washing with water.
  • the plate was then subjected to electrolytic surface roughening treatment in a 1% aqueous nitric acid solution using an alternating waveform current of sign wave under the condition of V A of 12.7 V in an amount of electricity of 260 C/dm 2 at anode.
  • the surface roughness of the plate was measured and found to be 0.55 ⁇ m (in Ra). Subsequently, the plate was immersed in a 30% aqueous sulfuric acid solution at 55°C for 2 minutes to conduct desmutting and then subjected to anodic oxidation in a 20% aqueous sulfuric acid solution at a current density of 14 A/dm 2 so as to form an anodic oxide layer having a thickness of 2.5 g/m 2 , followed by washing with water to prepare Substrate (A).
  • Substrate (A) was treated with a 0.15% by weight aqueous sodium silicate solution at 22°C for 10 seconds to prepare Substrate (B). Also, Substrate (A) was treated with a 2.5% by weight aqueous sodium silicate solution at 30°C for 10 seconds to prepare Substrate (C). Further, Substrate (A) was treated with a 2.5% by weight aqueous sodium silicate solution at 50°C for 5 seconds to prepare Substrate (D).
  • a photosensitive lithographic printing plate precursor was prepared in the same manner as in Example 1 except for eliminating the formation of intermediate layer in Example 1, and the plate-making was conducted in the same manner as in Example 1.
  • the printing plate was subjected to printing by a printing machine (R 201 Type manufactured by Man Roland Co., Ltd.) using ink (GEOS G Black (TM) (N) manufactured by Dai-Nippon Ink & Chemicals, Inc.) and the press life was evaluated from the number of sheets in which disappearance of dots of 3% was observed.
  • a printing machine R 201 Type manufactured by Man Roland Co., Ltd.
  • ink GEOS G Black (TM) (N) manufactured by Dai-Nippon Ink & Chemicals, Inc.
  • the printing stain was evaluated by conducting printing by a printing machine (Dia (TM) IF2 Type manufactured by Mitsubishi Heavy Industry Co., Ltd.) using ink (GEOS G Red (TM) (S) manufactured by Dai-Nippon Ink & Chemicals, Inc.) and visually observing the printing stain in the non-image area.
  • TM printing machine
  • GEOS G Red (TM) (S) manufactured by Dai-Nippon Ink & Chemicals, Inc.
  • each lithographic printing plate precursor of the examples according to the invention exhibits the sufficient results.
  • the lithographic printing plate precursor prepared without the formation of intermediate layer in Comparative Example 1 exhibits the background stain even before the forced aging.
  • the lithographic printing plate precursor of the invention free from background stain even after the forced aging and having high press life can be obtained.
  • the photosensitive lithographic printing plate precursor of the invention which comprises an aluminum support having provided thereon an intermediate layer and a photopolymerizable photosensitive layer in this order and the intermediate layer includes a polymer compound containing a constituting component having an acid group and a constituting component capable of reacting with an alkali developing solution to increase the dissolution rate in the alkali developing solution, has the improved developing property in the non-image areas and is prevented from the occurrence of background stain even after preservation.
  • the photosensitive lithographic printing plate precursor is advantageous in that the adhesion between the intermediate layer and the aluminum support in the exposed area is not impaired and it can exhibit the high press life.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Claims (5)

  1. Précurseur photosensible de plaque d'impression lithographique, qui comprend un support d'aluminium sur lequel une couche intermédiaire et une couche photosensible photopolymérisable sont déposées dans cet ordre, la couche intermédiaire comprenant un copolymère qui contient un composant constitutif doté d'un groupe acide et un composant constitutif qui contient un groupe acétal, un cycle de lactone ou un groupe oxycarboxylique capable de réagir avec une solution de métal alcalin de développement de manière à augmenter la vitesse de dissolution dans la solution de métal alcalin de développement.
  2. Précurseur photosensible de plaque d'impression lithographique selon la revendication 1, dans lequel le groupe acide est un groupe -COOH, -SO3H, -OSO3H, -PO3H2, -OPO3H2, -CONHSO2- ou un groupe -SO2NHSO2-.
  3. Précurseur photosensible de plaque d'impression lithographique selon la revendication 2, dans lequel le groupe acide est -COOH.
  4. Précurseur photosensible de plaque d'impression lithographique selon l'une quelconque des revendications précédentes, dans lequel le composant constitutif doté d'un groupe acide est représenté par la formule (1) ou la formule (2) :
    Figure imgb0074
    Figure imgb0075
     dans lesquelles A représente un groupe divalent de liaison, B représente un groupe aromatique ou un groupe aromatique substitué, D et E représentent chacun indépendamment un groupe divalent de liaison, G représente un groupe trivalent de liaison, X et X' représentent chacun indépendamment un groupe acide dont le pKa n'est pas supérieur à 7 ou un sel de métal alcalin ou d'ammonium de ces acides, R1 représente un atome d'hydrogène, un groupe alkyle ou un atome d'halogène, a, b, d et e représentent chacun indépendamment 0 ou 1 et t représente un entier compris entre 1 et 3.
  5. Précurseur photosensible de plaque d'impression lithographique selon la revendication 4, dans lequel le composant constitutif contenant un groupe acide est représenté par la formule (1) dans laquelle B représente un groupe phénylène ou un groupe phénylène substitué dont le substituant est un groupe hydroxyle ou un groupe alkyle qui compte de 1 à 3 atomes de carbone, D représente un groupe alkylène qui compte de 1 à 2 atomes de carbone ou un groupe alkylène qui compte de 1 à 2 atomes de carbone reliés par un atome d'oxygène, R1 représente un atome d'hydrogène ou un groupe méthyle, X représente un groupe acide carboxylique, a représente 0 et b représente 1.
EP03022901A 2002-10-09 2003-10-09 Précurseur photosensible de plaque d'impression lithographique Expired - Lifetime EP1407894B1 (fr)

Applications Claiming Priority (2)

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JP2002296404A JP2004133125A (ja) 2002-10-09 2002-10-09 感光性平版印刷版
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JP2006091838A (ja) * 2004-05-19 2006-04-06 Fuji Photo Film Co Ltd 画像記録方法
JP5572423B2 (ja) * 2010-03-09 2014-08-13 富士フイルム株式会社 感活性光線性又は感放射線性樹脂組成物、及びそれを用いたパターン形成方法
CN113122843B (zh) * 2021-04-05 2022-12-09 烟台通鼎舟汽车零部件有限公司 一种铝合金复合板材的制备方法

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BE507657A (fr) 1950-12-06
US3511661A (en) 1966-07-01 1970-05-12 Eastman Kodak Co Lithographic printing plate
ZA6807938B (fr) 1967-12-04
JPS56107238A (en) 1980-01-31 1981-08-26 Konishiroku Photo Ind Co Ltd Photosensitive composition for photosensitive printing plate
CA1153611A (fr) 1980-04-30 1983-09-13 Minnesota Mining And Manufacturing Company Compose photosensible developpable dans l'eau et plaque d'impression
JP3518632B2 (ja) 1995-03-06 2004-04-12 富士写真フイルム株式会社 平版印刷版の製版方法
JP3784933B2 (ja) 1997-08-25 2006-06-14 コダックポリクロームグラフィックス株式会社 感光性平版印刷版の現像処理方法
JP2000081711A (ja) 1998-09-04 2000-03-21 Fuji Photo Film Co Ltd 平版印刷版の作成法
US6806031B2 (en) * 2000-05-15 2004-10-19 Fuji Photo Film Co., Ltd. Support for lithographic printing plate and presensitized plate
US6716569B2 (en) * 2000-07-07 2004-04-06 Fuji Photo Film Co., Ltd. Preparation method for lithographic printing plate
US6749987B2 (en) * 2000-10-20 2004-06-15 Fuji Photo Film Co., Ltd. Positive photosensitive composition
CN100470365C (zh) * 2001-01-12 2009-03-18 富士胶片株式会社 正型成像材料
JP4319363B2 (ja) * 2001-01-15 2009-08-26 富士フイルム株式会社 ネガ型画像記録材料

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DE60319484D1 (de) 2008-04-17
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JP2004133125A (ja) 2004-04-30
ATE388023T1 (de) 2008-03-15
EP1407894A2 (fr) 2004-04-14

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