WO2015064331A1 - Composition de révélation des couleurs, précurseur de plaque d'impression lithographique et procédé pour le fabriquer - Google Patents

Composition de révélation des couleurs, précurseur de plaque d'impression lithographique et procédé pour le fabriquer Download PDF

Info

Publication number
WO2015064331A1
WO2015064331A1 PCT/JP2014/077051 JP2014077051W WO2015064331A1 WO 2015064331 A1 WO2015064331 A1 WO 2015064331A1 JP 2014077051 W JP2014077051 W JP 2014077051W WO 2015064331 A1 WO2015064331 A1 WO 2015064331A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
compound
color
spirooxazine
printing plate
Prior art date
Application number
PCT/JP2014/077051
Other languages
English (en)
Japanese (ja)
Inventor
憲晃 佐藤
昭太 鈴木
明夫 水野
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Publication of WO2015064331A1 publication Critical patent/WO2015064331A1/fr

Links

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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
    • C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0066—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of a carbocyclic ring,(e.g. benzene, naphtalene, cyclohexene, cyclobutenene-quadratic acid)
    • 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
    • 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
    • B41C2210/08—Developable by water or the fountain 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
    • B41C2210/26—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 not involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a color forming composition, a lithographic printing plate precursor in which the color forming composition is applied to an image recording layer, and a plate making method using the same.
  • the present invention relates to a lithographic printing plate precursor that can be directly made by laser image exposure and a plate making method for developing the lithographic printing plate precursor on-press.
  • Patent Document 1 describes a lithographic printing plate precursor having an image recording layer containing an infrared absorber, a polymerizable compound, a polymerization initiator, a spirooxazine compound and an acid generator on a support. It is described that this lithographic printing plate precursor has good visibility of a plate after exposure and can be made by on-press development.
  • Patent Document 2 discloses a color developing composition containing a polymer having a glass transition temperature of 50 ° C. or higher, a photoinitiator, a microgel containing an infrared absorbing dye, and a binder polymer, and an image recording containing the color developing photosensitive composition.
  • a lithographic printing plate precursor having a layer on a support is described. This lithographic printing plate precursor has good storage stability, high plate inspection, high printing durability, and can be made by on-press development.
  • Patent Document 2 describes that the microgel includes a spiropyran compound or a spirooxazine compound as an acid color former, and describes a spirooxazine compound having one isocyanate group as a specific example of the color former.
  • An object of the present invention is to provide a color-forming composition that has high color development and suppresses fading over time. Another object of the present invention is to suppress degradation of image visibility (plate inspection) even when stored over time, and in particular, to suppress degradation of image visibility due to aging after exposure. It is to provide a lithographic printing plate precursor having excellent properties. A further object of the present invention is to suppress a decrease in image visibility (plate inspection property) even when stored over time. In particular, a decrease in image visibility over time after exposure is suppressed. It is intended to provide an on-press development type lithographic printing plate precursor and a plate-making method thereof, in which a decrease in printing durability is suppressed and the on-press developability is excellent.
  • A1 Spirooxazine or spiropyran compound having two or more isocyanate groups in the molecule (a2) Compound having an active hydrogen group (A1)
  • the spirooxazine or spiropyran compound is a spirooxazine or spiropyran compound having 3 to 8 isocyanate groups in the molecule.
  • the (a1) spirooxazine or spiropyran compound is a spirooxazine compound represented by the following general formula (I): Or 2.
  • R 1 to R 11 each independently represents a hydrogen atom or an organic group. Alternatively, R 1 and R 2 may be connected to each other to form a ring. However, at least two of R 1 to R 11 have an isocyanate group, or at least one has two or more isocyanate groups. 4).
  • the spirooxazine compound is a spirooxazine compound represented by the following general formula (I-1) The color-forming composition as described in 1.
  • R 1 to R 6 and R 8 to R 13 each independently represent a hydrogen atom or an organic group.
  • R 1 and R 2 may be connected to each other to form a ring, or R 12 and R 13 may be connected to each other to form a ring.
  • at least two of R 1 to R 6 and R 8 to R 13 have an isocyanate group, or at least one has two or more isocyanate groups.
  • the spirooxazine compound is a spirooxazine compound represented by the following general formula (I-2) The color-forming composition as described in 1.
  • X represents O, CR 14 R 15 or NR 16 .
  • R 1 , R 2 , R 5 , R 14 , R 15 , R 16 each independently represents a hydrogen atom or an organic group. Alternatively, R 1 and R 2 may be connected to each other to form a ring. However, at least two of R 1 , R 2 , R 5 , R 14 , R 15 , R 16 have an isocyanate group, or at least one has two or more isocyanate groups. 6).
  • (A1) The spirooxazine or spiropyran compound has a 1-methylene-1,3,3-trimethylcyclohexane-5-yl group. ⁇ 5.
  • the color-forming composition according to any one of the above.
  • the compound (a2) having an active hydrogen group is at least one selected from water, a compound having two or more hydroxy groups, a compound having two or more amino groups, and a compound having two or more mercapto groups. There is one. ⁇ 6.
  • the compound having an active hydrogen group is water.
  • the (B) infrared absorbing dye is a cyanine dye represented by the following general formula (II): ⁇ 8.
  • R 17 represents a hydrogen atom, a halogen atom, —OR 26 , —N (R 27 ) (R 28 ) or —SR 29 .
  • R 26 and R 29 each independently represent a hydrocarbon group, an aryl group, a heteroaryl group, or a hydrocarbon group having 1 to 12 carbon atoms including a hetero atom.
  • R 27 and R 28 each independently represent a hydrogen atom, an alkyl group or an aryl group, or R 27 and R 28 may be linked to each other to form a ring.
  • R 18 and R 19 each independently represent a hydrogen atom or an alkyl group, or R 18 and R 19 may be linked to each other to form a ring.
  • Ar 1 and Ar 2 each independently represents an atomic group necessary for forming an aromatic ring or a heterocyclic ring.
  • Y 1 and Y 2 each independently represents —NR 30 —, —S—, —O—, —C ⁇ C— or a dialkylmethylene group.
  • R 20 and R 21 each independently represent a hydrocarbon group.
  • R 22 , R 23 , R 24 , R 25 , and R 30 each independently represent a hydrogen atom or a hydrocarbon group.
  • Za represents a counter ion that neutralizes the charge.
  • the polymer fine particle is a reaction product of the following (a1), (a2) and (a3). ⁇ 5. And 7. ⁇ 9. The color-forming composition according to any one of the above.
  • (A1) Spirooxazine or spiropyran compound having two or more isocyanate groups in the molecule (a2) Compound having an active hydrogen group (a3) Infrared absorbing dye having two or more isocyanate groups in the molecule 9.
  • the (a3) infrared absorbing dye is a cyanine dye represented by the following general formula (III) The color-forming composition as described in 1.
  • R 17 represents a hydrogen atom, a halogen atom, —OR 26 , —N (R 27 ) (R 28 ) or —SR 29 .
  • R 26 and R 29 each independently represent a hydrocarbon group, an aryl group, a heteroaryl group, or a hydrocarbon group having 1 to 12 carbon atoms including a hetero atom.
  • R 27 and R 28 each independently represent a hydrogen atom, an alkyl group or an aryl group, or R 27 and R 28 may be linked to each other to form a ring.
  • Ar 1 and Ar 2 each independently represents an atomic group necessary for forming an aromatic ring or a heterocyclic ring.
  • Y 1 and Y 2 each independently represents —NR 30 —, —S—, —O—, —C ⁇ C— or a dialkylmethylene group.
  • R 22 , R 23 , R 24 , R 25 , and R 30 each independently represent a hydrogen atom or a hydrocarbon group.
  • L 1 and L 2 represent a divalent or higher organic group, and n represents an integer of 1 to 6.
  • m represents 1 or 2.
  • Za represents a counter ion that neutralizes the charge. 12 9.
  • At least one of the (a1) spirooxazine or spiropyran compound and (a3) infrared absorbing dye has a 1-methylene-1,3,3-trimethylcyclohexane-5-yl group. Or 11.
  • the binder polymer (C) is a binder polymer having an alkylene oxide group.
  • the unexposed portion of the previous image recording layer can be removed by at least one of dampening water and printing ink.
  • a plate making method in which the lithographic printing plate precursor described in 1 is image-exposed with an infrared laser, and then an unexposed portion of the image recording layer is removed on a printing machine by at least one of dampen
  • the present invention it is possible to provide a color-forming composition that has high color development and is suppressed from fading over time.
  • a reduction in image visibility (plate inspection) is suppressed, and in particular, a decrease in image visibility is suppressed over time after exposure, and lithographic printing with excellent printing durability
  • An original version can be provided.
  • deterioration in image visibility (plate inspection) is suppressed, and in particular, deterioration in image visibility is suppressed over time after exposure, and printing durability when stored over time.
  • the color forming composition comprises (A) polymer fine particles having a spirooxazine or spiropyran structure, (B) an infrared absorbing dye, and (C) a binder polymer, and the (A) polymer fine particles are (a1). It is a reaction product of a spirooxazine or spiropyran compound having two or more isocyanate groups in the molecule and a compound having (a2) an active hydrogen group.
  • the exposed portion is colored by infrared laser exposure to form an image with high visibility.
  • This color image has little fading even after elapse of time after exposure.
  • the color development performance of the color forming composition according to the present invention does not deteriorate over time, and the storage stability is good.
  • the polymerization inhibiting action derived from spirooxazine or spiropyran can be suppressed, and the polymerization is inhibited. The effect that the fall of property is prevented is acquired.
  • the color forming composition will be described in detail.
  • the color-forming composition according to the present invention includes (A) polymer fine particles having a spirooxazine or spiropyran structure (hereinafter also referred to as “specific polymer fine particles”).
  • the specific polymer fine particle is a reaction product of (a1) a spirooxazine or spiropyran compound having two or more isocyanate groups in the molecule and (a2) a compound having an active hydrogen group, and has two or more isocyanate groups in the molecule.
  • Spirooxazine or spiropyran compound having a spirooxazine or spiropyran structure and a urea or urethane bond derived from a spirooxazine or spiropyran compound formed by the reaction of an isocyanate group of a spirooxazine or spiropyran compound with an active hydrogen group of a compound having an active hydrogen group.
  • A1 Spirooxazine or spiropyran compound having two or more isocyanate groups in the molecule is a spirooxazine compound or a spiropyran compound, and is characterized by having two or more isocyanate groups in the molecule.
  • a spirooxazine compound is a compound having a basic structure in which an oxazine ring and another ring (aliphatic ring or heterocyclic ring) are spiro-bonded.
  • a spiropyran compound is a compound having a basic structure in which a pyran ring and another ring (aliphatic ring or heterocyclic ring) are spiro-bonded.
  • Another ring aromatic ring, aliphatic ring or heterocyclic ring
  • the oxazine ring or the pyran ring, the ring spiro-bonded to them, and the condensed ring thereof may have a substituent.
  • the position of the spiro bond in the oxazine ring is the 2-position (2H-oxazine ring).
  • the position of the spiro bond in the pyran ring is the 2-position (2H-pyran ring) or the 4-position (4H-pyran ring).
  • the 2nd position is more preferable than the 4th position.
  • the ring that is spiro-bonded to the oxazine ring or the pyran ring is preferably a heterocyclic ring rather than an aliphatic ring.
  • the spirooxazine compound is more preferable than the spiropyran compound from the viewpoint of stability.
  • the number of isocyanate groups contained in the molecule is preferably 2 to 10 and more preferably 3 to 8 from the viewpoint of color development. 3 to 6 are preferred, and particularly preferred.
  • the spirooxazine compound having two or more isocyanate groups in the molecule is preferably a spirooxazine compound having two or more isocyanate groups in the molecule represented by the following general formula (I). .
  • R 1 to R 11 each independently represents a hydrogen atom or an organic group. Alternatively, R 1 and R 2 may be connected to each other to form a ring. However, at least two of R 1 to R 11 have an isocyanate group, or at least one has two or more isocyanate groups.
  • the ring formed by connecting R 1 and R 2 to each other is preferably a 6-membered ring, and more preferably a benzene ring.
  • the spirooxazine or spiropyran compound having two or more isocyanate groups in the molecule is more preferably a spirooxazine compound having two or more isocyanate groups in the molecule represented by the following general formula (I-1) .
  • R 1 to R 6 and R 8 to R 13 each independently represents a hydrogen atom or an organic group.
  • R 1 and R 2 may be connected to each other to form a ring, or R 12 and R 13 may be connected to each other to form a ring.
  • at least two of R 1 to R 6 and R 8 to R 13 have an isocyanate group, or at least one has two or more isocyanate groups.
  • R 12 and R 13 are preferably connected to each other to form a ring, and the formed ring is more preferably a 6-membered ring.
  • the spirooxazine or spiropyran compound having two or more isocyanate groups in the molecule is more preferably a spirooxazine compound having two or more isocyanate groups in the molecule represented by the following general formula (I-2) .
  • X represents O, CR 14 R 15 or NR 16 .
  • R 1 , R 2 , R 5 , R 14 , R 15 , R 16 each independently represents a hydrogen atom or an organic group. Alternatively, R 1 and R 2 may be connected to each other to form a ring. However, at least two of R 1 , R 2 , R 5 , R 14 , R 15 , R 16 have an isocyanate group, or at least one has two or more isocyanate groups.
  • the organic group represented by R 1 to R 16 is an organic group constituted by combining the following structures or a plurality of these structures: The group can be mentioned.
  • the spirooxazine or spiropyran compound (a1) having two or more isocyanate groups in the molecule according to the present invention is a polymer having a 1-methylene-1,3,3-trimethylcyclohexane-5-yl group in the molecule. It is preferable from the viewpoint of solubility in a solvent during the production of fine particles.
  • the 1-methylene-1,3,3-trimethylcyclohexane-5-yl group is a divalent group represented by the following formula (X).
  • the 1-methylene-1,3,3-trimethylcyclohexane-5-yl group is, for example, in the compounds represented by the general formulas (I), (I-1) and (I-2), R 1 to contained in the organic group represented by R 16.
  • Spirooxazine or a spiropyran compound having two or more isocyanate groups in the molecule may be used alone or in combination of two or more.
  • Spirooxazine or spiropyran compound having two or more isocyanate groups in the molecule includes two spirooxazines or spiropyrans having two or more functional groups such as a hydroxyl group, a primary amino group, a secondary amino group, and a mercapto group. It can be obtained by addition reaction with the above compound having an isocyanate group. Two or more functional groups in spirooxazine or spiropyran may be the same or different.
  • the compound having an active hydrogen group may be any compound that forms polymer fine particles by reacting with the (a1) spirooxazine or spiropyran compound having two or more isocyanate groups in the molecule.
  • a compound having the above hydroxy group, a compound having two or more amino groups, a compound having two or more mercapto groups, and the like are used.
  • water is preferably used as the compound having an active hydrogen group.
  • Polyols, polyamines, and polythiols can also be preferably used.
  • the specific polymer fine particles according to the present invention comprise an oil phase component and an aqueous phase component using (a1) a spirooxazine or spiropyran compound having two or more isocyanate groups in the molecule and (a2) a compound having an active hydrogen group. It can be manufactured by performing a known operation applied to a general method for producing fine polymer particles, which is prepared and mixed to prepare an emulsified dispersion. Specifically, (a1) an oil phase component containing at least a spirooxazine or spiropyran compound having two or more isocyanate groups in the molecule and an organic solvent, and (a2) an aqueous phase component containing at least a compound having an active hydrogen group.
  • An aqueous dispersion containing specific polymer fine particles can be obtained by preparing and mixing both, preparing an emulsified dispersion using an emulsifier such as a homogenizer, and removing the organic solvent by heating or the like.
  • the aqueous phase component (aqueous solution) containing a compound having an active hydrogen group may be simply water when the compound having an active hydrogen group is water.
  • a dispersant, a polymerizable monomer, a surfactant and the like may be added in addition to the above-described constituent components.
  • the dispersant, the polymerizable monomer, and the surfactant are added to the oil phase component and / or the aqueous phase component depending on the solubility thereof.
  • a hydrophilic polymer is preferably used as the dispersant.
  • the hydrophilic polymer includes, for example, a compound having a polyoxyalkylene chain, polyvinyl alcohol and its modified product, polyacrylic acid amide and its derivative, ethylene / vinyl acetate copolymer, styrene / maleic anhydride copolymer, ethylene / anhydrous Maleic acid copolymer, isobutylene / maleic anhydride copolymer, polyvinylpyrrolidone, ethylene / acrylic acid copolymer, vinyl acetate / acrylic acid copolymer, carboxymethylcellulose, methylcellulose, casein, gelatin, starch derivative, gum arabic and Mention may be made of sodium alginate.
  • the hydrophilic polymer is preferably (a1) a compound that does not react or is extremely difficult to react with a spirooxazine or spiropyran compound having two or more isocyanate groups in the molecule, or a compound that has only one reaction point.
  • a spirooxazine or spiropyran compound having two or more isocyanate groups in the molecule or a compound that has only one reaction point.
  • those having a reactive amino group in the molecular chain, such as gelatin need to have no reactivity in advance.
  • the hydrophilic polymers compounds having a polyoxyalkylene chain are preferred.
  • a compound having a polyoxyalkylene chain functions as a protective colloid for specific polymer fine particles
  • the use of a compound having a polyoxyalkylene chain improves the dispersion stability of the specific polymer fine particles, and when used for a lithographic printing plate precursor It is particularly preferable from the viewpoint of improving the developability.
  • the compound having a polyoxyalkylene chain include a compound having a polyoxyalkylene chain having one reactive terminal capable of reacting with an isocyanate group.
  • the compound having a polyoxyalkylene chain is incorporated into the specific polymer fine particle by utilizing the reaction of the reactive terminal group. Can be introduced.
  • a spirooxazine or spiropyran compound having two or more isocyanate groups is dissolved in a water-immiscible solvent, and the solution has a polyoxyalkylene chain having one reactive terminal capable of reacting with an isocyanate group.
  • the solvent is removed from the oil droplets of the emulsified dispersion, whereby the compound having a polyoxyalkylene chain is introduced into the specific polymer fine particles.
  • a polyfunctional alkylene compound different from a spirooxazine or spiropyran compound having two or more isocyanate groups is reacted with a compound having a polyoxyalkylene chain having one reactive terminal capable of reacting with an isocyanate group to produce a polyoxyalkylene.
  • a polyfunctional isocyanate compound having a chain is synthesized, and a polyfunctional isocyanate compound having a polyoxyalkylene chain and a spirooxazine or spiropyran compound having two or more isocyanate groups are dissolved in a water-immiscible solvent, and this solution May be emulsified and dispersed in an aqueous solution containing a compound having an active hydrogen group, and then the compound having a polyoxyalkylene chain may be introduced into the specific polymer fine particles by removing the solvent from the oil droplets of the emulsion dispersion.
  • Examples of the sex terminal capable of reacting with an isocyanate group in a compound having a polyoxyalkylene chain having one reactive terminal capable of reacting with an isocyanate group include a hydroxy group, an amino group, and a mercapto group. In particular, a hydroxy group and an amino group are preferable.
  • the mass average molar mass (Mw) of the compound having a polyoxyalkylene chain having a reactive end is preferably from 300 to 500,000, more preferably from 500 to 100,000. When Mw is 300 to 500,000, it has a sufficient function as a dispersant (protective colloid), can ensure sufficient dispersion stability of the specific polymer fine particles, and imparts hydrophilicity to the surface of the specific polymer fine particles. Thus, the developability when used for a lithographic printing plate precursor is also improved.
  • the compound having a polyoxyalkylene chain include, for example, polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polystyrene oxide, polycyclohexylene oxide, polyethylene oxide-polypropylene oxide-block copolymer, polyethylene oxide-polypropylene oxide. A random copolymer etc. are mentioned. Of these, polyethylene oxide, polypropylene oxide, and polyethylene oxide-polypropylene oxide block copolymers are preferable, and polyethylene oxide is more preferable.
  • Polyethylene oxide monoethers include monomethyl ether, monoethyl ether, etc.
  • polyethylene oxide monoesters include monoacetate, mono (meth) acrylate, etc.
  • a compound having a polyoxyalkylene chain having one reactive end is formed by, for example, ring-opening polymerization of a cyclic compound such as ethylene oxide or propylene oxide using an alcohol, alkoxide, carboxylic acid, carboxylate or the like as a polymerization initiation end, and then polymerization. It can be synthesized by converting the starting end to a hydroxy group or amino group which is a reactive end by a conventionally known reaction (for example, hydrolysis reaction, reduction reaction, etc.).
  • the amount of the dispersant added is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, and particularly preferably 1 to 30% by mass with respect to the total solid content of the oil phase.
  • polymerizable monomer examples include a compound having an ethylenically unsaturated group, a compound having an epoxy group, and the like. A compound having an ethylenically unsaturated group having a relatively high photopolymerization rate is preferred.
  • the polymerizable monomer contributes to the improvement in printing durability of the resulting lithographic printing plate.
  • the polymerizable monomers may be used alone or in combination of two or more. When the polymerizable monomer is added, the addition amount is preferably 1 to 80% by mass, more preferably 5 to 70% by mass, and particularly preferably 10 to 60% by mass with respect to the total solid content of the oil phase.
  • surfactant In order to improve the stability of the emulsified dispersion containing the specific polymer fine particles, it is preferable to add a surfactant.
  • the surfactant may be added to either the oil phase or the aqueous phase, but is usually easier to add to the aqueous phase because of its low solubility in organic solvents.
  • the amount added is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass, based on the total solid content of the oil phase.
  • surfactants used for emulsification and dispersion are considered to be excellent surfactants having a relatively long-chain hydrophobic group.
  • alkali metal salts such as alkylsulfonic acid and alkylbenzenesulfonic acid can be used.
  • compounds such as a formalin condensate of aromatic sulfonate and a formalin condensate of aromatic carboxylate can be used as a surfactant (emulsification aid).
  • a surfactant emulsification aid
  • Specific examples include compounds represented by the following general formula (W-1). This compound is described in JP-A-06-297856.
  • R represents an alkyl group having a carbon number of 1 ⁇ 4
  • X is SO 3 - or COO - represents
  • M represents Na + or K +
  • q is 1 to 20 Represents an integer.
  • alkyl glucoside compounds can also be used. Specifically, a compound represented by the following general formula (W-2) can be given.
  • R represents an alkyl group having 4 to 18 carbon atoms
  • q represents an integer of 0 to 2.
  • Surfactants may be used alone or in combination of two or more.
  • the following method is preferably used.
  • the polymer fine particle has one solution (oil phase component) obtained by dissolving a spirooxazine or spiropyran compound having two or more isocyanate groups in an organic solvent immiscible with water at one reactive end capable of reacting with the isocyanate groups. It is produced by emulsifying and dispersing an aqueous solution (aqueous phase component) containing a compound having a polyoxyalkylene chain and a surfactant, and then removing the organic solvent from the oil droplets of the emulsified dispersion.
  • aqueous phase component obtained by dissolving a spirooxazine or spiropyran compound having two or more isocyanate groups in an organic solvent immiscible with water at one reactive end capable of reacting with the isocyanate groups. It is produced by emulsifying and dispersing an aqueous solution (aqueous phase component) containing a compound having a polyoxyalkylene chain and a sur
  • the polymer fine particle is a reaction product that also contains an infrared absorbing dye having two or more isocyanate groups, which will be described later, the infrared absorbing dye is also dissolved in a water-immiscible solvent to adjust the oil phase component and emulsify It is preferable to disperse.
  • the water-immiscible organic solvent used to prepare the oil phase component can be used without particular limitation as long as it is a solvent that is immiscible with water and can be removed from oil droplets by heating and stirring after emulsification and dispersion.
  • hydrocarbon solvents, aromatic solvents, ketone solvents, ester solvents, ether solvents and the like are preferable.
  • ethyl acetate, butyl acetate, methyl ethyl ketone, diethyl ether, diisopropyl ether, methyl tertiary butyl ether and the like are preferable, and ethyl acetate and methyl ethyl ketone are particularly preferable.
  • an oil phase component and an aqueous phase component are mixed, and the mixture is vigorously stirred and mixed, for example, at 12,000 rpm for 10 to 15 minutes using an emulsifier / disperser such as a homogenizer.
  • An emulsified dispersion in which oil droplets are emulsified and dispersed is obtained.
  • the obtained emulsified dispersion is heated and stirred to evaporate the solvent, thereby obtaining an aqueous dispersion of the target polymer fine particles.
  • the specific polymer fine particles according to the present invention preferably have (a1) a spirooxazine or spiropyran compound having two or more isocyanate groups in the molecule, (a2) a compound having an active hydrogen group, and (a3) 2 in the molecule. It may be a reaction product of an infrared absorbing dye having one or more isocyanate groups.
  • the distance between the spirooxazine or spiropyran compound and the infrared absorbing dye becomes close, and the heat generated from the infrared absorbing dye by exposure is efficiently spiro Since it can be transmitted to the oxazine or spiropyran compound, the color developability is further improved.
  • the infrared absorbing dye when used in a lithographic printing plate precursor, by introducing the infrared absorbing dye into the polymer fine particles, the polymerization inhibiting action of the infrared absorbing dye is reduced, so that a decrease in printing durability can be suppressed.
  • Infrared absorbing dye having two or more isocyanate groups in the molecule is an infrared absorbing dye and is characterized by having two or more isocyanate groups in the molecule.
  • the number of isocyanate groups contained in the molecule is preferably 2 to 10, more preferably 2 to 8, and particularly preferably 2 to 6.
  • the mother nucleus structure of an infrared absorbing dye having two or more isocyanate groups in the molecule is described in commercially available dyes and, for example, documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970).
  • a host structure of a known infrared absorbing dye can be used.
  • dyes such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes Is mentioned.
  • dyes preferred are cyanine dyes, squarylium dyes, pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes.
  • cyanine dyes and indolenine cyanine dyes are preferred.
  • a cyanine dye represented by the following general formula (III) is preferable.
  • R 17 represents a hydrogen atom, a halogen atom, —OR 26 , —N (R 27 ) (R 28 ) or —SR 29 .
  • R 26 and R 29 each independently represent a hydrocarbon group, an aryl group, a heteroaryl group, or a hydrocarbon group having 1 to 12 carbon atoms including a hetero atom.
  • R 27 and R 28 each independently represent a hydrogen atom, an alkyl group or an aryl group, or R 27 and R 28 may be linked to each other to form a ring.
  • Ar 1 and Ar 2 each independently represents an atomic group necessary for forming an aromatic ring or a heterocyclic ring.
  • Y 1 and Y 2 each independently represents —NR 30 —, —S—, —O—, —C ⁇ C— or a dialkylmethylene group.
  • R 22 , R 23 , R 24 , R 25 , and R 30 each independently represent a hydrogen atom or a hydrocarbon group.
  • L 1 and L 2 represent a divalent or higher organic group, and n represents an integer of 1 to 6.
  • m represents 1 or 2.
  • Za represents a counter ion that neutralizes the charge.
  • R 17 is preferably a hydrogen atom, a halogen atom or —N (R 27 ) (R 28 ), particularly preferably a halogen atom.
  • R 27 and R 28 may be the same or different, preferably an aryl group having 6 to 10 carbon atoms which may have a substituent, or 1 to carbon atoms which may have a substituent.
  • 8 represents an alkyl group or a hydrogen atom, and R 27 and R 28 may be linked to each other to form a ring. Of these, a phenyl group is preferred (—NPh 2 ).
  • R 26 and R 29 are preferably a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, an aryl group which may have a substituent, and a hetero which may have a substituent.
  • An aryl group and a hydrocarbon group having 1 to 12 carbon atoms including a hetero atom are represented.
  • the hetero atom represents a nitrogen atom, a sulfur atom, an oxygen atom, a halogen atom, or a selenium atom.
  • an aryl group for example, phenyl group
  • a heteroaryl group for example, tetrazolyl group
  • Ar 1 and Ar 2 may be the same or different and each represents an atomic group necessary for forming an aromatic ring or a heterocyclic ring which may have a substituent.
  • a preferable aromatic ring or heterocyclic ring includes a benzene ring or a naphthalene ring.
  • Preferred examples of the substituent include a hydrocarbon group having 12 or less carbon atoms, a halogen atom, and an alkoxy group having 12 or less carbon atoms.
  • Y 1 and Y 2 may be the same as or different from each other, and preferably represent —NR 30 —, —S—, —O—, —C ⁇ C— or a dialkylmethylene group having 12 or less carbon atoms, R 30 represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.
  • R 22 , R 23 , R 24 and R 25 may be the same or different, and preferably represent a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. In view of easy availability of the raw material, a hydrogen atom is preferred.
  • Za ⁇ represents a counter anion. However, Za ⁇ is not necessary when the cyanine dye represented by formula (a) has an anionic substituent in its structure and neutralization of charge is not necessary.
  • Preferred Za ⁇ is preferably a halide ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, or a sulfonate ion when used for a lithographic printing plate precursor because of the storage stability of the image recording layer coating solution.
  • Perchlorate ion, hexafluorophosphate ion, and aryl sulfonate ion are more preferable.
  • the infrared absorbing dye having two or more isocyanate groups in the molecule may have a 1-methylene-1,3,3-trimethylcyclohexane-5-yl group in the molecule against the solvent at the time of producing polymer fine particles. It is preferable from the viewpoint of solubility.
  • the 1-methylene-1,3,3-trimethylcyclohexane-5-yl group is, for example, a divalent or higher-valent organic group represented by L 1 or L 2 in the compound represented by the general formula (III). include.
  • Infrared absorbing dyes having two or more isocyanate groups in the molecule may be used alone or in admixture of two or more.
  • An infrared absorbing dye having two or more isocyanate groups in the molecule is an infrared absorbing dye having two or more functional groups such as a hydroxyl group, a primary amino group, a secondary amino group, or a mercapto group, and two or more isocyanates.
  • the compound having a group can be synthesized by addition reaction. Two or more functional groups in the infrared absorbing dye may be the same or different.
  • infrared absorbing dye having two or more isocyanate groups in the molecule (a3) used in the present invention are shown below, but the present invention is not limited thereto.
  • the specific polymer fine particle according to the present invention includes (a3) the structure of an infrared absorbing dye having two or more isocyanate groups in the molecule, the specific polymer fine particle can be produced according to the method for producing the specific polymer fine particle.
  • SP, SO and IR2 respectively represent the spiropyran compound having two or more isocyanate groups, the spirooxazine compound having two or more isocyanate groups, and the infrared dye having two or more isocyanate groups.
  • SP-1 to SP-4, SO-1 to SO-15, and IR2-1 to IR2-10 are the compounds described as specific examples.
  • Distilled water 50 g was added to the oil phase component as an aqueous phase component, mixed, and emulsified at 12,000 rpm for 10 minutes using a homogenizer.
  • the obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours.
  • the polymer fine particle liquid thus obtained was diluted with distilled water so that the solid content concentration was 15% by mass to obtain polymer fine particles SP MG1.
  • the average particle diameter of the polymer fine particles measured by the light scattering method was 0.25 ⁇ m.
  • Distilled water (50 g) was added to the oil phase component as an aqueous phase component, mixed, and emulsified at 12,000 rpm for 10 minutes using a homogenizer. The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours. Distilled water was used to dilute the solid content concentration of the polymer fine particle liquid thus obtained to 15% by mass to obtain polymer fine particle SP-IR MG1. The average particle diameter of the polymer fine particles measured by the light scattering method was 0.25 ⁇ m.
  • Distilled water 50 g was added to the oil phase component as an aqueous phase component, mixed, and emulsified at 12,000 rpm for 10 minutes using a homogenizer.
  • the obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours.
  • the polymer fine particle liquid thus obtained was diluted with distilled water so that the solid content concentration was 15% by mass to obtain polymer fine particle SOMG1.
  • the average particle diameter of the polymer fine particles measured by the light scattering method was 0.25 ⁇ m.
  • Distilled water 50 g was added to the oil phase component as an aqueous phase component, mixed, and emulsified at 12,000 rpm for 10 minutes using a homogenizer.
  • the obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours.
  • the polymer fine particle liquid thus obtained was diluted with distilled water so that the solid content concentration was 15% by mass, to obtain polymer fine particle SO-IR MG1.
  • the average particle diameter of the polymer fine particles measured by the light scattering method was 0.25 ⁇ m.
  • the average particle size of the specific polymer fine particles is preferably 0.01 to 5.0 ⁇ m, more preferably 0.05 to 1.0 ⁇ m, and particularly preferably 0.10 to 0.5 ⁇ m.
  • the content of the specific polymer fine particles is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass with respect to the total solid content of the color forming composition.
  • the color-forming composition according to the invention contains an infrared absorbing dye.
  • the infrared absorbing dye has a function of converting absorbed infrared rays into heat. The generated heat causes the spirooxazine or spiropyran compound in the polymer fine particles to develop a color image.
  • a color-forming composition containing a polymerization initiator and a polymerizable compound for example, a color-forming composition used for an image recording layer of a lithographic printing plate precursor described later, with the function of converting absorbed infrared rays into heat, Excited by infrared rays, has a function of transferring electrons or energy to the polymerization initiator. As a result, radicals are generated, and the polymerization reaction of the polymerizable compound is initiated and accelerated to form a colored cured image.
  • dyes such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes Is mentioned.
  • cyanine dyes preferred are cyanine dyes, squarylium dyes, pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes. Further, cyanine dyes and indolenine cyanine dyes are preferred, and particularly preferred examples include cyanine dyes represented by the following general formula (II).
  • R 17 represents a hydrogen atom, a halogen atom, —OR 26 , —N (R 27 ) (R 28 ) or —SR 29 .
  • R 26 and R 29 each independently represent a hydrocarbon group, an aryl group, a heteroaryl group, or a hydrocarbon group having 1 to 12 carbon atoms including a hetero atom.
  • R 27 and R 28 each independently represent a hydrogen atom, an alkyl group or an aryl group, or R 27 and R 28 may be linked to each other to form a ring.
  • R 18 and R 19 each independently represent a hydrogen atom or an alkyl group, or R 18 and R 19 may be linked to each other to form a ring.
  • Ar 1 and Ar 2 each independently represents an atomic group necessary for forming an aromatic ring or a heterocyclic ring.
  • Y 1 and Y 2 each independently represents —NR 30 —, —S—, —O—, —C ⁇ C— or a dialkylmethylene group.
  • R 20 and R 21 each independently represent a hydrocarbon group.
  • R 22 , R 23 , R 24 , R 25 , and R 30 each independently represent a hydrogen atom or a hydrocarbon group.
  • Za represents a counter ion that neutralizes the charge.
  • R 17 is preferably a hydrogen atom, a halogen atom or —N (R 27 ) (R 28 ), particularly preferably a halogen atom.
  • R 27 and R 28 may be the same or different, preferably an aryl group having 6 to 10 carbon atoms which may have a substituent, or 1 to carbon atoms which may have a substituent.
  • 8 represents an alkyl group or a hydrogen atom, and R 27 and R 28 may be linked to each other to form a ring. Of these, a phenyl group is preferred (—NPh 2 ).
  • R 26 and R 29 are preferably a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, an aryl group which may have a substituent, and a substituent.
  • a heteroaryl group a hydrocarbon group having 1 to 12 carbon atoms containing a hetero atom;
  • a hetero atom shows a nitrogen atom, a sulfur atom, an oxygen atom, a halogen atom, and a selenium atom.
  • an aryl group for example, phenyl group
  • a heteroaryl group for example, tetrazolyl group
  • R 18 and R 19 each independently preferably represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.
  • R 18 and R 19 are preferably a hydrocarbon group having 2 or more carbon atoms from the storage stability of the image recording layer coating solution.
  • R 18 and R 19 may be connected to each other to form a ring, and in the case of forming a ring, it is particularly preferable to form a 5-membered ring or a 6-membered ring.
  • Ar 1 and Ar 2 may be the same or different and each represents an atomic group necessary for forming an aromatic ring or a heterocyclic ring which may have a substituent.
  • a preferable aromatic ring or heterocyclic ring includes a benzene ring or a naphthalene ring.
  • Preferred examples of the substituent include a hydrocarbon group having 12 or less carbon atoms, a halogen atom, and an alkoxy group having 12 or less carbon atoms.
  • Y 1 and Y 2 may be the same as or different from each other, and preferably represent —NR 30 —, —S—, —O—, —C ⁇ C— or a dialkylmethylene group having 12 or less carbon atoms
  • R 30 represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms
  • R 20 and R 21 may be the same or different, and each preferably represents a hydrocarbon group having 20 or less carbon atoms, which may have a substituent.
  • Preferred substituents include an alkoxy group having 12 or less carbon atoms, an acyl group, a carboxy group, and a sulfo group.
  • R 22 , R 23 , R 24 and R 25 may be the same or different, and preferably represent a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. In view of easy availability of the raw material, a hydrogen atom is preferred.
  • Za ⁇ represents a counter anion that neutralizes the charge.
  • the cyanine dye represented by the general formula (II) has an anionic substituent in the structure thereof, and charge neutralization is not necessary. Za - is not necessary.
  • Za ⁇ is preferably a halide ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, or a sulfonate ion in view of the storage stability of the image recording layer coating solution when used for a lithographic printing plate precursor.
  • Perchlorate ion, hexafluorophosphate ion, and aryl sulfonate ion are more preferable.
  • cyanine dye represented by the general formula (II) include compounds described in paragraph numbers [0017] to [0019] of JP-A No. 2001-133969, and paragraph numbers of JP-A No. 2002-023360.
  • 0016] to [0021] compounds described in paragraphs [0012] to [0037] of JP-A No. 2002-040638, preferably paragraphs [0034] to [0041] of JP-A No. 2002-278057
  • the compounds described in paragraph Nos. [0080] to [0086] of Kaikai 2008-195018, particularly preferably the compounds described in paragraph Nos. [0035] to [0043] of JP-A-2007-90850 are exemplified.
  • the content of the (B) infrared absorbing dye is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, and particularly preferably 0.2% with respect to the total solid content of the color forming composition. ⁇ 10% by mass.
  • the color forming composition according to the invention contains a binder polymer in order to impart film properties.
  • the binder polymer any conventionally known binder polymer can be used as long as it can impart film properties.
  • the binder polymer may be a linear binder polymer or a star structure polymer as described in JP-A-2007-249036.
  • the binder polymer in the case where the color forming composition is used for an image recording layer of a lithographic printing plate precursor described later is described below.
  • the following addition polymers and urethane resins having a crosslinkable group in the side chain are preferably used.
  • the image recording layer of the lithographic printing plate precursor according to the invention it is preferable to use a binder polymer corresponding to the developing method.
  • (C1) Binder polymer for on-press development As the binder polymer used in the image recording layer of the on-press development type lithographic printing plate precursor, a binder polymer having an alkylene oxide group is preferable.
  • the binder polymer having an alkylene oxide group used in the image recording layer may have a poly (alkylene oxide) moiety in the main chain or a side chain, and may have a poly (alkylene oxide) moiety.
  • the graft polymer in the side chain may be a block copolymer composed of a block composed of a poly (alkylene oxide) -containing repeating unit and a block composed of a (alkylene oxide) -free repeating unit.
  • a polyurethane resin is preferred when it has a poly (alkylene oxide) moiety in the main chain.
  • the main chain polymer is acrylic resin, polyvinyl acetal resin, polyurethane resin, polyurea resin, polyimide resin, polyamide resin, epoxy resin, methacrylic resin, polystyrene resin, novolac type A phenol resin, a polyester resin, a synthetic rubber, and a natural rubber are exemplified, and an acrylic resin is particularly preferable.
  • the alkylene oxide at the poly (alkylene oxide) moiety is preferably an alkylene oxide having 2 to 6 carbon atoms, and particularly preferably ethylene oxide or propylene oxide.
  • the number of repeating alkylene oxides at the poly (alkylene oxide) site is suitably 2 to 120, preferably 2 to 70, more preferably 2 to 50. If the number of alkylene oxide repeats is 120 or less, it is preferable that both the printing durability due to abrasion and the printing durability due to ink acceptance do not deteriorate.
  • the poly (alkylene oxide) moiety is preferably contained as a side chain of the binder polymer in a structure represented by the following general formula (a). More preferably, it is contained as a side chain of the acrylic resin in a structure represented by the following general formula (a).
  • y represents 2 to 120
  • R 1 represents a hydrogen atom or an alkyl group
  • R 2 represents a hydrogen atom or an organic group.
  • y is preferably 2 to 70, more preferably 2 to 50.
  • an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, Examples thereof include t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, cyclopentyl group, and cyclohexyl group.
  • R 1 is preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.
  • R 2 is particularly preferably a hydrogen atom or a methyl group.
  • the binder polymer may have crosslinkability in order to improve the film strength of the image area.
  • a crosslinkable functional group such as an ethylenically unsaturated bond may be introduced into the main chain or side chain of the polymer.
  • the crosslinkable functional group may be introduced by copolymerization. Examples of the polymer having an ethylenically unsaturated bond in the main chain of the molecule include poly-1,4-butadiene and poly-1,4-isoprene.
  • polymers having an ethylenically unsaturated bond in the side chain of the molecule are polymers of esters or amides of acrylic acid or methacrylic acid, where the ester or amide residue (-COOR or CONHR R) is ethylene.
  • ester or amide residue is ethylene.
  • polymers having a polymerizable unsaturated bond examples include polymers having a polymerizable unsaturated bond.
  • R 1 to R 3 are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 20 carbon atoms, aryl R 1 and R 2 or R 3 may be bonded to each other to form a ring, n represents an integer of 1 to 10, and X represents dicyclopentadi.
  • Specific examples of the amide residue include —CH 2 CH ⁇ CH 2 , —CH 2 CH 2 —Y (wherein Y represents a cyclohexene residue), —CH 2 CH 2 —OCO—CH ⁇ CH 2. Is mentioned.
  • the binder polymer having crosslinkability for example, has a free radical (polymerization initiation radical or a growth radical in the polymerization process of the polymerizable compound) added to the crosslinkable functional group, and the polymerization chain of the polymerizable compound is formed directly between the polymers. Through addition polymerization, a cross-link is formed between the polymer molecules and cured.
  • atoms in the polymer eg, hydrogen atoms on carbon atoms adjacent to the functional bridging group
  • free radicals in the polymer are abstracted by free radicals to form polymer radicals that are bonded together, thereby causing cross-linking between polymer molecules. Forms and cures.
  • the content of the crosslinkable group in the binder polymer is preferably 0.1 to 10.0 mmol, more preferably 1.0 to 1.0 g per 1 g of the polymer. 7.0 mmol, particularly preferably 2.0 to 5.5 mmol. Within this range, good sensitivity and good storage stability can be obtained.
  • a numerical value written together with each repeating unit represents a mole percentage of the repeating unit.
  • the numerical value written together with the repeating unit of the side chain indicates the number of repetitions of the repeating site.
  • the mass average molar mass (Mw) of the binder polymer is preferably 2000 or more, more preferably 5000 or more, and further preferably 10,000 to 300,000 as a polystyrene conversion value by the GPC method.
  • hydrophilic polymer compounds such as polyacrylic acid and polyvinyl alcohol described in JP-A-2008-195018 can be used in combination as required. Further, a lipophilic polymer compound and a hydrophilic polymer compound can be used in combination.
  • the form of the binder polymer in the image recording layer may be present in the image recording layer as a binder that functions as a linking material, or may be present in the form of fine particles.
  • the average particle size is 10 to 1000 nm, preferably 20 to 300 nm, and particularly preferably 30 to 120 nm.
  • the content of the binder polymer is preferably 3 to 90% by mass and more preferably 6 to 80% by mass with respect to the total solid content of the image recording layer.
  • the color forming composition according to the present invention may further contain (D) a polymerization initiator and (E) a polymerizable compound.
  • Such a color forming composition is preferably used as an image recording layer of a lithographic printing plate precursor.
  • the polymerization initiator used in the present invention is a compound that generates radicals by light, heat, or both, and initiates and accelerates polymerization of the polymerizable monomer (C).
  • the polymerization initiator include (a) an organic halide, (b) a carbonyl compound, (c) an azo compound, (d) an organic peroxide, (e) a metallocene compound, (f) an azide compound, (g) Hexaarylbiimidazole compounds, (h) borate compounds, (i) disulfone compounds, (j) oxime ester compounds, and (k) onium salt compounds can be used.
  • the polymerization initiator (h) a borate compound and (k) an onium salt compound are preferably used.
  • Examples of onium salt compounds include European Patent Nos. 104 and 143, US Patent Application Publication Nos. 2008/0311520, JP-A-2-150848, JP-A-2008-195018, and J . V. Ivonium salts described in Crivello et al, Macromolecules, 10 (6), 1307 (1977), European Patent Nos. 370,693, 233,567, 297,443, 297,442, US Patent No. 4,933,377, 4,760,013, 4,734,444, 2,833,827, German Patents 2,904,626, 3,604,580, Examples include onium salts such as sulfonium salts described in the specifications of US Pat. No. 3,604,581.
  • an onium salt having a cyanine structure as shown below is also preferably used.
  • iodonium salts and borate compounds are preferred. Specific examples of these compounds are shown below, but the present invention is not limited thereto.
  • the iodonium salt is preferably a diphenyl iodonium salt, more preferably a diphenyl iodonium salt substituted with an electron donating group such as an alkyl group or an alkoxyl group, and more preferably an asymmetric diphenyl iodonium salt.
  • diphenyliodonium hexafluorophosphate
  • 4-methoxyphenyl-4- (2-methylpropyl) phenyliodonium hexafluorophosphate
  • 4- (2-methylpropyl) phenyl-p-tolyliodonium hexa Fluorophosphate
  • 4-hexyloxyphenyl-2,4,6-trimethoxyphenyliodonium hexafluorophosphate
  • 4-hexyloxyphenyl-2,4-diethoxyphenyliodonium tetrafluoroborate
  • 4-octyloxy Phenyl-2,4,6-trimethoxyphenyliodonium 1-perfluorobutanesulfonate
  • 4-octyloxyphenyl-2,4,6-trimethoxyphenyliodonium hexafluorophosphate, bis ( -t- butylphenyl) iodonium
  • borate compound examples include tetraphenylborate salt, tetratolylborate salt, tetrakis (4-methoxyphenyl) borate salt, tetrakis (pentafluorophenyl) borate salt, tetrakis (3,5-bis (trifluoromethyl) phenyl ) Borate salt, tetrakis (4-chlorophenyl) borate salt, tetrakis (4-fluorophenyl) borate salt, tetrakis (2-thienyl) borate salt, tetrakis (4-phenylphenyl) borate salt, tetrakis (4-t-butylphenyl) ) Borate salt, ethyl triphenyl borate salt, butyl triphenyl borate salt and the like.
  • a tetraphenylborate salt is preferable.
  • the counter cation of the borate compound include known cations such as alkali metal cations, alkaline earth metal cations, ammonium cations, phosphonium cations, sulfonium cations, iodonium cations, diazonium cations, and azinium cations.
  • the polymerizable compound used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has at least one terminal ethylenically unsaturated bond, preferably two. It is selected from the compounds having the above. These have chemical forms such as monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof.
  • Examples of monomers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, preferably unsaturated carboxylic acids.
  • unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters and amides thereof preferably unsaturated carboxylic acids.
  • An ester of an acid and a polyhydric alcohol compound and an amide of an unsaturated carboxylic acid and a polyvalent amine compound are used.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, amino group, mercapto group and the like with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional A dehydration-condensation reaction product with carboxylic acid is also preferably used.
  • addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, thiols, halogen groups, tosyloxy A substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
  • a compound group in which the unsaturated carboxylic acid is replaced with unsaturated phosphonic acid, styrene, vinyl ether or the like can be used.
  • JP-T-2006-508380 JP-A-2002-287344, JP-A-2008-256850, JP-A-2001-342222, JP-A-9-179296, JP-A-9-179297.
  • JP-A-9-179298 JP-A-2004-294935, JP-A-2006-243493, JP-A-2002-275129, JP-A-2003-64130, JP-A-2003-280187, It is described in references including Kaihei 10-333321.
  • monomers of esters of polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, Examples include trimethylolpropane triacrylate, hexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, isocyanuric acid ethylene oxide (EO) -modified triacrylate, and polyester acrylate oligomer.
  • acrylic acid esters such as ethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate
  • Examples include trimethylolpropane triacrylate, hexanediol diacrylate, tetraethylene glycol diacrylate, pentaery
  • Methacrylic acid esters include tetramethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, pentaerythritol trimethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl ] Dimethylmethane, bis- [p- (methacryloxyethoxy) phenyl] dimethylmethane, and the like.
  • amide monomers of polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methacrylic.
  • examples include amide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.
  • urethane-based addition-polymerizable compounds produced using an addition reaction of isocyanate and hydroxyl group.
  • Specific examples include, for example, two or more per molecule described in JP-B-48-41708.
  • a vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to the polyisocyanate compound having the above isocyanate group. It is done.
  • CH 2 C (R 4) COOCH 2 CH (R 5) OH formula (A) (However, R 4 and R 5 represent H or CH 3.
  • urethanes as described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-A-2003-344997, JP-A-2006-65210 are disclosed.
  • Acrylates, JP-B 58-49860, JP-B 56-17654, JP-B 62-39417, JP-B 62-39418, JP-A 2000-250211, JP-A 2007-94138 Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 7153632, hydrophilic groups described in US Pat. No.
  • urethane compounds having.
  • the isocyanuric acid ethylene oxide modified acrylates are particularly preferred.
  • the content of the polymerizable compound is preferably 0.5 to 75% by mass, more preferably 1 to 70% by mass, based on the total solid content of the image recording layer.
  • the color forming composition according to the present invention may further contain other components according to the purpose.
  • a color forming composition is dissolved or dispersed in an appropriate solvent to prepare a coating solution, which is coated on a support to form a color forming composition layer, whereby an image forming material is produced.
  • an image forming material is used as an image forming material utilizing coloring and curing by infrared image exposure, such as a printed wiring board, a color filter, and a photomask.
  • the color forming composition containing the polymerization initiator and the polymerizable compound can be preferably used as an image recording layer of a lithographic printing plate precursor. That is, the lithographic printing plate precursor according to the invention has an image recording layer containing the color forming composition on a support. In the lithographic printing plate precursor according to the invention, an undercoat layer can be provided between the support and the image recording layer, and a protective layer can be provided on the image recording layer, if necessary.
  • the image recording layer of the lithographic printing plate precursor according to the invention is a reaction product of (A) (a1) a spirooxazine or spiropyran compound having two or more isocyanate groups in the molecule and (a2) a compound having an active hydrogen group. It contains polymer fine particles having a spirooxazine or spiropyran structure, (B) an infrared absorbing dye, (C) a binder polymer, (D) a polymerization initiator, and (E) a polymerizable compound. Since the lithographic printing plate precursor according to the invention contains the specific polymer fine particles, good image visibility is maintained even when the lithographic printing plate precursor is stored over time.
  • spirooxazine or spiropyran compounds are fixed in specific polymer fine particles by urea bonds or urethane bonds, so they are prevented from reacting with other components constituting the image recording layer during storage over time. Further, it is considered that migration from the image recording layer to another layer is also suppressed, and spirooxazine or a spiropyran compound can function efficiently and participate in the color development reaction even after storage over time.
  • the spirooxazine or spiropyran compound is fixed in the specific polymer fine particles, the influence of the polymerization inhibiting action of the spirooxazine or spiropyran compound is suppressed, and as a result, a decrease in printing durability is prevented. It is done.
  • the image recording layer of the lithographic printing plate precursor according to the invention is preferably an image recording layer in which an unexposed portion can be removed by at least one of dampening water and printing ink.
  • the image recording layer of the lithographic printing plate precursor according to the invention may further contain the following components as necessary.
  • the image recording layer may contain a low molecular weight hydrophilic compound in order to improve the on-press developability without reducing the printing durability.
  • a low molecular weight hydrophilic compound for example, as the water-soluble organic compound, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and the like glycols and ether or ester derivatives thereof, glycerin, Polyols such as pentaerythritol and tris (2-hydroxyethyl) isocyanurate, organic amines such as triethanolamine, diethanolamine and monoethanolamine and salts thereof, organic sulfones such as alkylsulfonic acid, toluenesulfonic acid and benzenesulfonic acid Acids and salts thereof, organic sulfamic acids such as alkylsulfamic acid and salts thereof, organic sulfuric acids such as alkyl
  • organic sulfonates include alkyl sulfonates such as sodium n-butyl sulfonate, sodium n-hexyl sulfonate, sodium 2-ethylhexyl sulfonate, sodium cyclohexyl sulfonate, sodium n-octyl sulfonate; Sodium 11-trioxapentadecane-1-sulfonate, sodium 5,8,11-trioxaheptadecane-1-sulfonate, sodium 13-ethyl-5,8,11-trioxaheptadecane-1-sulfonate, Alkyl sulfonates containing ethylene oxide chains such as sodium 5,8,11,14-tetraoxatetracosane-1-sulfonate; sodium benzenesulfonate, sodium p-toluenesulfonate, sodium p-hydroxybenzenesulfonate
  • organic sulfates examples include polyethylene oxide alkyl, alkenyl, alkynyl, aryl, or heterocyclic monoether sulfates.
  • the number of ethylene oxide units is preferably 1 to 4, and the salt is preferably a sodium salt, potassium salt or lithium salt. Specific examples include the compounds described in paragraph numbers [0034] to [0038] of JP-A-2007-276454.
  • betaines compounds in which the hydrocarbon substituent on the nitrogen atom has 1 to 5 carbon atoms are preferable.
  • Specific examples include trimethylammonium acetate, dimethylpropylammonium acetate, 3-hydroxy-4-trimethyl.
  • a low molecular weight hydrophilic compound may be used independently and may be used in mixture of 2 or more types.
  • the amount of the low molecular weight hydrophilic compound added to the image recording layer is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and still more preferably 2 to 2%, based on the total solid content of the image recording layer. 10% by mass. In this range, good on-press developability and printing durability can be obtained.
  • the image-recording layer can contain a oil-sensitizing agent such as a phosphonium compound, a nitrogen-containing low molecular weight compound, or an ammonium group-containing polymer in order to improve the inking property.
  • a oil-sensitizing agent such as a phosphonium compound, a nitrogen-containing low molecular weight compound, or an ammonium group-containing polymer in order to improve the inking property.
  • these compounds function as a surface coating agent for the inorganic stratiform compound, and decrease in the inking property during printing by the inorganic stratiform compound. To prevent.
  • nitrogen-containing low molecular weight compounds examples include amine salts and quaternary ammonium salts. Also included are imidazolinium salts, benzoimidazolinium salts, pyridinium salts, and quinolinium salts. Of these, quaternary ammonium salts and pyridinium salts are preferable.
  • tetramethylammonium hexafluorophosphate
  • tetrabutylammonium hexafluorophosphate
  • dodecyltrimethylammonium p-toluenesulfonate
  • benzyltriethylammonium hexafluorophosphate
  • benzyldimethyloctylammonium hexafluorophosphate.
  • the ammonium group-containing polymer may be any polymer as long as it has an ammonium group in its structure, but is preferably a polymer containing 5 to 80 mol% of (meth) acrylate having an ammonium group in the side chain as a copolymerization component. Specific examples include the polymers described in paragraph numbers [0089] to [0105] of JP2009-208458A.
  • the ammonium salt-containing polymer preferably has a reduced specific viscosity (unit: ml / g) determined by the following measurement method of 5 to 120, more preferably 10 to 110, particularly 15 to 100. preferable.
  • Mw mass average molar mass
  • ⁇ Measurement method of reduced specific viscosity> 1 g of polymer solid content was weighed into a 20 ml volumetric flask and diluted with N-methylpyrrolidone. This solution is allowed to stand for 30 minutes in a constant temperature bath at 30 ° C., placed in an Ubbelohde reduced specific viscosity tube (viscosity constant 0.010 cSt / s), and the time for flowing down at 30 ° C. is measured. The measurement is performed twice with the same sample, and the average value is calculated. Similarly, in the case of a blank (N-methylpyrrolidone only), the reduced specific viscosity (ml / g) was calculated from the following formula.
  • the content of the sensitizer is preferably 0.01 to 30.0% by mass, more preferably 0.1 to 15.0% by mass, and more preferably 1 to 10% by mass with respect to the total solid content of the image recording layer. Further preferred.
  • the image recording layer is prepared by dispersing or dissolving the necessary components described above in a known solvent. It is formed by coating this on a support by a known method such as bar coater coating and drying.
  • the image recording layer coating amount (solid content) on the support obtained after coating and drying varies depending on the application, but is generally preferably 0.3 to 3.0 g / m 2 . Within this range, good sensitivity and good film characteristics of the image recording layer can be obtained.
  • an undercoat layer (sometimes referred to as an intermediate layer) is preferably provided between the image recording layer and the support.
  • the undercoat layer enhances the adhesion between the support and the image recording layer in the exposed area, and easily peels off the image recording layer from the support in the unexposed area. Contributes to improvement.
  • the undercoat layer functions as a heat insulating layer, thereby preventing the heat generated by the exposure from diffusing to the support and reducing the sensitivity.
  • the compound used for the undercoat layer is preferably a compound having an acid group such as phosphonic acid, phosphoric acid or sulfonic acid. Further, an adsorbable group that can be adsorbed on the surface of the support and a compound having a crosslinkable group in order to improve adhesion to the image recording layer are preferred. These compounds may be low molecular weight compounds or polymers. Moreover, you may use these compounds in mixture of 2 or more types as needed.
  • a copolymer of a monomer having an adsorptive group, a monomer having a hydrophilic group, and a monomer having a crosslinkable group is preferable.
  • the adsorptive group that can be adsorbed on the support surface include phenolic hydroxy group, carboxyl group, —PO 3 H 2 , —OPO 3 H 2 , —CONHSO 2 —, —SO 2 NHSO 2 —, —COCH 2 COCH 3 Is preferred.
  • a sulfo group is preferable.
  • the crosslinkable group is preferably a methacryl group or an allyl group.
  • the polymer may have a crosslinkable group introduced by salt formation between a polar substituent of the polymer, a substituent having a counter charge and a compound having an ethylenically unsaturated bond, or a monomer other than the above, preferably May be further copolymerized with a hydrophilic monomer.
  • the phosphorus compound which has a heavy bond reactive group is mentioned suitably.
  • crosslinkable groups described in JP-A-2005-238816, JP-A-2005-125649, JP-A-2006-239867, JP-A-2006-215263, and JP-A-2011-24584 (preferably an ethylenic group) Saturated bonding groups), those containing a low molecular compound or polymer having a functional group interacting with the support surface and a hydrophilic group are also preferably used. More preferably, it has an adsorptive group, a hydrophilic group, and a crosslinkable group that can be adsorbed on the surface of the support described in JP-A No. 2005-125749, JP-A No. 2006-188038, and JP-A No. 2011-245846. Polymers.
  • the content of unsaturated double bonds in the polymer for the undercoat layer is preferably 0.1 to 10.0 mmol, particularly preferably 0.2 to 5.5 mmol, per 1 g of the polymer.
  • the polymer for the undercoat layer preferably has a mass average molar mass of 5000 or more, more preferably 10,000 to 300,000.
  • the undercoat layer according to the present invention includes a chelating agent, a secondary or tertiary amine, a polymerization inhibitor, an amino group, or a functional group having a polymerization inhibitory ability, in addition to the above-mentioned undercoat layer compound, to prevent contamination over time.
  • a compound having a group that interacts with the surface of an aluminum support for example, 1,4-diazabicyclo [2,2,2] octane (DABCO), 2,3,5,6-tetrahydroxy-p-quinone, chloranil
  • DABCO 1,4-diazabicyclo [2,2,2] octane
  • Sulfophthalic acid hydroxyethylethylenediaminetriacetic acid, dihydroxyethylethylenediaminediacetic acid, hydroxyethyliminodiacetic acid, and the like.
  • the undercoat layer is applied by a known method.
  • the coating amount (solid content) of the undercoat layer is preferably 0.1 ⁇ 100mg / m 2, and more preferably 1 ⁇ 30mg / m 2.
  • a known lithographic printing plate precursor support is used as the support for the lithographic printing plate precursor according to the invention.
  • an aluminum plate that has been roughened and anodized by a known method is preferred.
  • the aluminum plate is subjected to micropore enlargement treatment or sealing treatment of an anodized film described in JP-A-2001-253181 or JP-A-2001-322365, and US Pat. 714,066, 3,181,461, 3,280,734 and 3,902,734, or alkali metal silicates as described in U.S. Pat.
  • the support preferably has a center line average roughness of 0.10 to 1.2 ⁇ m.
  • the support used in the lithographic printing plate precursor is provided with an organic polymer compound described in JP-A-5-45885 on the back surface, and silicon described in JP-A-6-35174.
  • a backcoat layer containing an alkoxy compound can be provided.
  • a protective layer (sometimes referred to as an overcoat layer) is preferably provided on the image recording layer.
  • the protective layer has a function of preventing scratches in the image recording layer and preventing ablation during high-illuminance laser exposure.
  • the protective layer can be formed of two or more layers.
  • the protective layer may have a two-layer structure including an upper protective layer and a lower protective layer.
  • the protective layer having such characteristics is described in, for example, US Pat. No. 3,458,311 and Japanese Patent Publication No. 55-49729.
  • the low oxygen permeability polymer used for the protective layer either a water-soluble polymer or a water-insoluble polymer can be appropriately selected and used, and two or more types can be mixed and used as necessary. it can.
  • Specific examples of the polymer include polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble cellulose derivatives, poly (meth) acrylonitrile, and the like.
  • modified polyvinyl alcohol acid-modified polyvinyl alcohol having a carboxy group or a sulfo group is preferably used.
  • modified polyvinyl alcohols described in JP-A-2005-250216 and JP-A-2006-259137 are preferable.
  • a hydrophilic polymer having at least a repeating unit represented by the general formula (1) and a repeating unit represented by the general formula (2) described in JP 2012-73597 A should be used. Can do.
  • it preferably contains a hydrophilic polymer having repeating units represented by the following general formulas (3) and (4) (hereinafter also referred to as a specific hydrophilic polymer (e)).
  • R 1 and R 4 each independently represent a hydrogen atom or a methyl group.
  • R 2 and R 3 each independently represents a hydrogen atom, a methyl group or an ethyl group.
  • R 5 represents a linear, branched or cyclic unsubstituted alkyl group having 2 to 8 carbon atoms, a substituted alkyl group, or a substituent represented by the following general formula (5). Examples of the substituent that can be introduced into the substituted alkyl group include an aromatic ring group, a heterocyclic group, and a polyether group.
  • L represents an alkylene group having 2 to 6 carbon atoms
  • R 6 represents a linear, branched or cyclic unsubstituted alkyl group having 4 to 8 carbon atoms or an aromatic substituted alkyl group.
  • n is the average number of moles of polyether added and represents a number of 2 to 4. It is preferable that R 2 and R 3 of the repeating unit represented by the general formula (3) are both hydrogen atoms.
  • R 5 of the repeating unit represented by the general formula (4) is preferably a linear, branched or cyclic unsubstituted alkyl group having 2 to 8 carbon atoms.
  • R 1 and R 4 in the general formula (3) and the general formula (4) are both hydrogen atoms
  • the general formula ( Most preferred is a combination in which R 2 and R 3 in 3) are both hydrogen atoms
  • R 5 in formula (4) is a branched and unsubstituted alkyl group having 4 carbon atoms.
  • the specific hydrophilic polymer (e) is preferably a hydrophilic polymer having a repeating unit represented by the following general formula (6).
  • R 7 represents a hydrogen atom or a methyl group.
  • X is a single bond, a divalent linking group selected from the structures shown in the following structural group (1), or a divalent linking group formed by combining a plurality of selected from the structures shown in the structural group (1).
  • Y is a carboxylic acid group, a carboxylic acid group, a sulfonic acid group, a sulfonic acid group, a phosphoric acid group, a phosphoric acid group, a phosphonic acid group, a phosphonic acid group, a hydroxyl group, a carboxybetaine group, a sulfobetaine group, an ammonium group, or Represents a polyether group represented by the following general formula (7).
  • Y is preferably a sulfonic acid group, a sulfonic acid group, a carboxybetaine group, a sulfobetaine group, or an ammonium group from the viewpoint of water solubility and on-press development property. More preferred are groups, sulfonate groups and sulfobetaine groups.
  • X is preferably a linking group containing any of divalent linking chains selected from the structural group (1).
  • L ′ represents an alkylene group having 2 to 3 carbon atoms
  • R 8 represents a hydrogen atom or a methyl group
  • n ′ is an average added mole number of the polyether and is a number of 2 to 4.
  • the monomer derived from the repeating unit represented by the general formula (3) include acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N , N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, N-diethylmethacrylamide, N, N-ethylmethylacrylamide, N, N-ethylmethylmethacrylamide.
  • the monomer derived from the repeating unit represented by the general formula (4) include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, i-butyl acrylate, T-butyl acrylate, pentyl acrylate, hexyl acrylate, cyclohexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, 2- (2-ethylhexyloxyethoxy) ) Ethyl, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, pentyl methacrylate,
  • the repeating unit represented by the general formula (3) preferably contains 65 to 96.7 mol%, more preferably 70 to 80 mol%, and particularly preferably 74 to 80 mol%.
  • the repeating unit represented by the general formula (4) preferably contains 3 to 30 mol%, more preferably 20 to 30 mol%, particularly preferably 20 to 26 mol%.
  • the monomer derived from the repeating unit represented by the general formula (6) include 2-acryloylamino-2-methyl-propanesulfonic acid, sodium 2-acryloylamino-2-methyl-propanesulfonate, -Potassium acryloylamino-2-methyl-propanesulfonate, 4-((3-methacrylamidopropyl) dimethylammonio) butane-1-sulfonate, 4-((3-acrylamidopropyl) dimethylammonio) butane-1- Sulfonate, vinyl alcohol, acrylic acid, methacrylic acid, sodium styrene sulfonate, diethylene glycol monomethyl ether methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, methacrylcholine chloride, 3-sulfomethacrylate Ropirukariumu, 2- phosphate (methacryloyloxy) ethyl, dimethyl -N
  • the specific hydrophilic polymer (e) preferably contains 0.3 mol% to 5 mol% of the repeating unit represented by the general formula (6), more preferably contains 0.3 to 3 mol%, Those containing 0.3 mol% to 1.5 mol% are more preferable.
  • the specific hydrophilic polymer (e) contains the repeating unit represented by the general formula (6) in the above preferable range, the lithographic printing plate precursor has better on-press developability, inking property and printing durability. Indicates.
  • the mass average molecular weight (Mw) of the specific hydrophilic polymer (e) as a polystyrene equivalent value by GPC method is preferably 10,000 to 200,000, more preferably 10,000 to 100,000, and 10,000 to 30. Is particularly preferred.
  • the content of the specific hydrophilic polymer (e) in the protective layer is preferably 40% by mass or more, more preferably 60% by mass or more, and particularly preferably 80% by mass or more of the solid content of the protective layer. Within this range, it is possible to obtain a lithographic printing plate precursor that provides a lithographic printing plate that is superior in on-press developability, has better inking properties, and has higher printing durability.
  • the protective layer can contain an inorganic layered compound such as natural mica and synthetic mica described in JP-A-2005-119273.
  • the protective layer is applied by a known method described in, for example, US Pat. No. 3,458,311 and JP-A-55-49729.
  • the coating amount of the protective layer is a coating amount after drying is preferably 0.01 ⁇ 10g / m 2, more preferably 0.02 ⁇ 3g / m 2, particularly preferably 0.02 ⁇ 1g / m 2.
  • the plate making method of the lithographic printing plate precursor according to the present invention comprises at least a step of image-exposing the lithographic printing plate precursor (hereinafter also referred to as “exposure step”) and a step of developing with a processing liquid (hereinafter referred to as “development step”). Also called).
  • the lithographic printing plate precursor according to the invention is exposed using a light source having a wavelength of 750 nm to 1400 nm.
  • a light source having a wavelength of 750 nm to 1400 nm.
  • a solid-state laser and a semiconductor laser emitting infrared rays are preferable, and a scanning exposure method using these infrared lasers is particularly preferable.
  • the exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like.
  • An image-exposed lithographic printing plate precursor is developed with water or a developer having a pH of 2 to 14 (developer treatment), or developed with at least one of oil-based ink and aqueous component on a printing press (on-press development). ).
  • Developer treatment is usually performed in the following steps. (1) Remove non-image area with developer, (2) Implement gum solution treatment, (3) Dry in drying step.
  • the lithographic printing plate precursor according to the invention can be developed by the usual steps (normal development), but the steps (1) and (2) are preferably carried out simultaneously (simple development). In any development method, a water washing step for removing the protective layer may be performed before the step (1).
  • the development in the step (1) is carried out according to a conventional method at a temperature of 0 to 60 ° C., preferably about 15 to 40 ° C., for example, by immersing an image-exposed lithographic printing plate precursor in a developer and rubbing with a brush, spraying By a method of spraying a developer and rubbing with a brush.
  • a water washing step for removing excess developer may be inserted between step (1) and step (2).
  • a well-known alkali developing solution as a developing solution used for a process (1).
  • the developer used in simple development is an aqueous solution having a pH of 2 to 11.
  • An aqueous solution containing water as a main component containing 60% by mass or more of water
  • an aqueous solution containing a surfactant anionic, nonionic, cationic, amphoteric ion, etc.
  • An aqueous solution containing is preferred.
  • An aqueous solution containing both a surfactant and a water-soluble polymer compound is also preferred.
  • the pH of the developer is more preferably 5 to 10.7, still more preferably 6 to 10.5, and particularly preferably 7.5 to 10.3.
  • the entire surface may be heated before exposure, during exposure, and between exposure and development, if necessary.
  • an image forming reaction in the image recording layer is promoted, and advantages such as improvement in sensitivity and printing durability and stabilization of sensitivity may occur.
  • the heating before development is usually preferably performed under mild conditions of 150 ° C. or lower. If the temperature is too high, problems such as curing of the unexposed area may occur. Very strong conditions are used for heating after development. Usually, it is in the range of 100 to 500 ° C. If the temperature is low, sufficient image reinforcing action cannot be obtained. If the temperature is too high, problems such as deterioration of the support and thermal decomposition of the image area may occur.
  • On-press development includes a step of supplying oil-based ink and aqueous component on a printing press without performing any development processing on the lithographic printing plate precursor after image exposure, and in the course of the printing step. An unexposed portion of the planographic printing plate precursor is removed. Image exposure may be performed on the printing machine after the planographic printing plate precursor is mounted on the printing machine, or may be separately performed using a plate setter or the like. In the latter case, the exposed lithographic printing plate precursor is mounted on the printing machine as it is without undergoing development processing.
  • printing is performed by supplying oil-based ink and water-based components using a printing machine, so that the on-press development process, that is, the image recording layer in the unexposed area is removed in the initial stage of printing, and accordingly, hydrophilicity is removed.
  • the surface of the conductive support is exposed to form a non-image part.
  • oil-based ink and the aqueous component ordinary lithographic printing ink and fountain solution are used.
  • the fountain solution or printing ink may be supplied to the printing plate first, but the printing ink should be supplied first in order to prevent the fountain solution from being contaminated by the removed image recording layer components. Is preferred.
  • the lithographic printing plate precursor according to the invention is developed on the machine on an offset printing machine and used as it is for printing a large number of sheets.
  • the molecular weight is a mass average molar mass (Mw) in terms of polystyrene converted by the GPC method, and the ratio of repeating units is a mole percentage.
  • the color forming composition coating solution (1) or (2) having the following composition was bar coated on the following support A, and then oven-dried at 100 ° C. for 60 seconds to produce a color developing property of a dry coating amount of 1.0 g / m 2 .
  • a composition layer was formed.
  • the coloring composition coating solution (1) was prepared by mixing and stirring the following photosensitive solution S1 and polymer fine particle solution P1 immediately before coating.
  • the coloring composition coating solution (2) was prepared by mixing and stirring the following photosensitive solution S2 and the polymer fine particle solution P1 immediately before coating.
  • Etching was performed by immersing the aluminum plate in a 25 mass% sodium hydroxide aqueous solution at 45 ° C for 9 seconds, washing with water, and further immersed in a 20 mass% nitric acid aqueous solution at 60 ° C for 20 seconds, followed by washing with water. At this time, the etching amount of the grained surface was about 3 g / m 2 .
  • the electrolytic solution was a 1% by mass nitric acid aqueous solution (containing 0.5% by mass of aluminum ions) and a liquid temperature of 50 ° C.
  • the AC power source waveform is electrochemical roughening treatment using a trapezoidal rectangular wave alternating current with a time ratio TP of 0.8 msec until the current value reaches a peak from zero, a duty ratio of 1: 1, and a trapezoidal rectangular wave alternating current. Went. Ferrite was used for the auxiliary anode.
  • the current density was 30 A / dm 2 at the peak current value, and 5% of the current flowing from the power source was shunted to the auxiliary anode.
  • the amount of electricity in nitric acid electrolysis was 175 C / dm 2 when the aluminum plate was the anode. Then, water washing by spraying was performed.
  • nitric acid electrolysis was performed with an aqueous solution of 0.5% by mass of hydrochloric acid (containing 0.5% by mass of aluminum ions) and an electrolytic solution having a liquid temperature of 50 ° C. under the condition of an electric quantity of 50 C / dm 2 when the aluminum plate was the anode.
  • Electrochemical surface roughening treatment was carried out in the same manner as above, followed by washing with water by spraying.
  • a 2.5 g / m 2 direct current anodic oxide film with a current density of 15 A / dm 2 is provided on an aluminum plate as an electrolyte using a 15 mass% sulfuric acid aqueous solution (containing 0.5 mass% of aluminum ions), and then washed with water.
  • the support A was prepared by drying.
  • Distilled water 50 g was added to the oil phase component as an aqueous phase component, mixed, and emulsified at 12,000 rpm for 10 minutes using a homogenizer.
  • the obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours.
  • the polymer fine particle liquid thus obtained was diluted with distilled water so that the solid content concentration was 15% by mass to obtain polymer fine particles SO MGR.
  • the average particle diameter of the polymer fine particles measured by the light scattering method was 0.25 ⁇ m.
  • Distilled water 50 g was added to the oil phase component as an aqueous phase component, mixed, and emulsified at 12,000 rpm for 10 minutes using a homogenizer.
  • the obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours.
  • the polymer fine particle liquid thus obtained was diluted with distilled water so that the solid content concentration was 15% by mass to obtain polymer fine particle SO-IR MGR.
  • the average particle diameter of the polymer fine particles measured by the light scattering method was 0.25 ⁇ m.
  • microgel 1 As oil phase components, trimethylolpropane and xylene diisocyanate adduct (Mitsui Chemicals, Takenate D-110N) 10 g, pentaerythritol triacrylate (Nippon Kayaku Co., Ltd.) SR444) 3.15 g, and alkylbenzene sulfonate (manufactured by Takemoto Yushi Co., Ltd., Pionein A-41C) 0.1 g were dissolved in ethyl acetate 16 g.
  • trimethylolpropane and xylene diisocyanate adduct Mitsubishi Chemicals, Takenate D-110N
  • pentaerythritol triacrylate Nippon Kayaku Co., Ltd.
  • alkylbenzene sulfonate manufactured by Takemoto Yushi Co., Ltd., Pionein A-41C
  • aqueous phase component 40 g of a 4% by mass aqueous solution of polyvinyl alcohol (PVA-205 manufactured by Kuraray Co., Ltd.) was prepared. The oil phase component and the aqueous phase component were mixed and emulsified for 10 minutes at 12,000 rpm using a homogenizer. The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours. The polymer fine particle liquid thus obtained was diluted with distilled water to a solid content concentration of 15% by mass to obtain microgel 1. The average particle diameter of the polymer fine particles measured by the light scattering method was 0.25 ⁇ m.
  • the measurement was performed by the SCE (regular reflected light removal) method using a spectrocolorimeter CM2600d manufactured by KONICA-MINOLTA and operation software CM-S100W.
  • SCE regular reflected light removal
  • CM2600d manufactured by KONICA-MINOLTA
  • CM-S100W operation software
  • an undercoat layer coating solution having the following composition was applied so that the dry coating amount was 20 mg / m 2 to prepare a support having an undercoat layer.
  • An image recording layer coating solution having the following composition was bar coated on the undercoat layer, and then oven-dried at 100 ° C. for 60 seconds to form an image recording layer having a dry coating amount of 1.0 g / m 2 .
  • the image recording layer coating solution was prepared by mixing and stirring the following photosensitive solution and polymer fine particle solution immediately before coating.
  • Binder polymer 1 [above] 0.240 g Infrared absorbing dye IR-10 [above] 0.020 g ⁇ Polymerization initiator 1 [above] 0.2 g ⁇ Borate compound (TPB) [above] 0.020 g ⁇ Polymerizable monomer 0.192g Tris (acryloyloxyethyl) isocyanurate (NK ester A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.) ⁇ Low molecular weight hydrophilic compound 0.062g Tris (2-hydroxyethyl) isocyanurate ⁇ Low molecular weight hydrophilic compound (1) [below] 0.050 g -Sensitizer Phosphonium compound (1) [below] 0.055 g ⁇ Fat Sensitizer 0.018g Benzyl-dimethyl-octylammonium PF 6 salt -Sensitizing agent Ammonium group-containing polymer [below] 0.035 g
  • the structures of the fluorosurfactant (1), the low molecular weight hydrophilic compound (1), the phosphonium compound (1) and the ammonium group-containing polymer used in the image recording layer coating solution are as follows.
  • a protective layer coating solution having the following composition was bar-coated, followed by oven drying at 120 ° C. for 60 seconds to form a protective layer having a dry coating amount of 0.15 g / m 2. Was made.
  • Inorganic layered compound dispersion (1) 1.5 g -Polyvinyl alcohol (Nippon Synthetic Chemical Industry Co., Ltd. CKS50, sulfonic acid modification, Saponification degree 99 mol% or more, polymerization degree 300) 6% by mass aqueous solution 0.55 g ⁇ Polyvinyl alcohol (PVA-405 manufactured by Kuraray Co., Ltd.) Degree of saponification 81.5 mol%, degree of polymerization 500) 6% by weight aqueous solution 0.03 g 0.86 g of polyoxyethylene lauryl ether (surfactant EMALEX 710 1 mass% aqueous solution manufactured by Nippon Emulsion Co., Ltd.) ⁇ Ion-exchanged water 6.0g
  • lithographic printing plate precursor was evaluated for visibility, visibility after time, on-press developability and printing durability as follows.
  • the lithographic printing plate precursor was exposed with a Trendsetter 3244VX manufactured by Creo equipped with a water-cooled 40 W infrared semiconductor laser under the conditions of an output of 11.7 W, an outer drum rotational speed of 250 rpm, and a resolution of 2400 dpi.
  • the exposed lithographic printing plate precursor was allowed to stand for 2 hours in a dark place at 25 ° C. and in an atmosphere with a relative humidity of 50%, and then the visibility was evaluated. Visibility was evaluated by the difference ⁇ L between the L value of the exposed area and the L value of the unexposed area using the L value (brightness) of the L * a * b * color system. It means that visibility is excellent, so that the value of (DELTA) L is large.
  • the measurement was performed by the SCE (regular reflected light removal) method using a spectrocolorimeter CM2600d manufactured by KONICA-MINOLTA and operation software CM-S100W.
  • SCE regular reflected light removal
  • CM2600d manufactured by KONICA-MINOLTA
  • CM-S100W operation software
  • the planographic printing plate precursor was stored in an oven at 60 ° C. for 2.5 days, and after aging, it was output on a Trendsetter 3244VX manufactured by Creo equipped with a water-cooled 40 W infrared semiconductor laser. The exposure was performed under conditions of a rotational speed of 250 rpm and a resolution of 2400 dpi. The exposed lithographic printing plate precursor was allowed to stand for 2 hours in a dark place at 25 ° C. and in an atmosphere with a relative humidity of 50%, and then the visibility was evaluated. The evaluation of visibility was performed by the method described in (1) Visibility. The results are shown in Table 3.
  • the lithographic printing plate precursor was stored in an oven at 60 ° C. for 2.5 days, and after a lapse of time, the external drum rotation speed was measured with a Luxel PLANETTER T-6000III equipped with an infrared semiconductor laser. The exposure was performed under the conditions of 1000 rpm, laser output 70%, and resolution 2400 dpi. The exposure image included a solid image and a 50% halftone dot chart of a 20 ⁇ m dot FM screen.
  • the exposed lithographic printing plate precursor was mounted on the plate cylinder of a printing machine LITHRONE 26 manufactured by Komori Corporation without developing.
  • On-press development was evaluated as the on-press developability of the number of print sheets required until the on-press development of the unexposed portion of the image recording layer was completed on the printing press and no ink was transferred to the non-image portion. The results are shown in Table 3.
  • the lithographic printing plate precursor having an image recording layer containing the color forming composition containing the specific polymer fine particles of the present invention is a polymer containing a spirooxazine compound having one isocyanate group instead of the specific polymer fine particles.
  • the color is very high and the visibility is extremely excellent.
  • the excellent visibility of the lithographic printing plate precursor according to the present invention is maintained very well even when it is stored over time after infrared exposure.
  • excellent characteristics can be obtained by slight differences in structure, and the effect of the specific polymer fine particles of the present invention is extremely specific and unexpected.
  • the present invention it is possible to provide a color-forming composition that has high color development and is suppressed from fading over time.
  • a reduction in image visibility (plate inspection) is suppressed, and in particular, a decrease in image visibility is suppressed over time after exposure, and lithographic printing with excellent printing durability
  • An original version can be provided.
  • deterioration in image visibility (plate inspection) is suppressed, and in particular, deterioration in image visibility is suppressed over time after exposure, and printing durability when stored over time.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)

Abstract

La présente invention concerne une composition de révélation des couleurs comprenant (A) des microparticules de polymère ayant chacune une structure spirooxazine ou spiropyrane, (B) un colorant absorbant le rayonnement infrarouge et (C) un liant polymère, où les microparticules de polymère (A) sont un produit de la réaction de (a1) un composé spirooxazine ou spiropyrane ayant au moins deux groupes isocyanate dans la molécule avec (a2) un composé comprenant un groupe à hydrogène actif. L'invention concerne également un précurseur de plaque d'impression lithographique, dans lequel la composition de révélation des couleurs est utilisée dans une couche d'enregistrement d'image. Est divulguée une composition de révélation des couleurs apte à révéler les couleurs à un niveau élevé et qui ne subit pas de décoloration dans le temps. Est également divulgué un précurseur de plaque d'impression lithographique ne subissant pas de détérioration de la visibilité d'une image (c'est-à-dire de l'aptitude à l'inspection des données de l'image) même après un stockage prolongé; en particulier ledit précurseur ne subit pas la détérioration de visibilité d'une image dans le temps après avoir été exposé à la lumière, et il offre une excellente durabilité d'impression. L'invention concerne également : un précurseur de plaque d'impression lithographique développable sur presse qui ne subit pas la détérioration de la visibilité d'une image (c'est-à-dire de l'aptitude à l'inspection des données de l'image) même après un stockage prolongé, qui en particulier ne subit pas la détérioration de visibilité d'une image dans le temps après avoir été exposé à la lumière, ne subit pas la détérioration de durabilité de l'impression même après un stockage prolongé et présente une excellente aptitude à la révélation sur presse; et un procédé de production du précurseur de plaque d'impression lithographique développable sur presse.
PCT/JP2014/077051 2013-10-30 2014-10-09 Composition de révélation des couleurs, précurseur de plaque d'impression lithographique et procédé pour le fabriquer WO2015064331A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013226040 2013-10-30
JP2013-226040 2013-10-30

Publications (1)

Publication Number Publication Date
WO2015064331A1 true WO2015064331A1 (fr) 2015-05-07

Family

ID=53003942

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/077051 WO2015064331A1 (fr) 2013-10-30 2014-10-09 Composition de révélation des couleurs, précurseur de plaque d'impression lithographique et procédé pour le fabriquer

Country Status (1)

Country Link
WO (1) WO2015064331A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106832213A (zh) * 2017-02-21 2017-06-13 东莞市雄林新材料科技股份有限公司 一种光敏型tpu薄膜及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4705817B2 (ja) * 2004-07-27 2011-06-22 富士フイルム株式会社 平版印刷版原版および平版印刷方法
JP2011213114A (ja) * 2010-03-19 2011-10-27 Fujifilm Corp 発色感光性組成物、平版印刷版原版及びその製版方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4705817B2 (ja) * 2004-07-27 2011-06-22 富士フイルム株式会社 平版印刷版原版および平版印刷方法
JP2011213114A (ja) * 2010-03-19 2011-10-27 Fujifilm Corp 発色感光性組成物、平版印刷版原版及びその製版方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CORISSA K. LEE: "Exploiting force sensitive spiropyrans as molecular level probes", MACROMOLECULES, vol. 46, no. 10, 28 May 2013 (2013-05-28), pages 3746 - 3752 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106832213A (zh) * 2017-02-21 2017-06-13 东莞市雄林新材料科技股份有限公司 一种光敏型tpu薄膜及其制备方法

Similar Documents

Publication Publication Date Title
JP5205505B2 (ja) 平版印刷版原版及びその平版印刷方法
JP5645743B2 (ja) 平版印刷版原版、その製版方法、及び、多価イソシアネート化合物
JP5828045B2 (ja) 平版印刷版原版及び製版方法
JP5894905B2 (ja) 新聞印刷用平版印刷版原版及びその製造方法、並びに平版印刷版の製版方法
JP5581250B2 (ja) 発色感光性組成物、平版印刷版原版及びその製版方法
JP5786099B2 (ja) 平版印刷版原版及び平版印刷版の製版方法
WO2018043259A1 (fr) Composition colorante, précurseur de plaque d'impression lithographique, procédé de production de plaque d'impression lithographique, et composé
JP6832427B2 (ja) 平版印刷版原版、及び平版印刷版の作製方法
JP5789448B2 (ja) 平版印刷版原版及びその製版方法
JP5537980B2 (ja) 平版印刷版原版及びその製版方法
JP5651554B2 (ja) 機上現像型平版印刷版原版及びそれを用いる製版方法
JP5244987B2 (ja) 平版印刷版原版及びその製版方法
JP5448882B2 (ja) 平版印刷版原版及びその製版方法
JP5757732B2 (ja) マイクロカプセルを用いた平版印刷版原版及び製版方法
WO2014192509A1 (fr) Liquide de traitement et procédé de traitement pour une plaque originale d'impression lithographique
JP2012176606A (ja) 平版印刷版原版及びその製版方法
WO2018043150A1 (fr) Composition colorante, plaque maîtresse d'impression planographique, procédé de fabrication de plaque d'impression planographique, et composé
JP2011073370A (ja) 平版印刷版原版、及びその製版方法
JP2013052515A (ja) 平版印刷版原版及びその製版方法
JP5183598B2 (ja) 平版印刷版原版
WO2015064331A1 (fr) Composition de révélation des couleurs, précurseur de plaque d'impression lithographique et procédé pour le fabriquer
JP2017047564A (ja) 平版印刷版原版、及び、平版印刷版の製版方法
WO2016121667A1 (fr) Composition colorante, précurseur de plaque d'impression lithographique, procédé de production de plaque d'impression lithographique, et agent colorant
JP5453023B2 (ja) 印刷用湿し水及び平版印刷版の印刷方法
JP5277026B2 (ja) 平版印刷版原版及びその製版方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14857229

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14857229

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP