WO2018043150A1 - Composition colorante, plaque maîtresse d'impression planographique, procédé de fabrication de plaque d'impression planographique, et composé - Google Patents

Composition colorante, plaque maîtresse d'impression planographique, procédé de fabrication de plaque d'impression planographique, et composé Download PDF

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Publication number
WO2018043150A1
WO2018043150A1 PCT/JP2017/029546 JP2017029546W WO2018043150A1 WO 2018043150 A1 WO2018043150 A1 WO 2018043150A1 JP 2017029546 W JP2017029546 W JP 2017029546W WO 2018043150 A1 WO2018043150 A1 WO 2018043150A1
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group
formula
atom
ring structure
compound
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PCT/JP2017/029546
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English (en)
Japanese (ja)
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健太 牛島
洋平 石地
和朗 榎本
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富士フイルム株式会社
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Publication of WO2018043150A1 publication Critical patent/WO2018043150A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • B41C1/1016—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/02—Cover layers; Protective layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/12—Location, type or constituents of the non-imaging layers in lithographic printing formes characterised by non-macromolecular organic compounds
    • 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

Definitions

  • the present disclosure relates to a coloring composition, a lithographic printing plate precursor, a method for preparing a lithographic printing plate, and a compound.
  • a lithographic printing plate is composed of an oleophilic image area that receives ink and a hydrophilic non-image area that receives dampening water in the printing process.
  • Lithographic printing utilizes the property that water and oil-based ink repel each other, so that the oleophilic image area of the lithographic printing plate is dampened with the ink receiving area and the hydrophilic non-image area is dampened with the water receiving area (ink non-receiving area). ), A difference in ink adhesion is caused on the surface of the lithographic printing plate, the ink is applied only to the image area, and then the ink is transferred to a printing medium such as paper for printing.
  • image exposure is performed by CTP (computer to plate) technology. That is, the image exposure is performed by scanning exposure or the like directly on the lithographic printing plate precursor using a laser or a laser diode without using a lith film.
  • CTP computer to plate
  • On-press development is a method in which, after image exposure of a lithographic printing plate precursor, conventional development processing is not carried out, but it is directly attached to a printing press and the non-image area of the image recording layer is removed at the initial stage of the normal printing process .
  • an operation is performed to inspect and identify an image on the lithographic printing plate to check whether the image is recorded as intended.
  • a lithographic printing plate precursor with a normal development processing step generally gives a colored image by coloring the image recording layer and developing it, so that the image can be easily confirmed before attaching the printing plate to the printing press. it can.
  • an on-press development type or non-processing (no development) type lithographic printing plate precursor that does not involve a normal development processing step, an image on the lithographic printing plate precursor is confirmed at the stage of attaching the lithographic printing plate precursor to the printing press. It is difficult to perform plate inspection sufficiently.
  • on-machine development type or non-processed (no development) type lithographic printing plate precursor is formed with a means for confirming an image at the stage of exposure, that is, a so-called printout image in which the exposed area is colored or erased is formed. Is required. Furthermore, from the viewpoint of improving workability, it is also important to maintain the color developed or erased exposure area after the passage of time.
  • Patent Document 1 or 2 As conventional techniques, those described in Patent Document 1 or 2 are known.
  • the problem to be solved by one embodiment of the present invention is to provide a coloring composition having excellent coloring properties.
  • the problem to be solved by another embodiment of the present invention is to provide a lithographic printing plate precursor excellent in plate inspection by color development and a method for preparing a lithographic printing plate using the lithographic printing plate precursor.
  • Another problem to be solved by another embodiment of the present invention is to provide a novel compound that can be suitably used as a color former.
  • a coloring composition comprising a compound represented by the following formula 1.
  • A represents a ring structure containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom
  • a + represents a ring structure containing N + , O + or S +
  • Each X independently represents a carbon atom or a nitrogen atom, and at least one of X is a nitrogen atom, and when X is a nitrogen atom, R 1 , R 2 or R 3 bonded to the nitrogen atom is present
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxy group, alkoxycarbonyl group, acyloxy group, an amino group, a urethane group, a urea group, an amide group, a nitrile group or an imino group, the 2 or more of R 1 ⁇ R 3 may form a ring structure
  • A represents a ring structure containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom
  • Ar represents a ring structure containing N + , O + or S +
  • L represents —CH 2 —, —CHR a —, —C (R a ) 2 —, —NR a —, —O— or —S—
  • each R a independently represents a hydrocarbon group
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxy group, alkoxycarbonyl group, acyloxy group, amino group
  • urethane representss a group, a urea group, an amide group, a nitrile group or an imino group, and two or more R 1 to R 3 may combine to form
  • A represents a ring structure containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, one of the two A 1 represents N + , and the other represents a carbon atom.
  • L represents —CH 2 —, —CHR a —, —C (R a ) 2 —, —NR a —, —O— or —S—, and each R a independently represents a hydrocarbon group.
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxy group, alkoxycarbonyl group, acyloxy group, amino group Represents a group, a urethane group, a urea group, an amide group, a nitrile group or an imino group, and two or more R 1 to R 3 may combine to form a ring structure, and one or more of R 1 to R 3 and A , L or one or more R 4 to R 7 may combine with each other to form a ring structure, and R 4 to R 7 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, Represents a hydroxy group, an alkoxycarbon
  • A represents a ring structure containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, one of the two A 1 represents N + , and the other represents a carbon atom.
  • L represents —CH 2 —, —CHR a —, —C (R a ) 2 —, —NR a —, —O— or —S—, and each R a independently represents a hydrocarbon group.
  • R 4 to R 14 are each independently a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxy group, alkoxycarbonyl group, acyloxy group, amino group, urethane Group, urea group, amide group, nitrile group, imino group, carboxylic acid group, sulfonic acid group or phosphoric acid group, and two or more R 4 to R 14 may be bonded to form a ring structure. or more of R 4 ⁇ 14 and the A or L may form a ring structure, Z is a counter ion for neutralizing a charge.
  • R 15 represents a hydrocarbon group
  • R 16 each independently represents a group represented by the following Formula 6, a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group
  • a hydrogen atom represents a hydrocarbon group
  • an alkoxy group represents a hydrocarbon group
  • an aryloxy group represents an alkylthio group
  • an arylthio group Represents an acyl group, a hydroxy group, an alkoxycarbonyl group, an acyloxy group, an amino group, a urethane group, a urea group, an amide group, a nitrile group, or an imino group
  • at least one of R 16 is represented by the following formula 6.
  • R 15 represents a hydrocarbon group
  • R 16 each independently represents a group represented by the following Formula 6, a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group
  • a hydrogen atom represents a hydrocarbon group
  • an alkoxy group represents a hydrocarbon group
  • an aryloxy group represents an alkylthio group
  • an arylthio group Represents an acyl group, a hydroxy group, an alkoxycarbonyl group, an acyloxy group, an amino group, a urethane group, a urea group, an amide group, a nitrile group, or an imino group
  • at least one of R 16 is represented by the following formula 6.
  • ⁇ 8> The color forming composition according to any one of ⁇ 1> to ⁇ 7>, further including a polymer.
  • ⁇ 9> The color forming composition according to any one of ⁇ 1> to ⁇ 8>, further including a polymerization initiator and a polymerizable compound.
  • a lithographic printing plate precursor having at least one layer containing the color forming composition according to any one of the above ⁇ 1> to ⁇ 10> on a support.
  • A represents a ring structure containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom
  • a + represents a ring structure containing N + , O + or S +
  • Each X independently represents a carbon atom or a nitrogen atom, and at least one of X is a nitrogen atom, and when X is a nitrogen atom, R 1 , R 2 or R 3 bonded to the nitrogen atom is present
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxy group, alkoxycarbonyl group, acyloxy group, an amino group, a urethane group, a urea group, an amide group, a nitrile group or an imino group, the 2 or more of R 1 ⁇ R 3 may form a ring structure
  • a color forming composition having excellent color developability.
  • a lithographic printing plate precursor having excellent plate inspection property by color development and a method for preparing a lithographic printing plate using the lithographic printing plate precursor.
  • a novel compound that can be suitably used as a color former can be provided.
  • xx to yy represents a numerical range including xx and yy.
  • (meth) acryl represents both and / or acryl and methacryl
  • (meth) acrylate” represents both and / or acrylate and methacrylate.
  • mass% and wt% are synonymous, and “part by mass” and “part by weight” are synonymous.
  • the combination of two or more preferable aspects is a more preferable aspect.
  • the above group when there is no substitution or no substitution, the above group can further have a substituent unless otherwise specified.
  • a group having a substituent is also included.
  • R represents an alkyl group, an aryl group or a heterocyclic group
  • R is an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, a substituted aryl group, an unsubstituted group” Represents a heterocyclic group or a substituted heterocyclic group.
  • the term “process” is not only an independent process, but is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
  • the color forming composition according to the present disclosure includes a compound represented by Formula 1. Moreover, the coloring composition according to the present disclosure can be suitably used as a heat-sensitive, infrared-sensitive, or heat-sensitive and infrared-sensitive coloring composition. Furthermore, the color forming composition according to the present disclosure can be suitably used for producing an image recording layer, a protective layer, or both an image recording layer and a protective layer of a lithographic printing plate precursor.
  • A represents a ring structure containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom
  • a + represents a ring structure containing N + , O + or S +
  • Each X independently represents a carbon atom or a nitrogen atom, and at least one of X is a nitrogen atom, and when X is a nitrogen atom, R 1 , R 2 or R 3 bonded to the nitrogen atom is present
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxy group, alkoxycarbonyl group, acyloxy group, an amino group, a urethane group, a urea group, an amide group, a nitrile group or an imino group, the 2 or more of R 1 ⁇ R 3 may form a ring structure
  • the compound represented by Formula 1 is a compound that is denatured or decomposed by exposure to heat or infrared rays to generate a color-forming compound.
  • color development means that there is almost no absorption in the visible light region (400 or more and less than 750 nm) before heating or infrared exposure, and there is a strong coloring after heating or infrared exposure, or the absorption becomes shorter in wavelength and visible light. Indicates that the region has absorption.
  • the infrared ray in the present disclosure has a wavelength of 750 nm to 1 mm, and preferably a wavelength of 750 nm to 1,400 nm.
  • N + , O + or S + cation structure in the conjugated chain so that N + in A + of Formula 1 is exposed by thermal or infrared exposure.
  • O + or S + in the vicinity of the chemical structure is denatured or decomposed, and the length of the conjugated chain between A + to A in Formula 1 and the electronic state change, whereby the absorption wavelength changes and the color develops.
  • the inventors have estimated.
  • the compound represented by Formula 1 has a decomposable group which couple
  • the decomposable group not only the coloring mechanism in the vicinity of the N + , O + or S + , but also the structure of the heteroatom by the decomposition of the decomposable group by heat or infrared exposure.
  • the present inventors presume that the electronic state changes, structurally and electronically affects the conjugated chain, the absorption wavelength changes, and the color development improves.
  • details of Formula 1 will be described.
  • a + in Formula 1 is preferably a ring structure having 3 to 20 carbon atoms including N + , O +, or S + .
  • a + preferably contains an aromatic ring structure.
  • a + preferably contains N + from the viewpoint of color developability, more preferably has at least one 5-membered or 6-membered ring structure containing N +, and a pyridinium ring structure It is particularly preferred that Further, the group on the nitrogen atom in the pyridinium ring structure preferably has a hydrocarbon group having 1 to 20 carbon atoms, more preferably has a hydrocarbon group having 1 to 15 carbon atoms, and has 1 to 10 carbon atoms. It is particularly preferable to have the following hydrocarbon group.
  • a in Formula 1 is preferably a ring structure having 3 to 20 carbon atoms including N, O, or S. Further, A preferably contains N from the viewpoint of color developability, more preferably has at least one 5-membered ring or 6-membered ring structure containing N, and a 6-membered ring containing N A structure is particularly preferred. At least one of X in Formula 1 is a nitrogen atom. Since at least one is a nitrogen atom, the color developability is excellent. Further, from the viewpoint of color developability, X that is directly bonded to A + is preferably a nitrogen atom. Further, from the viewpoint of color developability, at least two of X are preferably nitrogen atoms. In Expression 1, since the bonds of the nitrogen atom is a 3, X may be nitrogen atom, R 1, R 2 or R 3 which binds to the nitrogen atom and are not present.
  • R 1 , R 2 and R 3 in formula 1 are each independently a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, acyloxy group, amino group , Urethane group, urea group, amide group, nitrile group or imino group, and at least one of R 1 , R 2 and R 3 is a hydrogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio A group, an arylthio group, an amino group, or an anilino group is more preferable.
  • R 1, R 2 and R 3 are preferably form a ring structure, at least two of R 1, R 2 and R 3 can form a ring structure More preferred.
  • R 1 , R 2 and R 3 are each independently preferably a group having 0 to 60 carbon atoms, more preferably a group having 0 to 40 carbon atoms, and a group having 0 to 20 carbon atoms. It is particularly preferred.
  • alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, acyloxy group, amino group, urethane group, urea group, amide group and imino group in R 1 , R 2 and R 3 are 1 You may have the above substituent.
  • Substituents include halogen atoms, hydrocarbon groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, acyl groups, alkoxycarbonyl groups, acyloxy groups, amino groups, urethane groups, urea groups, amide groups, nitrile groups, imino groups. Group and pyridinium group.
  • the urethane group is preferably —NR N —CO—OR X or —O—CO—NR N R X
  • the urea group is —NR N —CO—NR N R X
  • the imino group is preferably —N ⁇ C (R X ) 2 . Note that each R N independently represents a hydrogen atom or an alkyl group, R X independently represents a hydrocarbon group.
  • N in Formula 1 is preferably an integer of 2 to 6, more preferably an integer of 3 to 6, and particularly preferably 4 or 5.
  • Z in Formula 1 represents a counter ion for neutralizing the charge, but the compound represented by Formula 1 has a corresponding ionic substituent in its structure, and charge neutralization is not necessary Does not have to exist.
  • Z is an anion, halide ion, sulfonate ion, carboxylate ion, tetrafluoroborate ion, hexafluorophosphate ion, p-toluenesulfonate ion, p-chlorobenzenesulfonate ion, or perchlorate ion is preferable, and halide Ions, tetrafluoroborate ions, hexafluorophosphate ions, or p-toluenesulfonate ions are more preferable, and hexafluorophosphate ions are still more preferable.
  • an alkali metal ion, an alkaline earth metal ion, an ammonium ion, a pyridinium ion, or a sulfonium ion is preferable, a sodium ion, a potassium ion, an ammonium ion, a pyridinium ion, or a sulfonium ion is more preferable, and sodium Ions, potassium ions, or ammonium ions are more preferable.
  • the compound represented by Formula 1 preferably has a decomposable group that is bonded to a conjugated chain via a heteroatom from the viewpoints of color developability and color retention after time, and R 1 , R 2 And R 3 more preferably has a decomposable group bonded to the conjugated chain via a hetero atom.
  • R 1 , R 2 And R 3 more preferably has a decomposable group bonded to the conjugated chain via a hetero atom.
  • the hetero atom in the decomposable group bonded to the conjugated chain via the hetero atom an oxygen atom, a nitrogen atom, or a sulfur atom is preferably mentioned from the viewpoint of color developability and decomposability, and the oxygen atom is particularly preferable.
  • the decomposable group bonded to the conjugated chain through the heteroatom is preferably a group having a pyridinium structure, more preferably a group represented by the following formula 5, and represented by the following formula D. Particularly preferred is a group.
  • R 15 represents a hydrocarbon group
  • R 16 each independently represents a group represented by the following Formula 6, a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group
  • a hydrogen atom represents a hydrocarbon group
  • an alkoxy group represents a hydrocarbon group
  • an aryloxy group represents an alkylthio group
  • an arylthio group Represents an acyl group, a hydroxy group, an alkoxycarbonyl group, an acyloxy group, an amino group, a urethane group, a urea group, an amide group, a nitrile group, or an imino group
  • at least one of R 16 is represented by the following formula 6.
  • R 15 in Formula 5 is preferably an alkyl group having 1 to 12 carbon atoms, more preferably a linear alkyl group having 1 to 12 carbon atoms, and a linear alkyl group having 1 to 8 carbon atoms. More preferred is a methyl group.
  • R 16 in Formula 5 it is preferable that one of R 16 is a group represented by Formula 6 above.
  • R 16 in Formula 5 is preferably independently a group represented by Formula 6 above, a hydrogen atom, or a hydrocarbon group, and is a group represented by Formula 6 above or a hydrogen atom. It is more preferable.
  • an oxygen atom, a nitrogen atom, or a sulfur atom is mentioned preferably from a coloring property and a decomposable viewpoint, An oxygen atom is especially preferable.
  • R D1 represents an alkyl group
  • R D2 represents a hydrogen atom or an alkyl group
  • Z D represents a counter ion that neutralizes charge
  • the bonding position between the pyridinium ring in Formula D and the hydrocarbon group containing R D2 is preferably the 3rd or 4th position of the pyridinium ring, and more preferably the 4th position of the pyridinium ring.
  • the alkyl groups in R D1 and R D2 in Formula D may be linear, branched, or have a ring structure.
  • the alkyl group may have a substituent, and preferred examples of the substituent include an alkoxy group and a terminal alkoxy polyalkyleneoxy group.
  • R D1 in Formula D is preferably an alkyl group having 1 to 12 carbon atoms, more preferably a linear alkyl group having 1 to 12 carbon atoms, and a linear alkyl group having 1 to 8 carbon atoms. More preferred is a methyl group.
  • R D2 in Formula D is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and a branched alkyl group having 3 to 8 carbon atoms. It is more preferable that it is an isopropyl group or a t-butyl group.
  • Z D in formula D may be any counterion for neutralizing the electric charge, also the Z and the above Z D are the same, i.e., the Z D in Formula 1 may exist as the Z .
  • Z D is preferably a sulfonate ion, a carboxylate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, a p-toluenesulfonate ion, or a perchlorate ion, and a p-toluenesulfonate ion, or More preferably, it is a hexafluorophosphate ion.
  • the compound represented by Formula 1 contained in the coloring composition according to the present disclosure is preferably a compound represented by Formula 2 from the viewpoint of color developability.
  • A represents a ring structure containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom
  • Ar represents a ring structure containing N + , O + or S +
  • L represents —CH 2 —, —CHR a —, —C (R a ) 2 —, —NR a —, —O— or —S—
  • each R a independently represents a hydrocarbon group
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxy group, alkoxycarbonyl group, acyloxy group, amino group
  • urethane representss a group, a urea group, an amide group, a nitrile group or an imino group, and two or more R 1 to R 3 may combine to form
  • A, n, and Z in Formula 2 are the same as A, n, and Z in Formula 1, respectively, and the preferred embodiments are also the same. Further, each of R 1, R 2 and R 3 in Formula 2, except that which may form one or more R 1 ⁇ R 3 and L or Ar and is bonded to a ring structure, R 1 in Formula 1 , R 2 and R 3 , and preferred embodiments are also the same.
  • Ar in Formula 2 is preferably a ring structure having 3 to 20 carbon atoms including any of N + , O + , and S + . Ar preferably includes an aromatic ring structure.
  • Ar preferably contains N + from the viewpoint of color developability, more preferably contains at least one 6-membered ring structure containing N +, and particularly preferably a pyridinium ring structure.
  • L in Formula 2 is preferably —CH 2 —, —CHR a —, —C (R a ) 2 —, —O—, or —S—, and —C (R a ) 2 —, —O -Or -S- is more preferable, and -C (R a ) 2- or -O- is particularly preferable.
  • R a in Formula 2 is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 15 carbon atoms, and a hydrocarbon group having 1 to 10 carbon atoms. Is particularly preferred.
  • the compound represented by Formula 1 contained in the coloring composition according to the present disclosure is more preferably a compound represented by Formula 3 from the viewpoint of color developability.
  • A represents a ring structure containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, one of the two A 1 represents N + , and the other represents a carbon atom.
  • L represents —CH 2 —, —CHR a —, —C (R a ) 2 —, —NR a —, —O— or —S—, and each R a independently represents a hydrocarbon group.
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxy group, alkoxycarbonyl group, acyloxy group, amino group Represents a group, a urethane group, a urea group, an amide group, a nitrile group or an imino group, and two or more R 1 to R 3 may combine to form a ring structure, and one or more of R 1 to R 3 and A , L or one or more R 4 to R 7 may combine with each other to form a ring structure, and R 4 to R 7 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, Represents a hydroxy group, an alkoxycarbon
  • A, n, and Z in Formula 3 are the same as A, n, and Z in Formula 1, respectively, and the preferred embodiments are also the same.
  • R 1, R 2 and R 3, except that which may form one or more R 1 ⁇ R 3 and L or one or more R 4 ⁇ R 7 are bonded to the ring structure in Formula 3 Is synonymous with R 1 , R 2 and R 3 in Formula 1, and the preferred embodiments are also the same.
  • One of the two A 1 in Formula 3 represents N +, the other represents a carbon atom, it is preferable A 1 where R 4 is bound is N +.
  • R 4 to R 7 in Formula 3 are each independently a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxy group, alkoxycarbonyl group, acyloxy group, amino group , Anilino group, urethane group, urea group, amide group, nitrile group or imino group, preferably a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, an amino group, an anilino group.
  • a group, a urethane group, a urea group, or an amide group is more preferable.
  • two or more R 4 to R 7 are preferably bonded to form a ring structure.
  • the compound represented by Formula 1 contained in the coloring composition according to the present disclosure is more preferably a compound represented by Formula 4 from the viewpoint of color developability.
  • A represents a ring structure containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, one of the two A 1 represents N + , and the other represents a carbon atom.
  • L represents —CH 2 —, —CHR a —, —C (R a ) 2 —, —NR a —, —O— or —S—, and each R a independently represents a hydrocarbon group.
  • R 4 to R 14 are each independently a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxy group, alkoxycarbonyl group, acyloxy group, amino group, urethane Group, urea group, amide group, nitrile group, imino group, carboxylic acid group, sulfonic acid group or phosphoric acid group, and two or more R 4 to R 14 may be bonded to form a ring structure. or more of R 4 ⁇ 14 and the A or L may form a ring structure, Z is a counter ion for neutralizing a charge.
  • a and Z in Formula 4 have the same meanings as A and Z in Formula 1, respectively, and preferred embodiments are also the same. Further, each of A 1, L and R a in Formula 4, has the same meaning as A 1, L and R a in Formula 3, preferred embodiment is also the same.
  • R 8 to R 14 in Formula 4 are each independently a hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, acyloxy group, amino group, urethane group , Urea group, amide group, nitrile group, or imino group, hydrogen atom, halogen atom, hydrocarbon group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, acyloxy It is more preferably a group or an amino group, and particularly preferably a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, or an amino group.
  • R 4 to R 14 are preferably bonded to form a ring structure, and R 10 and R 12 are bonded to form a ring structure. More preferred.
  • the ring structure formed by combining R 10 and R 12 is preferably a ring structure having at least one 5- or 6-membered ring structure from the viewpoint of color development, and preferably has at least one 5-membered ring structure. It is more preferable that the ring structure has one or more.
  • R 11 in Formula 4 is preferably a group represented by Formula 5 from the viewpoint of color developability.
  • TsO ⁇ represents a tosylate anion
  • the compound represented by Formula 1 may be used individually by 1 type, or may use 2 or more types together.
  • the content of the compound represented by Formula 1 is preferably 0.1 to 95% by mass, more preferably 1 to 50% by mass, based on the total solid content of the color forming composition. More preferable is 40 mass%.
  • the total solid content in the present disclosure is the total amount of components excluding volatile components such as a solvent in the composition.
  • the compound represented by Formula 1 can be synthesized by applying a known method. For example, after synthesizing 2,3,3-trimethyl-3H-pyrrolo [2,3-b] pyridine by the method described in JP-A-2006-299230, the method described in International Publication No. 2016/027886 is used. It can be synthesized by dyeing and substitution reaction at the meso position.
  • the coloring composition according to the present disclosure preferably contains a polymer from the viewpoints of coatability and film formability.
  • the type of polymer is not particularly limited as long as it is a known polymer, but a film-forming polymer, a microgel described later, or a polymer particle described later is preferably exemplified.
  • the film-forming polymer include (meth) acrylic resin, polyurethane, polyester, polyamide, polyether, polycarbonate, polyurea, polyolefin, vinyl resin, polyamine and the like.
  • the polymer used in the coloring composition may be added after being dissolved in the composition, or may be added as a polymer dispersion such as a microgel described later or polymer particles described later.
  • the polymer added by dissolving in the composition is preferably a (meth) acrylic resin, polyurethane, polyester, or vinyl resin, and the microgel or polymer particle dispersion is a (meth) acrylic resin, polyurethane, polyamide, polyurea, polyolefin, Vinyl resin is preferred.
  • the polymer suitable for the on-press development type lithographic printing plate precursor is preferably a (meth) acrylic resin, polyurethane, polyester or vinyl resin, more preferably a (meth) acrylic resin or polyurethane. preferable.
  • a polymer having an alkylene oxide chain is particularly preferable.
  • the polymer having an alkylene oxide chain may have a poly (alkylene oxide) moiety in the main chain or a side chain.
  • poly (alkylene oxide) in the side chain may be a graft polymer having poly (alkylene oxide) in the side chain, or a block copolymer of a block composed of poly (alkylene oxide) -containing repeating units and a block composed of (alkylene oxide) -free repeating units.
  • Polyurethane is preferred when it has a poly (alkylene oxide) moiety in the main chain.
  • the main chain polymer with a poly (alkylene oxide) moiety in the side chain is (meth) acrylic resin, polyvinyl acetal, polyurethane, polyurea, polyimide, polyamide, epoxy resin, polystyrene, novolac phenolic resin, polyester, synthesis Examples thereof include rubber and natural rubber, and (meth) acrylic resin is particularly preferable.
  • alkylene oxide an alkylene oxide having 2 to 6 carbon atoms is preferable, and ethylene oxide or propylene oxide is particularly preferable.
  • the repeating number of alkylene oxide at the poly (alkylene oxide) site is preferably 2 to 120, more preferably 2 to 70, and still more preferably 2 to 50. If the repeating number of alkylene oxide is 120 or less, a decrease in film strength is suppressed.
  • the poly (alkylene oxide) moiety is preferably contained as a side chain of the polymer in a structure represented by the following formula (AO), and is represented by the following formula (AO) as a side chain of the (meth) acrylic resin. More preferably, it is contained in a structure.
  • y represents 2 to 120
  • R 1 represents a hydrogen atom or an alkyl group
  • R 2 represents a hydrogen atom or a monovalent organic group.
  • the monovalent organic group an alkyl group having 1 to 6 carbon atoms is preferable.
  • methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n- Examples include a hexyl group, an isohexyl group, a 1,1-dimethylbutyl group, a 2,2-dimethylbutyl group, a cyclopentyl group, and a cyclohexyl group.
  • y is preferably 2 to 70, more preferably 2 to 50.
  • 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 polymer preferably has crosslinkability in order to improve the film strength of the layer.
  • a crosslinkable group such as an ethylenically unsaturated bond may be introduced to impart photocrosslinkability, or thermoplasticity may be imparted to impart thermal crosslinkability.
  • the crosslinkable group can be introduced into either the main chain or the side chain of the polymer, and examples thereof include a method of introducing by copolymerization and a method of introducing by polymerization after polymerization.
  • thermoplasticity the glass transition temperature of the polymer may be adjusted.
  • the polymer having an ethylenically unsaturated bond in the main chain include polybutadiene and polyisoprene.
  • Examples of the polymer having an ethylenically unsaturated bond in the side chain include a polymer having a (meth) acrylate group, a (meth) acrylamide group, a vinyl group, or an allyl group in the side chain.
  • a method for adjusting the glass transition temperature the composition of the monomer to be copolymerized and the molecular weight of the polymer can be changed and adjusted.
  • the content of the crosslinkable group in the polymer is preferably 0.1 to 10.0 mmol per 1 g of the binder polymer from the viewpoint of film strength. 0.0 to 7.0 mmol is more preferable, and 2.0 to 5.5 mmol is particularly preferable.
  • 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 repeating parts. Me represents a methyl group, Et represents an ethyl group, and Ph represents a phenyl group.
  • the weight average molecular weight (Mw) is preferably 2,000 or more, preferably 5,000 or more, as a polystyrene conversion value by gel permeation chromatography (GPC). More preferably, it is 10,000 to 300,000.
  • the oligomer is Mw 800 or more and less than 2,000, and the polymer is Mw 2,000 or more.
  • hydrophilic polymers such as polyacrylic acid and polyvinyl alcohol described in JP-A-2008-195018 can be used in combination. Further, a lipophilic polymer and a hydrophilic polymer can be used in combination.
  • the polymers may be used alone or in combination of two or more.
  • the polymer can be contained in the coloring composition in any amount.
  • the content of the polymer can be appropriately selected depending on the use of the color forming composition, but is preferably 1 to 90% by mass, and more preferably 5 to 80% by mass with respect to the total solid content of the color forming composition.
  • the coloring composition according to the present disclosure may contain a polymerization initiator.
  • the polymerization initiator used in the coloring composition is a compound that generates polymerization initiation species such as radicals and cations by energy of light, heat, or both, and has a known thermal polymerization initiator and a bond with small bond dissociation energy. It can be appropriately selected from compounds, photopolymerization initiators, and the like.
  • a polymerization initiator an infrared photosensitive polymerization initiator is preferable.
  • a radical polymerization initiator is preferable.
  • radical polymerization initiator examples 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) disulfone compounds, (i) oxime ester compounds, and (j) onium salt compounds.
  • (a) organic halide for example, compounds described in paragraphs 0022 to 0023 of JP-A-2008-195018 are preferable.
  • (b) carbonyl compound for example, compounds described in paragraph 0024 of JP-A-2008-195018 are preferable.
  • (c) azo compounds include the azo compounds described in JP-A-8-108621.
  • (d) organic peroxide for example, compounds described in paragraph 0025 of JP-A-2008-195018 are preferable.
  • (e) metallocene compound for example, compounds described in paragraph 0026 of JP-A-2008-195018 are preferred.
  • Examples of (f) an azide compound include compounds such as 2,6-bis (4-azidobenzylidene) -4-methylcyclohexanone.
  • Examples of (h) disulfone compounds include compounds described in JP-A Nos. 61-166544 and 2002-328465.
  • Examples of the oxime ester compound for example, compounds described in paragraphs 0028 to 0030 of JP-A-2008-195018 are preferable.
  • oxime ester compounds and onium salts are more preferable, and onium salts such as iodonium salts, sulfonium salts, and azinium salts are more preferable.
  • onium salts such as iodonium salts, sulfonium salts, and azinium salts are more preferable.
  • iodonium salts and sulfonium salts are particularly preferred. Specific examples of the iodonium salt and the sulfonium salt are shown below, but the present disclosure is not limited thereto.
  • a diphenyl iodonium salt is preferable, and a diphenyl iodonium salt having an electron donating group as a substituent, for example, substituted with an alkyl group or an alkoxyl group is preferable, and an asymmetric diphenyl iodonium salt is also preferable. preferable.
  • 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
  • Scan 4-t-t- butylphenyl) iodonium
  • a triarylsulfonium salt is preferable, and in particular, a triarylsulfonium salt having an electron withdrawing group as a substituent, for example, at least a part of the group on the aromatic ring is substituted with a halogen atom is preferable.
  • triphenylsulfonium hexafluorophosphate
  • triphenylsulfonium benzoylformate
  • bis (4-chlorophenyl) phenylsulfonium benzoylformate
  • bis (4-chlorophenyl) -4-methylphenylsulfonium tetrafluoro.
  • a polymerization initiator may be used individually by 1 type, and may use 2 or more types together.
  • the content of the polymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and particularly preferably 0.8 to 20% by mass with respect to the total solid content of the color forming composition. .
  • the coloring composition according to the present disclosure may contain a polymerizable compound.
  • the color forming composition according to the present disclosure containing a polymerizable compound is preferably a curable color forming composition having a polymerization curing function in addition to the color formation by application of heat and infrared exposure.
  • the coloring composition according to the present disclosure can be suitably used as a curable composition containing a polymerization initiator and a polymerizable compound from the viewpoint of curability, and as an infrared curable and infrared photosensitive coloring composition. It can be used more suitably.
  • the polymerizable compound used in the coloring composition may be, for example, a radical polymerizable compound or a cationic polymerizable compound, but an addition polymerizable compound having at least one ethylenically unsaturated bond (ethylene A unsaturated unsaturated compound).
  • ethylene A unsaturated unsaturated compound ethylene A unsaturated unsaturated compound.
  • a compound having at least one terminal ethylenically unsaturated bond is preferable, and a compound having two or more terminal ethylenically unsaturated bonds is more preferable.
  • the polymerizable compound can have a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer or an oligomer, or a mixture thereof.
  • Examples of monomers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid), esters thereof, and amides.
  • esters of unsaturated carboxylic acid and polyhydric alcohol compound, and amides of unsaturated carboxylic acid and 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, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or A dehydration condensation reaction product with a polyfunctional carboxylic acid is also preferably used.
  • an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group and an addition reaction product of a monofunctional or polyfunctional alcohol, amine or thiol, further a halogen atom A substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy 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, 9-179298, JP 2004-294935, JP 2006-243493, JP 2002-275129, JP 2003-64130, JP 2003-280187, It is described in JP-A-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] Examples thereof include dimethylmethane and bis [p- (methacryloxyethoxy) phenyl] dimethylmethane.
  • amide monomers of polyamine compounds and unsaturated carboxylic acids include methylene bisacrylamide, methylene bismethacrylamide, 1,6-hexamethylene bisacrylamide, 1,6-hexamethylene bismethacrylamide, Examples include diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.
  • urethane-based addition-polymerizable compounds produced by the addition reaction of isocyanate and hydroxy groups.
  • Specific examples thereof include, for example, one molecule described in JP-B-48-41708.
  • a urethane compound etc. are mentioned.
  • R M4 and R M5 each independently represent a hydrogen atom or a methyl group.
  • Urethane compounds having an oxide skeleton, urethane compounds having a hydrophilic group described in US Pat. No. 7,153,632, JP-A-8-505958, JP-A-2007-293221, and JP-A-2007-293223 Are also suitable.
  • the content of the polymerizable compound is preferably 5 to 75% by mass, more preferably 10 to 70% by mass, and particularly preferably 15 to 60% by mass with respect to the total solid content of the color forming composition.
  • the coloring composition according to the present disclosure may contain a radical generation aid.
  • the radical generation aid contributes to the improvement of the printing durability in the lithographic printing plate when the color forming composition is used in the image recording layer of the lithographic printing plate precursor.
  • Examples of radical generation aids include the following five types.
  • (Ii) Aminoacetic acid compound It is considered that a C—X bond on carbon adjacent to nitrogen is cleaved by oxidation to generate an active radical.
  • X is preferably a hydrogen atom, a carboxy group, a trimethylsilyl group or a benzyl group.
  • Specific examples include N-phenylglycines (which may have a substituent on the phenyl group), N-phenyliminodiacetic acid (which may have a substituent on the phenyl group), and the like. It is done.
  • Sulfur-containing compound A compound in which the nitrogen atom of the aminoacetic acid compound described above is replaced with a sulfur atom can generate an active radical by the same action.
  • Specific examples include phenylthioacetic acid (which may have a substituent on the phenyl group).
  • Tin-containing compound A compound in which the nitrogen atom of the above-mentioned aminoacetic acid compound is replaced with a tin atom can generate an active radical by the same action.
  • Sulfinic acid salts Active radicals can be generated by oxidation. Specific examples include sodium arylsulfinate.
  • the color forming composition preferably contains a borate compound.
  • a borate compound a tetraarylborate compound or a monoalkyltriarylborate compound is preferable. From the viewpoint of stability of the compound and a potential difference described later, a tetraarylborate compound is more preferable, and from the viewpoint of a potential difference described later, an electron withdrawing property.
  • a tetraaryl borate compound having one or more aryl groups having a group is particularly preferable.
  • the electron withdrawing group is preferably a group having a positive Hammett's ⁇ value, and more preferably a group having a Hammett's ⁇ value of 0 to 1.2.
  • a halogen atom, a trifluoromethyl group or a cyano group is preferable, and a fluorine atom, a chlorine atom, a trifluoromethyl group or a cyano group is more preferable.
  • the counter cation possessed by the borate compound is preferably an alkali metal ion or a tetraalkylammonium ion, more preferably a sodium ion, a potassium ion or a tetrabutylammonium ion.
  • the potential difference ⁇ G2 between the highest occupied orbit (HOMO) of the compound represented by the formula 1 and the highest occupied orbit of the borate compound ( ⁇ G2 expressed by the above formula (1)).
  • HOMO-borate compound HOMO is preferably 0.500 eV or more, more preferably 0.585 eV or more, particularly preferably 0.608 eV or more and 1.000 eV or less.
  • the borate other than at the time of heat or infrared exposure
  • electron transfer occurs from the HOMO of the borate compound to the HOMO of the compound represented by the above formula 1 at the time of heat or infrared exposure, so that the lowest empty orbit of the compound represented by the above formula 1 It is considered that the excitation to (LUMO) is promoted and the decomposition of the compound represented by Formula 1 is promoted.
  • the electron transfer from the compound represented by the above formula 1 to the polymerization initiator is promoted, and when the color forming composition is used for the image recording layer of the lithographic printing plate precursor, it contributes to the improvement of printing durability in the lithographic printing plate. I think that.
  • Calculation of HOMO and LUMO of the compound represented by Formula 1 is performed by the following method. First, the counter anion in the compound to be calculated is ignored.
  • the structure optimization is performed by DFT (B3LYP / 6-31G (d)) using quantum chemistry calculation software Gaussian09.
  • the MO energy Epre (unit: hartree) obtained by the MO energy calculation is converted into Eaft (unit: eV) used as values of HOMO and LUMO in the present disclosure by the following formula.
  • Eaft 0.823168 ⁇ 27.2114 ⁇ Epre ⁇ 1.07634
  • 27.2114 is a coefficient for simply converting heartree to eV
  • 0.823168 and -1.07634 are adjustment coefficients
  • HOMO and LUMO of the compound to be calculated are calculated values. It was decided to suit.
  • X c + represents a monovalent cation, preferably an alkali metal ion or a tetraalkylammonium ion, and more preferably an alkali metal ion or a tetrabutylammonium ion.
  • Bu represents an n-butyl group.
  • radical generation aid Only one type of radical generation aid may be added, or two or more types may be used in combination.
  • the content of the radical generation aid is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass, and still more preferably 0.1 to 20% by mass with respect to the total solid content of the color forming composition. .
  • the coloring composition according to the present disclosure may contain a chain transfer agent.
  • the chain transfer agent contributes to the improvement of the printing durability in the lithographic printing plate when the color forming composition is used for the image recording layer of the lithographic printing plate precursor.
  • a thiol compound is preferable, a thiol compound having 7 or more carbon atoms is more preferable from the viewpoint of boiling point (difficult to volatilize), and a compound having a mercapto group on an aromatic ring (aromatic thiol compound) is more preferable.
  • the thiol compound is preferably a monofunctional thiol compound.
  • chain transfer agent examples include the following compounds.
  • a chain transfer agent may add only 1 type or may use 2 or more types together.
  • the content of the chain transfer agent is preferably 0.01 to 50% by mass, more preferably 0.05 to 40% by mass, and still more preferably 0.1 to 30% by mass with respect to the total solid content of the color forming composition.
  • the color forming composition according to the present disclosure may contain an infrared absorber.
  • an infrared absorber By containing an infrared absorber, the coloring composition according to the present disclosure can be more suitably used as an infrared photosensitive coloring composition. Moreover, even if it is a case where the coloring composition which concerns on this indication is used as a heat-sensitive coloring composition, it may contain the infrared absorber.
  • An infrared absorber is a compound having a function of converting absorbed infrared rays into heat. Further, the infrared absorber may have a function of transferring electrons or transferring energy to a polymerization initiator or the like to be described later when excited by infrared rays.
  • the infrared absorber preferably has a maximum absorption in a wavelength region of 750 to 1,400 nm. As the infrared absorber, a dye or a pigment is preferably 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 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, squarylium dyes, and pyrylium salts are preferable.
  • cyanine dyes are preferable
  • cyanine dyes include compounds described in paragraphs 0017 to 0019 of JP-A-2001-133969, paragraphs 0016 to 0021 of JP-A-2002-023360, paragraphs 0012 to 0037 of JP-A-2002-040638.
  • Compounds described in JP-A-2002-278057, preferably paragraphs 0034 to 0041 of JP-A-2002-278057, JP-A-2008-195018, paragraphs 0080 to 0086, particularly preferably JP-A-2007-90850, paragraph 0035 To 0043 are mentioned.
  • the infrared absorber can be contained in an arbitrary amount in the coloring composition.
  • the content of the infrared absorber is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, based on 100 parts by mass of the total solid content of the color forming composition. More preferably, it is 2 to 10% by mass.
  • the coloring composition according to the present disclosure may contain additives other than those described above (for example, a surfactant) as necessary.
  • Each component contained in the coloring composition according to the present disclosure is dissolved or dispersed in an appropriate solvent to prepare a coating solution, and the coating solution is applied to a support and dried to form a coloring composition film.
  • a known solvent can be used as the solvent.
  • the coloring composition according to the present disclosure can be used for heat-sensitive coloring materials, infrared-sensitive coloring materials, and the like.
  • Thermosensitive coloring materials can be widely used as thermal recording media such as tickets and receipts in facsimile machines, computer terminal printers, automatic ticket vending machines, measurement recorders, supermarkets and convenience store cash registers.
  • the color forming composition according to the present disclosure is preferably used for an image forming material.
  • image forming materials include lithographic printing plate precursors, printed wiring boards, color filters, photomasks, and other image forming materials that use color development by image exposure, and image forming materials that use color development and polymerization curing.
  • the image forming material using the color forming composition according to the present disclosure forms a color image by being exposed to heat or a light source that emits infrared rays.
  • known heating means can be used, and examples thereof include a heater, an oven, a hot plate, an infrared lamp, and an infrared laser.
  • light sources that emit infrared light include solid-state lasers and semiconductor lasers that emit infrared light.
  • the lithographic printing plate precursor according to the present disclosure preferably has at least one layer containing the color forming composition according to the present disclosure on a support.
  • the coloring composition according to the present disclosure can be used for any of the undercoat layer, the image recording layer, and the protective layer in the lithographic printing plate precursor, but is particularly preferably used for the image recording layer.
  • the type of the lithographic printing plate precursor according to the present disclosure is not particularly limited, and examples thereof include an alkali developing type and an on-press developing type, and an on-press developing type is particularly preferable.
  • an on-press development type lithographic printing plate precursor in which the characteristics of the color forming composition according to the present disclosure are remarkably exhibited will be described as an example.
  • the image recording layer in the lithographic printing plate precursor is required to have developability and printability.
  • the coloring composition preferably contains the compound represented by Formula 1 and the polymer.
  • the above-mentioned polymer for film formation is preferably used as the polymer.
  • the color forming composition used for the image recording layer preferably further contains a polymerizable compound and a polymerization initiator, and further contains a radical generation aid and a chain transfer agent alone or in combination. Is more preferable.
  • the coloring composition used for the image recording layer further contains microgel or polymer particles.
  • the image recording layer of the lithographic printing plate precursor according to the present disclosure preferably contains each component contained in the color forming composition.
  • Each of the compounds represented by Formula 1 contained in the image recording layer such as a polymer (for example, a film-forming polymer, microgel, polymer particles, etc.), a polymerizable compound, a polymerization initiator, a radical generation aid, a chain transfer agent, etc.
  • a polymer for example, a film-forming polymer, microgel, polymer particles, etc.
  • a polymerizable compound for example, a film-forming polymer, microgel, polymer particles, etc.
  • a radical generation aid for example, a radical generation aid
  • a chain transfer agent a radical generation aid
  • the image recording layer may further contain a low molecular weight hydrophilic compound, a sensitizer, a solvent, and other components in addition to the above-described components.
  • the image recording layer may contain microgel and / or polymer particles.
  • the microgel and polymer particles are preferably crosslinked, melted, or both caused by light or heat generated by infrared irradiation, or changed to hydrophobicity.
  • the microgel and polymer particles are preferably at least one selected from the group consisting of non-crosslinkable microgels, crosslinkable microgels, thermoplastic polymer particles, thermally reactive polymer particles, and polymer particles having a polymerizable group. These may have a core-shell structure and may contain other compounds.
  • Thermoplastic polymer particles include Research Disclosure No. 1 of January 1992. Preferred examples include polymer particles described in Japanese Patent No. 33303, JP-A-9-123387, JP-A-9-131850, JP-A-9-171249, JP-A-9-171250 and European Patent 931647. Specific examples of the polymer constituting the thermoplastic polymer particles include ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, vinyl carbazole, and polyalkylene structures.
  • polystyrene, a copolymer containing styrene and acrylonitrile, and polymethyl methacrylate are used.
  • thermally reactive polymer particles examples include polymer particles having a thermally reactive group.
  • the polymer particles having a thermoreactive group form a hydrophobized region by crosslinking by a thermal reaction and a functional group change at that time.
  • thermoreactive group in the polymer particles having a thermoreactive group may be any functional group that performs any reaction as long as a chemical bond is formed, and is preferably a polymerizable group.
  • examples include ethylenically unsaturated groups that undergo radical polymerization reactions (eg, acryloyl groups, methacryloyl groups, vinyl groups, allyl groups, etc.), cationic polymerizable groups (eg, vinyl groups, vinyloxy groups, epoxy groups, oxetanyl groups).
  • Etc. isocyanato group that performs an addition reaction or a block thereof, an epoxy group, a vinyloxy group, and a functional group having an active hydrogen atom that is a reaction partner thereof (for example, an amino group, a hydroxy group, a carboxy group, etc.), a condensation reaction Preferred examples include a carboxyl group to be performed and a hydroxy group or amino group which is a reaction partner, an acid anhydride which performs a ring-opening addition reaction, and an amino group or hydroxy group which is a reaction partner.
  • microcapsule examples include those in which all or part of the constituent components of the image recording layer are encapsulated in the microcapsule as described in JP-A Nos. 2001-277740 and 2001-277742.
  • the constituent components of the image recording layer can also be contained outside the microcapsules.
  • the image recording layer containing microcapsules is preferably a mode in which hydrophobic constituent components are encapsulated in microcapsules and hydrophilic constituent components are contained outside the microcapsules.
  • the microgel can contain a part of the constituent components of the image recording layer in at least one of the inside and the surface thereof.
  • a reactive microgel is formed by having a radical polymerizable group on the surface thereof is preferable from the viewpoint of image forming sensitivity and printing durability.
  • the constituent components of the image recording layer a known method can be used.
  • the coloring composition according to the present disclosure contains a polymer in the form of microcapsules, microgels or polymer particles
  • the average primary particle diameter of the microcapsules, microgels or polymer particles is preferably 10 to 1,000 nm. 20 to 300 nm is more preferable, and 30 to 120 nm is still more preferable.
  • the average primary particle diameter of each particle in the present disclosure is measured by a light scattering method, or an electron micrograph of the particle is taken, and a total of 5,000 particle diameters are measured on the photograph. The value shall be calculated.
  • the particle size of spherical particles having the same particle area as that on the photograph is used as the particle size.
  • the content of the microgel or polymer particles is preferably 5 to 90% by mass with respect to the total solid content of the image recording layer.
  • 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.
  • the low molecular weight hydrophilic compound is preferably a compound having a molecular weight of less than 1,000, more preferably a compound having a molecular weight of less than 800, and still more preferably a compound having a molecular weight of less than 500.
  • the 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 alkylsulfuric acid and alkylethersulfuric acid and salts thereof, phenylphosphonic acid Organic phosphonic acids and salts thereof, tartaric acid, o
  • the low molecular weight hydrophilic compound it is preferable to contain at least one selected from the group consisting of polyols, organic sulfates, organic sulfonates, and betaines.
  • 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; 5 , 8,11-Trioxapentadecane-1-sulfonic acid sodium salt, 5,8,11-trioxaheptadecane-1-sulfonic acid sodium salt, 13-ethyl-5,8,11-trioxaheptadecane-1-sulfone Alkyl sulfonates containing ethylene oxide chains such as sodium acid, sodium 5,8,11,14-tetraoxatetracosane-1-sulfonate; sodium benzenesulfonate, sodium p-toluenesulfonate, p-hydroxybenzen
  • 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 paragraphs 0034 to 0038 of JP-A-2007-276454.
  • the betaines are preferably compounds in which the hydrocarbon substituent on the nitrogen atom has 1 to 5 carbon atoms. Specific examples include trimethylammonium acetate, dimethylpropylammonium acetate, 3-hydroxy-4-trimethylammonium. Obtylate, 4- (1-pyridinio) butyrate, 1-hydroxyethyl-1-imidazolioacetate, trimethylammonium methanesulfonate, dimethylpropylammonium methanesulfonate, 3-trimethylammonio-1-propanesulfonate, 3 -(1-pyridinio) -1-propanesulfonate and the like.
  • a low molecular weight hydrophilic compound has a small hydrophobic part structure and almost no surface activity, so that dampening water penetrates into the exposed part of the image recording layer (image part) and decreases the hydrophobicity and film strength of the image part.
  • the ink receptivity and printing durability of the image recording layer can be maintained satisfactorily.
  • the content of the low molecular weight hydrophilic compound is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and still more preferably 2 to 10% by mass with respect to the total solid content of the image recording layer. Within the above range, good on-press developability and printing durability can be obtained.
  • a low molecular weight hydrophilic compound may be used individually by 1 type, and 2 or more types may be mixed and used for it.
  • the image recording layer may contain a 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 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 layered compound, and can suppress a decrease in the inking property during printing by the inorganic layered compound.
  • the sensitizer it is preferable to use a phosphonium compound, a nitrogen-containing low molecular weight compound, and an ammonium group-containing polymer in combination, and use a phosphonium compound, a quaternary ammonium salt, and an ammonium group-containing polymer in combination. Is more preferable.
  • nitrogen-containing low molecular weight compounds examples include amine salts and quaternary ammonium salts. Also included are imidazolinium salts, benzimidazolinium salts, pyridinium salts, and quinolinium salts. Of these, quaternary ammonium salts and pyridinium salts are preferred.
  • the ammonium group-containing polymer may have an ammonium group in its structure, and a polymer containing 5 to 80 mol% of (meth) acrylate having an ammonium group in the side chain as a copolymerization component is preferable.
  • Specific examples include the polymers described in paragraphs 0089 to 0105 of JP2009-208458A.
  • the ammonium salt-containing polymer preferably has a reduced specific viscosity (unit: ml / g) determined in accordance with the measurement method described in JP-A-2009-208458, in the range of 5 to 120, and in the range of 10 to 110. Are more preferable, and those in the range of 15 to 100 are particularly preferable.
  • Mw weight average molecular weight
  • 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, based on the total solid content of the image recording layer. Is more preferable.
  • the image recording layer can contain, as other components, a surfactant, a polymerization inhibitor, a higher fatty acid derivative, a plasticizer, inorganic particles, an inorganic layered compound, and the like. Specifically, reference can be made to the descriptions in paragraphs 0114 to 0159 of JP-A-2008-284817.
  • the image recording layer in the lithographic printing plate precursor according to the present disclosure is coated by dispersing or dissolving the necessary components in a known solvent as described in paragraphs 0142 to 0143 of JP-A-2008-195018, for example. It can be formed by preparing a liquid, coating the coating liquid on a support by a known method such as bar coater coating, and drying.
  • the coating amount (solid content) of the image recording layer after coating and drying varies depending on the application, but is preferably 0.3 to 3.0 g / m 2 . Within the above range, good sensitivity and good film properties of the image recording layer can be obtained.
  • the lithographic printing plate precursor according to the present disclosure preferably has an undercoat layer (sometimes referred to as an intermediate layer) 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. It contributes to improving.
  • the undercoat layer functions as a heat insulating layer, and thus has an effect of preventing the heat generated by the exposure from diffusing to the support and lowering the sensitivity.
  • Examples of the compound used for the undercoat layer include polymers having an adsorptive group and a hydrophilic group that can be adsorbed on the surface of the support. In order to improve the adhesion to the image recording layer, a polymer having an adsorptive group and a hydrophilic group and further having a crosslinkable group is preferable.
  • the compound used for the undercoat layer may be a low molecular compound or a polymer. The compounds used for the undercoat layer may be used as a mixture of two or more if necessary.
  • the compound used for the undercoat layer is a polymer
  • 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 a phenolic hydroxy group, a carboxy group, —PO 3 H 2 , —OPO 3 H 2 , —CONHSO 2 —, —SO 2 NHSO 2 —, —COCH 2 COCH 3 Is preferred.
  • a hydrophilic group a sulfo group or a salt thereof, or a salt of a carboxy group is preferable.
  • the polymer may have a crosslinkable group introduced by salt formation between a polar substituent of the polymer, a substituent having a counter charge with the polar substituent, and a compound having an ethylenically unsaturated bond, Other monomers, preferably hydrophilic monomers, may be further copolymerized.
  • the phosphorus compound which has a heavy bond reactive group is mentioned suitably.
  • Crosslinkable groups (preferably ethylenically unsaturated bond groups) described in JP-A-2005-238816, JP-A-2005-12549, JP-A-2006-239867, and JP-A-2006-215263, a support
  • a low molecular or high molecular compound having a functional group interacting with the surface and a hydrophilic group is also preferably used.
  • More preferable are polymer polymers having an adsorbing group, a hydrophilic group, and a crosslinkable group that can be adsorbed on the surface of the support described in JP-A Nos. 2005-125749 and 2006-188038.
  • the content of the ethylenically unsaturated bond group in the polymer used for the undercoat layer is preferably from 0.1 to 10.0 mmol, more preferably from 0.2 to 5.5 mmol, per 1 g of the polymer.
  • the weight average molecular weight (Mw) of the polymer used for the undercoat layer is preferably 5,000 or more, and more preferably 10,000 to 300,000.
  • the undercoat layer is a chelating agent, a secondary or tertiary amine, a polymerization inhibitor, an amino group, or a functional group having a polymerization inhibitory ability and a support surface in order to prevent contamination with time.
  • a group that interacts with eg, 1,4-diazabicyclo [2.2.2] octane (DABCO), 2,3,5,6-tetrahydroxy-p-quinone, chloranil, sulfophthalic acid, hydroxy Ethylethylenediaminetriacetic 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.
  • the lithographic printing plate precursor according to the present disclosure preferably has a protective layer (sometimes referred to as an overcoat layer) on the image recording layer.
  • the protective layer has a function of preventing the formation of scratches in the image recording layer and ablation during high-illuminance laser exposure, in addition to the function of suppressing the image formation inhibition reaction by blocking oxygen.
  • the protective layer in the lithographic printing plate precursor according to the present disclosure may include a coloring composition according to the present disclosure, that is, a compound represented by Formula 1.
  • the protective layer having such characteristics is described in, for example, US Pat. No. 3,458,311 and Japanese Patent Publication No. 55-49729.
  • 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 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.
  • Specific examples include modified polyvinyl alcohols described in JP-A-2005-250216 and JP-A-2006-259137.
  • the protective layer preferably contains an inorganic layered compound in order to enhance oxygen barrier properties.
  • the inorganic layered compound is a particle having a thin flat plate shape, for example, mica group such as natural mica and synthetic mica, talc, teniolite, montmorillonite, saponite, hector represented by the formula: 3MgO ⁇ 4SiO ⁇ H 2 O Light, zirconium phosphate, etc. are mentioned.
  • the inorganic layered compound preferably used is a mica compound.
  • the mica compound include, for example, the formula: A (B, C) 2-5 D 4 O 10 (OH, F, O) 2 [where A is at least one selected from the group consisting of K, Na, and Ca. B and C are at least one element selected from the group consisting of Fe (II), Fe (III), Mn, Al, Mg and V, and D is Si or Al. is there. ]
  • Mica groups such as natural mica and synthetic mica represented by
  • natural mica includes muscovite, soda mica, phlogopite, biotite, and sericite.
  • synthetic mica non-swelling mica such as fluor-phlogopite mica KMg 3 (AlSi 3 O 10 ) F 2 , potassium tetrasilicon mica KMg 2.5 Si 4 O 10 ) F 2 , and Na tetrasilicic mica NaMg2 .
  • the lattice layer is deficient in positive charge, and in order to compensate for this, cations such as Li + , Na + , Ca 2+ , and Mg 2+ are adsorbed between the layers.
  • the cations present between these layers are called exchangeable cations and can be exchanged with various cations.
  • the bond between the layered crystal lattices is weak because the ionic radius is small, and the layer swells greatly with water. If shear is applied in this state, it will easily cleave and form a stable sol in water.
  • Swelling synthetic mica has a strong tendency and is particularly preferably used.
  • the aspect ratio is preferably 20 or more, more preferably 100 or more, and particularly preferably 200 or more.
  • the aspect ratio is the ratio of the major axis to the thickness of the particle, and can be measured, for example, from a projection drawing of a particle by a micrograph. The larger the aspect ratio, the greater the effect that can be obtained.
  • the average major axis of the mica compound is preferably 0.3 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m, and particularly preferably 1 to 5 ⁇ m.
  • the average thickness of the particles is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and particularly preferably 0.01 ⁇ m or less.
  • preferred embodiments have a thickness of about 1 to 50 nm and a surface size (major axis) of about 1 to 20 ⁇ m.
  • the content of the inorganic stratiform compound is preferably 0 to 60% by mass and more preferably 3 to 50% by mass with respect to the total solid content of the protective layer. Even when a plurality of types of inorganic layered compounds are used in combination, the total amount of the inorganic layered compounds is preferably the above content. Within the above range, the oxygen barrier property is improved and good sensitivity can be obtained. Further, it is possible to prevent a decrease in inking property.
  • the protective layer may contain known additives such as a plasticizer for imparting flexibility, a surfactant for improving coating properties, and inorganic fine particles for controlling the slipperiness of the surface. Further, the protective layer may contain the sensitizer described in the image recording layer.
  • the protective layer is applied by a known method.
  • the coating amount of the protective layer (solid content) is preferably 0.01 ⁇ 10g / m 2, more preferably 0.02 ⁇ 3g / m 2, particularly preferably 0.02 ⁇ 1g / m 2.
  • the support of the lithographic printing plate precursor according to the present disclosure can be appropriately selected from known lithographic printing plate precursor supports.
  • As the support an aluminum plate which has been roughened and anodized by a known method is preferable. If necessary, the aluminum plate may further be subjected to micropore enlargement treatment or sealing treatment of an anodized film described in JP-A-2001-253181 and JP-A-2001-322365, US Pat. No. 2,714, Surface hydrophilization treatment with alkali metal silicate as described in US Pat. Nos. 066, 3,181,461, 3,280,734 and 3,902,734, US The surface hydrophilization treatment with polyvinyl phosphonic acid or the like as described in the specifications of Patent Nos. 3,276,868, 4,153,461 and 4,689,272 is appropriately selected. You may go.
  • the support preferably has a center line average roughness of 0.10 to 1.2 ⁇ m.
  • the support may be provided on the surface opposite to the image recording layer, such as an organic polymer compound described in JP-A-5-45885, or an alkoxy compound of silicon described in JP-A-6-35174. You may have the backcoat layer containing.
  • the method of preparing a lithographic printing plate according to the present disclosure includes a step of exposing the lithographic printing plate precursor according to the present disclosure (exposure step), and printing the lithographic printing plate precursor after imagewise exposure on a printing machine with printing ink and moisture. It is preferable to include a step (on-press development step) of removing an unexposed portion of the image recording layer by at least one selected from the group consisting of water.
  • Image exposure is preferably performed by a method of scanning exposure of digital data with an infrared laser or the like.
  • the wavelength of the exposure light source is preferably 750 to 1,400 nm.
  • a solid laser or semiconductor laser that emits infrared light is suitable.
  • the exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like.
  • the exposure step can be performed by a known method using a plate setter or the like.
  • the exposure may be performed on the printing machine after the planographic printing plate precursor is mounted on the printing machine using a printing machine equipped with an exposure device.
  • On-machine development process at least one selected from the group consisting of printing ink and fountain solution on the printing press without performing any development treatment on the lithographic printing plate precursor after image exposure, preferably printing ink
  • printing ink and fountain solution known lithographic printing ink and fountain solution are used.
  • the lithographic printing plate precursor may be initially supplied with the printing ink or fountain solution, but the printing ink is first used in order to prevent the fountain solution from being contaminated by the removed image recording layer components. Is preferably supplied. In this way, the lithographic printing plate precursor is subjected to on-press development on an offset printing machine and used as it is for printing a large number of sheets.
  • the method for producing a lithographic printing plate according to the present disclosure may include other known steps in addition to the above steps.
  • Examples of other processes include a plate inspection process for confirming the position and orientation of the lithographic printing plate precursor before each process, a confirmation process for confirming a printed image after the on-machine development process, and the like.
  • the lithographic printing plate precursor according to the present disclosure can be prepared as a lithographic printing plate by a development process using a developer by appropriately selecting a polymer or the like which is a constituent component of the image recording layer.
  • the development process using a developer is at least one selected from the group consisting of an embodiment (also referred to as alkali development) using a developer having a high pH of 14 or less containing an alkali agent, and a surfactant and a water-soluble polymer compound.
  • the compound represented by the above formula 1 is a novel compound, and can be suitably used as a color former, particularly a heat-sensitive color former, an infrared-sensitive color former, or a heat-sensitive and infrared-sensitive color former.
  • a preferred embodiment of the compound represented by Formula 1 as the novel compound is the same as the preferred embodiment of the compound represented by Formula 1 in the color forming composition according to the present disclosure described above.
  • the molecular weight is a weight average molecular weight (Mw) in terms of polystyrene converted by a gel permeation chromatography (GPC) method, and the ratio of repeating units is a mole percentage.
  • Mw weight average molecular weight
  • GPC gel permeation chromatography
  • part means “part by mass” unless otherwise specified.
  • 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.
  • the etching amount of the grained surface was about 3 g / m 2 .
  • the electrolytic solution was a 1% by mass aqueous nitric acid solution (containing 0.5% by mass aluminum ions), and the liquid temperature was 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 having a current density of 15 A / dm 2 is formed on an aluminum plate as an electrolyte using a 15 mass% aqueous sulfuric acid solution (containing 0.5 mass% of aluminum ions), and then washed with water.
  • the support A was prepared by drying.
  • the average pore diameter (surface average pore diameter) in the surface layer of the anodized film was 10 nm.
  • the pore diameter in the surface layer of the anodized film is measured using an ultra-high resolution SEM (S-900, manufactured by Hitachi, Ltd.), with a deposition process that imparts conductivity at a relatively low acceleration voltage of 12V. Without applying, the surface was observed at a magnification of 150,000 times, and 50 pores were randomly extracted to obtain an average value.
  • the standard deviation error was ⁇ 10% or less.
  • the support A was subjected to silicate treatment at 60 ° C. for 10 seconds using a 2.5 mass% No. 3 sodium silicate aqueous solution, and then washed with water to obtain the support B.
  • the adhesion amount of Si was 10 mg / m 2 .
  • the center line average roughness (Ra) of the support B was measured using a needle having a diameter of 2 ⁇ m, it was 0.51 ⁇ m.
  • Support C was prepared in the same manner as the support A, except that the electrolyte for forming the direct current anodized film was changed to a 22% by mass phosphoric acid aqueous solution.
  • the average pore diameter (surface average pore diameter) in the surface layer of the anodized film was 25 nm as measured by the same method as described above.
  • the support C was subjected to a silicate treatment at 60 ° C. for 10 seconds using a 2.5 mass% No. 3 sodium silicate aqueous solution, and then washed with water to obtain the support D.
  • the adhesion amount of Si was 10 mg / m 2 .
  • the center line average roughness (Ra) of the support D was measured using a needle having a diameter of 2 ⁇ m, it was 0.52 ⁇ m.
  • BLEMMER PME-4000 Methoxypolyethylene glycol methacrylate (Repeating number of oxyethylene units: 90)
  • VA-046B 2,2′-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate
  • an image recording layer coating solution (1) having the following composition was coated with a bar and 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 (1) was prepared by mixing and stirring the following photosensitive solution (1) and microgel solution immediately before coating.
  • Binder polymer (1), polymerization initiator (1), TPB, low molecular weight hydrophilic compound (1), phosphonium compound (1), ammonium group-containing polymer (1) and fluorine-based interface used in the photosensitive solution (1) The structure of the active agent (1) is shown below.
  • Me represents a methyl group
  • the number on the lower right of the parenthesis of each structural unit of the following polymer represents a molar ratio.
  • the method for preparing the microgel (1) used in the microgel solution is shown below.
  • a protective layer coating solution having the following composition is bar-coated on the image recording layer and oven-dried at 120 ° C. for 60 seconds to form a protective layer having a dry coating amount of 0.15 g / m 2.
  • Table 1 summarizes the support used in the preparation of each lithographic printing plate precursor, the compound A or the comparative compound in the image recording layer coating solution (1).
  • CKS50 manufactured by Nippon Synthetic Chemical Industry Co., Ltd., sulfonic acid modification, saponification degree 99 mol% or more, polymerization degree 300
  • the method for preparing the inorganic layered compound dispersion (1) used in the protective layer coating solution is shown below.
  • the aspect ratio of the obtained dispersed particles was 100 or more.
  • lithographic printing plate precursor B In preparation of the lithographic printing plate precursor A, the following lithographic printing plate precursor A is used in place of the image recording layer coating liquid (1) except that the following image recording layer coating liquid (2) is used.
  • a lithographic printing plate precursor B was prepared in the same manner as the preparation.
  • the image recording layer coating solution (2) was prepared by mixing and stirring the following photosensitive solution (2) and microgel solution immediately before coating. Table 1 summarizes the support used in the preparation of each lithographic printing plate precursor, the compound D in the image recording layer coating solution (2) or the comparative compound.
  • Sensitizer Phosphonium compound (1) [above]: 0.055 parts. Aburakazai benzyl - dimethyl - octylammonium, PF 6 salt: 0.018 parts Oil-sensitizing agent ammonium group-containing polymer (1) [the]: 0.035 parts fluorine-containing surfactant (1) [the]: 0.008 parts 2-Butanone 1.091 parts 1-Methoxy-2-propanol: 8.609 parts
  • Microgel (1) [above]: 2.640 parts Distilled water: 2.425 parts
  • the structure of the chain transfer agent (S-1) used in the photosensitive solution (2) is shown below.
  • lithographic printing plate precursor C In preparation of the lithographic printing plate precursor A, an image recording layer coating liquid (3) having the following composition was bar-coated instead of the image recording layer coating liquid (1), and 60 ° C. at 60 ° C. The plate was subjected to oven drying for 2 seconds to form an image recording layer having a dry coating amount of 0.6 g / m 2 to prepare a lithographic printing plate precursor C.
  • the lithographic printing plate precursor C is a lithographic printing plate precursor having no protective layer.
  • Table 1 summarizes the support used in the preparation of each lithographic printing plate precursor, the compound D or the comparative compound in the image recording layer coating solution (3).
  • the preparation method of the polymer particle aqueous dispersion (1) used in the image recording layer coating liquid (3) is shown below.
  • the particle size distribution is obtained by taking an electron micrograph of polymer particles, measuring the total particle size of 5,000 particles on the photo, and using a logarithmic scale between the maximum value of the obtained particle size measurement value and zero. The frequency of appearance of each particle size was plotted by dividing it into 50 and determined. For non-spherical particles, the particle size of spherical particles having the same particle area as that on the photograph was used as the particle size.
  • lithographic printing plate precursor D In preparation of the lithographic printing plate precursor A, an image recording layer coating aqueous solution (4) having the following composition after coating was applied by bar instead of the image recording layer coating liquid (1). Then, it was oven dried at 50 ° C. for 60 seconds to form an image recording layer having a dry coating amount of 0.93 g / m 2 to prepare a lithographic printing plate precursor D.
  • the lithographic printing plate precursor D is a lithographic printing plate precursor having no protective layer.
  • the support used in the preparation of each lithographic printing plate precursor, the compound D or the comparative compound in the image recording layer coating solution (4) are collectively shown in Table 1.
  • ⁇ Image recording layer coating solution (4)> Compound D shown in Table 1 or comparative compound: 0.038 g / m 2 Borate compound TPB [above]: 0.01 g / m 2 -Polymer particle aqueous dispersion (2): 0.693 g / m 2 -Glascol E15 (manufactured by Allied Colloids Manufacturing): 0.09 g / m 2 ⁇ ERKOL WX48 / 20 (manufactured by ERKOL): 0.09 g / m 2 ⁇ Zonyl FSO100 (manufactured by DuPont): 0.0075 g / m 2
  • the compound described in the trade name and the polymer particle aqueous dispersion (2) used in the image recording layer coating aqueous solution (4) are as follows.
  • -Glascol E15 Polyacrylic acid-ERKOL WX48 / 20: Polyvinyl alcohol / polyvinyl acetate copolymer-Zonyl FSO100: Surfactant-Polymer particle water dispersion (2): Styrene stabilized with an anionic wetting agent / Acrylonitrile copolymer (molar ratio 50/50, average particle size 61 nm, solid content about 20% by mass)
  • SCE regular reflection light removal
  • the color developability 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.
  • the lithographic printing plate precursor was subjected to an external drum rotation speed of 1,000 rpm, a laser output of 70%, and a resolution of 2,400 dpi using a Luxel PLANETTER T-6000III equipped with an infrared semiconductor laser. Exposed.
  • 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.
  • the lithographic printing plate precursor having the image recording layer containing the compound according to the present disclosure is superior in color developability as compared with the lithographic printing plate precursor of the comparative example containing the comparative compound. It is clear. Furthermore, it can be seen that the lithographic printing plate precursor having the image recording layer containing the compound according to the present disclosure has good on-press developability and printing durability.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

La présente invention concerne une composition colorante qui contient le composé représenté par la formule 1. Une plaque maîtresse d'impression planographique comprend au moins une couche contenant la composition colorante. Un procédé de fabrication d'une plaque d'impression planographique utilise la plaque maîtresse d'impression planographique. L'invention concerne également le composé représenté par la formule 1, qui peut être utilisé de manière appropriée en tant que colorant.
PCT/JP2017/029546 2016-08-29 2017-08-17 Composition colorante, plaque maîtresse d'impression planographique, procédé de fabrication de plaque d'impression planographique, et composé WO2018043150A1 (fr)

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JP2016166950A JP2019194274A (ja) 2016-08-29 2016-08-29 発色組成物、平版印刷版原版、平版印刷版の作製方法、及び、化合物
JP2016-166950 2016-08-29

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Publication number Priority date Publication date Assignee Title
WO2020090995A1 (fr) * 2018-10-31 2020-05-07 富士フイルム株式会社 Plaque originale de plaque d'impression lithographique, procédé de production de plaque d'impression lithographique et procédé d'impression lithographique
CN112930266A (zh) * 2018-10-31 2021-06-08 富士胶片株式会社 平版印刷版原版、平版印刷版的制作方法及平版印刷方法
CN113165410A (zh) * 2018-10-31 2021-07-23 富士胶片株式会社 平版印刷版原版、平版印刷版的制作方法及平版印刷方法

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JP2003034697A (ja) * 2001-07-19 2003-02-07 Fuji Photo Film Co Ltd 蛍光ヌクレオチド及びそれを用いた標識法
JP2003034696A (ja) * 2001-07-19 2003-02-07 Fuji Photo Film Co Ltd 蛍光ヌクレオチド及びそれを用いた標識法
JP2005145819A (ja) * 2003-11-11 2005-06-09 Konica Minolta Medical & Graphic Inc 蛍光造影剤および体外蛍光造影方法
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
JP2016506420A (ja) * 2012-10-24 2016-03-03 ベクトン・ディキンソン・アンド・カンパニーＢｅｃｔｏｎ， Ｄｉｃｋｉｎｓｏｎ Ａｎｄ Ｃｏｍｐａｎｙ ヒドロキサメート置換アザインドリン−シアニン染料およびそのバイオ複合体

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JP2003034697A (ja) * 2001-07-19 2003-02-07 Fuji Photo Film Co Ltd 蛍光ヌクレオチド及びそれを用いた標識法
JP2003034696A (ja) * 2001-07-19 2003-02-07 Fuji Photo Film Co Ltd 蛍光ヌクレオチド及びそれを用いた標識法
JP2005145819A (ja) * 2003-11-11 2005-06-09 Konica Minolta Medical & Graphic Inc 蛍光造影剤および体外蛍光造影方法
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
JP2016506420A (ja) * 2012-10-24 2016-03-03 ベクトン・ディキンソン・アンド・カンパニーＢｅｃｔｏｎ， Ｄｉｃｋｉｎｓｏｎ Ａｎｄ Ｃｏｍｐａｎｙ ヒドロキサメート置換アザインドリン−シアニン染料およびそのバイオ複合体

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020090995A1 (fr) * 2018-10-31 2020-05-07 富士フイルム株式会社 Plaque originale de plaque d'impression lithographique, procédé de production de plaque d'impression lithographique et procédé d'impression lithographique
CN112930266A (zh) * 2018-10-31 2021-06-08 富士胶片株式会社 平版印刷版原版、平版印刷版的制作方法及平版印刷方法
CN113165410A (zh) * 2018-10-31 2021-07-23 富士胶片株式会社 平版印刷版原版、平版印刷版的制作方法及平版印刷方法
CN112930266B (zh) * 2018-10-31 2023-02-28 富士胶片株式会社 平版印刷版原版、平版印刷版的制作方法及平版印刷方法
CN113165410B (zh) * 2018-10-31 2023-09-26 富士胶片株式会社 平版印刷版原版、平版印刷版的制作方法及平版印刷方法

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