WO2019150998A1 - Précurseur positif de plaque d'impression lithographique et procédé de fabrication d'une plaque d'impression lithographique - Google Patents

Précurseur positif de plaque d'impression lithographique et procédé de fabrication d'une plaque d'impression lithographique Download PDF

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Publication number
WO2019150998A1
WO2019150998A1 PCT/JP2019/001559 JP2019001559W WO2019150998A1 WO 2019150998 A1 WO2019150998 A1 WO 2019150998A1 JP 2019001559 W JP2019001559 W JP 2019001559W WO 2019150998 A1 WO2019150998 A1 WO 2019150998A1
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group
printing plate
positive
aluminum
treatment
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PCT/JP2019/001559
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English (en)
Japanese (ja)
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尚志 佐藤
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富士フイルム株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N1/00—Printing plates or foils; Materials therefor
    • B41N1/04—Printing plates or foils; Materials therefor metallic
    • B41N1/08—Printing plates or foils; Materials therefor metallic for lithographic printing
    • B41N1/083—Printing plates or foils; Materials therefor metallic for lithographic printing made of aluminium or aluminium alloys or having such surface layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • 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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • 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
    • B41C2210/02—Positive working, i.e. the exposed (imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/06—Developable by an alkaline solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
    • B41C2210/266—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/12—Anodising more than once, e.g. in different baths
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment

Definitions

  • This disclosure relates to a positive lithographic printing plate precursor and a method for producing a lithographic printing plate.
  • a lithographic printing plate comprises an oleophilic image area that receives ink in the printing process and a hydrophilic non-image area that receives dampening water.
  • 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 (that is, ink non-receptive area).
  • a difference in ink adhesion is caused on the surface of the lithographic printing plate, and after ink is applied only to the image part, the ink is transferred to a printing medium such as paper and printed.
  • the non-image portion of the lithographic printing plate is formed by, for example, an aluminum support (hereinafter also simply referred to as “support”) that may be subjected to a surface treatment.
  • lithographic printing plate precursor or lithographic printing plate support used in such a lithographic printing plate examples include those described in Patent Document 1 and Patent Document 2 below.
  • Patent Document 1 includes an anodic oxide film having a pore with a surface mouth diameter of 0 to 30 nm and an internal maximum diameter of 20 to 300 nm on a metal support, and a photothermal conversion agent on the anodic oxide film.
  • a lithographic printing plate precursor having an image forming layer is described.
  • Patent Document 2 discloses a lithographic printing plate comprising an aluminum plate and an aluminum anodic oxide film thereon, and having micropores extending in the depth direction from the surface opposite to the aluminum plate in the anodic oxide film.
  • Patent Document 1 JP 2002-365791 A
  • Patent Document 2 JP 2014-198453 A
  • planographic printing plate As a planographic printing plate, a planographic printing plate having a large number of printable sheets is required. In a lithographic printing plate, the property that the number of printable sheets is large is also referred to as “excellent printing durability”. Conventionally, regarding an aluminum support having an anodized film used for a lithographic printing plate precursor, after forming the anodized film, a micropore is formed on the surface of the anodized film, and then treated with an acid or alkali solution to form a surface layer.
  • the printing durability (hereinafter also referred to as “small dot printing durability”) of a small dot (for example, an image portion having a diameter (that is, an equivalent diameter of a circle) of several ⁇ m to several tens of ⁇ m, etc.) I found it.
  • the equivalent circle diameter means the diameter of a circle having the same area as the projected area of the image portion on the photograph.
  • excellent small dot printing durability is a very important characteristic, for example, when halftone printing is performed.
  • Problems to be solved by the embodiments of the present disclosure include a positive lithographic printing plate precursor from which a lithographic printing plate excellent in small-point printing durability can be obtained, and production of a lithographic printing plate using the positive lithographic printing plate precursor Is to provide a method.
  • Means for solving the above problems include the following aspects.
  • the aluminum support and a positive image recording layer are included in this order,
  • the aluminum support includes an aluminum plate and an anodized film of aluminum disposed on the aluminum plate, and the anodized film is located on the positive image recording layer side of the aluminum plate,
  • the anodized film has micropores extending in the depth direction from the surface opposite to the aluminum plate,
  • the average diameter of the micropores on the surface of the anodic oxide film is 10 nm to 100 nm
  • the positive image recording layer contains a photothermal conversion agent and at least one polymer selected from the group consisting of polyurethane, polyurea, polyamide, and acetal resin, and the polymer has an acid group
  • a positive lithographic printing plate precursor wherein the polymer content is 20% by mass or more based on the total solid content of the positive image recording layer.
  • ⁇ 2> The positive planographic printing plate precursor as described in ⁇ 1> above, wherein the anodic oxide film has a thickness of 200 nm to 2,000 nm.
  • the micropore extends from the anodic oxide film surface to a position exceeding a depth of 10 nm, and the ratio of the average diameter of the micropore bottom to the average micropore diameter on the anodic oxide film surface is 0.8 times.
  • ⁇ 4> A small-diameter hole in which the micropore communicates with a large-diameter hole extending from the surface of the anodized film to a position exceeding a depth of 10 nm and a bottom of the large-diameter hole, and further extending in the depth direction from the communication position.
  • the positive type according to ⁇ 1> or ⁇ 2>, wherein an average diameter of the small diameter hole portion at the communication position is smaller than an average diameter of the large diameter hole portion on the surface of the anodized film A lithographic printing plate precursor.
  • the average diameter of the micropores on the surface of the anodic oxide film is 10 nm to 30 nm, the average value of the internal maximum diameter is 20 nm to 300 nm, and the average value of the internal maximum diameter is the surface of the anodic oxide film.
  • the above polymer contains at least one polymer selected from the group consisting of a polyurethane containing a structural unit represented by the following formula 1 and a polyurea containing a structural unit represented by the following formula 1.
  • X 1 represents —CR 2 —, —O— or —S—, and each R 2 independently represents a hydrogen atom or an alkyl group.
  • X 1 represents —CR 2 —, —O— or —S—, and each R 2 independently represents a hydrogen atom or an alkyl group.
  • ⁇ 9> The positive planographic printing plate precursor as described in any one of ⁇ 1> to ⁇ 8>, wherein the polymer contains an acetal resin.
  • ⁇ 10> The positive planographic printing plate precursor as described in any one of ⁇ 1> to ⁇ 9> above, wherein the polymer contains an acetal resin having a structural unit represented by the following formula 2.
  • X B is> CH-, or> N-a represents, L B represents a single bond or a divalent linking group, Ar represents an aromatic ring structure, R represents a substituent, m is 1 N represents an integer of 0 or more, and n + m represents the maximum number of substituents of the aromatic ring structure represented by Ar.
  • N-a represents, L B represents a single bond or a divalent linking group, Ar represents an aromatic ring structure, R represents a substituent, m is 1 N represents an integer of 0 or more, and n + m represents the maximum number of substituents of the aromatic ring structure represented by Ar.
  • ⁇ 11> The positive lithographic printing plate precursor as described in any one of ⁇ 1> to ⁇ 10> above, further having an image recording layer as an upper layer on the positive image recording layer.
  • ⁇ 12> The positive planographic printing plate precursor as described in any one of ⁇ 1> to ⁇ 11> above, which has an undercoat layer between the aluminum support and the positive image recording layer.
  • a method for producing a lithographic printing plate comprising a development step in which development is performed using a zero aqueous alkali solution in this order.
  • a positive lithographic printing plate precursor from which a lithographic printing plate excellent in small dot printing durability can be obtained, and a method for producing a lithographic printing plate using the positive lithographic printing plate precursor. be able to.
  • the amount of each component in the composition is the total amount of the plurality of corresponding substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means.
  • the notation that does not indicate substitution and non-substitution includes those not having a substituent and those having a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • (meth) acryl is a term used in a concept including both acryl and methacryl
  • (meth) acryloyl is a term used as a concept including both acryloyl and methacryloyl. is there.
  • the notation of the group in the compound represented by the formula when there is no substitution or no substitution, there is no other special provision when the group can further have a substituent. As long as the group includes not only an unsubstituted group but also a group having a substituent.
  • 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
  • process in the present disclosure is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, it is included in this term if the intended purpose of the process is achieved. It is.
  • mass% and wt% are synonymous, and “part by mass” and “part by weight” are synonymous. Furthermore, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
  • weight average molecular weight (Mw) and number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both trade names manufactured by Tosoh Corporation) unless otherwise specified.
  • the total solid content means the total mass of components excluding volatile components such as a solvent in the composition.
  • the term “lithographic printing plate precursor” includes not only a lithographic printing plate precursor but also a discarded plate precursor. Further, the term “lithographic printing plate” includes not only a lithographic printing plate prepared by subjecting a lithographic printing plate precursor to operations such as exposure and development, but also a discarded plate. In the case of a discarded original plate, exposure and development operations are not necessarily required. The discarded plate is a lithographic printing plate precursor to be attached to a plate cylinder that is not used when, for example, printing a part of paper in single color or two colors in color newspaper printing.
  • the present disclosure will be described in detail.
  • a positive lithographic printing plate precursor according to the present disclosure includes an aluminum support and a positive image recording layer in this order.
  • FIG. 1 A schematic cross-sectional view of an embodiment of the lithographic printing plate precursor according to the present disclosure is shown in FIG.
  • a lithographic printing plate precursor 10 has an aluminum support 12 having an anodized film, an undercoat layer 14 and a positive image recording layer 16.
  • the lithographic printing plate precursor according to the present disclosure can provide a lithographic printing plate having excellent small-point printing durability.
  • the detailed mechanism by which the above effect is obtained is unknown, it is presumed as follows.
  • the lithographic printing plate precursor according to the present disclosure includes at least one polymer selected from the group consisting of polyurethane, polyurea, polyamide, and acetal resin in a positive image recording layer.
  • Polyurethanes, polyureas, and polyamides have hydrogen bonding sites in the backbone of the main chain. It is considered that the hydrogen bonding property is high and the strength is high because of the high cohesiveness.
  • Acetal resin is considered to have high strength because it has a rigid ring structure and polymer chains are easily oriented. By using such a high-strength polymer on a support having a micropore of a specific shape, these polymers enter into the micropore at the small point of the image area.
  • anchor effect Is suppressed (hereinafter also referred to as “anchor effect”), and is presumed to be excellent in small dot printing durability.
  • an effect of excellent small dot printing durability is considered to be obtained if the specific polymer is present in the positive image recording layer at a certain ratio or more, specifically, the positive type It is considered that the effect is exhibited when the content is 20% by mass or more with respect to the total solid content of the image recording layer.
  • the specific polymer has an acid group. By having an acid group, it becomes soluble in an alkaline aqueous solution having a pH of 8.5 to 14.0.
  • the inventor of the present invention can also improve the printing durability of a solid image portion by using a specific polymer having a high strength as described above and a support having a micropore of a specific shape. I found out. Furthermore, the present inventor uses a micropore having a specific shape and the above specific polymer, so that the penetration of the developer into the interface with the small-point support is suppressed, and the small-point dropout during development is eliminated. It has been found that a lithographic printing plate excellent in the stability of small dots with respect to development conditions can be easily obtained. In the present disclosure, it is difficult to drop out even under severe development conditions as described above, the tolerance for the development conditions is wide, and the stability of the small spots with respect to the development conditions is excellent.
  • the present inventor has found that the lithographic printing plate precursor according to the present disclosure can easily obtain a lithographic printing plate having excellent neglectability.
  • excellent neglectability means that after printing is performed using a lithographic printing plate, printing is interrupted (for example, interrupted for several hours, etc.), and when the printing is resumed, the stain is removed. It means that the number of printed sheets required until an unacceptable printed matter is obtained is small.
  • details of the planographic printing plate according to the present disclosure will be described.
  • the aluminum support in the positive planographic printing plate precursor according to the present disclosure will be described.
  • the aluminum support used in the present disclosure is an aluminum support having an anodized film.
  • the thickness of the anodized film is preferably 200 nm to 2,000 nm.
  • a schematic cross-sectional view of one embodiment of an aluminum support having an anodized film is shown in FIG. 2A.
  • an aluminum support 12 having an anodized film has an aluminum plate 18 and an aluminum anodized film 20 (hereinafter also simply referred to as “anodized film 20”) in this order.
  • the anodized film 20 in the aluminum support 12 is located on the positive image recording layer 16 side of the planographic printing plate precursor 10 in FIG. That is, the lithographic printing plate precursor 10 includes an aluminum plate 18, an anodized film 20, an undercoat layer 14, and a positive image recording layer 16.
  • the aluminum plate 18 (that is, the aluminum support) is made of a dimensionally stable aluminum-based metal, that is, aluminum or an aluminum alloy.
  • the aluminum plate 18 is made of a pure aluminum plate or an alloy plate containing aluminum as a main component and a trace amount of foreign elements.
  • the different elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium.
  • the content of foreign elements in the alloy is preferably 10% by mass or less.
  • the aluminum plate 18 is preferably a pure aluminum plate, but may be aluminum containing slightly different elements from the viewpoint of smelting technology.
  • the composition of the aluminum plate 18 is not limited, and a publicly known material (for example, JIS A 1050, JIS A 1100, JIS A 3103, and JIS A 3005) can be used as appropriate.
  • the width of the aluminum plate 18 is preferably about 400 mm to 2,000 mm, and the thickness is preferably about 0.1 mm to 0.6 mm.
  • the width or thickness of the aluminum plate 18 can be appropriately changed according to the size of the printing press, the size of the printing plate, and the user's desire.
  • the anodized film 20 is generally produced on the surface of the aluminum plate 18 by anodizing treatment, and is substantially perpendicular to the film surface, and has anodized aluminum having ultrafine micropores 22 that are uniformly distributed. Refers to the film.
  • the micropore 22 extends along the thickness direction (that is, the aluminum plate 18 side) from the surface of the anodized film.
  • the thickness X1 of the anodized film is preferably 200 nm to 2,000 nm, more preferably 500 nm to 1,800 nm, and still more preferably 750 nm to 1,500 nm.
  • micropore is a commonly used term for pores in an anodized film and does not define the size of the pores.
  • the micropore extends from the surface of the anodic oxide film to a position exceeding a depth of 10 nm, and the ratio of the average diameter of the bottom of the micropore to the average diameter of the micropore on the surface of the anodic oxide film is 0.8 times or more. 2 times or less.
  • the micropore has a large-diameter hole extending from the anodic oxide film surface to a position exceeding a depth of 10 nm, a small-diameter hole communicating with the bottom of the large-diameter hole, and extending further in the depth direction from the communication position. And the average diameter of the small-diameter hole portion at the communication position is smaller than the average diameter of the large-diameter hole portion on the surface of the anodized film.
  • the average diameter of the micropores on the surface of the anodic oxide film is 10 nm to 30 nm, the average value of the internal maximum diameter is 20 nm to 300 nm, and the average value of the internal maximum diameter is the micropore on the surface of the anodic oxide film. It is larger than the average diameter of the pores.
  • each aspect is demonstrated using drawing.
  • FIG. 2A is a schematic cross-sectional view showing an embodiment of the first aspect.
  • the micropore 22 extends from the surface of the anodized film 20 to a position exceeding a depth of 10 nm, and the ratio of the average diameter of the bottom of the micropore to the average diameter of the micropore on the surface of the anodized film is 0.8. 2 times or more and 1.2 times or less.
  • the depth X2 of the micropore 22 exceeds 10 nm, preferably 50 nm or more, and more preferably 75 nm or more.
  • the depth X2 of the micropore 22 was determined by observing the cross section of the anodic oxide film 20 with a field emission scanning electron microscope (FE-SEM) (magnification: 150,000 times). In the obtained image, 25 micropores were obtained. Is measured as the arithmetic average value.
  • FE-SEM field emission scanning electron microscope
  • the average diameter Y1 of the micropores 22 on the surface of the anodic oxide film is preferably 10 nm to 100 nm, more preferably 15 nm to 75 nm, and still more preferably 20 nm to 50 nm.
  • the ratio (X2 / Y1) of the average diameter Y1 to the depth X2 of the micropores 22 on the surface of the anodized film is preferably 2 to 10 times, more preferably 2.5 to 7 times, and more preferably 3 times. More preferably, it is 6 times or less.
  • the average diameter Y2 at the bottom of the micropore 22 is preferably 10 nm or more and 100 nm or less, more preferably 15 nm or more and 75 nm or less, and further preferably 20 nm or more and 50 nm or less.
  • the ratio of the average diameter Y2 at the bottom of the micropore 22 to the average diameter Y1 of the micropore 22 on the surface of the anodized film is preferably 0.8 times or more and 1.2 or less, and more preferably 0.85 times or more and 1.15. It is more preferable that it is not more than twice, and it is still more preferable that it is not less than 0.9 times and not more than 1.1 times.
  • the ratio of the average diameter Y2 at the bottom of the micropore 22 to the average diameter Y1 of the micropore 22 on the surface of the anodized film is a value obtained by the following formula 1A.
  • Formula 1A (Average diameter Y2 of the bottom of the micropore 22) / (Average diameter Y1 of the micropore 22 on the anodized film surface)
  • the diameter (that is, the diameter) of the bottom of the micropore 22 is measured and obtained as an arithmetic average value.
  • the upper part of the anodized film 20 is cut horizontally with the anodized film (for example, cutting with argon gas), and then the surface of the anodized film 20 is coated with the FE.
  • FIG. 2B is an enlarged schematic cross-sectional view of one of the micropores in FIG. 2A.
  • the shape of the micropore 22 in the aspect 1 is not particularly limited.
  • the micropore 22 has a substantially straight tube shape, a substantially cylindrical shape, a conical shape whose diameter decreases in the depth direction (that is, the thickness direction), and the depth direction (that is, the thickness).
  • a conical shape with a larger diameter in the direction) a cylindrical shape with a larger central diameter, a cylindrical shape with a smaller central diameter, and the like.
  • a substantially straight tube is preferable.
  • the shape of the bottom of the micropore 22 is not particularly limited, and may be a curved surface (for example, a concave shape) or a planar shape.
  • the ratio (Y1A / Y1) of the diameter Y1A of the central portion to the average diameter Y1 of the micropores 22 on the anodized film surface is preferably 0.8 times or more and 1.2 times or less.
  • the diameter (that is, the diameter) of the central portion of the micropore 22 to be measured is measured and obtained as an arithmetic average value.
  • the upper part of the anodized film 20 is cut horizontally with the anodized film (for example, cutting with argon gas), and then the surface of the anodized film 20 is FE.
  • the diameter Y1A at the center of the bottom of the micropore 22 may be obtained by observation with a SEM.
  • the density of the micropores 22 on the surface of the anodic oxide coating 20 is not particularly limited, but is preferably 200 / ⁇ m 2 to 2,000 / ⁇ m 2 with respect to the unit area of the anodic oxide coating, 200 / More preferably, it is from ⁇ m 2 to 1,000 / ⁇ m 2 .
  • the number of micropores to be measured is measured and calculated as an arithmetic average value of the measured values.
  • the micropores 22 may be distributed over the entire surface of the anodic oxide coating, or may be distributed over at least a part, but preferably distributed over the entire surface.
  • the micropores 22 are preferably substantially perpendicular to the anodized film surface 22. Moreover, it is preferable that the micropores 22 are distributed in an almost uniform state.
  • FIG. 3A is a schematic cross-sectional view showing an embodiment of the second aspect.
  • the micropores 22 in the anodized film 20 communicate with the large-diameter hole 24 extending from the anodized film surface to a position where the depth (depth A: see FIG. 3A) exceeds 10 nm, and the bottom of the large-diameter hole 24.
  • the small-diameter hole 26 extends further in the depth direction from the communication position. Below, the large diameter hole part 24 and the small diameter hole part 26 are explained in full detail.
  • the average diameter (that is, the average opening diameter) of the large-diameter hole portion 24 on the anodized film surface is preferably larger than 10 nm and not larger than 100 nm.
  • the average diameter is more preferably 15 nm to 60 nm, and still more preferably 18 nm to 40 nm, from the viewpoint that the effect according to the present disclosure is more excellent.
  • the diameter (that is, the diameter) of the micropore (that is, the large-diameter hole portion) existing in the range of ⁇ 600 nm is measured and obtained as an arithmetic average value.
  • an equivalent circle diameter is used.
  • the bottom of the large-diameter hole 24 is at a position where the depth (hereinafter also referred to as “depth A”) exceeds 10 nm from the surface of the anodized film. That is, the large-diameter hole 24 is a hole extending more than 10 nm in the depth direction (that is, the thickness direction) from the surface of the anodized film.
  • the depth A is preferably more than 10 nm and 1,000 nm or less, more preferably 25 nm to 200 nm, and still more preferably 70 nm to 100 nm in that the effect of the present disclosure is more excellent.
  • the depth A When the depth A is 25 nm or more, a lithographic printing plate excellent in small dot printing durability, small dot development latitude, and solid plate portion printing durability is easily obtained. Further, when the depth A is 200 nm or less, a lithographic printing plate having particularly excellent neglectability is easily obtained.
  • the depth from the surface of the anodized film was measured by observing the cross section of the anodized film 20 with FE-SEM (magnification: 150,000 times) and measuring the depth of 25 large-diameter holes in the obtained image. And obtained as an arithmetic average value.
  • the shape of the large-diameter hole 24 is not particularly limited, and is, for example, a substantially straight tubular shape, a substantially cylindrical shape, a conical shape whose diameter decreases in the depth direction (that is, the thickness direction), and the depth direction (that is, the thickness direction). ), An inverted conical shape whose diameter increases toward the surface). Among these, a substantially straight tube shape is preferable.
  • the diameter at the bottom of the large-diameter hole may usually differ from the diameter of the opening by about 1 nm to 10 nm.
  • the shape of the bottom portion of the large-diameter hole portion 24 is not particularly limited, and may be a curved surface shape (for example, a concave shape) or a planar shape.
  • the micropores 22 in the anodized film 20 are holes that communicate with the bottom of the large-diameter hole 24 and extend further in the depth direction (that is, the thickness direction) than the communication position. It is preferable to have a small-diameter hole 26. Although one small diameter hole portion 26 normally communicates with one large diameter hole portion 24, two or more small diameter hole portions 26 may communicate with the bottom of one large diameter hole portion 24.
  • the average diameter at the communication position of the small diameter hole portion 26 is not particularly limited, but the average diameter of the small diameter hole portion 26 at the communication position with the bottom of the large diameter hole portion 24 is smaller than the average diameter of the large diameter hole portion 24 and is 20 nm.
  • the average diameter is preferably 5 nm or more. When the average diameter is less than 20 nm, it is easy to obtain a lithographic printing plate excellent in neglectability.
  • the diameter (that is, the diameter) of the (that is, the small-diameter hole portion) is measured and obtained as an arithmetic average value.
  • the upper part of the anodized film 20 that is, the region having the large-diameter hole
  • the surface of the film 20 may be observed with the FE-SEM to determine the average diameter of the small diameter holes.
  • an equivalent circle diameter is used.
  • the bottom of the small-diameter hole 26 is located at a position extending from 100 nm to less than 1,940 nm in the depth direction from the communication position with the large-diameter hole 24 (corresponding to the depth A described above).
  • the depth of the small diameter hole 26 is preferably 100 nm to less than 1,940 nm.
  • the small diameter hole portion 26 preferably extends from the communicating position to a position with a depth of 300 nm to 1,600 nm, and the small diameter hole portion 26 has a depth of 900 nm to 1,300 nm from the communicating position, in order to further improve the effect of the present disclosure. It is more preferable to extend to the position.
  • the depth of the small-diameter hole is determined by observing the cross section of the anodized film 20 with FE-SEM (magnification: 50,000 times), and measuring the depth of 25 small-diameter holes in the obtained image. It is obtained as an average value.
  • the shape of the small-diameter hole portion 26 is not particularly limited, and for example, a substantially straight tube shape (ie, a substantially cylindrical shape), a conical shape whose diameter decreases in the depth direction, and a dendritic shape that branches in the depth direction Among these, a substantially straight tube is preferable.
  • the diameter at the bottom of the small-diameter hole 26 may usually have a difference of about 1 nm to 5 nm from the diameter at the communication position.
  • the shape of the bottom of the small-diameter hole 26 is not particularly limited, and may be a curved surface (for example, a concave shape) or a planar shape.
  • the average diameter of the small-diameter hole at the communication position is smaller than the average diameter of the large-diameter hole on the surface of the anodized film. Since the average diameter of the small-diameter hole is smaller than the average diameter of the large-diameter hole, a lithographic printing plate excellent in stain resistance (that is, neglectability) can be easily obtained.
  • the ratio of the average diameter of the large-diameter hole to the average diameter of the small-diameter hole that is, the average diameter of the large-diameter hole / the average diameter of the small-diameter hole
  • 1.1 to 12.5 is preferable, and 1.5 to 10 is more preferable.
  • the average diameter at the bottom of the large-diameter hole may be larger than the average diameter at the surface of the anodized film, and further has a small-diameter hole that communicates with the bottom of the large-diameter hole.
  • a micropore may be used.
  • the average diameter at the bottom of the large-diameter hole is larger than the average diameter at the surface of the anodized film
  • the average diameter at the surface of the anodized film is preferably 10 nm to 100 nm, and the average diameter at the bottom is 20 nm to 300 nm. Preferably there is.
  • the average diameter on the surface of the anodized film is preferably 10 nm to 100 nm, and preferably 10 nm to 30 nm from the viewpoint of stain resistance (that is, neglectability).
  • the average diameter at the bottom may be 20 nm to 300 nm, but is preferably 40 nm to 200 nm.
  • the thickness of the 10 nm to 100 nm portion of the anodic oxide coating surface is preferably 10 nm to 500 nm, but more preferably 50 nm to 300 nm from the viewpoint of scratch resistance.
  • the density of the micropores 22 on the surface of the anodic oxide coating 20 is not particularly limited, but is preferably 200 / ⁇ m 2 to 2,000 / ⁇ m 2 with respect to the unit area of the anodic oxide coating, 200 / More preferably, it is from ⁇ m 2 to 1,000 / ⁇ m 2 .
  • the number of micropores to be measured is measured and calculated as an arithmetic average value of the measured values.
  • the micropores 22 may be distributed over the entire surface of the anodic oxide coating, or may be distributed over at least a part, but preferably distributed over the entire surface.
  • the micropores 22 are preferably substantially perpendicular to the anodized film surface 22. Moreover, it is preferable that the micropores 22 are distributed in an almost uniform state.
  • FIG. 4A is a schematic cross-sectional view showing one embodiment of aspect 3 described above.
  • the average diameter Y3 of the micropores 22 on the surface of the anodic oxide film is 10 nm to 30 nm
  • the average value Y4 of the internal maximum diameter is 20 nm to 300 nm
  • the average value Y4 of the internal maximum diameter is The surface pore diameter is larger than the average diameter Y3 of the micropores on the surface of the anodized film.
  • the depth X4 of the micropore 22 exceeds 10 nm, preferably 30 nm or more, and more preferably 75 nm or more.
  • the depth X4 of the micropore 22 is determined by observing the cross section of the anodic oxide film 20 with FE-SEM (magnification: 150,000 times), and measuring the depth of 25 micropores in the obtained image, and calculating It is obtained as an average value.
  • the average diameter Y3 of the micropores 22 on the surface of the anodic oxide film is preferably 10 nm or more and 30 nm or less, more preferably 11 nm or more and 25 nm or less, and further preferably 12 nm or more and 20 nm or less.
  • the average value Y4 of the maximum diameter inside the micropore is preferably 10 nm or more and 300 nm or less, more preferably 15 nm or more and 200 nm or less, and further preferably 20 nm or more and 100 nm or less.
  • the ratio of the average value Y4 of the maximum diameter inside the micropore 22 to the average diameter Y3 of the micropore on the surface of the anodized film is preferably 1.2 times or more and 10 times or less, and more preferably 1.5 times or more and 8 times. More preferably, it is more preferably 2 times or more and 5 times or less.
  • the ratio of the average value Y4 of the maximum diameter inside the micropore 22 to the average diameter Y3 of the micropore 22 is a value obtained by the following formula 1B.
  • Formula 1B (Average value Y4 of maximum diameter inside micropore 22) / (Average diameter Y3 of micropore 22 on the surface of the anodized film)
  • the average diameter Y3 of the micropores on the surface of the anodized film is obtained by the same method as Y1 in the above-described aspect 1.
  • the upper part of the anodized film 20 is cut horizontally with the anodized film (for example, cutting with argon gas), and then the surface of the anodized film 20 is coated with the FE. -By observing with SEM, the average diameter Y4 of the bottom of the micropore 22 may be obtained.
  • an equivalent circle diameter is used.
  • the shape of the micropore 22 in the aspect 3 is not particularly limited.
  • the micropore 22 has a substantially straight tube shape, a substantially cylindrical shape, a conical shape whose diameter decreases in the depth direction (ie, the thickness direction), and the depth direction (ie, the thickness).
  • a conical shape having a larger diameter in the direction), a columnar shape having a larger central portion diameter, a columnar shape having a smaller central portion diameter, and the like, and a substantially straight tube shape is preferred.
  • the shape of the bottom of the micropore 22 is not particularly limited, and may be a curved surface (for example, a concave shape) or a planar shape. Moreover, as shown to FIG.
  • the form which combined the cylinder with a small diameter and the cylinder with a large diameter may be sufficient.
  • These cylinders are not particularly limited, and may be substantially straight tubular, conical, inverted conical, cylindrical with a large central diameter, cylindrical with a small central diameter, and the like. A straight tube is preferred.
  • the shape of the bottom of the micropore 22 is not particularly limited, and may be a curved surface (for example, a concave shape) or a planar shape.
  • the density of the micropores 22 on the surface of the anodic oxide coating 20 is not particularly limited, but is preferably 200 / ⁇ m 2 to 2,000 / ⁇ m 2 with respect to the unit area of the anodic oxide coating, 200 / More preferably, it is from ⁇ m 2 to 1,000 / ⁇ m 2 .
  • the number of micropores to be measured is measured and calculated as an arithmetic average value of the measured values.
  • the micropores 22 may be distributed over the entire surface of the anodic oxide coating, or may be distributed over at least a part, but preferably distributed over the entire surface.
  • the micropores 22 are preferably substantially perpendicular to the anodized film surface 22. Moreover, it is preferable that the micropores 22 are distributed in an almost uniform state.
  • Roughening treatment step A step of roughening the aluminum plate (first anodizing step) A step of anodizing the roughened aluminum plate Pore wide treatment step: Obtained in the first anodizing step The step of bringing the aluminum plate having the anodized film into contact with an acid aqueous solution or an alkali aqueous solution to enlarge the diameter of the micropores in the anodized film Second anodizing treatment step: The aluminum plate obtained in the pore wide treatment step Step of hydrophilizing: Step of applying hydrophilization to the aluminum plate obtained in the second anodizing step The above steps will be described in detail below. Note that the roughening treatment step and the hydrophilic treatment step may be omitted if not necessary.
  • FIG. 5 shows a schematic cross-sectional view of an aluminum support having an anodized film showing the order from the first anodizing step to the second anodizing step.
  • the roughening treatment step is a step of performing a roughening treatment including an electrochemical roughening treatment on the surface of the aluminum plate.
  • the roughening treatment step is preferably performed before the first anodizing treatment step described later, but may not be performed as long as the surface of the aluminum plate already has a preferable surface shape.
  • the surface roughening treatment may be performed only by electrochemical surface roughening treatment, but may be performed by combining electrochemical surface roughening treatment with mechanical surface roughening treatment and / or chemical surface roughening treatment. Also good. When the mechanical surface roughening treatment and the electrochemical surface roughening treatment are combined, it is preferable to perform the electrochemical surface roughening treatment after the mechanical surface roughening treatment.
  • the mechanical surface roughening process is performed using, for example, the apparatus shown in FIG. Specifically, for example, while supplying a suspension of a polishing agent (pumice) having a specific gravity of 1.1 g / cm 3 and water as a polishing slurry liquid to the surface of an aluminum plate, Surface processing is performed.
  • 1 is an aluminum plate
  • 2 and 4 are roller-like brushes (for example, bundled brushes, etc.)
  • 3 is a polishing slurry
  • 5, 6, 7 and 8 are support rollers.
  • the electrochemical surface roughening treatment is preferably performed in an aqueous solution of nitric acid or hydrochloric acid.
  • the mechanical roughening treatment is generally performed for the purpose of setting the surface of the aluminum plate to a surface roughness Ra: 0.35 ⁇ m to 1.0 ⁇ m.
  • Various conditions for the mechanical surface-roughening treatment are not particularly limited, and for example, they can be applied according to the method described in JP-B-50-40047.
  • Examples of the mechanical surface roughening treatment include a brush grain treatment using a pumiston suspension, a treatment using a transfer method, and the like.
  • the chemical surface roughening treatment is not particularly limited, and can be performed according to a known method.
  • the following chemical etching treatment is preferably performed.
  • the chemical etching treatment performed after the mechanical roughening treatment smoothes the uneven edge portion of the surface of the aluminum plate, prevents ink from being caught during printing, and stain resistance of the lithographic printing plate (that is, This is carried out to improve neglectability and to remove unnecessary substances such as abrasive particles remaining on the surface.
  • acid etching or alkali etching is known, but as a method that is particularly excellent in terms of etching efficiency, chemical etching treatment using an alkaline solution (hereinafter also referred to as “alkali etching treatment”). ).
  • the alkaline agent used in the alkaline solution is not particularly limited, and preferred examples include caustic soda, caustic potash, sodium metasilicate, sodium carbonate, sodium aluminate, and sodium gluconate.
  • the alkaline agent may contain aluminum ions.
  • the concentration of the alkaline solution is preferably 0.01% by mass or more, more preferably 3% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less.
  • the temperature of the alkaline solution is preferably room temperature (25 ° C.) or higher, more preferably 30 ° C. or higher, 80 ° C. or lower, more preferably 75 ° C. or lower.
  • the etching amount is preferably 0.1 g / m 2 or more, more preferably 1 g / m 2 or more, and preferably 20 g / m 2 or less, more preferably 10 g / m 2 or less.
  • the treatment time is preferably 2 seconds to 5 minutes corresponding to the etching amount, and more preferably 2 to 10 seconds from the viewpoint of improving productivity.
  • a chemical etching process (hereinafter also referred to as “desmut process”) is performed using a low-temperature acidic solution in order to remove products generated by the alkali etching process. It is preferable to apply.
  • the acid used for an acidic solution is not specifically limited, For example, a sulfuric acid, nitric acid, hydrochloric acid etc. are mentioned.
  • the concentration of the acidic solution is preferably 1% by mass to 50% by mass.
  • the temperature of the acidic solution is preferably 20 ° C. to 80 ° C. When the concentration and temperature of the acidic solution are within the above ranges, the stain resistance (that is, neglectability) of the planographic printing plate is further improved.
  • the surface roughening treatment is a treatment in which an electrochemical surface roughening treatment is performed after performing a mechanical surface roughening treatment and a chemical etching treatment, if desired.
  • the chemical etching treatment can be performed using an alkaline aqueous solution such as caustic soda (that is, sodium hydroxide) before the electrochemical roughening treatment. Thereby, impurities existing in the vicinity of the surface of the aluminum plate can be removed.
  • the electrochemical surface roughening treatment is suitable for producing a lithographic printing plate excellent in printability because it is easy to impart fine irregularities (that is, pits) to the surface of the aluminum plate.
  • the electrochemical surface roughening treatment is preferably carried out in an aqueous solution mainly composed of nitric acid or hydrochloric acid using direct current or alternating current.
  • the following chemical etching treatment is preferably performed after the electrochemical surface roughening treatment.
  • On the surface of the aluminum plate after the electrochemical surface roughening treatment there is smut or intermetallic compound mainly composed of aluminum hydroxide produced when the electrochemical surface roughening treatment is performed.
  • a chemical etching process that is, an alkali etching process
  • an alkaline solution in order to efficiently remove smut.
  • the treatment temperature is preferably 20 ° C. to 80 ° C.
  • the treatment time is preferably 1 second to 60 seconds. It is preferable to contain aluminum ions in the alkaline solution.
  • a chemical etching process using an alkaline solution is performed after the electrochemical surface roughening process, and then a chemical etching process (that is, a desmut process) is performed using a low-temperature acidic solution in order to remove the resulting product. Is preferred. Even when the alkali etching process is not performed after the electrochemical surface roughening process, it is preferable to perform a desmut process in order to efficiently remove the smut.
  • the above-described chemical etching treatment can be performed by a dipping method, a shower method, a coating method, or the like, and is not particularly limited.
  • first anodizing treatment step an aluminum plate having micropores extending in the depth direction (that is, the thickness direction) is formed on the surface of the aluminum plate by anodizing the aluminum plate that has been subjected to the roughening treatment described above. This is a step of forming an oxide film.
  • an aluminum anodized film 32a having micropores 33a is formed on the surface of the aluminum plate 31, as shown in FIG.
  • the first anodizing treatment can be performed by a method conventionally used in this field, but manufacturing conditions are appropriately set so that the above-described micropores can be finally formed.
  • the average diameter (that is, average opening diameter) of the micropores 33a formed in the first anodizing treatment step is preferably about 4 nm to 14 nm, and more preferably 5 nm to 10 nm. If it is in the said range, the micropore which has the predetermined shape mentioned above will be easy to form, and the performance of the obtained lithographic printing plate precursor will be more excellent.
  • the depth of the micropore 33a is preferably about 60 nm to less than 200 nm, more preferably 70 nm to 100 nm. If it is in the said range, the micropore which has the predetermined shape mentioned above will be easy to form, and the performance of the obtained lithographic printing plate precursor will be more excellent.
  • the pore density of the micropore 33a is not particularly limited, but the pore density is preferably 50 / ⁇ m 2 to 4,000 / ⁇ m 2 , and preferably 100 / ⁇ m 2 to 3,000 / ⁇ m 2. Is more preferable. Within the above range, the resulting lithographic printing plate is excellent in printing durability and neglectability and developability of the lithographic printing plate precursor.
  • the film thickness of the anodized film obtained by the first anodizing treatment step is preferably 70 nm to 300 nm, more preferably 80 nm to 150 nm.
  • the resulting lithographic printing plate is excellent in printing durability, neglectability, stain resistance (that is, neglectability) and developability of the lithographic printing plate precursor.
  • the coating amount of the anodized film obtained by the first anodizing treatment step is preferably 0.1 g / m 2 to 0.3 g / m 2 , more preferably 0.12 g / m 2 to 0.25 g / m 2 . is there.
  • the resulting lithographic printing plate is excellent in printing durability, neglectability, stain resistance (that is, neglectability) and developability of the lithographic printing plate precursor.
  • an aqueous solution of sulfuric acid, oxalic acid, phosphoric acid or the like can be used mainly as an electrolytic bath.
  • chromic acid, sulfamic acid, benzenesulfonic acid, etc., or an aqueous solution or a non-aqueous solution combining two or more of these may be used.
  • direct current or alternating current is passed through the aluminum plate in the electrolytic bath as described above, an anodized film can be formed on the surface of the aluminum plate. It is known that the pore diameter changes greatly when the type of electrolyte is changed.
  • the pore diameter is determined as follows: pore diameter in sulfuric acid electrolyte ⁇ pore diameter in oxalic acid electrolyte ⁇ phosphorus
  • the pore diameter increases in the acid electrolyte solution. Therefore, the electrolytic solution is exchanged, and the treatment is performed twice, or the treatment apparatus is connected in two or three steps, and the treatment is continuously performed in two or three steps to form an anodized film structure. It is possible. For example, by using a phosphoric acid electrolytic solution by a method as described in Japanese Patent Application Laid-Open No. 2002-365791, a film having a large pore at the bottom is maintained while maintaining the pore diameter at the surface mouth of the anodized film. Can be obtained.
  • the electrolytic bath may contain aluminum ions.
  • the content of aluminum ions is not particularly limited, but is preferably 1 g / L to 10 g / L.
  • the conditions of the anodizing treatment are appropriately set depending on the electrolytic solution used.
  • the concentration of the electrolytic solution is 1% by mass to 80% by mass (preferably 5% by mass to 20% by mass), and the liquid temperature is 5%.
  • ° C to 70 ° C preferably 10 ° C to 60 ° C
  • current density 0.5 A / dm 2 to 60 A / dm 2 (preferably 5 A / dm 2 to 50 A / dm 2 )
  • voltage 1 V to 100 V preferably 5 V to 50V
  • an electrolysis time of 1 second to 100 seconds preferably 5 seconds to 60 seconds
  • the pore-wide treatment process is a process (that is, a pore diameter enlargement process) for enlarging the diameter (that is, the pore diameter) of the micropores present in the anodized film formed by the first anodizing process.
  • a pore diameter enlargement process for enlarging the diameter (that is, the pore diameter) of the micropores present in the anodized film formed by the first anodizing process.
  • the diameter of the micropore 33a is enlarged, and an anodic oxide film 32b having the micropore 33b having a larger average diameter is formed.
  • the average diameter of the micropores 33b is expanded to a range of 10 nm to 100 nm (preferably 15 nm to 60 nm, more preferably 18 nm to 40 nm).
  • the micropore 33b is a portion corresponding to the large-diameter hole 24 (FIG. 5A) described above. It is preferable to adjust the depth from the surface of the micropore 33b to the same level as the above-described depth A (FIG. 3A) by the pore wide processing.
  • the pore-wide treatment is performed by bringing the aluminum plate obtained by the above-described first anodizing treatment step into contact with an acid aqueous solution or an alkali aqueous solution.
  • the method of making it contact is not specifically limited, For example, the immersion method, the spray method, etc. are mentioned. Of these, the dipping method is preferred.
  • an alkaline aqueous solution is used in the pore wide treatment step, it is preferable to use at least one alkaline aqueous solution selected from the group consisting of sodium hydroxide, potassium hydroxide, and lithium hydroxide.
  • the concentration of the alkaline aqueous solution is preferably 0.1% by mass to 5% by mass.
  • the aluminum plate is placed in the alkaline aqueous solution for 1 second to 300 seconds (preferably 1 second to 50 seconds) under conditions of 10 ° C. to 70 ° C. (preferably 20 ° C. to 50 ° C.). Seconds) is suitable.
  • the alkali treatment liquid may contain a metal salt of a polyvalent weak acid such as carbonate, borate or phosphate.
  • an aqueous acid solution When an aqueous acid solution is used in the pore-wide treatment step, it is preferable to use an aqueous solution of an inorganic acid such as sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, or a mixture thereof.
  • the concentration of the acid aqueous solution is preferably 1% by mass to 80% by mass, and more preferably 5% by mass to 50% by mass.
  • the aluminum plate is brought into contact with the aqueous acid solution for 1 second to 300 seconds (preferably 1 second to 150 seconds) under the condition of the acid temperature of the acid aqueous solution of 5 ° C to 70 ° C (preferably 10 ° C to 60 ° C). is there.
  • Aluminum ions may be contained in the aqueous alkali solution or the aqueous acid solution.
  • the content of aluminum ions is not particularly limited, but is preferably 1 g / L to 10 g / L.
  • the second anodizing treatment step is a step of forming micropores extending in the depth direction (that is, the thickness direction) by subjecting the aluminum plate subjected to the above-described pore wide treatment to anodizing treatment.
  • an anodized film 32c having micropores 33c extending in the depth direction is formed as shown in FIG. 5C.
  • the second anodizing treatment step communicates with the bottom of the micropore 33b whose average diameter is enlarged, the average diameter is smaller than the average diameter of the micropore 33b (ie, corresponding to the large-diameter hole portion 24), and deep from the communication position.
  • a new hole extending in the vertical direction is formed. The hole corresponds to the small-diameter hole 26 described above.
  • the second anodizing treatment step treatment is performed so that the average diameter of newly formed holes is greater than 0 nm and less than 20 nm, and the depth from the communication position with the large-diameter hole 20 is within the predetermined range described above. Is implemented.
  • the electrolytic bath used for the treatment is the same as that in the first anodizing treatment step, and the treatment conditions are appropriately set according to the material used.
  • the conditions of the anodizing treatment are appropriately set depending on the electrolytic solution used. In general, the concentration of the electrolytic solution is 1% by mass to 80% by mass (preferably 5% by mass to 20% by mass), and the liquid temperature is 5%.
  • ° C to 70 ° C (preferably 10 ° C to 60 ° C), current density 0.5A / dm 2 to 60A / dm 2 (preferably 1A / dm 2 to 30A / dm 2 ), voltage 1V to 100V (preferably 5V to 50V) and an electrolysis time of 1 second to 100 seconds (preferably 5 seconds to 60 seconds) are appropriate.
  • the film thickness of the anodized film obtained by the second anodizing treatment step is preferably 200 nm to 2,000 nm, more preferably 750 nm to 1,500 nm. Within the above range, the resulting lithographic printing plate has excellent printing durability and neglectability.
  • the amount of the anodized film obtained by the second anodizing treatment step is preferably 2.2 g / m 2 to 5.4 g / m 2 , more preferably 2.2 g / m 2 to 4.0 g / m 2. a m 2.
  • the resulting lithographic printing plate is excellent in printing durability and neglectability, and developability and scratch resistance of the lithographic printing plate precursor.
  • the ratio of the thickness of the anodized film obtained by the first anodizing treatment process (namely, film thickness 1) and the thickness of the anodized film obtained by the second anodizing treatment process (namely, film thickness 2) (that is, film thickness 2) is preferably 0.01 to 0.15, more preferably 0.02 to 0.10. Within the above range, the lithographic printing plate support is excellent in scratch resistance.
  • the voltage to be applied may be increased stepwise or continuously during the second anodizing process.
  • the voltage to be applied is increased, the diameter of the hole to be formed is increased, and as a result, a shape like the small diameter hole 26 described above is obtained.
  • a third anodizing treatment step may be performed following the second anodizing treatment step.
  • the anodizing treatment in the third anodizing treatment step is performed by appropriately setting the liquid component, current density, time, and the like according to the required surface state of the support by the same method as in the second anodizing treatment step. Just do it.
  • the manufacturing method of the aluminum support body which has an anodized film may have the hydrophilic treatment process which performs a hydrophilic treatment after the polar oxidation process mentioned above.
  • the hydrophilization treatment a known method disclosed in paragraphs 0109 to 0114 of JP-A-2005-254638 can be used.
  • Hydrophilic treatment is preferably performed by a method of immersing in an aqueous solution of an alkali metal silicate such as sodium silicate (that is, sodium silicate) or potassium silicate (that is, potassium silicate).
  • an alkali metal silicate such as sodium silicate (that is, sodium silicate) or potassium silicate (that is, potassium silicate).
  • Hydrophilization treatment with an aqueous solution of an alkali metal silicate such as sodium silicate and potassium silicate is described in US Pat. No. 2,714,066 and US Pat. No. 3,181,461. It can be performed according to methods and procedures.
  • the aluminum support having an anodized film of the present disclosure is preferably a support obtained by subjecting the aluminum plate to the treatments shown in the following aspects A to D in the order shown below. From this point, the A embodiment is particularly preferable. It is desirable to perform water washing between the following processes. However, in the case where two steps (that is, treatments) to be performed consecutively use a liquid having the same composition, washing with water may be omitted.
  • (1) a mechanical surface roughening process may be performed as necessary. From the viewpoint of printing durability and the like, it is preferable that the processing of (1) is not included in each embodiment.
  • the mechanical surface roughening treatment, electrochemical surface roughening treatment, chemical etching treatment, anodizing treatment and hydrophilization treatment in the above (1) to (12) are the same as the above-mentioned treatment methods and conditions. However, the treatment is preferably performed under the treatment method and conditions described below.
  • the mechanical roughening treatment is preferably mechanically roughened with a rotating nylon brush roll having a bristle diameter of 0.2 mm to 1.61 mm and a slurry liquid supplied to the surface of the aluminum plate.
  • a well-known thing can be used as an abrasive
  • the specific gravity (g / cm 3 ) of the slurry liquid is preferably 1.05 g / cm 3 to 1.3 g / cm 3 .
  • a method of spraying a slurry liquid, a method of using a wire brush, a method of transferring the surface shape of an uneven rolling roll to an aluminum plate, or the like may be used.
  • the concentration of the alkaline aqueous solution used for the chemical etching treatment in the alkaline aqueous solution is preferably 1% by mass to 30% by mass.
  • the alloy component contained in the aluminum alloy may be contained in an amount of 0 to 10% by mass.
  • As the alkaline aqueous solution an aqueous solution mainly composed of caustic soda is particularly preferable.
  • the liquid temperature is preferably from room temperature (25 ° C.) to 95 ° C. for 1 to 120 seconds. After the etching process is completed, in order not to bring the treatment liquid into the next process, it is preferable to perform liquid removal by a nip roller and water washing by spraying.
  • the dissolution amount of the aluminum plate in the first alkali etching treatment is preferably 0.5 g / m 2 to 30 g / m 2, more preferably 1.0 g / m 2 to 20 g / m 2 , and 3.0 g / m 2 to 15 g. / M 2 is more preferable.
  • the dissolution amount of the aluminum plate in the second alkali etching treatment is preferably 0.001 g / m 2 to 30 g / m 2, more preferably 0.1 g / m 2 to 4 g / m 2 , and 0.2 g / m 2 to 1. More preferably, 5 g / m 2 .
  • the dissolution amount of the aluminum plate in the third alkali etching treatment is preferably 0.001 g / m 2 to 30 g / m 2, more preferably 0.01 g / m 2 to 0.8 g / m 2 , and 0.02 g / m 2. ⁇ 0.3 g / m 2 is more preferable.
  • the chemical etching process (that is, the first alkaline etching process, the second alkaline etching process, and the third desmut process) in an acidic aqueous solution, phosphoric acid, nitric acid, sulfuric acid, chromic acid, hydrochloric acid, or two or more acids thereof are used.
  • the mixed acid containing is used suitably.
  • the concentration of the acidic aqueous solution is preferably 0.5% by mass to 60% by mass.
  • the acidic aqueous solution 0 mass% to 5 mass% of the alloy components contained in aluminum and the aluminum alloy may be dissolved.
  • the liquid temperature is from room temperature to 95 ° C., and the treatment time is preferably from 1 second to 120 seconds. After the desmut treatment is completed, it is preferable to carry out liquid removal by a nip roller and water washing by spraying in order not to bring the treatment liquid into the next process.
  • the aqueous solution used for the electrochemical surface roughening treatment will be described.
  • an aqueous solution used for the electrochemical surface roughening treatment using a normal direct current or alternating current can be used, and a concentration of 1 g / L to 100 g / L
  • Add 1 or more of hydrochloric acid or nitric acid compound containing nitric acid ions such as aluminum nitrate, sodium nitrate, ammonium nitrate; hydrochloric acid ions such as aluminum chloride, sodium chloride, ammonium chloride, etc.
  • hydrochloric acid ions such as aluminum chloride, sodium chloride, ammonium chloride, etc.
  • a metal contained in an aluminum alloy such as iron, copper, manganese, nickel, titanium, magnesium, or silica may be dissolved.
  • aluminum chloride and aluminum nitrate are added so that aluminum ions are 3 g / L to 50 g / L in an aqueous solution of 0.5% to 2% by mass nitric acid.
  • the liquid temperature is preferably 10 ° C. to 90 ° C., more preferably 40 ° C. to 80 ° C.
  • an aqueous solution used for an electrochemical surface roughening treatment using a normal direct current or alternating current can be used, and a concentration of 1 to 100 g / L.
  • Add 1 or more of hydrochloric acid or nitric acid compound containing nitric acid ions such as aluminum nitrate, sodium nitrate, ammonium nitrate; hydrochloric acid ions such as aluminum chloride, sodium chloride, ammonium chloride, etc. can be used.
  • a metal contained in an aluminum alloy such as iron, copper, manganese, nickel, titanium, magnesium, or silica may be dissolved.
  • aluminum chloride and aluminum nitrate are added so that the aluminum ions are 3 g / L to 50 g / L in a 0.5% by mass to 2% by mass hydrochloric acid aqueous solution.
  • the liquid temperature is preferably 10 ° C to 60 ° C, more preferably 20 ° C to 50 ° C. Hypochlorous acid may be added.
  • the aqueous solution mainly composed of hydrochloric acid used in the electrochemical surface roughening treatment in the aqueous hydrochloric acid solution in the embodiment B can use the aqueous solution used for the electrochemical surface roughening treatment using ordinary direct current or alternating current, Sulfuric acid can be used by adding 0 g / L to 30 g / L to a 1 g / L to 100 g / L hydrochloric acid aqueous solution.
  • hydrochloric acid or nitric acid compound having nitrate ions such as aluminum nitrate, sodium nitrate, ammonium nitrate
  • hydrochloric acid ions such as aluminum chloride, sodium chloride, ammonium chloride
  • a metal contained in an aluminum alloy such as iron, copper, manganese, nickel, titanium, magnesium, or silica may be dissolved.
  • the liquid temperature is preferably 10 ° C to 60 ° C, more preferably 20 ° C to 50 ° C. Hypochlorous acid may be added.
  • Sine wave, rectangular wave, trapezoidal wave, triangular wave, etc. can be used as the alternating current power supply waveform for electrochemical roughening treatment.
  • the frequency is preferably 0.1 Hz to 250 Hz.
  • FIG. 6 shows a graph showing an example of an alternating waveform current waveform diagram used for the electrochemical roughening treatment in the method for producing an aluminum support having an anodized film.
  • ta is the anode reaction time
  • tc is the cathode reaction time
  • tp is the time until the current reaches the peak from
  • Ia is the peak current on the anode cycle side
  • Ic is the peak current on the cathode cycle side It is.
  • the time tp until the current reaches a peak from 0 is preferably 1 ms to 10 ms.
  • tp Due to the influence of the impedance of the power supply circuit, when tp is 1 or more, the power supply voltage required at the rise of the current waveform is reduced, which is preferable from the viewpoint of the equipment cost of the power supply. If tp is 10 ms or less, it becomes difficult to be influenced by a trace amount component in the electrolytic solution, and uniform surface roughening is easily performed.
  • the condition of one cycle of alternating current used for electrochemical surface roughening is that the ratio tc / ta of the cathode reaction time tc to the anode reaction time ta of the aluminum plate is 1 to 20, the quantity of electricity Qc when the aluminum plate is anode and the anode It is preferable that the ratio Qc / Qa of the amount of electricity Qa is 0.3 to 20 and the anode reaction time ta is in the range of 5 ms to 1,000 ms. tc / ta is more preferably 2.5 to 15. Qc / Qa is more preferably 2.5 to 15.
  • the current density is preferably a trapezoidal wave peak value of 10 A / dm 2 to 200 A / dm 2 for both the anode cycle side Ia and the cathode cycle side Ic of the current.
  • Ic / Ia is preferably in the range of 0.3 to 20.
  • the total amount of electricity furnished to anode reaction of the aluminum plate at the time the electrochemical graining is finished 25C / dm 2 ⁇ 1,000C / dm 2 is preferred.
  • electrolytic cell used for electrochemical surface roughening using alternating current known electrolytic cells such as a vertical type, a flat type, and a radial type can be used, but described in JP-A-5-195300.
  • a radial electrolytic cell as described above is particularly preferred.
  • FIG. 7 is a side view showing an example of a radial cell in an electrochemical surface roughening treatment using alternating current in the method for producing an aluminum support having an anodized film.
  • 50 is a main electrolytic cell
  • 51 is an AC power source
  • 52 is a radial drum roller
  • 53a and 53b are main electrodes
  • 54 is an electrolyte supply port
  • 55 is an electrolyte
  • 56 is a slit
  • 57 is an electrolyte passage
  • 58 is an auxiliary anode
  • 60 is an auxiliary anode tank
  • W is an aluminum plate.
  • the electrolysis conditions may be the same or different.
  • the aluminum plate W is wound around a radial drum roller 52 disposed so as to be immersed in the main electrolytic cell 50, and is subjected to electrolytic treatment by main electrodes 53a and 53b connected to the AC power source 51 in the course of conveyance.
  • the electrolytic solution 55 is supplied from the electrolytic solution supply port 54 through the slit 56 to the electrolytic solution passage 57 between the radial drum roller 52 and the main electrodes 53a and 53b.
  • the aluminum plate W treated in the main electrolytic cell 50 is then subjected to electrolytic treatment in the auxiliary anode cell 60.
  • An auxiliary anode 58 is disposed in the auxiliary anode tank 60 so as to face the aluminum plate W, and the electrolytic solution 55 is supplied so as to flow in the space between the auxiliary anode 58 and the aluminum plate W.
  • the positive image recording layer in the lithographic printing plate precursor according to the present disclosure will be described.
  • the positive-type image recording layer includes a photothermal conversion agent and at least one polymer selected from the group consisting of polyurethane, polyurea, polyamide, and acetal resin (hereinafter also referred to as “specific polymer”).
  • the polymer has an acid group, and the content of the specific polymer is 20% by mass or more based on the total solid content of the positive type image recording layer.
  • the positive image recording layer may be a single image recording layer or a layer including a plurality of image recording layers.
  • the photothermal conversion agent in the image recording layer is preferably an infrared absorber, and is preferably a thermal positive type image recording layer capable of imagewise exposure with an infrared laser.
  • the thermal positive type image recording layer of the present disclosure contains a specific polymer, and the specific polymer has an acid group.
  • the specific polymer is preferably alkali-soluble.
  • alkali-soluble refers to being soluble in a 1 mol / l sodium hydroxide solution at 25 ° C.
  • the photothermal conversion agent preferably contains an infrared absorber (hereinafter also referred to as “IR dye”) so that an image can be recorded with an infrared laser.
  • the specific polymer includes a homopolymer containing an acid group in the main chain and / or side chain in the polymer, a copolymer thereof, and a mixture thereof. Therefore, the thermal positive type heat-sensitive layer has a property of dissolving when contacted with an alkali developer.
  • the specific polymer those having at least one of the following acid groups (1) to (7) in the main chain and / or side chain of the polymer are preferable from the viewpoint of solubility in an alkali developer.
  • Phenolic hydroxy group (—Ar—OH) (2) Sulfonamide group (a divalent group represented by —SO 2 NH—R or —SO 2 NH—) (3) Substituted sulfonamide acid group (—SO 2 NHCOR, —SO 2 NHSO 2 R, —CONHSO 2 R) (hereinafter referred to as “active imide group”) (4) Carboxy group (—CO 2 H) (5) Sulfo group (—SO 3 H) (6) Phosphate group (—OPO 3 H 2 ) (7) Phosphonic acid group (—PO 3 H 2 )
  • Ar represents a divalent aryl group which may have a substituent
  • R represents a hydrocarbon group which may have a substituent
  • the specific polymers having an acid group selected from the above (1) to (7) (1) a specific polymer having a phenolic hydroxy group, (2) a sulfonamide group or (3) an active imide group is preferred, A specific polymer having a) phenolic hydroxy group or (2) a sulfonamide group is particularly preferred from the viewpoint of sufficiently ensuring solubility in an alkali developer and film strength.
  • the acid group contained in the specific polymer is at least one selected from the group consisting of (4) a carboxy group, (2) a sulfonamide group, and (1) a phenolic hydroxy group.
  • the acid group is preferably.
  • polyurethane or polyurea contained in the specific polymer used in the present disclosure is not particularly limited as long as it is a conventionally known one.
  • the following urea resins and urethane resins are preferably used.
  • a polymer having a main chain formed by a urea bond is referred to as a urea resin.
  • the “urea bond” is represented by the formula: —NR 1 CONR 2 —.
  • R 1 and R 2 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, A cyclohexyl group or the like, and more preferably a hydrogen atom or an alkyl group having 5 or less carbon atoms.
  • the urea bond may be formed by any means, but can be obtained by a reaction between an isocyanate compound and an amine compound.
  • a terminal hydroxyl group or a hydroxyl group such as 1,3-bis (2-aminoethyl) urea, 1,3-bis (2-hydroxyethyl) urea, 1,3-bis (2-hydroxypropyl) urea, etc.
  • a urea compound substituted with an alkyl group having an amino group may be synthesized as a raw material.
  • the isocyanate compound used as a raw material can be used without particular limitation as long as it is a polyisocyanate compound having two or more isocyanate groups in the molecule, but a diisocyanate compound is preferred.
  • the polyisocyanate compound include 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,3-cyclopentane diisocyanate, 9H-fluorene.
  • the amine compound used as a raw material can be used without particular limitation as long as it is a polyamine compound having two or more amino groups in the molecule, but a diamine compound is preferred.
  • polyamine compounds include 2,7-diamino-9H-fluorene, 3,6-diaminoacridine, acriflavine, acridine yellow, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4′-diamino Benzophenone, bis (4-aminophenyl) sulfone, 4,4′-diaminodiphenyl ether, bis (4-aminophenyl) sulfide, 1,1-bis (4-aminophenyl) cyclohexane, 4,4′-diaminodiphenylmethane, 3 , 3'-diaminodiphenylmethane, 3,3'-diaminobenzophenone, 4,4
  • a polymer whose main chain is formed by a urethane bond is referred to as a urethane resin.
  • the “urethane bond” is represented by the formula: —OC ( ⁇ O) NR 3 —.
  • R 3 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, etc.). It is preferably a hydrogen atom or an alkyl group having 5 or less carbon atoms, more preferably a hydrogen atom or a methyl group.
  • the urethane bond may be formed by any means, but can be obtained by a reaction between an isocyanate compound and a compound having a hydroxy group.
  • the isocyanate compound used as a raw material is preferably a polyisocyanate compound having two or more isocyanate groups in the molecule, and more preferably a diisocyanate compound.
  • a polyisocyanate compound the polyisocyanate compound mentioned as a raw material which forms the said urea bond can be mentioned.
  • the compound having a hydroxy group used as a raw material include a polyol compound, an aminoalcohol compound, an aminophenol compound, and an alkylaminophenol compound, and a polyol compound or an aminoalcohol compound is preferable.
  • the polyol compound is a compound having at least two or more hydroxy groups in the molecule, and preferably a diol compound.
  • the polyol compound may have an ester bond or an ether bond in the molecule.
  • Examples of the polyol compound include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, polyethylene glycol, polytetramethylene glycol, 1,4-cyclohexane.
  • the amino alcohol compound is a compound having an amino group and a hydroxy group in the molecule, and may further have an ether bond in the molecule.
  • amino alcohols examples include aminoethanol, 3-amino-1-propanol, 2- (2-aminoethoxy) ethanol, 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3- Examples thereof include propanediol and 1,3-diamino-2-propanol.
  • a diol compound or a polyol compound having a sulfone group such as bis (4- (2-hydroxyethoxy) phenylsulfone may be used.
  • the polyurea or polyurethane used in the present disclosure further has an acid group.
  • the acid group is preferably at least one group selected from the group consisting of a phenolic hydroxy group, a sulfonamide group, an active imide group, and a carboxy group, and a phenolic hydroxy group, a sulfonamide group, and a carboxy group It is more preferably at least one group selected from the group consisting of, more preferably a phenolic hydroxy group or a sulfonamide group.
  • the acid group may be present in either the main chain or the side chain of the polymer, but is preferably present in the main chain.
  • having a phenolic hydroxyl group in the main chain means having an arylene group bonded to the phenolic hydroxyl group in the main chain.
  • having a sulfonamide group in the main chain means having a divalent group represented by —SO 2 NH— in the main chain.
  • the polyurea or polyurethane used in the present disclosure is at least one selected from the group consisting of a polyurethane containing a structural unit represented by the following formula 1 and a polyurea containing a structural unit represented by the following formula 1.
  • a polyurethane containing a structural unit represented by the following formula 1 Preferably it contains a polymer.
  • X 1 represents —CR 2 —, —O— or —S—, and each R 2 independently represents a hydrogen atom or an alkyl group.
  • the structural unit represented by the above formula 1 is preferably contained in the main chain of polyurethane or polyurea.
  • X 1 is -CH 2 -, - preferably O- or -S-, -CH 2 -, or, more preferably -O-, -CH 2 - to be Further preferred.
  • the halogen atom of the alkyl group in X 1 may be substituted with a halogen atom or the like.
  • two groups represented by —NHC ( ⁇ O) — bonded to two benzene rings are each bonded to —O— to form a urethane bond, or each —NH— To form a urea bond.
  • the bonding position of —NHC ( ⁇ O) — bonded to two benzene rings is not particularly limited, but each is preferably a meta position of X 1 in the benzene ring.
  • the structural unit represented by Formula 1 is preferably a structural unit derived from a diisocyanate compound represented by the following Formula 1A.
  • the diisocyanate compound represented by the formula 1A is reacted with an amine compound (for example, a diamine compound) or an alcohol compound (for example, a diol compound) to include the structural unit represented by the formula 1. It is possible to synthesize polyurea or polyurethane.
  • an amine compound for example, a diamine compound
  • an alcohol compound for example, a diol compound
  • a polyamide resin having an amide bond in the main chain can be used as the specific polymer.
  • the polyamide resin for example, polymers as described in JP-A Nos. 2004-157461 and 2005-91429 are preferably used. However, it is not limited to these as long as it has an acid group and has an amide bond in the main chain because it is alkali-soluble. Specific examples of these compounds include, but are not limited to, polymers represented by the following formula PA-1.
  • polyvinyl acetal can also be used as a polymer having an acetal structure contained in a specific polymer in the main chain.
  • the polyvinyl acetal contains structural units other than the acetal-containing structural unit. May be included.
  • the non-acetal-containing structural units may have the same or different pendant phenol groups, or they may be structural units that do not have pendant phenol groups, or These may include both types of building blocks.
  • poly (vinyl acetal) can also contain structural units containing itaconic acid or crotonic acid groups.
  • these structural units can also have different phenol groups (for example, polyvinyl acetal has two types including an acetal-containing structural unit and different pendant phenol groups. Or three or more different types of structural units.
  • a minor molar amount (less than 20 mol%) of the acetal group in the polyvinyl acetal can be reacted with a cyclic anhydride or an isocyanate compound such as toluenesulfonyl isocyanate.
  • polyvinyl acetal examples include those containing a phenol resin (for example, a novolak resin) or polyvinyl acetal having an acetal-containing structural unit of about 40 mol% to about 80 mol%.
  • a phenol resin for example, a novolak resin
  • polyvinyl acetal has the following structure (PVAc):
  • Preferred examples include polyvinyl acetals containing at least 40 mol% and up to 80 mol% of structural units represented by
  • R and R ′ are each independently a hydrogen atom or a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, n-propyl group).
  • R and R ′ are each independently a hydrogen atom, a substituted or unsubstituted methyl group or a chloro group, and more preferably a hydrogen atom or a methyl group.
  • R and R ′ groups of different structural units in the polyvinyl acetal may be the same or different.
  • R 2 is a substituted or unsubstituted phenol group, a substituted or unsubstituted naphthol group, or a substituted or unsubstituted anthracenol group.
  • These phenol groups, naphthol groups and anthracenol groups can have up to three additional substituents as required, including additional hydroxy groups, methoxy groups, alkoxy groups, aryloxy groups, Thioaryloxy group, halomethyl group, trihalomethyl group, halogeno group, nitro group, azo group, thiohydroxy group, thioalkoxy group, cyano group, amino group, carboxy group, ethenyl group, carboxyalkyl group, phenyl group, alkyl group Alkenyl group, alkynyl group, cycloalkyl group, aryl group, heteroaryl group and heteroalicyclic group.
  • R 2 is preferably an unsubstituted phenol group or a naphthol
  • a preferred polyvinyl acetal has the following structure (I) containing the above structural units:
  • A is the following structure (Ia):
  • m is 5 mol% to 40 mol% (more preferably 15 to 35 mol%)
  • n is 10 mol% to 60 mol% (more preferably 20 mol% to 40 mol%)
  • p is 0 mol% % To 20 mol% (more preferably 0 to 10 mol%)
  • q is 1 mol% to 20 mol% (more preferably 1 mol% to 15 mol%)
  • r is 5 mol% to 49 mol%. It is preferably a mol% (more preferably 15 mol% to 49 mol%).
  • R, R ′, R 1 and R 2 are as defined above for the structure (PVAc) except as noted below.
  • Each R 1 is preferably independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and more preferably an n-propyl group.
  • R 3 represents a substituted or unsubstituted alkynyl group having 2 to 4 carbon atoms (for example, ethynyl group), or a substituted or unsubstituted phenyl group (for example, phenyl group, 4-carboxyphenyl, carboxyalkyleneoxyphenyl group, and A carboxyalkylphenyl group, a 4-carboxyphenyl group, or a carboxyalkyleneoxyphenyl group.
  • R 4 represents a —O—C ( ⁇ O) —R 5 group
  • R 5 represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or a substituted group having 6 or 10 carbon atoms in the aromatic ring.
  • R 6 represents a hydroxy group.
  • the polyvinyl acetal can be at least a tetramer depending on the number of different structural units present.
  • the polyvinyl acetal having the structure (I) may have a structural unit represented by the structure (Ia) having a different R 1 .
  • Such various structural units also apply to the structural units represented by any one of the structures (Ib) to (Ie).
  • the polyvinyl acetal represented by structure (I) may contain structural units other than those defined by structures (Ia), (Ib), (Ic), (Id) and (Ie), such as The building blocks will be apparent to those skilled in the art. Thus, in the broadest sense, structure (I) is not limited to a defined structural unit, but in some embodiments, only the structural unit in structure (I) is present.
  • polyvinyl acetals described herein can be prepared using known starting materials and reaction conditions, including those described in US Pat. No. 6,541,181.
  • polyvinyl acetal a polyvinyl acetal represented by the following formula VA is preferable.
  • R 1A each independently represents an alkyl group, an aryl group, a carboxy group, or an aryl group having a hydroxy group
  • R 2A each independently represents an alkyl group
  • a, b, c and d Represents the molar ratio of each structural unit.
  • R 1A in formula VA is preferably each independently an alkyl group, a carboxy group, or an aryl group having a hydroxy group, more preferably an aryl group having a hydroxy group, a 2-hydroxyphenyl group, 3 -Hydroxyphenyl group, 4-hydroxyphenyl group, 2,3-dihydroxyphenyl group, 2,4-dihydroxyphenyl group, 2-hydroxy-3-methoxyphenyl group, 2,6-dihydroxyphenyl group, 2,4,6 It is more preferably a trihydroxyphenyl group, a 1- (2-hydroxy) naphthyl group, a 2- (3-hydroxy) naphthyl group, or a 3-hydroxy-4-methoxyphenyl group.
  • R 2A in formula VA is preferably each independently an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group.
  • a in Formula VA is preferably 10 mol% to 50 mol%, more preferably 15 mol% to 45 mol%, and still more preferably 20 mol% to 35 mol%.
  • B in the formula VA is preferably 15 mol% to 60 mol%, more preferably 20 mol% to 50 mol%, still more preferably 25 mol% to 45 mol%.
  • C in the formula VA is preferably 10 mol% to 60 mol%, more preferably 15 mol% to 50 mol%, still more preferably 20 mol% to 30 mol%.
  • D in the formula VA is preferably 0 mol% to 10 mol%, more preferably 0 mol% to 3 mol%, and still more preferably 0 mol% to 1 mol%.
  • the specific polymer preferably contains an acetal resin having a structural unit represented by the following formula 2.
  • X B is> CH-, or> N-a represents, L B represents a single bond or a divalent linking group, Ar represents an aromatic ring structure, R represents a substituent, m is 1 N represents an integer of 0 or more, and n + m represents the maximum number of substituents of the aromatic ring structure represented by Ar.
  • X B is preferably> CH—.
  • L B represents a single bond, an alkylene group, an arylene group, or is preferably a group represented by these two or more binding, and more preferably a single bond.
  • Ar is preferably a benzene ring structure, a naphthalene ring structure or an anthracene ring structure, and preferably a benzene ring structure.
  • m is preferably 1 to 3, more preferably 1 or 2, and still more preferably 1.
  • n represents an integer of 0 or more, preferably 0 to 3, more preferably 0 or 1, and still more preferably 0.
  • R is a hydroxy group, a methoxy group, an alkoxy group, an aryloxy group, a thioaryloxy group, a halomethyl group, a trihalomethyl group, a halogeno group, a nitro group, an azo group, a thiohydroxy group, a thioalkoxy group, Examples include cyano group, amino group, carboxy group, ethenyl group, carboxyalkyl group, phenyl group, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, heteroaryl group and heteroalicyclic group.
  • linked to L B (R) n-Ar- (OH) m is unsubstituted phenol groups or naphthol group, such as 2-hydroxyphenyl group or a hydroxy naphthyl group are preferably exemplified.
  • the content of the structural unit represented by the formula 2 is preferably 10 mol% and 60 mol%, and more preferably 20 mol% to 40 mol% with respect to all the structural units of the acetal resin.
  • the weight average molecular weight (Mw) of the polyvinyl acetal used in the present disclosure is preferably 1,500 or more, more preferably 3,000 or more and 300,000 or less, and 10,000 or more and 150,000 or less. More preferably it is.
  • the specific polymer used in the present disclosure preferably includes at least one polymer selected from the group consisting of polyurethane and polyurea from the viewpoint of exhibiting higher printing durability even in a thin film thickness. From the viewpoint of developability, it is preferable to include polyurethane. From the viewpoint of small dot printing durability and solid image area printing durability, the specific polymer preferably contains polyamide. From the viewpoint of the small spot development latitude, the specific polymer preferably contains an acetal resin.
  • the content of the specific polymer with respect to the total solid content of the positive image recording layer is 20% by mass or more, preferably 20% by mass to 95% by mass, more preferably 50% by mass to 90% by mass, and more preferably 60% by mass to 85 mass% is more preferable.
  • the content is 20% by mass or more, in addition to the effect of improving the printing durability, the pattern formability upon development is good.
  • the positive photosensitive resin layer may contain components such as an infrared absorber, an acid generator, and a surfactant described later.
  • the positive image recording layer may further contain another alkali-soluble resin.
  • the other alkali-soluble resin is not particularly limited as long as it has a property of dissolving when contacted with an alkaline developer, but at least one of the main chain and the side chain in the polymer has a sulfonic acid group or a phosphoric acid group. And those having an acidic functional group such as a sulfonamide group and an active imide group are preferred, and examples thereof include resins containing 10 mol% or more of monomers having an acidic functional group imparting alkali solubility. A resin containing 20 mol% or more of a monomer having an acidic functional group to be imparted is more preferable. When the copolymerization component of the monomer imparting alkali solubility is 10 mol% or more, alkali solubility is sufficiently obtained and developability is excellent.
  • novolak resins are also preferred as other alkali-soluble resins.
  • the novolak resin that can be used in the positive photosensitive resin composition according to the present disclosure include phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, and phenol / cresol. (M-, p-, or m- / p-mixing may be used.)
  • Preferred are novolak resins such as mixed formaldehyde resins and pyrogallol acetone resins. Still further, as described in US Pat. No.
  • the weight average molecular weight (Mw) is preferably 500 or more, more preferably 1,000 to 700,000.
  • the number average molecular weight (Mn) is preferably 500 or more, and more preferably 750 to 650,000.
  • the dispersity (weight average molecular weight / number average molecular weight) is preferably 1.1 to 10.
  • the polymerizable monomer having a phenolic hydroxyl group includes a polymerizable monomer composed of a low molecular compound having at least one phenolic hydroxyl group and one or more polymerizable unsaturated bonds. Examples include acrylamides having a hydroxyl group, methacrylamides, acrylic acid esters or methacrylic acid esters, and hydroxystyrene. A monomer having a phenolic hydroxyl group may be used in combination of two or more.
  • the polymerizable monomer having a sulfonamide group includes a sulfonamide group (—NH—SO 2 —) in which at least one hydrogen atom is bonded to a nitrogen atom in one molecule, and a polymerizable unsaturated bond.
  • examples thereof include polymerizable monomers each having one or more low molecular weight compounds.
  • low molecular weight compounds having an acryloyl group, an allyl group or a vinyloxyl group and a mono-substituted aminosulfonyl group or a substituted sulfonylimino group are preferred.
  • Examples of such compounds include compounds represented by general formulas (I) to (V) described in JP-A-8-123029.
  • m-aminosulfonylphenyl methacrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) acrylamide and the like are preferably used as the polymerizable monomer having a sulfonamide group. be able to.
  • Preferred examples of the polymer obtained from the polymerizable monomer having a sulfonamide group include polymers having at least one of the structural unit represented by the following formula S-1 and the structural unit represented by the following formula S-2. .
  • R s1 represents a hydrogen atom or an alkyl group.
  • Z represents —O— or —NR s2 , where R s2 represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group.
  • Ar 1 and Ar 2 each independently represent an aromatic group, and at least one of them is a heteroaromatic group.
  • sa and sb each independently represents 0 or 1;
  • R s1 represents a hydrogen atom or an alkyl group, and the alkyl group is a substituted or unsubstituted alkyl group, and preferably has no substituent.
  • the alkyl group represented by R s1 include lower alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group.
  • R s1 is preferably a hydrogen atom or a methyl group.
  • Z represents —O— or —NR s2 —, preferably —NR s2 —.
  • R s2 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted alkynyl group, preferably a hydrogen atom or an unsubstituted alkyl group, and more Preferably it is a hydrogen atom.
  • sa and sb each independently represents 0 or 1, and a preferred embodiment is the case where sa is 0 and sb is 1, more preferably sa and sb are both 0, particularly preferably sa. And sb are both 1. More specifically, in the above structural unit, when sa is 0 and sb is 1, Z is preferably O. When both sa and sb are 1, Z is preferably NR s2 , where R s2 is preferably a hydrogen atom.
  • Ar 1 and Ar 2 each independently represent an aromatic group, and at least one of them is a heteroaromatic group.
  • Ar 1 is a divalent aromatic group
  • Ar 2 is a monovalent aromatic group.
  • An aromatic group is a substituent formed by replacing one or two hydrogen atoms constituting an aromatic ring with a linking group.
  • the aromatic ring and heteroaromatic ring in the aromatic group may be selected from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, etc., and furan, thiophene, pyrrole, imidazole, 1,2,3-triazole 1,2,4-triazole, tetrazole, oxazole, isoxazole, thiazole, isothiazole, thiadiazole, oxadiazole, pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine Or a heteroaromatic ring such as 1,2,3-triazine.
  • a plurality of rings may be condensed to form a condensed ring such as benzofuran, benzothiophene, indole, indazole, benzoxazole, quinoline, quinazoline, benzimidazole, or benzotriazole.
  • the aromatic group and heteroaromatic group may further have a substituent.
  • substituents that can be introduced include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and a heteroaryl group. , Hydroxy group, mercapto group, carboxy group or alkyl ester thereof, sulfonic acid group or alkyl ester thereof, phosphinic acid group or alkyl ester thereof, amino group, sulfonamide group, amide group, nitro group, halogen atom, or these Examples include a substituent formed by a plurality of bonds, and the substituent may further have the substituents listed here.
  • Ar 2 is preferably an optionally substituted heteroaromatic group, more preferably pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, Examples include heteroaromatic rings containing a nitrogen atom selected from 1,2,3-triazine, tetrazole, oxazole, isoxazole, thiazole, isothiazole, thiadiazole, and oxadiazole.
  • the content of the structural unit represented by Formula S-1 or Formula S-2 (however, converted as a monomer unit) is preferably 10 mol% to 100 mol% with respect to the total amount of monomer units in the polymer, 20 mol% to 90 mol% is more preferable, 30 mol% to 80 mol% is still more preferable, and 30 mol% to 70 mol% is particularly preferable.
  • the polymer may be a copolymer containing other structural units in addition to the structural unit represented by the formula S-1 or S-2.
  • Other structural units include a hydrophobic monomer having a substituent such as an alkyl group or an aryl group in the side chain structure of the monomer, an acid group, an amide group, a hydroxy group or an ethylene oxide group in the side chain structure of the monomer. From these, it is important to select the monomer species to be copolymerized within a range that does not impair the alkali solubility of the polymer. .
  • copolymer components include (meth) acrylamide, N-substituted (meth) acrylamide, N-substituted maleimide, (meth) acrylic acid ester, (meth) acrylic acid ester having a polyoxyethylene chain, 2-hydroxyethyl (Meth) acrylate, styrene, styrene sulfonic acid, o-, p-, or m-vinyl benzene acid, vinyl pyridine, N-vinyl caprolactam, N-vinyl pyrrolidine, (meth) acrylic acid, itaconic acid, maleic acid, glycidyl (Meth) acrylate, hydrolyzed vinyl acetate, vinylphosphonic acid and the like.
  • Preferable copolymer components include N-benzyl (meth) acrylamide, (meth) acrylic acid and the like.
  • the number average molecular weight (Mn) of the polymer having at least one of the structural unit represented by the formula S-1 and the structural unit represented by the formula S-2 is preferably 10,000 to 500,000, More preferred is 10,000 to 200,000, and particularly preferred is 10,000 to 100,000.
  • the weight average molecular weight (Mw) is preferably 10,000 to 1,000,000, more preferably 20,000 to 500,000, and particularly preferably 20,000 to 200,000.
  • the polymerizable monomer having an active imide group is preferably a compound having an active imide group in the molecule described in JP-A No. 11-84657, and can be polymerized with the active imide group in one molecule.
  • polymerizable monomers composed of low-molecular compounds each having one or more unsaturated bonds Specifically, N- (p-toluenesulfonyl) methacrylamide, N- (p-toluenesulfonyl) acrylamide and the like can be preferably used as the polymerizable monomer having an active imide group.
  • the blending mass ratio of these components is 50:50 to 5: It is preferably in the range of 95, more preferably in the range of 40:60 to 10:90.
  • the other alkali-soluble resin is a polymerizable monomer having a phenolic hydroxyl group, a polymerizable monomer having a sulfonamide group, or a polymerizable monomer having an active imide group and another polymerizable monomer
  • the monomer imparting alkali solubility is preferably contained in an amount of 10 mol% or more, more preferably 20 mol% or more, based on the total molar amount of monomers used for copolymerization. Those are more preferred.
  • Examples of the monomer component to be copolymerized with the polymerizable monomer having a phenolic hydroxyl group, the polymerizable monomer having a sulfonamide group, or the polymerizable monomer having an active imide group include the compounds listed in the following (m1) to (m12). However, the present invention is not limited to these.
  • (M1) Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate.
  • Alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, and glycidyl acrylate.
  • Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate and glycidyl methacrylate.
  • (M4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide.
  • (M5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
  • (M6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
  • (M7) Styrenes such as styrene, ⁇ -methylstyrene, methylstyrene, chloromethylstyrene.
  • (M8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
  • (M9) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene.
  • (M11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
  • (M12) Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride and itaconic acid.
  • the other alkali-soluble resin preferably has a weight average molecular weight of 2,000 or more and a number average molecular weight of 500 or more, a weight average molecular weight of more than 5,000 and not more than 300,000, and a number average molecular weight of 800. More preferably, it is ⁇ 250,000.
  • the dispersity (weight average molecular weight / number average molecular weight) of the other alkali-soluble resin is preferably 1.1 to 10.
  • the alkali-soluble resin in the present disclosure may be used alone or in combination of two or more.
  • the content of the alkali-soluble resin in the present disclosure is preferably 5% by mass to 75% by mass, and preferably 10% by mass to 60% by mass with respect to the total solid content of the positive photosensitive resin composition. Is more preferable, and it is still more preferable that it is 15 mass% to 50 mass%.
  • the photothermal conversion agent contained in the thermal positive type image recording layer is a substance that absorbs light and generates heat. It is preferable that an infrared absorber is included as the photothermal conversion agent.
  • the infrared absorber enables the interaction energy of the exposed area of the heat sensitive layer to be efficiently released by converting the exposure energy into heat. From the viewpoint of recording sensitivity, the infrared absorber is preferably a pigment or dye having a light absorption region in the infrared region of a wavelength of 700 nm to 1,200 nm.
  • pigments examples include commercially available pigments, Color Index (CI) Handbook, “Latest Pigment Handbook” (edited by the Japan Pigment Technology Association, published in 1977), “Latest Pigment Applied Technology” (published by CMC, published in 1986) and The pigments described in “Printing Ink Technology” published by CMC (published in 1984) can be used.
  • pigments examples include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and polymer-bonded pigments.
  • a quinophthalone pigment, a dyed lake pigment, an azine pigment, a nitroso pigment, a nitro pigment, a natural pigment, a fluorescent pigment, an inorganic pigment, or carbon black can be used.
  • the pigment may be used without being surface-treated, or may be used after being subjected to a conventionally known surface treatment.
  • the particle diameter of the pigment is preferably 0.01 ⁇ m to 10 ⁇ m, more preferably 0.05 ⁇ m to 1 ⁇ m, and still more preferably 0.1 ⁇ m to 1 ⁇ m.
  • the above range is preferable in terms of the stability of the pigment dispersion in the heat-sensitive layer coating solution and the uniformity of the heat-sensitive layer.
  • a method for dispersing the pigment for example, a known dispersion technique used for ink production or toner production described in “Latest Pigment Application Technology” (CMC Publishing, published in 1986) or the like can be used.
  • dyes commercially available dyes and known ones described in literature (for example, “Dye Handbook”, published by Kodansha (1986), “Dye Handbook”, edited by the Society of Synthetic Organic Chemistry, published in 1970) are used. It can. Specifically, azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, azurenium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal complexes ( For example, dyes such as dithiol metal complexes and metal-containing phthalocyanines can be used.
  • pigments or dyes those that absorb infrared light or near infrared light are particularly preferable because they are suitable for use with lasers that emit infrared light or near infrared light.
  • phthalocyanine including metal-containing phthalocyanine
  • carbon black are preferably used as such a pigment that absorbs infrared light or near infrared light.
  • the dye that absorbs infrared light or near infrared light include cyanine dyes, merocyanine dyes, iminium dyes, oxonol dyes, pyrylium (including thiopyrylium, serenapyrylium, ternapyrylium) dyes, naphthoquinone dyes, Examples thereof include squarylium dyes, phthalocyanine (including metal-containing phthalocyanine) dyes, organometallic complexes (metal complex compounds with dithiol, diamine, etc.), and the like.
  • the dye is a near-infrared absorbing dye described in US Pat. No. 4,756,993 as formula (I) or (II), described in JP-A No. 2000-267265.
  • Infrared absorbing dyes that are soluble in an alkaline aqueous solution Infrared absorbing dyes containing functional groups that change hydrophilicity by heat as described in JP-A-11-309952, JP-A-2000-160131 And polymethine dyes described in JP-A Nos. 2000-330271, 2001-117216 and 2001-174980, and phthalocyanine dyes described in JP-A No. 2000-352817.
  • dye as an infrared absorber used in this indication is not limited to these.
  • the content of the infrared absorber is preferably 0.01% by mass to 50% by mass, more preferably 0.01% by mass to 30% by mass, and still more preferably 0.1% by mass with respect to the total solid content of the heat-sensitive layer. % To 10% by mass, particularly preferably 0.5% to 10% by mass in the case of dyes, and particularly preferably 1 to 10% by mass in the case of pigments.
  • the content of the infrared absorber is less than 0.01% by mass, the sensitivity may be lowered.
  • the content exceeds 50% by mass, the uniformity of the heat-sensitive layer is lost and the durability of the heat-sensitive layer is deteriorated. There is.
  • the positive image recording layer of the thermal positive type further contains other components such as an acid generator, an acid proliferation agent, a development accelerator, a surfactant, a printing / coloring agent, a plasticizer, and a wax agent. Also good. Regarding these components, the description in paragraphs 0119 to 0147 of JP-A No. 2003-1956 can be referred to. For these components, the compounds described in paragraphs 0112 to 0142 of International Publication No. 2016/047392 can be used without particular limitation.
  • the thermal positive type image recording layer may have a two-layer structure comprising a lower layer close to an aluminum support having an anodized film and an upper layer present thereon.
  • An image recording layer having a two-layer structure is described, for example, in JP-A-11-218914.
  • the image recording layer has a two-layer structure, and the lower layer includes a photothermal conversion agent and a specific polymer, the specific polymer has an acid group, and the content of the specific polymer is a positive image.
  • a preferred embodiment is a positive image recording layer that is 20% by mass or more based on the total solid content of the recording layer, and further has an image recording layer as an upper layer.
  • preferred embodiments of the upper layer will be described.
  • the upper layer of the positive-type planographic printing plate precursor having a two-layer structure in the present disclosure may be a layer containing a photothermal conversion agent and a specific polymer, but may be a layer containing another resin.
  • the upper layer of the positive-type planographic printing plate precursor having a two-layer structure in the present disclosure is preferably an infrared-sensitive positive-type image recording layer whose solubility in an aqueous alkali solution is improved by heat.
  • the mechanism for improving the solubility in an aqueous alkali solution by heat in the upper layer and any mechanism can be used as long as it includes a binder resin and improves the solubility of the heated region.
  • the upper layer whose solubility in an alkaline aqueous solution is improved by heat includes, for example, a layer containing an alkali-soluble resin having a hydrogen bonding ability such as novolak and urethane, a water-insoluble and alkali-soluble resin, and a compound having a dissolution inhibiting action.
  • Preferred examples include a layer and a layer containing a compound capable of ablation.
  • the heat generated in the upper layer can also be used for image formation.
  • the upper layer containing the infrared absorber for example, a layer containing an infrared absorber, a water-insoluble and alkali-soluble resin and a compound having a dissolution inhibiting action, an infrared absorber, a water-insoluble and alkali-soluble resin, and an acid generator A layer containing is preferred.
  • the upper layer and the manufacturing method thereof described in Paragraph 0147 to Paragraph 0163 of International Publication No. 2016/047392 can be used without particular limitation.
  • the lower layer and the upper layer can be formed by dissolving the above components in a solvent and applying them.
  • Solvents used include ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxyethane, Methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, ⁇ -butyrolactone, toluene, 1,3-dimethyl-2-imidazolidinone
  • a solvent is used individually or in mixture.
  • the coating amount of the lower layer component after drying is preferably 0.5 g / m 2 to 4.0 g / m 2, more preferably 0.6 g / m 2 to 2.5 g / m 2 .
  • Coating amount after drying of the upper layer component is preferably from 0.05g / m 2 ⁇ 1.0g / m 2, 0.08g / m 2 ⁇ 0.7g / m 2 is more preferable.
  • the coating amount after drying of the lower layer and the upper layer is preferably from 0.6 g / m 2 to 4.0 g / m 2, and more preferably from 0.7 g / m 2 to 2.5 g / m 2 .
  • 0.6 g / m 2 or more printing durability is excellent, and when it is 4.0 g / m 2 or less, image reproducibility and sensitivity are excellent.
  • the lower layer and the upper layer are preferably formed by separating the two layers.
  • a component contained in the lower layer and a component contained in the upper layer examples thereof include a method utilizing the difference in solvent solubility, or a method of rapidly drying and removing the solvent after the upper layer is applied. Use of the latter method in combination is preferable because separation between layers can be performed more satisfactorily.
  • a conventional positive type image recording layer is typically a photosensitive layer containing an alkali-soluble polymer and an o-quinonediazide compound.
  • the description in paragraphs 0042 to 0066 of JP-A No. 2003-1956 can be referred to.
  • an undercoat layer can be provided between the aluminum support having an anodized film and the positive image recording layer, if necessary.
  • the component contained in the undercoat layer is not particularly limited, and various organic compounds described in paragraph [0151] of JP-A-2003-1956 can be used.
  • a polymer having a component having an acid group and a component having an onium group described in JP-A-2000-105462 is also preferably used.
  • this undercoat layer it has sufficient alkali developability, is excellent in stain resistance at the time of printing, suppresses a decrease in image strength, and can obtain a large number of printed images with clear images. .
  • a polymer containing an acid group selected from a phosphonic acid group, a phosphoric acid group, a sulfonic acid group, and a carboxylic acid group is preferably used. It is preferable that it is a copolymer containing the monomer unit which has the said acid group. Further, it may contain a monomer unit having a highly hydrophilic betaine structure at the terminal. More preferred examples of the copolymer include those described in JP-A 2010-284963, paragraphs 0012 to 0036.
  • the undercoat layer component may be used alone or in combination of two or more.
  • the undercoat layer can be formed by the following method. That is, a method in which water or an organic solvent such as methanol, ethanol, methyl ethyl ketone, or a mixed solvent thereof is dissolved in an undercoating layer component applied onto an aluminum support having an anodized film and dried, Alternatively, an aluminum support having an anodized film is immersed in a solution obtained by dissolving an undercoat layer component in an organic solvent such as methanol, ethanol, methyl ethyl ketone, or a mixed solvent thereof to adsorb the above undercoat layer component, and then water. It is a method of forming by washing and drying by, for example.
  • a solution having a concentration of preferably 0.005% by mass to 10% by mass of the undercoat layer component can be applied by various methods.
  • the concentration of the solution is preferably 0.01% by mass to 20% by mass, more preferably 0.05% by mass to 5% by mass
  • the immersion temperature is preferably 20 ° C. to 90 ° C., more preferably
  • the immersion time is preferably 0.1 second to 20 minutes, more preferably 2 seconds to 1 minute.
  • the solution used in the above method can be adjusted to a pH range of 1 to 12 with a basic substance such as ammonia, triethylamine, potassium hydroxide, or an acidic substance such as hydrochloric acid or phosphoric acid.
  • a yellow dye can be contained for improving the tone reproducibility of the lithographic printing plate precursor.
  • the coverage of the undercoat layer is suitably 2 mg / m 2 to 200 mg / m 2 , and preferably 5 mg / m 2 to 100 mg / m 2 .
  • a backcoat layer may be provided on the back surface of the lithographic printing plate precursor as required.
  • a coating comprising a metal oxide obtained by hydrolysis and polycondensation of an organic polymer described in JP-A-5-45885 and an organic or inorganic metal compound described in JP-A-6-35174 A layer is preferably used.
  • silicon alkoxy compounds such as Si (OCH 3 ) 4 , Si (OC 2 H 5 ) 4 , Si (OC 3 H 7 ) 4 , and Si (OC 4 H 9 ) 4 are easily available at low cost and obtained from this.
  • the metal oxide coating layer is preferable because it is excellent in anti-developing solution.
  • the method for preparing a lithographic printing plate according to the present disclosure includes an exposure step of image-exposing the positive lithographic printing plate precursor according to the present disclosure, and an alkali having a pH of 8.5 to pH 13.5 after exposing the exposed positive lithographic printing plate precursor.
  • a development step of developing using an aqueous solution (hereinafter also referred to as “developer”) is included in this order.
  • developer an aqueous solution
  • a lithographic printing plate can be produced by performing conventionally known image formation (for example, exposure) and development processing according to the type of the positive image recording layer.
  • the method for producing a lithographic printing plate according to the present disclosure includes an exposure step of performing image exposure on the positive lithographic printing plate precursor according to the present disclosure. Details are the same as those described in paragraphs 0173 to 0175 of International Publication No. 2016/047392.
  • the actinic ray light source used for image exposure can be appropriately selected according to the type of the positive image recording layer. Specifically, the light source described in paragraph 0268 of JP-A-2003-1956 can be used.
  • the method for producing a lithographic printing plate according to the present disclosure includes a development step of developing using an alkaline aqueous solution (hereinafter also referred to as “developer”) having a pH of 8.5 to 14.0.
  • developer an alkaline aqueous solution having a pH of 8.5 to 14.0.
  • a thermal type lithographic printing plate precursor that is exposed to a desired image by irradiating a laser beam based on digital data is preferably developed by a method using an alkaline developer.
  • the laser light is efficiently absorbed by the infrared absorbent contained in the image recording layer of the exposed portion, and only the image recording layer of the exposed portion is stored due to the accumulation of absorbed energy by exposure.
  • the heat generation generates alkali solubility, and the image recording layer in the exposed area is removed by a development process using an alkali developer, whereby a desired image is formed.
  • the image recording layer is of a conventional positive type, it can be developed using an alkaline developer.
  • the alkaline developer used in the development treatment is an alkaline aqueous solution, which can be appropriately selected from conventionally known alkaline aqueous solutions.
  • an aqueous alkali solution containing an alkali silicate or non-reducing sugar and a base is preferable, and a pH of 12.5 to 14.0 is particularly preferable.
  • the alkali developer reference can be made to the descriptions in paragraphs 0270 to 0292 of JP-A No. 2003-1956.
  • % and “part” mean “% by mass” and “part by mass”, respectively, unless otherwise specified.
  • the molecular weight is a weight average molecular weight (Mw), and the ratio of the structural units is a mole percentage, unless otherwise specified.
  • a weight average molecular weight (Mw) is the value measured as a polystyrene conversion value by a gel permeation chromatography (GPC) method.
  • Desmut treatment in acidic aqueous solution (first desmut treatment) The desmut treatment was performed in an acidic aqueous solution.
  • the acidic aqueous solution used for the desmut treatment was an aqueous solution of 150 g / L sulfuric acid.
  • the liquid temperature was 30 ° C.
  • the desmutting liquid was sprayed and sprayed for 3 seconds.
  • Electrochemical roughening treatment in aqueous hydrochloric acid solution Using an electrolytic solution having an hydrochloric acid concentration of 14 g / L, an aluminum ion concentration of 13 g / L, and a sulfuric acid concentration of 3 g / L, electrochemical roughening is performed. Surface treatment was performed. The liquid temperature of the electrolytic solution was 30 ° C. The aluminum ion concentration was adjusted by adding aluminum chloride.
  • the waveform of the alternating current is a sine wave in which positive and negative waveforms are symmetrical, the frequency is 50 Hz, the anode reaction time and the cathode reaction time in one cycle of the alternating current are 1: 1, and the current density is the peak current value of the alternating current waveform.
  • the amount of electricity was 450 C / dm 2 in terms of the total amount of electricity left by the aluminum plate for the anodic reaction, and the electrolytic treatment was performed four times at intervals of 125 C / dm 2 for 4 seconds.
  • a carbon electrode was used as the counter electrode of the aluminum plate.
  • Alkaline etching treatment An aluminum plate was etched by spraying a caustic soda aqueous solution having a caustic soda concentration of 5 mass% and an aluminum ion concentration of 0.5 mass% with a spray tube at a temperature of 45 ° C. The amount of aluminum dissolved was 0.2 g / m 2 .
  • Desmut treatment in acidic aqueous solution Desmut treatment in acidic aqueous solution was performed.
  • the acidic aqueous solution used for the desmut treatment the waste solution generated in the anodizing treatment step (dissolved in aluminum solution of 5.0 g / L of aluminum ions in a 170 g / L aqueous solution of sulfuric acid) was used.
  • the liquid temperature was 30 ° C.
  • the desmutting liquid was sprayed and sprayed for 3 seconds.
  • the first stage anodizing treatment was performed using a direct current electrolysis anodizing apparatus having the structure shown in FIG.
  • the electrolytic solution was anodized under the conditions shown in Table 1 using a 170 g / L aqueous solution of sulfuric acid.
  • (Ah) Second stage anodizing treatment The second stage anodizing treatment was performed using a direct current electrolysis anodizing apparatus having the structure shown in FIG.
  • the electrolytic solution was anodized under the conditions shown in Table 1 using a 170 g / L aqueous solution of sulfuric acid.
  • the support S1 of the example was obtained from the above surface treatment A. Further, the treatments (Aa) to (Af) of the surface treatment A were performed to obtain a support S5 of a comparative example.
  • BB Desmutting treatment in acidic aqueous solution
  • the desmut treatment was performed in an acidic aqueous solution.
  • the acidic aqueous solution used for the desmut treatment was an aqueous solution of 150 g / L sulfuric acid.
  • the liquid temperature was 30 ° C.
  • the desmutting liquid was sprayed and sprayed for 3 seconds.
  • Electrochemical roughening treatment in aqueous hydrochloric acid solution Using an electrolytic solution having a hydrochloric acid concentration of 14 g / L, an aluminum ion concentration of 13 g / L, and a sulfuric acid concentration of 3 g / L, electrochemical roughening is performed. Surface treatment was performed. The liquid temperature of the electrolytic solution was 30 ° C. The aluminum ion concentration was adjusted by adding aluminum chloride.
  • the waveform of the alternating current is a sine wave in which positive and negative waveforms are symmetrical, the frequency is 50 Hz, the anode reaction time and the cathode reaction time in one cycle of the alternating current are 1: 1, and the current density is the peak current value of the alternating current waveform.
  • the amount of electricity was 450 C / dm 2 in terms of the total amount of electricity left by the aluminum plate for the anodic reaction, and the electrolytic treatment was performed four times at intervals of 125 C / dm 2 for 4 seconds.
  • a carbon electrode was used as the counter electrode of the aluminum plate.
  • the first stage anodizing treatment was performed using a direct current electrolysis anodizing apparatus having the structure shown in FIG.
  • the electrolytic solution was anodized under the conditions shown in Table 1 using a 170 g / L aqueous solution of sulfuric acid.
  • ⁇ Surface treatment C> The following processes (Cb) to (Ci) were performed.
  • the acidic aqueous solution used for the desmut treatment was an aqueous solution of 150 g / L sulfuric acid.
  • the liquid temperature was 30 ° C.
  • the desmutting liquid was sprayed and sprayed for 3 seconds.
  • Electrochemical roughening treatment in aqueous hydrochloric acid solution Using an electrolytic solution having a hydrochloric acid concentration of 14 g / L, an aluminum ion concentration of 13 g / L, and a sulfuric acid concentration of 3 g / L, electrochemical roughening using an alternating current Surface treatment was performed.
  • the liquid temperature of the electrolytic solution was 30 ° C.
  • the aluminum ion concentration was adjusted by adding aluminum chloride.
  • the waveform of the alternating current is a sine wave in which positive and negative waveforms are symmetrical, the frequency is 50 Hz, the anode reaction time and the cathode reaction time in one cycle of the alternating current are 1: 1, and the current density is the peak current value of the alternating current waveform.
  • the amount of electricity was 450 C / dm 2 in terms of the total amount of electricity left by the aluminum plate for the anodic reaction, and the electrolytic treatment was performed four times at intervals of 125 C / dm 2 for 4 seconds.
  • a carbon electrode was used as the counter electrode of the aluminum plate.
  • (Cd) Alkaline Etching Treatment Etching was carried out by spraying an aqueous caustic soda solution having a caustic soda concentration of 5 mass% and an aluminum ion concentration of 0.5 mass% with a spray tube at a temperature of 45 ° C. The amount of aluminum dissolved was 0.2 g / m 2 .
  • (Ce) Desmutting treatment in acidic aqueous solution Desmutting treatment in acidic aqueous solution was performed.
  • the acidic aqueous solution used for the desmut treatment the waste solution generated in the anodizing treatment step (dissolved in aluminum solution of 5.0 g / L of aluminum ions in a 170 g / L aqueous solution of sulfuric acid) was used.
  • the liquid temperature was 30 ° C.
  • the desmutting liquid was sprayed and sprayed for 3 seconds.
  • the first step anodizing treatment was performed using a direct current electrolysis anodizing apparatus having the structure shown in FIG.
  • the electrolytic solution was anodized under the conditions shown in Table 1 using a phosphoric acid 170 g / L aqueous solution.
  • (Ch) Second stage anodizing treatment The second stage anodizing treatment was performed using an anodizing apparatus using direct current electrolysis having the structure shown in FIG.
  • the electrolytic solution was anodized under the conditions shown in Table 1 using the waste liquid generated in the anodizing step (dissolved in aluminum solution: 170 g / L of aluminum ions: 5.0 g / L).
  • (Ci) Third stage anodizing treatment The second stage anodizing treatment was performed using a direct current electrolysis anodizing apparatus having the structure shown in FIG.
  • the electrolytic solution was anodized under the conditions shown in Table 1 using the waste liquid generated in the anodizing step (dissolved in aluminum solution: 170 g / L of aluminum ions: 5.0 g / L). From the above surface treatment C, the support S3 of the example was obtained.
  • Desmut treatment in acidic aqueous solution (first desmut treatment) The desmut treatment was performed in an acidic aqueous solution.
  • the acidic aqueous solution used for the desmut treatment was an aqueous solution of 150 g / L sulfuric acid.
  • the liquid temperature was 30 ° C.
  • the desmutting liquid was sprayed and sprayed for 3 seconds.
  • Electrochemical roughening treatment in aqueous hydrochloric acid solution Using an electrolytic solution having a hydrochloric acid concentration of 14 g / L, an aluminum ion concentration of 13 g / L, and a sulfuric acid concentration of 3 g / L, electrochemical roughening using an alternating current Surface treatment was performed.
  • the liquid temperature of the electrolytic solution was 30 ° C.
  • the aluminum ion concentration was adjusted by adding aluminum chloride.
  • the waveform of the alternating current is a sine wave in which positive and negative waveforms are symmetrical, the frequency is 50 Hz, the anode reaction time and the cathode reaction time in one cycle of the alternating current are 1: 1, and the current density is the peak current value of the alternating current waveform.
  • the amount of electricity was 450 C / dm 2 in terms of the total amount of electricity left by the aluminum plate for the anodic reaction, and the electrolytic treatment was performed four times at intervals of 125 C / dm 2 for 4 seconds.
  • a carbon electrode was used as the counter electrode of the aluminum plate.
  • (Cd) Alkaline Etching Treatment Etching was carried out by spraying an aqueous caustic soda solution having a caustic soda concentration of 5 mass% and an aluminum ion concentration of 0.5 mass% with a spray tube at a temperature of 45 ° C. The amount of aluminum dissolved was 0.2 g / m 2 .
  • (Ce) Desmutting treatment in acidic aqueous solution Desmutting treatment in acidic aqueous solution was performed.
  • the acidic aqueous solution used for the desmut treatment the waste solution generated in the anodizing treatment step (dissolved in aluminum solution of 5.0 g / L of aluminum ions in a 170 g / L aqueous solution of sulfuric acid) was used.
  • the liquid temperature was 30 ° C.
  • the desmutting liquid was sprayed and sprayed for 3 seconds.
  • the first step anodizing treatment was performed using a direct current electrolysis anodizing apparatus having the structure shown in FIG.
  • the electrolytic solution was anodized under the conditions shown in Table 1 using a phosphoric acid 170 g / L aqueous solution. From the above surface treatment D, a support S4 was obtained.
  • the surface treatment conditions for the supports S1 to S5 are shown in Table 1 below.
  • the description “A (up to Af)” in the comparative example indicates that the surface treatment of the aluminum plate is performed according to ⁇ Surface Treatment A> (Af) First stage anodization This means that the process up to the processing step was performed and the subsequent steps were not performed.
  • Table 2 shows the average diameter of the large-diameter hole portion on the surface of the anodized film and the average diameter of the small-diameter hole portion at the communication position.
  • the support described as “-” in the “connection position pore diameter (nm)” and “shape” columns of the small-diameter hole means that the small-diameter hole has no small-diameter hole.
  • the depth of the large-diameter hole was deep and it was difficult to measure the diameter of the small-diameter hole
  • the upper part of the anodized film was cut, and then the diameter of the small-diameter hole was obtained.
  • the depth of the micropores was observed by FE-SEM through the cross section of the anodized film (large-diameter hole depth observation: 150,000 times, small-diameter hole depth) Observation: 50,000 times) In the obtained image, the depth of 25 micropores was measured and averaged.
  • the amount of P and the amount of Ca on the support after the treatment were 25 mg / m 2 and 1.9 mg / m 2 , respectively.
  • A- -Polyurethane 1 0.82 parts below-Infrared absorber (IR dye (1) below): 0.017 parts-Crystal violet (manufactured by Hodogaya Chemical Co., Ltd.): 0.017 parts-Megafac (registered trademark) F -177 (manufactured by DIC Corporation, fluorosurfactant): 0.015 part N, N-dimethylacetamide: 10 parts Methyl ethyl ketone: 10 parts 1-methoxy-2-propanol: 8 parts
  • Polyurethane 1 A diisocyanate compound represented by the following formula and a diol compound were polymerized so as to have a molar ratio of 1: 1 (mass average molecular weight 36,000).
  • the composition was the same as that of the lower layer forming coating solution A except that the polyurethane 1 was changed to the following polyurethane 2.
  • Polyurethane 2 >> Copolymer of dimethylolpropionic acid / bis (4- (2-hydroxyethoxy) phenylsulfone / 1,10-decandiol / diphenylmethane diisocyanate / 2,4-tolylene diisocyanate (mass ratio: 20/17/5/40 / 8, mass average molecular weight 16,000)
  • the composition was the same as that of the lower layer forming coating solution A except that the polyurethane 1 was changed to the polyurea 1 described below.
  • Polyurea 1 Polyurea represented by the above formula PU-1 (molar ratio 50/50, weight average molecular weight 20,000)
  • the composition was the same as the coating liquid A for forming the lower layer except that the polyurethane 1 was changed to the following polyamide 1.
  • Polyamide 1 Polyamide represented by the following formula (molar ratio 35/15/45/5, mass average molecular weight 18,000)
  • Acetal 1 Acetal resin represented by the following formula (molar ratio 35/15/50/5, mass average molecular weight 52,000)
  • Acetal 2 Acetal resin represented by the following formula (n / m / o ratio (molar ratio): 40/30/30, mass average molecular weight 48,000)
  • the composition is the same as that of the coating solution A for forming the lower layer except that the amount of polyurethane 1 added is changed from 0.82 to 0.21 part and 0.61 part of the novolak 1 is further added. I made it.
  • the image recording layer is a single layer (hereinafter referred to as “single layer”)
  • the following coating solution for forming an image recording layer is formed on the obtained support so that the dry coating amount is 1.0 g / m 2.
  • I to K were applied and oven-dried at 140 ° C. for 50 seconds to form an image recording layer.
  • I- -Acetal 1 2.47 parts-Novolak 1: 0.374 parts-Infrared absorber (IR dye (1)): 0.155 parts-2-methoxy-4- (N-phenylamino) benzenediazonium -Hexafluorophosphate: 0.03 parts-Tetrahydrophthalic anhydride: 0.19 parts-Ethyl violet counter ion converted to 6-hydroxy- ⁇ -naphthalenesulfonic acid: 0.11 parts-Fluorosurfactant (Mega Fax F-780, manufactured by DIC Corporation): 0.07 parts p-Toluenesulfonic acid: 0.008 parts Bis-p-hydroxyphenylsulfone: 0.13 parts Methyl ethyl ketone: 24 parts 1-methoxy- 2-propanol: 11 parts
  • the composition was the same as that of the coating liquid I for forming a single layer, except that acetal 1 was changed to the above acetal 2.
  • the composition was the same as that of the coating liquid I for forming a single layer except that the acetal 1 was excluded and the novolak 1 was used as the acetal 1.
  • the planographic printing plate precursor is exposed with a Lotem 400 Quantum imager manufactured by CREO at an energy of 80 mJ / cm 2 , and using a developer Goldstar Premium Plate Developer (pH 13.0) manufactured by Kodak, InterPlater manufactured by Glunz & Jensen. Development was carried out in a processor at 25 ° C. for 30 seconds, and gumming was performed with Finisher FP2W (1: 1 dilution) manufactured by Fuji Film Co., Ltd.
  • the exposure image includes a solid image, a 50% halftone dot and a 3% halftone dot of TAFFETA20 (FM screen) manufactured by FUJIFILM Corporation, and a letter cut chart of 7 points tomorrow morning.
  • Solid image area printing durability Printing is performed in the same manner as the evaluation of the small dot printing durability, and the number of copies when the density value of the solid image in the printed matter is 5% lower than the measurement value of the 100th printed sheet is calculated. Printing durability was evaluated as the number of printed sheets. Tables 3 to 5 show the number of completed sheets. The greater the number of printed sheets, the better the printing durability.
  • the planographic printing plate obtained by the above exposure and development was attached to the plate cylinder of a printing machine LITHRONE 26 manufactured by Komori Corporation.
  • Equality-2 manufactured by FUJIFILM Corporation
  • tap water 2/98 (volume ratio) dampening water and Values-G (N) black ink (manufactured by Dainippon Ink & Chemicals, Inc.) Supplying dampening water and ink using the standard automatic printing start method of LITHRNE26 and printing over 100 sheets on Tokishi Art (continuous weight 76.5 kg) paper, confirming that good prints have been obtained After that, printing was temporarily stopped, and left on a printing machine in a room at a temperature of 25 ° C.
  • the lithographic printing plate precursor according to the present disclosure As shown in Tables 3 to 5 above, according to the lithographic printing plate precursor according to the present disclosure, a lithographic printing plate excellent in small dot printing durability was obtained. Moreover, according to the lithographic printing plate precursor according to the present disclosure, a lithographic printing plate excellent in solid image area printing durability and neglectability was obtained. Furthermore, the lithographic printing plate precursor according to the present disclosure was excellent in the stability of small points with respect to development conditions. When the supports S1, S2, S3, S4 and the specific polymer are combined, the solid image portion has excellent printing durability compared to the combination of the support S5 and the specific polymer, and the combination with the specific polymer. It can be seen that small dot printing durability and small dot latitude with respect to development conditions are improved.

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Abstract

L'invention concerne un précurseur positif de plaque d'impression lithographique comprenant, dans cet ordre, un support en aluminium et une couche d'enregistrement d'image positive, et dans lequel : le support en aluminium comprend une plaque d'aluminium et un film d'oxyde anodique d'aluminium disposé sur la plaque d'aluminium ; le film d'oxyde anodique est situé plus près de la couche d'enregistrement d'image positive que ne l'est la plaque d'aluminium ; le film d'oxyde anodique possède des micropores s'étendant dans le sens de la profondeur à partir de la surface située sur le côté opposé à la plaque d'aluminium ; le diamètre moyen des micropores sur la surface du film d'oxyde anodique est de 10 à 100 nm ; la couche d'enregistrement d'image positive comprend un agent de conversion photothermique et un polymère spécifique ; le polymère comprend un groupe acide ; et le polymère est présent dans une quantité spécifique. La présente invention concerne également un procédé de fabrication d'une plaque d'impression lithographique.
PCT/JP2019/001559 2018-01-31 2019-01-18 Précurseur positif de plaque d'impression lithographique et procédé de fabrication d'une plaque d'impression lithographique WO2019150998A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI775465B (zh) * 2020-06-03 2022-08-21 日商昭和電工股份有限公司 正型感光性樹脂組成物，及有機ｅｌ元件隔膜

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004287194A (ja) * 2003-03-24 2004-10-14 Fuji Photo Film Co Ltd 感熱性平版印刷版
JP2006058430A (ja) * 2004-08-18 2006-03-02 Fuji Photo Film Co Ltd 平版印刷版原版
JP2011245844A (ja) * 2009-12-28 2011-12-08 Fujifilm Corp 平版印刷版用支持体、平版印刷版用支持体の製造方法、および平版印刷版原版
JP2014198453A (ja) * 2012-07-27 2014-10-23 富士フイルム株式会社 平版印刷版用支持体およびその製造方法、並びに、平版印刷版原版

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004287194A (ja) * 2003-03-24 2004-10-14 Fuji Photo Film Co Ltd 感熱性平版印刷版
JP2006058430A (ja) * 2004-08-18 2006-03-02 Fuji Photo Film Co Ltd 平版印刷版原版
JP2011245844A (ja) * 2009-12-28 2011-12-08 Fujifilm Corp 平版印刷版用支持体、平版印刷版用支持体の製造方法、および平版印刷版原版
JP2014198453A (ja) * 2012-07-27 2014-10-23 富士フイルム株式会社 平版印刷版用支持体およびその製造方法、並びに、平版印刷版原版

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI775465B (zh) * 2020-06-03 2022-08-21 日商昭和電工股份有限公司 正型感光性樹脂組成物，及有機ｅｌ元件隔膜

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