WO2020045587A1 - Matrice de plaque d'impression lithographique, procédé de production de plaque d'impression lithographique, procédé d'impression lithographique et composition durcissable - Google Patents

Matrice de plaque d'impression lithographique, procédé de production de plaque d'impression lithographique, procédé d'impression lithographique et composition durcissable Download PDF

Info

Publication number
WO2020045587A1
WO2020045587A1 PCT/JP2019/033985 JP2019033985W WO2020045587A1 WO 2020045587 A1 WO2020045587 A1 WO 2020045587A1 JP 2019033985 W JP2019033985 W JP 2019033985W WO 2020045587 A1 WO2020045587 A1 WO 2020045587A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
lithographic printing
printing plate
mass
compound
Prior art date
Application number
PCT/JP2019/033985
Other languages
English (en)
Japanese (ja)
Inventor
俊佑 柳
洋平 石地
健次郎 荒木
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Publication of WO2020045587A1 publication Critical patent/WO2020045587A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • 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
    • B41N1/12—Printing plates or foils; Materials therefor non-metallic other than stone, e.g. printing plates or foils comprising inorganic materials in an organic matrix
    • B41N1/14—Lithographic printing foils
    • 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
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

  • the present disclosure relates to a lithographic printing plate precursor, a method for preparing a lithographic printing plate, a lithographic printing method, and a curable composition.
  • a lithographic printing plate is composed of an oleophilic image area that receives ink during the printing process and a hydrophilic non-image area that receives fountain solution.
  • Lithographic printing utilizes the property that water and oil-based ink repel each other, so that the lipophilic image area of the lithographic printing plate is an ink receiving area and the hydrophilic non-image area is a dampening water receiving area (ink non-receiving area).
  • a difference in the adhesiveness of ink is caused on the surface of a lithographic printing plate, the ink is applied only to an image portion, and then the ink is transferred to a printing medium such as paper and printed.
  • a lithographic printing plate precursor comprising a hydrophilic support and a lipophilic photosensitive resin layer (image recording layer) provided thereon.
  • PS plate lithographic printing plate precursor
  • image recording layer a lipophilic photosensitive resin layer
  • a lithographic printing plate is obtained by performing plate making by dissolving and removing with a solvent and exposing a hydrophilic support surface to form a non-image portion.
  • lithographic printing plate precursor As one of the simple manufacturing methods, a method called “on-press development” is performed. That is, after exposure of the lithographic printing plate precursor, conventional development is not performed, and the lithographic printing plate precursor is directly mounted on a printing machine to remove unnecessary portions of the image recording layer at an initial stage of a normal printing process.
  • Conventional lithographic printing plate precursors include, for example, those described in Patent Literature 1 and Patent Literature 2.
  • Patent Literature 1 discloses a lithographic printing plate precursor including a substrate and having an image-forming layer thereon, wherein the precursor includes polymer particles having an average diameter of 3 to 20 ⁇ m in an outermost layer, and the polymer particles include: Including a crosslinked polymer core, and having a graft hydrophilic polymer surface group, the polymer surface group is grafted on the particle surface by polymerizing a hydrophilic monomer in the presence of the crosslinked polymer particles The lithographic printing plate precursor is described.
  • Patent Document 2 discloses that (A) an infrared absorber, (B) a radical polymerization initiator, (C) a radical polymerizable monomer, and (D) a mercapto group in one molecule on a roughened aluminum support.
  • a lithographic printing plate precursor having a compound having two or more containing groups and (E) polymer fine particles having a polyalkylene oxide segment in an image recording layer is described.
  • Patent Document 1 Japanese Patent Application Publication No. 2013-503365
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2010-234587
  • a lithographic printing plate excellent in the number of printable plates (hereinafter, also referred to as “printing durability”) is required.
  • ink that is cured by irradiation with ultraviolet light (UV) (also referred to as “ultraviolet curable ink”) may be used as the ink in printing.
  • UV-curable inks have high productivity because they can be instantaneously dried, generally have a low solvent content, or they are solvent-free, so that environmental pollution is easily reduced. Since an image can be formed in a short drying time, there is an advantage that an application range such as an object to be printed is widened.
  • a lithographic printing plate capable of providing a lithographic printing plate excellent in printing durability (hereinafter, also referred to as “UV printing durability”) when using an ultraviolet curable ink is extremely useful industrially. Conceivable.
  • the lithographic printing plate precursors described in Patent Document 1 or Patent Document 2 show that, when an ultraviolet-curable ink is used as the ink, the printing durability of the obtained lithographic printing plate is reduced. We found that there was room for further improvement.
  • a problem to be solved by an embodiment of the present disclosure is to provide a lithographic printing plate precursor from which a lithographic printing plate excellent in printing durability can be obtained even when an ultraviolet curable ink is used.
  • a problem to be solved by another embodiment of the present disclosure is to provide a method of manufacturing a planographic printing plate or a planographic printing method which is excellent in printing durability even when using an ultraviolet curable ink.
  • a problem to be solved by yet another embodiment of the present disclosure is to provide a curable composition including the novel polymer particles.
  • Means for solving the above problems include the following aspects. ⁇ 1> having a support and an image recording layer in this order;
  • the image recording layer contains polymer particles containing an addition polymerization type resin,
  • a lithographic printing plate precursor wherein the addition-polymerizable resin has a polymerizable group and a crosslinked structure.
  • the addition-polymerizable resin further has a hydrophilic structure.
  • ⁇ 3> The lithographic printing plate precursor according to ⁇ 2>, wherein the hydrophilic structure contains a group represented by the following formula Z.
  • Q represents a divalent linking group
  • W represents a divalent group having a hydrophilic structure or a divalent group having a hydrophobic structure
  • Y is a monovalent group having a hydrophilic structure or Represents a monovalent group having a hydrophobic structure
  • one of W and Y has a hydrophilic structure
  • * represents a binding site to another structure.
  • R 1 , R 2 , R 3, and R 4 each independently represent an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a heterocyclyl group, or R 1 , R 2 2 , R 3 and R 4 represent a structure in which two or more of them combine to form a heterocyclic ring containing a boron atom as a ring member described in Formula I, and Z + represents a cation.
  • Z + represents a cation.
  • ⁇ 7> The lithographic printing plate precursor as described in any one of ⁇ 1> to ⁇ 6> above, wherein the polymer particles are organic solvent-dispersible polymer particles.
  • ⁇ 8> The lithographic printing plate precursor as described in any one of ⁇ 1> to ⁇ 7> above, wherein the median diameter of the polymer particles is 1,000 nm or less.
  • ⁇ 9> The lithographic printing plate precursor as described in any one of ⁇ 1> to ⁇ 8> above, wherein the variation coefficient of the particle size of the polymer particles is 100% or less.
  • the image recording layer contains an infrared absorber, a polymerization initiator, and core-shell particles
  • the core of the core-shell particles contains an addition polymerization type resin A having a functional group A
  • the addition polymerizable resin A in the core portion includes a crosslinked structure
  • the shell portion of the core-shell particles contains a functional group B capable of binding or interacting with the functional group A, and a compound B having a polymerizable group.
  • Lithographic printing plate precursor ⁇ 11> The lithographic printing plate precursor according to ⁇ 10>, wherein the functional group B is a group that can be covalently bonded to the functional group A.
  • ⁇ 12> The lithographic printing plate precursor according to ⁇ 10>, wherein the functional group B is a group capable of ion-bonding with the functional group A.
  • the functional group B is a group capable of performing a dipole interaction with the functional group A.
  • the functional group B is a group capable of hydrogen bonding with the functional group A.
  • the polymerizable group of the compound B is a (meth) acryloxy group.
  • lithographic printing plate precursor according to any one of ⁇ 1> to ⁇ 15> above, which is an on-press development type lithographic printing plate precursor.
  • ⁇ 17> a step of imagewise exposing the lithographic printing plate precursor according to any one of the above ⁇ 1> to ⁇ 16>, Supplying at least one selected from the group consisting of a printing ink and a fountain solution to remove an image recording layer in a non-image area on a printing press.
  • ⁇ 18> a step of imagewise exposing the lithographic printing plate precursor according to any one of the above ⁇ 1> to ⁇ 16>, A step of providing a lithographic printing plate by supplying at least one selected from the group consisting of printing ink and fountain solution and removing the image recording layer of the non-image portion on a printing press, Printing with the obtained lithographic printing plate.
  • ⁇ 19> containing polymer particles containing an addition polymerization type resin, A curable composition wherein the addition polymerization type resin has a polymerizable group and a crosslinked structure.
  • the curable composition according to ⁇ 19>, wherein the addition polymerization type resin further has a hydrophilic structure.
  • ⁇ 21> The curable composition according to ⁇ 19>, wherein the hydrophilic structure includes a polyalkylene oxide structure.
  • ⁇ 22> The curable composition according to any one of ⁇ 19> to ⁇ 21>, which is used for manufacturing a lithographic printing plate precursor.
  • a lithographic printing plate precursor from which a lithographic printing plate having excellent printing durability can be obtained even when an ultraviolet curable ink is used.
  • a method of manufacturing a planographic printing plate or a planographic printing method which is excellent in printing durability even when an ultraviolet curable ink is used.
  • a curable composition including the novel polymer particles can be provided.
  • 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. It is.
  • the term “step” in the present specification is not limited to an independent step, and even if it cannot be clearly distinguished from other steps, the term is used as long as the intended purpose of the step is achieved. included.
  • each component in the composition or each constituent unit in the polymer in the present disclosure may be included alone or in combination of two or more.
  • the amount of each component in the composition, or each constituent unit in the polymer, each component in the composition, or a plurality of substances or constituent units corresponding to each constituent unit in the polymer are present in this case, unless otherwise specified, it refers to the total amount of the corresponding plural substances present in the composition or the corresponding plural structural units present in the polymer.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • TSKgel @ GMHxL TSKgel @ G4000HxL
  • TSKgel @ G2000HxL all trade names manufactured by Tosoh Corporation
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • It is a molecular weight detected by a gel permeation chromatography (GPC) analyzer using a solvent THF (tetrahydrofuran) and a differential refractometer and converted using polystyrene as a standard substance.
  • GPC gel permeation chromatography
  • the median diameter of the polymer particles in the present disclosure refers to a value measured by a light scattering method, unless otherwise specified, and the median diameter is such that when the powder is divided into two from a certain particle diameter, the larger side and the smaller Refers to the diameter of the same number of sides.
  • the measurement of the median diameter of the polymer particles by the light scattering method is performed using LA-920 (manufactured by HORIBA, Ltd.) in accordance with the manual of the above instrument.
  • the term “lithographic printing plate precursor” includes not only the lithographic printing plate precursor but also a discarded plate precursor. Further, the term “lithographic printing plate” includes not only a lithographic printing plate precursor but also a lithographic printing plate produced through operations such as exposure and development, if necessary, as well as a discarded plate. In the case of a discarded plate master, exposure and development operations are not necessarily required.
  • the discarded plate is a lithographic printing plate precursor to be attached to an unused plate cylinder, for example, when printing a part of the paper surface in monochrome or two colors in color newspaper printing.
  • “*” in the chemical structural formula represents a bonding position with another structure.
  • the lithographic printing plate precursor according to the present disclosure has a support and an image recording layer in this order, and the image recording layer has polymer particles containing an addition-polymerizable resin (hereinafter, also referred to as “specific polymer particles”). ), And the addition-polymerizable resin has a polymerizable group and a crosslinked structure.
  • the lithographic printing plate precursor according to the present disclosure is preferably a negative type lithographic printing plate precursor.
  • the lithographic printing plate precursor according to the present disclosure can be suitably used as an on-press development type lithographic printing plate precursor.
  • an on-press development type lithographic printing plate precursor refers to a lithographic printing plate precursor that can be developed by an on-press development method described later.
  • the lithographic printing plate precursor having the above-described configuration provides a lithographic printing plate excellent in printing durability (UV printing durability) even when using an ultraviolet curable ink.
  • the detailed mechanism for obtaining the above effects is unknown, but is presumed as follows.
  • the specific polymer particles include an addition-polymerizable resin having a crosslinked structure, thereby increasing the hardness of the specific polymer particles themselves.
  • the addition-polymerizable resin has a polymerizable group, for example, a polymerizable compound, a binder It is easy to form a cross-linked structure with a matrix such as a polymer, so the strength of the entire image recording layer is improved, and even when using an ultraviolet-curable ink, which deteriorates the plate more easily than other inks, the printing durability is improved. It is considered that a lithographic printing plate precursor excellent in the above is obtained.
  • the specific polymer particles used in the present disclosure have a crosslinked structure, their stability (chemical resistance) with respect to chemicals other than ultraviolet curable inks (for example, a plate cleaner used for cleaning the plate surface during printing). ) Are easy to improve, and because the stability of the specific polymer particles is high, scum is hardly generated during on-press development, and it is considered that a lithographic printing plate precursor excellent in on-press development scum suppression property is easily obtained. Also, the lithographic printing plate precursor according to the present disclosure is considered to be excellent in printing durability even when using a solvent ink that is not an ultraviolet curable ink.
  • the lithographic printing plate precursor according to the present disclosure has an image recording layer containing specific polymer particles.
  • the image recording layer used in the present disclosure is preferably a negative type image recording layer.
  • the image recording layer in the present disclosure is preferably one of the following first and second embodiments from the viewpoint of printing durability and photosensitivity.
  • First Embodiment Contains specific polymer particles, an infrared absorber, a polymerization initiator, and a polymerizable compound.
  • Second embodiment contains specific polymer particles, an infrared absorber and hydrophobic thermoplastic polymer particles.
  • the image recording layer used in the present disclosure preferably further contains a binder polymer in the first embodiment from the viewpoint of printing durability, particularly UV printing durability.
  • the image recording layer used in the present disclosure may further contain hydrophobic thermoplastic polymer particles in the first aspect from the viewpoint of on-press developability.
  • the unexposed portion of the image recording layer is preferably removable with at least one of a fountain solution and a printing ink from the viewpoint of on-press developability.
  • the image recording layer in the lithographic printing plate precursor according to the present disclosure includes polymer particles (specific polymer particles) containing an addition-polymerizable resin having a polymerizable group and a crosslinked structure.
  • the specific polymer particles preferably contain the addition-polymerizable resin in an amount of 80% by mass or more based on the total mass of the specific polymer particles, from the viewpoint of UV printing durability and on-press developability. It is more preferable that it contains 90% by mass or more, further preferably contains 95% by mass or more of the above-mentioned addition polymerization type resin, and it is particularly preferable that the particles are made of the above addition polymerization type resin.
  • the upper limit of the content of the addition polymerization type resin is not particularly limited, and may be 100% by mass or less.
  • the content of the resin component in the specific polymer particles is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more.
  • the upper limit of the content of the resin component is not particularly limited, and may be 100% by mass or less.
  • the addition polymerization type resin is preferably a resin obtained by polymerizing an ethylenically unsaturated compound from the viewpoint of UV printing durability and ease of production, and is preferably a polyfunctional ethylenically unsaturated compound or a monofunctional ethylenically unsaturated compound. More preferably, it is a resin obtained by copolymerizing a compound.
  • the polymerizable group and the crosslinked structure in the addition polymerization type resin may each have only one type, or may have either or both two or more types.
  • the addition polymerization type resin has at least a polymerizable group.
  • the polymerizable group may be, for example, a cationic polymerizable group or a radical polymerizable group, but is preferably a radical polymerizable group from the viewpoint of reactivity.
  • the polymerizable group is not particularly limited, but is preferably an ethylenically unsaturated group from the viewpoint of reactivity, and is more preferably a vinylphenyl group (styryl group) or a (meth) acryloxy group or a (meth) acrylamide group.
  • a (meth) acryloxy group is most preferred.
  • the introduction of these polymerizable groups into specific polymer particles includes a method of introducing a polymerizable group due to the residual polyfunctional monomer added during particle synthesis and a method of introducing the polymerizable group to the particle surface by a polymer reaction after particle synthesis.
  • a method in which the particles are introduced by a polymer reaction after synthesis is desirable. This is because introducing polymerizable groups after particle synthesis allows more active polymerizable groups to be present on the surface of the particles, so the reactivity with the matrix increases and it is easy to form a strong crosslink with the matrix. Because it is possible.
  • the structural unit having a polymerizable group can be introduced into the above addition polymerization type resin by, for example, a polymer reaction.
  • a method in which a compound having an epoxy group and a polymerizable group (for example, glycidyl methacrylate) is reacted with a polymer into which a structural unit having a carboxy group such as methacrylic acid is introduced It can be introduced by, for example, a method in which a compound having an isocyanate group and a polymerizable group (such as 2-isocyanatoethyl methacrylate) is reacted with a polymer into which a structural unit having a group having an active hydrogen such as a group is introduced.
  • a structural unit having a carboxy group such as the methacrylic acid or a structural unit having a group having an active hydrogen (hereinafter, also referred to as a “structural unit before the reaction”; Adjusting the reaction rate of a compound having an epoxy group and a polymerizable group, or a compound having an isocyanate group and a polymerizable group, with respect to these structural units after being introduced, which are also referred to as “post-reaction structural units”).
  • post-reaction structural units a structural unit having a carboxy group, a structural unit having a group having active hydrogen, or the like can be left in the addition polymerization type resin.
  • the structural unit having a carboxy group such as the methacrylic acid or the structural unit having a group having an active hydrogen (the structural unit before the reaction) is reacted at a later stage of the particle synthesis.
  • a method of polymerizing by increasing the ratio of the previous constituent units that is, by synthesizing particles by a seed polymerization method, a large number of constituent units before the reaction can be present on the surface of the particles, and during the subsequent polymer reaction, Many polymerizable groups can be introduced to the particle surface.
  • the addition-polymerizable resin has a hydrophilic structure (an ionic group such as a carboxy group or an amino group). ) Can be further included in the addition-polymerizable resin to further improve the dispersibility of the specific polymer particles, the developability of the lithographic printing plate precursor, and the like.
  • the reaction rate is, for example, preferably from 10% to 100%, more preferably from 30% to 70%.
  • the conversion is a value defined by the following formula R.
  • Reaction rate (molar number of structural units in the obtained addition-polymerizable resin after reaction / total number of moles of structural units in the obtained addition-polymerization resin before reaction) ⁇ 100 Formula R
  • the structural unit having a polymerizable group is added by a method such as reacting a compound having a carboxy group and a polymerizable group with a polymer into which a structural unit having an epoxy group such as glycidyl (meth) acrylate is introduced. It may be introduced into a polymerizable resin. Further, the constituent unit having a polymerizable group may be introduced into the above addition polymerization type resin by using, for example, a monomer having a partial structure represented by the following formula d1 or d2.
  • an ethylenically unsaturated group is formed by a elimination reaction using a base compound on a partial structure represented by the following formula d1 or the following formula d2.
  • a structural unit having a polymerizable group is introduced into the addition polymerization type resin.
  • R d represents a hydrogen atom or an alkyl group
  • a d represents a halogen atom
  • X d is -O- or -NR N - represents
  • R N represents a hydrogen atom or an alkyl group
  • R d is preferably a hydrogen atom or a methyl group.
  • a d is a chlorine atom, a bromine atom, or preferably a iodine atom.
  • X d is preferably -O-.
  • R N is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom.
  • Examples of the structural unit having a polymerizable group include a structural unit represented by the following formula D1.
  • L D1 represents a single bond or a divalent linking group
  • L D2 represents an m + 1-valent linking group
  • X D1 and X D2 each independently represent -O- or -NR N-
  • R N represents a hydrogen atom or an alkyl group
  • R D1 and R D2 each independently represent a hydrogen atom or a methyl group
  • m represents an integer of 1 or more.
  • L D1 is preferably a single bond.
  • LD1 represents a divalent linking group
  • an alkylene group, an arylene group, or a divalent group in which two or more of these groups are bonded is preferable, and an alkylene group having 2 to 10 carbon atoms or a phenylene group is more preferable.
  • L D2 is preferably a linking group containing a group represented by any of the following Formulas D2 to D6, and a group represented by any of the following Formulas D2 to D6, an ester bond , An alkylene group, and a group represented by a bond of at least two structures selected from the group consisting of an alkyleneoxy group.
  • X D1 and X D2 are preferably both —O—. Further, at least one of X D1 and X D2 is -NR N - when referring to, R N is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom. In the formula D1, R D1 is preferably a methyl group. In the formula D1, at least one of m R D2 is preferably a methyl group. In the formula D1, m is preferably an integer of 1 to 4, more preferably 1 or 2, and still more preferably 1.
  • L D3 to L D7 represent a divalent linking group
  • L D5 and L D6 may be different
  • X D5 is —O— or —NR N —
  • R N is represents a hydrogen atom or an alkyl group
  • * represents a bonding site with X D1 in the formula D1
  • wavy line section represents a bonding site with X D2 in the formula D1.
  • LD3 is preferably an alkylene group, an arylene group, or a group having two or more of these bonded, and is preferably an alkylene group having 1 to 10 carbon atoms, a phenylene group, or a group having two or more of these bonded. More preferred.
  • LD4 is preferably an alkylene group, an arylene group, or a group having two or more of these bonded, and is preferably an alkylene group having 1 to 10 carbon atoms, a phenylene group, or a group having two or more of these bonded. More preferred.
  • LD5 is preferably an alkylene group, an arylene group, or a group having two or more of these bonded, and is preferably an alkylene group having 1 to 10 carbon atoms, a phenylene group, or a group having two or more of these bonded. More preferred.
  • XD5 is preferably -O- or -NH-.
  • LD6 is preferably an alkylene group, an arylene group, or a group having two or more of these bonded, and is preferably an alkylene group having 1 to 10 carbon atoms, a phenylene group, or a group having two or more of these bonded. More preferred.
  • L D7 is preferably an alkylene group, an arylene group, or a group having two or more of these bonded, and is preferably an alkylene group having 1 to 10 carbon atoms, a phenylene group, or a group having two or more of these bonded. More preferred.
  • the number of atoms between the polymerizable group (for example, a (meth) acryloxy group) and the main chain of the addition polymerization type resin is preferably from 69 to 278 from the viewpoint of reactivity, and is preferably from 135 to 278. Is more preferable.
  • the content of the structural unit having a polymerizable group in the addition polymerization type resin is preferably 1% by mass to 50% by mass based on the total mass of the addition polymerization type resin from the viewpoint of UV printing durability. It is more preferably from 5% by mass to 45% by mass, still more preferably from 10% by mass to 40% by mass, particularly preferably from 10% by mass to 35% by mass.
  • the polymerizable group value (the amount of the polymerizable group per 1 g of the addition polymerization type resin) of the addition polymerization type resin is preferably 0.1 mmol / g to 5 mmol / g, and is preferably 1 mmol / g to 5 mmol / g. Is more preferable.
  • the polymerizable group value is measured by an iodine titration method.
  • the addition polymerization type resin has at least a crosslinked structure.
  • the crosslinked structure is not particularly limited, but is a structural unit obtained by polymerizing a polyfunctional ethylenically unsaturated compound, or a structural unit in which one or more reactive groups form a covalent bond inside the particle. Is preferred.
  • the functional number of the polyfunctional ethylenically unsaturated compound is preferably 2 to 15, more preferably 3 to 10, and more preferably 4 to 10, from the viewpoints of UV printing durability and on-press developability. More preferably, it is particularly preferably 5 to 10.
  • the structural unit having a crosslinked structure is preferably a difunctional to 15-functional branched unit, and is preferably a trifunctional to 10-functional branch unit. It is more preferably a functional branching unit, further preferably a tetrafunctional to 10-functional branching unit, and particularly preferably a pentafunctional to 10-functional branching unit.
  • the n-functional branch unit refers to a branch unit having n molecular chains, in other words, a structural unit having an n-functional branch point (crosslinked structure).
  • the ethylenically unsaturated group in the polyfunctional ethylenically unsaturated compound is not particularly limited, and examples thereof include a (meth) acryloxy group, a (meth) acrylamide group, an aromatic vinyl group, and a maleimide group.
  • the polyfunctional ethylenically unsaturated compound is preferably a polyfunctional (meth) acrylate compound, a polyfunctional (meth) acrylamide compound, or a polyfunctional aromatic vinyl compound.
  • polyfunctional (meth) acrylate compound examples include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, 1,4-butanediol diacrylate, 1,6 -Hexanediol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tricyclodecane dimethylol diacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol triacrylate, dipentaerythritol hexaacrylate Acrylate, tris ( ⁇ -hydroxyethyl Triacrylate of isocyanurate.
  • polyfunctional (meth) acrylate compound examples include N, N'-methylenebisacrylamide, N- [tris (3-acrylamidopropoxymethyl) methyl] acrylamide and the like.
  • polyfunctional aromatic vinyl compound examples include divinylbenzene.
  • the number of carbon atoms in the branch unit is not particularly limited, but is preferably from 8 to 100, and more preferably from 8 to 70.
  • the structural unit having the crosslinked structure is selected from the group consisting of the following structural units represented by BR-1 to BR-17 from the viewpoints of UV printing durability, on-press developability, and particle strength. At least one type of structural unit is preferable, and it is more preferable that at least one type of structural unit selected from the group consisting of the following structural units represented by BR-1 to BR-10 or BR-13 to BR-17 is contained. And at least one structural unit selected from the group consisting of structural units represented by the following BR-1 to BR-7 or BR-13 to BR-17, more preferably a structural unit represented by the following BR-1 Is particularly preferred.
  • R BR each independently represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 20.
  • the content of the structural unit having a crosslinked structure in the addition polymerization type resin is 1% by mass to 50% by mass based on the total mass of the addition polymerization type resin from the viewpoint of UV printing durability and on-press developability. It is preferably from 5% by mass to 45% by mass, more preferably from 10% by mass to 40% by mass, particularly preferably from 10% by mass to 35% by mass.
  • the addition polymerization type resin preferably further has a hydrophilic structure in addition to the polymerizable group and the crosslinked structure.
  • the addition-polymerizable resin has, as the hydrophilic structure, a UV printing durability, an on-press development property, an on-press development residue suppression property, and a dispersion stability of particles, particularly from the viewpoint of dispersion stability in water.
  • it preferably has an acid group, and more preferably has an ionic group.
  • an ionic group refers to a group at least partially dissociable into an anion or a cation in water.
  • the addition polymerization type resin as the hydrophilic structure, UV printing durability, on-press developability, on-press development residue suppression and dispersion stability of particles, particularly from the viewpoint of dispersion stability in water, sulfone It is more preferable to have an acid base (salt of a sulfonic acid group) or a sulfonic acid group.
  • the addition polymerization type resin has a UV printing durability, an on-press development property, an on-press development residue suppressing property and a dispersion stability of particles, particularly from the viewpoint of dispersion stability in an organic solvent. It preferably has an oxide structure or a polyester structure, and more preferably has a polyalkylene oxide structure.
  • the addition polymerization type resin as the hydrophilic structure, from the viewpoint of UV printing durability, on-press development property, on-press development debris suppression properties and dispersion stability of particles, an ionic group or an acid group, It is particularly preferred to have an alkylene oxide structure.
  • a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, or a sulfuric acid monoester group is preferably exemplified from the viewpoints of on-press development property, on-press development residue suppression property, and dispersion stability of particles.
  • a sulfonic acid group or a carboxylic acid group is more preferable, and a carboxylic acid group is particularly preferable.
  • the ionic group is preferably a group that dissociates a counter ion to generate an anion (anionic group) from the viewpoints of UV printing durability, on-press development property, suppression of on-press development residue, and dispersion stability of particles.
  • a salt of an acid group more preferably a sulfonate group, a carboxylate group, or a sulfuric acid monoester base, and particularly preferably a carboxylate group.
  • the counter cation in the salt of the acid group may be an inorganic cation or an organic cation, but is preferably an inorganic cation. Further, the counter cation may be not only a monovalent cation but also a polyvalent cation, but is preferably a monovalent cation.
  • an alkali metal ion or an alkaline earth metal ion is more preferable, an alkali metal ion is more preferable, and a lithium ion, a sodium ion or a potassium ion is particularly preferable.
  • the organic cation include a quaternary ammonium cation and a cation obtained by alkylating a nitrogen atom of an aromatic nitrogen-containing heterocycle.
  • Examples of the quaternary ammonium cation include a tetramethylammonium cation, a tetraethylammonium cation, and dimethylbenzylammonium cation, and examples of the cation obtained by alkylating the nitrogen atom of the aromatic nitrogen-containing heterocycle include a pyridinium cation.
  • the counter cation is preferably an alkali metal ion or a quaternary ammonium cation, and particularly preferably an alkali metal ion.
  • the addition polymerization type resin is represented by the following formula A-1 as a structural unit having the hydrophilic structure. It is preferable to have a structural unit represented by the formula:
  • X 1 represents —O— or NR 3
  • L 1 represents a divalent linking group having 1 to 20 carbon atoms
  • R 1 represents an ionic group or an acid group
  • R 2 represents R 3 represents a hydrogen atom, an alkyl group or an aryl group
  • X 1 is preferably -O-.
  • L 1 is preferably a divalent linking group having 2 to 10 carbon atoms, more preferably a divalent linking group having 2 to 8 carbon atoms, and is preferably an alkylene group having 2 to 8 carbon atoms. More preferred is an alkylene group having 2 to 5 carbon atoms.
  • the divalent linking group may be an alkylene group or a group in which at least one alkylene group is bonded to at least one structure selected from the group consisting of an ether bond and an ester bond. Preferably, it is an alkylene group.
  • R 3 is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and more preferably a hydrogen atom.
  • the polyalkylene oxide structure is preferably a polyethylene oxide structure, a polypropylene oxide structure, or a poly (ethylene oxide / propylene oxide) structure from the viewpoint of dispersion stability of particles, particularly dispersion stability in an organic solvent.
  • the number of alkylene oxide structures in the polyalkylene oxide structure is preferably 2 or more, more preferably 5 or more, and more preferably 5 or more from the viewpoint of dispersion stability of particles, particularly dispersion stability in an organic solvent. It is more preferably 200, and particularly preferably 8 to 150.
  • the polyester structure is not particularly limited, but preferably includes a ring-opening polymer chain of lactone and a polycondensation chain of hydroxycarboxylic acid.
  • the number of hydroxycarboxylic acid structures (lactone structures) in the polyester structure is preferably 2 or more, and more preferably 2 to 20, from the viewpoint of dispersion stability of particles, particularly dispersion stability in an organic solvent. Preferably, it is 2 to 10, more preferably 4 to 10.
  • the addition polymerization type resin is represented by the following formula A-3 or formula A as a structural unit having the hydrophilic structure. It preferably has a structural unit represented by A-4, and more preferably has a structural unit represented by the following formula A-3.
  • L 2 represents an ethylene group or a propylene group
  • L 3 represents an alkylene group having 2 to 10 carbon atoms
  • L 4 represents an alkylene group having 1 to 10 carbon atoms
  • R 4 and R 6 each independently represent a hydrogen atom, an alkyl group or an aryl group
  • R 5 and R 7 each independently represent a hydrogen atom or a methyl group
  • m1 represents an integer of 2 to 200
  • L 2 is preferably an ethylene group or a 1,2-propylene group.
  • L 3 is preferably an alkylene group having 2 to 8 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, and further preferably an ethylene group.
  • L 4 is preferably an alkylene group having 2 to 8 carbon atoms, more preferably an alkylene group having 3 to 8 carbon atoms, and further preferably an alkylene group having 4 to 6 carbon atoms.
  • R 4 and R 6 are each independently preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, More preferably, it is a methyl group.
  • m1 is preferably an integer of 5 to 200, and more preferably an integer of 8 to 150.
  • m2 is preferably an integer of 2 to 10, more preferably an integer of 4 to 10.
  • the addition polymerization type resin is composed of the structural unit represented by the formula A-1 and the formula A-3 Or, it is particularly preferable to have the structural unit represented by the formula A-4, and it is most preferable to have the structural unit represented by the formula A-1 and the structural unit represented by the formula A-3.
  • the addition polymerization type resin preferably has, as a group having the hydrophilic structure, a group represented by the following formula Z from the viewpoints of on-press development property, on-press development residue suppression property, and dispersion stability of particles. . * -QWY Formula Z
  • Q represents a divalent linking group
  • W represents a divalent group having a hydrophilic structure or a divalent group having a hydrophobic structure
  • Y is a monovalent group having a hydrophilic structure or Represents a monovalent group having a hydrophobic structure
  • one of W and Y has a hydrophilic structure
  • * represents a binding site to another structure.
  • Q is preferably a divalent linking group having 1 to 20 carbon atoms, and more preferably a divalent linking group having 1 to 10 carbon atoms.
  • Q is preferably an alkylene group, an arylene group, an ester bond, an amide bond, or a group obtained by combining two or more thereof, and more preferably a phenylene group, an ester bond, or an amide bond.
  • the divalent group having a hydrophilic structure in W is preferably a polyalkyleneoxy group or a group in which —CH 2 CH 2 NR W — is bonded to one end of the polyalkyleneoxy group.
  • R W represents a hydrogen atom or an alkyl group.
  • R WA is each independently a straight-chain, branched or cyclic alkylene group having 6 to 120 carbon atoms, a haloalkylene group having 6 to 120 carbon atoms, an arylene group having 6 to 120 carbon atoms, and an alkylene group having 6 to 120 carbon atoms.
  • the alkyleneoxy group is preferably a group in which —CH 2 CH 2 N (R W ) — is bonded to the other end.
  • R WB represents an alkyl group having 6 to 20 carbon atoms.
  • the content of the structural unit having a hydrophilic structure in the addition polymerization type resin is, from the viewpoint of on-press developability, on-press development debris suppression and dispersion stability of the particles, based on the total mass of the addition polymerization type resin, It is preferably from 1% by mass to 50% by mass, more preferably from 5% by mass to 40% by mass, particularly preferably from 10% by mass to 30% by mass. Further, when the hydrophilic structure is an ionic group, the content of the structural unit having an ionic group in the addition-polymerizable resin is determined as on-press developability, on-press development residue suppression, and particle dispersion stability.
  • it is preferably 1% by mass to 30% by mass, more preferably 2% by mass to 20% by mass, and more preferably 4% by mass to 10% by mass, based on the total mass of the addition polymerization type resin. It is particularly preferred that there is.
  • the addition polymerization type resin may have a structural unit (other structural unit) other than the structural unit having the polymerizable group, the structural unit having the hydrophilic structure, and the structural unit having the crosslinked structure.
  • Compounds forming other structural units include simple compounds such as styrene compounds, (meth) acrylate compounds, (meth) acrylonitrile compounds, (meth) acrylamide compounds, vinyl halide compounds, vinyl ester compounds, vinyl ether compounds, ⁇ -olefin compounds and the like.
  • styrene methyl methacrylate, acrylonitrile, methacrylonitrile, N, N-dimethylacrylamide, 2-hydroxyethyl acrylate, 2,3-dihydroxypropyl methacrylate, 2-ethylhexyl methacrylate, acryloylmorpholine, diacetone Acrylamide, N-isopropylacrylamide, cyclohexyl methacrylate, acryloxymethyl ethylene carbonate, pt-butylstyrene, methacrylamide and the like are more preferable.
  • the addition polymerization type resin further preferably has at least one structural unit selected from the group consisting of a structural unit composed of acrylonitrile, a structural unit composed of methyl methacrylate, and a structural unit composed of styrene, and acrylonitrile. It is particularly preferred to have a structural unit consisting of The structural unit composed of acrylonitrile is a structural unit represented by the following X-1, a structural unit composed of methyl methacrylate is a structural unit represented by the following X-2, and the structural unit composed of styrene is: This is a structural unit represented by the following X-3.
  • the addition polymerization type resin may have one or more other structural units alone, or may or may not have two or more types.
  • the content of the other structural units in the addition polymerization type resin may be 10% by mass to 90% by mass based on the total mass of the addition polymerization type resin from the viewpoint of UV printing durability and on-press developability. It is more preferably from 20% by mass to 85% by mass, further preferably from 40% by mass to 80% by mass, and particularly preferably from 50% by mass to 75% by mass.
  • the specific polymer particles used in the present disclosure are preferably water-dispersible polymer particles from the viewpoint of developability and on-press developability.
  • 5.0 g of specific polymer particles are mixed with 100 mL of water in a 20 ° C. environment, dispersed by stirring at a stirring speed of 300 rpm for 10 minutes, and allowed to stand for 1 hour in a 20 ° C. environment. When placed, no precipitate is visually confirmed, or a small amount of precipitate is visually confirmed, but when easily redispersible, the specific polymer particles are water-dispersible. That.
  • the specific polymer particles no precipitate is visually observed after the above-mentioned standing for 1 hour, or a small amount of precipitate is visually confirmed.
  • the specific polymer particles it is preferable that the specific polymer particles be in an easily redispersible state. More preferably, no precipitate is observed and the dispersibility is good.
  • the specific polymer particles used in the present disclosure are preferably organic solvent-dispersible polymer particles from the viewpoints of printing durability, UV printing durability, developability, and developability.
  • organic solvent dispersible When dispersed in at least one organic solvent among alcoholic organic solvents (methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, MFG, etc.), such particles are called organic solvent dispersible.
  • an image recording layer in the lithographic printing plate precursor according to the present disclosure can be formed.
  • MEK represents methyl ethyl ketone
  • MFG represents 1-methoxy-2-propanol.
  • 5.0 g of the specific polymer particles is mixed with 100 mL of at least one of the organic solvents, and dispersed by stirring at a stirring speed of 300 rpm for 10 minutes. When left for 1 hour in an environment, a small amount of precipitate is visually observed. When the precipitate is easily redispersible, the specific polymer particles are said to be dispersible in an organic solvent.
  • the specific polymer particles In the specific polymer particles, a small amount of precipitate is visually confirmed after the above-mentioned one-hour standing, but it is preferable that the precipitate is easily redispersible. The precipitate is not visually confirmed, and the dispersibility is good. More preferably, it is in a state.
  • the coating can be performed in a state where the particles are well dispersed in the coating liquid at the time of forming the image recording layer.
  • the preferred solvent SP value for the coating solvent is 9.3 to 18.0, more preferably 10.0 to 15.0, and still more preferably 10.5 to 12.5.
  • the specific polymer particles in the present disclosure are preferably dispersible in an organic solvent having the above SP value.
  • the SP values of typical solvents are as follows.
  • SP value 9.3
  • the SP value in the present specification is calculated by the Okitsu method (Toshina Okitsu, “Journal of the Adhesion Society of Japan”, 29 (5) (1993)). Specifically, the SP value is calculated by the following equation. Note that ⁇ F is a value described in the literature.
  • the SP value ( ⁇ ) ⁇ F (Molar Attraction Constants) / V (molar volume)
  • the unit of the SP value in this specification is MPa 1/2 .
  • the SP value is determined as a weighted average value according to the content ratio of each organic solvent.
  • the weighted average value is “X” obtained by the following Equation 1.
  • the SP value of the organic solvent A containing two or more kinds of organic solvents is the SP value of the i-th type (i represents an integer of 1 or more) organic solvent contained in Si in the following formula 1. X, which is calculated by substituting the mass content of the i-th organic solvent in the entire organic solvent A into Wi.
  • the median diameter of the specific polymer particles is preferably 1,000 nm or less, more preferably 50 nm to 300 nm, from the viewpoint of improving UV printing durability.
  • the method for measuring the median diameter is as described above.
  • the coefficient of variation of the particle diameter of the specific polymer particles is preferably 100% or less, more preferably 40% or less, and even more preferably 25% or less.
  • the lower limit of the variation coefficient is not particularly limited, and may be 0%.
  • the coefficient of variation is reduced by appropriately setting reaction conditions such as stirring speed and temperature, and increasing the content of hydrophilic structure (particularly, the amount of polyalkylene oxide structure) in the addition polymerization type resin. Can be.
  • the variation coefficient of the particle diameter of specific polymer particles is measured by direct observation of the particle diameter by the following microscope method.
  • Sample preparation 1 g of a dispersion containing specific polymer particles is spread on an aluminum cup, solidified by natural drying, and ground in a mortar to obtain a powder sample.
  • Coefficient of variation After developing the numerical values in the order of particle diameter, as in the definition of the median diameter, the point where the number of large particles and the number of small particles are the same is defined as the central particle diameter. Find the coefficient of variation.
  • the lithographic printing plate precursor according to the present disclosure has a support, and, on the support, an image recording layer, the image recording layer contains an infrared absorber, a polymerization initiator, and core-shell particles,
  • the core portion of the core-shell particles contains an addition-polymerizable resin A having a functional group A (hereinafter, also simply referred to as “resin A”), and the addition-polymerizable resin A in the core portion has a crosslinked structure.
  • the shell portion of the core-shell particles contains a functional group B capable of binding or interacting with the functional group A, and a compound B having a polymerizable group.
  • each of the constituent units described below in the resin A or the compound B may have the resin A or the resin B independently independently or may have two or more kinds, unless otherwise specified. Good.
  • the functional groups A and B are functional groups capable of binding or interacting with each other.
  • Examples of the mode in which the functional group A and the functional group B can be bonded include a covalent bond, an ionic bond, and a hydrogen bond.
  • Examples of the mode in which the functional group A and the functional group B can interact include a dipole interaction.
  • the group to which the functional group A and functional group B can be covalently bonded is not particularly limited as long as the group can form a covalent bond by the reaction of the functional group A and the functional group B, and examples thereof include a hydroxy group, a carboxy group, and an amino group.
  • Groups, amide groups, epoxy groups, isocyanate groups, thiol groups, glycidyl groups, aldehyde groups, sulfonic acid groups and the like are preferred, and a hydroxy group and a carboxy group are more preferred.
  • the group to which the functional group A and the functional group B can be ion-bonded is not particularly limited as long as one of the functional groups A and B has a cationic group and the other has an anionic group.
  • the cationic group is preferably an onium group. Examples of the onium group include an ammonium group, a pyridinium group, a phosphonium group, an oxonium group, a sulfonium group, a selenonium group, and an iodonium group.
  • an ammonium group, a pyridinium group, a phosphonium group, or a sulfonium group is preferable, an ammonium group or a phosphonium group is more preferable, and an ammonium group is particularly preferable.
  • the anionic group is not particularly limited, and includes, for example, a phenolic hydroxyl group, a carboxy group, —SO 3 H, —OSO 3 H, —PO 3 H, —OPO 3 H 2 , —CONHSO 2 —, and —SO 2 NHSO. 2- and the like.
  • a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfuric acid group, a sulfonic acid group, a sulfinic acid group or a carboxy group is preferable, and a phosphoric acid group or a carboxy group is more preferable. Is more preferable.
  • the group capable of hydrogen bonding is not particularly limited as long as one of the functional groups A and B has a hydrogen bond donating site and the other has a hydrogen bond accepting site.
  • the hydrogen bond-donating site may be any structure having an active hydrogen atom capable of hydrogen bonding, and is preferably a structure represented by XH.
  • X represents a hetero atom, and is preferably a nitrogen atom or an oxygen atom.
  • a hydroxy group, a carboxy group, a primary amide group, a secondary amide group, a primary amino group, a secondary amino group, a primary amino group It is preferably a sulfonamide group, a secondary sulfonamide group, an imide group, a urea bond, and at least one structure selected from the group consisting of a urethane bond, a hydroxy group, a carboxy group, a primary amide group, It is more preferably at least one structure selected from the group consisting of a secondary amide group, a primary sulfonamide group, a secondary sulfonamide group, a maleimide group, a urea bond, and a urethane bond, and a hydroxy group , A carboxy group, a primary amide group, a secondary amide group, a primary sulfonamide group, a secondary sulfonamide group, and a
  • the hydrogen bond-accepting site preferably has a structure containing an atom having a lone pair, preferably has a structure containing an oxygen atom having a lone pair, and has a carbonyl group (carboxy group, amide group, imide group , A urea bond, a carbonyl structure such as a urethane bond, etc.), and a sulfonyl group (including a sulfonyl structure such as a sulfonamide group).
  • a carbonyl group including a carbonyl structure such as a carboxy group, an amide group, an imide group, a urea bond, and a urethane bond.
  • the group capable of forming a hydrogen bond with the functional group A and the functional group B is preferably a group having the above-described hydrogen bond donating site and hydrogen bond accepting site, and may be a carboxy group, an amide group, an imide group, a urea bond, or a urethane. It preferably has a bond or a sulfonamide group, and more preferably has a carboxy group, an amide group, an imide group, or a sulfonamide group.
  • -A group in which the functional group A and the functional group B can interact with each other examples include a structure represented by XH (X represents a hetero atom, a nitrogen atom or an oxygen atom) in the above-mentioned hydrogen bondable group.
  • XH represents a hetero atom, a nitrogen atom or an oxygen atom
  • Any group having a polarized structure other than that described above may be used, and a group to which atoms having different electronegativities are bonded is preferred.
  • a combination of a carbon atom with at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom is preferable, and an oxygen atom, a nitrogen atom, And a combination of at least one atom selected from the group consisting of sulfur atoms and carbon atoms is more preferable.
  • a combination of a nitrogen atom and a carbon atom, and a combination of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom are preferable.
  • a cyano group, a cyanuric group, Sulfonamide groups are more preferred.
  • the functional group A and the functional group B are the same groups capable of interacting with each other.
  • the binding between the functional group A and the functional group B and the interaction between the functional group A and the functional group B can be confirmed by the following method. Specifically, 2 g of a resin A (aqueous solution having a solid content of 20% by mass) and 8 g of a compound B (a MFG (a 2-methoxy-2-propanol solution having a solid content of 7.5% by mass)) were reacted. After mixing, the mixture was centrifuged at 21,000 ⁇ g for 60 minutes to collect a precipitate, which was then washed with a solvent in which compound B was dissolved, and reacted with the functional group A. Alternatively, the compound B containing the non-interacting functional group B was washed away, and the precipitate was dried at 40 ° C.
  • a resin A aqueous solution having a solid content of 20% by mass
  • a MFG a 2-methoxy-2-propanol solution having a solid content of 7.5% by mass
  • IR Infrared absorption spectrum
  • the functional group B capable of binding or interacting with the functional group A is a group capable of covalently bonding with the functional group A from the viewpoint of UV printing durability.
  • group capable of covalent bonding a group capable of ionic bonding with functional group A
  • group capable of ionic bonding a group capable of hydrogen bonding with functional group A
  • group capable of hydrogen bonding a group capable of dipole interaction with functional group A
  • group capable of dipole interaction a group capable of dipole interaction
  • a group capable of ionic bonding, a group capable of hydrogen bonding, or a group capable of dipole interaction is more preferable.
  • the group capable of covalent bonding is appropriately selected depending on the types of the functional groups A and B.
  • the functional group A and the functional group B is, for example, a carboxy group
  • examples of the group that can be covalently bonded to the carboxy group include a hydroxy group and a glycidyl group.
  • the group capable of covalently bonding to —NH 2 includes an isocyanate group and a glycidyl group. .
  • the group that can be ionically bonded to the functional group A is appropriately selected according to the types of the functional groups A and B.
  • the bondable compound B is required to have a basic group.
  • the acidic group include a carboxylic acid, a sulfonic acid, a phosphoric acid group, a polymerized residue of (meth) acrylic acid, and a polymerized residue of a (meth) acrylic acid derivative having a carboxy group terminal.
  • the group capable of ion-bonding with the carboxy group includes a tertiary amino group, a pyridyl group, a piperidyl group, and the like.
  • the ionic bond with the sulfonic acid group includes a tertiary amino group.
  • the group capable of ionic bonding with —SO 3 — includes a cationic group such as a quaternary ammonium group.
  • a cationic group such as a quaternary ammonium group.
  • a tertiary amino group is an example of the group capable of ion-bonding to the phosphate group.
  • the group capable of hydrogen bonding is appropriately selected depending on the types of the functional groups A and B.
  • the functional groups A and B are a carboxy group, examples thereof include an amide group and a carboxy group.
  • examples of the group capable of hydrogen bonding with the functional group A include phenolic hydroxyl.
  • the group capable of dipole interaction is appropriately selected depending on the types of the functional groups A and B.
  • the dipole interaction acts on the compound B that can bind to the surface of the core-shell particle (resin A).
  • the compound B has a functional group having the same skeleton.
  • the functional group in which the dipole interaction works include a sulfonamide group, a cyano group, and a cyanuric group, and are preferably a cyano group.
  • the group capable of dipole interaction with the cyano group includes a cyano group.
  • the group capable of dipole interaction with the sulfonic acid amide group includes a sulfonic acid amide group.
  • the core portion of the core-shell particles contains an addition polymerizable resin A having a functional group A (resin A), and the addition polymerizable resin A has a crosslinked structure.
  • the crosslinked structure has the same meaning as the crosslinked structure in the specific polymer particles, and the preferred embodiment is also the same.
  • the addition polymerization type resin A is preferably an acrylic resin, a styrene-acrylic copolymer, a polyurea resin or a polyurethane resin from the viewpoint of UV printing durability and ease of production, and is preferably an acrylic resin, styrene-acrylic resin. It is more preferably a copolymer or a polyurethane resin, and further preferably an acrylic resin.
  • the acrylic resin a resin in which the content of the structural unit formed by the (meth) acrylic compound (the structural unit derived from the (meth) acrylic compound) is 50% by mass or more based on the total mass of the resin is preferable.
  • Preferred examples of the (meth) acrylic compound include a (meth) acrylate compound and a (meth) acrylamide compound.
  • the resin A may be used alone or in combination of two or more. Further, the resin A may be in a latex state.
  • the functional group A contained in the resin A is not particularly limited as long as it can bond or interact with the functional group B contained in the compound B.
  • the functional group A can be appropriately set according to the type of the functional group B described later.
  • the resin A may contain one kind of the functional group A alone, or two or more kinds thereof may be used in combination.
  • the functional group A is preferably at least one group selected from the group consisting of a carboxy group, a cyano group, and an amino group from the viewpoint of UV printing durability, and is an amino group. Is more preferred. Further, the resin A preferably has a structural unit having a functional group A.
  • the resin A preferably contains a structural unit formed of a compound having a cyano group from the viewpoint of UV printing durability.
  • the cyano group is usually preferably introduced into the resin A as a structural unit containing a cyano group using a compound (monomer) having the cyano group.
  • Examples of the compound having a cyano group include acrylonitrile compounds, and preferably include (meth) acrylonitrile.
  • the structural unit having a cyano group is preferably a structural unit formed of an acrylonitrile compound, and more preferably a structural unit formed of (meth) acrylonitrile.
  • a structural unit formed by a compound having a cyano group a structural unit represented by the following formula a1 is preferably exemplified.
  • RA1 represents a hydrogen atom or an alkyl group.
  • R A1 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.
  • the content of the structural unit having a cyano group is 5% by mass to 90% by mass based on the total mass of the resin A from the viewpoint of UV printing durability. It is preferably from 20% by mass to 80% by mass, more preferably from 30% by mass to 60% by mass.
  • the resin A preferably contains a structural unit having a carboxy group from the viewpoint of UV printing durability.
  • the carboxy group is usually preferably introduced into the resin A as a carboxy-containing structural unit using a compound having a carboxy group (monomer).
  • the structural unit having a carboxy group may be, for example, a structural unit formed by a compound having a carboxy group such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid.
  • Resin A preferably contains at least one structural unit selected from the group consisting of a structural unit formed of acrylic acid and a structural unit represented by the following formula a2.
  • R 3 represents a hydrogen atom or a methyl group
  • X 3 represents —O— or —NR 7 —
  • R 7 represents a hydrogen atom or an alkyl group
  • L 3 represents a single bond or a carbon atom. Represents one or more divalent hydrocarbon groups.
  • R 7 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. Is more preferable.
  • L 3 represents a single bond or a divalent hydrocarbon group having 1 or more carbon atoms, and is a single bond or a divalent hydrocarbon group which may have an ester bond or an ether bond therein. Is preferably a single bond or a divalent hydrocarbon group, and more preferably a single bond or a divalent aliphatic saturated hydrocarbon group.
  • L 3 represents a divalent hydrocarbon group
  • L 3 preferably has 2 to 15 carbon atoms, and more preferably 3 to 12 carbon atoms.
  • the content of the structural unit having a carboxy group is preferably from 5% by mass to 70% by mass, and more preferably from 10% by mass to 55% by mass with respect to the total mass of the resin A. Is more preferable.
  • the resin A preferably contains a structural unit formed of a compound having an amino group from the viewpoint of UV printing durability.
  • the amino group may be a primary amino group, a secondary amino group, or a tertiary amino group, but preferably has a (meth) acrylamide group from the viewpoint of UV printing durability, and preferably has a methacrylamide group. Or acrylamide is more preferred.
  • the content of the structural unit having an amino group is preferably from 5% by mass to 70% by mass, more preferably from 10% by mass to 50% by mass, and more preferably from 10% by mass to 50% by mass, based on the total mass of the resin A. % Or more and 40% by mass or less.
  • the resin A contained in the core portion of the core-shell particles has a crosslinked structure, and more preferably has a structural unit having a crosslinked structure.
  • Examples of the structural unit having a crosslinked structure include the structural units having a crosslinked structure described above, and preferred embodiments are also the same.
  • the content of the structural unit having a crosslinked structure in the resin A is preferably 1% by mass to 50% by mass with respect to the total mass of the resin A from the viewpoint of UV printing durability and on-press developability.
  • the content is more preferably from 50% by mass to 45% by mass, still more preferably from 10% by mass to 40% by mass, particularly preferably from 10% by mass to 35% by mass.
  • the resin A contained in the core portion may contain a structural unit having a hydrophobic group from the viewpoint of ink adhesion.
  • the hydrophobic group include an alkyl group, an aryl group, and an aralkyl group.
  • the structural unit containing a hydrophobic group a structural unit formed of an alkyl (meth) acrylate compound, an aryl (meth) acrylate compound, or an aralkyl (meth) acrylate compound is preferable, and a structural unit formed of an alkyl (meth) acrylate compound is preferred. Is more preferable.
  • the alkyl (meth) acrylate compound preferably has 1 to 10 carbon atoms in the alkyl group.
  • the alkyl group may be linear or branched, and may have a cyclic structure.
  • Examples of the alkyl (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. Is mentioned.
  • the aryl group in the aryl (meth) acrylate compound preferably has 6 to 20 carbon atoms, and more preferably a phenyl group. Further, the aryl group may have a known substituent. Preferred examples of the aryl (meth) acrylate compound include phenyl (meth) acrylate.
  • the aralkyl (meth) acrylate compound preferably has 1 to 10 carbon atoms in the alkyl group.
  • the alkyl group may be linear or branched, and may have a cyclic structure.
  • the aryl group in the aralkyl (meth) acrylate compound preferably has 6 to 20 carbon atoms, and more preferably a phenyl group.
  • benzyl (meth) acrylate is preferably exemplified.
  • the content of the structural unit having a hydrophobic group in the resin A contained in the core portion is preferably 5% by mass to 50% by mass, and more preferably 10% by mass to 50% by mass with respect to the total mass of the resin A. More preferably, it is 30% by mass.
  • the resin A contained in the shell portion can have other structural units other than the above-described structural units in the resin A without any particular limitation, and examples thereof include structural units formed of a vinyl ether compound or the like.
  • the vinyl ether compound include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexylmethyl vinyl ether, and 4-methylcyclohexyl.
  • the content of the other structural units is preferably 5% by mass to 50% by mass, and more preferably 10% by mass to 30% by mass based on the total mass of the resin A. Is more preferable.
  • the resin A contained in the core portion of the core-shell particles preferably further has a hydrophilic structure, and more preferably has a structural unit having a hydrophilic structure.
  • the hydrophilic structure and the structural unit having the hydrophilic structure are the same as those described above, and the preferred embodiments are also the same.
  • the content of the structural unit having a hydrophilic structure is preferably 50% by mass or less based on the total mass of the resin A from the viewpoint of UV printing durability. It is more preferably from 1% by mass to 20% by mass, and still more preferably from 2% by mass to 10% by mass.
  • the core portion may contain the resin A, but the content of the resin A in the core portion is preferably 80% by mass or more, and more preferably 90% by mass or more from the viewpoint of UV printing durability. The content is more preferably 95% by mass or more, and the core portion is particularly preferably made of resin A. Further, the core portion is preferably a particle, and more preferably a particle made of resin A.
  • the shell portion of the core-shell particles contains a functional group B capable of binding or interacting with the functional group A, and a compound B having a polymerizable group.
  • the compound B contained in the shell part of the core-shell particles has a functional group B capable of binding or interacting with the functional group A, and a polymerizable group.
  • the compound B may be a monomer or a polymer.
  • a polymer refers to a compound having a weight average molecular weight of 1,000 or more.
  • the case where the compound B is a polymer is also referred to as a resin B.
  • the monomer refers to a compound having a weight average molecular weight of less than 1,000.
  • the resin B may be an addition polymerization type resin or a polycondensation resin, but from the viewpoint of UV printing durability and easiness in forming, an acrylic resin, a polyurea resin or a polyurethane. It is preferably a resin, more preferably an acrylic resin or a polyurethane resin, and particularly preferably an acrylic resin.
  • the acrylic resin a resin in which the content of the structural unit formed by the (meth) acrylic compound (the structural unit derived from the (meth) acrylic compound) is 50% by mass or more based on the total mass of the resin is preferable.
  • Preferred examples of the (meth) acrylic compound include a (meth) acrylate compound and a (meth) acrylamide compound.
  • Compound B has a functional group B capable of binding or interacting with the functional group A.
  • Examples of the functional group B capable of binding or interacting with the functional group A include the groups capable of binding or interacting as described above.
  • Compound B may have one kind of functional group B alone, or may have two or more kinds.
  • the functional group B is at least one group selected from the group consisting of primary to tertiary amino groups, carboxy groups, epoxy groups, and cyano groups from the viewpoint of UV printing durability.
  • it is a primary to tertiary amino group or a cyano group, more preferably a primary to tertiary amino group.
  • compound B When compound B is a polymer, compound B preferably has a structural unit having functional group B.
  • the compound B in the resin B, as the structural unit having the functional group B capable of binding or interacting with the functional group A, a structural unit having an amino group from the viewpoint of UV printing durability; Or a structural unit represented by the formula a1 (a structural unit having a cyano group).
  • R 4 represents a hydrogen atom or a methyl group
  • X 4 represents —O— or —NR 8 —
  • R 8 represents a hydrogen atom or an alkyl group
  • L 4 , R 5 and R 6 And at least two of them may combine to form a ring
  • L 4 represents a single bond or a divalent hydrocarbon group having 1 or more carbon atoms
  • R 5 and R 6 each independently represent a carbon atom. It represents one or more monovalent hydrocarbon groups, and * independently represents a binding site to another structure.
  • R 8 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. Is more preferable.
  • L 4 represents a single bond or a divalent hydrocarbon group having 1 or more carbon atoms, and is preferably a single bond or a divalent hydrocarbon group which may have a urea bond or an ether bond. Alternatively, a divalent hydrocarbon group is more preferable, and a single bond or a divalent aliphatic saturated hydrocarbon group is still more preferable.
  • L 4 preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms.
  • R 5 and R 6 each independently represent a monovalent hydrocarbon group having 1 or more carbon atoms, and is preferably an aliphatic saturated hydrocarbon group having 1 or more carbon atoms.
  • the carbon numbers of R 5 and R 6 are each independently preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.
  • X 4 in the formula a3 is —O—
  • L 4 is a divalent aliphatic having 2 to 10 carbon atoms.
  • R 5 and R 6 are each independently an aliphatic saturated hydrocarbon group having 1 to 5 carbon atoms
  • X 4 is —O—
  • L 4 is a saturated hydrocarbon group.
  • the number is a divalent aliphatic saturated hydrocarbon group having 2 to 8, and R 5 and R 6 are more preferably each independently an aliphatic saturated hydrocarbon group having 1 to 3 carbon atoms.
  • the resin B preferably has a structural unit having a hydrophilic structure from the viewpoint of UV printing durability.
  • the hydrophilic structure preferably contains a group represented by the above formula Z.
  • the group represented by the formula Z is the same as the group represented by the formula Z, and the preferred range is also the same.
  • the content of the structural unit having the hydrophilic structure in the resin B is from 10% by mass to 60% by mass based on the total mass of the resin B from the viewpoint of UV printing durability. Preferably, it is 20% by mass to 55% by mass, more preferably 30% by mass to 50% by mass.
  • Compound B has a polymerizable group.
  • the polymerizable group of the compound B may be a cationic polymerizable group or a radical polymerizable group, but is preferably a radical polymerizable group from the viewpoint of reactivity.
  • the polymerizable group of the compound B is not particularly limited as long as it is a polymerizable group. From the viewpoint of reactivity and UV printing durability, an ethylenically unsaturated group is preferable, and a vinylphenyl group (styryl group), A (meth) acryloxy group or a (meth) acrylamide group is more preferable, and a (meth) acryloxy group is particularly preferable.
  • these polymerizable groups may be introduced into the compound B by introducing a polymerizable group due to the residual polyfunctional monomer added during the synthesis of the core-shell particles, or by introducing a polymer reaction to the particle surface after the synthesis of the core-shell particles. Can be appropriately selected.
  • a method of introducing by core-molecule reaction after synthesis of core-shell particles is desirable. This is because introducing a polymerizable group after the synthesis of the core-shell particles allows more active polymerizable groups to be present on the surface of the core-shell particles, thereby increasing the reactivity with the matrix and forming a strong crosslink with the matrix. This is because it is considered easy.
  • the content of the structural unit having a polymerizable group in the resin B is from 10% by mass to 60% by mass with respect to the total mass of the resin B from the viewpoint of UV printing durability. Is preferably 20% by mass to 55% by mass, and particularly preferably 30% by mass to 50% by mass.
  • the polymerizable group value (the amount of the polymerizable group per 1 g of the compound B) (preferably the ethylenically unsaturated group value) of the core-shell particles is preferably 0.05 mmol / g to 5 mmol / g, and 0.2 mmol / g. / G to 3 mmol / g is more preferable.
  • the above polymerizable value and ethylenically unsaturated group value shall be measured by an iodine titration method.
  • the resin B may further have a structural unit formed of an aromatic vinyl compound from the viewpoint of UV printing durability, but preferably does not have a structural unit.
  • the constitutional unit formed by the aromatic vinyl compound in the resin B has the same meaning as the constitutional unit formed by the aromatic vinyl compound in the resin A, and the preferred embodiment is also the same.
  • the content of the constituent unit formed by the aromatic vinyl compound is preferably 20% by mass or less, and more preferably 10% by mass or less, with respect to the total mass of the resin B, from the viewpoint of ink adhesion. More preferably, it is particularly preferable that the resin B does not have a structural unit formed by an aromatic vinyl compound.
  • the resin B may have a crosslinked structure from the viewpoint of UV printing durability.
  • the cross-linked structure and the structural unit having a cross-linked structure in the resin B have the same meanings as the above-described cross-linked structure and the structural unit having a cross-linked structure, respectively, and preferred embodiments are also the same.
  • the content of the structural unit having a crosslinked structure in the resin B may be 0.1% by mass to 20% by mass based on the total mass of the resin B from the viewpoint of UV printing durability and on-press developability. More preferably, it is from 0.5% by mass to 15% by mass, particularly preferably from 1% by mass to 10% by mass.
  • the resin B may contain a structural unit having a hydrophobic group from the viewpoint of ink adhesion.
  • the structural unit having a hydrophobic group in the resin B has the same meaning as the structural unit having a hydrophobic group in the resin A, and the preferred embodiment is also the same.
  • the content of the structural unit having a hydrophobic group is preferably 1% by mass to 50% by mass, and more preferably 5% by mass with respect to the total mass of the resin B. More preferably, it is 30% by mass.
  • the resin B when the compound B is a polymer, from the viewpoint of UV printing durability, the resin B includes a structural unit having a functional group B, a structural unit having a hydrophilic structure, and a structural unit having a polymerizable group. It is preferred to include.
  • the content of the constituent unit having the functional group B, the constituent unit having the hydrophilic structure, and the constituent unit having the polymerizable group in the resin B is 1% by mass to 80% by mass with respect to all the constituent units of the resin B.
  • the amount can be appropriately selected from the range of from 10% by mass to 50% by mass from the viewpoint of UV printing durability.
  • the resin B when the compound B is a polymer, can have other structural units other than the above-described structural units in the resin A without any particular limitation.
  • the structural unit formed by a vinyl ether compound or the like Is mentioned.
  • the content of the other structural units is preferably from 1% by mass to 50% by mass, and more preferably from 5% by mass to 30% by mass based on the total mass of the resin B. Is more preferable.
  • the compound B is a monomer
  • the compound B is a monomer having a functional group B and a polymerizable group.
  • the functional group and the polymerizable group are the same as the functional group B and the polymerizable group described above. Yes, the preferred embodiment is also the same.
  • the compound B when the resin A has a (meth) acrylamide group, the compound B is a monomer, and when the functional group B of the monomer is a group capable of hydrogen bonding, the compound B is a compound of (meth) acrylic acid.
  • a compound having a polymerized residue or a polymerized residue of a (meth) acrylic acid derivative having a carboxylic acid terminal may be mentioned. From the viewpoint of increasing the number of functional groups per the same weight ratio, a polymerized residue of (meth) acrylic acid is used. Preferably, there is.
  • the compound B is a monomer, and when the functional group B of the monomer is a group capable of hydrogen bonding, the compound B is (meth) acrylamide. Is preferred.
  • the compound B is a monomer, and the functional group B of the monomer is a group capable of ion bonding.
  • Compound B is preferably dimethylaminoethyl (meth) acrylate from the viewpoint of increasing the number of functional groups per compound.
  • the compound B is a monomer, and when the functional group B of the monomer is a group capable of dipole interaction, the compound B is (meth) acrylonitrile. Is preferred.
  • the content of the compound B with respect to the content of the resin A in the core-shell particles (hereinafter, also referred to as “coverage”) can be appropriately set, but from the viewpoint of UV printing durability, the total content of the resin A in the core-shell particles is reduced. It is preferably from 1% by mass to 90% by mass, more preferably from 5% by mass to 80% by mass, and particularly preferably from 10% by mass to 70% by mass, based on the mass.
  • IR infrared absorption spectrum
  • the number average molecular weight (Mn) of the resin B is preferably 500 to 1,000,000, more preferably 5,000 to 500,000, and more preferably 10,000 to 200,000. Is more preferred. Further, the number average molecular weight of the resin A is preferably larger than the number average molecular weight of the resin B from the viewpoint of UV printing durability.
  • the arithmetic average particle size of the core portion is preferably from 10 nm to 1,000 nm, more preferably from 30 nm to 800 nm, and particularly preferably from 50 nm to 600 nm, from the viewpoint of UV printing durability.
  • the arithmetic average particle size of the core-shell particles is preferably from 10 nm to 1,000 nm, more preferably from 50 nm to 800 nm, particularly preferably from 70 nm to 600 nm, from the viewpoint of UV printing durability.
  • the arithmetic average particle size of the core-shell particles in the present disclosure refers to a value measured by a dynamic light scattering method (DLS), unless otherwise specified.
  • the arithmetic mean particle size of the core-shell particles by DLS is measured using a Brookhaven BI-90 (manufactured by Brookhaven Instrument Company) in accordance with the manual of the above instrument.
  • the average thickness of the shell portion is preferably from 1 nm to 100 nm, more preferably from 1 nm to 50 nm, and particularly preferably from 2 nm to 20 nm, from the viewpoint of UV printing durability.
  • the average thickness of the shell portion in the present disclosure is that the particle cross section is dyed by a known method and observed with an electron microscope, and the average value of the total thickness of the shell portion at 10 or more positions in 10 or more particles is taken. I do.
  • the method for producing the resin contained in the core-shell particles is not particularly limited, and the resin can be produced by a known method.
  • a compound used to form a structural unit having a functional group A or a compound used to form a structural unit having a functional group B, and a compound used to form other structural units are polymerized by a known method. It is obtained by doing.
  • A-13 represents an example of a particle in which a large amount of resin shown on the left is present inside the core portion and a large amount of resin A is shown on the right toward the outside.
  • specific polymer particles suitably used include the following G-1 to G-20 and S-1.
  • the content of each structural unit is a mass ratio
  • the subscript at the lower right of the parenthesis of the polyalkyleneoxy structure or the polyhydroxycarboxylic acid structure indicates the number of repetitions
  • * indicates other structures. Represents the bonding position with
  • the content of each constituent unit of the specific polymer particles described above is the content of the constituent unit before adding a polymerizable group.
  • the constitutional unit derived from methacrylamide / the constitutional unit derived from methylenebisacrylamide / the constitutional unit derived from methacrylic acid / the constitutional unit derived from polyethylene glycol monomethyl ether methacrylate 30
  • the content of the specific polymer particles in the image recording layer of the lithographic printing plate precursor according to the present disclosure is from 10% by mass to 90% by mass based on the total mass of the image recording layer from the viewpoint of UV printing durability and on-press developability. Is preferably 20% by mass to 80% by mass, more preferably 30% by mass to 70% by mass, and particularly preferably 35% by mass to 65% by mass.
  • the image recording layer preferably contains an infrared absorbing agent.
  • the infrared absorber has a function of converting the absorbed infrared rays into heat and a function of being excited by the infrared rays and transferring electrons and / or energy to a polymerization initiator described later.
  • the infrared absorber used in the present disclosure is preferably a dye having an absorption maximum at a wavelength of 750 nm to 1,400 nm.
  • dyes commercially available dyes and known dyes described in documents such as "Dye Handbook” (edited by the Society of Synthetic Organic Chemistry, published in 1970) can be used. Specifically, azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, dyes such as metal thiolate complexes Is mentioned.
  • cyanine dyes preferred are cyanine dyes, squarylium dyes, pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes. Further, a cyanine dye and an indolenine cyanine dye are more preferable. Among them, cyanine dyes are particularly preferred.
  • cyanine dye examples include compounds described in paragraphs 0017 to 0019 of JP-A-2001-133969, paragraphs 0016 to 0021 of JP-A-2002-023360, and paragraphs 0012 to 0037 of JP-A-2002-040638.
  • the compounds described in paragraphs 0034 to 0041 of JP-A-2002-278057, and the compounds described in paragraphs 0080 to 1986 of JP-A-2008-195018 are particularly preferable.
  • the compounds described in paragraphs 0105 to 0113 of JP-A-2012-206495 are particularly preferable.
  • One infrared absorber may be used alone, or two or more infrared absorbers may be used in combination. Further, a pigment and a dye may be used in combination as an infrared absorber.
  • the content of the infrared absorbent in the image recording layer is preferably from 0.1% by mass to 10.0% by mass, more preferably from 0.5% by mass to 5.0% by mass, based on the total mass of the image recording layer. preferable.
  • the image recording layer used in the present disclosure preferably contains a polymerization initiator (electron-accepting polymerization initiator), and more preferably contains a polymerization initiator and a polymerizable compound.
  • the polymerization initiator is a compound that initiates and promotes the polymerization of the polymerizable compound.
  • a known thermal polymerization initiator, a compound having a bond having a small bond dissociation energy, a photopolymerization initiator, or the like can be used.
  • the radical polymerization initiators described in paragraphs 0092 to 0106 of JP-A-2014-104631 can be used.
  • preferred compounds include onium salts. Among them, iodonium salts and sulfonium salts are particularly preferred. Preferred specific compounds among the salts are the same as the compounds described in paragraphs 0104 to 0106 of JP-A-2014-104631.
  • the content of the polymerization initiator is preferably from 0.1% by mass to 50% by mass, more preferably from 0.5% by mass to 30% by mass, and preferably from 0.8% by mass to 20% by mass, based on the total mass of the image recording layer. % By weight is particularly preferred. When the content is in the above range, better sensitivity and better resistance to contamination of the non-image portion during printing can be obtained.
  • the image recording layer used in the present disclosure preferably contains a polymerizable compound.
  • the polymerizable compound in the present disclosure does not include a compound corresponding to the specific polymer described above.
  • the polymerizable compound used in the image recording layer may be, for example, a radical polymerizable compound or a cationic polymerizable compound, but may be an addition polymerizable compound having at least one ethylenically unsaturated bond (ethylene Unsaturated unsaturated compound).
  • ethylene Unsaturated unsaturated compound ethylene Unsaturated unsaturated compound
  • the polymerizable compound can have a chemical form such as, for example, a monomer, a prepolymer, ie, a dimer, trimer or oligomer, or a mixture thereof.
  • Examples of monomers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid), esters and amides thereof.
  • esters of an unsaturated carboxylic acid and a polyhydric alcohol compound and amides of an unsaturated carboxylic acid and a polyamine compound are used.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or an epoxy, and a monofunctional or Dehydration condensation products with polyfunctional carboxylic acids are also preferably used.
  • JP-T-2006-508380 JP-A-2002-287344, JP-A-2008-256850, JP-A-2001-342222, JP-A-9-179296, and JP-A-9-179297.
  • JP-A-9-179298 JP-A-2004-294935, JP-A-2006-243493, JP-A-2002-275129, JP-A-2003-64130, JP-A-2003-280187, It is described in JP-A-10-333321.
  • the monomer of the ester of the polyhydric alcohol compound and the unsaturated carboxylic acid include, as acrylates, ethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, Examples include trimethylolpropane triacrylate, hexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, isocyanuric acid ethylene oxide (EO) -modified triacrylate, and polyester acrylate oligomer.
  • EO isocyanuric acid ethylene oxide
  • methacrylic acid esters As methacrylic acid esters, tetramethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, pentaerythritol trimethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] Examples include dimethylmethane and bis [p- (methacryloxyethoxy) phenyl] dimethylmethane.
  • the monomer of the amide of the polyvalent amine compound and the unsaturated carboxylic acid include methylene bisacrylamide, methylene bismethacrylamide, 1,6-hexamethylenebisacrylamide, 1,6-hexamethylenebismethacrylamide, Examples include diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like.
  • Urethane-based addition-polymerizable compounds produced by an addition reaction between an isocyanate and a hydroxy group are also suitable. Specific examples thereof include one molecule described in JP-B-48-41708. Vinyl containing two or more polymerizable vinyl groups in one molecule obtained by adding a hydroxyl-containing vinyl monomer represented by the following formula (M) to a polyisocyanate compound having two or more isocyanate groups Urethane compounds and the like.
  • CH 2 CC (R M4 ) C ( O) OCH 2 CH (R M5 ) OH (M)
  • RM4 and RM5 each independently represent a hydrogen atom or a methyl group.
  • urethane acrylates described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-A-2003-344997, and JP-A-2006-65210 are disclosed.
  • Urethane compounds having a system skeleton, urethane compounds having a hydrophilic group described in US Pat. No. 7,153,632, Japanese Patent Application Laid-Open No. 8-505958, JP-A-2007-293221, and JP-A-2007-293223. are also suitable.
  • the content of the polymerizable compound is preferably from 5% by mass to 75% by mass, more preferably from 10% by mass to 70% by mass, particularly preferably from 15% by mass to 60% by mass, based on the total mass of the image recording layer. is there.
  • the image recording layer used in the present disclosure preferably contains a binder polymer.
  • a binder polymer a (meth) acrylic resin, a polyvinyl acetal resin, or a polyurethane resin is preferable.
  • a known binder polymer used for an image recording layer of a lithographic printing plate precursor can be suitably used as the binder polymer.
  • a binder polymer hereinafter also referred to as a binder polymer for on-press development
  • a binder polymer for on-press development a binder polymer having an alkylene oxide chain is preferable.
  • the binder polymer having an alkylene oxide chain may have a poly (alkylene oxide) site in the main chain or a side chain.
  • a graft polymer having a poly (alkylene oxide) in a side chain or a block copolymer of a block composed of a poly (alkylene oxide) -containing repeating unit and a block composed of a (alkylene oxide) -free repeating unit may be used.
  • a poly (alkylene oxide) moiety is present in the main chain, a polyurethane resin is preferred.
  • the main chain polymer having a poly (alkylene oxide) moiety in the side chain include (meth) acrylic resin, polyvinyl acetal resin, polyurethane resin, polyurea resin, polyimide resin, polyamide resin, epoxy resin, polystyrene resin, and novolak type. Phenol resins, polyester resins, synthetic rubbers, and natural rubbers are exemplified, and (meth) acrylic resins are particularly preferred.
  • alkylene oxide an alkylene oxide having 2 to 6 carbon atoms is preferable, and ethylene oxide or propylene oxide is particularly preferable.
  • the number of repeating alkylene oxides in the poly (alkylene oxide) site is preferably from 2 to 120, more preferably from 2 to 70, and even more preferably from 2 to 50. When the number of repetitions of the alkylene oxide is 120 or less, it is preferable because both the printing durability due to abrasion and the printing durability due to ink receptivity are suppressed.
  • the poly (alkylene oxide) moiety is preferably contained in the structure represented by the following formula (AO) as a side chain of the binder polymer, and is represented by the following formula (AO) as a side chain of the (meth) acrylic resin. More preferably, it is contained in a structure to be formed.
  • y represents 2 to 120
  • R 1 represents a hydrogen atom or an alkyl group
  • R 2 represents a hydrogen atom or a monovalent organic group.
  • the monovalent organic group an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group , N-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, cyclopentyl and cyclohexyl.
  • y is preferably 2 to 70, more preferably 2 to 50.
  • R 1 is preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.
  • R 2 is particularly preferably a hydrogen atom or a methyl group.
  • the binder polymer may have a crosslinking property in order to improve the film strength of the image area.
  • a crosslinkable functional group such as an ethylenically unsaturated bond may be introduced into the main chain or side chain of the polymer.
  • the crosslinkable functional group may be introduced by copolymerization or by a polymer reaction. Examples of the polymer having an ethylenically unsaturated bond in the main chain of the molecule include poly-1,4-butadiene, poly-1,4-isoprene, and the like.
  • Examples of the polymer having an ethylenically unsaturated bond in the side chain of the molecule include an ester or amide polymer of acrylic acid or methacrylic acid, wherein the ester or amide residue (R of —COOR or —CONHR) is A polymer having an ethylenically unsaturated bond can be mentioned.
  • a binder polymer having crosslinkability for example, free radicals (polymerization initiation radicals or growth radicals in the polymerization process of the polymerizable compound) are added to the crosslinkable functional group, and the polymerization chain of the polymerizable compound is directly added between the polymers. Through addition polymerization through the polymer, a crosslink is formed between the polymer molecules and the polymer is cured.
  • atoms in the polymer eg, a hydrogen atom on a carbon atom adjacent to the functional cross-linking group
  • free radicals are abstracted by free radicals to form polymer radicals, which are bonded to each other to form a cross-link between polymer molecules. Formed and cured.
  • the content of the crosslinkable group (content of the radically polymerizable unsaturated double bond by iodometric titration) in the binder polymer is preferably 0 per g of the binder polymer. 0.1 mmol to 10.0 mmol, more preferably 1.0 mmol to 7.0 mmol, and particularly preferably 2.0 mmol to 5.5 mmol.
  • the weight average molecular weight (Mw) is preferably 2,000 or more, more preferably 5,000 or more, and more preferably 10,000 to 300,000 in terms of polystyrene by the GPC method. It is even more preferred.
  • hydrophilic polymers such as polyacrylic acid and polyvinyl alcohol described in JP-A-2008-195018 can be used in combination. Further, a lipophilic polymer and a hydrophilic polymer can be used in combination.
  • the binder polymer may be present as a polymer that functions as a binder for each component in the image recording layer, or may be present in the form of particles.
  • the average primary particle diameter is preferably 1,000 nm or less, more preferably 10 nm to 500 nm, and still more preferably 50 nm to 300 nm.
  • the compound corresponding to the above-mentioned specific polymer particles or other polymer particles described below does not correspond to the binder polymer.
  • one type of binder polymer may be used alone, or two or more types may be used in combination.
  • the binder polymer can be contained in an arbitrary amount in the image recording layer.
  • the content of the binder polymer can be appropriately selected depending on the use of the image recording layer, but is preferably 1% by mass to 90% by mass, more preferably 5% by mass to 80% by mass, based on the total mass of the image recording layer.
  • the image recording layer used in the present disclosure may contain an electron donating polymerization initiator (radical generation auxiliary).
  • the electron donating type polymerization initiator contributes to improvement of the printing durability of the planographic printing plate.
  • Examples of the electron donating polymerization initiator include the following five types.
  • Aminoacetic acid compound It is considered that the CX bond on carbon adjacent to nitrogen is cleaved by oxidation to generate an active radical.
  • X is preferably a hydrogen atom, a carboxy group, a trimethylsilyl group or a benzyl group.
  • Specific examples include N-phenylglycine (a phenyl group may have a substituent), N-phenyliminodiacetic acid (a phenyl group may have a substituent), and the like.
  • Specific examples include phenylthioacetic acid (a phenyl group may have a substituent) and the like.
  • Tin-containing compound The above-described aminoacetic acid compound in which a nitrogen atom is replaced with a tin atom can generate an active radical by the same action.
  • Sulfinates Active radicals can be generated by oxidation. Specific examples include sodium arylsulfin.
  • the image recording layer preferably contains a borate compound.
  • a borate compound a tetraaryl borate compound or a monoalkyltriaryl borate compound is preferable, and from the viewpoint of the stability of the compound and the potential difference described below, a tetraaryl borate compound is more preferable.
  • a tetraaryl borate compound having at least one aryl group having a group is particularly preferred.
  • the electron withdrawing group is preferably a group having a positive Hammett's ⁇ value, more preferably a group having a Hammett's ⁇ value of 0 to 1.2.
  • Hammett's ⁇ values ( ⁇ p value and ⁇ m value) are described in Hansch, C .; Leo, A .; Taft, R .; W. Chem. Rev .. , 1991, 91, 165-195.
  • a halogen atom, a trifluoromethyl group or a cyano group is preferable, and a fluorine atom, a chlorine atom, a trifluoromethyl group or a cyano group is more preferable.
  • an alkali metal ion or a tetraalkylammonium ion is preferable, and a sodium ion, a potassium ion, or a tetrabutylammonium ion is more preferable.
  • the counter cation may be an iodonium cation contained in an onium salt in the above-mentioned polymerization initiator (electron-accepting polymerization initiator), or may be a dye structure in the above-mentioned infrared absorber.
  • a salt of an iodonium cation and a borate anion iodonium borate described in paragraph 0048 of Japanese Patent No. 5129242 is also preferably exemplified.
  • the image recording layer in the present disclosure preferably further contains a compound represented by the following formula I as an electron donating polymerization initiator (borate compound). It is preferable to further contain the compound represented.
  • R 1 , R 2 , R 3, and R 4 each independently represent an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a heterocyclyl group, or R 1 , R 2 2 , R 3 and R 4 represent a structure in which two or more of them combine to form a heterocyclic ring containing a boron atom as a ring member described in Formula I, and Z + represents a cation.
  • R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and 2 carbon atoms. It is preferably an alkynyl group having 12 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a heterocyclyl group having a total number of carbon atoms of 5 to 10 of carbon, oxygen, sulfur and nitrogen, and an alkyl group having 1 to 12 carbon atoms. Alternatively, an aryl group having 6 to 10 carbon atoms is more preferable.
  • heterocyclyl group examples include a pyridyl group, a pyrimidyl group, and a triazolyl group.
  • the alkyl group, the aryl group, the alkenyl group, the alkynyl group, the cycloalkyl group, or the heterocyclyl group may have a substituent.
  • Preferred substituents include the electron-withdrawing groups in the above-described aryl groups having an electron-withdrawing group.
  • at least three of R 1 , R 2 , R 3, and R 4 are preferably aryl groups, at least three are aryl groups, one is more preferably an alkyl group, and all four are aryl groups. More preferably, it is a group.
  • Examples of the heterocycle containing a boron atom as a ring member described in the above formula I include a hydrocarbon ring containing a boron atom.
  • the number of ring members of the above heterocycle is preferably 7 or less.
  • Z + represents a monovalent cation or a polyvalent cation, and is preferably a monovalent cation.
  • Z + is preferably an alkali metal ion or a tetraalkylammonium ion, and more preferably a sodium ion, a potassium ion, or a tetrabutylammonium ion.
  • Z + may be an iodonium cation in an onium salt in the above-mentioned polymerization initiator (electron-accepting polymerization initiator), or may be a dye structure in the above-mentioned infrared absorber.
  • X c + represents a counter cation in the above borate compound, and is preferably an alkali metal ion or a tetraalkylammonium ion, more preferably an alkali metal ion or a tetrabutylammonium ion.
  • Bu represents an n-butyl group.
  • the electron donating polymerization initiator may be used alone or in combination of two or more.
  • the content of the electron donating polymerization initiator is preferably 0.01% by mass to 30% by mass, more preferably 0.05% by mass to 25% by mass, and more preferably 0.1% by mass, based on the total mass of the image recording layer. -20% by mass is more preferred.
  • the image recording layer used in the present disclosure may contain a chain transfer agent.
  • the chain transfer agent contributes to improving the printing durability of the lithographic printing plate.
  • a thiol compound is preferable, a thiol having 7 or more carbon atoms is more preferable from the viewpoint of a boiling point (difficulty of volatilization), and a compound having a mercapto group on an aromatic ring (aromatic thiol compound) is further preferable.
  • the thiol compound is preferably a monofunctional thiol compound.
  • chain transfer agent examples include the following compounds.
  • the content of the chain transfer agent is preferably 0.01% by mass to 50% by mass, more preferably 0.05% by mass to 40% by mass, and more preferably 0.1% by mass to 30% by mass based on the total mass of the image recording layer. % Is more preferred.
  • the image recording layer may contain other polymer particles.
  • the other polymer particles are preferably polymer particles capable of converting the image recording layer to hydrophobic when heat is applied.
  • the polymer particles corresponding to the above-described polymer particles do not correspond to other polymer particles.
  • the other polymer particles are at least selected from hydrophobic thermoplastic polymer particles, thermoreactive polymer particles, polymer particles having a polymerizable group, microcapsules containing a hydrophobic compound, and microgels (crosslinked polymer particles).
  • there is one there is one.
  • polymer particles having a polymerizable group and microgels are preferable.
  • hydrophobic thermoplastic polymer particles Research Disclosure No. 1 of January 1992 can be used. No. 33303, hydrophobic thermoplastic polymer particles described in JP-A-9-123387, JP-A-9-131850, JP-A-9-171249, JP-A-9-171250 and European Patent No. 931647 are preferable. It is listed. Specific examples of the polymer constituting the hydrophobic thermoplastic polymer particles include ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, vinyl carbazole, and a polyalkylene structure.
  • homopolymers or copolymers of monomers such as acrylates or methacrylates or mixtures thereof.
  • a copolymer containing polystyrene, styrene and acrylonitrile, and polymethyl methacrylate are used.
  • the volume average particle diameter of the hydrophobic thermoplastic polymer particles is preferably 0.01 ⁇ m to 2.0 ⁇ m.
  • heat-reactive polymer particles examples include polymer particles having a heat-reactive group.
  • the polymer particles having a thermoreactive group form a hydrophobized region due to crosslinking by a thermal reaction and a change in the functional group at that time.
  • the heat-reactive group in the polymer particles having a heat-reactive group may be any functional group that performs any reaction as long as a chemical bond is formed, and a polymerizable group is preferable.
  • a polymerizable group examples thereof include an ethylenically unsaturated group (for example, an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, etc.) which performs a radical polymerization reaction, and a cationically polymerizable group (for example, a vinyl group, a vinyloxy group, an epoxy group, an oxetanyl group) ),
  • Preferable examples include
  • microcapsules for example, as described in JP-A-2001-277740 and JP-A-2001-277742, those in which all or a part of the components of the image recording layer are included in the microcapsules can be mentioned.
  • the components of the image recording layer can be contained outside the microcapsules.
  • the microcapsule-containing image recording layer contains a hydrophobic component in the microcapsule and contains a hydrophilic component outside the microcapsule.
  • the microgel (crosslinked polymer particles) can contain a part of the constituent components of the image recording layer on at least one of the inside and the surface thereof.
  • a radical polymerizable group is provided on the surface to form a reactive microgel is preferable from the viewpoint of image forming sensitivity and printing durability.
  • a known method can be used to microencapsulate or microgel the constituent components of the image recording layer.
  • the average particle size of the microcapsules and microgels is preferably 0.01 ⁇ m to 3.0 ⁇ m, more preferably 0.05 ⁇ m to 2.0 ⁇ m, and particularly preferably 0.10 ⁇ m to 1.0 ⁇ m. Within this range, good resolution and stability over time can be obtained.
  • the content of the other polymer particles is preferably from 5% by mass to 90% by mass based on the total mass of the image recording layer.
  • the image recording layer may contain a low molecular weight hydrophilic compound in order to improve on-press developability while suppressing a decrease in printing durability.
  • the low molecular weight hydrophilic compound is preferably a compound having a molecular weight of less than 1,000, more preferably a compound having a molecular weight of less than 800, and further preferably a compound having a molecular weight of less than 500.
  • low-molecular hydrophilic compound examples include, as water-soluble organic compounds, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycols such as tripropylene glycol and ether or ester derivatives thereof, glycerin, Polyols such as pentaerythritol and tris (2-hydroxyethyl) isocyanurate, organic amines such as triethanolamine, diethanolamine and monoethanolamine and salts thereof, and organic sulfones such as alkylsulfonic acid, toluenesulfonic acid and benzenesulfonic acid.
  • organic sulfamic acids and salts thereof such as alkylsulfamic acid, organic sulfuric acids and salts thereof such as alkyl sulfate and alkyl ether sulfate, and phenylphosphonic acid
  • organic phosphonic acids and salts thereof tartaric acid, oxalic acid, citric acid, malic acid, lactic acid, gluconic acid, organic carboxylic acids and salts thereof such as amino acids, betaines, and the like.
  • the low molecular weight hydrophilic compound contains at least one selected from polyols, organic sulfates, organic sulfonates, and betaines.
  • organic sulfonates include alkyl sulfonates such as sodium n-butylsulfonate, sodium n-hexylsulfonate, sodium 2-ethylhexylsulfonate, sodium cyclohexylsulfonate and sodium n-octylsulfonate; Sodium 8,8,11-trioxapentadecane-1-sulfonate, sodium 5,8,11-trioxaheptadecane-1-sulfonate, 13-ethyl-5,8,11-trioxaheptadecane-1-sulfonate Alkyl sulfonates containing an ethylene oxide chain such as sodium silicate, sodium 5,8,11,14-tetraoxatetracosane-1-sulfonate; sodium benzenesulfonate, sodium p-toluenesulfonate, p-hydroxybenzenesulfonic
  • organic sulfates examples include alkyl, alkenyl, alkynyl, aryl and heterocyclic monoether sulfates of polyethylene oxide.
  • the number of ethylene oxide units is preferably from 1 to 4, and the salt is preferably a sodium salt, a potassium salt or a lithium salt.
  • Specific examples include the compounds described in paragraphs 0034 to 0038 of JP-A-2007-276454.
  • betaines compounds in which the number of carbon atoms in the hydrocarbon substituent on the nitrogen atom is 1-5 are preferable. Specific examples include trimethylammonium acetate, dimethylpropylammonium acetate, and 3-hydroxy-4-trimethylammonium. Obutyrate, 4- (1-pyridinio) butyrate, 1-hydroxyethyl-1-imidazolioacetate, trimethylammonium methanesulfonate, dimethylpropylammonium methanesulfonate, 3-trimethylammonio-1-propanesulfonate, 3 -(1-pyridinio) -1-propanesulfonate and the like.
  • the fountain solution penetrates into the exposed portion (image portion) of the image recording layer and lowers the hydrophobicity and film strength of the image portion. Therefore, the ink receptivity and printing durability of the image recording layer can be maintained satisfactorily.
  • the content of the low molecular weight hydrophilic compound is preferably 0.5% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and more preferably 2% by mass to 10% by mass based on the total mass of the image recording layer. Is more preferred. Within this range, good on-press developability and printing durability can be obtained.
  • the low molecular weight hydrophilic compound may be used alone or in combination of two or more.
  • the image recording layer may contain a sensitizing agent such as a phosphonium compound, a nitrogen-containing low molecular weight compound, or an ammonium group-containing polymer in order to improve the inking property.
  • a sensitizing agent such as a phosphonium compound, a nitrogen-containing low molecular weight compound, or an ammonium group-containing polymer in order to improve the inking property.
  • these compounds function as a surface coating agent for the inorganic layered compound, and can suppress a decrease in the inking property of the inorganic layered compound during printing.
  • the sensitizer it is preferable to use a phosphonium compound, a nitrogen-containing low-molecular compound, and an ammonium group-containing polymer in combination, and it is preferable to use a phosphonium compound, a quaternary ammonium salt, and an ammonium group-containing polymer in combination. Is more preferred.
  • nitrogen-containing low molecular weight compound examples include amine salts and quaternary ammonium salts. Further, imidazolinium salts, benzimidazolinium salts, pyridinium salts, and quinolinium salts are also included. Among them, quaternary ammonium salts and pyridinium salts are preferred.
  • tetramethylammonium hexafluorophosphate
  • tetrabutylammonium hexafluorophosphate
  • dodecyltrimethylammonium p-toluenesulfonate
  • benzyltriethylammonium hexafluorophosphate
  • benzyldimethyloctylammonium hexafluorophosphate
  • the compounds described in paragraphs 0021 to 0037 of JP-A-2008-284858 and paragraphs 0030 to 0057 of JP-A-2009-90645 are exemplified.
  • the ammonium group-containing polymer only needs to have an ammonium group in its structure, and is preferably a polymer containing (meth) acrylate having an ammonium group in a side chain as a copolymer component in an amount of 5 mol% to 80 mol%.
  • Specific examples include the polymers described in paragraphs 0089 to 0105 of JP-A-2009-208458.
  • the ammonium salt-containing polymer preferably has a reduced specific viscosity (unit: ml / g) in the range of 5 to 120, preferably 10 to 110, determined according to the measuring method described in JP-A-2009-208458. Are more preferable, and those in the range of 15 to 100 are particularly preferable.
  • Mw weight average molecular weight
  • the content of the sensitizer is preferably 0.01% by mass to 30.0% by mass, more preferably 0.1% by mass to 15.0% by mass, and more preferably 1% by mass, based on the total mass of the image recording layer. % To 10% by mass is more preferred.
  • the image recording layer used in the present disclosure preferably contains an acid coloring agent.
  • the “acid color former” used in the present disclosure means a compound having a property of developing a color when heated while receiving an electron accepting compound (for example, a proton such as an acid).
  • an electron accepting compound for example, a proton such as an acid.
  • the acid coloring agent in particular, it has a partial skeleton such as lactone, lactam, sultone, spiropyran, ester, and amide, and when contacted with an electron accepting compound, these partial skeletons are rapidly opened or cleaved. Compounds are preferred.
  • Such acid color formers include 3,3-bis (4-dimethylaminophenyl) -6-dimethylaminophthalide (referred to as “crystal violet lactone”), 3,3-bis (4- Dimethylaminophenyl) phthalide, 3- (4-dimethylaminophenyl) -3- (4-diethylamino-2-methylphenyl) -6-dimethylaminophthalide, 3- (4-dimethylaminophenyl) -3- (1 , 2-Dimethylindol-3-yl) phthalide, 3- (4-dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3,3-bis (1,2-dimethylindol-3) -Yl) -5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindol-3-yl) -6-dimethylaminophthalide, 3,3-bi (9-ethylcarba
  • the acid color former used in the present disclosure is preferably at least one compound selected from the group consisting of a spiropyran compound, a spirooxazine compound, a spirolactone compound, and a spirolactam compound.
  • the hue of the dye after coloring is preferably green, blue or black from the viewpoint of visibility.
  • ETAC, S-205, BLACK305, BLACK400, BLACK100, BLACK500, H-7001, GREEN300, NIRBLACK78, H-3035, ATP, H-1046, H-2114, GREEN-DCF, Blue-63 , GN-169, and crystal violet lactone are preferable because the visible light absorption of the formed film is good.
  • These acid colorants may be used alone or in combination of two or more.
  • the image recording layer of the lithographic printing plate precursor according to the present disclosure can contain a dye having a large absorption in a visible light region as a colorant for an image.
  • a dye having a large absorption in a visible light region As a colorant for an image.
  • pigments such as phthalocyanine pigments, azo pigments, carbon black, and titanium oxide can also be suitably used.
  • the inclusion of the coloring agent makes it easier to distinguish between the image area and the non-image area after image formation.
  • the amount of the colorant added is preferably 0.005% by mass to 10% by mass based on the total mass of the image recording layer.
  • the image recording layer may contain, as other components, a surfactant, a polymerization inhibitor, a higher fatty acid derivative, a plasticizer, inorganic particles, an inorganic layer compound, and the like. Specifically, the description in paragraphs 0114 to 0159 of JP-A-2008-284817 can be referred to.
  • the image recording layer in the lithographic printing plate precursor according to the present disclosure may be formed by dispersing the necessary components in a known solvent (coating solvent) as described in paragraphs 0142 to 0143 of JP-A-2008-195018, for example. It can be formed by dissolving to prepare a coating solution, coating the coating solution on a support by a known method such as bar coating, and drying.
  • the coating amount (solid content) of the image recording layer after coating and drying varies depending on the use, but is preferably from 0.3 g / m 2 to 3.0 g / m 2 . Within this range, good sensitivity and good film properties of the image recording layer can be obtained.
  • the support in the planographic printing plate precursor according to the present disclosure can be appropriately selected from known hydrophilic supports for planographic printing plate precursors and used.
  • a support having a hydrophilic surface is preferable.
  • the hydrophilic surface preferably has a contact angle with water of less than 10 °, more preferably less than 5 °.
  • the contact angle with water is measured using a fully automatic contact angle meter (model number: DM-701, manufactured by Kyowa Interface Science Co., Ltd.) as a measuring device under the conditions of an ambient temperature of 25 ° C. and a relative humidity of 50%.
  • the hydrophilic support an aluminum plate which has been subjected to a surface roughening treatment and anodized by a known method is preferable.
  • the aluminum plate may be further processed, if necessary, by enlarging or sealing the micropores of the anodic oxide film described in JP-A-2001-253181 and JP-A-2001-322365, US Pat. No. 066, 3,181,461, 3,280,734 and 3,902,734, a surface hydrophilization treatment with an alkali metal silicate, U.S.A.
  • the surface hydrophilization treatment with polyvinylphosphonic acid or the like described in each specification of Patent Nos. 3,276,868, 4,153,461 and 4,689,272 is appropriately selected. You may go.
  • the support preferably has a center line average roughness of 0.10 ⁇ m to 1.2 ⁇ m.
  • the support may have an organic polymer compound described in JP-A-5-45885 or a silicon alkoxy compound described in JP-A-6-35174, if necessary, on the surface opposite to the image recording layer. May be included.
  • the lithographic printing plate precursor according to the present disclosure preferably has an undercoat layer (sometimes called an intermediate layer) between the image recording layer and the support.
  • the undercoat layer enhances the adhesion between the support and the image recording layer in the exposed area, and easily peels off the image recording layer from the support in the unexposed area. It contributes to improving.
  • the undercoat layer functions as a heat insulating layer, which also has the effect of preventing heat generated by exposure from diffusing to the support and lowering the sensitivity.
  • Examples of the compound used for the undercoat layer include a polymer having an adsorptive group and a hydrophilic group that can be adsorbed on the support surface. In order to improve the adhesion to the image recording layer, a polymer having an adsorptive group and a hydrophilic group and further having a crosslinkable group is preferable.
  • the compound used for the undercoat layer may be a low molecular compound or a polymer. The compounds used in the undercoat layer may be used as a mixture of two or more as necessary.
  • the compound used in the undercoat layer is a polymer
  • a copolymer of a monomer having an adsorptive group, a monomer having a hydrophilic group, and a monomer having a crosslinkable group is preferable.
  • the adsorptive group that can be adsorbed on the support surface include a phenolic hydroxy group, a carboxy group, —PO 3 H 2 , —OPO 3 H 2 , —CONHSO 2 —, —SO 2 NHSO 2 —, and —COCH 2 COCH 3. Is preferred.
  • the hydrophilic group a sulfo group or a salt thereof, and a salt of a carboxy group are preferable.
  • the polymer may have a polar substituent of the polymer, a substituent having a countercharge with the polar substituent and a crosslinkable group introduced by salt formation with a compound having an ethylenically unsaturated bond, Other monomers, preferably hydrophilic monomers, may be further copolymerized.
  • a silane coupling agent having an addition-polymerizable ethylenic double bond reactive group described in JP-A-10-282679 and an ethylenic double bond described in JP-A-2-304441 are disclosed.
  • a preferred example is a phosphorus compound having a heavy bond reactive group.
  • Low-molecular or high-molecular compounds having a functional group and a hydrophilic group that interact with the surface are also preferably used. More preferred are high-molecular polymers having an adsorptive group, a hydrophilic group and a crosslinkable group that can be adsorbed on the support surface described in JP-A-2005-125749 and JP-A-2006-188038.
  • the content of the ethylenically unsaturated bonding group in the polymer used for the undercoat layer is preferably 0.1 mmol to 10.0 mmol, more preferably 0.2 mmol to 5.5 mmol, per 1 g of the polymer.
  • the weight average molecular weight (Mw) of the polymer used for the undercoat layer is preferably 5,000 or more, more preferably 10,000 to 300,000.
  • the undercoat layer is, in addition to the undercoat layer compound described above, a chelating agent, a secondary or tertiary amine, a polymerization inhibitor, an amino group or a functional group having a polymerization inhibiting ability, and a support surface in order to prevent contamination with time.
  • a chelating agent such as 1,4-diazabicyclo [2.2.2] octane (DABCO), 2,3,5,6-tetrahydroxy-p-quinone, chloranil, sulfophthalic acid, Ethylethylenediaminetriacetic acid, dihydroxyethylethylenediaminediacetic acid, hydroxyethyliminodiacetic acid, etc.
  • the undercoat layer is applied by a known method.
  • the coating amount (solid content) of the undercoat layer is preferably from 0.1 mg / m 2 to 100 mg / m 2, more preferably from 1 mg / m 2 to 30 mg / m 2 .
  • the lithographic printing plate precursor according to the present disclosure preferably has a protective layer (sometimes called an overcoat layer) on the image recording layer.
  • the protective layer has a function of preventing damage to the image recording layer and a function of preventing ablation at the time of high-intensity laser exposure, in addition to a function of suppressing an image formation inhibition reaction by blocking oxygen.
  • the protective layer having such properties is described, for example, in US Pat. No. 3,458,311 and Japanese Patent Publication No. 55-49729.
  • any of a water-soluble polymer and a water-insoluble polymer can be appropriately selected and used, and if necessary, a mixture of two or more types may be used. it can.
  • Specific examples include polyvinyl alcohol, modified polyvinyl alcohol, polyvinylpyrrolidone, water-soluble cellulose derivatives, poly (meth) acrylonitrile, and the like.
  • the modified polyvinyl alcohol an acid-modified polyvinyl alcohol having a carboxy group or a sulfo group is preferably used.
  • Specific examples include modified polyvinyl alcohols described in JP-A-2005-250216 and JP-A-2006-259137.
  • the protective layer preferably contains an inorganic layered compound in order to enhance oxygen barrier properties.
  • the inorganic layered compound is a particle having a thin tabular shape, for example, a group of mica such as natural mica and synthetic mica, talc, teniolite, montmorillonite, saponite, hectotype represented by the formula: 3MgO.4SiO.H 2 O Light, zirconium phosphate and the like.
  • the inorganic layer compound preferably used is a mica compound.
  • Examples of the mica compound include a compound represented by the formula: A (B, C) 2-5 D 4 O 10 (OH, F, O) 2 [where A is any of K, Na, and Ca; One of Fe (II), Fe (III), Mn, Al, Mg, and V, and D is Si or Al. ] Mica groups such as natural mica and synthetic mica.
  • natural mica includes muscovite, soda mica, phlogopite, biotite and scale mica.
  • synthetic mica include non-swelling mica such as fluorophlogopite mica 3 (AlSi 3 O 10 ) F 2 , potassium tetrasilicic mica KMg 2.5 Si 4 O 10 ) F 2 , and Na tetrasilic mica NaMg 2.
  • the lattice layer has a shortage of positive charges, and cations such as Li + , Na + , Ca 2+ , and Mg 2+ are adsorbed between the layers to compensate for the shortage.
  • the cations interposed between these layers are called exchangeable cations and can exchange with various cations.
  • the shape of the mica compound is preferably as thin as possible, and the plane size is preferably as large as possible as long as the smoothness of the coated surface and the transmittance of active light rays are not impaired. Therefore, the aspect ratio is preferably 20 or more, more preferably 100 or more, and particularly preferably 200 or more.
  • the aspect ratio is the ratio of the major axis to the thickness of the particle, and can be measured, for example, from a projection of a particle by a micrograph. The greater the aspect ratio, the greater the effect obtained.
  • the average particle diameter of the mica compound is preferably 0.3 ⁇ m to 20 ⁇ m, more preferably 0.5 ⁇ m to 10 ⁇ m, and particularly preferably 1 ⁇ m to 5 ⁇ m.
  • the average thickness of the particles is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, particularly preferably 0.01 ⁇ m or less.
  • the preferred embodiment has a thickness of about 1 nm to 50 nm and a plane size (major axis) of about 1 ⁇ m to 20 ⁇ m.
  • the content of the inorganic layered compound is preferably 0% by mass to 60% by mass, more preferably 3% by mass to 50% by mass, based on the total solid content of the protective layer. Even when a plurality of types of inorganic layered compounds are used in combination, the total amount of the inorganic layered compounds is preferably the above-mentioned content. Within the above range, oxygen barrier properties are improved, and good sensitivity is obtained. Further, it is possible to prevent a decrease in the inking property.
  • the protective layer may contain known additives such as a plasticizer for imparting flexibility, a surfactant for improving coating properties, and inorganic particles for controlling surface slipperiness. Further, the sensitizer described in the image recording layer may be contained in the protective layer.
  • the protective layer is applied by a known method.
  • the coating amount of the protective layer (solid content) is preferably from 0.01g / m 2 ⁇ 10g / m 2, more preferably 0.02g / m 2 ⁇ 3g / m 2, 0.02g / m 2 ⁇ 1g / m 2 is particularly preferred.
  • the lithographic printing plate precursor according to the present disclosure is subjected to image exposure and development processing to produce a lithographic printing plate.
  • One embodiment of the method for producing a lithographic printing plate according to the present disclosure is an image-forming exposure of the lithographic printing plate precursor according to the present disclosure, an exposure step of forming an exposed portion and an unexposed portion, and a printing ink and dampening.
  • An on-press development step of supplying at least one selected from the group consisting of water to remove an image recording layer in a non-image area on a printing press.
  • another embodiment of the method of manufacturing a lithographic printing plate according to the present disclosure is an image-forming exposure of the lithographic printing plate precursor according to the present disclosure, an exposure step of forming an exposed portion and an unexposed portion, And supplying a developing solution of 2 to 11 to remove the unexposed portion.
  • One embodiment of the lithographic printing method according to the present disclosure is an imagewise exposing the lithographic printing plate precursor according to the present disclosure, an exposure step of forming an exposed portion and an unexposed portion, and includes a printing ink and a fountain solution.
  • Another embodiment of the lithographic printing method according to the present disclosure includes an exposure step of imagewise exposing the lithographic printing plate precursor according to the present disclosure to form an exposed portion and an unexposed portion, and having a pH of 2 or more and 11 or less. And a printing step of printing with the obtained lithographic printing plate.
  • a preferred embodiment of each step of the method for preparing a lithographic printing plate according to the present disclosure and the lithographic printing method according to the present disclosure will be described in order.
  • the lithographic printing plate precursor according to the present disclosure can be developed with a developer.
  • the method for preparing a lithographic printing plate according to the present disclosure preferably includes an exposure step of exposing the lithographic printing plate precursor according to the present disclosure imagewise to form an exposed portion and an unexposed portion.
  • the lithographic printing plate precursor according to the present disclosure is preferably exposed imagewise by laser exposure through a transparent original having a line image, a halftone dot image, or the like, or by laser beam scanning using digital data.
  • the wavelength of the light source is preferably from 750 nm to 1,400 nm.
  • a solid-state laser and a semiconductor laser that emit infrared rays are suitable.
  • the output is preferably 100 mW or more, the exposure time per pixel is preferably within 20 microseconds, and the irradiation energy amount is 10 mJ / cm 2 to 300 mJ / cm 2. preferable. Further, it is preferable to use a multi-beam laser device in order to shorten the exposure time.
  • the exposure mechanism may be any of an internal drum system, an external drum system, a flatbed system, and the like. Image exposure can be performed by a conventional method using a plate setter or the like. In the case of on-press development, after the lithographic printing plate precursor is mounted on the printing press, image exposure may be performed on the printing press.
  • the method for preparing a lithographic printing plate according to the present disclosure preferably includes an on-press development step of supplying at least one of a printing ink and a fountain solution to remove the unexposed portions. Further, the method of preparing a lithographic printing plate according to the present disclosure may be performed by a method of developing with a developer (a developer processing method). For example, the method of preparing a lithographic printing plate according to the present disclosure includes a developing step of supplying a developer having a pH of 2 to 11 to remove the unexposed portions.
  • the on-press development method will be described below.
  • an imagewise exposed lithographic printing plate precursor is supplied with an oil-based ink and an aqueous component on a printing press, and the image recording layer in the non-image area is removed to produce a lithographic printing plate.
  • the lithographic printing plate precursor is directly mounted on a printing machine without any development processing, or, after the lithographic printing plate precursor is mounted on a printing machine, image exposure is performed on the printing machine.
  • an uncured image recording layer is formed in a non-image portion at an early stage during printing by one or both of the supplied oil-based ink and the aqueous component. It is removed by dissolution or dispersion, and a hydrophilic surface is exposed at that portion. On the other hand, in the exposed portion, the image recording layer cured by exposure forms an oil-based ink receiving portion having a lipophilic surface.
  • An oil-based ink or an aqueous component may be supplied to the plate first, but the oil-based ink is supplied first in order to prevent the aqueous component from being contaminated by the components of the image recording layer from which the aqueous component has been removed. Is preferred.
  • the lithographic printing plate precursor is developed on-press on a printing press and used as is for printing a large number of sheets.
  • the oil-based ink and the aqueous component a normal printing ink for lithographic printing and a fountain solution are suitably used.
  • a lithographic printing plate can be produced by a developing treatment using a developer by appropriately selecting a binder polymer or the like, which is a component of the image recording layer.
  • the development processing using a developer is an embodiment using a developer having a pH of 2 to 11 which may contain at least one compound selected from the group consisting of a surfactant and a water-soluble polymer compound (also referred to as simple development processing). )including.
  • a developer and a gum solution treatment step can be performed simultaneously by adding a water-soluble polymer compound to the developer. Therefore, the post-water washing step is not particularly required, and the drying step can be performed after the development and the gum solution treatment are performed in one step per one solution. Therefore, as a development treatment using a developer, a method for preparing a lithographic printing plate including a step of developing the lithographic printing plate precursor after image exposure with a developer having a pH of 2 to 11 is preferable. After the development, it is preferable to remove excess developer using a squeeze roller and then dry.
  • Performing the development and the gum solution treatment in one step of one solution means that the development process and the gum solution treatment are not performed as separate steps, but the development and the gum solution treatment are performed in one step with one solution.
  • the developing process can be suitably performed by an automatic developing machine equipped with a developer supply means and a rubbing member.
  • An automatic development processor using a rotating brush roll as the rubbing member is particularly preferred.
  • the number of rotating brush rolls is preferably two or more.
  • the automatic developing machine is provided with a means for removing excess developer such as a squeeze roller after the developing means and a drying means such as a hot air device.
  • the automatic development processor may be provided with a pre-heating means for heating the lithographic printing plate precursor after image exposure before the development processing means.
  • the processing by such an automatic development processor has an advantage that it is free from the handling of the development residue derived from the protective layer and / or the image recording layer which occurs in the case of the so-called on-press development processing.
  • a development processing method for example, a method in which an aqueous solution is contained in a sponge, absorbent cotton, or the like, the processing is performed while rubbing the entire plate surface, and drying is performed after the processing is completed.
  • the immersion treatment for example, a method in which the lithographic printing plate precursor is immersed in a vat or a deep tank containing an aqueous solution for about 60 seconds, stirred, and dried while rubbing with absorbent cotton, sponge, or the like is preferably exemplified.
  • an apparatus having a simplified structure and a simplified process be used for the development processing.
  • the protective layer is removed by a pre-washing step, then development is performed with a high pH alkaline developing solution, and then the alkali is removed in a post-water washing step, a gum treatment is performed in a gumming step, and a drying step is performed. Dry with.
  • development and gumming can be performed simultaneously with one solution. Therefore, it is possible to omit the post-water washing step and the gum treatment step, and it is preferable to perform development and gumming (gum solution treatment) with one liquid, and then perform a drying step as necessary.
  • the removal of the protective layer, the development, and the gumming are performed simultaneously with one liquid without performing the pre-washing step. After development and gumming, it is preferable to remove excess developer using a squeeze roller and then dry.
  • a method of immersing the developer once in the developing solution or a method of immersing the developer twice or more may be used.
  • a method of immersing the developer once or twice in the developer is preferable.
  • the exposed lithographic printing plate precursor may be passed through a developing solution tank in which the developing solution is stored, or the developing solution may be sprayed from a spray or the like onto the plate surface of the exposed lithographic printing plate precursor.
  • the developing solution Even when immersed in a developer twice or more, twice using the same developer or a developer and a developer (fatigue solution) in which the components of the image recording layer are dissolved or dispersed by the development process.
  • the case of immersion as described above is referred to as development processing with one liquid (one-liquid processing).
  • a rubbing member is preferably used, and a rubbing member such as a brush is preferably provided in a developing bath for removing a non-image portion of the image recording layer.
  • the development treatment is carried out according to a conventional method, preferably at a temperature of 0 ° C. to 60 ° C., more preferably at a temperature of 15 ° C. to 40 ° C., for example, immersing the exposed lithographic printing plate precursor in a developer and rubbing with a brush, or
  • the treatment can be performed by, for example, pumping up a processing liquid charged in an external tank, spraying the processing liquid from a spray nozzle, and rubbing with a brush.
  • the developer charged in an external tank is pumped up, sprayed from a spray nozzle and rubbed with a brush
  • the developer can be sprayed again from the spray nozzle and rubbed with a brush.
  • the developer becomes fatigued due to an increase in the processing amount. Therefore, it is preferable to recover the processing ability by using a replenisher or a fresh developer.
  • a gum coater or an automatic developing machine which is conventionally known for PS plates (Presensitized Plate) and CTP (Computer to Plate) can also be used.
  • an automatic developing machine for example, a system in which a developer charged in a developing tank or a developer charged in an external tank is pumped up and sprayed from a spray nozzle for processing, in a tank filled with the developer. Any of a system in which a printing plate is immersed and conveyed by a submerged guide roll or the like, and a so-called disposable processing system in which substantially unused developer is supplied and processed for each plate as needed can be applied. .
  • a device having a rubbing mechanism using a brush, a moleton or the like is more preferable.
  • commercially available automatic developing machines (Clean Out Unit C85 / C125, Clean-Out Unit + C85 / 120, FCF 85V, FCF 125V, FCF News (Glunz & Jensen), Azura CX85, Azura CXAXRA, Crazy It is also possible to use a device in which a laser exposure unit and an automatic developing unit are integrated.
  • the pH of the developer is preferably 2 to 11, more preferably 5 to 9, and even more preferably 7 to 9. From the viewpoint of the developing property and the dispersibility of the image recording layer, it is advantageous to set the pH value to a higher value, but it is more effective to set the pH value to a lower value for printability, especially for suppression of dirt. is there.
  • the pH is a value measured at 25 ° C. using a pH meter (model number: HM-31, manufactured by Toa DKK Ltd.).
  • the developer may contain a surfactant such as an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant.
  • the developer preferably contains at least one member selected from the group consisting of an anionic surfactant and an amphoteric surfactant from the viewpoint of scumming.
  • the developer preferably contains a nonionic surfactant, and contains a nonionic surfactant and at least one selected from the group consisting of an anionic surfactant and an amphoteric surfactant. Is more preferred.
  • R 1 represents an optionally substituted alkyl group, cycloalkyl group, alkenyl group, aralkyl group or aryl group.
  • alkyl group for example, an alkyl group having 1 to 20 carbon atoms is preferable.
  • a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group Preferred examples include an octyl group, a decyl group, a dodecyl group, a hexadecyl group, a stearyl group and the like.
  • the cycloalkyl group may be monocyclic or polycyclic.
  • the monocyclic type is preferably a monocyclic cycloalkyl group having 3 to 8 carbon atoms, and more preferably a cyclopropyl group, a cyclopentyl group, a cyclohexyl group or a cyclooctyl group.
  • Preferred examples of the polycyclic type include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an ⁇ -pinel group, and a tricyclodecanyl group.
  • the alkenyl group is preferably, for example, an alkenyl group having 2 to 20 carbon atoms, and specific examples include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.
  • the aralkyl group is preferably, for example, an aralkyl group having 7 to 12 carbon atoms, and specific examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.
  • the aryl group is preferably, for example, an aryl group having 6 to 15 carbon atoms, specifically, phenyl, tolyl, dimethylphenyl, 2,4,6-trimethylphenyl, naphthyl, anthryl And a 9,10-dimethoxyanthryl group.
  • a monovalent nonmetallic atomic group other than a hydrogen atom is used.
  • Preferred examples thereof include a halogen atom (F, Cl, Br or I), a hydroxy group, an alkoxy group, an aryloxy group, an acyl group, Examples include an amide group, an ester group, an acyloxy group, a carboxy group, a carboxylate anion group, and a sulfonate anion group.
  • alkoxy group in the substituent examples include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, a pentyloxy group, a hexyloxy group, a dodecyloxy group, a stearyloxy group, a methoxyethoxy group, and a poly ( Preferred are those having 1 to 40 carbon atoms, more preferably 1 to 20 carbon atoms, such as an ethyleneoxy) group and a poly (propyleneoxy) group.
  • Examples of the aryloxy group include those having 6 to 18 carbon atoms such as phenoxy, tolyloxy, xylyloxy, mesityloxy, cumenyloxy, methoxyphenyloxy, ethoxyphenyloxy, chlorophenyloxy, bromophenyloxy, and naphthyloxy.
  • Examples of the acyl group include those having 2 to 24 carbon atoms such as an acetyl group, a propanoyl group, a butanoyl group, a benzoyl group and a naphthoyl group.
  • Examples of the amide group include those having 2 to 24 carbon atoms such as an acetamide group, a propionamide group, a dodecanoic acid amide group, a palmitic acid amide group, a stearic acid amide group, a benzoic acid amide group, and a naphthoic acid amide group.
  • Examples of the acyloxy group include those having 2 to 20 carbon atoms such as an acetoxy group, a propanoyloxy group, a benzoyloxy group and a naphthoyloxy group.
  • ester group examples include those having 1 to 24 carbon atoms such as a methyl ester group, an ethyl ester group, a propyl ester group, a hexyl ester group, an octyl ester group, a dodecyl ester group, and a stearyl ester group.
  • the substituent may be a combination of two or more of the above substituents.
  • X 1 represents a sulfonate group, a sulfate monoester group, a carboxylate group or a phosphate group.
  • Y 1 is a single bond, —C n H 2n —, —C nm H 2 (nm) OC m H 2m —, —O— (CH 2 CH 2 O) n —, —O— ⁇ CH 2 CH (CH 3 ) O ⁇ n- , -O- ⁇ CH (CH 3 ) CH 2 O ⁇ n- , -O- (CH 2 CH 2 CH 2 O) n- , -CO-NH-, or It represents a divalent linking group consisting of a combination of two or more of these, and satisfies n ⁇ 1 and n ⁇ m ⁇ 0.
  • the compounds represented by the following formulas (IA) or (IB) are preferable from the viewpoint of scratch resistance.
  • R A1 to R A10 each independently represent a hydrogen atom or an alkyl group
  • nA represents an integer of 1 to 3
  • X A1 and X A2 each represent Independently represents a sulfonate group, a sulfate monoester base, a carboxylate group or a phosphate group
  • Y A1 and Y A2 each independently represent a single bond, —CnH 2n —, —C nm H 2 (nm ) OC m H 2m —, —O— (CH 2 CH 2 O) n —, —O— ⁇ CH 2 CH (CH 3 ) O ⁇ n —, —O— ⁇ CH (CH 3 ) CH 2 O ⁇ n —, —O— (CH 2 CH 2 CH 2 O) n —, —CO—NH—, or a divalent linking group obtained by combining two or more thereof, and satisfies n
  • the total carbon number of R A1 to R A5 and Y 1A or R A6 to R A10 and Y A2 is 25 or less. And more preferably 4 to 20.
  • the structure of the above-mentioned alkyl group may be linear or branched.
  • X A1 and X A2 in the compound represented by the formula (IA) or (IB) are preferably a sulfonate group or a carboxylate group.
  • an alkali metal salt is particularly preferable because of its good solubility in an aqueous solvent. Among them, a sodium salt or a potassium salt is particularly preferable.
  • amphoteric surfactant used in the developer is not particularly limited, but includes amine oxides such as alkyldimethylamine oxide, alkylbetaines, fatty acid amidopropyl betaines, betaines such as alkylimidazoles, and amino acids such as sodium alkylamino fatty acids. No.
  • alkyldimethylamine oxide optionally having a substituent alkylcarboxybetaine optionally having a substituent, and alkylsulfobetaine optionally having a substituent are preferably used.
  • Specific examples thereof include the compound represented by the formula (2) in paragraph 0256 of JP-A-2008-203359, the formula (I), the formula (II) and the formula (II) in paragraph 0028 of JP-A-2008-276166.
  • Compounds represented by VI) and the compounds described in paragraphs 0022 to 0029 of JP-A-2009-47927 can be exemplified.
  • amphoteric surfactant used in the developer a compound represented by the following formula (1) or a compound represented by the following formula (2) is preferable.
  • R 1 and R 11 each independently represent an alkyl group having 8 to 20 carbon atoms or an alkyl group having a linking group having 8 to 20 carbon atoms.
  • R 2 , R 3 , R 12 and R 13 each independently represent a hydrogen atom, an alkyl group or a group containing an ethylene oxide structure.
  • R 4 and R 14 each independently represent a single bond or an alkylene group. Further, two groups of R 1 , R 2 , R 3 and R 4 may be bonded to each other to form a ring structure, and two groups of R 11 , R 12 , R 13 and R 14 may be mutually bonded. They may combine to form a ring structure.
  • the hydrophobic portion increases, and the solubility in an aqueous developer decreases.
  • the solubility is improved by mixing an organic solvent such as alcohol which assists dissolution with water as a solubilizing agent, but if the total carbon number is too large, the surfactant may be used within an appropriate mixing range. Cannot be dissolved. Therefore, the total number of carbon atoms of R 1 to R 4 or R 11 to R 14 is preferably 10 to 40, more preferably 12 to 30.
  • the alkyl group having a linking group represented by R 1 or R 11 represents a structure having a linking group between the alkyl groups. That is, when there is one connecting group, it can be represented by "-alkylene group-connecting group-alkyl group".
  • the linking group include an ester bond, a carbonyl bond, and an amide bond. Although there may be two or more linking groups, one is preferable, and an amide bond is particularly preferable.
  • the total number of carbon atoms of the alkylene group bonded to the linking group is preferably 1 to 5.
  • the alkylene group may be linear or branched, but is preferably a linear alkylene group.
  • the alkyl group bonded to the linking group preferably has 3 to 19 carbon atoms and may be linear or branched, but is preferably linear alkyl.
  • R 2 or R 12 is an alkyl group, it preferably has 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms. It may be linear or branched, but is preferably a linear alkyl group.
  • R 3 or R 13 is an alkyl group, it preferably has 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms. It may be linear or branched, but is preferably a linear alkyl group.
  • Examples of the group having an ethylene oxide structure represented by R 3 or R 13 include a group represented by —R a (CH 2 CH 2 O) n R b .
  • Ra represents a single bond, an oxygen atom or a divalent organic group (preferably having 10 or less carbon atoms)
  • Rb represents a hydrogen atom or an organic group (preferably having 10 or less carbon atoms)
  • n represents 1 Represents an integer of up to 10.
  • R 4 and R 14 are an alkylene group, it preferably has 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms. It may be straight-chain or branched, but is preferably a straight-chain alkylene group.
  • the compound represented by the formula (1) or the compound represented by the formula (2) preferably has an amide bond, and more preferably has an amide bond as a linking group of R 1 or R 11 . Representative examples of the compound represented by the formula (1) or the compound represented by the formula (2) are shown below, but the present disclosure is not limited thereto.
  • the compound represented by the formula (1) or (2) can be synthesized according to a known method. Further, commercially available ones can also be used.
  • Commercially available compounds represented by the formula (1) include Softazoline LPB, Softazoline LPB-R and VistaMAP manufactured by Kawaken Fine Chemical Co., Ltd., and Takesurf C-157L manufactured by Takemoto Yushi Co., Ltd.
  • Examples of the compound represented by the formula (2) include Softazoline LAO manufactured by Kawaken Fine Chemical Co., Ltd., and Amogen AOL manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • the zwitterionic surfactants may be used alone in the developer or may be used in combination of two or more.
  • nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ether, glycerin fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol fatty acid partial esters, Propylene glycol monofatty acid ester, sucrose fatty acid partial ester, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene sorbitol fatty acid partial ester, polyethylene glycol fatty acid ester, polyglycerin fatty acid partial ester, polyoxyethylene glycerin fatty acid partial ester , Polyoxyethylene diglycerins, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamine , Polyoxyethylene alkylamine, triethanolamine fatty acid esters, trialkylamine oxides, polyoxyethylene alkyl phenyl ethers, polyoxyethylene - polyoxypropylene block cop
  • the nonionic surfactant is a nonionic aromatic ether-based surfactant represented by the following formula (N1).
  • N1 nonionic aromatic ether-based surfactant represented by the following formula (N1).
  • X N represents an aromatic group which may have a substituent
  • Y N represents a single bond or an alkylene group having 1 to 10 carbon atoms
  • a 1 and A 2 are different groups.
  • nB and mB each independently represent an integer of 0 to 100, provided that nB and mB are simultaneously If it is not 0 and either nB or mB is 0, then nB and mB are not 1.
  • organic group having 1 to 100 carbon atoms include an aliphatic hydrocarbon group which may be saturated or unsaturated, and may be linear or branched, and an aromatic hydrocarbon group such as an alkyl group, an alkenyl group and an alkynyl group.
  • the cationic surfactant is not particularly limited, and a conventionally known cationic surfactant can be used.
  • a conventionally known cationic surfactant can be used.
  • alkylamine salts, quaternary ammonium salts, alkylimidazolinium salts, polyoxyethylene alkylamine salts, polyethylene polyamine derivatives and the like can be mentioned.
  • the content of the surfactant is preferably 1% by mass to 25% by mass, more preferably 2% by mass to 20% by mass, still more preferably 3% by mass to 15% by mass, based on the total mass of the developer. % To 10% by weight is particularly preferred. When the content is within the above range, scratch resistance and stain resistance are excellent, dispersibility of developed scum is excellent, and ink adhesion of a lithographic printing plate obtained is excellent.
  • the developer may contain a water-soluble polymer compound from the viewpoint of adjusting the viscosity of the developer and protecting the plate surface of the resulting lithographic printing plate.
  • a water-soluble polymer compound examples include soybean polysaccharide, modified starch, gum arabic, dextrin, cellulose derivatives (eg, carboxymethylcellulose, carboxyethylcellulose, methylcellulose, etc.) and modified products thereof, pullulan, polyvinyl alcohol and its derivatives, polyvinylpyrrolidone
  • water-soluble polymer compounds such as polyacrylamide and acrylamide copolymers, vinyl methyl ether / maleic anhydride copolymers, vinyl acetate / maleic anhydride copolymers, and styrene / maleic anhydride copolymers. it can.
  • soybean polysaccharide those conventionally known can be used.
  • Soyafive (trade name, manufactured by Fuji Oil Co., Ltd.), and various grades can be used.
  • Those that can be preferably used are those in which the viscosity of the 10% by mass aqueous solution is in the range of 10 mPa ⁇ s to 100 mPa ⁇ s.
  • a starch represented by the following formula (III) is preferable.
  • any starch such as corn, potato, tapioca, rice, wheat and the like can be used.
  • the modification of these starches can be carried out by a method in which the number of glucose residues per molecule is decomposed in the range of 5 to 30 with an acid or an enzyme, and oxypropylene is further added in an alkali.
  • degree of etherification (degree of substitution) is in the range of 0.05 to 1.2 per glucose unit
  • n is an integer of 3 to 30
  • m is an integer of 1 to 3.
  • water-soluble polymer compounds are soybean polysaccharides, modified starch, gum arabic, dextrin, carboxymethylcellulose, polyvinyl alcohol and the like.
  • Two or more water-soluble polymer compounds can be used in combination.
  • the content of the water-soluble polymer compound is preferably 3% by mass or less, more preferably 1% by mass or less, based on the total mass of the developer.
  • the viscosity of the developing solution is appropriate, and it is possible to suppress the accumulation of developing scum and the like on the roller member of the automatic developing machine.
  • the developer used in the present disclosure may contain, in addition to the above, a wetting agent, a preservative, a chelating compound, an antifoaming agent, an organic acid, an organic solvent, an inorganic acid, an inorganic salt, and the like.
  • wetting agent ethylene glycol, propylene glycol, triethylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, diglycerin and the like are suitably used.
  • the wetting agents may be used alone or in combination of two or more.
  • the content of the wetting agent is preferably from 0.1% by mass to 5% by mass based on the total mass of the developer.
  • preservatives include phenol or derivatives thereof, formalin, imidazole derivatives, sodium dehydroacetate, 4-isothiazolin-3-one derivatives, benzoisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, benzotriazole derivatives , Amidating anidine derivatives, quaternary ammonium salts, derivatives such as pyridine, quinoline, guanidine, diazine, triazole derivatives, oxazole, oxazine derivatives, nitrobromoalcohol-based 2-bromo-2-nitropropane-1,3-diol, 1,1-Dibromo-1-nitro-2-ethanol, 1,1-dibromo-1-nitro-2-propanol and the like can be preferably used.
  • the amount of the preservative added is an amount that exerts a stable effect on bacteria, molds, yeasts and the like, and varies depending on the types of bacteria, molds and yeasts.
  • the range is preferably from 01% to 4% by mass. Further, it is preferable to use two or more preservatives in combination so as to be effective against various molds and sterilization.
  • the chelating compound examples include ethylenediaminetetraacetic acid, its potassium salt and its sodium salt; diethylenetriaminepentaacetic acid, its potassium salt and its sodium salt; triethylenetetraminehexaacetic acid, its potassium salt, its sodium salt, and hydroxyethylethylenediaminetriacetic acid , Potassium salt, sodium salt thereof; nitrilotriacetic acid, sodium salt thereof; 1-hydroxyethane-1,1-diphosphonic acid, potassium salt, sodium salt thereof; aminotri (methylenephosphonic acid), potassium salt, sodium salt thereof And organic phosphonic acids such as Organic amine salts are also effective instead of the sodium and potassium salts of chelating agents.
  • the chelating agent is preferably one that is stably present in the composition of the treatment liquid and does not inhibit printability.
  • the content of the chelating agent is preferably 0.001% by mass to 1.0% by mass based on the total mass of the developer.
  • the defoaming agent a general silicone-based self-emulsifying type, emulsifying type, or nonionic compound having an HLB (Hydrophilic-Lipophilic Balance) of 5 or less can be used. Silicone defoamers are preferred. It should be noted that the silicone surfactant is regarded as an antifoaming agent. The content of the antifoaming agent is preferably in the range of 0.001% by mass to 1.0% by mass based on the total mass of the developer.
  • organic acid examples include citric acid, acetic acid, oxalic acid, malonic acid, salicylic acid, caprylic acid, tartaric acid, malic acid, lactic acid, levulinic acid, p-toluenesulfonic acid, xylenesulfonic acid, phytic acid, and organic phosphonic acid.
  • Organic acids can also be used in the form of their alkali metal or ammonium salts.
  • the content of the organic acid is preferably 0.01% by mass to 0.5% by mass based on the total mass of the developer.
  • organic solvent examples include aliphatic hydrocarbons (hexane, heptane, “Isoper E, H, G” (manufactured by Esso Chemical Co., Ltd.)), aromatic hydrocarbons (toluene, xylene, etc.), halogenated Examples include hydrocarbons (methylene dichloride, ethylene dichloride, trichlene, monochlorobenzene, etc.), polar solvents and the like.
  • aliphatic hydrocarbons hexane, heptane, “Isoper E, H, G” (manufactured by Esso Chemical Co., Ltd.)
  • aromatic hydrocarbons toluene, xylene, etc.
  • halogenated Examples include hydrocarbons (methylene dichloride, ethylene dichloride, trichlene, monochlorobenzene, etc.), polar solvents and the like.
  • the polar solvent examples include alcohols (methanol, ethanol, propanol, isopropanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether Propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, etc.) , Tons (acetone, methyl ethyl ketone, ethyl butyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, propy
  • the organic solvent When the organic solvent is insoluble in water, it can be used after solubilizing in water using a surfactant or the like. If the developer contains an organic solvent, it is safe and flammable. From the viewpoint, the concentration of the solvent in the developer is preferably less than 40% by mass.
  • the inorganic acid and the inorganic salt phosphoric acid, metaphosphoric acid, ammonium monophosphate, ammonium phosphate dibasic, sodium phosphate monobasic, sodium phosphate dibasic, potassium phosphate monobasic, potassium phosphate dibasic, Examples thereof include sodium tripolyphosphate, potassium pyrophosphate, sodium hexametaphosphate, magnesium nitrate, sodium nitrate, potassium nitrate, ammonium nitrate, sodium sulfate, potassium sulfate, ammonium sulfate, sodium sulfite, ammonium sulfite, sodium hydrogen sulfate, and nickel sulfate.
  • the content of the inorganic salt is preferably from 0.01% by mass to 0.5% by mass based on the total mass of the developer.
  • the developer is prepared by dissolving or dispersing the above-mentioned components in water as needed.
  • the solid content concentration of the developer is preferably from 2% by mass to 25% by mass.
  • a concentrated solution may be prepared in advance and diluted with water at the time of use.
  • the developer is preferably an aqueous developer.
  • the developer contains an alcohol compound from the viewpoint of dispersibility of developing scum.
  • the alcohol compound include methanol, ethanol, propanol, isopropanol, benzyl alcohol and the like. Among them, benzyl alcohol is preferred.
  • the content of the alcohol compound is preferably 0.01% by mass to 5% by mass, more preferably 0.1% by mass to 2% by mass, and more preferably 0.1% by mass to 2% by mass with respect to the total mass of the developer, from the viewpoint of the dispersibility of the developing residue. From 2 to 1% by weight is particularly preferred.
  • the lithographic printing method includes a printing step of supplying a printing ink to the lithographic printing plate developed in the on-press development step or the development step to print a recording medium.
  • the printing ink is not particularly limited, and various known inks can be used as desired. Further, as the printing ink, oil-based ink or ultraviolet-curable ink (UV ink) is preferable, and UV ink is more preferable.
  • a dampening solution may be supplied as needed. Further, the printing step may be performed continuously to the on-press development step without stopping the printing press.
  • the recording medium is not particularly limited, and a known recording medium can be used as desired.
  • the lithographic printing In the method of preparing a lithographic printing plate from the lithographic printing plate precursor according to the present disclosure, and the lithographic printing method according to the present disclosure, if necessary, before the exposure, during the exposure, between the exposure and the development, the lithographic printing The entire surface of the plate master may be heated. By such heating, an image forming reaction in the image recording layer is promoted, and advantages such as improvement of sensitivity and printing durability, stabilization of sensitivity, and the like can be generated. Heating before development is preferably performed under mild conditions of 150 ° C. or less. According to the above aspect, problems such as hardening of the non-image portion can be prevented. It is preferable to use very strong conditions for heating after development, and it is preferable that the temperature be in the range of 100 ° C. to 500 ° C. When the content is in the above range, a sufficient image strengthening effect can be obtained, and problems such as deterioration of the support and thermal decomposition of the image portion can be suppressed.
  • the polymer particles according to the present disclosure include an addition polymerization type resin having a polymerizable group and a crosslinked structure.
  • the polymer particles according to the present disclosure have the same meaning as the specific polymer particles contained in the image recording layer of the lithographic printing plate precursor described above, and the preferred embodiments are also the same.
  • the curable composition according to the present disclosure includes the polymer particles according to the present disclosure. Further, the curable composition according to the present disclosure preferably further contains a polymerization initiator, and more preferably further contains an infrared absorber, a polymerization initiator, and a polymerizable compound. According to the above aspect, it can be suitably used as a photosensitive resin composition, and can be suitably used for forming an image recording layer in the lithographic printing plate precursor according to the present disclosure.
  • the infrared absorber, the polymerizable compound and the polymerization initiator contained in the curable composition according to the present disclosure are respectively the infrared absorber, the polymerizable compound, and the polymer contained in the image recording layer of the lithographic printing plate precursor described above. It has the same meaning as the initiator, and the preferred embodiment is also the same.
  • the curable composition according to the present disclosure includes the binder polymer described above, an electron donating polymerization initiator, a chain transfer agent, other polymer particles, a low-molecular hydrophilic compound, a sensitizer, an acid colorant, and At least one selected from the group consisting of known solvents (such as the above-mentioned coating solvents) may be further contained.
  • each component contained in the composition according to the present disclosure corresponds to the content of each component contained in the image recording layer of the lithographic printing plate precursor described above, which is replaced with the solid content in the curable composition. .
  • the curable composition according to the present disclosure is preferably a curable composition used for manufacturing a lithographic printing plate precursor. That is, a lithographic printing plate precursor can be suitably obtained by using the curable composition according to the present disclosure.
  • % and “parts” mean “% by mass” and “parts by mass”, respectively, unless otherwise specified.
  • the molecular weight is the weight average molecular weight (Mw), and the ratio of the constituent repeating units is a mole percentage.
  • the weight average molecular weight (Mw) is a value measured as a polystyrene equivalent value by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the reaction solution was allowed to cool to room temperature (25 ° C., the same applies hereinafter) to obtain a dispersion (solid content: 5%) of polymer particles G-1 ′.
  • the median diameter of the polymer particles G-1 ′ in the dispersion was 160 nm.
  • 0.254 g of sodium hydrogen carbonate was added to 100 g of the obtained dispersion (solid content: 5%) of the polymer particles G-1 ′ to adjust the pH of the system to 7.5, and then the temperature was raised to 90 ° C.
  • the reaction solution was allowed to cool to room temperature (25 ° C., the same applies hereinafter) to obtain a dispersion of polymer particles G-3 ′ (solid content: ⁇ 5%).
  • the median diameter of the polymer particles G-3 ′ in the dispersion obtained by light scattering was 125 nm.
  • Glycidyl methacrylate: 5.4 g, tetrabutylammonium bromide (TBAB): 0.12 g, OH-TEMPO (4-hydroxy-2,2) were added to 100 g of a dispersion (solid content: 5%) of the obtained polymer particles G-3 ′.
  • Polymer particles H-3 were synthesized according to the example of JP-A-2010-234587 (manufacture of aqueous dispersion of polymer fine particles (A)). Further, polymer particles H-4 were synthesized according to Examples (Preparation 1) of JP-T-2013-503365.
  • Polymer particles H-3 and H-4 are particles having the following structure. (In the polymer particles H-3, commercially available SBX-6 (manufactured by Sekisui Plastics Co. LTD (Japan)) is used as styrene and divinylbenzene particles, and the ratio of styrene and divinylbenzene is unknown.)
  • the evaluation index of dispersibility is as follows. A is the highest evaluation, and D is the lowest evaluation in the order of A, B, C, and D. The evaluation results are shown in Table 1. A: No precipitate is visually observed, and the dispersibility is good. B: A small amount of precipitate is visually observed, but is in a redispersible state by stirring for 5 minutes. C: A large amount of precipitate is visually observed, but cannot be redispersed by stirring for 5 minutes, but can be redispersed by stirring for 10 minutes. D: Precipitate or fixed matter is visually observed, and cannot be redispersed even with stirring for 10 minutes.
  • etching on the grained surface was about 3 g / m 2 .
  • the electrolytic solution was a 1% by mass aqueous solution of nitric acid (containing 0.5% by mass of aluminum ions), and the temperature of the solution was 50 ° C.
  • the AC power supply waveform is an electrochemical roughening process using a trapezoidal rectangular wave alternating current with a time TP for the current value from zero to a peak to reach a peak of 0.8 ms, a duty ratio of 1: 1 and a carbon electrode as a counter electrode.
  • Ferrite was used for the auxiliary anode.
  • the current density was 30 A / dm 2 at the peak value of the current, and 5% of the current flowing from the power supply was shunted to the auxiliary anode.
  • the amount of electricity in the nitric acid electrolysis was 175 C / dm 2 when the aluminum plate was an anode. Thereafter, water washing by spraying was performed.
  • Electrochemical surface roughening treatment was performed in the same manner as in the electrolysis, and then water washing was performed by spraying.
  • a direct current anodic oxide film having a current density of 15 A / dm 2 and a current density of 2.5 g / m 2 was formed on an aluminum plate using a 15% by mass aqueous solution of sulfuric acid (containing 0.5% by mass of aluminum ions) at a liquid temperature of 54 ° C. as an electrolytic solution.
  • the average pore diameter (surface average pore diameter) in the surface layer of the anodized film was 10 nm.
  • the pore diameter of the surface layer of the anodic oxide film was measured using an ultra-high resolution type SEM (S-900, manufactured by Hitachi, Ltd.) using a relatively low accelerating voltage of 12 V and a deposition process for imparting conductivity. Without application, the surface was observed at a magnification of 150,000 times, and 50 pores were randomly extracted to obtain an average value. Standard error was less than ⁇ 10%.
  • Support C was prepared in the same manner as in the preparation of support A, except that the electrolytic solution during the formation of the direct current anodic oxide film was changed to a 22% by mass phosphoric acid aqueous solution.
  • the average pore diameter (surface average pore diameter) in the surface layer of the anodic oxide film was measured by the same method as described above, it was 25 nm.
  • the support B was subjected to a silicate treatment at 60 ° C. for 10 seconds using a 2.5% by mass aqueous solution of No. 3 sodium silicate, and then washed with water to obtain the support D.
  • the amount of Si attached was 10 mg / m 2 .
  • the center line average roughness (Ra) of the support D was measured using a needle having a diameter of 2 ⁇ m, and was found to be 0.52 ⁇ m.
  • An image recording layer coating solution was prepared according to the following image recording layer coating solution (1) and Tables 2 to 4.
  • the content of each compound shown in Tables 2 to 4 is a solid content (parts by mass).
  • the coating solution for the image recording layer containing the specific polymer particles was prepared by mixing a photosensitive solution obtained by mixing the components described below in the coating solution for the image recording layer (1) other than the specific polymer particles with each of the specific solutions synthesized in the above synthesis examples.
  • the dispersion was mixed with the dispersion containing the polymer particles immediately before the application so as to obtain the compositions shown in Tables 2 to 4, and the mixture was stirred.
  • Example 1 to 27, Example 101, and Comparative Examples 1 to 4 ⁇ Preparation of lithographic printing plate precursor A>
  • the lithographic printing plate precursors of Examples 1 to 27, Example 101, and Comparative Examples 1 to 4 were produced by the following methods, respectively.
  • the undercoat layer coating solution having the above composition was applied onto the support B so that the dry coating amount was 20 mg / m 2 to form an undercoat layer.
  • the above-mentioned respective image recording layer coating solutions (1) were coated on the undercoat layer with a bar, followed by oven drying at 120 ° C. for 40 seconds to form an image recording layer having a dry coating amount of 1.0 g / m 2 .
  • the coating solution for the image recording layer was prepared by mixing and stirring the polymer particles immediately before coating.
  • a protective layer coating solution having the above composition was coated on the image recording layer with a bar, followed by oven drying at 120 ° C. for 60 seconds to form a protective layer having a dry coating amount of 0.15 g / m 2 .
  • “Yes” was described in the column of the protective layer in Tables 2 to 4.
  • lithographic printing plate precursor prepared as described above was output by Kodak Magnus 800 Quantum equipped with an infrared semiconductor laser at an output of 27 W, an external drum rotation speed of 450 rpm (revolutions per minute), and a resolution of 2,400 dpi (dot per inch, 1 inch).
  • the exposure image included a solid image and a chart of 3% halftone dots on an AM screen (Amplitude Modulation Screen).
  • On-press developability The exposed original plate was mounted on a cylinder of a printing machine SX-74 manufactured by Heidelberg Co., Ltd. having a Kikuchi size (636 mm ⁇ 939 mm) without developing.
  • the printing press was connected to a 100 L dampening water circulation tank containing a nonwoven fabric filter and a temperature controller.
  • 80 L of dampening water S-Z1 (manufactured by FUJIFILM Corporation) of 2.0 mass% is charged into the circulation device, and T & K UV OFS K-HS Sumi GE-M is an ultraviolet curable ink as a printing ink.
  • UV printing durability After the evaluation of the on-press developability described above, printing was further continued. As the number of prints was increased, the image area gradually became worn, and the ink density on the printed matter was reduced. The number of copies is defined as the number of copies when the value obtained by measuring the dot area ratio of the 3% halftone dot of the AM screen with a Gretag densitometer (manufactured by GretagMacbeth) by 1% from the measured value of the 500th print is defined as the number of printed sheets.
  • the UV printing durability was evaluated. The evaluation was made based on the relative printing durability when the number of printed sheets was 50,000, with 100 being the value. The larger the value, the better the UV printing durability. The evaluation results are shown in Tables 2 to 4.
  • Relative printing durability (number of target lithographic printing plate precursors printed) / 50,000 ⁇ 100
  • the lithographic printing plate precursor according to the present disclosure shows a case where a polymer particle containing a polymerizable group and an addition-polymerizable resin having a cross-linked structure is used, and a case where an ultraviolet curable ink is used. It can be seen that the ink has excellent printing durability, chemical resistance, and development residue, and has a hydrophilic structure, whereby the developability (on-press developability) is further improved. Also, compared with the lithographic printing plate precursors according to Comparative Examples 1 to 4, it is clear that the lithographic printing plate precursors according to Examples 1 to 27 and Example 101 are more excellent in the balance of printing durability, chemical resistance, and development residue. It is.
  • a protective layer coating solution having the above composition was coated on the image recording layer with a bar, followed by oven drying at 120 ° C. for 60 seconds to form a protective layer having a dry coating amount of 0.15 g / m 2 .
  • “Yes” was described in the column of the protective layer in Tables 5 and 6.
  • the resulting lithographic printing plate precursor B was evaluated for UV printing durability, on-press development property, development residue suppression, and chemical resistance in the same manner as the lithographic printing plate precursor A described above. 5 and Table 6.
  • Acid coloring agent S-205, 2'-anilino-6).
  • n-propanol 50.0 parts by mass
  • 2-butanone 20.0 parts by mass
  • specific polymer particles amounts described in Tables 5 and 6, and contents of each compound shown in Tables 5 and 6 Is the solid content (parts by mass).
  • Example 49 to 54 ⁇ Preparation of coating solution for image recording layer>
  • the lithographic printing plate precursors of Examples 48 to 54 were produced by the following methods.
  • the undercoat layer coating solution having the above composition was applied onto the support B so that the dry coating amount was 20 mg / m 2 to form an undercoat layer.
  • the following image recording layer coating liquid (3) was coated on the undercoat layer with a bar, followed by oven drying at 120 ° C. for 40 seconds to form an image recording layer having a dry coating amount of 1.0 g / m 2 .
  • an image recording layer coating solution was prepared.
  • the content of each compound shown in Table 7 is the solid content (parts by mass).
  • the core-shell particle dispersion shown in Table 7 is obtained by separately mixing the resin A (polymer particle liquid) and the additive compound B (monomer or polymer) in Table 7 and heating and stirring at 40 ° C. for 8 hours.
  • the image recording layer coating liquid (3) containing the core-shell particles was prepared by mixing the above-mentioned core-shell particle dispersion liquid with the following image recording layer coating liquid (3) other than the core-shell particles immediately before coating, followed by stirring.
  • Acid coloring agent S-205, 2′-anilino-6 ′-(N-ethyl-N-iso) (Pentylamino) -3′-methylspiro [phthalide-3,9′-xanthen], (manufactured by Fukui Yamada Chemical Industry Co., Ltd.): 0.060 parts by mass.
  • 2-butanone 1.091 parts by mass.
  • 1-methoxy- 2-propanol 8.609 parts by mass
  • distilled water 2.425 parts by mass
  • core-shell particle liquid Amount shown in Table 7
  • the compounds used in the image recording layer coating solutions (1), (2) and (3) are as follows.
  • the content of each structural unit indicates the mass ratio
  • the subscript at the lower right of the parenthesis of the ethyleneoxy structure indicates the number of repetitions.
  • M-1 Tris (acryloyloxyethyl) isocyanurate, NK ester A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.
  • M-2 Dipentaerythritol pentaacrylate, SR-399, Sartomer M-3: Dipenta Erythritol hexaacrylate, A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.
  • M-4 dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer, UA-510H, manufactured by Kyoeisha Chemical Co., Ltd.
  • TsO 2 — represents a tosylate anion
  • Ph represents a phenyl group.
  • T-1 Tris (2-hydroxyethyl) isocyanurate
  • T-2 Compound having the following structure
  • T-3 Hydroxypropylcellulose, Klucel M, manufactured by Hercules

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)

Abstract

Cette invention concerne une matrice de plaque d'impression lithographique ayant, dans l'ordre, un substrat et une couche d'enregistrement d'image. La couche d'enregistrement d'image contient des particules polymères contenant une résine de type à polymérisation par addition. La résine de type à polymérisation par addition a un groupe polymérisable et une structure réticulée. L'invention concerne également un procédé de production d'une plaque d'impression lithographique à l'aide de la matrice de plaque d'impression lithographique, un procédé d'impression lithographique utilisant la matrice de plaque d'impression lithographique, et une composition durcissable contenant les particules polymères.
PCT/JP2019/033985 2018-08-31 2019-08-29 Matrice de plaque d'impression lithographique, procédé de production de plaque d'impression lithographique, procédé d'impression lithographique et composition durcissable WO2020045587A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2018-163526 2018-08-31
JP2018163526 2018-08-31
JP2019016537 2019-01-31
JP2019-016537 2019-01-31

Publications (1)

Publication Number Publication Date
WO2020045587A1 true WO2020045587A1 (fr) 2020-03-05

Family

ID=69643909

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/033985 WO2020045587A1 (fr) 2018-08-31 2019-08-29 Matrice de plaque d'impression lithographique, procédé de production de plaque d'impression lithographique, procédé d'impression lithographique et composition durcissable

Country Status (1)

Country Link
WO (1) WO2020045587A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020262694A1 (fr) * 2019-06-28 2020-12-30 富士フイルム株式会社 Précurseur de plaque d'impression lithographique, procédé de production de plaque d'impression lithographique et procédé d'impression lithographique
WO2020262687A1 (fr) * 2019-06-28 2020-12-30 富士フイルム株式会社 Plaque originale d'impression planographique, procédé de fabrication de plaque d'impression planographique, et procédé d'impression planographique

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006317716A (ja) * 2005-05-12 2006-11-24 Eastman Kodak Co 変性シリカ粒子並びにそれを含む感光性組成物及び感光性平版印刷版
US20090183647A1 (en) * 2008-01-22 2009-07-23 Mathias Jarek Imageable elements with coalescing core-shell particles
JP2010234587A (ja) * 2009-03-30 2010-10-21 Fujifilm Corp 平版印刷版原版およびその製版方法
JP2013503365A (ja) * 2009-08-25 2013-01-31 イーストマン コダック カンパニー 平版印刷版原版及び積層体
WO2017018262A1 (fr) * 2015-07-30 2017-02-02 富士フイルム株式会社 Original de plaque d'impression lithographique, procédé de fabrication de plaque d'impression lithographique, et particules hybrides organiques-inorganiques
WO2017150039A1 (fr) * 2016-02-29 2017-09-08 富士フイルム株式会社 Plaque originale d'impression lithographique, et procédé de fabrication de plaque pour plaques d'impression lithographique

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006317716A (ja) * 2005-05-12 2006-11-24 Eastman Kodak Co 変性シリカ粒子並びにそれを含む感光性組成物及び感光性平版印刷版
US20090183647A1 (en) * 2008-01-22 2009-07-23 Mathias Jarek Imageable elements with coalescing core-shell particles
JP2010234587A (ja) * 2009-03-30 2010-10-21 Fujifilm Corp 平版印刷版原版およびその製版方法
JP2013503365A (ja) * 2009-08-25 2013-01-31 イーストマン コダック カンパニー 平版印刷版原版及び積層体
WO2017018262A1 (fr) * 2015-07-30 2017-02-02 富士フイルム株式会社 Original de plaque d'impression lithographique, procédé de fabrication de plaque d'impression lithographique, et particules hybrides organiques-inorganiques
WO2017150039A1 (fr) * 2016-02-29 2017-09-08 富士フイルム株式会社 Plaque originale d'impression lithographique, et procédé de fabrication de plaque pour plaques d'impression lithographique

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020262694A1 (fr) * 2019-06-28 2020-12-30 富士フイルム株式会社 Précurseur de plaque d'impression lithographique, procédé de production de plaque d'impression lithographique et procédé d'impression lithographique
WO2020262687A1 (fr) * 2019-06-28 2020-12-30 富士フイルム株式会社 Plaque originale d'impression planographique, procédé de fabrication de plaque d'impression planographique, et procédé d'impression planographique

Similar Documents

Publication Publication Date Title
JP7062635B2 (ja) 硬化性組成物、平版印刷版原版、平版印刷版の作製方法、及び、化合物
JP6956787B2 (ja) 平版印刷版原版、平版印刷版の製版方法、有機ポリマー粒子、及び、感光性樹脂組成物
WO2019013268A1 (fr) Plaque originale de plaque d'impression lithographique, et procédé de fabrication de plaque d'impression lithographique
JP6934939B2 (ja) 平版印刷版原版、及び平版印刷版の作製方法
JP7065979B2 (ja) 平版印刷版原版、平版印刷版の作製方法、平版印刷方法、及び、硬化性組成物
JP6832431B2 (ja) 平版印刷版原版、平版印刷版の作製方法、及び、発色組成物
JP6977065B2 (ja) 平版印刷版原版、及び、平版印刷版の作製方法
JP6942799B2 (ja) 平版印刷版原版、及び、平版印刷版の作製方法
WO2021171862A1 (fr) Plaque originale de plaque d'impression lithographique, procédé de fabrication de plaque d'impression lithographique et procédé d'impression lithographique
JPWO2018221134A1 (ja) 平版印刷版原版、平版印刷版原版作製用樹脂組成物、及び、平版印刷版の作製方法
WO2020045587A1 (fr) Matrice de plaque d'impression lithographique, procédé de production de plaque d'impression lithographique, procédé d'impression lithographique et composition durcissable
WO2020158139A1 (fr) Plaque originale pour plaque d'impression lithographique, procédé de fabrication de plaque d'impression lithographique, et procédé d'impression lithographique
WO2020137919A1 (fr) Composition photosensible, précurseur de plaque d'impression lithographique, procédé de production de plaque d'impression lithographique, et procédé d'impression lithographique
WO2019146769A1 (fr) Plaque originale de plaque d'impression lithographique, et procédé de fabrication de plaque d'impression lithographique
WO2020158288A1 (fr) Plaque originale pour plaque d'impression lithographique, procédé de fabrication de plaque d'impression lithographique, et procédé d'impression lithographique
WO2020026808A1 (fr) Précurseur de plaque d'impression lithographique de type à développement sur presse, procédé de fabrication de plaque d'impression lithographique, et procédé d'impression lithographique
WO2020026810A1 (fr) Précurseur de plaque d'impression lithographique de type à développement sur presse, procédé de production de plaque d'impression lithographique et procédé d'impression lithographique associé
WO2020066377A1 (fr) Original de plaque d'impression lithographique et procédé de fabrication de plaque d'impression lithographique
WO2020066378A1 (fr) Original de plaque d'impression lithographique et procédé de fabrication de plaque d'impression lithographique
JP2021133666A (ja) 機上現像型平版印刷版原版、平版印刷版の作製方法、及び、平版印刷方法
WO2020027069A1 (fr) Plaque originale pour plaque d'impression planographique de type à développement sur presse, procédé de production de plaque d'impression planographique, et procédé d'impression planographique
JP2021053987A (ja) 平版印刷版原版、平版印刷版の作製方法、及び平版印刷方法
WO2020027071A1 (fr) Plaque originale de plaque d'impression à plat du type sur machine, procédé de production de plaque d'impression à plat, et procédé d'impression à plat

Legal Events

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

Ref document number: 19855040

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19855040

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP