[go: up one dir, main page]

WO2015115599A1 - Composition de résine pour gravure au laser, plaque originale d'impression flexographique pour gravure au laser, procédé de production d'une plaque originale d'impression flexographique pour gravure au laser, plaque d'impression flexographique, et procédé de fabrication de plaque pour plaque d'impression flexographique - Google Patents

Composition de résine pour gravure au laser, plaque originale d'impression flexographique pour gravure au laser, procédé de production d'une plaque originale d'impression flexographique pour gravure au laser, plaque d'impression flexographique, et procédé de fabrication de plaque pour plaque d'impression flexographique Download PDF

Info

Publication number
WO2015115599A1
WO2015115599A1 PCT/JP2015/052671 JP2015052671W WO2015115599A1 WO 2015115599 A1 WO2015115599 A1 WO 2015115599A1 JP 2015052671 W JP2015052671 W JP 2015052671W WO 2015115599 A1 WO2015115599 A1 WO 2015115599A1
Authority
WO
WIPO (PCT)
Prior art keywords
laser engraving
flexographic printing
resin composition
component
printing plate
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2015/052671
Other languages
English (en)
Japanese (ja)
Inventor
和博 ▲濱▼田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
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 Fujifilm Corp filed Critical Fujifilm Corp
Publication of WO2015115599A1 publication Critical patent/WO2015115599A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • B41C1/02—Engraving; Heads therefor
    • B41C1/04—Engraving; Heads therefor using heads controlled by an electric information signal
    • B41C1/05—Heat-generating engraving heads, e.g. laser beam, electron beam
    • 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
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/24—Curved surfaces

Definitions

  • direct engraving CTP methods have been proposed in which a relief forming layer is directly engraved with a laser to make a plate.
  • the flexographic printing plate precursor is directly irradiated with a laser to cause thermal decomposition and volatilization by photothermal conversion, thereby forming recesses.
  • the direct engraving CTP method can freely control the relief shape. For this reason, when an image such as a letter is formed, the area is engraved deeper than other areas, or the fine halftone dot image is engraved with a shoulder in consideration of resistance to printing pressure. Is also possible.
  • a laser used in this method a high output carbon dioxide laser is often used.
  • Patent Document 1 describes a laser processing composition containing (A1) 100 parts by mass of a thermoplastic elastomer and (B) 0.1 to 50 parts by mass of silica particles.
  • U.S. Pat. No. 6,089,075 includes an elastomeric relief-forming laser platenable thermally and / or photochemically crosslinkable layer provided on a dimensionally stable flexible support. Syndiotactic 1,2-polybutadiene having a content of ⁇ 100% 1,2-crosslinked butadiene units, a crystallinity of 5 ⁇ 30%, and an average molecular weight of 20,000 ⁇ 300,000 g / mol as a binder in an amount of 5% by weight or more.
  • a laser-engravable flexographic printing element characterized in that it is described.
  • JP 2006-206872 A JP-T-2004-523401
  • the problem to be solved by the present invention is to use a resin composition for laser engraving, which can obtain a flexographic printing plate excellent in sheet processability, ink resistance and printing durability, and the resin composition for laser engraving. It is intended to provide a flexographic printing plate precursor for laser engraving and a production method thereof, a flexographic printing plate making method using the flexographic printing plate precursor, and a flexographic printing plate obtained by the plate making method.
  • Component A is a polymer having a monomer unit derived from a conjugated diene hydrocarbon
  • Component B is trans polyisoprene and / or polyoctenylene in an amount of 1 part by mass or more based on 100 parts by mass of component A (preferably 3 parts by mass or more, more preferably 5 parts by mass or more, preferably 300 parts by mass or less, more preferably 150 parts by mass or less, still more preferably 80 parts by mass or less, particularly preferably 50 parts by mass or less, and most preferably 35 parts by mass.
  • a resin composition for laser engraving wherein component A is a polymer different from component B, ⁇ 2>
  • the proportion of monomer units derived from butadiene, isoprene or hydrogenated products thereof contained in Component A is 30 mol% or more in total (more preferably 50 mol% or more, more preferably 80 mol% or more).
  • the resin composition for laser engraving according to any one of ⁇ 1> to ⁇ 3>, ⁇ 5> Component A has a weight average molecular weight of 10,000 or more (more preferably 10,000 to 2,000,000, still more preferably 30,000 to 1,800,000, particularly preferably 50,000 to 1,500,000), ⁇ 1> to ⁇ 4>, the resin composition for laser engraving according to any one of ⁇ 6>
  • the resin composition for laser engraving contains 0 to 5% by mass of a solvent (more preferably 0 to 3% by mass, and more preferably 0% by mass).
  • Component A is composed of polybutadiene, partially hydrogenated polybutadiene, terminal-modified polybutadiene, polyisoprene, partially hydrogenated polyisoprene, terminal-modified polyisoprene, SBR, SBS, ABS, SIS, and isoprene / butadiene copolymer.
  • Selected from the group (more preferably, polybutadiene, partially hydrogenated polybutadiene, hydroxyl-terminated polybutadiene, glycidyl ether-modified polybutadiene, polyisoprene, partially hydrogenated polyisoprene, hydroxyl-terminated polyisoprene, glycidyl ether-modified polyisoprene, SBS, and Selected from the group consisting of SIS, more preferably selected from the group consisting of polybutadiene, partially hydrogenated polybutadiene, polyisoprene, partially hydrogenated polyisoprene, SBS, and SIS.
  • the laser is selected from the group consisting of polybutadiene, polyisoprene, SBS, and SIS, and most preferably polybutadiene and / or polyisoprene), ⁇ 1> to ⁇ 11> Engraving resin composition, ⁇ 13>
  • the total content of component A is 10 to 90% by mass (more preferably 20 to 85% by mass, still more preferably 30 to 80% by mass) based on the total mass of the solid content of the resin composition for laser engraving.
  • a flexographic printing plate precursor for laser engraving comprising a relief forming layer comprising the resin composition for laser engraving according to any one of ⁇ 1> to ⁇ 15> on a support, ⁇ 17> Laser engraving provided on a support with a crosslinked relief forming layer obtained by crosslinking the relief forming layer comprising the resin composition for laser engraving according to any one of ⁇ 1> to ⁇ 15> with heat and / or light
  • a flexographic printing plate precursor for laser engraving according to ⁇ 17> comprising a crosslinked relief-forming layer crosslinked by heat, ⁇ 19>
  • a method for producing a flexographic printing plate precursor for laser engraving according to ⁇ 19>, ⁇ 21> The method for producing a flexographic printing plate precursor for laser engraving according to ⁇ 20>, wherein the step of forming into a sheet is a step of forming into a sheet by hot pressing or extrusion, ⁇ 22>
  • a step of preparing the flexographic printing plate precursor for laser engraving according to any one of ⁇ 16> to ⁇ 18>, and an engraving for forming a relief layer by laser engraving the flexographic printing plate precursor for laser engraving A process for making a flexographic printing plate, comprising: ⁇ 24> The method for making a flexographic printing plate according to ⁇ 23>, further comprising a rinsing step of rinsing the relief layer surface with an a
  • a resin composition for laser engraving capable of obtaining a flexographic printing plate having excellent sheet processability and excellent ink resistance and printing durability, and a flexo for laser engraving using the above resin composition for laser engraving.
  • a printing plate precursor and a method for producing the same, a method for making a flexographic printing plate using the flexographic printing plate precursor, and a flexographic printing plate obtained by the plate making method can be provided.
  • “parts by mass” and “% by mass” have the same meanings as “parts by weight” and “% by weight”, respectively.
  • the description which does not describe substitution and unsubstituted includes the thing which has a substituent with the thing which does not have a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • a combination of preferred embodiments in the following description is a more preferred embodiment.
  • the surface is a flat layer as an image forming layer to be subjected to laser engraving, and is uncrosslinked
  • a crosslinkable layer is referred to as a relief forming layer
  • a layer obtained by crosslinking the relief forming layer is referred to as a crosslinked relief forming layer
  • a layer in which irregularities are formed on the surface by laser engraving is referred to as a relief layer.
  • being excellent in sheet workability means that there is little deformation or shrinkage when the resin composition for laser engraving is processed into a sheet shape.
  • component B is kneaded with component A
  • a phase-separated structure is appropriately formed and shrinkage after kneading of component A is suppressed.
  • sheet workability is greatly improved.
  • the improvement in strength due to the crystal portion of component B is one cause of the improvement in workability.
  • Component A Polymer Having Monomer Unit Derived from Conjugated Diene Hydrocarbon
  • the resin composition of the present invention contains, as Component A, a polymer having a monomer unit derived from a conjugated diene hydrocarbon.
  • Component A is a polymer different from Component B described later. That is, it is a polymer having monomer units derived from conjugated diene hydrocarbons excluding transisoprene and polyoctenylene.
  • the polymer refers to a compound having a molecular weight (when having a molecular weight distribution, a weight average molecular weight) of 3,000 or more.
  • Component A has at least a monomer unit derived from a conjugated diene hydrocarbon.
  • component A a polymer obtained by polymerizing a conjugated diene hydrocarbon, a copolymer obtained by polymerizing a conjugated diene hydrocarbon and another unsaturated compound, preferably a monoolefin unsaturated compound, etc.
  • the above-mentioned polymer and copolymer may be modified, for example, a reactive group such as a (meth) acryloyl group may be introduced at the terminal, and a part of the internal olefin is hydrogen. It may be added.
  • polybutadiene in which part of the internal olefin is hydrogenated is also referred to as “partially hydrogenated polybutadiene”, and similarly, polyisoprene in which part of the internal olefin is hydrogenated is also referred to as “partially hydrogenated polyisoprene”.
  • the copolymer may be a random copolymer, a block copolymer, or a graft copolymer, and is not particularly limited.
  • the conjugated diene hydrocarbon is a hydrocarbon having a conjugated diene with a double bond separated by one single bond, and a part of it may be substituted by another atom.
  • Examples of the other atom include a halogen atom, and specific examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • a chlorine atom is preferably exemplified as the substituent.
  • conjugated diene hydrocarbon examples include 1,3-butadiene, isoprene, chloroprene and the like. These compounds are used alone or in combination of two or more.
  • monoolefin unsaturated compound examples include styrene, ⁇ -methylstyrene, o-methylstyrene, p-methylstyrene, isobutene, (meth) acrylonitrile, vinyl chloride, vinylidene chloride, (meth ) Acrylamide, (meth) acrylamide vinyl acetate, (meth) acrylic acid ester, (meth) acrylic acid and the like.
  • the polymer obtained by polymerizing the conjugated diene hydrocarbon or the copolymer obtained by polymerizing the conjugated diene hydrocarbon and the monoolefin unsaturated compound is not particularly limited, and specifically, Butadiene polymer, isoprene polymer, chloroprene polymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-chloroprene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-isoprene copolymer, acrylonitrile-chloroprene Copolymer, Acrylic ester-isoprene copolymer, Acrylic ester-chloroprene copolymer, Copolymer of methacrylic acid ester and conjugated diene, Acrylonitrile-butadiene-styrene copolymer, Styrene-isopren
  • component A is preferably a polymer having monomer units derived from butadiene and / or isoprene.
  • component A is preferably a polymer having monomer units derived from butadiene and / or isoprene.
  • the terminal modification means that the main chain or side chain terminal is modified with an amide group, a carboxy group, a hydroxy group, a (meth) acryloyl group, a glycidyl group, or the like.
  • polybutadiene, partially hydrogenated polybutadiene, hydroxyl-terminated polybutadiene, glycidyl ether-modified polybutadiene, polyisoprene, partially hydrogenated polyisoprene, hydroxyl-terminated polyisoprene, glycidyl ether-modified polyisoprene, SBS, and SIS are preferable.
  • Polybutadiene, partially hydrogenated polybutadiene, polyisoprene, partially hydrogenated polyisoprene, SBS and SIS are more preferred, polybutadiene, polyisoprene, SBS and SIS are more preferred, and polybutadiene and polyisoprene are particularly preferred.
  • the proportion of monomer units derived from butadiene, isoprene or hydrogenated product thereof is preferably 30 mol% or more in total, more preferably 50 mol% or more, and more preferably 80 mol% or more. More preferably it is.
  • Isoprene is known to polymerize by 1,2-, 3,4-, or 1,4-addition depending on the catalyst and reaction conditions.
  • isoprene is polymerized by any of the above additions.
  • Isoprene may be used.
  • cis-1,4-polyisoprene it is preferable to contain cis-1,4-polyisoprene as a main component.
  • component A is polyisoprene
  • the content of cis-1,4-polyisoprene is preferably 50% by mass or more, more preferably 65% by mass or more, and 80% by mass or more. More preferably, it is particularly preferably 90% by mass or more.
  • natural rubber may be used, and commercially available polyisoprene may be used, and examples thereof include the NIPOL IR series (manufactured by Nippon Zeon Co., Ltd.).
  • butadiene is known to be polymerized by 1,2- or 1,4-addition depending on the catalyst and reaction conditions.
  • polybutadiene polymerized by any of the above additions may be used.
  • 1,4-polybutadiene is a main component.
  • the content of 1,4-polybutadiene is preferably 50% by mass or more, more preferably 65% by mass or more, and further preferably 80% by mass or more. It is preferably 90% by mass or more.
  • the content of the cis body and the trans body is not particularly limited, but from the viewpoint of developing rubber elasticity, the cis body is preferable, and the content of cis-1,4-polybutadiene is preferably 50% by mass or more. , 65% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • a commercially available product may be used as the polybutadiene, and examples thereof include the NIPOL BR series (manufactured by ZEON Corporation), the UBEPOL BR series (manufactured by Ube Industries, Ltd.), and the like.
  • Component A is preferably a polymer having a main chain mainly composed of isoprene or butadiene as a monomer unit, and a part thereof may be hydrogenated to be converted into a saturated bond.
  • the main chain or the terminal of the polymer may be modified with an amide, a carboxy group, a hydroxy group, a (meth) acryloyl group or the like, or may be epoxidized.
  • Component A has an ethylenically unsaturated group based on at least a conjugated diene hydrocarbon.
  • the component A may have an ethylenically unsaturated group at the main chain terminal or side chain as described above.
  • Plastomer is a term for an elastomer (having the property of instantly deforming according to the external force when an external force is applied and restoring the original shape in a short time when the external force is removed). It does not show such elastic deformation and easily plastically deforms.
  • the plastomer can be deformed to 200% with a small external force at room temperature (20 ° C.) when the original size is 100%, and does not return to 130% or less even when the external force is removed. Means things.
  • the small external force specifically refers to an external force having a tensile strength of 1 to 100 MPa.
  • a polymer that cannot be measured as described above that is, in a tensile test, a polymer that does not return to its original shape even if a tensile external force is not applied, or a polymer that breaks by applying a small external force at the time of measurement corresponds to a plastomer.
  • the elastomer can be stretched without breaking to twice the distance between the marked lines before tension, and is 60 when stretched to twice the distance between the marked lines before tension. It means a polymer having a tensile set of less than 30% after 5 minutes after holding for 5 minutes and excluding tensile external force.
  • Thermoplastic elastomer means an elastomer that can be repeatedly softened by heating and cured by cooling.
  • component A is more preferably a plastomer.
  • the sheet processability is more excellent.
  • the component A has a glass transition temperature (Tg) of 20 degrees C or less.
  • the glass transition temperature of component A is measured according to JIS K7121-1987 using a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the component A has a glass transition temperature of 2 or more, at least one is preferably 20 ° C. or lower, and all glass transition temperatures are more preferably 20 ° C. or lower.
  • Component A is a plastomer
  • Component A has a glass transition temperature of 2 or higher, all glass transition temperatures are 20 ° C. or lower.
  • the weight average molecular weight of component A is 3,000 or more, preferably 10,000 or more, more preferably 10,000 to 2,000,000, still more preferably 30,000 to 1.8 million, and 50,000 to 1,500,000. It is particularly preferred that When the weight average molecular weight is 10,000 or more, the form retainability as a single resin is excellent, and when it is 2 million or less, a resin composition for laser engraving is prepared from the viewpoint of viscosity and compatibility with other components. It is suitable for. In the present invention, the weight average molecular weight is measured by a gel permeation chromatography (GPC) method and is determined by conversion with standard polystyrene.
  • GPC gel permeation chromatography
  • GPC uses HLC-8220GPC (manufactured by Tosoh Corporation), and TSKgeL SuperHZM-H, TSKgeL SuperHZ4000, TSKgeL SuperHZ2000 (4.6 mm ID ⁇ 15 cm, manufactured by Tosoh Corporation) are used as columns. Three are used and THF (tetrahydrofuran) is used as an eluent. As conditions, the sample concentration is 0.35% by mass, the flow rate is 0.35 ml / min, the sample injection amount is 10 ⁇ l, the measurement temperature is 40 ° C., and an IR detector is used.
  • the component A preferably has an SP value of 9.0 or less.
  • the SP value is also called a solubility parameter or solubility coefficient, and is a measure of the miscibility between liquids.
  • An SP value of 9.0 or less is preferable because resistance to solvent ink and UV ink is improved and printing durability is improved.
  • the SP value is more preferably from 8.0 to 9.0, and even more preferably from 8.0 to 8.5.
  • the SP value is calculated based on the Okitsu method described in Journal of the Japan Adhesion Society 29 (3) 1993, 204-211.
  • Component B trans polyisoprene and / or polyoctenylene
  • the resin composition for laser engraving of the present invention contains, as component B, at least 1 part by mass of trans polyisoprene and / or polyoctenylene with respect to 100 parts by mass of component A.
  • component B trans polyisoprene or polyoctenylene may be used alone, or both may be used in combination.
  • 1 mass part or more of component B is contained with respect to 100 mass parts of component A.
  • the total amount of both may be 1 part by mass or more with respect to 100 parts by mass of Component A.
  • the content of Component B in the resin composition for laser engraving of the present invention is 1 part by mass or more, preferably 3 parts by mass or more, and more preferably 5 parts by mass or more with respect to 100 parts by mass of Component A. preferable. Further, it is preferably 300 parts by mass or less, more preferably 150 parts by mass or less, further preferably 80 parts by mass or less, particularly preferably 50 parts by mass or less, and 35 parts by mass or less. Most preferably it is. It is preferable for the content of component B to be in the above range since sheet workability and printing durability are excellent.
  • Trans polyisoprene and polyoctenylene are both crystalline resins and have a melting point (Tm).
  • Component B is preferably a resin having a crystallinity of 5% or more.
  • the crystallinity means the ratio of the mass of the crystalline portion of the polymer solid to the total mass.
  • the degree of crystallinity of Component B is more preferably 5 to 70%, further preferably 5 to 50%, and particularly preferably 10 to 50%.
  • Component A is preferably a resin having a crystallinity of less than 5%.
  • the crystallinity of component A is more preferably 3% or less, further preferably 1% or less, and a resin having no crystal part, that is, the crystallinity is particularly 0%. preferable.
  • the crystallinity is measured by the density gradient method described in JIS-K7112-1999, and converted from the theoretical crystal density and the theoretical amorphous density, and calculated from the density; amorphous by X-ray diffraction Any method can be used such as a method of calculating using a halo; a method of calculating using a calorific value measured by a differential scanning calorimeter (DSC) and a calorie of melting of a complete crystal;
  • DSC differential scanning calorimeter
  • Trans polyisoprene is trans-1,4-polyisoprene.
  • transpolyisoprene is a main component of gutta-percha and balata, which are rubber-like resins obtained from red iron family trees and their sap. In recent years, it has been produced by solution polymerization of isoprene using a Ziegler type catalyst.
  • the weight average molecular weight of trans polyisoprene is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,000,000, and 25,000 to 500,000. Is more preferable.
  • transpolyisoprene When the weight average molecular weight of transpolyisoprene is within the above range, a polymer having a high degree of crystallinity can be obtained, and the sheet processability can be improved.
  • Commercially available products may be used as transpolyisoprene, and examples thereof include Kuraray transpolyisoprene TP-301 (manufactured by Kuraray Co., Ltd.).
  • Polyoctenylene can be obtained by polymerizing cyclooctene by metathesis polymerization using 1,3-butanediene as a starting material. In the polymerization by the metathesis reaction, the double bond of cyclooctene is retained, and polyoctenylene regularly has a structure having a double bond for every 8 carbons. Depending on the molecular weight, it is a mixture of macrocycles and linear ones, but it is presumed that when the molecular weight is about several thousand to 10,000, it has a cyclic structure, and beyond that, it is linear.
  • the weight average molecular weight of polyoctenylene is preferably 5,000 to 2,000,000, more preferably 10,000 to 1,000,000, and further preferably 25,000 to 300,000. preferable.
  • the resin composition for laser engraving of the present invention contains trans polyisoprene and / or polyoctenylene as component B.
  • Trans polyisoprene or polyoctenylene may be used alone, trans polyisoprene having different molecular weight or crystallinity, or polyoctenylene may be used in combination, and trans polyisoprene and polyoctenylene may be used in combination. It is not limited. Among these, it is preferable to use trans polyisoprene or polyoctenylene, and it is particularly preferable to use polyoctenylene.
  • the resin composition for laser engraving may contain a polymer component other than Component A and Component B, and the content thereof is 0 to 5% by mass relative to the total mass of the solid content of the resin composition. It is preferably 0 to 3% by mass, more preferably 0 to 1% by mass, and most preferably not contained.
  • Component C Crosslinking Agent
  • the resin composition for laser engraving of the present invention may contain a crosslinking agent as Component C in order to promote the formation of a crosslinked structure.
  • a crosslinking agent of the present invention any compound that promotes cross-linking of internal olefins of component A and component B can be used without limitation among those skilled in the art, but is known as a radical polymerization initiator. It is preferable to use the compound of.
  • a thermal polymerization initiator and a photoinitiator can be used, it is preferable to use a thermal polymerization initiator. Although described in detail below, the present invention is not limited by these descriptions.
  • preferred crosslinking agents include: a: aromatic ketones, b: onium salt compounds, c: organic peroxides, d: thio compounds, e: hexaarylbiimidazole compounds, f: ketoxime ester compounds, g: borate compound, h: azinium compound, i: metallocene compound, j: active ester compound, k: compound having carbon halogen bond, l: azo compound, and the like.
  • compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554 can be preferably used. Specific examples of the above a to l are given below, but the present invention is not limited thereto.
  • Aromatic ketones Preferred as a crosslinking agent that can be used in the present invention include benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone 4,4'-dichlorobenzophenone, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 2-tolyl-2-dimethylamino-1- ( Benzophenones or acetophenones such as 4-morpholinophenyl) butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane are preferred, and acetophenone is more preferred.
  • Organic peroxide Preferred as a crosslinking agent that can be used in the present invention c: As the organic peroxide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-Tetra (t-amylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (T-octylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (cumylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (p-isopropylcumylperoxycarbonyl) benzophenone Di-t-butyldiperoxyisophthalate, t-butylperoxybenzoate, t-butylperoxy-3-methylbenzoate,
  • l Azo-based compound Preferred as a crosslinking agent that can be used in the present invention: l: Azo-based compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobispropionitrile, 1,1 '-Azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis ( 4-methoxy-2,4-dimethylvaleronitrile), 4,4′-azobis (4-cyanovaleric acid), dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis (2-methylpropionamide oxime) 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis ⁇ 2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl ] Propionamide ⁇ , 2,2′-azobis [2-methyl-N-
  • a crosslinking agent may be used individually by 1 type, and may use 2 or more types together.
  • the content of component C in the resin composition for laser engraving is preferably 0.1 to 10% by mass, and preferably 0.5 to 5% by mass with respect to the total solid content of the resin composition. %, More preferably 0.8 to 3% by mass.
  • the photothermal conversion agent a compound having a maximum absorption wavelength at 700 to 1,300 nm is preferably used.
  • Various dyes or pigments are used as the photothermal conversion agent that can be used in the present invention.
  • the dye commercially available dyes and known ones described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specific examples include those having a maximum absorption wavelength in the range of 700 to 1,300 nm. Azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, diimmonium compounds, quinone imines And dyes such as dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes.
  • Dyes preferably used in the present invention include cyanine dyes such as heptamethine cyanine dyes, oxonol dyes such as pentamethine oxonol dyes, phthalocyanine dyes, and paragraphs 0124 to 0137 of JP-A-2008-63554. Mention may be made of dyes.
  • the carbon black that can be used in the present invention preferably has a DBP oil absorption of less than 150 ml / 100 g. It is more preferably 100 ml / 100 g or less, and further preferably 70 ml / 100 g or less.
  • Carbon black is a conductive carbon black having a BET specific surface area of at least 100 m 2 / g from the viewpoint of improving engraving sensitivity by efficiently transferring heat generated by photothermal conversion to surrounding polymers. preferable.
  • the above-described carbon black may be acidic or basic carbon black.
  • the carbon black is preferably basic carbon black.
  • mixtures of different binders can also be used.
  • thermal crosslinking is preferred from the viewpoint of film curability rather than photocrosslinking utilizing UV light or the like, and the above-mentioned preferred combination component (component C) crosslinking agent. It is more preferable to use it in combination with an organic peroxide, because the engraving sensitivity is extremely high.
  • a polymerization initiator (more preferably a thermal polymerization initiator) as a crosslinking agent and a photothermal conversion agent capable of absorbing light having a wavelength of 700 to 1,300 nm are used in combination. It is particularly preferable to use an organic peroxide as component C and carbon black as component D in combination.
  • the polymerization initiator (preferably thermal polymerization initiator) remaining in the crosslinked relief forming layer is decomposed by the heat generated from the photothermal conversion agent, and component A and the like are decomposed. This can be further promoted and the engraving sensitivity can be improved.
  • component D In the resin composition for laser engraving of the present invention, only one type of component D may be used, or two or more types may be used in combination.
  • the content of component D: photothermal conversion agent in the resin composition for laser engraving of the present invention varies greatly depending on the molecular extinction coefficient inherent to the molecule, but is 2 to 2 with respect to the total solid mass of the resin composition. 60 mass% is preferable, 5-30 mass% is more preferable, and 5-20 mass% is still more preferable.
  • Component E Factis
  • the resin composition for laser engraving of the present invention preferably contains Component E: Factis.
  • Component E Factis.
  • factice only 1 type may be used and 2 or more types may be used together.
  • the factis refers to a rubber-like substance obtained by reacting oil and fat with a crosslinking agent. Note that the factis is also called a sub-rubber-substate, as will be described later.
  • the fats and oils include vegetable oils, fish oils, mineral oils (eg, naphthenic mineral oils), synthetic esters, modified alkyd resins, and the like. Among these, vegetable oils are preferred.
  • the factis is preferably at least one selected from the group consisting of a sulfur factis and a sulfur chloride factice. From the standpoint of migration control, the factis is at least selected from the group consisting of (a) a sulfur factice having an acetone extract of 10 to 50%, and (b) a sulfur chloride factice having an acetone extract of 1 to 10%. More preferably, it is one.
  • acetone extract (%) is a value calculated as follows. About 0.5 g of the factice sample is wrapped in filter paper or placed in a cylindrical filter paper and placed in the siphon cup of the Kunefrel extractor. Moreover, 50 mL of acetone is put into the extraction flask.
  • the addition amount of factice is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 15 to 35% by mass with respect to the total mass of the solid content of the resin composition for laser engraving.
  • the resin composition for laser engraving of the present invention may contain a solvent as Component F.
  • the solvent used in preparing the resin composition for laser engraving of the present invention is preferably mainly an aprotic organic solvent from the viewpoint of solubility of each component. More specifically, aprotic organic solvent / protic organic solvent is preferably used at 100/0 to 50/50 (mass ratio), and preferably used at 100/0 to 70/30 (mass ratio). More preferably, it is more preferably used at 100/0 to 90/10 (mass ratio).
  • Preferred examples of the aprotic organic solvent include acetonitrile, tetrahydrofuran, dioxane, toluene, propylene glycol monomethyl ether acetate, methyl ethyl ketone, acetone, methyl isobutyl ketone, ethyl acetate, butyl acetate, ethyl lactate, N, N-dimethylacetamide. N-methylpyrrolidone and dimethyl sulfoxide.
  • the resin composition for laser engraving preferably contains no solvent or the content of the solvent is 10% by mass or less ( Hereinafter, “not contained” or that the content is 10% by mass or less is described as “contained from 0 to 10% by mass”.) This is preferable because a flexographic printing plate precursor for laser engraving can be produced without going through a solvent removal step.
  • the content of the solvent is more preferably 0 to 5% by mass, still more preferably 0 to 3% by mass, and particularly preferably 0% by mass.
  • additives other than the above components A to E can be appropriately blended as long as the effects of the present invention are not impaired.
  • examples include waxes, process oils, organic acids, metal oxides, fragrances, antiozonants, antioxidants, thermal polymerization inhibitors, colorants, etc., and these may be used alone. Two or more kinds may be used in combination.
  • Process oil When process oil is used, for example, aromatic process oil, naphthenic process oil, and paraffinic process oil can be mentioned.
  • the addition amount is preferably 1 to 70 parts by mass with respect to 100 parts by mass of component A.
  • the organic acid can be used as an auxiliary agent for vulcanization acceleration in combination with a conventional vulcanizing agent as a metal salt.
  • examples of the organic acid include stearic acid, oleic acid, and myristic acid.
  • Examples of the metal source used in combination include metal oxides such as zinc oxide (zinc white) and magnesium oxide.
  • organic acids and metal oxides form metal salts in the rubber, and the activation of vulcanizing agents such as sulfur is promoted.
  • the addition amount of the metal oxide for forming such a metal salt in the system is preferably 0.1 to 10 parts by mass, more preferably 2 to 10 parts by mass with respect to 100 parts by mass of Component A.
  • the addition amount of the organic acid is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of Component A.
  • the resin composition for laser engraving of the present invention preferably contains a fragrance in order to reduce odor.
  • the fragrance is effective for reducing the odor during the production of the flexographic printing plate precursor and during laser engraving.
  • the resin composition for laser engravings of this invention can mask the solvent odor which volatilizes when drying the liquid resin composition apply
  • the fragrance reference is made to paragraphs 0081 to 0088 of JP 2011-245818 A.
  • the content of the fragrance is preferably 0.003 to 1.5% by mass, more preferably 0.005 to 1.0% by mass, based on the total mass of the solid content of the resin composition.
  • the masking effect can be sufficiently exhibited, the fragrance of the fragrance is moderate, the working environment is improved, and the engraving sensitivity is excellent.
  • nitrocellulose or a highly heat conductive material may be added as an additive for improving engraving sensitivity. Since nitrocellulose is a self-reactive compound, it generates heat during laser engraving and assists in the thermal decomposition of coexisting binder polymers. As a result, it is estimated that the engraving sensitivity is improved.
  • the highly heat conductive material is added for the purpose of assisting heat transfer, and examples of the heat conductive material include inorganic compounds such as metal particles and organic compounds such as a conductive polymer.
  • the conductive polymer is preferably a gold fine particle, silver fine particle, or copper fine particle having a particle size of micrometer order to several nanometer order.
  • a conjugated polymer particularly preferred is a conjugated polymer, and specific examples include polyaniline and polythiophene. It is done. Moreover, the sensitivity at the time of photocuring the resin composition for laser engraving can be further improved by using a co-sensitizer. Furthermore, it is preferable to add a small amount of a thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the composition. Colorants such as dyes or pigments may be added for the purpose of coloring the resin composition for laser engraving. Thereby, properties such as the visibility of the image portion and the suitability of the image density measuring device can be improved.
  • the resin composition for laser engraving does not contain a polymerizable monomer and a polymerizable oligomer.
  • a polymerizable monomer or polymerizable oligomer By containing a polymerizable monomer or polymerizable oligomer, the viscosity of the resin composition for laser engraving decreases, and shrinkage due to polymerization may occur, so that the sheet processability may be deteriorated.
  • the polymerizable monomer means a compound having at least one polymerizable group, preferably a radical polymerizable group in the molecule, and having a molecular weight of less than 1,000.
  • the polymerizable oligomer is a compound having at least one polymerizable group, preferably a radical polymerizable group in the molecule, and means a compound having a molecular weight of 1,000 or more and less than 3,000.
  • the content of the polymerizable monomer and polymerizable oligomer is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, and more preferably 0 to 3% by mass with respect to the solid content of the resin composition for laser engraving.
  • the content is more preferably 1% by mass, and it is particularly preferably not contained, that is, 0% by mass.
  • Flexographic printing plate precursor for laser engraving and manufacturing method thereof (flexographic printing plate precursor for laser engraving)
  • the first embodiment of the flexographic printing plate precursor for laser engraving in the present invention has a relief forming layer comprising the resin composition for laser engraving of the present invention.
  • the second embodiment of the flexographic printing plate precursor for laser engraving in the present invention has a crosslinked relief forming layer obtained by crosslinking the relief forming layer made of the resin composition for laser engraving of the present invention.
  • a flexographic printing plate precursor for laser engraving means a state in which a relief-forming layer having a crosslinkability made of a resin composition for laser engraving is in a state before being crosslinked and cured by light or heat. Both or either one.
  • the “relief-forming layer” refers to a layer in a state before being crosslinked, that is, a layer made of the resin composition for laser engraving of the present invention, and may be dried if necessary. Good.
  • the “crosslinked relief forming layer” refers to a layer obtained by crosslinking the relief forming layer.
  • the crosslinking can be performed by heat and / or light.
  • the crosslinking is not particularly limited as long as the resin composition is cured, and is a concept including a crosslinked structure by a reaction between components A, a reaction between components B, and a reaction between components A and B, Any cross-linked structure may be used.
  • a “flexographic printing plate” is produced by laser engraving a printing plate precursor having a crosslinked relief forming layer.
  • the “relief layer” refers to a layer engraved with a laser in a flexographic printing plate, that is, the crosslinked relief forming layer after laser engraving.
  • the resin composition for laser engraving of the present invention can be widely used for applications other than forming a relief forming layer of a flexographic printing plate precursor subjected to laser engraving without any particular limitation.
  • a relief forming layer of a flexographic printing plate precursor subjected to laser engraving without any particular limitation.
  • the relief forming layer of the printing plate precursor that forms the convex relief described in detail below by laser engraving but also other material shapes that form irregularities and openings on the surface, such as intaglio, stencil, stamp, etc. It can be applied to the formation of various printing plates and various molded articles on which necessary images are formed by laser engraving.
  • the resin composition of the present invention is preferably used to form a relief-forming layer on a suitable support to form a flexographic printing plate precursor for laser engraving.
  • the flexographic printing plate precursor for laser engraving in the present invention has a relief forming layer made of a resin composition for laser engraving containing the above components.
  • the (crosslinked) relief forming layer is preferably provided on the support.
  • the flexographic printing plate precursor for laser engraving further has an adhesive layer between the support and the (crosslinked) relief forming layer, if necessary, and a slip coat layer and a protective film on the (crosslinked) relief forming layer. May be.
  • the relief forming layer is a layer made of the resin composition for laser engraving of the present invention, and is preferably a thermally crosslinkable layer.
  • the flexographic printing plate precursor using the flexographic printing plate precursor for laser engraving includes a flexographic printing plate precursor having a crosslinked relief forming layer by crosslinking the relief forming layer, and then a crosslinked relief forming layer (hard relief forming layer).
  • a mode in which a relief layer is formed by laser engraving to produce a flexographic printing plate is preferred.
  • the relief forming layer can be formed by molding a resin composition for laser engraving having the above components for the relief forming layer into a sheet shape or a sleeve shape.
  • the relief forming layer is usually provided on a support which will be described later.
  • the relief forming layer can be directly formed on the surface of a member such as a cylinder provided in an apparatus for plate making and printing, or can be arranged and fixed there. It does not necessarily require a support.
  • the case where the relief forming layer is formed into a sheet shape will be mainly described as an example.
  • the material used for the support of the flexographic printing plate precursor for laser engraving is not particularly limited, but materials having high dimensional stability are preferably used.
  • metals such as steel, stainless steel, aluminum, polyester (for example, PET (polyethylene terephthalate)) , Plastic resins such as PBT (polybutylene terephthalate), PAN (polyacrylonitrile)) and polyvinyl chloride, synthetic rubbers such as styrene-butadiene rubber, and plastic resins reinforced with glass fibers (such as epoxy resins and phenol resins) It is done.
  • a PET film or a steel substrate is preferably used as the support.
  • the form of the support is determined depending on whether the relief forming layer is a sheet or a sleeve.
  • an adhesive layer may be provided between the two for the purpose of enhancing the adhesive strength between the layers.
  • materials that can be used for the adhesive layer include: Those described in the edition of Skeist, “Handbook of Adhesives”, the second edition (1977) can be used.
  • a protective film may be provided on the surface of the relief forming layer or the surface of the crosslinked relief forming layer.
  • the thickness of the protective film is preferably 25 to 500 ⁇ m, more preferably 50 to 200 ⁇ m.
  • a polyester film such as PET, or a polyolefin film such as PE (polyethylene) or PP (polypropylene) can be used.
  • PE polyethylene
  • PP polypropylene
  • the surface of the film may be matted.
  • the protective film is preferably peelable.
  • a slip coat layer may be provided between both layers.
  • the material used for the slip coat layer is composed mainly of a resin that is soluble or dispersible in water, such as polyvinyl alcohol, polyvinyl acetate, partially saponified polyvinyl alcohol, hydroxyalkyl cellulose, alkyl cellulose, and polyamide resin, and that is less sticky. It is preferable to do.
  • the method for producing the flexographic printing plate precursor for laser engraving is not particularly limited.
  • a resin composition for laser engraving is prepared, and the solvent is removed from the resin composition for laser engraving as necessary. Later, the method of extruding on a support body and the method of pressing are mentioned.
  • the resin composition for laser engraving may be cast on a support and dried in an oven to remove the solvent from the resin composition.
  • the method for producing a flexographic printing plate precursor for laser engraving in the present invention includes a layer forming step for forming a relief forming layer comprising the resin composition for laser engraving of the present invention, and heat and / or light on the relief forming layer. It is preferable that the production method includes a crosslinking step of obtaining a flexographic printing plate precursor having a crosslinked relief-forming layer crosslinked by the above.
  • a protective film may be laminated on the relief forming layer as necessary. Lamination can be performed by pressure-bonding the protective film and the relief forming layer with a heated calendar roll or the like, or by bringing the protective film into close contact with the relief forming layer impregnated with a small amount of solvent on the surface.
  • a protective film a method of first laminating a relief forming layer on the protective film and then laminating the support may be employed.
  • providing an adhesive layer it can respond by using the support body which apply
  • the method for producing a flexographic printing plate precursor for laser engraving in the present invention preferably includes a layer forming step of forming a relief forming layer comprising the resin composition for laser engraving of the present invention.
  • the resin composition for laser engraving of the present invention is prepared, and if necessary, after removing the solvent from the resin composition for laser engraving, the method of extruding onto the support, There is a method using a press or a method in which the resin composition for laser engraving of the present invention is prepared, the resin composition for laser engraving of the present invention is cast on a support, and this is dried in an oven to remove the solvent. Preferred examples can be given.
  • the layer forming step preferably includes a step of kneading the resin composition for laser engraving of the present invention and a step of molding the obtained kneaded product into a sheet shape.
  • a step of forming into a sheet any of extrusion, pressing, calendaring, etc. may be used.
  • the extrusion process include rubber extrusion and melt extrusion
  • examples of the press process include hot press.
  • the step of forming into a sheet shape is preferably extrusion or pressing, and more preferably formed into a sheet shape by extrusion or hot pressing.
  • the processing temperature is preferably 20 ° C.
  • the processing temperature is preferably 40 ° C. to 130 ° C., more preferably 50 ° C. to 100 ° C., and further preferably 60 ° C. to 80 ° C.
  • the resin composition for laser engraving is preferably prepared, for example, by kneading components A and B and optional components C to E and other components.
  • component C is preferably added after kneading other components such as component A, component B and component D.
  • components A and B, and optional components C to E and other components may be dissolved or dispersed in a suitable solvent, and then these solutions may be mixed.
  • the solvent is a low-molecular alcohol that easily volatilizes (eg, methanol, ethanol, n-propanol, isopropanol, propylene glycol monomethyl ether). It is preferable to keep the total amount of solvent added as small as possible by adjusting the temperature.
  • the thickness of the (crosslinked) relief forming layer in the flexographic printing plate precursor for laser engraving is preferably from 0.05 mm to 10 mm, more preferably from 0.05 mm to 7 mm, and more preferably from 0.05 mm to 3 mm before and after crosslinking. Further preferred.
  • the method for producing a flexographic printing plate precursor for laser engraving in the present invention may be a production method including a crosslinking step of obtaining a flexographic printing plate precursor having a crosslinked relief forming layer obtained by crosslinking the relief forming layer with heat and / or light.
  • the production method includes a crosslinking step for obtaining a flexographic printing plate precursor having a crosslinked relief-forming layer obtained by crosslinking the relief-forming layer with heat.
  • polymerization inhibition may occur in the presence of oxygen. Therefore, crosslinking may be performed in a state in which at least the central part of the surface of the relief forming layer is covered with a material capable of blocking air.
  • the surface of the relief forming layer may be cross-linked in direct contact with air, or the relief forming layer may be cross-linked in a vacuumed state with a sheet of a material capable of blocking air such as vinyl chloride.
  • the relief forming layer can be crosslinked (thermal crosslinking step).
  • a heating means for crosslinking by heat a printing plate precursor is heated for a predetermined time in a hot air oven or a far-infrared oven, a method of contacting a heated roll for a predetermined time, or pressing while heating with a hot press machine. The method (hot press) is mentioned.
  • crosslinking in order to form bridge
  • the relief-forming layer contains a photopolymerization initiator
  • the relief-forming layer is crosslinked by irradiating the relief-forming layer with light that triggers the photopolymerization initiator (also referred to as “active light”).
  • active light also referred to as “active light”.
  • active light also referred to as “active light”.
  • the surface may only be irradiated with light, but the support should be a transparent film that transmits actinic rays. For example, it is preferable to irradiate light from the back side.
  • the irradiation from the surface may be performed while the protective film is provided, or may be performed after the protective film is peeled off. Since polymerization inhibition may occur in the presence of oxygen, actinic rays may be irradiated after the relief forming layer is covered with a vinyl chloride sheet and evacuated.
  • the method of making a flexographic printing plate in the present invention comprises the steps of preparing the flexographic printing plate precursor for laser engraving in the present invention, and the engraving step of laser engraving the flexographic printing plate precursor for laser engraving It is preferable to contain.
  • the flexographic printing plate in the present invention is obtained by making a plate by the above-described flexographic printing plate making method.
  • the method for making a flexographic printing plate in the present invention preferably includes an engraving step of laser engraving the flexographic printing plate precursor having the crosslinked relief forming layer.
  • the engraving step is a step of forming a relief layer by laser engraving the crosslinked relief forming layer crosslinked in the crosslinking step.
  • crosslinking relief forming layer is mentioned preferably.
  • an infrared laser is preferably used.
  • the molecules in the crosslinked relief forming layer undergo molecular vibrations and generate heat.
  • a high-power laser such as a carbon dioxide laser or YAG laser is used as an infrared laser
  • a large amount of heat is generated in the laser irradiation part, and molecules in the crosslinked relief forming layer are selectively cut by molecular cutting or ionization. That is, engraving is performed.
  • the advantage of laser engraving is that the engraving depth can be set arbitrarily, so that the structure can be controlled three-dimensionally.
  • the portion that prints fine halftone dots can be engraved shallowly or with a shoulder so that the relief does not fall down due to printing pressure, and the portion of the groove that prints fine punched characters is engraved deeply As a result, the ink is less likely to be buried in the groove, and it is possible to suppress the crushing of the extracted characters.
  • the crosslinked relief forming layer can be selectively removed with higher sensitivity, and a relief layer having a sharp image can be obtained.
  • a carbon dioxide laser (CO 2 laser) or a semiconductor laser is preferable from the viewpoints of productivity and cost.
  • a semiconductor infrared laser with a fiber (FC-LD) is preferably used.
  • a semiconductor laser can be downsized with high efficiency and low cost of laser oscillation compared to a CO 2 laser. Moreover, since it is small, it is easy to form an array. Furthermore, the beam shape can be controlled by processing the fiber.
  • the semiconductor laser preferably has a wavelength of 700 to 1,300 nm, more preferably 800 to 1,200 nm, still more preferably 860 to 1,200 nm, and particularly preferably 900 to 1,100 nm.
  • the semiconductor laser with a fiber can output a laser beam efficiently by attaching an optical fiber, it is effective for the engraving process in the present invention.
  • the beam shape can be controlled by processing the fiber.
  • the beam profile can have a top hat shape, and energy can be stably given to the plate surface. Details of the semiconductor laser are described in “Laser Handbook 2nd Edition” edited by Laser Society, “Practical Laser Technology” edited by Electronic Communication Society, and the like.
  • a plate making apparatus equipped with a fiber-coupled semiconductor laser that can be suitably used in a method for making a flexographic printing plate using a flexographic printing plate precursor according to the present invention is disclosed in JP 2009-172658 A and JP 2009-214334 A. Which can be used for making a flexographic printing plate according to the present invention.
  • rinsing step a step of rinsing the engraved surface of the relief layer after engraving with an aqueous rinse solution.
  • Drying step A step of drying the relief layer after the rinsing step.
  • Post-crosslinking step a step of imparting energy to the relief layer after engraving and further crosslinking the relief layer.
  • a rinse step is added to rinse the engraving residue by rinsing the engraving surface with an aqueous rinsing liquid (hereinafter also simply referred to as “rinsing liquid”).
  • the aqueous rinse liquid is water or a liquid containing water as a main component.
  • a rinsing there is a method of washing with tap water, a method of spraying high-pressure water, and a known batch type or conveying type brush type washing machine as a photosensitive resin relief printing machine.
  • a rinsing liquid to which soap or a surfactant is added may be used.
  • the rinsing process for rinsing the engraving surface it is preferable to add a drying process for drying the engraved relief forming layer and volatilizing the rinsing liquid. Furthermore, you may add the post-crosslinking process which further bridge
  • the pH of the rinsing solution that can be used in the present invention is preferably 9 or more, more preferably 10 or more, and still more preferably 11 or more.
  • the pH of the rinsing liquid is preferably 14 or less, more preferably 13.5 or less, still more preferably 13.2 or less, and particularly preferably 12.5 or less. Handling is easy in the said range. What is necessary is just to adjust pH using an acid and / or a base suitably in order to make a rinse liquid into said pH range, and the acid and base to be used are not specifically limited.
  • the rinsing liquid that can be used in the present invention preferably contains water as a main component.
  • the rinse liquid may contain water miscible solvents, such as alcohol, acetone, tetrahydrofuran, as solvents other than water.
  • the rinse liquid contains a surfactant.
  • a surfactant that can be used in the present invention, a carboxybetaine compound, a sulfobetaine compound, a phosphobetaine compound, an amine oxide compound, or a viewpoint of reducing engraving residue removal and the influence on the flexographic printing plate
  • betaine compounds such as phosphine oxide compounds.
  • surfactant examples include known anionic surfactants, cationic surfactants, and nonionic surfactants. Furthermore, fluorine-based and silicone-based nonionic surfactants can be used in the same manner. Surfactant may be used individually by 1 type, or may use 2 or more types together. The amount of the surfactant used is not particularly limited, but is preferably 0.01 to 20% by mass, and more preferably 0.05 to 10% by mass with respect to the total mass of the rinsing liquid.
  • a flexographic printing plate having a relief layer on the surface of an arbitrary substrate such as a support can be obtained.
  • the thickness of the relief layer of the flexographic printing plate is preferably 0.05 mm or more and 10 mm or less, more preferably 0.05 mm or more and 7 mm, from the viewpoint of satisfying various printability such as abrasion resistance and ink transferability.
  • it is particularly preferably 0.05 mm or more and 3 mm or less.
  • the Shore A hardness of the relief layer which a flexographic printing plate has is 50 degree or more and 90 degrees or less.
  • the Shore A hardness of the relief layer is 50 ° or more, even if the fine halftone dots formed by engraving are subjected to the strong printing pressure of the relief printing press, they do not collapse and can be printed normally.
  • the Shore A hardness of the relief layer is 90 ° or less, it is possible to prevent faint printing in a solid portion even in flexographic printing with a kiss touch.
  • the Shore A hardness in this specification is quantified by measuring the amount of deformation (indentation depth) by indenting and deforming an indenter (called a push needle or indenter) on the surface to be measured at 25 ° C. It is a value measured with a durometer (spring type rubber hardness meter).
  • the flexographic printing plate of the present invention is particularly suitable for printing with water-based ink by a flexographic printing machine, but printing is possible with any of water-based ink, oil-based ink and UV ink by a relief printing press. In addition, printing with UV ink by a flexographic printing machine is also possible.
  • the flexographic printing plate of the present invention has excellent rinsing properties, no engraving residue remains, and the obtained relief layer is excellent in elasticity, so that it has excellent water-based ink transfer properties and printing durability, and a relief layer over a long period of time. Thus, printing can be carried out without concern for plastic deformation or deterioration of printing durability.
  • the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
  • “parts” and “%” represent “parts by mass” and “mass%”.
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the compounds in the examples are the values measured by gel permeation chromatography (GPC) method (eluent: tetrahydrofuran) unless otherwise specified. Yes.
  • Component B trans polyisoprene and / or polyoctenylene
  • B-1 TP-301 (manufactured by Kuraray Co., Ltd.), trans-1,4-polyisoprene, melting point 67 ° C., trans bond 99%, crystallinity 36%, Weight average molecular weight 250,000
  • B-2 Bestenamer 8012 (manufactured by Evonik), polyoctenylene, melting point 54 ° C., crystallinity 33%, weight average molecular weight 90,000 B-3 (comparative example): BR810 (manufactured by JSR Corporation), syndiotactic 1,2-polybutadiene, crystallinity 18%, weight average molecular weight 180,000
  • Crosslinking agent PCD-40 Park mill D40 (manufactured by NOF Corporation), dicumyl peroxide, purity 40%
  • Photothermal conversion agent # 45L Mitsubishi carbon black # 45L (manufactured by Mitsubishi Chemical Corporation), carbon black, arithmetic average particle diameter 24 nm, DBP oil absorption 45 ml / 100 g, pH 8, BET specific surface area (JIS K 6217) 125 m 2 / g
  • Component E Factis White Sub 1: Acetone extract; 2 to 5%, Sulfur Chloride Factis made from refined rapeseed oil, manufactured by Tenma Sub Chemical Co., Ltd.
  • Black Sub 21 Acetone extract 19 to 27%, mainly vegetable oil Sulfur factice used as raw material, manufactured by Tenma Sub Chemical Co., Ltd.
  • flexographic printing plate precursor for laser engraving-1 (Making a kneaded sheet)
  • the kneaded material obtained above and a spacer having a predetermined film thickness (0.8 mm) were placed in a hot press machine and pressed at 60 ° C. and 15 MPa for 1 minute to prepare an uncrosslinked sheet.
  • the obtained sheet was subjected to a shrinkage test for workability evaluation.
  • ⁇ Ink resistance Swell ratio measurement>
  • the flexographic printing plate precursor was cut into about 1 cm square and placed in a sample bottle. Thereto was added 2 mL of solvent ink (UV flexo indigo PHA, manufactured by T & K TOKA, SP value 9.2 to 11.1), and the mixture was allowed to stand at 20 ° C. After 24 hours, the flexographic printing plate precursor was taken out, the mass after wiping the surface was measured, and the swelling ratio was calculated by the following equation.
  • Swelling ratio (mass%) (mass after immersion) / (mass before immersion) ⁇ 100 This value is preferably as close to 100 wt%.
  • the evaluation criteria are as follows. If the evaluation result is 1, there is no practical problem. 1: Less than 105 mass% swelling ratio 2: 105 mass% or more swelling ratio
  • Log (tan ⁇ / ⁇ ) was adopted as an index of printing durability.
  • tan ⁇ is a value at 50 ° C. and 1 Hz
  • ⁇ is elongation at break [%] / 100.
  • the printing durability index is less than -1.6, the printing durability is 40 km or more with respect to the solvent ink.
  • the evaluation criteria are as follows. If the evaluation standard is 1 or 2, there is no practical problem. 1: Log (tan ⁇ / ⁇ ) is less than ⁇ 2.0 2: Log (tan ⁇ / ⁇ ) is ⁇ 2.0 or more and less than ⁇ 1.6 3: Log (tan ⁇ / ⁇ ) is ⁇ 1.6 or more

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Plasma & Fusion (AREA)
  • Manufacturing & Machinery (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Manufacture Or Reproduction Of Printing Formes (AREA)

Abstract

La présente invention aborde le problème de fourniture : d'une composition de résine pour gravure au laser, qui est capable de fournir une plaque d'impression flexographique qui présente d'excellentes propriétés d'aptitude au traitement en feuille, de résistance d'encre et de durabilité d'impression ; d'une plaque originale d'impression flexographique pour gravure au laser, qui utilise cette composition de résine pour la gravure au laser ; d'un procédé de production de cette plaque originale d'impression flexographique pour la gravure au laser ; d'un procédé de fabrication de plaque pour une plaque d'impression flexographique, qui utilise cette plaque originale d'impression flexographique ; et d'une plaque d'impression flexographique qui est obtenue par ce procédé de fabrication de plaque. Une composition de résine pour gravure au laser selon la présente invention est caractérisée en ce qu'elle contient un polymère qui possède un motif monomère dérivé d'un hydrocarbure diène conjugué (composant (A)) et d'un transpolyisoprène et/ou un polyocténylène (composant (B)) en une quantité de 1 partie en masse ou plus pour 100 parties en masse du composant (A). Cette composition de résine pour gravure au laser est également caractérisée en ce que le composant (A) et le composant (B) sont des polymères différents.
PCT/JP2015/052671 2014-01-31 2015-01-30 Composition de résine pour gravure au laser, plaque originale d'impression flexographique pour gravure au laser, procédé de production d'une plaque originale d'impression flexographique pour gravure au laser, plaque d'impression flexographique, et procédé de fabrication de plaque pour plaque d'impression flexographique Ceased WO2015115599A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2014016672 2014-01-31
JP2014-016672 2014-01-31
JP2014124365 2014-06-17
JP2014-124365 2014-06-17

Publications (1)

Publication Number Publication Date
WO2015115599A1 true WO2015115599A1 (fr) 2015-08-06

Family

ID=53757166

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/052671 Ceased WO2015115599A1 (fr) 2014-01-31 2015-01-30 Composition de résine pour gravure au laser, plaque originale d'impression flexographique pour gravure au laser, procédé de production d'une plaque originale d'impression flexographique pour gravure au laser, plaque d'impression flexographique, et procédé de fabrication de plaque pour plaque d'impression flexographique

Country Status (1)

Country Link
WO (1) WO2015115599A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004523401A (ja) * 2001-04-18 2004-08-05 ビーエーエスエフ　ドルクズュステーメ、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツング シンジオタクチック１，２−ポリブタジエンを含有するレリーフ形成性エラストマー性の層を有するレーザー製版可能なフレキソ印刷要素
JP2006206872A (ja) * 2004-12-28 2006-08-10 Jsr Corp レーザー加工用組成物、レーザー加工用シート、及びフレキソ印刷版
JP2009298103A (ja) * 2008-06-17 2009-12-24 Toyobo Co Ltd レーザー彫刻可能なフレキソ印刷原版

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004523401A (ja) * 2001-04-18 2004-08-05 ビーエーエスエフ　ドルクズュステーメ、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツング シンジオタクチック１，２−ポリブタジエンを含有するレリーフ形成性エラストマー性の層を有するレーザー製版可能なフレキソ印刷要素
JP2006206872A (ja) * 2004-12-28 2006-08-10 Jsr Corp レーザー加工用組成物、レーザー加工用シート、及びフレキソ印刷版
JP2009298103A (ja) * 2008-06-17 2009-12-24 Toyobo Co Ltd レーザー彫刻可能なフレキソ印刷原版

Similar Documents

Publication Publication Date Title
US10518524B2 (en) Flexo printing plate
JPWO2017119236A1 (ja) フレキソ印刷版、フレキソ印刷版原版、および、これらの製造方法
US20170368863A1 (en) Flexo printing plate and method for manufacturing flexo printing plate
CN107531071B (zh) 柔版印刷版
JP6061911B2 (ja) レーザー彫刻用樹脂組成物、レーザー彫刻用フレキソ印刷版原版及びその製造方法、並びに、フレキソ印刷版の製版方法
WO2017135118A1 (fr) Plaque d'impression cylindrique, un cliché original d'impression cylindrique, procédé de fabrication de cliché original d'impression cylindrique, et procédé de fabrication de plaque d'impression cylindrique
JP5918731B2 (ja) レーザー彫刻用樹脂組成物、レーザー彫刻用フレキソ印刷版原版及びその製造方法、並びに、フレキソ印刷版及びその製版方法
JP5613121B2 (ja) レーザー彫刻用組成物、レーザー彫刻用レリーフ印刷版原版及びその製造方法、レリーフ印刷版の製版方法及びレリーフ印刷版
JP2015123714A (ja) レーザー彫刻用樹脂組成物、レーザー彫刻型フレキソ印刷版原版及びその製造方法、並びに、フレキソ印刷版の製版方法
JPWO2014051028A1 (ja) 円筒状印刷原版の製造方法、及び、円筒状印刷版の製版方法
WO2015115599A1 (fr) Composition de résine pour gravure au laser, plaque originale d'impression flexographique pour gravure au laser, procédé de production d'une plaque originale d'impression flexographique pour gravure au laser, plaque d'impression flexographique, et procédé de fabrication de plaque pour plaque d'impression flexographique
JP6055092B2 (ja) フレキソ印刷版の製版方法
JP5752752B2 (ja) レーザー彫刻用樹脂組成物、レーザー彫刻用フレキソ印刷版原版の製造方法、フレキソ印刷版原版、フレキソ印刷版の製版方法及びフレキソ印刷版
JP2016210104A (ja) 接着層付フレキソ印刷版、接着層付フレキソ印刷版原版、積層構造物およびこれらの製造方法
WO2013180051A1 (fr) Composition de résine pour gravure au laser, procédé de fabrication d'original de plaque d'impression en relief pour gravure au laser, original de plaque d'impression en relief, procédé de fabrication de plaque d'impression en relief et plaque d'impression en relief
JP2012196900A (ja) レーザー彫刻用樹脂組成物、レーザー彫刻用レリーフ印刷版原版及びその製造方法、並びに、レリーフ印刷版及びその製版方法
JP2014233936A (ja) レーザー彫刻用樹脂組成物、レーザー彫刻用フレキソ印刷版原版及びその製造方法、並びに、フレキソ印刷版及びその製版方法
JP2015150805A (ja) レーザー彫刻用樹脂組成物、レーザー彫刻型フレキソ印刷版原版及びその製造方法、並びに、フレキソ印刷版及びその製版方法
JPWO2015046297A1 (ja) レーザー彫刻用樹脂組成物、レーザー彫刻用フレキソ印刷版原版及びその製造方法、並びに、フレキソ印刷版及びその製版方法
JP2016221921A (ja) フレキソ印刷版、フレキソ印刷版原版、および、これらの製造方法
WO2016052494A1 (fr) Procédé de fabrication d'une plaque d'impression flexographique
JP2015047747A (ja) レーザー彫刻用樹脂組成物、レーザー彫刻用フレキソ印刷版原版及びその製造方法、並びに、フレキソ印刷版及びその製版方法
JP2015208929A (ja) レーザー彫刻用樹脂組成物、レーザー彫刻用フレキソ印刷版原版の製造方法、フレキソ印刷版原版、フレキソ印刷版の製版方法及びフレキソ印刷版

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: 15743572

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: 15743572

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP