WO2020090978A1 - Flexographic printing plate precursor, and flexographic printing plate - Google Patents
Flexographic printing plate precursor, and flexographic printing plate Download PDFInfo
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- WO2020090978A1 WO2020090978A1 PCT/JP2019/042783 JP2019042783W WO2020090978A1 WO 2020090978 A1 WO2020090978 A1 WO 2020090978A1 JP 2019042783 W JP2019042783 W JP 2019042783W WO 2020090978 A1 WO2020090978 A1 WO 2020090978A1
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- Prior art keywords
- printing plate
- flexographic printing
- photosensitive layer
- meth
- water
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Classifications
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- 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
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- 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
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- 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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
Definitions
- the present invention relates to a flexographic printing plate precursor and a flexographic printing plate.
- Flexographic printing is a printing method in which ink is applied to the convex portions of a printing plate using an anilox roll or the like and transferred to a printing medium.
- a flexographic printing plate precursor having a photosensitive layer which is imagewise exposed and developed, is used.
- flexographic printing plate precursors are also required to be developable with an aqueous developer.
- claim 1 of Patent Document 1 discloses a photosensitive resin composition which can be developed with an aqueous developer when used as a flexographic printing plate precursor.
- the present invention is excellent in water developability, and exhibits excellent printing durability, handling property and rear end inking property when made into a flexographic printing plate, a flexographic printing plate precursor, Another object is to provide a flexographic printing plate obtained by exposing and developing the above flexographic printing plate precursor.
- the present inventor has water-dispersible particles, a polymer having reactive functional groups at both ends and having a weight average molecular weight of 5,000 or more, and three or more ethylenically unsaturated groups.
- the inventors have found that the above problem can be solved by using a polyfunctional monomer in combination, and completed the present invention. That is, the present inventor has found that the above problems can be solved by the following configurations.
- a flexographic printing plate obtained by exposing and developing the above flexographic printing plate precursor can be provided.
- the present invention will be described in detail.
- the description of the constituents described below may be made based on a typical embodiment of the present invention, but the present invention is not limited to such an embodiment.
- the numerical range represented by “to” means a range including the numerical values before and after “to” as the lower limit value and the upper limit value.
- each component may be used alone or in combination of two or more.
- the content of the component means the total content unless otherwise specified.
- (meth) acrylic is a notation representing “acrylic” or “methacrylic
- (meth) acrylate is a notation representing “acrylate” or “methacrylate”
- (meth) acryloyl Is a notation representing "acryloyl” or "methacryloyl”.
- the water-developable flexographic printing plate precursor of the invention (hereinafter, also referred to as “printing plate precursor of the invention”) has water-dispersible particles and a weight average molecular weight of 5,000 or more having reactive functional groups at both ends.
- Water-developable flexographic printing having a photosensitive layer containing a polymer (hereinafter, also referred to as "specific polymer”) and a polyfunctional monomer having three or more ethylenically unsaturated groups (hereinafter, also referred to as "specific monomer”) The original version.
- the printing plate precursor of the present invention has such a configuration, it can be considered that the above-mentioned effects can be obtained.
- a polymer having a reactive functional group at both ends and having a weight average molecular weight of 5,000 or more (specific polymer) and a polyfunctional monomer having three or more ethylenically unsaturated groups (specific monomer) are used. Is considered to form a three-dimensional structure excellent in toughness and rubber elasticity.
- the photosensitive layer of the printing plate precursor of the present invention (hereinafter, also referred to as “the photosensitive layer of the present invention”) is a water-dispersible particle and a polymer having a reactive functional group at both ends and having a weight average molecular weight of 5,000 or more. It has a photosensitive layer containing (specific polymer) and a polyfunctional monomer (specific monomer) having three or more ethylenically unsaturated groups.
- each component contained in the photosensitive layer will be described.
- the photosensitive layer of the present invention contains water-dispersible particles.
- the water-dispersible particles are not particularly limited, but the water dispersibility is more excellent, the flexographic printing plate obtained has more printing durability, handling property and rear end part inking property, and is excellent in development reproducibility and solid quality.
- a polymer is preferable for the reason that the pressure latitude becomes wide.
- “more excellent water dispersibility, printing durability of the resulting flexographic printing plate, handling property and trailing edge part inking property are more excellent, development reproducibility and solid quality are excellent, and printing pressure latitude is wide” Is also referred to as "the effect of the present invention is more excellent".
- polystyrene-based polymers eg, polybutadiene, natural rubber, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, methylmethacrylate-butadiene copolymer, polychloroprene, polyisoprene), polyurethane.
- diene-based polymers eg, polybutadiene, natural rubber, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, methylmethacrylate-butadiene copolymer, polychloroprene, polyisoprene
- polyurethane eg., Vinyl pyridine polymers, butyl polymers, thiochol polymers, acrylate polymers, polymers obtained by copolymerizing these polymers with other components such as acrylic acid and methacrylic acid, and the like. They may be used alone or in combination of two or more.
- the polymer is preferably a diene polymer, more preferably polybutadiene, for the reason that the effects of the present invention are more excellent.
- the polymer preferably does not have a reactive functional group (for example, a (meth) acryloyloxy group) at both ends.
- the above-mentioned polymer is preferably a polymer obtained by removing water from the water-dispersed latex because the effect of the present invention is more excellent.
- Specific examples of the above water-dispersed latex include the water-dispersed latex of the above-mentioned specific examples of the polymer.
- the content of the water-dispersible particles in the photosensitive layer of the present invention is preferably 5 to 80% by mass based on the total solid content of the photosensitive layer of the present invention, because the effects of the present invention are more excellent.
- the amount is more preferably 10 to 50% by mass, further preferably 20 to 40% by mass.
- the photosensitive layer of the present invention contains a polymer (specific polymer) having a reactive functional group at both ends and having a weight average molecular weight of 5,000 or more.
- the specific polymer is a polymer having reactive functional groups at both ends and having a weight average molecular weight of 5,000 or more. It is preferable that the specific polymer does not have water dispersibility.
- telechelic polymer refers to a polymer having reactive functional groups at both ends
- specific polymer is a telechelic polymer having a weight average molecular weight of 5,000 or more.
- the polymer constituting the main chain of the specific polymer is not particularly limited, and examples thereof include thermoplastic polymers.
- the thermoplastic polymer is not particularly limited as long as it is a polymer exhibiting thermoplasticity, and specific examples thereof include polystyrene resin, polyester resin, polyamide resin, polysulfone resin, polyether sulfone resin, polyimide resin, acrylic resin, acetal resin. , Epoxy resin, polycarbonate resin, rubber, thermoplastic elastomer and the like. Of these, rubber and thermoplastic elastomers are preferred, rubber is more preferred, and diene rubber is even more preferred, because a softer and more flexible film is likely to be formed.
- the rubber examples include butadiene rubber (BR), nitrile rubber (NBR), acrylic rubber, epichlorohydrin rubber, urethane rubber, isoprene rubber, styrene isoprene rubber, styrene butadiene rubber, ethylene-propylene copolymer. , Chlorinated polyethylene and the like, and these may be used alone or in combination of two or more.
- BR butadiene rubber
- NBR nitrile rubber
- acrylic rubber epichlorohydrin rubber
- urethane rubber urethane rubber
- isoprene rubber styrene isoprene rubber
- styrene butadiene rubber ethylene-propylene copolymer.
- Chlorinated polyethylene and the like Chlorinated polyethylene and the like, and these may be used alone or in combination of two or more.
- thermoplastic elastomer examples include polybutadiene-based thermoplastic elastomer, polyisoprene-based thermoplastic elastomer, polyolefin-based thermoplastic elastomer, and acrylic-based thermoplastic elastomer.
- SB polystyrene-polybutadiene
- SBS polystyrene-polybutadiene-polystyrene
- SIS polystyrene-polyisoprene-polystyrene
- SEBS polystyrene-polyethylene / polybutylene-polystyrene
- ABS acrylonitrile-butadiene-styrene
- ACM acrylic ester rubber
- ACS acrylonitrile chlorinated polyethylene styrene copolymer
- acrylonitrile styrene copolymer syndiotactic 1,2-polybutadiene, polymethyl methacrylate-polybutyl acrylate-poly Examples thereof include methyl methacrylate.
- SBS and SIS are particularly preferable from the viewpoints of better water developability, and the viewpoint of drying property and image reproducibility.
- the specific polymer has reactive functional groups at both ends.
- the reactive functional group is not particularly limited, but is preferably an ethylenically unsaturated group because the effects of the present invention are more excellent.
- the ethylenically unsaturated group is a vinyl group (CH 2 ⁇ CH—), an allyl group (CH 2 ⁇ CH—CH 2 —), a (meth) acryloyl group, or, for the reason that the effects of the present invention are more excellent. It is preferably a (meth) acryloyl group, and more preferably a (meth) acryloyloxy group.
- the specific polymer may have a reactive functional group at both ends of the polymer constituting the main chain via a divalent linking group.
- the divalent linking group is not particularly limited, but is, for example, a linear, branched or cyclic divalent aliphatic hydrocarbon group (for example, an alkylene group such as a methylene group, an ethylene group or a propylene group), a divalent group.
- Aromatic hydrocarbon group (eg, phenylene group), —O—, —S—, —SO 2 —, —NR L —, —CO—, —NH—, —COO—, —CONR L —, —O —CO—O—, —SO 3 —, —NHCOO—, —SO 2 NR L —, —NH—CO—NH— or a group combining two or more thereof (eg, an alkyleneoxy group, an alkyleneoxycarbonyl group, Alkylene carbonyloxy group) and the like.
- R L represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
- the weight average molecular weight (Mw) of the specific polymer is 5,000 or more.
- the Mw of the specific polymer is preferably 6,000 or more, more preferably 7,000 or more, and further preferably 8,000 or more, for the reason that the effects of the present invention are more excellent. It is particularly preferable that it is 1,000 or more.
- the upper limit of Mw of the specific polymer is not particularly limited, it is preferably 500,000 or less, more preferably 100,000 or less for the reason that the effects of the present invention are more excellent.
- the weight average molecular weight is measured by a gel permeation chromatographic method (GPC) method, and is calculated by conversion with standard polystyrene.
- GPC gel permeation chromatographic method
- HLC-8220GPC manufactured by Tosoh Corporation
- TSKgeL Super HZM-H TSKgeL Super HZ4000
- TSKgeL Super HZ2000 manufactured by Tosoh Corporation, 4.6 mm ID ⁇ 15 cm
- THF tetrahydrofuran
- 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.
- an IR detector is used.
- the calibration curve is “standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “A-5000”, It is prepared from 8 samples of "A-2500", "A-1000” and "n-propylbenzene”.
- the HSP value of the specific polymer is not particularly limited, but is preferably 8 to 12, more preferably 8.5 to 11, and more preferably 8 to 11 for the reason that the effects of the present invention are more excellent. It is more preferably 5 to 10.5.
- the content of the specific polymer in the photosensitive layer of the present invention is preferably 1 to 50% by mass based on the total solid content of the photosensitive layer of the present invention, for the reason that the effects of the present invention are more excellent. It is more preferably 40% by mass, further preferably 7 to 30% by mass, and particularly preferably 10 to 20% by mass.
- the photosensitive layer of the present invention contains a polyfunctional monomer (specific monomer) having three or more ethylenically unsaturated groups.
- the specific monomer is not particularly limited as long as it is a compound having three or more ethylenically unsaturated groups.
- the ethylenically unsaturated group is a vinyl group (CH 2 ⁇ CH—), an allyl group (CH 2 ⁇ CH—CH 2 —), a (meth) acryloyl group, or, for the reason that the effects of the present invention are more excellent. It is preferably a (meth) acryloyl group, and more preferably a (meth) acryloyloxy group.
- Specific monomers include, for example, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, Tetramethylolmethane tetra (meth) acrylate, triallyl trimellitate and the like can be mentioned.
- the content of the specific monomer in the photosensitive layer of the present invention is preferably 1 to 40% by mass, based on the total solid content of the photosensitive layer of the present invention, for the reason that the effects of the present invention are more excellent. It is more preferably 30% by mass, further preferably 5 to 30% by mass, and particularly preferably 10 to 20% by mass.
- the ratio of the content of the above-mentioned specific monomer to the content of the above-mentioned specific polymer is preferably 5.0 or less in terms of mass ratio because the effect of the present invention is more excellent. , 3.0 or less is more preferable, 2.0 or less is more preferable, and 1.5 or less is particularly preferable.
- the lower limit of the ratio is not particularly limited, but is preferably 0.2 or more, more preferably 0.4 or more, further preferably 0.6 or more, and more preferably 0.7 or more. Particularly preferred.
- the ratio (mass ratio) of the content of the specific monomer described above to the content of the specific polymer described above is also referred to as “specific monomer / specific polymer”.
- the photosensitive layer of the present invention may contain a component (optional component) other than the above-mentioned components.
- the photosensitive layer of the present invention preferably contains a monofunctional monomer because the effects of the present invention are more excellent.
- the monofunctional monomer is preferably a compound having one ethylenically unsaturated group for the reason that the effects of the present invention are more excellent. Specific examples of the ethylenically unsaturated group are as described above.
- Examples of the compound having one ethylenically unsaturated group include: N-vinyl compounds such as N-vinylformamide; (Meth) acrylamide, N-methylol (meth) acrylamide, diacetone (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, (meth) (Meth) acrylamide compounds such as acryloylmorpholine and (meth) acrylamide; 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, tridecyl (meth) acrylate, 2 -Phenoxyethyl (me
- the content of the monofunctional monomer in the photosensitive layer of the present invention is preferably 0.1 to 30% by mass based on the total solid content of the photosensitive layer of the present invention, because the effects of the present invention are more excellent. It is more preferably 1 to 10% by mass.
- the ratio of the content of the monofunctional monomer described above to the content of the specific monomer described above is 1.0 or less in terms of mass ratio because the effect of the present invention is more excellent. It is preferably 0.5 or less, more preferably 0.4 or less.
- the lower limit of the ratio is not particularly limited, but is preferably 0.1 or more, more preferably 0.2 or more.
- the ratio (mass ratio) of the content of the above-mentioned monofunctional monomer to the content of the above-mentioned specific monomer is also referred to as "monofunctional monomer / specific monomer".
- the photosensitive layer of the present invention preferably contains a bifunctional monomer because the effects of the present invention are more excellent.
- the bifunctional monomer is preferably a compound having two ethylenically unsaturated groups, because the effects of the present invention are more excellent. Specific examples of the ethylenically unsaturated group are as described above.
- Examples of the compound having two ethylenically unsaturated groups include, for example, Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, di Propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol Glycol di (meth) acrylate compounds such as di (meth) acrylate; Divinyl ether compounds such as ethylene glycol divinyl ether, diethylene glycol diviny
- the content of the bifunctional monomer in the photosensitive layer of the present invention is preferably 0.1 to 30% by mass based on the total solid content of the photosensitive layer of the present invention, because the effects of the present invention are more excellent. ..
- the photosensitive layer of the present invention preferably contains a hydrophobic polymer because the effects of the present invention are more excellent.
- the hydrophobic polymer preferably does not have a reactive functional group (for example, a (meth) acryloyloxy group) at both ends. Further, it is preferable that the hydrophobic polymer does not have water dispersibility.
- the hydrophobic polymer is preferably a rubber, more preferably a diene rubber, and even more preferably a butadiene rubber, for the reason that the effects of the present invention are more excellent.
- the weight average molecular weight (Mw) of the hydrophobic polymer is not particularly limited, but is preferably 200,000 or more, and preferably 300,000 to 2,000,000 for the reason that the effects of the present invention are more excellent. Is more preferable, 300,000 to 1,500,000 is more preferable, 300,000 to 700,000 is particularly preferable.
- the content of the hydrophobic polymer in the photosensitive layer of the present invention is preferably 5 to 60 mass% with respect to the total solid content of the photosensitive layer of the present invention, for the reason that the effects of the present invention are more excellent. It is more preferably from about 40% by mass.
- the photosensitive layer of the present invention preferably contains a photopolymerization initiator because the effects of the present invention are more excellent.
- the photopolymerization initiator is not particularly limited, and examples thereof include photopolymerization initiators such as alkylphenones, acetophenones, benzoin ethers, benzophenones, thioxanthones, anthraquinones, benzyls, and biacetyls. More specifically, for example, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, methyl-o-benzoylbenzoate, 1-hydroxycyclohexyl phenyl ketone and the like can be mentioned.
- the content of the photopolymerization initiator in the photosensitive layer of the present invention is preferably 0.3 to 15% by mass based on the total solid content of the photosensitive layer of the present invention, from the viewpoint of sensitivity and the like. It is more preferably from about 10% by mass.
- the photosensitive layer of the present invention preferably contains a plasticizer for the reason that the flexibility is further improved.
- plasticizer examples include liquid rubber, oil, polyester, and phosphoric acid compounds.
- liquid rubber include liquid polybutadiene, liquid polyisoprene, and those obtained by modifying these with maleic acid or an epoxy group.
- oil examples include paraffin, naphthene, and aroma.
- polyester examples include adipic acid-based polyester.
- phosphoric acid compound examples include phosphoric acid esters.
- the content of the plasticizer in the photosensitive layer of the present invention is preferably 0.1 to 40% by mass based on the total solid content of the photosensitive layer of the present invention, for the reason of further improving flexibility. It is more preferably 30% by mass.
- the photosensitive layer of the present invention preferably contains a surfactant from the viewpoint of further improving water developability.
- the surfactant include a cationic surfactant, an anionic surfactant, and a nonionic surfactant. Among them, anionic surfactants are preferable because the effects of the present invention are more excellent.
- Aliphatic carboxylates such as sodium laurate and sodium oleate
- Higher alcohol sulfate salts such as sodium lauryl sulfate, sodium cetyl sulfate and sodium oleyl sulfate
- Polyoxyethylene alkyl allyl ether sulfuric acid ester salts such as sodium polyoxyethylene octyl phenyl ether sulfuric acid ester and sodium polyoxyethylene nonyl phenyl ether sulfuric acid ester
- Alkyl sulfonates such as alkyl diphenyl ether disulfonate, sodium dodecyl sulfonate, sodium dialkyl sulfosuccinate
- Alkyl allyl sulfonates such as alkyl disulfonate, sodium dodecylbenzene s
- sulfonic acid type surfactants such as alkyl sulfonates and alkyl allyl sulfonates are preferable because the water developability is further improved.
- the content of the surfactant in the photosensitive layer of the present invention is preferably 0.1 to 20% by mass based on the total solid content of the photosensitive layer of the present invention from the viewpoint of developability and drying property after development. Preferably, it is 1 to 10% by mass, and more preferably.
- the photosensitive layer of the present invention may contain a thermal polymerization inhibitor (stabilizer) from the viewpoints of enhancing the thermal stability during kneading, enhancing the storage stability, and the like.
- thermal polymerization inhibitors include phenols, hydroquinones, and catechols.
- the content of the thermal polymerization inhibitor in the photosensitive layer of the present invention is 0.001 to 5% by mass based on the total solid content of the photosensitive layer of the present invention, because the effects of the present invention are more excellent. preferable.
- an additive such as an ultraviolet absorber, a dye, a pigment, a defoaming agent, and a fragrance can be appropriately added within the range not impairing the effects of the present invention for the purpose of improving various characteristics. ..
- the method for producing the photosensitive layer of the present invention is not particularly limited, and examples thereof include a method of preparing a composition (photosensitive resin composition) containing each of the above-mentioned components, and coating the composition on a substrate or the like.
- the printing plate precursor of the present invention is a so-called analog type printing plate precursor in which a negative film (on which an image has already been formed) is brought into close contact with the photosensitive layer at the time of use because the effects of the present invention are more excellent.
- it is preferably a printing plate precursor of a LAM (Laseration mask) system included in a so-called CTP (Computer to plate) system in which an infrared ablation layer is in close contact with a photosensitive layer in advance.
- LAM Laseration mask
- CTP Computer to plate
- the analog type printing plate precursor is, for the reason that the effects of the present invention are more excellent, on the substrate, an adhesive layer made of an adhesive or the like for adhering the substrate and the photosensitive layer, the photosensitive layer of the present invention, and the photosensitive layer surface. It is preferable that an anti-adhesion layer for preventing the sticking of the photosensitive layer and a protective film for preventing scratches on the photosensitive layer before use are laminated in this order.
- the substrate include a plastic film or a plastic sheet such as a polyethylene terephthalate (PET) film; a metal sheet such as stainless steel or aluminum; a rubber sheet such as butadiene rubber;
- PET polyethylene terephthalate
- the protective film is peeled off at the time of use, and a negative film on which an image is formed in advance is adhered onto the exposed anti-adhesion layer.
- the analog type printing plate precursor is, for example, one side of the substrate is pre-coated with an adhesive, one side of the protective film is pre-coated with an anti-adhesive agent, the photosensitive resin composition described above, a substrate pre-coated with an adhesive. It can be manufactured by sandwiching it between a protective film coated with an anti-adhesive agent in advance and pressing it so that the thickness of the photosensitive layer becomes a predetermined thickness.
- the LAM printing plate precursor is different from the analog printing plate precursor in that it has an infrared ray ablation layer between the photosensitive layer and the protective film, and other configurations are the same as those of the analog printing plate precursor. It is the structure of. That is, the adhesive layer, the photosensitive layer, the infrared ablation layer, and the protective film are laminated in this order on the substrate. When using the LAM type printing plate precursor, the protective film is peeled off and the infrared ablation layer is exposed.
- the infrared ablation layer is a layer capable of removing a portion irradiated with an infrared laser, and is a layer which itself has a function of blocking transmission of ultraviolet rays at a practical level and forms an image on it. As a result, it can act as a negative or a positive.
- the infrared ablation layer is mainly composed of a binder resin or rubber, an infrared absorbing substance, an ultraviolet absorbing substance, a plasticizer, and the like.
- the infrared ablation layer can be produced, for example, by dissolving the above material in a solvent, applying the solution to a base material, and drying the solution to remove the solvent.
- the LAM printing plate precursor is, for example, a substrate on which one side of a substrate is coated with an adhesive in advance, one side of a protective film is coated with an infrared ablation layer in advance, and the photosensitive resin composition is coated with an adhesive in advance. It can be manufactured by sandwiching it between a protective film coated with an infrared ablation layer in advance and pressing it so that the photosensitive layer has a predetermined thickness.
- the thickness of the photosensitive layer is preferably in the range of 0.01 to 10 mm because the effects of the present invention are more excellent. If the thickness of the photosensitive layer is 0.01 mm or more, a sufficient relief depth can be secured.
- the flexographic printing plate of the present invention (hereinafter, also referred to as “printing plate of the present invention”) is a flexographic printing plate having an image portion and a non-image portion.
- the image area is an image area obtained by imagewise exposing and developing the photosensitive layer (the photosensitive layer of the invention) included in the printing plate precursor of the invention.
- the printing plate of the present invention is preferably obtained by the following method, because it is more excellent in printing durability, handling property, and rear end portion inking property.
- UV irradiation is performed from the substrate side of the printing plate precursor (back exposure).
- the photosensitive layer is cured by irradiating ultraviolet rays from above the negative film or infrared ablation layer (main exposure).
- Ultraviolet rays can be usually irradiated by a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp, a chemical lamp, or the like, which can irradiate light having a wavelength of 300 to 400 nm.
- the photosensitive layer is cured by irradiation with ultraviolet rays.
- the photosensitive layer covered with the negative film or the infrared ablation layer has a cured portion irradiated with ultraviolet rays and an uncured portion not irradiated with ultraviolet rays.
- a relief image is formed by removing the uncured portion of the photosensitive layer in a developing solution.
- a water-based developer (water-based developer) is used as the developer.
- the water-based developer is made of water to which a surfactant, a pH adjuster, or the like is added, if necessary.
- the uncured portion of the photosensitive layer can be removed by washing out the uncured portion using, for example, a spray type developing device or a brush type washing machine.
- the flexographic printing plate precursors of Examples and Comparative Examples were manufactured as follows.
- the manufactured flexographic printing plate precursor corresponds to the above-mentioned LAM printing plate precursor.
- Acrylic resin (Negami Kogyo, Hyper M-5000) 50 parts by mass, elastomer (Nippon Zeon, Nipol DN-101) 50 parts by mass, carbon black (Mitsubishi Chemical, MA-8) 100 parts by mass and methyl. 812 parts by mass of isobutyl ketone was added and mixed by stirring with a blade. The resulting mixed liquid was dispersed with a paint shaker, and then methyl isobutyl ketone was further added so that the solid content was 15% by mass to obtain a polymer / carbon black dispersion (infrared ablation layer coating liquid). Obtained.
- a coating liquid for infrared ablation layer was applied with a bar coater so that the thickness after drying was 1.0 ⁇ m, and then set at 140 ° C. By drying in the oven for 5 minutes, a laminate having an infrared ablation layer formed on the protective film (infrared ablation layer laminate) was produced.
- flexographic printing plate precursor Preparation of flexographic printing plate precursor
- An adhesive was applied to one side of a 125 ⁇ m thick PET film (substrate) to form an adhesive layer on the substrate.
- the photosensitive resin composition prepared as described above is sandwiched between the adhesive layer and the infrared ablation layer of the infrared ablation layer laminate prepared as described above to form a layer of the photosensitive resin composition (photosensitive layer).
- a flexographic printing plate precursor having a substrate, an adhesive layer, a photosensitive layer, an infrared ablation layer and a protective film in this order was prepared by pressing with a press machine heated to 80 ° C. so that the thickness of the layer) was 1 mm.
- Examples other than Example 1 and Comparative Examples> A flexographic printing plate precursor was produced according to the same procedure as in Example 1 except that the kind of each component in the photosensitive resin composition and the mass ratio (% by mass) to the total solid content were changed as shown in Table 1.
- the obtained flexographic printing plate precursor was exposed (back exposure) for 15 seconds from a distance of 15 cm from the substrate side using an exposure device in which 15 40 W chemical lamps were arranged. Then, the protective film was peeled off, and a negative pattern was formed on the infrared ablation layer using CDI Spark2120 manufactured by ESKO. Then, using the said exposure apparatus, it exposed (main exposure) from the infrared ablation layer side from the distance of 15 cm for 8 minutes. After that, development is carried out for 10 minutes using a brush-type washing machine (liquid temperature 50 ° C) containing an aqueous developer adjusted so that the concentration of detergent (made by Miyoshi soap, additive-free dishwashing soap) is 0.5%.
- a brush-type washing machine liquid temperature 50 ° C
- an aqueous developer adjusted so that the concentration of detergent (made by Miyoshi soap, additive-free dishwashing soap) is 0.5%.
- the flexographic printing plate thus obtained was evaluated for its rear end inking property as follows.
- a flexo printer manufactured by Taiyo Kikai, TLF-270
- the flexographic printing plate thus obtained was attached to a plate cylinder (drum) via a cushion tape (manufactured by Lohmann) and set on a printing machine.
- a kiss touch printing pressure at which the entire surface of the image starts to be inked
- 0 reference printing pressure
- -Nipol LX111NF manufactured by Japan ZEON water dispersion latex of polybutadiene, solid content 55% ⁇ Nippon A & L Smartex
- Kyoeisha Chemical's light ester TMP trimethylolpropane trimethacrylate
- Shin-Nakamura Kogyo Kagaku NK Ester A-GLY-9E structure below
- Kyoeisha Chemical Light Ester IB-X isobornyl methacrylate
- Asahi Kasei NF35R butadiene rubber
- the flexographic printing plate precursor having a photosensitive layer containing water-dispersible particles, a specific polymer and a specific monomer has excellent water developability and excellent printing durability when used as a flexographic printing plate. In addition, handling property and rear end part inking property were exhibited. From the comparison between the examples, Examples 1 to 9 and 11 in which the above-mentioned “specific monomer / specific polymer” was 3.0 or less showed more excellent rear end part inking property. Among them, Examples 1 to 2, 5 to 9 and 11 in which the above-mentioned “specific monomer / specific polymer” was 2.0 or less showed further excellent rear end part inking property.
- Examples 1 to 10 in which the above-mentioned “monofunctional monomer / specific monomer” was 0.5 or less showed more excellent printing durability and handleability.
- Examples 1 to 5 and 7 to 10 in which the above-mentioned “monofunctional monomer / specific monomer” was 0.4 or less showed further excellent printing durability and handling property.
- a flexographic printing plate precursor and a flexographic printing plate were manufactured according to the same procedure except that an analog type printing plate original plate was used instead of the LAM type printing plate original plate, and evaluated in the same manner. As a result, the same results as in Table 1 were obtained.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Materials For Photolithography (AREA)
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- Manufacture Or Reproduction Of Printing Formes (AREA)
Abstract
The purpose of the present invention is to provide: a flexographic printing plate precursor which has excellent water developability and with which a flexographic printing plate having excellent printing durability, handleability, and rear end ink receptivity can be obtained; and a flexographic printing plate obtained by exposing and developing the flexographic printing plate precursor. The water-developable flexographic printing plate precursor according to the present invention has a photosensitive layer containing: water-dispersible particles; a polymer having reactive functional groups at both ends thereof and having a weight average molecular weight of at least 5,000; and a polyfunctional monomer having three or more ethylenically unsaturated groups.
Description
本発明は、フレキソ印刷版原版及びフレキソ印刷版に関する。
The present invention relates to a flexographic printing plate precursor and a flexographic printing plate.
フレキソ印刷は、アニロックスロール等を用いて印刷版状の凸部にインキをつけて、被印刷体に転写する印刷方式である。フレキソ印刷に使用されるフレキソ印刷版としては、例えば、感光層を有するフレキソ印刷版原版を画像様に露光及び現像したものなどが用いられている。
一方、作業環境改善や地球環境の保全の観点から有機溶剤の使用を減らそうという動きが各種産業界から出ており、フレキソ印刷版原版についても水系現像液で現像することが可能なものが求められている。
例えば、特許文献1の請求項1には、フレキソ印刷版原版にしたときに水系現像液で現像できるとされる感光性樹脂組成物が開示されている。 Flexographic printing is a printing method in which ink is applied to the convex portions of a printing plate using an anilox roll or the like and transferred to a printing medium. As the flexographic printing plate used in flexographic printing, for example, a flexographic printing plate precursor having a photosensitive layer, which is imagewise exposed and developed, is used.
On the other hand, there is a movement from various industries to reduce the use of organic solvents from the viewpoint of improving the working environment and preserving the global environment, and flexographic printing plate precursors are also required to be developable with an aqueous developer. Has been.
For example, claim 1 of Patent Document 1 discloses a photosensitive resin composition which can be developed with an aqueous developer when used as a flexographic printing plate precursor.
一方、作業環境改善や地球環境の保全の観点から有機溶剤の使用を減らそうという動きが各種産業界から出ており、フレキソ印刷版原版についても水系現像液で現像することが可能なものが求められている。
例えば、特許文献1の請求項1には、フレキソ印刷版原版にしたときに水系現像液で現像できるとされる感光性樹脂組成物が開示されている。 Flexographic printing is a printing method in which ink is applied to the convex portions of a printing plate using an anilox roll or the like and transferred to a printing medium. As the flexographic printing plate used in flexographic printing, for example, a flexographic printing plate precursor having a photosensitive layer, which is imagewise exposed and developed, is used.
On the other hand, there is a movement from various industries to reduce the use of organic solvents from the viewpoint of improving the working environment and preserving the global environment, and flexographic printing plate precursors are also required to be developable with an aqueous developer. Has been.
For example, claim 1 of Patent Document 1 discloses a photosensitive resin composition which can be developed with an aqueous developer when used as a flexographic printing plate precursor.
このようななか、本発明者が特許文献1の実施例に記載の感光性樹脂組成物を用いてフレキソ印刷版原版を作製したところ、確かに水系現像液による現像性(水現像性)に優れることが確認されたが、一方で、上記フレキソ印刷版原版を用いてフレキソ印刷版を作製したところ、画像部の欠け折れは生じ難い(耐刷性及びハンドリング性に優れる)ものの、後端部で白抜けが発生し易い(後端部着肉性が不十分であること)が明らかになった。
Under such circumstances, when the present inventor produced a flexographic printing plate precursor using the photosensitive resin composition described in Example of Patent Document 1, it was confirmed that the flexographic printing plate precursor was certainly excellent in developability (water developability) with an aqueous developer. On the other hand, when a flexographic printing plate was prepared using the above flexographic printing plate precursor, chipping and folding of the image area was less likely to occur (excellent in printing durability and handling), but white at the rear edge. It became clear that slip-out easily occurs (the rear end part has insufficient inking property).
そこで、本発明は、上記実情に鑑みて、水現像性に優れ、且つ、フレキソ印刷版にしたときに優れた耐刷性、ハンドリング性及び後端部着肉性を示す、フレキソ印刷版原版、並びに、上記フレキソ印刷版原版を露光及び現像することにより得られるフレキソ印刷版を提供することを課題とする。
Therefore, in view of the above situation, the present invention is excellent in water developability, and exhibits excellent printing durability, handling property and rear end inking property when made into a flexographic printing plate, a flexographic printing plate precursor, Another object is to provide a flexographic printing plate obtained by exposing and developing the above flexographic printing plate precursor.
本発明者は、上記課題について鋭意検討した結果、水分散性粒子と、両末端に反応性官能基を有する重量平均分子量が5,000以上のポリマーと、エチレン性不飽和基を3つ以上有する多官能モノマーとを併用することで、上記課題が解決できることを見出し、本発明に至った。
すなわち、本発明者は、以下の構成により上記課題が解決できることを見出した。 As a result of diligent studies on the above problems, the present inventor has water-dispersible particles, a polymer having reactive functional groups at both ends and having a weight average molecular weight of 5,000 or more, and three or more ethylenically unsaturated groups. The inventors have found that the above problem can be solved by using a polyfunctional monomer in combination, and completed the present invention.
That is, the present inventor has found that the above problems can be solved by the following configurations.
すなわち、本発明者は、以下の構成により上記課題が解決できることを見出した。 As a result of diligent studies on the above problems, the present inventor has water-dispersible particles, a polymer having reactive functional groups at both ends and having a weight average molecular weight of 5,000 or more, and three or more ethylenically unsaturated groups. The inventors have found that the above problem can be solved by using a polyfunctional monomer in combination, and completed the present invention.
That is, the present inventor has found that the above problems can be solved by the following configurations.
(1) 水分散性粒子と、両末端に反応性官能基を有する重量平均分子量が5,000以上のポリマーと、エチレン性不飽和基を3つ以上有する多官能モノマーとを含有する感光層を有する、水現像性フレキソ印刷版原版。
(2) 上記感光層が、さらに、単官能モノマーを含有する、上記(1)に記載の水現像性フレキソ印刷版原版。
(3) 上記感光層において、上記多官能モノマーの含有量に対する上記単官能モノマーの含有量の比率が、質量比で、0.5以下である、上記(2)に記載の水現像性フレキソ印刷版原版。
(4) 上記感光層において、上記ポリマーの含有量に対する上記多官能モノマーの含有量の比率が、質量比で、3.0以下である、上記(1)~(3)のいずれかに記載の水現像性フレキソ印刷版原版。
(5) 画像部と非画像部とを有するフレキソ印刷版であって、
上記画像部が、上記(1)~(4)のいずれかに記載の水現像性フレキソ印刷版原版が有する感光層を画像様に露光し、現像することにより得られる画像部である、フレキソ印刷版。 (1) A photosensitive layer containing water-dispersible particles, a polymer having a reactive functional group at both ends and having a weight average molecular weight of 5,000 or more, and a polyfunctional monomer having three or more ethylenically unsaturated groups. A water-developable flexographic printing plate precursor.
(2) The water-developable flexographic printing plate precursor as described in (1) above, wherein the photosensitive layer further contains a monofunctional monomer.
(3) The water-developable flexographic printing according to (2), wherein the ratio of the content of the monofunctional monomer to the content of the polyfunctional monomer in the photosensitive layer is 0.5 or less in terms of mass ratio. Original edition.
(4) The photosensitive layer as described in any one of (1) to (3) above, wherein the ratio of the content of the polyfunctional monomer to the content of the polymer is 3.0 or less in terms of mass ratio. Water-developable flexographic printing plate precursor.
(5) A flexographic printing plate having an image portion and a non-image portion,
Flexographic printing, wherein the image area is an image area obtained by imagewise exposing and developing the photosensitive layer of the water-developable flexographic printing plate precursor according to any one of (1) to (4) above. Edition.
(2) 上記感光層が、さらに、単官能モノマーを含有する、上記(1)に記載の水現像性フレキソ印刷版原版。
(3) 上記感光層において、上記多官能モノマーの含有量に対する上記単官能モノマーの含有量の比率が、質量比で、0.5以下である、上記(2)に記載の水現像性フレキソ印刷版原版。
(4) 上記感光層において、上記ポリマーの含有量に対する上記多官能モノマーの含有量の比率が、質量比で、3.0以下である、上記(1)~(3)のいずれかに記載の水現像性フレキソ印刷版原版。
(5) 画像部と非画像部とを有するフレキソ印刷版であって、
上記画像部が、上記(1)~(4)のいずれかに記載の水現像性フレキソ印刷版原版が有する感光層を画像様に露光し、現像することにより得られる画像部である、フレキソ印刷版。 (1) A photosensitive layer containing water-dispersible particles, a polymer having a reactive functional group at both ends and having a weight average molecular weight of 5,000 or more, and a polyfunctional monomer having three or more ethylenically unsaturated groups. A water-developable flexographic printing plate precursor.
(2) The water-developable flexographic printing plate precursor as described in (1) above, wherein the photosensitive layer further contains a monofunctional monomer.
(3) The water-developable flexographic printing according to (2), wherein the ratio of the content of the monofunctional monomer to the content of the polyfunctional monomer in the photosensitive layer is 0.5 or less in terms of mass ratio. Original edition.
(4) The photosensitive layer as described in any one of (1) to (3) above, wherein the ratio of the content of the polyfunctional monomer to the content of the polymer is 3.0 or less in terms of mass ratio. Water-developable flexographic printing plate precursor.
(5) A flexographic printing plate having an image portion and a non-image portion,
Flexographic printing, wherein the image area is an image area obtained by imagewise exposing and developing the photosensitive layer of the water-developable flexographic printing plate precursor according to any one of (1) to (4) above. Edition.
以下に示すように、本発明によれば、水現像性に優れ、且つ、フレキソ印刷版にしたときに優れた耐刷性、ハンドリング性及び後端部着肉性を示す、フレキソ印刷版原版、並びに、上記フレキソ印刷版原版を露光及び現像することにより得られるフレキソ印刷版を提供することができる。
As shown below, according to the present invention, excellent in water developability, and, when it is a flexographic printing plate, showing excellent printing durability, handling property and rear end inking property, flexographic printing plate precursor, In addition, a flexographic printing plate obtained by exposing and developing the above flexographic printing plate precursor can be provided.
以下、本発明について詳細に説明する。
以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。
なお、本明細書において、「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
また、各成分は、1種を単独でも用いても、2種以上を併用してもよい。ここで、各成分について2種以上を併用する場合、その成分について含有量とは、特段の断りが無い限り、合計の含有量を指す。
また、「(メタ)アクリル」は、「アクリル」または「メタクリル」を表す表記であり、「(メタ)アクリレート」は、「アクリレート」または「メタクリレート」を表す表記であり、「(メタ)アクリロイル」は、「アクリロイル」または「メタクリロイル」を表す表記である。 Hereinafter, the present invention will be described in detail.
The description of the constituents described below may be made based on a typical embodiment of the present invention, but the present invention is not limited to such an embodiment.
In the present specification, the numerical range represented by “to” means a range including the numerical values before and after “to” as the lower limit value and the upper limit value.
In addition, each component may be used alone or in combination of two or more. Here, when two or more kinds of each component are used in combination, the content of the component means the total content unless otherwise specified.
Further, "(meth) acrylic" is a notation representing "acrylic" or "methacrylic", "(meth) acrylate" is a notation representing "acrylate" or "methacrylate", and "(meth) acryloyl" Is a notation representing "acryloyl" or "methacryloyl".
以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。
なお、本明細書において、「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
また、各成分は、1種を単独でも用いても、2種以上を併用してもよい。ここで、各成分について2種以上を併用する場合、その成分について含有量とは、特段の断りが無い限り、合計の含有量を指す。
また、「(メタ)アクリル」は、「アクリル」または「メタクリル」を表す表記であり、「(メタ)アクリレート」は、「アクリレート」または「メタクリレート」を表す表記であり、「(メタ)アクリロイル」は、「アクリロイル」または「メタクリロイル」を表す表記である。 Hereinafter, the present invention will be described in detail.
The description of the constituents described below may be made based on a typical embodiment of the present invention, but the present invention is not limited to such an embodiment.
In the present specification, the numerical range represented by “to” means a range including the numerical values before and after “to” as the lower limit value and the upper limit value.
In addition, each component may be used alone or in combination of two or more. Here, when two or more kinds of each component are used in combination, the content of the component means the total content unless otherwise specified.
Further, "(meth) acrylic" is a notation representing "acrylic" or "methacrylic", "(meth) acrylate" is a notation representing "acrylate" or "methacrylate", and "(meth) acryloyl" Is a notation representing "acryloyl" or "methacryloyl".
[水現像性フレキソ印刷版原版]
本発明の水現像性フレキソ印刷版原版(以下、「本発明の印刷版原版」とも言う)は、水分散性粒子と、両末端に反応性官能基を有する重量平均分子量が5,000以上のポリマー(以下、「特定ポリマー」とも言う)と、エチレン性不飽和基を3つ以上有する多官能モノマー(以下、「特定モノマー」とも言う)とを含有する感光層を有する、水現像性フレキソ印刷版原版である。 [Water-developable flexographic printing plate precursor]
The water-developable flexographic printing plate precursor of the invention (hereinafter, also referred to as “printing plate precursor of the invention”) has water-dispersible particles and a weight average molecular weight of 5,000 or more having reactive functional groups at both ends. Water-developable flexographic printing having a photosensitive layer containing a polymer (hereinafter, also referred to as "specific polymer") and a polyfunctional monomer having three or more ethylenically unsaturated groups (hereinafter, also referred to as "specific monomer") The original version.
本発明の水現像性フレキソ印刷版原版(以下、「本発明の印刷版原版」とも言う)は、水分散性粒子と、両末端に反応性官能基を有する重量平均分子量が5,000以上のポリマー(以下、「特定ポリマー」とも言う)と、エチレン性不飽和基を3つ以上有する多官能モノマー(以下、「特定モノマー」とも言う)とを含有する感光層を有する、水現像性フレキソ印刷版原版である。 [Water-developable flexographic printing plate precursor]
The water-developable flexographic printing plate precursor of the invention (hereinafter, also referred to as “printing plate precursor of the invention”) has water-dispersible particles and a weight average molecular weight of 5,000 or more having reactive functional groups at both ends. Water-developable flexographic printing having a photosensitive layer containing a polymer (hereinafter, also referred to as "specific polymer") and a polyfunctional monomer having three or more ethylenically unsaturated groups (hereinafter, also referred to as "specific monomer") The original version.
本発明の印刷版原版はこのような構成をとるため、上述した効果が得られるものと考えらえる。その理由は明らかではないが、両末端に反応性官能基を有する重量平均分子量が5,000以上のポリマー(特定ポリマー)とエチレン性不飽和基を3つ以上有する多官能モノマー(特定モノマー)とが強靭性とゴム弾性に優れた3次元構造を形成するためと考えられる。
Since the printing plate precursor of the present invention has such a configuration, it can be considered that the above-mentioned effects can be obtained. Although the reason for this is not clear, a polymer having a reactive functional group at both ends and having a weight average molecular weight of 5,000 or more (specific polymer) and a polyfunctional monomer having three or more ethylenically unsaturated groups (specific monomer) are used. Is considered to form a three-dimensional structure excellent in toughness and rubber elasticity.
以下、まず本発明の印刷版原版が有する感光層について説明してから、本発明の印刷版原版の好適な態様について説明する。
Hereinafter, first, the photosensitive layer of the printing plate precursor of the invention will be described, and then preferred embodiments of the printing plate precursor of the invention will be described.
〔感光層〕
本発明の印刷版原版が有する感光層(以下、「本発明の感光層」とも言う)は、水分散性粒子と、両末端に反応性官能基を有する重量平均分子量が5,000以上のポリマー(特定ポリマー)と、エチレン性不飽和基を3つ以上有する多官能モノマー(特定モノマー)とを含有する感光層を有する。
以下、感光層に含有される各成分について説明する。 [Photosensitive layer]
The photosensitive layer of the printing plate precursor of the present invention (hereinafter, also referred to as “the photosensitive layer of the present invention”) is a water-dispersible particle and a polymer having a reactive functional group at both ends and having a weight average molecular weight of 5,000 or more. It has a photosensitive layer containing (specific polymer) and a polyfunctional monomer (specific monomer) having three or more ethylenically unsaturated groups.
Hereinafter, each component contained in the photosensitive layer will be described.
本発明の印刷版原版が有する感光層(以下、「本発明の感光層」とも言う)は、水分散性粒子と、両末端に反応性官能基を有する重量平均分子量が5,000以上のポリマー(特定ポリマー)と、エチレン性不飽和基を3つ以上有する多官能モノマー(特定モノマー)とを含有する感光層を有する。
以下、感光層に含有される各成分について説明する。 [Photosensitive layer]
The photosensitive layer of the printing plate precursor of the present invention (hereinafter, also referred to as “the photosensitive layer of the present invention”) is a water-dispersible particle and a polymer having a reactive functional group at both ends and having a weight average molecular weight of 5,000 or more. It has a photosensitive layer containing (specific polymer) and a polyfunctional monomer (specific monomer) having three or more ethylenically unsaturated groups.
Hereinafter, each component contained in the photosensitive layer will be described.
<水分散性粒子>
上述のとおり、本発明の感光層は水分散性粒子を含有する。
水分散性粒子は特に制限されないが、水分散性がより優れ、得られるフレキソ印刷版の耐刷性、ハンドリング性及び後端部着肉性がより優れ、現像再現性及びベタ品質に優れ、印圧ラティチュードが広くなる理由から、重合体であることが好ましい。以下、「水分散性がより優れ、得られるフレキソ印刷版の耐刷性、ハンドリング性及び後端部着肉性がより優れ、現像再現性及びベタ品質に優れ、印圧ラティチュードが広くなる」ことを「本発明の効果等がより優れる」とも言う。
上記重合体の具体例としては、ジエン系ポリマー(例えば、ポリブタジエン、天然ゴム、スチレン-ブタジエン共重合体、アクリロニトリル-ブタジエン共重合体、メチルメタクリレート-ブタジエン共重合体、ポリクロロプレン、ポリイソプレン)、ポリウレタン、ビニルピリジン重合体、ブチル重合体、チオコール重合体、アクリレート重合体、これら重合体にアクリル酸、メタクリル酸などの他の成分を共重合して得られる重合体等が挙げられ、これらを1種単独で用いてもよく、2種以上を併用してもよい。
上記重合体は、本発明の効果等がより優れる理由から、ジエン系ポリマーであることが好ましく、ポリブタジエンであることがより好ましい。
上記重合体は、両末端に反応性官能基(例えば、(メタ)アクリロイルオキシ基)を有さないものであることが好ましい。 <Water dispersible particles>
As described above, the photosensitive layer of the present invention contains water-dispersible particles.
The water-dispersible particles are not particularly limited, but the water dispersibility is more excellent, the flexographic printing plate obtained has more printing durability, handling property and rear end part inking property, and is excellent in development reproducibility and solid quality. A polymer is preferable for the reason that the pressure latitude becomes wide. Hereinafter, "more excellent water dispersibility, printing durability of the resulting flexographic printing plate, handling property and trailing edge part inking property are more excellent, development reproducibility and solid quality are excellent, and printing pressure latitude is wide" Is also referred to as "the effect of the present invention is more excellent".
Specific examples of the polymer include diene-based polymers (eg, polybutadiene, natural rubber, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, methylmethacrylate-butadiene copolymer, polychloroprene, polyisoprene), polyurethane. , Vinyl pyridine polymers, butyl polymers, thiochol polymers, acrylate polymers, polymers obtained by copolymerizing these polymers with other components such as acrylic acid and methacrylic acid, and the like. They may be used alone or in combination of two or more.
The polymer is preferably a diene polymer, more preferably polybutadiene, for the reason that the effects of the present invention are more excellent.
The polymer preferably does not have a reactive functional group (for example, a (meth) acryloyloxy group) at both ends.
上述のとおり、本発明の感光層は水分散性粒子を含有する。
水分散性粒子は特に制限されないが、水分散性がより優れ、得られるフレキソ印刷版の耐刷性、ハンドリング性及び後端部着肉性がより優れ、現像再現性及びベタ品質に優れ、印圧ラティチュードが広くなる理由から、重合体であることが好ましい。以下、「水分散性がより優れ、得られるフレキソ印刷版の耐刷性、ハンドリング性及び後端部着肉性がより優れ、現像再現性及びベタ品質に優れ、印圧ラティチュードが広くなる」ことを「本発明の効果等がより優れる」とも言う。
上記重合体の具体例としては、ジエン系ポリマー(例えば、ポリブタジエン、天然ゴム、スチレン-ブタジエン共重合体、アクリロニトリル-ブタジエン共重合体、メチルメタクリレート-ブタジエン共重合体、ポリクロロプレン、ポリイソプレン)、ポリウレタン、ビニルピリジン重合体、ブチル重合体、チオコール重合体、アクリレート重合体、これら重合体にアクリル酸、メタクリル酸などの他の成分を共重合して得られる重合体等が挙げられ、これらを1種単独で用いてもよく、2種以上を併用してもよい。
上記重合体は、本発明の効果等がより優れる理由から、ジエン系ポリマーであることが好ましく、ポリブタジエンであることがより好ましい。
上記重合体は、両末端に反応性官能基(例えば、(メタ)アクリロイルオキシ基)を有さないものであることが好ましい。 <Water dispersible particles>
As described above, the photosensitive layer of the present invention contains water-dispersible particles.
The water-dispersible particles are not particularly limited, but the water dispersibility is more excellent, the flexographic printing plate obtained has more printing durability, handling property and rear end part inking property, and is excellent in development reproducibility and solid quality. A polymer is preferable for the reason that the pressure latitude becomes wide. Hereinafter, "more excellent water dispersibility, printing durability of the resulting flexographic printing plate, handling property and trailing edge part inking property are more excellent, development reproducibility and solid quality are excellent, and printing pressure latitude is wide" Is also referred to as "the effect of the present invention is more excellent".
Specific examples of the polymer include diene-based polymers (eg, polybutadiene, natural rubber, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, methylmethacrylate-butadiene copolymer, polychloroprene, polyisoprene), polyurethane. , Vinyl pyridine polymers, butyl polymers, thiochol polymers, acrylate polymers, polymers obtained by copolymerizing these polymers with other components such as acrylic acid and methacrylic acid, and the like. They may be used alone or in combination of two or more.
The polymer is preferably a diene polymer, more preferably polybutadiene, for the reason that the effects of the present invention are more excellent.
The polymer preferably does not have a reactive functional group (for example, a (meth) acryloyloxy group) at both ends.
上記重合体は、本発明の効果等がより優れる理由から、水分散ラテックスから水を除去することで得られる重合体であることが好ましい。上記水分散ラテックスの具体例としては、上述した重合体の具体例の水分散ラテックスが挙げられる。
The above-mentioned polymer is preferably a polymer obtained by removing water from the water-dispersed latex because the effect of the present invention is more excellent. Specific examples of the above water-dispersed latex include the water-dispersed latex of the above-mentioned specific examples of the polymer.
本発明の感光層において水分散性粒子の含有量は、本発明の効果等がより優れる理由から、本発明の感光層の全固形分に対して、5~80質量%であることが好ましく、10~50質量%であることがより好ましく、20~40質量%であることがさらに好ましい。
The content of the water-dispersible particles in the photosensitive layer of the present invention is preferably 5 to 80% by mass based on the total solid content of the photosensitive layer of the present invention, because the effects of the present invention are more excellent. The amount is more preferably 10 to 50% by mass, further preferably 20 to 40% by mass.
<特定ポリマー>
上述のとおり、本発明の感光層は、両末端に反応性官能基を有する重量平均分子量が5,000以上のポリマー(特定ポリマー)を含有する。
特定ポリマーは、両末端に反応性官能基を有し、且つ、重量平均分子量が5,000以上のポリマーである。
特定ポリマーは、水分散性を有さないものであることが好ましい。
なお、本明細書において、「テレケリックポリマー」とは、両末端に反応性官能基を有するポリマーを言い、「特定ポリマー」とは、テレケリックポリマーのうち重量平均分子量が5,000以上のものを言う。 <Specific polymer>
As described above, the photosensitive layer of the present invention contains a polymer (specific polymer) having a reactive functional group at both ends and having a weight average molecular weight of 5,000 or more.
The specific polymer is a polymer having reactive functional groups at both ends and having a weight average molecular weight of 5,000 or more.
It is preferable that the specific polymer does not have water dispersibility.
In the present specification, "telechelic polymer" refers to a polymer having reactive functional groups at both ends, and "specific polymer" is a telechelic polymer having a weight average molecular weight of 5,000 or more. Say
上述のとおり、本発明の感光層は、両末端に反応性官能基を有する重量平均分子量が5,000以上のポリマー(特定ポリマー)を含有する。
特定ポリマーは、両末端に反応性官能基を有し、且つ、重量平均分子量が5,000以上のポリマーである。
特定ポリマーは、水分散性を有さないものであることが好ましい。
なお、本明細書において、「テレケリックポリマー」とは、両末端に反応性官能基を有するポリマーを言い、「特定ポリマー」とは、テレケリックポリマーのうち重量平均分子量が5,000以上のものを言う。 <Specific polymer>
As described above, the photosensitive layer of the present invention contains a polymer (specific polymer) having a reactive functional group at both ends and having a weight average molecular weight of 5,000 or more.
The specific polymer is a polymer having reactive functional groups at both ends and having a weight average molecular weight of 5,000 or more.
It is preferable that the specific polymer does not have water dispersibility.
In the present specification, "telechelic polymer" refers to a polymer having reactive functional groups at both ends, and "specific polymer" is a telechelic polymer having a weight average molecular weight of 5,000 or more. Say
(主鎖)
特定ポリマーの主鎖を構成するポリマーは特に制限されないが、例えば、熱可塑性ポリマーなどが挙げられる。
上記熱可塑性ポリマーは、熱可塑性を示すポリマーであれば特に限定されず、その具体例としては、ポリスチレン樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリイミド樹脂、アクリル樹脂、アセタール樹脂、エポキシ樹脂、ポリカーボネート樹脂、ゴム、熱可塑性エラストマーなどが挙げられる。
これらのうち、より柔軟で可撓性を有する膜が形成されやすくなる理由から、ゴム、熱可塑性エラストマーが好ましく、ゴムがより好ましく、ジエン系ゴムがさらに好ましい。 (Main chain)
The polymer constituting the main chain of the specific polymer is not particularly limited, and examples thereof include thermoplastic polymers.
The thermoplastic polymer is not particularly limited as long as it is a polymer exhibiting thermoplasticity, and specific examples thereof include polystyrene resin, polyester resin, polyamide resin, polysulfone resin, polyether sulfone resin, polyimide resin, acrylic resin, acetal resin. , Epoxy resin, polycarbonate resin, rubber, thermoplastic elastomer and the like.
Of these, rubber and thermoplastic elastomers are preferred, rubber is more preferred, and diene rubber is even more preferred, because a softer and more flexible film is likely to be formed.
特定ポリマーの主鎖を構成するポリマーは特に制限されないが、例えば、熱可塑性ポリマーなどが挙げられる。
上記熱可塑性ポリマーは、熱可塑性を示すポリマーであれば特に限定されず、その具体例としては、ポリスチレン樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリイミド樹脂、アクリル樹脂、アセタール樹脂、エポキシ樹脂、ポリカーボネート樹脂、ゴム、熱可塑性エラストマーなどが挙げられる。
これらのうち、より柔軟で可撓性を有する膜が形成されやすくなる理由から、ゴム、熱可塑性エラストマーが好ましく、ゴムがより好ましく、ジエン系ゴムがさらに好ましい。 (Main chain)
The polymer constituting the main chain of the specific polymer is not particularly limited, and examples thereof include thermoplastic polymers.
The thermoplastic polymer is not particularly limited as long as it is a polymer exhibiting thermoplasticity, and specific examples thereof include polystyrene resin, polyester resin, polyamide resin, polysulfone resin, polyether sulfone resin, polyimide resin, acrylic resin, acetal resin. , Epoxy resin, polycarbonate resin, rubber, thermoplastic elastomer and the like.
Of these, rubber and thermoplastic elastomers are preferred, rubber is more preferred, and diene rubber is even more preferred, because a softer and more flexible film is likely to be formed.
上記ゴムとしては、具体的には、例えば、ブタジエンゴム(BR)、ニトリルゴム(NBR)、アクリルゴム、エピクロルヒドリンゴム、ウレタンゴム、イソプレンゴム、スチレンイソプレンゴム、スチレンブタジエンゴム、エチレン-プロピレン共重合体、塩素化ポリエチレンなどが挙げられ、これらを1種単独で用いてもよく、2種以上を併用してもよい。これらのうち、水現像性がより良好となる理由、また、乾燥性および画像再現性の観点から、ブタジエンゴム(BR)およびニトリルゴム(NBR)からなる群から選択される少なくとも1種のゴムであることが好ましく、ブタジエンゴムがより好ましい。
Specific examples of the rubber include butadiene rubber (BR), nitrile rubber (NBR), acrylic rubber, epichlorohydrin rubber, urethane rubber, isoprene rubber, styrene isoprene rubber, styrene butadiene rubber, ethylene-propylene copolymer. , Chlorinated polyethylene and the like, and these may be used alone or in combination of two or more. Of these, at least one rubber selected from the group consisting of butadiene rubber (BR) and nitrile rubber (NBR) is used for the reason that the water developability is better, and from the viewpoint of the drying property and the image reproducibility. Preferably, butadiene rubber is more preferable.
上記熱可塑性エラストマーとしては、ポリブタジエン系熱可塑性エラストマー、ポリイソプレン系熱可塑性エラストマー、ポリオレフィン系熱可塑性エラストマー、アクリル系熱可塑性エラストマーが挙げられる。具体的には、例えば、SB(ポリスチレン-ポリブタジエン)、SBS(ポリスチレン-ポリブタジエン-ポリスチレン)、SIS(ポリスチレン-ポリイソプレン-ポリスチレン)、SEBS(ポリスチレン-ポリエチレン/ポリブチレン-ポリスチレン)、ABS(アクリロニトリルブタジエンスチレン共重合体)、ACM(アクリル酸エステルゴム)、ACS(アクリロニトリル塩素化ポリエチレンスチレン共重合体)、アクリロニトリルスチレン共重合体、シンジオタクチック1,2-ポリブタジエン、ポリメタクリル酸メチル-ポリアクリル酸ブチル-ポリメタクリル酸メチルなどが挙げられる。これらのうち、水現像性がより良好となる理由、また、乾燥性および画像再現性の観点から、SBS、SISが特に好ましい。
Examples of the thermoplastic elastomer include polybutadiene-based thermoplastic elastomer, polyisoprene-based thermoplastic elastomer, polyolefin-based thermoplastic elastomer, and acrylic-based thermoplastic elastomer. Specifically, for example, SB (polystyrene-polybutadiene), SBS (polystyrene-polybutadiene-polystyrene), SIS (polystyrene-polyisoprene-polystyrene), SEBS (polystyrene-polyethylene / polybutylene-polystyrene), ABS (acrylonitrile-butadiene-styrene) Polymer), ACM (acrylic ester rubber), ACS (acrylonitrile chlorinated polyethylene styrene copolymer), acrylonitrile styrene copolymer, syndiotactic 1,2-polybutadiene, polymethyl methacrylate-polybutyl acrylate-poly Examples thereof include methyl methacrylate. Among these, SBS and SIS are particularly preferable from the viewpoints of better water developability, and the viewpoint of drying property and image reproducibility.
(末端)
特定ポリマーは、両末端に反応性官能基を有する。
上記反応性官能基は特に制限されないが、本発明の効果等がより優れる理由から、エチレン性不飽和基であることが好ましい。
上記エチレン性不飽和基は、本発明の効果等がより優れる理由から、ビニル基(CH2=CH-)、アリル基(CH2=CH-CH2-)、(メタ)アクリロイル基、又は、(メタ)アクリロイル基であることが好ましく、(メタ)アクリロイルオキシ基であることがより好ましい。 (End)
The specific polymer has reactive functional groups at both ends.
The reactive functional group is not particularly limited, but is preferably an ethylenically unsaturated group because the effects of the present invention are more excellent.
The ethylenically unsaturated group is a vinyl group (CH 2 ═CH—), an allyl group (CH 2 ═CH—CH 2 —), a (meth) acryloyl group, or, for the reason that the effects of the present invention are more excellent. It is preferably a (meth) acryloyl group, and more preferably a (meth) acryloyloxy group.
特定ポリマーは、両末端に反応性官能基を有する。
上記反応性官能基は特に制限されないが、本発明の効果等がより優れる理由から、エチレン性不飽和基であることが好ましい。
上記エチレン性不飽和基は、本発明の効果等がより優れる理由から、ビニル基(CH2=CH-)、アリル基(CH2=CH-CH2-)、(メタ)アクリロイル基、又は、(メタ)アクリロイル基であることが好ましく、(メタ)アクリロイルオキシ基であることがより好ましい。 (End)
The specific polymer has reactive functional groups at both ends.
The reactive functional group is not particularly limited, but is preferably an ethylenically unsaturated group because the effects of the present invention are more excellent.
The ethylenically unsaturated group is a vinyl group (CH 2 ═CH—), an allyl group (CH 2 ═CH—CH 2 —), a (meth) acryloyl group, or, for the reason that the effects of the present invention are more excellent. It is preferably a (meth) acryloyl group, and more preferably a (meth) acryloyloxy group.
特定ポリマーは、主鎖を構成するポリマーの両末端に2価の連結基を介して反応性官能基を有していてもよい。
上記2価の連結基は特に制限されないが、例えば、直鎖状、分岐状若しくは環状の2価の脂肪族炭化水素基(例えば、メチレン基、エチレン基、プロピレン基などのアルキレン基)、2価の芳香族炭化水素基(例えば、フェニレン基)、-O-、-S-、-SO2-、-NRL-、-CO-、-NH-、-COO-、-CONRL-、-O-CO-O-、-SO3-、-NHCOO-、-SO2NRL-、-NH-CO-NH-またはこれらを2種以上組み合わせた基(例えば、アルキレンオキシ基、アルキレンオキシカルボニル基、アルキレンカルボニルオキシ基など)などが挙げられる。ここで、RLは、水素原子またはアルキル基(好ましくは炭素数1~10)を表す。 The specific polymer may have a reactive functional group at both ends of the polymer constituting the main chain via a divalent linking group.
The divalent linking group is not particularly limited, but is, for example, a linear, branched or cyclic divalent aliphatic hydrocarbon group (for example, an alkylene group such as a methylene group, an ethylene group or a propylene group), a divalent group. Aromatic hydrocarbon group (eg, phenylene group), —O—, —S—, —SO 2 —, —NR L —, —CO—, —NH—, —COO—, —CONR L —, —O —CO—O—, —SO 3 —, —NHCOO—, —SO 2 NR L —, —NH—CO—NH— or a group combining two or more thereof (eg, an alkyleneoxy group, an alkyleneoxycarbonyl group, Alkylene carbonyloxy group) and the like. Here, R L represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
上記2価の連結基は特に制限されないが、例えば、直鎖状、分岐状若しくは環状の2価の脂肪族炭化水素基(例えば、メチレン基、エチレン基、プロピレン基などのアルキレン基)、2価の芳香族炭化水素基(例えば、フェニレン基)、-O-、-S-、-SO2-、-NRL-、-CO-、-NH-、-COO-、-CONRL-、-O-CO-O-、-SO3-、-NHCOO-、-SO2NRL-、-NH-CO-NH-またはこれらを2種以上組み合わせた基(例えば、アルキレンオキシ基、アルキレンオキシカルボニル基、アルキレンカルボニルオキシ基など)などが挙げられる。ここで、RLは、水素原子またはアルキル基(好ましくは炭素数1~10)を表す。 The specific polymer may have a reactive functional group at both ends of the polymer constituting the main chain via a divalent linking group.
The divalent linking group is not particularly limited, but is, for example, a linear, branched or cyclic divalent aliphatic hydrocarbon group (for example, an alkylene group such as a methylene group, an ethylene group or a propylene group), a divalent group. Aromatic hydrocarbon group (eg, phenylene group), —O—, —S—, —SO 2 —, —NR L —, —CO—, —NH—, —COO—, —CONR L —, —O —CO—O—, —SO 3 —, —NHCOO—, —SO 2 NR L —, —NH—CO—NH— or a group combining two or more thereof (eg, an alkyleneoxy group, an alkyleneoxycarbonyl group, Alkylene carbonyloxy group) and the like. Here, R L represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
(分子量)
特定ポリマーの重量平均分子量(Mw)は、5,000以上である。
特定ポリマーのMwは、本発明の効果等がより優れる理由から、6,000以上であることが好ましく、7,000以上であることがより好ましく、8,000以上であることがさらに好ましく、9,000以上であることが特に好ましい。特定ポリマーのMwの上限は特に制限されないが、本発明の効果等がより優れる理由から、500,000以下であることが好ましく、100,000以下であることがより好ましい。
ここで、重量平均分子量は、ゲル透過クロマトグラフ法(GPC)法にて測定され、標準ポリスチレンで換算して求められる。具体的には、例えば、GPCは、HLC-8220GPC(東ソー株式会社製)を用い、カラムとして、TSKgeL Super HZM-H、TSKgeL SuperHZ4000、TSKgeL SuperHZ2000(東ソー株式会社製、4.6mmID×15cm)を3本用い、溶離液としてTHF(テトラヒドロフラン)を用いる。また、条件としては、試料濃度を0.35質量%、流速を0.35mL/min、サンプル注入量を10μL、測定温度を40℃とし、IR検出器を用いて行う。また、検量線は、東ソー株式会社製「標準試料TSK standard,polystyrene」:「F-40」、「F-20」、「F-4」、「F-1」、「A-5000」、「A-2500」、「A-1000」、「n-プロピルベンゼン」の8サンプルから作製する。 (Molecular weight)
The weight average molecular weight (Mw) of the specific polymer is 5,000 or more.
The Mw of the specific polymer is preferably 6,000 or more, more preferably 7,000 or more, and further preferably 8,000 or more, for the reason that the effects of the present invention are more excellent. It is particularly preferable that it is 1,000 or more. Although the upper limit of Mw of the specific polymer is not particularly limited, it is preferably 500,000 or less, more preferably 100,000 or less for the reason that the effects of the present invention are more excellent.
Here, the weight average molecular weight is measured by a gel permeation chromatographic method (GPC) method, and is calculated by conversion with standard polystyrene. Specifically, for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used as the GPC, and TSKgeL Super HZM-H, TSKgeL Super HZ4000, TSKgeL Super HZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) are used as columns. This is 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 μL, the measurement temperature is 40 ° C., and an IR detector is used. The calibration curve is “standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “A-5000”, It is prepared from 8 samples of "A-2500", "A-1000" and "n-propylbenzene".
特定ポリマーの重量平均分子量(Mw)は、5,000以上である。
特定ポリマーのMwは、本発明の効果等がより優れる理由から、6,000以上であることが好ましく、7,000以上であることがより好ましく、8,000以上であることがさらに好ましく、9,000以上であることが特に好ましい。特定ポリマーのMwの上限は特に制限されないが、本発明の効果等がより優れる理由から、500,000以下であることが好ましく、100,000以下であることがより好ましい。
ここで、重量平均分子量は、ゲル透過クロマトグラフ法(GPC)法にて測定され、標準ポリスチレンで換算して求められる。具体的には、例えば、GPCは、HLC-8220GPC(東ソー株式会社製)を用い、カラムとして、TSKgeL Super HZM-H、TSKgeL SuperHZ4000、TSKgeL SuperHZ2000(東ソー株式会社製、4.6mmID×15cm)を3本用い、溶離液としてTHF(テトラヒドロフラン)を用いる。また、条件としては、試料濃度を0.35質量%、流速を0.35mL/min、サンプル注入量を10μL、測定温度を40℃とし、IR検出器を用いて行う。また、検量線は、東ソー株式会社製「標準試料TSK standard,polystyrene」:「F-40」、「F-20」、「F-4」、「F-1」、「A-5000」、「A-2500」、「A-1000」、「n-プロピルベンゼン」の8サンプルから作製する。 (Molecular weight)
The weight average molecular weight (Mw) of the specific polymer is 5,000 or more.
The Mw of the specific polymer is preferably 6,000 or more, more preferably 7,000 or more, and further preferably 8,000 or more, for the reason that the effects of the present invention are more excellent. It is particularly preferable that it is 1,000 or more. Although the upper limit of Mw of the specific polymer is not particularly limited, it is preferably 500,000 or less, more preferably 100,000 or less for the reason that the effects of the present invention are more excellent.
Here, the weight average molecular weight is measured by a gel permeation chromatographic method (GPC) method, and is calculated by conversion with standard polystyrene. Specifically, for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used as the GPC, and TSKgeL Super HZM-H, TSKgeL Super HZ4000, TSKgeL Super HZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) are used as columns. This is 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 μL, the measurement temperature is 40 ° C., and an IR detector is used. The calibration curve is “standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “A-5000”, It is prepared from 8 samples of "A-2500", "A-1000" and "n-propylbenzene".
(HSP値)
特定ポリマーのHSP(ハンセン溶解度パラメーター)値は特に制限されないが、本発明の効果等がより優れる理由から、8~12であることが好ましく、8.5~11であることがより好ましく、8.5~10.5であることがさらに好ましい。 (HSP value)
The HSP (Hansen solubility parameter) value of the specific polymer is not particularly limited, but is preferably 8 to 12, more preferably 8.5 to 11, and more preferably 8 to 11 for the reason that the effects of the present invention are more excellent. It is more preferably 5 to 10.5.
特定ポリマーのHSP(ハンセン溶解度パラメーター)値は特に制限されないが、本発明の効果等がより優れる理由から、8~12であることが好ましく、8.5~11であることがより好ましく、8.5~10.5であることがさらに好ましい。 (HSP value)
The HSP (Hansen solubility parameter) value of the specific polymer is not particularly limited, but is preferably 8 to 12, more preferably 8.5 to 11, and more preferably 8 to 11 for the reason that the effects of the present invention are more excellent. It is more preferably 5 to 10.5.
(含有量)
本発明の感光層において特定ポリマーの含有量は、本発明の効果等がより優れる理由から、本発明の感光層の全固形分に対して、1~50質量%であることが好ましく、5~40質量%であることがより好ましく、7~30質量%であることがさらに好ましく、10~20質量%であることが特に好ましい。 (Content)
The content of the specific polymer in the photosensitive layer of the present invention is preferably 1 to 50% by mass based on the total solid content of the photosensitive layer of the present invention, for the reason that the effects of the present invention are more excellent. It is more preferably 40% by mass, further preferably 7 to 30% by mass, and particularly preferably 10 to 20% by mass.
本発明の感光層において特定ポリマーの含有量は、本発明の効果等がより優れる理由から、本発明の感光層の全固形分に対して、1~50質量%であることが好ましく、5~40質量%であることがより好ましく、7~30質量%であることがさらに好ましく、10~20質量%であることが特に好ましい。 (Content)
The content of the specific polymer in the photosensitive layer of the present invention is preferably 1 to 50% by mass based on the total solid content of the photosensitive layer of the present invention, for the reason that the effects of the present invention are more excellent. It is more preferably 40% by mass, further preferably 7 to 30% by mass, and particularly preferably 10 to 20% by mass.
<特定モノマー>
上述のとおり、本発明の感光層は、エチレン性不飽和基を3つ以上有する多官能モノマー(特定モノマー)を含有する。
上記特定モノマーは、エチレン性不飽和基を3つ以上有する化合物であれば特に制限されない。
上記エチレン性不飽和基は、本発明の効果等がより優れる理由から、ビニル基(CH2=CH-)、アリル基(CH2=CH-CH2-)、(メタ)アクリロイル基、又は、(メタ)アクリロイル基であることが好ましく、(メタ)アクリロイルオキシ基であることがより好ましい。
特定モノマーとしては、例えば、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールテトラ(メタ)アクリレート、トリメチロールエタントリ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、テトラメチロールメタンテトラ(メタ)アクリレート、トリアリルトリメリテート等が挙げられる。 <Specific monomer>
As described above, the photosensitive layer of the present invention contains a polyfunctional monomer (specific monomer) having three or more ethylenically unsaturated groups.
The specific monomer is not particularly limited as long as it is a compound having three or more ethylenically unsaturated groups.
The ethylenically unsaturated group is a vinyl group (CH 2 ═CH—), an allyl group (CH 2 ═CH—CH 2 —), a (meth) acryloyl group, or, for the reason that the effects of the present invention are more excellent. It is preferably a (meth) acryloyl group, and more preferably a (meth) acryloyloxy group.
Specific monomers include, for example, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, Tetramethylolmethane tetra (meth) acrylate, triallyl trimellitate and the like can be mentioned.
上述のとおり、本発明の感光層は、エチレン性不飽和基を3つ以上有する多官能モノマー(特定モノマー)を含有する。
上記特定モノマーは、エチレン性不飽和基を3つ以上有する化合物であれば特に制限されない。
上記エチレン性不飽和基は、本発明の効果等がより優れる理由から、ビニル基(CH2=CH-)、アリル基(CH2=CH-CH2-)、(メタ)アクリロイル基、又は、(メタ)アクリロイル基であることが好ましく、(メタ)アクリロイルオキシ基であることがより好ましい。
特定モノマーとしては、例えば、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールテトラ(メタ)アクリレート、トリメチロールエタントリ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、テトラメチロールメタンテトラ(メタ)アクリレート、トリアリルトリメリテート等が挙げられる。 <Specific monomer>
As described above, the photosensitive layer of the present invention contains a polyfunctional monomer (specific monomer) having three or more ethylenically unsaturated groups.
The specific monomer is not particularly limited as long as it is a compound having three or more ethylenically unsaturated groups.
The ethylenically unsaturated group is a vinyl group (CH 2 ═CH—), an allyl group (CH 2 ═CH—CH 2 —), a (meth) acryloyl group, or, for the reason that the effects of the present invention are more excellent. It is preferably a (meth) acryloyl group, and more preferably a (meth) acryloyloxy group.
Specific monomers include, for example, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, Tetramethylolmethane tetra (meth) acrylate, triallyl trimellitate and the like can be mentioned.
本発明の感光層において特定モノマーの含有量は、本発明の効果等がより優れる理由から、本発明の感光層の全固形分に対して、1~40質量%であることが好ましく、2~30質量%であることがより好ましく、5~30質量%であることがさらに好ましく、10~20質量%であることが特に好ましい。
The content of the specific monomer in the photosensitive layer of the present invention is preferably 1 to 40% by mass, based on the total solid content of the photosensitive layer of the present invention, for the reason that the effects of the present invention are more excellent. It is more preferably 30% by mass, further preferably 5 to 30% by mass, and particularly preferably 10 to 20% by mass.
<特定モノマー/特定ポリマー>
本発明の感光層において、上述した特定ポリマーの含有量に対する上述した特定モノマーの含有量の比率は、本発明の効果等がより優れる理由から、質量比で、5.0以下であることが好ましく、3.0以下であることがより好ましく、2.0以下であることがさらに好ましく、1.5以下であることが特に好ましい。上記比率の下限は特に制限されないが、0.2以上であることが好ましく、0.4以上であることがより好ましく、0.6以上であることがさらに好ましく、0.7以上であることが特に好ましい。
以下、上述した特定ポリマーの含有量に対する上述した特定モノマーの含有量の比率(質量比)を「特定モノマー/特定ポリマー」とも言う。 <Specific monomer / Specific polymer>
In the photosensitive layer of the present invention, the ratio of the content of the above-mentioned specific monomer to the content of the above-mentioned specific polymer is preferably 5.0 or less in terms of mass ratio because the effect of the present invention is more excellent. , 3.0 or less is more preferable, 2.0 or less is more preferable, and 1.5 or less is particularly preferable. The lower limit of the ratio is not particularly limited, but is preferably 0.2 or more, more preferably 0.4 or more, further preferably 0.6 or more, and more preferably 0.7 or more. Particularly preferred.
Hereinafter, the ratio (mass ratio) of the content of the specific monomer described above to the content of the specific polymer described above is also referred to as “specific monomer / specific polymer”.
本発明の感光層において、上述した特定ポリマーの含有量に対する上述した特定モノマーの含有量の比率は、本発明の効果等がより優れる理由から、質量比で、5.0以下であることが好ましく、3.0以下であることがより好ましく、2.0以下であることがさらに好ましく、1.5以下であることが特に好ましい。上記比率の下限は特に制限されないが、0.2以上であることが好ましく、0.4以上であることがより好ましく、0.6以上であることがさらに好ましく、0.7以上であることが特に好ましい。
以下、上述した特定ポリマーの含有量に対する上述した特定モノマーの含有量の比率(質量比)を「特定モノマー/特定ポリマー」とも言う。 <Specific monomer / Specific polymer>
In the photosensitive layer of the present invention, the ratio of the content of the above-mentioned specific monomer to the content of the above-mentioned specific polymer is preferably 5.0 or less in terms of mass ratio because the effect of the present invention is more excellent. , 3.0 or less is more preferable, 2.0 or less is more preferable, and 1.5 or less is particularly preferable. The lower limit of the ratio is not particularly limited, but is preferably 0.2 or more, more preferably 0.4 or more, further preferably 0.6 or more, and more preferably 0.7 or more. Particularly preferred.
Hereinafter, the ratio (mass ratio) of the content of the specific monomer described above to the content of the specific polymer described above is also referred to as “specific monomer / specific polymer”.
<任意成分>
本発明の感光層は、上述した各成分以外の成分(任意成分)を含有していてもよい。 <Arbitrary ingredients>
The photosensitive layer of the present invention may contain a component (optional component) other than the above-mentioned components.
本発明の感光層は、上述した各成分以外の成分(任意成分)を含有していてもよい。 <Arbitrary ingredients>
The photosensitive layer of the present invention may contain a component (optional component) other than the above-mentioned components.
(単官能モノマー)
本発明の感光層は、本発明の効果等がより優れる理由から、単官能モノマーを含有するのが好ましい。
上記単官能モノマーは、本発明の効果等がより優れる理由から、エチレン性不飽和基を1つ有する化合物であることが好ましい。上記エチレン性不飽和基の具体例は上述のとおりである。 (Monofunctional monomer)
The photosensitive layer of the present invention preferably contains a monofunctional monomer because the effects of the present invention are more excellent.
The monofunctional monomer is preferably a compound having one ethylenically unsaturated group for the reason that the effects of the present invention are more excellent. Specific examples of the ethylenically unsaturated group are as described above.
本発明の感光層は、本発明の効果等がより優れる理由から、単官能モノマーを含有するのが好ましい。
上記単官能モノマーは、本発明の効果等がより優れる理由から、エチレン性不飽和基を1つ有する化合物であることが好ましい。上記エチレン性不飽和基の具体例は上述のとおりである。 (Monofunctional monomer)
The photosensitive layer of the present invention preferably contains a monofunctional monomer because the effects of the present invention are more excellent.
The monofunctional monomer is preferably a compound having one ethylenically unsaturated group for the reason that the effects of the present invention are more excellent. Specific examples of the ethylenically unsaturated group are as described above.
エチレン性不飽和基を1つ有する化合物としては、例えば、
N-ビニルホルムアミド等のN-ビニル化合物;
(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、ジアセトン(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、N,N-ジエチル(メタ)アクリルアミド、N-イソプロピル(メタ)アクリルアミド、(メタ)アクリロイルモルホリン、(メタ)アクリルアミド等の(メタ)アクリルアミド化合物;
2-ヒドロキシエチル(メタ)アクリレート、ブトキシエチル(メタ)アクリレート、カルビトール(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、テトラヒドロフルフリル(メタ)アクリレート、ベンジル(メタ)アクリレート、トリデシル(メタ)アクリレート、2-フェノキシエチル(メタ)アクリレート、グリシジル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、ジシクロペンテニルオキシエチル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、2-ヒドロキシ-3-フェノキシプロピル(メタ)アクリレート、2-(メタ)アクリロイロキシエチルフタル酸、メトキシ-ポリエチレングリコール(メタ)アクリレート、2-(メタ)アクリロイロキシエチル-2-ヒドロキシエチルフタル酸、2-(2-エトキシエトキシ)エチル(メタ)アクリレート、2-メトキシエチル(メタ)アクリレート、3-メトキシブチル(メタ)アクリレート、エトキシ化フェニル(メタ)アクリレート、2-(メタ)アクリロイロキシエチルコハク酸、ノニルフェノールEO付加物(メタ)アクリレート、フェノキシ-ポリエチレングリコール(メタ)アクリレート、2-(メタ)アクリロイロキシエチルヘキサヒドロフタル酸、ラクトン変性(メタ)アクリレート、ステアリル(メタ)アクリレート、イソアミル(メタ)アクリレート、イソミリスチル(メタ)アクリレート、イソステアリル(メタ)アクリレート、サイクリックトリメチロールプロパンフォルマル(メタ)アクリレート等の(メタ)アクリレート化合物;
メチルビニルエーテル、エチルビニルエーテル、n-プロピルビニルエーテル、イソプロピルビニルエーテル、n-ブチルビニルエーテル、イソブチルビニルエーテル、t-ブチルビニルエーテル、n-オクタデシルビニルエーテル、2-エチルヘキシルビニルエーテル、n-ノニルビニルエーテル、ドデシルビニルエーテル、オクタデシルビニルエーテル、シクロヘキシルビニルエーテル、シクロヘキシルメチルビニルエーテル、4-メチルシクロヘキシルメチルビニルエーテル、ベンジルビニルエーテル、ジシクロペンテニルビニルエーテル、2-ジシクロペンテノキシエチルビニルエーテル、メトキシエチルビニルエーテル、エトキシエチルビニルエーテル、ブトキシエチルビニルエーテル、メトキシエトキシエチルビニルエーテル、エトキシエトキシエチルビニルエーテル、メトキシポリエチレングリコールビニルエーテル、テトラヒドロフリフリルビニルエーテル、2-ヒドロキシエチルビニルエーテル、2-ヒドロキシプロピルビニルエーテル、4-ヒドロキシブチルビニルエーテル、4-ヒドロキシメチルシクロヘキシルメチルビニルエーテル、ジエチレングリコールモノビニルエーテル、ポリエチレングリコールビニルエーテル、クロルエチルビニルエーテル、クロルブチルビニルエーテル、クロルエトキシエチルビニルエーテル、フェニルエチルビニルエーテル、フェノキシポリエチレングリコールビニルエーテル、シクロヘキサンジメタノールモノビニルエーテル、イソプロペニルエーテル-O-プロピレンカーボネート等のモノビニルエーテル化合物;
等が挙げられる。なお、EOはエチレンオキシドを示す。 Examples of the compound having one ethylenically unsaturated group include:
N-vinyl compounds such as N-vinylformamide;
(Meth) acrylamide, N-methylol (meth) acrylamide, diacetone (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, (meth) (Meth) acrylamide compounds such as acryloylmorpholine and (meth) acrylamide;
2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, tridecyl (meth) acrylate, 2 -Phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-hydroxy -3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl phthalic acid, methoxy-polyethylene glycol (meth) acrylate, 2- (meth) a Lylyloxyethyl-2-hydroxyethylphthalic acid, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxylated phenyl (meth) acrylate , 2- (meth) acryloyloxyethyl succinic acid, nonylphenol EO adduct (meth) acrylate, phenoxy-polyethylene glycol (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, lactone modified (meth) Acrylate, stearyl (meth) acrylate, isoamyl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate The (meth) acrylate compound;
Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, n-octadecyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether , Cyclohexylmethyl vinyl ether, 4-methylcyclohexyl methyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, Toxyethoxyethyl vinyl ether, methoxy polyethylene glycol vinyl ether, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexylmethyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloro Monovinyl ether compounds such as ethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxyethyl vinyl ether, phenylethyl vinyl ether, phenoxy polyethylene glycol vinyl ether, cyclohexanedimethanol monovinyl ether, isopropenyl ether-O-propylene carbonate;
Etc. In addition, EO shows ethylene oxide.
N-ビニルホルムアミド等のN-ビニル化合物;
(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、ジアセトン(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、N,N-ジエチル(メタ)アクリルアミド、N-イソプロピル(メタ)アクリルアミド、(メタ)アクリロイルモルホリン、(メタ)アクリルアミド等の(メタ)アクリルアミド化合物;
2-ヒドロキシエチル(メタ)アクリレート、ブトキシエチル(メタ)アクリレート、カルビトール(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、テトラヒドロフルフリル(メタ)アクリレート、ベンジル(メタ)アクリレート、トリデシル(メタ)アクリレート、2-フェノキシエチル(メタ)アクリレート、グリシジル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、ジシクロペンテニルオキシエチル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、2-ヒドロキシ-3-フェノキシプロピル(メタ)アクリレート、2-(メタ)アクリロイロキシエチルフタル酸、メトキシ-ポリエチレングリコール(メタ)アクリレート、2-(メタ)アクリロイロキシエチル-2-ヒドロキシエチルフタル酸、2-(2-エトキシエトキシ)エチル(メタ)アクリレート、2-メトキシエチル(メタ)アクリレート、3-メトキシブチル(メタ)アクリレート、エトキシ化フェニル(メタ)アクリレート、2-(メタ)アクリロイロキシエチルコハク酸、ノニルフェノールEO付加物(メタ)アクリレート、フェノキシ-ポリエチレングリコール(メタ)アクリレート、2-(メタ)アクリロイロキシエチルヘキサヒドロフタル酸、ラクトン変性(メタ)アクリレート、ステアリル(メタ)アクリレート、イソアミル(メタ)アクリレート、イソミリスチル(メタ)アクリレート、イソステアリル(メタ)アクリレート、サイクリックトリメチロールプロパンフォルマル(メタ)アクリレート等の(メタ)アクリレート化合物;
メチルビニルエーテル、エチルビニルエーテル、n-プロピルビニルエーテル、イソプロピルビニルエーテル、n-ブチルビニルエーテル、イソブチルビニルエーテル、t-ブチルビニルエーテル、n-オクタデシルビニルエーテル、2-エチルヘキシルビニルエーテル、n-ノニルビニルエーテル、ドデシルビニルエーテル、オクタデシルビニルエーテル、シクロヘキシルビニルエーテル、シクロヘキシルメチルビニルエーテル、4-メチルシクロヘキシルメチルビニルエーテル、ベンジルビニルエーテル、ジシクロペンテニルビニルエーテル、2-ジシクロペンテノキシエチルビニルエーテル、メトキシエチルビニルエーテル、エトキシエチルビニルエーテル、ブトキシエチルビニルエーテル、メトキシエトキシエチルビニルエーテル、エトキシエトキシエチルビニルエーテル、メトキシポリエチレングリコールビニルエーテル、テトラヒドロフリフリルビニルエーテル、2-ヒドロキシエチルビニルエーテル、2-ヒドロキシプロピルビニルエーテル、4-ヒドロキシブチルビニルエーテル、4-ヒドロキシメチルシクロヘキシルメチルビニルエーテル、ジエチレングリコールモノビニルエーテル、ポリエチレングリコールビニルエーテル、クロルエチルビニルエーテル、クロルブチルビニルエーテル、クロルエトキシエチルビニルエーテル、フェニルエチルビニルエーテル、フェノキシポリエチレングリコールビニルエーテル、シクロヘキサンジメタノールモノビニルエーテル、イソプロペニルエーテル-O-プロピレンカーボネート等のモノビニルエーテル化合物;
等が挙げられる。なお、EOはエチレンオキシドを示す。 Examples of the compound having one ethylenically unsaturated group include:
N-vinyl compounds such as N-vinylformamide;
(Meth) acrylamide, N-methylol (meth) acrylamide, diacetone (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, (meth) (Meth) acrylamide compounds such as acryloylmorpholine and (meth) acrylamide;
2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, tridecyl (meth) acrylate, 2 -Phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-hydroxy -3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl phthalic acid, methoxy-polyethylene glycol (meth) acrylate, 2- (meth) a Lylyloxyethyl-2-hydroxyethylphthalic acid, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxylated phenyl (meth) acrylate , 2- (meth) acryloyloxyethyl succinic acid, nonylphenol EO adduct (meth) acrylate, phenoxy-polyethylene glycol (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, lactone modified (meth) Acrylate, stearyl (meth) acrylate, isoamyl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate The (meth) acrylate compound;
Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, n-octadecyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether , Cyclohexylmethyl vinyl ether, 4-methylcyclohexyl methyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, Toxyethoxyethyl vinyl ether, methoxy polyethylene glycol vinyl ether, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexylmethyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloro Monovinyl ether compounds such as ethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxyethyl vinyl ether, phenylethyl vinyl ether, phenoxy polyethylene glycol vinyl ether, cyclohexanedimethanol monovinyl ether, isopropenyl ether-O-propylene carbonate;
Etc. In addition, EO shows ethylene oxide.
本発明の感光層において単官能モノマーの含有量は、本発明の効果等がより優れる理由から、本発明の感光層の全固形分に対して、0.1~30質量%であることが好ましく、1~10質量%であることがより好ましい。
The content of the monofunctional monomer in the photosensitive layer of the present invention is preferably 0.1 to 30% by mass based on the total solid content of the photosensitive layer of the present invention, because the effects of the present invention are more excellent. It is more preferably 1 to 10% by mass.
本発明の感光層において、上述した特定モノマーの含有量に対する上述した単官能モノマーの含有量の比率は、本発明の効果等がより優れる理由から、質量比で、1.0以下であることが好ましく、0.5以下であることがより好ましく、0.4以下であることがさらに好ましい。上記比率の下限は特に制限されないが、0.1以上であることが好ましく、0.2以上であることがより好ましい。
以下、上述した特定モノマーの含有量に対する上述した単官能モノマーの含有量の比率(質量比)を「単官能モノマー/特定モノマー」とも言う。 In the photosensitive layer of the present invention, the ratio of the content of the monofunctional monomer described above to the content of the specific monomer described above is 1.0 or less in terms of mass ratio because the effect of the present invention is more excellent. It is preferably 0.5 or less, more preferably 0.4 or less. The lower limit of the ratio is not particularly limited, but is preferably 0.1 or more, more preferably 0.2 or more.
Hereinafter, the ratio (mass ratio) of the content of the above-mentioned monofunctional monomer to the content of the above-mentioned specific monomer is also referred to as "monofunctional monomer / specific monomer".
以下、上述した特定モノマーの含有量に対する上述した単官能モノマーの含有量の比率(質量比)を「単官能モノマー/特定モノマー」とも言う。 In the photosensitive layer of the present invention, the ratio of the content of the monofunctional monomer described above to the content of the specific monomer described above is 1.0 or less in terms of mass ratio because the effect of the present invention is more excellent. It is preferably 0.5 or less, more preferably 0.4 or less. The lower limit of the ratio is not particularly limited, but is preferably 0.1 or more, more preferably 0.2 or more.
Hereinafter, the ratio (mass ratio) of the content of the above-mentioned monofunctional monomer to the content of the above-mentioned specific monomer is also referred to as "monofunctional monomer / specific monomer".
(2官能モノマー)
本発明の感光層は、本発明の効果等がより優れる理由から、2官能モノマーを含有するのが好ましい。
上記2官能モノマーは、本発明の効果等がより優れる理由から、エチレン性不飽和基を2つ有する化合物であることが好ましい。上記エチレン性不飽和基の具体例は上述のとおりである。 (Bifunctional monomer)
The photosensitive layer of the present invention preferably contains a bifunctional monomer because the effects of the present invention are more excellent.
The bifunctional monomer is preferably a compound having two ethylenically unsaturated groups, because the effects of the present invention are more excellent. Specific examples of the ethylenically unsaturated group are as described above.
本発明の感光層は、本発明の効果等がより優れる理由から、2官能モノマーを含有するのが好ましい。
上記2官能モノマーは、本発明の効果等がより優れる理由から、エチレン性不飽和基を2つ有する化合物であることが好ましい。上記エチレン性不飽和基の具体例は上述のとおりである。 (Bifunctional monomer)
The photosensitive layer of the present invention preferably contains a bifunctional monomer because the effects of the present invention are more excellent.
The bifunctional monomer is preferably a compound having two ethylenically unsaturated groups, because the effects of the present invention are more excellent. Specific examples of the ethylenically unsaturated group are as described above.
エチレン性不飽和基を2つ有する化合物としては、例えば、
エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ジプロピレングリコールジ(メタ)アクリレート、トリプロピレングリコールジ(メタ)アクリレート、テトラプロピレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、エトキシ化ネオペンチルグリコールジ(メタ)アクリレート、プロポキシ化ネオペンチルグリコールジ(メタ)アクリレート等のグリコールジ(メタ)アクリレート化合物;
エチレングリコールジビニルエーテル、ジエチレングリコールジビニルエーテル、トリエチレングリコールジビニルエーテル、プロピレングリコールジビニルエーテル、ジプロピレングリコールジビニルエーテル、ブタンジオールジビニルエーテル、ヘキサンジオールジビニルエーテル、シクロヘキサンジメタノールジビニルエーテル等のジビニルエーテル化合物;
ビスフェノールAジグリシジルエーテル(メタ)アクリル酸付加物、変性ビスフェノールAジ(メタ)アクリレート、ビスフェノールAのPO付加物ジ(メタ)アクリレート、ビスフェノールAのEO付加物ジ(メタ)アクリレート等のビスフェノールAのジ(メタ)アクリレート化合物;
等が挙げられる。なお、POはプロピレンオキシド、EOはエチレンオキシドを示す。 Examples of the compound having two ethylenically unsaturated groups include, for example,
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, di Propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol Glycol di (meth) acrylate compounds such as di (meth) acrylate;
Divinyl ether compounds such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether;
Of bisphenol A such as bisphenol A diglycidyl ether (meth) acrylic acid adduct, modified bisphenol A di (meth) acrylate, PO adduct of bisphenol A di (meth) acrylate, EO adduct of bisphenol A di (meth) acrylate, etc. Di (meth) acrylate compound;
Etc. PO is propylene oxide and EO is ethylene oxide.
エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ジプロピレングリコールジ(メタ)アクリレート、トリプロピレングリコールジ(メタ)アクリレート、テトラプロピレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、エトキシ化ネオペンチルグリコールジ(メタ)アクリレート、プロポキシ化ネオペンチルグリコールジ(メタ)アクリレート等のグリコールジ(メタ)アクリレート化合物;
エチレングリコールジビニルエーテル、ジエチレングリコールジビニルエーテル、トリエチレングリコールジビニルエーテル、プロピレングリコールジビニルエーテル、ジプロピレングリコールジビニルエーテル、ブタンジオールジビニルエーテル、ヘキサンジオールジビニルエーテル、シクロヘキサンジメタノールジビニルエーテル等のジビニルエーテル化合物;
ビスフェノールAジグリシジルエーテル(メタ)アクリル酸付加物、変性ビスフェノールAジ(メタ)アクリレート、ビスフェノールAのPO付加物ジ(メタ)アクリレート、ビスフェノールAのEO付加物ジ(メタ)アクリレート等のビスフェノールAのジ(メタ)アクリレート化合物;
等が挙げられる。なお、POはプロピレンオキシド、EOはエチレンオキシドを示す。 Examples of the compound having two ethylenically unsaturated groups include, for example,
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, di Propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol Glycol di (meth) acrylate compounds such as di (meth) acrylate;
Divinyl ether compounds such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether;
Of bisphenol A such as bisphenol A diglycidyl ether (meth) acrylic acid adduct, modified bisphenol A di (meth) acrylate, PO adduct of bisphenol A di (meth) acrylate, EO adduct of bisphenol A di (meth) acrylate, etc. Di (meth) acrylate compound;
Etc. PO is propylene oxide and EO is ethylene oxide.
本発明の感光層において2官能モノマーの含有量は、本発明の効果等がより優れる理由から、本発明の感光層の全固形分に対して、0.1~30質量%であることが好ましい。
The content of the bifunctional monomer in the photosensitive layer of the present invention is preferably 0.1 to 30% by mass based on the total solid content of the photosensitive layer of the present invention, because the effects of the present invention are more excellent. ..
(疎水性ポリマー)
本発明の感光層は、本発明の効果等がより優れる理由から、疎水性ポリマーを含有することが好ましい。
上記疎水性ポリマーは両末端に反応性官能基(例えば、(メタ)アクリロイルオキシ基)を有さないものであることが好ましい。また、上記疎水性ポリマーは水分散性を有さないものであることが好ましい。 (Hydrophobic polymer)
The photosensitive layer of the present invention preferably contains a hydrophobic polymer because the effects of the present invention are more excellent.
The hydrophobic polymer preferably does not have a reactive functional group (for example, a (meth) acryloyloxy group) at both ends. Further, it is preferable that the hydrophobic polymer does not have water dispersibility.
本発明の感光層は、本発明の効果等がより優れる理由から、疎水性ポリマーを含有することが好ましい。
上記疎水性ポリマーは両末端に反応性官能基(例えば、(メタ)アクリロイルオキシ基)を有さないものであることが好ましい。また、上記疎水性ポリマーは水分散性を有さないものであることが好ましい。 (Hydrophobic polymer)
The photosensitive layer of the present invention preferably contains a hydrophobic polymer because the effects of the present invention are more excellent.
The hydrophobic polymer preferably does not have a reactive functional group (for example, a (meth) acryloyloxy group) at both ends. Further, it is preferable that the hydrophobic polymer does not have water dispersibility.
上記疎水性ポリマーの具体例及び好適な態様は、上述した特定ポリマーの主鎖を構成するポリマーと同じである。
上記疎水性ポリマーは、本発明の効果等がより優れる理由から、ゴムであることが好ましく、ジエン系ゴムであることがより好ましく、ブタジエンゴムであることがさらに好ましい。
上記疎水性ポリマーの重量平均分子量(Mw)は特に制限されないが、本発明の効果等がより優れる理由から、200,000以上であることが好ましく、300,000~2,000,000であることがより好ましく、300,000~1,500,000であることが更に好ましく、300,000~700,000であることが特に好ましい。 Specific examples and preferable embodiments of the above hydrophobic polymer are the same as the polymers constituting the main chain of the above-mentioned specific polymer.
The hydrophobic polymer is preferably a rubber, more preferably a diene rubber, and even more preferably a butadiene rubber, for the reason that the effects of the present invention are more excellent.
The weight average molecular weight (Mw) of the hydrophobic polymer is not particularly limited, but is preferably 200,000 or more, and preferably 300,000 to 2,000,000 for the reason that the effects of the present invention are more excellent. Is more preferable, 300,000 to 1,500,000 is more preferable, 300,000 to 700,000 is particularly preferable.
上記疎水性ポリマーは、本発明の効果等がより優れる理由から、ゴムであることが好ましく、ジエン系ゴムであることがより好ましく、ブタジエンゴムであることがさらに好ましい。
上記疎水性ポリマーの重量平均分子量(Mw)は特に制限されないが、本発明の効果等がより優れる理由から、200,000以上であることが好ましく、300,000~2,000,000であることがより好ましく、300,000~1,500,000であることが更に好ましく、300,000~700,000であることが特に好ましい。 Specific examples and preferable embodiments of the above hydrophobic polymer are the same as the polymers constituting the main chain of the above-mentioned specific polymer.
The hydrophobic polymer is preferably a rubber, more preferably a diene rubber, and even more preferably a butadiene rubber, for the reason that the effects of the present invention are more excellent.
The weight average molecular weight (Mw) of the hydrophobic polymer is not particularly limited, but is preferably 200,000 or more, and preferably 300,000 to 2,000,000 for the reason that the effects of the present invention are more excellent. Is more preferable, 300,000 to 1,500,000 is more preferable, 300,000 to 700,000 is particularly preferable.
本発明の感光層において疎水性ポリマーの含有量は、本発明の効果等がより優れる理由から、本発明の感光層の全固形分に対して、5~60質量%であることが好ましく、10~40質量%であることがより好ましい。
The content of the hydrophobic polymer in the photosensitive layer of the present invention is preferably 5 to 60 mass% with respect to the total solid content of the photosensitive layer of the present invention, for the reason that the effects of the present invention are more excellent. It is more preferably from about 40% by mass.
(光重合開始剤)
本発明の感光層は、本発明の効果等がより優れる理由から、光重合開始剤を含有するのが好ましい。
光重合開始剤は特に限定されないが、例えば、アルキルフェノン類、アセトフェノン類、ベンゾインエーテル類、ベンゾフェノン類、チオキサントン類、アントラキノン類、ベンジル類、ビアセチル類等の光重合開始剤を挙げることができる。
より具体的には、例えば、ベンジルジメチルケタール、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン、メチル-o-ベンゾイルベンゾエート、1-ヒドロキシシクロヘキシルフェニルケトンなどを挙げることができる。 (Photopolymerization initiator)
The photosensitive layer of the present invention preferably contains a photopolymerization initiator because the effects of the present invention are more excellent.
The photopolymerization initiator is not particularly limited, and examples thereof include photopolymerization initiators such as alkylphenones, acetophenones, benzoin ethers, benzophenones, thioxanthones, anthraquinones, benzyls, and biacetyls.
More specifically, for example, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, methyl-o-benzoylbenzoate, 1-hydroxycyclohexyl phenyl ketone and the like can be mentioned.
本発明の感光層は、本発明の効果等がより優れる理由から、光重合開始剤を含有するのが好ましい。
光重合開始剤は特に限定されないが、例えば、アルキルフェノン類、アセトフェノン類、ベンゾインエーテル類、ベンゾフェノン類、チオキサントン類、アントラキノン類、ベンジル類、ビアセチル類等の光重合開始剤を挙げることができる。
より具体的には、例えば、ベンジルジメチルケタール、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン、メチル-o-ベンゾイルベンゾエート、1-ヒドロキシシクロヘキシルフェニルケトンなどを挙げることができる。 (Photopolymerization initiator)
The photosensitive layer of the present invention preferably contains a photopolymerization initiator because the effects of the present invention are more excellent.
The photopolymerization initiator is not particularly limited, and examples thereof include photopolymerization initiators such as alkylphenones, acetophenones, benzoin ethers, benzophenones, thioxanthones, anthraquinones, benzyls, and biacetyls.
More specifically, for example, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, methyl-o-benzoylbenzoate, 1-hydroxycyclohexyl phenyl ketone and the like can be mentioned.
本発明の感光層において光重合開始剤の含有量は、感度などの観点から、本発明の感光層の全固形分に対して、0.3~15質量%であることが好ましく、0.5~10質量%であることがより好ましい。
The content of the photopolymerization initiator in the photosensitive layer of the present invention is preferably 0.3 to 15% by mass based on the total solid content of the photosensitive layer of the present invention, from the viewpoint of sensitivity and the like. It is more preferably from about 10% by mass.
(可塑剤)
本発明の感光層は、柔軟性がより向上する理由から、可塑剤を含有することが好ましい。 (Plasticizer)
The photosensitive layer of the present invention preferably contains a plasticizer for the reason that the flexibility is further improved.
本発明の感光層は、柔軟性がより向上する理由から、可塑剤を含有することが好ましい。 (Plasticizer)
The photosensitive layer of the present invention preferably contains a plasticizer for the reason that the flexibility is further improved.
可塑剤としては、具体的には、液状ゴム、オイル、ポリエステル、リン酸系化合物などが挙げられる。
液状ゴムとしては、具体的には、例えば、液状のポリブタジエン、液状のポリイソプレン、または、これらをマレイン酸やエポキシ基により変性したものなどが挙げられる。
オイルとしては、具体的には、例えば、パラフィン、ナフテン、アロマなどが挙げられる。
ポリエステルとしては、具体的には、例えば、アジピン酸系ポリエステルなどが挙げられる。
リン酸系化合物としては、具体的には、例えば、リン酸エステルなどが挙げられる。 Specific examples of the plasticizer include liquid rubber, oil, polyester, and phosphoric acid compounds.
Specific examples of the liquid rubber include liquid polybutadiene, liquid polyisoprene, and those obtained by modifying these with maleic acid or an epoxy group.
Specific examples of the oil include paraffin, naphthene, and aroma.
Specific examples of the polyester include adipic acid-based polyester.
Specific examples of the phosphoric acid compound include phosphoric acid esters.
液状ゴムとしては、具体的には、例えば、液状のポリブタジエン、液状のポリイソプレン、または、これらをマレイン酸やエポキシ基により変性したものなどが挙げられる。
オイルとしては、具体的には、例えば、パラフィン、ナフテン、アロマなどが挙げられる。
ポリエステルとしては、具体的には、例えば、アジピン酸系ポリエステルなどが挙げられる。
リン酸系化合物としては、具体的には、例えば、リン酸エステルなどが挙げられる。 Specific examples of the plasticizer include liquid rubber, oil, polyester, and phosphoric acid compounds.
Specific examples of the liquid rubber include liquid polybutadiene, liquid polyisoprene, and those obtained by modifying these with maleic acid or an epoxy group.
Specific examples of the oil include paraffin, naphthene, and aroma.
Specific examples of the polyester include adipic acid-based polyester.
Specific examples of the phosphoric acid compound include phosphoric acid esters.
本発明の感光層において可塑剤の含有量は、柔軟性が更に向上する理由から、本発明の感光層の全固形分に対して、0.1~40質量%であることが好ましく、5~30質量%であることがより好ましい。
The content of the plasticizer in the photosensitive layer of the present invention is preferably 0.1 to 40% by mass based on the total solid content of the photosensitive layer of the present invention, for the reason of further improving flexibility. It is more preferably 30% by mass.
(界面活性剤)
本発明の感光層は、水現像性をより向上させる観点から、界面活性剤を含有していることが好ましい。
界面活性剤としては、カチオン性界面活性剤、アニオン性界面活性剤、ノニオン性界面活性剤を挙げることができる。なかでも、本発明の効果等がより優れる理由から、アニオン性界面活性剤が好ましい。 (Surfactant)
The photosensitive layer of the present invention preferably contains a surfactant from the viewpoint of further improving water developability.
Examples of the surfactant include a cationic surfactant, an anionic surfactant, and a nonionic surfactant. Among them, anionic surfactants are preferable because the effects of the present invention are more excellent.
本発明の感光層は、水現像性をより向上させる観点から、界面活性剤を含有していることが好ましい。
界面活性剤としては、カチオン性界面活性剤、アニオン性界面活性剤、ノニオン性界面活性剤を挙げることができる。なかでも、本発明の効果等がより優れる理由から、アニオン性界面活性剤が好ましい。 (Surfactant)
The photosensitive layer of the present invention preferably contains a surfactant from the viewpoint of further improving water developability.
Examples of the surfactant include a cationic surfactant, an anionic surfactant, and a nonionic surfactant. Among them, anionic surfactants are preferable because the effects of the present invention are more excellent.
アニオン性界面活性剤としては、具体的には、例えば、
ラウリン酸ナトリウム、オレイン酸ナトリウム等の脂肪族カルボン酸塩;
ラウリル硫酸エステルナトリウム、セチル硫酸エステルナトリウム、オレイル硫酸エステルナトリウム等の高級アルコール硫酸エステル塩;
ポリオキシエチレンラウリルエーテル硫酸エステルナトリウム等のポリオキシエチレンアルキルエーテル硫酸エステル塩;
ポリオキシエチレンオクチルフェニルエーテル硫酸エステルナトリウム、ポリオキシエチレンノニルフェニルエーテル硫酸エステルナトリウム等のポリオキシエチレンアルキルアリルエーテル硫酸エステル塩;
アルキルジフェニルエーテルジスルホン酸塩、ドデシルスルホン酸ナトリウム、ジアルキルスルホコハク酸ナトリウム等のアルキルスルホン酸塩;
アルキルジスルホン酸塩、ドデシルベンゼンスルホン酸ナトリウム、ジブチルナフタレンスルホン酸ナトリウム、トリイソプロピルナフタレンスルホン酸ナトリウム等のアルキルアリルスルホン酸塩;
ラウリルリン酸モノエステルジナトリウム、ラウリルリン酸ジエステルナトリウム等の高級アルコールリン酸エステル塩;
ポリオキシエチレンラウリルエーテルリン酸モノエステルジナトリウム、ポリオキシエチレンラウリルエーテルリン酸ジエステルナトリウム等のポリオキシエチレンアルキルエーテルリン酸エステル塩;
等が挙げられる。これらは1種単独で用いてもよく、2種以上を併用してもよい。 As the anionic surfactant, specifically, for example,
Aliphatic carboxylates such as sodium laurate and sodium oleate;
Higher alcohol sulfate salts such as sodium lauryl sulfate, sodium cetyl sulfate and sodium oleyl sulfate;
Polyoxyethylene lauryl ether sulfate sodium salt and other polyoxyethylene alkyl ether sulfate salts;
Polyoxyethylene alkyl allyl ether sulfuric acid ester salts such as sodium polyoxyethylene octyl phenyl ether sulfuric acid ester and sodium polyoxyethylene nonyl phenyl ether sulfuric acid ester;
Alkyl sulfonates such as alkyl diphenyl ether disulfonate, sodium dodecyl sulfonate, sodium dialkyl sulfosuccinate;
Alkyl allyl sulfonates such as alkyl disulfonate, sodium dodecylbenzene sulfonate, sodium dibutyl naphthalene sulfonate, sodium triisopropyl naphthalene sulfonate;
Higher alcohol phosphoric acid ester salts such as disodium lauryl phosphoric acid monoester and sodium lauryl phosphoric acid diester;
Polyoxyethylene lauryl ether phosphate monoester disodium, polyoxyethylene lauryl ether phosphate diester sodium, and other polyoxyethylene alkyl ether phosphate ester salts;
Etc. These may be used alone or in combination of two or more.
ラウリン酸ナトリウム、オレイン酸ナトリウム等の脂肪族カルボン酸塩;
ラウリル硫酸エステルナトリウム、セチル硫酸エステルナトリウム、オレイル硫酸エステルナトリウム等の高級アルコール硫酸エステル塩;
ポリオキシエチレンラウリルエーテル硫酸エステルナトリウム等のポリオキシエチレンアルキルエーテル硫酸エステル塩;
ポリオキシエチレンオクチルフェニルエーテル硫酸エステルナトリウム、ポリオキシエチレンノニルフェニルエーテル硫酸エステルナトリウム等のポリオキシエチレンアルキルアリルエーテル硫酸エステル塩;
アルキルジフェニルエーテルジスルホン酸塩、ドデシルスルホン酸ナトリウム、ジアルキルスルホコハク酸ナトリウム等のアルキルスルホン酸塩;
アルキルジスルホン酸塩、ドデシルベンゼンスルホン酸ナトリウム、ジブチルナフタレンスルホン酸ナトリウム、トリイソプロピルナフタレンスルホン酸ナトリウム等のアルキルアリルスルホン酸塩;
ラウリルリン酸モノエステルジナトリウム、ラウリルリン酸ジエステルナトリウム等の高級アルコールリン酸エステル塩;
ポリオキシエチレンラウリルエーテルリン酸モノエステルジナトリウム、ポリオキシエチレンラウリルエーテルリン酸ジエステルナトリウム等のポリオキシエチレンアルキルエーテルリン酸エステル塩;
等が挙げられる。これらは1種単独で用いてもよく、2種以上を併用してもよい。 As the anionic surfactant, specifically, for example,
Aliphatic carboxylates such as sodium laurate and sodium oleate;
Higher alcohol sulfate salts such as sodium lauryl sulfate, sodium cetyl sulfate and sodium oleyl sulfate;
Polyoxyethylene lauryl ether sulfate sodium salt and other polyoxyethylene alkyl ether sulfate salts;
Polyoxyethylene alkyl allyl ether sulfuric acid ester salts such as sodium polyoxyethylene octyl phenyl ether sulfuric acid ester and sodium polyoxyethylene nonyl phenyl ether sulfuric acid ester;
Alkyl sulfonates such as alkyl diphenyl ether disulfonate, sodium dodecyl sulfonate, sodium dialkyl sulfosuccinate;
Alkyl allyl sulfonates such as alkyl disulfonate, sodium dodecylbenzene sulfonate, sodium dibutyl naphthalene sulfonate, sodium triisopropyl naphthalene sulfonate;
Higher alcohol phosphoric acid ester salts such as disodium lauryl phosphoric acid monoester and sodium lauryl phosphoric acid diester;
Polyoxyethylene lauryl ether phosphate monoester disodium, polyoxyethylene lauryl ether phosphate diester sodium, and other polyoxyethylene alkyl ether phosphate ester salts;
Etc. These may be used alone or in combination of two or more.
これらのうち、水現像性が更に良好となる理由から、アルキルスルホン酸塩、アルキルアリルスルホン酸塩などのスルホン酸系界面活性剤が好ましい。
Among these, sulfonic acid type surfactants such as alkyl sulfonates and alkyl allyl sulfonates are preferable because the water developability is further improved.
本発明の感光層において界面活性剤の含有量は、現像性や現像後の乾燥性の観点から、本発明の感光層の全固形分に対して、0.1~20質量%であることが好ましく、1~10質量%であることがより好ましい。
The content of the surfactant in the photosensitive layer of the present invention is preferably 0.1 to 20% by mass based on the total solid content of the photosensitive layer of the present invention from the viewpoint of developability and drying property after development. Preferably, it is 1 to 10% by mass, and more preferably.
(熱重合禁止剤)
本発明の感光層は、混練時の熱安定性を高める、貯蔵安定性を高めるなどの観点から、熱重合禁止剤(安定剤)を添加することができる。
熱重合禁止剤としては、フェノール類、ハイドロキノン類、カテコール類のものなどを挙げることができる。 (Thermal polymerization inhibitor)
The photosensitive layer of the present invention may contain a thermal polymerization inhibitor (stabilizer) from the viewpoints of enhancing the thermal stability during kneading, enhancing the storage stability, and the like.
Examples of thermal polymerization inhibitors include phenols, hydroquinones, and catechols.
本発明の感光層は、混練時の熱安定性を高める、貯蔵安定性を高めるなどの観点から、熱重合禁止剤(安定剤)を添加することができる。
熱重合禁止剤としては、フェノール類、ハイドロキノン類、カテコール類のものなどを挙げることができる。 (Thermal polymerization inhibitor)
The photosensitive layer of the present invention may contain a thermal polymerization inhibitor (stabilizer) from the viewpoints of enhancing the thermal stability during kneading, enhancing the storage stability, and the like.
Examples of thermal polymerization inhibitors include phenols, hydroquinones, and catechols.
本発明の感光層において熱重合禁止剤の含有量は、本発明の効果等がより優れる理由から、本発明の感光層の全固形分に対して、0.001~5質量%であることが好ましい。
The content of the thermal polymerization inhibitor in the photosensitive layer of the present invention is 0.001 to 5% by mass based on the total solid content of the photosensitive layer of the present invention, because the effects of the present invention are more excellent. preferable.
(その他の添加剤)
本発明の感光層は、本発明の効果を阻害しない範囲において、種々の特性向上を目的として、さらに紫外線吸収剤、染料、顔料、消泡剤、香料などの添加剤を適宜添加することができる。 (Other additives)
In the photosensitive layer of the present invention, an additive such as an ultraviolet absorber, a dye, a pigment, a defoaming agent, and a fragrance can be appropriately added within the range not impairing the effects of the present invention for the purpose of improving various characteristics. ..
本発明の感光層は、本発明の効果を阻害しない範囲において、種々の特性向上を目的として、さらに紫外線吸収剤、染料、顔料、消泡剤、香料などの添加剤を適宜添加することができる。 (Other additives)
In the photosensitive layer of the present invention, an additive such as an ultraviolet absorber, a dye, a pigment, a defoaming agent, and a fragrance can be appropriately added within the range not impairing the effects of the present invention for the purpose of improving various characteristics. ..
<感光層の作製方法>
本発明の感光層を作製する方法は特に制限されないが、上述した各成分を含有する組成物(感光性樹脂組成物)を調製し、これを基板等に塗布する方法等が挙げられる。 <Method for preparing photosensitive layer>
The method for producing the photosensitive layer of the present invention is not particularly limited, and examples thereof include a method of preparing a composition (photosensitive resin composition) containing each of the above-mentioned components, and coating the composition on a substrate or the like.
本発明の感光層を作製する方法は特に制限されないが、上述した各成分を含有する組成物(感光性樹脂組成物)を調製し、これを基板等に塗布する方法等が挙げられる。 <Method for preparing photosensitive layer>
The method for producing the photosensitive layer of the present invention is not particularly limited, and examples thereof include a method of preparing a composition (photosensitive resin composition) containing each of the above-mentioned components, and coating the composition on a substrate or the like.
〔好適な態様〕
本発明の印刷版原版は、本発明の効果等がより優れる理由から、使用時に、感光層の上にネガフィルム(すでに画像が形成されているもの)を密着させる、いわゆるアナログ方式の印刷版原版、又は、予め感光層の上に赤外線アブレーション層が密着している、いわゆるCTP(Computerto plate)方式に含まれるLAM(Laserablation mask)方式の印刷版原版であることが好ましい。 [Preferred embodiment]
The printing plate precursor of the present invention is a so-called analog type printing plate precursor in which a negative film (on which an image has already been formed) is brought into close contact with the photosensitive layer at the time of use because the effects of the present invention are more excellent. Alternatively, it is preferably a printing plate precursor of a LAM (Laseration mask) system included in a so-called CTP (Computer to plate) system in which an infrared ablation layer is in close contact with a photosensitive layer in advance.
本発明の印刷版原版は、本発明の効果等がより優れる理由から、使用時に、感光層の上にネガフィルム(すでに画像が形成されているもの)を密着させる、いわゆるアナログ方式の印刷版原版、又は、予め感光層の上に赤外線アブレーション層が密着している、いわゆるCTP(Computerto plate)方式に含まれるLAM(Laserablation mask)方式の印刷版原版であることが好ましい。 [Preferred embodiment]
The printing plate precursor of the present invention is a so-called analog type printing plate precursor in which a negative film (on which an image has already been formed) is brought into close contact with the photosensitive layer at the time of use because the effects of the present invention are more excellent. Alternatively, it is preferably a printing plate precursor of a LAM (Laseration mask) system included in a so-called CTP (Computer to plate) system in which an infrared ablation layer is in close contact with a photosensitive layer in advance.
アナログ方式の印刷版原版は、本発明の効果等がより優れる理由から、基板上に、基板と感光層とを接着する接着剤などからなる接着層と、本発明の感光層と、感光層表面が粘着しないようにするための粘着防止層と、使用前において感光層の傷を防止する保護フィルムと、がこの順で積層されたものからなるのが好ましい。
上記基板としては、具体的には、例えば、ポリエチレンテレフタレート(PET)フィルムなどのプラスチックフィルムもしくはプラスチックシート;ステンレス、アルミニウムなどの金属シート;ブタジエンゴムなどのゴムシート;等を挙げることができる。
なお、アナログ方式の印刷版原版は、使用時には、保護フィルムを剥がし、露出された粘着防止層の上に、予め画像が形成されているネガフィルムが密着される。 The analog type printing plate precursor is, for the reason that the effects of the present invention are more excellent, on the substrate, an adhesive layer made of an adhesive or the like for adhering the substrate and the photosensitive layer, the photosensitive layer of the present invention, and the photosensitive layer surface. It is preferable that an anti-adhesion layer for preventing the sticking of the photosensitive layer and a protective film for preventing scratches on the photosensitive layer before use are laminated in this order.
Specific examples of the substrate include a plastic film or a plastic sheet such as a polyethylene terephthalate (PET) film; a metal sheet such as stainless steel or aluminum; a rubber sheet such as butadiene rubber;
When using the analog type printing plate precursor, the protective film is peeled off at the time of use, and a negative film on which an image is formed in advance is adhered onto the exposed anti-adhesion layer.
上記基板としては、具体的には、例えば、ポリエチレンテレフタレート(PET)フィルムなどのプラスチックフィルムもしくはプラスチックシート;ステンレス、アルミニウムなどの金属シート;ブタジエンゴムなどのゴムシート;等を挙げることができる。
なお、アナログ方式の印刷版原版は、使用時には、保護フィルムを剥がし、露出された粘着防止層の上に、予め画像が形成されているネガフィルムが密着される。 The analog type printing plate precursor is, for the reason that the effects of the present invention are more excellent, on the substrate, an adhesive layer made of an adhesive or the like for adhering the substrate and the photosensitive layer, the photosensitive layer of the present invention, and the photosensitive layer surface. It is preferable that an anti-adhesion layer for preventing the sticking of the photosensitive layer and a protective film for preventing scratches on the photosensitive layer before use are laminated in this order.
Specific examples of the substrate include a plastic film or a plastic sheet such as a polyethylene terephthalate (PET) film; a metal sheet such as stainless steel or aluminum; a rubber sheet such as butadiene rubber;
When using the analog type printing plate precursor, the protective film is peeled off at the time of use, and a negative film on which an image is formed in advance is adhered onto the exposed anti-adhesion layer.
アナログ方式の印刷版原版は、例えば、基板の片面に予め接着剤を塗布し、保護フィルムの片面に予め粘着防止剤を塗布し、上述した感光性樹脂組成物を、予め接着剤を塗布した基板と予め粘着防止剤を塗布した保護フィルムとの間に挟み、感光層の厚みが所定の厚みになるようにプレスすることにより、製造できる。
The analog type printing plate precursor is, for example, one side of the substrate is pre-coated with an adhesive, one side of the protective film is pre-coated with an anti-adhesive agent, the photosensitive resin composition described above, a substrate pre-coated with an adhesive. It can be manufactured by sandwiching it between a protective film coated with an anti-adhesive agent in advance and pressing it so that the thickness of the photosensitive layer becomes a predetermined thickness.
LAM方式の印刷版原版は、アナログ方式の印刷版原版と比較して、感光層と保護フィルムとの間に赤外線アブレーション層を有する点が異なり、その他の構成についてはアナログ方式の印刷版原版と同様の構成である。すなわち、基板上に、接着層と、感光層と、赤外線アブレーション層と、保護フィルムと、がこの順で積層されたものからなる。LAM方式の印刷版原版は、使用時には、保護フィルムを剥がし、赤外線アブレーション層が露出される。
The LAM printing plate precursor is different from the analog printing plate precursor in that it has an infrared ray ablation layer between the photosensitive layer and the protective film, and other configurations are the same as those of the analog printing plate precursor. It is the structure of. That is, the adhesive layer, the photosensitive layer, the infrared ablation layer, and the protective film are laminated in this order on the substrate. When using the LAM type printing plate precursor, the protective film is peeled off and the infrared ablation layer is exposed.
赤外線アブレーション層は、赤外線レーザにより照射された部分を除去することが可能な層であり、それ自体は実用上のレベルで紫外線の透過を遮蔽できる機能を併せ持つ層であって、それに画像を形成することによりネガもしくはポジとしての役割をすることができるものである。
The infrared ablation layer is a layer capable of removing a portion irradiated with an infrared laser, and is a layer which itself has a function of blocking transmission of ultraviolet rays at a practical level and forms an image on it. As a result, it can act as a negative or a positive.
赤外線アブレーション層は、主に、バインダーである樹脂やゴム、赤外線吸収物質、紫外線吸収物質、可塑剤などで構成されている。赤外線アブレーション層は、例えば、上記材料を溶剤に溶かし、これを基材に塗布した後、乾燥させ溶剤を除去することにより製造できる。
The infrared ablation layer is mainly composed of a binder resin or rubber, an infrared absorbing substance, an ultraviolet absorbing substance, a plasticizer, and the like. The infrared ablation layer can be produced, for example, by dissolving the above material in a solvent, applying the solution to a base material, and drying the solution to remove the solvent.
LAM方式の印刷版原版は、例えば、基板の片面に予め接着剤を塗布し、保護フィルムの片面に予め赤外線アブレーション層を塗布し、上述した感光性樹脂組成物を、予め接着剤を塗布した基板と予め赤外線アブレーション層を塗布した保護フィルムとの間に挟み、感光層の厚みが所定の厚みになるようにプレスすることにより、製造できる。
The LAM printing plate precursor is, for example, a substrate on which one side of a substrate is coated with an adhesive in advance, one side of a protective film is coated with an infrared ablation layer in advance, and the photosensitive resin composition is coated with an adhesive in advance. It can be manufactured by sandwiching it between a protective film coated with an infrared ablation layer in advance and pressing it so that the photosensitive layer has a predetermined thickness.
いずれの印刷版原版においても、感光層の厚みは、本発明の効果等がより優れる理由から、0.01~10mmの範囲内であることが好ましい。感光層の厚みが0.01mm以上であれば、レリーフ深度を十分に確保できる。
In any of the printing plate precursors, the thickness of the photosensitive layer is preferably in the range of 0.01 to 10 mm because the effects of the present invention are more excellent. If the thickness of the photosensitive layer is 0.01 mm or more, a sufficient relief depth can be secured.
[フレキソ印刷版]
本発明のフレキソ印刷版(以下、「本発明の印刷版」とも言う)は、画像部と非画像部とを有するフレキソ印刷版である。
ここで、上記画像部は、上述した本発明の印刷版原版が有する感光層(本発明の感光層)を画像様に露光し、現像することにより得られる画像部である。
本発明の印刷版は、耐刷性、ハンドリング性及び後端部着肉性がより優れる理由から、以下の方法で得られるものであることが好ましい。 [Flexographic printing plate]
The flexographic printing plate of the present invention (hereinafter, also referred to as “printing plate of the present invention”) is a flexographic printing plate having an image portion and a non-image portion.
Here, the image area is an image area obtained by imagewise exposing and developing the photosensitive layer (the photosensitive layer of the invention) included in the printing plate precursor of the invention.
The printing plate of the present invention is preferably obtained by the following method, because it is more excellent in printing durability, handling property, and rear end portion inking property.
本発明のフレキソ印刷版(以下、「本発明の印刷版」とも言う)は、画像部と非画像部とを有するフレキソ印刷版である。
ここで、上記画像部は、上述した本発明の印刷版原版が有する感光層(本発明の感光層)を画像様に露光し、現像することにより得られる画像部である。
本発明の印刷版は、耐刷性、ハンドリング性及び後端部着肉性がより優れる理由から、以下の方法で得られるものであることが好ましい。 [Flexographic printing plate]
The flexographic printing plate of the present invention (hereinafter, also referred to as “printing plate of the present invention”) is a flexographic printing plate having an image portion and a non-image portion.
Here, the image area is an image area obtained by imagewise exposing and developing the photosensitive layer (the photosensitive layer of the invention) included in the printing plate precursor of the invention.
The printing plate of the present invention is preferably obtained by the following method, because it is more excellent in printing durability, handling property, and rear end portion inking property.
印刷版原版の感光層にレリーフ像を形成するには、まず、印刷版原版の基板側から紫外線照射を行う(裏露光)。
To form a relief image on the photosensitive layer of the printing plate precursor, first, UV irradiation is performed from the substrate side of the printing plate precursor (back exposure).
アナログ方式の印刷版原版を用いる場合、保護フィルムを剥がし、露出された粘着防止層の上に、予め画像が形成されているネガフィルムを密着させる。一方、LAM方式の印刷版原版を用いる場合、保護フィルムを剥がし、露出された赤外線アブレーション層に赤外線レーザを照射するなどして所望の画像を形成する。
When using an analog printing plate precursor, peel off the protective film and adhere the negative film on which an image is formed in advance onto the exposed anti-adhesion layer. On the other hand, when using the LAM printing plate precursor, the protective film is peeled off, and the exposed infrared ablation layer is irradiated with an infrared laser to form a desired image.
次いで、ネガフィルムあるいは赤外線アブレーション層の上から紫外線を照射することにより、感光層を硬化させる(主露光)。紫外線は、通常、300~400nmの波長の光を照射できる高圧水銀灯、超高圧水銀灯、メタルハライドランプ、キセノン灯、カーボンアーク灯、ケミカル灯などにより照射できる。感光層は、紫外線照射により、照射された部分が硬化する。ネガフィルムあるいは赤外線アブレーション層で覆われた感光層には、紫外線が照射された硬化部分と、紫外線が照射されていない未硬化部分とが生じる。
Next, the photosensitive layer is cured by irradiating ultraviolet rays from above the negative film or infrared ablation layer (main exposure). Ultraviolet rays can be usually irradiated by a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp, a chemical lamp, or the like, which can irradiate light having a wavelength of 300 to 400 nm. The photosensitive layer is cured by irradiation with ultraviolet rays. The photosensitive layer covered with the negative film or the infrared ablation layer has a cured portion irradiated with ultraviolet rays and an uncured portion not irradiated with ultraviolet rays.
次いで、現像液中で感光層の未硬化部分を除去することにより、レリーフ像を形成する。現像液には、水系の現像液(水系現像液)を用いる。水系現像液は、水に、必要に応じて界面活性剤やpH調整剤などを添加したものからなる。感光層の未硬化部分の除去は、例えばスプレー式現像装置やブラシ式洗い出し機などを用いて未硬化部分を洗い出すことにより行うことができる。
Next, a relief image is formed by removing the uncured portion of the photosensitive layer in a developing solution. A water-based developer (water-based developer) is used as the developer. The water-based developer is made of water to which a surfactant, a pH adjuster, or the like is added, if necessary. The uncured portion of the photosensitive layer can be removed by washing out the uncured portion using, for example, a spray type developing device or a brush type washing machine.
次いで、現像液から印刷版材を取り出してこれを乾燥させる。次いで、必要に応じて乾燥させた印刷版材全体に紫外線を照射する(後露光)。これにより、フレキソ印刷版が得られる。
Next, remove the printing plate material from the developer and dry it. Then, if necessary, the dried printing plate material is irradiated with ultraviolet rays (post-exposure). This gives a flexographic printing plate.
以下に、実施例を挙げて本発明を更に詳細に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す実施例により限定的に解釈されるべきものではない。
The present invention will be described in more detail below with reference to examples. The materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the following examples.
〔フレキソ印刷版原版の製造〕
以下のとおり、実施例及び比較例のフレキソ印刷版原版を製造した。なお、製造したフレキソ印刷版原版は上述したLAM方式の印刷版原版に該当する。 [Manufacture of flexographic printing plate precursor]
The flexographic printing plate precursors of Examples and Comparative Examples were manufactured as follows. The manufactured flexographic printing plate precursor corresponds to the above-mentioned LAM printing plate precursor.
以下のとおり、実施例及び比較例のフレキソ印刷版原版を製造した。なお、製造したフレキソ印刷版原版は上述したLAM方式の印刷版原版に該当する。 [Manufacture of flexographic printing plate precursor]
The flexographic printing plate precursors of Examples and Comparative Examples were manufactured as follows. The manufactured flexographic printing plate precursor corresponds to the above-mentioned LAM printing plate precursor.
<実施例1>
<Example 1>
(感光性樹脂組成物の調製)
水分散ラテックス(日本ZEON製、Nipol LX111NF、ポリブタジエンの水分散ラテックス、固形分55%)63.6質量部と、テレケリックポリマー(大阪有機化学工業製、BAC-45)(両末端にアクリロイルオキシ基を有するポリブタジエン、Mw=10,000)(上述した特定ポリマーに該当)10質量部と、多官能モノマー(共栄社化学製、ライトエステルTMP)(トリメチロールプロパントリメタクリレート)(上述した特定モノマーに該当)10質量部と、単官能モノマー(共栄社化学製、ライトエステルIB-X)(イソボルニルメタクリレート)3質量部とを混合し、60℃に加熱した乾燥機で3時間水分を蒸発させて、水分散ラテックスから得られた重合体(上述した水分散性粒子に該当)と特定ポリマーと特定モノマーと単官能モノマーとを含有する混合物を得た。
この混合物と、ブタジエンゴム(旭化成製、NF35R)20質量部と、可塑剤(出光製、ダイアナプロセスオイルPW-32)15質量部と、界面活性剤(日油製、ラピゾールA-90、有効分90%)4.4質量部とを110℃に設定したニーダー中で45分混練した。その後、ニーダー中に、熱重合禁止剤0.2質量部と、光重合開始剤(東京化学工業製、ベンジルジメチルケタール)3質量部とを投入し、5分間混練して、感光性樹脂組成物を得た。 (Preparation of photosensitive resin composition)
63.6 parts by mass of water-dispersed latex (Nipol LX111NF manufactured by Japan ZEON, water-dispersed latex of polybutadiene, solid content 55%) and telechelic polymer (BAC-45 manufactured by Osaka Organic Chemical Industry) (acryloyloxy group at both ends) With polybutadiene having Mw = 10,000) (corresponding to the above-mentioned specific polymer) and 10 parts by mass of a polyfunctional monomer (Kyoeisha Chemical Co., Ltd., light ester TMP) (trimethylolpropane trimethacrylate) (corresponding to the above-mentioned specific monomer). 10 parts by mass and 3 parts by mass of a monofunctional monomer (Kyoeisha Chemical Co., Ltd., light ester IB-X) (isobornyl methacrylate) were mixed, and water was evaporated for 3 hours in a dryer heated to 60 ° C. to obtain water. Polymer obtained from dispersed latex (corresponding to the above water-dispersible particles) and specific poly A mixture containing the mer, the specific monomer and the monofunctional monomer was obtained.
This mixture, 20 parts by mass of butadiene rubber (NF35R manufactured by Asahi Kasei), 15 parts by mass of a plasticizer (manufactured by Idemitsu, Diana Process Oil PW-32), and a surfactant (manufactured by NOF CORPORATION, Rapisol A-90, effective ingredient) 90%) 4.4 parts by mass were kneaded in a kneader set at 110 ° C. for 45 minutes. Then, 0.2 part by mass of a thermal polymerization inhibitor and 3 parts by mass of a photopolymerization initiator (manufactured by Tokyo Chemical Industry Co., benzyl dimethyl ketal) were put into a kneader and kneaded for 5 minutes to prepare a photosensitive resin composition. Got
水分散ラテックス(日本ZEON製、Nipol LX111NF、ポリブタジエンの水分散ラテックス、固形分55%)63.6質量部と、テレケリックポリマー(大阪有機化学工業製、BAC-45)(両末端にアクリロイルオキシ基を有するポリブタジエン、Mw=10,000)(上述した特定ポリマーに該当)10質量部と、多官能モノマー(共栄社化学製、ライトエステルTMP)(トリメチロールプロパントリメタクリレート)(上述した特定モノマーに該当)10質量部と、単官能モノマー(共栄社化学製、ライトエステルIB-X)(イソボルニルメタクリレート)3質量部とを混合し、60℃に加熱した乾燥機で3時間水分を蒸発させて、水分散ラテックスから得られた重合体(上述した水分散性粒子に該当)と特定ポリマーと特定モノマーと単官能モノマーとを含有する混合物を得た。
この混合物と、ブタジエンゴム(旭化成製、NF35R)20質量部と、可塑剤(出光製、ダイアナプロセスオイルPW-32)15質量部と、界面活性剤(日油製、ラピゾールA-90、有効分90%)4.4質量部とを110℃に設定したニーダー中で45分混練した。その後、ニーダー中に、熱重合禁止剤0.2質量部と、光重合開始剤(東京化学工業製、ベンジルジメチルケタール)3質量部とを投入し、5分間混練して、感光性樹脂組成物を得た。 (Preparation of photosensitive resin composition)
63.6 parts by mass of water-dispersed latex (Nipol LX111NF manufactured by Japan ZEON, water-dispersed latex of polybutadiene, solid content 55%) and telechelic polymer (BAC-45 manufactured by Osaka Organic Chemical Industry) (acryloyloxy group at both ends) With polybutadiene having Mw = 10,000) (corresponding to the above-mentioned specific polymer) and 10 parts by mass of a polyfunctional monomer (Kyoeisha Chemical Co., Ltd., light ester TMP) (trimethylolpropane trimethacrylate) (corresponding to the above-mentioned specific monomer). 10 parts by mass and 3 parts by mass of a monofunctional monomer (Kyoeisha Chemical Co., Ltd., light ester IB-X) (isobornyl methacrylate) were mixed, and water was evaporated for 3 hours in a dryer heated to 60 ° C. to obtain water. Polymer obtained from dispersed latex (corresponding to the above water-dispersible particles) and specific poly A mixture containing the mer, the specific monomer and the monofunctional monomer was obtained.
This mixture, 20 parts by mass of butadiene rubber (NF35R manufactured by Asahi Kasei), 15 parts by mass of a plasticizer (manufactured by Idemitsu, Diana Process Oil PW-32), and a surfactant (manufactured by NOF CORPORATION, Rapisol A-90, effective ingredient) 90%) 4.4 parts by mass were kneaded in a kneader set at 110 ° C. for 45 minutes. Then, 0.2 part by mass of a thermal polymerization inhibitor and 3 parts by mass of a photopolymerization initiator (manufactured by Tokyo Chemical Industry Co., benzyl dimethyl ketal) were put into a kneader and kneaded for 5 minutes to prepare a photosensitive resin composition. Got
(赤外線アブレーション層用積層体の作製)
アクリル樹脂(根上工業製、ハイパール M-5000)50質量部と、エラストマー(日本ゼオン製、Nipol DN-101)50質量部と、カーボンブラック(三菱化学製、MA-8)100質量部とにメチルイソブチルケトン812質量部を加え、羽撹拌にて混合した。得られた混合液をペイントシェイカーで分散させた後、固形分が15質量%となるように、さらにメチルイソブチルケトンを加えることにより、ポリマー/カーボンブラック分散液(赤外線アブレーション層用塗工液)を得た。
次いで、厚さ75μmのPETフィルム(保護フィルム)の片面に、乾燥後の厚さが1.0μmとなるように、バーコーターで赤外線アブレーション層用塗工液を塗工した後、140℃に設定したオーブンで5分間乾燥させることにより、保護フィルム上に赤外線アブレーション層が形成された積層体(赤外線アブレーション層用積層体)を作製した。 (Preparation of laminated body for infrared ablation layer)
Acrylic resin (Negami Kogyo, Hyper M-5000) 50 parts by mass, elastomer (Nippon Zeon, Nipol DN-101) 50 parts by mass, carbon black (Mitsubishi Chemical, MA-8) 100 parts by mass and methyl. 812 parts by mass of isobutyl ketone was added and mixed by stirring with a blade. The resulting mixed liquid was dispersed with a paint shaker, and then methyl isobutyl ketone was further added so that the solid content was 15% by mass to obtain a polymer / carbon black dispersion (infrared ablation layer coating liquid). Obtained.
Then, on one side of a PET film (protective film) having a thickness of 75 μm, a coating liquid for infrared ablation layer was applied with a bar coater so that the thickness after drying was 1.0 μm, and then set at 140 ° C. By drying in the oven for 5 minutes, a laminate having an infrared ablation layer formed on the protective film (infrared ablation layer laminate) was produced.
アクリル樹脂(根上工業製、ハイパール M-5000)50質量部と、エラストマー(日本ゼオン製、Nipol DN-101)50質量部と、カーボンブラック(三菱化学製、MA-8)100質量部とにメチルイソブチルケトン812質量部を加え、羽撹拌にて混合した。得られた混合液をペイントシェイカーで分散させた後、固形分が15質量%となるように、さらにメチルイソブチルケトンを加えることにより、ポリマー/カーボンブラック分散液(赤外線アブレーション層用塗工液)を得た。
次いで、厚さ75μmのPETフィルム(保護フィルム)の片面に、乾燥後の厚さが1.0μmとなるように、バーコーターで赤外線アブレーション層用塗工液を塗工した後、140℃に設定したオーブンで5分間乾燥させることにより、保護フィルム上に赤外線アブレーション層が形成された積層体(赤外線アブレーション層用積層体)を作製した。 (Preparation of laminated body for infrared ablation layer)
Acrylic resin (Negami Kogyo, Hyper M-5000) 50 parts by mass, elastomer (Nippon Zeon, Nipol DN-101) 50 parts by mass, carbon black (Mitsubishi Chemical, MA-8) 100 parts by mass and methyl. 812 parts by mass of isobutyl ketone was added and mixed by stirring with a blade. The resulting mixed liquid was dispersed with a paint shaker, and then methyl isobutyl ketone was further added so that the solid content was 15% by mass to obtain a polymer / carbon black dispersion (infrared ablation layer coating liquid). Obtained.
Then, on one side of a PET film (protective film) having a thickness of 75 μm, a coating liquid for infrared ablation layer was applied with a bar coater so that the thickness after drying was 1.0 μm, and then set at 140 ° C. By drying in the oven for 5 minutes, a laminate having an infrared ablation layer formed on the protective film (infrared ablation layer laminate) was produced.
(フレキソ印刷版原版の作製)
厚さ125μmのPETフィルム(基板)の片面に接着剤を塗布して、基板に接着層を形成した。そして、上記接着層と、上述のとおり作製した赤外線アブレーション層用積層体の赤外線アブレーション層との間に、上述のとおり調製した感光性樹脂組成物を挟んで、感光性樹脂組成物の層(感光層)の厚みが1mmになるように80℃に加熱したプレス機でプレスすることにより、基板と接着層と感光層と赤外線アブレーション層と保護フィルムとをこの順に有するフレキソ印刷版原版を作製した。 (Preparation of flexographic printing plate precursor)
An adhesive was applied to one side of a 125 μm thick PET film (substrate) to form an adhesive layer on the substrate. Then, the photosensitive resin composition prepared as described above is sandwiched between the adhesive layer and the infrared ablation layer of the infrared ablation layer laminate prepared as described above to form a layer of the photosensitive resin composition (photosensitive layer). A flexographic printing plate precursor having a substrate, an adhesive layer, a photosensitive layer, an infrared ablation layer and a protective film in this order was prepared by pressing with a press machine heated to 80 ° C. so that the thickness of the layer) was 1 mm.
厚さ125μmのPETフィルム(基板)の片面に接着剤を塗布して、基板に接着層を形成した。そして、上記接着層と、上述のとおり作製した赤外線アブレーション層用積層体の赤外線アブレーション層との間に、上述のとおり調製した感光性樹脂組成物を挟んで、感光性樹脂組成物の層(感光層)の厚みが1mmになるように80℃に加熱したプレス機でプレスすることにより、基板と接着層と感光層と赤外線アブレーション層と保護フィルムとをこの順に有するフレキソ印刷版原版を作製した。 (Preparation of flexographic printing plate precursor)
An adhesive was applied to one side of a 125 μm thick PET film (substrate) to form an adhesive layer on the substrate. Then, the photosensitive resin composition prepared as described above is sandwiched between the adhesive layer and the infrared ablation layer of the infrared ablation layer laminate prepared as described above to form a layer of the photosensitive resin composition (photosensitive layer). A flexographic printing plate precursor having a substrate, an adhesive layer, a photosensitive layer, an infrared ablation layer and a protective film in this order was prepared by pressing with a press machine heated to 80 ° C. so that the thickness of the layer) was 1 mm.
<実施例1以外の実施例及び比較例>
感光性樹脂組成物における各成分の種類及び全固形分に対する質量比(質量%)を表1に記載のとおり変更した以外は、実施例1と同様の手順に従って、フレキソ印刷版原版を製造した。 <Examples other than Example 1 and Comparative Examples>
A flexographic printing plate precursor was produced according to the same procedure as in Example 1 except that the kind of each component in the photosensitive resin composition and the mass ratio (% by mass) to the total solid content were changed as shown in Table 1.
感光性樹脂組成物における各成分の種類及び全固形分に対する質量比(質量%)を表1に記載のとおり変更した以外は、実施例1と同様の手順に従って、フレキソ印刷版原版を製造した。 <Examples other than Example 1 and Comparative Examples>
A flexographic printing plate precursor was produced according to the same procedure as in Example 1 except that the kind of each component in the photosensitive resin composition and the mass ratio (% by mass) to the total solid content were changed as shown in Table 1.
〔フレキソ印刷版の製造〕
得られたフレキソ印刷版原版について、40Wのケミカル灯を15本並べた露光装置を用いて、基板側から15cmの距離から15秒間露光(裏露光)した。その後、保護フィルムを剥がし、ESKO社製CDI Spark2120を用いて赤外線アブレーション層にネガパターンを形成した。その後、上記露光装置を用いて、赤外線アブレーション層側から15cmの距離から8分間露光(主露光)した。その後、洗剤(ミヨシ石鹸製、無添加 食器洗いせっけん)の濃度が0.5%になるように調整した水系現像液を入れたブラシ式洗い出し機(液温50℃)を用いて10分間現像を行った。その後、60℃の熱風を用いて水分が除去されるまで乾燥を行った。その後、上記露光装置を用いてで感光層側から15cmの距離から8分間露光(後露光)した。
このようにして、フレキソ印刷版を得た。 [Manufacture of flexographic printing plates]
The obtained flexographic printing plate precursor was exposed (back exposure) for 15 seconds from a distance of 15 cm from the substrate side using an exposure device in which 15 40 W chemical lamps were arranged. Then, the protective film was peeled off, and a negative pattern was formed on the infrared ablation layer using CDI Spark2120 manufactured by ESKO. Then, using the said exposure apparatus, it exposed (main exposure) from the infrared ablation layer side from the distance of 15 cm for 8 minutes. After that, development is carried out for 10 minutes using a brush-type washing machine (liquid temperature 50 ° C) containing an aqueous developer adjusted so that the concentration of detergent (made by Miyoshi soap, additive-free dishwashing soap) is 0.5%. It was Then, it was dried using hot air at 60 ° C. until the water content was removed. After that, exposure (post-exposure) was carried out for 8 minutes from a distance of 15 cm from the photosensitive layer side using the above-mentioned exposure apparatus.
In this way, a flexographic printing plate was obtained.
得られたフレキソ印刷版原版について、40Wのケミカル灯を15本並べた露光装置を用いて、基板側から15cmの距離から15秒間露光(裏露光)した。その後、保護フィルムを剥がし、ESKO社製CDI Spark2120を用いて赤外線アブレーション層にネガパターンを形成した。その後、上記露光装置を用いて、赤外線アブレーション層側から15cmの距離から8分間露光(主露光)した。その後、洗剤(ミヨシ石鹸製、無添加 食器洗いせっけん)の濃度が0.5%になるように調整した水系現像液を入れたブラシ式洗い出し機(液温50℃)を用いて10分間現像を行った。その後、60℃の熱風を用いて水分が除去されるまで乾燥を行った。その後、上記露光装置を用いてで感光層側から15cmの距離から8分間露光(後露光)した。
このようにして、フレキソ印刷版を得た。 [Manufacture of flexographic printing plates]
The obtained flexographic printing plate precursor was exposed (back exposure) for 15 seconds from a distance of 15 cm from the substrate side using an exposure device in which 15 40 W chemical lamps were arranged. Then, the protective film was peeled off, and a negative pattern was formed on the infrared ablation layer using CDI Spark2120 manufactured by ESKO. Then, using the said exposure apparatus, it exposed (main exposure) from the infrared ablation layer side from the distance of 15 cm for 8 minutes. After that, development is carried out for 10 minutes using a brush-type washing machine (liquid temperature 50 ° C) containing an aqueous developer adjusted so that the concentration of detergent (made by Miyoshi soap, additive-free dishwashing soap) is 0.5%. It was Then, it was dried using hot air at 60 ° C. until the water content was removed. After that, exposure (post-exposure) was carried out for 8 minutes from a distance of 15 cm from the photosensitive layer side using the above-mentioned exposure apparatus.
In this way, a flexographic printing plate was obtained.
〔評価〕
得られたフレキソ印刷版原版及びフレキソ印刷版について、以下の評価を行った。 [Evaluation]
The following evaluations were performed on the obtained flexographic printing plate precursor and flexographic printing plate.
得られたフレキソ印刷版原版及びフレキソ印刷版について、以下の評価を行った。 [Evaluation]
The following evaluations were performed on the obtained flexographic printing plate precursor and flexographic printing plate.
<水現像性>
得られたフレキソ印刷版について、定圧厚さ測定器を使用し、非画像部の厚みを測定した。そして、以下の基準で評価した。
結果を表1に示す。実用上、Aであることが好ましい。
(評価基準)
A:非画像部厚さが700μm未満
B:非画像部の厚さが700μm以上800μm未満
C:非画像部厚さが800μm以上 <Water developability>
About the obtained flexographic printing plate, the thickness of the non-image part was measured using the constant pressure thickness measuring device. And the following criteria evaluated.
The results are shown in Table 1. Practically, A is preferable.
(Evaluation criteria)
A: Non-image area thickness is less than 700 μm B: Non-image area thickness is 700 μm or more and less than 800 μm C: Non-image area thickness is 800 μm or more
得られたフレキソ印刷版について、定圧厚さ測定器を使用し、非画像部の厚みを測定した。そして、以下の基準で評価した。
結果を表1に示す。実用上、Aであることが好ましい。
(評価基準)
A:非画像部厚さが700μm未満
B:非画像部の厚さが700μm以上800μm未満
C:非画像部厚さが800μm以上 <Water developability>
About the obtained flexographic printing plate, the thickness of the non-image part was measured using the constant pressure thickness measuring device. And the following criteria evaluated.
The results are shown in Table 1. Practically, A is preferable.
(Evaluation criteria)
A: Non-image area thickness is less than 700 μm B: Non-image area thickness is 700 μm or more and less than 800 μm C: Non-image area thickness is 800 μm or more
<耐刷性及びハンドリング性>
得られたフレキソ印刷版について、連続加重式引掻強度試験機(HEIDON TYPE:18)を使用し、500gの荷重および往復速度100mm/分の条件で、擦り部材として綿ウエスを用い、画像部を4回擦った。擦り試験前に特定した、直径が500μmの独立小点10個について、擦り試験後に独立小点に欠け折れが発生しているか否かを以下の基準で評価した。
結果を表1に示す。耐刷性及びハンドリング性の両方の観点から、実用上、2~4点であることが好ましく、3~4点であることがより好ましく、4点であることがさらに好ましい。
(評価基準)
4点:10個の独立小点のいずれも欠けていない、折れていない
3点:10個の独立小点のうち1個が欠けている、折れている
2点:10個の独立小点のうち2個が欠けている、折れている
1点:10個の独立小点のうち3個以上が欠けている、折れている <Printing durability and handling>
About the obtained flexographic printing plate, a continuous weight type scratching strength tester (HEIDON TYPE: 18) was used, a cotton waste was used as a rubbing member under a load of 500 g and a reciprocating speed of 100 mm / min, and an image portion was formed. Rubbed 4 times. With respect to 10 independent small dots having a diameter of 500 μm, which were specified before the rubbing test, whether or not the individual small dots were broken after the rubbing test was evaluated based on the following criteria.
The results are shown in Table 1. From the viewpoints of both printing durability and handleability, practically, it is preferably 2 to 4 points, more preferably 3 to 4 points, and further preferably 4 points.
(Evaluation criteria)
4 points: none of 10 independent dots, not broken 3 points: 1 out of 10 independent dots, broken 2 points: 10 independent dots Two of them are missing or broken 1 point: 3 or more of 10 independent dots are missing or broken
得られたフレキソ印刷版について、連続加重式引掻強度試験機(HEIDON TYPE:18)を使用し、500gの荷重および往復速度100mm/分の条件で、擦り部材として綿ウエスを用い、画像部を4回擦った。擦り試験前に特定した、直径が500μmの独立小点10個について、擦り試験後に独立小点に欠け折れが発生しているか否かを以下の基準で評価した。
結果を表1に示す。耐刷性及びハンドリング性の両方の観点から、実用上、2~4点であることが好ましく、3~4点であることがより好ましく、4点であることがさらに好ましい。
(評価基準)
4点:10個の独立小点のいずれも欠けていない、折れていない
3点:10個の独立小点のうち1個が欠けている、折れている
2点:10個の独立小点のうち2個が欠けている、折れている
1点:10個の独立小点のうち3個以上が欠けている、折れている <Printing durability and handling>
About the obtained flexographic printing plate, a continuous weight type scratching strength tester (HEIDON TYPE: 18) was used, a cotton waste was used as a rubbing member under a load of 500 g and a reciprocating speed of 100 mm / min, and an image portion was formed. Rubbed 4 times. With respect to 10 independent small dots having a diameter of 500 μm, which were specified before the rubbing test, whether or not the individual small dots were broken after the rubbing test was evaluated based on the following criteria.
The results are shown in Table 1. From the viewpoints of both printing durability and handleability, practically, it is preferably 2 to 4 points, more preferably 3 to 4 points, and further preferably 4 points.
(Evaluation criteria)
4 points: none of 10 independent dots, not broken 3 points: 1 out of 10 independent dots, broken 2 points: 10 independent dots Two of them are missing or broken 1 point: 3 or more of 10 independent dots are missing or broken
<後端部着肉性>
得られたフレキソ印刷版について以下のとおり後端部着肉性を評価した。
印刷機はフレキソ印刷機(太陽機械製、TLF-270)を使用した。得られたフレキソ印刷版を、クッションテープ(Lohmann社製)を介して、版胴(ドラム)に張り込み、印刷機に設置した。その後、キスタッチ(画像全面が着肉し始める印圧)を0(基準印圧)とし、そこから、80μm押し込んだ条件で、印刷速度150m/分印刷を行った。評価に使用した被印刷体は、上記条件で5,000回押し込んだ後にサンプリングした。被印刷体としては、50μmOPPフィルム(阿部紙業製)を用いた。また、インキとしては、水性フレキソインキ、ハイドリックFCF(大日精化製)を用いた。そして、被印刷体における画像部の後端部を、20倍のマイクロスコープ(キーエンス製、VHX-1000)で観察し、以下の基準で評価した。
結果を表1に示す。実用上、2~4点であることが好ましく、3~4点であることがより好ましく、4点であることがさらに好ましい。
(評価基準)
4点:全く着肉不良がないもの
3点:後端部の濃度がやや薄いもの
2点:後端部の幅方向で白抜けが途切れ途切れ確認されるもの
1点:後端部の幅方向で白抜けが全面に渡って確認されるもの <Rear end part inking property>
The flexographic printing plate thus obtained was evaluated for its rear end inking property as follows.
A flexo printer (manufactured by Taiyo Kikai, TLF-270) was used as the printer. The flexographic printing plate thus obtained was attached to a plate cylinder (drum) via a cushion tape (manufactured by Lohmann) and set on a printing machine. After that, a kiss touch (printing pressure at which the entire surface of the image starts to be inked) was set to 0 (reference printing pressure), and printing was performed at a printing speed of 150 m / min under the condition that 80 μm was pushed in from there. The printing medium used for evaluation was sampled after being pressed 5,000 times under the above conditions. As the material to be printed, a 50 μm OPP film (manufactured by Abe Paper Industry) was used. As the ink, water-based flexo ink and Hydric FCF (manufactured by Dainichiseika) were used. Then, the rear end portion of the image portion on the printing medium was observed with a 20 times microscope (VHX-1000, manufactured by KEYENCE) and evaluated according to the following criteria.
The results are shown in Table 1. Practically, it is preferably 2 to 4 points, more preferably 3 to 4 points, and further preferably 4 points.
(Evaluation criteria)
4 points: No inking defects at all 3 points: The density of the rear edge is slightly low 2 points: White spots are observed in the widthwise direction of the rear edge 1 point: The widthwise direction of the rear edge White spots are confirmed over the entire surface
得られたフレキソ印刷版について以下のとおり後端部着肉性を評価した。
印刷機はフレキソ印刷機(太陽機械製、TLF-270)を使用した。得られたフレキソ印刷版を、クッションテープ(Lohmann社製)を介して、版胴(ドラム)に張り込み、印刷機に設置した。その後、キスタッチ(画像全面が着肉し始める印圧)を0(基準印圧)とし、そこから、80μm押し込んだ条件で、印刷速度150m/分印刷を行った。評価に使用した被印刷体は、上記条件で5,000回押し込んだ後にサンプリングした。被印刷体としては、50μmOPPフィルム(阿部紙業製)を用いた。また、インキとしては、水性フレキソインキ、ハイドリックFCF(大日精化製)を用いた。そして、被印刷体における画像部の後端部を、20倍のマイクロスコープ(キーエンス製、VHX-1000)で観察し、以下の基準で評価した。
結果を表1に示す。実用上、2~4点であることが好ましく、3~4点であることがより好ましく、4点であることがさらに好ましい。
(評価基準)
4点:全く着肉不良がないもの
3点:後端部の濃度がやや薄いもの
2点:後端部の幅方向で白抜けが途切れ途切れ確認されるもの
1点:後端部の幅方向で白抜けが全面に渡って確認されるもの <Rear end part inking property>
The flexographic printing plate thus obtained was evaluated for its rear end inking property as follows.
A flexo printer (manufactured by Taiyo Kikai, TLF-270) was used as the printer. The flexographic printing plate thus obtained was attached to a plate cylinder (drum) via a cushion tape (manufactured by Lohmann) and set on a printing machine. After that, a kiss touch (printing pressure at which the entire surface of the image starts to be inked) was set to 0 (reference printing pressure), and printing was performed at a printing speed of 150 m / min under the condition that 80 μm was pushed in from there. The printing medium used for evaluation was sampled after being pressed 5,000 times under the above conditions. As the material to be printed, a 50 μm OPP film (manufactured by Abe Paper Industry) was used. As the ink, water-based flexo ink and Hydric FCF (manufactured by Dainichiseika) were used. Then, the rear end portion of the image portion on the printing medium was observed with a 20 times microscope (VHX-1000, manufactured by KEYENCE) and evaluated according to the following criteria.
The results are shown in Table 1. Practically, it is preferably 2 to 4 points, more preferably 3 to 4 points, and further preferably 4 points.
(Evaluation criteria)
4 points: No inking defects at all 3 points: The density of the rear edge is slightly low 2 points: White spots are observed in the widthwise direction of the rear edge 1 point: The widthwise direction of the rear edge White spots are confirmed over the entire surface
以下に、表1中の一部の成分について詳細を示す。
・日本ZEON製 Nipol LX111NF:ポリブタジエンの水分散ラテックス、固形分55%
・日本エイアンドエル製 スマーテックスPA-3974:メタクリル酸メチル-ブタジエン系共重合体(メチルメタクリレート-ブタジエン共重合体)の水分散ラテックス、固形分50%
・大阪有機化学工業製 BAC-45:両末端にアクリロイルオキシ基を有するポリブタジエン、Mw=10,000(上述した特定ポリマーに該当)
・共栄社化学製 ABU-2S:両末端にアクリロイルオキシ基を有するポリブタジエン、Mw=5,000未満(Mwが5,000未満であるため、上述した特定ポリマーに該当しない)
・共栄社化学製 ライトエステルTMP(トリメチロールプロパントリメタクリレート)(上述した特定モノマーに該当)
・新中村工業化学製 NKエステルA-GLY-9E(下記構造)(上述した特定モノマーに該当)
・共栄社化学製 ライトエステルIB-X(イソボルニルメタクリレート)
・旭化成製 NF35R(ブタジエンゴム)(上述した水分散性粒子及び特定ポリマーのいずれにも該当しない)
・新中村工業化学製 NKエステルNOD-N(1,9-ノナンジオールジメタクリレート) The details of some components in Table 1 are shown below.
-Nipol LX111NF manufactured by Japan ZEON: water dispersion latex of polybutadiene, solid content 55%
・ Nippon A & L Smartex PA-3974: Water-dispersed latex of methyl methacrylate-butadiene copolymer (methyl methacrylate-butadiene copolymer), solid content 50%
BAC-45 manufactured by Osaka Organic Chemical Industry: polybutadiene having an acryloyloxy group at both ends, Mw = 10,000 (corresponding to the above-mentioned specific polymer)
-Kyoeisha Chemical Co., Ltd. ABU-2S: polybutadiene having acryloyloxy groups at both ends, Mw = less than 5,000 (because Mw is less than 5,000, it does not correspond to the above-mentioned specific polymer).
・ Kyoeisha Chemical's light ester TMP (trimethylolpropane trimethacrylate) (corresponding to the above-mentioned specific monomer)
・ Shin-Nakamura Kogyo Kagaku NK Ester A-GLY-9E (structure below)
・ Kyoeisha Chemical Light Ester IB-X (isobornyl methacrylate)
Asahi Kasei NF35R (butadiene rubber) (Neither of the above-mentioned water-dispersible particles nor the specific polymer)
・ Shin-Nakamura Industrial Chemical NK ester NOD-N (1,9-nonanediol dimethacrylate)
・日本ZEON製 Nipol LX111NF:ポリブタジエンの水分散ラテックス、固形分55%
・日本エイアンドエル製 スマーテックスPA-3974:メタクリル酸メチル-ブタジエン系共重合体(メチルメタクリレート-ブタジエン共重合体)の水分散ラテックス、固形分50%
・大阪有機化学工業製 BAC-45:両末端にアクリロイルオキシ基を有するポリブタジエン、Mw=10,000(上述した特定ポリマーに該当)
・共栄社化学製 ABU-2S:両末端にアクリロイルオキシ基を有するポリブタジエン、Mw=5,000未満(Mwが5,000未満であるため、上述した特定ポリマーに該当しない)
・共栄社化学製 ライトエステルTMP(トリメチロールプロパントリメタクリレート)(上述した特定モノマーに該当)
・新中村工業化学製 NKエステルA-GLY-9E(下記構造)(上述した特定モノマーに該当)
・旭化成製 NF35R(ブタジエンゴム)(上述した水分散性粒子及び特定ポリマーのいずれにも該当しない)
・新中村工業化学製 NKエステルNOD-N(1,9-ノナンジオールジメタクリレート) The details of some components in Table 1 are shown below.
-Nipol LX111NF manufactured by Japan ZEON: water dispersion latex of polybutadiene, solid content 55%
・ Nippon A & L Smartex PA-3974: Water-dispersed latex of methyl methacrylate-butadiene copolymer (methyl methacrylate-butadiene copolymer), solid content 50%
BAC-45 manufactured by Osaka Organic Chemical Industry: polybutadiene having an acryloyloxy group at both ends, Mw = 10,000 (corresponding to the above-mentioned specific polymer)
-Kyoeisha Chemical Co., Ltd. ABU-2S: polybutadiene having acryloyloxy groups at both ends, Mw = less than 5,000 (because Mw is less than 5,000, it does not correspond to the above-mentioned specific polymer).
・ Kyoeisha Chemical's light ester TMP (trimethylolpropane trimethacrylate) (corresponding to the above-mentioned specific monomer)
・ Shin-Nakamura Kogyo Kagaku NK Ester A-GLY-9E (structure below)
Asahi Kasei NF35R (butadiene rubber) (Neither of the above-mentioned water-dispersible particles nor the specific polymer)
・ Shin-Nakamura Industrial Chemical NK ester NOD-N (1,9-nonanediol dimethacrylate)
表1中、「単官能モノマー/特定モノマー」は、上述した「単官能モノマー/特定モノマー」を表す。また、表1中、「特定モノマー/特定ポリマー」は、上述した「特定モノマー/特定ポリマー」を表す。
In Table 1, "monofunctional monomer / specific monomer" represents "monofunctional monomer / specific monomer" described above. Moreover, in Table 1, "specific monomer / specific polymer" represents the above-mentioned "specific monomer / specific polymer".
表1から分かるように、水分散性粒子と特定ポリマーと特定モノマーとを含有する感光層を有するフレキソ印刷版原版は水現像性に優れ、且つ、フレキソ印刷版にしたときに優れた耐刷性、ハンドリング性及び後端部着肉性を示した。
実施例間の対比から、上述した「特定モノマー/特定ポリマー」が3.0以下である実施例1~9及び11は、より優れた後端部着肉性を示した。なかでも、上述した「特定モノマー/特定ポリマー」が2.0以下である実施例1~2、5~9及び11は、さらに優れた後端部着肉性を示した。
また、実施例間の対比から、上述した「単官能モノマー/特定モノマー」が0.5以下である実施例1~10は、より優れた耐刷性及びハンドリング性を示した。なかでも、上述した「単官能モノマー/特定モノマー」が0.4以下である実施例1~5及び7~10は、さらに優れた耐刷性及びハンドリング性を示した。 As can be seen from Table 1, the flexographic printing plate precursor having a photosensitive layer containing water-dispersible particles, a specific polymer and a specific monomer has excellent water developability and excellent printing durability when used as a flexographic printing plate. In addition, handling property and rear end part inking property were exhibited.
From the comparison between the examples, Examples 1 to 9 and 11 in which the above-mentioned “specific monomer / specific polymer” was 3.0 or less showed more excellent rear end part inking property. Among them, Examples 1 to 2, 5 to 9 and 11 in which the above-mentioned “specific monomer / specific polymer” was 2.0 or less showed further excellent rear end part inking property.
Further, from the comparison between Examples, Examples 1 to 10 in which the above-mentioned “monofunctional monomer / specific monomer” was 0.5 or less showed more excellent printing durability and handleability. Among them, Examples 1 to 5 and 7 to 10 in which the above-mentioned “monofunctional monomer / specific monomer” was 0.4 or less showed further excellent printing durability and handling property.
実施例間の対比から、上述した「特定モノマー/特定ポリマー」が3.0以下である実施例1~9及び11は、より優れた後端部着肉性を示した。なかでも、上述した「特定モノマー/特定ポリマー」が2.0以下である実施例1~2、5~9及び11は、さらに優れた後端部着肉性を示した。
また、実施例間の対比から、上述した「単官能モノマー/特定モノマー」が0.5以下である実施例1~10は、より優れた耐刷性及びハンドリング性を示した。なかでも、上述した「単官能モノマー/特定モノマー」が0.4以下である実施例1~5及び7~10は、さらに優れた耐刷性及びハンドリング性を示した。 As can be seen from Table 1, the flexographic printing plate precursor having a photosensitive layer containing water-dispersible particles, a specific polymer and a specific monomer has excellent water developability and excellent printing durability when used as a flexographic printing plate. In addition, handling property and rear end part inking property were exhibited.
From the comparison between the examples, Examples 1 to 9 and 11 in which the above-mentioned “specific monomer / specific polymer” was 3.0 or less showed more excellent rear end part inking property. Among them, Examples 1 to 2, 5 to 9 and 11 in which the above-mentioned “specific monomer / specific polymer” was 2.0 or less showed further excellent rear end part inking property.
Further, from the comparison between Examples, Examples 1 to 10 in which the above-mentioned “monofunctional monomer / specific monomer” was 0.5 or less showed more excellent printing durability and handleability. Among them, Examples 1 to 5 and 7 to 10 in which the above-mentioned “monofunctional monomer / specific monomer” was 0.4 or less showed further excellent printing durability and handling property.
一方、感光層が水分散性粒子を含有しない比較例1、感光層が特定ポリマーを含有しない比較例2、感光層が特定モノマーを含有しない比較例3、感光層が特定モノマーを含有しない(2官能モノマーを含有する)比較例4、及び、感光層が特定ポリマーを含有しない(両末端に反応性官能基を有する重量平均分子量が5,000未満のポリマーを含有する)比較例5は、水現像性、耐刷性、ハンドリング性及び後端部着肉性のいずれかが不十分であった。
On the other hand, Comparative Example 1 in which the photosensitive layer does not contain water-dispersible particles, Comparative Example 2 in which the photosensitive layer does not contain a specific polymer, Comparative Example 3 in which the photosensitive layer does not contain a specific monomer, and the photosensitive layer does not contain a specific monomer (2 Comparative Example 4 (containing a functional monomer) and Comparative Example 5 in which the photosensitive layer does not contain a specific polymer (containing a polymer having reactive functional groups at both ends and having a weight average molecular weight of less than 5,000) are water. Any of the developing property, printing durability, handling property and trailing edge part inking property was insufficient.
また、上述した実施例及び比較例について、LAM方式の印刷版原版とする代わりにアナログ方式の印刷版原版とする以外は同様の手順に従ってフレキソ印刷版原版及びフレキソ印刷版を製造し、同様に評価したところ、表1と同様の結果が得られた。
Further, with respect to the above-mentioned Examples and Comparative Examples, a flexographic printing plate precursor and a flexographic printing plate were manufactured according to the same procedure except that an analog type printing plate original plate was used instead of the LAM type printing plate original plate, and evaluated in the same manner. As a result, the same results as in Table 1 were obtained.
Claims (5)
- 水分散性粒子と、両末端に反応性官能基を有する重量平均分子量が5,000以上のポリマーと、エチレン性不飽和基を3つ以上有する多官能モノマーとを含有する感光層を有する、水現像性フレキソ印刷版原版。 Water having a photosensitive layer containing water-dispersible particles, a polymer having a reactive functional group at both ends and having a weight average molecular weight of 5,000 or more, and a polyfunctional monomer having three or more ethylenically unsaturated groups, Developable flexographic printing plate precursor.
- 前記感光層が、さらに、単官能モノマーを含有する、請求項1に記載の水現像性フレキソ印刷版原版。 The water-developable flexographic printing plate precursor according to claim 1, wherein the photosensitive layer further contains a monofunctional monomer.
- 前記感光層において、前記多官能モノマーの含有量に対する前記単官能モノマーの含有量の比率が、質量比で、0.5以下である、請求項2に記載の水現像性フレキソ印刷版原版。 The water-developable flexographic printing plate precursor according to claim 2, wherein the ratio of the content of the monofunctional monomer to the content of the polyfunctional monomer in the photosensitive layer is 0.5 or less in terms of mass ratio.
- 前記感光層において、前記ポリマーの含有量に対する前記多官能モノマーの含有量の比率が、質量比で、3.0以下である、請求項1~3のいずれか1項に記載の水現像性フレキソ印刷版原版。 4. The water-developable flexo according to claim 1, wherein the ratio of the content of the polyfunctional monomer to the content of the polymer in the photosensitive layer is 3.0 or less in terms of mass ratio. Original printing plate.
- 画像部と非画像部とを有するフレキソ印刷版であって、
前記画像部が、請求項1~4のいずれか1項に記載の水現像性フレキソ印刷版原版が有する感光層を画像様に露光し、現像することにより得られる画像部である、フレキソ印刷版。 A flexographic printing plate having an image part and a non-image part,
A flexographic printing plate, wherein the image area is an image area obtained by imagewise exposing and developing the photosensitive layer of the water-developable flexographic printing plate precursor according to any one of claims 1 to 4. ..
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JP2020554039A JP7366924B2 (en) | 2018-10-31 | 2019-10-31 | Flexo printing plate original plate and flexo printing plate |
JP2023063519A JP2023083372A (en) | 2018-10-31 | 2023-04-10 | Flexographic printing plate precursor and flexographic printing plate |
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WO2024024612A1 (en) * | 2022-07-28 | 2024-02-01 | 富士フイルム株式会社 | Original plate for flexographic printing plate and method for manufacturing flexographic printing plate |
Citations (2)
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JP2004295120A (en) * | 2003-03-13 | 2004-10-21 | Toray Ind Inc | Photosensitive resin laminate and printing plate material using same |
JP2006154038A (en) * | 2004-11-26 | 2006-06-15 | Toray Ind Inc | Photosensitive resin plate material |
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JP4442187B2 (en) | 2002-10-24 | 2010-03-31 | 東レ株式会社 | Photosensitive resin printing plate precursor, method for producing the same, and method for producing resin relief printing plate using the same |
PL2833202T3 (en) * | 2012-03-30 | 2019-11-29 | Toyo Boseki | Photosensitive resin composition for ctp flexographic printing original plate and printing original plate prepared therefrom |
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- 2019-10-31 WO PCT/JP2019/042783 patent/WO2020090978A1/en active Application Filing
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JP2004295120A (en) * | 2003-03-13 | 2004-10-21 | Toray Ind Inc | Photosensitive resin laminate and printing plate material using same |
JP2006154038A (en) * | 2004-11-26 | 2006-06-15 | Toray Ind Inc | Photosensitive resin plate material |
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WO2024024612A1 (en) * | 2022-07-28 | 2024-02-01 | 富士フイルム株式会社 | Original plate for flexographic printing plate and method for manufacturing flexographic printing plate |
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JPWO2020090978A1 (en) | 2021-09-24 |
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