WO2010074210A1 - Cliché d'impression original en relief pour gravure au laser et cliché d'impression en relief obtenu à partir de celui-ci - Google Patents

Cliché d'impression original en relief pour gravure au laser et cliché d'impression en relief obtenu à partir de celui-ci Download PDF

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Publication number
WO2010074210A1
WO2010074210A1 PCT/JP2009/071554 JP2009071554W WO2010074210A1 WO 2010074210 A1 WO2010074210 A1 WO 2010074210A1 JP 2009071554 W JP2009071554 W JP 2009071554W WO 2010074210 A1 WO2010074210 A1 WO 2010074210A1
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Prior art keywords
photosensitive resin
laser engraving
resin composition
printing
original plate
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PCT/JP2009/071554
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English (en)
Japanese (ja)
Inventor
敏 高橋
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東洋紡績株式会社
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Priority to JP2010508649A priority Critical patent/JP5316534B2/ja
Publication of WO2010074210A1 publication Critical patent/WO2010074210A1/fr

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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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
    • 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

Definitions

  • the present invention relates to a letterpress printing original plate for laser engraving for forming a printing plate by forming an image by laser light irradiation, and a letterpress printing plate obtained using the same.
  • a relief printing plate used for various packaging materials, seals, label printing, and other various types of printing is conventionally exposed to a printing original plate made of a photosensitive resin according to an image to crosslink the resin in the exposed portion, and then to the non-exposed portion.
  • printing plates by laser engraving that form a relief image directly on a printing original plate using a laser are becoming popular in order to improve the efficiency of printing plate production in recent years. is there.
  • unevenness is formed on the plate surface by irradiating the printing original plate with a laser beam according to the image to decompose the image forming material in the irradiated portion.
  • Patent Documents 1 and 2 As a printing original plate for laser engraving, technical application to a flexographic plate is progressing, and a flexographic original plate capable of laser engraving or a flexographic plate obtained by laser engraving is disclosed in Patent Documents 1 and 2.
  • a flexographic printing plate precursor is produced by mixing a monomer with elastomeric rubber as a binder, and is cured by thermal crosslinking or photocrosslinking, followed by laser engraving to obtain a flexographic printing plate.
  • these are flexographic printing plates suitable for water-based inks and ester inks, and are not suitable for resin letterpress applications in which oil-based inks are mainly used.
  • the method of blending a filler such as silica fine powder requires a large amount of filler in order to sufficiently reduce the adhesiveness of the printing original plate, and there is a problem that the moldability and physical properties of the printing original plate are remarkably impaired. there were.
  • the conventional filler addition method adversely affects the moldability and plate physical properties of the printing original plate. Therefore, it is possible to reduce the adhesiveness of the printing original plate without adding a filler and to improve the fine part forming property. A master for sculpture was awaited.
  • the present invention was devised in view of the current state of the prior art, and the purpose thereof is a letterpress printing original plate for laser engraving, which can produce a printing plate that does not cause printing defects even during high-speed printing and has excellent resolution, and laser engraving. It is to provide a cured relief printing original plate and a photosensitive resin relief printing plate.
  • the present invention (1) cures a photosensitive resin composition layer obtained from a photosensitive resin composition containing at least a soluble synthetic polymer compound, a photopolymerizable unsaturated compound, and a photopolymerization initiator as basic components by ultraviolet irradiation.
  • the photosensitive resin layer is composed of polyether urea urethane as a soluble synthetic polymer compound and ethylenic as a photopolymerizable unsaturated compound It consists of the said photosensitive resin composition which has an unsaturated monomer and a photoinitiator as an essential component, and content of the (meth) acryloyl group in the said photosensitive resin composition is 2 per 1000 mass grams of the said photosensitive resin composition. 2.
  • a letterpress printing original plate for laser engraving characterized by containing from 2 mol to 3.7 mol, (2) the ethylenically unsaturated monomer (1) a printing original plate for laser engraving according to (1), which has at least two acryloyl groups or methacryloyl groups, and is contained in the photosensitive resin composition in an amount of 20 to 45% by mass;
  • the ethylenically unsaturated monomer contains a ring-opening addition reaction product of polyglycidyl ether of polyhydric alcohol and methacrylic acid or acrylic acid.
  • the polyether urethane urea contains a basic tertiary nitrogen atom, and 0.50 to 2.00 mol of the basic tertiary nitrogen atom in 1000 mass grams of the polyether urethane urea, the number average (1) to (3), which is a block copolymer having a soft segment of polyethylene glycol having a molecular weight of 400 to 1500 (5)
  • the polyether urethane urea contains a basic tertiary nitrogen atom quaternized by 25 mol% or more with a protic quaternizing agent (4) A photosensitive resin relief printing plate obtained from the laser engraving printing original plate (6), (1) to (5).
  • the laser engraving printing original plate described in any one of (7) (1) to (5) is irradiated with ultraviolet rays, and the (meth) acryloyl group content in the photosensitive resin composition layer is reduced to ultraviolet rays.
  • a cured letterpress printing original plate for laser engraving that is less than 30 mol% before irradiation, and a laser engraving printing original plate according to any one of (8) (1) to (5), which is irradiated with ultraviolet rays, and a photosensitive resin composition Cured letterpress printing original plate for laser engraving wherein the (meth) acryloyl group content in the layer is less than 1 mol in 1000 mass grams of the photosensitive resin composition, (9) at least a soluble synthetic polymer compound, photopolymerizable
  • the printing original plate for laser engraving of the present invention uses polyether urea urethane, which is a block copolymer in which a soluble synthetic polymer compound is composed of a hard segment and a soft segment, more preferably (meta )
  • the content of the acryloyl group is 2.2 mol or more and 3.7 mol or less per 1000 mass grams of the photosensitive resin composition, thereby achieving the present invention.
  • excellent laser engraving performance can be obtained by using the soluble polymer compound, and particularly excellent printing characteristics can be obtained in terms of high-speed printing performance.
  • the cured printing original plate for laser engraving of the present invention can be obtained by exposing the printing original plate for laser engraving to ultraviolet rays and curing it, whereby excellent laser engraving performance is obtained, and particularly excellent in terms of high-speed printing performance. Printing characteristics can be obtained.
  • the polyether urethane urea as the soluble polymer compound in the present invention preferably contains a basic tertiary nitrogen atom, and the basic tertiary nitrogen atom is added in an amount of 0.50 to 1,000 mass grams in the polyether urethane urea. It is preferable to contain 2.00 mol, and it is preferable to be a block copolymer having polyethylene glycol having a number average molecular weight of 400 to 1500 as a soft segment, and quaternization of 25 mol% or more by a protic quaternizing agent It is preferable to contain the made base tertiary nitrogen atom.
  • the resin residue can be easily removed by brush cleaning using water as a solvent. Further, by quaternizing a basic tertiary nitrogen atom with a protic quaternizing agent, it becomes possible to easily remove the resin residue during laser engraving. If the tertiary nitrogen atom content in the polyether urethane urea is less than 0.50 mol in 1000 grams of the polyether urethane urea, the resin residue removal is insufficient, and if it exceeds 2.00 mol, the resin This is not preferable because the image is easily damaged during the removal of debris.
  • the basic tertiary nitrogen atom content in 1000 grams of the soluble synthetic polymer compound is contained in 0.50 to 2.00 mol in the hard synthetic segment. It is also possible to set according to the blending ratio of raw materials.
  • the quaternization rate is the ratio of the number of moles of basic tertiary nitrogen atoms quaternized to the number of moles of basic tertiary nitrogen atoms contained in the soluble synthetic polymer compound. , Expressed in mole percent.
  • the soluble synthetic polymer compound used in the present invention is a block copolymer containing a soft segment, and is high by containing an amide bond, urea bond or urethane bond capable of forming a hydrogen bond in the hard segment in the molecule. It has crystallinity. Therefore, the photosensitive resin composition also has a high impact resilience of 30% or more, and the content of (meth) acryloyl groups in the photosensitive resin composition is 2.2 per 1000 mass grams of the photosensitive resin composition. When it is contained in a molar amount of 3.7 mol or less, it is sufficiently photocrosslinked, and it becomes possible to reduce thermal deformation caused by heat generated during laser engraving. As a result, the printing original plate for laser engraving using the present invention achieves excellent laser engraving performance that could not be obtained with conventional printing original plates having high rebound resilience, and satisfies excellent printability even at high printing speeds. Is.
  • the quaternizing agent used in the present invention is a protic quaternizing agent, and may be a compound containing a photopolymerizable group that is polymerized by ultraviolet rays or a compound not containing a photopolymerizable group.
  • a known general compound can be used as the protic quaternizing agent.
  • Specific examples of the compound containing a photopolymerizable group include maleic acid, itaconic acid, acrylic acid, methacrylic acid, cinnamic acid, and the like, and acrylic acid and methacrylic acid are preferable from the viewpoint of resin residue removal.
  • the compound not containing a photopolymerizable group include glycolic acid, succinic acid, adipic acid as an aliphatic quaternizing agent, and benzoic acid as an aromatic quaternizing agent. Of these, adipic acid and benzoic acid are preferable in terms of resin residue removal.
  • the soluble synthetic polymer compound used in the present invention has a high rebound resilience in order to satisfy excellent high-speed printability as a printing plate.
  • the rebound resilience is preferably 30% or more, and more preferably 40% or more. A rebound resilience of less than 30% is not preferable because the solid ink is poor when printing at 100 m / min or higher.
  • As a method for obtaining a soluble synthetic polymer compound having a high rebound resilience of 30% or more it is preferable to use polyethylene glycol having a number average molecular weight of 400 to 1500 as a soft segment, and a more preferable number average molecular weight is 400 to 1000.
  • the number average molecular weight is particularly preferably 400 to 600.
  • the content of polyethylene glycol contained in the soluble synthetic polymer compound is also important, and the preferable content is 40% by mass to 75% by mass, and the more preferable content is 40% by mass to 60% by mass. If the soft segment content is less than 40% by mass, it does not play the role of a soft segment, and if it exceeds 75% by mass, the function of the hard segment is not exhibited and sufficient resin hardness is obtained, which is not preferable.
  • the polyether urea urethane used in the present invention can be obtained by addition polymerization of a diamine and a terminal diisocyanate compound containing polyethylene glycol in a solvent.
  • known addition polymerization methods such as a heat polymerization method and a solution polymerization method can be used.
  • the diamine component is preferably used in combination with a diamine containing no tertiary nitrogen atom and a diamine containing a tertiary nitrogen atom.
  • diamines that do not contain a tertiary nitrogen atom examples include trimethylenediamine, tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4, or 2,4.
  • 1,4 -trimethylhexamethylenediamine, 1,3-or 1,4 -bis (aminomethyl) cyclohexane, 1,3-or 1,4 -aminocyclohexane, and the like preferably 2-methylpentamethylene Diamine, 2,2,4 or 2,4,4 -trimethylhexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane.
  • a specific example of a diamine containing a tertiary nitrogen atom is a diamine having a basic tertiary nitrogen atom in the main chain or side chain.
  • the diamine include a diamine having a piperazine ring and other diamines.
  • diamines having a piperazine ring include N, N′-bis (aminomethyl) piperazine, N, N′-bis (2-aminoethyl) piperazine, and N, N′-bis (3-aminopropyl).
  • Piperazine N, N′-bis (2-aminoethyl) methylpiperazine, N- (aminomethyl) -N ′-(2-aminoethyl) piperazine, N, N′-bis (3-aminopentyl) piperazine, N- (2-aminoethyl) piperazine, N- (aminopropyl) piperazine, N- ( ⁇ -aminohexyl) piperazine, N- (3-aminocyclohexyl) piperazine, N- (2-aminoethyl) -3-methyl Piperazine, N- (2-aminoethyl) -2,5-dimethylpiperazine, N- (2-aminopropyl) -3-methylpiperazine, N- (3-amino Propyl) -2,5 - diamine having a piperazine ring such as dimethyl piperazine.
  • diamines having a piperazine ring such as N, N′-bis (aminoethyl) -piperazine, N, N′-bis (3-aminopropyl) piperazine, and N- (2-aminoethyl) piperazine are polymerized. It is preferable because it is superior in terms of properties and physical properties.
  • the above diisocyanate compound which is another raw material used for polyether urea urethane, is obtained by reacting a known aliphatic, alicyclic or aromatic diisocyanate with an equimolar or less polyoxyethylene glycol. It is a diisocyanate compound having an isocyanate group at the terminal.
  • a conventionally well-known method can be utilized for the manufacturing method of this diisocyanate compound. That is, a method of reacting both in a solvent-free state while mixing and stirring, a method of reacting both by dissolving in an inert solvent, and the like.
  • the reaction temperature, reaction time, etc. should be determined optimally considering the reactivity and thermal stability of both.
  • the use ratio of diisocyanate is preferably 2.0 mol or more, particularly 2.05 mol or more with respect to polyoxyethylene glycol.
  • diisocyanate used for obtaining the diisocyanate compound known aliphatic, alicyclic and aromatic diisocyanates can be used.
  • 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, p-xylylene diisocyanate, 1,3-cyclohexanedimethyl isocyanate, p- Examples include xylylene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-diisocyanate methyl caproate, diphenyl ether-4,4′-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc.
  • hexamethylene diisocyanate is particularly preferred.
  • the reaction ratio between diamine and diisocyanate compound is amino group / isocyanate group (equivalent ratio) of 1.0 or more, preferably 1.02 or more.
  • amino group / isocyanate group equivalent ratio
  • the amino group / isocyanate group (equivalent ratio) is less than 1.0, an undesirable reaction such as gelation tends to occur, which is not preferable. Since the reactivity between amine and isocyanate is extremely high, the reaction between the two can be carried out in an active solvent such as water, alcohols such as methanol, or a mixture of water and alcohols.
  • the soluble polymer compound used in the present invention is a block copolymer having a crystal layer with a urea urethane bond, and can increase the concentration of the photopolymerizable compound in the soft segment without disturbing the crystallinity, resulting in the occurrence of laser engraving. It is considered that the resin (relief) at the boundary part is less likely to cause thermal deformation due to heat. On the other hand, when a block copolymer having a urea urethane bond crystal layer is not used, the crystallinity of the polymer is disturbed by the photopolymerizable compound, and the resin (relief) at the boundary is heated by the heat generated during laser engraving. It is thought that deformation is likely to occur.
  • photopolymerizable unsaturated compound used in the present invention known photopolymerizable unsaturated compounds can be used.
  • the photopolymerizable unsaturated compound preferably used is a ring-opening addition reaction product of a known glycidyl ether of a dihydric or trihydric alcohol with methacrylic acid and acrylic acid, and the polyhydric alcohol is ethylene glycol.
  • Diethylene glycol, triethylene glycol, ethylene oxide adducts of phthalic acid, glycerin, bisphenol A, trimerol propane and diglycidyl ether acrylic acid adducts of bisphenol F, etc. Can also be used.
  • glycerin dimethacrylate, ethylene glycol diepoxy acrylate, and trimerol propane triepoxy acrylate are preferable from the viewpoint of laser engraving, and glycerol dimethacrylate is particularly preferable.
  • the photopolymerizable unsaturated compound used in the present invention may be used alone, but may be mixed in order to bring the content of the photopolymerizable unsaturated group into a specific range.
  • the content of the photopolymerizable unsaturated group is important.
  • the content of the photopolymerizable unsaturated group contained in the photosensitive resin composition as a whole is controlled within a certain range, and a proton acid is used. It is preferable to control the content of the quaternized basic tertiary nitrogen atom to a constant amount.
  • the preferable content of the photopolymerizable unsaturated group of the present invention is such that it is contained in an amount of 2.2 to 3.7 mol, more preferably 2.4 to 3.4 mol in 1000 g of the photosensitive resin composition. It is to let you.
  • the content of the photopolymerizable unsaturated group in 1000 grams of the photosensitive resin relief printing composition is less than 2.2 mol, the laser engraving performance is poor, and when it exceeds 3.7 mol, the printing plate becomes too hard and the ink is carried on the surface. Is unfavorable because it decreases.
  • the amount of the photopolymerizable compound is increased or decreased.
  • the distance (molecular weight) between them it is possible to increase or decrease the amount of the photopolymerizable group in the photosensitive resin composition while being blended in the same photosensitive resin composition.
  • photopolymerization initiator used in the present invention known ones can be used. Specifically, for example, benzophenones, benzoins, acetophenones, benzyls, benzoin alkyl ethers, benzyl alkyl ketals, anthra Quinones and thioxanthones can be used. Specific examples include benzophenone, benzoin, acetophenone, benzoin methyl ether, benzoin ethyl ether, benzyldimethyl ketal, anthraquinone, 2-chloroanthraquinone, thioxanthone, 2-chlorothioxanthone and the like.
  • the photosensitive resin composition preferably contains in an amount of 0.05 to 5% by mass.
  • the amount is less than 0.05% by mass, the photopolymerization initiation ability is hindered.
  • the amount is more than 5% by mass, the photocurability in the thickness direction of the printing plate when producing a relief for printing is lowered, and the laser engraving performance is degraded. .
  • thermal polymerization inhibitor may be added.
  • the thermal polymerization inhibitor is added in order to prevent unscheduled thermal polymerization due to heating during preparation, production, molding, etc. of the photosensitive resin letterpress composition, or dark reaction during storage of the composition.
  • examples of such compounds include hydroquinones such as hydroquinone, mono-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, hydroquinone monomethyl ether, benzoquinone, 2,5-diphenyl-p-benzoquinone, etc.
  • Catechols such as benzoquinones, phenols, catechol, p-tert-butylcatechol, aromatic amine compounds, vicrinic acids, phenothiazine, ⁇ -naphthoquinones, anthraquinones, nitro compounds, sulfur compounds, etc. .
  • the amount of the thermal polymerization inhibitor used is from 0.001% to 2% by weight, particularly preferably from 0.005% to 1% by weight, based on the total composition. Two or more of these compounds may be used in combination.
  • the photosensitive resin composition of the present invention is a target product by any known method such as hot pressing, casting, melt extrusion, solution casting, etc. in addition to the melt molding method for obtaining a relief plate for printing. Can be formed into a desired shape.
  • a molded product (raw plate) obtained by molding the photosensitive resin composition of the present invention into a sheet is laminated on a support with or without a known adhesive.
  • a support any material such as a plastic film such as steel, aluminum, glass, polyethylene terephthalate, or a metal-deposited film can be used.
  • a protective layer may be further laminated in contact with the sheet-like molded product (raw plate).
  • the protective layer for example, a film-like plastic such as a 125 ⁇ m-thick polyethylene terephthalate film coated with a non-sticky transparent polymer with a thickness of 1 to 3 ⁇ m is used. Even if the surface adhesiveness of the sheet-like molded product (raw plate) is strong by contacting the protective layer having this thin polymer film with the sheet-shaped molded product (raw plate), the next exposure treatment (photocuring) ) The protective layer can be easily peeled off during operation.
  • a film-like plastic such as a 125 ⁇ m-thick polyethylene terephthalate film coated with a non-sticky transparent polymer with a thickness of 1 to 3 ⁇ m is used. Even if the surface adhesiveness of the sheet-like molded product (raw plate) is strong by contacting the protective layer having this thin polymer film with the sheet-shaped molded product (raw plate), the next exposure treatment (photocuring) ) The protective layer can be easily peeled off during operation.
  • the photocuring in the present invention means, for example, that the photosensitive resin composition is molded and solidified into a sheet shape, and then this sheet-shaped molded product (raw plate) is 8 mW / cm 2 from a distance of 5 cm higher than the surface.
  • the front and back surfaces are exposed for 10 minutes each by an ultraviolet exposure machine (light source: 10R manufactured by Philips), and are cured by crosslinking.
  • the cured letterpress printing original plate for laser engraving in the present invention is obtained by photocuring (crosslinking) the exposure relief printing original plate for laser engraving in the present invention, but the exposure treatment may be performed through a cover film. And you may expose after a cover film peeling.
  • the cured letterpress printing original plate for laser engraving thus obtained is attached to the surface of a plate mounting drum of a laser engraving apparatus, for example, and the irradiated portion of the original plate is decomposed by laser irradiation according to the image to form a concave portion, A printing plate is produced.
  • the Shore D hardness and rebound resilience were measured by the following methods after the photosensitive resin composition was molded into a sheet-like molded product and photocured.
  • the sample for a measurement uses a photosensitive resin laminated body which provided the photosensitive resin layer of 3 mm on the polyester support body of 250 micrometers, and also laminated
  • Using a chemical lamp exposure was performed for 10 minutes from a distance of 5 cm from the surface of the photosensitive resin laminate, and photocuring was performed. Next, samples that were stored for 24 to 36 hours at 20 ° C. and 65% relative humidity were used as samples for evaluation.
  • Shore D hardness measured at 25 ° C. using a Shore durometer (Shore D type) manufactured by West German Zbic.
  • Resin residue evaluation As evaluation of the resin residue removal property, the ease of removal was evaluated using the resin residue attached to the printing plate surface after laser engraving. The ease of removal was evaluated as follows using a 10 cm ⁇ 10 cm brush in which fibers made of polyethylene terephthalate having a diameter of 160 ⁇ m were implanted. ⁇ : Can be removed by rubbing work within 10 times, ⁇ : Can be removed by rubbing work within 30 times, ⁇ : Can not be removed by rubbing work more than 30 times, and the resin adheres to the brush.
  • Example 1 After dissolving 77 parts by mass of N, N′-bis (3-aminopropyl) piperazine and 22 parts by mass of 2-methylpentamethylenediamine in 550 parts by mass of methanol, 600 parts by mass of polyethylene glycol (average molecular weight 600) is added to the diamine solution. 451 parts by mass of a urethane oligomer having isocyanate groups at both ends substantially obtained by reacting 369 parts by mass with hexamethylene diisocyanate was gradually added. Both reactions were completed in about 15 minutes under conditions of a polymer solids concentration of 50%.
  • the obtained photosensitive resin composition solution contained 3.3 mol of (meth) acryloyl group in 1000 g of the solid content of the photosensitive resin composition excluding methanol and water, and was quaternized with a protonic acid 3 It also contained 0.42 mol of secondary nitrogen atoms.
  • This solution was cast on a Teflon (registered trademark) -coated petri dish and dried under reduced pressure at 40 ° C. overnight to obtain a sheet of a photosensitive composition having a thickness of 800 ⁇ m.
  • composition sheet was sandwiched between a polyethylene terephthalate film having a thickness of 250 ⁇ m and a polyethylene terephthalate film having a thickness of 100 ⁇ m, and a polyethylene terephthalate film having a thickness of 100 ⁇ m.
  • a sheet-like molded product laser engraving printing original plate
  • the sheet-like preform (for laser engraving Printing plate precursor) an ultraviolet exposure machine (light source: Philips 10R) by the height from the surface 5cm distance from 8 mW / cm 2 of UV exposure machine (light source: Philips 10R) was exposed from the 100 ⁇ m-thick polyethylene terephthalate film side for 10 minutes and crosslinked and cured, and then the 100 ⁇ m-thick polyethylene terephthalate film was peeled off to prepare a cured printing original plate for laser engraving.
  • the prepared cured printing original plate for laser engraving was immersed in ethyl acetate at 25 ° C. for 48 hours, and the content of the extracted (meth) acryloyl group was quantified.
  • the content of (meth) acryloyl group was determined by the print curing for laser engraving. It was 0.3 mol in 1000 g of the photosensitive resin composition constituting the finished original plate.
  • Examples 2 to 3 As shown in Table 1, the type and amount of the quaternizing agent were changed, the composition was adjusted in the same manner as in Example 1, and a sheet-like molded product (laser engraving master) and laser were prepared in the same manner as in Example 1. A print-cured original plate for engraving was obtained.
  • Examples 4-7, 15, 16 As shown in Table 1, the addition amount and type of the photopolymerizable unsaturated compound of Example 1 were changed to change the content of the photopolymerizable group, and a part of other ingredients was changed to change the photosensitive resin composition. In the same manner as in Example 1, laser beam engraving printing original plates and laser engraving print-cured original plates of Examples 4 to 7, 15, and 16 were produced.
  • Examples 9-11 The number average molecular weight of polyethylene glycol, which is the soft segment of Example 1, was changed as shown in Table 1, and the laser engraving printing original plates and laser engraving printing cured original plates of Examples 9 to 11 were prepared in the same manner as in Example 1. Produced.
  • Examples 8, 12-14 The diamine component of Example 1 was changed as shown in Table 1, and in the same manner as in Example 1, laser beam engraving printing original plates and laser engraving print-cured original plates of Examples 8 and 12 to 14 were produced.
  • Comparative Example 1 and Comparative Example 2 are photosensitive resin compositions in which the total number of moles of photopolymerizable groups contained in 1000 grams of the photosensitive resin composition contains values outside the range of claim 1.
  • a laser engraving printing original plate and a laser engraving print cured original plate were prepared.
  • Comparative Example 3 55.0 parts by mass of ⁇ -caprolactam having a different structure from polyether urea urethane, 40.0 parts by mass of N, N′-bis ( ⁇ -aminopropyl) piperazine and adipic acid nylon salt, and 1,3-bisamino Methylcyclohexane and 7.5 parts by mass of adipic acid nylon salt were melt polycondensed to obtain a copolymerized polyamide. 50.0 parts by mass of the obtained polyamide was dissolved in 100 parts by mass of methanol and 20 parts by mass of water in a heat-dissolved kettle with stirring at 60 ° C.
  • Comparative Examples 4 and 5 In Comparative Example 4, the polyamide of Comparative Example 3 was used and blended in the same manner as in Comparative Example 3 based on the composition ratio in Table 2, and the photopolymerizable group amount of 2.48 mol was contained in 1000 grams of the composition. A photosensitive resin composition was obtained. In Comparative Example 5, the polyamide was reduced to 40.0 parts by mass in Comparative Example 3, and a photosensitive resin composition having a high photopolymerizable compound content of 53.7% by mass as shown in the composition ratio of Table 2 was used. In the same manner as in Example 1, a laser engraving printing original plate and a laser engraving print cured original plate were prepared.
  • Comparative Example 6 In Comparative Example 6, a cured printing original plate for laser engraving was prepared by setting the ultraviolet irradiation time for the sheet-like molded product in Example 1 to 1 minute.
  • the laser engraving machine is a FlexPose equipped with a 300W carbon dioxide laser from Luescher Flexo! direct was used.
  • the specifications of this apparatus were a laser wavelength of 10.6 ⁇ m, a beam diameter of 30 ⁇ m, a plate mounting drum diameter of 300 mm, and a processing speed of 1.5 hours / 0.5 m 2 .
  • the conditions for laser engraving are as follows. Note that (1) to (3) are conditions specific to the apparatus. Conditions can be arbitrarily set in (4) to (7), and the standard conditions of this apparatus are adopted for each condition.
  • the photosensitive resin composition using polyether urea urethane as the soluble polymer compound has a (meth) acryloyl group content in the photosensitive resin. It can be seen that a composition containing 2.2 mol or more and 3.7 mol or less in 1000 mass grams of the composition is an original plate for laser engraving excellent in laser engraving properties and printability, and particularly contains 2.4 to 3.4 mol. It can be seen that even better laser engraving properties can be obtained.
  • Example 11 a soluble polymer compound in which the diamine component is changed from that in Example 1 is used.
  • a basic tertiary nitrogen atom-containing diamine a diamine having a piperazine ring is used for laser engraving. It turns out that it is preferable from a surface.
  • Comparative Examples 1 and 2 the content of the (meth) acryloyl group in the photosensitive resin composition is outside the scope of the claims, and both the laser engraving property and the printability cannot be satisfied. Is clear. Further, Comparative Examples 3 and 4 are photosensitive resin compositions that do not use polyether urea urethane and do not satisfy both the laser engraving property and the printability. Further, Comparative Example 5 is a case where 50% by mass or more of the photopolymerizable unsaturated compound is contained using the polyamide of Comparative Example 3, and laser engraving by containing 50% by mass or more of the photopolymerizable unsaturated compound. Although satisfactory, the printing performance cannot satisfy solid ink.
  • Comparative Example 6 is a case where the amount of residual (meth) acryloyl groups remaining in the photosensitive resin composition layer at the time of laser engraving is shortened by reducing the ultraviolet irradiation time. It is clear that both the laser engraving property and the printability are not satisfied.
  • the resin composition of the present invention satisfies both the laser engraving property and the high-speed printing performance because there is little resin residue adhesion to the plate surface at the time of laser irradiation during printing plate preparation and almost no rounding of the relief edge.
  • Laser engraving printing plate and cured printing plate can be provided.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Manufacture Or Reproduction Of Printing Formes (AREA)

Abstract

Cette invention se rapporte à un cliché d'impression original en relief pour gravure au laser, capable de produire un cliché d'impression qui peut empêcher une défaillance d'impression au moment d'une impression à grande vitesse et qui présente une résolution supérieure. L'invention se rapporte également à un cliché d'impression original en relief durci pour gravure au laser et à un cliché d'impression en relief en résine photosensible. Le cliché d'impression original en relief pour gravure au laser est utilisé pour former un cliché d'impression par durcissement, à l'aide d'un rayonnement ultra-violet, d'une couche d'une composition de résine photosensible obtenue à partir d'une composition de résine photosensible qui comprend au moins un polymère synthétique soluble, un composé insaturé photopolymérisé et un initiateur de photopolymérisation comme composants principaux, et ensuite, par formation d'une image obtenue par exposition à un faisceau laser. L'invention est caractérisée en ce que la couche d'une composition de résine photosensible est formée par une composition de résine photosensible qui comprend un poly(éther-uréthane-urée) en tant que polymère synthétique soluble, un monomère insaturé à base d'éthylène en tant que composé insaturé photopolymérisé et un initiateur de photopolymérisation en tant que composants essentiels et en ce que la teneur du groupe (méth)acryloyle dans la composition de résine photosensible est comprise entre 2,2 et 3,7 moles pour 1000 grammes de la masse de la composition de résine photosensible.
PCT/JP2009/071554 2008-12-25 2009-12-25 Cliché d'impression original en relief pour gravure au laser et cliché d'impression en relief obtenu à partir de celui-ci WO2010074210A1 (fr)

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JP2008-329947 2008-12-25

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017021111A (ja) * 2015-07-08 2017-01-26 東洋紡株式会社 凸版印刷原版用感光性樹脂組成物、及びそれから得られる凸版印刷原版
CN114258350A (zh) * 2019-08-23 2022-03-29 东洋纺株式会社 柔性印刷版

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0497154A (ja) * 1990-08-09 1992-03-30 Toyobo Co Ltd 感光性樹脂組成物
JP2008225464A (ja) * 2007-02-14 2008-09-25 Toyobo Co Ltd 感光性樹脂凸用原版
WO2009081899A1 (fr) * 2007-12-26 2009-07-02 Toyo Boseki Kabushiki Kaisha Cliché d'impression original en relief pour gravure au laser et cliché d'impression en relief obtenu de celui-ci

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0497154A (ja) * 1990-08-09 1992-03-30 Toyobo Co Ltd 感光性樹脂組成物
JP2008225464A (ja) * 2007-02-14 2008-09-25 Toyobo Co Ltd 感光性樹脂凸用原版
WO2009081899A1 (fr) * 2007-12-26 2009-07-02 Toyo Boseki Kabushiki Kaisha Cliché d'impression original en relief pour gravure au laser et cliché d'impression en relief obtenu de celui-ci

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017021111A (ja) * 2015-07-08 2017-01-26 東洋紡株式会社 凸版印刷原版用感光性樹脂組成物、及びそれから得られる凸版印刷原版
CN114258350A (zh) * 2019-08-23 2022-03-29 东洋纺株式会社 柔性印刷版
CN114258350B (zh) * 2019-08-23 2023-05-26 东洋纺株式会社 柔性印刷版

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