Classifications

• • 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
  • G03F7/12—Production of screen printing forms or similar printing forms, e.g. stencils
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
  • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
  • G03F7/2014—Contact or film exposure of light sensitive plates such as lithographic plates or circuit boards, e.g. in a vacuum frame
  • G03F7/2016—Contact mask being integral part of the photosensitive element and subject to destructive removal during post-exposure processing
  • G03F7/202—Masking pattern being obtained by thermal means, e.g. laser ablation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
  • B41C1/00—Forme preparation
  • B41C1/18—Curved printing formes or printing cylinders
  • B41C1/184—Curved printing formes or printing cylinders by transfer of the design to the cylinder, e.g. from a lithographic printing plate; by drawing the pattern on the cylinder; by direct cutting of the pattern on the cylinder
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
  • B41C1/00—Forme preparation
  • B41C1/06—Transferring
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
  • B41N1/00—Printing plates or foils; Materials therefor
  • B41N1/16—Curved printing plates, especially cylinders
  • B41N1/22—Curved printing plates, especially cylinders made of other substances
• • 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
  • G03F7/094—Multilayer resist systems, e.g. planarising layers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
  • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
  • G03F7/2012—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image using liquid photohardening compositions, e.g. for the production of reliefs such as flexographic plates or stamps

Definitions

• the present invention relates to a film for producing a flexographic printing plate, a laminate, and a method for producing a flexographic printing plate.
• flexographic printing using a flexographic printing plate has been widely used as a method for printing on soft packaging materials such as paper and film.
• methods for manufacturing flexographic printing plates include the following methods.
• the photosensitive resin composition layer is exposed to ultraviolet light (back exposure) from the support side to form a uniform photocured layer.
• relief exposure is performed from the back side, that is, the side of the photosensitive resin composition layer in an uncured state, which is the side opposite to the side exposed to the ultraviolet rays.
• Methods for the relief exposure include a method in which UV exposure is performed through a transparent image carrier (mask) such as a negative film that selectively transmits UV rays, and a method in which an image that has become digital information is ablated with an infrared laser to emit UV rays.
• Examples include a method of exposing to ultraviolet light through a thin layer in which a transparent portion is formed. Then, the photosensitive resin composition in the unexposed portions of the flexographic printing original plate is washed and removed, and developed to form a relief image, thereby obtaining a flexographic printing plate.
• the photosensitive resin composition in the unexposed area is recovered and reused in the production of the flexographic printing plate, which is a method of manufacturing a flexographic printing plate using a liquid photosensitive resin composition.
• a manufacturing method has been proposed (see, for example, Patent Document 1).
• the method for manufacturing a flexographic printing plate described in Patent Document 1 has high environmental adaptability because it can reduce the amount of waste of the photosensitive resin composition in the unexposed area and reduce the production cost of the flexographic printing plate. It is widely used as a method for manufacturing flexographic printing plates.
• CTP Computer To Plate
• an ablation layer that can be ablated with infrared rays is provided on a photosensitive resin composition layer, and the ablation layer is removed into a desired shape by irradiation with an infrared laser, which corresponds to a negative. Forms a transparent portion for actinic rays.
• the photosensitive resin composition layer is irradiated with ultraviolet rays to react with the photosensitive resin composition in the same shape as the transparent part formed in the ablation layer, performing relief exposure.
• the resulting ablation layer and the unexposed area of the photosensitive resin composition are developed and removed to produce a flexographic printing plate.
• the ablation layer and the photosensitive resin composition are designed to have high adhesion, so after relief exposure, the photosensitive resin in the unexposed area is
• the problem is that it is difficult to isolate and recover the composition.
• elution and migration of the ablation layer into the photosensitive resin composition cannot be suppressed, which not only makes it difficult to isolate and recover unexposed areas, but also makes it difficult to improve the quality of flexographic printing plates.
• the problem is that there is still room.
• “elution” refers to the individual components of the ablation layer being mixed into the photosensitive resin composition
• “migration” refers to the separation of the ablation layer from the substrate while maintaining its film shape. This means that it is mixed into the photosensitive resin composition.
• an infrared laser is irradiated on a flexographic printing original plate having a photosensitive resin composition layer, a film layer, and an optical density changing layer corresponding to an ablation layer on a predetermined support.
• a method of forming an image mask has been proposed (for example, see Patent Document 2). In this method, the entire surface is exposed by irradiating ultraviolet rays from above the image mask, and then the image mask is peeled off along with the film layer, and then developed to obtain a flexographic printing plate.
• the optical density changing layer corresponding to the ablation layer is removed before development, there is an advantage that elution and migration into the photosensitive resin composition layer can be suppressed.
• the film layer between the photosensitive resin composition layer and the optical density variable layer is thick, the ultraviolet rays are likely to be bent and scattered, resulting in a problem of reduced image reproducibility. There is.
• a water-insoluble heat-sensitive mask layer that is laminated on the photosensitive resin composition layer is a technology that prevents the above-mentioned deterioration of image reproducibility and also prevents the elution and migration of the ablation layer to the photosensitive resin composition layer.
• a method for producing a flexographic printing plate has been proposed in which pattern exposure is performed using a layer crosslinked with a curable resin (for example, see Patent Document 3).
• Patent No. 5996197 International Publication No. 01/18605 Patent No. 4442187
• the present invention provides flexographic printing for suppressing elution and migration of the ablation layer to the photosensitive resin composition layer and producing a flexographic printing plate with excellent image reproducibility.
• the purpose of the present invention is to provide a plate manufacturing film and a method for manufacturing a flexographic printing plate using the same.
• the present inventors discovered that the above-mentioned problems could be solved by a film having an infrared ablation layer and a base material having a specific configuration, and thus completed the present invention.
• Ta That is, the present invention is as follows.
• the ablation layer contains a resin having a structural unit (1) represented by the following general formula (1),
• the thickness of the base material is 10 ⁇ m or more and less than 100 ⁇ m. Film for flexo printing plate production.
• R 1 and R 2 each independently represent a nonpolar group
• R 3 and R 4 each independently represent a hydrogen atom or a nonpolar group.
• R 1 and R 2 are each independently selected from the group consisting of an alkyl group, an alkenyl group, and an alkynyl group
• R 3 and R 4 are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, and an alkynyl group
• R 1 and R 2 are each independently an alkyl group
• R 3 and R 4 are each independently a hydrogen atom or an alkyl group
• the resin further includes a structural unit (2) derived from a monovinyl-substituted aromatic hydrocarbon, The film for producing a flexographic printing plate according to any one of [1] to [3] above.
• the base material includes a resin having a polyester or polyolefin skeleton, The film for producing a flexographic printing plate according to any one of [1] to [4] above.
• the base material is made of a resin having a polyester or polyolefin skeleton, The film for producing a flexographic printing plate according to any one of [1] to [5] above.
• the base material is made of a resin having a polyolefin skeleton, The film for producing a flexographic printing plate according to any one of [1] to [6] above.
• a flexographic printing original plate having a photosensitive resin composition layer On the flexographic printing original plate, the film for producing a flexographic printing plate according to any one of [1] to [7] above, A laminate having.
• a method for manufacturing a flexographic printing plate comprising manufacturing a flexographic printing plate using the laminate according to [8] above, a drawing step of drawing and processing a pattern by irradiating infrared rays onto the film for producing a flexographic printing plate according to any one of [1] to [7] above; an exposure step of irradiating the photosensitive resin composition layer with ultraviolet rays to form a pattern using the ablation layer on which the pattern has been drawn in the drawing step as a mask; a developing step of removing an unexposed area of the photosensitive resin composition layer;
• a method for producing a flexographic printing plate having the following.
• the photosensitive resin composition contains a polymer having a carbonyl group, The method for producing a flexographic printing plate according to [9] above.
• the base material of the film for producing a flexographic printing plate is made of a resin having a polyester or polyolefin skeleton, The method for producing a flexographic printing plate according to [9] or [10] above.
• a film for producing a flexographic printing plate, a laminate, and a laminate for producing a flexographic printing plate which can suppress elution and migration of an ablation layer to a photosensitive resin composition layer and produce a flexographic printing plate with excellent image reproducibility.
• a method for manufacturing a flexographic printing plate can be provided.
• 1 is a schematic cross-sectional view of a film for producing a flexographic printing plate of the present invention. 1 shows a schematic diagram of a method for producing a flexographic printing plate using the film for producing a flexographic printing plate of the present invention.
• this embodiment a mode for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail. Note that the following embodiment is an illustration for explaining the present invention, and is not intended to limit the present invention to the following content. The present invention can be implemented with appropriate modifications without departing from the gist thereof.
• the flexographic printing plate manufacturing film of this embodiment is It has a base material and an ablation layer laminated on the base material, the ablation layer contains a resin having a structural unit (1) represented by the following general formula (1), and the thickness of the base material is 10 ⁇ m or more and less than 100 ⁇ m.
• R 1 and R 2 each independently represent a nonpolar group
• R 3 and R 4 each independently represent a hydrogen atom or a nonpolar group.
• FIG. 1 shows a schematic cross-sectional view of a film for producing a flexographic printing plate according to the present embodiment.
• the film for producing a flexographic printing plate of this embodiment has a base material 1 and an ablation layer 2 that functions as a mask when forming a concavo-convex pattern on the intended flexographic printing plate.
• ablation layer 2 that functions as a mask when forming a concavo-convex pattern on the intended flexographic printing plate.
• the film for producing a flexographic printing plate of this embodiment has a base material 1 and an ablation layer 2 laminated on the base material 1, and the ablation layer 2 has an image drawn thereon, so that the flexographic printing plate described below It plays the role of negative film to form relief in the manufacturing process.
• the quality of the relief is greatly influenced by negative films through which ultraviolet light is transmitted during relief exposure.
• the greater the thickness of the negative film the greater the bending and scattering of ultraviolet light in the negative film, which tends to reduce image reproducibility. Since the thickness of the base material 1 shown in FIG. 1 accounts for most of the thickness of the entire negative film, the smaller the thickness of the base material 1, the better from the viewpoint of the quality of the flexographic printing plate.
• the negative film has certain rigidity and dimensional stability. If the negative film is easily deformed, the image formed on the negative film in the step before relief exposure will be deformed or damaged, and as a result, image reproducibility will tend to deteriorate. However, if the rigidity of the negative film is too high, problems may occur in its compatibility with equipment during the manufacturing process of the desired flexographic printing plate, and excessive stress concentration on the ablation layer during handling may occur, causing scratches and wrinkles. tend to cause irreversible damage. From the above-mentioned viewpoint, the thickness of the base material 1 shall be 10 ⁇ m or more and less than 100 ⁇ m.
• the thickness is preferably 20 ⁇ m or more, more preferably 40 ⁇ m or more.
• the thickness of the base material 1 is 10 ⁇ m or more, practically sufficient strength and rigidity can be obtained, and deformation and damage to images can be suppressed during the manufacturing process of a flexographic printing plate.
• the thickness of the base material 1 shall be less than 100 ⁇ m, preferably 90 ⁇ m or less, and 70 ⁇ m or less. More preferred.
• the base material 1 preferably contains a resin having a polyester or polyolefin skeleton.
• the resin contained in the base material 1 may be a mixture of polyester and a resin having a polyolefin skeleton, or may be a copolymer.
• the polyester include, but are not limited to, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and the like.
• the resin having a polyolefin skeleton include, but are not limited to, polyethylene, polypropylene, and resins obtained by copolymerizing these.
• the base material 1 is more preferably made of a resin having a polyester or polyolefin skeleton, and even more preferably made of a resin having a polyolefin skeleton.
• oxygen permeability is one of the physical property values of a film, and represents the amount of oxygen that passes per 1 m 2 of film per day under the condition of 1 atm (1 atm).
• the unit is cm3 / m2 ⁇ 24h ⁇ atm, and the larger the value, the easier it is to pass through, and the smaller the value, the harder it is to pass through.
• the curing proceeds by radical polymerization. If oxygen coexists during this radical polymerization, the radical-generating compound and oxygen will react and the polymerization reaction will be inhibited. That is, by reducing the amount of oxygen coexisting during exposure of the photosensitive resin composition layer, the degree of polymerization can be improved, and the image reproducibility of the final flexographic printing plate can be improved.
• the base material 1 of the film for producing a flexographic printing plate of this embodiment which is laminated on the photosensitive resin composition, has a high oxygen permeability, the surface and/or interior of the photosensitive resin composition layer will be removed when irradiated with ultraviolet rays. This makes it easier for oxygen remaining in the polymer to diffuse to the outside, making it possible to suppress the influence of oxygen on inhibiting the polymerization reaction.
• the base material may be used in an untreated state, but may be subjected to a predetermined surface treatment as necessary, or may be provided with functions such as antistatic treatment. You may use the one provided. Examples of the surface treatment include corona treatment and matte treatment.
• the flexographic printing plate manufacturing film of this embodiment has an ablation layer 2 laminated on a base material 1.
• the ablation layer 2 contains a predetermined resin, can be ablated with an infrared laser, and has a function as a layer that shields rays other than infrared rays.
• the adhesion between the base material 1 and the ablation layer 2 must be improved. It is preferable to improve the compatibility or to decrease the compatibility between the ablation layer 2 and the photosensitive resin composition layer.
• the components contained in the ablation layer 2 refer to a resin, an infrared absorbing substance, a shielding substance, and the like. From the viewpoint of improving the adhesion between the base material 1 and the ablation layer 2, it is important to strengthen the interaction between the layers. Examples of such a method of strengthening the interaction between layers include a method of imparting a similar molecular structure to the constituent materials of both the base material 1 and the ablation layer 2 in order to improve chemical interaction; Examples include methods to improve physical interaction. Examples of methods for improving physical interaction include methods for improving the flexibility of the ablation layer 2 or imparting appropriate flexibility to the ablation layer 2 in order to suppress peeling when the film is bent.
• the film for producing a flexographic printing plate of the present embodiment is such that the ablation layer 2 is a structural unit containing a quaternary carbon atom to which two nonpolar groups are bonded, represented by the following general formula (1) 1).
• the said resin may have other structural units as needed.
• the term “monomer” refers to a compound before polymerization
• the term “constituent unit” refers to a predetermined repeating unit formed by polymerizing the monomer.
• R 1 and R 2 each independently represent a nonpolar group
• R 3 and R 4 each independently represent a hydrogen atom or a nonpolar group.
• the ablation layer 2 of the film for producing a flexographic printing plate of this embodiment contains a resin having the structural unit (1) represented by the general formula (1).
• the resin contained in the ablation layer 2 has a polar group in its main chain, strong non-covalent bonds are formed between molecules, and the strength of the ablation layer 2 is improved.
• the structure used for interaction with the constituent raw materials of the base material 1 decreases, and the adhesion between the base material 1 and the ablation layer 2 tends to decrease.
• the rigidity of the ablation layer 2 becomes too high, and stress caused by bending or stretching tends to concentrate between the layers, which tends to cause interfacial peeling.
• the resin contained in the ablation layer 2 has a polar group in its side chain, this tends to be unfavorable from the viewpoint of laser ablation efficiency of the ablation layer 2, as described below.
• “Depolymerization” is the reverse reaction of a polymerization reaction, and refers to a reaction in which a polymer decomposes into monomers.
• the ablation layer 2 instantaneously reaches a high temperature of several hundred degrees by irradiation with the infrared laser. At this time, decomposition of the main chain in the resin occurs, the molecular weight rapidly decreases, and the resin is removed from the ablation layer 2.
• main chain cleavage tends to start from thermally unstable parts such as branches in polymers.
• the side chain involved in branching has polarity at this time, decomposition of the side chain tends to occur dominantly, and cleavage of the main chain is less likely to occur, which is not preferable. Therefore, it is important that the side chain of the resin contained in the ablation layer 2 of the film for producing a flexographic printing plate of this embodiment is a nonpolar group.
• the main chain cleavage progresses, the contribution of intramolecular or intermolecular chain transfer cannot be ignored. Therefore, it is preferable not to have tertiary hydrogen that is easily abstracted by chain transfer.
• the content of the resin having the structural unit (1) represented by the general formula (1) in the ablation layer is 20% by mass or more. It is preferably at least 30% by mass, more preferably at least 40% by mass.
• the nonpolar group in the above general formula (1) is any one of an alkyl group, an aryl group, a cycloalkyl group, a phenyl group, an alkenyl group, an aralkyl group, a cycloalkenyl group, an alkynyl group, a silyl group, and a siloxanyl group. It is preferable that there be. Note that the nonpolar group does not contain a hydrogen atom.
• R 1 and R 2 are each independently an alkyl group, an alkenyl group, It is more preferable that it is selected from the group consisting of alkynyl groups and alkynyl groups, and it is even more preferable that it is an alkyl group in terms of its low polarity.
• Monomers that can form the structural unit represented by the general formula (1) include, but are not limited to, for example, isobutylene, 2-methyl-2-butene, 2,3 dimethyl-2-butene, and Products in which these methyl groups are replaced with other alkyl groups such as ethyl groups; modified products of these; ⁇ -methylstyrene, cis-(1-methyl-1-propenyl)benzene, trans-(1-methyl-1- (propenyl)benzene, those in which the methyl group is replaced with another alkyl group such as ethyl group, and modified products thereof; 1,1-diphenylethylene and the like.
• R 3 and R 4 each independently represent a hydrogen atom or a nonpolar group. It is preferable that R 3 and R 4 are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, and an alkynyl group, and more preferably a hydrogen atom or an alkyl group. It is even more preferable that R 3 and R 4 are both hydrogen atoms, since this further improves the depolymerizability of the resin.
• the structural unit (1) represented by the general formula (1) constituting the resin may be used alone or in combination of two or more.
• the resin includes, as the structural unit (1), a structural unit in which R 1 and R 2 are an alkyl group, and a structural unit in which one of R 1 and R 2 is an alkyl group and the other is a phenyl group. It may have. By having both an alkyl group and a phenyl group, the properties of both groups can be obtained.
• the above-mentioned resin contained in the ablation layer 2 further contains a structural unit (2) derived from a monovinyl-substituted aromatic hydrocarbon, in addition to the structural unit (1).
• the monovinyl aromatic hydrocarbon may be chemically combined with the structural unit (1) represented by the general formula (1) or may be added as a separate resin, but the dispersibility and From the viewpoint of laser processing uniformity, the structural unit (2) derived from the monovinyl-substituted aromatic hydrocarbon is chemically bonded to the structural unit (1) represented by the general formula (1) above, and the copolymer and It is preferable that the Since the resin used for the ablation layer contains the structural unit (2) derived from a monovinyl-substituted aromatic hydrocarbon, the adhesion between the ablation layer 2 and the base material 1 is improved, and the flexographic printing plate production of this embodiment is improved.
• Compounds used to form the structural unit (2) derived from monovinyl aromatic hydrocarbons include, but are not limited to, styrene, t-butylstyrene, N,N-dimethyl-p-aminoethylstyrene, Examples include monomers such as N,N-diethyl-p-aminoethylstyrene, vinylpyridine, p-methylstyrene, and tertiary-butylstyrene.
• styrene is preferred from the viewpoint that the film for producing a flexographic printing plate of this embodiment can be smoothly molded at a relatively low temperature.
• the structural unit (2) may be used alone or in combination of two or more.
• the ablation layer 2 may contain an infrared absorbing substance for performing ablation processing.
• the infrared absorbing substance include simple substances or compounds that have strong absorption in the range of 750 to 2000 nm.
• the infrared absorbing substance include, but are not limited to, inorganic pigments such as carbon black, graphite, copper chromite, and chromium oxide; pigments such as polyphthalocyanine compounds, cyanine dyes, and metal thiolate dyes.
• Carbon black can also function as a shielding substance as described below.
• the ablation layer 2 plays a role as a mask, it may contain a substance that shields non-infrared rays such as ultraviolet rays.
• a substance that shields non-infrared rays such as ultraviolet rays.
• the non-infrared shielding material a material that reflects or absorbs ultraviolet light can be used.
• the shielding substance include, but are not limited to, ultraviolet absorbers, carbon black, graphite, and the like.
• the ablation layer 2 of the film for producing a flexographic printing plate of this embodiment is preferably thicker from the viewpoint of ensuring shielding properties against ultraviolet rays during the exposure process described later, and thinner from the viewpoint of increasing ablation properties. It's better. From the above-mentioned viewpoint, the thickness of the ablation layer 2 is preferably 0.1 ⁇ m or more and 20 ⁇ m or less, more preferably 0.5 ⁇ m or more and 15 ⁇ m or less, and even more preferably 1.0 ⁇ m or more and 10 ⁇ m or less. As for the non-infrared shielding effect of the ablation layer 2, the optical density of the ablation layer 2 is preferably 2 or more, and more preferably 3 or more.
• the optical density can be measured using a D200-II transmission densitometer (manufactured by Gretag Macbeth). Further, the optical density is a so-called visual perception (ISO visual), and the light to be measured has a wavelength range of about 400 to 750 nm.
• ISO visual visual perception
• the method for producing the film for producing a flexographic printing plate of this embodiment is not limited to the following, but for example, when carbon black is used as both an infrared absorbing substance and a non-infrared shielding substance, first, a predetermined solvent is A solution of a resin having the structural unit (1) represented by the general formula (1) described above is prepared using the method, carbon black and a dispersant are added thereto, and the carbon black is dispersed in the solution of the resin. By this, a solution or dispersion liquid for forming the ablation layer 2 is obtained.
• a method of manufacturing the ablation layer by coating a predetermined base material 1 with a solution or dispersion for forming the ablation layer may be mentioned.
• An effective method for dispersing carbon black in the resin solution is to use a combination of forced stirring using a stirring blade and stirring using ultrasonic waves or various types of mills.
• a method in which a resin, carbon black, and a dispersant are preliminarily kneaded using an extruder or kneader and then dissolved in a solvent is also an effective method for obtaining good dispersibility of carbon black.
• Another example is a method of forcibly dispersing carbon black into a resin in the form of a latex dispersion.
• the solvent used for preparing the solution, dispersion, etc. for forming the ablation layer 2 can be appropriately selected in consideration of the solubility of the resin and infrared absorber used. Only one type of solvent may be used, or a mixture of two or more types of solvents may be used. Further, for example, the film quality of the ablation layer 2 can be improved by mixing a relatively low boiling point solvent and a high boiling point solvent and controlling the volatilization rate of the solvent.
• solvents for forming the ablation layer 2 include, but are not limited to, toluene, xylene, cyclohexane, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methyl ethyl ketone, acetone, cyclohexanone, and ethylene glycol.
• propylene glycol propylene glycol
• ethanol water
• propylene glycol monomethyl ether propylene glycol monomethyl ether acetate
• dimethyl acetamide dimethyl formamide
• n-propyl alcohol i-propyl alcohol
• 1,4-dioxane 1,4-dioxane
• tetrahydrofuran diethyl ether
• n-hexane examples include n-heptane, n-pentane, acetonitrile and analogs thereof.
• the laminate of this embodiment has a configuration in which a flexographic printing original plate having a photosensitive resin composition layer and the above-described film for producing a flexographic printing plate of this embodiment are laminated on the flexographic printing original plate.
• the flexographic printing original plate has a support and a photosensitive resin composition layer laminated on the support.
• a desired flexographic printing plate is obtained by forming a relief on the flexographic printing original plate by pattern exposure and developing and removing the unexposed areas.
• Examples of the support for the printing original plate include, but are not limited to, polyester films, polyamide films, polyacrylonitrile films, and polyvinyl chloride films. Among these, polyester film is preferred as the support. Examples of the polyester used for the support include, but are not limited to, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and the like.
• the thickness of the support is not particularly limited, but is preferably 50 to 300 ⁇ m.
• a predetermined adhesive layer may be provided on the support for the purpose of increasing the adhesive force between the support and a photosensitive resin composition layer to be described later.
• the adhesive layer is not particularly limited, and examples thereof include adhesive layers described in International Publication No. 2004/104701, Japanese Patent No. 3094647, and Japanese Patent No. 2634429.
• the printing original plate has a photosensitive resin composition layer on a support.
• the photosensitive resin composition layer may be directly laminated on the support, or may be laminated indirectly via a predetermined adhesive layer or the like.
• the photosensitive resin composition layer preferably contains, for example, a polymer (b-1), an ethylenically unsaturated compound (b-2), and a photopolymerization initiator (b-3), which will be described later. These can be used selectively as appropriate.
• the photosensitive resin composition layer may further contain an auxiliary additive component, if necessary. Each component of the photosensitive resin composition layer will be explained in detail below.
• the polymer (b-1) may be a linear, branched or dendritic polymer, and may be a homopolymer or a copolymer.
• the copolymer may be a random copolymer, an alternating copolymer, or a block copolymer.
• polymer (b-1) examples include completely or partially hydrolyzed polyvinyl ester, partially hydrolyzed polyvinyl acetate, polyvinyl alcohol derivatives, partially hydrolyzed vinyl acetate/ Mention may be made of those conventionally used for the production of flexographic printing plates, such as alkylene oxide graft copolymers or polyvinyl alcohols, polybutadienes, polyamides and mixtures thereof, which are subsequently acrylated by polymer-analogous reactions. In addition to those mentioned above, for example thermoplastic elastomer block copolymers can also be used.
• Thermoplastic elastomeric block copolymers include those containing at least one block containing an alkenyl aromatic monomer unit and at least one block containing a 1,3-diene monomer unit.
• alkenyl aromatic compound forming the alkenyl aromatic monomer unit include styrene, ⁇ -methylstyrene, or vinyltoluene.
• 1,3-diene for example, butadiene and isoprene are preferred from the viewpoint of reducing steric hindrance of vinyl groups, increasing photocrosslinking efficiency, and preventing elution of the ablation layer into the printing original plate after exposure.
• the polymer (b-1) preferably contains a compound having a carbonyl group.
• a compound having a highly polar carbonyl group as the polymer (b-1), the compatibility with the resin having a non-polar group in the ablation layer can be reduced, and the photosensitive resin composition of the ablation layer can be reduced. It tends to suppress elution into the physical layer.
• the polymer (b-1) is not limited to the following, but includes, for example, polyester, polyamide, and polyurethane, and is used to prevent damage to the relief surface due to the load when peeling off the film for flexographic printing plate production after the exposure process. From this point of view, it is more preferable to include polyurethane. Furthermore, from the viewpoint of improving the mechanical properties of the flexographic printing plate finally obtained by photocrosslinking, it is preferable that the polyurethane has a (meth)acrylic group in the terminal group.
• a method for producing a polyurethane having a (meth)acrylic group at the terminal group for example, a diol having a repeating unit in the molecule is reacted with a diisocyanate to form a polyurethane having an isocyanate group at the terminal with a desired molecular weight,
• a method of producing the polyurethane by reacting the polyurethane with a compound containing active hydrogen and a (meth)acrylic group in one molecule can be mentioned.
• a diol having a repeating unit in the molecule and a diisocyanate are reacted to form a polyurethane having an isocyanate group at the terminal with a desired molecular weight, and then the polyurethane is combined with a hydroxyl group and a (meth)acrylic group in one molecule.
• the polyurethane structure obtained by the above-mentioned manufacturing method is a structure formed by reacting a diol having a repeating unit in the molecule with a diisocyanate.
• the "polyurethane having a (meth)acrylic group at the end group" produced by the above method will be referred to as "unsaturated prepolymer”.
• the "diol having a repeating unit in the molecule" used in the production of the unsaturated prepolymer is not limited to, but includes, for example, polyester diol consisting of dicarboxylic acid and diol; polyether diol; polyether polyester copolymer diol ; Examples include 1,2-polybutadiene compounds having a terminal hydroxyl group. Diols having repeating units in the molecule may be used alone or in combination of two or more.
• the dicarboxylic acids constituting the polyester diol include, but are not limited to, succinic acid, glutaric acid, adipic acid, pimenlic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, terephthalic acid, isophthalic acid, and Examples include 1,5-naphthalene dicarboxylic acid.
• Diols constituting the polyester diol include, but are not limited to, 1,4-butanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, and neopentyldiol. , 1,6-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, and diethylene glycol (dioxyethylenediol).
• polyether diol examples include, but are not limited to, polyoxyethylene diol, polyoxypropylene diol, polyoxytetramethylene diol, polyoxy 1,2-butylene diol, and polyoxyethylene/polyoxypropylene random copolymer. Examples include diol, polyoxyethylene/polyoxypropylene block copolymer diol, polyoxyethylene/polyoxytetramethylene random copolymer diol, and polyoxyethylene/polyoxytetramethylene block copolymer diol.
• the polyether polyester copolymerized diol is not limited to the following, but for example, the repeating units forming the molecular chain of the above-mentioned polyether diol and the repeating units forming the molecular chain of the above-mentioned polyester diol are block or random. Examples include copolymers having a chain structure.
• the 1,2-polybutadiene compound having a terminal hydroxyl group may be a hydrogenated compound.
• the 1,2-polybutadiene compound having a terminal hydroxyl group is not limited to the following, but includes, for example, a hydride of poly-1-butene, a hydride of 1,2-polybutadiene, and the like.
• the number of terminal hydroxyl groups is not particularly limited, but from the viewpoint of preventing damage to the relief surface due to the load when peeling off the film for printing plate production after exposure, it is preferably 1.2 or more per molecule, and 1.5 More preferably, the number is 2.0 or more, and even more preferably 2.0 or less.
• diisocyanate examples include, but are not limited to, tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and norbornene diisocyanate. .
• One type of diisocyanate may be used alone, or two or more types may be used in combination.
• the photosensitive resin composition layer preferably contains the ethylenically unsaturated compound (b-2).
• the ethylenically unsaturated compound (b-2) is a compound having a radically polymerizable unsaturated double bond.
• Examples of the ethylenically unsaturated compound (b-2) include, but are not limited to, olefins such as ethylene, propylene, vinyltoluene, styrene, and divinylbenzene; acetylenes; (meth)acrylic acid and/or derivatives thereof; ; Haloolefins; Unsaturated nitriles such as acrylonitrile; Unsaturated amides and their derivatives such as acrylamide and methacrylamide; Unsaturated dicarboxylic acids and their derivatives such as maleic anhydride, maleic acid, and fumaric acid; Vinyl acetate; N -vinylpyrrolidone; N-vinylcarbazole; N-substituted maleimide compounds and the like.
• olefins such as ethylene, propylene, vinyltoluene, styrene, and divinylbenzene
• acetylenes (me
• Examples of the derivatives include, but are not limited to, alicyclic compounds having a cycloalkyl group, a bicycloalkyl group, a cycloalkenyl group, a bicycloalkenyl group; a benzyl group, a phenyl group, a phenoxy group, or a naphthalene skeleton; Aromatic compounds having an anthracene skeleton, biphenyl skeleton, phenanthrene skeleton, fluorene skeleton, etc.; compounds having an alkyl group, halogenated alkyl group, alkoxyalkyl group, hydroxyalkyl group, aminoalkyl group, glycidyl group, etc.; alkylene glycol, polyoxy Examples include ester compounds with polyhydric alcohols such as alkylene glycol, polyalkylene glycol and trimethylolpropane; compounds having a polysiloxane structure such as polydimethylsiloxane and poly
• the ethylenically unsaturated compound (b-2) may be a heteroaromatic compound containing elements such as nitrogen and sulfur.
• the (meth)acrylic acid and/or its derivatives include, but are not limited to, diacrylates and dimethacrylates of alkanediols such as hexanediol and nonanediol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol; Polyethylene glycol, butylene glycol diacrylate and dimethacrylate; trimethylolpropane tri(meth)acrylate; dimethyloltricyclodecane di(meth)acrylate; isobornyl(meth)acrylate; phenoxypolyethylene glycol(meth)acrylate; pentaerythritol tetra Examples include (meth)acrylate. These may be used alone or in combination of two or more.
• the ethylenically unsaturated compound (b-2) is It is preferable to use at least one type of (meth)acrylate, and more preferably to use at least one type of bifunctional (meth)acrylate.
• the photosensitive resin composition layer preferably contains a photopolymerization initiator (b-3).
• Photopolymerization initiator (b-3) is a compound that absorbs light energy and generates radicals, and can be used as a decomposition type photopolymerization initiator, a hydrogen abstraction type photopolymerization initiator, or a hydrogen abstraction type photopolymerization initiator. Examples include compounds that have a functional site and a site that functions as a degradable photopolymerization initiator in the same molecule.
• photopolymerization initiators (b-3) include, but are not limited to, benzophenone, 4,4-bis(diethylamino)benzophenone, and 3,3',4,4'-benzophenone tetracarboxylic anhydride.
• benzophenones such as 3,3',4,4'-tetramethoxybenzophenone; anthraquinones such as t-butylanthraquinone and 2-ethylanthraquinone; 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone Thioxanthone such as; Michler's ketone; diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone , 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-propan-1-one, 2-benzyl-2- Acetophenones such as dimethylamino-1-(4-morph
• the content of the photopolymerization initiator (b-3) in the photosensitive resin composition layer is determined to prevent damage to the ultimately obtained flexographic printing original plate and to prevent damage when the film for producing a printing plate of this embodiment is peeled off after exposure. From the viewpoint of preventing damage to the relief surface due to the load of % or less, more preferably 0.3% by mass or more and 5% by mass or less.
• auxiliary additive ingredients include, but are not limited to, plasticizers, thermal polymerization inhibitors, antioxidants, light stabilizers, ultraviolet absorbers, dyes and pigments, and the like.
• plasticizers include, but are not limited to, liquid polybutadiene, liquid polyisoprene, modified products of liquid polybutadiene, modified products of liquid polyisoprene, liquid acrylonitrile-butadiene copolymers, and liquid styrene-butadiene copolymers.
• Hydrocarbon oils such as naphthenic oil and paraffin oil
• Polystyrene examples include ester plasticizers such as sebacic acid ester and phthalic acid ester.
• plasticizers may have a hydroxyl group or a carboxyl group. Further, these plasticizers may be provided with a photopolymerizable reactive group such as a (meth)acryloyl group.
• the plasticizers may be used alone or in combination of two or more.
• liquid refers to a property of being easily fluidized and deformed and solidified into the deformed shape by cooling. The content of the plasticizer in the photosensitive resin composition layer improves the flexibility of the resulting flexographic printing original plate, and reduces damage to the ablation layer when peeling off the printing plate manufacturing film of this embodiment after exposure, and reduces photosensitivity.
• the total amount of the photosensitive resin composition layer is 100% by mass, it is preferably 0% by mass or more and 30% by mass or less, more preferably 8% by mass or more and 30% by mass or less. , more preferably 8% by mass or more and 25% by mass or less.
• thermal polymerization inhibitor and antioxidant those commonly used in the field of resin materials or rubber materials can be used, and examples thereof include phenolic materials.
• phenolic materials that are thermal polymerization inhibitors and antioxidants include, but are not limited to, vitamin E, tetrakis-(methylene-3-(3',5'-di-t-butyl-4') -hydroxyphenyl)propionate)methane, 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, 3,9-bis- ⁇ 1,1-dimethyl-2-[3 -(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl ⁇ -2,4,8,10-tetraoxaspiro(5,5)undecane, 2-t-butyl-6-( Examples include 3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate. Examples of other thermal polymerization
• Examples of the light stabilizer and ultraviolet absorber include, but are not limited to, known benzophenone compounds, salicylate compounds, acrylonitrile compounds, metal complex compounds, and hindered amine compounds. Further, dyes and pigments shown below may be used as ultraviolet absorbers. Examples of such light stabilizers and ultraviolet absorbers include, but are not limited to, 2-ethoxy-2'-ethyloxalic acid bisanilide, 2,2'-dihydroxy-4-methoxybenzophenone, bis( Examples include 1,2,2,6,6-pentamethyl-4-piperidyl)-decanedioate and 1,2,3-benzotriazole. Dyes and pigments are effective as coloring means to improve visibility.
• the dye examples include, but are not limited to, water-soluble basic dyes, acid dyes, direct dyes, etc., and water-insoluble sulfur dyes, oil-soluble dyes, disperse dyes, etc. Particularly preferred are anthraquinone dyes, indigoid dyes, and azo dyes.
• pigments include, but are not limited to, natural pigments, synthetic inorganic pigments, synthetic organic pigments, and the like.
• synthetic organic pigments include azo pigments, triphenylmethane pigments, quinoline pigments, anthraquinone pigments, and phthalocyanine pigments.
• Method for manufacturing a flexographic printing plate of this embodiment uses the laminate of this embodiment described above. As described above, the laminate has a structure in which a flexographic printing original plate having a photosensitive resin composition layer and the film for producing a flexographic printing plate of this embodiment are laminated.
• the method for manufacturing a flexographic printing plate includes a drawing step in which a pattern is drawn by irradiating the flexographic printing plate manufacturing film with infrared rays, and an ablation layer on which a pattern is drawn in the drawing step is used as a mask.
• the method includes an exposure step of irradiating the photosensitive resin composition layer with ultraviolet rays to form a pattern, and a developing step of removing an unexposed portion of the photosensitive resin composition layer.
• the object to be irradiated with infrared rays may be a flexographic printing plate manufacturing film that constitutes a laminate; It may also be a film for the production of flexographic printing plates in the preliminary stage. That is, the flexographic printing plate manufacturing film constituting the laminate of the present embodiment includes any form before or after pattern drawing.
• the method for manufacturing the flexographic printing plate of the present embodiment includes a step of irradiating ultraviolet rays from the support side of the flexographic printing original plate constituting the laminate of the present embodiment (first step), and flexographic printing.
• a drawing step (second step) in which the ablation layer of the plate manufacturing film is irradiated with infrared rays to draw a pattern, and the photosensitive resin composition layer is irradiated with ultraviolet rays using the ablation layer on which the pattern has been drawn as a mask.
• the method includes an exposure step (third step) to form a pattern, and a development step (fourth step) to remove an unexposed portion of the photosensitive resin composition layer.
• the flexographic printing plate manufacturing film constituting the laminate in the second step is in a form before pattern drawing and constitutes the laminate in the third step.
• Films for producing flexographic printing plates are in the form after pattern writing.
• the surface of the flexographic printing plate may be brought into contact with a liquid containing a silicone compound and/or a fluorine compound.
• FIG. 2 is a schematic diagram showing a method for manufacturing a flexographic printing plate using the film for manufacturing a flexographic printing plate of this embodiment. Each step will be explained in detail below.
• the photosensitive resin composition layer 4 is irradiated with ultraviolet light from the support 3 side of the flexographic printing original plate.
• the ultraviolet irradiation method is not particularly limited, and can be performed using a known irradiation unit.
• the wavelength of the ultraviolet rays to be irradiated is preferably 150 to 500 nm, more preferably 300 to 400 nm.
• Examples of the ultraviolet light source include, but are not limited to, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, xenon lamps, zirconium lamps, carbon arc lamps, ultraviolet fluorescent lamps, and the like. Note that this first step may be performed before or after the second step described below.
• the ablation layer 2 of the film for producing a flexographic printing plate is irradiated with infrared rays to draw a pattern.
• the drawing processing method is not particularly limited, and can be performed using a known irradiation unit.
• the ablation layer 2 can be irradiated with infrared rays from the ablation layer 2 side.
• the ablation layer 2 is irradiated with infrared rays in a pattern to decompose the resin in the infrared irradiated area, and a pattern is drawn. Thereby, a mask of an ablation layer is formed on the film for producing a flexographic printing plate.
• an ablation layer 2' having a pattern drawn thereon is obtained.
• the infrared laser used in the second step include an ND/YAG laser (eg, 1064 nm) or a diode laser (eg, 830 nm).
• Laser systems suitable for CTP platemaking technology are commercially available, and for example, the diode laser system CDI Spark (manufactured by ESKO GRAPHICS) can be used.
• the laser system includes a rotating cylindrical drum holding a flexographic printing plate production film, an IR laser irradiation device, and a layout computer from which image information is transmitted directly to the laser device.
• the second step may be performed in a state in which the film for flexographic printing plate manufacturing is laminated with the photosensitive resin composition layer, It may be carried out at a stage before being laminated to a material layer.
• the photosensitive resin composition layer 4 is exposed to ultraviolet light using the ablation layer 2' on which the pattern has been drawn as a mask. At this time, the light passing through the mask promotes the curing reaction of the photosensitive resin composition layer 4, and the pattern formed on the ablation layer 2' is transferred to the photosensitive resin composition layer 4 with the unevenness reversed. , a pattern-exposed photosensitive resin composition layer 4' is obtained. Irradiation with ultraviolet light may be carried out over the entire surface or partially.
• the front and back sides of the film for producing flexographic printing plates of this embodiment can be used without any particular restrictions, but from the perspective of reducing the effects of bending and scattering of ultraviolet light irradiated to the photosensitive resin composition layer, the film for producing flexographic printing plates of this embodiment It is preferable that the surface on the ablation layer 2' side on which the upper pattern is drawn is in contact with the photosensitive resin composition layer.
• a separate film may be provided between the patterned flexographic printing plate manufacturing film and the photosensitive resin composition layer 4.
• one or more intermediate layers may be further provided between the photosensitive resin composition layer 4 and the ablation layer 2'. Examples of the intermediate layer include, but are not limited to, an oxygen inhibition layer, an adhesive layer, and a protective layer. Each layer will be explained below.
• the intermediate layer is preferably an oxygen inhibiting layer having oxygen inhibiting ability. If the radical polymerization reaction during curing of the photosensitive resin composition layer 4 by irradiation with ultraviolet rays is suppressed by oxygen, there is a risk that unreacted portions will remain in the exposed areas of the photosensitive resin composition layer 4. Since this unreacted portion is removed in the fourth step described below, the pattern finally formed on the flexographic printing plate has a curved portion at the tip.
• the portion of the photosensitive resin composition layer 4 on the ablation layer 2' side is particularly susceptible to polymerization inhibition by oxygen, and an unreacted portion occurs in the photosensitive resin composition layer 4 directly under the ablation layer 2'. This is because it is easy.
• the intermediate layer has an oxygen inhibiting ability, and thereby the amount of oxygen in contact with the photosensitive resin composition layer 4 can be reduced.
• the intermediate layer may be an adhesive layer that improves the adhesion between the photosensitive resin composition layer 4 and the ablation layer 2'.
• the intermediate layer may also have the function of protecting the ablation layer 2'.
• the ablation layer 2' comes into contact with the operator's fingers and the jig when laminating the photosensitive resin composition layer 4 on the flexographic printing plate manufacturing film or during film handling. Doing so may cause physical damage, resulting in scratches or pinholes.
• the intermediate layer preferably has physical strength and heat resistance as a protective layer.
• the fourth step is a step of removing the unexposed portions of the pattern-exposed photosensitive resin composition layer 4'.
• the method for removing the unexposed area in the fourth step (developing step) is not particularly limited, and conventionally known methods can be applied. Specific methods include, for example, exposing the photosensitive resin composition layer 4 and then washing away the unexposed areas with a solvent for solvent development or a cleaning solution for water development, or using a method that can absorb the unexposed areas.
• One example is a method in which the unexposed portion is removed by contacting a predetermined absorption layer and removing the absorption layer. Note that, as a pre-removal step, the unexposed area may be removed in advance using a spatula or a roll.
• a flexographic printing plate is manufactured by post-exposure treatment as required.
• an intermediate layer is provided between the ablation layer 2' and the photosensitive resin composition layer 4', it may be removed at the same time in the development process.
• the photosensitive resin composition is liquid at room temperature, in the first to third steps described above, the photosensitive resin composition is usually uniformly spread on the support inside a dedicated device (plate making machine). A predetermined molding process is included so that the film is molded into a thick film.
• the exposure step when using a liquid photosensitive resin composition at room temperature, it is preferable to carry out each of the following steps (A1) to (A3), for example.
• step (A1) a flexographic printing plate manufacturing film on which a mask has been formed by pattern drawing is placed on an ultraviolet-transparent glass plate (lower glass plate), and a photosensitive resin composition is placed on top of the film.
• a base film serving as a support is bonded to the base film through a spacer so that it has a constant thickness, and then a UV-transparent glass plate (upper glass plate) is pressed onto the base film to form a photosensitive resin composition layer.
• the purpose of this step is to securely fix the flexographic printing plate production film and to remove oxygen inhibiting factors. It is preferable to vacuum the film.
• the evacuation mechanism is not particularly limited, but for example, a method of evacuation using a pump through a groove provided around the lower glass can be mentioned. If the rigidity of the film for producing a flexographic printing plate is insufficient, wrinkles will appear in the film for producing a flexographic printing plate during the vacuuming step, and in severe cases, the wrinkles cannot be removed and remain. The generated wrinkles may be transferred to the relief surface after curing, and may significantly reduce image reproducibility. Furthermore, if the dimensional stability of the film for producing a flexographic printing plate is insufficient, the drawn pattern will be deformed, which will also be a factor in reducing image reproducibility.
• the rigidity of the film for producing a flexographic printing plate is too high, it will not be able to completely follow the lower glass during vacuuming, resulting in a gap and air remaining. As a result, the influence of oxygen inhibition increases, which may adversely affect image reproducibility.
• stress caused by deformation of a highly elastic film for producing a flexographic printing plate may concentrate on the ablation layer, causing wrinkles and pinholes. That is, it is extremely important that the film for producing a flexographic printing plate of this embodiment has rigidity within an appropriate range.
• a separate film may be provided between the pattern-drawn film for producing a flexographic printing plate and the photosensitive resin composition.
• the photosensitive resin composition layer on the upper glass plate side is coated with It is preferable to form a shelf layer that serves as a base.
• a special negative film is sandwiched between the upper glass plate and the base film to form the photosensitive resin composition layer.
• step (A2) after the forming step of the photosensitive resin composition layer, active light from an ultraviolet fluorescent lamp or the like as an active light source (for example, light having a wavelength distribution of 300 nm or more) is applied to the base film from the upper glass plate side. Back exposure is performed to deposit a uniform thin cured resin layer (i.e., floor forming layer (back deposited layer)) over the entire surface of the base film side of the plate.
• a masking film is provided in the photosensitive resin composition layer forming step, a shelf layer is formed by similar exposure. In this case, it is called a masking exposure step.
• Both the back deposition layer and the shelf layer are formed by curing the photosensitive resin composition layer on the side opposite to the relief forming layer side, that is, on the support side. .
• the entire photosensitive resin composition layer on the support side is cured, it becomes a back deposition layer, and when the photosensitive resin composition layer is partially cured depending on the position of the relief forming layer, it becomes a shelf layer. .
• step (A3) after the back exposure step or the masking exposure step, the photosensitive resin composition layer is exposed to the photosensitive resin composition layer from the lower glass side through a flexographic printing plate manufacturing film on which a mask has been formed by pattern drawing processing. , the same active light as in (A2) above is irradiated to deposit an image forming layer (relief forming layer), and relief forming exposure is performed.
• the shelf layer is formed by a masking exposure process
• a recovery step is performed in which the photosensitive resin composition in the unexposed area removed in the above-described development step is recovered as a photosensitive resin composition for manufacturing a new flexographic printing plate. can be carried out.
• This recovered photosensitive resin composition can be reused as a photosensitive resin composition in the production of new flexographic printing plates.
• the recovered photosensitive resin composition may be put into an exposure machine when producing a new flexographic printing plate, and if the photosensitive resin composition is processed and molded before exposure, the above-mentioned You may use the photosensitive resin composition recovered as follows.
• the exposure machine into which the recovered photosensitive resin composition is charged refers to an exposure machine equipped with a unit for laminating the support and the photosensitive resin composition in layers, and when filling the unit with the photosensitive resin composition.
• the recovered photosensitive resin composition can be used. By using the recovered photosensitive resin composition, waste can be reduced and material costs can also be reduced. On the other hand, if a large amount of ablation layer dissolves or migrates into the recovered photosensitive resin composition, various problems such as scattering of actinic rays may occur in the flexographic printing plate manufacturing process using the recovered photosensitive resin composition. This may result in a loss of quality of the final flexographic printing plate.
• the film for flexographic printing plate production of this embodiment By using the film for flexographic printing plate production of this embodiment, elution and migration of the ablation layer to the photosensitive resin composition layer in the finally obtained flexographic printing plate is suppressed, so it is inferior to that when not used. photosensitive resin compositions of poor quality can be recovered in high yield. For this reason, even in a new flexographic printing plate manufactured using the recovered photosensitive resin composition, it is possible to maintain quality such as improved whiteout depth.
• the method for manufacturing a flexographic printing plate of this embodiment has the following effects (1) to (4).
• a liquid tube was connected, and isobutylene monomer was fed into the polymerization container using nitrogen pressure.
• 0.647 g (2.8 mmol) of p-dicumyl chloride and 1.22 g (14 mmol) of N,N-dimethylacetamide were added.
• 8.67 mL (79.1 mmol) of titanium tetrachloride was further added to initiate polymerization. After stirring at the same temperature for 1.5 hours from the start of polymerization, about 1 mL of the polymerization solution was taken out for sampling.
• suspension polymerization was carried out while maintaining the temperature at about 75°C, and after observing an exothermic peak, the temperature was raised to 92°C at a rate of 1°C/min. Then, the mixture was aged for 60 minutes to substantially complete the polymerization reaction. Next, 20% by mass sulfuric acid was added in order to cool to 50° C. and dissolve the suspending agent. Then, the polymerization reaction solution was passed through a 1.68 mm mesh sieve to remove aggregates, and the resulting beaded polymer was washed, dehydrated, and dried to obtain Resin 7.
• Resin 9 As resin 8, Tuffprene 315 (manufactured by Asahi Kasei Corporation, styrene-butadiene block copolymer) was used. As resin 9, Miractran E394POTA (manufactured by Tosoh Corporation, thermoplastic polyurethane elastomer) was used.
• Table 1 below shows resins 1 to 9 (sometimes referred to as ablation layer-containing resins) to be contained in the ablation layer.
• PP represents polypropylene and PET represents polyethylene terephthalate.
• An unsaturated prepolymer composition used in a photosensitive resin composition was produced as follows.
• diols 1200 g of poly(3-methyl-1,5-pentanediol adipate) diol (Kurapol P3010 manufactured by Kuraray Co., Ltd.), polyoxyethylene (EO)-oxypropylene (PO) block copolymer diol (manufactured by Sanyo Chemical Industries, Ltd.) 800 g of "SANNIX PL2100" (manufactured by Co., Ltd.) and 0.03 g of dibutyltin dilaurate were added, and the mixture was stirred at 40° C.
• a photosensitive resin composition was prepared in the same manner as photosensitive resin composition a, except that liquid polybutadiene ("LBR-305" manufactured by Kuraray Co., Ltd.) was used in place of the unsaturated prepolymer composition in the above production example. I got item b.
• a flexographic printing plate was produced by sequentially passing through a drying process.
• a film for producing a flexographic printing plate was installed in Esko CDI SPARK2530, and a test image having an image pattern described below was laser-drawn on the ablation layer at a resolution of 8000 dpi and a laser intensity of 3.0 J.
• ((5) Molding/exposure process) Molding and exposure were performed in steps (A1) to (A3) using an "ALF-213E plate making machine" manufactured by Asahi Kasei Corporation.
• a photosensitive resin composition is poured on top of this, and a base film serving as a support is laminated via a spacer so that it has a constant thickness, and then a UV-transparent glass plate (upper glass plate) is pressed on top of it.
• a photosensitive resin composition layer was formed. Before relief exposure, a special masking film was sandwiched between the upper glass plate and the base film to form a photosensitive resin composition layer.
• active light light having a wavelength distribution of 300 nm or more
• an ultraviolet fluorescent lamp or the like as an active light source was irradiated from the upper glass plate side through the base film.
• a photosensitive resin composition layer was formed using (A1) as described above.
• the test image and masking film have a shelf layer of 300 mm x 500 mm, and a linear unexposed area (hereinafter referred to as "white outline” or "white line”) with a width of 500 ⁇ m in a solid image of 200 mm ⁇ 250 mm. ) was used.
• the photosensitive resin composition layer was exposed to light to obtain a flexographic printing original plate having a plate thickness of 3 mm and a relief depth of 2 mm.
• the relief depth is an idiom expressing the length obtained by subtracting the height of the shelf layer from the plate thickness, that is, the depth of the printed image relief.
• the masking exposure amount was adjusted as appropriate. Relief formation was performed under conditions where the relief exposure amount was 600 mJ/cm 2 .
• main agent anionic surfactant
• APR registered trademark surface treatment agent type A-10
• Nonionic surfactant, benzophenone 0.5% by mass
• Asahi Kasei Co., Ltd.'s "defoaming agent SH-4" silicone mixture 0.3% by mass as a developer, and the solution temperature was 40%. Development was carried out at 10° C. for 10 minutes. After development, the film was washed with tap water to the extent that bubbles caused by the developer were removed.
• Post-exposure was carried out using an underwater exposure method using an "AL-200UP model post-exposure machine" manufactured by Asahi Kasei Corporation, which is equipped with both an ultraviolet fluorescent lamp and a germicidal lamp. Exposure was performed at an exposure time such that the amount of light irradiated from each light source was 2000 mJ/cm 2 for an ultraviolet fluorescent lamp and 2000 mJ/cm 2 for a germicidal lamp on the surface of the photosensitive resin composition.
• Example 1' in Table 5 in the manufacturing process of the flexographic printing plate of Example 1, the recovered photosensitive resin composition of the unexposed area was re-processed in the manufacturing process of the flexographic printing plate of Example 1.
• This is an example in which one cycle is to use the material as a photosensitive resin composition, and this cycle is repeated five times.
• Comparative Example 1 is an example in which a flexographic printing plate manufacturing film having an ablation layer containing resin 7 instead of resin 1 was used in the flexographic printing plate manufacturing process of Example 1.
• Comparative Example 1' in the flexographic printing plate manufacturing process of Example 1, a flexographic printing plate manufacturing film having an ablation layer containing resin 7 instead of resin 1 was used, and the recovered unexposed photosensitive film was used.
• one cycle was to use the photosensitive resin composition again as a photosensitive resin composition in the process of manufacturing a flexographic printing plate, and this cycle was repeated five times.
• Example 1' As shown in Table 5, it was found that in Example 1', the evaluation of the elution property of the ablation layer was superior to that of Comparative Example 1', and the evaluation of the produced flexographic printing plate was also excellent. Ta.
• the film for producing flexographic printing plates and the method for producing flexographic printing plates of the present invention have industrial applicability in a wide range of general commercial printing fields.
• Base material Ablation layer 2' Ablation layer with pattern drawn 3 Substrate 4 Photosensitive resin composition layer 4' Photosensitive resin composition layer with pattern exposure

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  • 2023-06-07 CN CN202380050594.4A patent/CN119452306A/zh active Pending
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