WO2022215283A1 - Layered film for pattern formation, non-photosensitive screen printing plate, and method for manufacturing same - Google Patents

Layered film for pattern formation, non-photosensitive screen printing plate, and method for manufacturing same Download PDF

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Publication number
WO2022215283A1
WO2022215283A1 PCT/JP2021/029866 JP2021029866W WO2022215283A1 WO 2022215283 A1 WO2022215283 A1 WO 2022215283A1 JP 2021029866 W JP2021029866 W JP 2021029866W WO 2022215283 A1 WO2022215283 A1 WO 2022215283A1
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WIPO (PCT)
Prior art keywords
photosensitive resin
layer
laminated film
pattern formation
component
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PCT/JP2021/029866
Other languages
French (fr)
Japanese (ja)
Inventor
大作 安達
護 近江
修次 岩田
豊司 大上
直己 宮下
Original Assignee
株式会社 ムラカミ
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Application filed by 株式会社 ムラカミ filed Critical 株式会社 ムラカミ
Priority to KR1020227004911A priority Critical patent/KR20220139851A/en
Priority to CN202180004813.6A priority patent/CN115443436A/en
Publication of WO2022215283A1 publication Critical patent/WO2022215283A1/en

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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
    • G03F7/016—Diazonium salts or compounds
    • G03F7/021—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/14—Forme preparation for stencil-printing or silk-screen printing
    • 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
    • B41N1/24—Stencils; Stencil materials; Carriers therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/016—Diazonium salts or compounds
    • G03F7/021—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders
    • G03F7/0212—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders characterised by the polymeric binder or the macromolecular additives other than the diazo resins or the polymeric diazonium compounds
    • G03F7/0215—Natural gums; Proteins, e.g. gelatins; Macromolecular carbohydrates, e.g. cellulose; Polyvinyl alcohol and derivatives thereof, e.g. polyvinylacetals
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • 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
    • 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
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing 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
    • G03F7/12—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
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers

Definitions

  • the present invention relates to a laminated film for pattern formation, an unexposed screen printing plate, and methods for producing these.
  • a method of using a pattern forming film as a method of manufacturing a screen printing plate.
  • this method uses a pattern-forming film to transfer the photosensitive resin layer, forming a smooth photosensitive resin film on the screen and reducing thickness variations within the plate. It is excellent in that it can be suppressed. Therefore, it is possible to produce a printing plate with sharp edges of the pattern after development and little unevenness in the amount of ink transfer and high printing accuracy.
  • a stencil for screen printing using such a pattern-forming film When producing a stencil for screen printing using such a pattern-forming film, first, water, a photosensitive resin, or the like is applied to the screen, the photosensitive resin layer of the pattern-forming film is adhered, and the film is sufficiently dried. After that, by peeling off the support layer, the photosensitive resin layer is transferred to the screen, then the photosensitive resin layer is exposed through a pattern mask, and then developed with water or the like to form a predetermined pattern on the screen. can be formed.
  • the surface of the photosensitive resin layer is often tacky due to its constituent components, it is difficult to align the pattern mask during exposure, and uniform close contact with the pattern mask is hindered.
  • the photosensitive resin layer may be partially damaged, causing problems such as contamination of the pattern mask.
  • JP-A-58-60745 and WO 2013-080958 a pattern forming method in which polyvinyl alcohol or a fluorine compound is arranged as an intermediate layer between the support layer and the photosensitive resin layer Laminated films have been proposed.
  • polyvinyl alcohol is a water-soluble polymer, it absorbs moisture in the air, and it seems that it is not sufficient to suppress the tackiness of the printing plate.
  • the intermediate layer is originally a non-photosensitive material and is removed during development. It migrates and becomes insoluble in the developer during exposure. Therefore, the components of the intermediate layer may remain on the surface of the plate film without being removed by development. As a result, the originally designed performance of the photosensitive resin could not be achieved in some cases.
  • the present invention does not absorb moisture in the air, does not leave unnecessary components on the surface of the plate film, suppresses the tackiness of the photosensitive resin layer, and improves poor adhesion and workability during exposure.
  • the challenge is to
  • the laminated film for pattern formation according to the present invention is characterized by comprising a support layer, a glue layer, a water-insoluble polymer layer and a photosensitive resin layer in this order.
  • Such a laminated film for pattern formation according to the present invention preferably includes one in which the photosensitive resin layer is a photosensitive resin that can be developed with neutral water.
  • Such a laminated film for pattern formation according to the present invention preferably has an interlayer adhesion (x) between the support layer and the glue layer, and a layer between the glue layer and the water-insoluble polymer layer.
  • the inter-layer adhesive strength (y) and the inter-layer adhesive strength (z) between the water-insoluble polymer layer and the photosensitive resin layer include those having the following relationship. Interlayer adhesive strength (x) > Interlayer adhesive strength (y) Interlayer adhesion (z) > Interlayer adhesion (y)
  • the interlayer adhesive strength (y) between the glue layer and the water-insoluble polymer layer is preferably 0.001 to 1.0 N/25 mm. includes things.
  • Such a laminated film for pattern formation according to the present invention preferably includes one in which the water-insoluble polymer layer has a haze value of 5.0% or less.
  • Such a laminated film for pattern formation according to the present invention preferably includes one in which the water-insoluble polymer layer has a thickness of 1 to 100 ⁇ m.
  • the photosensitive resin layer preferably comprises a photosensitive resin containing the following components (A) and (B).
  • the photosensitive resin layer preferably comprises a photosensitive resin containing the following components (A), (C) and (D). , including Component (A): Polyvinyl alcohol having a degree of saponification of 50 mol % or more Component (C): Epoxy compound having at least one epoxy group Component (D): Photoacid generator.
  • the photosensitive resin layer preferably comprises a photosensitive resin containing the following component (E).
  • the photosensitive resin layer preferably comprises a photosensitive resin further containing component (F) and component (G) below.
  • component (F) Radically polymerizable compound having at least one ethylenically unsaturated bond
  • component (G) Radical photopolymerization initiator.
  • the photosensitive resin layer preferably comprises a photosensitive resin further containing the following component (H).
  • Such a laminated film for pattern formation according to the present invention preferably includes a film obtained by further laminating a protective layer on the photosensitive resin layer side of the laminated film for pattern formation.
  • the unexposed screen printing plate according to the present invention comprises a laminated film obtained by removing the support layer and the adhesive layer from the laminated film for pattern formation, and a screen laminated on the photosensitive resin layer side of the laminated film. and a mesh.
  • the method for producing an unexposed screen printing plate according to the present invention is characterized by comprising the following steps (a) and (b).
  • the screen printing plate according to the present invention comprises a laminated film obtained by removing the support layer and the adhesive layer from the pattern-forming laminated film, and a screen mesh laminated on the photosensitive resin layer side of the laminated film. It is characterized by forming a latent image on an unexposed screen printing plate and developing a photosensitive resin layer.
  • the method for producing a screen printing plate according to the present invention is characterized by comprising the following steps (a) to (f).
  • E) The step of peeling off the water-insoluble polymer layer.
  • a photosensitive resist base material according to the present invention is characterized by comprising the above-described pattern-forming laminated film and a base material laminated on the photosensitive resin layer side of the pattern-forming laminated film. It is something to do.
  • the laminated film for pattern formation according to the present invention has a water-insoluble polymer layer laminated on the surface of a photosensitive resin layer. Since the water-insoluble polymer layer has a smooth surface, it is easy to position the pattern mask on the surface of the water-insoluble polymer layer.
  • the adhesion between the pattern mask and the water-insoluble polymer layer is high and the uniformity is high, the distortion of the pattern mask is suppressed. As a result, the exposure of the photosensitive resin layer and the formation of the latent image can be performed very accurately.
  • This water-insoluble polymer layer functions as a so-called protective layer for the photosensitive resin layer, and prevents the photosensitive resin layer from being affected by the ambient environment, degraded components, and the like. For example, it prevents the photosensitive resin layer from absorbing moisture and prevents harmful components from migrating from other layers, so that the original excellent properties of the photosensitive resin can be maintained for a long period of time. Therefore, according to the pattern-forming laminated film of the present invention, it is possible to obtain a screen printing plate on which a desired high-definition pattern is accurately formed.
  • the water-insoluble polymer layer is present on the photosensitive resin layer at the time of exposure, there is no moisture absorption or residue, which is a concern in the case of a conventional water-soluble polymer layer. , contamination of the pattern mask by the photosensitive resin component can be prevented.
  • FIG. 1 is a schematic diagram of a preferred unexposed screen printing plate according to the present invention.
  • BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram of a preferred unexposed screen printing plate according to the present invention; BRIEF DESCRIPTION OF THE DRAWINGS The figure which shows the outline
  • the laminated film for pattern formation according to the present invention is characterized by comprising a support layer, a glue layer, a water-insoluble polymer layer and a photosensitive resin layer in this order.
  • a laminated film for pattern formation according to the present invention comprises a support layer, a glue layer, a water-insoluble polymer layer and a photosensitive resin layer.
  • the term “comprising” refers to those comprising only the listed layers (i.e., the support layer, the adhesive layer, the water-insoluble polymer layer and the photosensitive resin layer), as well as the layers other than the listed layers. Also includes those comprising a layer or material of Representative examples of layers other than the listed layers include, for example, a protective layer.
  • the pattern-forming laminated film according to the present invention can be applied, for example, to various printing technical fields, particularly preferably to the screen printing field.
  • the laminated film for pattern formation according to the present invention is applied to such a printing field, first, after removing the support layer and the adhesive layer by peeling the interface between the adhesive layer and the water-insoluble polymer layer, Stripping the water-insoluble polymeric layer may be performed.
  • the interlayer adhesive strength (y) between the molecular layer and the interlayer adhesive strength (z) between the water-insoluble polymer layer and the photosensitive resin layer have the following relationship. .
  • the interlayer adhesion (x) and the interlayer adhesion (z) are determined when (x) is larger than (z), when (x) is smaller than (z), and (x) and ( If z) is equal, then there is
  • ⁇ Support layer> various materials can be used as the support layer.
  • various materials can be used as the support layer.
  • one made of various resin materials can be used, and one made of natural materials can also be used.
  • Preferred materials include, for example, paper, release paper, polyesters such as polyethylene terephthalate, polyolefins such as polymethylpentene, polypropylene and polyethylene, halogen-containing vinyl polymers such as polyvinyl fluoride and polyvinyl chloride, polyamides such as nylon, and cellophane. cellulose, polystyrene, acrylic resin, polyimide, and the like.
  • the support layer may be transparent or opaque, and one side or both sides thereof may be subjected to release treatment, matte treatment, or easy-adhesion treatment for the purpose of improving the functions of the laminated film.
  • the above treatment facilitates controlling the interlayer adhesion (x) between, for example, the support layer and the glue layer.
  • the thickness of the support layer is not particularly limited, it is preferably 10 to 200 ⁇ m, particularly preferably 30 to 125 ⁇ m.
  • the paste layer can be made of various materials. That is, the paste material used for the paste layer is not particularly limited, and various paste materials can be used.
  • Preferable adhesives include, for example, acrylic (one-component or two-component) adhesives or pressure-sensitive adhesives, rubber-based or urethane-based adhesives or pressure-sensitive adhesives, silicone-based adhesives or pressure-sensitive adhesives, and acetic acid.
  • Various adhesives including vinyl adhesives can be used.
  • the thickness of the glue layer is not particularly limited, it is preferably 0.5 to 30 ⁇ m, particularly preferably 0.5 to 20 ⁇ m.
  • the glue layer is formed by a conventional coating method such as gravure, comma, air knife, doctor knife, bar coater, die coat method, doctor blade method, etc. After applying the above glue material on the support layer, heat treatment, UV irradiation, etc. It can be carried out by drying and curing by irradiation treatment, electron beam irradiation treatment, or the like.
  • the glue material for forming this glue layer preferably has an interlayer adhesion (y) between the glue layer and the water-insoluble polymer layer of preferably 0.001 to 1.0 N/25 mm, particularly preferably 0.001 to 1.0 N/25 mm. 005-0.5N/25mm (versus PET). If it is less than 0.001 N/25 mm, it may cause peeling or floating due to insufficient adhesion to the water-insoluble polymer layer, which is not preferable. , it is not preferable because it may become difficult to peel off from the water-insoluble polymer layer, may leave an adhesive residue after peeling, and may increase surface contamination.
  • y interlayer adhesion
  • the interlaminar adhesive strength (y) is obtained by forming a glue layer on a polyethylene terephthalate film having a width of 25 mm, and bonding the polyethylene terephthalate film together under pressure. It is expressed in terms of force when peeling at an angle of 180 degrees at a speed of 300 mm/min after 1 minute at 23° C. (according to JIS-Z0237).
  • the glue constituting the glue layer does not remain on the surface of the water-insoluble polymer layer.
  • the residual amount of the glue on the surface of the water-insoluble polymer layer after the glue layer is peeled off is preferably 5% or less, more preferably 1% or less, particularly preferably 1% or less, when the mass of the glue material of 10 cm 2 is taken as 100. , 0.1% or less.
  • the resin constituting the photosensitive resin layer is cured by the light transmitted through the water-insoluble polymer layer.
  • the water-insoluble polymer layer preferably has a low haze value.
  • the haze value is preferably 0.01 to 5.0%, particularly preferably 0.05 to 3.0%.
  • the haze value is according to JIS-K7136.
  • the photosensitive resin layer can be cured satisfactorily even with a small amount of light irradiation, and a high-definition desired pattern can be formed on the photosensitive resin layer. can be done.
  • Preferred water-insoluble polymer layers include, for example, polyesters such as polyethylene terephthalate, polyolefins such as polymethylpentene, polypropylene and polyethylene, halogen-containing vinyl polymers such as polyvinyl fluoride and polyvinyl chloride, polyamides such as nylon, and cellophane. cellulose, polystyrene, acrylic resin, polyimide, polyethersulfone resin, and the like. As long as the haze value is within the range, one side or both sides of the water-insoluble polymer layer can be subjected to release treatment or adhesion-facilitating treatment for the purpose of improving the functions of the laminated film.
  • the above treatment controls the interlayer adhesion (y) between the glue layer and the water-insoluble polymer layer and the interlayer adhesion (z) between the water-insoluble polymer layer and the photosensitive resin layer. becomes easier.
  • water-insoluble polymer layers polyester films and polyolefin films are suitably used.
  • the thickness is preferably 1-100 ⁇ m.
  • the photosensitive resin layer of the laminated film for pattern formation according to the present invention can form a latent image by light irradiation, and can be made of a resin that can be developed with neutral water. And it is preferable to use water as a solvent to form a coating film.
  • Preferred examples of such a photosensitive resin layer include the following first specific example, second specific example and third specific example.
  • a first specific example of the photosensitive resin layer is composed of a photosensitive resin containing the following component (A) and component (B).
  • Component (A) Polyvinyl alcohol having a degree of saponification of 50 mol% or more
  • Component (B) Diazo resin
  • “comprising” means each listed component (that is, component (A) and component (B)) In addition to those containing only, those containing components other than the listed components are also included. Representative examples of components other than those listed include, for example, components (F) to (H) (details will be described later).
  • the abundance ratio (% by mass) of component (A) and component (B) is component (A):component (B), preferably 1:0.005 to 1:0.5, particularly preferably 1:0 .01 to 1:0.2.
  • the photosensitive resin comprising the above component (A) and component (B) can contain any one or more of components (F) to (H) as required.
  • Component (A) is polyvinyl alcohol having a degree of saponification of 50 mol % or more. Those having a degree of saponification of 50 to 100 mol %, particularly 70 to 100% are preferred, and copolymers with other vinyl monomers may be used as long as the water solubility is not impaired.
  • the average degree of polymerization is preferably 200-5000, more preferably 300-4000. Two or more polyvinyl alcohols with different degrees of saponification and polymerization can be mixed. Modified products such as cation-modified and anion-modified products can also be used.
  • Component (B) is a diazo resin.
  • Specific examples include condensates of p-diazodiphenylamine or 3-methoxy-4-diazodiphenylamine with 4,4′-bismethoxymethyldiphenyl ether, and their sulfates, phosphates and zinc chloride double salt anion complexes. diazo resins of sulfate, phosphate and zinc chloride double salt anion complexes of the condensates of p-diazodiphenylamine or 3-methoxy-4-diazodiphenylamine with paraformaldehyde.
  • Diazo resins of this kind include, in addition to para-aminodiphenylamine, 4-amino-4'-methyldiphenylamine, 4-amino-4'-ethyldiphenylamine, 4-amino-4'-methoxydiphenylamine and 4-amino-4'.
  • -chlorodiphenylamine, 4-amino-4'-nitrodiphenylamine, etc. is condensed with aldehydes such as paraformaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, and water-soluble diazo resin. can be used.
  • condensates of p-diazodiphenylamine and paraformaldehyde condensates of 3-methoxy-4-diazodiphenylamine and paraformaldehyde, condensates of p-diazodiphenylamine and 4,4'-bismethoxymethyldiphenyl ether , 3-methoxy-4-diazodiphenylamine and 4,4'-bismethoxymethyldiphenyl ether are preferred.
  • One kind of the above component (B) can be used alone, or two or more kinds can be used in combination.
  • Component (F) is a radically polymerizable compound having at least one ethylenically unsaturated bond, and includes monomers and oligomers described in "Photocuring Technical Data Book” (Technonet, 2000).
  • monofunctional monomers include 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, ) acrylate, 2-ethoxyethyl (meth)acrylate, 2(2-ethoxyethoxy)ethyl (meth)acrylate, n-butoxyethyl (meth)acrylate, morpholinoethyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate ) acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethy (propy)ene glycol (meth) acrylate, methoxytetraethy (propy) lene glycol (meth) acrylate, methoxypolyethylene (propy) lene glycol (meth) acryl
  • polyfunctional monomers having two or more ethylenically unsaturated bonds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, 1,3-trimethylene glycol di(meth)acrylate, 1 ,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene oxide-modified bisphenol A diacrylate, neopentyl glycol di(meth)acrylate, bis(acryloxyneopentyl) glycol) adipate, bis(methacryloxyneopentylglycol)adipate, epichlorohydrin-modified 1,6-hexanediol di(meth)acrylate, neopentylglycol hydroxypivalate di(meth)acrylate, caprolactone-modified neopentylglycol hydroxypivalate ( meth)acrylate, polyethylene glycol di(
  • epoxy (meth)acrylate such as polyester (meth)acrylate oligomer, bisphenol A type epoxy (meth)acrylate, caprolactone addition (meth)acrylate, phenol novolac type epoxy (meth)acrylate, cresol novolak type epoxy (meth)acrylate, etc.
  • Meth)acrylate, urethane (meth)acrylate, and the like can be used.
  • an ethylenically unsaturated bond-containing polyester dendrimer or the like can be used. Specific examples of such ethylenically unsaturated bond-containing polyester dendrimers are described, for example, in JP-A-2005-76005, JP-A-2005-47979, and JP-A-2005-76005.
  • component (F) can be used alone, or two or more kinds can be used in combination.
  • the abundance (% by mass) of component (F) is preferably 1.0 to 800% by mass, particularly preferably 10 to 800% by mass, when the total of component (A) and component (B) is 100% by mass. 600% by mass.
  • Component (G) is a photopolymerization initiator, but examples thereof include benzophenones such as benzophenone and bis-N,N-dimethylaminobenzophenone, and thioxanthones such as thioxanthone and isopropylthioxanthone.
  • oil-soluble photoradical polymerization initiators include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2, 2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane -1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1 - acetophenones such as hydroxycyclohexylphenyl ketone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1,
  • Component (H) is an aqueous polymer emulsion such as polyvinyl acetate, vinyl acetate/ethylene copolymer, vinyl acetate/acrylate copolymer, (meth)acrylic acid polymer, styrene/butadiene copolymer. , methyl methacrylate/butadiene copolymer, acrylonitrile/butadiene copolymer, chloroprene polymer, isoprene polymer, polyvinyl chloride, polyvinylidene chloride, polystyrene, silicone resin, polyethylene, polyurethane, fluorine resin, and the like. .
  • hydrophobic polymer particles are polyvinyl acetate emulsion, ethylene/vinyl acetate copolymer emulsion, vinyl acetate/acrylic copolymer emulsion, ethylene/vinyl acetate/acrylic terpolymer emulsion, vinyl chloride/vinyl acetate obtained during the polymerization process.
  • Copolymer emulsion, acrylic emulsion, styrene/butadiene latex emulsion, MBR latex emulsion, acrylonitrile/butadiene rubber latex emulsion, chloroprene rubber latex emulsion, vinylidene chloride emulsion and the like can be mentioned.
  • an aqueous emulsion of a polymer having a crosslinked structure obtained by emulsion polymerization of an aqueous emulsion prepared from a polyfunctional (meth)acrylate with a thermal polymerization initiator or a photopolymerization initiator can also be preferably used.
  • Useful synthetic polymer dispersions include polyethylene dispersions, polyolefin ionomer dispersions, urethane ionomer dispersions, and the like.
  • the abundance ratio (% by mass) of component (H) is preferably 1 to 1500% by mass, particularly preferably 10 to 1000% by mass, when the total of component (A) and component (B) is 100% by mass. %.
  • other components include a cross-linking agent, organic or inorganic particles, silane coupling agent, pigment, dye, thermal polymerization inhibitor, surfactant, antifoaming agent, and antioxidant.
  • Agents, adhesion imparting agents, plasticizers, solvents, surface tension modifiers, stabilizers, chain transfer inhibitors, flame retardants, antibacterial agents, preservatives and the like can be added as necessary.
  • a second specific example of the photosensitive resin layer is composed of a photosensitive resin containing the following components (A), (C) and (D).
  • component (A), component (C) and component (D) refers to those containing only the listed components (i.e., component (A), component (C) and component (D)), as well as components other than the listed components. etc. is also included.
  • Representative examples of layers other than the listed layers include, for example, components (F) to (H).
  • the abundance ratio (% by mass) of component (A) and component (C) is component (A):component (C), preferably 1:1 to 1:10, particularly preferably 1:2 to 1:6. is.
  • the amount (% by mass) of component (D) is preferably 1 to 20% by mass, particularly preferably 3 to 10% by mass, based on the above component (C).
  • the photosensitive resin comprising the component (A), the component (C) and the component (D) may optionally contain one or more of the components (F) to (H). .
  • Component (A) As the component (A) in the second specific example, those exemplified as the component (A) in the first specific example of the photosensitive resin can be used.
  • Component (C) is a compound having at least one epoxy group.
  • di- or higher functional glycidyl-type epoxy compounds include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, resorcinol di Glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, terephthalic acid diglycidyl ester, diphthalic acid glycidyl ester, hydrogenated diglycidyl phthalate, bisphenol A PO 2mol
  • alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate and ⁇ -adducts of caprolactone, 1,2,8,9-diepoxylimonene, (3,3'4,4'-diepoxy)bicyclohexyl, 1,2-epoxy-4-vinylcyclohexane), 2,2-bis 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of (hydroxymethyl)-1-butanol, butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ⁇ -caprolactone, 3,4-epoxy Cyclohexylmethyl methacrylate and the like can be mentioned.
  • Monofunctional epoxy compounds include 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol (EO) 5 glycidyl ether, p-tert-butylphenyl glycidyl ether, dibromophenyl glycidyl ether, lauryl alcohol (EO) 15 glycidyl ether, Cl 2 , Cl 3 mixed alcohol glycidyl ether, N-glycidyl phthalimide and the like. If these are used as reactive diluents, high viscosity or solid epoxy resins can be used.
  • phenol novolak type epoxy resin cresol novolak type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, biphenol type epoxy resin, bisphenol -A novolac type epoxy resin, naphthalene skeleton-containing epoxy resin, heterocyclic epoxy resin, epoxidized polybutadiene, epoxidized styrene-butadiene block copolymer, brominated epoxy resin, biphenyl type epoxy resin, amine type epoxy resin, etc.
  • a compound having at least one oxetane group can be used in combination with the above epoxy compound.
  • Oxetane compounds are described in JVCrivello and H. Sasaki, JMS Pure Appl. Chem., A30(2&3), 189 (1993) or JHSasaki and V. Crivello, JMS Pure Appl. and the compound of For example, 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol), 2-ethylhexyloxetane, (3-ethyloxetan-3-yl)methyl methacrylate, (3-ethyloxetan-3-yl)methylacrylate, 3-ethyl -monofunctional oxetane compounds such as 3-(4-hydroxybutyloxymethyl)oxetane, xylylene bisoxetane, 3-ethyl-3 ⁇ [(3-ethyloxetane-3-yl)methoxy]methyl ⁇ oxetane, 4,4 '-bis[(3-ethyl-3-oxetanyl
  • Component (D) is an acid generator, and compounds used in chemically amplified photoresists and photo-cationic polymerization are used (Organic Electronics Materials Study Group, "Organic Materials for Imaging", Bunshin Publishing (1993). ), see pages 187-192).
  • acid generators include onium cation compounds, halogen-containing compounds that generate hydrohalic acid, and sulfonated compounds that generate sulfonic acid.
  • onium cations such as diazonium, ammonium, iodonium, sulfonium, phosphonium, ferrocenium, Cl ⁇ , Br ⁇ , I ⁇ , ZnCl 3 ⁇ , HSO 3 ⁇ , BF 4 ⁇ , PF 6 ⁇ , AsF 6 ⁇ , SbF 6 ⁇ , CH 3 SO 3 ⁇ , CF 3 SO 3 ⁇ , perfluorobutanesulfonate, perfluorooctane sulfonate, camphorsulfonate, benzenesulfonate, p-toluenesulfonate, 9,10-dimethoxyanthracene-2 -sulfonate, cyclohexylaminosulfonate, (C 6 F 5 ) 4 B ⁇ , (C 4 H 9 ) 4 B ⁇ and the like.
  • onium cations such as diazonium,
  • onium cations include phenyldiazonium, p-methoxydiazonium, ⁇ -naphthyldiazonium, biphenyldiazonium, diphenylamine-4-diazonium, 3-methoxydiphenylamine-4-diazonium, and 2,5-diethoxy-4-methoxy.
  • Acid generators that generate hydrohalic acids include 1-methyl-3,5-bis(trichloromethyl)-s-triazine, 1-phenyl-3,5-bis(trichloromethyl)-s-triazine, 1 -(4-chlorophenyl)-3,5-bis(trichloromethyl)-s-triazine, 1-(4-methoxyphenyl)-3,5-bis(trichloromethyl)-s-triazine, 1-(4-butoxy Phenyl)-3,5-bis(trichloromethyl)-s-triazine, 1-(3,4-methylenedioxyphenyl)-3,5-bis(trichloromethyl)-s-triazine, 1-(3,4 -dimethoxyphenyl)-3,5-bis(trichloromethyl)-s-triazine, 1-(4-methoxynaphthyl-1)-3,5-bis(trichloromethyl)-s-triazine,
  • Acid generators that generate sulfonic acid include 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, 1-(p-toluenesulfonyloxyimino)-1-phenylethanenitrile, 1- (p-toluenesulfonyloxyimino)-1-phenylethanenitrile, benzoin p-toluenesulfonate, 2-p-toluenesulfonyloxy-2-benzoylpropane, p-nitrobenzyl 9,10-dimethoxyanthracene-2-sulfonate, N -trifluoromethanesulfonyloxydiphenylmaleimide, Np-toluenesulfonyloxysuccinimide, N-camphorsulfonyloxysuccinimide, N-trifluoromethanes
  • sensitizers having such properties include aromatic polycyclic compounds, porphyrin compounds, phthalocyanine compounds, polymethine dye compounds, merocyanine compounds, coumarin compounds, thiopyrylium compounds, pyrylium compounds, p-dialkylaminostyryl compounds, thioxanthene compounds. etc., but not limited to these.
  • Component (F) As the component (F) in the second specific example, those exemplified as the component (F) in the first specific example of the photosensitive resin can be used.
  • the abundance ratio (% by mass) of component (F) is preferably 1 to 60% by mass, particularly preferably 1 to 60% by mass, when the total of component (A), component (C) and component (D) is 100% by mass. is 5 to 30% by mass.
  • Component (G) As the component (G) in the second specific example, those exemplified as the component (G) in the first specific example of the photosensitive resin can be used.
  • the content ratio (% by mass) of component (G) is preferably 0 to 20% by mass, particularly preferably 0.1 to 10% by mass, relative to component (F).
  • Component (H) As the component (H) in the second specific example, those exemplified as the component (H) in the first specific example of the photosensitive resin can be used.
  • the abundance ratio (% by mass) of component (H) is preferably 0.5 to 200% by mass when the total of component (A), component (C) and component (D) is taken as 100% by mass, Particularly preferably, it is 1 to 100% by mass.
  • the second photosensitive resin layer contains other components such as a cross-linking agent, organic or inorganic particles, a silane coupling agent, a pigment, a dye, a thermal polymerization inhibitor, a surfactant, an antifoaming agent, and an antioxidant.
  • a cross-linking agent organic or inorganic particles
  • a silane coupling agent organic or inorganic particles
  • a pigment organic or inorganic particles
  • a silane coupling agent e.g., a silane coupling agent
  • a pigment e.g., a pigment, a dye, a thermal polymerization inhibitor, a surfactant, an antifoaming agent, and an antioxidant.
  • a third specific example of the photosensitive resin layer is composed of a photosensitive resin containing the following component (E).
  • Component (E) is a saponified product of a vinyl acetate polymer having a styryl-substituted pyridinium group or a styryl-substituted quinolinium group and having a degree of saponification of 50 mol % or more, and itself has photocrosslinkability.
  • Preferred specific examples include compounds represented by the following general formula (1) or general formula (2).
  • R 1 represents a hydrogen atom, an alkyl group or an aralkyl group, which may be substituted with a hydroxy group or a carbamoyl group, and their carbon-carbon bond is through an oxygen atom or an unsaturated bond.
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m is an integer of 1 to 6, n is 0 or 1, X - is a halogen ion, Phosphate ions, methosulfate ions, sulfonate ions, radically polymerizable monomers with anion dissociation ability, or mixtures of these anions)
  • the alkyl group or aralkyl group for R 1 preferably has 1 to 10 carbon atoms. Those of 1 to 7 are particularly preferred.
  • R 1 Specific residues (R 1 ) include methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-methoxyethyl, 3-methoxypropyl, allyl, crotyl, benzyl, etc. can be mentioned.
  • m exceeds the range of 1 to 6, the film tends to swell after photoinsolubilization, and 1 to 4 is more preferable.
  • n can be either 0 or 1.
  • X - includes phosphate ion, methosulfate ion, halogen ion Cl - or Br - , sulfonate ion CH 3 SO 3 - , CH 3 CH 2 SO 3 - , C 6 H 5 SO 3 - , p -CH 3 C 6 H 4 SO 3 - is preferred. Further, as X 1 ⁇ , a radically polymerizable monomer having at least one ethylenically unsaturated bond and having anion dissociation ability can also be mentioned.
  • Residues having anion dissociation ability include sulfonic acid, carboxylic acid and phosphoric acid, and alkali salts thereof or ammonium salts of aliphatic amines are used as radical monomers having an anion group.
  • examples of radically polymerizable unsaturated groups in the monomers used for this purpose include (meth)acryloyl groups (hereinafter, (meth)acryloyl means both acryloyl and methacryloyl), maleic acid monoester groups, styryl groups, An allyl group and the like can be mentioned.
  • undissociated acid-type monomers examples include acrylic acid, methacrylic acid, maleic acid monomethyl ester, maleic acid monoethyl ester, phthalic acid 2-(meth)acryloyloxyethyl ester, phthalic acid 3-(meth)acryloyloxy -2-propyl ester, 3-(meth)acryloyloxy-2-propyl phthalate, 2-(meth)acryloyloxyethyl cyclohexane-3-ene-1,2-dicarboxylic acid, 2-(meth)succinic acid acryloyloxyethyl ester, cyclohexane-1,2-carboxylic acid 2-(meth)acryloyloxyethyl ester, maleic acid 2-(meth)acryloyloxyethyl ester, ⁇ -carboxy-polycaprolactone monoacrylate, acrylic acid dimer, 2- (meth) acryloyloxyethyl phosphate, 3-
  • Component (F) As the component (F) in the third specific example, those exemplified as the component (F) in the first specific example of the photosensitive resin can be used.
  • the abundance ratio (% by mass) of component (F) is preferably 1.0 to 800% by mass, particularly preferably 10 to 600% by mass, based on 100% by mass of component (E).
  • Component (G) As the component (G) in the third specific example, those exemplified as the component (E) in the first specific example of the photosensitive resin can be used.
  • the abundance ratio (% by mass) of the component (G) is preferably 0.1 to 20% by mass, particularly preferably 0.5 to 10% by mass, when the above component (F) is 100% by mass. be.
  • Component (H) As the component (H) in the third specific example, those exemplified as the component (H) in the first specific example of the photosensitive resin can be used.
  • the content ratio (% by mass) of component (H) is preferably 1 to 1500% by mass, particularly preferably 10 to 1000% by mass, based on 100% by mass of component (E).
  • the third photosensitive resin layer contains other components such as cross-linking agents, organic or inorganic particles, silane coupling agents, pigments, dyes, thermal polymerization inhibitors, surfactants, antifoaming agents, and antioxidants. Agents, adhesion imparting agents, plasticizers, solvents, surface tension modifiers, stabilizers, chain transfer inhibitors, flame retardants, antibacterial agents, preservatives and the like can be used as necessary.
  • the laminated film for pattern formation according to the present invention may contain layers other than the support layer, glue layer, water-insoluble polymer layer and photosensitive resin layer.
  • Representative examples of such other layers include, for example, protective layers.
  • This protective layer mainly has the function of protecting the laminated film for pattern formation according to the present invention. , damage due to impact or pressure from the outside, and deterioration due to humidity, gas, light, or the like can be prevented. In addition, it is easy to store the laminated film for pattern formation according to the present invention by stacking it or winding it into a roll.
  • various materials can be used as the protective layer.
  • one made of various resin materials can be used, and one made of natural materials can also be used.
  • the material of the protective layer there is no specific limitation on the material of the protective layer, and for example, the same material as that of the support layer can be used.
  • the thickness of the protective layer is not particularly limited, it is preferably 1 to 50 ⁇ m.
  • the protective layer is applied prior to the other layers constituting the laminated film for pattern formation according to the present invention. Then, the protective layer is peeled off. Therefore, the inter-layer adhesion between this protective layer and the photosensitive layer must be lower than the other inter-layer adhesion (x) to (z) (that is, lower than the inter-layer adhesion (y)). preferable. Therefore, one side or both sides may be subjected to mold release treatment.
  • the film may be transparent or opaque.
  • examples include paper, release paper, polyesters such as polyethylene terephthalate, polyolefins such as polymethylpentene, polypropylene and polyethylene, halogen-containing vinyl polymers such as polyvinyl fluoride and polyvinyl chloride, polyamides such as nylon, cellulose such as cellophane, and polystyrene. , acrylic resin, and polyimide.
  • release treatment, matte treatment, or easy-adhesion treatment may be performed on one or both sides of the film as long as the function of the laminated film is not lost.
  • a first unexposed screen printing plate according to the present invention comprises the above laminated film for pattern formation and a screen mesh laminated on the photosensitive resin layer side of the laminated film for pattern formation. Characterized by
  • FIG. 1 shows a preferred specific example of the first unexposed screen printing plate 8 according to the present invention.
  • a preferable unexposed screen printing plate 8 according to the present invention shown in FIG. 5 comprises a pattern-forming laminated film 1) configured in this order and a screen mesh 6 laminated on the photosensitive resin layer 5 side of the pattern-forming laminated film 1).
  • the screen mesh 6 is pasted on the frame material 7 like a normal screen printing plate.
  • step (a) when the screen mesh 6 is bonded to the photosensitive resin layer 5 side of the pattern forming laminated film 1, preferably, for example, (1) the screen mesh 6 is coated with a photosensitive material (preferably, A photosensitive material which is the same as or similar to the photosensitive resin forming the photosensitive resin layer 5) or water is applied in advance, and the photosensitive resin layer 5 of the laminated film for pattern formation 1 is bonded thereto.
  • a photosensitive material preferably, A photosensitive material which is the same as or similar to the photosensitive resin forming the photosensitive resin layer 5
  • Method (2) After the photosensitive resin layer 5 of the laminated film for pattern formation 1 is superimposed on the screen mesh 6, the same or similar photosensitive resin is used to form a photosensitive resin layer on the superposed portion. Examples include a method of applying a photosensitive material or water.
  • Second unexposed screen printing plate comprises a laminated film obtained by removing the support layer and the adhesive layer from the pattern forming laminated film, and a screen mesh laminated on the photosensitive resin layer side of the laminated film.
  • FIG. 2 shows a preferred embodiment of the second unexposed screen printing plate 9 according to the invention.
  • the preferred unexposed screen printing plate 9 according to the present invention shown in FIG. It comprises a film 1' and a screen mesh 6 laminated on the photosensitive resin layer 5 side of the laminated film 1'.
  • the method for producing an unexposed screen printing plate (second unexposed screen printing plate) according to the present invention is characterized by comprising the following steps (a) and (b).
  • FIG. 2 shows a preferred specific example of an unexposed screen printing plate 9 obtained by such a manufacturing method.
  • a method for producing a screen printing plate according to the present invention is characterized by comprising the following steps (a) to (f).
  • E) The step of peeling off the water-insoluble polymer layer.
  • FIG. 3 is a diagram showing an overview of the method for manufacturing a screen printing plate according to the present invention
  • FIG. 3A shows an outline of the step (a) of bonding the screen mesh 6 to the photosensitive resin layer 5 side of the pattern forming laminated film 1
  • FIG. 3B shows an outline of the step (b) of peeling off the support layer 2 and the adhesive layer 3 from the water-insoluble polymer layer 4 of the pattern-forming laminated film 1.
  • FIG. 3C shows an outline of the step (c) of placing a pattern mask 10 on the surface of the water-insoluble polymer layer 4, FIG.
  • FIG. 3D shows an outline of the step (d) of irradiating the photosensitive resin layer 5 with energy rays from the surface of the pattern mask 10 to form a latent image ⁇ on the photosensitive resin
  • FIG. 3E shows an outline of the step (e) of peeling off the water-insoluble polymer layer 4
  • FIG. 3F shows an outline of the screen printing plate 11 obtained by carrying out the step (f) of developing the photosensitive resin layer 5 on which the latent image ⁇ is formed.
  • the photosensitive resin layer 5 on which the latent image ⁇ is formed is washed with water (for example, neutral water) to form an uncured region of the photosensitive resin layer 5 (that is, the latent image ⁇ ).
  • a development process consisting of removing the untreated areas) is performed. After that, by drying the developed product, a screen printing plate 11 having a predetermined aperture pattern can be obtained.
  • a pattern-forming laminated film 1 according to the present invention has a water-insoluble polymer layer 3.
  • a pattern mask 10 is placed on the surface of the water-insoluble polymer layer 3, and then the pattern mask 10 is applied. Energy beam irradiation and formation of a latent image .alpha.
  • the water-insoluble polymer layer 3 prevents the photosensitive resin layer from becoming tacky due to moisture absorption and migration of constituent components. is easy.
  • the surface of the finished printing plate is finished flat, so the printing reproducibility is good, and the adhesion to the printing material is also good, so the ink does not flow to the back side of the printing plate. can be suppressed, and the number of stencil wipes can be reduced.
  • a photosensitive resist base material according to the present invention is characterized by comprising the above laminated film for pattern formation and a base material laminated on the photosensitive resin layer side of the laminated film for pattern formation.
  • Various materials can be used as the base material laminated on the photosensitive resin layer side.
  • wood, stone, textiles, paper, ceramics, glass, synthetic resins such as cellulose acetate and polyester, polyolefins, polyimides, epoxy resins, glass fiber reinforced resins, aluminum, copper, nickel, iron, zinc, magnesium, cobalt, etc. metals, semiconductor materials such as silicon and gallium arsenide germanium, and insulating materials such as silicon nitride and silicon oxide.
  • the photosensitive resist base material according to the present invention is a photosensitive resin that can be developed with neutral water, it is more environmentally friendly and work-friendly than conventional photosensitive resist base materials in that no solvent or alkaline aqueous solution is used in the developer. is advantageous.
  • a photosensitive resist base material can be obtained by bonding this pattern-forming laminated film to a base material such as metal or glass.
  • a base material such as metal or glass.
  • neutral water causes less environmental pollution. Since development can be done with neutral water without using organic solvents or alkaline water, it is advantageous from the viewpoints of environment, workability, storage and treatment of developer.
  • base material there are some that are discolored or deformed by organic solvents or alkalis, and a wide range of base materials can be selected because they can be developed with neutral water.
  • Example 1 A polyethylene terephthalate film having a thickness of 75 ⁇ m was prepared as a support layer for producing a laminated film for pattern formation, and an ethylene-vinyl acetate emulsion type adhesive was applied thereon using a bar coater, followed by heating and drying at 100° C. for 3 minutes. , a glue layer having a thickness of 10 ⁇ m was formed. Furthermore, a polyethylene terephthalate film having a thickness of 6 ⁇ m was laminated thereon as a layer composed of a water-insoluble polymer using a laminator.
  • the photosensitive resin 1 consisting of the above components (A) and components (B), (F), (G), and (H) was coated with a bar coater and dried by heating at 40° C. for 30 minutes to obtain a film having a thickness of 20 ⁇ m.
  • a photosensitive resin layer was formed to obtain a laminated film for pattern formation.
  • Example 2 After forming the photosensitive resin layer of Example 1, a laminated film for pattern formation was produced in the same manner as in Example 1, except that a polyethylene film having a thickness of 25 ⁇ m was laminated thereon as a protective layer.
  • Example 3 A laminated film for pattern formation was produced in the same manner as in Example 1, except that an acrylic pressure-sensitive adhesive was used for the glue layer and a polyolefin film having a thickness of 12 ⁇ m was used for the layer C) composed of a water-insoluble polymer.
  • ⁇ Comparative Example 1> A polyethylene terephthalate film having a thickness of 75 ⁇ m was prepared as a support layer for producing a laminated film for pattern formation, and a 5.0% by mass aqueous solution of polyvinyl alcohol (Kuraray Poval 95-88 manufactured by Kuraray Co., Ltd.) was coated thereon using a bar coater. , and dried at 40°C for 30 minutes to form a water-soluble polymer layer having a thickness of 5 ⁇ m. Further thereon, a photosensitive resin 1 consisting of the components (A) and components (B), (F), (G), and (H) described above is coated with a bar coater and dried by heating at 40° C. for 30 minutes to obtain a thickness. A 20 ⁇ m thick photosensitive resin layer was formed to obtain a laminated film for pattern formation.
  • a photosensitive resin 1 consisting of the components (A) and components (B), (F), (G), and (H) described above is coated with a bar coater and dried by heating at
  • ⁇ Comparative Example 2> A laminated film for pattern formation was produced in the same manner as in Comparative Example 1, except that a fluorine compound-containing resin (SP-2050UC diazo resin manufactured by Murakami Co., Ltd. was not added) was used as the layer composed of a water-soluble polymer.
  • a fluorine compound-containing resin SP-2050UC diazo resin manufactured by Murakami Co., Ltd. was not added
  • a polyethylene terephthalate film having a thickness of 75 ⁇ m was prepared as a support layer, and a photosensitive resin 1 comprising the above components (A), (B), (F), (G) and (H) was coated thereon by a bar coater. and dried at 40° C. for 30 minutes to form a photosensitive resin layer having a thickness of 20 ⁇ m, thereby obtaining a film for pattern formation.
  • a polyester fiber mesh fixed to an aluminum frame is coated with a photosensitive resin 1 consisting of the above components (A) and components (B) (F) (G) (H) using a stainless steel bucket.
  • the photosensitive resin layer side of the laminated film for pattern formation prepared in 1. was pasted together.
  • the protective layer was peeled off and the photosensitive resin layer side was laminated. After drying for 30 minutes at 40° C., the support layer was peeled off.
  • the glue layer was also peeled off at the same time as the support layer was peeled off.
  • a pattern mask was overlaid, vacuum was applied, and a 3 kW metal halide lamp was used as a light source, and the photosensitive resin layer was exposed under the conditions of a distance of 1 m between the light source and the plate surface and an irradiation time of 2 minutes. Subsequently, after removing the pattern mask, the resin layer was developed using tap water. A screen printing plate was thus obtained. In Examples 1, 2 and 3, development was carried out after removing the water-insoluble polymer layer before development.
  • Table 1 shows the evaluation results.
  • Example 4 Preparation of laminated film for pattern formation
  • a polyethylene terephthalate film with a thickness of 75 ⁇ m was prepared as a support layer, and a silicone-based pressure-sensitive adhesive was applied thereon using a bar coater, followed by heating and drying at 100°C for 3 minutes to obtain an adhesive with a thickness of 5 ⁇ m. formed a layer.
  • a polyolefin film having a thickness of 12 ⁇ m was laminated thereon as a layer composed of a water-insoluble polymer using a laminator.
  • the photosensitive resin 2 composed of the components (E) and components (F), (G), and (H) described above was coated with a bar coater and dried by heating at 40° C. for 30 minutes to obtain a photosensitive resin having a thickness of 30 ⁇ m. Layers were formed to obtain a laminated film for pattern formation.
  • Example 5 A laminated film for pattern formation was produced in the same manner as in Example 4, except that an ethylene-vinyl acetate emulsion type adhesive was used for the glue layer.
  • Example 6 A laminated film for pattern formation was produced in the same manner as in Example 4, except that a urethane adhesive was used for the glue layer.
  • Example 7 A laminated film for pattern formation was produced in the same manner as in Example 4, except that an acrylic pressure-sensitive adhesive was used for the glue layer.
  • ⁇ Comparative Example 4> Preparation of laminated film for pattern formation The pattern formation was performed in the same manner as in Example 4, except that a release film obtained by subjecting a polyester film having a thickness of 25 ⁇ m to one side to a silicone release treatment was used as the layer composed of a water-insoluble polymer. A laminated film was produced. The release film was laminated with the silicone release-treated surface on the side of the photosensitive resin layer.
  • Example 5 A laminated film for pattern formation was produced in the same manner as in Example 5, except that a release film obtained by subjecting a polyester film having a thickness of 75 ⁇ m to a silicone release treatment on one side was used as the support layer. The release film was laminated with the silicone release-treated surface on the adhesive layer side.
  • Example 6 A laminated film for pattern formation was produced in the same manner as in Example 6, except that an easy-adhesive film obtained by subjecting a 25 ⁇ m-thick polyester film to one-sided corona discharge treatment was used as the layer composed of a water-insoluble polymer. The easy-adhesive film was laminated with the corona-treated surface on the adhesive layer side.
  • ⁇ Evaluation method 2> The polyester fiber mesh fixed to the aluminum frame was coated with the photosensitive resin used for each pattern forming film using a stainless steel bucket, and the photosensitive resin layer side of the pattern forming laminate film prepared above was coated. pasted together. After drying at 40°C for 30 minutes, a test plate was obtained. After storage for 24 hours in a 25° C. 50% environment, a cellophane tape was attached to the support layer, and when the tape was pulled upward and peeled off, it was confirmed at which interface 1 to 3 the tape would be peeled off.
  • Interface 1 support layer/glue layer
  • Interface 2 glue layer/water-insoluble polymer layer
  • Interface 3 water-insoluble polymer layer/photosensitive resin layer
  • ⁇ Peeled off at interface 2, glue layer remaining on water-insoluble polymer layer not.
  • x It peels off except the interface 2.
  • Example 8> Preparation of laminated film for pattern formation A polyethylene terephthalate film with a thickness of 75 ⁇ m was prepared as a support layer, and a silicone-based pressure-sensitive adhesive was applied thereon using a bar coater and dried by heating at 100° C. for 3 minutes to form a glue layer with a thickness of 3 ⁇ m. formed. Furthermore, a polyolefin film having a thickness of 12 ⁇ m and a haze value of 0.3% was laminated thereon as a layer composed of a water-insoluble polymer using a laminator.
  • the photosensitive resin 4 composed of the components (A) and components (B), (F), and (G) described above was coated with a bar coater and dried by heating at 40° C. for 30 minutes to obtain a photosensitive resin having a thickness of 15 ⁇ m. Layers were formed to obtain a laminated film for pattern formation.
  • the stainless steel fiber mesh fixed to the aluminum frame is coated with the photosensitive resin used for each pattern forming film using a stainless steel bucket, and the photosensitive resin layer of the laminated film for pattern forming prepared above. glued the sides together. After drying at 40° C. for 30 minutes, the support layer and glue layer were peeled off.
  • a pattern mask is superimposed on the water-insoluble polymer layer, vacuumed, a metal halide lamp of 3 kW is used as a light source, the distance between the light source and the plate surface is 1 m, the irradiation time is 2 minutes, 3 minutes, 4 minutes, The photosensitive resin layer was exposed for 5 minutes. Subsequently, after removing the pattern mask, the resin layer was developed using tap water. A screen printing plate was thus obtained.
  • Example 9 A screen printing plate was obtained in the same manner as in Example 8, except that a highly transparent polyethylene terephthalate film having a thickness of 50 ⁇ m and a haze value of 1.0% was used as the water-insoluble polymer layer.
  • Example 10 A screen printing plate was obtained in the same manner as in Example 8, except that the photosensitive resin layer 5 consisting of the above components (A), (C) and (D) was used.
  • Example 8 A screen printing plate was obtained in the same manner as in Example 8 except that a polyolefin film having a thickness of 30 ⁇ m and a haze value of 6% was used as the water-insoluble polymer layer.
  • Example 9 A laminated film for pattern formation was produced in the same manner as in Example 8, except that a general-purpose polyethylene terephthalate film having a thickness of 25 ⁇ m and a haze value of 5.7% was used as the water-insoluble polymer layer.
  • Example 10 A laminated film for pattern formation was produced in the same manner as in Example 10, except that a polyolefin film having a thickness of 125 ⁇ m and a haze value of 1.5% was used as the water-insoluble polymer layer.
  • ⁇ Evaluation method 3> The pattern of the obtained screen printing plate was confirmed with a 100x magnifying glass to determine the sensitivity and resolution.

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Abstract

[Problem] To provide a layered film for pattern formation which does not absorb moisture in the air or leave unnecessary components on the surface of a plate film, and in which the tackiness of a photosensitive resin layer is suppressed. [Solution] Provided are: a layered film for pattern formation characterized by comprising a support layer, an adhesive layer, a water-insoluble polymer layer, and a photosensitive resin layer in the given order; a non-photosensitive screen printing plate in which the layered film for pattern formation is employed; and a method for manufacturing same.

Description

パターン形成用積層フィルムおよび未感光のスクリーン印刷版ならびにこれらの製造方法Laminate film for pattern formation, unexposed screen printing plate, and production method thereof
　本発明は、パターン形成用積層フィルムおよび未感光のスクリーン印刷版ならびにこれらの製造方法に関する。 The present invention relates to a laminated film for pattern formation, an unexposed screen printing plate, and methods for producing these.
　スクリーン印刷版を製造する方法として、パターン形成用フィルムを使う方法がある。この方法は、直接感光性樹脂を塗布する方法と比較してパターン形成用フィルムを使用して感光性樹脂層を転写するとスクリーン上の感光性樹脂膜が平滑に形成され、版内の厚みばらつきを抑えることができる点で優れている。そのため、現像後のパターンのエッジがシャープでインク転移量にムラの少ない印刷精度の高い版の作製が可能である。 There is a method of using a pattern forming film as a method of manufacturing a screen printing plate. Compared to the method of applying the photosensitive resin directly, this method uses a pattern-forming film to transfer the photosensitive resin layer, forming a smooth photosensitive resin film on the screen and reducing thickness variations within the plate. It is excellent in that it can be suppressed. Therefore, it is possible to produce a printing plate with sharp edges of the pattern after development and little unevenness in the amount of ink transfer and high printing accuracy.
　このようなパターン形成用フィルムを用いてスクリーン印刷用ステンシルを製造するときは、まずスクリーンに水や感光性樹脂等を塗布し、パターン形成用フィルムの感光性樹脂層を貼り合わせ、十分乾燥させた後、支持層を剥離することで、感光性樹脂層をスクリーンに転写し、その後、パターンマスクを介して感光性樹脂層を露光し、続いて水等により現像することで、スクリーンに所定のパターンを形成することができる。 When producing a stencil for screen printing using such a pattern-forming film, first, water, a photosensitive resin, or the like is applied to the screen, the photosensitive resin layer of the pattern-forming film is adhered, and the film is sufficiently dried. After that, by peeling off the support layer, the photosensitive resin layer is transferred to the screen, then the photosensitive resin layer is exposed through a pattern mask, and then developed with water or the like to form a predetermined pattern on the screen. can be formed.
　しかしながら、感光性樹脂層の表面は、構成成分上、タック性を帯びることが多いので、露光時にパターンマスクの位置あわせがし難く、また、パターンマスクとの均一な密着が阻害されたり、或いは、露光後にパターンマスクを感光性樹脂層から剥離する際に、感光性樹脂層の一部が損傷し、パターンマスクを汚染したりする等の問題が発生することがあった。 However, since the surface of the photosensitive resin layer is often tacky due to its constituent components, it is difficult to align the pattern mask during exposure, and uniform close contact with the pattern mask is hindered. When the pattern mask is peeled off from the photosensitive resin layer after exposure, the photosensitive resin layer may be partially damaged, causing problems such as contamination of the pattern mask.
　それらを防止するために、特開昭５８－６０７４５号公報や国際公開２０１３－０８０９５８号公報では、支持層と感光性樹脂層との間にポリビニルアルコールやフッ素化合物を中間層として配するパターン形成用積層フィルムが提案されている。 In order to prevent them, in JP-A-58-60745 and WO 2013-080958, a pattern forming method in which polyvinyl alcohol or a fluorine compound is arranged as an intermediate layer between the support layer and the photosensitive resin layer Laminated films have been proposed.
　しかしながら、ポリビニルアルコールは水溶性高分子であるところから、空気中の水分を吸水してしまい、印刷版のタック性を抑制するには十分ではないように思われる。 However, since polyvinyl alcohol is a water-soluble polymer, it absorbs moisture in the air, and it seems that it is not sufficient to suppress the tackiness of the printing plate.
　また、この中間層は、本来非感光性材料であり、現像時に除去されるものであるが、実際には感光性樹脂層と長時間接していることにより、感光性成分が一部中間層に移行してしまい露光の際に現像液に不溶化してしまう。そのため現像で除去できずに版膜表面に中間層の成分が残存してしまうことがある。このことにより本来の感光性樹脂の設計通りの性能が出せずにいることがあった。 In addition, the intermediate layer is originally a non-photosensitive material and is removed during development. It migrates and becomes insoluble in the developer during exposure. Therefore, the components of the intermediate layer may remain on the surface of the plate film without being removed by development. As a result, the originally designed performance of the photosensitive resin could not be achieved in some cases.
特開昭５８－６０７４５号公報JP-A-58-60745 国際公開２０１３－０８０９５８号公報International Publication No. 2013-080958
　本発明によれば、空気中の水分を吸水することもなく、不要成分の版膜表面への残存もない、感光性樹脂層のタック性を抑制し露光時の密着不良や作業性を向上させることを課題とする。 According to the present invention, it does not absorb moisture in the air, does not leave unnecessary components on the surface of the plate film, suppresses the tackiness of the photosensitive resin layer, and improves poor adhesion and workability during exposure. The challenge is to
　本発明は、所定のパターン形成用積層フィルムを提供することによって、上記課題を解決するものである。
　したがって、本発明によるパターン形成用積層フィルムは、支持層、糊層、非水溶性高分子層および感光性樹脂層が、この順序で構成されてなること、を特徴とするものである。 The present invention solves the above problems by providing a predetermined pattern-forming laminated film.
Accordingly, the laminated film for pattern formation according to the present invention is characterized by comprising a support layer, a glue layer, a water-insoluble polymer layer and a photosensitive resin layer in this order.
　このような本発明によるパターン形成用積層フィルムは、好ましくは、前記の感光性樹脂層が、中性水で現像が可能な感光性樹脂であるもの、を包含する。 Such a laminated film for pattern formation according to the present invention preferably includes one in which the photosensitive resin layer is a photosensitive resin that can be developed with neutral water.
　このような本発明によるパターン形成用積層フィルムは、好ましくは、前記の支持層と糊層との間の層間接着力（ｘ）、前記の糊層と非水溶性高分子層との間の層間接着力（ｙ）、および前記の非水溶性高分子層と感光性樹脂層との間の層間接着力（ｚ）は、下記の関係にあるもの、を包含する。
　　　　　　　　　層間接着力（ｘ）　＞　層間接着力（ｙ）
　　　　　　　　　層間接着力（ｚ）　＞　層間接着力（ｙ） Such a laminated film for pattern formation according to the present invention preferably has an interlayer adhesion (x) between the support layer and the glue layer, and a layer between the glue layer and the water-insoluble polymer layer. The inter-layer adhesive strength (y) and the inter-layer adhesive strength (z) between the water-insoluble polymer layer and the photosensitive resin layer include those having the following relationship.
Interlayer adhesive strength (x) > Interlayer adhesive strength (y)
Interlayer adhesion (z) > Interlayer adhesion (y)
　このような本発明によるパターン形成用積層フィルムは、好ましくは、前記の糊層と非水溶性高分子層との間の層間接着力（ｙ）は、０．００１～１．０Ｎ／２５ｍｍであるもの、を包含する。 In such a laminated film for pattern formation according to the present invention, the interlayer adhesive strength (y) between the glue layer and the water-insoluble polymer layer is preferably 0.001 to 1.0 N/25 mm. includes things.
　このような本発明によるパターン形成用積層フィルムは、好ましくは、前記の非水溶性高分子層のヘイズ値が５．０％以下であるもの、を包含する。 Such a laminated film for pattern formation according to the present invention preferably includes one in which the water-insoluble polymer layer has a haze value of 5.0% or less.
　このような本発明によるパターン形成用積層フィルムは、好ましくは、前記の非水溶性高分子層は、厚さが１～１００μｍであるもの、を包含する。 Such a laminated film for pattern formation according to the present invention preferably includes one in which the water-insoluble polymer layer has a thickness of 1 to 100 μm.
　このような本発明によるパターン形成用積層フィルムは、好ましくは、前記の感光性樹脂層は、下記の成分（Ａ）および成分（Ｂ）を含んでなる感光性樹脂からなるもの、を包含する。
　成分（Ａ）：けん化度５０モル％以上のポリビニルアルコール
　成分（Ｂ）：ジアゾ樹脂。 In such a laminated film for pattern formation according to the present invention, the photosensitive resin layer preferably comprises a photosensitive resin containing the following components (A) and (B).
Component (A): Polyvinyl alcohol having a degree of saponification of 50 mol% or more Component (B): Diazo resin.
　このような本発明によるパターン形成用積層フィルムは、好ましくは、前記の感光性樹脂層は、下記の成分（Ａ）、成分（Ｃ）および成分（Ｄ）を含んでなる感光性樹脂からなるもの、を包含する。
　成分（Ａ）：けん化度５０モル％以上のポリビニルアルコール
　成分（Ｃ）：少なくとも一つのエポキシ基を有するエポキシ化合物
　成分（Ｄ）：光酸発生剤。 In such a laminated film for pattern formation according to the present invention, the photosensitive resin layer preferably comprises a photosensitive resin containing the following components (A), (C) and (D). , including
Component (A): Polyvinyl alcohol having a degree of saponification of 50 mol % or more Component (C): Epoxy compound having at least one epoxy group Component (D): Photoacid generator.
　このような本発明によるパターン形成用積層フィルムは、好ましくは、前記の感光性樹脂層は、下記の成分（Ｅ）を含んでなる感光性樹脂からなるもの、を包含する。
　成分（Ｅ）：スチリル置換されたピリジニウム基またはスチリル置換されたキノリニウム基を有するけん化度５０モル％以上のポリビニルアルコール。 In such a laminated film for pattern formation according to the present invention, the photosensitive resin layer preferably comprises a photosensitive resin containing the following component (E).
Component (E): Polyvinyl alcohol having a styryl-substituted pyridinium group or a styryl-substituted quinolinium group and having a degree of saponification of 50 mol % or more.
　このような本発明によるパターン形成用積層フィルムは、好ましくは、前記の感光性樹脂層は、下記の成分（Ｆ）および成分（Ｇ）をさらに含んでなる感光性樹脂からなるもの、を包含する。
　成分（Ｆ）：少なくとも一つのエチレン性不飽和結合を有するラジカル重合性化合物
　成分（Ｇ）：光ラジカル重合開始剤。 In such a laminated film for pattern formation according to the present invention, the photosensitive resin layer preferably comprises a photosensitive resin further containing component (F) and component (G) below. .
Component (F): Radically polymerizable compound having at least one ethylenically unsaturated bond Component (G): Radical photopolymerization initiator.
　このような本発明によるパターン形成用積層フィルムは、好ましくは、前記の感光性樹脂層は、下記の成分（Ｈ）をさらに含んでなる感光性樹脂からなるもの、を包含する。
　成分（Ｈ）：水性ポリマーエマルジョン。 In such a laminated film for pattern formation according to the present invention, the photosensitive resin layer preferably comprises a photosensitive resin further containing the following component (H).
Component (H): Aqueous polymer emulsion.
　このような本発明によるパターン形成用積層フィルムは、好ましくは、前記のパターン形成用積層フィルムの感光性樹脂層側に、さらに保護層が積層されてなるもの、を包含する。 Such a laminated film for pattern formation according to the present invention preferably includes a film obtained by further laminating a protective layer on the photosensitive resin layer side of the laminated film for pattern formation.
　そして、本発明による未感光のスクリーン印刷版は、前記のパターン形成用積層フィルムから前記の支持層および糊層を除いた積層フィルムと、前記の積層フィルムの感光性樹脂層側に積層されたスクリーンメッシュとを含んでなること、を特徴とするものである。 The unexposed screen printing plate according to the present invention comprises a laminated film obtained by removing the support layer and the adhesive layer from the laminated film for pattern formation, and a screen laminated on the photosensitive resin layer side of the laminated film. and a mesh.
　そして、本発明による未感光のスクリーン印刷版の製造方法は、下記の工程（イ）および工程（ロ）を含んでなること、を特徴とするものである。
　工程（イ）：前記のパターン形成用積層フィルムの前記感光性樹脂層側に、スクリーンメッシュを接合する工程
　工程（ロ）：前記のパターン形成用積層フィルムの非水溶性高分子層から、前記の支持層および糊層を剥離する工程。 The method for producing an unexposed screen printing plate according to the present invention is characterized by comprising the following steps (a) and (b).
Step (a): A step of bonding a screen mesh to the photosensitive resin layer side of the laminated film for pattern formation Step (b): From the water-insoluble polymer layer of the laminated film for pattern formation, the above A step of peeling off the support layer and the glue layer.
　そして、本発明によるスクリーン印刷版は、前記のパターン形成用積層フィルムから前記の支持層および糊層を除いた積層フィルムと、前記の積層フィルムの感光性樹脂層側に積層されたスクリーンメッシュとを含んでなる未感光のスクリーン印刷版に、潜像を形成し感光性樹脂層を現像してなること、を特徴とするものである。 The screen printing plate according to the present invention comprises a laminated film obtained by removing the support layer and the adhesive layer from the pattern-forming laminated film, and a screen mesh laminated on the photosensitive resin layer side of the laminated film. It is characterized by forming a latent image on an unexposed screen printing plate and developing a photosensitive resin layer.
　そして、本発明によるスクリーン印刷版の製造方法は、下記の工程（イ）～工程（ヘ）を含んでなること、を特徴とするものである。 The method for producing a screen printing plate according to the present invention is characterized by comprising the following steps (a) to (f).
　工程（イ）：前記のパターン形成用積層フィルムの前記感光性樹脂層側に、スクリーンメッシュを接合する工程
　工程（ロ）：前記のパターン形成用積層フィルムの非水溶性高分子層から、前記の支持層および糊層を剥離する工程
　工程（ハ）：前記の非水溶性高分子層の表面にパターンマスクを配置する工程
　工程（ニ）：前記の感光性樹脂層に潜像を形成する工程
　工程（ホ）：前記の非水溶性高分子層を剥離する工程
　工程（ヘ）：前記の潜像が形成された感光性樹脂層を現像する工程。 Step (a): A step of bonding a screen mesh to the photosensitive resin layer side of the laminated film for pattern formation Step (b): From the water-insoluble polymer layer of the laminated film for pattern formation, the above A step of peeling off the support layer and the adhesive layer Step (c): A step of placing a pattern mask on the surface of the water-insoluble polymer layer Step (d): A step of forming a latent image on the photosensitive resin layer (E): The step of peeling off the water-insoluble polymer layer. Step (F): The step of developing the photosensitive resin layer on which the latent image is formed.
　そして、本発明による感光性レジスト基材は、前記のパターン形成用積層フィルムと、前記パターン形成用積層フィルムの前記感光性樹脂層側に積層された基材とを含んでなること、を特徴とするものである。 A photosensitive resist base material according to the present invention is characterized by comprising the above-described pattern-forming laminated film and a base material laminated on the photosensitive resin layer side of the pattern-forming laminated film. It is something to do.
　本発明によるパターン形成用積層フィルムは、感光性樹脂層の表面に非水溶性高分子層が積層されている。この非水溶性高分子層は、表面が平滑であることから、非水溶性高分子層の表面においてパターンマスクを位置決めするのが容易である。 The laminated film for pattern formation according to the present invention has a water-insoluble polymer layer laminated on the surface of a photosensitive resin layer. Since the water-insoluble polymer layer has a smooth surface, it is easy to position the pattern mask on the surface of the water-insoluble polymer layer.
　そして、パターンマスクと非水溶性高分子層との密着性が高くかつ均一性が高いので、パターンマスクの歪み等が抑制される。このことから、感光性樹脂層の露光および潜像の形成をきわめて正確に行なうことができる。 Further, since the adhesion between the pattern mask and the water-insoluble polymer layer is high and the uniformity is high, the distortion of the pattern mask is suppressed. As a result, the exposure of the photosensitive resin layer and the formation of the latent image can be performed very accurately.
　そして、この非水溶性高分子層は、感光性樹脂層の所謂保護層として機能して、周囲環境や劣化成分等が感光性樹脂層へ影響を与えるのを防止する。例えば、感光性樹脂層が吸湿するのを防止したり、他層からの有害成分等が移行するのが防止されるので、感光性樹脂本来の優れた特性が長期間維持される。
　よって、本発明によるパターン形成用積層フィルムによれば、高精細な所望のパターンが正確に形成されたスクリーン印刷版を得ることができる。 This water-insoluble polymer layer functions as a so-called protective layer for the photosensitive resin layer, and prevents the photosensitive resin layer from being affected by the ambient environment, degraded components, and the like. For example, it prevents the photosensitive resin layer from absorbing moisture and prevents harmful components from migrating from other layers, so that the original excellent properties of the photosensitive resin can be maintained for a long period of time.
Therefore, according to the pattern-forming laminated film of the present invention, it is possible to obtain a screen printing plate on which a desired high-definition pattern is accurately formed.
　本発明によるパターン形成用積層フィルムは、露光時に感光性樹脂層上に非水溶性高分子層が存在することで、従来の水溶性高分子層である場合に懸念されていた吸湿、残存がなく、感光性樹脂成分によるパターンマスクの汚染を防止することができる。 In the laminated film for pattern formation according to the present invention, since the water-insoluble polymer layer is present on the photosensitive resin layer at the time of exposure, there is no moisture absorption or residue, which is a concern in the case of a conventional water-soluble polymer layer. , contamination of the pattern mask by the photosensitive resin component can be prevented.
　そして、感光性樹脂層のタックによる密着不良を防止でき、位置合わせも容易であって、かつ異物の付着を抑制し、付着した異物を取り除くのも容易である。
　さらに、ポリマー層を有するため、タックを気にすることがなくなり、感光材の設計の幅が広がる。 In addition, poor adhesion due to tackiness of the photosensitive resin layer can be prevented, alignment is easy, adhesion of foreign matter is suppressed, and adhering foreign matter can be easily removed.
Furthermore, since it has a polymer layer, there is no need to worry about tackiness, and the range of design of the photosensitive material is widened.
本発明による好ましい未感光のスクリーン印刷版の概要を示す図。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram of a preferred unexposed screen printing plate according to the present invention; 本発明による好ましい未感光のスクリーン印刷版の概要を示す図。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram of a preferred unexposed screen printing plate according to the present invention; 本発明による好ましいスクリーン印刷版の製造方法の概要を示す図。BRIEF DESCRIPTION OF THE DRAWINGS The figure which shows the outline|summary of the manufacturing method of the preferable screen-printing plate by this invention.
　〔パターン形成用積層フィルム〕
　本発明によるパターン形成用積層フィルムは、支持層、糊層、非水溶性高分子層および感光性樹脂層が、この順序で構成されてなること、を特徴とするものである。 [Laminate film for pattern formation]
The laminated film for pattern formation according to the present invention is characterized by comprising a support layer, a glue layer, a water-insoluble polymer layer and a photosensitive resin layer in this order.
　本発明によるパターン形成用積層フィルムは、支持層、糊層、非水溶性高分子層および感光性樹脂層を含んでなる。ここで、「含んでなる」とは、挙示の各層（即ち、支持層、糊層、非水溶性高分子層および感光性樹脂層）のみを含んでなるもののほかに、挙示の各層以外の層あるいは材料等を含んでなるものをも包含する。そのような挙示の各層以外の層の代表例としては、例えば保護層を挙げることができる。 A laminated film for pattern formation according to the present invention comprises a support layer, a glue layer, a water-insoluble polymer layer and a photosensitive resin layer. Here, the term "comprising" refers to those comprising only the listed layers (i.e., the support layer, the adhesive layer, the water-insoluble polymer layer and the photosensitive resin layer), as well as the layers other than the listed layers. Also includes those comprising a layer or material of Representative examples of layers other than the listed layers include, for example, a protective layer.
　本発明によるパターン形成用積層フィルムは、例えば、各種の印刷技術分野、特に好ましくは、スクリーン印刷分野に適用可能なものである。本発明によるパターン形成用積層フィルムを、このような印刷分野に適用する際には、先ず、糊層と非水溶性高分子層との界面を剥離して支持層および糊層を除去した後に、非水溶性高分子層を剥離することが行なわれることがある。 The pattern-forming laminated film according to the present invention can be applied, for example, to various printing technical fields, particularly preferably to the screen printing field. When the laminated film for pattern formation according to the present invention is applied to such a printing field, first, after removing the support layer and the adhesive layer by peeling the interface between the adhesive layer and the water-insoluble polymer layer, Stripping the water-insoluble polymeric layer may be performed.
　したがって、スクリーン印刷分野に適用可能な、本発明の特に好ましいパターン形成用積層フィルムとしては、前記の支持層と糊層との間の層間接着力（ｘ）、前記の糊層と非水溶性高分子層との間の層間接着力（ｙ）、および前記の非水溶性高分子層と感光性樹脂層との間の層間接着力（ｚ）が、下記の関係にあるものを挙げることができる。
　　　　　　　　層間接着力（ｘ）　＞　層間接着力（ｙ）
　　　　　　　　層間接着力（ｚ）　＞　層間接着力（ｙ）
　なお、層間接着力（ｘ）と層間接着力（ｚ）とは、（ｘ）の方が（ｚ）より大きい場合、（ｘ）の方が（ｚ）より小さい場合、および（ｘ）と（ｚ）とが等しい場合、がある。 Therefore, as a particularly preferred pattern forming laminated film of the present invention applicable to the screen printing field, the interlayer adhesion (x) between the support layer and the glue layer, the glue layer and the water-insoluble high The interlayer adhesive strength (y) between the molecular layer and the interlayer adhesive strength (z) between the water-insoluble polymer layer and the photosensitive resin layer have the following relationship. .
Interlayer adhesive strength (x) > Interlayer adhesive strength (y)
Interlayer adhesion (z) > Interlayer adhesion (y)
The interlayer adhesion (x) and the interlayer adhesion (z) are determined when (x) is larger than (z), when (x) is smaller than (z), and (x) and ( If z) is equal, then there is
　＜支持層＞
　本発明において、支持層としては各種の材料からなるものを用いることができる。例えば、各種の樹脂材料からなるものを用いることができ、また天然素材からなるものも用いることができる。 <Support layer>
In the present invention, various materials can be used as the support layer. For example, one made of various resin materials can be used, and one made of natural materials can also be used.
　好ましい材質としては、例えば、紙、離型紙、ポリエチレンテレフタレート等のポリエステル、ポリメチルペンテン、ポリプロピレン、ポリエチレン等のポリオレフィン、ポリフッ化ビニル、ポリ塩化ビニル等のハロゲン含有ビニル重合体、ナイロン等のポリアミド、セロファン等のセルロース、ポリスチレン、アクリル樹脂、ポリイミドなどのフィルムを挙げることができる。支持層は、透明であっても不透明であってもよく、積層フィルムの機能等の向上を目的として片面または両面に離型処理、マット処理、易接着処理を施すことができる。例えば、上記処理によって、例えば、支持層と糊層との間の層間接着力（ｘ）を制御することが容易になる。
　支持層の厚みは特に限定はないが、１０～２００μｍであることが好ましく、３０～１２５μｍであることが特に好ましい。 Preferred materials include, for example, paper, release paper, polyesters such as polyethylene terephthalate, polyolefins such as polymethylpentene, polypropylene and polyethylene, halogen-containing vinyl polymers such as polyvinyl fluoride and polyvinyl chloride, polyamides such as nylon, and cellophane. cellulose, polystyrene, acrylic resin, polyimide, and the like. The support layer may be transparent or opaque, and one side or both sides thereof may be subjected to release treatment, matte treatment, or easy-adhesion treatment for the purpose of improving the functions of the laminated film. For example, the above treatment facilitates controlling the interlayer adhesion (x) between, for example, the support layer and the glue layer.
Although the thickness of the support layer is not particularly limited, it is preferably 10 to 200 μm, particularly preferably 30 to 125 μm.
　＜糊層＞
　本発明において、糊層としては各種の材料からなるものを用いることができる。すなわち、糊層に使用する糊材は特に制限されず、種々の糊材を使用することができる。
　好ましい糊材としては、例えば、アクリル系（一液型または二液型）の接着剤ないし粘着剤、ゴム系またはウレタン系の接着剤ないし粘着剤、シリコーン系の接着剤ないし粘着剤粘着剤、酢酸ビニル系をはじめとする種々の糊剤を使用することができる。 <Glue layer>
In the present invention, the paste layer can be made of various materials. That is, the paste material used for the paste layer is not particularly limited, and various paste materials can be used.
Preferable adhesives include, for example, acrylic (one-component or two-component) adhesives or pressure-sensitive adhesives, rubber-based or urethane-based adhesives or pressure-sensitive adhesives, silicone-based adhesives or pressure-sensitive adhesives, and acetic acid. Various adhesives including vinyl adhesives can be used.
　さらに、無溶剤タイプ、溶剤タイプ、エマルジョンタイプ、熱硬化タイプ、ＵＶ硬化タイプ、ＥＢ硬化タイプ、ホットメルトタイプ等を使用することができる。
　糊層の厚みは特に限定はないものの、０．５～３０μｍが好ましく、０．５～２０μｍが特に好ましい。 Further, solvent-free type, solvent type, emulsion type, heat curing type, UV curing type, EB curing type, hot melt type, etc. can be used.
Although the thickness of the glue layer is not particularly limited, it is preferably 0.5 to 30 μm, particularly preferably 0.5 to 20 μm.
　糊層の形成は、グラビア、コンマ、エアーナイフ、ドクターナイフ、バーコーター、ダイコート法、ドクターブレード法等の通常のコーティング方法で、支持層上に上記の糊材を塗布した後、加熱処理、紫外線照射処理、電子線照射処理等の方法で乾燥、硬化させることで実施できる。 The glue layer is formed by a conventional coating method such as gravure, comma, air knife, doctor knife, bar coater, die coat method, doctor blade method, etc. After applying the above glue material on the support layer, heat treatment, UV irradiation, etc. It can be carried out by drying and curing by irradiation treatment, electron beam irradiation treatment, or the like.
　この糊層を形成するための糊材は、糊層と非水溶性高分子層との間の層間接着力（ｙ）が、好ましくは０．００１～１．０Ｎ／２５ｍｍ、特に好ましくは０．００５～０．５Ｎ／２５ｍｍ（対PET）、となるように選択することができる。０．００１Ｎ／２５ｍｍ未満であるときは、非水溶性高分子層への付着力が不足することによる剥がれや浮き等が発生することがあるため好ましくなく、一方、１．０Ｎ／２５ｍｍより大きいと、非水溶性高分子層から剥離しにくくなることや、剥離後に糊残りが発生したり、表面汚染性が高くなることがある等により、好ましくない。層間接着力（ｙ）は、２５ｍｍ幅のポリエチレンテレフタレートフィルムに糊層を形成し、さらに、ポリエチレンテレフタレートフィルムを貼り合わせ圧着する。２３℃下で１分後に、３００ｍｍ／分の速度で１８０度の角度で剥離するときの力で表したものである（ＪＩＳ－Ｚ０２３７に準ずるものである）。 The glue material for forming this glue layer preferably has an interlayer adhesion (y) between the glue layer and the water-insoluble polymer layer of preferably 0.001 to 1.0 N/25 mm, particularly preferably 0.001 to 1.0 N/25 mm. 005-0.5N/25mm (versus PET). If it is less than 0.001 N/25 mm, it may cause peeling or floating due to insufficient adhesion to the water-insoluble polymer layer, which is not preferable. , it is not preferable because it may become difficult to peel off from the water-insoluble polymer layer, may leave an adhesive residue after peeling, and may increase surface contamination. The interlaminar adhesive strength (y) is obtained by forming a glue layer on a polyethylene terephthalate film having a width of 25 mm, and bonding the polyethylene terephthalate film together under pressure. It is expressed in terms of force when peeling at an angle of 180 degrees at a speed of 300 mm/min after 1 minute at 23° C. (according to JIS-Z0237).
　本発明によるパターン形成用積層フィルムは、支持層および糊層を非水溶性高分子層から剥離した後において、糊層を構成していた糊剤が非水溶性高分子層の表面に残留しないことが好ましい。糊層剥離後の非水溶性高分子層の表面における糊剤の残留量は、１０ｃｍ２の糊材の質量を１００とした時に、好ましくは５％以下、さらに好ましくは１％以下、特に好ましくは、０.１％以下、である。 In the laminated film for pattern formation according to the present invention, after the support layer and the glue layer are separated from the water-insoluble polymer layer, the glue constituting the glue layer does not remain on the surface of the water-insoluble polymer layer. is preferred. The residual amount of the glue on the surface of the water-insoluble polymer layer after the glue layer is peeled off is preferably 5% or less, more preferably 1% or less, particularly preferably 1% or less, when the mass of the glue material of 10 cm 2 is taken as 100. , 0.1% or less.
　＜非水溶性高分子層＞
　本発明によるパターン形成用積層フィルムでは、非水溶性高分子層を透過した光によって、感光性樹脂層を構成する樹脂の硬化がなされる。
　非水溶性高分子層はヘイズ値が低いものが好ましい。例えば、ヘイズ値が０．０１～５．０％であるものが好ましく、０．０５～３．０％であるものが特に好ましい。ここで、ヘイズ値は、ＪＩＳ－Ｋ７１３６によるものである。 <Water-insoluble polymer layer>
In the laminated film for pattern formation according to the present invention, the resin constituting the photosensitive resin layer is cured by the light transmitted through the water-insoluble polymer layer.
The water-insoluble polymer layer preferably has a low haze value. For example, the haze value is preferably 0.01 to 5.0%, particularly preferably 0.05 to 3.0%. Here, the haze value is according to JIS-K7136.
　ヘイズ値が、上記好ましい範囲内であることによって、光照射量が少なくても感光性樹脂層の硬化が良好に行なうことができ、かつ、感光性樹脂層に高精細な所望パターンを形成させることができる。 When the haze value is within the above preferable range, the photosensitive resin layer can be cured satisfactorily even with a small amount of light irradiation, and a high-definition desired pattern can be formed on the photosensitive resin layer. can be done.
　好ましい非水溶性高分子層としては、例えば、ポリエチレンテレフタレート等のポリエステル、ポリメチルペンテン、ポリプロピレン、ポリエチレン等のポリオレフィン、ポリフッ化ビニル、ポリ塩化ビニル等のハロゲン含有ビニル重合体、ナイロン等のポリアミド、セロファン等のセルロース、ポリスチレン、アクリル樹脂、ポリイミド、ポリエーテルスルホン樹脂などのフィルムを挙げることができる。
　非水溶性高分子層は、ヘイズ値の範囲内であれば、積層フィルムの機能等の向上を目的として片面または両面に離型処理、易接着処理を施すことができる。例えば、上記処理によって、例えば、糊層と非水溶性高分子層の間の層間接着力（ｙ）、非水溶性高分子層と感光性樹脂層の間の層間接着力（ｚ）を制御することが容易になる。
　特に好ましい非水溶性高分子層としては、ポリエステルフィルム、ポリオレフィンフィルムが好適に使用される。厚みは１～１００μｍであることが好ましい。 Preferred water-insoluble polymer layers include, for example, polyesters such as polyethylene terephthalate, polyolefins such as polymethylpentene, polypropylene and polyethylene, halogen-containing vinyl polymers such as polyvinyl fluoride and polyvinyl chloride, polyamides such as nylon, and cellophane. cellulose, polystyrene, acrylic resin, polyimide, polyethersulfone resin, and the like.
As long as the haze value is within the range, one side or both sides of the water-insoluble polymer layer can be subjected to release treatment or adhesion-facilitating treatment for the purpose of improving the functions of the laminated film. For example, the above treatment controls the interlayer adhesion (y) between the glue layer and the water-insoluble polymer layer and the interlayer adhesion (z) between the water-insoluble polymer layer and the photosensitive resin layer. becomes easier.
As particularly preferred water-insoluble polymer layers, polyester films and polyolefin films are suitably used. The thickness is preferably 1-100 μm.
　＜感光性樹脂層＞
　本発明によるパターン形成用積層フィルムの感光性樹脂層は、光照射によって潜像が形成可能なものであって、中性水によって現像可能な樹脂からなることができる。そして、溶媒に水を用いて塗膜を形成可能なものが好ましい。
　そのような感光性樹脂層の好ましいものとしては、次の第一の具体例、第二の具体例および第三の具体例を挙げることができる。 <Photosensitive resin layer>
The photosensitive resin layer of the laminated film for pattern formation according to the present invention can form a latent image by light irradiation, and can be made of a resin that can be developed with neutral water. And it is preferable to use water as a solvent to form a coating film.
Preferred examples of such a photosensitive resin layer include the following first specific example, second specific example and third specific example.
　<<第一の感光性樹脂層>>
　感光性樹脂層の第一の具体例は、下記の成分（Ａ）および成分（Ｂ）を含んでなる感光性樹脂からなるものである。
成分（Ａ）：けん化度５０モル％以上のポリビニルアルコール
成分（Ｂ）：ジアゾ樹脂
　ここで、「含んでなる」とは、挙示の各成分（即ち、成分（Ａ）および成分（Ｂ））のみを含んでなるもののほかに、挙示の成分以外の成分等を含んでなるものをも包含する。そのような挙示の成分以外の成分の代表例としては、例えば成分（Ｆ）～（Ｈ）を挙げることができる（詳細後記）。 <<First photosensitive resin layer>>
A first specific example of the photosensitive resin layer is composed of a photosensitive resin containing the following component (A) and component (B).
Component (A): Polyvinyl alcohol having a degree of saponification of 50 mol% or more Component (B): Diazo resin Here, "comprising" means each listed component (that is, component (A) and component (B)) In addition to those containing only, those containing components other than the listed components are also included. Representative examples of components other than those listed include, for example, components (F) to (H) (details will be described later).
　成分（Ａ）と成分（Ｂ）との存在比率（質量％）は、成分（Ａ）：成分（Ｂ）が、好ましくは１：０．００５～１：０．５、特に好ましくは１：０．０１～１：０．２である。
　上記の成分（Ａ）および成分（Ｂ）を含んでなる感光性樹脂は、必要に応じて、成分（Ｆ）～（Ｈ）のいずれか一種あるいは複数種を含むことができる。 The abundance ratio (% by mass) of component (A) and component (B) is component (A):component (B), preferably 1:0.005 to 1:0.5, particularly preferably 1:0 .01 to 1:0.2.
The photosensitive resin comprising the above component (A) and component (B) can contain any one or more of components (F) to (H) as required.
　成分（Ａ）
　成分（Ａ）は、けん化度５０モル％以上のポリビニルアルコールである。けん化度が５０～１００モル％、特に７０～１００％、のものが好ましく、水溶性が損なわれない限り、他のビニルモノマーとの共重合体でもよい。その平均重合度は、２００～５０００、特に３００～４０００のものが好ましい。けん化度および重合度が異なる２種類以上のポリビニルアルコールを混合することもできる。また、カチオン変性やアニオン変性などの変性物も同様に使用可能である。 Component (A)
Component (A) is polyvinyl alcohol having a degree of saponification of 50 mol % or more. Those having a degree of saponification of 50 to 100 mol %, particularly 70 to 100% are preferred, and copolymers with other vinyl monomers may be used as long as the water solubility is not impaired. The average degree of polymerization is preferably 200-5000, more preferably 300-4000. Two or more polyvinyl alcohols with different degrees of saponification and polymerization can be mixed. Modified products such as cation-modified and anion-modified products can also be used.
　成分（Ｂ）
成分（Ｂ）は、ジアゾ樹脂である。具体例としては、ｐ‐ジアゾジフェニルアミンもしくは３‐メトキシ‐４‐ジアゾジフェニルアミンと４，４’‐ビスメトキシメチルジフェニルエーテルとの縮合物、およびこれらの硫酸塩、リン酸塩および塩化亜鉛複塩陰イオンコンプレックスのジアゾ樹脂、ｐ‐ジアゾジフェニルアミンもしくは３‐メトキシ‐４‐ジアゾジフェニルアミンとパラホルムアルデヒドとの縮合物の硫酸塩、リン酸塩および塩化亜鉛複塩陰イオンコンプレックスのジアゾ樹脂、を挙げることができる。この種のジアゾ樹脂としては、パラアミノジフェニルアミンの他に、４‐アミノ‐４’‐メチルジフェニルアミン、４‐アミノ‐４’‐エチルジフェニルアミン、４‐アミノ‐４’‐メトキシジフェニルアミン、４‐アミノ‐４’‐クロロジフェニルアミン、４‐アミノ‐４’‐ニトロジフェニルアミン等のジフェニルアミン類のジアゾ化物を、パラホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ｎ‐ブチルアルデヒド等のアルデヒド類を用いて縮合させた水溶性のジアゾ樹脂を用いることができる。 Component (B)
Component (B) is a diazo resin. Specific examples include condensates of p-diazodiphenylamine or 3-methoxy-4-diazodiphenylamine with 4,4′-bismethoxymethyldiphenyl ether, and their sulfates, phosphates and zinc chloride double salt anion complexes. diazo resins of sulfate, phosphate and zinc chloride double salt anion complexes of the condensates of p-diazodiphenylamine or 3-methoxy-4-diazodiphenylamine with paraformaldehyde. Diazo resins of this kind include, in addition to para-aminodiphenylamine, 4-amino-4'-methyldiphenylamine, 4-amino-4'-ethyldiphenylamine, 4-amino-4'-methoxydiphenylamine and 4-amino-4'. -chlorodiphenylamine, 4-amino-4'-nitrodiphenylamine, etc., is condensed with aldehydes such as paraformaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, and water-soluble diazo resin. can be used.
　その中でも、特にｐ‐ジアゾジフェニルアミンとパラホルムアルデヒドとの縮合物、３‐メトキシ‐４‐ジアゾジフェニルアミンとパラホルムアルデヒドとの縮合物、ｐ‐ジアゾジフェニルアミンと４，４’‐ビスメトキシメチルジフェニルエーテルとの縮合物、３‐メトキシ‐４‐ジアゾジフェニルアミンと４，４’‐ビスメトキシメチルジフェニルエーテルとの縮合物が好ましい。
　上記成分（Ｂ）の一種を単独で用いることができ、また二種以上を併用することができる。 Among them, particularly condensates of p-diazodiphenylamine and paraformaldehyde, condensates of 3-methoxy-4-diazodiphenylamine and paraformaldehyde, condensates of p-diazodiphenylamine and 4,4'-bismethoxymethyldiphenyl ether , 3-methoxy-4-diazodiphenylamine and 4,4'-bismethoxymethyldiphenyl ether are preferred.
One kind of the above component (B) can be used alone, or two or more kinds can be used in combination.
　成分（Ｆ）
　成分（Ｆ）は、少なくとも一つのエチレン性不飽和結合を有するラジカル重合性化合物であり、「光硬化技術データブック」（テクノネット社、２０００年）に記載のモノマーおよびオリゴマーなどが該当する。 Component (F)
Component (F) is a radically polymerizable compound having at least one ethylenically unsaturated bond, and includes monomers and oligomers described in "Photocuring Technical Data Book" (Technonet, 2000).
　単官能性モノマーの具体例としては、たとえば、２‐エチルヘキシル（メタ）アクリレート、イソデシル（メタ）アクリレート、２‐ヒドロキシエチル（メタ）アクリレート、２‐ヒドロキシプロピル（メタ）アクリレート、２‐ヒドロキシブチル（メタ）アクリレート、２‐エトキシエチル（メタ）アクリレート、２（２‐エトキシエトキシ）エチル（メタ）アクリレート、ｎ‐ブトキシエチル（メタ）アクリレート、モルホリノエチル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、メトキシジエチレングリコール（メタ）アクリレート、メトキシトリエチ（プロピ）レングリコール（メタ）アクリレート、メトキシテトラエチ（プロピ）レングリコール（メタ）アクリレート、メトキシポリエチ（プロピ）レングリコール（メタ）アクリレート、エトキシジエチ（プロピ）レングリコール（メタ）アクリレート、エトキシトリエチ（プロピ）レングリコール（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、テトラヒドロフリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、Ｎ，Ｎ‐ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ‐ジエチルアミノエチル（メタ）アクリレート、オキサイド変性リン酸（メタ）アクリレート、ω－カルボキシ－ポリカプロラクトンモノアクリレート、フタル酸モノヒドロキシエチルアクリレートなどが挙げられる。
　なお、本明細書において、「（メタ）アクリレート」とは、「メタクリレート」および「アクリレート」の両者を意味し、「エチ（プロピ）レン」とは、「エチレン」および「プロピレン」の両者を意味する。 Specific examples of monofunctional monomers include 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, ) acrylate, 2-ethoxyethyl (meth)acrylate, 2(2-ethoxyethoxy)ethyl (meth)acrylate, n-butoxyethyl (meth)acrylate, morpholinoethyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate ) acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethy (propy)ene glycol (meth) acrylate, methoxytetraethy (propy) lene glycol (meth) acrylate, methoxypolyethylene (propy) lene glycol (meth) acrylate, ethoxydiethyl ( Propy)ene glycol (meth)acrylate, ethoxytriethy(propyl)ene glycol (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofuryl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, oxide-modified phosphoric acid (meth)acrylate, ω-carboxy-polycaprolactone monoacrylate, phthalate monohydroxyethyl acrylate, etc. be done.
In this specification, "(meth)acrylate" means both "methacrylate" and "acrylate", and "ethylene(propylene)rene" means both "ethylene" and "propylene". do.
　エチレン性不飽和結合を二以上有する多官能性モノマーの具体例としては、たとえば、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、１，３‐トリメチレングリコールジ（メタ）アクリレート、１，４‐ブタンジオールジ（メタ）アクリレート、１，６‐ヘキサンジオールジ（メタ）アクリレート、エチ（プロピ）レンオキサイド変性ビスフェノールＡジアクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ビス（アクリロキシネオペンチルグリコール）アジペート、ビス（メタクリロキシネオペンチルグリコール）アジペート、エピクロルヒドリン変性１，６‐ヘキサンジオールジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレート、カプロラクトン変性ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、テトラプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジトリメチロールプロパントリ（メタ）アクリレート、ネオペンチルグリコール変性トリメチロールプロパンジ（メタ）アクリレート、エチ（プロピ）レンオキサイド変性トリメチロールプロパントリ（メタ）アクリレート、ヒドロキシプロピルアクリレート変性トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールポリプロポキシアクリレート、ステアリン酸変性ペンタエリスリトールジ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールモノヒドロキシペンタ（メタ）アクリレート、アルキル変性ジペンタエリスリトールポリ（メタ）アクリレート、カプロラクトン変性ジペンタエリスリトールポリ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、エピクロルヒドリン変性グリセロールトリ（メタ）アクリレート、オキサイド変性グリセロールトリ（メタ）アクリレート、トリス（アクリロキシエチル）イソシアヌレート、トリス（メタクリロキシエチル）イソシアヌレート、カプロラクトン変性トリス（アクリロキシエチル）イソシアヌレート、カプロラクトン変性トリス（メタクリロキシエチル）イソシアヌレート、オキサイド変性ビスフェノール（メタ）アクリレートなどが挙げられる。 Specific examples of polyfunctional monomers having two or more ethylenically unsaturated bonds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, 1,3-trimethylene glycol di(meth)acrylate, 1 ,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene oxide-modified bisphenol A diacrylate, neopentyl glycol di(meth)acrylate, bis(acryloxyneopentyl) glycol) adipate, bis(methacryloxyneopentylglycol)adipate, epichlorohydrin-modified 1,6-hexanediol di(meth)acrylate, neopentylglycol hydroxypivalate di(meth)acrylate, caprolactone-modified neopentylglycol hydroxypivalate ( meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate (Meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, neopentyl glycol modified trimethylolpropane di(meth)acrylate, ethyl(propy)ene oxide modified trimethylolpropane tri(meth)acrylate Acrylate, hydroxypropyl acrylate-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol polypropoxyacrylate, stearic acid-modified pentaerythritol di(meth)acrylate, dipenta Erythritol hexa(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, alkyl-modified dipentaerythritol poly(meth)acrylate, caprolactone-modified dipentaerythritol poly(meth)acrylate, glycerin di(meth)acrylate, epichlorohydrin-modified glycerol Tri(meth)acrylate, oxide-modified glycerol tri(meth)acrylate, tris(acryloxyethyl)isocyanurate , tris(methacryloxyethyl) isocyanurate, caprolactone-modified tris(acryloxyethyl) isocyanurate, caprolactone-modified tris(methacryloxyethyl) isocyanurate, oxide-modified bisphenol (meth)acrylate, and the like.
　オリゴマーとしては、たとえば、ポリエステル（メタ）アクリレートオリゴマー、ビスフェノールＡ型エポキシ（メタ）アクリレート、カプロラクトン付加（メタ）アクリレート、フェノールノボラック型エポキシ（メタ）アクリレート、クレゾールノボラック型エポキシ（メタ）アクリレート等のエポキシ（メタ）アクリレート、ウレタン（メタ）アクリレート等を用いることができる。
　さらに、エチレン性不飽和結合含有ポリエステルデンドリマーなどを用いることができる。このようなエチレン性不飽和結合含有ポリエステルデンドリマーの具体例は、例えば特開２００５－７６００５号、特開２００５－４７９７９号、特開２００５－７６００５号各公報などに記載されている。 As the oligomer, for example, epoxy (meth)acrylate such as polyester (meth)acrylate oligomer, bisphenol A type epoxy (meth)acrylate, caprolactone addition (meth)acrylate, phenol novolac type epoxy (meth)acrylate, cresol novolak type epoxy (meth)acrylate, etc. Meth)acrylate, urethane (meth)acrylate, and the like can be used.
Furthermore, an ethylenically unsaturated bond-containing polyester dendrimer or the like can be used. Specific examples of such ethylenically unsaturated bond-containing polyester dendrimers are described, for example, in JP-A-2005-76005, JP-A-2005-47979, and JP-A-2005-76005.
　上記の成分（Ｆ）の一種を単独で用いることができ、また二種以上を併用することができる。
　成分（Ｆ）の存在量（質量％）は、上記の成分（Ａ）および成分（Ｂ）の合計を１００質量％としたときに、好ましくは１．０～８００質量％、特に好ましくは１０～６００質量％、である。 One kind of the above component (F) can be used alone, or two or more kinds can be used in combination.
The abundance (% by mass) of component (F) is preferably 1.0 to 800% by mass, particularly preferably 10 to 800% by mass, when the total of component (A) and component (B) is 100% by mass. 600% by mass.
　成分（Ｇ）
　成分（Ｇ）は、光重合開始剤であり、特に制限は無いが一例として、ベンゾフェノン、ビス‐Ｎ，Ｎ‐ジメチルアミノベンゾフェノン、などのベンゾフェノン類、チオキサントン、イソプロピルチオキサントンなどのチオキサントン類が挙げられる。 Component (G)
Component (G) is a photopolymerization initiator, but examples thereof include benzophenones such as benzophenone and bis-N,N-dimethylaminobenzophenone, and thioxanthones such as thioxanthone and isopropylthioxanthone.
　また、油溶性の光ラジカル重合開始剤としては、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテルなどのベンゾインとベンゾインアルキルエーテル類；アセトフェノン、２，２‐ジメトキシ‐２‐フェニルアセトフェノン、２，２‐ジエトキシ‐２‐フェニルアセトフェノン、１，１‐ジクロロアセトフェノン、２‐ヒドロキシ‐２‐メチル‐１‐フェニルプロパン‐１‐オン、１‐（４‐イソプロピルフェニル）‐２‐ヒドロキシ‐２‐メチルプロパン‐１‐オン、１‐（４‐ドテシルフェニル）‐２‐ヒドロキシ‐２‐メチルプロパン‐１‐オン、４‐（２‐ヒドロキシエトキシ）‐フェニル（２‐ヒドロキシ‐２‐プロピル）ケトン、１‐ヒドロキシシクロヘキシルフェニルケトンなどのアセトフェノン類；２‐メチル‐１‐［４‐（メチルチオ）フェニル］‐２‐モルホリノプロパノン‐１、２‐ベンジル‐２‐ジメチルアミノ‐１‐（４‐モルホリノフェニル）‐ブタノン‐１などのアミノアセトフェノン類；２‐メチルアントラキノン、２‐エチルアントラキノン、２‐ターシャリーブチルアントラキノン、１‐クロロアントラキノンなどのアントラキノン類；２，４‐ジメチルチオキサントン、２，４‐ジエチルチオキサントン、２‐クロロチオキサントン、イソプロピルチオキサントン、２，４‐ジイソプロピルチオキサントンなどのチオキサントン類；アセトフェノンジメチルケタール、ベンジルジメチルケタールなどのケタール類；ベンゾフェノンなどのベンゾフェノン類又はキサントン類などがあり、これらは、単独で又は２種類以上組み合わせて用いることができ、また、第３級アミン類のような公知の増感剤を単独で又は２種類以上組み合わせて用いることができる。
　成分（Ｇ）の量（質量％）は、上記の成分（Ｆ）に対し、好ましくは０．１～２０質量％、特に好ましくは０．５～１０質量％、である。 Examples of oil-soluble photoradical polymerization initiators include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2, 2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane -1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1 - acetophenones such as hydroxycyclohexylphenyl ketone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) -butanone-1 and other aminoacetophenones; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 1-chloroanthraquinone and other anthraquinones; thioxanthones such as 2-chlorothioxanthone, isopropylthioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone and xanthones; More than one type can be used in combination, and known sensitizers such as tertiary amines can be used alone or in combination of two or more types.
The amount (% by mass) of component (G) is preferably 0.1 to 20% by mass, particularly preferably 0.5 to 10% by mass, based on the above component (F).
　成分（Ｈ）
　成分（Ｈ）は、水性ポリマーエマルジョンであり、例えば、ポリ酢酸ビニル、酢酸ビニル／エチレン共重合体、酢酸ビニル／アクリル酸エステル共重合体、（メタ）アクリル酸重合体、スチレン／ブタジエン共重合体、メタクリル酸メチル／ブタジエン共重合体、アクリロニトリル／ブタジエン共重合体、クロロプレン重合体、イソプレン重合体、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリスチレン、シリコーン樹脂、ポリエチレン、ポリウレタン、フッ素樹脂等を挙げることができる。これら疎水性重合体粒子は、重合工程中により得られるポリ酢酸ビニルエマルジョン、エチレン・酢酸ビニルコポリマーエマルジョン、酢酸ビニル・アクリルコポリマーエマルジョン、エチレン・酢酸ビニル・アクリル３元共重合エマルジョン、塩化ビニル・酢酸ビニルコポリマーエマルジョン、アクリルエマルジョン、スチレン・ブタジエンラテックスエマルジョン、ＭＢＲラテックスエマルジョン、アクリロニトリル・ブタジエンゴムラテックスエマルジョン、クロロプレンゴムラテックスエマルジョン、塩化ビニリデンエマルジョン等を挙げることができる。さらには、多官能性（メタ）アクリレートから調製される水性エマルジョンを熱重合開始剤あるいは光重合開始剤によって乳化重合し、架橋構造を有するポリマーの水性エマルジョンも好適に用いることができる。合成高分子ディスパージョンとしては、ポリエチレンディスパージョン、ポリオレフィンアイオノマーディスパージョン、ウレタンアイオノマーディスパージョン等が有用である。
　成分（Ｈ）の存在比率（質量％）は、上記の成分（Ａ）および成分（Ｂ）の合計を１００質量％としたときに、好ましくは１～１５００質量％、特に好ましくは１０～１０００質量％、である。 Component (H)
Component (H) is an aqueous polymer emulsion such as polyvinyl acetate, vinyl acetate/ethylene copolymer, vinyl acetate/acrylate copolymer, (meth)acrylic acid polymer, styrene/butadiene copolymer. , methyl methacrylate/butadiene copolymer, acrylonitrile/butadiene copolymer, chloroprene polymer, isoprene polymer, polyvinyl chloride, polyvinylidene chloride, polystyrene, silicone resin, polyethylene, polyurethane, fluorine resin, and the like. . These hydrophobic polymer particles are polyvinyl acetate emulsion, ethylene/vinyl acetate copolymer emulsion, vinyl acetate/acrylic copolymer emulsion, ethylene/vinyl acetate/acrylic terpolymer emulsion, vinyl chloride/vinyl acetate obtained during the polymerization process. Copolymer emulsion, acrylic emulsion, styrene/butadiene latex emulsion, MBR latex emulsion, acrylonitrile/butadiene rubber latex emulsion, chloroprene rubber latex emulsion, vinylidene chloride emulsion and the like can be mentioned. Furthermore, an aqueous emulsion of a polymer having a crosslinked structure obtained by emulsion polymerization of an aqueous emulsion prepared from a polyfunctional (meth)acrylate with a thermal polymerization initiator or a photopolymerization initiator can also be preferably used. Useful synthetic polymer dispersions include polyethylene dispersions, polyolefin ionomer dispersions, urethane ionomer dispersions, and the like.
The abundance ratio (% by mass) of component (H) is preferably 1 to 1500% by mass, particularly preferably 10 to 1000% by mass, when the total of component (A) and component (B) is 100% by mass. %.
　その他の成分
　第一の感光性樹脂層には、その他の成分として、架橋剤、有機または無機粒子、シランカップリング剤、顔料、染料、熱重合防止剤、界面活性剤、消泡剤、酸化防止剤、密着性付与剤、可塑剤、溶剤、表面張力調節剤、安定剤、連鎖移動防止剤、難燃剤、抗菌剤、防腐剤などを必要に応じて添加できる。 Other Components In the first photosensitive resin layer, other components include a cross-linking agent, organic or inorganic particles, silane coupling agent, pigment, dye, thermal polymerization inhibitor, surfactant, antifoaming agent, and antioxidant. Agents, adhesion imparting agents, plasticizers, solvents, surface tension modifiers, stabilizers, chain transfer inhibitors, flame retardants, antibacterial agents, preservatives and the like can be added as necessary.
　<<第二の感光性樹脂層>>
　感光性樹脂層の第二の具体例は、下記の成分（Ａ）、成分（Ｃ）および成分（Ｄ）を含んでなる感光性樹脂からなるものである。
　成分（Ａ）：けん化度５０モル％以上のポリビニルアルコール
　成分（Ｃ）：少なくとも一つのエポキシ基を有するエポキシ化合物
　成分（Ｄ）：光酸発生剤 <<Second photosensitive resin layer>>
A second specific example of the photosensitive resin layer is composed of a photosensitive resin containing the following components (A), (C) and (D).
Component (A): Polyvinyl alcohol having a degree of saponification of 50 mol% or more Component (C): Epoxy compound having at least one epoxy group Component (D): Photoacid generator
　ここで、「含んでなる」とは、挙示の各成分（即ち、成分（Ａ）、成分（Ｃ）および成分（Ｄ））のみを含んでなるもののほかに、挙示の成分以外の成分等を含んでなるをも包含する。そのような挙示の各層以外の層の代表例としては、例えば成分（Ｆ）～（Ｈ）を挙げることができる。 Here, the term "comprising" refers to those containing only the listed components (i.e., component (A), component (C) and component (D)), as well as components other than the listed components. etc. is also included. Representative examples of layers other than the listed layers include, for example, components (F) to (H).
　成分（Ａ）と成分（Ｃ）との存在比率（質量％）は、成分（Ａ）：成分（Ｃ）が、好ましくは１：１～１：１０、特に好ましくは１：２～１：６である。成分（Ｄ）の量（質量％）は、上記の成分（Ｃ）に対し、好ましくは１～２０質量％、特に好ましくは３～１０質量％である。
　上記の成分（Ａ）、成分（Ｃ）および成分（Ｄ）を含んでなる感光性樹脂は、必要に応じて、成分（Ｆ）～（Ｈ）のいずれか一種あるいは複数種を含むことができる。 The abundance ratio (% by mass) of component (A) and component (C) is component (A):component (C), preferably 1:1 to 1:10, particularly preferably 1:2 to 1:6. is. The amount (% by mass) of component (D) is preferably 1 to 20% by mass, particularly preferably 3 to 10% by mass, based on the above component (C).
The photosensitive resin comprising the component (A), the component (C) and the component (D) may optionally contain one or more of the components (F) to (H). .
　成分（Ａ）
　第二の具体例における成分（Ａ）としては、第一の感光性樹脂の具体例において成分（Ａ）として例示したものを用いることができる。 Component (A)
As the component (A) in the second specific example, those exemplified as the component (A) in the first specific example of the photosensitive resin can be used.
　成分（Ｃ）
　成分（Ｃ）は、少なくとも一つのエポキシ基を有する化合物である。
　２官能以上のグリシジル型エポキシ化合物として、たとえば、エチレングリコールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、レゾルシノールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，６‐ヘキサンジオールジグリシジルエーテル、グリセリンジグリシジルエーテル、ジブロモネオペンチルグリコールジグリシジルエーテル、水添ビスフェノールＡジグリシジルエーテル、テレフタル酸ジグリシジルエステル、フタル酸ジグリシジルエステル、水添フタル酸ジグリシジルエステル、ビスフェノールＡ　ＰＯ　２ｍｏｌ付加物ジグリシジルエーテル、ソルビトールポリグリシジルエーテル、グリセロールポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテルなどを挙げることができる。さらには、脂環式エポキシ化合物としては、３，４－エポキシシクロヘキシルメチル－３’，４’－エポキシシクロヘキサンカルボキシレート、３，４－エポキシシクロヘキシルメチル－３’，４’－エポキシシクロヘキサンカルボキシレートとε－カプロラクトンの付加物、１，２，８，９－ジエポキシリモネン、（３，３’４，４’－ジエポキシ）ビシクロヘキシル、１，２‐エポキシ‐４‐ビニルシクロヘキサン）、２，２‐ビス(ヒドロキシメチル)‐１‐ブタノールの１，２‐エポキシ‐４‐(２‐オキシラニル)シクロヘキサン付加物、ブタンテトラカルボン酸 テトラ（３，４‐エポキシシクロヘキシルメチル) 修飾ε‐カプロラクトン、３，４‐エポキシシクロヘキシルメチルメタアクリレートなどを挙げることができる。 Component (C)
Component (C) is a compound having at least one epoxy group.
Examples of di- or higher functional glycidyl-type epoxy compounds include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, resorcinol di Glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, terephthalic acid diglycidyl ester, diphthalic acid glycidyl ester, hydrogenated diglycidyl phthalate, bisphenol A PO 2mol adduct diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, Pentaerythritol polyglycidyl ether and the like can be mentioned. Furthermore, alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate and ε -adducts of caprolactone, 1,2,8,9-diepoxylimonene, (3,3'4,4'-diepoxy)bicyclohexyl, 1,2-epoxy-4-vinylcyclohexane), 2,2-bis 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of (hydroxymethyl)-1-butanol, butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone, 3,4-epoxy Cyclohexylmethyl methacrylate and the like can be mentioned.
　単官能性エポキシ化合物としては、２‐エチルヘキシルグリシジルエーテル、フェニルグリシジルエーテル、フェノール（ＥＯ）５グリシジルエーテル、ｐ‐ｔｅｒｔ‐ブチルフェニルグリシジルエーテル、ジブロモフェニルグリシジルエーテル、ラウリルアルコール（ＥＯ）１５グリシジルエーテル、Ｃｌ２、Ｃｌ３混合アルコールグリシジルエーテル、Ｎ‐グリシジルフタルイミドなどを挙げることができる。これらを反応性希釈剤として用いれば、高粘度あるいは固形のエポキシ樹脂を用いることができる。たとえば、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、トリスヒドロキシフェニルメタン型エポキシ樹脂、ジシクロペンタジエンフェノール型エポキシ樹脂、ビスフェノール‐Ａ型エポキシ樹脂、ビスフェノール‐Ｆ型エポキシ樹脂、ビフェノール型エポキシ樹脂、ビスフェノール‐Ａノボラック型エポキシ樹脂、ナフタレン骨格含有エポキシ樹脂、複素環式エポキシ樹脂、エポキシ化ポリブタジエン、スチレン‐ブタジエンブロック共重合体のエポキシ化物、臭素化エポキシ樹脂、ビフェニル型エポキシ樹脂、アミン型エポキシ樹脂などを用いることができる。
　また、少なくとも一つのオキセタン基を有する化合物を上記のエポキシ化合物と混合して用いることができる。 Monofunctional epoxy compounds include 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol (EO) 5 glycidyl ether, p-tert-butylphenyl glycidyl ether, dibromophenyl glycidyl ether, lauryl alcohol (EO) 15 glycidyl ether, Cl 2 , Cl 3 mixed alcohol glycidyl ether, N-glycidyl phthalimide and the like. If these are used as reactive diluents, high viscosity or solid epoxy resins can be used. For example, phenol novolak type epoxy resin, cresol novolak type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, biphenol type epoxy resin, bisphenol -A novolac type epoxy resin, naphthalene skeleton-containing epoxy resin, heterocyclic epoxy resin, epoxidized polybutadiene, epoxidized styrene-butadiene block copolymer, brominated epoxy resin, biphenyl type epoxy resin, amine type epoxy resin, etc. can be used.
Also, a compound having at least one oxetane group can be used in combination with the above epoxy compound.
　オキセタン化合物としては、J.V.Crivello and H.Sasaki,J.M.S.Pure　Appl.Chem.,A30(2&3),189(1993) あるいは J.H.Sasaki and V.Crivello,J.M.S.Pure Appl.Chem.,A30(2&3),915(1993) に記載の化合物が挙げられる。たとえば、３‐エチル‐３‐ヒドロキシメチルオキセタン（オキセタンアルコール）、２‐エチルヘキシルオキセタン、（３‐エチルオキセタン‐３‐イル)メチルメタクリレート、（３‐エチルオキセタン‐３‐イル)メチルアクリレート、３‐エチル‐３‐（４‐ヒドロキシブチルオキシメチル）オキセタンなどの単官能オキセタン化合物、キシリレンビスオキセタン、３‐エチル‐３｛［（３‐エチルオキセタン‐３‐イル）メトキシ］メチル｝オキセタン、４，４’‐ビス［（３‐エチル‐３‐オキセタニル）メトキシメチル］ビフェニル）、ビス［（３‐エチル‐３‐オキセタニル）メチル］イソフタレートなどの２官能オキセタン化合物、ペンタエリスリトールトリス（３‐エチル‐３‐オキセタニルメチル）エーテル、ペンタエリスリトールテトラキス（３‐エチル‐３‐オキセタニルメチル）エーテル、ジペンタエリスリトールヘキサ（３‐エチル‐３‐オキセタニルメチル）エーテル、ジペンタエリスリトールペンタキス（３‐エチル‐３‐オキセタニルメチル）エーテル、ジペンタエリスリトールテトラキス（３‐エチル‐３‐オキセタニルメチル）エーテル、カプロラクトン変性ジペンタエリスリトールヘキサ（３‐エチル‐３‐オキセタニルメチル）エーテル、カプロラクトン変性ジペンタエリスリトールペンタキス（３‐エチル‐３‐オキセタニルメチル）エーテル、ジトリメチロールプロパンテトラキス（３‐エチル‐３‐オキセタニルメチル）エーテルなどの多官能オキセタン化合物を挙げることができる。
　上記成分（Ｃ）の一種を単独で用いることができ、また二種以上を併用することができる。 Oxetane compounds are described in JVCrivello and H. Sasaki, JMS Pure Appl. Chem., A30(2&3), 189 (1993) or JHSasaki and V. Crivello, JMS Pure Appl. and the compound of For example, 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol), 2-ethylhexyloxetane, (3-ethyloxetan-3-yl)methyl methacrylate, (3-ethyloxetan-3-yl)methylacrylate, 3-ethyl -monofunctional oxetane compounds such as 3-(4-hydroxybutyloxymethyl)oxetane, xylylene bisoxetane, 3-ethyl-3{[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane, 4,4 '-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), bis[(3-ethyl-3-oxetanyl)methyl]isophthalate and other bifunctional oxetane compounds, pentaerythritol tris(3-ethyl-3 -oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanyl) ether methyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl- 3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, and other polyfunctional oxetane compounds.
One type of component (C) can be used alone, or two or more types can be used in combination.
　成分（Ｄ）
　成分（Ｄ）は、酸発生剤であり、化学増幅型フォトレジストや光カチオン重合に利用される化合物が用いられる（有機エレクトロニクス材料研究会編、「イメージング用有機材料」、ぶんしん出版（１９９３年）、１８７～１９２ページ参照）。酸発生剤の具体例としては、例えば、オニウムカチオン化合物、ハロゲン化水素酸を発生する含ハロゲン化合物、スルホン酸を発生するスルホン化化合物を挙げることができる。 Component (D)
Component (D) is an acid generator, and compounds used in chemically amplified photoresists and photo-cationic polymerization are used (Organic Electronics Materials Study Group, "Organic Materials for Imaging", Bunshin Publishing (1993). ), see pages 187-192). Specific examples of acid generators include onium cation compounds, halogen-containing compounds that generate hydrohalic acid, and sulfonated compounds that generate sulfonic acid.
　イオン性酸発生剤として、たとえば、ジアゾニウム、アンモニウム、ヨードニウム、スルホニウム、ホスホニウム、フェロセニウムなどのオニウムカチオンの、Ｃｌ－、Ｂｒ－、Ｉ－、ＺｎＣｌ３ －、ＨＳＯ３ －、ＢＦ４ －、ＰＦ６ －、ＡｓＦ６ －、ＳｂＦ６ －、ＣＨ３ＳＯ３ －、ＣＦ３ＳＯ３ －、パーフルオロブタンスルホネート、パーフルオロオクタンスルホネート、カンファースルホネート、ベンゼンスルホネート、ｐ‐トルエンスルホネート、９，１０‐ジメトキシアントラセン‐２‐スルホネート、シクロヘキシルアミノスルホネート、（Ｃ６Ｆ５）４Ｂ－、（Ｃ４Ｈ９）４Ｂ－ などの塩を挙げることができる。 As ionic acid generators, for example, onium cations such as diazonium, ammonium, iodonium, sulfonium, phosphonium, ferrocenium, Cl − , Br − , I − , ZnCl 3 − , HSO 3 − , BF 4 − , PF 6 − , AsF 6 − , SbF 6 − , CH 3 SO 3 − , CF 3 SO 3 − , perfluorobutanesulfonate, perfluorooctane sulfonate, camphorsulfonate, benzenesulfonate, p-toluenesulfonate, 9,10-dimethoxyanthracene-2 -sulfonate, cyclohexylaminosulfonate, (C 6 F 5 ) 4 B − , (C 4 H 9 ) 4 B − and the like.
　前記オニウムカチオンの具体的な例として、フェニルジアゾニウム、ｐ‐メトキシジアゾニウム、α‐ナフチルジアゾニウム、ビフェニルジアゾニウム、ジフェニルアミン‐４‐ジアゾニウム、３‐メトキシジフェニルアミン‐４‐ジアゾニウム、２，５‐ジエトキシ‐４‐メトキシベンゾイルアミドフェニルジアゾニウム、２，５‐ジプロポキシ‐４‐（４‐トリル）チオフェニルジアゾニウム、４‐メトキシジフェニルアミン‐４‐ジアゾニウム、４‐ジアゾジフェニルアミンとホルムアルデヒドとの縮合物、１‐メトキシキノリニウム、１‐エトキシイソキノリニウム、１‐フェナシルピリジニウム、１‐ベンジル‐４‐ベンゾイルピリジニウム、１‐ベンジルキノリニウム、Ｎ‐置換ベンゾチアゾリウム（特開平５－１４０１４３号公報参照）などが挙げられる。 Specific examples of the onium cations include phenyldiazonium, p-methoxydiazonium, α-naphthyldiazonium, biphenyldiazonium, diphenylamine-4-diazonium, 3-methoxydiphenylamine-4-diazonium, and 2,5-diethoxy-4-methoxy. benzoylamidophenyldiazonium, 2,5-dipropoxy-4-(4-tolyl)thiophenyldiazonium, 4-methoxydiphenylamine-4-diazonium, condensate of 4-diazodiphenylamine and formaldehyde, 1-methoxyquinolinium, 1 -ethoxyisoquinolinium, 1-phenacylpyridinium, 1-benzyl-4-benzoylpyridinium, 1-benzylquinolinium, N-substituted benzothiazolium (see JP-A-5-140143), and the like. .
　さらに、ベンジルトリフェニルスルホニウム、ｐ‐メトキシフェニルジフェニルスルホニウム、ビス（ｐ‐メトキシフェニル）フェニルスルホニウム、トリス（ｐ‐メトキシフェニル）スルホニウム、ｐ‐フェニルチオフェニルジフェニルスルホニウム、ベンジルテトラメチレンスルホニウム、フェナシルテトラメチレンスルホニウム、フェナシルジメチルスルホニウム、ｐ‐メトキシフェニルジエチルスルホニウム、ナフチルジアルキルスルホニウム（特開平９－１１８６６３号公報、特開平５－１４０２０９号公報参照）、（２‐ナフチルカルボニルメチル）テトラメチレンスルホニウム、（ｐ‐ヒドロキシフェニル）ジチメルスルホニウム、（４‐ヒドロキシナフチル）‐ジメチルスルホニウム、（４，７‐ジヒドロキシナフチル）‐１‐ジメチルスルホニウム、（４，８‐ジヒドロキシナフチル）‐１‐ジメチルスルホニウム、ジフェニルヨードニウム、フェニル（４‐メトキシフェニル）ヨードニウム、フェニル｛４‐（ｔｅｒｔ‐ブチル）フェニル｝ヨードニウム、４‐ビス｛４‐（ｔｅｒｔ‐ブチル）フェニル｝ヨードニウム、ビス（４‐ドデシルフェニル）ヨードニウム、（４‐メトキシフェニル）（４‐オクチルオキシフェニル）ヨードニウム、フェナシルトリフェニルホスホニウム、シアノメチルトリフェニルホスホニウムなどが挙げられる。 Furthermore, benzyltriphenylsulfonium, p-methoxyphenyldiphenylsulfonium, bis(p-methoxyphenyl)phenylsulfonium, tris(p-methoxyphenyl)sulfonium, p-phenylthiophenyldiphenylsulfonium, benzyltetramethylenesulfonium, phenacyltetramethylene sulfonium, phenacyldimethylsulfonium, p-methoxyphenyldiethylsulfonium, naphthyldialkylsulfonium (see JP-A-9-118663 and JP-A-5-140209), (2-naphthylcarbonylmethyl)tetramethylenesulfonium, (p- hydroxyphenyl)dithymersulfonium, (4-hydroxynaphthyl)-dimethylsulfonium, (4,7-dihydroxynaphthyl)-1-dimethylsulfonium, (4,8-dihydroxynaphthyl)-1-dimethylsulfonium, diphenyliodonium, phenyl ( 4-methoxyphenyl)iodonium, phenyl{4-(tert-butyl)phenyl}iodonium, 4-bis{4-(tert-butyl)phenyl}iodonium, bis(4-dodecylphenyl)iodonium, (4-methoxyphenyl) (4-octyloxyphenyl)iodonium, phenacyltriphenylphosphonium, cyanomethyltriphenylphosphonium and the like.
　ハロゲン化水素酸を発生する酸発生剤としては、１‐メチル‐３，５‐ビス（トリクロロメチル）‐ｓ‐トリアジン、１‐フェニル‐３，５‐ビス（トリクロロメチル）‐ｓ‐トリアジン、１‐（４‐クロロフェニル）‐３，５‐ビス（トリクロロメチル）‐ｓ‐トリアジン、１‐（４‐メトキシフェニル）‐３，５‐ビス（トリクロロメチル）‐ｓ‐トリアジン、１‐（４‐ブトキシフェニル）‐３，５‐ビス（トリクロロメチル）‐ｓ‐トリアジン、１‐（３，４‐メチレンジオキシフェニル）‐３，５‐ビス（トリクロロメチル）‐ｓ‐トリアジン、１‐（３，４‐ジメトキシフェニル）‐３，５‐ビス（トリクロロメチル）‐ｓ‐トリアジン、１‐（４‐メトキシナフチル‐１）‐３，５‐ビス（トリクロロメチル）‐ｓ‐トリアジン、１‐｛２‐（４‐メトキシフェニル）エテニル｝‐３，５‐ビス（トリクロロメチル）‐ｓ‐トリアジン、１‐｛２‐（２‐メトキシフェニル）エテニル｝‐３，５‐ビス（トリクロロメチル）‐ｓ‐トリアジン、１‐｛２‐（３，４‐ジメトキシフェニル）エテニル｝‐３，５‐ビス（トリクロロメチル）‐ｓ‐トリアジン、１‐｛２‐（３‐クロロ‐４‐メトキシフェニル）エテニル｝‐３，５‐ビス（トリクロロメチル）‐ｓ‐トリアジン、１‐（ビフェニル‐１）‐３，５‐ビス（トリクロロメチル）‐ｓ‐トリアジン、１‐（４‐ヒドロキシビフェニル‐１）‐３，５‐ビス（トリクロロメチル）‐ｓ‐トリアジン、１‐（４‐メトキシビフェニル‐１）‐３，５‐ビス（トリクロロメチル）‐ｓ‐トリアジン、１‐（４‐メチルビフェニル‐１）‐３，５‐ビス（トリクロロメチル）‐ｓ‐トリアジン、１，３，５‐トリス（トリクロロメチル）‐ｓ‐トリアジン、１，３‐ジクロロ‐４‐トリクロロメチルベンゼン、１，１，１‐トリクロロ‐｛２，２‐８４‐クロロフェニル｝エタン、フェニルトリブロモメチルスルホン、１‐ケト‐４‐メチル‐４‐トリクロロメチル‐２，５‐ジクロヘキサジエン、２‐トリブロモキノリン、１‐ケト‐２，３‐ベンゾ‐４，４，５，６‐テトラクロロヘキサエン‐５、などが挙げられる。 Acid generators that generate hydrohalic acids include 1-methyl-3,5-bis(trichloromethyl)-s-triazine, 1-phenyl-3,5-bis(trichloromethyl)-s-triazine, 1 -(4-chlorophenyl)-3,5-bis(trichloromethyl)-s-triazine, 1-(4-methoxyphenyl)-3,5-bis(trichloromethyl)-s-triazine, 1-(4-butoxy Phenyl)-3,5-bis(trichloromethyl)-s-triazine, 1-(3,4-methylenedioxyphenyl)-3,5-bis(trichloromethyl)-s-triazine, 1-(3,4 -dimethoxyphenyl)-3,5-bis(trichloromethyl)-s-triazine, 1-(4-methoxynaphthyl-1)-3,5-bis(trichloromethyl)-s-triazine, 1-{2-( 4-methoxyphenyl)ethenyl}-3,5-bis(trichloromethyl)-s-triazine, 1-{2-(2-methoxyphenyl)ethenyl}-3,5-bis(trichloromethyl)-s-triazine, 1-{2-(3,4-dimethoxyphenyl)ethenyl}-3,5-bis(trichloromethyl)-s-triazine, 1-{2-(3-chloro-4-methoxyphenyl)ethenyl}-3, 5-bis(trichloromethyl)-s-triazine, 1-(biphenyl-1)-3,5-bis(trichloromethyl)-s-triazine, 1-(4-hydroxybiphenyl-1)-3,5-bis (trichloromethyl)-s-triazine, 1-(4-methoxybiphenyl-1)-3,5-bis(trichloromethyl)-s-triazine, 1-(4-methylbiphenyl-1)-3,5-bis (trichloromethyl)-s-triazine, 1,3,5-tris(trichloromethyl)-s-triazine, 1,3-dichloro-4-trichloromethylbenzene, 1,1,1-trichloro-{2,2- 84-chlorophenyl}ethane, phenyltribromomethylsulfone, 1-keto-4-methyl-4-trichloromethyl-2,5-dichlorohexadiene, 2-tribromoquinoline, 1-keto-2,3-benzo-4, 4,5,6-tetrachlorohexaene-5, and the like.
　スルホン酸を発生する酸発生剤としては、２‐ニトロベンジルｐ‐トルエンスルホネート、２，６‐ジニトロベンジルｐ‐トルエンスルホネート、１‐（ｐ‐トルエンスルホニルオキシイミノ）‐１‐フェニルエタンニトリル、１‐（ｐ‐トルエンスルホニルオキシイミノ）‐１‐フェニルエタンニトリル、ベンゾインｐ‐トルエンスルホネート、２‐ｐ‐トルエンスルホニルオキシ‐２‐ベンゾイルプロパン、ｐ‐ニトロベンジル９，１０‐ジメトキシアントラセン‐２‐スルホネート、Ｎ‐トリフルオロメタンスルホニルオキシジフェニルマレイミド、Ｎ‐ｐ‐トルエンスルホニルオキシサクシンイミド、Ｎ‐カンファースルホニルオキシサクシンイミド、Ｎ‐トルフルオロメタンスルホニルオキシサクシンイミド、Ｎ‐パーフルオロブタンスルホニルオキシサクシンイミド、Ｎ‐ｐ‐トルエンスルホニルオキシフタルイミド、Ｎ‐カンファースルホニルオキシフタルイミド、Ｎ‐トルフルオロメタンスルホニルオキシフタルイミド、Ｎ‐パーフルオロブタンスルホニルオキシフタルイミド、Ｎ‐ｐ‐トルエンスルホニルオキシ‐１，８‐ナフタレンカルボキシイミド、Ｎ‐カンファースルホニルオキシ‐１，８‐ナフタレンカルボキシイミド、Ｎ‐トリフルオロメタンスルホニルオキシ‐１，８‐ナフタレンカルボキシイミド、Ｎ‐パーフルオロブタンスルホニルオキシ‐１，８‐ナフタレンカルボキシイミド、１，２，３‐トリス（ｐ‐トルエンスルホニルオキシ）ベンゼン、ビス（フェニルスルホン）、ビス（フェニルスルホニル）メタン、などを挙げることができる。 Acid generators that generate sulfonic acid include 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, 1-(p-toluenesulfonyloxyimino)-1-phenylethanenitrile, 1- (p-toluenesulfonyloxyimino)-1-phenylethanenitrile, benzoin p-toluenesulfonate, 2-p-toluenesulfonyloxy-2-benzoylpropane, p-nitrobenzyl 9,10-dimethoxyanthracene-2-sulfonate, N -trifluoromethanesulfonyloxydiphenylmaleimide, Np-toluenesulfonyloxysuccinimide, N-camphorsulfonyloxysuccinimide, N-trifluoromethanesulfonyloxysuccinimide, N-perfluorobutanesulfonyloxysuccinimide, Np- toluenesulfonyloxyphthalimide, N-camphorsulfonyloxyphthalimide, N-tolufluoromethanesulfonyloxyphthalimide, N-perfluorobutanesulfonyloxyphthalimide, Np-toluenesulfonyloxy-1,8-naphthalenecarboximide, N-camphorsulfonyl oxy-1,8-naphthalenecarboximide, N-trifluoromethanesulfonyloxy-1,8-naphthalenecarboximide, N-perfluorobutanesulfonyloxy-1,8-naphthalenecarboximide, 1,2,3-tris(p -toluenesulfonyloxy)benzene, bis(phenylsulfone), bis(phenylsulfonyl)methane, and the like.
　また、酸発生剤と併用して増感剤を使用することが可能であり、用いられる増感剤としては、電子供与性化合物であることが望ましい。このような特性を持つ増感剤としては、芳香族多環化合物、ポルフィリン化合物、フタロシアニン化合物、ポリメチン色素化合物、メロシアニン化合物、クマリン化合物、チオピリリウム化合物、ピリリウム化合物、ｐ‐ジアルキルアミノスチリル化合物、チオキサンテン化合物等を挙げることができるが、これに限定されるものではない。これらの多くは、大河、平嶋、松岡、北尾編集、「色素ハンドブック」（講談社）、社団法人色材協会編集、「色材工学ハンドブック」、朝倉書店（１９８９年発行）、林原生物化学研究所感光色素研究所「Ｄｙｅ　Ｃａｔａｌｏｇｕｅ」などに掲載されている。 In addition, it is possible to use a sensitizer in combination with the acid generator, and the sensitizer used is preferably an electron-donating compound. Sensitizers having such properties include aromatic polycyclic compounds, porphyrin compounds, phthalocyanine compounds, polymethine dye compounds, merocyanine compounds, coumarin compounds, thiopyrylium compounds, pyrylium compounds, p-dialkylaminostyryl compounds, thioxanthene compounds. etc., but not limited to these. Many of these have been published by Taiga, Hirashima, Matsuoka, Kitao, "Color Handbook" (Kodansha), Edited by The Color Material Association, "Color Material Engineering Handbook", Asakura Shoten (1989), Hayashibara Biochemical Laboratory Photosensitivity It is published in Dye Catalogue, etc.
　成分（Ｆ）
　第二の具体例における成分（Ｆ）としては、第一の感光性樹脂の具体例において成分（Ｆ）として例示したものを用いることができる。
　成分（Ｆ）の存在比率（質量％）は、上記の成分（Ａ）および成分（Ｃ）および成分（Ｄ）の合計を１００質量％としたときに、好ましくは１～６０質量％、特に好ましくは５～３０質量％、である。 Component (F)
As the component (F) in the second specific example, those exemplified as the component (F) in the first specific example of the photosensitive resin can be used.
The abundance ratio (% by mass) of component (F) is preferably 1 to 60% by mass, particularly preferably 1 to 60% by mass, when the total of component (A), component (C) and component (D) is 100% by mass. is 5 to 30% by mass.
　成分（Ｇ）
　第二の具体例における成分（Ｇ）としては、第一の感光性樹脂の具体例において成分（Ｇ）として例示したものを用いることができる。
　成分（Ｇ）の存在比率（質量％）は、上記の成分（Ｆ）に対して、好ましくは０～２０質量％、特に好ましくは０．１～１０質量％、である。 Component (G)
As the component (G) in the second specific example, those exemplified as the component (G) in the first specific example of the photosensitive resin can be used.
The content ratio (% by mass) of component (G) is preferably 0 to 20% by mass, particularly preferably 0.1 to 10% by mass, relative to component (F).
　成分（Ｈ）
　第二の具体例における成分（Ｈ）としては、第一の感光性樹脂の具体例において成分（Ｈ）として例示したものを用いることができる。
　成分（Ｈ）の存在比率（質量％）は、上記の成分（Ａ）および成分（Ｃ）および成分（Ｄ）の合計を１００質量％としたときに、好ましくは０．５～２００質量％、特に好ましくは１～１００質量％、である。 Component (H)
As the component (H) in the second specific example, those exemplified as the component (H) in the first specific example of the photosensitive resin can be used.
The abundance ratio (% by mass) of component (H) is preferably 0.5 to 200% by mass when the total of component (A), component (C) and component (D) is taken as 100% by mass, Particularly preferably, it is 1 to 100% by mass.
　その他の成分
　第二の感光性樹脂層には、その他の成分として、架橋剤、有機または無機粒子、シランカップリング剤、顔料、染料、熱重合防止剤、界面活性剤、消泡剤、酸化防止剤、密着性付与剤、可塑剤、溶剤、表面張力調節剤、安定剤、連鎖移動防止剤、難燃剤、抗菌剤、防腐剤などを必要に応じて用いることができる。 Other Components The second photosensitive resin layer contains other components such as a cross-linking agent, organic or inorganic particles, a silane coupling agent, a pigment, a dye, a thermal polymerization inhibitor, a surfactant, an antifoaming agent, and an antioxidant. Agents, adhesion imparting agents, plasticizers, solvents, surface tension modifiers, stabilizers, chain transfer inhibitors, flame retardants, antibacterial agents, preservatives and the like can be used as necessary.
　<<第三の感光性樹脂層>>
　感光性樹脂層の第三の具体例は、下記の成分（Ｅ）を含んでなる感光性樹脂からなるものである。
　成分（Ｅ）：スチリル置換されたピリジニウム基またはスチリル置換されたキノリニウム基を有するけん化度５０モル％以上のポリビニルアルコール
　上記の成分（Ｅ）を含んでなる感光性樹脂は、必要に応じて、成分（Ｆ）～（Ｈ）のいずれか一種あるいは複数種を含むことができる。 <<Third photosensitive resin layer>>
A third specific example of the photosensitive resin layer is composed of a photosensitive resin containing the following component (E).
Component (E): Polyvinyl alcohol having a saponification degree of 50 mol% or more and having a styryl-substituted pyridinium group or a styryl-substituted quinolinium group. Any one or more of (F) to (H) may be included.
　成分（Ｅ）
　成分（Ｅ）は、スチリル置換されたピリジニウム基又はスチリル置換されたキノリニウム基を有するけん化度５０モル％以上の酢酸ビニル重合体けん化物で、それ自体光架橋性を有する。好ましい具体的としては、下記の一般式（１）または一般式（２）で示される化合物を挙げることができる。
Figure JPOXMLDOC01-appb-C000001
 Component (E)
Component (E) is a saponified product of a vinyl acetate polymer having a styryl-substituted pyridinium group or a styryl-substituted quinolinium group and having a degree of saponification of 50 mol % or more, and itself has photocrosslinkability. Preferred specific examples include compounds represented by the following general formula (1) or general formula (2).
Figure JPOXMLDOC01-appb-C000001
（式中、Ｒ１は、水素原子、アルキル基またはアラルキル基を示し、これらはヒドロキシ基、カルバモイル基で置換されていてもよく、また、それらの炭素炭素結合は酸素原子あるいは不飽和結合を介していても良い。Ｒ２は、水素原子または炭素数１～３のアルキル基を示す。ｍは、１～６の整数である。ｎは、０または１である。Ｘ－ は、ハロゲンイオン、リン酸イオン、メト硫酸イオン、スルホン酸イオン、アニオン解離能をもつラジカル重合性モノマーまたはこれら陰イオンの混合物を表す）
　Ｒ１のアルキル基またはアラルキル基としては、炭素数１～１０のものが好ましい。特に１～７のものが好ましい。具体的な残基（Ｒ１）としては、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、２‐ヒドロキシエチル、３‐ヒドロキシプロピル、２‐メトキシエチル、３‐メトキシプロピル、アリル、クロチル、ベンジルなどを挙げることができる。ｍは１～６の範囲を越えると光不溶化後の膜が膨潤しやすくなり、１～４がより好ましい。ｎは０または１のいずれでもよい。 (In the formula, R 1 represents a hydrogen atom, an alkyl group or an aralkyl group, which may be substituted with a hydroxy group or a carbamoyl group, and their carbon-carbon bond is through an oxygen atom or an unsaturated bond. R 2 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m is an integer of 1 to 6, n is 0 or 1, X - is a halogen ion, Phosphate ions, methosulfate ions, sulfonate ions, radically polymerizable monomers with anion dissociation ability, or mixtures of these anions)
The alkyl group or aralkyl group for R 1 preferably has 1 to 10 carbon atoms. Those of 1 to 7 are particularly preferred. Specific residues (R 1 ) include methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-methoxyethyl, 3-methoxypropyl, allyl, crotyl, benzyl, etc. can be mentioned. When m exceeds the range of 1 to 6, the film tends to swell after photoinsolubilization, and 1 to 4 is more preferable. n can be either 0 or 1.
　Ｘ－ としては、リン酸イオン、メト硫酸イオン、ハロゲンイオンとしてＣｌ－またはＢｒ－、スルホン酸イオンとして、ＣＨ３ＳＯ３ －、ＣＨ３ＣＨ２ＳＯ３ －、Ｃ６Ｈ５ＳＯ３ －、ｐ‐ＣＨ３Ｃ６Ｈ４ＳＯ３ － が好ましい。また、Ｘ－ として少なくとも一つのエチレン性不飽和結合を持ち、かつ、アニオン解離能を有するラジカル重合性モノマーも挙げることができる。アニオン解離能を有する残基としては、スルホン酸、カルボン酸、リン酸を挙げることができ、これらのアルカリ塩あるいは脂肪族アミンのアンモニウム塩とすることによりアニオン基を持つラジカルモノマーとして用いられる。このために用いられるモノマーにおけるラジカル重合性不飽和基としては、（メタ）アクリロイル基（以下、（メタ）アクリロイルとは、アクリロイルおよびメタクロイルの両者を意味する）、マレイン酸モノエステル基、スチリル基、アリル基などを挙げることができる。解離していない酸型のモノマーの例として、アクリル酸、メタクリル酸、マレイン酸モノメチルエステル、マレイン酸モノエチルエステル、フタル酸２‐（メタ）アクリロイルオキシエチルエステル、フタル酸３‐（メタ）アクリロイルオキシ‐２‐プロピルエステル、フタル酸３‐（メタ）アクリロイルオキシ‐２‐プロピルエステル、シクロヘキサン‐３‐エン‐１，２‐ジカルボン酸２‐（メタ）アクリロイルオキシエチルエステル、コハク酸２‐（メタ）アクリロイルオキシエチルエステル、シクロヘキサン‐１，２‐カルボン酸２‐（メタ）アクリロイルオキシエチルエステル、マレイン酸２‐（メタ）アクリロイルオキシエチルエステル、ω‐カルボキシ‐ポリカプロラクトンモノアクリレート、アクリル酸ダイマー、２‐（メタ）アクリロイルオキシエチルリン酸、３‐（メタ）アクリロイルオキシプロピルリン酸、２‐（メタ）アクリロイルオキシ‐３‐プロピルリン酸、ω‐（メタ）アクリロイルポリエチレンオキシエチレンリン酸、ω‐（メタ）アクリロイルポリプロピレンオキシエチレンリン酸、スチレンスルホン酸、Ｎ‐（２‐スルホエチル）アクリルアミド、Ｎ‐（２‐スルホエチル）メタアクリルアミド、などを挙げることができるが、この限りではない。 X - includes phosphate ion, methosulfate ion, halogen ion Cl - or Br - , sulfonate ion CH 3 SO 3 - , CH 3 CH 2 SO 3 - , C 6 H 5 SO 3 - , p -CH 3 C 6 H 4 SO 3 - is preferred. Further, as X 1 − , a radically polymerizable monomer having at least one ethylenically unsaturated bond and having anion dissociation ability can also be mentioned. Residues having anion dissociation ability include sulfonic acid, carboxylic acid and phosphoric acid, and alkali salts thereof or ammonium salts of aliphatic amines are used as radical monomers having an anion group. Examples of radically polymerizable unsaturated groups in the monomers used for this purpose include (meth)acryloyl groups (hereinafter, (meth)acryloyl means both acryloyl and methacryloyl), maleic acid monoester groups, styryl groups, An allyl group and the like can be mentioned. Examples of undissociated acid-type monomers include acrylic acid, methacrylic acid, maleic acid monomethyl ester, maleic acid monoethyl ester, phthalic acid 2-(meth)acryloyloxyethyl ester, phthalic acid 3-(meth)acryloyloxy -2-propyl ester, 3-(meth)acryloyloxy-2-propyl phthalate, 2-(meth)acryloyloxyethyl cyclohexane-3-ene-1,2-dicarboxylic acid, 2-(meth)succinic acid acryloyloxyethyl ester, cyclohexane-1,2-carboxylic acid 2-(meth)acryloyloxyethyl ester, maleic acid 2-(meth)acryloyloxyethyl ester, ω-carboxy-polycaprolactone monoacrylate, acrylic acid dimer, 2- (meth) acryloyloxyethyl phosphate, 3-(meth) acryloyloxypropyl phosphate, 2-(meth) acryloyloxy-3-propyl phosphate, ω-(meth) acryloyl polyethyleneoxyethylene phosphate, ω-(meth) ) acryloylpolypropyleneoxyethylene phosphate, styrenesulfonic acid, N-(2-sulfoethyl)acrylamide, N-(2-sulfoethyl)methacrylamide, etc., but not limited thereto.
　成分（Ｆ）
　第三の具体例における成分（Ｆ）としては、第一の感光性樹脂の具体例において成分（Ｆ）として例示したものを用いることができる。
　成分（Ｆ）の存在比率（質量％）は、上記の成分（Ｅ）を１００質量％としたときに、好ましくは１．０～８００質量％、特に好ましくは１０～６００質量％、である。 Component (F)
As the component (F) in the third specific example, those exemplified as the component (F) in the first specific example of the photosensitive resin can be used.
The abundance ratio (% by mass) of component (F) is preferably 1.0 to 800% by mass, particularly preferably 10 to 600% by mass, based on 100% by mass of component (E).
　成分（Ｇ）
　第三の具体例における成分（Ｇ）としては、第一の感光性樹脂の具体例において成分（Ｅ）として例示したものを用いることができる。
　成分（Ｇ）の存在比率（質量％）は、上記の成分（Ｆ）を１００質量％としたときに、好ましくは０．１～２０質量％、特に好ましくは０．５～１０質量％、である。 Component (G)
As the component (G) in the third specific example, those exemplified as the component (E) in the first specific example of the photosensitive resin can be used.
The abundance ratio (% by mass) of the component (G) is preferably 0.1 to 20% by mass, particularly preferably 0.5 to 10% by mass, when the above component (F) is 100% by mass. be.
　成分（Ｈ）
　第三の具体例における成分（Ｈ）としては、第一の感光性樹脂の具体例において成分（Ｈ）として例示したものを用いることができる。
　成分（Ｈ）の存在比率（質量％）は、上記の成分（Ｅ）を１００質量％としたときに、好ましくは１～１５００質量％、特に好ましくは１０～１０００質量％、である。 Component (H)
As the component (H) in the third specific example, those exemplified as the component (H) in the first specific example of the photosensitive resin can be used.
The content ratio (% by mass) of component (H) is preferably 1 to 1500% by mass, particularly preferably 10 to 1000% by mass, based on 100% by mass of component (E).
　その他の成分
　第三の感光性樹脂層には、その他の成分として、架橋剤、有機または無機粒子、シランカップリング剤、顔料、染料、熱重合防止剤、界面活性剤、消泡剤、酸化防止剤、密着性付与剤、可塑剤、溶剤、表面張力調節剤、安定剤、連鎖移動防止剤、難燃剤、抗菌剤、防腐剤などを必要に応じて用いることができる。 Other Components The third photosensitive resin layer contains other components such as cross-linking agents, organic or inorganic particles, silane coupling agents, pigments, dyes, thermal polymerization inhibitors, surfactants, antifoaming agents, and antioxidants. Agents, adhesion imparting agents, plasticizers, solvents, surface tension modifiers, stabilizers, chain transfer inhibitors, flame retardants, antibacterial agents, preservatives and the like can be used as necessary.
　＜保護層＞
　本発明によるパターン形成用積層フィルムには、支持層、糊層、非水溶性高分子層および感光性樹脂層以外の他の層を含むことができる。そのような他の層の代表例としては、例えば保護層を挙げることができる。 <Protective layer>
The laminated film for pattern formation according to the present invention may contain layers other than the support layer, glue layer, water-insoluble polymer layer and photosensitive resin layer. Representative examples of such other layers include, for example, protective layers.
　この保護層は、主として、本発明によるパターン形成用積層フィルムを保護する機能を有するものであって、例えば、この保護層を感光性樹脂層の表面に配置した場合には、感光性樹脂層を、外部からの衝撃や圧力等によって傷つくのを防止し、湿気やガス、光等によって劣化するのを防止することができる。そして、本発明によるパターン形成用積層フィルムを重ね合わせたり、ロール状に巻き回して貯蔵することを容易にする。 This protective layer mainly has the function of protecting the laminated film for pattern formation according to the present invention. , damage due to impact or pressure from the outside, and deterioration due to humidity, gas, light, or the like can be prevented. In addition, it is easy to store the laminated film for pattern formation according to the present invention by stacking it or winding it into a roll.
　本発明において、保護層としては各種の材料からなるものを用いることができる。例えば、各種の樹脂材料からなるものを用いることができ、また天然素材からなるものも用いることができる。
　保護層の具体的な材質に制限はなく、例えば、支持層と同様の材質を用いることができる。保護層の厚みは特に限定はないが、１～５０μｍであることが好ましい。 In the present invention, various materials can be used as the protective layer. For example, one made of various resin materials can be used, and one made of natural materials can also be used.
There is no specific limitation on the material of the protective layer, and for example, the same material as that of the support layer can be used. Although the thickness of the protective layer is not particularly limited, it is preferably 1 to 50 μm.
　保護層が感光剤層の表面に配置された本発明によるパターン形成用積層フィルムを、例えばスクリーン印刷版に適用する場合には、本発明によるパターン形成用積層フィルムを構成する他の層よりも先に、この保護層を剥離することが行われる。従って、この保護層と感光剤層との間の層間接着力は、他の層間接着力（ｘ）～（ｚ）よりも低いこと（即ち、層間接着力（ｙ）よりも低いこと）が、好ましい。そのため、片面または両面に離型処理が施されたものであってもよい。 When the laminated film for pattern formation according to the present invention, in which the protective layer is arranged on the surface of the photosensitive layer, is applied to, for example, a screen printing plate, the protective layer is applied prior to the other layers constituting the laminated film for pattern formation according to the present invention. Then, the protective layer is peeled off. Therefore, the inter-layer adhesion between this protective layer and the photosensitive layer must be lower than the other inter-layer adhesion (x) to (z) (that is, lower than the inter-layer adhesion (y)). preferable. Therefore, one side or both sides may be subjected to mold release treatment.
　また、透明であっても不透明であってもよい。例えば、紙、離型紙、ポリエチレンテレフタレート等のポリエステル、ポリメチルペンテン、ポリプロピレン、ポリエチレン等のポリオレフィン、ポリフッ化ビニル、ポリ塩化ビニル等のハロゲン含有ビニル重合体、ナイロン等のポリアミド、セロファン等のセルロース、ポリスチレン、アクリル樹脂、ポリイミドなどのフィルムを挙げることができる。また、積層フィルムの機能を失わなければ片面または両面に離型処理、マット処理、易接着処理が施されていてもよい。 Also, it may be transparent or opaque. Examples include paper, release paper, polyesters such as polyethylene terephthalate, polyolefins such as polymethylpentene, polypropylene and polyethylene, halogen-containing vinyl polymers such as polyvinyl fluoride and polyvinyl chloride, polyamides such as nylon, cellulose such as cellophane, and polystyrene. , acrylic resin, and polyimide. In addition, release treatment, matte treatment, or easy-adhesion treatment may be performed on one or both sides of the film as long as the function of the laminated film is not lost.
　＜未感光のスクリーン印刷版（第一の未感光のスクリーン印刷版）＞
　本発明による第一の未感光のスクリーン印刷版は、上記のパターン形成用積層フィルムと、前記パターン形成用積層フィルムの前記感光性樹脂層側に積層されたスクリーンメッシュとを含んでなること、を特徴とする。 <Unexposed screen printing plate (first unexposed screen printing plate)>
A first unexposed screen printing plate according to the present invention comprises the above laminated film for pattern formation and a screen mesh laminated on the photosensitive resin layer side of the laminated film for pattern formation. Characterized by
　図１は、本発明による第一の未感光のスクリーン印刷版８の好ましい具体例を示すものである。図１に示される本発明による好ましい未感光のスクリーン印刷版８は、パターン形成用積層フィルム１（具体的には、支持層２、糊層３、非水溶性高分子層４および感光性樹脂層５が、この順序で構成されてなるパターン形成用積層フィルム１）と、このパターン形成用積層フィルム１の前記感光性樹脂層５側に積層されたスクリーンメッシュ６とを含んでなるものである。ここで、スクリーンメッシュ６は、通常の一般的なスクリーン印刷版と同様に、枠材７に貼設されている。 FIG. 1 shows a preferred specific example of the first unexposed screen printing plate 8 according to the present invention. A preferable unexposed screen printing plate 8 according to the present invention shown in FIG. 5 comprises a pattern-forming laminated film 1) configured in this order and a screen mesh 6 laminated on the photosensitive resin layer 5 side of the pattern-forming laminated film 1). Here, the screen mesh 6 is pasted on the frame material 7 like a normal screen printing plate.
　＜未感光のスクリーン印刷版（第一の未感光のスクリーン印刷版）の製造方法＞
　本発明による未感光のスクリーン印刷版（第一の未感光のスクリーン印刷版）の製造方法は、下記の工程（イ）を含んでなること、を特徴とする。
　工程（イ）：上記のパターン形成用積層フィルムの前記感光性樹脂層側に、スクリーンメッシュを接合する工程
　このスクリーン印刷版の製造方法によれば、例えば図１に示される未感光のスクリーン印刷版８を製造することができる。 <Method for producing unexposed screen printing plate (first unexposed screen printing plate)>
The method for producing an unexposed screen printing plate (first unexposed screen printing plate) according to the present invention is characterized by comprising the following step (a).
Step (a): A step of bonding a screen mesh to the photosensitive resin layer side of the pattern-forming laminated film. 8 can be produced.
　工程（イ）において、パターン形成用積層フィルム１の感光性樹脂層５側に、スクリーンメッシュ６を接合するときは、好ましくは、例えば、（１）スクリーンメッシュ６に、感光性材料（好ましくは、感光性樹脂層５を形成している感光性樹脂と同一ないし類似する感光性材料）または水を予め塗工しておいて、そこにパターン形成用積層フィルム１の感光性樹脂層５を接合する方法、（２）スクリーンメッシュ６に、パターン形成用積層フィルム１の感光性樹脂層５を重ね合わせた後、その重ね合わせ部に感光性樹脂層を形成している感光性樹脂と同一ないし類似する感光性材料または水を塗工する方法を挙げることができる。 In the step (a), when the screen mesh 6 is bonded to the photosensitive resin layer 5 side of the pattern forming laminated film 1, preferably, for example, (1) the screen mesh 6 is coated with a photosensitive material (preferably, A photosensitive material which is the same as or similar to the photosensitive resin forming the photosensitive resin layer 5) or water is applied in advance, and the photosensitive resin layer 5 of the laminated film for pattern formation 1 is bonded thereto. Method (2) After the photosensitive resin layer 5 of the laminated film for pattern formation 1 is superimposed on the screen mesh 6, the same or similar photosensitive resin is used to form a photosensitive resin layer on the superposed portion. Examples include a method of applying a photosensitive material or water.
　＜未感光のスクリーン印刷版（第二の未感光のスクリーン印刷版）＞
　本発明による第二の未感光のスクリーン印刷版の他の好ましい態様（第二の未感光のスクリーン印刷版）は、パターン形成用積層フィルムから前記の支持層および糊層を除いた積層フィルムと、前記の積層フィルムの前記感光性樹脂層側に積層されたスクリーンメッシュとを含んでなること、を特徴とする。 <Unexposed screen printing plate (second unexposed screen printing plate)>
Another preferred embodiment of the second unexposed screen printing plate according to the present invention (second unexposed screen printing plate) comprises a laminated film obtained by removing the support layer and the adhesive layer from the pattern forming laminated film, and a screen mesh laminated on the photosensitive resin layer side of the laminated film.
　図２は、本発明による第二の未感光のスクリーン印刷版９の好ましい具体例を示すものである。
　図２に示される本発明による好ましい未感光のスクリーン印刷版９は、図１に示された未感光のスクリーン印刷版８におけるパターン形成用積層フィルム１から支持層２および糊層３を除いた積層フィルム１’と、前記の積層フィルム１’の前記感光性樹脂層５側に積層されたスクリーンメッシュ６とを含んでなるものである。 FIG. 2 shows a preferred embodiment of the second unexposed screen printing plate 9 according to the invention.
The preferred unexposed screen printing plate 9 according to the present invention shown in FIG. It comprises a film 1' and a screen mesh 6 laminated on the photosensitive resin layer 5 side of the laminated film 1'.
　＜未感光のスクリーン印刷版（第二の未感光のスクリーン印刷版）の製造方法＞
　本発明による未感光のスクリーン印刷版（第二の未感光のスクリーン印刷版）の製造方法は、下記の工程（イ）および工程（ロ）を含んでなること、を特徴とする。
　工程（イ）：前記のパターン形成用積層フィルムの前記感光性樹脂層面側に、スクリーンメッシュを接合する工程
　工程（ロ）：前記のパターン形成用積層フィルムの非水溶性高分子層から、前記の支持層および糊層を剥離する工程
　図２は、このような製造方法で得られた未感光のスクリーン印刷版９の好ましい具体例を示すものである。 <Method for producing unexposed screen printing plate (second unexposed screen printing plate)>
The method for producing an unexposed screen printing plate (second unexposed screen printing plate) according to the present invention is characterized by comprising the following steps (a) and (b).
Step (a): A step of bonding a screen mesh to the photosensitive resin layer side of the laminated film for pattern formation. Step (b): From the water-insoluble polymer layer of the laminated film for pattern formation, the above Step of Peeling Supporting Layer and Adhesive Layer FIG. 2 shows a preferred specific example of an unexposed screen printing plate 9 obtained by such a manufacturing method.
　＜スクリーン印刷版の製造方法＞
　本発明によるスクリーン印刷版の製造方法は、下記の工程（イ）～工程（ヘ）を含んでなること、を特徴とする。
　工程（イ）：前記のパターン形成用積層フィルムの前記感光性樹脂層側に、スクリーンメッシュを接合する工程
　工程（ロ）：前記のパターン形成用積層フィルムの非水溶性高分子層から、前記の支持層および糊層を剥離する工程
　工程（ハ）：前記の非水溶性高分子層の表面にパターンマスクを配置する工程
　工程（ニ）：前記の感光性樹脂層に潜像を形成する工程
　工程（ホ）：前記の非水溶性高分子層を剥離する工程
　工程（ヘ）：前記の潜像が形成された感光性樹脂層を現像する工程。 <Method for producing screen printing plate>
A method for producing a screen printing plate according to the present invention is characterized by comprising the following steps (a) to (f).
Step (a): A step of bonding a screen mesh to the photosensitive resin layer side of the laminated film for pattern formation Step (b): From the water-insoluble polymer layer of the laminated film for pattern formation, the above A step of peeling off the support layer and the adhesive layer Step (c): A step of placing a pattern mask on the surface of the water-insoluble polymer layer Step (d): A step of forming a latent image on the photosensitive resin layer (E): The step of peeling off the water-insoluble polymer layer. Step (F): The step of developing the photosensitive resin layer on which the latent image is formed.
　図３は、本発明によるスクリーン印刷版の製造方法の概要を示す図であって、
　図３Ａは、前記のパターン形成用積層フィルム１の前記感光性樹脂層５側に、スクリーンメッシュ６を接合する工程（イ）の概要を示し、
　図３Ｂは、前記のパターン形成用積層フィルム１の非水溶性高分子層４から、前記の支持層２および糊層３を剥離する工程（ロ）の概要を示し、
　図３Ｃは、前記の非水溶性高分子層４の表面に、パターンマスク１０を配置する工程（ハ）の概要を示し、
　図３Ｄは、前記の感光性樹脂層５に、前記パターンマスク１０面からエネルギー線を照射して、感光性樹脂に潜像αを形成する工程（ニ）の概要を示し、
　図３Ｅは、前記の非水溶性高分子層４を剥離する工程（ホ）の概要を示し、
　図３Ｆは、前記の潜像αが形成された感光性樹脂層５を現像する工程（ヘ）を実施して得られたスクリーン印刷版１１の概要を示している。この工程（ヘ）では、潜像αが形成された感光性樹脂層５を水（例えば、中性水）で洗浄して、感光性樹脂層５の未硬化領域（即ち、潜像αが形成されていない領域）を除去することからなる現像処理が行われる。その後、現像処理物を乾燥することによって、所定の開孔パターンを有するスクリーン印刷版１１を得ることができる。 FIG. 3 is a diagram showing an overview of the method for manufacturing a screen printing plate according to the present invention,
FIG. 3A shows an outline of the step (a) of bonding the screen mesh 6 to the photosensitive resin layer 5 side of the pattern forming laminated film 1,
FIG. 3B shows an outline of the step (b) of peeling off the support layer 2 and the adhesive layer 3 from the water-insoluble polymer layer 4 of the pattern-forming laminated film 1.
FIG. 3C shows an outline of the step (c) of placing a pattern mask 10 on the surface of the water-insoluble polymer layer 4,
FIG. 3D shows an outline of the step (d) of irradiating the photosensitive resin layer 5 with energy rays from the surface of the pattern mask 10 to form a latent image α on the photosensitive resin,
FIG. 3E shows an outline of the step (e) of peeling off the water-insoluble polymer layer 4,
FIG. 3F shows an outline of the screen printing plate 11 obtained by carrying out the step (f) of developing the photosensitive resin layer 5 on which the latent image α is formed. In this step (f), the photosensitive resin layer 5 on which the latent image α is formed is washed with water (for example, neutral water) to form an uncured region of the photosensitive resin layer 5 (that is, the latent image α). A development process consisting of removing the untreated areas) is performed. After that, by drying the developed product, a screen printing plate 11 having a predetermined aperture pattern can be obtained.
　本発明によるパターン形成用積層フィルム１は、非水溶性高分子層３を有しており、この非水溶性高分子層３の表面にパターンマスク１０を配置して、その後、このパターンマスク１０を介してエネルギー線の照射ならびに潜像αの形成が行なわれる。この非水溶性高分子層３により、感光性樹脂層の吸湿や構成成分の移行によるタック性を帯びることを防止することから、非水溶性高分子層３の表面においてマスクパターン１０を位置決めするのが容易である。 A pattern-forming laminated film 1 according to the present invention has a water-insoluble polymer layer 3. A pattern mask 10 is placed on the surface of the water-insoluble polymer layer 3, and then the pattern mask 10 is applied. Energy beam irradiation and formation of a latent image .alpha. The water-insoluble polymer layer 3 prevents the photosensitive resin layer from becoming tacky due to moisture absorption and migration of constituent components. is easy.
　本発明によるスクリーン印刷版によれば、出来上がった印刷版は表面がフラットに仕上がるため、印刷再現性が良好であり、被印刷物との密着も良好なことから、インクが印刷版の裏側に回り込むことを抑制し、版ふき回数の減少を図ることができる。 According to the screen printing plate according to the present invention, the surface of the finished printing plate is finished flat, so the printing reproducibility is good, and the adhesion to the printing material is also good, so the ink does not flow to the back side of the printing plate. can be suppressed, and the number of stencil wipes can be reduced.
　＜感光性レジスト基材＞
　本発明による感光性レジスト基材は、前記のパターン形成用積層フィルムと、前記パターン形成用積層フィルムの前記感光性樹脂層側に積層された基材とを含んでなること、を特徴とする。 <Photosensitive resist base material>
A photosensitive resist base material according to the present invention is characterized by comprising the above laminated film for pattern formation and a base material laminated on the photosensitive resin layer side of the laminated film for pattern formation.
　感光性樹脂層側に積層される基材としては、各種の材料からなるものを用いることができる。例えば木、石、織物、紙、セラミックス、ガラス、酢酸セルロースやポリエステル、ポリオレフィン、ポリイミド、エポキシ樹脂のような合成樹脂、ガラス繊維強化樹脂、アルミニウム、銅、ニッケル、鉄、亜鉛、マグネジウム、コバルトのような金属、シリコン、ガリウムヒ素ゲルマニウムなどの半導体材料、窒化ケイ素、酸化ケイ素などの絶縁材料を挙げることができる。 Various materials can be used as the base material laminated on the photosensitive resin layer side. For example, wood, stone, textiles, paper, ceramics, glass, synthetic resins such as cellulose acetate and polyester, polyolefins, polyimides, epoxy resins, glass fiber reinforced resins, aluminum, copper, nickel, iron, zinc, magnesium, cobalt, etc. metals, semiconductor materials such as silicon and gallium arsenide germanium, and insulating materials such as silicon nitride and silicon oxide.
　この本発明による感光性レジスト基材は中性水で現像できる感光性樹脂であるので、現像液に溶剤やアルカリ水溶液を使用しないという点で従来の感光性レジスト基材よりも環境面・作業面で有利である。 Since the photosensitive resist base material according to the present invention is a photosensitive resin that can be developed with neutral water, it is more environmentally friendly and work-friendly than conventional photosensitive resist base materials in that no solvent or alkaline aqueous solution is used in the developer. is advantageous.
　スクリーンメッシュ以外にも金属やガラス等の基材にこのパターン形成用積層フィルムを接合することで感光性レジスト基材を得ることができる。従来の有機溶剤含有型樹脂とは異なり、溶媒に中性水を使用しているため環境汚染が低い。現像も有機溶剤やアルカリ水を使用せず中性水で可能なことから、環境面・作業面・現像液の保管・処理などの点からも有利である。また基材によっては有機溶剤やアルカリにより変色、変形などしてしまうものがあり、中性水で現像できることで幅広い基材が選択できる。 In addition to the screen mesh, a photosensitive resist base material can be obtained by bonding this pattern-forming laminated film to a base material such as metal or glass. Unlike conventional organic solvent-containing resins, the use of neutral water as a solvent causes less environmental pollution. Since development can be done with neutral water without using organic solvents or alkaline water, it is advantageous from the viewpoints of environment, workability, storage and treatment of developer. In addition, depending on the base material, there are some that are discolored or deformed by organic solvents or alkalis, and a wide range of base materials can be selected because they can be developed with neutral water.
　＜実施例１＞
　パターン形成用積層フィルムの作製
　支持層として厚み７５μｍのポリエチレンテレフタレートフィルムを用意し、その上にエチレン‐酢酸ビニル系エマルジョンタイプの粘着剤をバーコーターにより塗工し、１００℃３分加熱乾燥することで、厚み１０μｍの糊層を形成した。さらに、その上に非水溶性の高分子からなる層として厚み６μｍのポリエチレンテレフタレートフィルムをラミネーターによって貼り合わせた。
　続いて、上述の成分（Ａ）および成分（Ｂ）（Ｆ）（Ｇ）（Ｈ）からなる感光性樹脂１をバーコーターにより塗工し、４０℃３０分加熱乾燥することで、厚み２０μｍの感光性樹脂層を形成し、これによりパターン形成用積層フィルムを得た。 <Example 1>
A polyethylene terephthalate film having a thickness of 75 μm was prepared as a support layer for producing a laminated film for pattern formation, and an ethylene-vinyl acetate emulsion type adhesive was applied thereon using a bar coater, followed by heating and drying at 100° C. for 3 minutes. , a glue layer having a thickness of 10 μm was formed. Furthermore, a polyethylene terephthalate film having a thickness of 6 μm was laminated thereon as a layer composed of a water-insoluble polymer using a laminator.
Subsequently, the photosensitive resin 1 consisting of the above components (A) and components (B), (F), (G), and (H) was coated with a bar coater and dried by heating at 40° C. for 30 minutes to obtain a film having a thickness of 20 μm. A photosensitive resin layer was formed to obtain a laminated film for pattern formation.
　＜実施例２＞
　実施例１の感光性樹脂層を形成した後、その上に保護層として厚み２５μｍのポリエチレンフィルムを貼り合わせた以外は実施例１と同様にしてパターン形成用積層フィルムを作製した。 <Example 2>
After forming the photosensitive resin layer of Example 1, a laminated film for pattern formation was produced in the same manner as in Example 1, except that a polyethylene film having a thickness of 25 μm was laminated thereon as a protective layer.
　＜実施例３＞
　糊層にアクリル系粘着剤、Ｃ）非水溶性の高分子からなる層に厚み１２μｍのポリオレフィンフィルムを使用した以外は実施例１と同様にしてパターン形成用積層フィルムを作製した。 <Example 3>
A laminated film for pattern formation was produced in the same manner as in Example 1, except that an acrylic pressure-sensitive adhesive was used for the glue layer and a polyolefin film having a thickness of 12 μm was used for the layer C) composed of a water-insoluble polymer.
　＜比較例１＞
　パターン形成用積層フィルムの作製
　支持層として厚み７５μｍのポリエチレンテレフタレートフィルムを用意し、その上にポリビニルアルコール（クラレ株式会社製クラレポバール９５－８８）の５．０質量％水溶液をバーコーターにより塗工し、４０℃３０分加熱乾燥することで、厚み５μｍの水溶性の高分子からなる層を形成した。さらにその上に、上述の成分（Ａ）および成分（Ｂ）（Ｆ）（Ｇ）（Ｈ）からなる感光性樹脂１をバーコーターにより塗工し、４０℃３０分加熱乾燥することで、厚み２０μｍの感光性樹脂層を形成し、これによりパターン形成用積層フィルムを得た。 <Comparative Example 1>
A polyethylene terephthalate film having a thickness of 75 μm was prepared as a support layer for producing a laminated film for pattern formation, and a 5.0% by mass aqueous solution of polyvinyl alcohol (Kuraray Poval 95-88 manufactured by Kuraray Co., Ltd.) was coated thereon using a bar coater. , and dried at 40°C for 30 minutes to form a water-soluble polymer layer having a thickness of 5 µm. Further thereon, a photosensitive resin 1 consisting of the components (A) and components (B), (F), (G), and (H) described above is coated with a bar coater and dried by heating at 40° C. for 30 minutes to obtain a thickness. A 20 μm thick photosensitive resin layer was formed to obtain a laminated film for pattern formation.
　＜比較例２＞
　水溶性の高分子からなる層としてフッ素化合物含有樹脂（株式会社ムラカミ製ＳＰ－２０５０ＵＣジアゾ樹脂未添加）を使用した以外は比較例１と同様にしてパターン形成用積層フィルムを作製した。 <Comparative Example 2>
A laminated film for pattern formation was produced in the same manner as in Comparative Example 1, except that a fluorine compound-containing resin (SP-2050UC diazo resin manufactured by Murakami Co., Ltd. was not added) was used as the layer composed of a water-soluble polymer.
　＜比較例３＞
　支持層として厚み７５μｍのポリエチレンテレフタレートフィルムを用意し、その上に、上述の成分（Ａ）および成分（Ｂ）（Ｆ）（Ｇ）（Ｈ）からなる感光性樹脂１をバーコーターにより塗工し、４０℃３０分加熱乾燥することで、厚み２０μｍの感光性樹脂層を形成し、これによりパターン形成用フィルムを得た。 <Comparative Example 3>
A polyethylene terephthalate film having a thickness of 75 μm was prepared as a support layer, and a photosensitive resin 1 comprising the above components (A), (B), (F), (G) and (H) was coated thereon by a bar coater. and dried at 40° C. for 30 minutes to form a photosensitive resin layer having a thickness of 20 μm, thereby obtaining a film for pattern formation.
　＜評価方法１＞
　アルミニウム枠に固定したポリエステル繊維製メッシュに、上述の成分（Ａ）および成分（Ｂ）（Ｆ）（Ｇ）（Ｈ）からなる感光性樹脂１をステンレス鋼製バケットを用いて塗工し、上記で作製したパターン形成用積層フィルムの感光性樹脂層側を貼り合わせた。実施例２で作製したパターン形成用積層フィルムは貼り合わせる直前に、保護層を剥がしてから感光性樹脂層側を貼り合わせた。４０℃３０分乾燥させた後、支持層を剥がした。実施例１、２、３で作製したパターン形成用積層フィルムは支持層を剥がす際に同時に糊層も剥がした。 <Evaluation method 1>
A polyester fiber mesh fixed to an aluminum frame is coated with a photosensitive resin 1 consisting of the above components (A) and components (B) (F) (G) (H) using a stainless steel bucket. The photosensitive resin layer side of the laminated film for pattern formation prepared in 1. was pasted together. Immediately before lamination of the laminated film for pattern formation prepared in Example 2, the protective layer was peeled off and the photosensitive resin layer side was laminated. After drying for 30 minutes at 40° C., the support layer was peeled off. In the laminated films for pattern formation prepared in Examples 1, 2 and 3, the glue layer was also peeled off at the same time as the support layer was peeled off.
　次に、パターンマスクを重ねて、真空引きし、光源として３ｋＷのメタルハライドランプを用い、光源と版表面との距離１ｍ、照射時間２分の条件で、感光性樹脂層を露光した。続いて、パターンマスクを取り除いた後、水道水を用いて樹脂層を現像した。これにより、スクリーン印刷版を得た。
　実施例１、２、３においては現像前に非水溶性高分子層を除去してから現像をおこなった。 Next, a pattern mask was overlaid, vacuum was applied, and a 3 kW metal halide lamp was used as a light source, and the photosensitive resin layer was exposed under the conditions of a distance of 1 m between the light source and the plate surface and an irradiation time of 2 minutes. Subsequently, after removing the pattern mask, the resin layer was developed using tap water. A screen printing plate was thus obtained.
In Examples 1, 2 and 3, development was carried out after removing the water-insoluble polymer layer before development.
　表面タック性１
　パターンマスクを重ね合わせたときのパターンマスクの位置合わせのし易さにより、Ａ～Ｃで評価した。
Ａ：パターンマスクをスムーズに動かすことができ、位置合わせがし易い。
Ｂ：パターンマスクをスムーズに動かすことができず、位置合わせがし難い。
Ｃ：パターンマスクが表面に張り付いてしまい、位置合わせができない。 Surface tackiness 1
Evaluations were made from A to C according to the easiness of alignment of the pattern masks when the pattern masks were superimposed.
A: The pattern mask can be moved smoothly and alignment is easy.
B: The pattern mask cannot be moved smoothly and alignment is difficult.
C: The pattern mask sticks to the surface and alignment cannot be performed.
　表面タック性２
　真空露光した後のパターンマスクの剥がし易さにより、Ａ～Ｃで評価した。
Ａ：パターンマスクを剥がす際に抵抗なく、容易に剥がすことができた。
Ｂ：パターンマスクを剥がす際に抵抗があり、スムーズに剥がせなかった。
Ｃ：パターンマスクが表面に張り付いてしまい、表面の一部が破損してしまった。 Surface tackiness 2
Evaluation was made from A to C according to the ease of peeling of the pattern mask after vacuum exposure.
A: The pattern mask was easily peeled off without resistance.
B: There was resistance when peeling the pattern mask, and it could not be peeled off smoothly.
C: The pattern mask stuck to the surface, and a part of the surface was damaged.
　表面状態
　現像後のスクリーン印刷版の表面状態により、○～×で評価した。
　　○：感光性樹脂層の表面に何も残っていない。
　　×：感光性樹脂層の表面に別の成分が残存している。 The surface condition of the screen printing plate after development was evaluated on a scale of ◯ to ×.
◯: Nothing remained on the surface of the photosensitive resin layer.
x: Another component remains on the surface of the photosensitive resin layer.
評価結果を表１に示す。 Table 1 shows the evaluation results.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　＜実施例４＞
　パターン形成用積層フィルムの作製
　支持層として厚み７５μｍのポリエチレンテレフタレートフィルムを用意し、その上にシリコーン系の粘着剤をバーコーターにより塗工し、１００℃３分加熱乾燥することで、厚み５μｍの糊層を形成した。さらに、その上に非水溶性の高分子からなる層として厚み１２μｍのポリオレフィンフィルムをラミネーターによって貼り合わせた。
　続いて、上述の成分（Ｅ）および成分（Ｆ）（Ｇ）（Ｈ）からなる感光性樹脂２をバーコーターにより塗工し、４０℃３０分加熱乾燥することで、厚み３０μｍの感光性樹脂層を形成し、これによりパターン形成用積層フィルムを得た。 <Example 4>
Preparation of laminated film for pattern formation A polyethylene terephthalate film with a thickness of 75 µm was prepared as a support layer, and a silicone-based pressure-sensitive adhesive was applied thereon using a bar coater, followed by heating and drying at 100°C for 3 minutes to obtain an adhesive with a thickness of 5 µm. formed a layer. Furthermore, a polyolefin film having a thickness of 12 μm was laminated thereon as a layer composed of a water-insoluble polymer using a laminator.
Subsequently, the photosensitive resin 2 composed of the components (E) and components (F), (G), and (H) described above was coated with a bar coater and dried by heating at 40° C. for 30 minutes to obtain a photosensitive resin having a thickness of 30 μm. Layers were formed to obtain a laminated film for pattern formation.
　＜実施例５＞
　糊層にエチレン‐酢酸ビニル系エマルジョンタイプの粘着剤を使用した以外は実施例４と同様にしてパターン形成用積層フィルムを作製した。 <Example 5>
A laminated film for pattern formation was produced in the same manner as in Example 4, except that an ethylene-vinyl acetate emulsion type adhesive was used for the glue layer.
　＜実施例６＞
　糊層にウレタン系粘着剤を使用した以外は実施例４と同様にしてパターン形成用積層フィルムを作製した。 <Example 6>
A laminated film for pattern formation was produced in the same manner as in Example 4, except that a urethane adhesive was used for the glue layer.
　＜実施例７＞
　糊層にアクリル系粘着剤を使用した以外は実施例４と同様にしてパターン形成用積層フィルムを作製した。 <Example 7>
A laminated film for pattern formation was produced in the same manner as in Example 4, except that an acrylic pressure-sensitive adhesive was used for the glue layer.
　＜比較例４＞
　パターン形成用積層フィルムの作製
　非水溶性の高分子からなる層として厚み２５μｍのポリエステルフィルムにシリコーン離型処理を片面に施した離型フィルムを使用した以外は実施例４と同様にしてパターン形成用積層フィルムを作製した。離型フィルムはシリコーン離型処理面を感光性樹脂層側に貼り合わせた。 <Comparative Example 4>
Preparation of laminated film for pattern formation The pattern formation was performed in the same manner as in Example 4, except that a release film obtained by subjecting a polyester film having a thickness of 25 μm to one side to a silicone release treatment was used as the layer composed of a water-insoluble polymer. A laminated film was produced. The release film was laminated with the silicone release-treated surface on the side of the photosensitive resin layer.
　＜比較例５＞
　支持層として厚み７５μｍのポリエステルフィルムにシリコーン離型処理を片面に施した離型フィルムを使用した以外は実施例５と同様にしてパターン形成用積層フィルムを作製した。離型フィルムはシリコーン離型処理面を糊層側に貼り合わせた。 <Comparative Example 5>
A laminated film for pattern formation was produced in the same manner as in Example 5, except that a release film obtained by subjecting a polyester film having a thickness of 75 μm to a silicone release treatment on one side was used as the support layer. The release film was laminated with the silicone release-treated surface on the adhesive layer side.
　＜比較例６＞
　非水溶性の高分子からなる層として厚み２５μｍのポリエステルフィルムに片面コロナ放電処理を施した易接着フィルムを使用した以外は実施例６と同様にしてパターン形成用積層フィルムを作製した。易接着フィルムはコロナ処理面を糊層側に貼り合わせた。 <Comparative Example 6>
A laminated film for pattern formation was produced in the same manner as in Example 6, except that an easy-adhesive film obtained by subjecting a 25 μm-thick polyester film to one-sided corona discharge treatment was used as the layer composed of a water-insoluble polymer. The easy-adhesive film was laminated with the corona-treated surface on the adhesive layer side.
　＜比較例７＞
　感光性樹脂層に上述の成分（Ａ）および成分（Ｂ）（Ｈ）からなる感光性樹脂３を使用した以外は実施例７と同様にしてパターン形成用積層フィルムを作製した。 <Comparative Example 7>
A laminated film for pattern formation was produced in the same manner as in Example 7, except that the photosensitive resin 3 composed of the above components (A), (B) and (H) was used for the photosensitive resin layer.
　＜評価方法２＞
　アルミニウム枠に固定したポリエステル繊維製メッシュに、各パターン形成用フィルムに使用した感光性樹脂をステンレス鋼製バケットを用いて塗工し、上記で作製したパターン形成用積層フィルムの感光性樹脂層側を貼り合わせた。４０℃３０分乾燥させて、試験版を得た。
　２５℃５０％環境下に２４時間保管した後、支持層にセロハンテープを貼り付け、上部へ引っ張るように剥がしたとき、界面１～３のどこで剥がれるかを確認した。
　界面１　支持層／糊層
　界面２　糊層／非水溶性高分子層
　界面３　非水溶性高分子層／感光性樹脂層
　　○：界面２で剥がれ、非水溶性高分子層上に糊層が残留していない。
　　 ×：界面２以外で剥がれる。 <Evaluation method 2>
The polyester fiber mesh fixed to the aluminum frame was coated with the photosensitive resin used for each pattern forming film using a stainless steel bucket, and the photosensitive resin layer side of the pattern forming laminate film prepared above was coated. pasted together. After drying at 40°C for 30 minutes, a test plate was obtained.
After storage for 24 hours in a 25° C. 50% environment, a cellophane tape was attached to the support layer, and when the tape was pulled upward and peeled off, it was confirmed at which interface 1 to 3 the tape would be peeled off.
Interface 1: support layer/glue layer Interface 2: glue layer/water-insoluble polymer layer Interface 3: water-insoluble polymer layer/photosensitive resin layer ○: Peeled off at interface 2, glue layer remaining on water-insoluble polymer layer not.
x: It peels off except the interface 2.
評価結果を下記表２に示す。 The evaluation results are shown in Table 2 below.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　＜実施例８＞
　パターン形成用積層フィルムの作製
　支持層として厚み７５μｍのポリエチレンテレフタレートフィルムを用意し、その上にシリコーン系粘着剤をバーコーターにより塗工し、１００℃３分加熱乾燥することで、厚み３μｍの糊層を形成した。さらに、その上に非水溶性の高分子からなる層として厚み１２μｍ、ヘイズ値０．３％のポリオレフィンフィルムをラミネーターによって貼り合わせた。 <Example 8>
Preparation of laminated film for pattern formation A polyethylene terephthalate film with a thickness of 75 μm was prepared as a support layer, and a silicone-based pressure-sensitive adhesive was applied thereon using a bar coater and dried by heating at 100° C. for 3 minutes to form a glue layer with a thickness of 3 μm. formed. Furthermore, a polyolefin film having a thickness of 12 μm and a haze value of 0.3% was laminated thereon as a layer composed of a water-insoluble polymer using a laminator.
　続いて、上述の成分（Ａ）および成分（Ｂ）（Ｆ）（Ｇ）からなる感光性樹脂４をバーコーターにより塗工し、４０℃３０分加熱乾燥することで、厚み１５μｍの感光性樹脂層を形成し、これによりパターン形成用積層フィルムを得た。 Subsequently, the photosensitive resin 4 composed of the components (A) and components (B), (F), and (G) described above was coated with a bar coater and dried by heating at 40° C. for 30 minutes to obtain a photosensitive resin having a thickness of 15 μm. Layers were formed to obtain a laminated film for pattern formation.
　さらに、アルミニウム枠に固定したステンレス繊維製メッシュに、各パターン形成用フィルムに使用した感光性樹脂をステンレス鋼製バケットを用いて塗工し、上記で作製したパターン形成用積層フィルムの感光性樹脂層側を貼り合わせた。４０℃３０分乾燥させて、支持層及び糊層を剥離した。 Furthermore, the stainless steel fiber mesh fixed to the aluminum frame is coated with the photosensitive resin used for each pattern forming film using a stainless steel bucket, and the photosensitive resin layer of the laminated film for pattern forming prepared above. glued the sides together. After drying at 40° C. for 30 minutes, the support layer and glue layer were peeled off.
　次に、パターンマスクを、非水溶性高分子層に重ねて、真空引きし、光源として３ｋＷのメタルハライドランプを用い、光源と版表面との距離１ｍ、照射時間２分、３分、４分、５分の条件で、感光性樹脂層を露光した。
　続いて、パターンマスクを取り除いた後、水道水を用いて樹脂層を現像した。これにより、スクリーン印刷版を得た。 Next, a pattern mask is superimposed on the water-insoluble polymer layer, vacuumed, a metal halide lamp of 3 kW is used as a light source, the distance between the light source and the plate surface is 1 m, the irradiation time is 2 minutes, 3 minutes, 4 minutes, The photosensitive resin layer was exposed for 5 minutes.
Subsequently, after removing the pattern mask, the resin layer was developed using tap water. A screen printing plate was thus obtained.
　＜実施例９＞
　非水溶性高分子層に厚み５０μｍ、ヘイズ値１．０％の高透明ポリエチレンテレフタレートフィルムを使用した以外は実施例８と同様にしてスクリーン印刷版を得た。 <Example 9>
A screen printing plate was obtained in the same manner as in Example 8, except that a highly transparent polyethylene terephthalate film having a thickness of 50 μm and a haze value of 1.0% was used as the water-insoluble polymer layer.
　＜実施例１０＞
　感光性樹脂層に上述の成分（Ａ）および成分（Ｃ）（Ｄ）からなる感光性樹脂５を使用した以外は実施例８と同様にしてスクリーン印刷版を得た。 <Example 10>
A screen printing plate was obtained in the same manner as in Example 8, except that the photosensitive resin layer 5 consisting of the above components (A), (C) and (D) was used.
　＜比較例８＞
　非水溶性高分子層に厚み３０μｍ、ヘイズ値６％のポリオレフィンフィルムを使用した以外は実施例８と同様にしてスクリーン印刷版を得た。 <Comparative Example 8>
A screen printing plate was obtained in the same manner as in Example 8 except that a polyolefin film having a thickness of 30 μm and a haze value of 6% was used as the water-insoluble polymer layer.
　＜比較例９＞
　非水溶性高分子層に厚み２５μｍ、ヘイズ値５．７％の汎用ポリエチレンテレフタレートフィルムを使用した以外は実施例８と同様にしてパターン形成用積層フィルムを作製した。 <Comparative Example 9>
A laminated film for pattern formation was produced in the same manner as in Example 8, except that a general-purpose polyethylene terephthalate film having a thickness of 25 μm and a haze value of 5.7% was used as the water-insoluble polymer layer.
　＜比較例１０＞
　非水溶性高分子層に厚み１２５μｍ、ヘイズ値１．５％のポリオレフィンフィルムを使用した以外は実施例１０と同様にしてパターン形成用積層フィルムを作製した。 <Comparative Example 10>
A laminated film for pattern formation was produced in the same manner as in Example 10, except that a polyolefin film having a thickness of 125 μm and a haze value of 1.5% was used as the water-insoluble polymer layer.
　＜評価方法３＞
　得られたスクリーン印刷版のパターンを１００倍ルーペで確認し、感度と解像性を決定した。
　感度：ステップタブレット７段以上の最短露光時間を感度とした。
　解像性：上記で決定した感度で解像したＬ／Ｓの最狭幅(μｍ)を解像性とした。
　評価結果を下記表３に示す。 <Evaluation method 3>
The pattern of the obtained screen printing plate was confirmed with a 100x magnifying glass to determine the sensitivity and resolution.
Sensitivity: The sensitivity was defined as the shortest exposure time of 7 steps or more of the step tablet.
Resolution: The resolution was defined as the narrowest width (μm) of L/S resolved with the sensitivity determined above.
The evaluation results are shown in Table 3 below.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
１：パターン形成用積層フィルム、２：支持層、３：糊層、４：非水溶性高分子層、５感光性樹脂層、６：スクリーンメッシュ、７：枠材、８：第一の未感光のスクリーン印刷版、９：第二の未感光のスクリーン印刷版、１’：積層フィルム、１０：パターンマスク、１１：スクリーン印刷版 1: laminated film for pattern formation, 2: support layer, 3: glue layer, 4: water-insoluble polymer layer, 5: photosensitive resin layer, 6: screen mesh, 7: frame material, 8: first unexposed film screen printing plate, 9: second unexposed screen printing plate, 1′: laminated film, 10: pattern mask, 11: screen printing plate

Claims (17)

  1. 　支持層、糊層、非水溶性高分子層および感光性樹脂層が、この順序で構成されてなることを特徴とする、パターン形成用積層フィルム。 A laminated film for pattern formation characterized by comprising a support layer, a glue layer, a water-insoluble polymer layer and a photosensitive resin layer in this order.
  2. 　前記の感光性樹脂層が、中性水で現像が可能な感光性樹脂である、請求項１に記載のパターン形成用積層フィルム。 The laminated film for pattern formation according to claim 1, wherein the photosensitive resin layer is a photosensitive resin that can be developed with neutral water.
  3. 　前記の支持層と糊層との間の層間接着力（ｘ）、前記の糊層と非水溶性高分子層との間の層間接着力（ｙ）、および前記の非水溶性高分子層と感光性樹脂層との間の層間接着力（ｚ）は、下記の関係にある、請求項１または２に記載のパターン形成用積層フィルム。
    　　　　　　　　　層間接着力（ｘ）　＞　層間接着力（ｙ）
    　　　　　　　　　層間接着力（ｚ）　＞　層間接着力（ｙ）     Interlayer adhesion (x) between the support layer and the glue layer, interlayer adhesion (y) between the glue layer and the water-insoluble polymer layer, and with the water-insoluble polymer layer 3. The laminated film for pattern formation according to claim 1, wherein the interlayer adhesive strength (z) with the photosensitive resin layer has the following relationship.
    Interlayer adhesive strength (x) > Interlayer adhesive strength (y)
    Interlayer adhesion (z) > Interlayer adhesion (y)
  4. 　前記の糊層と非水溶性高分子層との間の層間接着力（ｙ）は、０．００１～１．０Ｎ／２５ｍｍである、請求項１～３のいずれか１項に記載のパターン形成用積層フィルム。 The pattern formation according to any one of claims 1 to 3, wherein the interlayer adhesion (y) between the glue layer and the water-insoluble polymer layer is 0.001 to 1.0 N/25 mm. laminated film for.
  5. 　前記の非水溶性高分子層のヘイズ値が５．０％以下である、請求項１～４のいずれか１項に記載のパターン形成用積層フィルム。 The laminated film for pattern formation according to any one of claims 1 to 4, wherein the water-insoluble polymer layer has a haze value of 5.0% or less.
  6. 　前記の非水溶性高分子層は、厚さが１～１００μｍである、請求項１～５のいずれか１項に記載のパターン形成用積層フィルム。 The laminated film for pattern formation according to any one of claims 1 to 5, wherein the water-insoluble polymer layer has a thickness of 1 to 100 µm.
  7. 　前記の感光性樹脂層は、下記の成分（Ａ）および成分（Ｂ）を含んでなる感光性樹脂からなる、請求項１～６のいずれか１項に記載のパターン形成用積層フィルム。
    　成分（Ａ）：けん化度５０モル％以上のポリビニルアルコール
    　成分（Ｂ）：ジアゾ樹脂     The laminated film for pattern formation according to any one of claims 1 to 6, wherein the photosensitive resin layer comprises a photosensitive resin containing the following components (A) and (B).
    Component (A): Polyvinyl alcohol with a degree of saponification of 50 mol% or more Component (B): Diazo resin
  8. 　前記の感光性樹脂層は、下記の成分（Ａ）、成分（Ｃ）および成分（Ｄ）を含んでなる感光性樹脂からなる、請求項１～６のいずれか１項に記載のパターン形成用積層フィルム。
    　成分（Ａ）：けん化度５０モル％以上のポリビニルアルコール
    　成分（Ｃ）：少なくとも一つのエポキシ基を有するエポキシ化合物
    　成分（Ｄ）：光酸発生剤     7. The pattern forming method according to any one of claims 1 to 6, wherein the photosensitive resin layer is made of a photosensitive resin containing the following components (A), (C) and (D): laminated film.
    Component (A): Polyvinyl alcohol having a degree of saponification of 50 mol% or more Component (C): Epoxy compound having at least one epoxy group Component (D): Photoacid generator
  9. 　前記の感光性樹脂層は、下記の成分（Ｅ）を含んでなる感光性樹脂からなる、請求項１～６のいずれか１項に記載のパターン形成用積層フィルム。
    　成分（Ｅ）：スチリル置換されたピリジニウム基またはスチリル置換されたキノリニウム基を有するけん化度５０モル％以上のポリビニルアルコール     The laminated film for pattern formation according to any one of claims 1 to 6, wherein the photosensitive resin layer comprises a photosensitive resin containing the following component (E).
    Component (E): Polyvinyl alcohol having a styryl-substituted pyridinium group or a styryl-substituted quinolinium group and having a degree of saponification of 50 mol% or more
  10. 　前記の感光性樹脂層は、下記の成分（Ｆ）および成分（Ｇ）をさらに含んでなる感光性樹脂からなる、請求項７～９のいずれか１項に記載のパターン形成用積層フィルム。
    　成分（Ｆ）：少なくとも一つのエチレン性不飽和結合を有するラジカル重合性化合物
    　成分（Ｇ）：光ラジカル重合開始剤     10. The laminated film for pattern formation according to any one of claims 7 to 9, wherein the photosensitive resin layer is made of a photosensitive resin further containing component (F) and component (G) below.
    Component (F): Radically polymerizable compound having at least one ethylenically unsaturated bond Component (G): Radical photopolymerization initiator
  11. 　前記の感光性樹脂層は、下記の成分（Ｈ）をさらに含んでなる感光性樹脂からなる、請求項７～１０のいずれか１項に記載のパターン形成用積層フィルム。
    　成分（Ｈ）：水性ポリマーエマルジョン     The laminated film for pattern formation according to any one of claims 7 to 10, wherein the photosensitive resin layer is made of a photosensitive resin further containing the following component (H).
    Component (H): Aqueous polymer emulsion
  12. 　前記のパターン形成用積層フィルムの感光性樹脂層側に、さらに保護層が積層されてなる、請求項１～１１のいずれか１項に記載のパターン形成用積層フィルム。 The laminated film for pattern formation according to any one of claims 1 to 11, wherein a protective layer is further laminated on the photosensitive resin layer side of the laminated film for pattern formation.
  13. 　請求項１～１１のいずれか１項に記載のパターン形成用積層フィルムから前記の支持層および糊層を除いた積層フィルムと、前記の積層フィルムの感光性樹脂層側に積層されたスクリーンメッシュとを含んでなることを特徴とする、未感光のスクリーン印刷版。 A laminated film obtained by removing the support layer and the glue layer from the laminated film for pattern formation according to any one of claims 1 to 11, and a screen mesh laminated on the photosensitive resin layer side of the laminated film. An unexposed screen printing plate comprising:
  14. 　下記の工程（イ）および工程（ロ）を含んでなることを特徴とする、未感光のスクリーン印刷版の製造方法。
    　工程（イ）：請求項１～１１のいずれか１項に記載のパターン形成用積層フィルムの前記感光性樹脂層側に、スクリーンメッシュを接合する工程
    　工程（ロ）：前記のパターン形成用積層フィルムの非水溶性高分子層から、前記の支持層および糊層を剥離する工程     A method for producing an unexposed screen printing plate, comprising the following steps (a) and (b).
    Step (a): A step of bonding a screen mesh to the photosensitive resin layer side of the laminated film for pattern formation according to any one of Claims 1 to 11. Step (b): The laminated film for pattern formation. The step of peeling off the support layer and glue layer from the water-insoluble polymer layer of
  15. 　請求項１～１１のいずれか１項に記載のパターン形成用積層フィルムから前記の支持層および糊層を除いた積層フィルムと、前記の積層フィルムの感光性樹脂層側に積層されたスクリーンメッシュとを含んでなる未感光のスクリーン印刷版に、潜像を形成し感光性樹脂層を現像してなることを特徴とする、スクリーン印刷版。 A laminated film obtained by removing the support layer and the glue layer from the laminated film for pattern formation according to any one of claims 1 to 11, and a screen mesh laminated on the photosensitive resin layer side of the laminated film. A screen printing plate, which is obtained by forming a latent image on an unexposed screen printing plate containing and developing a photosensitive resin layer.
  16. 　下記の工程（イ）～工程（ヘ）を含んでなることを特徴とする、スクリーン印刷版の製造方法。
    　工程（イ）：請求項１～１１のいずれか１項に記載のパターン形成用積層フィルムの前記感光性樹脂層側に、スクリーンメッシュを接合する工程
    　工程（ロ）：前記のパターン形成用積層フィルムの非水溶性高分子層から、前記の支持層および糊層を剥離する工程
    　工程（ハ）：前記の非水溶性高分子層の表面にパターンマスクを配置する工程
    　工程（ニ）：前記の感光性樹脂層に潜像を形成する工程
    　工程（ホ）：前記の非水溶性高分子層を剥離する工程
    　工程（ヘ）：前記の潜像が形成された感光性樹脂層を現像する工程     A method for producing a screen printing plate, comprising the following steps (a) to (f).
    Step (a): A step of bonding a screen mesh to the photosensitive resin layer side of the laminated film for pattern formation according to any one of Claims 1 to 11. Step (b): The laminated film for pattern formation. A step of peeling off the support layer and the glue layer from the water-insoluble polymer layer Step (c): A step of placing a pattern mask on the surface of the water-insoluble polymer layer Step (d): The photosensitive step (e): step of peeling off the water-insoluble polymer layer step (f): step of developing the photosensitive resin layer on which the latent image is formed
  17. 　請求項１～１１のいずれか１項に記載のパターン形成用積層フィルムと、前記パターン形成用積層フィルムの前記感光性樹脂層側に積層された基材とを含んでなることを特徴とする、感光性レジスト基材。 The laminated film for pattern formation according to any one of claims 1 to 11, and a substrate laminated on the photosensitive resin layer side of the laminated film for pattern formation, Photosensitive resist base.
PCT/JP2021/029866 2021-04-06 2021-08-16 Layered film for pattern formation, non-photosensitive screen printing plate, and method for manufacturing same WO2022215283A1 (en)

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