TWI831047B - Laminated films for pattern formation, unsensitized screen printing plates, their manufacturing methods, and photoresist substrates - Google Patents

Laminated films for pattern formation, unsensitized screen printing plates, their manufacturing methods, and photoresist substrates Download PDF

Info

Publication number
TWI831047B
TWI831047B TW110133300A TW110133300A TWI831047B TW I831047 B TWI831047 B TW I831047B TW 110133300 A TW110133300 A TW 110133300A TW 110133300 A TW110133300 A TW 110133300A TW I831047 B TWI831047 B TW I831047B
Authority
TW
Taiwan
Prior art keywords
layer
photosensitive resin
laminated film
component
pattern
Prior art date
Application number
TW110133300A
Other languages
Chinese (zh)
Other versions
TW202240296A (en
Inventor
安達大作
近江護
岩田修次
大上豊司
宮下直己
Original Assignee
日商村上股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日商村上股份有限公司 filed Critical 日商村上股份有限公司
Publication of TW202240296A publication Critical patent/TW202240296A/en
Application granted granted Critical
Publication of TWI831047B publication Critical patent/TWI831047B/en

Links

Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/016Diazonium salts or compounds
    • G03F7/021Macromolecular diazonium compounds; Macromolecular additives, e.g. binders
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41CPROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00Forme preparation
    • B41C1/14Forme preparation for stencil-printing or silk-screen printing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41NPRINTING 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
    • B41N1/00Printing plates or foils; Materials therefor
    • B41N1/24Stencils; Stencil materials; Carriers therefor
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/016Diazonium salts or compounds
    • G03F7/021Macromolecular diazonium compounds; Macromolecular additives, e.g. binders
    • G03F7/0212Macromolecular 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
    • G03F7/0215Natural gums; Proteins, e.g. gelatins; Macromolecular carbohydrates, e.g. cellulose; Polyvinyl alcohol and derivatives thereof, e.g. polyvinylacetals
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031Organic compounds not covered by group G03F7/029
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/09Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/09Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/12Production of screen printing forms or similar printing forms, e.g. stencils
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20Exposure; Apparatus therefor
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26Processing photosensitive materials; Apparatus therefor
    • G03F7/30Imagewise removal using liquid means
    • G03F7/32Liquid compositions therefor, e.g. developers

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Manufacturing & Machinery (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Materials For Photolithography (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Manufacture Or Reproduction Of Printing Formes (AREA)

Abstract

本發明提供一種圖案形成用積層膜,係既不吸收空氣中之水分,亦不於版膜表面殘存多餘成分,且防止了感光性樹脂層之黏性。 本發明係一種圖案形成用積層膜、採用該圖案形成用積層膜的未感光之網版印刷版以及此等之製造方法,前述圖案形成用積層膜之特徵在於:係支撐層、糊層、非水溶性高分子層及感光性樹脂層依此順序所構成。 The present invention provides a laminated film for pattern formation that does not absorb moisture in the air, does not retain excess components on the surface of the plate film, and prevents the stickiness of the photosensitive resin layer. The present invention relates to a pattern-forming laminated film, a non-photosensitive screen printing plate using the pattern-forming laminated film, and a manufacturing method thereof. The pattern-forming laminated film is characterized by: a support layer, a paste layer, and a non-photosensitive screen printing plate. The water-soluble polymer layer and the photosensitive resin layer are composed in this order.

Description

圖案形成用積層膜及未感光之網版印刷版以及此等之製造方法、感光性阻劑基材Laminated films for pattern formation, unsensitized screen printing plates, their manufacturing methods, and photoresist substrates

本發明係關於一種圖案形成用積層膜及未感光之網版印刷版以及此等之製造方法。The present invention relates to a laminated film for pattern formation, a non-photosensitive screen printing plate, and a manufacturing method thereof.

作為製造網版印刷版之方法,有使用圖案形成用膜之方法。該方法與直接塗佈感光性樹脂之方法比較,於下述方面優異:若使用圖案形成用膜轉印感光性樹脂層,則網版上之感光性樹脂膜係平滑地形成,能夠抑制版內之厚度不均。因此,能夠製作顯影後之圖案之邊緣清晰(sharp)且油墨轉印量之不均少的印刷精度高之版。As a method of manufacturing a screen printing plate, there is a method of using a pattern forming film. Compared with the method of directly applying photosensitive resin, this method is superior in that if a pattern forming film is used to transfer the photosensitive resin layer, the photosensitive resin film on the screen is formed smoothly, and the inside of the screen can be suppressed. The thickness is uneven. Therefore, it is possible to produce a plate with high printing accuracy in which the edges of the developed pattern are sharp and the ink transfer amount is less uneven.

於使用此種圖案形成用膜製造網版印刷用模板(stencil)時,首先於網版塗佈水或感光性樹脂等,貼合圖案形成用膜之感光性樹脂層,加以充分乾燥後,剝離支撐層,藉此將感光性樹脂層轉印至網版,然後經由圖案遮罩將感光性樹脂層加以曝光,繼而利用水等進行顯影,藉此可於網版形成預定之圖案。When using such a pattern-forming film to produce a screen printing stencil, first apply water or photosensitive resin to the screen, adhere the photosensitive resin layer of the pattern-forming film, dry it sufficiently, and then peel it off. The support layer is used to transfer the photosensitive resin layer to the screen, and then expose the photosensitive resin layer through a pattern mask, and then develop it with water, so that a predetermined pattern can be formed on the screen.

然而,感光性樹脂層之表面於構成成分上大多帶有黏性,故而有時產生下述問題:於曝光時圖案遮罩之對位困難,而且與圖案遮罩之均勻密接受到妨礙,或者於曝光後自感光性樹脂層剝離圖案遮罩時,感光性樹脂層之一部分損傷,污染圖案遮罩等。However, the surface of the photosensitive resin layer is mostly sticky in terms of constituents, so the following problems sometimes occur: it is difficult to align the pattern mask during exposure, and the uniform close contact with the pattern mask is hindered, or the problem occurs. When the pattern mask is peeled off from the photosensitive resin layer after exposure, part of the photosensitive resin layer may be damaged and the pattern mask may be contaminated.

為了防止這些情況,於日本特開昭58-60745號公報或國際公開2013-080958號公報中,提出有一種圖案形成用積層膜,係於支撐層與感光性樹脂層之間配置聚乙烯醇或氟化合物作為中間層。In order to prevent these situations, Japanese Patent Application Laid-Open No. 58-60745 or International Publication No. 2013-080958 proposes a pattern-forming laminated film in which polyvinyl alcohol or polyvinyl alcohol is disposed between a support layer and a photosensitive resin layer. Fluorine compound serves as an intermediate layer.

然而,聚乙烯醇為水溶性高分子,故而吸收空氣中之水分,可認為於抑制印刷版之黏性之方面不充分。However, polyvinyl alcohol is a water-soluble polymer, so it absorbs moisture in the air and is considered insufficient in suppressing the viscosity of the printing plate.

另外,該中間層原本為非感光性材料,雖於顯影時被去除,但實際上因與感光性樹脂層長時間接觸而導致感光性成分局部轉移至中間層,於曝光時不溶於顯影液。因此,有時無法由顯影去除,中間層之成分殘存於版膜表面。由此導致有時無法發揮原本之感光性樹脂所設計之性能。 [先前技術文獻] [專利文獻] In addition, the intermediate layer is originally a non-photosensitive material. Although it is removed during development, the photosensitive components are actually partially transferred to the intermediate layer due to long-term contact with the photosensitive resin layer and are insoluble in the developer during exposure. Therefore, sometimes it cannot be removed by development, and the components of the intermediate layer remain on the surface of the plate film. As a result, the photosensitive resin may not be able to exhibit its originally designed performance. [Prior technical literature] [Patent Document]

[專利文獻1]日本特開昭58-60745號公報。 [專利文獻2]國際公開2013-080958號公報。 [Patent Document 1] Japanese Patent Application Publication No. Sho 58-60745. [Patent Document 2] International Publication No. 2013-080958.

[發明所欲解決之課題][Problem to be solved by the invention]

根據本發明,課題在於既不吸收空氣中之水分,亦不於版膜表面殘存多餘成分,抑制感光性樹脂層之黏性而改善曝光時之密接不良或作業性。 [用以解決課題之手段] According to the present invention, the object is to neither absorb moisture in the air nor leave excess components on the surface of the plate film, suppress the stickiness of the photosensitive resin layer, and improve poor adhesion or workability during exposure. [Means used to solve problems]

本發明藉由提供預定之圖案形成用積層膜而解決上述課題。 因此,本發明之圖案形成用積層膜之特徵在於:係支撐層、糊層、非水溶性高分子層及感光性樹脂層依此順序所構成。 The present invention solves the above problems by providing a laminated film for forming a predetermined pattern. Therefore, the laminated film for pattern formation of the present invention is characterized in that it is composed of a support layer, a paste layer, a water-insoluble polymer layer, and a photosensitive resin layer in this order.

此種本發明之圖案形成用積層膜較佳為包含下述情況:前述感光性樹脂層為能夠利用中性水進行顯影之感光性樹脂。The laminated film for pattern formation of the present invention preferably includes a case where the photosensitive resin layer is a photosensitive resin that can be developed with neutral water.

此種本發明之圖案形成用積層膜較佳為包含下述情況:前述支撐層與糊層之間之層間接著力(x)、前述糊層與非水溶性高分子層之間之層間接著力(y)、及前述非水溶性高分子層與感光性樹脂層之間之層間接著力(z)係處於下述關係:層間接著力(x) > 層間接著力(y);層間接著力(z) > 層間接著力(y)。The pattern-forming laminated film of the present invention preferably includes the following: interlayer adhesion (x) between the support layer and the paste layer, and interlayer adhesion between the paste layer and the water-insoluble polymer layer. (y), and the interlayer adhesion force (z) between the aforementioned water-insoluble polymer layer and the photosensitive resin layer are in the following relationship: interlayer adhesion force (x) > interlayer adhesion force (y); interlayer adhesion force ( z) > Layer indirect force (y).

此種本發明之圖案形成用積層膜較佳為包含下述情況:前述糊層與非水溶性高分子層之間之層間接著力(y)為0.001N/25mm至1.0N/25mm。The pattern-forming laminated film of the present invention preferably includes a case where the interlayer adhesive force (y) between the paste layer and the water-insoluble polymer layer is 0.001 N/25 mm to 1.0 N/25 mm.

此種本發明之圖案形成用積層膜較佳為包含下述情況:前述非水溶性高分子層之霧值為5.0%以下。The pattern-forming laminated film of the present invention preferably includes a case where the haze value of the water-insoluble polymer layer is 5.0% or less.

此種本發明之圖案形成用積層膜較佳為包含下述情況:前述非水溶性高分子層係厚度為1μm至100μm。The pattern-forming laminated film of the present invention preferably includes a case where the thickness of the water-insoluble polymer layer is 1 μm to 100 μm.

此種本發明之圖案形成用積層膜較佳為包含下述情況:前述感光性樹脂層係由包含下述成分(A)及成分(B)而成之感光性樹脂所構成。 成分(A):皂化度為50mol%以上之聚乙烯醇;成分(B):重氮樹脂。 The laminated film for pattern formation of the present invention preferably includes a case where the photosensitive resin layer is composed of a photosensitive resin containing the following component (A) and component (B). Ingredient (A): polyvinyl alcohol with a saponification degree of more than 50 mol%; Ingredient (B): diazo resin.

此種本發明之圖案形成用積層膜較佳為包含下述情況:前述感光性樹脂層係由包含下述成分(A)、成分(C)及成分(D)而成之感光性樹脂所構成。 成分(A):皂化度為50mol%以上之聚乙烯醇;成分(C):具有至少一個環氧基之環氧化合物;成分(D):光酸產生劑。 The pattern-forming laminated film of the present invention preferably includes a case where the photosensitive resin layer is composed of a photosensitive resin containing the following component (A), component (C), and component (D). . Component (A): polyvinyl alcohol with a saponification degree of 50 mol% or more; Component (C): an epoxy compound with at least one epoxy group; Component (D): photoacid generator.

此種本發明之圖案形成用積層膜較佳為包含下述情況:前述感光性樹脂層係由包含下述成分(E)而成之感光性樹脂所構成。 成分(E):具有經苯乙烯基取代之吡啶鎓基或經苯乙烯基取代之喹啉鎓基的皂化度為50mol%以上之聚乙烯醇。 The laminated film for pattern formation of the present invention preferably includes a case where the photosensitive resin layer is composed of a photosensitive resin containing the following component (E). Component (E): Polyvinyl alcohol having a pyridinium group substituted with a styrene group or a quinolinium group substituted with a styrene group and a saponification degree of 50 mol% or more.

此種本發明之圖案形成用積層膜較佳為包含下述情況:前述感光性樹脂層係由更包含下述成分(F)及成分(G)而成之感光性樹脂所構成。 成分(F):具有至少一個乙烯性不飽和鍵之自由基聚合性化合物;成分(G):光自由基聚合起始劑。 The laminated film for pattern formation of the present invention preferably includes a case where the photosensitive resin layer is composed of a photosensitive resin further containing the following component (F) and component (G). Component (F): a radically polymerizable compound having at least one ethylenically unsaturated bond; Component (G): photoradical polymerization initiator.

此種本發明之圖案形成用積層膜較佳為包含下述情況:前述感光性樹脂層係由更包含下述成分(H)而成之感光性樹脂所構成。 成分(H):水性聚合物乳液。 The laminated film for pattern formation of the present invention preferably includes a case where the photosensitive resin layer is composed of a photosensitive resin further containing the following component (H). Ingredients (H): Aqueous polymer emulsion.

此種本發明之圖案形成用積層膜較佳為包含下述情況:係於前述圖案形成用積層膜之感光性樹脂層側進而積層保護層而成。The pattern-forming laminated film of the present invention preferably includes a case in which a protective layer is further laminated on the photosensitive resin layer side of the pattern-forming laminated film.

而且,本發明之未感光之網版印刷版之特徵在於:包含自前述圖案形成用積層膜去掉前述支撐層及糊層而得之積層膜、以及積層於前述積層膜的感光性樹脂層側之網版絲網(mesh)而成。Furthermore, the non-photosensitive screen printing plate of the present invention is characterized by including a laminated film obtained by removing the support layer and the paste layer from the pattern-forming laminated film, and a photosensitive resin layer laminated on the side of the photosensitive resin layer of the laminated film. It is made of screen mesh (mesh).

而且,本發明之未感光之網版印刷版之製造方法之特徵在於:包含下述步驟(a)及步驟(b)而成。 步驟(a):於前述圖案形成用積層膜的前述感光性樹脂層側接合網版絲網之步驟;步驟(b):自前述圖案形成用積層膜的非水溶性高分子層剝離前述支撐層及糊層之步驟。 Moreover, the manufacturing method of the non-photosensitive screen printing plate of this invention is characterized by including the following steps (a) and (b). Step (a): The step of joining the screen mesh to the photosensitive resin layer side of the pattern-forming laminated film; Step (b): Peeling off the support layer from the water-insoluble polymer layer of the pattern-forming laminated film. And the steps of paste layer.

而且,本發明之網版印刷版之特徵在於:於未感光之網版印刷版形成潛像並將感光性樹脂層加以顯影而成,前述未感光之網版印刷版係包含自前述圖案形成用積層膜去掉前述支撐層及糊層而得之積層膜、以及積層於前述積層膜的感光性樹脂層側之網版絲網而成。Furthermore, the screen printing plate of the present invention is characterized in that a latent image is formed on a non-photosensitive screen printing plate, and the photosensitive resin layer is developed, and the non-photosensitive screen printing plate is formed from the pattern-forming plate. The laminated film is a laminated film obtained by removing the support layer and paste layer, and a screen mesh laminated on the photosensitive resin layer side of the laminated film.

而且,本發明之網版印刷版之製造方法之特徵在於:包含下述步驟(a)至步驟(f)而成。Moreover, the manufacturing method of the screen printing plate of this invention is characterized by including the following steps (a) to (f).

步驟(a):於前述圖案形成用積層膜的前述感光性樹脂層側接合網版絲網之步驟;步驟(b):自前述圖案形成用積層膜之非水溶性高分子層剝離前述支撐層及糊層之步驟;步驟(c):於前述非水溶性高分子層的表面配置圖案遮罩之步驟;步驟(d):於前述感光性樹脂層形成潛像之步驟;步驟(e):剝離前述非水溶性高分子層之步驟;步驟(f):將形成有前述潛像之感光性樹脂層加以顯影之步驟。Step (a): The step of joining the screen mesh to the photosensitive resin layer side of the pattern-forming laminated film; Step (b): Peeling off the support layer from the water-insoluble polymer layer of the pattern-forming laminated film. and paste layer; step (c): the step of arranging a pattern mask on the surface of the aforementioned water-insoluble polymer layer; step (d): the step of forming a latent image on the aforementioned photosensitive resin layer; step (e): The step of peeling off the aforementioned water-insoluble polymer layer; step (f): the step of developing the photosensitive resin layer on which the aforementioned latent image is formed.

而且,本發明之感光性阻劑基材之特徵在於:包含前述圖案形成用積層膜、以及積層於前述圖案形成用積層膜的前述感光性樹脂層側之基材而成。 [發明功效] Moreover, the photoresist base material of this invention is characterized by including the said pattern-forming laminated film, and the base material laminated|stacked on the said photosensitive resin layer side of the said pattern-forming laminated film. [Invention effect]

本發明之圖案形成用積層膜係於感光性樹脂層的表面積層有非水溶性高分子層。該非水溶性高分子層係表面平滑,故而容易於非水溶性高分子層之表面將圖案遮罩加以定位。The pattern-forming laminated film of the present invention has a water-insoluble polymer layer laminated on the surface of the photosensitive resin layer. The water-insoluble polymer layer has a smooth surface, so it is easy to position the pattern mask on the surface of the water-insoluble polymer layer.

而且,圖案遮罩與非水溶性高分子層之密接性高且均勻性高,故而可抑制圖案遮罩之變形等。因此,可極準確地進行感光性樹脂層之曝光及潛像之形成。Furthermore, the pattern mask and the water-insoluble polymer layer have high adhesion and high uniformity, so deformation of the pattern mask can be suppressed. Therefore, the exposure of the photosensitive resin layer and the formation of the latent image can be performed extremely accurately.

而且,該非水溶性高分子層作為感光性樹脂層之所謂保護層發揮功能,防止周圍環境或劣化成分等對感光性樹脂層造成影響。例如,防止感光性樹脂層吸濕,或防止來自他層之有害成分等轉移,因而長期間維持感光性樹脂原本之優異特性。 因此,根據本發明之圖案形成用積層膜,可獲得準確地形成有高精細之所需圖案的網版印刷版。 Furthermore, the water-insoluble polymer layer functions as a so-called protective layer for the photosensitive resin layer, preventing the surrounding environment, deteriorating components, etc. from affecting the photosensitive resin layer. For example, it prevents the photosensitive resin layer from absorbing moisture or preventing the transfer of harmful components from other layers, thereby maintaining the original excellent properties of the photosensitive resin for a long time. Therefore, according to the laminated film for pattern formation of the present invention, it is possible to obtain a screen printing plate in which a high-definition desired pattern is accurately formed.

本發明之圖案形成用積層膜藉由在曝光時於感光性樹脂層上存在非水溶性高分子層,而並無先前之水溶性高分子層之情形時令人擔憂之吸濕、殘留,能夠防止感光性樹脂成分對圖案遮罩之污染。The pattern-forming laminated film of the present invention has a water-insoluble polymer layer on the photosensitive resin layer during exposure, and does not have the worrisome moisture absorption and residue in the case of the conventional water-soluble polymer layer. Prevent photosensitive resin components from contaminating the pattern mask.

而且,能夠防止由感光性樹脂層之黏性所致之密接不良,對位亦容易,且容易抑制異物之附著並去掉附著之異物。 進而,由於具有聚合物層,故而不用在意黏性,感光材之設計範圍變廣。 Moreover, poor adhesion due to the stickiness of the photosensitive resin layer can be prevented, positioning is easy, and adhesion of foreign matter can be suppressed and adhesion of foreign matter can be easily removed. Furthermore, since it has a polymer layer, there is no need to worry about viscosity, and the design range of photosensitive materials becomes wider.

[圖案形成用積層膜] 本發明之圖案形成用積層膜之特徵在於:係支撐層、糊層、非水溶性高分子層及感光性樹脂層依此順序所構成。 [Laminated film for pattern formation] The laminated film for pattern formation of the present invention is characterized in that it is composed of a support layer, a paste layer, a water-insoluble polymer layer, and a photosensitive resin layer in this order.

本發明之圖案形成用積層膜係包含支撐層、糊層、非水溶性高分子層及感光性樹脂層而成。此處,所謂「包含…而成」,除了僅包含列舉之各層(亦即支撐層、糊層、非水溶性高分子層及感光性樹脂層)而成之情況以外,亦包括包含列舉之各層以外之層或材料等而成之情況。作為此種列舉之各層以外之層之代表例,例如可列舉保護層。The laminated film for pattern formation of the present invention includes a support layer, a paste layer, a water-insoluble polymer layer and a photosensitive resin layer. Here, the term “composed of” includes the case where it only includes each of the listed layers (i.e., support layer, paste layer, water-insoluble polymer layer, and photosensitive resin layer). It also includes each of the listed layers. Made of other layers or materials. Typical examples of layers other than the listed layers include protective layers.

本發明之圖案形成用積層膜例如能夠應用於各種印刷技術領域,尤佳為網版印刷領域。於將本發明之圖案形成用積層膜應用於此種印刷領域時,有時進行下述操作:先將糊層與非水溶性高分子層之界面剝離而去除支撐層及糊層後,剝離非水溶性高分子層。The pattern-forming laminated film of the present invention can be applied to various printing technical fields, for example, and is particularly preferably used in the screen printing field. When applying the pattern-forming laminated film of the present invention to such a printing field, the following operation may be performed: first peeling off the interface between the paste layer and the water-insoluble polymer layer to remove the support layer and paste layer, and then peeling off the non-water-soluble polymer layer. Water-soluble polymer layer.

因此,作為可適用於網版印刷領域的本發明之尤佳之圖案形成用積層膜,可列舉:前述支撐層與糊層之間之層間接著力(x)、前述糊層與非水溶性高分子層之間之層間接著力(y)、及前述非水溶性高分子層與感光性樹脂層之間之層間接著力(z)處於下述關係的圖案形成用積層膜。 層間接著力(x) > 層間接著力(y);層間接著力(z) > 層間接著力(y)。 再者,層間接著力(x)與層間接著力(z)存在(x)大於(z)之情形、(x)小於(z)之情形、及(x)與(z)相等之情形。 Therefore, particularly preferred pattern-forming laminated films of the present invention applicable to the field of screen printing include: interlayer adhesion (x) between the above-mentioned support layer and the paste layer, the above-mentioned paste layer and the water-insoluble high A laminated film for pattern formation in which the interlayer adhesion (y) between the molecular layers and the interlayer adhesion (z) between the water-insoluble polymer layer and the photosensitive resin layer are in the following relationship. The layer-indirect force (x) > the layer-indirect force (y); the layer-indirect force (z) > the layer-indirect force (y). Furthermore, the inter-layer contact force (x) and the inter-layer contact force (z) may occur when (x) is greater than (z), when (x) is less than (z), or when (x) and (z) are equal.

[支撐層] 於本發明中,作為支撐層可使用由各種材料所構成之支撐層。例如,可使用由各種樹脂材料所構成之支撐層,另外可使用由天然材料所構成之支撐層。 [support layer] In the present invention, a support layer made of various materials can be used as the support layer. For example, a support layer composed of various resin materials may be used, and a support layer composed of natural materials may be used.

作為較佳之材質,例如可列舉:紙;脫模紙;聚對苯二甲酸乙二酯等聚酯,聚甲基戊烯、聚丙烯、聚乙烯等聚烯烴,聚氟乙烯、聚氯乙烯等含鹵素之乙烯基聚合物,尼龍等聚醯胺,賽珞凡等纖維素,聚苯乙烯,丙烯酸樹脂,聚醯亞胺等之膜。支撐層可為透明亦可為不透明,可為了改良積層膜之功能等而對單面或兩面實施脫模處理、粗面(matt)處理、易接著處理。例如,藉由上述處理,例如容易控制支撐層與糊層之間之層間接著力(x)。 支撐層之厚度並無特別限定,較佳為10μm至200μm,尤佳為30μm至125μm。 Preferable materials include, for example, paper; release paper; polyesters such as polyethylene terephthalate; polyolefins such as polymethylpentene, polypropylene, and polyethylene; polyvinyl fluoride, polyvinyl chloride, etc. Films containing halogen-containing vinyl polymers, polyamides such as nylon, cellulose such as cellulose, polystyrene, acrylic resin, polyimide, etc. The support layer may be transparent or opaque, and may be subjected to release treatment, matt treatment, or adhesion treatment on one or both sides in order to improve the function of the laminated film. For example, through the above process, it is easy to control the interlayer adhesion force (x) between the support layer and the paste layer. The thickness of the support layer is not particularly limited, but is preferably 10 μm to 200 μm, particularly preferably 30 μm to 125 μm.

[糊層] 於本發明中,作為糊層可使用由各種材料所構成之糊層。即,用於糊層之糊材並無特別限制,可使用各種糊材。 作為較佳之糊材,例如可使用:以丙烯酸系(一液型或二液型)之接著劑或黏著劑、橡膠系或胺基甲酸酯系之接著劑或黏著劑、聚矽氧系之接著劑或黏著劑、乙酸乙烯酯系為代表之各種糊劑。 [paste layer] In the present invention, a paste layer composed of various materials can be used as the paste layer. That is, the paste material used for the paste layer is not particularly limited, and various paste materials can be used. As preferred pastes, for example, acrylic-based (one- or two-component) adhesives or adhesives, rubber-based or urethane-based adhesives or adhesives, polysiloxane-based adhesives or adhesives can be used. Various pastes including adhesives, adhesives, and vinyl acetate.

進而,可使用無溶劑型、溶劑型、乳液型、熱硬化型、UV(Ultra Violet;紫外線)硬化型、EB(Electron Beam;電子束)硬化型、熱熔型等。 糊層之厚度並無特別限定,但較佳為0.5μm至30μm,尤佳為0.5μm至20μm。 Furthermore, solvent-free type, solvent type, emulsion type, thermosetting type, UV (Ultra Violet; ultraviolet ray) curing type, EB (Electron Beam; electron beam) curing type, hot melt type, etc. can be used. The thickness of the paste layer is not particularly limited, but is preferably 0.5 μm to 30 μm, particularly preferably 0.5 μm to 20 μm.

糊層之形成可藉由下述方式實施:藉由凹版、缺角輪(comma)、氣刀、刮刀片、棒塗機、模塗法、刮刀法等通常之塗佈方法於支撐層上塗佈上述糊材後,藉由加熱處理、紫外線照射處理、電子束照射處理等方法加以乾燥、硬化。The formation of the paste layer can be carried out by the following methods: coating on the support layer by common coating methods such as gravure, comma, air knife, doctor blade, rod coater, die coating method, doctor blade method, etc. After the above paste is spread, it is dried and hardened by methods such as heat treatment, ultraviolet irradiation treatment, and electron beam irradiation treatment.

用以形成該糊層之糊材係能以糊層與非水溶性高分子層之間之層間接著力(y)較佳為成為0.001N/25mm至1.0N/25mm、尤佳為成為0.005N/25mm至0.5N/25mm(對PET)之方式選擇。於未達0.001N/25mm時,有時產生對非水溶性高分子層之附著力不足所致之剝落或隆起等,因而欠佳,另一方面,若大於1.0N/25mm,則有時難以自非水溶性高分子層剝離,或於剝離後產生殘糊或表面污染性變高等,因而欠佳。層間接著力(y)係於25mm寬之聚對苯二甲酸乙二酯膜形成糊層,進而貼合聚對苯二甲酸乙二酯膜並壓接。於23℃下經過1分鐘後,以300mm/min之速度以180度之角度剝離,以此時之力來表示(依據JIS(Japanese Industrial Standards;日本工業標準)-Z0237)。The paste used to form the paste layer is such that the interlayer adhesion force (y) between the paste layer and the water-insoluble polymer layer is preferably 0.001N/25mm to 1.0N/25mm, particularly preferably 0.005N. /25mm to 0.5N/25mm (for PET) method selection. When it is less than 0.001N/25mm, peeling or bulging may occur due to insufficient adhesion to the water-insoluble polymer layer, which is undesirable. On the other hand, when it is more than 1.0N/25mm, it may be difficult to It is undesirable because it peels off the water-insoluble polymer layer, produces a residue after peeling, or increases surface contamination. The interlayer bonding force (y) is to form a paste layer on a 25mm wide polyethylene terephthalate film, which is then laminated to the polyethylene terephthalate film and pressed. After 1 minute at 23°C, peel off at an angle of 180 degrees at a speed of 300mm/min, expressed as the force at this time (according to JIS (Japanese Industrial Standards; Japanese Industrial Standards)-Z0237).

本發明之圖案形成用積層膜較佳為於自非水溶性高分子層剝離支撐層及糊層後,原先構成糊層之糊劑不殘留於非水溶性高分子層之表面。關於糊層剝離後之非水溶性高分子層的表面中之糊劑之殘留量,於將10cm 2之糊材之質量設為100時,較佳為5%以下,進而佳為1%以下,尤佳為0.1%以下。 In the pattern-forming laminated film of the present invention, it is preferable that the paste originally constituting the paste layer does not remain on the surface of the water-insoluble polymer layer after the support layer and the paste layer are peeled off from the water-insoluble polymer layer. The residual amount of paste on the surface of the water-insoluble polymer layer after peeling off the paste layer is preferably 5% or less, and more preferably 1% or less, when the mass of 10 cm 2 of paste is 100. Particularly preferably, it is less than 0.1%.

[非水溶性高分子層] 本發明之圖案形成用積層膜中,藉由透過非水溶性高分子層之光來進行構成感光性樹脂層之樹脂之硬化。 非水溶性高分子層較佳為霧值低。例如,霧值較佳為0.01%至5.0%,尤佳為0.05%至3.0%。此處,霧值係依據JIS-K7136進行測定。 [Water-insoluble polymer layer] In the pattern-forming laminated film of the present invention, the resin constituting the photosensitive resin layer is cured by light passing through the water-insoluble polymer layer. The water-insoluble polymer layer preferably has a low haze value. For example, the fog value is preferably 0.01% to 5.0%, and particularly preferably 0.05% to 3.0%. Here, the fog value is measured in accordance with JIS-K7136.

藉由霧值為上述較佳範圍內,即便光照射量少,感光性樹脂層之硬化亦能夠良好地進行,且能夠於感光性樹脂層形成高精細之所需圖案。When the haze value is within the above-mentioned preferred range, even if the amount of light irradiation is small, the photosensitive resin layer can be cured favorably, and a high-definition desired pattern can be formed on the photosensitive resin layer.

作為較佳之非水溶性高分子層,例如可列舉:聚對苯二甲酸乙二酯等聚酯,聚甲基戊烯、聚丙烯、聚乙烯等聚烯烴,聚氟乙烯、聚氯乙烯等含鹵素之乙烯基聚合物,尼龍等聚醯胺,賽珞凡等纖維素,聚苯乙烯,丙烯酸樹脂,聚醯亞胺,聚醚碸樹脂等之膜。 非水溶性高分子層若為霧值之範圍內,則可為了改良積層膜之功能等而對單面或兩面實施脫模處理、易接著處理。例如,藉由上述處理,例如容易控制糊層與非水溶性高分子層之間之層間接著力(y)、非水溶性高分子層與感光性樹脂層之間之層間接著力(z)。 作為尤佳之非水溶性高分子層,可適宜地使用聚酯膜、聚烯烴膜。厚度較佳為1μm至100μm。 Preferable water-insoluble polymer layers include, for example, polyesters such as polyethylene terephthalate, polyolefins such as polymethylpentene, polypropylene, and polyethylene, polyvinyl fluoride, polyvinyl chloride, and the like. Films of halogen vinyl polymers, polyamides such as nylon, cellulose such as cellulose, polystyrene, acrylic resin, polyimide, polyether resin, etc. If the water-insoluble polymer layer is within the range of the haze value, in order to improve the function of the laminated film, one or both sides can be subjected to mold release treatment and easy adhesion treatment. For example, the above-mentioned treatment makes it easy to control the interlayer adhesion (y) between the paste layer and the water-insoluble polymer layer, and the interlayer adhesion (z) between the water-insoluble polymer layer and the photosensitive resin layer. As particularly preferred water-insoluble polymer layers, polyester films and polyolefin films can be suitably used. The thickness is preferably 1 μm to 100 μm.

[感光性樹脂層] 本發明之圖案形成用積層膜之感光性樹脂層可由能夠藉由光照射而形成潛像、且能夠藉由中性水進行顯影之樹脂所構成。而且,較佳為可將水用作溶媒而形成塗膜。 作為此種感光性樹脂層之較佳者,可列舉下述第一具體例、第二具體例及第三具體例。 [Photosensitive resin layer] The photosensitive resin layer of the pattern-forming laminated film of the present invention can be composed of a resin that can form a latent image by light irradiation and can be developed with neutral water. Furthermore, it is preferable to use water as a solvent to form a coating film. Preferable examples of such a photosensitive resin layer include the following first specific example, second specific example, and third specific example.

[第一感光性樹脂層] 感光性樹脂層之第一具體例係由包含下述成分(A)及成分(B)而成之感光性樹脂所構成。 成分(A):皂化度為50mol%以上之聚乙烯醇;成分(B):重氮樹脂。 此處,所謂「包含…而成」,除了僅包含列舉之各成分(亦即成分(A)及成分(B))而成之情況以外,亦包括包含列舉之成分以外之成分等而成之情況。作為此種列舉之成分以外之成分的代表例,例如可列舉成分(F)至成分(H)(詳細將於後述)。 [First photosensitive resin layer] The first specific example of the photosensitive resin layer is composed of a photosensitive resin containing the following component (A) and component (B). Ingredient (A): polyvinyl alcohol with a saponification degree of more than 50 mol%; Ingredient (B): diazo resin. Here, the term “comprising” includes not only the case where it is composed of only the listed components (that is, component (A) and component (B)), but also the case where it is composed of components other than the listed components. condition. Representative examples of components other than the components listed above include component (F) to component (H) (details will be described later).

成分(A)與成分(B)之存在比率(質量%)係成分(A):成分(B)較佳為1:0.005至1:0.5,尤佳為1:0.01至1:0.2。 包含上述成分(A)及成分(B)而成之感光性樹脂可根據需要而含有成分(F)至成分(H)中的任一種或多種。 The presence ratio (mass %) of component (A) and component (B) is component (A):component (B). Preferably it is 1:0.005 to 1:0.5, particularly preferably 1:0.01 to 1:0.2. The photosensitive resin containing the said component (A) and component (B) may contain any one or more types of components (F) to component (H) as needed.

[成分(A)] 成分(A)係皂化度為50mol%以上之聚乙烯醇。皂化度較佳為50mol%至100mol%,尤佳為70mol%至100 mol %,只要不損及水溶性,則亦可為與其他乙烯基單體之共聚物。該成分(A)之平均聚合度較佳為200至5000,尤佳為300至4000。亦可將皂化度及聚合度不同之兩種以上之聚乙烯醇加以混合。另外,陽離子改質或陰離子改質等之改質物亦可同樣地使用。 [Ingredients (A)] Component (A) is polyvinyl alcohol with a saponification degree of more than 50 mol%. The saponification degree is preferably 50 mol% to 100 mol%, especially 70 mol% to 100 mol%. As long as the water solubility is not impaired, it can also be a copolymer with other vinyl monomers. The average degree of polymerization of component (A) is preferably 200 to 5000, particularly preferably 300 to 4000. It is also possible to mix two or more polyvinyl alcohols with different degrees of saponification and polymerization. In addition, modified substances such as cationic modification or anion modification can also be used in the same manner.

[成分(B)] 成分(B)為重氮樹脂。作為具體例,可列舉:對重氮二苯基胺或3‐甲氧基‐4‐重氮二苯基胺與4,4’‐雙甲氧基甲基二苯基醚之縮合物、及這些之硫酸鹽、磷酸鹽及氯化鋅複鹽陰離子錯合物之重氮樹脂,對重氮二苯基胺或3‐甲氧基‐4‐重氮二苯基胺與三聚甲醛之縮合物之硫酸鹽、磷酸鹽及氯化鋅複鹽陰離子錯合物之重氮樹脂。作為此種重氮樹脂,除了對胺基二苯基胺以外,可使用:利用三聚甲醛、乙醛、丙醛、正丁醛等醛類使4‐胺基‐4’‐甲基二苯基胺、4‐胺基‐4’‐乙基二苯基胺、4‐胺基‐4’‐甲氧基二苯基胺、4‐胺基‐4’‐氯二苯基胺、4‐胺基‐4’‐硝基二苯基胺等二苯基胺類之重氮化物縮合而得的水溶性之重氮樹脂。 [Ingredients (B)] Component (B) is diazo resin. Specific examples include p-diazodiphenylamine or the condensate of 3-methoxy-4-diazodiphenylamine and 4,4'-bismethoxymethyldiphenyl ether, and Diazo resins of these sulfate, phosphate and zinc chloride double salt anion complexes, condensation of p-diazodiphenylamine or 3-methoxy-4-diazodiphenylamine and trimerformaldehyde Diazo resin of sulfate, phosphate and zinc chloride double salt anion complex. As such diazo resin, in addition to p-aminodiphenylamine, 4-amino-4'-methyldiphenyl can be used using aldehydes such as parformaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, etc. amine, 4-amino-4'-ethyldiphenylamine, 4-amino-4'-methoxydiphenylamine, 4-amino-4'-chlorodiphenylamine, 4- Water-soluble diazo resin obtained by condensation of diazo compounds of diphenylamines such as amino-4'-nitrodiphenylamine.

其中,尤佳為對重氮二苯基胺與三聚甲醛之縮合物、3‐甲氧基‐4‐重氮二苯基胺與三聚甲醛之縮合物、對重氮二苯基胺與4,4’‐雙甲氧基甲基二苯基醚之縮合物、3‐甲氧基‐4‐重氮二苯基胺與4,4’‐雙甲氧基甲基二苯基醚之縮合物。 可單獨使用上述成分(B)之一種,另外亦可併用兩種以上。 Among them, the condensate of p-diazodiphenylamine and trimerformaldehyde, the condensate of 3-methoxy-4-diazodiphenylamine and trimerformaldehyde, and the condensate of p-diazodiphenylamine and trimerformaldehyde are particularly preferred. Condensate of 4,4'-bismethoxymethyldiphenyl ether, 3-methoxy-4-diazodiphenylamine and 4,4'-bismethoxymethyldiphenyl ether condensate. One type of the above-mentioned component (B) may be used alone, or two or more types may be used in combination.

[成分(F)] 成分(F)為具有至少一個乙烯性不飽和鍵之自由基聚合性化合物,「光硬化技術資料冊」(Technonet公司,2000年)記載之單體及寡聚物等相當於該成分(F)。 [Ingredients (F)] Component (F) is a radically polymerizable compound having at least one ethylenically unsaturated bond, and the monomers and oligomers described in "Photohardening Technical Data Book" (Technonet, 2000) are equivalent to this component (F) .

作為單官能性單體之具體例,例如可列舉:(甲基)丙烯酸-2‐乙基己酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸-2‐羥基乙酯、(甲基)丙烯酸-2‐羥基丙酯、(甲基)丙烯酸-2‐羥基丁酯、(甲基)丙烯酸-2‐乙氧基乙酯、(甲基)丙烯酸-2(2‐乙氧基乙氧基)乙酯、(甲基)丙烯酸正丁氧基乙酯、(甲基)丙烯酸嗎啉基乙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯酯、甲氧基二乙二醇(甲基)丙烯酸酯、甲氧基三乙(丙)二醇(甲基)丙烯酸酯、甲氧基四乙(丙)二醇(甲基)丙烯酸酯、甲氧基聚乙(丙)二醇(甲基)丙烯酸酯、乙氧基二乙(丙)二醇(甲基)丙烯酸酯、乙氧基三乙(丙)二醇(甲基)丙烯酸酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸四氫呋喃酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸-N,N‐二甲基胺基乙酯、(甲基)丙烯酸-N,N‐二乙基胺基乙酯、氧化物改質磷酸(甲基)丙烯酸酯、ω-羧基-聚己內酯單丙烯酸酯、鄰苯二甲酸單羥基乙基丙烯酸酯等。 再者,本說明書中,所謂「(甲基)丙烯酸酯」,意指「甲基丙烯酸酯」及「丙烯酸酯」兩者,所謂「伸乙(丙)基」,意指「伸乙基」及「伸丙基」兩者。 Specific examples of the monofunctional monomer include: (meth)ethylhexyl acrylate, isodecyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylate (Meth)acrylic acid-2-hydroxypropyl ester, (meth)acrylic acid-2-hydroxybutyl ester, (meth)acrylic acid-2-ethoxyethyl ester, (meth)acrylic acid-2-ethoxyethyl ester Oxy)ethyl ester, n-butoxyethyl (meth)acrylate, morpholinoethyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, methoxydiethyl Glycol (meth)acrylate, methoxytriethyl(propylene)glycol(meth)acrylate, methoxytetraethyl(propylene)glycol(meth)acrylate, methoxypolyethylene(propylene) ) glycol (meth)acrylate, ethoxydiethylene (propylene) glycol (meth)acrylate, ethoxytriethyl (propylene) glycol (meth)acrylate, (meth)acrylic acid ring Hexyl ester, tetrahydrofuryl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, -N,N-dimethylaminoethyl (meth)acrylate, (meth)acrylate base) acrylic acid-N,N-diethylaminoethyl ester, oxide modified phosphate (meth)acrylate, ω-carboxy-polycaprolactone monoacrylate, phthalic acid monohydroxyethyl acrylate wait. Furthermore, in this specification, "(meth)acrylate" means both "methacrylate" and "acrylate", and "ethylidene(propylene)" means "ethylidene" and "propyl" both.

作為具有兩個以上之乙烯性不飽和鍵的多官能性單體之具體例,例如可列舉:乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、1,3‐三亞甲基二醇二(甲基)丙烯酸酯、1,4‐丁二醇二(甲基)丙烯酸酯、1,6‐己二醇二(甲基)丙烯酸酯、環氧乙(丙)烷改質雙酚A二丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、雙(丙烯醯氧基新戊二醇)己二酸酯、雙(甲基丙烯醯氧基新戊二醇)己二酸酯、表氯醇改質1,6‐己二醇二(甲基)丙烯酸酯、羥基特戊酸新戊二醇二(甲基)丙烯酸酯、己內酯改質羥基特戊酸新戊二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、四丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二-三羥甲基丙烷三(甲基)丙烯酸酯、新戊二醇改質三羥甲基丙烷二(甲基)丙烯酸酯、環氧乙(丙)烷改質三羥甲基丙烷三(甲基)丙烯酸酯、丙烯酸羥基丙酯改質三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、季戊四醇聚丙氧基丙烯酸酯、硬脂酸改質季戊四醇二(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、二季戊四醇單羥基五(甲基)丙烯酸酯、烷基改質二季戊四醇聚(甲基)丙烯酸酯、己內酯改質二季戊四醇聚(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、表氯醇改質甘油三(甲基)丙烯酸酯、氧化物改質甘油三(甲基)丙烯酸酯、異氰脲酸三(丙烯醯氧基乙基)酯、異氰脲酸三(甲基丙烯醯氧基乙基)酯、己內酯改質異氰脲酸三(丙烯醯氧基乙基)酯、己內酯改質異氰脲酸三(甲基丙烯醯氧基乙基)酯、氧化物改質雙酚(甲基)丙烯酸酯等。Specific examples of the polyfunctional monomer 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 (propylene oxide) )Alkane modified bisphenol A diacrylate, neopentyl glycol di(meth)acrylate, bis(acryloxyneopentyl glycol) adipate, bis(methacryloxyneopentyl glycol) Alcohol) adipate, epichlorohydrin-modified 1,6-hexanediol di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, caprolactone-modified hydroxytetra Neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tri(meth)acrylate Acrylate, neopentyl glycol modified trimethylolpropane di(meth)acrylate, ethylene oxide (prop)ane modified trimethylolpropane tri(meth)acrylate, modified hydroxypropyl acrylate Trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol polypropoxyacrylate, stearic acid modified pentaerythritol di(meth)acrylate Ester, dipentaerythritol hexa(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, alkyl modified dipentaerythritol poly(meth)acrylate, caprolactone modified dipentaerythritol poly(meth)acrylate Acrylate, glyceryl di(meth)acrylate, epichlorohydrin modified glyceryl tri(meth)acrylate, oxide modified glyceryl tri(meth)acrylate, isocyanuric acid tri(acryloxyethyl) ester, tris(methacryloxyethyl) isocyanurate, caprolactone-modified tris(acryloxyethyl)isocyanurate, caprolactone-modified isocyanuric acid Tris(methacryloxyethyl) ester, oxide modified bisphenol (meth)acrylate, etc.

作為寡聚物,例如可使用:聚酯(甲基)丙烯酸酯寡聚物、雙酚A型環氧(甲基)丙烯酸酯、己內酯加成(甲基)丙烯酸酯、苯酚酚醛清漆型環氧(甲基)丙烯酸酯、甲酚酚醛清漆型環氧(甲基)丙烯酸酯等環氧(甲基)丙烯酸酯、(甲基)丙烯酸胺基甲酸酯等。 進而,可使用含乙烯性不飽和鍵之聚酯樹枝狀聚合物等。關於此種含乙烯性不飽和鍵之聚酯樹枝狀聚合物之具體例,例如係記載於日本特開2005-76005號、日本特開2005-47979號、日本特開2005-76005號各公報等。 As the oligomer, for example, 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. Epoxy (meth)acrylate, (meth)acrylic urethane, etc. Furthermore, polyester dendrimers containing ethylenically unsaturated bonds, etc. can be used. Specific examples of such ethylenically unsaturated bond-containing polyester dendrimers are described in Japanese Patent Application Laid-Open Nos. 2005-76005, 2005-47979, and Japanese Patent Application Laid-Open Nos. 2005-76005, for example. .

可單獨使用上述成分(F)之一種,另外可併用兩種以上。 於將上述成分(A)及成分(B)之合計設為100質量%時,成分(F)之存在量(質量%)較佳為1.0質量%至800質量%,尤佳為10質量%至600質量%。 One type of the above-mentioned component (F) may be used alone, or two or more types may be used in combination. When the total of the above-mentioned component (A) and component (B) is 100 mass%, the presence amount (mass%) of component (F) is preferably 1.0 mass% to 800 mass%, particularly preferably 10 mass% to 600% by mass.

[成分(G)] 成分(G)為光聚合起始劑,並無特別限制,作為一例,可列舉:二苯甲酮、雙‐N,N‐二甲基胺基二苯甲酮等二苯甲酮類,噻噸酮、異丙基噻噸酮等噻噸酮類。 [Ingredients (G)] Component (G) is a photopolymerization initiator and is not particularly limited. Examples thereof include: benzophenones such as benzophenone and bis-N,N-dimethylaminobenzophenone, and thiophene. Thioxanthones such as xanthone and isopropylthioxanthone.

另外,作為油溶性之光自由基聚合起始劑有:安息香、安息香甲基醚、安息香乙基醚、安息香異丙基醚等安息香及安息香烷基醚類;苯乙酮、2,2‐二甲氧基‐2‐苯基苯乙酮、2,2‐二乙氧基‐2‐苯基苯乙酮、1,1‐二氯苯乙酮、2‐羥基‐2‐甲基‐1‐苯基丙烷‐1‐酮、1‐(4‐異丙基苯基)‐2‐羥基‐2‐甲基丙烷‐1‐酮、1‐(4‐十二烷基苯基)‐2‐羥基‐2‐甲基丙烷‐1‐酮、4‐(2‐羥基乙氧基)‐苯基(2‐羥基‐2‐丙基)酮、1‐羥基環己基苯基酮等苯乙酮類;2‐甲基‐1‐[4‐(甲硫基)苯基]‐2‐嗎啉基丙酮‐1、2‐苄基‐2‐二甲基胺基‐1‐(4‐嗎啉基苯基)‐丁酮‐1等胺基苯乙酮類;2‐甲基蒽醌、2‐乙基蒽醌、2‐第三丁基蒽醌、1‐氯蒽醌等蒽醌類;2,4‐二甲基噻噸酮、2,4‐二乙基噻噸酮、2‐氯噻噸酮、異丙基噻噸酮、2,4‐二異丙基噻噸酮等噻噸酮類;苯乙酮二甲基縮酮、苯偶醯二甲基縮酮等縮酮類;二苯甲酮等二苯甲酮類或氧雜蒽酮類等,這些可單獨使用或組合使用兩種以上,另外,可將三級胺類般之公知之增感劑單獨使用或組合使用兩種以上。 相對於上述成分(F),成分(G)之量(質量%)較佳為0.1質量%至20質量%,尤佳為0.5質量%至10質量%。 In addition, oil-soluble photoradical polymerization initiators include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and other benzoin and benzoin alkyl ethers; acetophenone, 2,2-di Methoxy‐2‐phenylacetophenone, 2,2‐diethoxy‐2‐phenylacetophenone, 1,1‐dichloroacetophenone, 2‐hydroxy‐2‐methyl‐1‐ Phenylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 1-(4-dodecylphenyl)-2-hydroxy Acetophenones such as ‐2‐methylpropane‐1‐one, 4‐(2‐hydroxyethoxy)‐phenyl (2‐hydroxy‐2‐propyl) ketone, 1‐hydroxycyclohexyl phenyl ketone; 2‐methyl‐1‐[4‐(methylthio)phenyl]‐2‐morpholinoacetone‐1, 2‐benzyl‐2‐dimethylamino‐1‐(4‐morpholinobenzene Aminoacetophenones such as methyl)-butanone-1; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone; 2, Thioxanthone types such as 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, isopropylthioxanthone, and 2,4-diisopropylthioxanthone ; Ketals such as acetophenone dimethyl ketal and benzoyl dimethyl ketal; benzophenones such as benzophenone or xanthones, etc. These can be used alone or in combination. As mentioned above, well-known sensitizers such as tertiary amines may be used alone or in combination of two or more types. The amount (mass %) of component (G) is preferably 0.1 mass % to 20 mass %, particularly preferably 0.5 mass % to 10 mass %, relative to the above-mentioned component (F).

[成分(H)] 成分(H)為水性聚合物乳液,例如可列舉:聚乙酸乙烯酯、乙酸乙烯酯/乙烯共聚物、乙酸乙烯酯/丙烯酸酯共聚物、(甲基)丙烯酸聚合物、苯乙烯/丁二烯共聚物、甲基丙烯酸甲酯/丁二烯共聚物、丙烯腈/丁二烯共聚物、氯丁二烯聚合物、異戊二烯聚合物、聚氯乙烯、聚偏二氯乙烯、聚苯乙烯、聚矽氧樹脂、聚乙烯、聚胺基甲酸酯、氟樹脂等。這些疏水性聚合物粒子可列舉:藉由聚合步驟中而獲得之聚乙酸乙烯酯乳液、乙烯-乙酸乙烯酯共聚物乳液、乙酸乙烯酯-丙烯酸共聚物乳液、乙烯-乙酸乙烯酯-丙烯酸三元共聚合乳液、氯乙烯-乙酸乙烯酯共聚物乳液、丙烯酸乳液、苯乙烯-丁二烯乳膠乳液、MBR乳膠乳液、丙烯腈-丁二烯橡膠乳膠乳液、氯丁二烯橡膠乳膠乳液、偏二氯乙烯乳液等。進而,亦可適宜地使用:藉由熱聚合起始劑或光聚合起始劑將由多官能性(甲基)丙烯酸酯所製備之水性乳液加以乳化聚合而具有交聯結構的聚合物之水性乳液。作為合成高分子分散液,聚乙烯分散液、聚烯烴離子聚合物分散液、胺基甲酸酯離子聚合物分散液等有用。 於將上述成分(A)及成分(B)之合計設為100質量%時,成分(H)之存在比率(質量%)較佳為1質量%至1500質量%,尤佳為10質量%至1000質量%。 [Ingredients (H)] Component (H) is an aqueous polymer emulsion, for example, 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 Ethylene, polysilicone resin, polyethylene, polyurethane, fluororesin, etc. Examples of these hydrophobic polymer particles include polyvinyl acetate emulsion, ethylene-vinyl acetate copolymer emulsion, vinyl acetate-acrylic acid copolymer emulsion, and ethylene-vinyl acetate-acrylic acid ternary emulsion obtained in the polymerization step. Copolymer emulsion, vinyl chloride-vinyl acetate copolymer emulsion, acrylic emulsion, styrene-butadiene latex emulsion, MBR latex emulsion, acrylonitrile-butadiene rubber latex emulsion, chloroprene rubber latex emulsion, partial di Vinyl chloride emulsion, etc. Furthermore, an aqueous emulsion of a polymer having a cross-linked structure by emulsion polymerization of an aqueous emulsion prepared from a polyfunctional (meth)acrylate using a thermal polymerization initiator or a photopolymerization initiator can also be suitably used. . As synthetic polymer dispersions, polyethylene dispersions, polyolefin ionomer dispersions, urethane ionomer dispersions, and the like are useful. When the total of the above-mentioned component (A) and component (B) is 100 mass%, the presence ratio (mass%) of component (H) is preferably 1 to 1500 mass%, particularly preferably 10 to 1500 mass%. 1000% by mass.

[其他成分] 於第一感光性樹脂層,可根據需要而添加交聯劑、有機或無機粒子、矽烷偶合劑、顏料、染料、熱聚合防止劑、界面活性劑、消泡劑、抗氧化劑、密接性賦予劑、塑化劑、溶劑、表面張力調節劑、穩定劑、防鏈轉移劑、難燃劑、抗菌劑、防腐劑等作為其他成分。 [Other ingredients] To the first photosensitive resin layer, cross-linking agents, organic or inorganic particles, silane coupling agents, pigments, dyes, thermal polymerization inhibitors, surfactants, defoaming agents, antioxidants, and adhesion-imparting agents can be added as needed. , plasticizers, solvents, surface tension regulators, stabilizers, anti-chain transfer agents, flame retardants, antibacterial agents, preservatives, etc. as other ingredients.

[第二感光性樹脂層] 感光性樹脂層之第二具體例係由包含下述成分(A)、成分(C)及成分(D)而成之感光性樹脂所構成。 成分(A):皂化度為50mol%以上之聚乙烯醇;成分(C):具有至少一個環氧基之環氧化合物;成分(D):光酸產生劑。 [Second photosensitive resin layer] The second specific example of the photosensitive resin layer is composed of a photosensitive resin containing the following component (A), component (C) and component (D). Component (A): polyvinyl alcohol with a saponification degree of 50 mol% or more; Component (C): an epoxy compound with at least one epoxy group; Component (D): photoacid generator.

此處,所謂「包含…而成」,除了僅包含列舉之各成分(亦即成分(A)、成分(C)及成分(D))而成之情況以外,亦包括包含列舉之成分以外之成分等而成之情況。作為此種列舉之各層以外之層之代表例,例如可列舉成分(F)至成分(H)。Here, the term "consisting of" includes, in addition to the case where it contains only the listed components (i.e., component (A), component (C), and component (D)), it also includes components other than the listed components. The ingredients are equal. As a representative example of the layers other than each layer listed above, the component (F) to the component (H) can be mentioned, for example.

成分(A)與成分(C)之存在比率(質量%)係成分(A):成分(C)較佳為1:1至1:10,尤佳為1:2至1:6。相對於上述成分(C),成分(D)之量(質量%)較佳為1質量%至20質量%,尤佳為3質量%至10質量%。 包含上述成分(A)、成分(C)及成分(D)而成之感光性樹脂可根據需要而含有成分(F)至成分(H)中的任一種或多種。 The presence ratio (mass %) of component (A) and component (C) is component (A):component (C). Preferably it is 1:1 to 1:10, particularly preferably 1:2 to 1:6. The amount (mass %) of component (D) is preferably 1 mass % to 20 mass %, particularly preferably 3 mass % to 10 mass %, relative to the above-mentioned component (C). The photosensitive resin containing the above-mentioned component (A), component (C), and component (D) may contain any one or more of component (F) to component (H) as needed.

[成分(A)] 作為第二具體例中之成分(A),可使用第一感光性樹脂之具體例中作為成分(A)而例示之成分。 [Ingredients (A)] As the component (A) in the second specific example, the component exemplified as the component (A) in the specific example of the first photosensitive resin can be used.

[成分(C)] 成分(C)為具有至少一個環氧基之化合物。 作為二官能以上之縮水甘油基型環氧化合物,例如可列舉:乙二醇二縮水甘油醚、二乙二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、三丙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚、間苯二酚二縮水甘油醚、新戊二醇二縮水甘油醚、1,6‐己二醇二縮水甘油醚、甘油二縮水甘油醚、二溴新戊二醇二縮水甘油醚、氫化雙酚A二縮水甘油醚、對苯二甲酸二縮水甘油酯、鄰苯二甲酸二縮水甘油酯、氫化鄰苯二甲酸二縮水甘油酯、雙酚A之PO(Propylene Oxide;環氧丙烷)2mol加成物二縮水甘油醚、山梨糖醇聚縮水甘油醚、甘油聚縮水甘油醚、二甘油聚縮水甘油醚、聚甘油聚縮水甘油醚、三羥甲基丙烷聚縮水甘油醚、季戊四醇聚縮水甘油醚等。進而,作為脂環式環氧化合物,可列舉:3’,4’-環氧環己甲酸-3,4-環氧環己基甲酯、3’,4’-環氧環己甲酸-3,4-環氧環己基甲酯與ε-己內酯之加成物、1,2,8,9-二環氧檸檬烯、(3,3’4,4’-二環氧)雙環己基、1,2‐環氧‐4‐乙烯基環己烷)、2,2‐雙(羥基甲基)‐1‐丁醇之1,2‐環氧‐4‐(2‐氧雜環丁基)環己烷加成物、丁烷四羧酸-四(3,4‐環氧環己基甲基)修飾ε‐己內酯、甲基丙烯酸-3,4‐環氧環己基甲酯等。 [Ingredients (C)] Component (C) is a compound having at least one epoxy group. Examples of the bifunctional or higher-functional glycidyl type epoxy compound include: ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, triglycidyl ether, and triglycidyl ether. Propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, resorcin diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, diglycidyl ether Bromoneopentyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, diglycidyl terephthalate, diglycidyl phthalate, hydrogenated diglycidyl phthalate, bisphenol A PO (Propylene Oxide; propylene oxide) 2 mol adduct diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, trimethylol propane polyglycidyl ether, pentaerythritol polyglycidyl ether, etc. Furthermore, examples of alicyclic epoxy compounds include: 3',4'-epoxycyclohexylcarboxylic acid-3,4-epoxycyclohexylmethyl ester, 3',4'-epoxycyclohexylcarboxylic acid-3, Adduct of 4-epoxycyclohexylmethyl ester and ε-caprolactone, 1,2,8,9-diepoxylimonene, (3,3'4,4'-diepoxy)dicyclohexyl, 1 ,2-epoxy-4-vinylcyclohexane), 1,2-epoxy-4-(2-oxetanyl) ring of 2,2-bis(hydroxymethyl)-1-butanol Hexane adduct, butanetetracarboxylic acid-tetrakis (3,4-epoxycyclohexylmethyl) modified ε-caprolactone, methacrylic acid-3,4-epoxycyclohexylmethyl ester, etc.

作為單官能性環氧化合物,可列舉:2‐乙基己基縮水甘油醚、苯基縮水甘油醚、苯酚(EO)5縮水甘油醚、對第三丁基苯基縮水甘油醚、二溴苯基縮水甘油醚、月桂醇(EO)15縮水甘油醚、Cl 2、Cl 3混合醇縮水甘油醚、N‐縮水甘油基鄰苯二甲醯亞胺等。若將這些用作反應性稀釋劑,則可使用高黏度或固形之環氧樹脂。例如可使用:苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、三羥基苯基甲烷型環氧樹脂、二環戊二烯苯酚型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、聯苯酚型環氧樹脂、雙酚A酚醛清漆型環氧樹脂、含萘骨架之環氧樹脂、雜環式環氧樹脂、環氧化聚丁二烯、苯乙烯‐丁二烯嵌段共聚物之環氧化物、溴化環氧樹脂、聯苯型環氧樹脂、胺型環氧樹脂等。 另外,可將具有至少一個氧雜環丁基之化合物與上述環氧化合物混合使用。 Examples of monofunctional epoxy compounds include: 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol (EO) 5 glycidyl ether, p-tert-butylphenyl glycidyl ether, and dibromophenyl Glycidyl ether, lauryl alcohol (EO) 15 glycidyl ether, Cl 2 , Cl 3 mixed alcohol glycidyl ether, N-glycidyl phthalimide, etc. 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, trihydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, bisphenol A type epoxy resin, Bisphenol F epoxy resin, biphenol epoxy resin, bisphenol A novolac epoxy resin, epoxy resin containing naphthalene skeleton, heterocyclic epoxy resin, epoxidized polybutadiene, styrene- Butadiene block copolymer epoxy, brominated epoxy resin, biphenyl epoxy resin, amine epoxy resin, etc. In addition, a compound having at least one oxetanyl group and the above-mentioned epoxy compound may be mixed and used.

作為氧雜環丁烷化合物,可列舉:J.V.Crivello及H.Sasaki、J.M.S.Pure之應用化學(Appl.Chem.)(A30(2&3),189(1993))或J.H.Sasaki及V.Crivello、J.M.S.Pure之應用化學(Appl.Chem.)(A30(2&3),915(1993))所記載之化合物。例如可列舉:3‐乙基‐3‐羥基甲基氧雜環丁烷(氧雜環丁醇)、2‐乙基己基氧雜環丁烷、甲基丙烯酸(3‐乙基氧雜環丁烷‐3‐基)甲酯、丙烯酸(3‐乙基氧雜環丁烷‐3‐基)甲酯、3‐乙基‐3‐(4‐羥基丁氧基甲基)氧雜環丁烷等單官能氧雜環丁烷化合物;二甲苯雙氧雜環丁烷、3‐乙基‐3{[(3‐乙基氧雜環丁烷‐3‐基)甲氧基]甲基}氧雜環丁烷、4,4’‐雙[(3‐乙基‐3‐氧雜環丁基)甲氧基甲基]聯苯)、間苯二甲酸雙[(3‐乙基‐3‐氧雜環丁基)甲基]酯等二官能氧雜環丁烷化合物;季戊四醇三(3‐乙基‐3‐氧雜環丁基甲基)醚、季戊四醇四(3‐乙基‐3‐氧雜環丁基甲基)醚、二季戊四醇六(3‐乙基‐3‐氧雜環丁基甲基)醚、二季戊四醇五(3‐乙基‐3‐氧雜環丁基甲基)醚、二季戊四醇四(3‐乙基‐3‐氧雜環丁基甲基)醚、己內酯改質二季戊四醇六(3‐乙基‐3‐氧雜環丁基甲基)醚、己內酯改質二季戊四醇五(3‐乙基‐3‐氧雜環丁基甲基)醚、二-三羥甲基丙烷四(3‐乙基‐3‐氧雜環丁基甲基)醚等多官能氧雜環丁烷化合物。 可單獨使用上述成分(C)之一種,另外可併用兩種以上。 Examples of oxetane compounds include: J.V. Crivello and H. Sasaki, J.M.S. Pure, Appl. Chem. (A30 (2&3), 189 (1993)) or J.H. Sasaki, V. Crivello, J.M.S. Pure Compounds described in Appl. Chem. (A30 (2&3), 915 (1993)). Examples include: 3-ethyl-3-hydroxymethyloxetane (oxetanol), 2-ethylhexyloxetane, methacrylic acid (3-ethyloxetane Alk-3-yl)methyl ester, (3-ethyloxetan-3-yl)methyl acrylate, 3-ethyl-3-(4-hydroxybutoxymethyl)oxetane and other monofunctional oxetane compounds; xylenedioxetane, 3-ethyl-3{[(3-ethyloxetane-3-yl)methoxy]methyl}oxy Hetetane, 4,4'‐bis[(3‐ethyl‐3‐oxetanyl)methoxymethyl]biphenyl), isophthalic acid bis[(3‐ethyl‐3‐ Difunctional oxetane compounds such as oxetanyl)methyl] ester; pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxa cyclobutylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol penta(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3- Ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol penta(3-ethyl) Polyfunctional oxetane compounds such as -3-oxetanylmethyl) ether and di-trimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether. One type of the above-mentioned component (C) may be used alone, and two or more types may be used in combination.

[成分(D)] 成分(D)為酸產生劑,可使用化學增幅型光阻劑或用於光陽離子聚合之化合物(有機電子材料研究會編,「成像用有機材料」,文伸出版(1993年)、參照187至192頁)。作為酸產生劑之具體例,例如可列舉:鎓陽離子化合物、產生氫鹵酸之含鹵素化合物、產生磺酸之磺化化合物。 [Ingredients (D)] Component (D) is an acid generator, which can be a chemically amplified photoresist or a compound used for photocationic polymerization (Organic Electronic Materials Research Association, "Organic Materials for Imaging", Wenxin Publishing (1993), Reference 187 to page 192). Specific examples of the acid generator include onium cation compounds, halogen-containing compounds that generate hydrohalic acid, and sulfonated compounds that generate sulfonic acid.

作為離子性酸產生劑,例如可列舉:重氮鎓、銨、錪、鋶、鏻、鈰鐵等鎓陽離子之Cl -、Br -、I -、ZnCl 3 -、HSO 3 -、BF 4 -、PF 6 -、AsF 6 -、SbF 6 -、CH 3SO 3 -、CF 3SO 3 -、全氟丁磺酸鹽、全氟辛磺酸鹽、樟腦磺酸鹽、苯磺酸鹽、對甲苯磺酸鹽、9,10‐二甲氧基蒽‐2‐磺酸鹽、環己基胺基磺酸鹽、(C 6F 5) 4B -、(C 4H 9) 4B -等鹽。 Examples of the ionic acid generator include Cl - , Br - , I - , ZnCl 3 - , HSO 3 - , BF 4 - , and other onium cations such as diazonium, ammonium, iodonium, sulfonium, phosphonium, and ferric cerium. PF 6 - , AsF 6 - , SbF 6 - , CH 3 SO 3 - , CF 3 SO 3 - , perfluorobutanesulfonate, perfluorooctane sulfonate, camphorsulfonate, benzenesulfonate, p-toluene Sulfonate, 9,10-dimethoxyanthracene-2-sulfonate, cyclohexylamine sulfonate, (C 6 F 5 ) 4 B - , (C 4 H 9 ) 4 B - and other salts.

作為前述鎓陽離子之具體例,可列舉:苯基重氮鎓、對甲氧基重氮鎓、α‐萘基重氮鎓、聯苯重氮鎓、二苯基胺‐4‐重氮鎓、3‐甲氧基二苯基胺‐4‐重氮鎓、2,5‐二乙氧基‐4‐甲氧基苯甲醯基醯胺苯基重氮鎓、2,5‐二丙氧基‐4‐(4‐甲苯基)噻吩基重氮鎓、4‐甲氧基二苯基胺‐4‐重氮鎓、4‐重氮二苯基胺與甲醛之縮合物、1‐甲氧基喹啉鎓、1‐乙氧基異喹啉鎓、1‐苯甲醯甲基吡啶鎓、1‐苄基‐4‐苯甲醯基吡啶鎓、1‐苄基喹啉鎓、N‐取代苯并噻唑鎓(參照日本特開平5-140143號公報)等。Specific examples of the onium cation include: phenyldiazonium, p-methoxydiazonium, α-naphthyldiazonium, biphenyldiazonium, diphenylamine-4-diazonium, 3‐methoxydiphenylamine‐4‐diazonium, 2,5‐diethoxy‐4‐methoxybenzoylamide phenyldiazonium, 2,5‐dipropoxy ‐4‐(4‐tolyl)thienyldiazonium, 4‐methoxydiphenylamine‐4‐diazonium, the condensate of 4‐diazodiphenylamine and formaldehyde, 1‐methoxy Quinolinium, 1-ethoxyisoquinolinium, 1-benzylmethylpyridinium, 1-benzyl-4-benzylpyridinium, 1-benzylquinolinium, N-substituted benzene Thiazolium (see Japanese Patent Application Laid-Open No. 5-140143) and the like.

進而可列舉:苄基三苯基鋶、對甲氧基苯基二苯基鋶、雙(對甲氧基苯基)苯基鋶、三(對甲氧基苯基)鋶、對苯基噻吩基二苯基鋶、苄基四亞甲基鋶、苯甲醯甲基四亞甲基鋶、苯甲醯甲基二甲基鋶、對甲氧基苯基二乙基鋶、萘基二烷基鋶(參照日本特開平9-118663號公報、日本特開平5-140209號公報)、(2‐萘基羰基甲基)四亞甲基鋶、(對羥基苯基)二甲基鋶、(4‐羥基萘基)‐二甲基鋶、(4,7‐二羥基萘基)‐1‐二甲基鋶、(4,8‐二羥基萘基)‐1‐二甲基鋶、二苯基錪、苯基(4‐甲氧基苯基)錪、苯基{4‐(第三丁基)苯基}錪、4‐雙{4‐(第三丁基)苯基}錪、雙(4‐十二烷基苯基)錪、(4‐甲氧基苯基)(4‐辛氧基苯基)錪、苯甲醯甲基三苯基鏻、氰基甲基三苯基鏻等。Further examples include: benzyl triphenyl sulfonium, p-methoxyphenyl diphenyl sulfonium, bis (p-methoxyphenyl) phenyl sulfonium, tris (p-methoxyphenyl) sulfonium, and p-phenylthiophene Benzyl diphenyl sulfonium, benzyl tetramethylene sulfonium, benzyl tetramethylene sulfonium, benzyl methyl dimethyl sulfonium, p-methoxyphenyl diethyl sulfonium, naphthyl dialkane methylsulfonium (refer to Japanese Patent Application Publication No. 9-118663, Japanese Patent Application Publication No. 5-140209), (2-naphthylcarbonylmethyl)tetramethylenesulfonium, (p-hydroxyphenyl)dimethylsulfonium, ( 4-Hydroxynaphthyl)-dimethylsulfonium, (4,7-dihydroxynaphthyl)-1-dimethylsulfonium, (4,8-dihydroxynaphthyl)-1-dimethylsulfonium, diphenyl Phenyl (4-methoxyphenyl) iodide, phenyl {4-(tert-butyl)phenyl} iodide, 4-bis {4-(tert-butyl)phenyl} iodide, bis (4-Dodecylphenyl)phosphonium, (4-methoxyphenyl)(4-octoxyphenyl)phosphonium, benzylmethyltriphenylphosphonium, cyanomethyltriphenylphosphonium wait.

作為產生氫鹵酸之酸產生劑,可列舉:1‐甲基‐3,5‐雙(三氯甲基)‐均三嗪、1‐苯基‐3,5‐雙(三氯甲基)‐均三嗪、1‐(4‐氯苯基)‐3,5‐雙(三氯甲基)‐均三嗪、1‐(4‐甲氧基苯基)‐3,5‐雙(三氯甲基)‐均三嗪、1‐(4‐丁氧基苯基)‐3,5‐雙(三氯甲基)‐均三嗪、1‐(3,4‐亞甲基二氧基苯基)‐3,5‐雙(三氯甲基)‐均三嗪、1‐(3,4‐二甲氧基苯基)‐3,5‐雙(三氯甲基)‐均三嗪、1‐(4‐甲氧基萘基‐1)‐3,5‐雙(三氯甲基)‐均三嗪、1‐{2‐(4‐甲氧基苯基)乙烯基}‐3,5‐雙(三氯甲基)‐均三嗪、1‐{2‐(2‐甲氧基苯基)乙烯基}‐3,5‐雙(三氯甲基)‐均三嗪、1‐{2‐(3,4‐二甲氧基苯基)乙烯基}‐3,5‐雙(三氯甲基)‐均三嗪、1‐{2‐(3‐氯‐4‐甲氧基苯基)乙烯基}‐3,5‐雙(三氯甲基)‐均三嗪、1‐(聯苯‐1)‐3,5‐雙(三氯甲基)‐均三嗪、1‐(4‐羥基聯苯‐1)‐3,5‐雙(三氯甲基)‐均三嗪、1‐(4‐甲氧基聯苯‐1)‐3,5‐雙(三氯甲基)‐均三嗪、1‐(4‐甲基聯苯‐1)‐3,5‐雙(三氯甲基)‐均三嗪、1,3,5‐三(三氯甲基)‐均三嗪、1,3‐二氯‐4‐三氯甲基苯、1,1,1‐三氯‐{2,2‐84‐氯苯基}乙烷、苯基三溴甲基碸、1‐酮基‐4‐甲基‐4‐三氯甲基‐2,5‐二氯己二烯、2‐三溴喹啉、1‐酮基‐2,3‐苯并‐4,4,5,6‐四氯六烯‐5等。Examples of acid generators that generate hydrohalic acid 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(tri Chloromethyl)-s-triazine, 1-(4-butoxyphenyl)-3,5-bis(trichloromethyl)-s-triazine, 1-(3,4-methylenedioxy Phenyl)-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)vinyl}-3 ,5-bis(trichloromethyl)-s-triazine, 1-{2-(2-methoxyphenyl)vinyl}-3,5-bis(trichloromethyl)-s-triazine, 1 ‐{2‐(3,4‐dimethoxyphenyl)vinyl}‐3,5‐bis(trichloromethyl)‐s‐triazine, 1‐{2‐(3‐chloro‐4‐methoxy phenyl)vinyl}-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) base)-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, phenyltribromomethylbenzene, 1-keto-4-methyl-4-trichloromethyl-2,5-dichlorohexadiene, 2-tribromoquinoline, 1-keto-2,3-benzo-4,4, 5,6-Tetrachlorohexene-5, etc.

作為產生磺酸之酸產生劑,可列舉:2‐硝基苄基對甲苯磺酸酯、2,6‐二硝基苄基對甲苯磺酸酯、1‐(對甲苯磺醯氧基亞胺基)‐1‐苯基乙烷腈、1‐(對甲苯磺醯氧基亞胺基)‐1‐苯基乙烷腈、安息香對甲苯磺酸酯、2‐對甲苯磺醯氧基‐2‐苯甲醯基丙烷、對硝基苄基9,10‐二甲氧基蒽‐2‐磺酸酯、N‐三氟甲磺醯氧基二苯基馬來醯亞胺、N‐對甲苯磺醯氧基琥珀醯亞胺、N‐樟腦磺醯氧基琥珀醯亞胺、N‐三氟甲磺醯氧基琥珀醯亞胺、N‐全氟丁磺醯氧基琥珀醯亞胺、N‐對甲苯磺醯氧基鄰苯二甲醯亞胺、N‐樟腦磺醯氧基鄰苯二甲醯亞胺、N‐三氟甲磺醯氧基鄰苯二甲醯亞胺、N‐全氟丁磺醯氧基鄰苯二甲醯亞胺、N‐對甲苯磺醯氧基‐1,8‐萘羧基醯亞胺、N‐樟腦磺醯氧基‐1,8‐萘羧基醯亞胺、N‐三氟甲磺醯氧基‐1,8‐萘羧基醯亞胺、N‐全氟丁磺醯氧基‐1,8‐萘羧基醯亞胺、1,2,3‐三(對甲苯磺醯氧基)苯、雙(苯基碸)、雙(苯基磺醯基)甲烷等。Examples of acid generators that generate sulfonic acid include: 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate, and 1-(p-toluenesulfonyloxyimine) base)-1-phenylethane nitrile, 1-(p-toluenesulfonyloxyimino)-1-phenylethanenitrile, benzoin p-toluenesulfonate, 2-p-toluenesulfonyloxy-2 ‐Benzoylpropane, p-nitrobenzyl 9,10-dimethoxyanthracene-2-sulfonate, N-trifluoromethanesulfonyloxydiphenylmaleimide, N-p-toluene Sulfonyloxysuccinimide, N-camphorsulfonyloxysuccinimide, N-trifluoromethanesulfonyloxysuccinimide, N-perfluorobutanesulfonyloxysuccinimide, N ‐p-Toluenesulfonyloxyphthalimide, N-camphorsulfonyloxyphthalimide, N-trifluoromethanesulfonyloxyphthalimide, N-all Fluorobutanesulfonyloxyphthalimide, N-p-toluenesulfonyloxy-1,8-naphthylcarboxylimide, N-camphorsulfonyloxy-1,8-naphthylcarboxylimide , N-trifluoromethanesulfonyloxy-1,8-naphthylcarboxylimide, N-perfluorobutanesulfonyloxy-1,8-naphthalenecarboxylimide, 1,2,3-tris(p Toluenesulfonyloxy)benzene, bis(phenylsulfonyl), bis(phenylsulfonyl)methane, etc.

另外,可與酸產生劑併用而使用增感劑,作為所使用之增感劑,較理想為供電子性化合物。作為具有此種特性之增感劑,可列舉:芳香族多環化合物、卟啉化合物、酞菁化合物、聚次甲基色素化合物、部花青化合物、香豆素化合物、噻喃鎓化合物、吡喃鎓化合物、對二烷基胺基苯乙烯基化合物、噻噸化合物等,但不限定於此。這些大多係揭載於:大河、平嶋、松岡、北尾編輯之「色素手冊」(講談社),社團法人色材協會編輯之「色材工學手冊」(朝倉書店(1989年發行)),林原生物化學研究所感光色素研究所「Dye Catalogue」等。In addition, a sensitizer may be used in combination with an acid generator, and the sensitizer used is preferably an electron-donating compound. Examples of sensitizers having such characteristics include aromatic polycyclic compounds, porphyrin compounds, phthalocyanine compounds, polymethine pigment compounds, merocyanine compounds, coumarin compounds, thiopyranium compounds, and pyridine compounds. Pyramide compounds, p-dialkylaminostyrene compounds, thioxanthene compounds, etc., but are not limited thereto. Most of these are published in: "Pigment Handbook" (Kodansha) edited by Ohga, Hirajima, Matsuoka, and Kitao, "Color Material Engineering Handbook" edited by the Color Material Association (Asakura Shoten (published in 1989)), Hayashihara Biology Institute of Chemistry, Photopigment Research Institute "Dye Catalog", etc.

[成分(F)] 作為第二具體例中之成分(F),可使用第一感光性樹脂之具體例中作為成分(F)而例示之成分。 於將上述成分(A)及成分(C)及成分(D)之合計設為100質量%時,成分(F)之存在比率(質量%)較佳為1質量%至60質量%,尤佳為5質量%至30質量%。 [Ingredients (F)] As the component (F) in the second specific example, the component exemplified as the component (F) in the specific example of the first photosensitive resin can be used. When the total of the above-mentioned component (A), component (C), and component (D) is 100 mass%, the presence ratio (mass%) of component (F) is preferably 1 to 60 mass%, and particularly preferably It is 5 mass % to 30 mass %.

[成分(G)] 作為第二具體例中之成分(G),可使用第一感光性樹脂之具體例中作為成分(G)而例示之成分。 相對於上述成分(F),成分(G)之存在比率(質量%)較佳為0質量%至20質量%,尤佳為0.1質量%至10質量%。 [Ingredients (G)] As the component (G) in the second specific example, the component exemplified as the component (G) in the specific example of the first photosensitive resin can be used. The presence ratio (mass %) of the component (G) relative to the above-mentioned component (F) is preferably 0 to 20 mass %, and particularly preferably 0.1 to 10 mass %.

[成分(H)] 作為第二具體例中之成分(H),可使用第一感光性樹脂之具體例中作為成分(H)而例示之成分。 於將上述成分(A)及成分(C)及成分(D)之合計設為100質量%時,成分(H)之存在比率(質量%)較佳為0.5質量%至200質量%,尤佳為1質量%至100質量%。 [Ingredients (H)] As the component (H) in the second specific example, the component exemplified as the component (H) in the specific example of the first photosensitive resin can be used. When the total of the above-mentioned component (A), component (C) and component (D) is 100 mass %, the presence ratio (mass %) of the component (H) is preferably 0.5 mass % to 200 mass %, particularly preferably It is 1 mass % to 100 mass %.

[其他成分] 於第二感光性樹脂層,可根據需要而使用交聯劑、有機或無機粒子、矽烷偶合劑、顏料、染料、熱聚合防止劑、界面活性劑、消泡劑、抗氧化劑、密接性賦予劑、塑化劑、溶劑、表面張力調節劑、穩定劑、防鏈轉移劑、難燃劑、抗菌劑、防腐劑等作為其他成分。 [Other ingredients] In the second photosensitive resin layer, a cross-linking agent, organic or inorganic particles, silane coupling agent, pigment, dye, thermal polymerization inhibitor, surfactant, defoaming agent, antioxidant, and adhesion-imparting agent can be used as needed. , plasticizers, solvents, surface tension regulators, stabilizers, anti-chain transfer agents, flame retardants, antibacterial agents, preservatives, etc. as other ingredients.

[第三感光性樹脂層] 感光性樹脂層之第三具體例係由包含下述成分(E)而成之感光性樹脂所構成。 成分(E):具有經苯乙烯基取代之吡啶鎓基或經苯乙烯基取代之喹啉鎓基的皂化度為50mol%以上之聚乙烯醇。 包含上述成分(E)而成之感光性樹脂可根據需要而包含成分(F)至成分(H)中的任一種或多種。 [Third photosensitive resin layer] The 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 pyridinium group substituted with a styrene group or a quinolinium group substituted with a styrene group and a saponification degree of 50 mol% or more. The photosensitive resin containing the said component (E) may contain any one or more types of components (F) to component (H) as needed.

[成分(E)] 成分(E)為具有經苯乙烯基取代之吡啶鎓基或經苯乙烯基取代之喹啉鎓基的皂化度為50mol%以上之乙酸乙烯酯聚合物皂化物,自身具有光交聯性。作為較佳之具體例,可列舉下述通式(1)或通式(2)所表示之化合物。 [Component (E)] Component (E) is a vinyl acetate polymer saponified product having a pyridinium group substituted with a styryl group or a quinolinium group substituted with a styryl group and a saponification degree of 50 mol% or more. Photo-crosslinkability. Preferable specific examples include compounds represented by the following general formula (1) or general formula (2).

(式中,R 1表示氫原子、烷基或芳烷基,這些可經羥基、胺甲醯基取代,另外,這些之碳碳鍵亦可介有氧原子或不飽和鍵。R 2表示氫原子或碳數1至3之烷基。m為1至6之整數。n為0或1。X -表示鹵素離子、磷酸根離子、甲基硫酸根離子、磺酸根離子、具有陰離子解離能力之自由基聚合性單體或這些陰離子之混合物)。 作為R 1之烷基或芳烷基,較佳為碳數1至10。尤佳為1至7。作為具體之殘基(R 1),可列舉:甲基、乙基、丙基、丁基、戊基、己基、2‐羥基乙基、3‐羥基丙基、2‐甲氧基乙基、3‐甲氧基丙基、烯丙基、巴豆基、苄基等。若m超過1至6之範圍,則光不溶化後之膜容易膨潤,更佳為1至4。n為0或1的任一個。 (In the formula, R 1 represents a hydrogen atom, an alkyl group or an aralkyl group, which can be substituted by a hydroxyl group or an amine methane group. In addition, the carbon-carbon bonds of these can also be interposed with oxygen atoms or unsaturated bonds. R 2 represents hydrogen Atom or alkyl group with 1 to 3 carbon atoms. m is an integer from 1 to 6. n is 0 or 1 . radically polymerizable monomers or mixtures of these anions). The alkyl group or aralkyl group of R 1 is preferably one having 1 to 10 carbon atoms. Especially preferably 1 to 7. Specific residues (R 1 ) include: methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-methoxyethyl, 3-methoxypropyl, allyl, crotyl, benzyl, etc. If m exceeds the range of 1 to 6, the film after photoinsolubilization will easily swell, and it is more preferably 1 to 4. n is either 0 or 1.

作為X -,較佳為磷酸根離子、甲基硫酸根離子,作為鹵素離子,較佳為Cl -或Br -,作為磺酸根離子,較佳為CH 3SO 3 -、CH 3CH 2SO 3 -、C 6H 5SO 3 -、p-CH 3C 6H 4SO 3 -。另外,作為X -,亦可列舉具有至少一個乙烯性不飽和鍵且具有陰離子解離能力之自由基聚合性單體。作為具有陰離子解離能力之殘基,可列舉磺酸、羧酸、磷酸,藉由製成這些之鹼鹽或脂肪族胺之銨鹽而可用作具有陰離子基之自由基單體。作為用於該目的之單體中之自由基聚合性不飽和基,可列舉:(甲基)丙烯醯基(以下,所謂(甲基)丙烯醯基,意指丙烯醯基及甲基丙烯醯基兩者)、馬來酸單酯基、苯乙烯基、烯丙基等。作為不解離之酸型之單體之例,可列舉:丙烯酸酸、甲基丙烯酸、馬來酸單甲酯、馬來酸單乙酯、鄰苯二甲酸2‐(甲基)丙烯醯氧基乙酯、鄰苯二甲酸3‐(甲基)丙烯醯氧基‐2‐丙酯、鄰苯二甲酸3‐(甲基)丙烯醯氧基‐2‐丙酯、環己烷‐3‐烯‐1,2‐二羧酸2‐(甲基)丙烯醯氧基乙酯、琥珀酸2‐(甲基)丙烯醯氧基乙酯、環己烷‐1,2‐羧酸2‐(甲基)丙烯醯氧基乙酯、馬來酸2‐(甲基)丙烯醯氧基乙酯、ω‐羧基‐聚己內酯d單丙烯酸酯、丙烯酸二聚物、2‐(甲基)丙烯醯氧基乙基磷酸、3‐(甲基)丙烯醯氧基丙基磷酸、2‐(甲基)丙烯醯氧基‐3‐丙基磷酸、ω‐(甲基)丙烯醯基聚伸乙氧基乙烯磷酸、ω‐(甲基)丙烯醯基聚伸丙氧基乙烯磷酸、苯乙烯磺酸、N‐(2‐磺基乙基)丙烯醯胺、N‐(2‐磺基乙基)甲基丙烯醯胺等,但不限於此。 X - is preferably a phosphate ion or methylsulfate ion, a halide ion is preferably Cl - or Br - , and a sulfonate ion is preferably CH 3 SO 3 - or CH 3 CH 2 SO 3 - , C 6 H 5 SO 3 - , p-CH 3 C 6 H 4 SO 3 - . Examples of X - include radically polymerizable monomers having at least one ethylenically unsaturated bond and having anion dissociation ability. Examples of residues having anion dissociation ability include sulfonic acid, carboxylic acid, and phosphoric acid. By making these alkali salts or ammonium salts of aliphatic amines, they can be used as radical monomers having anionic groups. Examples of the radically polymerizable unsaturated group in the monomer used for this purpose include: (meth)acrylyl group (hereinafter, (meth)acrylyl group means an acrylyl group and a methacrylyl group). Both groups), maleic acid monoester group, styrene group, allyl group, etc. Examples of non-dissociable acid-type monomers include: acrylic acid, methacrylic acid, maleic acid monomethyl ester, maleic acid monoethyl ester, 2-(meth)acryloxy phthalate Ethyl ester, 3-(meth)acryloxy-2-propyl phthalate, 3-(meth)acryloxy-2-propyl phthalate, cyclohexane-3-ene ‐1,2‐dicarboxylic acid 2‐(meth)acryloxyethyl ester, succinic acid 2‐(meth)acryloxyethyl ester, cyclohexane‐1,2‐carboxylic acid 2‐(methane acrylic acid ethyl ester, 2-(meth)acryloxyethyl maleate, ω-carboxy-polycaprolactone d monoacrylate, acrylic acid dimer, 2-(meth)propylene Cyloxyethyl phosphate, 3-(meth)acrylyloxypropyl phosphate, 2-(meth)acrylyloxy-3-propylphosphate, ω-(meth)acryloxypolyethylene Oxyethylene phosphate, ω-(meth)acrylyl polypropoxyethylene phosphate, styrene sulfonic acid, N-(2-sulfoethyl)acrylamide, N-(2-sulfoethyl ) methacrylamide, etc., but are not limited to these.

[成分(F)] 作為第三具體例中之成分(F),可使用第一感光性樹脂之具體例中作為成分(F)而例示之成分。 於將上述成分(E)設為100質量%時,成分(F)之存在比率(質量%)較佳為1.0質量%至800質量%,尤佳為10質量%至600質量%。 [Ingredients (F)] As the component (F) in the third specific example, the component exemplified as the component (F) in the specific example of the first photosensitive resin can be used. When the above-mentioned component (E) is set to 100 mass %, the presence ratio (mass %) of the component (F) is preferably 1.0 mass % to 800 mass %, particularly preferably 10 mass % to 600 mass %.

[成分(G)] 作為第三具體例中之成分(G),可使用第一感光性樹脂之具體例中作為成分(E)而例示之成分。 於將上述成分(F)設為100質量%時,成分(G)之存在比率(質量%)較佳為0.1質量%至20質量%,尤佳為0.5質量%至10質量%。 [Ingredients (G)] As the component (G) in the third specific example, the component exemplified as the component (E) in the specific example of the first photosensitive resin can be used. When the above-mentioned component (F) is set to 100 mass %, the presence ratio (mass %) of the component (G) is preferably 0.1 mass % to 20 mass %, particularly preferably 0.5 mass % to 10 mass %.

[成分(H)] 作為第三具體例中之成分(H),可使用第一感光性樹脂之具體例中作為成分(H)而例示之成分。 於將上述成分(E)設為100質量%時,成分(H)之存在比率(質量%)較佳為1質量%至1500質量%,尤佳為10質量%至1000質量%。 [Ingredients (H)] As the component (H) in the third specific example, the component exemplified as the component (H) in the specific example of the first photosensitive resin can be used. When the above-mentioned component (E) is set to 100 mass%, the presence ratio (mass%) of the component (H) is preferably 1 to 1500 mass%, particularly preferably 10 to 1000 mass%.

[其他成分] 於第三感光性樹脂層,可根據需要而使用交聯劑、有機或無機粒子、矽烷偶合劑、顏料、染料、熱聚合防止劑、界面活性劑、消泡劑、抗氧化劑、密接性賦予劑、塑化劑、溶劑、表面張力調節劑、穩定劑、防鏈轉移劑、難燃劑、抗菌劑、防腐劑等作為其他成分。 [Other ingredients] In the third photosensitive resin layer, cross-linking agents, organic or inorganic particles, silane coupling agents, pigments, dyes, thermal polymerization inhibitors, surfactants, defoaming agents, antioxidants, and adhesion-imparting agents can be used as needed. , plasticizers, solvents, surface tension regulators, stabilizers, anti-chain transfer agents, flame retardants, antibacterial agents, preservatives, etc. as other ingredients.

[保護層] 於本發明之圖案形成用積層膜,可包含支撐層、糊層、非水溶性高分子層及感光性樹脂層以外之其他層。作為此種其他層之代表例,例如可列舉保護層。 [protective layer] The laminated film for pattern formation of the present invention may include layers other than the support layer, paste layer, water-insoluble polymer layer, and photosensitive resin layer. Representative examples of such other layers include protective layers.

該保護層主要具有保護本發明之圖案形成用積層膜之功能,並且,例如於將該保護層配置於感光性樹脂層的表面之情形時,可防止由來自外部之衝擊或壓力等損傷感光性樹脂層,防止因濕氣或氣體、光等而劣化。而且,容易將本發明之圖案形成用積層膜重疊或捲繞成輥狀而儲藏。This protective layer mainly has the function of protecting the pattern-forming laminated film of the present invention, and, for example, when the protective layer is disposed on the surface of the photosensitive resin layer, it can prevent damage to the photosensitivity due to impact or pressure from the outside. The resin layer prevents deterioration due to moisture, gas, light, etc. Furthermore, the laminated film for pattern formation of the present invention can be easily stacked or wound into a roll shape and stored.

於本發明中,作為保護層,可使用由各種材料所構成之層。例如,可使用由各種樹脂材料所構成之層,另外可使用由天然材料所構成之層。 保護層之具體材質並無限制,例如可使用與支撐層同樣之材質。保護層之厚度並無特別限定,較佳為1μm至50μm。 In the present invention, as the protective layer, layers composed of various materials can be used. For example, a layer composed of various resin materials may be used, and a layer composed of natural materials may be used. The specific material of the protective layer is not limited, for example, the same material as the supporting layer can be used. The thickness of the protective layer is not particularly limited, but is preferably 1 μm to 50 μm.

於將在感光劑層的表面配置有保護層的本發明之圖案形成用積層膜適用於例如網版印刷版之情形時,於構成本發明之圖案形成用積層膜的其他層之前,先剝離該保護層。因此,該保護層與感光劑層之間之層間接著力較佳為低於其他層間接著力(x)至(z)(亦即,亦低於層間接著力(y))。因此,亦可對單面或兩面實施有脫模處理。When the pattern-forming laminated film of the present invention having a protective layer disposed on the surface of the photosensitive agent layer is applied to, for example, a screen printing plate, the pattern-forming laminated film of the present invention is peeled off before other layers constituting the pattern-forming laminated film of the present invention. protective layer. Therefore, the inter-layer adhesion force between the protective layer and the photosensitive agent layer is preferably lower than the other inter-layer adhesion forces (x) to (z) (that is, also lower than the inter-layer adhesion force (y)). Therefore, it is also possible to perform demoulding treatment on one or both sides.

另外,可為透明亦可為不透明。例如可列舉:紙;脫模紙;聚對苯二甲酸乙二酯等聚酯,聚甲基戊烯、聚丙烯、聚乙烯等聚烯烴,聚氟乙烯、聚氯乙烯等含鹵素之乙烯基聚合物,尼龍等聚醯胺,賽珞凡等纖維素,聚苯乙烯,丙烯酸樹脂,聚醯亞胺等之膜。另外,只要不喪失積層膜之功能,則亦可對單面或兩面實施有脫模處理、粗面處理、易接著處理。In addition, it may be transparent or opaque. Examples include: paper; release paper; polyesters such as polyethylene terephthalate; polyolefins such as polymethylpentene, polypropylene, and polyethylene; and halogen-containing vinyls such as polyvinyl fluoride and polyvinyl chloride. Polymers, polyamides such as nylon, cellulose such as cellulose, polystyrene, acrylic resin, polyimide, etc. In addition, as long as the function of the laminated film is not lost, one or both sides can also be subjected to release treatment, roughening treatment, and easy adhesion treatment.

[未感光之網版印刷版(第一未感光之網版印刷版)] 本發明之第一未感光之網版印刷版之特徵在於:包含上述圖案形成用積層膜、以及積層於前述圖案形成用積層膜的前述感光性樹脂層側之網版絲網而成。 [Unsensitized screen printing plate (the first unsensitized screen printing plate)] The first non-photosensitive screen printing plate of the present invention is characterized in that it includes the above-mentioned pattern forming laminated film, and a screen mesh laminated on the side of the photosensitive resin layer of the above-mentioned pattern forming laminated film.

圖1係表示本發明之第一未感光之網版印刷版8之較佳具體例。圖1所示之本發明之較佳未感光之網版印刷版8係包含圖案形成用積層膜1(具體而言為依序構成支撐層2、糊層3、非水溶性高分子層4及感光性樹脂層5而成之圖案形成用積層膜1)、以及積層於該圖案形成用積層膜1的前述感光性樹脂層5側之網版絲網6而成。此處,網版絲網6係與通常之一般的網版印刷版同樣地貼設於框材7。Figure 1 shows a preferred specific example of the first non-photosensitive screen printing plate 8 of the present invention. The preferred non-photosensitive screen printing plate 8 of the present invention shown in Figure 1 includes a laminated film 1 for pattern formation (specifically, a support layer 2, a paste layer 3, a water-insoluble polymer layer 4 and a It is composed of a pattern-forming laminated film 1) made of a photosensitive resin layer 5, and a screen mesh 6 laminated on the photosensitive resin layer 5 side of the pattern-forming laminated film 1. Here, the screen screen 6 is attached to the frame material 7 in the same manner as a normal screen printing plate.

[未感光之網版印刷版(第一未感光之網版印刷版)之製造方法] 本發明之未感光之網版印刷版(第一未感光之網版印刷版)之製造方法之特徵在於:包含下述步驟(a)而成。 步驟(a):於上述圖案形成用積層膜的前述感光性樹脂層側接合網版絲網之步驟。 根據該網版印刷版之製造方法,例如可製造圖1所示之未感光之網版印刷版8。 [Manufacturing method of unsensitized screen printing plate (the first unsensitized screen printing plate)] The manufacturing method of the non-photosensitive screen printing plate (first non-photosensitive screen printing plate) of the present invention is characterized by including the following step (a). Step (a): A step of joining a screen screen to the photosensitive resin layer side of the pattern-forming laminated film. According to this method of manufacturing a screen printing plate, for example, a non-photosensitive screen printing plate 8 shown in FIG. 1 can be manufactured.

於步驟(a)中,於圖案形成用積層膜1的感光性樹脂層5側接合網版絲網6時,較佳可列舉例如下述方法:(1)於網版絲網6預先塗敷感光性材料(較佳為與形成感光性樹脂層5之感光性樹脂相同或類似之感光性材料)或水,於此處接合圖案形成用積層膜1的感光性樹脂層5之方法;(2)於網版絲網6重疊圖案形成用積層膜1的感光性樹脂層5後,於該重疊部塗敷與形成感光性樹脂層之感光性樹脂相同或類似之感光性材料或水之方法。In step (a), when joining the screen mesh 6 to the photosensitive resin layer 5 side of the pattern forming laminated film 1, the following method may be preferably used: (1) Coating the screen mesh 6 in advance A method of joining the photosensitive resin layer 5 of the pattern forming laminated film 1 here with a photosensitive material (preferably a photosensitive material that is the same as or similar to the photosensitive resin forming the photosensitive resin layer 5) or water; (2 ) is a method of overlapping the photosensitive resin layer 5 of the pattern-forming laminated film 1 on the screen screen 6, and then applying a photosensitive material or water that is the same as or similar to the photosensitive resin used to form the photosensitive resin layer on the overlapping portion.

[未感光之網版印刷版(第二未感光之網版印刷版)] 本發明之未感光之網版印刷版之其他較佳態樣(第二未感光之網版印刷版)之特徵在於:包含自圖案形成用積層膜去掉前述支撐層及糊層而得之積層膜、以及積層於前述積層膜的前述感光性樹脂層側之網版絲網而成。 [Unsensitized screen printing plate (second unsensitized screen printing plate)] Another preferred aspect of the non-photosensitive screen printing plate of the present invention (the second non-photosensitive screen printing plate) is characterized in that it includes a laminated film obtained by removing the aforementioned support layer and paste layer from the pattern-forming laminated film. , and a screen mesh laminated on the photosensitive resin layer side of the laminated film.

圖2係表示本發明之第二未感光之網版印刷版9之較佳具體例。 圖2所示之本發明之較佳未感光之網版印刷版9係包含自圖1所示之未感光之網版印刷版8中的圖案形成用積層膜1去掉支撐層2及糊層3而得之積層膜1’、以及積層於前述積層膜1’的前述感光性樹脂層5側之網版絲網6而成。 Figure 2 shows a preferred specific example of the second non-photosensitive screen printing plate 9 of the present invention. The preferred non-photosensitive screen printing plate 9 of the present invention shown in Figure 2 is composed of the pattern-forming laminated film 1 in the non-photosensitive screen printing plate 8 shown in Figure 1 without the support layer 2 and the paste layer 3 The obtained laminated film 1' and the screen mesh 6 laminated|stacked on the said photosensitive resin layer 5 side of the said laminated film 1' are formed.

[未感光之網版印刷版(第二未感光之網版印刷版)之製造方法] 本發明之未感光之網版印刷版(第二未感光之網版印刷版)之製造方法之特徵在於:包含下述步驟(a)及步驟(b)而成。 步驟(a):於前述圖案形成用積層膜的前述感光性樹脂層面側接合網版絲網之步驟;步驟(b):自前述圖案形成用積層膜的非水溶性高分子層剝離前述支撐層及糊層之步驟。 圖2係表示由此種製造方法所得之未感光之網版印刷版9之較佳具體例。 [Method for manufacturing unsensitized screen printing plate (second unsensitized screen printing plate)] The manufacturing method of the non-photosensitive screen printing plate (the second non-photosensitive screen printing plate) of the present invention is characterized by including the following steps (a) and (b). Step (a): The step of joining the screen mesh to the photosensitive resin layer side of the pattern-forming laminated film; Step (b): Peeling off the support layer from the water-insoluble polymer layer of the pattern-forming laminated film. And the steps of paste layer. Figure 2 shows a preferred specific example of the non-photosensitive screen printing plate 9 obtained by this manufacturing method.

[網版印刷版之製造方法] 本發明之網版印刷版之製造方法之特徵在於:包含下述步驟(a)至步驟(f)而成。 步驟(a):於前述圖案形成用積層膜的前述感光性樹脂層側接合網版絲網之步驟;步驟(b):自前述圖案形成用積層膜的非水溶性高分子層剝離前述支撐層及糊層之步驟;步驟(c):於前述非水溶性高分子層的表面配置圖案遮罩之步驟;步驟(d):於前述感光性樹脂層形成潛像之步驟;步驟(e):剝離前述非水溶性高分子層之步驟;步驟(f):將形成有前述潛像之感光性樹脂層加以顯影之步驟。 [Manufacturing method of screen printing plate] The method for manufacturing a screen printing plate of the present invention is characterized by comprising the following steps (a) to (f). Step (a): The step of joining the screen mesh to the photosensitive resin layer side of the pattern-forming laminated film; Step (b): Peeling off the support layer from the water-insoluble polymer layer of the pattern-forming laminated film. and paste layer; step (c): the step of arranging a pattern mask on the surface of the aforementioned water-insoluble polymer layer; step (d): the step of forming a latent image on the aforementioned photosensitive resin layer; step (e): The step of peeling off the aforementioned water-insoluble polymer layer; step (f): the step of developing the photosensitive resin layer on which the aforementioned latent image is formed.

圖3係表示本發明之網版印刷版之製造方法之概要的圖;並且,圖3A係表示於前述圖案形成用積層膜1的前述感光性樹脂層5側接合網版絲網6之步驟(a)之概要;圖3B係表示自前述圖案形成用積層膜1的非水溶性高分子層4剝離前述支撐層2及糊層3之步驟(b)之概要;圖3C係表示於前述非水溶性高分子層4的表面配置圖案遮罩10之步驟(c)之概要;圖3D係表示自前述圖案遮罩10面對前述感光性樹脂層5照射能量線,於感光性樹脂形成潛像α之步驟(d)之概要;圖3E係表示剝離前述非水溶性高分子層4之步驟(e)之概要;圖3F係表示實施將形成有前述潛像α之感光性樹脂層5加以顯影之步驟(f)而得的網版印刷版11之概要。該步驟(f)中,進行由下述步驟所構成之顯影處理:以水(例如中性水)清洗形成有潛像α之感光性樹脂層5,去除感光性樹脂層5之未硬化區域(亦即未形成有潛像α之區域)。然後,藉由將顯影處理物加以乾燥,可獲得具有預定之開孔圖案之網版印刷版11。3 is a diagram showing an outline of the manufacturing method of the screen printing plate of the present invention; and FIG. 3A shows a step of joining the screen mesh 6 to the photosensitive resin layer 5 side of the pattern forming laminated film 1 ( a); Figure 3B shows an outline of the step (b) of peeling off the support layer 2 and the paste layer 3 from the water-insoluble polymer layer 4 of the pattern-forming laminated film 1; Figure 3C shows the step (b) of peeling off the water-insoluble polymer layer 4 of the pattern-forming laminated film 1; An overview of step (c) of arranging the pattern mask 10 on the surface of the flexible polymer layer 4; FIG. 3D shows that energy rays are irradiated from the pattern mask 10 to the photosensitive resin layer 5 to form a latent image α on the photosensitive resin. The outline of step (d); Figure 3E shows the outline of step (e) of peeling off the water-insoluble polymer layer 4; Figure 3F shows the implementation of developing the photosensitive resin layer 5 on which the latent image α is formed. Summary of the screen printing plate 11 obtained in step (f). In this step (f), a development process is performed, which consists of cleaning the photosensitive resin layer 5 on which the latent image α is formed with water (for example, neutral water), and removing the unhardened areas of the photosensitive resin layer 5 ( That is, the area where the latent image α is not formed). Then, by drying the developed product, the screen printing plate 11 having a predetermined opening pattern can be obtained.

本發明之圖案形成用積層膜1係具有非水溶性高分子層3,於該非水溶性高分子層3的表面配置圖案遮罩10,然後介隔該圖案遮罩10進行能量線之照射以及潛像α之形成。藉由該非水溶性高分子層3來防止因感光性樹脂層之吸濕或構成成分之轉移而帶有黏性,因而容易於非水溶性高分子層3的表面中將遮罩圖案10定位。The laminated film 1 for pattern formation of the present invention has a water-insoluble polymer layer 3. A pattern mask 10 is disposed on the surface of the water-insoluble polymer layer 3, and then energy ray irradiation and latent energy are irradiated through the pattern mask 10. Like the formation of α. The water-insoluble polymer layer 3 prevents the photosensitive resin layer from becoming sticky due to moisture absorption or transfer of components, so that the mask pattern 10 can be easily positioned on the surface of the water-insoluble polymer layer 3 .

根據本發明之網版印刷版,所製成之印刷版係表面加工地平坦,故而印刷再現性良好,與被印刷物之密接亦良好,故而可抑制油墨繞到印刷版之背側,可實現版擦拭次數之減少。According to the screen printing plate of the present invention, the surface of the produced printing plate is processed to be flat, so the printing reproducibility is good, and the close contact with the printed object is also good, so the ink can be suppressed from flowing around the back side of the printing plate, and the screen printing plate can be realized Reduce the number of wipes.

[感光性阻劑基材] 本發明之感光性阻劑基材之特徵在於:包含前述圖案形成用積層膜、以及積層於前述圖案形成用積層膜的前述感光性樹脂層側之基材而成。 [Photoresist base material] The photoresist base material of the present invention is characterized by including the above-mentioned laminated film for pattern formation, and a base material laminated on the side of the photosensitive resin layer of the above-mentioned laminated film for pattern formation.

作為積層於感光性樹脂層側之基材,可使用由各種材料所構成之基材。例如可列舉:木、石、織物、紙、陶瓷、玻璃,乙酸纖維素或聚酯、聚烯烴、聚醯亞胺、環氧樹脂般之合成樹脂,玻璃纖維強化樹脂,鋁、銅、鎳、鐵、鋅、鎂、鈷般之金屬,矽、鎵、砷、鍺等半導體材料,氮化矽、氧化矽等絕緣材料。As the base material laminated on the photosensitive resin layer side, a base material made of various materials can be used. Examples include: wood, stone, fabric, paper, ceramics, glass, cellulose acetate or polyester, polyolefin, polyimide, synthetic resin like epoxy resin, glass fiber reinforced resin, aluminum, copper, nickel, Metals like iron, zinc, magnesium, and cobalt, semiconductor materials such as silicon, gallium, arsenic, and germanium, and insulating materials such as silicon nitride and silicon oxide.

該本發明之感光性阻劑基材為能夠利用中性水進行顯影之感光性樹脂,故而於顯影液不使用溶劑或鹼性水溶液之方面,較先前之感光性阻劑基材於環境方面、作業方面更有利。The photoresist base material of the present invention is a photosensitive resin that can be developed with neutral water. Therefore, the developer does not use solvents or alkaline aqueous solutions. Compared with previous photoresist base materials, it is environmentally friendly and environmentally friendly. It’s more beneficial in terms of homework.

藉由除了網版絲網以外亦於金屬或玻璃等基材接合該圖案形成用積層膜,而可獲得感光性阻劑基材。與先前之含有機溶劑型樹脂不同,溶媒係使用中性水,故而環境污染低。顯影亦不使用有機溶劑或鹼性水而能夠使用中性水,因而於環境方面、作業方面、顯影液之保管、處理等方面亦有利。另外,視基材不同,有時因有機溶劑或鹼而變色、變形等,由於能夠利用中性水進行顯影,由此能夠選擇廣泛之基材。 [實施例] By bonding the pattern-forming laminated film to a base material such as metal or glass in addition to the screen screen, a photoresist base material can be obtained. Unlike previous resins containing organic solvents, neutral water is used as the solvent, so environmental pollution is low. Development also does not use organic solvents or alkaline water but can use neutral water, so it is also advantageous in terms of the environment, work, storage and handling of the developer, etc. In addition, depending on the base material, there may be discoloration, deformation, etc. due to organic solvents or alkalis. Since it can be developed with neutral water, a wide range of base materials can be selected. [Example]

[實施例1] [圖案形成用積層膜之製作] 準備厚度75μm之聚對苯二甲酸乙二酯膜作為支撐層,於該支撐層上藉由棒塗機塗敷乙烯‐乙酸乙烯酯系乳液型之黏著劑,於100℃加熱乾燥3分鐘,藉此形成厚度10μm之糊層。進而,於該糊層上藉由層壓機貼合厚度6μm之聚對苯二甲酸乙二酯膜作為由非水溶性之高分子所構成之層。 繼而,藉由棒塗機塗敷由上述成分(A)及成分(B)、成分(F)、成分(G)、成分(H)所構成之感光性樹脂1,於40℃加熱乾燥30分鐘,藉此形成厚度20μm之感光性樹脂層,藉此獲得圖案形成用積層膜。 [Example 1] [Production of laminated film for pattern formation] Prepare a polyethylene terephthalate film with a thickness of 75 μm as a support layer, apply an ethylene-vinyl acetate emulsion type adhesive on the support layer with a bar coater, and heat and dry at 100°C for 3 minutes. This formed a paste layer with a thickness of 10 μm. Furthermore, a polyethylene terephthalate film with a thickness of 6 μm was laminated on the paste layer using a laminator as a layer composed of a water-insoluble polymer. Then, the photosensitive resin 1 composed of the above-mentioned component (A), component (B), component (F), component (G), and component (H) was applied with a bar coater, and dried by heating at 40° C. for 30 minutes. , thereby forming a photosensitive resin layer with a thickness of 20 μm, thereby obtaining a laminated film for pattern formation.

[實施例2] 形成實施例1之感光性樹脂層後,於該感光性樹脂層上貼合厚度25μm之聚乙烯膜作為保護層,除此以外,與實施例1同樣地製作圖案形成用積層膜。 [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 with a thickness of 25 μm was bonded on the photosensitive resin layer as a protective layer.

[實施例3] 糊層係使用丙烯酸系黏著劑,由非水溶性之高分子所構成之層係使用厚度12μm之聚烯烴膜,除此以外,與實施例1同樣地製作圖案形成用積層膜。 [Example 3] A laminated film for pattern formation was produced in the same manner as in Example 1, except that an acrylic adhesive was used for the paste layer and a polyolefin film with a thickness of 12 μm was used for the layer composed of a water-insoluble polymer.

[比較例1] [圖案形成用積層膜之製作] 準備厚度75μm之聚對苯二甲酸乙二酯膜作為支撐層,於該支撐層上藉由棒塗機塗敷聚乙烯醇(可樂麗(Kuraray)股份有限公司製造之Kuraray Poval 95-88)之5.0質量%水溶液,於40℃加熱乾燥30分鐘,藉此形成厚度5μm之由水溶性之高分子所構成之層。進而於該層上藉由棒塗機塗敷由上述成分(A)及成分(B)、成分(F)、成分(G)、成分(H)所構成之感光性樹脂1,於40℃加熱乾燥30分鐘,藉此形成厚度20μm之感光性樹脂層,藉此獲得圖案形成用積層膜。 [Comparative example 1] [Production of laminated film for pattern formation] A polyethylene terephthalate film with a thickness of 75 μm was prepared as a support layer, and polyvinyl alcohol (Kuraray Poval 95-88 manufactured by Kuraray Co., Ltd.) was coated on the support layer with a bar coater. A 5.0% by mass aqueous solution was heated and dried at 40° C. for 30 minutes to form a layer of water-soluble polymer with a thickness of 5 μm. Furthermore, the photosensitive resin 1 composed of the above-mentioned component (A), component (B), component (F), component (G), and component (H) is coated on this layer with a bar coater, and heated at 40°C. It was dried for 30 minutes to form a photosensitive resin layer with a thickness of 20 μm, thereby obtaining a laminated film for pattern formation.

[比較例2] 使用含氟化合物之樹脂(村上(Murakami)股份有限公司製造之SP-2050UC,未添加重氮樹脂)作為由水溶性之高分子所構成之層,除此以外,與比較例1同樣地製作圖案形成用積層膜。 [Comparative example 2] A pattern was produced in the same manner as in Comparative Example 1, except that a fluorochemical-containing resin (SP-2050UC manufactured by Murakami Co., Ltd., no diazo resin was added) was used as the layer composed of a water-soluble polymer. A laminated film is formed.

[比較例3] 準備厚度75μm之聚對苯二甲酸乙二酯膜作為支撐層,於該支撐層上藉由棒塗機塗敷由上述成分(A)及成分(B)、成分(F)、成分(G)、成分(H)所構成之感光性樹脂1,於40℃加熱乾燥30分鐘,藉此形成厚度20μm之感光性樹脂層,藉此獲得圖案形成用膜。 [Comparative example 3] A polyethylene terephthalate film with a thickness of 75 μm was prepared as a support layer, and the above-mentioned component (A), component (B), component (F), and component (G) were coated on the support layer using a bar coater. The photosensitive resin 1 composed of component (H) was heated and dried at 40° C. for 30 minutes to form a photosensitive resin layer with a thickness of 20 μm, thereby obtaining a pattern forming film.

[評價方法1] 使用不銹鋼製桶(bucket),將由上述成分(A)及成分(B)、成分(F)、成分(G)、成分(H)所構成之感光性樹脂1塗敷於固定於鋁框之聚酯纖維製絲網,貼合上述所製作之圖案形成用積層膜的感光性樹脂層側。實施例2中製作之圖案形成用積層膜係於即將貼合之前,剝下保護層後貼合感光性樹脂層側。於40℃乾燥30分鐘後,剝下支撐層。實施例1、實施例2、實施例3中製作之圖案形成用積層膜係於剝下支撐層之時亦同時剝下糊層。 [Evaluation method 1] Using a stainless steel bucket, the photosensitive resin 1 composed of the above-mentioned component (A), component (B), component (F), component (G), and component (H) is coated on the polyester fixed to the aluminum frame. A screen made of ester fiber is bonded to the photosensitive resin layer side of the pattern-forming laminated film produced above. The laminated film for pattern formation produced in Example 2 was peeled off the protective layer immediately before lamination, and then the photosensitive resin layer side was laminated. After drying at 40°C for 30 minutes, the support layer was peeled off. When peeling off the support layer of the pattern-forming laminated film produced in Example 1, Example 2, and Example 3, the paste layer was also peeled off at the same time.

繼而,重疊圖案遮罩,進行抽真空,使用3kW之金屬鹵素燈作為光源,以光源與版表面之距離1m、照射時間2分鐘之條件將感光性樹脂層加以曝光。繼而,去掉圖案遮罩後,使用自來水將樹脂層加以顯影。藉此,獲得網版印刷版。 實施例1、實施例2、實施例3中,於顯影前去除非水溶性高分子層後進行顯影。 Then, the pattern mask was overlapped and evacuated, and a 3kW metal halide lamp was used as the light source to expose the photosensitive resin layer under the conditions of a distance of 1m between the light source and the plate surface and an irradiation time of 2 minutes. Then, after removing the pattern mask, tap water is used to develop the resin layer. With this, a screen printing version is obtained. In Example 1, Example 2, and Example 3, the non-water-soluble polymer layer was removed before development and then developed.

[表面黏性1] 根據重疊圖案遮罩時的圖案遮罩之對位之容易程度,以A至C進行評價。 A:能夠順利移動圖案遮罩,對位容易。 B:無法順利移動圖案遮罩,對位困難。 C:圖案遮罩貼附於表面,無法對位。 [Surface Stickiness 1] Evaluate from A to C based on the ease of positioning of pattern masks when overlapping pattern masks. A: The pattern mask can be moved smoothly and the positioning is easy. B: The pattern mask cannot be moved smoothly and alignment is difficult. C: The pattern mask is attached to the surface and cannot be aligned.

[表面黏性2] 根據真空曝光後之圖案遮罩之剝下容易程度,以A至C進行評價。 A:於剝下圖案遮罩時無阻力,能夠容易地剝下。 B:於剝下圖案遮罩時有阻力,無法順利剝下。 C:圖案遮罩貼附於表面,表面的一部分破損。 [Surface Stickiness 2] Evaluate from A to C based on the ease of peeling off the pattern mask after vacuum exposure. A: There is no resistance when peeling off the pattern mask and it can be peeled off easily. B: There is resistance when peeling off the pattern mask and it cannot be peeled off smoothly. C: The pattern mask is attached to the surface and part of the surface is damaged.

[表面狀態] 根據顯影後之網版印刷版之表面狀態,以○至×進行評價。 ○:於感光性樹脂層的表面無任何殘留。 ×:於感光性樹脂層的表面殘存其他成分。 [surface condition] Based on the surface condition of the screen printing plate after development, evaluation is made from ○ to ×. ○: No residue remains on the surface of the photosensitive resin layer. ×: Other components remain on the surface of the photosensitive resin layer.

評價結果示於表1。The evaluation results are shown in Table 1.

[表1] 實施例1 實施例2 實施例3 支撐層 聚對苯二甲酸乙二酯膜 聚對苯二甲酸乙二酯膜 聚對苯二甲酸乙二酯膜 糊層 乙烯-乙酸乙烯酯系乳液型之黏著劑 乙烯-乙酸乙烯酯系乳液型之黏著劑 丙烯酸系黏著劑 非水溶性高分子層 聚對苯二甲酸乙二酯膜 聚對苯二甲酸乙二酯膜 聚烯烴膜 感光性樹脂層 感光性樹脂1 感光性樹脂1 感光性樹脂1 保護層 - 聚乙烯膜 - 於曝光時與圖案遮罩接觸之層 聚對苯二甲酸乙二酯膜 聚對苯二甲酸乙二酯膜 聚烯烴膜 表面黏性1 A A A 表面黏性2 A A A 表面狀態 比較例1 比較例2 比較例3 支撐層 聚對苯二甲酸乙二酯膜 聚對苯二甲酸乙二酯膜 聚對苯二甲酸乙二酯膜 水溶性高分子層 皂化度88%PVA 撥油性乳液 - 感光性樹脂層 感光性樹脂1 感光性樹脂1 感光性樹脂1 於曝光時與圖案遮罩接觸之層 Kuraray Poval 95-88 SP-2050UC未添加重氮樹脂 感光性樹脂1 表面黏性1 B B C 表面黏性2 B B C 表面狀態 × × 破損(無法評價) ※感光性樹脂1 成分A:皂化度88mol%、聚合度1000之聚乙烯醇 成分B:對重氮二苯基胺與三聚甲醛之縮合物之磷酸鹽 成分F:季戊四醇三丙烯酸酯 成分G:二乙基噻噸酮 成分H:聚乙酸乙烯酯乳液 [Table 1] Example 1 Example 2 Example 3 support layer Polyethylene terephthalate film Polyethylene terephthalate film Polyethylene terephthalate film Paste layer Ethylene-vinyl acetate emulsion type adhesive Ethylene-vinyl acetate emulsion type adhesive Acrylic adhesive water-insoluble polymer layer Polyethylene terephthalate film Polyethylene terephthalate film polyolefin film Photosensitive resin layer Photosensitive resin 1 Photosensitive resin 1 Photosensitive resin 1 protective layer - polyethylene film - The layer in contact with the pattern mask during exposure Polyethylene terephthalate film Polyethylene terephthalate film polyolefin film Surface viscosity1 A A A Surface stickiness 2 A A A surface state Comparative example 1 Comparative example 2 Comparative example 3 support layer Polyethylene terephthalate film Polyethylene terephthalate film Polyethylene terephthalate film water soluble polymer layer Saponification degree 88%PVA oil repellent lotion - Photosensitive resin layer Photosensitive resin 1 Photosensitive resin 1 Photosensitive resin 1 The layer in contact with the pattern mask during exposure Kuraray Poval 95-88 SP-2050UC does not add diazo resin Photosensitive resin 1 Surface viscosity1 B B C Surface stickiness 2 B B C surface state × × Damaged (cannot evaluate) ※Photosensitive resin 1 Component A: Polyvinyl alcohol with a saponification degree of 88 mol% and a polymerization degree of 1000 Component B: Phosphate component of the condensate of p-diazodiphenylamine and trimerformaldehyde Component F: Pentaerythritol triacrylate Component G: Diethylthioxanthone ingredient H: polyvinyl acetate emulsion

[實施例4] [圖案形成用積層膜之製作] 準備厚度75μm之聚對苯二甲酸乙二酯膜作為支撐層,於該支撐層上藉由棒塗機塗敷聚矽氧系之黏著劑,於100℃加熱乾燥3分鐘,藉此形成厚度5μm之糊層。進而,於該糊層上藉由層壓機貼合厚度12μm之聚烯烴膜作為由非水溶性之高分子所構成之層。 繼而,藉由棒塗機塗敷由上述成分(E)及成分(F)、成分(G)、成分(H)所構成之感光性樹脂2,於40℃加熱乾燥30分鐘,藉此形成厚度30μm之感光性樹脂層,藉此獲得圖案形成用積層膜。 [Example 4] [Production of laminated film for pattern formation] Prepare a polyethylene terephthalate film with a thickness of 75 μm as a support layer, apply a polysiloxane-based adhesive on the support layer with a bar coater, and heat and dry at 100°C for 3 minutes to form a thickness of 5 μm. The mushy layer. Furthermore, a polyolefin film with a thickness of 12 μm was laminated on the paste layer using a laminator as a layer composed of a water-insoluble polymer. Then, the photosensitive resin 2 composed of the above-mentioned component (E), component (F), component (G), and component (H) is coated with a bar coater, and heated and dried at 40° C. for 30 minutes to form a thickness. A 30 μm photosensitive resin layer was used to obtain a laminated film for pattern formation.

[實施例5] 除了糊層使用乙烯‐乙酸乙烯酯系乳液型之黏著劑以外,與實施例4同樣地製作圖案形成用積層膜。 [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 paste layer.

[實施例6] 除了糊層使用胺基甲酸酯系黏著劑以外,與實施例4同樣地製作圖案形成用積層膜。 [Example 6] A laminated film for pattern formation was produced in the same manner as in Example 4 except that a urethane-based adhesive was used for the paste layer.

[實施例7] 除了糊層使用丙烯酸系黏著劑以外,與實施例4同樣地製作圖案形成用積層膜。 [Example 7] A laminated film for pattern formation was produced in the same manner as in Example 4 except that an acrylic adhesive was used for the paste layer.

[比較例4] [圖案形成用積層膜之製作] 作為由非水溶性之高分子所構成之層,使用對厚度25μm之聚酯膜於單面實施了聚矽氧脫模處理之脫模膜,除此以外,與實施例4同樣地製作圖案形成用積層膜。脫模膜係將聚矽氧脫模處理面貼合於感光性樹脂層側。 [Comparative example 4] [Production of laminated film for pattern formation] As a layer made of a water-insoluble polymer, a pattern was produced in the same manner as in Example 4, except that a release film in which a polyester film with a thickness of 25 μm was subjected to polysilicone release treatment on one side was used. Use laminated film. The release film is made by bonding the silicone release treated surface to the photosensitive resin layer side.

[比較例5] 作為支撐層,使用對厚度75μm之聚酯膜於單面實施了聚矽氧脫模處理之脫模膜,除此以外,與實施例5同樣地製作圖案形成用積層膜。脫模膜係將聚矽氧脫模處理面貼合於糊層側。 [Comparative example 5] As a support layer, a laminated film for pattern formation was produced in the same manner as in Example 5, except that a release film in which a polyester film with a thickness of 75 μm was subjected to polysiloxane release treatment on one side was used. The release film is made by attaching the silicone release treatment surface to the paste layer side.

[比較例6] 作為由非水溶性之高分子所構成之層,使用對厚度25μm之聚酯膜實施了單面電暈放電處理之易接著膜,除此以外,與實施例6同樣地製作圖案形成用積層膜。易接著膜係將電暈處理面貼合於糊層側。 [Comparative example 6] As a layer made of a water-insoluble polymer, a pattern-forming laminated film was produced in the same manner as in Example 6, except that an easily adhesive film obtained by subjecting a 25 μm-thick polyester film to one-sided corona discharge treatment was used. . The easy-adhesive film system attaches the corona-treated surface to the paste layer side.

[比較例7] 感光性樹脂層使用由上述成分(A)及成分(B)、成分(H)所構成之感光性樹脂3,除此以外,與實施例7同樣地製作圖案形成用積層膜。 [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-mentioned component (A), component (B), and component (H) was used as the photosensitive resin layer.

[評價方法2] 使用不銹鋼製桶將用於各圖案形成用膜之感光性樹脂塗敷於固定於鋁框之聚酯纖維製絲網,貼合上述所製作之圖案形成用積層膜的感光性樹脂層側。於40℃乾燥30分鐘,獲得試驗版。 於25℃50%環境下保管24小時後,於支撐層貼附賽珞凡膠帶,以向上部拉扯的方式剝下時,確認於界面1至界面3的何處界面剝落。 界面1  支撐層/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。 ○:於界面2剝落,於非水溶性高分子層上未殘留糊層。 ×:於界面2以外剝落。 [Evaluation method 2] The photosensitive resin used for each pattern forming film was applied to the polyester fiber mesh fixed to the aluminum frame using a stainless steel barrel, and the photosensitive resin layer side of the pattern forming laminated film produced above was bonded. Dry at 40°C for 30 minutes to obtain a test version. After storage for 24 hours in an environment of 25°C and 50%, attach Cellophane tape to the support layer and peel it off by pulling upward to confirm where the interface peels off from interface 1 to interface 3. Interface 1 is the support layer/paste layer; interface 2 is the paste layer/water-insoluble polymer layer; interface 3 is the water-insoluble polymer layer/photosensitive resin layer. ○: Peeling off at interface 2, and no paste layer remains on the water-insoluble polymer layer. ×: Peeling off outside interface 2.

評價結果表示於下述表2。The evaluation results are shown in Table 2 below.

[表2] 實施例4 實施例5 實施例6 實施例7 支撐層 聚對苯二甲酸乙二酯膜 聚對苯二甲酸乙二酯膜 聚對苯二甲酸乙二酯膜 聚對苯二甲酸乙二酯膜 糊層 聚矽氧系黏著劑 乙烯-乙酸乙烯酯系乳液型之黏著劑 胺基甲酸酯系黏著劑 丙烯酸系黏著劑 非水溶性高分子層 聚烯烴膜 聚烯烴膜 聚烯烴膜 聚烯烴膜 感光性樹脂層 感光性樹脂2 感光性樹脂2 感光性樹脂2 感光性樹脂2 層間接著力之關係 (x)>(y),(z)>(y) (x)>(y),(z)>(y) (x)>(y),(z)>(y) (x)>(y),(z)>(y) 剝落之部位 界面2 界面2 界面2 界面2 判定 比較例4 比較例5 比較例6 比較例7 支撐層 聚對苯二甲酸乙二酯膜 聚對苯二甲酸乙二酯膜(單面脫模處理) 聚對苯二甲酸乙二酯膜 聚對苯二甲酸乙二酯膜 糊層 聚矽氧系黏著劑 乙烯-乙酸乙烯酯系乳液型之黏著劑 胺基甲酸酯系黏著劑 丙烯酸系黏著劑 非水溶性高分子層 聚對苯二甲酸乙二酯膜(單面脫模處理) 聚烯烴膜 聚對苯二甲酸乙二酯膜(單面易接著處理) 聚烯烴膜 感光性樹脂層 感光性樹脂2 感光性樹脂2 感光性樹脂2 感光性樹脂3 層間接著力之關係 (x)>(y),(z)<(y) (x)>(y),(z)>(y) (x)<(y),(z)>(y) (x)>(y),(z)<(y) 剝落之部位 界面3 界面1 界面1 界面3 判定 × × × × ※感光性樹脂2 成分E:具有經苯乙烯基取代之吡啶鎓基的皂化度88mol%、聚合度1700之聚乙烯醇 成分F:三羥甲基丙烷三丙烯酸酯 成分G:異丙基噻噸酮 成分H:乙酸乙烯酯-丙烯酸共聚物乳液 ※感光性樹脂3 成分A:皂化度88mol%、聚合度2400之聚乙烯醇 成分B:3-甲氧基-4-重氮二苯基胺與三聚甲醛之縮合物之磷酸鹽 成分H:聚乙酸乙烯酯乳液 [Table 2] Example 4 Example 5 Example 6 Example 7 support layer Polyethylene terephthalate film Polyethylene terephthalate film Polyethylene terephthalate film Polyethylene terephthalate film Paste layer Polysilicone adhesive Ethylene-vinyl acetate emulsion type adhesive Urethane adhesive Acrylic adhesive water-insoluble polymer layer polyolefin film polyolefin film polyolefin film polyolefin film Photosensitive resin layer Photosensitive resin 2 Photosensitive resin 2 Photosensitive resin 2 Photosensitive resin 2 The relationship between layer and indirect force (x)>(y),(z)>(y) (x)>(y),(z)>(y) (x)>(y),(z)>(y) (x)>(y),(z)>(y) peeling part Interface 2 Interface 2 Interface 2 Interface 2 determination Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7 support layer Polyethylene terephthalate film Polyethylene terephthalate film (single side release treatment) Polyethylene terephthalate film Polyethylene terephthalate film Paste layer Polysilicone adhesive Ethylene-vinyl acetate emulsion type adhesive Urethane adhesive Acrylic adhesive water-insoluble polymer layer Polyethylene terephthalate film (single side release treatment) polyolefin film Polyethylene terephthalate film (easy to adhere to one side) polyolefin film Photosensitive resin layer Photosensitive resin 2 Photosensitive resin 2 Photosensitive resin 2 Photosensitive resin 3 The relationship between layer and indirect force (x)>(y),(z)<(y) (x)>(y),(z)>(y) (x)<(y),(z)>(y) (x)>(y),(z)<(y) peeling part Interface 3 Interface 1 Interface 1 Interface 3 determination × × × × ※Photosensitive resin 2 Component E: Polyvinyl alcohol with a saponification degree of pyridinium group substituted by a styrene group of 88 mol% and a polymerization degree of 1700 Component F: Trimethylolpropane triacrylate Component G: Isopropylthioxanthene Ketone component H: Vinyl acetate-acrylic acid copolymer emulsion ※Photosensitive resin 3 Component A: Polyvinyl alcohol with a saponification degree of 88 mol% and a polymerization degree of 2400 Component B: 3-methoxy-4-diazodiphenylamine and Phosphate component H of the condensation product of paraformaldehyde: polyvinyl acetate emulsion

[實施例8] [圖案形成用積層膜之製作] 準備厚度75μm之聚對苯二甲酸乙二酯膜作為支撐層,於該支撐層上藉由棒塗機塗敷聚矽氧系黏著劑,於100℃加熱乾燥3分鐘,藉此形成厚度3μm之糊層。進而,於該糊層上藉由層壓機貼合厚度12μm、霧值0.3%之聚烯烴膜作為由非水溶性之分子所構成之層。 [Example 8] [Production of laminated film for pattern formation] Prepare a polyethylene terephthalate film with a thickness of 75 μm as a support layer, apply a polysiloxane adhesive on the support layer with a bar coater, and heat and dry at 100°C for 3 minutes to form a 3 μm-thick polyethylene terephthalate film. Paste layer. Furthermore, a polyolefin film with a thickness of 12 μm and a haze value of 0.3% was laminated on the paste layer using a laminator as a layer composed of water-insoluble molecules.

繼而,藉由棒塗機塗敷由上述成分(A)及成分(B)、成分(F)、成分(G)所構成之感光性樹脂4,於40℃加熱乾燥30分鐘,藉此形成厚度15μm之感光性樹脂層,藉此獲得圖案形成用積層膜。Then, the photosensitive resin 4 composed of the above-mentioned component (A), component (B), component (F), and component (G) is coated with a bar coater, and heated and dried at 40° C. for 30 minutes to form a thickness. A 15 μm photosensitive resin layer was used to obtain a laminated film for pattern formation.

進而,使用不銹鋼製桶將用於各圖案形成用膜之感光性樹脂塗敷於固定於鋁框之不銹鋼纖維製絲網,貼合上述所製作之圖案形成用積層膜的感光性樹脂層側。於40℃乾燥30分鐘,剝離支撐層及糊層。Furthermore, the photosensitive resin used for each pattern forming film was applied to the stainless steel fiber mesh fixed to the aluminum frame using a stainless steel barrel, and the photosensitive resin layer side of the pattern forming laminated film produced above was bonded. Dry at 40°C for 30 minutes and peel off the support layer and paste layer.

繼而,將圖案遮罩重疊於非水溶性高分子層,進行抽真空,使用3kW之金屬鹵素燈作為光源,以光源與版表面之距離1m且照射時間為2分鐘、3分鐘、4分鐘、5分鐘之條件將感光性樹脂層加以曝光。 繼而,去掉圖案遮罩後,使用自來水將樹脂層加以顯影。藉此,獲得網版印刷版。 Then, the pattern mask was overlapped on the water-insoluble polymer layer, evacuated, and a 3kW metal halide lamp was used as the light source. The distance between the light source and the plate surface was 1m and the irradiation time was 2 minutes, 3 minutes, 4 minutes, 5 minutes. The photosensitive resin layer is exposed under conditions of minutes. Then, after removing the pattern mask, tap water is used to develop the resin layer. With this, a screen printing version is obtained.

[實施例9] 非水溶性高分子層係使用厚度50μm、霧值1.0%之高透明聚對苯二甲酸乙二酯膜,除此以外,與實施例8同樣地獲得網版印刷版。 [Example 9] A screen printing plate was obtained in the same manner as in Example 8, except that a highly transparent polyethylene terephthalate film with a thickness of 50 μm and a haze value of 1.0% was used as the water-insoluble polymer layer.

[實施例10] 感光性樹脂層係使用由上述成分(A)及成分(C)、成分(D)所構成之感光性樹脂5,除此以外,與實施例8同樣地獲得網版印刷版。 [Example 10] A screen printing plate was obtained in the same manner as in Example 8, except that the photosensitive resin 5 composed of the above-mentioned component (A), component (C), and component (D) was used for the photosensitive resin layer.

[比較例8] 非水溶性高分子層係使用厚度30μm、霧值6%之聚烯烴膜,除此以外,與實施例8同樣地獲得網版印刷版。 [Comparative example 8] A screen printing plate was obtained in the same manner as in Example 8, except that a polyolefin film with a thickness of 30 μm and a haze value of 6% was used as the water-insoluble polymer layer.

[比較例9] 非水溶性高分子層係使用厚度25μm、霧值5.7%之通用聚對苯二甲酸乙二酯膜,除此以外,與實施例8同樣地製作圖案形成用積層膜。 [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 with a thickness of 25 μm and a haze value of 5.7% was used as the water-insoluble polymer layer.

[比較例10] 非水溶性高分子層係使用厚度125μm、霧值1.5%之聚烯烴膜,除此以外,與實施例10同樣地製作圖案形成用積層膜。 [Comparative Example 10] A laminated film for pattern formation was produced in the same manner as in Example 10, except that a polyolefin film with a thickness of 125 μm and a haze value of 1.5% was used as the water-insoluble polymer layer.

[評價方法3] 以100倍放大鏡來確定所得之網版印刷版之圖案,決定感度及解析性。 感度:將階段式曝光表7段以上之最短曝光時間作為感度。 解析性:將以上述所決定之感度進行解析的L/S之最窄寬度(μm)作為解析性。 評價結果表示於下述表3。 [Evaluation method 3] Use a 100x magnifying glass to determine the pattern of the screen printing plate and determine the sensitivity and resolution. Sensitivity: Use the shortest exposure time above segment 7 of the step-type exposure meter as the sensitivity. Analytical property: The narrowest width (μm) of L/S analyzed at the sensitivity determined above is used as the analytical property. The evaluation results are shown in Table 3 below.

[表3] 實施例8 實施例9 實施例10 支撐層 聚對苯二甲酸乙二酯膜 聚對苯二甲酸乙二酯膜 聚對苯二甲酸乙二酯膜 糊層 聚矽氧系黏著劑 聚矽氧系黏著劑 聚矽氧系黏著劑 非水溶性高分子層 聚烯烴膜 高透明聚對苯二甲酸乙二酯膜 聚烯烴膜 非水溶性高分子層之厚度 12μm 25μm 12μm 霧值 0.3% 1.0% 0.3% 感光性樹脂層 感光性樹脂4 感光性樹脂4 感光性樹脂5 感度 4分鐘 4分鐘 3分鐘 解析度 40μm 40μm 30μm 比較例8 比較例9 比較例10 支撐層 聚對苯二甲酸乙二酯膜 聚對苯二甲酸乙二酯膜 聚對苯二甲酸乙二酯膜 糊層 聚矽氧系黏著劑 聚矽氧系黏著劑 聚矽氧系黏著劑 非水溶性高分子層 聚烯烴膜 通用聚對苯二甲酸乙二酯膜 高透明聚對苯二甲酸乙二酯膜 非水溶性高分子層之厚度 30μm 25μm 125μm 霧值 6.0% 5.7% 1.5% 感光性樹脂層 感光性樹脂4 感光性樹脂4 感光性樹脂5 感度 6分鐘 6分鐘 4分鐘 解析度 90μm 90μm 100μm ※感光性樹脂4 成分A:皂化度88mol%、聚合度3500之聚乙烯醇 成分B:3-甲氧基-4-重氮二苯基胺與4,4'-雙甲氧基甲基二苯基醚之縮合物之磷酸鹽 成分F:二季戊四醇六丙烯酸酯 成分G:2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙酮-1 ※感光性樹脂5 成分A:皂化度88mol%、聚合度2000之聚乙烯醇 成分C:雙酚A型環氧樹脂 成分D:雙(4-第三丁基苯基)錪六氟磷酸鹽(光酸產生劑) 異丙基噻噸酮(增感劑) [table 3] Example 8 Example 9 Example 10 support layer Polyethylene terephthalate film Polyethylene terephthalate film Polyethylene terephthalate film Paste layer Polysilicone adhesive Polysilicone adhesive Polysilicone adhesive water-insoluble polymer layer polyolefin film Highly transparent polyethylene terephthalate film polyolefin film Thickness of water-insoluble polymer layer 12μm 25μm 12μm fog value 0.3% 1.0% 0.3% Photosensitive resin layer Photosensitive resin 4 Photosensitive resin 4 Photosensitive resin 5 Sensitivity 4 minutes 4 minutes 3 minutes Resolution 40μm 40μm 30μm Comparative example 8 Comparative example 9 Comparative example 10 support layer Polyethylene terephthalate film Polyethylene terephthalate film Polyethylene terephthalate film Paste layer Polysilicone adhesive Polysilicone adhesive Polysilicone adhesive water-insoluble polymer layer polyolefin film General purpose polyethylene terephthalate film Highly transparent polyethylene terephthalate film Thickness of water-insoluble polymer layer 30μm 25μm 125μm fog value 6.0% 5.7% 1.5% Photosensitive resin layer Photosensitive resin 4 Photosensitive resin 4 Photosensitive resin 5 Sensitivity 6 minutes 6 minutes 4 minutes Resolution 90μm 90μm 100μm ※Photosensitive resin 4 Component A: Polyvinyl alcohol with a saponification degree of 88 mol% and a polymerization degree of 3500 Component B: 3-methoxy-4-diazodiphenylamine and 4,4'-bismethoxymethyldiamine Phosphate component F of the condensate of phenyl ether: dipentaerythritol hexaacrylate component G: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone-1 ※Photosensitivity Resin 5 Component A: Polyvinyl alcohol with a saponification degree of 88 mol% and a polymerization degree of 2000. Component C: Bisphenol A-type epoxy resin. Component D: Bis(4-tert-butylphenyl)quinone hexafluorophosphate (photoacid generation Agent) Isopropylthioxanthone (sensitizer)

1:圖案形成用積層膜 1’:積層膜 2:支撐層 3:糊層 4:非水溶性高分子層 5:感光性樹脂層 6:網版絲網 7:框材 8:第一未感光之網版印刷版 9:第二未感光之網版印刷版 10:圖案遮罩 11:網版印刷版 1:Laminated film for pattern formation 1’:Laminated film 2: Support layer 3: Paste layer 4: Water-insoluble polymer layer 5: Photosensitive resin layer 6:Screen screen 7: Frame material 8: The first unsensitized screen printing plate 9: Second unsensitized screen printing plate 10: Pattern mask 11:Screen printing version

[圖1]係表示本發明之較佳之未感光之網版印刷版之概要圖。 [圖2]係表示本發明之較佳之未感光之網版印刷版之概要圖。 [圖3A至圖3F]係表示本發明之較佳之網版印刷版之製造方法之概要圖。 [Fig. 1] is a schematic diagram showing a preferred non-photosensitive screen printing plate of the present invention. [Fig. 2] is a schematic diagram showing a preferred non-photosensitive screen printing plate of the present invention. [Fig. 3A to Fig. 3F] are schematic diagrams showing a preferred method of manufacturing a screen printing plate according to the present invention.

1:圖案形成用積層膜 1:Laminated film for pattern formation

2:支撐層 2: Support layer

3:糊層 3: Paste layer

4:非水溶性高分子層 4: Water-insoluble polymer layer

5:感光性樹脂層 5: Photosensitive resin layer

6:網版絲網 6:Screen screen

7:框材 7: Frame material

8:第一未感光之網版印刷版 8: The first unsensitized screen printing plate

Claims (16)

一種圖案形成用積層膜,係支撐層、糊層、非水溶性高分子層及感光性樹脂層依此順序所構成,前述感光性樹脂層為能夠利用中性水進行顯影之感光性樹脂。 A laminated film for pattern formation is composed of a support layer, a paste layer, a water-insoluble polymer layer and a photosensitive resin layer in this order. The photosensitive resin layer is a photosensitive resin that can be developed with neutral water. 如請求項1所記載之圖案形成用積層膜,其中前述支撐層與糊層之間之層間接著力(x)、前述糊層與非水溶性高分子層之間之層間接著力(y)、及前述非水溶性高分子層與感光性樹脂層之間之層間接著力(z)係處於下述關係:層間接著力(x)>層間接著力(y);層間接著力(z)>層間接著力(y)。 The laminated film for pattern formation according to claim 1, wherein the interlayer adhesive force (x) between the aforementioned support layer and the paste layer, the interlayer adhesive force (y) between the aforementioned paste layer and the water-insoluble polymer layer, And the inter-layer adhesion force (z) between the aforementioned water-insoluble polymer layer and the photosensitive resin layer is in the following relationship: inter-layer adhesion force (x) > inter-layer adhesion force (y); inter-layer adhesion force (z) > inter-layer adhesion force (z) > inter-layer adhesion force (y) Then force(y). 如請求項1或2所記載之圖案形成用積層膜,其中前述糊層與非水溶性高分子層之間之層間接著力(y)為0.001N/25mm至1.0N/25mm。 The laminated film for pattern formation according to claim 1 or 2, wherein the interlayer adhesion (y) between the paste layer and the water-insoluble polymer layer is 0.001N/25mm to 1.0N/25mm. 如請求項1或2所記載之圖案形成用積層膜,其中前述非水溶性高分子層之霧值為5.0%以下。 The laminated film for pattern formation according to claim 1 or 2, wherein the haze value of the water-insoluble polymer layer is 5.0% or less. 如請求項1或2所記載之圖案形成用積層膜,其中前述非水溶性高分子層係厚度為1μm至100μm。 The laminated film for pattern formation according to claim 1 or 2, wherein the thickness of the water-insoluble polymer layer is 1 μm to 100 μm. 如請求項1或2所記載之圖案形成用積層膜,其中前述感光性樹脂層係由包含下述成分(A)及成分(B)而成之感光性樹脂所構成;成分(A):皂化度為50mol%以上之聚乙烯醇;成分(B):重氮樹脂。 The laminated film for pattern formation according to claim 1 or 2, wherein the photosensitive resin layer is composed of a photosensitive resin containing the following component (A) and component (B); component (A): saponification Polyvinyl alcohol with a concentration of more than 50 mol%; component (B): diazo resin. 如請求項1或2所記載之圖案形成用積層膜,其中前述感光性樹脂層係由包含下述成分(A)、成分(C)及成分(D)而成之感光性樹脂所構成;成分(A):皂化度為50mol%以上之聚乙烯醇; 成分(C):具有至少一個環氧基之環氧化合物;成分(D):光酸產生劑。 The pattern-forming laminated film according to claim 1 or 2, wherein the photosensitive resin layer is composed of a photosensitive resin containing the following component (A), component (C) and component (D); component (A): Polyvinyl alcohol with a saponification degree of more than 50 mol%; Component (C): an epoxy compound having at least one epoxy group; component (D): photoacid generator. 如請求項1或2所記載之圖案形成用積層膜,其中前述感光性樹脂層係由包含下述成分(E)而成之感光性樹脂所構成;成分(E):具有經苯乙烯基取代之吡啶鎓基或經苯乙烯基取代之喹啉鎓基的皂化度為50mol%以上之聚乙烯醇。 The laminated film for pattern formation according to claim 1 or 2, wherein the photosensitive resin layer is composed of a photosensitive resin containing the following component (E); component (E): having a styrene group substituted The saponification degree of the pyridinium group or the quinolinium group substituted by the styrene group is above 50 mol%. 如請求項6所記載之圖案形成用積層膜,其中前述感光性樹脂層係由進而包含下述成分(F)及成分(G)而成之感光性樹脂所構成;成分(F):具有至少一個乙烯性不飽和鍵之自由基聚合性化合物;成分(G):光自由基聚合起始劑。 The laminated film for pattern formation according to claim 6, wherein the photosensitive resin layer is composed of a photosensitive resin further containing the following component (F) and component (G); component (F): having at least A radically polymerizable compound with an ethylenically unsaturated bond; component (G): photoradical polymerization initiator. 如請求項6所記載之圖案形成用積層膜,其中前述感光性樹脂層係由進而含有下述成分(H)而成之感光性樹脂所構成;成分(H):水性聚合物乳液。 The laminated film for pattern formation according to claim 6, wherein the photosensitive resin layer is composed of a photosensitive resin further containing the following component (H): component (H): aqueous polymer emulsion. 如請求項1或2所記載之圖案形成用積層膜,係於前述圖案形成用積層膜的感光性樹脂層側進而積層保護層而成。 The pattern-forming laminated film according to claim 1 or 2 is a product in which a protective layer is further laminated on the photosensitive resin layer side of the pattern-forming laminated film. 一種未感光之網版印刷版,係包含自如請求項1至10中任一項所記載之圖案形成用積層膜去掉前述支撐層及糊層而得之積層膜、以及積層於前述積層膜的感光性樹脂層側之網版絲網而成。 A non-photosensitive screen printing plate, comprising a laminated film obtained by removing the aforementioned support layer and paste layer from the pattern-forming laminated film described in any one of claims 1 to 10, and a photosensitive laminated film laminated on the aforementioned laminated film It is made of screen mesh on the side of the resin layer. 一種未感光之網版印刷版之製造方法,係包含下述步驟(a)及步驟(b)而成; 步驟(a):於如請求項1至10中任一項所記載之圖案形成用積層膜的前述感光性樹脂層側接合網版絲網之步驟;步驟(b):自前述圖案形成用積層膜的非水溶性高分子層剝離前述支撐層及糊層之步驟。 A method of manufacturing a non-photosensitive screen printing plate, which includes the following steps (a) and (b); Step (a): The step of joining the screen mesh to the photosensitive resin layer side of the pattern-forming laminated film according to any one of claims 1 to 10; Step (b): From the aforementioned pattern-forming laminated film The water-insoluble polymer layer of the membrane is peeled off the aforementioned support layer and paste layer. 一種網版印刷版,係於未感光之網版印刷版形成潛像並將感光性樹脂層加以顯影而成,前述未感光之網版印刷版係包含自如請求項1至10中任一項所記載之圖案形成用積層膜去掉前述支撐層及糊層而得之積層膜、以及積層於前述積層膜的感光性樹脂層側之網版絲網而成。 A screen printing plate, which is formed by forming a latent image on an unsensitized screen printing plate and developing a photosensitive resin layer. The aforementioned unsensitized screen printing plate includes any one of claims 1 to 10. The described pattern formation uses a laminated film obtained by removing the aforementioned support layer and paste layer, and a screen mesh laminated on the photosensitive resin layer side of the aforementioned laminated film. 一種網版印刷版之製造方法,係包含下述步驟(a)至步驟(f)而成;步驟(a):於如請求項1至10中任一項所記載之圖案形成用積層膜的前述感光性樹脂層側接合網版絲網之步驟;步驟(b):自前述圖案形成用積層膜的非水溶性高分子層剝離前述支撐層及糊層之步驟;步驟(c):於前述非水溶性高分子層的表面配置圖案遮罩之步驟;步驟(d):於前述感光性樹脂層形成潛像之步驟;步驟(e):剝離前述非水溶性高分子層之步驟;步驟(f):將形成有前述潛像之感光性樹脂層加以顯影之步驟。 A method for manufacturing a screen printing plate, which includes the following steps (a) to (f); step (a): forming a laminated film for pattern formation as described in any one of claims 1 to 10. The step of joining the screen mesh to the photosensitive resin layer side; Step (b): The step of peeling off the aforementioned support layer and paste layer from the water-insoluble polymer layer of the aforementioned pattern-forming laminated film; Step (c): The aforementioned step The step of arranging a pattern mask on the surface of the water-insoluble polymer layer; step (d): the step of forming a latent image on the aforementioned photosensitive resin layer; step (e): the step of peeling off the aforementioned water-insoluble polymer layer; step ( f): The step of developing the photosensitive resin layer on which the aforementioned latent image is formed. 一種感光性阻劑基材,係包含如請求項1至10中任一項所記載之圖案形成用積層膜、以及積層於前述圖案形成用積層膜的前述感光性樹脂層側之基材而成。 A photosensitive resist base material comprising the pattern-forming laminated film according to any one of claims 1 to 10, and a base material laminated on the photosensitive resin layer side of the pattern-forming laminated film. .
TW110133300A 2021-04-06 2021-09-08 Laminated films for pattern formation, unsensitized screen printing plates, their manufacturing methods, and photoresist substrates TWI831047B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021-064868 2021-04-06
JP2021064868A JP2022160236A (en) 2021-04-06 2021-04-06 Laminated film for pattern formation and unexposed screen printing plate, and method for manufacturing them

Publications (2)

Publication Number Publication Date
TW202240296A TW202240296A (en) 2022-10-16
TWI831047B true TWI831047B (en) 2024-02-01

Family

ID=83545814

Family Applications (1)

Application Number Title Priority Date Filing Date
TW110133300A TWI831047B (en) 2021-04-06 2021-09-08 Laminated films for pattern formation, unsensitized screen printing plates, their manufacturing methods, and photoresist substrates

Country Status (5)

Country Link
JP (1) JP2022160236A (en)
KR (1) KR20220139851A (en)
CN (1) CN115443436A (en)
TW (1) TWI831047B (en)
WO (1) WO2022215283A1 (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003346648A (en) * 2002-05-29 2003-12-05 Nippon Paper Industries Co Ltd Phosphor transfer film
TW201224087A (en) * 2010-09-13 2012-06-16 Kaneka Corp Flexible printed circuit board with built-in stiffener, and method of manufacturing flexible printed circuit board with built-in stiffener

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5860745A (en) 1981-10-08 1983-04-11 Okamoto Kagaku Kogyo Kk Photosensitive film for use in screen plate
JP3992550B2 (en) * 2002-07-04 2007-10-17 國宏 市村 Active energy ray resin composition, active energy ray resin film, and pattern forming method using the film
JP2004086089A (en) * 2002-08-29 2004-03-18 Nippon Paper Industries Co Ltd Phosphor transfer film
JP2006243546A (en) * 2005-03-04 2006-09-14 Fuji Photo Film Co Ltd Pattern forming material, pattern forming apparatus, and pattern forming method
US20080197369A1 (en) 2007-02-20 2008-08-21 Cree, Inc. Double flip semiconductor device and method for fabrication
JP6985974B2 (en) * 2018-04-27 2021-12-22 富士フイルム株式会社 Photosensitive transfer material, resist pattern manufacturing method, circuit wiring manufacturing method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003346648A (en) * 2002-05-29 2003-12-05 Nippon Paper Industries Co Ltd Phosphor transfer film
TW201224087A (en) * 2010-09-13 2012-06-16 Kaneka Corp Flexible printed circuit board with built-in stiffener, and method of manufacturing flexible printed circuit board with built-in stiffener

Also Published As

Publication number Publication date
CN115443436A (en) 2022-12-06
JP2022160236A (en) 2022-10-19
KR20220139851A (en) 2022-10-17
TW202240296A (en) 2022-10-16
WO2022215283A1 (en) 2022-10-13

Similar Documents

Publication Publication Date Title
TWI585520B (en) Photoimageable compositions and processes for fabrication of relief patterns on low surface energy substrates
KR20070007080A (en) Permanent resist composition, cured product thereof, and use thereof
JP4789725B2 (en) Photosensitive resin composition, laminate thereof, cured product thereof, and pattern forming method using the composition
JP4789733B2 (en) Photosensitive resin composition, laminate thereof, cured product thereof, and pattern forming method using the composition
JP2008026667A (en) Permanent resist composition and resist laminate
JP2008020839A (en) Photosensitive resin composition, laminate and cured material of the composition, and pattern forming method using the composition
CN107250913A (en) Pattern formation method and the electronic equipment manufactured using it
JP4913142B2 (en) Photosensitive resin composition, laminate thereof, cured product thereof, and pattern formation method using the composition (3)
JP4890541B2 (en) Photosensitive resin composition, photosensitive film using the same, and stencil for screen printing
WO2020241370A1 (en) Screen printing plate and method for manufacturing same
TWI667131B (en) Resin laminate and letterpress printing plate precursor
TWI831047B (en) Laminated films for pattern formation, unsensitized screen printing plates, their manufacturing methods, and photoresist substrates
JP4789727B2 (en) Photosensitive resin composition, laminate thereof, cured product thereof, and pattern forming method using the composition
JP6683208B2 (en) Photosensitive resin composition and photosensitive resin plate original plate
JP5559976B2 (en) Image forming method, photocured image, and photocurable composition used in the method
JP4913141B2 (en) Photosensitive resin composition, laminate thereof, cured product thereof, and pattern formation method using the composition (2)
JPS6254253A (en) Formation of relief
JPS6254254A (en) Formation of relief
WO2014119562A1 (en) Photosensitive resin composition, photosensitive element, sandblasting mask material, and surface processing method of object to be processed
JP4789728B2 (en) Photosensitive resin composition, laminate thereof, cured product thereof, and pattern forming method using the composition
JP2001142082A (en) Method of producing electrode substrate for liquid crystal display device and liquid crystal display device
JP2023121310A (en) Photosensitive resin printing original plate
TWI400567B (en) A photosensitive resin composition, and a photosensitive film and a screen printing plate using the same
JP4385241B2 (en) Aqueous developer for resist film pattern formation
JP2000221691A (en) Resist pattern forming method