TW201404781A - Silane coupling agent, photosensitive resin composition, cured film, and component of touch panel - Google Patents

Silane coupling agent, photosensitive resin composition, cured film, and component of touch panel Download PDF

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TW201404781A
TW201404781A TW102111320A TW102111320A TW201404781A TW 201404781 A TW201404781 A TW 201404781A TW 102111320 A TW102111320 A TW 102111320A TW 102111320 A TW102111320 A TW 102111320A TW 201404781 A TW201404781 A TW 201404781A
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group
resin composition
acid
photosensitive resin
compound
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TWI560194B (en
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Hitoshi Araki
Mitsuhito Suwa
Toshiyasu Hibino
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Toray Industries
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
    • C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D305/04—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/20—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/16—Radicals substituted by singly bound hetero atoms other than halogen by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0751—Silicon-containing compounds used as adhesion-promoting additives or as means to improve adhesion
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)

Abstract

The purpose of the invention is to provide a silane coupling agent which shows good effective improvements of pattern peeling and scum during development, adhesion to the underlying substrate after being curing treated or chemical treated, as well as has heat resistance, and it does not require a compound with toxicity concern during synthesis. The silane coupling agent of the present invention is characterized by being represented by specific structural formula which has a monovalent organic group with heterocyclic structure having 1 to 30 carbon atoms.

Description

矽烷偶合劑、感光性樹脂組成物、硬化膜及觸控面板構件 Decane coupling agent, photosensitive resin composition, cured film, and touch panel member

本發明係關於矽烷偶合劑、感光性樹脂組成物、硬化膜及觸控面板用構件。 The present invention relates to a decane coupling agent, a photosensitive resin composition, a cured film, and a member for a touch panel.

近年來，隨著顯示器產業和觸控面板產業之成長，同時感光性透明材料的重要性提高。例如液晶顯示器的彩色濾光片需要用於抑制液晶之配向混亂的保護膜、TFT基板為了實現高開口率而需要被稱為平坦化膜之有機系鈍化膜(passivation film)，而感光性透明材料係使用於該等。又，隨著智慧型手機和平板電腦終端之普及，而同時受到關注之電容式觸控面板，需要配置於感應玻璃上所形成之ITO(Indium Tin Oxide)和金屬(銀、鉬、鋁等)配線之交錯部分的絕緣膜，和用於保護該等的保護膜，而感光性透明材料使用於該等之情形也很多。 In recent years, with the growth of the display industry and the touch panel industry, the importance of photosensitive transparent materials has increased. For example, a color filter of a liquid crystal display requires a protective film for suppressing misalignment of liquid crystals, and a TFT substrate requires an organic passivation film called a planarizing film in order to achieve a high aperture ratio, and a photosensitive transparent material. Used for these. In addition, with the popularity of smart phones and tablet terminals, capacitive touch panels that have attracted attention at the same time require ITO (Indium Tin Oxide) and metal (silver, molybdenum, aluminum, etc.) formed on the induction glass. The insulating film of the staggered portion of the wiring and the protective film for protecting the same are also used in the case where the photosensitive transparent material is used.

對該等感光性透明材料所要求的特性係因步驟而為各式各樣，但能夠舉出圖案加工性、透明性、與底層基板的接著性、耐藥品性、耐熱性、耐高溫高濕性等。其中特別是圖案加工性和耐藥品性係對於生產良率、硬化膜之接著性係對於製品的品質為重要的特性，但 在TFT基板和觸控面板所使用之金屬系的底層基板進行加工時，圖案加工時的圖案剝離、浮渣的問題、熱硬化處理後和藥品處理後之與底層基板的接著性問題，係成為感光性透明材料常有的課題。 The characteristics required for the photosensitive transparent materials are various depending on the steps, but the pattern processability, transparency, adhesion to the underlying substrate, chemical resistance, heat resistance, high temperature and high humidity are exemplified. Sex and so on. Among them, pattern processing property and chemical resistance are important characteristics for the production yield and the adhesion of the cured film to the quality of the product, but When the metal substrate of the TFT substrate and the touch panel is processed, the problem of pattern peeling during the pattern processing, the problem of dross, and the problem of adhesion to the underlying substrate after the heat curing treatment and after the drug treatment are A problem often associated with photosensitive transparent materials.

作為改善樹脂及基板之接著性的方法，最常被研究的是矽烷偶合劑之添加。例如在將負型感光性聚苯并唑前驅物組成物加工於矽晶圓時，為了抑制顯影剝離而有提案二脲型的矽烷偶合劑(專利文獻1)。又，對於硬化膜的接著性則有報告具有醯亞胺基的矽烷偶合劑(專利文獻2)、具有羧基，與酯基或醯胺基的矽烷偶合劑(專利文獻3)、含有聚合性基及胺甲酸乙酯基的矽烷偶合劑(專利文獻4~6)等為有效。 As a method of improving the adhesion between the resin and the substrate, the most frequently studied is the addition of a decane coupling agent. For example, in the case of negative photosensitive polybenzo When the azole precursor composition is processed on a tantalum wafer, a diurea type decane coupling agent is proposed in order to suppress development and peeling (Patent Document 1). In addition, a decane coupling agent having a quinone imine group (Patent Document 2), a decane coupling agent having a carboxyl group, an ester group or a guanamine group (Patent Document 3), and a polymerizable group are disclosed. A urethane coupling agent of urethane groups (Patent Documents 4 to 6) and the like are effective.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開2002-179688號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2002-179688

[專利文獻2]國際公開第2009/096050號 [Patent Document 2] International Publication No. 2009/096050

[專利文獻3]日本特開2006-316032號公報 [Patent Document 3] Japanese Laid-Open Patent Publication No. 2006-316032

[專利文獻4]日本特開2004-205615號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2004-205615

[專利文獻5]日本特開昭62-249992號公報 [Patent Document 5] Japanese Laid-Open Patent Publication No. 62-249992

[專利文獻6]日本特開平5-287215號公報 [Patent Document 6] Japanese Patent Laid-Open No. Hei 5-287215

但是，本發明者等發現以下的課題。專利文獻1因具有鹼性、專利文獻3因具有酸性基，任一者都留 下組成物保存安定性為課題。專利文獻2則因具有醯亞胺基而有透過率降低的課題。又，如專利文獻4~6之含有胺甲酸乙酯基的矽烷偶合劑則有耐熱性的課題。再者，合成時大多需要錫等有毒性之疑慮的化合物作為觸媒，而不見得進行了那麼多的研究。再者，任何矽烷偶合劑都改善在塑膠基板、矽基板、玻璃基板等的接著性，但對於改善在ITO等金屬基板的圖案剝離和硬化膜的接著性並不充分。 However, the inventors of the present invention have found the following problems. Patent Document 1 has basicity, and Patent Document 3 has an acidic group, and either one remains. The stability of the lower composition is a problem. Patent Document 2 has a problem that the transmittance is lowered because it has a quinone imine group. Further, the urethane coupling agent containing an urethane group of Patent Documents 4 to 6 has a problem of heat resistance. Further, in the synthesis, a compound having toxic and suspected properties such as tin is often used as a catalyst, and it is not necessary to conduct so much research. Further, any decane coupling agent improves the adhesion to a plastic substrate, a ruthenium substrate, a glass substrate, etc., but it is not sufficient for improving the pattern peeling of the metal substrate such as ITO and the adhesion of the cured film.

本發明之課題為提供一種矽烷偶合劑，其係於負型感光性樹脂組成物及正型感光性樹脂組成物中，不僅是塑膠基板、矽基板、玻璃基板，即便是金屬基板，亦展現顯影時之圖案剝離和浮渣的優良改善效果，展現熱硬化處理後和藥品處理後之與底層基板接著性的優良改善效果，具有耐熱性，合成時不需要有毒性之疑慮的化合物。 An object of the present invention is to provide a decane coupling agent which is used in a negative photosensitive resin composition and a positive photosensitive resin composition, and is not only a plastic substrate, a ruthenium substrate, or a glass substrate, but exhibits development even on a metal substrate. The excellent effect of improving the pattern peeling and scum at the time, exhibiting an excellent improvement effect on the adhesion to the underlying substrate after the heat hardening treatment and the drug treatment, and having heat resistance, and a compound which does not require toxicity at the time of synthesis.

本發明者等進行專心研究的結果，發現能夠藉由特定的矽烷偶合劑，而獲得顯影時不發生圖案剝離和浮渣、熱硬化處理後和藥品處理後之與底層基板之接著性良好的負型感光性樹脂組成物及正型感光性樹脂組成物。 As a result of intensive research by the inventors of the present invention, it has been found that a specific decane coupling agent can be used to obtain a negative adhesion to the underlying substrate after patterning, scumming, thermal hardening, and drug treatment by development. A photosensitive resin composition and a positive photosensitive resin composition.

本發明之目的係藉由特徵為以通式(1)表示之(A)矽烷偶合劑而達成。 The object of the present invention is achieved by the (A) decane coupling agent characterized by the formula (1).

(R1分別獨立地表示碳數1~6之烷基或是苯基，或該等的取代物。R2分別獨立地表示碳數1~6的烷基或是苯基，或該等的取代物。R3表示碳數1~30的2價有機基。R4表示具有雜環構造之碳數1~30的1價有機基。m表示0~2的整數。) (R 1 each independently represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, or a substituent thereof. R 2 each independently represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, or the like The substituent R 3 represents a divalent organic group having 1 to 30 carbon atoms, and R 4 represents a monovalent organic group having 1 to 30 carbon atoms having a heterocyclic structure. m represents an integer of 0 to 2.

本發明之目的係藉由含有通式(1)表示的(A)矽烷偶合劑、(B)鹼可溶性樹脂、(C)多官能丙烯酸單體、(D)光自由基聚合起始劑的(I)負型感光性樹脂組成物而達成。 The object of the present invention is to contain (A) a decane coupling agent represented by the general formula (1), (B) an alkali-soluble resin, (C) a polyfunctional acrylic monomer, and (D) a photoradical polymerization initiator ( I) A negative photosensitive resin composition is achieved.

本發明之目的係藉由含有通式(1)表示的(A)矽烷偶合劑、(B)鹼可溶性樹脂、(E)醌二疊氮化合物的(II)正型感光性樹脂組成物而達成。 The object of the present invention is achieved by a (II) positive photosensitive resin composition containing (A) a decane coupling agent represented by the formula (1), (B) an alkali-soluble resin, and (E) a quinonediazide compound. .

本發明之目的係藉由具備硬化上述(I)負型感光性樹脂組成物或(II)正型感光性樹脂組成物而成之硬化膜的觸控面板構件而達成。 The object of the present invention is achieved by a touch panel member comprising a cured film obtained by curing the (I) negative photosensitive resin composition or the (II) positive photosensitive resin composition.

本發明之目的係藉由具備硬化上述(I)負型感光性樹脂組成物或(II)正型感光性樹脂組成物而成之硬化膜的TFT基板而達成。 The object of the present invention is achieved by a TFT substrate comprising a cured film obtained by curing the (I) negative photosensitive resin composition or the (II) positive photosensitive resin composition.

本發明之矽烷偶合劑，係能夠藉由添加於樹脂組成物，而獲得在顯影時不發生圖案剝離和浮渣、熱 硬化處理後和藥品處理後之與底層基板之接著性良好的硬化膜。 The decane coupling agent of the present invention can be obtained by adding to a resin composition to obtain no pattern peeling and scumming and heat during development. A cured film having good adhesion to the underlying substrate after the hardening treatment and after the drug treatment.

a‧‧‧透明電極形成後之俯視圖 a‧‧‧Top view of the transparent electrode after formation

b‧‧‧絕緣膜形成後之俯視圖 b‧‧‧Top view after the formation of the insulating film

c‧‧‧金屬配線形成後之俯視圖 c‧‧‧Top view after metal wiring is formed

1‧‧‧玻璃基板 1‧‧‧ glass substrate

2‧‧‧透明電極 2‧‧‧Transparent electrode

3‧‧‧透明絕緣膜 3‧‧‧Transparent insulating film

4‧‧‧配線電極 4‧‧‧Wiring electrode

5‧‧‧透明保護膜 5‧‧‧Transparent protective film

第1圖係觸控面板構件製造中之各步驟後的概略俯視圖。 Fig. 1 is a schematic plan view showing each step in the manufacture of a touch panel member.

第2圖係表示觸控面板構件的概略剖面圖。 Fig. 2 is a schematic cross-sectional view showing a touch panel member.

[實施發明之形態] [Formation of the Invention]

本發明之(A)矽烷偶合劑，其特徵為以通式(1)表示。 The (A) decane coupling agent of the present invention is characterized by the formula (1).

(R1分別獨立地表示碳數1~6的烷基或是苯基，或該等的取代物。R2分別獨立地表示碳數1~6的烷基或是苯基，或該等的取代物。R3表示碳數1~30的2價有機基。R4表示具有雜環構造之碳數1~30的1價有機基。m表示0~2的整數。) (R 1 each independently represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, or such a substituent. R 2 each independently represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, or the like The substituent R 3 represents a divalent organic group having 1 to 30 carbon atoms, and R 4 represents a monovalent organic group having 1 to 30 carbon atoms having a heterocyclic structure. m represents an integer of 0 to 2.

以通式(1)表示的矽烷偶合劑，係具有較通常之胺甲酸乙酯化合物高的耐熱性，又附帶提升與各種樹脂和金屬之接著性的效果。此處，所謂矽烷偶合劑係表示含有水解性矽的化合物，係藉由和水的反應而生成矽醇基的化合物。作為水解性基，能夠舉例烷氧基、乙醯 氧基、苯氧基或氯基。 The decane coupling agent represented by the formula (1) has a heat resistance higher than that of a usual urethane compound, and has an effect of improving adhesion to various resins and metals. Here, the decane coupling agent is a compound containing a hydrolyzable hydrazine, and is a compound which forms a sterol group by a reaction with water. As the hydrolyzable group, an alkoxy group or an ethyl group can be exemplified. Oxy, phenoxy or chloro.

作為R1係以甲基、乙基、丁基、甲氧基乙基或苯基為佳，從原料取得的觀點來看，以甲基或乙基為特佳。作為R2係以甲基、乙基、丁基或苯基為佳，從原料取得的觀點來看，以甲基或苯基為特佳。作為R3係以具有亞甲基部位之以下述通式(2)或下述通式(3)表示的有機基為佳，伸丙基、伸丁基、伸戊基、伸己基或以通式(3)表示的有機基，係接著性改善效果大而較佳。 R 1 is preferably a methyl group, an ethyl group, a butyl group, a methoxyethyl group or a phenyl group, and a methyl group or an ethyl group is particularly preferable from the viewpoint of obtaining a raw material. The R 2 type is preferably a methyl group, an ethyl group, a butyl group or a phenyl group, and a methyl group or a phenyl group is particularly preferable from the viewpoint of obtaining a raw material. The R 3 is preferably an organic group represented by the following formula (2) or the following formula (3) having a methylene moiety, and a propyl group, a butyl group, a pentyl group, a hexyl group or a butyl group. The organic group represented by the formula (3) is preferred because it has a large effect of improving the adhesion.

(l表示1~30的整數。) (l represents an integer from 1 to 30.)

作為R4係以下述通式(4)表示之有機基、呋喃基、吡喃基、二氫吡喃基、噻吩基、四氫噻吩基、苯并呋喃基、異苯并呋喃基、咪唑基、吡咯基、吡啶基、吡咯啶基、哌啶基、噻唑基、唑基或是2,3-環氧環己基，或該等的取代物為佳，從樹脂組成物添加時之安定性的觀點來看，較佳為以通式(4)表示之有機基、呋喃基、吡喃基、二氫吡喃基、噻吩基、四氫噻吩基或2,3-環氧環己基，更佳為以通式(4)表示的有機基。 The R 4 group is an organic group represented by the following formula (4), a furyl group, a pyranyl group, a dihydropyranyl group, a thienyl group, a tetrahydrothiophenyl group, a benzofuranyl group, an isobenzofuranyl group, or an imidazolyl group. , pyrrolyl, pyridyl, pyrrolidinyl, piperidinyl, thiazolyl, The azole group or the 2,3-epoxycyclohexyl group, or the above-mentioned substitution product is preferred, and from the viewpoint of the stability at the time of addition of the resin composition, the organic group represented by the formula (4) is preferred, A furyl group, a pyranyl group, a dihydropyranyl group, a thienyl group, a tetrahydrothiophenyl group or a 2,3-epoxycyclohexyl group is more preferably an organic group represented by the formula (4).

(n及o分別獨立地表示0~4的整數。惟，n+o≧1。R5表示氫、碳數1~10的烷基。) (n and o each independently represent an integer of 0 to 4. However, n+o≧1. R 5 represents hydrogen and an alkyl group having 1 to 10 carbon atoms.)

作為R5，能夠舉例氫、甲基、乙基、正丙基、異丙基、正丁基、二級丁基、戊基或己基。 As R 5 , hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, pentyl or hexyl can be exemplified.

作為以通式(4)表示的有機基，以環氧基、2-甲基環氧基、環氧丙烷基、3-甲基環氧丙烷基、3-乙基環氧丙烷基、四氫呋喃基、2-甲基四氫呋喃基或四氫吡喃基為佳，從原料取得的觀點來看，較佳為環氧基、3-甲基環氧丙烷基、3-乙基環氧丙烷基或四氫呋喃基。 The organic group represented by the formula (4) is an epoxy group, a 2-methyl epoxy group, an propylene oxide group, a 3-methyl oxypropylene group, a 3-ethyl propylene oxide group, or a tetrahydrofuranyl group. Further, 2-methyltetrahydrofuranyl or tetrahydropyranyl is preferred, and from the viewpoint of obtaining a raw material, an epoxy group, a 3-methyl epoxide group, a 3-ethyl propylene oxide group or a tetrahydrofuran is preferred. base.

作為以通式(1)表示之矽烷偶合劑，能夠舉例(3-(三甲氧基甲矽烷基)丙基)胺基甲酸環氧丙酯、(3-(三乙氧基甲矽烷基)丙基)胺基甲酸環氧丙酯、(3-(甲基二甲氧基甲矽烷基)丙基)胺基甲酸環氧丙酯、(3-(三甲氧基甲矽烷基)丁基)胺基甲酸環氧丙酯、(2-((3-三甲氧基甲矽烷基丙基)胺基)乙基)胺基甲酸環氧丙酯、(3-(三甲氧基甲矽烷基)丙基)胺基甲酸環氧丙烷酯、(3-(三乙氧基甲矽烷基)丙基)胺基甲酸環氧丙烷酯、(3-(甲基二甲氧基甲矽烷基)丙基)胺基甲酸環氧丙烷酯、(3-(三甲氧基甲矽烷基)丁基)胺基甲酸環氧丙烷酯、(2-((3-三甲氧基甲矽烷基丙基)胺基)乙基)胺基甲酸環氧丙烷酯、(3-(三甲氧基甲矽烷基)丙基)胺基甲酸2-甲基環氧丙烷酯、(3-(三乙氧基甲矽烷基)丙基)胺基甲酸2-甲基環氧丙烷酯、(3-(甲基二甲氧基甲矽烷基)丙基)胺基甲酸2-甲基環氧丙烷酯、(3-(三甲氧基甲矽烷基)丁基)胺基甲酸2-甲基環氧丙烷酯、(2-((3-三甲氧基甲矽烷基丙基)胺基)乙基)胺基甲酸2-甲基環氧丙烷酯、(3-(三甲氧基甲矽烷基)丙基)胺基甲酸2-乙基環氧丙烷酯、(3-(三乙氧基甲矽烷基)丙基)胺基甲酸 2-乙基環氧丙烷酯、(3-(甲基二甲氧基甲矽烷基)丙基)胺基甲酸2-乙基環氧丙烷酯、(3-(三甲氧基甲矽烷基)丁基)胺基甲酸2-乙基環氧丙烷酯、(2-((3-三甲氧基甲矽烷基丙基)胺基)乙基)胺基甲酸2-乙基環氧丙烷酯、(3-(三甲氧基甲矽烷基)丙基)胺基甲酸四氫呋喃酯、(3-(三乙氧基甲矽烷基)丙基)胺基甲酸四氫呋喃酯、(3-(甲基二甲氧基甲矽烷基)丙基)胺基甲酸四氫呋喃酯、(3-(三甲氧基甲矽烷基)丁基)胺基甲酸四氫呋喃酯、(2-((3-三甲氧基甲矽烷基丙基)胺基)乙基)胺基甲酸四氫呋喃酯、(3-(三甲氧基甲矽烷基)丙基)胺基甲酸呋喃酯、(3-(三乙氧甲基矽烷基)丙基)胺基甲酸呋喃酯、(3-(甲基二甲氧基甲矽烷基)丙基)胺基甲酸呋喃酯、(3-(三甲氧基甲矽烷基)丁基)胺基甲酸呋喃酯、(3-(三甲氧基甲矽烷基)丙基)胺基甲酸(2H-哌喃-2-基)甲酯、(3-(三乙氧基甲矽烷基)丙基)胺基甲酸(2H-哌喃-2-基)甲酯、(3-(甲基二甲氧基甲矽烷基)丙基)胺基甲酸(2H-哌喃-2-基)甲酯、(3-(三甲氧基甲矽烷基)丁基)胺基甲酸(2H-哌喃-2-基)甲酯、(2-((3-三甲氧基甲矽烷基丙基)胺基)乙基)胺基甲酸(2H-哌喃-2-基)甲酯、(3-(三甲氧基甲矽烷基)丙基)胺基甲酸(4H-哌喃-2-基)甲酯、(3-(三乙氧基甲矽烷基)丙基)胺基甲酸(4H-哌喃-2-基)甲酯、(3-(甲基二甲氧基甲矽烷基)丙基)胺基甲酸(4H-哌喃-2-基)甲酯、(3-(三甲氧基甲矽烷基)丁基)胺基甲酸(4H-哌喃-2-基)甲酯、(2-((3-三甲氧基甲矽烷基丙基)胺基)乙基)胺基甲酸(4H-哌喃-2-基)甲酯、(3-(三甲氧基甲矽烷基)丙基)胺基甲酸(四氫哌喃-2-基)甲酯、(3-(三乙 氧基甲矽烷基)丙基)胺基甲酸(四氫哌喃-2-基)甲酯、(3-(甲基二甲氧基甲矽烷基)丙基)胺基甲酸(四氫哌喃-2-基)甲酯、(3-(三甲氧基甲矽烷基)丁基)胺基甲酸(四氫哌喃-2-基)甲酯、(2-((3-三甲氧基甲矽烷基)胺基)乙基)胺基甲酸(四氫哌喃-2-基)甲酯、(3-(三甲氧基甲矽烷基)丙基)胺基甲酸(吡咯啶-2-基)甲酯、(3-(三乙氧基甲矽烷基)丙基)胺基甲酸(吡咯啶-2-基)甲酯、(3-(甲基二甲氧基甲矽烷基)丙基)胺基甲酸(吡咯啶-2-基)甲酯、(3-(三甲氧基甲矽烷基)丁基)胺基甲酸(吡咯啶-2-基)甲酯、(2-((3-三甲氧基甲矽烷丙基)胺基)乙基)胺基甲酸(吡咯啶-2-基)甲酯、(3-(三甲氧基甲矽烷基)丙基)胺基甲酸(吡咯-2-基)甲酯、(3-(三乙氧基甲矽烷基)丙基)胺基甲酸(吡咯-2-基)甲酯、(3-(甲基二甲氧基甲矽烷基)丙基)胺基甲酸(吡咯-2-基)甲酯、(3-(三甲氧基甲矽烷基)丁基)胺基甲酸(吡咯-2-基)甲酯、(2-((3-三甲氧基甲矽烷基丙基)胺基)乙基)胺基甲酸(吡咯-2-基)甲酯、(3-(三甲氧基甲矽烷基)丙基)胺基甲酸(6-甲基吡啶-2-基)甲酯、(3-(三乙氧基甲矽烷基)丙基)胺基甲酸(6-甲基吡啶-2-基)甲酯、(3-(甲基二甲氧基甲矽烷基)丙基)胺基甲酸(6-甲基吡啶-2-基)甲酯、(3-(三甲氧基甲矽烷基)丁基)胺基甲酸(6-甲基吡啶-2-基)甲酯、(2((3-三甲氧基甲矽烷基丙基)胺基)乙基)胺基甲酸(6-甲基吡啶-2-基)甲酯、(3-(三甲氧基甲矽烷基)丙基)胺基甲酸(5-甲基噻吩-2-基)甲酯、(3-(三乙氧基甲矽烷基)丙基)胺基甲酸(5-甲基噻吩-2-基)甲酯、(3-(甲基二甲氧基甲矽烷基)丙基)胺基甲酸(5-甲基噻吩-2-基)甲酯、(3-(三甲氧 基甲矽烷基)丁基)胺基甲酸(5-甲基噻吩-2-基)甲酯或(2-((3-三甲氧基甲矽烷基丙基)胺基)乙基)胺基甲酸(5-甲基噻吩-2-基)甲酯，但較佳為(3-(三甲氧基甲矽烷基)丙基)胺基甲酸環氧丙酯、(3-(三乙氧基甲矽烷基)丙基)胺基甲酸環氧丙酯、(2-((3-三甲氧基甲矽烷基丙基)胺基)乙基)胺基甲酸環氧丙酯、(3-(三甲氧基甲矽烷基)丙基)胺基甲酸環氧丙烷酯、(3-(三乙氧基甲矽烷基)丙基)胺基甲酸環氧丙烷酯、(2-((3-三甲氧基甲矽烷基丙基)胺基)乙基)胺基甲酸環氧丙烷酯、(3-(三甲氧基甲矽烷基)丙基)胺基甲酸2-甲基環氧丙烷酯、(3-(三乙氧基甲矽烷基)丙基)胺基甲酸2-甲基環氧丙烷酯、(2-((3-三甲氧基甲矽烷基丙基)胺基)乙基)胺基甲酸2-甲基環氧丙烷酯、(3-(三甲氧基甲矽烷基)丙基)胺基甲酸2-乙基環氧丙烷酯、(3-(三乙氧基甲矽烷基)丙基)胺基甲酸2-乙基環氧丙烷酯、(2-((3-三甲氧基甲矽烷基丙基)胺基)乙基)胺基甲酸2-乙基環氧丙烷酯、(3-(三甲氧基甲矽烷基)丙基)胺基甲酸四氫呋喃酯、(3-(三乙氧基甲矽烷基)丙基)胺基甲酸四氫呋喃酯或(2-((3-三甲氧基甲矽烷基丙基)胺基)乙基)胺基甲酸四氫呋喃酯。 As the decane coupling agent represented by the formula (1), (3-(trimethoxymethyl decyl) propyl) carbamic acid glycidyl ester, (3-(triethoxymethyl decyl) propyl) can be exemplified. Glycidyl carbazate, glycidyl (3-(methyldimethoxycarbamido)propyl) propyl carbamate, (3-(trimethoxymethyl decyl) butyl) amide Glycidyl carbamic acid, (2-((3-trimethoxycarbamidopropyl))amino)ethyl)carbamic acid glycidyl, (3-(trimethoxymethyl)alkyl) ) propylene glycol carboxylate, (3-(triethoxymethyl decyl) propyl) carbamic acid propylene oxide, (3-(methyl dimethoxymethyl decyl) propyl) amine Propylene methacrylate, (3-(trimethoxymethyl decyl) butyl) carbamic acid propylene oxide, (2-((3-trimethoxycarbamidopropyl)amino)ethyl ) propylene glycol carboxylate, 2-methyl propylene oxide (3-(trimethoxymethyl decyl) propyl) carbamic acid, (3-(triethoxymethyl decyl) propyl) 2-methyl propylene oxide carbamic acid ester, 2-methyl propylene oxide (3-(methyl dimethoxycarbamido) propyl) propyl carboxamide, (3-(trimethoxy methoxy decane) Benzyl) carbamic acid 2-methyl propylene oxide, (2-((3-trimethoxycarbamidopropyl))amino)ethyl) carbamic acid 2-methyl propylene oxide, (3-(Trimethoxymethyl decyl) propyl) carbamic acid 2-ethyl propylene oxide, (3-(triethoxymethane alkyl) propyl) amide 2-ethyl propylene oxide ester, (3-(methyldimethoxycarbamido)propyl) propyl carbamate 2-ethyl propylene oxide, (3-(trimethoxymethyl decyl) butyl 2-ethyl propylene oxide carboxylate, 2-ethyl propylene oxide (2-((3-trimethoxycarbamidopropyl)amino)ethyl) carbamic acid, (3 -(Trimethoxymethyl decyl) propyl) carbamic acid tetrahydrofuran ester, (3-(triethoxymethane alkyl) propyl) carbamic acid tetrahydrofuran ester, (3-(methyl dimethoxymethyl)矽alkyl)propyl)tetrahydrofuranylcarbamate, (3-(trimethoxymethylidenealkyl)butyl)carbamic acid tetrahydrofuran ester, (2-((3-trimethoxycarbamidopropyl))) Ethyl) carbamic acid tetrahydrofuran ester, (3-(trimethoxymethyl decyl) propyl) hydroxy carbamate, furyl (3-(triethoxymethyl decyl) propyl) amide , (3-(methyldimethoxycarbamido)propyl) propyl carbamate, furyl ester (3-(trimethoxymethyl decyl) butyl) amide, (3-(trimethoxy) Methyl decyl) propyl) carbamic acid (2H-pyran-2-yl)methyl ester, (3-(triethoxymethyl hydroxyalkyl) propyl) carbamic acid (2H-pyran) -2-yl)methyl ester, (3-(methyldimethoxycarbamidino)propyl) carbamic acid (2H-piperidin-2-yl)methyl ester, (3-(trimethoxyformane) (2H-Pyridin-2-yl)methyl (2-((3-trimethoxycarbamidopropyl)amino)ethyl) carbamic acid (2H-peripiped) Methyl-2-yl)methyl, (3-(trimethoxymethyl)alkyl)propyl)carbamic acid (4H-pyran-2-yl)methyl, (3-(triethoxymethyl) ) propyl) carbamic acid (4H-piperidin-2-yl) methyl ester, (3-(methyldimethoxymethyl decyl) propyl) carbamic acid (4H-pyran-2-yl) Methyl ester, (3-(trimethoxycarbamido)butyl) carbamic acid (4H-methane-2-yl)methyl ester, (2-((3-trimethoxycarbamidopropyl)) Ethyl)ethyl)aminocarbamic acid (4H-piperidin-2-yl)methyl ester, (3-(trimethoxymethyl)alkyl)propyl)carbamic acid (tetrahydropyran-2-yl)methyl ester , (3-(three-three) Oxymethane alkyl)propyl)aminocarbamic acid (tetrahydropyran-2-yl)methyl ester, (3-(methyldimethoxymethylindenyl)propyl)aminocarboxylic acid (tetrahydropyran) -2-yl)methyl ester, (3-(trimethoxycarbamido)butyl) carbamic acid (tetrahydropyran-2-yl)methyl ester, (2-((3-trimethoxycarbamomethane) Amino)ethyl)amino)carbamic acid (tetrahydropyran-2-yl)methyl, (3-(trimethoxymethyl)alkyl) propyl) carbamic acid (pyrrolidin-2-yl) Ester, (3-(triethoxymethyl)alkyl)propyl)carbamic acid (pyrrolidin-2-yl)methyl, (3-(methyldimethoxymethyl)alkyl)propyl) (pyrrolidin-2-yl)methyl formate, (3-(trimethoxycarbamido)butyl) carbamic acid (pyrrolidin-2-yl)methyl, (2-((3-trimethoxy)) Mercaptopropyl)amino)ethyl)aminocarbamic acid (pyrrolidin-2-yl)methyl, (3-(trimethoxymethyl)alkyl) propyl) carbamic acid (pyrrol-2-yl) Ester, (3-(triethoxymethyl)alkyl)propyl)carbamic acid (pyrrol-2-yl)methyl ester, (3-(methyldimethoxycarbamidyl)propyl) carbamic acid (pyrrol-2-yl)methyl ester, (3-(trimethoxycarbamido)butyl)aminocarboxylic acid (pyrrol-2-yl)methyl ester, (2-((3- Trimethoxymethyl decyl propyl) amino) ethyl) carbamic acid (pyrrol-2-yl) methyl ester, (3-(trimethoxymethyl decyl) propyl) carbamic acid (6-methyl) Pyridin-2-yl)methyl ester, (3-(triethoxymethanealkyl)propyl)carbamic acid (6-methylpyridin-2-yl)methyl ester, (3-(methyldimethoxy) (6-methylpyridin-2-yl)methyl methacrylate, (3-(trimethoxymethyl decyl) butyl) carbamic acid (6-methylpyridine-2) -yl)methyl ester, (2((3-trimethoxycarbamidopropyl)amino)ethyl)aminocarbamic acid (6-methylpyridin-2-yl)methyl ester, (3-(trimethoxy) Methyl decyl) propyl) carbamic acid (5-methylthiophen-2-yl) methyl ester, (3-(triethoxymethyl sulfonyl) propyl) carbamic acid (5-methyl thiophene - 2-yl)methyl ester, (3-(methyldimethoxycarbamidino)propyl)carbamic acid (5-methylthien-2-yl)methyl ester, (3-(trimethoxy) (5-methylthien-2-yl)methyl ester or (2-((3-trimethoxycarbamidopropyl)amino)ethyl) carbamic acid (5-methylthien-2-yl)methyl ester, but preferably (3-(trimethoxymethyl decyl) propyl) carbamic acid glycidyl ester, (3-(triethoxymethane) Glycidyl propyl methacrylate, glycidyl (2-((3-trimethoxycarbamidopropyl))amino)ethyl)carbamate, (3-(trimethoxy) (Methyl decyl) propyl) carbamic acid propylene oxide, (3-(triethoxymethane alkyl) propyl) carboxylic acid propylene oxide, (2-((3-trimethoxycarbane) Propyl propyl)amino)ethyl)carbamic acid propylene oxide, (3-(trimethoxymethyl decyl)propyl) carbamic acid 2-methyl propylene oxide, (3-(triple-ethyl) 2-methyl propylene oxide of oxymethane alkyl) propyl) carbamic acid, 2-methyl 2-((3-trimethoxycarbamidopropyl)amino)ethyl) carbamic acid Propylene oxide, 2-ethyl propylene oxide (3-(trimethoxymethyl decyl) propyl) carbamic acid, (3-(triethoxymethane alkyl) propyl) carbamic acid 2 -ethyl propylene oxide ester, (2-((3-trimethoxy)) 2-(Ethyl propyl)amino)ethyl)amino)carbamic acid 2-ethyl propylene oxide, (3-(trimethoxymethyl decyl) propyl) carbamic acid tetrahydrofuran ester, (3-(triethoxy) Methyl decyl) propyl) carbamic acid tetrahydrofuran ester or (2-((3-trimethoxycarbamidopropyl))amino)ethyl) carbamic acid tetrahydrofuran ester.

以通式(1)表示之矽烷偶合劑的合成方法係無特別之限制，能夠舉例藉由含有水解性矽烷之異氰酸酯化合物與醇化合物之反應而合成的方法。作為異氰酸酯化合物，能夠舉例異氰酸三甲氧基甲矽烷基丙酯、異氰酸三乙氧基甲矽烷基丙酯、異氰酸三甲氧基甲矽烷基丁酯、異氰酸三乙氧基甲矽烷基丁酯、異氰酸三甲氧基 甲矽烷基戊酯、異氰酸三乙氧基甲矽烷基戊酯、異氰酸三甲氧基甲矽烷基戊酯、異氰酸三乙氧基甲矽烷基戊酯、異氰酸4-三甲氧基甲矽烷基苯酯、異氰酸4-三乙氧基甲矽烷基苯酯、異氰酸2-((3-三甲氧基甲矽烷基丙基)胺基)乙酯或異氰酸2-((3-三乙氧基甲矽烷基丙基)胺基)乙酯，但從原料取得的觀點、保存安定性的觀點來看，以異氰酸三甲氧基甲矽烷基丙酯、異氰酸三乙氧基甲矽烷基丙酯、異氰酸2-((3-甲氧基甲矽烷基丙基)胺基)乙酯或異氰酸2-((3-三乙氧基甲矽烷基丙基)胺基)乙酯為佳。作為醇化合物，能夠舉例環氧丙醇、二甲基環氧丙醇、環氧丙烷甲醇、2-甲基環氧丙烷甲醇、2-乙基環氧丙烷甲醇、糠醇、四氫糠醇、四氫哌喃醇、吡咯啶甲醇、N-甲基-吡咯甲醇、1-甲基-2-吡咯啶甲醇吡啶甲醇、6-甲基吡啶甲醇或噻吩甲醇，但從原料取得的觀點、保存安定性的觀點來看，以2-甲基環氧丙烷甲醇、2-乙基環氧丙烷甲醇或四氫糠醇為佳。異氰酸酯化合物與醇化合物之反應，係在無觸媒下實施或使用觸媒亦可，以不包含觸媒除去之步驟的無觸媒反應為佳。又，作為所使用之觸媒，能夠舉例月桂酸二丁錫、四丁氧基鈦、四異丙氧基鈦、四乙醯丙酮鈦或四乙醯丙酮鋯。 The method for synthesizing the decane coupling agent represented by the formula (1) is not particularly limited, and a method of synthesizing by reacting an isocyanate compound containing a hydrolyzable decane with an alcohol compound can be exemplified. As the isocyanate compound, trimethoxymethyl decyl propyl cyanate, triethoxy methoxy alkyl propyl cyanide, trimethoxy carbaryl butyl cyanide, and triethoxy isocyanate can be exemplified. Formyl butyl methacrylate, trimethoxy isocyanate Methyl decyl amyl ester, triethoxy carbaryl amyl cyanide, trimethoxy carbaryl amyl cyanide, triethoxy decyl amyl isocyanate, 4-trimethyl isocyanate Oxymethane alkyl phenyl ester, 4-triethoxymethyl decyl phenyl isocyanate, 2-((3-trimethoxymethyl hydroxyalkyl) amino) isocyanate or isocyanic acid 2-((3-triethoxycarbamidopropyl)amino)ethyl ester, but from the viewpoint of the raw material and the stability of storage, trimethoxycarbamimidyl isocyanate, Triethoxymethyl decyl propyl isocyanate, 2-((3-methoxymethyl decyl propyl) amino) isocyanate or 2-((3-triethoxy) isocyanate Mercaptopropyl propyl)amino)ethyl ester is preferred. As the alcohol compound, for example, glycidol, dimethylglycolpropanol, propylene oxide methanol, 2-methyl propylene oxide methanol, 2-ethyl propylene oxide methanol, decyl alcohol, tetrahydrofurfuryl alcohol, tetrahydrogen can be exemplified. Piperol, pyrrolidine methanol, N-methyl-pyrrole methanol, 1-methyl-2-pyrrolidine methanol pyridine methanol, 6-methylpyridine methanol or thiophene methanol, but from the viewpoint of raw materials, preservation stability From the viewpoint, 2-methyl propylene oxide methanol, 2-ethyl propylene oxide methanol or tetrahydrofurfuryl alcohol is preferred. The reaction of the isocyanate compound with the alcohol compound may be carried out without a catalyst or with a catalyst, and a non-catalytic reaction which does not include a catalyst removal step is preferred. Further, examples of the catalyst to be used include dibutyltin laurate, titanium tetrabutoxide, titanium tetraisopropoxide, titanium tetraethoxide, and zirconium tetraethoxide.

本發明之(I)負型感光性樹脂組成物，係含有以通式(1)表示之(A)矽烷偶合劑、(B)鹼可溶性樹脂、(C)多官能丙烯酸單體及(D)光自由基聚合起始劑。 The (I) negative photosensitive resin composition of the present invention contains (A) a decane coupling agent represented by the formula (1), (B) an alkali-soluble resin, (C) a polyfunctional acrylic monomer, and (D) Photoradical polymerization initiator.

本發明之(II)正型感光性樹脂組成物，係含有以通式(1)表示之(A)矽烷偶合劑、(B)鹼可溶性樹脂及(E) 醌二疊氮化合物。 The (II) positive photosensitive resin composition of the present invention contains (A) a decane coupling agent represented by the formula (1), (B) an alkali-soluble resin, and (E) Bismuth azide compound.

本發明之(I)負型感光性樹脂組成物及(II)正型感光性樹脂組成物，係含有以通式(1)表示之(A)矽烷偶合劑。係藉由含有該(A)矽烷偶合劑，而能夠抑制在金屬基板上鹼顯影時的剝離、滲透。又，熱硬化後之膜對金屬基板具有良好的接著性。該(A)矽烷偶合劑的較佳範圍、具體例係如上述。作為(A)矽烷偶合劑的添加量，當使(B)鹼可溶性樹脂及(C)多官能丙烯酸單體之和為100重量份時，以0.1~20重量份為佳。小於0.1重量份時，會有未充分展現接著改善效果之情形，若大於20重量份則有顯影性低落的可能性。 The (I) negative photosensitive resin composition of the present invention and (II) the positive photosensitive resin composition contain the (A) decane coupling agent represented by the formula (1). By containing the (A) decane coupling agent, peeling and penetration at the time of alkali development on a metal substrate can be suppressed. Further, the film after the heat curing has good adhesion to the metal substrate. The preferred range and specific examples of the (A) decane coupling agent are as described above. The amount of the (A) decane coupling agent to be added is preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the sum of the (B) alkali-soluble resin and the (C) polyfunctional acrylic monomer. When it is less than 0.1 part by weight, the effect of improving the effect may not be sufficiently exhibited, and if it is more than 20 parts by weight, the developability may be lowered.

本發明之(I)負型感光性樹脂組成物及(II)正型感光性樹脂組成物，係含有(B)鹼可溶性樹脂。鹼可溶性樹脂係無特別之限制，但從透明性及通用性的觀點來看，以聚矽氧烷、丙烯酸樹脂或聚酯樹脂為佳。 The (I) negative photosensitive resin composition of the present invention and (II) the positive photosensitive resin composition contain (B) an alkali-soluble resin. The alkali-soluble resin is not particularly limited, but from the viewpoint of transparency and versatility, polysiloxane, acrylic resin or polyester resin is preferred.

聚矽氧烷係無特別之限制，但從顯影性的觀點來看，其中又以含有羧基為佳。該聚矽氧烷的羧酸當量係無特別之限制，但由於200~1,400g/mol係良好地取得膜厚減損及顯影剝離的平衡，而較佳。又，從作為(I)負型感光性樹脂組成物之基礎聚合物使用時曝光感度的提升、和所獲得之硬化膜硬度的提升的觀點來看，以具有乙烯性不飽和鍵為佳。該聚矽氧烷之雙鍵當量係無特別之限制，但由於150~10,000g/mol係良好地取得硬度、解析度平衡，而較佳。又，從保存安定性的觀點來看，以具有芳基為佳。此處，所謂羧酸當量，係表示獲得1mol 量羧基所需要的樹脂重量，單位為g/mol。所謂雙鍵當量，係表示獲得1mol量雙鍵基所需要的樹脂重量，單位為g/mol。 The polyoxyalkylene system is not particularly limited, but from the viewpoint of developability, it is preferred to contain a carboxyl group. The carboxylic acid equivalent of the polyoxyalkylene is not particularly limited, but is preferably 200 to 1,400 g/mol in terms of a balance between film thickness loss and development peeling. Moreover, it is preferable to have an ethylenically unsaturated bond from the viewpoint of the improvement of the exposure sensitivity at the time of use as the base polymer of the (I) negative photosensitive resin composition and the improvement of the hardness of the obtained cured film. The double bond equivalent of the polyoxyalkylene is not particularly limited, but is preferably from 150 to 10,000 g/mol in terms of hardness and resolution balance. Further, from the viewpoint of preserving stability, it is preferred to have an aryl group. Here, the carboxylic acid equivalent means that 1 mol is obtained. The weight of the resin required for the amount of carboxyl groups, in g/mol. The double bond equivalent is the weight of the resin required to obtain 1 mol of the double bond group, and the unit is g/mol.

合成聚矽氧烷的方法並無特別之限制，通常係將有機矽烷化合物水解，且縮合該水解物而獲得的方法。水解反應條件能夠適宜地設定，但例如，以在溶劑中費時1~180分鐘於有機矽烷化合物添加酸觸媒及水後，在室溫以上110℃以下反應1~180分鐘為佳。藉由如此條件進行水解反應，能夠抑制激烈的反應。反應溫度以30~105℃為佳。水解反應以在酸觸媒的存在下進行為佳。作為酸觸媒，以含甲酸、乙酸或磷酸的酸性水溶液為佳。該等酸觸媒的較佳含量，相對於在水解反應時所使用之全部有機矽烷化合物100重量份，以0.1~5重量份為佳。藉由使酸觸媒量在上述範圍，能夠容易地控制水解反應必要且充分地進行。縮合反應的條件，例如，以如上述地藉由有機矽烷化合物的水解反應而獲得矽醇化合物後，直接將反應液在50℃以上、溶劑的沸點以下加熱1~100小時使反應進行為佳。又，為了提高聚矽氧烷的聚合度，亦可再加熱或添加鹼觸媒。又，亦可於因應目的而水解後，將生成醇等在加熱及/或減壓下餾出、除去適量，之後添加適當的溶劑。 The method for synthesizing the polyoxyalkylene is not particularly limited, and is usually a method obtained by hydrolyzing an organodecane compound and condensing the hydrolyzate. The hydrolysis reaction conditions can be appropriately set. For example, it is preferred to carry out the reaction at room temperature to 110 ° C for 1 to 180 minutes after adding an acid catalyst and water to the organodecane compound in a solvent for 1 to 180 minutes. By carrying out the hydrolysis reaction under such conditions, it is possible to suppress a vigorous reaction. The reaction temperature is preferably from 30 to 105 °C. The hydrolysis reaction is preferably carried out in the presence of an acid catalyst. As the acid catalyst, an acidic aqueous solution containing formic acid, acetic acid or phosphoric acid is preferred. The preferred content of the acid catalyst is preferably 0.1 to 5 parts by weight based on 100 parts by weight of all the organic decane compounds used in the hydrolysis reaction. By setting the amount of the acid catalyst in the above range, the hydrolysis reaction can be easily controlled and sufficiently carried out. For the conditions of the condensation reaction, for example, after the sterol compound is obtained by the hydrolysis reaction of the organodecane compound as described above, the reaction solution is preferably heated at 50 ° C or higher and the boiling point of the solvent or lower for 1 to 100 hours. Further, in order to increase the degree of polymerization of the polyoxyalkylene, it is also possible to reheat or add a base catalyst. Further, after hydrolysis in accordance with the purpose, the alcohol or the like may be distilled off under heating and/or reduced pressure to remove an appropriate amount, and then a suitable solvent may be added.

用於聚矽氧烷合成的有機矽烷化合物並無特別之限制，能夠舉例甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、己基三甲氧基矽烷、十八烷基三甲氧基矽烷、十八烷基三乙氧 基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、二苯基二甲氧基矽烷、二苯基二乙氧基矽烷、1-萘基三甲氧基矽烷、2-萘基三甲氧基矽烷、1-萘基三乙氧基矽烷、2-萘基三乙氧基矽烷、3-胺丙基三乙氧基矽烷、N-(2-胺乙基)-3-胺丙基三甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-(N,N-二環氧丙基)胺丙基三甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、γ-胺丙基三甲氧基矽烷、γ-胺丙基三乙氧基矽烷、N-β-(胺乙基)-γ-胺丙基三甲氧基矽烷、β-胺乙基三乙氧基矽烷、環氧丙氧基甲基三甲氧基矽烷、環氧丙氧基甲基三乙氧基矽烷、α-環氧丙氧基乙基三甲氧基矽烷、α-環氧丙氧基乙基三乙氧基矽烷、β-環氧丙氧基乙基三甲氧基矽烷、β-環氧丙氧基乙基三乙氧基矽烷、α-環氧丙氧基丙基三甲氧基矽烷、α-環氧丙氧基丙基三乙氧基矽烷、β-環氧丙氧基丙基三甲氧基矽烷、β-環氧丙氧基丙基三乙氧基矽烷、γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基三乙氧基矽烷、α-環氧丙氧基丁基三甲氧基矽烷、α-環氧丙氧基丁基三乙氧基矽烷、β-環氧丙氧基丁基三甲氧基矽烷、β-環氧丙氧基丁基三乙氧基矽烷、γ-環氧丙氧基丁基三甲氧基矽烷、γ-環氧丙氧基丁基三乙氧基矽烷、δ-環氧丙氧基丁基三甲氧基矽烷、δ-環氧丙氧基丁基三乙氧基矽烷、(3,4-環氧環己基)甲基三甲氧基矽烷、(3,4-環氧環己基)甲基三乙氧基矽烷、2-(3,4-環氧環己基)乙基三丙氧基矽烷、2-(3,4-環氧環己基)乙基三丁氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三乙氧 基矽烷、2-(3,4-環氧環己基)乙基三苯氧基矽烷、3-(3,4-環氧環己基)丙基三甲氧基矽烷、3-(3,4-環氧環己基)丙基三乙氧基矽烷、4-(3,4-環氧環己基)丁基三甲氧基矽烷、4-(3,4-環氧環己基)丁基三乙氧基矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、γ-環氧丙氧基丙基甲基二甲氧基矽烷、γ-胺丙基甲基二甲氧基矽烷、γ-胺丙基甲基二乙氧基矽烷、N-(2-胺乙基)-3-胺丙基甲基二甲氧基矽烷、環氧丙氧基甲基甲基二甲氧基矽烷、環氧丙氧基甲基甲基二乙氧基矽烷、α-環氧丙氧基乙基甲基二甲氧基矽烷、α-環氧丙氧基乙基甲基二乙氧基矽烷、β-環氧丙氧基乙基甲基二甲氧基矽烷、β-環氧丙氧基乙基甲基二乙氧基矽烷、α-環氧丙氧基丙基甲基二甲氧基矽烷、α-環氧丙氧基丙基甲基二乙氧基矽烷、β-環氧丙氧基丙基甲基二甲氧基矽烷、β-環氧丙氧基丙基甲基二乙氧基矽烷、γ-環氧丙氧基丙基甲基二甲氧基矽烷、γ-環氧丙氧基丙基甲基二乙氧基矽烷、γ-環氧丙氧基丙基乙基二甲氧基矽烷、γ-環氧丙氧基丙基乙基二乙氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基甲基二乙氧基矽烷、環己基甲基二甲氧基矽烷、十八烷基甲基二甲氧基矽烷、四甲氧基矽烷、四乙氧基矽烷、矽酸甲酯、三氟甲基三甲氧基矽烷、三氟甲基三乙氧基矽烷、三氟丙基三甲氧基矽烷或三氟丙基三乙氧基矽烷。再者，藉由使用3-三甲氧基甲矽烷基丙酸、3-三乙氧基甲矽烷基丙酸、3-二甲基甲氧基甲矽烷基丙酸、3-二甲基乙氧基甲矽烷基丙酸、4-三甲氧基甲矽烷基丁酸、4-三乙氧基甲矽烷基丁 酸、4-二甲基甲氧基甲矽烷基丁酸、4-二甲基乙氧基甲矽烷基丁酸、5-三甲氧基甲矽烷基戊酸、5-三乙氧基甲矽烷基戊酸、5-二甲基甲氧基甲矽烷基戊酸、5-二甲基乙氧基甲矽烷基戊酸、3-三甲氧基甲矽烷基丙基丁二酸酐、3-三乙氧基甲矽烷基丙基丁二酸酐、3-二甲基甲氧基甲矽烷基丁二酸酐、3-二甲基乙氧基甲矽烷基丙基丁二酸酐、3-三甲氧基甲矽烷基丙基環己二羧酸酐、3-三乙氧基甲矽烷基丙基環己二羧酸酐、3-二甲基甲氧基甲矽烷基丙基環己二羧酸酐、3-二甲基乙氧基甲矽烷基丙基環己二羧酸酐、3-三甲氧基甲矽烷基丙基酞酸酐、3-三乙氧基甲矽烷基丙基酞酸酐、3-二甲基甲氧基甲矽烷基丙基酞酸酐或3-二甲基乙氧基甲矽烷基丙基酞酸酐等，能夠容易地導入羧基。再者，藉由使用乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基甲基二甲氧基矽烷、乙烯基甲基二乙氧基矽烷、丙烯基三甲氧基矽烷、丙烯基三乙氧基矽烷、丙烯基甲基二甲氧基矽烷、丙烯基甲基二乙氧基矽烷、苯乙烯基三甲氧基矽烷、苯乙烯基三乙氧基矽烷、苯乙烯基甲基二甲氧基矽烷、苯乙烯基甲基二乙氧基矽烷、γ-丙烯醯基丙基三甲氧基矽烷、γ-丙烯醯基丙基三乙氧基矽烷、γ-甲基丙烯醯基丙基三甲氧基矽烷、γ-甲基丙烯醯基丙基三乙氧基矽烷、γ-甲基丙烯醯基丙基甲基二甲氧基矽烷、γ-甲基丙烯醯基丙基甲基二乙氧基矽烷、γ-丙烯醯基丙基甲基二甲氧基矽烷或γ-丙烯醯基丙基甲基二乙氧基矽烷等，能夠容易地導入乙烯性不飽和雙鍵基。 The organodecane compound used for the synthesis of polyoxyalkylene is not particularly limited, and examples thereof include methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, and hexyl. Trimethoxydecane, octadecyltrimethoxydecane, octadecyltriethoxy Baseline, phenyltrimethoxydecane, phenyltriethoxydecane, diphenyldimethoxydecane, diphenyldiethoxydecane, 1-naphthyltrimethoxydecane, 2-naphthyltrimethyl Oxydecane, 1-naphthyltriethoxydecane, 2-naphthyltriethoxydecane, 3-aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyl Trimethoxydecane, 3-chloropropyltrimethoxydecane, 3-(N,N-diepoxypropyl)aminopropyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, Γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-β-(aminoethyl)-γ-aminopropyltrimethoxydecane, β-aminoethyltriethoxy Decane, glycidoxymethyltrimethoxydecane, glycidoxymethyltriethoxydecane, α-glycidoxyethyltrimethoxydecane, α-glycidoxyethyl Triethoxydecane, β-glycidoxyethyltrimethoxydecane, β-glycidoxyethyltriethoxydecane, α-glycidoxypropyltrimethoxydecane, α -glycidoxypropyltriethoxydecane, β-glycidoxypropyltrimethoxydecane, -glycidoxypropyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane, α-glycidoxy Butyltrimethoxydecane, α-glycidoxybutyltriethoxydecane, β-glycidoxybutyltrimethoxydecane, β-glycidoxybutyltriethoxydecane , γ-glycidoxybutyltrimethoxydecane, γ-glycidoxybutyltriethoxydecane, δ-glycidoxybutyltrimethoxydecane, δ-glycidoxy Butyl triethoxy decane, (3,4-epoxycyclohexyl)methyltrimethoxy decane, (3,4-epoxycyclohexyl)methyltriethoxy decane, 2-(3,4 -Epoxycyclohexyl)ethyltripropoxydecane, 2-(3,4-epoxycyclohexyl)ethyltributyloxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Baseline, 2-(3,4-epoxycyclohexyl)ethyltriethoxy Baseline, 2-(3,4-epoxycyclohexyl)ethyltriphenoxydecane, 3-(3,4-epoxycyclohexyl)propyltrimethoxydecane, 3-(3,4-ring Oxycyclohexyl)propyltriethoxydecane, 4-(3,4-epoxycyclohexyl)butyltrimethoxydecane, 4-(3,4-epoxycyclohexyl)butyltriethoxydecane , dimethyldimethoxydecane, dimethyldiethoxydecane, γ-glycidoxypropylmethyldimethoxydecane, γ-aminopropylmethyldimethoxydecane, γ -aminopropylmethyldiethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, glycidoxymethylmethyldimethoxydecane, Glycidoxymethylmethyldiethoxydecane, α-glycidoxyethylmethyldimethoxydecane, α-glycidoxyethylmethyldiethoxydecane, β -glycidoxyethylmethyldimethoxydecane, β-glycidoxyethylmethyldiethoxydecane, α-glycidoxypropylmethyldimethoxydecane, --glycidoxypropylmethyldiethoxydecane, β-glycidoxypropylmethyldimethoxydecane, β-glycidoxypropylmethyldiethoxy Decane, γ-glycidoxypropylmethyldimethoxydecane, γ-glycidoxypropylmethyldiethoxydecane, γ-glycidoxypropylethyldimethoxy Baseline, γ-glycidoxypropylethyldiethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropylmethyldiethoxydecane, cyclohexylmethyl Dimethoxydecane, octadecylmethyldimethoxydecane, tetramethoxynonane, tetraethoxydecane, methyl decanoate, trifluoromethyltrimethoxydecane, trifluoromethyltriethyl Oxydecane, trifluoropropyltrimethoxydecane or trifluoropropyltriethoxydecane. Further, by using 3-trimethoxymethyl decyl propionic acid, 3-triethoxymethyl decyl propionic acid, 3-dimethylmethoxymethyl decyl propionic acid, 3-dimethyl ethoxy Methyl cyanopropionic acid, 4-trimethoxymethyl decyl butyric acid, 4-triethoxymethyl sulfonyl butyl Acid, 4-dimethylmethoxycarbamidylbutyric acid, 4-dimethylethoxycarbamylbutyric acid, 5-trimethoxymethylidene valeric acid, 5-triethoxymethylcarbonyl Valeric acid, 5-dimethylmethoxycarbamidyl valeric acid, 5-dimethylethoxycarbalyl valeric acid, 3-trimethoxymethyl methacrylate dianhydride, 3-triethoxy Mercaptoalkyl succinic anhydride, 3-dimethylmethoxyformamidine succinic anhydride, 3-dimethylethoxymethyl succinyl succinic anhydride, 3-trimethoxymethyl sulfonyl Propylcyclohexanedicarboxylic anhydride, 3-triethoxycarbamidopropylcyclohexanedicarboxylic anhydride, 3-dimethylmethoxycarbamidopropylcyclohexanedicarboxylic anhydride, 3-dimethylethyl Oxymethalyl propyl cyclohexanedicarboxylic anhydride, 3-trimethoxymethyl decyl propyl phthalic anhydride, 3-triethoxymethyl decyl propyl phthalic anhydride, 3-dimethyl methoxy decane A carboxy group can be easily introduced by a propyl phthalic anhydride or 3-dimethyl ethoxymethyl propyl propyl phthalic anhydride. Further, by using vinyl trimethoxy decane, vinyl triethoxy decane, vinyl methyl dimethoxy decane, vinyl methyl diethoxy decane, propylene trimethoxy decane, propylene Triethoxy decane, propylene methyl dimethoxy decane, propylene methyl diethoxy decane, styryl trimethoxy decane, styryl triethoxy decane, styryl methyl dimethyl Oxaloxane, styrylmethyldiethoxydecane, γ-acrylamidopropyltrimethoxydecane, γ-acrylamidopropyltriethoxydecane, γ-methylpropenylpropyltrimethyl Oxydecane, γ-methylpropenylpropyltriethoxydecane, γ-methylpropenylpropylmethyldimethoxydecane, γ-methylpropenylpropylmethyldiethoxy An ethylenically unsaturated double bond group can be easily introduced, such as decane, γ-acryloyl propylmethyldimethoxy decane or γ-propenyl propylmethyldiethoxy decane.

聚矽氧烷的羧酸當量，係能夠藉由1H-NMR及IR計算出聚矽氧烷中的矽醇基/羧基比例後，以測定酸價來計算。又，雙鍵當量能夠藉由測定碘價來計算。 The carboxylic acid equivalent of the polyoxyalkylene can be calculated by calculating the valence of the sterol group/carboxyl group in the polyoxyalkylene by 1 H-NMR and IR. Also, the double bond equivalent can be calculated by measuring the iodine value.

聚矽氧烷的重量平均分子量(Mw)並無特別之限制，以膠透層析術(GPC)所測定之聚苯乙烯換算，以1,000~100,000為佳。藉由使Mw在上述範圍，而能夠獲得良好的塗布特性，形成圖案時對於顯影液的溶解性亦為良好。 The weight average molecular weight (Mw) of the polyoxyalkylene is not particularly limited, and is preferably from 1,000 to 100,000 in terms of polystyrene measured by gel permeation chromatography (GPC). When the Mw is in the above range, good coating properties can be obtained, and the solubility in the developer is also good when the pattern is formed.

丙烯酸樹脂係無特別之限制，從鹼顯影性的觀點來看，以含羧基之丙烯酸樹脂為佳。該丙烯酸樹脂的羧酸當量並無特別之限制，以200~1400g/mol為佳，較佳為300g~1200g/mol，更佳為400~800g/mol。藉由使羧酸當量在此範圍，而能夠抑制(I)負型感光性樹脂組成物在鹼性水溶液顯影後的殘留，並同時抑制曝光部的膜厚減損，形成良好的圖案。在作為(I)負型感光性樹脂組成物之基礎聚合物使用時的感度提升和硬化膜硬度的觀點，係以於丙烯酸樹脂的至少一部分導入乙烯性不飽和雙鍵基為佳。藉由具有乙烯性不飽和雙鍵基，而能夠促進曝光時之硬化、提升感度，並同時提升熱硬化後的交聯密度、提升硬化膜的硬度。該丙烯酸樹脂的雙鍵當量係無特別之限制，以150~10,000g/mol為佳。藉由在上述範圍，而能夠以高水準兼具硬度及耐龜裂性。雙鍵當量能夠藉由測定碘價來計算。又，丙烯酸樹脂亦可形成分支構造。藉由形成分支構造，而能夠提升硬化膜的硬度及耐藥品性。 The acrylic resin is not particularly limited, and from the viewpoint of alkali developability, a carboxyl group-containing acrylic resin is preferred. The carboxylic acid equivalent of the acrylic resin is not particularly limited and is preferably from 200 to 1400 g/mol, more preferably from 300 g to 1200 g/mol, still more preferably from 400 to 800 g/mol. By setting the carboxylic acid equivalent in this range, it is possible to suppress the residual of the (I) negative photosensitive resin composition after development of the alkaline aqueous solution, and at the same time suppress the film thickness loss of the exposed portion, thereby forming a favorable pattern. In view of the sensitivity improvement and the hardness of the cured film when used as the base polymer of the (I) negative photosensitive resin composition, it is preferred to introduce an ethylenically unsaturated double bond group to at least a part of the acrylic resin. By having an ethylenically unsaturated double bond group, it is possible to promote hardening during exposure and enhance sensitivity, and at the same time, increase the crosslink density after thermosetting and increase the hardness of the cured film. The double bond equivalent of the acrylic resin is not particularly limited and is preferably from 150 to 10,000 g/mol. By being in the above range, it is possible to have both hardness and crack resistance at a high level. The double bond equivalent can be calculated by measuring the iodine value. Further, the acrylic resin may also form a branched structure. By forming the branched structure, the hardness and chemical resistance of the cured film can be improved.

丙烯酸樹脂的合成方法係無特別之限制，以將(甲基)丙烯酸化合物自由基聚合者為佳。作為(甲基)丙烯酸化合物，能夠舉例含有羧基及/或酸酐基的(甲基)丙烯酸化合物，或是其他的(甲基)丙烯酸酯。自由基聚合的觸媒係無特別之限制，通常使用偶氮雙異丁腈等的偶氮化合物和過氧化苯甲醯等的有機過氧化物。自由基聚合的條件係能夠適宜地設定，但以例如在溶劑中添加含有羧基及/或酸酐之(甲基)丙烯酸化合物、及其他(甲基)丙烯酸酯及自由基聚合觸媒，藉由起泡和減壓脫氣等充分地將反應容器內以氮氣取代之後，於60~110℃進行反應30~300分鐘為佳。使用含有酸酐基之(甲基)丙烯酸化合物時，以加入理論量的水於30~60℃使反應進行30~60分鐘為佳。又，亦可因應需要使用硫醇化合物等的鏈轉移劑。 The method for synthesizing the acrylic resin is not particularly limited, and it is preferred to radically polymerize the (meth)acrylic compound. The (meth)acrylic compound may, for example, be a (meth)acrylic compound containing a carboxyl group and/or an acid anhydride group, or another (meth)acrylate. The catalyst unit of the radical polymerization is not particularly limited, and an azo compound such as azobisisobutyronitrile or an organic peroxide such as benzamidine peroxide is usually used. The conditions of the radical polymerization can be appropriately set, for example, by adding a (meth)acrylic acid compound containing a carboxyl group and/or an acid anhydride, and other (meth)acrylic acid esters and a radical polymerization catalyst to a solvent, After the bubble and the degassing under reduced pressure are sufficiently substituted with nitrogen gas in the reaction vessel, the reaction is carried out at 60 to 110 ° C for 30 to 300 minutes. When a (meth)acrylic acid compound containing an acid anhydride group is used, it is preferred to carry out the reaction for 30 to 60 minutes by adding a theoretical amount of water at 30 to 60 °C. Further, a chain transfer agent such as a thiol compound may be used as needed.

作為用於丙烯酸樹脂之合成的(甲基)丙烯酸化合物，能夠舉例(甲基)丙烯酸、(甲基)丙烯酸酐、亞甲基丁二酸、亞甲基丁二酸酐、丁二酸單(2-丙烯醯氧基乙酯)、酞酸單(2-丙烯醯氧基乙酯)、四氫酞酸單(2-丙烯醯氧基乙酯)、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸環丙酯、(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸環己烯酯、(甲基)丙烯酸4-甲氧基環己酯、(甲基)丙烯酸2-環丙氧基羰基乙酯、(甲基)丙烯酸2-環戊氧基羰基乙酯、(甲基)丙烯酸2-環己氧基羰基乙酯、(甲基)丙烯酸2-環己烯氧基羰基乙酯、(甲基)丙烯酸2-(4-甲氧基環己基)氧羰基乙酯 、(甲基)丙烯酸降莰酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸三環癸酯、(甲基)丙烯酸四環癸酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸金剛烷基甲酯、(甲基)丙烯酸1-甲基金剛烷酯、(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸α-乙基環氧丙酯、(甲基)丙烯酸α-正丙基環氧丙酯、(甲基)丙烯酸α-正丁基環氧丙酯、(甲基)丙烯酸3,4-環氧丁酯、(甲基)丙烯酸3,4-環氧庚酯、(甲基)丙烯酸α-乙基-6,7-環氧庚酯或甲基丙烯酸芐酯，分別從顯影性的觀點來看係以(甲基)丙烯酸，從耐熱性的觀點來看係以(甲基)丙烯酸異莰酯、(甲基)丙烯酸三環癸酯或(甲基)丙烯酸二環庚酯為佳。 As the (meth)acrylic compound used for the synthesis of the acrylic resin, (meth)acrylic acid, (meth)acrylic anhydride, methylene succinic acid, methylene succinic anhydride, succinic acid mono- (2) can be exemplified. - propylene methoxyethyl ester), citric acid mono (2-propenyl methoxyethyl ester), tetrahydrofurfuric acid mono (2-propenyl methoxyethyl ester), methyl (meth) acrylate, (methyl Ethyl acrylate, propyl (meth) acrylate, cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexenyl (meth) acrylate, 4-methoxycyclohexyl (meth)acrylate, 2-cyclopropoxycarbonylethyl (meth)acrylate, 2-cyclopentyloxycarbonylethyl (meth)acrylate, (meth)acrylic acid 2 -cyclohexyloxycarbonylethyl ester, 2-cyclohexenyloxycarbonylethyl (meth)acrylate, 2-(4-methoxycyclohexyl)oxycarbonylethyl (meth)acrylate , (meth)acrylic acid decyl methacrylate, isodecyl (meth) acrylate, tricyclodecyl (meth) acrylate, tetracyclononyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Adamantyl (meth)acrylate, adamantyl (meth)acrylate, 1-methyladamantyl (meth)acrylate, glycidyl (meth)acrylate, α-(meth)acrylate Ethyl propyl ketone, α-n-propyl propyl propyl (meth) acrylate, α-n-butyl butyl propyl (meth) acrylate, 3, 4-butyl butyl (meth) acrylate , 3,4-epoxyheptyl (meth)acrylate, α-ethyl-6,7-epoxyheptyl (meth)acrylate or benzyl methacrylate, respectively, from the viewpoint of developability (Meth)acrylic acid is preferably isodecyl (meth)acrylate, tricyclodecyl (meth)acrylate or bicycloheptyl (meth)acrylate from the viewpoint of heat resistance.

又，丙烯酸樹脂亦能夠使用其他含有不飽和雙鍵單體作為共聚合單體。作為其他含有不飽和雙鍵單體，能夠舉例苯乙烯、對甲基苯乙烯、鄰甲基苯乙烯、間甲基苯乙烯、α-甲基苯乙烯、順丁烯二酸酐、降莰烯、降莰烯二羧酸、降莰烯二羧酸酐、環己烯、丁基乙烯基醚、丁基丙烯基醚、2-羥乙基乙烯基醚、2-羥乙基丙烯基醚、環己烷基乙烯基醚、環己烷基丙烯基醚、4-羥丁基乙烯基醚、4-羥丁基丙烯基醚、丙烯基環氧丙基醚、乙烯基環氧丙基醚、鄰乙烯基芐基環氧丙基醚、間乙烯基芐基環氧丙基醚、對乙烯基芐基環氧丙基醚、α-甲基鄰乙烯基芐基環氧丙基醚、α-甲基間乙烯基芐基環氧丙基醚、α-甲基對乙烯基芐基環氧丙基醚、2,3-二環氧丙氧基甲基苯乙烯、2,4-二環氧丙氧基甲基苯乙烯、2,5-二環氧丙氧基甲基苯乙烯、2,6-二環氧丙氧基甲基苯乙 烯、2,3,4-三環氧丙氧基甲基苯乙烯、2,3,5-三環氧丙氧基甲基苯乙烯、2,3,6-三環氧丙氧基甲基苯乙烯、3,4,5-三環氧丙氧基甲基苯乙烯或2,4,6-三環氧丙氧基甲基苯乙烯，但以苯乙烯為佳。藉由使苯乙烯共聚合來提升所獲得之硬化膜的耐濕熱性，而提升作為觸控面板和TFT之保護膜使用時的金屬耐腐蝕性。 Further, as the acrylic resin, other unsaturated double bond-containing monomers can be used as the copolymerizable monomer. As another unsaturated double bond-containing monomer, styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, α-methylstyrene, maleic anhydride, norbornene, and the like can be exemplified. Decalene dicarboxylic acid, norbornene dicarboxylic anhydride, cyclohexene, butyl vinyl ether, butyl propenyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxyethyl propylene ether, cyclohexane Alkyl vinyl ether, cyclohexane propylene ether, 4-hydroxybutyl vinyl ether, 4-hydroxybutyl propylene ether, propylene epoxy propyl ether, vinyl epoxy propyl ether, o-ethylene Base benzyl epoxypropyl ether, m-vinylbenzyl epoxy propyl ether, p-vinylbenzyl epoxy propyl ether, α-methyl-o-vinyl benzyl epoxy propyl ether, α-methyl M-vinylbenzylepoxypropyl ether, α-methyl-p-vinylbenzylepoxypropyl ether, 2,3-diepoxypropoxymethylstyrene, 2,4-di-glycidoxy Methylstyrene, 2,5-diepoxypropoxymethylstyrene, 2,6-diepoxypropoxymethylphenyl Alkene, 2,3,4-trisethoxypropoxymethylstyrene, 2,3,5-triepoxypropoxymethylstyrene, 2,3,6-triepoxypropoxymethyl Styrene, 3,4,5-triepoxypropoxymethylstyrene or 2,4,6-triepoxypropoxymethylstyrene, but preferably styrene. By enhancing the heat and humidity resistance of the obtained cured film by copolymerizing styrene, the metal corrosion resistance when used as a protective film of a touch panel and a TFT is improved.

丙烯酸樹脂具有乙烯性不飽和鍵時，作為丙烯酸樹脂，例如以將上述之含有羧基或酸酐之(甲基)丙烯酸化合物以及(甲基)丙烯酸酯及/或其他含有不飽和雙鍵單體自由基聚合之後，將具有乙烯性不飽和雙鍵基之環氧化合物加成反應而獲得之物為佳。用於具有乙烯性不飽和雙鍵基之環氧化合物之加成反應的觸媒並無特別之限制，能夠使用熟知的觸媒，例如能夠使用二甲基苯胺、2,4,6-參(二甲基胺甲基)酚、二甲基芐基胺等的胺基系觸媒、2-乙基己酸錫(II)、月桂酸二丁基錫等的錫系觸媒、2-乙基己酸鈦(IV)等的鈦系觸媒、三苯膦等的磷系觸媒及乙醯基丙酮鉻或氯化鉻等的鉻系觸媒等。 When the acrylic resin has an ethylenically unsaturated bond, as the acrylic resin, for example, a (meth)acrylic acid compound having a carboxyl group or an acid anhydride and a (meth)acrylic acid ester and/or another unsaturated double bond-containing monomer radical are contained. After the polymerization, it is preferred to obtain an epoxy compound having an ethylenically unsaturated double bond group for addition reaction. The catalyst for the addition reaction of the epoxy compound having an ethylenically unsaturated double bond group is not particularly limited, and a well-known catalyst can be used, for example, dimethylaniline, 2,4,6-gin can be used ( Amine-based catalyst such as dimethylaminomethyl)phenol or dimethylbenzylamine; tin-based catalyst such as tin (II) 2-ethylhexanoate or dibutyltin laurate; 2-ethylhexyl A titanium-based catalyst such as titanium (IV) or a phosphorus-based catalyst such as triphenylphosphine, or a chromium-based catalyst such as chromium acetonate or chromium chloride.

作為具有乙烯性不飽和雙鍵基的環氧化合物，能夠舉例(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸α-乙基環氧丙酯、(甲基)丙烯酸α-正丙基環氧丙酯、(甲基)丙烯酸α-正丁基環氧丙酯、(甲基)丙烯酸3,4-環氧丁酯、(甲基)丙烯酸3,4-環氧庚酯、(甲基)丙烯酸α-乙基-6,7-環氧庚酯、丁基乙烯基醚、丁基丙烯基醚、2-羥乙基乙烯基醚、2-羥乙基丙烯基醚、環己烷基乙烯基醚、環己烷基丙烯基醚、4-羥丁基乙烯基醚、4-羥丁基丙烯基醚、丙 烯基環氧丙基醚、乙烯基環氧丙基醚、鄰乙烯基芐基環氧丙基醚、間乙烯基芐基環氧丙基醚、對乙烯基芐基環氧丙基醚、α-甲基鄰乙烯基芐基環氧丙基醚、α-甲基間乙烯基芐基環氧丙基醚、α-甲基對乙烯基芐基環氧丙基醚、2,3-二環氧丙氧基甲基苯乙烯、2,4-二環氧丙氧基甲基苯乙烯、2,5-二環氧丙氧基甲基苯乙烯、2,6-二環氧丙氧基甲基苯乙烯、2,3,4-三環氧丙氧基甲基苯乙烯、2,3,5-三環氧丙氧基甲基苯乙烯、2,3,6-三環氧丙氧基甲基苯乙烯、3,4,5-三環氧丙氧基甲基苯乙烯或2,4,6-三環氧丙氧基甲基苯乙烯。 As the epoxy compound having an ethylenically unsaturated double bond group, glycidyl (meth)acrylate, α-ethylglycidyl (meth)acrylate, and α-n-propyl (meth)acrylate can be exemplified. Glycidyl propyl ester, α-n-butyl butyl propyl (meth) acrylate, 3,4-butyl butyl (meth) acrylate, 3,4-epoxyheptyl (meth) acrylate, (A) Alpha-ethyl-6,7-epoxyheptyl acrylate, butyl vinyl ether, butyl propylene ether, 2-hydroxyethyl vinyl ether, 2-hydroxyethyl propylene ether, cyclohexane Vinyl ether, cyclohexane propylene ether, 4-hydroxybutyl vinyl ether, 4-hydroxybutyl propylene ether, C Alkenyl epoxidized propyl ether, vinyl epoxidized propyl ether, o-vinyl benzyl epoxy propyl ether, m-vinyl benzyl epoxy propyl ether, p-vinylbenzyl epoxy propyl ether, α -methyl-o-vinylbenzylepoxypropyl ether, α-methyl-m-vinylbenzylepoxypropyl ether, α-methyl-p-vinylbenzylepoxypropyl ether, 2,3-bicyclo Oxypropoxymethylstyrene, 2,4-diepoxypropoxymethylstyrene, 2,5-diepoxypropoxymethylstyrene, 2,6-diepoxypropoxymethyl Styrene, 2,3,4-triepoxypropoxymethylstyrene, 2,3,5-triepoxypropoxymethylstyrene, 2,3,6-triepoxypropoxy Methylstyrene, 3,4,5-triepoxypropoxymethylstyrene or 2,4,6-triepoxypropoxymethylstyrene.

具有分支的丙烯酸樹脂，能夠藉由在聚合時使用具有複數個乙烯性不飽和雙鍵基及/或硫醇基的化合物而獲得。作為具有複數個乙烯性不飽和雙鍵基的化合物，能夠舉例丙三醇二丙烯酸酯、丙三醇二甲基丙烯酸酯、丙三醇丙烯酸酯甲基丙烯酸酯、丙三醇三丙烯酸酯、丙三醇三甲基丙烯酸酯、丙三醇二丙烯酸酯甲基丙烯酸酯、丙三醇丙烯酸酯二甲基丙烯酸酯、二乙烯苯、三乙烯苯、二乙二醇二丙烯酸酯、三乙二醇二丙烯酸酯、三羥甲基丙烷基二丙烯酸酯或三羥甲基丙烷基三丙烯酸酯。作為具有複數個硫醇基的化合物，能夠舉例季戊四醇肆(3-巰基丁酸酯)、三羥甲基乙烷參(3-巰基丁酸酯)、1,4-雙(3-巰丁醯氧基)丁烷或1,3,5-參(3-巰丁氧基乙基)-1,3,5-三-2,4,6(1H,3H,5H)-三酮。丙烯酸樹脂的重量平均分子量(Mw)係無特別之限制，以藉由膠透層析術(GPC)所測定之聚苯乙烯換算，以2,000~200,000為佳。 藉由使Mw為上述範圍，而能夠獲得良好的塗布特性，形成圖案時之對於顯影液的溶解性亦為良好。 The acrylic resin having a branch can be obtained by using a compound having a plurality of ethylenically unsaturated double bond groups and/or a thiol group at the time of polymerization. As a compound having a plurality of ethylenically unsaturated double bond groups, glycerol diacrylate, glycerin dimethacrylate, glycerin acrylate methacrylate, glycerin triacrylate, and C can be exemplified. Triol trimethacrylate, glycerol diacrylate methacrylate, glycerol acrylate dimethacrylate, divinylbenzene, trivinylbenzene, diethylene glycol diacrylate, triethylene glycol Diacrylate, trimethylolpropane diacrylate or trimethylolpropane triacrylate. As the compound having a plurality of thiol groups, pentaerythritol ruthenium (3-mercaptobutyrate), trimethylolethane ginate (3-mercaptobutyrate), and 1,4-bis(3-anthracene oxime) can be exemplified. Oxy)butane or 1,3,5-gin(3-indolyloxyethyl)-1,3,5-three -2,4,6(1H,3H,5H)-trione. The weight average molecular weight (Mw) of the acrylic resin is not particularly limited, and is preferably 2,000 to 200,000 in terms of polystyrene by gel permeation chromatography (GPC). When Mw is in the above range, good coating properties can be obtained, and the solubility in the developer at the time of pattern formation is also good.

聚酯係無特別之限制，經由多官能環氧化合物及多價羧酸化合物的加成聚合反應、或多元醇化合物及二元酸酐的加成聚合反應所獲得者，因合成容易、副反應少而佳。作為多元醇化合物，因容易導入自由基聚合性基及芳香環，而以藉由多官能環氧化合物及含有自由基聚合性基之一元酸化合物的反應所獲得者為佳。 The polyester is not particularly limited, and is obtained by an addition polymerization reaction of a polyfunctional epoxy compound and a polyvalent carboxylic acid compound or an addition polymerization reaction of a polyhydric alcohol compound and a dibasic acid anhydride, because the synthesis is easy and the side reaction is small. And good. The polyol compound is preferably obtained by a reaction of a polyfunctional epoxy compound and a radical polymerizable group monobasic acid compound because a radical polymerizable group and an aromatic ring are easily introduced.

作為經由多官能環氧化合物及多價羧酸化合物之加成聚合反應的方法，能夠舉例在觸媒存在下，相對於多官能環氧化合物加入1.01~2當量的多價羧酸化合物使聚合進行後，在末端的羧酸部位加成含有自由基聚合性基之環氧化合物，在所生成之羥基加成酸酐的方法。又，能夠舉出在觸媒存在下，相對於多價羧酸化合物加入1.01~2當量的多官能環氧化合物使聚合進行後，在末端的環氧部位加成含有自由基聚合性基之一元酸化合物，在所生成之羥基加成酸酐的方法。 As a method of addition polymerization of a polyfunctional epoxy compound and a polyvalent carboxylic acid compound, it is possible to carry out polymerization by adding 1.01 to 2 equivalents of a polyvalent carboxylic acid compound to a polyfunctional epoxy compound in the presence of a catalyst. Thereafter, an epoxy compound containing a radical polymerizable group is added to the terminal carboxylic acid moiety, and a method of adding an acid anhydride to the generated hydroxyl group is added. Further, it is possible to add 1.01 to 2 equivalents of a polyfunctional epoxy compound to the polyvalent carboxylic acid compound in the presence of a catalyst to carry out polymerization, and then add a radical polymerizable group at the terminal epoxy moiety. An acid compound, a method of adding an acid anhydride to a hydroxyl group formed.

作為經由多元醇化合物及二酸酐之加成聚合反應的方法，能夠舉例在觸媒存在下，以任意比例聚合多元醇化合物及二酸酐後，在所生成之羧基的一部分加成含有自由基聚合性基之環氧化合物的方法。還有，多元醇化合物具有自由基聚合性基時，不加成含有自由基聚合性基之環氧化合物亦無妨。 As a method of the addition polymerization reaction of a polyol compound and a dianhydride, the polyol compound and the dianhydride are polymerized in an arbitrary ratio in the presence of a catalyst, and a part of the generated carboxyl group is added to contain a radical polymerizable property. A method based on an epoxy compound. Further, when the polyol compound has a radical polymerizable group, it is not necessary to add an epoxy compound containing a radical polymerizable group.

作為用於加成聚合反應及加成反應的觸媒，能夠舉例乙酸四丁銨等的銨系觸媒、2,4,6-參(二甲基胺 甲基)酚或是二甲基芐基胺等的胺基系觸媒、三苯膦等的磷系觸媒、或乙醯基丙酮鉻或是氯化鉻等的鉻系觸媒等。 As a catalyst for the addition polymerization reaction and the addition reaction, an ammonium catalyst such as tetrabutylammonium acetate or a 2,4,6-gin (dimethylamine) can be exemplified. Methyl) phenol or an amine-based catalyst such as dimethylbenzylamine, a phosphorus-based catalyst such as triphenylphosphine, or a chromium-based catalyst such as chromium acetonate or chromium chloride.

作為多官能環氧化合物，為了提升硬化膜等之折射率的調整及耐藥品性，以下述通式(5)表示的化合物為佳。 The polyfunctional epoxy compound is preferably a compound represented by the following formula (5) in order to adjust the refractive index of the cured film or the like and to improve chemical resistance.

(R6及R7分別獨立地表示氫、碳數1~12的烷基或是環烷基、碳數6~20的芳基、或該等被取代之基，或者是R6及R7同時表示碳數2~12的環烷基、碳數5~12的芳香環、或該等被取代之基。R8及R9分別獨立地表示氫、碳數2~12的烷基、碳數6~20的芳基、或該等被取代之基。p及q分別獨立地表示0~10的整數。) (R 6 and R 7 each independently represent hydrogen, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group, an aryl group having 6 to 20 carbon atoms, or such substituted groups, or R 6 and R 7 Also, it represents a cycloalkyl group having 2 to 12 carbon atoms, an aromatic ring having 5 to 12 carbon atoms, or the substituted groups. R 8 and R 9 each independently represent hydrogen, an alkyl group having 2 to 12 carbon atoms, and carbon. An aryl group of 6 to 20 or such substituted groups. p and q each independently represent an integer of 0 to 10.

作為R6、R7、R8及R9，能夠舉例甲基、乙基、丙基、環戊基、環己基、苯基、萘基、鄰甲苯基或是聯苯基、或以下所示的取代基。 Examples of R 6 , R 7 , R 8 and R 9 include a methyl group, an ethyl group, a propyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a naphthyl group, an o-tolyl group or a biphenyl group, or the following Substituents.

又，R6及R7係形成環狀構造亦無妨。環狀構造係以5~7員環為佳。作為R6及R7所形成的環狀構造，能 夠舉例以下所示的取代基。 Further, R 6 and R 7 may form a ring structure. The ring structure is preferably a 5-7 member ring. The cyclic structure formed by R 6 and R 7 can be exemplified by the substituents shown below.

(*表示與R6及R7鍵結的碳。) (* indicates carbon bonded to R 6 and R 7 .)

作為多官能環氧化合物，能夠舉例以下所示 的化合物。 As the polyfunctional epoxy compound, the following can be exemplified compound of.

作為多價羧酸化合物，能夠舉例丁二酸、順丁烯二酸、反丁烯二酸、亞甲基丁二酸、苯二甲酸、對苯二甲酸、異苯二甲酸、偏苯三甲酸、苯均四酸、2,2’-聯苯二羧酸或4,4’-聯苯二羧酸，為了提升硬化膜等之耐藥品性及絕緣性，以苯二甲酸、對苯二甲酸、異苯二甲 酸、偏苯三甲酸、苯均四酸、2,2’-聯苯二羧酸或4,4’-聯苯二羧酸為佳。 As the polyvalent carboxylic acid compound, succinic acid, maleic acid, fumaric acid, methylene succinic acid, phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid can be exemplified. , pyromellitic acid, 2,2'-biphenyldicarboxylic acid or 4,4'-biphenyldicarboxylic acid, in order to improve the chemical resistance and insulation of the cured film, etc., phthalic acid, terephthalic acid Isophthalic acid The acid, trimellitic acid, pyromellitic acid, 2,2'-biphenyldicarboxylic acid or 4,4'-biphenyldicarboxylic acid is preferred.

作為多元醇化合物，能夠舉例乙二醇、丙二醇、丁二醇、丙三醇、四羥甲基丙烷或是季戊四醇等的脂肪族醇化合物、9,9-雙[4-(2-羥乙氧基)苯基]茀、藉由多官能環氧化合物與含有自由基聚合性基之一元酸化合物的反應所獲得的化合物或藉由以下述通式(6)表示之雙酚化合物與含有自由基聚合性基之環氧化合物的反應所獲得的化合物等的芳香族醇化合物，但以芳香族醇化合物為佳。還有通式(6)中的R6、R7、R8及R9，與通式(5)相同。 As the polyol compound, an aliphatic alcohol compound such as ethylene glycol, propylene glycol, butylene glycol, glycerin, tetramethylolpropane or pentaerythritol, and 9,9-bis[4-(2-hydroxyethoxyl) can be exemplified. a compound obtained by a reaction of a polyfunctional epoxy compound with a radical polymerizable group monobasic acid compound or a bisphenol compound represented by the following formula (6) and containing a radical The aromatic alcohol compound such as a compound obtained by the reaction of the epoxy group of the polymerizable group is preferably an aromatic alcohol compound. Further, R 6 , R 7 , R 8 and R 9 in the formula (6) are the same as those in the formula (5).

作為二酸酐，能夠舉例苯均四酸二酐、3,3’,4,4’-聯苯四羧酸二酐、2,3,3’,4’-聯苯四羧酸二酐、2,2’,3,3’-聯苯四羧酸二酐、3,3’,4,4’-二苯甲酮四羧酸二酐、2,2’,3,3’-二苯甲酮四羧酸酐、2,2-雙(3,4-二羧苯基)六氟丙烷二酸酐、2,2-雙(2,3-二羧苯基)六氟丙烷二酸酐、1,1-雙(3,4-二羧苯基)乙烷二酸酐、1,1-雙(2,3-二羧苯基)乙烷二酸酐、雙(3,4-二羧苯基)甲烷二酸酐、雙(2,3-二羧苯基)甲烷二酸酐、雙(3,4-二羧苯基)碸二酸酐、雙(3,4-二羧苯基)醚二酸酐、1,2,5,6-萘四羧酸二酐、2,3,6,7-萘四羧酸二酐、2,3,5,6-吡啶四羧酸二酐或是3,4,9,10-苝四羧酸二酐等的芳香族四羧酸二酐，或丁烷四羧酸二酐、環丁烷四羧酸二酐、1,2,3,4-環戊烷四羧酸二酐、環己 烷四羧酸二酐、雙環[2.2.1.]庚烷四羧酸二酐、雙環[3.3.1.]庚烷四羧酸二酐、雙環[3.1.1.]庚-2-烯四羧酸二酐、雙環[2.2.2.]辛烷四羧酸二酐或是金剛烷四羧酸二酐等的脂肪族四羧酸二酐，但為了提升硬化膜等之耐藥品性及絕緣性，以苯均四酸二酐、3,3’,4,4’-聯苯四羧酸二酐、2,3,3’,4’-聯苯四羧酸二酐或2,2’,3,3’-聯苯四羧酸二酐為佳，為了提升硬化膜等之透明性，以環丁烷四羧酸二酐、1,2,3,4-環戊烷四羧酸二酐或環己烷四羧酸二酐為佳。 As the dianhydride, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2 can be exemplified. , 2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-diphenyl Ketone tetracarboxylic anhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane dianhydride, 1,1 - bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane Anhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sebacic anhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2 , 5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride or 3,4,9,10 - an aromatic tetracarboxylic dianhydride such as tetracarboxylic dianhydride, or butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, and 1,2,3,4-cyclopentanetetracarboxylic acid Anhydride, cyclohexyl Alkane tetracarboxylic dianhydride, bicyclo [2.2.1.] heptane tetracarboxylic dianhydride, bicyclo [3.3.1.] heptane tetracarboxylic dianhydride, bicyclo [3.1.1.] hept-2-ene tetra An aliphatic tetracarboxylic dianhydride such as carboxylic acid dianhydride, bicyclo [2.2.2.] octane tetracarboxylic dianhydride or adamantane tetracarboxylic dianhydride, but in order to improve chemical resistance and insulation of a cured film or the like Sex, with pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride or 2,2' 3,3'-biphenyltetracarboxylic dianhydride is preferred. In order to improve the transparency of the cured film, etc., cyclobutane tetracarboxylic dianhydride and 1,2,3,4-cyclopentanetetracarboxylic acid Anhydride or cyclohexanetetracarboxylic dianhydride is preferred.

作為含有自由基聚合性基之一元酸化合物，能夠舉例(甲基)丙烯酸、丁二酸單(2-(甲基)丙烯醯氧基乙酯)、酞酸單(2-(甲基)丙烯醯氧基乙酯)、四氫酞酸單(2-(甲基)丙烯醯氧基乙酯)或對羥基苯乙烯。 Examples of the radical polymerizable group-containing monobasic acid compound include (meth)acrylic acid, succinic acid mono(2-(methyl)acryloxyethyl ester), and phthalic acid mono(2-(methyl) propylene. Ethyloxyethyl ester), tetrahydrofurfuric acid mono(2-(methyl)propenyloxyethyl ester) or p-hydroxystyrene.

作為含有自由基聚合性基之環氧化合物，能夠舉例(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸α-乙基環氧丙酯、(甲基)丙烯酸α-正丙基環氧丙酯、(甲基)丙烯酸α-正丁基環氧丙酯、(甲基)丙烯酸3,4-環氧基丁酯、(甲基)丙烯酸3,4-環氧基庚酯、(甲基)丙烯酸α-乙基-6,7-環氧基丁酯、丁基乙烯基醚、丁基丙烯基醚、2-羥乙基乙烯基醚、2-羥乙基丙烯基醚、環己烷基乙烯基醚、環己烷基丙烯基醚、4-羥丁基乙烯基醚、4-羥丁基丙烯基醚、丙烯基環氧丙基醚、乙烯基環氧丙基醚、鄰乙烯基芐基環氧丙基醚、間乙烯基芐基環氧丙基醚、對乙烯基芐基環氧丙基醚、α-甲基鄰乙烯基芐基環氧丙基醚、α-甲基間乙烯基芐基環氧丙基醚、α-甲基對乙烯基芐基環氧丙基 醚、2,3-二環氧丙氧基甲基苯乙烯、2,4-二環氧丙氧基甲基苯乙烯、2,5-二環氧丙氧基甲基苯乙烯、2,6-二環氧丙氧基甲基苯乙烯、2,3,4-三環氧丙氧基甲基苯乙烯、2,3,5-三環氧丙氧基甲基苯乙烯、2,3,6-三環氧丙氧基甲基苯乙烯、3,4,5-三環氧丙氧基甲基苯乙烯或2,4,6-三環氧丙氧基甲基苯乙烯。 Examples of the epoxy compound containing a radical polymerizable group include glycidyl (meth)acrylate, α-ethylglycidyl (meth)acrylate, and α-n-propyl (meth)acrylate. Propyl ester, α-n-butyl propylene acrylate (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 3,4-epoxyheptyl (meth)acrylate, (A) Alpha-ethyl-6,7-epoxybutyl acrylate, butyl vinyl ether, butyl propenyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxyethyl propylene ether, cyclohexyl Alkyl vinyl ether, cyclohexane propylene ether, 4-hydroxybutyl vinyl ether, 4-hydroxybutyl propylene ether, propylene epoxy propyl ether, vinyl epoxy propyl ether, o-ethylene Base benzyl epoxypropyl ether, m-vinylbenzyl epoxy propyl ether, p-vinylbenzyl epoxy propyl ether, α-methyl-o-vinyl benzyl epoxy propyl ether, α-methyl M-vinylbenzyl epoxypropyl ether, α-methyl-vinylvinyl epoxide Ether, 2,3-diepoxypropoxymethylstyrene, 2,4-diepoxypropoxymethylstyrene, 2,5-diepoxypropoxymethylstyrene, 2,6 - digoxypropyloxymethylstyrene, 2,3,4-triepoxypropoxymethylstyrene, 2,3,5-triepoxypropoxymethylstyrene, 2,3, 6-triepoxypropoxymethylstyrene, 3,4,5-triepoxypropoxymethylstyrene or 2,4,6-triepoxypropoxymethylstyrene.

作為酸酐，能夠舉例丁二酸酐、順丁烯二酸酐、亞甲基丁二酸酐、酞酸酐、偏苯三甲酸酐、苯均四酸一酐、2,3-聯苯二羧酸酐、3,4-聯苯二羧酸酐、六氫酞酸酐、戊二酸酐、3-甲基酞酸酐、降莰烯基二羧酸酐、環己烯基二羧酸酐或3-三甲氧基甲矽烷基丙基丁二酸酐。本發明之(I)負型感光性樹脂組成物的(B)鹼可溶性樹脂含量係無特別之限制，能夠隨著所期望之膜厚和用途而任意地選擇，在(B)鹼可溶性樹脂及(C)多官能單體之和為100重量份時，通常為10重量份以上70重量份以下。 As the acid anhydride, succinic anhydride, maleic anhydride, methylene succinic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,3-biphenyldicarboxylic anhydride, 3, 4 can be exemplified. -biphenyldicarboxylic anhydride, hexahydrophthalic anhydride, glutaric anhydride, 3-methylphthalic anhydride, nordecenyldicarboxylic anhydride, cyclohexenyldicarboxylic anhydride or 3-trimethoxyformamidinylpropyl Diacid anhydride. The (B) alkali-soluble resin content of the (I) negative photosensitive resin composition of the present invention is not particularly limited, and can be arbitrarily selected depending on the desired film thickness and use, and (B) an alkali-soluble resin and When the sum of the (C) polyfunctional monomers is 100 parts by weight, it is usually 10 parts by weight or more and 70 parts by weight or less.

本發明之(I)負型感光性樹脂組成物含有(C)多官能單體。(C)多官能單體的聚合係藉由光照射以下述(D)光聚合起始劑進行，且本發明之(I)負型感光性樹脂組成物的曝光部位不溶於鹼水溶液，而能夠形成負型的圖案。所謂多官能單體，係指在分子中具有至少2個以上之乙烯性不飽和雙鍵的化合物，雖無特別之限定，但以具有容易自由基聚合之(甲基)丙烯酸基的多官能單體為佳。又，從感度、硬度的觀點來看，(C)多官能單體的雙鍵當量係以80g/mol以上400g/mol以下為佳。 The (I) negative photosensitive resin composition of the present invention contains (C) a polyfunctional monomer. (C) Polymerization of a polyfunctional monomer is carried out by light irradiation with the following (D) photopolymerization initiator, and the exposed portion of the (I) negative photosensitive resin composition of the present invention is insoluble in an aqueous alkali solution, and A negative pattern is formed. The polyfunctional monomer refers to a compound having at least two or more ethylenically unsaturated double bonds in the molecule, and is not particularly limited, but is a polyfunctional single having a (meth)acrylic group which is easily polymerized by radical polymerization. The body is better. Further, from the viewpoint of sensitivity and hardness, the (C) polyfunctional monomer preferably has a double bond equivalent of from 80 g/mol to 400 g/mol.

作為(C)多官能單體，能夠舉例二乙二醇二丙 烯酸酯、三乙二醇二丙烯酸酯、四乙二醇二丙烯酸酯、二乙二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、四乙二醇二甲基丙烯酸酯、三羥甲基丙烷二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、三羥甲基丙烷二甲基丙烯酸酯、三羥甲基丙烷三甲基丙烯酸酯、1,3-丁二醇二丙烯酸酯、1,3-丁二醇二甲基丙烯酸酯、季戊四醇二丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯、1,6-己二醇二丙烯酸酯、1,9-壬二醇二甲基丙烯酸酯、1,10-癸二醇二甲基丙烯酸酯、二羥甲基-三環癸烷二丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇三甲基丙烯酸酯、季戊四醇四甲基丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、三季戊四醇七丙烯酸酯、三季戊四醇八丙烯酸酯、四季戊四醇九丙烯酸酯、四季戊四醇十丙烯酸酯、五季戊四醇十一丙烯酸酯、五季戊四醇十二丙烯酸酯、三季戊四醇七甲基丙烯酸酯、三季戊四醇八甲基丙烯酸酯、四季戊四醇九甲基丙烯酸酯、四季戊四醇十甲基丙烯酸酯、五季戊四醇十一甲基丙烯酸酯、五季戊四醇十二甲基丙烯酸酯、二羥甲基-三環癸烷二丙烯酸酯、環氧化雙酚A二丙烯酸酯、9,9-雙[4-(2-丙烯醯氧基乙氧基)苯基]茀、9,9-雙[4-(2-甲基丙烯醯氧基乙氧基)苯基]茀、9,9-雙[4-(2-甲基丙烯醯氧基乙氧基)-3-甲苯基]茀、9,9-雙[4-(2-丙烯醯氧基丙氧基)-3-甲苯基]茀、9,9-雙[4-(2-丙烯醯氧基乙氧基)-3,5-二甲苯基]茀或9,9-雙[4-(2-甲基丙烯醯氧基乙氧基)-3,5-二甲苯基]茀，但從感度提升的觀點來看，以季戊 四醇四丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、三季戊四醇七丙烯酸酯或三季戊四醇八丙烯酸酯為佳，從疏水性提升的觀點來看，以二羥甲基-三環癸烷二丙烯酸酯、二羥甲基-三環癸烷二甲基丙烯酸酯、環氧化雙酚A二丙烯酸酯或9,9-雙[4-(2-丙烯醯氧基乙氧基)苯基]茀為佳。 As the (C) polyfunctional monomer, diethylene glycol dipropylene can be exemplified Ethyl ester, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, Trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,3-butanediol diacrylate , 1,3-butanediol dimethacrylate, pentaerythritol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol Diacrylate, 1,9-nonanediol dimethacrylate, 1,10-nonanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate, pentaerythritol IV Acrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, pentaerythritol hexaacrylate, tetrakis pentaerythritol Acrylate, pentaerythritol ten Acrylate, pentaerythritol dodecyl acrylate, tripentaerythritol heptamethacrylate, tripentaerythritol octa methacrylate, pentaerythritol nonyl methacrylate, pentaerythritol decamethacrylate, pentaerythritol eleven methacrylate , pentaerythritol dodecyl methacrylate, dimethylol-tricyclodecane diacrylate, epoxidized bisphenol A diacrylate, 9,9-bis[4-(2-propenyloxyethoxy) Phenyl]fluorene, 9,9-bis[4-(2-methylpropenyloxyethoxy)phenyl]anthracene, 9,9-bis[4-(2-methylpropenyloxy) Oxy)-3-methyl] hydrazine, 9,9-bis[4-(2-propenyloxypropoxy)-3-methyl] hydrazine, 9,9-bis[4-(2-propene)醯oxyethoxy)-3,5-dimethylphenyl]anthracene or 9,9-bis[4-(2-methylpropenyloxyethoxy)-3,5-dimethylphenyl]anthracene, But from the point of view of improved sensitivity, Tetrahydrin tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate or tripentaerythritol octaacrylate, preferably from the viewpoint of hydrophobicity, dimethylol-tricycloquinone Alkenyl diacrylate, dimethylol-tricyclodecane dimethacrylate, epoxidized bisphenol A diacrylate or 9,9-bis[4-(2-propenyloxyethoxy)phenyl ] 茀 is better.

在本發明之(I)負型感光性樹脂組成物中，對於(C)多官能單體的含量並無特別之限制，能夠隨著所期望之膜厚和用途任意地選擇，但當(B)鹼可溶性樹脂及(C)多官能單體之和為100重量份時，通常為10~60重量份。 In the (I) negative photosensitive resin composition of the present invention, the content of the (C) polyfunctional monomer is not particularly limited, and can be arbitrarily selected depending on the desired film thickness and use, but when (B) When the sum of the alkali-soluble resin and the (C) polyfunctional monomer is 100 parts by weight, it is usually 10 to 60 parts by weight.

本發明之(I)負型感光性樹脂組成物含有(D)光聚合起始劑。(D)光聚合起始劑係以藉由光(包含紫外線、電子線)分解及/或反應、而使自由基產生者為佳。 The (I) negative photosensitive resin composition of the present invention contains (D) a photopolymerization initiator. (D) The photopolymerization initiator is preferably a radical generator by decomposition and/or reaction by light (including ultraviolet rays or electron beams).

作為光聚合起始劑，能夠舉例2-甲基-[4-(甲硫基)苯基]-2-啉基丙-1-酮、2-二甲胺基-2-(4-甲芐基)-1-(4-=啉-4-醯基-苯基)-丁-1-酮、2-芐基-2-二甲胺基-1-(4-啉苯基)-丁-1-酮、氧化2,4,6-三甲基苯甲醯基苯基膦、氧化雙(2,4,6-三甲基苯甲醯基)-苯基膦、氧化雙(2,6-二甲氧基苯甲醯基)-(2,4,4-三甲基戊基)-膦、1-苯基-1,2-丙二酮-2-(鄰乙氧基羧基)肟、1,2-辛二酮,1-[4-(苯硫基)-2-(O-苯甲醯基肟)]、1-苯基-1,2-丁二酮-2-(鄰甲氧基羧基)肟、1,3-二苯基丙三酮-2-(鄰乙氧基羧基)肟、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-醯基]-,1-(O-乙醯基肟)、4,4-雙(二甲胺基)二苯甲酮、4,4-雙(二乙胺 基)二苯甲酮、對二甲胺基安息香酸乙酯、對二甲胺基苯甲酸2-乙基己酯、對二乙安基安息香酸乙酯、二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙-1-酮、芐基二甲基酮縮醇、1-(4-異丙苯基)-2-羥基-2-甲基丙-1-酮、4-(2-羥乙氧基)苯基-(2-羥基-2-丙基)酮、1-羥基環己基-苯基酮、安息香、安息香甲醚、安息香***、安息香異丙醚、安息香異丁醚、二苯甲酮、對苯甲醯基安息香酸甲酯、4-苯基二苯甲酮、4,4-二氯二苯甲酮、羥基二苯甲酮、4-苯甲醯基-4’-甲基-二苯硫醚、烷化二苯甲酮、3,3’,4,4’-四(三級丁基過氧羧基)二苯甲酮、溴化4-苯甲醯基-N,N-二甲基-N-[2-(1-氧代-2-丙烯氧基)乙基]苯甲銨、氯化(4-苯甲醯基芐基)三甲銨、氯化2-羥基-3-(4-苯甲醯基苯氧基)-N,N,N-三甲基-1-丙烯銨單水合物、2-異丙基-9-氧硫、2,4-二甲基-9-氧硫、2,4-二乙基-9-氧硫、2,4-二氯-9-氧硫、氯化2-羥基-3-(3,4-二甲基-9-氧代-9H-硫-2-氧基)-N,N,N-三甲基-1-丙銨、2,2’-雙(對氯苯基)-4,5,4’,5’-四苯基-1,2-聯咪唑、10-丁基-2-氯吖啶酮、2-乙基蒽醌、苯甲醯、9,10-菲醌、樟腦醌、甲苯基乙醛酸酯、η5-環戊二烯基-η6-異丙苯基-鐵(1+)-六氟膦酸酯(1-)、二苯硫衍生物、雙(η5-2,4-環戊二烯-1-醯基)-雙(2,6-二氟-3-(1H-吡咯-1-醯基)-苯基)鈦、9-氧硫、2-甲基-9-氧硫、2-氯-9-氧硫、4-苯甲醯基-4-甲苯基酮、二芐基酮、茀酮、2,3-二乙氧基苯乙酮、2,2-二甲氧基-2-苯基-2-苯基苯乙酮、2-羥基-2-甲基苯丙酮、對三級丁基二氯苯乙酮、芐基甲氧基乙基縮醛、 蒽醌、2-三級丁基蒽醌、2-胺基蒽醌、β-氯蒽醌、蔥酮、苯并蒽酮、二苯并環庚酮、亞甲基蔥酮、4-疊氮亞芐基苯乙酮、2,6-雙(對疊氮苯亞甲基)環己烷、2,6-雙(對疊氮苯亞甲基)-4-甲基環己烷、萘磺醯基氯化物、喹啉磺醯基氯化物、N-苯基硫代吖啶酮、苯并唑二硫化物、三苯膦、四溴化碳、三溴苯基碸或是過氧化苯甲醯或曙紅或是亞甲藍等的光還原性色素與抗壞血酸或是三乙醇胺等之還原劑的組合。亦可含有該等之2種以上。 As a photopolymerization initiator, 2-methyl-[4-(methylthio)phenyl]-2- can be exemplified Orolinyl propan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-= phenyl-4-indolyl-phenyl)-butan-1-one, 2- Benzyl-2-dimethylamino-1-(4- Phenanylphenyl)-butan-1-one, 2,4,6-trimethylbenzimidylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide , bis(2,6-dimethoxybenzylidene)-(2,4,4-trimethylpentyl)-phosphine, 1-phenyl-1,2-propanedione-2-( O-ethoxycarboxy) hydrazine, 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzylidenehydrazine)], 1-phenyl-1,2-butyl Diketo-2-(o-methoxycarboxy)anthracene, 1,3-diphenylpropanetrione-2-(o-ethoxycarboxy)anthracene, ethyl ketone, 1-[9-ethyl-6-( 2-methylbenzhydryl)-9H-indazole-3-indenyl]-, 1-(O-ethylindenyl), 4,4-bis(dimethylamino)benzophenone, 4 , 4-bis(diethylamino)benzophenone, p-dimethylamino benzoic acid ethyl ester, p-dimethylaminobenzoic acid 2-ethylhexyl ester, p-diethyl benzoic acid ethyl ester, two Ethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1-(4-isopropylphenyl)-2-hydroxy- 2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl-phenyl ketone, benzoin, benzoin methyl ether , benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, paraben Methyl benzoic acid methyl ester, 4-phenyl benzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzylidene-4'-methyl-diphenyl sulfide , alkylated benzophenone, 3,3',4,4'-tetrakis(tertiary butylperoxycarboxy)benzophenone, 4-benzylidene-N,N-dimethyl-bromide N-[2-(1-oxo-2-propenyloxy)ethyl]benzylammonium chloride, (4-benzylidenebenzyl)trimethylammonium chloride, 2-hydroxy-3-(4-hydroxy-3-chloride) Benzyl phenoxy)-N,N,N-trimethyl-1-propenium monohydrate, 2-isopropyl-9-oxosulfur 2,4-dimethyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 2,4-dichloro-9-oxosulfur , 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-sulfur chloride -2-oxy)-N,N,N-trimethyl-1-propylammonium, 2,2'-bis(p-chlorophenyl)-4,5,4',5'-tetraphenyl-1 , 2-biimidazole, 10-butyl-2-chloroacridone, 2-ethylhydrazine, benzamidine, 9,10-phenanthrenequinone, camphorquinone, tolyl glyoxylate, η5-cyclopentane Dienyl-η6-isopropylphenyl-iron (1+)-hexafluorophosphonate (1-), diphenylthio derivative, bis(η5-2,4-cyclopentadien-1-yl) )-bis(2,6-difluoro-3-(1H-pyrrole-1-indenyl)-phenyl)titanium, 9-oxosulfur 2-methyl-9-oxosulfur 2-chloro-9-oxosulfur , 4-benzylidene-4-tolylone, dibenzyl ketone, fluorenone, 2,3-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2- Phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyldichloroacetophenone, benzylmethoxyethyl acetal, anthracene, 2-tertiary butyl hydrazine, 2-Aminoguanidine, β-chloropurine, onion ketone, benzoxanthone, dibenzocycloheptanone, methylene onion ketone, 4-azidobenzylidene acetophenone, 2,6-double (p-azidobenzylidene)cyclohexane, 2,6-bis(p-azidobenzylidene)-4-methylcyclohexane, naphthalenesulfonyl chloride, quinoline sulfonyl chloride , N-phenylthioacridone, benzoxazole disulfide, triphenylphosphine, carbon tetrabromide, tribromophenylphosphonium or light benzamidine or ruthenium or methylene blue A combination of a reducing pigment and a reducing agent such as ascorbic acid or triethanolamine. Two or more of these may be contained.

該等之中，為了更提高硬化膜的硬度，以α-胺烷基苯酮化合物、氧化醯基膦化合物、肟酯化合物、具有胺基的二苯甲酮化合物或具有胺基的安息香酸酯化合物為佳。 Among these, in order to further increase the hardness of the cured film, an α-aminoalkylphenone compound, a decylphosphine compound, an oxime ester compound, a benzophenone compound having an amine group, or a benzoic acid ester having an amine group may be used. The compound is preferred.

作為α-胺烷基苯酮化合物，能夠舉例2-甲基-[4-(甲硫基)苯基]-2-啉丙-1-酮、2-二甲胺基-2-(4-甲芐基)-1-(4-啉-4-醯基-苯基)-丁-1-酮或2-芐基-2-二甲胺基-1-(4-啉苯基)-丁-1-酮。作為氧化醯基膦化合物，能夠舉例氧化2,4,6-三甲基苯甲醯基苯基膦、氧化雙(2,4,6-三甲基苯甲醯基)-苯基膦或氧化雙(2,6-二甲氧基苯甲醯基)-(2,4,4-三甲基戊基)-膦。作為肟酯化合物，能夠舉例1-苯基-1,2-丙二酮-2-(鄰乙氧羧基)肟、1,2-辛二酮,1-[4-(苯硫基)-2-(O-苯甲醯基肟)]、1-苯基-1,2-丁二酮-2-(鄰甲氧羧基)肟、1,3-二苯基丙三酮-2-(鄰乙氧羧基)肟或乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-醯基]-,1-(O-乙醯基肟)。作為具有胺基的二苯甲酮化合物，能夠舉例4,4-雙(二甲胺基)二苯甲酮或4,4-雙(二乙胺基)二苯甲酮 。作為具有胺基的安息香酸酯化合物，能夠舉例對二甲胺基安息香酸乙酯、對二甲胺基安息香酸2-乙基己酯或對二乙胺基安息香酸乙酯。 As the α-aminoalkylphenone compound, 2-methyl-[4-(methylthio)phenyl]-2- can be exemplified Phenylpropan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4- Phenyl-4-mercapto-phenyl)-butan-1-one or 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butan-1-one. As the cerium phosphine oxide compound, for example, 2,4,6-trimethylbenzimidylphenylphosphine, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide or oxidation can be oxidized. Bis(2,6-dimethoxybenzylidene)-(2,4,4-trimethylpentyl)-phosphine. As the oxime ester compound, 1-phenyl-1,2-propanedione-2-(o-ethoxycarboxy)anthracene, 1,2-octanedione, 1-[4-(phenylthio)-2 can be exemplified. -(O-benzhydrylhydrazine)], 1-phenyl-1,2-butanedione-2-(o-methoxycarboxy)anthracene, 1,3-diphenylpropanetrione-2-(ortho Ethoxycarboxy) hydrazine or ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-indenyl]-, 1-(O-ethenyl)肟). As the benzophenone compound having an amine group, 4,4-bis(dimethylamino)benzophenone or 4,4-bis(diethylamino)benzophenone can be exemplified. As the benzoic acid ester compound having an amine group, ethyl dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate or ethyl p-diethylamine benzoate can be exemplified.

在本發明之(I)負型感光性樹脂組成物中，對於(D)光聚合起始劑的含量並無特別之限制，當(B)鹼可溶性樹脂及(C)多官能單體之和為100重量份時，以0.1~20重量份為佳。藉由為上述範圍，而能夠充分地進行硬化，並且能夠確保防止殘留之聚合起始劑之溶出等的耐溶劑性。 In the (I) negative photosensitive resin composition of the present invention, the content of the (D) photopolymerization initiator is not particularly limited, and the sum of (B) the alkali-soluble resin and (C) the polyfunctional monomer When it is 100 parts by weight, it is preferably 0.1 to 20 parts by weight. By being in the above range, the curing can be sufficiently performed, and the solvent resistance such as the elution of the remaining polymerization initiator can be ensured.

本發明之(II)正型感光性樹脂組成物係含有(E)醌二疊氮化合物。含有(E)醌二疊氮化合物之感光性組成物係形成以顯影液除去曝光部分的正型。所使用之醌二疊氮化合物的添加量並無特別之限制，但相對於(B)鹼可溶性樹脂，以3~30wt%為佳，較佳為4~15wt%。醌二疊氮化合物的添加量較3wt%少時，曝光部與未曝光部的溶解對比過低，不具有實際上的感光性。又，為了獲得更良好的溶解對比，以4wt%以上為佳。另一方面，醌二疊氮化合物的添加量較30wt%多時，則會有因鹼可溶性樹脂及醌二疊氮化合物的相溶性變差而發生塗布膜的白化，或因熱硬化時發生之醌二疊氮化合物的分解而著色變得明顯之故，硬化膜的無色透明性低落。 The (II) positive photosensitive resin composition of the present invention contains (E) a quinonediazide compound. The photosensitive composition containing the (E) quinonediazide compound forms a positive type in which the exposed portion is removed by the developer. The amount of the quinonediazide compound to be added is not particularly limited, but is preferably 3 to 30% by weight, more preferably 4 to 15% by weight based on the (B) alkali-soluble resin. When the amount of the quinonediazide compound added is less than 3 wt%, the dissolution ratio between the exposed portion and the unexposed portion is too low, and the actual photosensitivity is not obtained. Further, in order to obtain a better dissolution contrast, it is preferably 4% by weight or more. On the other hand, when the amount of the quinonediazide compound added is more than 30% by weight, the compatibility of the alkali-soluble resin and the quinonediazide compound may be deteriorated, and the coating film may be whitened or thermally cured. When the bismuth azide compound is decomposed and the coloration becomes conspicuous, the colorless transparency of the cured film is low.

所使用的醌二疊氮化合物係無特別之限制，但以在具有酚性羥基之化合物酯鍵結萘醌二疊氮磺酸的化合物為佳，較佳為該化合物的酚性羥基的鄰位及對位分別獨立為氫或以通式(5)表示之取代基的化合物。 The quinonediazide compound to be used is not particularly limited, but a compound in which a compound having a phenolic hydroxyl group is bonded to a naphthoquinonediazidesulfonic acid is preferred, and an ortho position of the phenolic hydroxyl group of the compound is preferred. And a compound which is independently a hydrogen or a substituent represented by the formula (5).

(R10~R12分別獨立表示碳數1~10的烷基、羧基、苯基或取代苯基。又，以R10及R11、R10及R12或R11及R12形成環狀構造亦無妨。) (R 10 to R 12 each independently represent an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group or a substituted phenyl group. Further, a ring is formed by R 10 and R 11 , R 10 and R 12 or R 11 and R 12 . Construction is fine.)

R10~R12為碳數1~10的烷基時，該烷基可具有取代基，又亦可不具有取代基的無取代物，能夠隨著組成物特性加以選擇。作為碳數1~10的烷基，能夠舉例甲基、乙基、正丙基、異丙基、正丁基、異丁基、三級丁基、正己基、環己基、正庚基、正辛基、三氟甲基或2-羧乙基。又，作為取代於苯基的取代基，能夠舉例羥基。又，以R10及R11、R10及R12或R11及R12形成環亦無妨，作為所形成之環狀構造，能夠舉例環戊烷環、環己烷環、金剛烷環、茀環。 When R 10 to R 12 are an alkyl group having 1 to 10 carbon atoms, the alkyl group may have a substituent or an unsubstituted substance having no substituent, and may be selected in accordance with the characteristics of the composition. Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, cyclohexyl, n-heptyl, and Octyl, trifluoromethyl or 2-carboxyethyl. Further, as a substituent substituted in the phenyl group, a hydroxyl group can be exemplified. Further, a ring may be formed by R 10 and R 11 , R 10 and R 12 or R 11 and R 12 . Examples of the cyclic structure to be formed include a cyclopentane ring, a cyclohexane ring, an adamantane ring and an anthracene. ring.

酚性羥基之鄰位及對位為上述以外，例如甲基時，會有因熱硬化而發生氧化分解，形成以醌構造為代表的共軛系化合物，硬化膜著色而無色透明性低落的情況。還有，該等醌二疊氮化合物能夠藉由具有酚性羥基之化合物、與氯化萘醌二疊氮磺酸之習知的酯化反應而合成。 When the phenolic hydroxyl group is ortho and para-positioned, for example, a methyl group is oxidatively decomposed by thermal curing, and a conjugated compound represented by a fluorene structure is formed, and the cured film is colored and the colorless transparency is lowered. . Further, the quinonediazide compound can be synthesized by a conventional esterification reaction with a compound having a phenolic hydroxyl group and chlorinated naphthoquinonediazidesulfonic acid.

作為具有酚性羥基的化合物，能夠舉例以下的化合物(均為本州化學工業(股)製)。 The compound having a phenolic hydroxyl group can be exemplified by the following compounds (all manufactured by Honshu Chemical Industry Co., Ltd.).

作為萘醌二疊氮磺酸，能夠使用4-萘醌二疊氮磺酸或5-萘醌二疊氮磺酸。4-萘醌二疊氮磺酸酯化合物係因在i射線(波長為365nm)範圍具有吸收，所以適合於i射線曝光。又，5-萘醌二疊氮磺酸酯化合物係因在寬範圍的波長範圍存在吸收，所以適合於以寬範圍之波長的曝光。以隨著所曝光之波長來選擇4-萘醌二疊氮磺酸酯化合物、5-萘醌二疊氮磺酸酯化合物為佳。亦能夠混合使用4-萘醌疊氮磺酸酯化合物及5-萘醌二疊氮磺酸酯化合物。 As the naphthoquinonediazidesulfonic acid, 4-naphthoquinonediazidesulfonic acid or 5-naphthoquinonediazidesulfonic acid can be used. The 4-naphthoquinonediazide sulfonate compound is suitable for i-ray exposure because it has absorption in the range of i-rays (wavelength: 365 nm). Further, the 5-naphthoquinonediazide sulfonate compound is suitable for exposure over a wide range of wavelengths because of absorption in a wide range of wavelengths. It is preferred to select a 4-naphthoquinonediazide sulfonate compound or a 5-naphthoquinonediazide sulfonate compound in accordance with the wavelength to be exposed. It is also possible to use a 4-naphthoquinone azide sulfonate compound and a 5-naphthoquinonediazide sulfonate compound in combination.

萘醌二疊氮化合物的分子量，係以300~1500為佳，較佳為350~1200。若萘醌二疊氮化合物的分子量 大於1500，則4~10wt%的添加量會有不能形成圖案的可能性。另一方面，若萘醌二疊氮化合物的分子量小於300，則有無色透明性低落的可能性。 The molecular weight of the naphthoquinonediazide compound is preferably from 300 to 1,500, more preferably from 350 to 1200. Molecular Weight of Naphthoquinonediazide Compound When it is more than 1,500, the addition amount of 4 to 10% by weight may not form a pattern. On the other hand, if the molecular weight of the naphthoquinonediazide compound is less than 300, there is a possibility that the colorless transparency is lowered.

本發明之(I)負型感光性樹脂組成物及(II)正型感光性樹脂組成物亦可含有(F)金屬氧化物粒子。能夠藉由含有(F)金屬氧化物粒子，而將折射率調整至所期望的範圍。又，能夠更提升硬化膜的硬度、耐擦傷性、耐龜裂性。(F)金屬酸化物粒子的數量平均粒徑係以1~200nm為佳。為了獲得透光率高的硬化膜，數量平均粒徑較佳為1~70nm。此處，金屬氧化物粒子的數量平均粒徑，能夠藉由氣體吸附法和動態光散射法、X射線小角度散射法、穿透型電子顯微鏡或掃描型電子顯微鏡加以測定。作為(F)金屬氧化物粒子，能夠舉例矽氧化物粒子、鋁氧化物粒子、錫氧化物粒子、鈦氧化物粒子、鋯氧化物粒子或鋇氧化物粒子等，能夠隨著用途而選擇適當者。例如為了獲得高折射率的硬化膜，以氧化鈦粒子或是鈦酸鋇粒子等之鈦氧化物粒子、或氧化鋯粒子等之鋯氧化物粒子為佳。又，為了獲得低折射率的硬化膜，以含有中空矽石粒子等為佳。 The (I) negative photosensitive resin composition of the present invention and (II) the positive photosensitive resin composition may further contain (F) metal oxide particles. The refractive index can be adjusted to a desired range by containing (F) metal oxide particles. Moreover, the hardness, scratch resistance, and crack resistance of the cured film can be further improved. The number average particle diameter of the (F) metal acidate particles is preferably from 1 to 200 nm. In order to obtain a cured film having a high light transmittance, the number average particle diameter is preferably from 1 to 70 nm. Here, the number average particle diameter of the metal oxide particles can be measured by a gas adsorption method, a dynamic light scattering method, an X-ray small angle scattering method, a transmission electron microscope, or a scanning electron microscope. Examples of the (F) metal oxide particles include cerium oxide particles, aluminum oxide particles, tin oxide particles, titanium oxide particles, zirconium oxide particles, cerium oxide particles, and the like, and can be appropriately selected depending on the use. . For example, in order to obtain a cured film having a high refractive index, titanium oxide particles such as titanium oxide particles or barium titanate particles or zirconium oxide particles such as zirconium oxide particles are preferable. Further, in order to obtain a cured film having a low refractive index, it is preferred to contain hollow vermiculite particles or the like.

作為市售的金屬氧化物粒子，能夠舉例Optolake(註冊商標)TR-502、(同商標)TR-503、(同商標)TR-504、(同商標)TR-513、(同商標)TR-520、(同商標)TR-527、(同商標)TR-528、(同商標)TR-529、(同商標)TR-544或是(同商標)TR-550等的氧化矽-氧化鈦複合粒子、Optolake(註冊商標)TR-505等的氧化鈦粒子(以上， 均為日揮觸媒化成工業(股)製)、或是Bairaru Zr-C20(平均粒徑=20nm；多木化學(股)製)、Nanouse OZ-30M(平均粒徑=7nm；日產化學工業(股)製)、或ZSL-10T(平均粒徑=15nm)或是ZSL-10A(平均粒徑=70nm)(以上，均為第一稀元素化學工業(股)製)等的氧化鋯粒子。還能夠舉出氧化錫-氧化鋯複合粒子(日揮觸媒化成工業(股)製)、氧化錫粒子(高純度化學研究所(股)製)或T-BTO-20RF(鈦酸鋇粒子；戶田工業股份有限公司製)。 As a commercially available metal oxide particle, Optolake (registered trademark) TR-502, (same trademark) TR-503, (same trademark) TR-504, (same trademark) TR-513, (same trademark) TR- can be exemplified. 520, (the same trademark) TR-527, (the same trademark) TR-528, (the same trademark) TR-529, (the same trademark) TR-544 or (the same trademark) TR-550 and other complexes of cerium oxide-titanium oxide Particles, titanium oxide particles such as Optolake (registered trademark) TR-505 (above, All are Nissan Catalyst Chemicals Co., Ltd.), or Bairaru Zr-C20 (average particle size = 20 nm; manufactured by Doki Chemical Co., Ltd.), Nanouse OZ-30M (average particle size = 7 nm; Nissan Chemical Industry ( Zirconium oxide particles, such as ZSL-10T (average particle diameter = 15 nm) or ZSL-10A (average particle diameter = 70 nm) (all of which are manufactured by the first dilute element chemical industry). Further, tin oxide-zirconia composite particles (manufactured by Nisshin Chemical Co., Ltd.), tin oxide particles (manufactured by High Purity Chemical Research Co., Ltd.), or T-BTO-20RF (barium titanate particles; households) Tian Industrial Co., Ltd.).

又，作為矽石粒子，能夠舉例數量平均粒徑12nm的IPA-ST或是MIBK-ST、數量平均粒徑45nm的IPA-ST-L、數量平均粒徑100nm的IPA-ST-ZL或數量平均粒徑15nm的PGM-ST(以上，均為日產化學工業(股)製)、數量平均粒徑12nm的Oscar(註冊商標)101、數量平均粒徑60nm的(同商標)105、數量平均粒徑120nm的(同商標)106或數量平均粒徑5~80nm的Cataloid(註冊商標)-S(以上，均為觸媒化成工業(股)製)、數量平均粒徑16nm的Quartron(註冊商標)PL-2L-PGME、數量平均粒徑17nm的(同商標)PL-2L-BL、(同商標)PL-2L-DAA或數量平均粒徑18~20nm的(同商標)PL-2L或是GP-2L(以上，均為扶桑化學工業(股)製)、數量平均粒徑100nm的矽石(SiO2)SG-SO100(共立材料(KCM)(股)製)、或是數量平均粒徑5~50nm的REOLOSIL(註冊商標)(德山(股)製)。又作為中空矽石粒子，能夠舉例「Optolake」TR-113。 Further, as the vermiculite particles, IPA-ST or MIBK-ST having a number average particle diameter of 12 nm, IPA-ST-L having a number average particle diameter of 45 nm, IPA-ST-ZL having a number average particle diameter of 100 nm, or number average can be exemplified. PGM-ST having a particle diameter of 15 nm (all of which are manufactured by Nissan Chemical Industries Co., Ltd.), Oscar (registered trademark) 101 having a number average particle diameter of 12 nm, (the same trademark) 105 having a number average particle diameter of 60 nm, and a number average particle diameter 120 nm (same trademark) 106 or Cataloid (registered trademark)-S having a number average particle diameter of 5 to 80 nm (all of which are manufactured by Catalyst Chemical Co., Ltd.) and Quartron (registered trademark) PL having a number average particle diameter of 16 nm -2L-PGME, the same average particle size of 17nm (same trademark) PL-2L-BL, (same trademark) PL-2L-DAA or the number average particle size of 18~20nm (same trademark) PL-2L or GP- 2L (above, all made by Fuso Chemical Industry Co., Ltd.), vermiculite (SiO 2 ) SG-SO100 (manufactured by KCM) (manufactured by KMC), or a number average particle size of 5~ 50nm REOLOSIL (registered trademark) (Deshan (stock) system). Further, as the hollow vermiculite particles, "Optolake" TR-113 can be exemplified.

對於金屬氧化物粒子的含量係無特別之限制，能夠隨著用途而設定適當量，但通常係設定為樹脂組 成物之固體成分的1~70wt%左右。 The content of the metal oxide particles is not particularly limited, and an appropriate amount can be set depending on the use, but it is usually set to a resin group. The solid content of the product is about 1 to 70% by weight.

本發明之(I)負型感光性樹脂組成物及(II)正型感光性樹脂組成物亦可含有其他的矽烷偶合劑。藉由含有其他的矽烷偶合劑，而與基板的接著性提升。 The (I) negative photosensitive resin composition of the present invention and the (II) positive photosensitive resin composition may contain other decane coupling agents. The adhesion to the substrate is improved by containing other decane coupling agents.

作為其他的矽烷偶合劑，能夠舉例甲基三甲氧基矽烷、甲基三乙氧基矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、正丙基三甲氧基矽烷、正丙基三乙氧基矽烷、正丁基三甲氧基矽烷、正丁基三乙氧基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、二苯基二甲氧基矽烷、二苯基二乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、3-胺丙基三甲氧基矽烷、3-胺丙基三乙氧基矽烷、3-三乙氧甲矽烷基-N-(1,3-二甲基-亞丁基)丙胺、N-苯基-3-胺丙基三甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三乙氧基矽烷、[(3-乙基-3-環氧丙烷基)甲氧基]丙基三甲氧基矽烷、[(3-乙基-3-環氧丙烷基)甲氧基]丙基三乙氧基矽烷、3-巰丙基三甲氧基矽烷、3-巰丙基甲基二甲氧基矽烷、3-脲丙基三乙氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷、3-三甲氧基甲矽烷基丙 基丁二酸或N-三級丁基-3-(3-三甲氧基甲矽烷基丙基)丁二酸醯亞胺。 As other decane coupling agents, methyl trimethoxy decane, methyl triethoxy decane, dimethyl dimethoxy decane, dimethyl diethoxy decane, ethyl trimethoxy decane, and B can be exemplified. Triethoxy decane, n-propyl trimethoxy decane, n-propyl triethoxy decane, n-butyl trimethoxy decane, n-butyl triethoxy decane, phenyl trimethoxy decane, phenyl Triethoxy decane, diphenyl dimethoxy decane, diphenyl diethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, 3-methyl propylene methoxy propyl trimethyl Oxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropylmethyl Diethoxydecane, 3-propenyloxypropyltrimethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxymethylindenyl-N -(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropane Propyl three Oxydecane, 3-glycidoxypropylmethyldiethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxy ring Hexyl)ethyltriethoxydecane, [(3-ethyl-3-epoxypropenyl)methoxy]propyltrimethoxydecane, [(3-ethyl-3-epoxypropenyl) A Oxy]propyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropylmethyldimethoxydecane, 3-ureidopropyltriethoxydecane, 3-isocyanatepropyl Triethoxy decane, 3-trimethoxymethyl decyl Butyric acid or N-tert-butyl butyl-3-(3-trimethoxyformamidopropyl)succinimide.

對於矽烷偶合劑的添加量並無特別之限制，但相對於100重量份樹脂以0.1~10重量份的範圍為佳。若添加量較0.1重量份少，則接著性提升的效果不足，若較10重量份多，則在保管中矽烷偶合劑彼此間進行縮合反應，而成為顯影時之溶解殘留的原因。 The amount of the decane coupling agent to be added is not particularly limited, but is preferably in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the resin. When the amount is less than 0.1 part by weight, the effect of improving the adhesion is insufficient. When the amount is more than 10 parts by weight, the decane coupling agent undergoes a condensation reaction during storage, which causes dissolution and retention during development.

本發明之(I)負型感光性樹脂組成物及(II)正型感光性樹脂組成物亦可含有促進樹脂組成物的硬化、或是使硬化變容易的各種硬化劑。作為硬化劑係能夠無特別限定地使用習知之物，但能夠舉例含氮有機物、矽氧烷樹脂硬化劑、各種金屬醇化物、各種金屬螯合化合物、異氰酸酯化合物或是其聚合物、羥甲基化三聚氰胺衍生物或羥甲基化尿素衍生物。亦可含有該等之2種以上。其中又從硬化劑的安定性、所獲得之塗布膜的加工性等來看，以金屬螯合化合物、羥甲基化三聚氰胺衍生物或羥甲基化脲衍生物為佳。 The (I) negative photosensitive resin composition of the present invention and the (II) positive photosensitive resin composition may contain various curing agents which promote curing of the resin composition or facilitate curing. As the curing agent, a conventional one can be used without particular limitation, but a nitrogen-containing organic substance, a siloxane oxide resin hardener, various metal alkoxides, various metal chelating compounds, an isocyanate compound or a polymer thereof, and a methylol group can be exemplified. A melamine derivative or a methylolated urea derivative. Two or more of these may be contained. Among them, a metal chelate compound, a methylolated melamine derivative or a methylolated urea derivative is preferred from the viewpoint of the stability of the hardener, the processability of the obtained coating film, and the like.

本發明之(I)負型感光性樹脂組成物及(II)正型感光性樹脂組成物亦可含有紫外線吸收劑。藉由含有紫外線吸收劑，所獲得之硬化膜的耐光性提升，且於必須要圖案加工之用途顯影後的解析度提升。作為紫外線吸收劑，能夠無特別限定地使用習知之物，從透明性、非著色性方面來看，以苯并***系化合物、二苯甲酮系化合物或三系化合物為佳。 The (I) negative photosensitive resin composition of the present invention and (II) the positive photosensitive resin composition may further contain an ultraviolet absorber. By containing an ultraviolet absorber, the cured film obtained has improved light resistance, and the resolution after development is required for use in pattern processing. As the ultraviolet absorber, a conventional one can be used without particular limitation, and a benzotriazole compound, a benzophenone compound or the like can be used from the viewpoint of transparency and non-coloring property. The compound is preferred.

作為苯并***系化合物的紫外線吸收劑，能 夠舉例2-(2H苯并***-2-基)酚、2-(2H-苯并***-2-基)-4,6-三級戊基酚、2-(2H苯并***-2-基)-4-(1,1,3,3-四甲基丁基)酚、2(2H-苯并***-2-基)-6-十二烷基-4-甲基酚或2-(2’-羥基-5’-甲基丙烯醯氧基乙基苯基)-2H-苯并***。作為二苯甲酮系化合物的紫外線吸收劑，能夠舉例2-羥基-4-甲氧基二苯甲酮。作為三系化合物的紫外線吸收劑，能夠舉例2-(4,6-二苯基-1,3,5-三-2-基)-5-[(己基)氧基]-酚。 As the ultraviolet absorber of the benzotriazole-based compound, 2-(2H benzotriazol-2-yl)phenol and 2-(2H-benzotriazol-2-yl)-4,6-three-stage can be exemplified. Pentylphenol, 2-(2H benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2(2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol or 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole. As the ultraviolet absorber of the benzophenone compound, 2-hydroxy-4-methoxybenzophenone can be exemplified. As three The ultraviolet absorber of the compound can be exemplified by 2-(4,6-diphenyl-1,3,5-three 2-yl)-5-[(hexyl)oxy]-phenol.

本發明之(I)負型感光性樹脂組成物亦可含有聚合抑制劑。藉由含有適量的聚合抑制劑，顯影後的解析度提升。作為聚合抑制劑，能夠無特別限定地使用習知之物，能夠舉例二-三級丁基羥基甲苯、丁基羥基苯甲醚、氫醌、氫醌甲基醚、1,4-苯醌或三級丁基兒茶酚。又，作為市售的聚合抑制劑，能夠舉例IRGANOX 1010、同1035、同1076、同1098、同1135、同1330、同1726、同1425、同1520、同245、同259、同3114、同565或同295(以上，均為BASF製)。 The (I) negative photosensitive resin composition of the present invention may further contain a polymerization inhibitor. By containing an appropriate amount of polymerization inhibitor, the resolution after development is improved. As the polymerization inhibitor, a conventional one can be used without particular limitation, and examples thereof include di-tertiary butylhydroxytoluene, butylhydroxyanisole, hydroquinone, hydroquinone methyl ether, 1,4-benzoquinone or trisole. Grade butyl catechol. Further, as a commercially available polymerization inhibitor, IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425, 1520, 245, 259, 3114, 565 can be exemplified. Or the same as 295 (above, both are BASF system).

本發明之(I)負型感光性樹脂組成物及(II)正型感光性樹脂組成物亦可含有溶劑。從能夠均勻地溶解各成分、使所獲得之塗布膜的透明性提升的觀點來看，以具有醇性羥基的化合物或具有羧基的環狀化合物為佳。亦可使用該等之2種以上。又，較佳為大氣壓下的沸點為110~250℃的化合物。藉由使沸點為110℃以上，在塗膜時乾燥係適度地進行，而能夠獲得無塗布不均之良好的塗膜。另一方面，當使沸點為250℃以下時，由於能夠 將膜中的殘存溶劑量抑制為少量，而能夠更降低熱硬化時的膜收縮，能夠獲得較良好的平坦性。 The (I) negative photosensitive resin composition of the present invention and (II) the positive photosensitive resin composition may further contain a solvent. From the viewpoint of being able to uniformly dissolve the components and improving the transparency of the obtained coating film, a compound having an alcoholic hydroxyl group or a cyclic compound having a carboxyl group is preferred. Two or more of these may be used. Further, a compound having a boiling point of 110 to 250 ° C at atmospheric pressure is preferred. When the boiling point is 110° C. or more, the drying is moderately performed at the time of coating, and a coating film excellent in coating unevenness can be obtained. On the other hand, when the boiling point is 250 ° C or less, The amount of residual solvent in the film is suppressed to a small amount, and film shrinkage at the time of thermosetting can be further reduced, and better flatness can be obtained.

作為具有醇性羥基，且大氣壓下的沸點為110~250℃的化合物，能夠舉例丙酮醇、3-羥基-3-甲基-2-丁酮、4-羥基-3-甲基-2-丁酮、5-羥基-2-戊酮、4-羥基-4-甲基-2-戊酮(二丙酮醇)、乳酸乙酯、乳酸丁酯、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單正丙基醚、丙二醇單正丁基醚、丙二醇單三級丁基醚、3-甲氧基-1-丁醇或3-甲基-3-甲氧基-1-丁醇，從保存安定性的觀點來看，以二丙酮醇為佳，從高低落差被覆性的觀點來看，以丙二醇單三級丁基醚為佳。 As a compound having an alcoholic hydroxyl group and having a boiling point of 110 to 250 ° C at atmospheric pressure, acetol, 3-hydroxy-3-methyl-2-butanone, and 4-hydroxy-3-methyl-2-butyl can be exemplified. Ketone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-tert-butyl ether, 3-methoxy-1-butanol or 3-methyl-3-methoxy-1-butanol From the viewpoint of preserving stability, diacetone alcohol is preferred, and from the viewpoint of coating with high and low drop, propylene glycol monotributyl ether is preferred.

作為具有羧基，且大氣壓下的沸點為110~250℃的環狀化合物，能夠舉例γ-丁內酯、γ-戊內酯、δ-戊內酯、碳酸丙烯酯、N-甲基吡咯啶酮、環己酮或環庚酮，但以γ-丁內酯為佳。 As a cyclic compound having a carboxyl group and having a boiling point of 110 to 250 ° C at atmospheric pressure, γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, and N-methylpyrrolidone can be exemplified. Cyclohexanone or cycloheptanone, but preferably γ-butyrolactone.

又，本發明之(I)負型感光性樹脂組成物及(II)正型感光性樹脂組成物亦可含有上述以外的溶劑。作為上述以外的溶劑，能夠舉例乙二醇二甲基醚、乙二醇二乙基醚、乙二醇二丁基醚或是二***等的醚類、甲基乙基酮、乙醯丙酮、甲基丙基酮、甲基丁基酮、甲基異丁基酮、二異丁基酮、環戊酮或是2-庚酮等的酮類、二甲基甲醯胺或是二乙基乙醯胺等的醯胺類、或乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酸異丁酯、乙二醇單乙基醚乙酸酯、丙二醇單甲基醚乙酸酯、乙酸3-甲氧基丁酯或是乙酸3-甲基-3-甲氧基丁酯等的乙酸酯類。 Further, the (I) negative photosensitive resin composition of the present invention and the (II) positive photosensitive resin composition may contain a solvent other than the above. Examples of the solvent other than the above include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethers such as diethyl ether, methyl ethyl ketone, and ethyl acetonacetone. Ketones such as methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone or 2-heptanone, dimethylformamide or diethyl Amidoxime such as acetamide, or ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, acetic acid 3- A methoxybutyl ester or an acetate such as 3-methyl-3-methoxybutyl acetate.

對於溶劑的含量係無特別之限制，能夠因應塗布方法等而使用任意的量。例如當藉由旋轉塗布進行膜形成時，通常為(I)負型感光性樹脂組成物全體的50~95wt%。 The content of the solvent is not particularly limited, and any amount can be used depending on the coating method and the like. For example, when film formation is performed by spin coating, it is usually 50 to 95% by weight of the entire (I) negative photosensitive resin composition.

本發明之(I)負型感光性樹脂組成物及(II)正型感光性樹脂組成物，為了塗布時的流動性提升，亦可含有氟系界面活性劑或矽氧烷系界面活性劑等的各種界面活性劑。界面活性劑的種類係無特別之限制，能夠舉例Megafac(註冊商標)F142D、同F172、同F173、同F183、同F445、同F470、同F475或是同F477(以上，均為大日本油墨化學工業(股)製)、或NBX-15或是FTX-218(以上，均為NEOS(股)製)等的氟系界面活性劑、BYK-333、BYK-301、BYK-331、BYK-345或是BYK-307(以上，均為BYK．日本(股)製)等的矽氧烷系界面活性劑、聚環氧烷系界面活性劑或是聚(甲基)丙烯酸酯系界面活性劑。亦可使用該等之2種以上。 The (I) negative photosensitive resin composition and the (II) positive photosensitive resin composition of the present invention may contain a fluorine-based surfactant or a siloxane-based surfactant, etc., in order to improve fluidity during coating. A variety of surfactants. The type of the surfactant is not particularly limited, and can be exemplified by Megafac (registered trademark) F142D, with F172, with F173, with F183, with F445, with F470, with F475 or with F477 (above, both of which are large Japanese ink chemistry). Industrial (share) system, or NBX-15 or FTX-218 (above, NEOS (share) system) fluorine-based surfactant, BYK-333, BYK-301, BYK-331, BYK-345 Or a phthalic surfactant such as BYK-307 (all of which is BYK. Japan), a polyalkylene oxide surfactant, or a poly(meth)acrylate surfactant. Two or more of these may be used.

本發明之(I)負型感光性樹脂組成物及(II)正型感光性樹脂組成物，因應需要，亦能夠含有溶解抑制劑、安定劑或消泡劑等的添加劑。 The (I) negative photosensitive resin composition and the (II) positive photosensitive resin composition of the present invention may contain an additive such as a dissolution inhibitor, a stabilizer or an antifoaming agent, if necessary.

本發明之(I)負型感光性樹脂組成物的固體成分濃度，係能夠無特別之限制地、因應塗布方法等而使用任意量的溶劑或溶質。例如如後述藉由旋轉塗布進行膜形成時，通常使固體成分濃度為5~50wt%。 The solid content concentration of the (I) negative photosensitive resin composition of the present invention can be any amount of a solvent or a solute, depending on the application method, etc., without particular limitation. For example, when film formation is performed by spin coating as described later, the solid content concentration is usually 5 to 50% by weight.

關於本發明之(I)負型感光性樹脂組成物之代表性的製造方法，例如添加(D)光聚合起始劑及其他添 加劑於任意的溶劑，攪拌使其溶解後，加入(A)以通式(1)表示之矽烷偶合劑、(B)鹼可溶性樹脂及(C)多官能單體並進一步攪拌20分鐘~3小時。過濾所獲得的溶液，而獲得(I)負型感光性樹脂組成物。 A representative production method of the (I) negative photosensitive resin composition of the present invention, for example, adding (D) a photopolymerization initiator and other additions After adding the solvent to any solvent and stirring to dissolve it, (A) a decane coupling agent represented by the formula (1), (B) an alkali-soluble resin, and (C) a polyfunctional monomer are added and further stirred for 20 minutes to 3 minutes. hour. The obtained solution was filtered to obtain (I) a negative photosensitive resin composition.

關於本發明之(II)正型感光性樹脂組成物之代表性的製造方法，例如添加(E)醌二疊氮化合物及其他添加劑於任意的溶劑，攪拌並使其溶解後，加入以通式(1)表示之(A)矽烷偶合劑及(B)鹼可溶性樹脂並進一步攪拌20分鐘~3小時。過濾所獲得的溶液，而獲得(II)正型感光性樹脂組成物。 In the representative production method of the (II) positive photosensitive resin composition of the present invention, for example, (E) quinonediazide compound and other additives are added, stirred and dissolved in an arbitrary solvent, and then added to the general formula. (1) The (A) decane coupling agent and (B) the alkali-soluble resin are further stirred for 20 minutes to 3 hours. The obtained solution was filtered to obtain (II) a positive photosensitive resin composition.

舉例說明使用本發明之(I)負型感光性樹脂組成物或(II)正型感光性樹脂組成物之硬化膜的形成方法。 A method of forming a cured film using the (I) negative photosensitive resin composition or the (II) positive photosensitive resin composition of the present invention will be exemplified.

將本發明之(I)負型感光性樹脂組成物或(II)正型感光性樹脂組成物，藉由微凹版塗布、旋轉塗布、浸漬塗布、簾流塗布、輥塗、噴塗或縫隙塗布等習知的方法，塗布於底層基板上，以加熱板或烤箱等的加熱裝置預烘烤。預烘烤係在50~150℃的範圍進行30秒~30分鐘，預烘烤後的膜厚以0.1~15μm為佳。 The (I) negative photosensitive resin composition or the (II) positive photosensitive resin composition of the present invention is applied by micro gravure coating, spin coating, dip coating, curtain coating, roll coating, spray coating or slit coating. A conventional method is applied to an underlying substrate and pre-baked by a heating means such as a hot plate or an oven. The prebaking is carried out in the range of 50 to 150 ° C for 30 seconds to 30 minutes, and the film thickness after prebaking is preferably 0.1 to 15 μm.

預烘烤後，使用步進曝光機(stepper)、鏡面投影光罩對準曝光機(mirror projection mask aligner,MPA)或平行光罩對準曝光機(parallel light mask aligner，以下，簡稱「PLA」)等的曝光機，隔著或不隔著所期望之遮罩照射10~4000J/m2左右(換算波長為365nm曝光量)的光。曝光光源係無限制，能夠使用i射線、g射線、 h射線等的紫外線、和KrF(波長248nm)雷射或ArF(波長193nm)雷射等。然後，亦可進行將該膜以加熱板或烤箱等的加熱裝置在150~450℃的範圍加熱1小時間左右的曝光後烘烤。 After prebaking, a stepper, a mirror projection mask aligner (MPA), or a parallel light mask aligner (hereinafter referred to as "PLA") is used. The exposure machine such as the light is irradiated with light of about 10 to 4000 J/m 2 (the conversion wavelength is 365 nm exposure amount) with or without a desired mask. The exposure light source is not limited, and ultraviolet rays such as i-rays, g-rays, and h-rays, and KrF (wavelength 248 nm) lasers or ArF (wavelength 193 nm) lasers can be used. Then, the film may be heated by a heating device such as a hot plate or an oven at a temperature of 150 to 450 ° C for about 1 hour.

本發明之(I)負型感光性樹脂組成物及(II)正型感光性樹脂組成物，以藉由將高壓水銀燈作為光源之PLA的曝光感度為100~4000J/m2為佳。藉由PLA之形成圖案曝光的感度係藉由例如以下的方法求出。使用旋轉塗布機以任意之轉速將組成物旋轉塗布於矽晶圓，使用加熱板在120℃預烘烤2分鐘，製作膜厚2μm之膜。將所製作之膜使用PLA(PLA-501F；佳能(股)製)，隔著感度測定用之灰階遮罩曝光於超高壓水銀燈後，使用自動顯影裝置(AD-2000；瀧澤產業(股)製)以0.4wt%氫氧化四甲銨水溶液進行任意時間的浸漬式顯影，接著以水進行30秒沖洗。在所形成之圖案，將30μm之線與間隙以1對1的寬度解析之曝光量求出作為感度。 In the (I) negative photosensitive resin composition of the present invention and (II) the positive photosensitive resin composition, the exposure sensitivity of PLA having a high pressure mercury lamp as a light source is preferably 100 to 4000 J/m 2 . The sensitivity of pattern formation by PLA is obtained by, for example, the following method. The composition was spin-coated on a crucible wafer at a random number of revolutions using a spin coater, and prebaked at 120 ° C for 2 minutes using a hot plate to prepare a film having a film thickness of 2 μm. The film produced by using PLA (PLA-501F; manufactured by Canon Co., Ltd.) was exposed to an ultrahigh pressure mercury lamp through a gray scale mask for sensitivity measurement, and an automatic developing device (AD-2000; Takizawa Industry Co., Ltd.) was used. The system was subjected to immersion development at any time with a 0.4 wt% aqueous solution of tetramethylammonium hydroxide, followed by rinsing with water for 30 seconds. In the formed pattern, the exposure amount in which the line of 30 μm and the gap were analyzed in a one-to-one width was determined as the sensitivity.

形成圖案曝光後，藉由顯影來溶解曝光部，能夠分別獲得負型或正型的圖案。作為顯影方法，係以淋浴、浸漬、覆液等的方法浸漬於顯影液5秒~10分鐘為佳。作為顯影液，能夠使用習知的鹼顯影液。作為習知的鹼顯影液，能夠舉例包含鹼金屬的氫氧化物、碳酸鹽、磷酸鹽、矽酸鹽或是硼酸鹽等的無機鹼、2-二乙胺基乙醇、單乙醇胺或是二乙醇胺等的胺類、或氫氧化四甲銨或是膽鹼等的4級銨鹽之1種或2種以上的水溶液。顯影後，以水沖洗為佳，亦可接著在50~150℃的範圍進行乾 燥烘烤。然後，藉由將該膜以加熱板或烤箱等的加熱裝置在120~280℃的範圍進行熱硬化1小時左右，而獲得硬化膜。 After the pattern exposure is performed, the exposed portion is dissolved by development, whereby a negative or positive pattern can be obtained. As the developing method, it is preferably immersed in the developing solution for 5 seconds to 10 minutes by a method such as showering, dipping, or liquid coating. As the developer, a conventional alkali developer can be used. The conventional alkali developing solution can be exemplified by an inorganic base such as an alkali metal hydroxide, carbonate, phosphate, citrate or borate, 2-diethylaminoethanol, monoethanolamine or diethanolamine. One or two or more aqueous solutions of an amine such as an amine or tetramethylammonium hydroxide or a quaternary ammonium salt such as choline. After development, it is better to rinse with water, and then dry in the range of 50~150 °C. Dry baking. Then, the film is thermally cured in a heating plate or an oven or the like at a temperature of 120 to 280 ° C for about 1 hour to obtain a cured film.

由本發明之(I)負型感光性樹脂組成物及(II)正型感光性樹脂組成物所獲得的硬化膜，對於該膜厚係無特別之限制，但以0.1~15μm為佳。又，以於1.5μm膜厚之硬度為4H以上、透光率為90%以上為佳。還有，透光率係指在波長400nm的透光率。硬度和透光率能夠依曝光量、熱硬化溫度的選擇來調整。 The cured film obtained from the (I) negative photosensitive resin composition of the present invention and the (II) positive photosensitive resin composition is not particularly limited as long as it is 0.1 to 15 μm. Further, it is preferable that the hardness of the film thickness of 1.5 μm is 4H or more and the light transmittance is 90% or more. Further, the light transmittance means a light transmittance at a wavelength of 400 nm. The hardness and light transmittance can be adjusted depending on the selection of the exposure amount and the heat hardening temperature.

硬化本發明之(I)負型感光性樹脂組成物及(II)正型感光性樹脂組成物而獲得的硬化膜，能夠使用於觸控面板用保護膜、各種硬被覆材、TFT用平坦化膜、彩色濾光片用保護膜、抗反射膜、鈍化膜(passivation film)等的各種保護膜、及光學濾光片、觸控面板用絕緣膜、TFT用絕緣膜或彩色濾光片用光間隔物(photo spacer)等。該等之中，又由於(I)負型感光性樹脂組成物具有高硬度、透明性、耐熱性，而能夠適用作為觸控面板用保護膜。作為觸控面板的方式，能夠舉出電阻膜式、光學式、電磁感應式或靜電容量式等。由於靜電容量式觸控面板係特別要求高硬度，而能夠適用本發明的硬化膜。由於(II)正型感光性樹脂組成物能夠高精細地加工且具有高接著性，而能夠適用於TFT用平坦化膜(有機鈍化膜)。 The cured film obtained by curing the (I) negative photosensitive resin composition of the present invention and (II) the positive photosensitive resin composition can be used for a protective film for a touch panel, various hard coating materials, and flattening for a TFT. Various protective films such as a protective film for a film, a color filter, an antireflection film, and a passivation film, and an optical filter, an insulating film for a touch panel, an insulating film for a TFT, or a color filter Spacer, etc. Among these, the negative photosensitive resin composition (I) has high hardness, transparency, and heat resistance, and can be suitably used as a protective film for a touch panel. Examples of the touch panel include a resistive film type, an optical type, an electromagnetic induction type, and an electrostatic capacity type. Since the electrostatic capacity type touch panel is particularly required to have high hardness, the cured film of the present invention can be applied. The (II) positive photosensitive resin composition can be applied to a planarizing film for TFT (organic passivation film) because it can be processed with high precision and has high adhesion.

[實施例] [Examples]

以下舉出實施例及比較例來詳細地說明本發 明，但本發明係不受該等限制者。 The present invention will be described in detail below by way of examples and comparative examples. It is to be understood that the invention is not limited thereto.

合成例1 矽烷偶合劑(A1)之合成 Synthesis Example 1 Synthesis of decane coupling agent (A1)

在200mL的燒瓶置入20g的異氰酸三乙氧基甲矽烷基丙酯及80g環氧丙醇，在40℃攪拌12小時。藉由氣相層析法確認原料的異氰酸三乙氧基甲矽烷基丙酯的尖峰之消失與生成物的尖峰之出現後，藉由旋轉蒸發器及附收集器(trap)的真空泵除去環氧丙醇，而獲得矽烷偶合劑(A1)。 Into a 200 mL flask, 20 g of triethoxymethane alkyl propyl cyanate and 80 g of glycidol were placed, and the mixture was stirred at 40 ° C for 12 hours. After disappearing from the disappearance of the peak of the triethoxy formamylpropyl isocyanate and the occurrence of the peak of the product by gas chromatography, the vacuum evaporator and the vacuum pump with a trap were removed. Glycol propanol to obtain a decane coupling agent (A1).

合成例2 矽烷偶合劑(A2)之合成 Synthesis Example 2 Synthesis of decane coupling agent (A2)

除了將環氧丙醇變更為2-乙基環氧丙烷基甲醇以外，與合成例1同樣地實施，而獲得矽烷偶合劑(A2)。 The decane coupling agent (A2) was obtained in the same manner as in Synthesis Example 1 except that the glycidol was changed to 2-ethyl propylene oxide-based methanol.

合成例3 矽烷偶合劑(A3)之合成 Synthesis Example 3 Synthesis of decane coupling agent (A3)

除了將環氧丙醇變更為四氫呋喃甲醇以外，與合成例1同樣地實施，而獲得矽烷偶合劑(A3)。 The decane coupling agent (A3) was obtained in the same manner as in Synthesis Example 1 except that the glycidol was changed to tetrahydrofuran methanol.

合成例4 矽烷偶合劑(A4)之合成 Synthesis Example 4 Synthesis of decane coupling agent (A4)

除了將環氧丙醇變更為呋喃甲醇以外，與合成例1同樣地實施，而獲得矽烷偶合劑(A4)。 The decane coupling agent (A4) was obtained in the same manner as in Synthesis Example 1 except that the glycidol was changed to furan methanol.

合成例5 矽烷偶合劑(A5)之合成 Synthesis Example 5 Synthesis of decane coupling agent (A5)

除了將環氧丙醇變更為噻吩甲醇以外，與合成例1同樣地實施，而獲得矽烷偶合劑(A5)。 The decane coupling agent (A5) was obtained in the same manner as in Synthesis Example 1 except that the glycidol was changed to thiophene methanol.

合成例6 矽烷偶合劑(A6)之合成 Synthesis Example 6 Synthesis of decane coupling agent (A6)

除了將環氧丙醇變更為1-甲基-2-吡咯啶甲醇以外，與合成例1同樣地實施，獲得矽烷偶合劑(A6)。 The decane coupling agent (A6) was obtained in the same manner as in Synthesis Example 1 except that the glycidol was changed to 1-methyl-2-pyrrolidinemethanol.

合成例7 矽烷偶合劑(A7)之合成 Synthesis Example 7 Synthesis of decane coupling agent (A7)

在200mL的燒瓶置入20g的異氰酸2-((3-三乙氧基甲 矽烷基丙基)胺基)乙酯及80g的四氫呋喃甲醇，在40℃攪拌12小時。藉由氣相層析法確認原料的異氰酸三乙氧基甲矽烷基丙酯的尖峰之消失與生成物的尖峰之出現後，藉由旋轉蒸發器及附收集器的真空泵除去四氫呋喃甲醇，而獲得矽烷偶合劑(A7)。 20 g of isocyanate 2-((3-triethoxy) was placed in a 200 mL flask The decylpropyl)amino)ethyl ester and 80 g of tetrahydrofuran methanol were stirred at 40 ° C for 12 hours. After confirming the disappearance of the peak of the triethoxymethoxymethyl propyl cyanate and the occurrence of the peak of the product by gas chromatography, the tetrahydrofuran methanol was removed by a rotary evaporator and a vacuum pump with a collector. The decane coupling agent (A7) was obtained.

比較合成例1 矽烷偶合劑(A8)之合成 Comparative Synthesis Example 1 Synthesis of decane coupling agent (A8)

除了將環氧丙醇變更為1-丁醇以外，與合成例1同樣地實施，而獲得矽烷偶合劑(A8)。 The decane coupling agent (A8) was obtained in the same manner as in Synthesis Example 1 except that the glycidol was changed to 1-butanol.

矽烷偶合劑(A1)~(A8)的構造式係如以下。 The structural formula of the decane coupling agents (A1) to (A8) is as follows.

合成例8 聚矽氧烷溶液(B1)之合成 Synthesis Example 8 Synthesis of Polyoxane Solution (B1)

在500mL的燒瓶置入40.86g(0.3mol)的甲基三甲氧基甲矽烷、69.41g(0.35mol)的苯基三甲氧基矽烷、82.04g(0.35mol)的γ-丙烯醯基丙基三甲氧基矽烷及192.3g的DAA(二丙酮醇)，浸漬於40℃的油浴一邊攪拌並同時以滴液漏斗費時10分鐘添加在54.0g的水(水解所需要的理論量)溶解0.39g的磷酸(相對於所置入之單體為 0.2重量份)的磷酸水溶液。在40℃攪拌1小時後，將油浴溫度設定於70℃並攪拌1小時，再者費時30分鐘將油浴升溫至115℃。在升溫開始1小時後溶液的內溫到達100℃，從此起加熱攪拌2小時(內溫為100~110℃)。在反應中蒸餾出總計120g的副產物甲醇、水。在所獲得之聚矽氧烷的DAA溶液，加入DAA使聚合物濃度成為40wt%而獲得聚矽氧烷溶液(B1)。還有，所獲得之聚合物的重量平均分子量(Mw)藉由GPC測定時為4500(以聚苯乙烯換算)。 In a 500 mL flask, 40.86 g (0.3 mol) of methyltrimethoxyformane, 69.41 g (0.35 mol) of phenyltrimethoxydecane, and 82.04 g (0.35 mol) of γ-acrylallylpropyltrimethyl were placed. Oxydecane and 192.3 g of DAA (diacetone alcohol) were immersed in an oil bath at 40 ° C while stirring and simultaneously added to 54.0 g of water (theoretical amount required for hydrolysis) to dissolve 0.39 g in a dropping funnel for 10 minutes. Phosphoric acid (relative to the monomer placed 0.2 parts by weight of an aqueous phosphoric acid solution. After stirring at 40 ° C for 1 hour, the oil bath temperature was set to 70 ° C and stirred for 1 hour, and the oil bath was heated to 115 ° C for 30 minutes. The internal temperature of the solution reached 100 ° C 1 hour after the start of the temperature rise, and the mixture was heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C). A total of 120 g of by-product methanol and water were distilled off in the reaction. In the DAA solution of the obtained polyoxyalkylene, DAA was added to make the polymer concentration 40% by weight to obtain a polysiloxane solution (B1). Further, the weight average molecular weight (Mw) of the obtained polymer was 4500 (in terms of polystyrene) as measured by GPC.

合成例9~11 聚矽氧烷溶液(B2)~(B4)之合成 Synthesis Example 9~11 Synthesis of Polyoxane Solution (B2)~(B4)

以如表1所示之置入比，藉由與合成例8同樣的方法合成聚矽氧烷溶液(B2)~(B4)。簡稱係如下述。 The polyoxoxane solutions (B2) to (B4) were synthesized in the same manner as in Synthesis Example 8 by the implantation ratio shown in Table 1. The abbreviation is as follows.

MTM：甲基三甲氧基矽烷 MTM: methyltrimethoxydecane

PTM：苯基三甲氧基矽烷 PTM: Phenyltrimethoxydecane

ETM：2-(3,4-環氧環己基)乙基三甲氧基矽烷 ETM: 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane

NphTM：1-萘基三甲氧基矽烷 NphTM: 1-naphthyltrimethoxydecane

TEOS：四乙氧基矽烷 TEOS: tetraethoxy decane

AcrTM：γ-丙烯醯基丙基三甲氧基矽烷 AcrTM: γ-propylene propyl propyl trimethoxy decane

SuTM：3-三甲氧基甲矽烷基丙基丁二酸酐 SuTM: 3-trimethoxyformamidopropyl succinic anhydride

合成例12 丙烯酸樹脂溶液(B5)之合成 Synthesis Example 12 Synthesis of Acrylic Resin Solution (B5)

在500mL的燒瓶置入1g的2,2’-偶氮雙(異丁腈)及50g的PGMEA(丙二醇甲基醚乙酸酯)。然後，置入23.0g的甲 基丙烯酸、31.5g的甲基丙烯酸芐酯及32.8g的三環[5.2.1.02,6]癸-8-醯基甲基丙烯酸酯，在室溫攪拌片刻，藉由起泡(bubbling)將燒瓶內充分氮氣取代後，在70℃加熱攪拌5小時。接著，在所獲得的溶液添加12.7g的甲基丙烯酸環氧丙酯、1g的二甲基芐基胺、0.2g的對甲氧基酚及100g的PGMEA，在90℃加熱攪拌4小時。反應結束後，為了除去加成觸媒而將反應溶液以1N甲酸水溶液分液萃取處理，並以硫酸鎂乾燥後，加入PGMEA使固體成分濃度成為40wt%，而獲得丙烯酸樹脂溶液(B5)。丙烯酸樹脂(B5)的重量平均分子量為30000。 1 g of 2,2'-azobis(isobutyronitrile) and 50 g of PGMEA (propylene glycol methyl ether acetate) were placed in a 500 mL flask. Then, 23.0 g of methacrylic acid, 31.5 g of benzyl methacrylate, and 32.8 g of tricyclo[5.2.1.0 2,6 ]癸-8-mercaptomethacrylate were placed, and stirred at room temperature for a while. The flask was sufficiently purged with nitrogen by bubbling, and then heated and stirred at 70 ° C for 5 hours. Next, 12.7 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, and the mixture was stirred under heating at 90 ° C for 4 hours. After the completion of the reaction, the reaction solution was subjected to extraction treatment with a 1 N aqueous solution of formic acid to remove the addition catalyst, and dried over magnesium sulfate, and then PGMEA was added to adjust the solid content to 40% by weight to obtain an acrylic resin solution (B5). The acrylic resin (B5) had a weight average molecular weight of 30,000.

合成例13~15 丙烯酸樹脂溶液(B6)~(B8)之合成 Synthesis Example 13-15 Synthesis of Acrylic Resin Solution (B6)~(B8)

以如表2表示之置入比，藉由與合成例12相同樣的方法合成丙烯酸樹脂溶液(B6)~(B8)。簡稱如下述。 The acrylic resin solutions (B6) to (B8) were synthesized in the same manner as in Synthesis Example 12 by the implantation ratios shown in Table 2. The abbreviation is as follows.

BzMA：甲基丙烯酸芐酯 BzMA: benzyl methacrylate

St：苯乙烯 St: Styrene

MA：甲基丙烯酸 MA: methacrylic acid

MA-GMA：甲基丙烯酸-甲基丙烯酸環氧丙酯加成 MA-GMA: methacrylic acid-glycidyl methacrylate addition

TCDMA：三環[5.2.1.02,6]癸-8-醯基甲基丙烯酸酯 TCDMA: Tricyclo[5.2.1.0 2,6 ]癸-8-mercaptomethacrylate

IBMA：甲基丙烯酸異莰酯 IBMA: isodecyl methacrylate

MMA：甲基丙烯酸甲酯 MMA: Methyl methacrylate

合成例16 聚酯樹脂溶液(B9)之合成 Synthesis Example 16 Synthesis of Polyester Resin Solution (B9)

置入148g的1,1-雙(4-(2,3-環氧丙氧基)苯基)-3-苯基茚烷、47g的丙烯酸、1g的乙酸四丁基銨(以下，簡稱為「TBAA」)、2.0g的三級丁基兒茶酚及244g的PGMEA，在120℃攪拌5小時。冷卻至室溫後，加入71g的聯苯基四羧酸二酐及1g的TBAA在110℃攪拌3小時。冷卻至室溫後，加入9g的四氫酞酸酐在120℃攪拌5小時。反應結束後，加入500g的PGMEA，為了除去加成觸媒而將反應溶液以1N甲酸水溶液分液萃取處理，以硫酸鎂乾燥後，以旋轉蒸發器濃縮使固體成分濃度成為40wt%，而獲得聚酯樹脂B9(Mw=5000(聚苯乙烯換算))。 148 g of 1,1-bis(4-(2,3-epoxypropoxy)phenyl)-3-phenylnonane, 47 g of acrylic acid, and 1 g of tetrabutylammonium acetate (hereinafter referred to as "TBAA"), 2.0 g of tertiary butyl catechol and 244 g of PGMEA were stirred at 120 ° C for 5 hours. After cooling to room temperature, 71 g of biphenyltetracarboxylic dianhydride and 1 g of TBAA were added and stirred at 110 ° C for 3 hours. After cooling to room temperature, 9 g of tetrahydrofurfuric anhydride was added and stirred at 120 ° C for 5 hours. After the completion of the reaction, 500 g of PGMEA was added, and the reaction solution was subjected to extraction extraction with a 1 N aqueous solution of formic acid to remove the addition catalyst, and dried with magnesium sulfate, and then concentrated by a rotary evaporator to have a solid concentration of 40% by weight to obtain a poly Ester resin B9 (Mw = 5000 (in terms of polystyrene)).

實施例1~7 Examples 1 to 7

針對在合成例1~7所合成之矽烷偶合劑(A1)~(A7)，使用熱重量分析裝置依下述條件測定10%重量減少溫度。還有，以在130℃保持30分鐘後的重量作為100%實施計算。 With respect to the decane coupling agents (A1) to (A7) synthesized in Synthesis Examples 1 to 7, a 10% weight loss temperature was measured using a thermogravimetric analyzer under the following conditions. Further, the calculation was carried out by taking the weight after holding at 130 ° C for 30 minutes as 100%.

裝置：TGA-50(島津製作所製) Device: TGA-50 (made by Shimadzu Corporation)

條件：在130℃保持30分鐘→升溫(10℃/分鐘)→500℃ Condition: Hold at 130 ° C for 30 minutes → heat (10 ° C / min) → 500 ° C

環境：空氣下、20mL/分鐘 Environment: under air, 20mL/min

比較例1 Comparative example 1

針對在比較合成例1所合成之矽烷偶合劑(A8)，與實施例1同樣地進行藉由熱重量分析之耐熱性的評估。 With respect to the decane coupling agent (A8) synthesized in Comparative Synthesis Example 1, the heat resistance by thermogravimetric analysis was evaluated in the same manner as in Example 1.

將實施例1~7及比較例1的結果顯示於表3。 The results of Examples 1 to 7 and Comparative Example 1 are shown in Table 3.

實施例8 Example 8

在黃色燈下將0.278g的1,2-辛二酮,1-[4-(苯硫基)-2-(O-苯甲醯基肟)](Irgacure OXE-01；BASF製)、0.017g的氫醌甲基醚(HQME)及0.166g的矽烷偶合劑(A1)溶解於2.846g的DAA(二丙酮醇)及4.033g的PGMEA，加入0.2000g矽氧烷系界面活性劑之BYK-333(BYK．日本(股)製)的PGMEA 1wt%溶液(相當於濃度100ppm)並攪拌。於該處，加入5.538g的二季戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA；新日本化藥製)的PGMEA 50wt%溶液、6.923g的聚矽氧烷溶液(B1)並攪拌。接著以0.45μm的過濾器進行過濾，而獲得負型感光性樹脂組成物(I-1)。針對所獲得的負型感光性樹脂組成物(I-1)，以下述方法評估透光率、圖案加工性、接著性。 0.278 g of 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzhydrylhydrazine)] (Irgacure OXE-01; manufactured by BASF), 0.017 under a yellow lamp g of hydroquinone methyl ether (HQME) and 0.166 g of decane coupling agent (A1) were dissolved in 2.846 g of DAA (diacetone alcohol) and 4.033 g of PGMEA, and added to the BYK- of 0.2000 g of a decane-based surfactant. 333 (BYK. Japan Co., Ltd.) PGMEA 1 wt% solution (corresponding to a concentration of 100 ppm) and stirred. Thereto, 5.538 g of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemical Co., Ltd.) PGMEA 50 wt% solution, 6.923 g of polyoxazane solution (B1) were added and stirred. Subsequently, the mixture was filtered with a 0.45 μm filter to obtain a negative photosensitive resin composition (I-1). With respect to the obtained negative photosensitive resin composition (I-1), light transmittance, pattern processability, and adhesion were evaluated by the following methods.

(1)圖案加工性 (1) Pattern processing

使用旋轉塗布機(1H-360S；Mikasa(股)製)旋轉塗布感光性樹脂組成物於基板上後，使用加熱板(SCW-636；大日本螢幕(Screen)製造(股)製)在90℃預烘烤2分鐘，而製作膜厚1.8μm的預烘烤膜。作為基板，係使用施加了ITO薄膜的玻璃基板(以下，稱為「ITO基板」)、或施加 了鉬/鋁/鉬(MAM)積層薄膜或是氮化矽薄膜(SiNx)的玻璃基板(以下，稱為「MAM基板」或「SiNx基板」)。在所獲得的預烘烤膜，使用PLA以超高壓水銀燈為光源，隔著具有1至60%透光率的灰階遮罩以100μm的間隔曝光2000J/m2。然後，使用自動顯影裝置(AD-2000；瀧澤產業(股)製)，以2.38%或0.4wt%的TMAH(氫氧化四甲銨)水溶液90秒鐘淋浴顯影，接著以水沖洗30秒鐘。曝光、顯影後，將30μm之線與間隙圖案形成為1對1之寬度的曝光量作為最適曝光量。曝光量以i射線照度計測定。 After the photosensitive resin composition was spin-coated on a substrate using a spin coater (1H-360S; manufactured by Mikasa Co., Ltd.), a heating plate (SCW-636; manufactured by Dainippon Screen Co., Ltd.) was used at 90 ° C. Prebaking was performed for 2 minutes to prepare a prebaked film having a film thickness of 1.8 μm. As the substrate, a glass-based substrate is applied using an ITO thin film (hereinafter referred to as "ITO substrate"), or the application of a molybdenum / aluminum / molybdenum (MAM) laminated film or a silicon nitride film (SiN x) glass substrate ( Hereinafter, it is referred to as "MAM substrate" or "SiN x substrate". In the obtained prebaking film, PLA was used as a light source with an ultrahigh pressure mercury lamp, and 2000 J/m 2 was exposed at intervals of 100 μm through a gray scale mask having a light transmittance of 1 to 60%. Then, using an automatic developing device (AD-2000; manufactured by Tosoh Corporation), it was developed by showering with 2.38% or 0.4% by weight of TMAH (tetramethylammonium hydroxide) aqueous solution for 90 seconds, followed by rinsing with water for 30 seconds. After exposure and development, a line of 30 μm and a gap pattern were formed into an exposure amount of a width of one to one as an optimum exposure amount. The amount of exposure was measured by an i-ray illuminometer.

解析度係測定最適曝光量之顯影後的最小圖案尺寸。 The resolution is the minimum pattern size after development for the optimum exposure amount.

顯影接著性係以最適曝光量中之殘留圖案在顯影後不剝落的最小圖案尺寸來評估。 The developmental adhesion was evaluated by the minimum pattern size in which the residual pattern in the optimum exposure amount did not peel off after development.

膜厚係使用Lambda Ace STM-602(大日本螢幕製造(股)製)以折射率為1.55來測定。惟，僅在使用(F)金屬氧化物粒子時，以折射率為1.65來測定。 The film thickness was measured using Lambda Ace STM-602 (manufactured by Dainippon Screen Co., Ltd.) with a refractive index of 1.55. However, only when (F) metal oxide particles were used, the refractive index was measured at 1.65.

(2)透光率之評估 (2) Evaluation of light transmittance

在5cm平方的TEMPAX玻璃基板(AGC Techno Glass(股)製)上，使用旋轉塗布機旋轉塗布感光性樹脂組成物後，使用加熱板在90℃預烘烤2分鐘，而製作膜厚為1.8μm的預烘烤膜。所使用之感光性樹脂組成物為(I)負型感光性樹脂組成物時，將所獲得的預烘烤膜以超高壓水銀燈2000J/m2全面曝光，使用自動顯影裝置以2.38wt%或0.4wt%的TMAH水溶液90秒鐘淋浴顯影，接著以水沖洗30秒鐘。所使用的樹脂組成物為(II)正型感光性樹脂組成 物時，將預烘烤膜使用自動顯影裝置以2.38wt%或0.4wt%的TMAH水溶液90秒鐘淋浴顯影，接著以水沖洗30秒鐘後，以超高壓水銀燈2000J/m2全面曝光。最後使用烤箱(ESPEC(股)製「IHPS-222」)在空氣中230℃硬化1小時來製作膜厚為1.5μm的硬化膜。 The photosensitive resin composition was spin-coated on a 5 cm square TEMPAX glass substrate (manufactured by AGC Techno Glass Co., Ltd.), and then prebaked at 90 ° C for 2 minutes using a hot plate to prepare a film thickness of 1.8 μm. Pre-baked film. When the photosensitive resin composition to be used is (I) a negative photosensitive resin composition, the obtained prebaked film is entirely exposed to an ultrahigh pressure mercury lamp of 2000 J/m 2 , and an automatic developing device is used at 2.38 wt% or 0.4. The wt% TMAH aqueous solution was shower developed for 90 seconds and then rinsed with water for 30 seconds. When the resin composition used is (II) a positive photosensitive resin composition, the prebaked film is developed by showering with a 2.38 wt% or 0.4 wt% aqueous TMAH solution for 90 seconds using an automatic developing device, followed by rinsing with water 30. After two seconds, the ultra-high pressure mercury lamp was fully exposed at 2000 J/m 2 . Finally, an oven (ESPEC-222 "IHPS-222") was used to harden at 230 ° C for 1 hour in the air to prepare a cured film having a film thickness of 1.5 μm.

針對所獲得的硬化膜，使用紫外-可見光分光光度計(UV-260)；島津製作所(股)製)，測定400nm的透光率。 For the obtained cured film, an ultraviolet-visible spectrophotometer (UV-260); Shimadzu Corporation (manufactured by Shimadzu Corporation) was used to measure the light transmittance at 400 nm.

(3)接著性之評估 (3) Evaluation of the continuity

在ITO基板、MAM基板或SiNx基板上，與上述(2)記載的方法同樣地進行，而形成膜厚1.5μm的硬化膜，依照JIS「K5600-5-6(制定年月日=1999/04/20)」來評估ITO或MAM與硬化膜之接著性。具體而言，係在ITO基板或MAM基板表面的硬化膜，使用截切刀以到達玻璃板的基質的方式，以1mm間隔拉出垂直縱橫各11條的平行直線，製作出100個1mm×1mm的格子。在所裁切之硬化膜表面張貼透明黏著膠帶(幅=18mm、黏著力=3.7N/10mm)，以橡皮擦(JIS S6050合格品)擦拭而使其密合，握住膠帶之一端，以目視評估在板上保持直角瞬間剝離時的格子殘存數。藉由格子的剝離面積如以下來判定，以4以上為合格。 On the ITO substrate, the MAM substrate, or the SiN x substrate, a cured film having a film thickness of 1.5 μm is formed in the same manner as the method described in the above (2), and is in accordance with JIS "K5600-5-6 (Date/Day = 1999/) 04/20)" to evaluate the adhesion of ITO or MAM to the cured film. Specifically, in the cured film on the surface of the ITO substrate or the MAM substrate, a parallel straight line of 11 vertical and horizontal lines is drawn at intervals of 1 mm by using a cutting blade to reach the substrate of the glass plate, and 100 pieces of 1 mm × 1 mm are produced. Plaid. Apply a transparent adhesive tape (web = 18 mm, adhesive force = 3.7 N/10 mm) to the surface of the cured film, and wipe it with an eraser (JIS S6050 qualified product) to hold it tightly. Hold one end of the tape to visually observe. The number of remaining lattices when the sheet was peeled off at a right angle was evaluated. The peeling area of the lattice was determined as follows, and 4 or more was passed.

5：剝離面積為0% 5: peeling area is 0%

4：剝離面積為1~4% 4: The peeling area is 1~4%

3：剝離面積為5~14% 3: The peeling area is 5~14%

2：剝離面積為15~34% 2: The peeling area is 15~34%

1：剝離面積為35%~64% 1: peeling area is 35%~64%

0：剝離面積為65%~100% 0: peeling area is 65%~100%

接著性之評估係在硬化膜製作後馬上及下述藥品處理後實施。 Subsequent evaluation was carried out immediately after the production of the cured film and after the following drug treatment.

3.5%的乙二酸水溶液(室溫、150秒) 3.5% aqueous solution of oxalic acid (room temperature, 150 seconds)

Nagasechemtex(股)製「N-321」(60℃、3分鐘) Nagasechemtex Co., Ltd. "N-321" (60 ° C, 3 minutes)

實施例9~35 Example 9~35

以如表4及表5表示的比例，藉由與實施例8同樣的方法來調配、評估(I)負型感光性樹脂組成物或(II)正型感光性樹脂組成物。在任何樹脂組成物均添加100ppm的BYK-333作為界面活性劑，加入DAA/PGMEA(重量比：50/50)混合溶液作為溶劑而調整固體成分濃度成為30wt%。 The (I) negative photosensitive resin composition or (II) positive photosensitive resin composition was prepared and evaluated in the same manner as in Example 8 at a ratio shown in Table 4 and Table 5. To each of the resin compositions, 100 ppm of BYK-333 was added as a surfactant, and a mixed solution of DAA/PGMEA (weight ratio: 50/50) was added as a solvent to adjust the solid content concentration to 30% by weight.

實施例36 Example 36

依照以下的順序，製作觸控面板構件。 The touch panel member is fabricated in the following order.

(1)ITO之製作 (1) Production of ITO

在厚度約0.5mm的玻璃基板使用噴鍍(sputtering)裝置(HSR-521A；島津製作所(股)製)，藉由以RF功率1.4kW、真空度6.65×10-1Pa噴鍍12.5分鐘，使膜厚為150nm的ITO成膜，塗布正型光阻劑(OFPR-800；東京應化工業(股)製)，在80℃預烘烤20分鐘而獲得膜厚為1.1μm的光阻膜。使用PLA，對所獲得的膜以超高壓水銀燈隔著遮罩圖案曝光後，使用自動顯影裝置以2.38wt%的TMAH水溶液淋浴顯影90秒鐘，接著以水沖洗30秒鐘。然後，藉由浸漬於3.5%的乙二酸水溶液150秒鐘來蝕刻ITO，以50℃的剝離液(N-321；Nagasechemtex(股)製)處理120秒鐘來除去光阻劑，在230℃施加30分鐘的回火(annealing)處理，而製作具有膜厚為150nm之經圖案加工的ITO(第1圖及 第2圖的符號2)的玻璃基板(相當於第1圖的a)。 A glass substrate having a thickness of about 0.5 mm was sprayed by a sputtering apparatus (HSR-521A; manufactured by Shimadzu Corporation) at an RF power of 1.4 kW and a degree of vacuum of 6.65 × 10 -1 Pa for 12.5 minutes. ITO was formed into a film having a film thickness of 150 nm, and a positive photoresist (OFPR-800; manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied, and baked at 80 ° C for 20 minutes to obtain a photoresist film having a film thickness of 1.1 μm. Using the PLA, the obtained film was exposed to an ultrahigh pressure mercury lamp through a mask pattern, and then developed with a 2.38 wt% aqueous TMAH solution for 90 seconds using an automatic developing device, followed by rinsing with water for 30 seconds. Then, ITO was etched by immersing in a 3.5% aqueous solution of oxalic acid for 150 seconds, and the photoresist was removed by a 50 ° C stripping solution (N-321; Nagasechemtex) for 120 seconds to remove the photoresist at 230 ° C. An annealing treatment was applied for 30 minutes to prepare a glass substrate (corresponding to a in Fig. 1) of patterned ITO (symbol 2 of Figs. 1 and 2) having a film thickness of 150 nm.

(2)透明絕緣膜之製作 (2) Production of transparent insulating film

在所獲得的玻璃基板上使用負型感光性樹脂組成物(I-1)，依照上述評估方法之順序製作透明絕緣膜(第1圖及第2圖的符號3)(相當於第1圖的b)。 Using a negative photosensitive resin composition (I-1) on the obtained glass substrate, a transparent insulating film (symbol 3 of FIGS. 1 and 2) was produced in accordance with the procedure of the above evaluation method (corresponding to FIG. 1) b).

(3)MAM配線之製作 (3) Production of MAM wiring

在所獲得的玻璃基板上，除了使用鉬及鋁作為標靶、使用H3PO4/HNO3/CH3COOH/H2O=65/3/5/27(重量比)混合溶液作為蝕刻液以外，藉由與(1)同樣的順序來製作MAM配線(第1圖及第2圖的符號4)(相當於第1圖的c)。又，MAM的膜厚係調整成250nm。 On the obtained glass substrate, a mixed solution of H 3 PO 4 /HNO 3 /CH 3 COOH/H 2 O=65/3/5/27 (weight ratio) was used as an etching solution, except that molybdenum and aluminum were used as targets. The MAM wiring (symbol 4 in the first and second figures) (corresponding to c in Fig. 1) is produced in the same order as (1). Further, the film thickness of the MAM was adjusted to 250 nm.

(4)透明保護膜之製作 (4) Production of transparent protective film

在所獲得的玻璃基板上使用負型感光性樹脂組成物(I-1)，依照上述評估方法的順序製作透明保護膜。使用測試器實施連接部之通電測試時，確認了電流的流通(相當於第2圖)。 A negative-type photosensitive resin composition (I-1) was used on the obtained glass substrate, and a transparent protective film was produced in the order of the evaluation method mentioned above. When the connection test was performed using the tester, the flow of current was confirmed (corresponding to Fig. 2).

比較例2~5 Comparative example 2~5

以如表6表示之比例，藉由與實施例8同樣的方法調配、評估(I)負型感光性樹脂組成物或(II)正型感光性樹脂組成物。 (I) The negative photosensitive resin composition or the (II) positive photosensitive resin composition was prepared and evaluated in the same manner as in Example 8 at a ratio shown in Table 6.

表7及表8顯示實施例8~35及比較例2~5的評估結果。 Tables 7 and 8 show the evaluation results of Examples 8 to 35 and Comparative Examples 2 to 5.

由實施例8~35所獲得之樹脂組成物所獲得的硬化膜均具有優良的圖案化構成、透明性、接著性，具有被視為特別是觸控面板用絕緣膜及保護膜、TFT用平坦化膜及CF用保護膜所必須之特性。 The cured film obtained from the resin compositions obtained in Examples 8 to 35 has excellent patterning, transparency, and adhesion, and is considered to be particularly an insulating film and a protective film for a touch panel, and a flat for TFT. The properties necessary for the film and the protective film for CF.

[產業上之可利用性] [Industrial availability]

硬化含有本發明之矽烷偶合劑的負型感光性樹脂組成物及正型感光性樹脂組成物所獲得的硬化膜，除了觸控面板之保護膜等的各種保護膜之外，亦適用於觸控感應器用絕緣膜、液晶或是有機EL顯示器之TFT用平坦化膜、金屬配線保護膜、絕緣膜、抗反射膜、抗反射薄膜、光學濾光片、彩色濾光片用保護膜或支撐材料等。 The cured film obtained by curing the negative photosensitive resin composition containing the decane coupling agent of the present invention and the positive photosensitive resin composition is also suitable for touch except for various protective films such as a protective film of a touch panel. Insulating film for inductor, liquid crystal or TFT flat film for organic EL display, metal wiring protective film, insulating film, anti-reflection film, anti-reflection film, optical filter, protective film for color filter, support material, etc. .

a‧‧‧透明電極形成後之俯視圖 a‧‧‧Top view of the transparent electrode after formation

b‧‧‧絕緣膜形成後之俯視圖 b‧‧‧Top view after the formation of the insulating film

c‧‧‧金屬配線形成後之俯視圖 c‧‧‧Top view after metal wiring is formed

1‧‧‧玻璃基板 1‧‧‧ glass substrate

2‧‧‧透明電極 2‧‧‧Transparent electrode

3‧‧‧透明絕緣膜 3‧‧‧Transparent insulating film

4‧‧‧配線電極 4‧‧‧Wiring electrode

Claims (8)

一種(A)矽烷偶合劑，其係以下述通式(1)表示； (R1分別獨立地表示碳數1~6的烷基或是苯基，或該等的取代物；R2分別獨立地表示碳數1~6的烷基或是苯基，或該等的取代物；R3表示碳數1~30之2價有機基；R4表示具有雜環式構造之碳數1~30的1價有機基；m表示0~2的整數)。 A (A) decane coupling agent represented by the following formula (1); (R 1 each independently represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, or a substituent thereof; and R 2 each independently represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, or the like a substituent; R 3 represents a divalent organic group having 1 to 30 carbon atoms; R 4 represents a monovalent organic group having 1 to 30 carbon atoms having a heterocyclic structure; and m represents an integer of 0 to 2). 如申請專利範圍第1項之(A)矽烷偶合劑，其中該R4係以下述通式(4)表示； (n及o分別獨立地表示0~4的整數；惟，n+o≧1；R5表示氫或碳數1~10的烷基)。 [A] a decane coupling agent according to the first aspect of the invention, wherein the R 4 is represented by the following formula (4); (n and o each independently represent an integer of 0 to 4; however, n+o≧1; R5 represents hydrogen or an alkyl group having 1 to 10 carbon atoms). 一種感光性樹脂組成物，其中含有如申請專利範圍第1或2項之(A)矽烷偶合劑、(B)鹼可溶性樹脂、(C)多官能丙烯酸單體、及(D)光自由基聚合起始劑或(E)醌二疊氮化合物。 A photosensitive resin composition containing (A) a decane coupling agent, (B) an alkali-soluble resin, (C) a polyfunctional acrylic monomer, and (D) photoradical polymerization as claimed in claim 1 or 2 Starting agent or (E) quinonediazide compound. 如申請專利範圍第3項之感光性樹脂組成物，其中該(B)鹼可溶性樹脂係選自包含聚矽氧烷、丙烯酸樹脂及聚酯樹脂之群組的樹脂。 The photosensitive resin composition of claim 3, wherein the (B) alkali-soluble resin is selected from the group consisting of polysiloxanes, acrylic resins, and polyester resins. 如申請專利範圍第3或4項之感光性樹脂組成物，其中更進一步含有(F)金屬氧化粒子。 The photosensitive resin composition of claim 3 or 4, further comprising (F) metal oxide particles. 一種硬化膜，其係硬化如申請專利範圍第3至5項中任一項之感光性樹脂組成物而成。 A cured film obtained by curing the photosensitive resin composition according to any one of claims 3 to 5. 一種觸控面板，其中具備如申請專利範圍第6項之硬化膜。 A touch panel comprising a cured film as in claim 6 of the patent application. 一種TFT基板，其中具備如申請專利範圍第6項之硬化膜。 A TFT substrate comprising a cured film as in claim 6 of the patent application.
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