CN105531652B - Touch screen, radiation-sensitive resin composition and cured film - Google Patents

Touch screen, radiation-sensitive resin composition and cured film Download PDF

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Publication number
CN105531652B
CN105531652B CN201480050552.1A CN201480050552A CN105531652B CN 105531652 B CN105531652 B CN 105531652B CN 201480050552 A CN201480050552 A CN 201480050552A CN 105531652 B CN105531652 B CN 105531652B
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China
Prior art keywords
radiation
resin composition
compound
sensitive resin
touch screen
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CN201480050552.1A
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CN105531652A (en
Inventor
本田晃久
奥田务
石川広树
坂井孝広
戸大吾
一戸大吾
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JSR Corp
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JSR Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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
    • 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
    • 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
    • G03F7/027—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
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • G06F3/0443—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a single layer of sensing electrodes
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • G06F3/0446—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a grid-like structure of electrodes in at least two directions, e.g. using row and column electrodes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • C08F222/402—Alkyl substituted imides
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04111—Cross over in capacitive digitiser, i.e. details of structures for connecting electrodes of the sensing pattern where the connections cross each other, e.g. bridge structures comprising an insulating layer, or vias through substrate
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04112—Electrode mesh in capacitive digitiser: electrode for touch sensing is formed of a mesh of very fine, normally metallic, interconnected lines that are almost invisible to see. This provides a quite large but transparent electrode surface, without need for ITO or similar transparent conductive material

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Human Computer Interaction (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Position Input By Displaying (AREA)
  • Formation Of Insulating Films (AREA)

Abstract

The present invention relates to a kind of touch screen, radiation-sensitive resin composition and cured films.It provides comprising metal wiring and the cured film for covering it, and the touch screen with high reliability, and the cured film and the radiation-sensitive resin composition to form it is provided.The hydrolytic condensate of compound and the compound containing (A) emulsion and (B) containing alkoxysilane group at least one and prepare the radiation-sensitive resin composition to the cured film (25) for forming touch screen (21).Use the radiation-sensitive resin composition, cured film (25) are formed on the transparent substrate (22) configured with the 1st detecting electrode (23), the 2nd detecting electrode (24) and wiring (31), it provides touch screen (21), the wiring (31) is containing the 1st layer comprising copper and the oxide comprising the 2nd metallic element other than copper and to cover the 2nd layer constituted in a manner of described 1st layer at least part of.

Description

Touch screen, radiation-sensitive resin composition and cured film
Technical field
The present invention relates to a kind of touch screen, radiation-sensitive resin composition and cured films.
Background technique
In recent years, in personal digital assistant (Personal Digital Assistant, PDA), notes type individual calculus Machine (Note Personal Computer, notes type PC), office automated machine (Office Automation Equipment, OA machine) and the e-machines such as auto-navigation system (Car Navigation System) in, it is prevailing to use touching Touch the input unit shielded as these displays.
Touch screen can be by touching (pressing) its surface with the finger of operator or pen etc., by the data of the touching operation Thus output can carry out the operation of e-machine into various processing units.Touch screen is instead of the defeated of keyboard (keyboard) Enter device, in above-mentioned e-machine etc., information input can be carried out with dialogic operation and easily.
In touch screen, according to operating principle, there are resistive film mode, electrostatic capacitance method, infrared mode, ultrasounds Wave mode and electromagnetic induction coupled modes etc..
In such touch screen, such as in the presence of such just like electrostatic capacitance method, it will extend in the prescribed direction existing Multiple 1st detecting electrodes upwardly extend existing 2nd detecting electrode in the side intersected with it and are combined, and are configured at glass etc. The touch screen of structure on transparent substrate.These detecting electrodes are utilized respectively the wiring of electric connection and guide to transparent substrate End.In another end for the wiring connecting with detecting electrode, it is formed with the terminal for example to connect the touch screen.
Moreover, in electrostatic capacitance method, such as disclosed in patent document 1, it is known in its of transparent substrate In on a face, configure the structure of the 1st detecting electrode and the 2nd detecting electrode in same layer.
The 1st detecting electrode of documented touch screen and the 2nd detecting electrode separately include in patent document 1: diamond shape And the multiple electrode pads that area is big, connect the coupling part of the narrower narrow shape of ratio electronic pads between these.Moreover, the 1st Detecting electrode intersects with the 2nd detecting electrode in each coupling part, but is configured with the layer of translucency in the cross section Between insulating film.Therefore, the touch screen of patent document 1 is constituted as follows: the 1st detecting electrode is with the 2nd detecting electrode each A coupling part is overlapped via interlayer dielectric, to ensure insulating properties.Moreover, these the 1st detecting electrodes and the 2nd detecting electrode It is utilized respectively the wiring of electric connection and guides to the end of transparent substrate.At another end for the wiring being connect with detecting electrode Portion is formed with the terminal to connect touch screen.
Existing technical literature
Patent document
Patent document 1: Japanese Patent Laid-Open 2008-310551 bulletin
Patent document 2: No. 2006/025347 specification of International Publication No.
Summary of the invention
Subject to be solved by the invention
The touch screen of such structure is in insulative substrate comprising detecting electrode, to be electrically connected with the detecting electrode And it will test electrode and guide the wiring to base ends and constitute.In touch screen, the wiring connecting with each detecting electrode is not Directly to the touching operation of the finger that detects operator etc..That is, in touch screen, the wiring that is connect with each detecting electrode Forming region become in touching operation and its detection and the region that does not use.
Therefore, it is small and narrow that wiring forming region is preferably in touch screen.By making as described above with linear Narrowing at region, the finger etc. that operator can be significantly arranged in touch screen touches and carries out the operating space of touching operation Domain.
In touch screen, in order to keep wiring forming region narrowing, preferably formed more carefully and detecting electrode electrical property Each wiring of connection.Therefore it is required that forming wiring using low-resistance material.In touch screen, what is connect with detecting electrode matches Line can for example be set as the metal wiring using metals such as copper, it can be achieved that low resistance.
However, touch screen is in the case where using glass substrate etc. as substrate, such as metal wiring and base comprising copper Contiguity power between plate is low.Touch screen operator's practical contact of finger, pressing operation region and whens the case where using etc., Ask can deformation resistant intensity.In a word, it is desirable that it is bad that touch screen does not generate the member of formation self-reference substrate such as wiring removing etc..Moreover, Touch screen is bad for the broken string or the removing that inhibit detecting electrode or wiring etc., becomes to use for a long time, it is desirable that has high Reliability.
In patent document 2, as adding copper alloy made of suitable addition element, the addition member in copper (Cu) Element forms oxidation film and becomes overlay film, inhibits Cu oxidation, and form the interface of the insulating layer abutted with the overlay film, prevents phase Counterdiffusion.Thus high conductivity is provided and the copper wiring excellent with the adhesion of substrate.
However, there are the following problems: as such oxidation film overlay film, with side that copper wiring is covered as organic film Formula and the adhesion between the protective film of wiring that is arranged is low, penetrated into from external moisture, corrode copper wiring.
The present invention is in view of made of project as described above.That is, the purpose of the present invention is to provide: match with metal Line, the overlay film and the cured film as the organic film for covering the metal wiring for be formed by metal wiring by metal oxide film Adhesion is good, and the touch screen with high reliability.
Moreover, the purpose of the present invention is to provide to formed covering touch screen metal wiring and with the metal wiring The good cured film of adhesion radiation-sensitive resin composition.
Moreover, the adhesion the purpose of the present invention is to provide the metal wiring of covering touch screen and with the metal wiring Good cured film.
Technical means to solve problem
1st embodiment of the invention is related to a kind of touch screen, is comprising metal wiring and to cover the metal wiring At least part of cured film touch screen, it is characterised in that:
The metal wiring is the metal wiring comprising the 2nd metallic element other than copper, copper,
The cured film is formed using radiation-sensitive resin composition, the radiation-sensitive resin composition At least the one of the hydrolytic condensate of compound and the compound containing (A) emulsion and (B) containing alkoxysilane group It is a.
In the 1st embodiment of the invention, preferably metal wiring be containing the 1st layer comprising copper, comprising copper with The oxide of the 2nd outer metallic element and to cover the 2nd layer of the metal in a manner of described 1st layer at least part of and constituted Wiring.
In the 1st embodiment of the invention, preferably described 2nd metallic element be selected from by lithium, germanium, strontium, tin, Group composed by barium, praseodymium, neodymium, phosphorus, manganese, magnesium, calcium, nickel, zinc, silicon, aluminium, beryllium, gallium, indium, iron, titanium, vanadium, cobalt, zirconium and hafnium is extremely Few one kind.
In the 1st embodiment of the invention, preferably described 2nd metallic element is manganese.
In the 1st embodiment of the invention, the preferably described cured film be using further contain (C) alkali-soluble The radiation-sensitive resin composition of resin and formed.
In the 1st embodiment of the invention, the radiation-sensitive resin composition of the cured film is preferably formed (C) ingredient include selected from least one as the acrylic resin with carboxyl, group composed by polyamide and polysiloxanes Kind.
In the 1st embodiment of the invention, the preferably described cured film be using further contain (D) antioxidant Radiation-sensitive resin composition and formed.
In the 1st embodiment of the invention, the preferably described cured film be use further containing (F) as comprising The oxide of at least one element selected from the group as composed by silicon, aluminium, zirconium, titanium, zinc, indium, tin, antimony, strontium, barium, cerium and hafnium Inorganic oxide particle radiation-sensitive resin composition and formed.
In the 1st embodiment of the invention, the radiation-sensitive resin composition of the cured film is preferably formed (A) ingredient include light acid generation and Photoepolymerizationinitiater initiater at least one.
In the 1st embodiment of the invention, the radiation-sensitive resin composition of the cured film is preferably formed (B) ingredient include with amino, block amino, isocyanate group and blocked isocyanate ester group at least one compound.
2nd embodiment of the invention is related to a kind of radiation-sensitive resin composition, be containing (A) emulsion, with And radiation made of at least one of the hydrolytic condensate of the compound of (B) containing alkoxysilane group and the compound Property resin combination, it is characterised in that:
To form the cured film of touch screen, the touch screen includes metal wiring and covers the metal wiring at least The cured film of a part, the metal wiring contain the 1st layer comprising copper and comprising the 2nd metallic elements other than copper Oxide and to cover the 2nd layer in a manner of described 1st layer at least part of and constituted.
In the 2nd embodiment of the invention, (C) alkali soluble resin is preferably further included.
It is described (C) preferably comprising (C) alkali soluble resin in the 2nd embodiment of the invention Ingredient includes selected from at least one as the acrylic resin with carboxyl, group composed by polyamide and polysiloxanes.
In the 2nd embodiment of the invention, the 2nd gold medal contained in the 2nd layer of the preferably described metal wiring Belong to element oxide be selected from by lithium, germanium, strontium, tin, barium, praseodymium, neodymium, phosphorus, manganese, magnesium, calcium, nickel, zinc, silicon, aluminium, beryllium, gallium, indium, The oxide of at least one element of group composed by iron, titanium, vanadium, cobalt, zirconium and hafnium.
In the 2nd embodiment of the invention, (D) antioxidant is preferably further included.
In the 2nd embodiment of the invention, (E) multifunctional (methyl) acrylate is preferably further included.
In the 2nd embodiment of the invention, preferably further include (F) as comprising selected from by silicon, aluminium, zirconium, The inorganic oxide grain of the oxide of at least one element of group composed by titanium, zinc, indium, tin, antimony, strontium, barium, cerium and hafnium Son.
In the 2nd embodiment of the invention, preferably (A) ingredient includes light acid generation and Photoepolymerizationinitiater initiater At least one.
In the 2nd embodiment of the invention, preferably (B) ingredient includes to have amino, block amino, isocyanates At least one compound of base and blocked isocyanate ester group.
3rd embodiment of the invention is related to a kind of cured film, is formed by radiation-sensitive resin composition Cured film, the radiation-sensitive resin composition are the chemical combination containing (A) emulsion and (B) containing alkoxysilane group Made of at least one of the hydrolytic condensate of object and the compound, it is characterised in that:
To cover at least part of the metal wiring of the touch screen comprising metal wiring, the metal wiring contains There are the 1st layer comprising copper and the oxide comprising the 2nd metallic element other than copper and at least one to cover described 1st layer Point mode and constitute the 2nd layer.
The effect of invention
1st embodiment according to the present invention and obtain with metal wiring, metal is formed by by metal oxide film and is matched The overlay film of line and the adhesion of the cured film as the organic film for covering the metal wiring are good, and with high reliability Touch screen.
2nd embodiment according to the present invention and obtain to formed covering touch screen metal wiring and with the metal The radiation-sensitive resin composition of the good cured film of the adhesion of wiring.
3rd embodiment according to the present invention and obtain the covering metal wiring of touch screen and close with the metal wiring The good cured film of connecing property.
Detailed description of the invention
Fig. 1 is the plan view for indicating an example of touch screen of the 1st implementation form of the invention.
Fig. 2 is the sectional view of the B-B ' line along Fig. 1.
Fig. 3 is an example for schematically showing the structure of wiring possessed by the touch screen of the 1st implementation form of the invention Sectional view.
Fig. 4 has been expressed as formation touch screen and has been formed by wiring, the 1st detecting electrode and the 2nd inspection on the transparent substrate Survey the plan view of electrode.
Fig. 5 has been expressed as formation touch screen and has been formed by wiring, the 1st detecting electrode, the 2nd detection on the transparent substrate Electrode, interlayer insulating film and the plan view for bridging wiring.
Description of symbols
21: touch screen
22: transparent substrate
23: the 1 detecting electrodes
24: the 2 detecting electrodes
25: cured film
28: cross part
29: interlayer dielectric
30: electronic pads
31: wiring
32: bridge joint wiring
41: the 1 layers
42: the 2 layers
Specific embodiment
Hereinafter, the use of attached drawing being suitable for explanation to implementation form of the invention.
In addition, in the present invention, " radioactive ray " that when exposure is irradiated include luminous ray, ultraviolet light, far ultraviolet, X Ray and charged particle beam etc..
Implementation form 1.
<touch screen>
The touch screen of implementation form of the invention is at least part comprising metal wiring and the covering metal wiring Cured film touch screen.That is, the touch screen of this implementation form is on substrate comprising to the finger that detects operator etc. Touch the detecting electrode of operation.Moreover, the touch screen of this implementation form includes the wiring being electrically connected with detecting electrode, it is described to match Line is the metal wiring formed using metal material.In the touch screen of this implementation form, the wiring that is connect with detecting electrode It comprising guiding will test electrode to the wiring of the end of the substrate of touch screen, and include the detecting electrode will be switched off The wiring that is connected to each other of part.In addition, the touch screen of this implementation form includes at least part of hard of covering metal wiring Change film.
The touch screen of this implementation form can be used as the touch screen of electrostatic capacitance method.
Fig. 1 is the plan view for indicating an example of touch screen of implementation form of the invention.
Fig. 2 is the sectional view of the B-B ' line along Fig. 1.
As shown in Figure 1, the touch screen 21 of this implementation form includes on the surface of transparent substrate 22: extending deposit in the X direction The 1st detecting electrode 23, extend existing 2nd detecting electrode 24 in the Y-direction orthogonal with X-direction.
Transparent substrate 22 can be set as glass substrate.Moreover, transparent substrate 22 can be set as resin substrate, in this case, Polyethylene terephthalate film can be used, polybutylene terephthalate film, polyethylene film, polypropylene screen, poly (ether sulfone) film, gather Carbonic ester film, polypropylene sorrel, polychloroethylene film, polyimide film, cyclic olefin ring-opening polymerization polymer film and include its hydrogenation The film etc. of object.As the thickness of transparent substrate 22, in the case where glass substrate, 0.1mm~3mm can be set as.In resin substrate In the case where, 10 μm~3000 μm can be set as.
1st detecting electrode 23 and the 2nd detecting electrode 24 are respectively configured multiple.Moreover, the 1st detecting electrode 23 and the 2nd detects Electrode 24 is configured to rectangular in the operating area of touch screen 21.Touch position of 1st detecting electrode 23 to detect operator Y-direction coordinate.The coordinate of the X-direction of touch position of 2nd detecting electrode 24 to detect operator.1st detecting electrode 23 and the 2nd detecting electrode 24 is set on the same layer of the same face of transparent substrate 22.In addition, the 1st detecting electrode 23 and the 2nd detects The quantity of electrode 24 is not limited to the example of Fig. 1, preferably according to the inspection of the size of operating area and required touch position Out precision and determine.That is, greater number or lesser amount of 1st detecting electrode 23 and the 2nd detecting electrode 24 can be used and structure At touch screen 21.
As shown in Figure 1, the 1st detecting electrode 23 and the 2nd detecting electrode 24 separately include the multiple electrode pads 30 of diamond shape. 1st detecting electrode 23 and the 2nd detecting electrode 24 are with the electronic pads 30 of the 1st detecting electrode 23 and its 2nd detecting electrode abutted The mode that 24 electronic pads 30 separate is configured.At this point, the gap between these electronic pads 30 is set as can ensure that insulating properties The minimal clearance of degree.
Moreover, the 1st detecting electrode 23 is matched in such a way that cross one another part is as small as possible with the 2nd detecting electrode 24 It sets.Moreover, the electronic pads 30 for constituting the 1st detecting electrode 23 and the 2nd detecting electrode 24 is made to be configured at the operating area of touch screen 21 Entirety.
As shown in Figure 1, electronic pads 30 can be set as diamond shape, kind shape that but it is not limited to this, such as hexagon can be set as Equal polygonal shapes.
Preferably the 1st detecting electrode 23 and the 2nd detecting electrode 24 are respectively transparent electrode.Herein, so-called transparent electrode It is that there is high radioparent electrode for visible light.1st detecting electrode 23 and the 2nd detecting electrode 24, which can be used, includes The electrode of ITO, electrode comprising indium oxide and zinc oxide etc. include the electrode of transparent conductive material.In the 1st detecting electrode 23 and In the case that 2nd detecting electrode 24 separately includes ITO, in order to ensure sufficient electric conductivity, preferably these thickness is set For 10nm~100nm.
The formation of 1st detecting electrode 23 and the 2nd detecting electrode 24 can be used well known method and carry out, such as can be by such as Under type and carry out: form the film comprising the transparent conductive materials such as ITO using sputtering method etc., carry out figure using photoetching process etc. Case.
As shown in Figures 1 and 2, the 1st detecting electrode 23 and the 2nd detecting electrode 24 are formed in the same face of transparent substrate 22 On, become same layer.Therefore, the 1st detecting electrode 23 and the 2nd detecting electrode 24 intersect, shape in operating area at multiple positions At cross part 28.
In the touch screen 21 of this implementation form, as shown in Fig. 2, in cross part 28, with the 1st detecting electrode 23 and the 2nd Any one of detecting electrode 24 with another not in contact with mode turn off.That is, in cross part 28, connection the 1st Detecting electrode 23, but it is formed in the 2nd detecting electrode 24 of the left and right directions stretching, extension of Fig. 2 with disconnecting.Moreover, in order to be electrically connected The position of the interruption of 2 detecting electrodes 24 is equipped with bridge joint wiring 32.Packet is equipped between bridge joint wiring 32 and the 1st detecting electrode 23 The interlayer dielectric 29 of the substance containing insulating properties.
As shown in Fig. 2, the interlayer dielectric 29 on the 1st detecting electrode 23 is excellent by translucency in cross part 28 Material and formed.Print process can be used and be coated with polysiloxanes, acrylic resin and acrylic monomer etc., in necessity In the case where patterned after, make its heat hardening and form interlayer dielectric 29.It is formed using polysiloxanes In the case of, interlayer dielectric 29, which becomes, includes silica (SiO2) inorganic insulation layer.Moreover, using acrylic resin, And in the case where acrylic monomer, interlayer dielectric 29, which becomes, wraps resiniferous organic insulator.In interlayer dielectric 29 Use SiO2In the case where, such as the sputtering method using mask can also be used, only on the 1st detecting electrode 23 of cross part 28 Form SiO2Film constitutes interlayer dielectric 29.
Bridge joint wiring 32 is equipped on the upper layer of interlayer dielectric 29.Bridge joint wiring 32 can be realized as described above and will intersect The function that the 2nd detecting electrode 24 that portion 28 is interrupted is electrically connected to each other.It bridges wiring 32 and is preferably excellent by translucency such as ITO Different material and formed.Moreover, bridging the metal material that wiring 32 can also be used resistance characteristic excellent and constituting, becomes metal and match Line.Bridge joint wiring 32 can make line width attenuate and being set as resistance characteristic excellent metal wiring, the operation for touch screen 21 It can be become difficult to for person obvious.In touch screen 21, wiring 32 is bridged by setting, the 2nd inspection can be electrically connected in the Y direction Survey electrode 24.
As shown in Fig. 2, the 1st detecting electrode 23 and the 2nd detecting electrode 24 have vertical as described above or are arranged with breadthways more The shape of the electronic pads 30 of a diamond shape.In the 1st detecting electrode 23, become positioned at the coupling part of cross part 28 than the 1st detection The narrower shape of the width of the electronic pads 30 of the diamond shape of electrode 23.Moreover, bridge joint wiring 32 is also the electronic pads 30 than diamond shape The narrower shape of width, is formed as short strip shape.
It is respectively equipped with terminal (not shown) in the 1st detecting electrode 23 of touch screen 21 and the end of the 2nd detecting electrode 24, from The terminal exports wiring 31 respectively.
Fig. 3 is the section for schematically showing the structure of wiring possessed by the touch screen of the 1st implementation form of the invention Figure.
In the touch screen 21 of the 1st implementation form of the invention, wiring 31 is metal wiring.Moreover, wiring 31 is preferred It is the metal wiring comprising the 2nd metallic element other than copper, copper.Moreover, the 2nd metallic element be selected from by lithium, Composed by germanium, strontium, tin, barium, praseodymium, neodymium, phosphorus, manganese, magnesium, calcium, nickel, zinc, silicon, aluminium, beryllium, gallium, indium, iron, titanium, vanadium, cobalt, zirconium and hafnium At least one of group, more preferably manganese.
More specifically, as shown in figure 3, preferably wiring 31 contains: the 1st layer 41 comprising copper, comprising copper other than 2nd metal and the surface to coat the 1st layer 41 it is at least part of in a manner of constituted the 2nd layer 42.Also, it is preferable that wiring The 1st layer 41 of 31 includes copper or copper alloy.Moreover, the 2nd layer 42 of wiring 31 is more preferably comprising the 2nd gold medal other than copper Belong to the oxide of element and constituted by covering in a manner of the 1st layer 41 at least part of, more preferably with using including institute State the 2nd metal as the oxide of principal component coat the 1st layer 41 surface at least part of mode and constitute.
In addition, in the touch screen 21 of this implementation form, particularly preferably the 2nd layer 42 the 1st layer 41 of cladding of surface All.In addition, in Fig. 3, it is schematically indicated the structure of wiring 31, cross-section structure are not limited in oblong-shaped.For example, 1st layer 41 of section shape of wiring 31 can be set as square shape, trapezoidal shape, parallelogram like etc., and the 2nd layer 42 can coat institute State the 1st layer of surface.
In wiring 31, as the preferred material for constituting the 1st layer 41, copper or copper alloy can be enumerated as described above.And And the copper alloy can enumerate comprising selected from by potassium, germanium, strontium, tin, barium, praseodymium, neodymium, phosphorus, manganese, magnesium, calcium, nickel, zinc, silicon, aluminium, beryllium, The copper alloy of at least one element of group composed by gallium, indium, iron, titanium, vanadium, cobalt, zirconium and hafnium.That is, constituting wiring 31 1st layer 41 of preferred material can be copper or the alloy of copper and above-mentioned 2nd metallic element.
Moreover, copper alloy more preferably, can enumerate comprising having the diffusion coefficient bigger than the self-diffusion coefficient of copper Element copper alloy.The concrete example of copper alloy more preferably, can enumerate comprising selected from by lithium, germanium, strontium, tin, barium, praseodymium, The copper alloy of at least one addition element of group composed by neodymium, manganese, zinc, gallium and indium.In this case, in copper alloy The range that it is 0.1atom%~25atom% that the additive amount of addition element, which is preferably for copper,.By by additive amount It is set as range as described above, the diffusion transfiguration of the addition element in the copper alloy due to caused by heating can be made easy.
And it is particularly preferred to copper alloy can enumerate the copper alloy comprising manganese namely copper-manganese alloy.
Moreover, wiring 31 be preferably coat the 2nd layer 42 of above-mentioned 1st layer 41 oxide comprising metallic element namely Metal oxide and constitute.In this case, the metal oxide in the 2nd layer 42 is preferably at least containing the gold other than copper The oxide of category more preferably includes the oxide containing above-mentioned 2nd metallic element other than copper.
Metal oxide contained in such 2nd layer 42 can specifically enumerate selected from by lithium, germanium, strontium, tin, barium, praseodymium, At least one of group composed by neodymium, phosphorus, manganese, magnesium, calcium, nickel, zinc, silicon, aluminium, beryllium, gallium, indium, iron, titanium, vanadium, cobalt, zirconium and hafnium The oxide of element, preferred metal oxide can enumerate the oxide of manganese.
The wiring 31 of structure shown in Fig. 3 can be formed in the following way: be used above-mentioned preferred as the 1st layer 41 Constituent material and the copper alloy enumerated and after forming Wiring pattern, heated.
That is, the Wiring pattern comprising above-mentioned copper alloy is heated in the presence of such as atmosphere inferior oxygen, thus And the oxide for constituting the metal of copper alloy is formed in the superficial layer of the Wiring pattern.Its result forms wiring 31, described to match Line 31 includes: the 1st comprising copper layer 41 that is formed by copper alloy, the oxide comprising the metallic element other than copper and with cladding 1st layer 41 of mode and constitute the 2nd layer 42.
At this point, as the copper alloy for forming Wiring pattern, it is preferred to use it is as described above comprising selected from by lithium, germanium, Copper alloy of at least one element of group composed by strontium, tin, barium, praseodymium, neodymium, manganese, zinc, gallium and indium as addition element, institute Element is stated with the diffusion coefficient bigger than the self-diffusion coefficient of copper.In this case, by heat treatment, have than copper The addition element of the bigger diffusion coefficient of self-diffusion coefficient quickly reaches copper surface, preferentially forms addition on the surface of copper alloy The oxidation coating layer of element.
Therefore, the 2nd layer 42 of the wiring 31 of touch screen 21 containing other than copper element namely selected from by lithium, germanium, strontium, tin, The metal oxide of at least one element of group composed by barium, praseodymium, neodymium, manganese, zinc, gallium and indium is described as main component Element has the diffusion coefficient bigger than the self-diffusion coefficient of copper.
For example, in order to form wiring 31, in the case where stating particularly preferred copper-manganese alloy comprising manganese in use, It constitutes and is formed on the substrate of touch screen comprising copper-manganese alloy Wiring pattern.Thereafter, wiring is formed and being heated 31, the wiring 31 contains: comprising the 1st layer 41 of copper or copper-manganese alloy, comprising metal oxide and to coat the 1st layer 41 At least part of mode and constitute the 2nd layer 42.In this case, metal oxide contained in the 1st layer 41 can contain The oxide of manganese.
In touch screen 21, it is not particularly limited to form the forming method of above-mentioned copper alloy of wiring 31.Such as it can With reference to documented method in Japanese Patent Laid-Open 2008-261895 bulletin.That is, electric field plating method, dissolution plating can be used It covers the physical vapor depositions such as the plating methods such as method, vacuum vapour deposition, sputtering method and forms copper alloy.Moreover, and to as described above The copper alloy of film forming is heat-treated and forms oxidation coating layer.Therefore, by making together with the forming method of above-mentioned copper alloy With well known patterning method, can get the Wiring pattern comprising above-mentioned copper alloy can be formed by heating to it Wiring 31.
Moreover, the heat treatment temperature as the above-mentioned copper alloy to form wiring 31, is preferably set as such as 150 DEG C~450 DEG C of range, heating treatment time, which is preferably, is set as such as 2 minutes~5 hours ranges.If heat treatment temperature Less than 150 DEG C, then the formation for aoxidizing overlay film needs to spend the time, and productivity reduces.On the other hand, if existing more than 450 DEG C The dysgenic worries such as deterioration are caused to other member of formation for constituting touch screen.Moreover, if heating treatment time divides less than 2 Clock, then the film thickness of metal oxide is thin, on the other hand, if more than 5 hours, when excessively spending there are the formation of oxide coating film Between, thus the worry for reducing the productivity of touch screen.
The wiring 31 formed as described above contains: the 1st layer 41 comprising copper, comprising what is formed by above-mentioned heating Metal oxide and formed the 2nd layer 42 in a manner of coating the 1st layer 41.The 1st layer 41 of wiring 31 includes the gold containing copper Belong to material, resistance characteristic is excellent.Moreover, wiring 31 contains the 2nd layer 42 formed comprising metal oxide, therefore can be to composition The transparent substrate 22 of touch screen 21 shows excellent adhesion.
Especially in the case where wiring 31 includes copper-manganese alloy, the 2nd layer of 42 oxide containing manganese of wiring 31 can Excellent adhesion is shown between the transparent substrate 22 comprising above-mentioned constituent material.
Therefore, touch screen 21 can realize the narrowing of the forming region of wiring 31, moreover, can inhibit 31 self-induced transparency base of wiring The removing of plate 22 etc. is bad and realizes high reliability.
In addition, touch screen 21 is equipped with the 2nd detecting electrode 24 that will be interrupted in cross part 28 each other electrically as described above The bridge joint wiring 32 of connection.The bridge joint wiring 32 can be formed by the excellent material of the translucency such as ITO as described above.And And bridge joint wiring 32 can also further be set as metal wiring same as wiring 31.In this case, bridge joint wiring 32 can be with Wiring 31 is used in the same manner above-mentioned copper alloy, is formed according to method same as wiring 31.For example, when forming wiring 31, Bridge joint wiring 32 can also be formed simultaneously.
Wiring 31 is applied using the connection terminal (not shown) of its end with to the 1st detecting electrode 23 and the 2nd detecting electrode 24 The control circuit of the outside of the position of making alive or detection touching operation is (not shown) to be electrically connected.
As shown in Figures 1 and 2, in the table configured with the 1st detecting electrode 23 and the transparent substrate 22 of the 2nd detecting electrode 24 Face is configured with the cured film 25 of translucency in a manner of covering wiring 31.Similarly, also to cover the 1st detecting electrode 23 and the 2nd The mode of detecting electrode 24 is configured with cured film 25.Therefore, in the feelings that bridge joint wiring 32 is metal wiring same as wiring 31 Under condition, cured film 25 can also cover wiring 31 and the bridge joint wiring 32 as metal wiring.
Cured film 25 is to proceed as follows patterning and formed: covering wiring in the wiring forming region of touch screen 21 31 and it is protected, and operating area cover the 1st detecting electrode 23 and the 2nd detecting electrode 24 etc. and to its etc. progress Protection.In addition, insulating film 25 is with the connection of the end of the wiring 31 derived from the 1st detecting electrode 23 and the 2nd detecting electrode 24 The mode of terminal exposing (not shown) is patterned and is formed.
In touch screen 21, cured film 25 is as covering wiring 31 and the 1st detecting electrode 23 and the 2nd detecting electrode 24 Protective film and function.Therefore, it can inhibit the removing of 31 self-induced transparency substrate 22 of wiring and realize high reliability.Moreover, can inhibit 1st detecting electrode 23 and the 2nd detecting electrode 24 deteriorate and realize high reliability.
The radiation-sensitive resin composition of implementation form of the invention can be used in the formation of cured film 25.Moreover, Can carry out defined patterning, thus be configured at least part of wiring 31 and the 1st detecting electrode 23 and the 2nd detection On electrode 24.About the radiation-sensitive resin composition of the implementation form of the invention to form cured film 25, later It is described in detail.The radiation-sensitive resin composition of implementation form of the invention be applied to as metal wiring wiring 31 extremely In few a part, is hardened and become the cured film protected to cover it to it.At this point, implementation shape of the invention The radiation-sensitive resin composition of state can not generate the ground such as the bad phenomenons such as wiring 31 of the corrosion as metal wiring and be formed Cured film 25, and the protective film as wiring 31.
Touch screen 21 can be in the formation of the wiring 31 and the 1st detecting electrode 23 and the 2nd detecting electrode 24 of transparent substrate 22 Face, such as the cover film comprising transparent resin is set using the following layer (not shown) comprising acrylic transparent solid (not shown).
Rectangular behaviour is configured in the 1st detecting electrode 23 and the 2nd detecting electrode 24 with the touch screen 21 constituted above Make in region, measures electrostatic capacitance, the change of generated electrostatic capacitance when being operated according to the touching there are the finger of operator etc. Change, can detect the contact position of finger etc..Moreover, touch screen 21 is via electrical with the 1st detecting electrode 23 and the 2nd detecting electrode 24 The wiring 31 of connection and connect, be placed on the displays such as liquid crystal display element or organic EL element, so as to as electronic machine The input unit of the display of device and properly use.
As described above, in the touch screen of implementation form of the invention, the cured film of this implementation form of protection wiring etc. As important constituent element.
Secondly, used in formation to the cured film of the touch screen as the 1st implementation form of the invention, as this The radiation-sensitive resin composition of 2nd implementation form of invention is described in detail.
Implementation form 2.
<radiation-sensitive resin composition>
The cured film of the touch screen of 1st implementation form of the invention can configuration performed in the following way as described above: The wiring is covered on the substrate of the touch screen configured with detecting electrode and the metalliferous wiring of packet, and covers detection electricity Pole.The radiation-sensitive resin composition of 2nd implementation form of the invention is adapted for forming the sense of the cured film of the touch screen Radiation resin composite.
Especially the case where forming the cured film of covering metal wiring etc. on the oxide of the high metal of the reproducibilities such as manganese Under, a part of the cured film is reduced, and is reduced with the adhesion of metal wiring, is generated and matched due to being mixed into for outside moisture Line corrosion.Cured film is formed by by the radiation-sensitive resin composition of the 2nd implementation form of the invention to be difficult to by manganese etc. also Original, therefore the adhesion with metal wiring can be maintained with high level.
The radiation-sensitive resin composition of 2nd implementation form of the invention contains: (A) emulsion (sometimes referred to simply as (A) Ingredient) and the compound of (B) containing alkoxysilane group and the compound hydrolytic condensate at least one (sometimes Referred to as (B) ingredient or (B) compound).Also, it is preferable that other than (A) ingredient and (B) ingredient, it can also containing (C) alkali Soluble resin (sometimes referred to simply as (C) ingredient).
In addition, if the radiation-sensitive resin composition of the 2nd implementation form of the invention does not undermine effect of the invention, Then other than (A) ingredient~(C) ingredient, arbitrary ingredient can be contained.For example, the radioactivity-sensitive resin group of this implementation form Closing object may include (D) antioxidant (sometimes referred to simply as (D) ingredient), (E) polyfunctional monomer (sometimes referred to simply as (E) ingredient), (F) Inorganic oxide particle (sometimes referred to simply as (F) ingredient).
Hereinafter, each ingredient contained in radiation-sensitive resin composition to this implementation form is illustrated.
[(A) emulsion]
(A) emulsion as (A) ingredient is photosensitive material, is the reactive species that reactivity is generated by exposure Material.(A) emulsion is preferably including, for example, at least one of light acid generation and Photoepolymerizationinitiater initiater.
[light acid generation]
As (A) emulsion, preferred light acid generation is the compound that acid is generated by irradiating radioactive ray.Herein, As radioactive ray, for example luminous ray, ultraviolet light, far ultraviolet, electron beam (charged particle beam), X can be used to penetrate as described above Line etc..The radiation-sensitive resin composition of this implementation form includes that light acid generation is used as (A) ingredient, thus this implementation form Radiation-sensitive resin composition can play eurymeric radiation characteristic.
As (A) emulsion, preferred light acid generation generates acid (such as carboxylic acid, sulphur if by irradiating radioactive ray Acid etc.) compound, then be not particularly limited.As light acid generation in the radiation resin combination of this implementation form Contain form, can be compound, that is, photoacid generator form as be described hereinafter, and can for conduct (C) alkali as be described hereinafter can The form of a part of soluble resin or other resins and the light acid generation base that group enters can also be the form of both these.
As (A) emulsion, preferred photoacid generator (also referred to as (A) photoacid generator) can enumerate oxime sulfonate Close object, salt, sulfimine compound, the compound containing halogen, diazomethane compound, sulphones, sulphonic acid ester chemical combination Object, carboxylate compound, quinone di-azido compound etc..
(oxime sulfonate compound)
Above-mentioned oxime sulfonate compound is preferably the compound for containing oxime sulfonate base represented by following formula (1).
[changing 1]
In above-mentioned formula (1), R21It is alkyl, naphthenic base or aryl, part or all of the hydrogen atom of these bases can also be through Substituent group replaces.
In above-mentioned formula (1), R21Alkyl be preferably carbon number be 1~10 straight-chain or branch-like alkyl.R21Alkane The alkoxy or ester ring type base that base can also be 1~10 through carbon number (have bridge-type comprising the side 7,7- dimethyl -2- oxygroup norborny etc. Ester ring type base, preferably bicyclic alkyl etc.) replace.R21Aryl be preferably carbon number be 6~11 aryl, more preferably Phenyl or naphthyl.R21Aryl can also through carbon number be 1~5 alkyl, alkoxy or halogen atom replace.
About the compound containing oxime sulfonate base represented by above-mentioned formula (1), preferred compound can illustrate following Oxime sulfonate compound represented by formula (2).
[changing 2]
In above-mentioned formula (2), R21With the R in above-mentioned formula (1)21Illustrate synonymous.X is alkyl, alkoxy or halogen atom.ml It is 0~3 integer.When ml is 2 or 3, multiple X be may be the same or different.It is 1~4 that alkyl as X, which is preferably carbon number, Straight-chain or branch-like alkyl.
In above-mentioned formula (2), the alkoxy as X is preferably straight-chain or the branch-like alkoxy that carbon number is 1~4.Make Chlorine atom or fluorine atom are preferably for the halogen atom of X.M is preferably 0 or 1.Particularly preferably in above-mentioned formula (2), Ml is l, and X is methyl, and the position of substitution of X is the compound at ortho position.
As the concrete example of above-mentioned oxime sulfonate compound, such as following formula (3-i)~formula (3-v) distinguished table can be enumerated Compound (3-i), compound (3-ii), compound (3-iii), compound (3-iv) and compound (3-v) for showing etc..
[changing 3]
These compounds can be used alone or two or more is applied in combination, can also be with other light acid as (A) ingredient Producing agent is applied in combination.Above compound (3-i) [(5- sulfonyl propyl base oxygroup imino group -5H- thiophene -2- subunit)-(2- first Base phenyl) acetonitrile], compound (3-ii) [(5H- octyl sulfonyl oxygroup imino group -5H- thiophene -2- subunit)-(2- methylbenzene Base) acetonitrile], compound (3-iii) [(camphor sulfonyl oxygroup imino group -5H- thiophene -2- subunit)-(2- aminomethyl phenyl) second Nitrile], compound (3-iv) [(5- p-toluenesulfonyl oxygroup imino group -5H- thiophene -2- subunit)-(2- aminomethyl phenyl) acetonitrile] And compound (3-v) 2- (octyl sulfonyloxyimino) -2- (4- methoxyphenyl) acetonitrile can be used as commercially available product and obtain.
(salt)
Above-mentioned salt can enumerate two benzene base Iodonium salt, triphenyl sulfonium salt, sulfonium salt, benzothiazolium salt, thiophane salt, sulphur Imide compound etc..
Above-mentioned sulfimine compound can for example enumerate N- (trimethyl fluoride sulfonyl oxygroup) succinimide, N- (camphor sulphur Acyloxy) succinimide, N- (4- methyl phenylsulfonyloxy) succinimide, N- (2- trifluoromethyl sulfonyloxy) Succinimide, N- (4- fluorophenyl sulfonyloxy) succinimide, N- (trimethyl fluoride sulfonyl oxygroup) phthalimide, N- (camphor sulfonyloxy) phthalimide, N- (2- trifluoromethyl sulfonyloxy) phthalimide, N- (2- Fluorophenyl sulfonyloxy) phthalimide, N- (trimethyl fluoride sulfonyl oxygroup) diphenylmaleimide, N- (camphor sulphur Acyloxy) diphenylmaleimide etc..
Documented light acid in Japanese Patent Laid-Open 2011-215503 bulletin can be used to generate for other photoacid generators Agent.
The oxime sulfonate compound of (A) photoacid generator discussed above, sulfimine compound, contains halogen at salt The compound of element, diazomethane compound, sulphones, in sulfonate compound and carboxylate compound, from radioactive ray sensitivity, From the viewpoint of dissolubility, preferably oxime sulfonate compound, more preferably containing oxime sulfonic acid represented by above-mentioned formula (1) The compound of alkali.Moreover, oxime sulfonate compound represented by above-mentioned formula (2) can be enumerated more preferably.
Moreover, in the compound containing oxime sulfonate base represented by above-mentioned formula (1), if considering to can be used as commercially available product Acquisition, particularly preferably (5- sulfonyl propyl base oxygroup imino group -5H- thiophene -2- subunit)-(2- aminomethyl phenyl) acetonitrile, (5H- octyl sulfonyl oxygroup imino group -5H- thiophene -2- subunit)-(2- aminomethyl phenyl) acetonitrile, (5- p-toluenesulfonyl oxygroup Imino group -5H- thiophene -2- subunit)-(2- aminomethyl phenyl) acetonitrile, (Asia camphor sulfonyl oxygroup imino group -5H- thiophene -2- Base)-(2- aminomethyl phenyl) acetonitrile, 2- (octyl sulfonyloxyimino) -2- (4- methoxyphenyl) acetonitrile.
Moreover, as (A) photoacid generator, for salt it is also preferred that, more preferably thiophane salt and benzyl Base sulfonium salt, particularly preferably 4,7- bis--n-butoxy -1- naphthalene thiophane fluoroform sulphonate and benzyl -4- hydroxyl Phenyl methyl sulfonium hexafluorophosphate.
(A) photoacid generator is oxime sulfonate compound, salt, sulfimine compound, the compound containing halogen, again In the case where any one of n-formyl sarcolysine hydride compounds, sulphones, sulfonate compound and carboxylate compound, it can be used alone 1 kind, two or more can also be used in mixed way.It is oxime sulfonate compound, salt, sulfimide chemical combination in (A) photoacid generator Appointing in object, the compound containing halogen, diazomethane compound, sulphones, sulfonate compound and carboxylate compound In the case where meaning person, as the content of (A) photoacid generator in the radiation-sensitive resin composition of this implementation form, relatively 0.1 mass parts~10 mass parts, more preferably 1 mass parts~5 mass parts are preferably for 100 mass parts of (B) ingredient. Moreover, the radiation-sensitive resin composition in this implementation form contains the alkali soluble resin of (C) ingredient being described in detail hereinafter In the case where, as the content of above-mentioned (A) photoacid generator such as oxime sulfonate compound, relative to 100 mass parts of (C) ingredient Speech is preferably 0.1 mass parts~10 mass parts, more preferably 1 mass parts~5 mass parts.If above-mentioned (A) photoacid generator Content be above range, then the radioactive ray sensitivity of the radiation-sensitive resin composition of this implementation form can be made to optimize, it is aobvious Show good patterning, to become the cured film for suitably forming this implementation form.
(quinone di-azido compound)
Conduct (A) emulsion of the radiation-sensitive resin composition of this implementation form and preferred photoacid generator in addition to Other than above-mentioned oxime sulfonate compound etc., quinone di-azido compound can also be enumerated.The quinone di-azido compound can be used as light acid Producing agent and particularly preferably use.
Quinone di-azido compound is the quinone di-azido compound that carboxylic acid is generated by irradiating radioactive ray.Two nitrine chemical combination of quinone The condensation product of phenoloid or alcohol compound (hereinafter referred to as " parent nucleus ") and 1,2- naphthoquinones, two nitrine sulfonic acid halide can be used in object.
Above-mentioned parent nucleus can for example enumerate trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxy Benzophenone, (polyhydroxy phenyl) alkane, other parent nucleus etc..
1,2- naphthoquinones, two nitrine sulfonic acid halide is preferably 1,2- naphthoquinones, two nitrine sulfonic acid chloride.1,2- naphthoquinones, two nitrine sulfonic acid chloride Such as 1,2- naphthoquinones, two nitrine -4- sulfonic acid chloride, 1,2- naphthoquinones, two nitrine -5- sulfonic acid chloride can be enumerated etc..In these more preferably 1,2- naphthoquinones, two nitrine -5- sulfonic acid chloride.
In the condensation reaction of phenoloid or alcohol compound (parent nucleus) and 1,2- naphthoquinones, two nitrine sulfonic acid halide, it can be used For the OH radix in phenoloid or alcohol compound, it is preferably equivalent to 30mol%~85mol%, more Preferably it is equivalent to 1,2- naphthoquinones, the two nitrine sulfonic acid halide of 50mol%~70mol%.Condensation reaction can utilize well known method And implement.
These quinone di-azido compounds can be suitable for using 4,4 '-[1- [4- [1- [4- hydroxy phenyl] -1- Methylethyl] benzene Base] ethylidene] bis-phenol (1.0 moles) and 1,2- naphthoquinones, two nitrine -5- sulfonic acid chloride (2.0 moles) condensation product.
These quinone di-azido compounds can be used alone or two or more is applied in combination.
Moreover, can also be with above-mentioned oxime sulfonate compound, salt, sulfimine compound, the compound containing halogen, again N-formyl sarcolysine hydride compounds, sulphones, sulfonate compound and carboxylate compound etc. are applied in combination together.
As the content of the quinone di-azido compound in the radiation-sensitive resin composition of this implementation form, relative to (B) for 100 mass parts of ingredient, preferably 5 mass parts~100 mass parts, more preferably 10 mass parts~50 mass parts. Moreover, the radiation-sensitive resin composition in this implementation form contains the alkali soluble resin of (C) ingredient for being described in detail hereinafter In the case of, as the content of quinone di-azido compound, for 100 mass parts of (C) ingredient, preferably 5 mass parts~ 100 mass parts, more preferably 10 mass parts~50 mass parts.By the way that the content of quinone di-azido compound is set as above-mentioned model It encloses, the irradiation part of radioactive ray and irradiated portion can be made to become relative to the poor solubility for the alkaline aqueous solution for becoming developer solution Greatly, patterning performance can be made to improve.Moreover, the radiation-sensitive resin composition can also will use and resulting cured film Solvent resistance becomes good.
[Photoepolymerizationinitiater initiater]
As (A) emulsion, preferred Photoepolymerizationinitiater initiater (also referred to as (A) Photoepolymerizationinitiater initiater) is induction radioactive ray And the ingredient for the reactive species that the polymerization for generating the compound that can make have polymerism causes.Photoepolymerizationinitiater initiater can for example enumerate light Radical polymerization initiator.
(A) Photoepolymerizationinitiater initiater can for example enumerate O- acyl group oxime compound, acetophenone compound, united imidazole etc.. These compounds can be used alone, and can also be used in mixed way two or more.
The O- acyl group oxime compound of concrete example as (A) Photoepolymerizationinitiater initiater, preferably 1,2- acetyl caproyl 1- [4- (thiophenyl) -2- (O- benzoyl oxime)], ethyl ketone -1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] -1- (O- acetyl oxime), ethyl ketone -1- [9- ethyl -6- (2- methyl -4- tetrahydrofuran base methoxybenzoyl base) -9.H.- carbazole -3- Base] -1- (O- acetyl oxime) or ethyl ketone -1- [9- ethyl -6- { 2- methyl -4- (2,2- dimethyl -1,3- dioxolane base) Methoxybenzoyl base } -9.H.- carbazole -3- base] -1- (O- acetyl oxime).
The acetophenone compound of concrete example as above-mentioned (A) Photoepolymerizationinitiater initiater can for example enumerate α-aminoketone chemical combination Object, alpha-hydroxyacetone compounds.
Japanese Patent Laid-Open 2013-164471 bulletin, Japanese Patent Laid-Open can be used in these (A) Photoepolymerizationinitiater initiaters Documented Photoepolymerizationinitiater initiater in 2012-212114 bulletin, Japanese Patent Laid-Open 2010-85929 bulletin.
The Photoepolymerizationinitiater initiater illustrated as (A) emulsion can be used alone or be used in mixed way two or more.
The content of the Photoepolymerizationinitiater initiater illustrated as (A) emulsion, it is excellent for 100 mass parts of (B) ingredient Choosing is 1 mass parts~40 mass parts, more preferably 5 mass parts~30 mass parts.Moreover, the sense in this implementation form is radiated In the case that linear resin composition contains the alkali soluble resin of (C) ingredient being described in detail hereinafter, relative to (C) ingredient 100 For mass parts, preferably 1 mass parts~40 mass parts, more preferably 5 mass parts~30 mass parts.By by (A) light The content of polymerization initiator is set as 1 mass parts~40 mass parts, even if the radiation-sensitive resin composition of this implementation form exists Under low light exposure, the cured film with high solvent resistance, high rigidity and high density of access can also be formed.
[(B) compound and its hydrolytic condensate containing alkoxysilane group]
(B) ingredient contained in the radiation-sensitive resin composition of this implementation form is that (B) contains alkoxy silane At least one ((B) compound) of the hydrolytic condensate of the compound of base and the compound containing alkoxysilane group.
(B) compound of the radiation-sensitive resin composition of this implementation form contains alkoxysilane group in the molecule. Alkoxysilane group can improve the adhesion to metal oxide by hydrolysis and condensation reaction.
Therefore, (B) ingredient contained in the radiation-sensitive resin composition of this implementation form can be improved use feeling and put Ray resin combination and the adhesion between the metal wiring of cured film and for example above-mentioned touch screen that is formed.
By containing (B) ingredient, the radiation-sensitive resin composition of this implementation form can provide excellent hard of adhesion Change film.The hard of excellent adhesion is shown for the wiring of the above-mentioned touch screen as metal wiring moreover, especially can provide Change film.
(B) ingredient preferably contains carboxyl, methylacryloyl, vinyl, amino, isocyanate group, oxa- cyclopropyl The compound of base isoreactivity functional group and alkoxysilane group.
In (B) ingredient, alkoxysilane group is preferably trimethoxy silane base, dimethoxymethylsilane base, first Oxygroup dimethylsilyl, triethoxysilicane alkyl, diethoxy ethylsilane base, ethyoxyl diethylsilyl etc..
Moreover, the compound with reactive functional group can for example enumerate trimethoxy silane Ji Benjia in (B) ingredient Acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, vinyltrimethoxysilane, γ-isocyanate group propyl-triethoxysilicane, gamma-amino propyl trimethoxy silicane, γ-glycidoxypropyl trimethoxy Base silane, β-(3,4- expoxycyclohexyl) ethyl trimethoxy silane etc..In addition, can also be suitable for using by specific protecting group pair Amino or isocyanate group are protected, by heating the block amino for making protecting group disengaging regenerate amino or isocyanate group Or blocked isocyanate ester group.
The concrete example of compound with block amino or blocked isocyanate ester group and alkoxysilane group can enumerate 3- tri- Ethoxysilane base-N- (1,3- dimethyl-butylidene) propyl amine, gamma-amino propyl trimethoxy silicane amino by front three Compound made of the protection of base silane base, γ-isocyanate group propyl-triethoxysilicane isocyanate group is by monoethanolamine, two Compound made of any one protection of ethanol amine, pyrazoles and methyl ethyl ketone oxime etc..
Moreover, the hydrolytic condensation compound of the above-mentioned compound containing alkoxysilane group can for example be enumerated: by 3- methyl Acryloyloxypropyltrimethoxysilane is rubbed with for 3- methacryloxypropyl trimethoxy silane for 1/4 Your water, the phosphoric acid of 0.05wt% are fitted into flask, and compound made of condensation is hydrolyzed at 60 DEG C.
Moreover, (B) ingredient of the radiation-sensitive resin composition of this implementation form preferably has amino, block ammonia At least one compound of base, isocyanate group and blocked isocyanate ester group.
The content of (B) ingredient in the radiation-sensitive resin composition of this implementation form is preferably set as radiation The 0.1 mass % of mass %~50 in the gross mass of property resin combination, in the alkali soluble resin comprising aftermentioned (C) ingredient In the case where, for 100 mass parts of (C) ingredient, preferably 1 mass parts~50 mass parts are more preferably in 10 mass parts~30 mass parts range.
Include (B) ingredient and making the radiation-sensitive resin composition of this implementation form with the range, can make In the cured film of this implementation form formed with it, the adhesion between the metal wiring of touch screen is improved.
[(C) alkali soluble resin]
The alkali soluble resin ((C) of (C) ingredient contained in the radiation-sensitive resin composition of this implementation form Alkali soluble resin) it is soluble in the resin in basic solvent, it is the resin with alkali-developable.(C) alkali soluble resin is It forms the cured film of touch screen and considers patterning property, but then have no especially if the resin (polymer) with alkali-developable It limits.
For example, it is preferable that (C) alkali soluble resin includes the acrylic resin being selected from by with carboxyl, polyamide and gathers At least one of group composed by siloxanes.
In the case where the radiation-sensitive resin composition of this implementation form contains (C) alkali soluble resin, institute as above It states, for 100 mass parts of (C) alkali soluble resin, (B) ingredient is preferably 1 mass parts~50 mass parts, more preferably Be in 10 mass parts~30 mass parts range.Moreover, the content about (A) ingredient, for oxime sulfonate compound, Salt, sulfimine compound, the compound containing halogen, diazomethane compound, sulphones, sulfonate compound and carboxylic acid In the case where any one of ester compounds, for 100 mass parts of (C) ingredient, preferably 0.1 mass parts~10 matter Measure part, more preferably 1 mass parts~5 mass parts.Moreover, in the case where (A) ingredient is quinone di-azido compound, as it Content, for 100 mass parts of (C) ingredient, preferably 5 mass parts~100 mass parts, more preferably 10 mass parts ~50 mass parts.Moreover, in the case where (A) ingredient is Photoepolymerizationinitiater initiater, as its content, relative to 100 matter of (C) ingredient For measuring part, preferably 1 mass parts~40 mass parts, more preferably 5 mass parts~30 mass parts.
Hereinafter, to as (C) alkali soluble resin and preferably with acrylic resin, polyamide and the poly- silicon of carboxyl The each of oxygen alkane is illustrated in more detail.
[acrylic resin with carboxyl]
It includes with carboxyl that as (C) alkali soluble resin, preferably the acrylic resin with carboxyl, which is preferably, Component units and the Component units with polymerism base.In this case, if comprising with carboxyl Component units with have The Component units of polymerism base, and there is alkali-developable (alkali-soluble), then it is not particularly limited.
Component units with polymerism base are selected from by the Component units with epoxy group and have (methyl) At least one Component units of group composed by the Component units of acryloxy.Acrylic resin with carboxyl passes through packet Containing above-mentioned specific Component units, and being formed has the indurative film of excellent Surface hardened layer and deep, can form the present invention Implementation form cured film.
Component units with (methyl) acryloxy can for example be formed by the following method: make the ring in copolymer Method that oxygroup is reacted with (methyl) acrylic acid, make carboxyl in copolymer with (methyl) acrylate reactions of epoxy group Method, make hydroxyl in copolymer and (methyl) acrylate reactions with isocyanate group method, make in copolymer The method etc. reacted with (methyl) crylic acid hydroxy ester of acid anhydrides position.Particularly preferably make the carboxyl in copolymer in these With the method for (methyl) acrylate reactions with epoxy group.
Comprising the Component units with carboxyl and there is acrylic resin of the epoxy group as the Component units of polymerism base (C1) can be made to be selected from at least one (hereinafter also referred to " (C1) of the group as composed by unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides Compound ") with (C2) containing epoxy group unsaturated compound (hereinafter also referred to " (C2) compound ") copolymerization and synthesize.At this In the case of kind, the acrylic resin with carboxyl becomes comprising as selected from as composed by unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides At least one of group is formed by Component units and is formed by Component units by the unsaturated compound containing epoxy group Copolymer.
Acrylic resin with carboxyl for example can be by a solvent, in the presence of polymerization initiator, containing offer (C2) copolymer compound of (C1) compound of the Component units of carboxyl and Component units of the offer containing epoxy group is provided and is manufactured. Moreover, (C3), which can also further be added, provides the unsaturated compound containing hydroxyl of the Component units containing hydroxyl (below Referred to as " (C3) compound ") and copolymer is made.In addition, in the manufacture of the acrylic resin with carboxyl, can also with it is above-mentioned (C1) (C4) compound is further added together and (provides and is originated from above-mentioned (C1) change for compound, (C2) compound and (C3) compound Close the unsaturated compound of the Component units other than the Component units of object, (C2) compound and (C3) compound) and copolymerization is made Object.Secondly, each compound of (C1)~(C3) is described in detail.
((C1) compound)
(C1) compound can enumerate unsaturated monocarboxylic, unsaturated dicarboxylic, the acid anhydrides of unsaturated dicarboxylic, polybasic carboxylic acid List [(methyl) acryloxyalkyl] ester etc..
Unsaturated monocarboxylic can for example enumerate acrylic acid, methacrylic acid, crotonic acid etc..
Unsaturated dicarboxylic can for example enumerate maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid etc..
The acid anhydrides of unsaturated dicarboxylic can for example enumerate the acid anhydrides etc. of the compound illustrated as above-mentioned dicarboxylic acids.
Acrylic acid, methacrylic acid, maleic anhydride are preferably in these (C1) compounds, from copolyreaction, to alkali Property aqueous solution dissolubility and the easiness of acquisition consider, more preferably acrylic acid, methacrylic acid, maleic anhydride.
These (C1) compounds can be used alone, and can also be used in mixed way two or more.
It (is optionally arbitrary based on (C1) compound and (C2) compound as the use ratio of (C1) compound (C3) compound and (C4) compound) it is total for, the preferably 5 mass % of mass %~40, more preferably 10 matter Measure the mass of %~25 %.By the way that the use ratio of (C1) compound is set as the 5 mass % of mass %~30, it can make that there is carboxyl Acrylic resin optimizes the dissolubility of alkaline aqueous solution, and can form the excellent film of radioactive ray sexuality degree.
((C2) compound)
(C2) compound is the unsaturated compound containing epoxy group.Epoxy group can enumerate oxiranyl (1,2- epoxy Structure) or oxetanylmethoxy (1,3- epoxy construction) etc..
Unsaturated compound with oxiranyl can for example enumerate glycidyl acrylate, Glycidyl methacrylate Glyceride, methacrylic acid -2- methylglycidyl esters, acrylic acid -3,4- epoxy butyl ester, methacrylic acid -3,4- epoxy fourth Ester, acrylic acid -6,7- epoxy heptyl ester, methacrylic acid -6,7- epoxy heptyl ester, α-ethylacrylate -6,7- epoxy heptyl ester, adjacent second Alkenyl benzyl glycidyl ether, vinylbenzyl glycidyl base ether, to vinylbenzyl glycidyl base ether, methyl-prop Olefin(e) acid -3,4- epoxycyclohexanecarboxylate etc..Consider from viewpoints such as the solvent resistances for improving copolyreaction and insulating film etc., these In preferably glycidyl methacrylate, methacrylic acid -2- methylglycidyl esters, methacrylic acid -6,7- ring Oxygen heptyl ester, adjacent vinylbenzyl glycidyl base ether, vinylbenzyl glycidyl base ether, to vinylbenzyl glycidyl Base ether, methacrylic acid -3,4- epoxycyclohexyethylSiOi ester, acrylic acid -3,4- epoxycyclohexyethylSiOi ester etc..
Unsaturated compound with oxetanylmethoxy can for example be enumerated:
3- (acryloyloxymethyl) oxetanes, 3- (acryloyloxymethyl) -2- methy oxetane, 3- (acryloyloxymethyl) -3- Ethyloxetane, 3- (acryloyloxymethyl) -2- phenyl oxetanes, 3- (2- third Alkene trimethylammonium) oxetanes, 3- (2- acryloyl-oxyethyl) -2- Ethyloxetane, 3- (2- acryloxy Ethyl) acrylate such as -3- Ethyloxetane, 3- (2- acryloyl-oxyethyl) -2- phenyl oxetanes；
3- (methacryloxymethyl) oxetanes, 3- (methacryloxymethyl) -2- methyl oxa- ring Butane, 3- (methacryloxymethyl) -3- Ethyloxetane, 3- (methacryloxymethyl) -2- phenyl oxygen Azetidine, 3- (2- methacryloxyethyl) oxetanes, 3- (2- methacryloxyethyl) -2- ethyl oxygen Azetidine, 3- (2- methacryloxyethyl) -3- Ethyloxetane, 3- (2- methacryloxyethyl) - Methacrylates such as 2- phenyl oxetanes, 3- (2- methacryloxyethyl) -2,2- difluoro oxetanes etc..
Glycidyl methacrylate, methacrylic acid -3,4- epoxy basic ring are preferably in these (C2) compounds Own ester, 3- (methacryloxymethyl) -3- Ethyloxetane.These (C2) compounds can be used alone, can also be by 2 Kind or more be used in mixed way.
It (is optionally arbitrary based on (C1) compound and (C2) compound as the use ratio of (C2) compound (C3) compound and (C4) compound) it is total for, the preferably 5 mass % of mass %~60, more preferably 10 matter Measure the mass of %~50 %.By the way that the use ratio of (C2) compound is set as the 5 mass % of mass %~60, can be formed with excellent Hardenability etc. this implementation form cured film.
((C3) compound)
(C3) compound can enumerate (methyl) acrylate with hydroxyl, (methyl) acrylic acid with phenolic hydroxyl group Ester, hydroxy styrenes.
Acrylate with hydroxyl can enumerate 2-Hydroxy ethyl acrylate, acrylic acid -3- hydroxy propyl ester, acrylic acid -4- Hydroxybutyl, acrylic acid -5- hydroxyl pentyl ester, the own ester of acrylic acid -6- hydroxyl etc..
As the use ratio of (C3) compound, based on (C1) compound, (C2) compound and (C3) compound (depending on needing To be arbitrary (C4) compound) it is total for, the preferably 1 mass % of mass %~30, more preferably 5 mass %~ 25 mass %.
((C4) compound)
(C4) compound is if the unsaturated chemical combination other than above-mentioned (C1) compound, (C2) compound and (C3) compound Object, then there is no particular restriction.(C4) compound can for example enumerate methacrylic acid chain-like alkyl ester, methacrylic acid cyclic alkyl Ester, acrylic acid chain-like alkyl ester, acrylic acid cyclic alkyl ester, aryl methacrylate, benzyl acrylate, unsaturated dicarboxyl Acid diesters, maleimide compound, unsaturated aromatic compound, conjugated diene, the insatiable hunger with tetrahydrofuran skeleton etc. With compound and other unsaturated compounds etc..
These (C4) compounds can be used alone, and can also be used in mixed way two or more.
As the use ratio of (C4) compound, (and appointed based on (C1) compound, (C2) compound and (C4) compound (C3) compound of meaning) it is total for, preferably 10 mass of mass %~80 %.
[polyamide]
(C) alkali soluble resin can be enumerated using structure represented by the following general formula (M-1) as the polymer of principal component.With logical Structure represented by formula (M-1) is that the polymer of principal component can be become using heating or catalyst appropriate with acid imide Ring, oxazole ring, other cyclic structures polymer.Preferably the polyamic acid of polyimide precursor or poly amic acid ester or The polyhydroxyamide of person's polybenzoxazoles precursor.Due to becoming cyclic structure, the tremendous raising of heat resistance, solvent resistance.Herein, So-called principal component is to indicate to have structure represented by the general formula (M-1) of the 50mol% or more of all structural units of polymer In n structural unit.Preferably contain 70mol% or more, more preferably contains 90mol% or more.
[changing 4]
In above-mentioned general formula (M-1), R1It indicates that carbon number is 2 or more divalent~8 valences organic group, indicates the constituent of acid. R1Acid as divalent can enumerate terephthalic acid (TPA), M-phthalic acid, diphenyl ether dicarboxylic acid, naphthalene dicarboxylic acids, bis- (carboxyl phenyls) The aromatic dicarboxylic acids such as propane, aliphatic dicarboxylic acids such as cyclohexane dicarboxylic acid, adipic acid etc..R1Acid as trivalent can be enumerated partially Tricarboxylic acids such as benzenetricarboxylic acid, trimesic acid etc..R1Acid as tetravalence can enumerate Pyromellitic Acid, benzophenone tetrabasic carboxylic acid, The aromatic tetracarboxylic acids such as biphenyltetracarboxyacid acid, diphenyl ether tetrabasic carboxylic acid, diphenyl sulfone tetrabasic carboxylic acid, butane tetracarboxylic acid, pentamethylene tetrabasic carboxylic acid Etc. aliphatic tetrabasic carboxylic acid, 2 hydrogen atoms of the carboxyl of these compounds become methyl or the diester compound of ethyl etc..Moreover, The acid that hydroxyl phthalic, hydroxyl trimellitic acid etc. have hydroxyl can also be enumerated.These sour components can also be used 2 kinds with On, it preferably include the residue of the tetrabasic carboxylic acid of 1mol%~40mol%.Moreover, from for alkaline-based developer dissolubility or From the aspect of photosensitive, preferably there is the residue of the acid of hydroxyl comprising 50mol% or more.
As R1, from from the aspect of heat resistance, preferably there is aromatic ring, more preferably carbon number is 6~30 Trivalent or tetravalence organic group.
In general formula (M-1), R2It indicates that carbon number is 2 or more divalent~8 valences organic groups, indicates the constituent of diamines. From from the aspect of heat resistance, preferably R2With aromatic ring.The specific example of diamines can enumerate phenylenediamine, diamino Diphenyl ether, amino-benzene oxygen benzene, diaminodiphenyl-methane, diamino-diphenyl sough, bis- (trifluoromethyl) benzidine, double (aminophenoxy phenyl) propane, bis- (aminophenoxy phenyl) sulfones, bis- (amino-hydroxy-phenyl) hexafluoropropane, diamino two Hydroxy pyrimidine, diamino dihydroxy-pyridine, hydroxyl-diamino-pyrimidine, diaminophenol, dihydroxybiphenyl amine, diaminobenzene first The hydrogen compound or aliphatic ring that are replaced by alkyl or halogen atom of acid, diamino terephthalic acid (TPA), these aromatic rings Hexamethylene diamine, methylenebiscyclohexylamine, hexamethylene diamine etc..
The R of general formula (M-1)3And R4Any monovalent organic radical identical also different, expression hydrogen or carbon number are 1~20 can be distinguished.From For alkaline-based developer dissolubility, with from the aspect of the stability of solution of resulting photosensitive polymer combination, preferably It is R3And R4Each 10mol%~90mol% be hydrogen.In addition, more preferably R3And R4Contain at least more than one respectively The monovalent hydrocarbon that carbon number is 1~16, other are hydrogen atom.
Moreover, 1 and m of general formula (M-1) indicates the number of carboxyl or ester group, 0~2 integer is indicated.Preferably 1 or 2. The p and q of general formula (M-1) indicate 0~4 integer, p+q > 0.The n of general formula (M-1) indicates the repeat number of the structural unit of polymer, It is 10~100000 range.If n, less than 10, the dissolubility that there are polymer in alkaline-based developer excessively becomes larger, fail The case where obtaining the contrast of exposure portion and unexposed portion and desired pattern can not be formed.On the other hand, if n is greater than 100000, then dissolubility of the polymer in alkaline-based developer excessively becomes smaller, and exposure portion does not dissolve simultaneously, can not be formed desired Pattern.From the aspect of deliquescent in alkaline-based developer of auto polymerization object, n is preferably 1000 hereinafter, more preferably 100 Below.Moreover, n is preferably 20 or more from from the aspect of elongation raising.
[polysiloxanes]
As (C) alkali soluble resin, preferred polysiloxanes is the poly- silicon oxygen with free-radical reactive functional group Alkane.In the case where polysiloxanes is the polysiloxanes with free-radical reactive functional group, if with siloxanes key The main chain or side chain of the polymer of compound have free-radical reactive functional group's, then are not particularly limited.In such case Under, polysiloxanes can be hardened by free radical polymerization, curing shrinkage can be suppressed to minimum limit.Free-radical reactive function Base can for example enumerate the unsaturated organic group such as vinyl, Alpha-Methyl vinyl, acryloyl group, methylacryloyl, styryl. From successfully carrying out sclerous reaction consideration, preferably with acryloyl group or methylacryloyl in these.
Polysiloxanes as (C) alkali soluble resin is preferably the hydrolytic condensate of hydrolysable silanes compound.Structure Being preferably at the hydrolysable silanes compound of polysiloxanes includes hydrolysable silanes chemical combination represented by (s1) following formula (S-1) Hydrolysable silanes compound represented by object (hereinafter also referred to (s1) compound) and (s2) following formula (S-2) is (hereinafter also referred to (s2) compound) hydrolysable silanes compound.
[changing 5]
[changing 6]
In above-mentioned formula (S-1), R11It is the alkyl that carbon number is 1~6.R12It is organic comprising free-radical reactive functional group Base.P is 1~3 integer.Wherein, in R11And R12In the case where multiple, multiple R11And R12Independently.
In above-mentioned formula (S-2), R13It is the alkyl that carbon number is 1~6.R14It is hydrogen atom, the alkyl that carbon number is 1~20, carbon number For 1~20 fluorinated alkyl, phenyl, tolyl, naphthalene, epoxy group, amino or isocyanate group.N is 0~20 integer.Q is 0~3 integer.Wherein, in R13And R14In the case where multiple, multiple R13And R14Independently.
In the present invention, so-called " hydrolysable silanes compound " typically refers to the compound with following base: by urging in nothing Agent, excessive water coexisting under, heated within the temperature range of room temperature (about 25 DEG C)~about 100 DEG C, hydrolyzable generates silicon The base of alcohol radical or the base that silicone condensation object can be formed.The hydrolysable silanes represented by above-mentioned formula (S-1) and above-mentioned formula (S-2) In the hydrolysis of compound, in polysiloxanes generated, a part of water-disintegrable base is remaining with unhydrolysed state.This Place, so-called " water-disintegrable base " refers to above-mentioned hydrolyzable and generates the base of silanol group or can form the base of silicone condensation object.Moreover, In the radiation-sensitive resin composition of this implementation form, a part of hydrolysable silanes compound is with a part in its molecule Or the whole unhydrolysed state of water-disintegrable base and the state not contracted with other hydrolysable silanes compounds combined into monomer it is residual It deposits.In addition, " hydrolytic condensate " is to indicate to hydrolyze contracting made of a part of silanol group of the silane compound of hydrolysis is condensed each other Close object.Hereinafter, (s1) compound and (s2) compound are described in detail.
((s1) compound)
In above-mentioned formula (S-1), R11It is the alkyl that carbon number is 1~6.R12It is organic comprising free-radical reactive functional group Base.P is 1~3 integer.Wherein, in R11And R12In the case where multiple, multiple R11And R12Independently.
As above-mentioned R11Carbon number be 1~6 alkyl can for example enumerate methyl, ethyl, n-propyl, isopropyl, butyl etc.. From from the viewpoint of the easiness of hydrolysis, preferably methyl, ethyl in these.It is examined from the viewpoint that condensation reaction is hydrolyzed Consider, above-mentioned p is preferably 1 or 2, more preferably 1.
Organic group with free-radical reactive functional group can enumerate 1 or more hydrogen atom through above-mentioned free-radical reactive Functional group replace straight-chain, branch-like or cricoid carbon number be 1~12 alkyl, carbon number be 6~12 aryl, carbon number 7 ~12 aralkyl etc..In same intramolecular, there are multiple R12When, these are independently.Moreover, R12Represented organic group There can be hetero atom.Such organic group can for example enumerate ether, ester group, thioether group etc..
It is excellent in these (s1) compounds from marresistance etc. can be reached with high level and condensation reaction gets higher consideration Choosing is vinyltrimethoxysilane, to styryl triethoxysilane, 3- methacryloxypropyl trimethoxy Silane, 3- acryloyloxypropyltrimethoxysilane, 3- methacryloxypropyl, 3- acryloyl-oxy Base propyl-triethoxysilicane, 3- (trimethoxy silane base) propylsuccinic anhydride.
((s2) compound)
In above-mentioned formula (S-2), R13It is the alkyl that carbon number is 1~6.R14It is hydrogen atom, the alkyl that carbon number is 1~20, carbon number For 1~20 fluorinated alkyl, phenyl, tolyl, naphthalene, epoxy group, amino or isocyanate group.N is 0~20 integer.Q is 0~3 integer.Wherein, in R13And R14Respectively become it is multiple in the case where, multiple R13And R14Independently.
As above-mentioned R13Carbon number be 1~6 alkyl can for example enumerate methyl, ethyl, n-propyl, isopropyl, butyl etc.. From from the viewpoint of the easiness of hydrolysis, preferably methyl, ethyl in these.It is examined from the viewpoint that condensation reaction is hydrolyzed Consider, in above-mentioned formula (S-2), q is preferably 1 or 2, more preferably 1.
In above-mentioned R14Be above-mentioned carbon number be 1~20 alkyl in the case where, the alkyl can for example enumerate methyl, ethyl, N-propyl, isopropyl, normal-butyl, sec-butyl, tert-butyl, n-pentyl.Preferably carbon number be 1~10 alkyl, more preferably It is the alkyl that carbon number is 1~3.
The silane compound replaced through 4 water-disintegrable bases is preferably in these (s2) compounds, through 1 non-hydrolyzable base The silane compound replaced with 3 water-disintegrable bases, the silicon more preferably replaced through 1 non-hydrolyzable base and 3 water-disintegrable bases Hydride compounds.Particularly preferred hydrolysable silanes compound can for example enumerate tetraethoxysilane, methyltrimethoxysilane, first Ethyl triethoxy silicane alkane, three isopropoxy silane of methyl, three butoxy silane of methyl, phenyltrimethoxysila,e, tolyl three Methoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane, three isopropoxy silane of ethyl, three butoxy of ethyl Silane, butyl trimethoxy silane, γ-glycidoxypropyltrimewasxysilane, naphthalene trimethoxy silane, γ-ammonia Base propyl trimethoxy silicane and γ-isocyanate group propyl trimethoxy silicane.Such hydrolysable silanes compound can be independent It is applied in combination using or by two or more.
Mixing ratio about above-mentioned (s1) compound and (s2) compound, it is generally desirable to which (s1) compound is more than 5mol%. In the case where (s1) compound is 5mol% situation below, there are following tendencies: exposure sensitivity when forming cured film is low, further Make the reduction such as marresistance of resulting protective film.
(hydrolytic condensation of (s1) compound and (s2) compound)
As the condition for being condensed above-mentioned (s1) compound and (s2) compound hydrolysis, if to (s1) compound and (s2) At least part of compound is hydrolyzed, and water-disintegrable base is converted to silanol group, generates condensation reaction, then has no special limit It is fixed, it can implement as described below as an example.
The solvent for being supplied to hydrolytic condensation can for example enumerate alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetic acid esters, diethyl Glycol alkyl ether, propylene-glycol monoalky lether, propylene-glycol monoalky lether acetic acid esters, propylene-glycol monoalky lether propionic ester, aromatic hydrocarbon Class, ketone, other esters etc..These solvents can be used alone or be used in combination of two or more and use.
Ethylene glycol alkyl ether acetic acid esters, diethylene glycol alkyl ether, propylene-glycol monoalky lether, third are preferably in these solvents Glycol monoalkyl ether acetic acid esters, methoxyacetic acid butyl ester, particularly preferably diethylene glycol dimethyl ether, diethylene glycol ethyl methyl Ether, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, methoxyacetic acid butyl ester.
Hydrolysis-condensation reaction preferably carries out in the presence of the catalyst such as acid catalyst, base catalyst or alkoxide.
The molecular weight distribution " Mw/Mn " of above-mentioned hydrolytic condensate is preferably 3-0 hereinafter, more preferably 2.6 or less.It is logical It crosses and the Mw/Mn of the hydrolytic condensate of (s1) compound and (s2) compound is set as 3.0 is formed by the aobvious of film hereinafter, can be improved Shadow.The radiation-sensitive resin composition of this implementation form comprising polysiloxanes can develop remaining generation less in development Ground is readily formed desired pattern form.
[(D) antioxidant]
(D) antioxidant of (D) ingredient contained in the radiation-sensitive resin composition of this implementation form becomes suppression System is formed by the ingredient of cured film oxidation.
As described above, wiring possessed by the touch screen of the 1st implementation form of the invention is that the metal containing following person is matched Line: the 1st layer comprising copper, the oxide comprising above-mentioned 2nd metallic element other than copper and at least one to cover described 1st layer Partial mode and constitute the 2nd layer.Therefore, the sense by this implementation form is being used in a manner of the wiring for covering touch screen Radiation resin composite and in the case where the cured film that is formed, exist due to the metal oxide in wiring surface, example The oxide of such as manganese and aoxidize, thus deterioration worry.It therefore, can be in the radiation-sensitive resin composition of this implementation form In contain (D) antioxidant be used as (D) ingredient.The radiation-sensitive resin composition of this implementation form contains (D) antioxidant, Even if the cured film for the implementation form of the invention that it thus will be used and formed is as the touching for covering implementation form of the invention It touches the film of the wiring of screen and uses, also can inhibit its oxidation, to inhibit to deteriorate.
(D) ingredient of the radiation-sensitive resin composition of this implementation form can enumerate phenolic antioxidant, sulphur system antioxygen Agent, amine antioxidant etc., particularly preferably phenolic antioxidant.
Above-mentioned phenolic antioxidant can specifically be enumerated: styrenated phenol, 2,6-Di-tert-butyl-4-methylphenol, 2,6- di-t-butyl-paraethyl phenols, 2,4,6- tri--tert-butyl phenols, butylated hydroxyanisole (BHA), 1- hydroxy-3-methyl -4- Cumene, single t-butyl-p-cresol, single tert-butyl-metacresol, 2,4- dimethyl -6- tert-butyl phenol, butylated bisphenol A, 2,2 '-methylene-bis--(4- methyl-6-tert-butylphenol), 2,2 '-methylene-bis--(4- ethyl -6- tert-butyl phenol), 2, 2 '-methylene-bis- (4- methyl-6-tert nonyl phenol), 2,2 '-isobutylidenes-bis--(4,6- xylenol), 4,4 '-Aden Base-is bis--(3 methy 6 tert butyl phenol), 4,4 '-methylene-bis--(2,6- di-t-butyl phenol), 2,2- sulfenyl-bis-- (4- methyl-6-tert-butylphenol), 4,4 '-sulfenyls-bis--(3 methy 6 tert butyl phenol), 4,4 '-sulfenyls-bis--(2- first Base -6- butylphenol), 4,4 '-sulfenyls-bis--(6- tert-butyl -3- methylphenol), bis- (3- methyl -4- hydroxyl -5- tert-butyls Benzene) thioether, 2,2- sulfenyl [bis- -3- of diethyl-(3,5- di-t-butyl -4- hydroxyl phenol) propionic ester], bis- [3,3- bis- (4 ' - Hydroxyl -3 '-tert-butyl phenol) butyric acid] diol ester, bis- [2- (2- hydroxy-5-methyl base -3- tert-butyl benzene) -4- methyl-6-tert-butyls Base phenyl] terephthalate, 1,3,5- tri- (3 ', 5 ' -4 '-hydroxybenzyl of di-t-butyl -) isocyanuric acid esters, N,-six Asia N ' Methyl-bis- (3,5- di-t-butyl 4- hydroxyls-hydroxy amide), N- octadecyl -3- (4 '-hydroxyls -3 ', 5 '-di-t-butyl benzene Phenol) propionic ester, four [methylene-(3 ', 5 '-di-t-butyl -4- hydroxy phenyl) propionic ester] methane, 1,1 '-bis- (4- hydroxy benzenes Base) hexamethylene, list (α-methylbenzyl) phenol, two (α-methylbenzyl) phenol, three (α-methylbenzyl) phenol, bis- (2 '-hydroxyls Base -3 '-tert-butyl -5 '-methylbenzyl) -4- methyl-phenol, 2,5-, bis--tertiary pentyl hydroquinone, 2,6-, bis--butyl-α-two The diethyl ester of methylamino-paracresol, 2,5- di-t-butyl hydroquinone, 3,5- di-t-butyl -4- hydroxybenzyl phosphate Deng.
These (D) antioxidants can be used alone or two or more is applied in combination.
As the content of (D) antioxidant, contained in the radiation-sensitive resin composition relative to this implementation form Resin component total 100 mass parts for, preferably 0.1 mass parts~10 mass parts, particularly preferably 0.2 mass Part~5 mass parts.
[(E) polyfunctional monomer]
(E) polyfunctional monomer of (E) ingredient contained in the radiation-sensitive resin composition as this implementation form, Preferably contain together with the Photoepolymerizationinitiater initiater of the example as above-mentioned (A) ingredient.By containing as (A) ingredient Photoepolymerizationinitiater initiater and (E) polyfunctional monomer, the radiation-sensitive resin composition of this implementation form can be used as with minus sense The radiation-sensitive resin composition of photosensitiveness and properly use.
(E) polyfunctional monomer is preferably allylation cyclohexyl two (methyl) acrylate, 2,5- hexylene glycol, two (first Base) acrylate, 1,3-BDO two (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, 1,3-BDO Two (methyl) acrylate, ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, 1,6- hexylene glycol two (methyl) acrylate, 1,9- nonanediol two (methyl) acrylate, 1,10- decanediol two (methyl) acrylate, three second two Alcohol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, glycerine two (methyl) acrylate, methoxylation ring Hexyl two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, polypropylene glycol Two (methyl) esters of acrylic acid such as two (methyl) acrylate, three glycerine two (methyl) acrylate；
Pentaerythrite three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane ring Ethylene Oxide (Propylene oxide, PO) is modified three (methyl) acrylate, trimethylolpropane ethylene oxide (Ethylene Oxide, EO) it is modified three (methyl) acrylate, benzyl mercaptan three (methyl) acrylate, two-trimethylolpropanes four (methyl) 3 functions such as acrylate, dipentaerythritol monohydroxy five (methyl) acrylate, dipentaerythritol six (methyl) acrylate with On (methyl) esters of acrylic acid；Etc. multifunctional (methyl) acrylates.
In the radiation-sensitive resin composition of this implementation form, as the content of (E) polyfunctional monomer, from for exposing From the aspect of the sensitivity of the light of light, resin contained in the radiation-sensitive resin composition relative to this implementation form at For total 100 parts by weight divided, preferably 10 weight % or more are more preferably in 50 weight of weight %~150 % Range.
[(F) inorganic oxide particle]
The radiation-sensitive resin composition of this implementation form contains alkoxysilane group in addition to (A) emulsion and (B) Compound and the compound hydrolytic condensate at least one other than, can contain (F) inorganic oxide particle as appoint Meaning ingredient.
(F) inorganic oxide particle of (F) ingredient of the radiation-sensitive resin composition as this implementation form can contain Have in radiation-sensitive resin composition, maintains the electric insulating quality of resulting hardening thing, and control as dielectric property Relative dielectric constant.Moreover, inorganic oxide particle also can control cured film refractive index, control cured film the transparency, Inhibit slight crack by mitigating curing shrinkage, improve the purpose of surface hardness of cured film and use.
(F) inorganic oxide particle of the radiation-sensitive resin composition of this implementation form is the inorganic of following oxide Oxide particle, the oxide are comprising selected from as composed by silicon, aluminium, zirconium, titanium, zinc, indium, tin, antimony, strontium, barium, cerium and hafnium The oxide of at least one element of group.
Moreover, the oxide particle of silicon, zirconium, titanium or zinc is preferably in the group, particularly preferably as silicon Silicon dioxide granule, zirconium or the titanyl compound particle or barium titanate (BaTiO of oxide particle3).These can be used alone a kind Or two or more is applied in combination.Moreover, (F) inorganic oxide particle can also be the composite oxide particle of above-mentioned element.It is described Composite oxide particle can for example enumerate barium titanate, strontium titanates etc..Moreover, the electric insulating quality of hardening thing can also not undermined Antimony tin (antimony-tin oxide, ATO), tin indium oxide (indium-tin oxide, ITO), oxygen are used in range Change indium zinc (indium-zinc oxide, IZO) etc..As these inorganic oxide particles, commercially available, such as uncommon love can be used The nano for being melted into limited liability company (C.I.Kasei CO., LTD.) reaches gram (Nanotec) (registered trademark) etc..
(F) shape of inorganic oxide particle is not particularly limited, can for it is spherical be also it is unsetting, can also be hollow Particle, Porous particle, core-shell particle etc..Moreover, utilizing (F) inorganic oxide particle calculated by dynamic light scattering method Volume average particle size be preferably 5nm~200nm, more preferably 5nm~100nm, particularly preferably 10nm~80nm. If the volume average particle size of (F) inorganic oxide particle exists using radiation-sensitive resin composition and gained less than 5nm Cured film hardness reduction anxiety or in the presence of the anxiety of desired relative dielectric constant can not be shown；If more than 200nm, It is got higher there are the mist degree of cured film and the anxiety of decrease in transmission, or there are the anxieties of the flatness variation of cured film.
It as the blending amount of (F) inorganic oxide particle, is not particularly limited, the radiation relative to this implementation form Property resin combination contained in resin component total 100 mass parts for, preferably 1 mass parts~500 mass parts, More preferably 5 mass parts~300 mass parts.If the blending amount of (F) inorganic oxide particle can not be incited somebody to action less than 1 mass parts The above-mentioned Characteristics Control of resulting cured film is in desired range.On the contrary, if the blending amount of (F) inorganic oxide particle is super 500 mass parts are crossed, then the hardenability that there is coating or film reduces, and the anxiety that the mist degree of resulting cured film is got higher.
[(G) solvent and other any ingredients]
The radiation-sensitive resin composition of this implementation form contains alkoxysilane group in addition to (A) emulsion and (B) Compound and the compound hydrolytic condensate at least one other than, (C) alkali soluble resin, (D) antioxygen can be contained Agent, (E) polyfunctional monomer, (F) inorganic oxide particle can further contain (G) solvent and other any ingredients.
In the case where the radiation-sensitive resin composition of this implementation form contains (F) inorganic oxide particle, pass through Further contain dispersing agent and is used as (G) ingredient, it can (F) inorganic oxide uniformly dispersing inside radiation-sensitive resin composition Object particle, can be improved coating.Moreover, the radiation-sensitive resin composition of this implementation form can be improved it is resulting using it Cured film is to the adhesion of substrate etc., in such a way that the characteristics such as relative dielectric constant or refractive index equally become desired value It is controlled.
Documented dispersing agent in Japanese Patent Laid-Open 2011-128469 bulletin can be used in such dispersing agent.
As the solvent of (G) ingredient, preferably in addition to can be by the radiation-sensitive resin composition tune of this implementation form Whole is that can make (A) ingredient and (B) uniform component other than desired solid component concentration and steadily dissolve, and can make (C) Ingredient or as (G) ingredient any other uniform component and steadily dissolve.Moreover, in the radioactivity-sensitive of this implementation form In the case that resin combination contains (F) inorganic oxide particle, it can preferably make described (F) inorganic oxide particle uniform And it is steadily scattered in radiation-sensitive resin composition.Additionally, it is preferable that can make the radiation of this implementation form Property coating and film forming of the resin combination when being coated on substrate improve.That is, as (G) if the solvent of ingredient has such as The upper function is then not particularly limited.
(G) alcohols such as methanol, ethyl alcohol, isopropanol, butanol, octanol can be used in solvent；Ethyl acetate, butyl acetate, lactic acid Ethyl ester, gamma-butyrolacton, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, 3- methoxy methyl propionate, 3- ethoxy The esters such as base ethyl propionate；The ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether；Dimethylformamide, The amides such as n,N-dimethylacetamide, N-Methyl pyrrolidone；Acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone etc. Ketone；Benzene,toluene,xylene, ethylo benzene etc. are aromatic hydrocarbon.(G) solvent can be used a kind or be mixed with two or more.
As (G) ingredient surfactant can in order to improve this implementation form radiation-sensitive resin composition painting Cloth lowers crawling, improves the developability of radioactive ray irradiation portion and be added.The example of preferred surfactant can Enumerate fluorine system surfactant and silicone-based surfactant.Japanese Patent Laid-Open 2011- can be used in such surfactant Documented dispersing agent in No. 128469 bulletins.
As the blending amount used of surfactants as in the case where (G) ingredient, the sense relative to this implementation form is put For total 100 mass parts of resin component contained in ray resin combination, preferably 0.01 mass parts~10 Mass parts, more preferably 0.05 mass parts~5 mass parts.By by the blending amount of surfactant be set as 0.01 mass parts~ 10 mass parts can be such that the coating of the radiation-sensitive resin composition of this implementation form optimizes.
<preparation of radiation-sensitive resin composition>
The radiation-sensitive resin composition of this implementation form can be by containing alkane for above-mentioned (A) emulsion and (B) At least one of the hydrolytic condensate of the compound of oxysilane base and the compound is with regulated proportion is mixed and is prepared. Moreover, (A) ingredient, (B) ingredient and (C) ingredient are mixed with regulated proportion in the case where containing (C) alkali soluble resin It closes and prepares.
Implementation form 3.
<manufacture of cured film and touch screen>
In the manufacturing method of the touch screen as the 3rd implementation form of the invention, comprising using above-mentioned this implementation shape The radiation-sensitive resin composition of state and as key step the step of form cured film.In the forming step of the cured film In, carry out the patterning of cured film.Hereinafter, being mainly illustrated to the forming step of the cured film as key step, to this The manufacturing method of the touch screen of implementation form is illustrated.
In the manufacturing method of the touch screen of this implementation form, in order on the substrate configured with detecting electrode and wiring etc. Cured film is formed, preferably at least in the following sequence includes following steps [1]~step [3].
[1] the step of forming the film of radiation-sensitive resin composition of the 2nd implementation form of the invention
[2] the step of radioactive ray being irradiated at least part of film formed in step [1]
[3] the step of developing to the film for having irradiated radioactive ray in step [2]
Hereinafter, being illustrated to each step of above-mentioned [1]~[3].
[1] the step of forming the film of radiation-sensitive resin composition on substrate
In step [1], the radiation-sensitive resin composition of the 2nd implementation form of the invention is coated on substrate.Its It is secondary, (prebake conditions) preferably are heated to coated face, the solvent is removed in the case where solvent is contained in film and Form film.
The substrate transparent substrate excellent preferably with visible light transmission.The example of workable substrate can enumerate glass Glass substrate or resin substrate etc..The concrete example of resin substrate can enumerate polyethylene terephthalate film, poly terephthalic acid fourth Diester film, polyethylene film, polypropylene screen, poly (ether sulfone) film, polycarbonate membrane, polypropylene sorrel, polychloroethylene film, polyimides Film, the ring-opening polymerization polymer film of cyclic olefin and film comprising its hydride etc..
Then, detecting electrode and wiring are formed on the substrate.Detecting electrode is formed using well known method. That is, forming the transparent conductive film comprising ITO or packet using well known method on above-mentioned glass substrate or resin substrate After transparent conductive film containing indium oxide and zinc oxide etc., in the case of necessary, it can carry out using photolithographic etching and shape At.
Moreover, can also be formed according to the above method about the wiring on substrate.That is, for example using electric field plating method, Dissolve the plating methods such as plating method, the physical vapor depositions such as vacuum vapour deposition, sputtering method and above-mentioned copper alloy is formed on substrate.And And well known patterning method is used together by the forming method with copper alloy, it can get the Wiring pattern comprising copper alloy, By heating to it, wiring can be formed on substrate.
As the coating method of radiation-sensitive resin composition, it is not particularly limited.Such as spray-on process, roller coating can be used The suitable method such as method, method of spin coating (spin-coating method), gap mold coating method, stick coating method, ink-jet method.It is special in these coating methods It You Xuanshi not spin-coating method or gap mold coating method.The condition of prebake conditions is different because of the type of each ingredient, allotment ratio etc., preferably Be to be carried out 1 minute~10 minutes or so at 70 DEG C~120 DEG C.
[2] the step of radioactive ray being irradiated at least part of film
In step [2], at least part of the film on substrate formed in step [1] irradiation radioactive ray (with It is lower also referred to as to expose).In this case, when being exposed to a part of film, usually via have suitably form touch The photomask of the predetermined pattern of the cured film of screen and be exposed.As radioactive ray used in exposure, such as can be used can Light-exposed line, ultraviolet light, far ultraviolet, electron beam, X-ray etc..In these radioactive ray be preferably wavelength be in 190nm~ The radioactive ray of the range of 450nm, the particularly preferably radioactive ray of the ultraviolet light comprising 365nm.
Light exposure in step [2] is to utilize illumination photometer (OAI mode1356, OAI optics affiliated company (OAI Optical Associates Inc.) manufacture) and measure the wavelength of radioactive ray for the value of the intensity of 365nm, preferably 100J/m2~10000J/m2, more preferably 500J/m2~6000J/m2。
[3] development step
In step [3], by developing to the film after exposing obtained in step [2], unwanted portion is removed Divide (is the irradiation part of radioactive ray in the case where the film of radiation-sensitive resin composition is eurymeric.The minus the case where Down it is the irradiated portion of radioactive ray), form defined pattern.
As developer solution used in development step, it is preferred to use the aqueous solution comprising alkali (alkali compounds) Alkaline-based developer.The example of alkali can enumerate the inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium metasilicate, sodium metasilicate, ammonia； Quarternary ammonium salts such as tetramethylammonium hydroxide, tetraethyl ammonium hydroxide etc..
Moreover, water-miscible organic solvents or the tables such as methanol, the ethyl alcohol of appropriate amount can also be added in such alkaline-based developer Face activating agent and use.From from the viewpoint of obtaining developability appropriate, the concentration of the alkali in alkaline-based developer preferably can It is set as 0.1 mass % or more, 5 mass % or less.Developing method is for example using covering liquid method, infusion process, oscillation infusion process, spray The suitable method such as method.Developing time different, preferably 10 seconds~180 seconds left sides due to the composition of radiation-sensitive resin composition It is right.After such development treatment, such as the flowing water carried out 30 seconds~90 seconds cleans, and then utilizes such as compressed air or compression Nitrogen carries out air-dried, thus can form desired pattern.
The transparency as described above by the cured film on step [1]~step [3] formation substrate is high, and to protect The mode of shield detecting electrode and wiring functions.
In addition, optionally cured film can also be made further to harden by exposure after the development of step [3].Moreover, can also Implement 80 DEG C~280 DEG C heat treatment and replace development after exposure or with exposure be implemented together 80 DEG C~280 DEG C plus Heat treatment.The cured film of higher intensity is carried out and obtained as described above.
The film thickness of cured film is preferably 0.1 μm~8 μm, and more preferably 0.1 μm~6 μm, even more preferably 0.1 μm~4 μm.The transparency of the cured film formed by radiation-sensitive resin composition of the invention is excellent, and for It may make up and be formed by metal wiring on the aforesaid substrate and the substrate of touch screen with excellent adhesion.
As described above, configuring detecting electrode, wiring, cured film, on the substrate with translucency so as to manufacture display The touch screen of the implementation form of the invention of high reliability.
Embodiment
Hereinafter, being described in more detail based on embodiment and to implementation form of the invention, but the present invention is not by reality It applies example and restrictively explains.
<synthesis containing the compound of alkoxysilane group or its hydrolytic condensate>
Synthesis example 1 (synthesis containing the compound of alkoxysilane group or its hydrolytic condensate (B-5))
It is packed into 20 parts by weight of propylene glycol monomethyl ether in the container with blender, is then packed into methyltrimethoxysilane (MTMS) 21 parts by weight, 22 parts by weight of tetraethoxysilane (TEOS), 3- acryloyloxypropyltrimethoxysilane (APTMS) 12 parts by weight and 3- (trimethoxy silane base) propylsuccinic anhydride (TMSPS) 4 parts by weight (MTMS/TEOS/APTMAS/ TMSPS (molar ratio)=50/30/15/5), heating is carried out until solution temperature becomes 60 DEG C.After solution temperature reaches 60 DEG C, 0.1 parts by weight of phosphoric acid, 20 parts by weight of ion exchange water are packed into, heating is carried out until becoming 75 DEG C, is kept for 3 hours.Secondly, cooling To after 45 DEG C, 29 parts by weight of original acid A ester are added as dehydrating agent, carry out stirring in 1 hour.Further solution temperature is set It is 40 DEG C, is evaporated when keeping temperature, thus removes methanol generated in ion exchange water and hydrolytic condensation. Pass through the above polysiloxanes (B-5) for obtaining the hydrolytic condensate as the compound containing alkoxysilane group.It is resulting Polysiloxanes (B-5) is in the state of solution (polymer solution), and solid component concentration is 30 weight %, polystyrene conversion Weight average molecular weight (Mw) is 2500, and molecular weight distribution (dispersion degree) (Mw/Mn) is 2.2.
<synthesis of alkali soluble resin>
Synthesis example 2 (synthesis of alkali soluble resin (C-1))
Be packed into the flask with condenser pipe and blender 2,2 '-azos bis- (2,4- methyl pentane nitriles) 7 parts by weight and 220 parts by weight of diethylene glycol ethyl methyl ether.Then 20 parts by weight of methacrylic acid, glycidyl methacrylate 20 are packed into Parts by weight, 7 parts by weight of 30 parts by weight of styrene, 30 parts by weight of N- N-cyclohexylmaleimide and α-methylstyrenedimer And after carrying out nitrogen displacement, slowly start to stir.The temperature of solution is risen to 70 DEG C, keeps the temperature 5 hours, is thus obtained Obtaining includes the polymer solution of alkali soluble resin (C-1) as copolymer.
The solid component concentration of the polymer solution (refers to polymer weight shared in the total weight of polymer solution Ratio.Similarly hereinafter.) it is 31.0 weight %.Moreover, the polystyrene converted weight average molecular weight of alkali soluble resin (C-1) It (Mw) is 10000, molecular weight distribution (dispersion degree) (Mw/Mn) is 2.5.
Synthesis example 3 (synthesis of alkali soluble resin (C-2))
Under drying nitrogen stream, make bis- (3- amino-4-hydroxylphenyl) hexafluoropropane (central nitre glass (CENTRAL GLASS) company) bis- (3- aminopropyl) the tetramethyl disiloxane 1.24g (0.005 mole) of 29.30g (0.08 mole), 1,3-, 3- amino-phenol (Tokyo chemical conversion industry company) 3.27g (0.03 mole) as end-capping reagent is dissolved in N- methyl -2- pyrrolidines In ketone (hereinafter referred to as NMP) 80g.Bis- (3,4- bis- carboxy phenyl) ether dianhydride (horse nanogram (MANAC) company) 31.2g are added wherein (0.1 mole) and NMP 20g reacts it 1 hour, reaction in 4 hours is then carried out at 50 DEG C.Thereafter, add Add dimethylbenzene 15g, make water azeotropic together with dimethylbenzene on one side, carries out stirring in 5 hours at 150 DEG C on one side.Terminate in stirring Afterwards, solution is put into water 3L and obtains white precipitate.The precipitating is collected by filtration, after carrying out 3 cleanings with water, with 80 DEG C of vacuum drier carries out drying in 20 hours, obtains alkali soluble resin (C-2).
<preparation of radiation-sensitive resin composition>
Embodiment 1
(solid component is scaled 100 mass to the polymer solution comprising polysiloxanes (B-5) obtained in synthesis example 1 Part) in ethyl ketone as (A) ingredient, 1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] -, 1- (O- is added Acetyl oxime) (A-1) 3 mass parts.Secondly, diethylene glycol ethyl methyl is added in such a way that solid component concentration becomes 25 weight % Ether and methyl -3- methoxy propyl acid esters (ratio of components becomes 30/70 (%)), prepare radiation sensitive compositions.
2~embodiment of embodiment 9
Respectively with documented type in table 1 and blending amount use (A) ingredient, (B) ingredient, (C) ingredient, (D) ingredient and (E) ingredient and (F) ingredient as inorganic oxide particle, prepare according to method similarly to Example 1 in addition to this The radiation-sensitive resin composition of 2~embodiment of embodiment 9.
1~comparative example of comparative example 3
(A) ingredient, (C) ingredient and (E) ingredient are used with documented type in table 1 and blending amount respectively, in addition to this The radiation-sensitive resin composition of 1~comparative example of comparative example 3 is prepared according to method similarly to Example 1.
By radiation-sensitive resin composition prepared in 1~embodiment of embodiment 9 and 1~comparative example of comparative example 3 Composition summary sheet is shown in Table 1, and being shown in detail for each ingredient of (A)~(F) is following.In addition, in the composition column of table 1 Comparable ingredient is not used in "-" expression.Moreover, (B) ingredient is slightly denoted as (B) and contains alkoxy in table 1 and the explanation of next The compound of silylation or its hydrolytic condensate.
(A) emulsion
A-1: ethyl ketone, 1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] -, 1- (O- acetyl oxime) (quotient The name of an article: gorgeous good solid (IRGACURE) (registered trademark) OX02, the manufacture of BASF (BASF) company)
A-2:2- (octyl sulfonyloxyimino) -2- (4- methoxyphenyl) acetonitrile (" CGI- of BASF AG 725”)
A-3:4,4 '-[1- [4- [1- [4- hydroxy phenyl] -1- Methylethyl] phenyl] ethylidene] bis-phenols (1.0 moles) with The condensation product of 1,2- naphthoquinones, two nitrine -5- sulfonic acid chloride (2.0 moles)
(B) containing the compound of alkoxysilane group or its hydrolytic condensate
B-1:3- glycidoxypropyltrimewasxysilane (trade name: Sa Laaisi (Sila-Ace) (registrar Mark) manufacture of S510, JNC company)
B-2:3- isocyanate group propyl trimethoxy silicane (trade name: KBE-9007, chemical industrial company of SHIN-ETSU HANTOTAI system It makes)
B-3:3- triethoxysilicane alkyl-N- (1,3- dimethyl-butylidene) propyl amine (trade name: KBE-9103, SHIN-ETSU HANTOTAI Chemical industrial company's manufacture)
The hydrolytic condensate of B-4: γ-methacryloxypropyl trimethoxy silane
The hydrolytic condensate of B-5:MTMS/TEOS/APTMS/TMSPS=50/30/15/5mol%
(C) alkali soluble resin
C-1: methacrylic acid/glycidyl methacrylate obtained in synthesis example 2/styrene N- cyclohexyl Malaysia Acid imide=20/20/30/30wt% copolymer
C-2: resin obtained in synthesis example 3
(D) antioxidant
D-1: sulphur di ethylene bis [3- (3,5- di-t-butyl -4- hydroxy phenyl) propionic ester] (trade name: easy fine jade Northey (IRGANOX) (registered trademark) 1035, the manufacture of Ciba limited liability company)
D-2: pentaerythrite=tetra- [3- (3,5- di-t-butyl -4- hydroxy phenyl) propionic ester] (trade name: easy fine jade Northey (IRGANOX) (registered trademark) 1010, the manufacture of Ciba limited liability company)
D-3: three (2,4- di-t-butyl phenyl) phosphite esters (trade name: Ai Di Coase tower wave (Adekastab) (registration Trade mark) 2112, the manufacture of Ai Dike (ADEKA) company)
(E) polyfunctional monomer
E-1: the mixture (molar ratio 50/50) of dipentaerythritol hexaacrylate and Dipentaerythritol Pentaacrylate (trade name: DPHA, Japanese chemical drug corporation are made)
(F) inorganic oxide particle
F-1:ZrO2Colloidal sol (trade name: ID191, the manufacture of Supreme Beingization (Tayca) limited liability company)
<evaluation of cured film>
Embodiment 10
Using radiation-sensitive resin composition prepared in 1~embodiment of embodiment 9 and 1~comparative example of comparative example 3, Cured film is formed as described below, carries out the evaluation of characteristic and its is compared.
Radioactivity-sensitive resin prepared in 1~embodiment of embodiment 9 and 1~comparative example of comparative example 3 is indicated in table 1 The composition of composition, and summarize the evaluation result for indicating the cured film manufactured using these.
[evaluation of transmissivity and heat resistant transparent]
On glass substrate (" healthy and free from worry 7059 " (Corning Incorporated's manufacture)), 1~embodiment of spin coater coating Examples 9 is used And it is carried out 2 minutes on hot plate, at 90 DEG C after prepared radiation-sensitive resin composition in 1~comparative example of comparative example 3 Prebake conditions and form film.Secondly, PLA-501F exposure machine (the super-pressure mercury manufactured using Canon, Inc. Lamp) it is exposed, the tetramethylammonium hydroxide aqueous solution using 0.4 mass % develops.30 are further carried out at 230 DEG C Minute heating, the cured film for being 2.0 μm thus to obtain film thickness.About the glass substrate for being formed with the cured film, light splitting is used Photometer " 150-20 type dual-beam (Double Beam) photometer " (Hitachi Co., Ltd's manufacture) and measure wave The light transmittance of the range of a length of 400nm~800nm evaluates the range that wavelength is 400nm~800nm about each glass substrate The minimum (also referred to as minimum light transmission rate) of light transmittance.Moreover, using the light transmittance that wavelength is 400nm as evaluation criteria, in wave In the case that the light transmittance of a length of 400nm is 85% or more, it is judged as that transmittance characteristics are especially good.
Evaluation result is set as " transmissivity (%) " and summarizes and be shown in aftermentioned table 1.Further use above-mentioned be formed with The substrate of each cured film carries out heating in 3 hours in cleaning oven, at 250 DEG C, uses spectrophotometer (Hitachi 150-20 type dual-beam (Double Beam) photometer of limited liability company's manufacture) and the wavelength of measurement heating front and back is After the light transmittance (%) of 400nm, " heat resistant transparent (%) " is calculated according to following formula.It is 10% or less in described value When, it is judged as that the heat resistant transparent of protective film is good.
The light transmittance (%) after light transmittance (%)-heating before heat resistant transparent (%)=heating
Using prepared radiation-sensitive resin composition in 1~embodiment of embodiment 9, resulting cured film is in wave Heat resistant transparent under a length of 400nm is 10% hereinafter, especially good.Use sense prepared in 1~comparative example of comparative example 3 It is 10% or more that radiation resin composite and resulting cured film, which are heat resistant transparent under 400nm in wavelength, is not obtained Obtain good heat resistant transparent.
[evaluation of the adhesion after adhesion and pressure cooker testing (Pressure Cooker Test, PCT)]
Cupromanganese is made using documented method in No. 4453845 bulletins of Japan Patent, resulting copper manganese is closed Gold is used as sputter target, and sputter is heated after on glass substrate (" healthy and free from worry 7059 " (Corning Incorporated's manufacture)) and obtains shape At the substrate for having metal electrode.On the substrate, 1~embodiment of spin coater coating Examples 9 and comparative example 1~compare are used In example 3 after prepared radiation-sensitive resin composition, on hot plate, 2 minutes prebake conditions are carried out at 90 DEG C and are formed Film.Secondly, being exposed using the PLA-501F exposure machine (extra-high-pressure mercury vapour lamp) that Canon, Inc. manufactures, use The tetramethylammonium hydroxide aqueous solution of 0.4 mass % develops.It further carries out heating for 30 minutes at 230 DEG C, thus obtain Obtain the cured film that film thickness is 2.0 μm.
Pressure cooker testing (120 DEG C, humidity 100%, 4 hour) are carried out to the substrate for being formed with the cured film.To pressure The substrate of pot test front and back carries out " the 8.5.3 adhesion grid tape method of JIS K-5400-1990 ", finds out in 100 grids The remaining grid number of institute, evaluates the adhesion of each cured film.Moreover, the evaluation result about the substrate before pressure cooker testing is made It is summarized in table 1 for " adhesion " of each cured film.Moreover, using about the evaluation result of the substrate after pressure cooker testing as each " adhesion after PCT " of cured film is summarized in table 1.About the evaluation of the adhesion after PCT, institute is residual in 100 grids The grid number stayed is that adhesion after PCT is judged as bad in 80 situations below.
The PCT of the cured film obtained using radiation-sensitive resin composition prepared in 1~embodiment of embodiment 9 Adhesion afterwards is that the remaining grid number of institute is good for 80 or more in 100 grids, uses 1~comparative example of comparative example Prepared radiation-sensitive resin composition in 3 and the cured film obtained is respectively 20 and 0, be bad.
[table 1]
<manufacture and evaluation of touch screen>
Embodiment 11
In the present embodiment, manufacture have in Fig. 1 illustrated by this implementation form 21 same structure of touch screen touching Screen is touched, is evaluated.In addition, below in the touch screen of the present embodiment, for convenience's sake, about total with the touch screen of Fig. 1 Constituent element is accompanied by identical symbol, is illustrated when being suitable for waiting referring to Fig.1.
Manufactured touch screen 21 in the present embodiment on transparent substrate 22 as shown in Figure 1, include vertical 3cm × horizontal 3cm's Operating area separately includes each 3 and arranges the 1st detecting electrode existing for the extension in the X direction formed as film thickness for the ITO of 30nm 23, extend existing 2nd detecting electrode 24 in the Y-direction orthogonal with X-direction.
In the manufacture of touch screen 21, prepare transparent substrate 22 first.As transparent substrate 22, used as alkali-free glass 0.55mm thickness glass substrate, using ultrapure water carry out surfactant processing, then using ultrasonic cleaning processing progress It cleans and uses.
Secondly, forming the wiring 31 as metal wiring on transparent substrate 22.Firstly, utilizing Japan Patent 4453845 Documented method in number bulletin and copper-manganese alloy is made, use made copper-manganese alloy to utilize sputter as sputter target Method is formed with the thickness of 30nm on transparent substrate 22 comprising copper-manganese alloy metal film.Then, using positive light sensitivity material Material, using photoetching process in the pattern for becoming wiring of the wiring region formation comprising copper alloy other than operating area.Secondly, using Baking oven carries out heat treatment in 5 minutes under atmospheric environment at 300 DEG C to the Wiring pattern on transparent substrate 22, and formation contains There is the wiring 31 comprising the 1st layer of copper-manganese alloy with the 2nd layer of the oxide comprising manganese.
Secondly, in order to form the 1st detecting electrode 23 and the 2nd detecting electrode on the transparent substrate 22 for be formed with wiring 31 24, ito film is formed in entire surface with the thickness of 30nm using sputtering method.Same eurymeric when then, using with formation wiring 31 Photosensitive material forms the 1st detecting electrode 23 and the 2nd detecting electrode 24 using photoetching process.
Fig. 4 has been expressed as formation touch screen and has been formed by wiring, the 1st detecting electrode and the 2nd inspection on the transparent substrate Survey the plan view of electrode.
As shown in figure 4, the 1st detecting electrode 23 and the 2nd detecting electrode 24 separately include 4 electronic pads 30 of diamond shape. Moreover, connecting the 1st detecting electrode 23 in the cross part 28 that the 1st detecting electrode 23 and the 2nd detecting electrode 24 intersect, disconnect ground Form the 2nd detecting electrode 24.
Secondly, being detected using acrylic materials (manufacture of JSR company, number NN902) being formed with wiring the 31, the 1st On the transparent substrate 22 of electrode 23 and the 2nd detecting electrode 24, film is formed using spin-coating method.Secondly, in 90 DEG C of heating plate The upper heating (prebake conditions) for carrying out 45 seconds, solvent composition is removed.After substrate is cooled to room temperature, using including interlayer insulating film 29 form the photomask for using mask pattern, PLA-501F exposure machine (the super-pressure mercury manufactured using Canon, Inc. Lamp), the light exposure at 365nm with 100mJ is exposed processing.Secondly, using inorganic alkali solution, (JSR company is manufactured CD150-CR immersion development) is carried out as developer solution, unexposed portion is removed, is subsequently formed as interlayer insulating film 29 Pattern.In addition, by be formed by transparent substrate 22 pattern carry out in an oven, under atmospheric environment, at 230 DEG C 1 hour plus Heat (rear baking) and make its hardening, the patterned layer that film thickness is 1.5 μm is formed on the 1st detecting electrode 23 of cross part 28 Between insulating layer 29.
Secondly, in order to be electrically connected the position of the interruption of the 2nd detecting electrode 24 on interlayer insulating film 29, in cross part 28 Interlayer insulating film 29 on formed bridge joint wiring 32.Specifically, using ITO first of all for bridge joint wiring 32 is formed, utilize Sputtering method is formed a film in substrate entire surface with the thickness of 50nm.Secondly, being used in the same manner eurymeric with the 1st detecting electrode 23 etc. Photosensitive material carries out the patterning of ito film using photoetching process, on the interlayer dielectric 29 of the cross part 28 of touch screen 21 Form multiple bridge joint wirings 32.
Fig. 5 has been expressed as formation touch screen and has been formed by wiring, the 1st detecting electrode, the 2nd detection on the transparent substrate Electrode, interlayer insulating film and the plan view for bridging wiring.
As shown in figure 5, the cross part 28 on transparent substrate 22, connects the 1st detecting electrode 23, disconnects ground and form the 2nd inspection Survey electrode 24.Therefore, in order to be electrically connected the 2nd detecting electrode 24 interruption position, be equipped with bridge joint wiring 32.In bridge joint wiring Interlayer dielectric 29 is equipped between 32 and the 1st detecting electrode 23.
Secondly, being coated on using radiation-sensitive resin composition prepared in above-described embodiment 5 using spin coater After in substrate entire surface, on hot plate, 2 minutes prebake conditions are carried out at 90 DEG C and form film.The sense of embodiment 5 is radiated Linear resin composition is according to the method being the same as in example 1 above, and includes alkali soluble resin obtained in the synthesis example 2 (C-1) ethyl ketone as (A) ingredient, 1- [9- ethyl-are added in polymer solution (solid component is scaled 100 mass parts) 6- (2- methyl benzoyl) -9H- carbazole -3- base] -, 1- (O- acetyl oxime) (A-1) 3 mass parts are added as (B) ingredient The sulphur as (D) ingredient is added in 3- triethoxysilicane alkyl-N- (1,3- dimethyl-butylidene) propyl amine (B-3) 10 parts by weight Di ethylene bis [3- (3,5- di-t-butyl -4- hydroxy phenyl) propionic ester] (D-1) 3 parts by weight are added as (E) ingredient 100 mass of mixture (molar ratio 50/50) (E-1) of dipentaerythritol hexaacrylate and Dipentaerythritol Pentaacrylate Part, secondly, diethylene glycol ethyl methyl ether and methyl -3- methoxyl group is added in such a way that solid component concentration becomes 25 weight % (ratio of components is prepared propionic ester as 30/70 (%)).
Secondly, using having, cured film 25 forms the photomask of mask pattern, Canon, Inc. manufactures PLA-501F exposure machine (extra-high-pressure mercury vapour lamp) and be exposed, using the tetramethylammonium hydroxide aqueous solution of 0.4 mass % Develop.In addition, carrying out heating in 30 minutes at 230 DEG C, 2.0 μm of film thickness of cured film 29 is consequently formed, is had The touch screen 21 of the present embodiment of structure same as Fig. 1.
Secondly, being set to the high temperature that temperature is 85 DEG C, humidity is 85% using the touch screen 21 of manufactured the present embodiment It in high wet sump, is taken out after 240 hours, evaluates the presence or absence of the removing between wiring 31 and cured film 25.Known to its result: In the touch screen 21 of the present embodiment, removing is not generated between wiring 31 and cured film 25, wiring 31 is close with cured film 25 Connecing property is good, has excellent reliability.
In addition, the present invention is not limited to above-mentioned each implementation form, can without departing from the spirit and scope of the invention, into Row various modifications and implement.
Industrial availability
Touch screen of the invention has high reliability.Therefore, touch screen of the invention is suitable for requiring excellent show Show the input unit of quality and reliability taken with information machine.

Claims (16)

1. a kind of touch screen is the touch comprising metal wiring and at least part of cured film for covering the metal wiring Screen, it is characterised in that:
The metal wiring is the metal wiring comprising the 2nd metallic element other than copper, copper,
The cured film is formed using radiation-sensitive resin composition, and the radiation-sensitive resin composition contains (A) hydrolytic condensate of the compound of emulsion, (B) containing alkoxysilane group and the compound at least one and (C) alkali soluble resin,
(C) alkali soluble resin includes at least one selected from the group as composed by polyamide and polysiloxanes.
2. touch screen according to claim 1, it is characterised in that: the metal wiring is containing the 1st layer, packet comprising copper Oxide containing the 2nd metallic element and to cover the 2nd layer of the gold in a manner of described 1st layer at least part of and constituted Belong to wiring.
3. touch screen according to claim 1 or 2, it is characterised in that: the 2nd metallic element be selected from by lithium, germanium, Group composed by strontium, tin, barium, praseodymium, neodymium, phosphorus, manganese, magnesium, calcium, nickel, zinc, silicon, aluminium, beryllium, gallium, indium, iron, titanium, vanadium, cobalt, zirconium and hafnium At least one of group.
4. touch screen according to claim 1 or 2, it is characterised in that: the 2nd metallic element is manganese.
5. touch screen according to claim 1 or 2, it is characterised in that: the cured film is anti-using (D) is further contained The radiation-sensitive resin composition of oxidant and formed.
6. touch screen according to claim 1 or 2, it is characterised in that: the cured film is using further containing (F) work To include at least one element selected from the group as composed by silicon, aluminium, zirconium, titanium, zinc, indium, tin, antimony, strontium, barium, cerium and hafnium The radiation-sensitive resin composition of the inorganic oxide particle of oxide and formed.
7. touch screen according to claim 1 or 2, it is characterised in that: (A) of the radiation-sensitive resin composition at At least one of subpackage acid containing light generation and Photoepolymerizationinitiater initiater.
8. touch screen according to claim 1 or 2, it is characterised in that: (B) of the radiation-sensitive resin composition at Subpackage contains at least one compound with amino, block amino, isocyanate group and blocked isocyanate ester group.
9. a kind of radiation-sensitive resin composition is the change containing (A) emulsion and (B) containing alkoxysilane group Close radiation-sensitive resin composition made of at least one of the hydrolytic condensate of object and the compound, it is characterised in that:
To form the cured film of touch screen, the touch screen includes at least one of metal wiring and the covering metal wiring The cured film divided, the metal wiring contain the 1st layer comprising copper and the oxidation comprising the 2nd metallic element other than copper Object and to cover the 2nd layer in a manner of described 1st layer at least part of and constituted,
The radiation-sensitive resin composition further includes (C) alkali soluble resin, and (C) alkali soluble resin includes At least one selected from the group as composed by polyamide and polysiloxanes.
10. radiation-sensitive resin composition according to claim 9, it is characterised in that: the 2nd layer of the metal wiring Contained in the 2nd metallic element oxide be selected from by lithium, germanium, strontium, tin, barium, praseodymium, neodymium, phosphorus, manganese, magnesium, calcium, nickel, The oxide of at least one element of group composed by zinc, silicon, aluminium, beryllium, gallium, indium, iron, titanium, vanadium, cobalt, zirconium and hafnium.
11. radiation-sensitive resin composition according to claim 9, it is characterised in that: it is anti-oxidant to further include (D) Agent.
12. radiation-sensitive resin composition according to claim 9, it is characterised in that: it is multifunctional to further include (E) (methyl) acrylate.
13. radiation-sensitive resin composition according to claim 9, it is characterised in that: further include (F) as packet Oxidation containing at least one element selected from the group as composed by silicon, aluminium, zirconium, titanium, zinc, indium, tin, antimony, strontium, barium, cerium and hafnium The inorganic oxide particle of object.
14. radiation-sensitive resin composition according to claim 9, it is characterised in that: (A) ingredient is generated comprising light acid At least one of object and Photoepolymerizationinitiater initiater.
15. radiation-sensitive resin composition according to claim 9, it is characterised in that: (B) ingredient includes to have ammonia Base, block amino, isocyanate group and blocked isocyanate ester group at least one compound.
16. a kind of cured film is by containing (A) emulsion and (B) containing the compound of alkoxysilane group and describedization The cured film for closing radiation-sensitive resin composition made of at least one of the hydrolytic condensate of object and being formed, feature exist In:
To cover at least part of the metal wiring of the touch screen comprising metal wiring, the metal wiring contains packet The 1st layer of cupric, with the oxide comprising the 2nd metallic element other than copper and to cover described 1st layer at least part of Mode and constitute the 2nd layer,
The radiation-sensitive resin composition further includes (C) alkali soluble resin, and (C) alkali soluble resin includes At least one selected from the group as composed by polyamide and polysiloxanes.
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