CN104541204B - The manufacturing method of photosensitive polymer combination, photosensitive element, the forming method of resist pattern and touch panel - Google Patents

The manufacturing method of photosensitive polymer combination, photosensitive element, the forming method of resist pattern and touch panel Download PDF

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CN104541204B
CN104541204B CN201380042172.9A CN201380042172A CN104541204B CN 104541204 B CN104541204 B CN 104541204B CN 201380042172 A CN201380042172 A CN 201380042172A CN 104541204 B CN104541204 B CN 104541204B
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photosensitive polymer
polymer combination
mass parts
compound
methyl
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CN104541204A (en
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玉田春仙
木村伯世
高崎俊彦
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Lishennoco Co ltd
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Hitachi Chemical Co Ltd
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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
    • 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
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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
    • 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

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Human Computer Interaction (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)

Abstract

A kind of ITO etching photosensitive polymer combination, containing binder polymer, photopolymerizable compound, Photoepolymerizationinitiater initiater and silane coupling agent, the silane coupling agent includes the silane compound with mercaptoalkyl.

Description

Photosensitive polymer combination, photosensitive element, resist pattern forming method and touching Control the manufacturing method of panel
Technical field
The present invention relates to photosensitive polymer combination, photosensitive element, the forming method of resist pattern and touch panels Manufacturing method.
Background technique
The touch sensing position of touch panel includes: not covering picture letter in the range (visible area) of visible picture Breath ground perceives the sensor sites of the information of contacts such as the finger of people and the wiring for transmitting the information (draws wiring part Position).
The absorption of visible light is formed less and conductive transparent electrode pattern in the sensor site of the visible area.Separately Outside, the wiring metal small using resistance value is drawn.
For example operation is manufactured as follows for these sensor sites and extraction wiring position.Firstly, with transparent electrode The polyethylene terephthalate or glass superstrate of layer fold photosensitive polymer combination (lamination process).Then, to photonasty The prescribed portion of resin combination irradiates active ray and makes exposed portion solidification (or dissolution) (exposure process).Later, will Uncured portion (or dissolution part) removes (development) from substrate, so that being formed on substrate includes photosensitive resin composition The resist pattern (developing procedure) of the solidfied material of object.Etching process is implemented to obtained resist pattern, is formed on substrate After the sensor patterns of visible area, resist is removed and removes (stripping process).Then, by using the screen printing of silver paste etc. Scopiform at from be formed by transparent electrode sensor draw extraction wiring, to manufacture the touch sensor department of touch panel Position.
In addition, Fig. 2 is the schematic section for indicating the pervious manufacturing method of touch panel.In this manufacturing method, as Photonasty tree is laminated in lamination process on the transparent electrode layer 14 of the laminated substrate comprising transparent electrode layer 14 and supporting base material 12 Oil/fat composition layer 16 (Fig. 2 (a)).Then, active ray is irradiated to the prescribed portion of photosensitive polymer combination layer 16 and makes to expose The solidification of light portion, uncured portion is removed from substrate, forms the resist pattern (Fig. 2 (b)) comprising cured portion.Then, Etching process is implemented to the laminated substrate for being formed with resist pattern, by a part of transparent electrode layer 14 from supporting base material 12 It removes (Fig. 2 (c)), then, resist is removed to the sensor patterns (Fig. 2 for removing and being formed in supporting base material 12 visible area (d)).It is formed by using the silk-screen printing of silver paste etc. from the extraction wiring 18 for being formed by sensor extraction, to manufacture The touch sensing position of touch panel.
It is most in the past to be carried out by being coated with the photosensitive polymer combination of liquid in lamination process.But in recent years With the slim lightweight of touch panel, it is desirable to it is formed with film and requires to get higher as the substrate at touch sensing position, and It is importing by being manufactured with the good photosensitive element of the matching of film base material.
In addition, due to touch panel frame (fluorescent screen) it is narrowing, also require draw wiring closet away from it is narrowing. In the silk-screen printing for having used silver paste, L/S (line width/interval is wide) is 70/70 (unit: μm) degree, but it is small necessarily to be formed L/S In or equal to 30/30 extraction wiring.
Therefore, the new forming method at the touch sensing position small as the L/S for drawing wiring, there is the following method.Make With from top to bottom comprising metal layer (draw wiring and form use), transparent electrode layer (sensor of visible area forms use), branch support group (lamination) photosensitive polymer combination layer (lamination process) is laminated in the laminated substrate in the laminated substrate of material (film) 3-tier architecture. Then, active ray is irradiated to the prescribed portion of photosensitive polymer combination layer and makes exposure portion solidification (or dissolution) (exposure Process).Later, uncured position (or dissolution part) is removed into (development) from substrate, so that formation includes on substrate The resist pattern (developing procedure) of photosensitive polymer combination solidfied material.For obtained resist pattern, at etching Metal layer and transparent electrode layer are removed (the 1st etching work procedure) by reason, form the transparent electrode figure drawn wiring and form visible area Case.Next, photosensitive polymer combination layer is laminated again, and is exposed, develops, thus only by visible area should not metal Layer removes (the 2nd etching).The narrow touch sensing position of the spacing for manufacturing extraction wiring by this method is (referring for example to patent Document 1).
For this method, can theoretically to make L/S be less than or equal to 30/30, touch panel can be greatly contributed to Slim light-weighted technology.But on the other hand, the surface smoothness of used substrate is very high, for the sense used Photosensitiveness component requirements high adhesion.
In addition, as photosensitive polymer combination used in formation in resist pattern etc., such as disclose patent Composition documented by document 2~6.
Existing technical literature
Patent document
Patent document 1: Japanese Patent No. 4855536
Patent document 2: Japanese Unexamined Patent Publication 07-146553 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2005-107121 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2008-112145 bulletin
Patent document 5: Japanese Unexamined Patent Publication 2010-276631 bulletin
Patent document 6: Japanese Unexamined Patent Publication 2011-128358 bulletin
Summary of the invention
Problems to be solved by the invention
In the case where using glass baseplate as supporting base material, the most following formation of transparent electrode: using non-crystalline ITO (tin indium oxide) is patterned, and is heated (annealing) processing to reduce resistance value later to carry out the knot of ITO Crystallization.But in the case where using film base material as supporting base material, the receipts of substrate can occur if being made annealing treatment Contracting, makes dimensional stability be deteriorated, therefore it is preferable to use crystalline ITO to be patterned.
But non-crystalline ITO can be completely dissolved in the weak acid such as oxalic acid, but crystallinity ITO must use concentrated hydrochloric acid (20 mass % of >) is etched under heating condition (40~50 DEG C of degree).Therefore, for patterning used resist It is required that highly-acidproof.
In addition, metal layer uses copper, the alloy of copper and nickel, molybdenum-aluminium-molybdenum layer stack, silver and palladium and the alloy of copper etc., in recent years To become mainstream configured with the metal layer of copper and nickel alloy in outmost surface for antirust.Therefore, for resist, it is desirable that with The adaptation of metal layer comprising copper, particularly the metal layer comprising copper and nickel alloy.
For pervious photosensitive polymer combination, it is difficult to be formed and sufficiently meet the against corrosion of these acid resistances and adaptation Agent pattern has the problems such as generation removing when carrying out ITO etching using hydrochloric acid.
The method for solving problem
The inventors of the present invention further investigate repeatedly to solve the above-mentioned problems, as a result, it has been found that: by photosensitive resin composition Addition has the silane compound of mercaptoalkyl as silane coupling agent in object, it can be expected that the raising of acid resistance and adaptation.
That is, the first form of the invention is related to a kind of ITO etching photosensitive polymer combination, it polymerize containing adhesive Object, photopolymerizable compound, Photoepolymerizationinitiater initiater and silane coupling agent, the silane coupling agent include the silicon with mercaptoalkyl Hydride compounds.
Such photosensitive polymer combination is capable of forming the resist pattern of acid resistance and excellent adhesion, therefore can It is suitable as the etching use that ITO etches the transparency conducting layer used, particularly comprising crystallinity ITO.
Above-mentioned silane coupling agent can further include the silane compound with amino.According to such photoresist Composition is able to suppress the development residual of resist on the metal layer, it can be expected that the shortening of etching period.
Above-mentioned silane coupling agent can further include the silane compound with (methyl) acryloxy.According in this way Photosensitive polymer combination, it can be expected that being further increased with the adaptation of metal layer.
Above-mentioned photopolymerizable compound can contain bisphenol A-type two (methyl) acrylate compounds.According to such sense The acid resistance of photosensitive resin composition, resist further increases, and further can inhibit ITO when etching by resist significantly Swelling caused by removing.
Above-mentioned photopolymerizable compound can contain the carbamic acid with (poly-) oxygen ethylidene and/or (poly-) oxygen propylidene Ester two (methyl) acrylate compounds.Thereby, it is possible to assign flexibility to resist, it can be ensured that for as film base material The superior adaptation of flexible substrate.
It includes above-mentioned first that second form of the invention, which is related to having support membrane and being arranged in the one side of the support membrane, The photosensitive element of the photosensitive polymer combination layer of the photosensitive polymer combination of form.According to such photosensitive element, Due to the photosensitive polymer combination layer with the photosensitive polymer combination comprising the first form, can be effectively formed Also there is sufficient adaptation even for the high substrate of flatness and there is excellent acid proof resist pattern.
Third form of the invention is related to a kind of forming method of resist pattern, has following process: the shape on substrate At the 1st process of the photosensitive polymer combination layer of the photosensitive polymer combination comprising above-mentioned first form；Pass through active light The irradiation of line is a part of regions curing by above-mentioned photosensitive polymer combination layer, forms the 2nd process for solidifying object area；And Region other than the above-mentioned solidification object area of above-mentioned photosensitive polymer combination layer is removed from above-mentioned substrate, is obtained comprising upper State the 3rd process of the resist pattern for solidifying object area.According to the forming method of such resist pattern, be capable of forming even if The substrate high for flatness also has sufficient adaptation and has excellent acid proof resist pattern.
4th form of the invention is related to a kind of manufacturing method of touch panel, has and resists to by above-mentioned third form The forming method of erosion agent pattern forms the process that the above-mentioned substrate of resist pattern is etched.In such touch surface In the manufacturing method of plate, since resist pattern is by the photoresist of the photosensitive polymer combination comprising above-mentioned first form Composition layer is formed, therefore can sufficiently inhibit the removing etc. of resist pattern in etching process, even the touch-control of thin space Panel (such as touch panel of the extraction wiring with L/S less than or equal to 30/30) also can be manufactured efficiently.
5th form of the invention is related to a kind of manufacturing method of touch panel, with following process: having support Substrate, the transparency conducting layer comprising tin indium oxide being arranged in the one side of the supporting base material and setting are on the transparency conducting layer Metal layer laminated substrate above-mentioned metal layer on, formed comprising above-mentioned first form photosensitive polymer combination solidification 1st process of the resist pattern of object；Above-mentioned metal layer and above-mentioned transparency conducting layer are etched, formed comprising above-mentioned transparent 2nd process of the lamination pattern of the remainder of the remainder of conductive layer and above-mentioned metal layer；And from above-mentioned lamination pattern A part above-mentioned metal layer is removed, formed comprising above-mentioned transparency conducting layer remainder transparent electrode and comprising above-mentioned 3rd process of the metal wiring of the remainder of metal layer.
According to the manufacturing method of such touch panel, the touch panel (example of thin space can be easily and efficiently manufactured Such as, the touch panel of the extraction wiring with L/S less than or equal to 30/30).
Above-mentioned transparency conducting layer may include crystalline tin indium oxide, and the etching in above-mentioned 2nd process can be utilization The etching that strong acid carries out.In above-mentioned manufacturing method, since resist pattern is by the photoresist comprising above-mentioned first form The photosensitive polymer combination layer of composition is formed, therefore can sufficiently inhibit resist pattern being etched using strong acid Removing etc..Therefore, above-mentioned manufacturing method can be suitble to be suitable for having used with leading comprising the transparent of crystallinity tin indium oxide The manufacture of the touch panel of the laminated substrate of electric layer.
Invention effect
According to the present invention, even if providing a kind of excellent adhesion for being capable of forming the substrate high for flatness and having ITO etching is carried out using hydrochloric acid to be also difficult to generate the photosensitive resin composition of the excellent acid proof resist pattern of removing etc. Object.In addition, according to the present invention, providing the formation of the photosensitive element, resist pattern that have used the photosensitive polymer combination The manufacturing method of method and touch panel.
Detailed description of the invention
Fig. 1 is the schematic section for indicating an embodiment of photosensitive element of the invention.
Fig. 2 is the schematic section for indicating the pervious manufacturing method of touch panel.
Fig. 3 is the schematic section for indicating a form of manufacturing method for touch panel of the invention.
Fig. 4 is the top view for indicating a form of the touch panel obtained using the present invention.
Specific embodiment
Mode for carrying out the present invention is described in detail below.But the present invention is not limited to embodiment party below Formula.In addition, in the present specification, (methyl) acrylic acid refers to acrylic acid or methacrylic acid, (methyl) acrylate refers to Perhaps corresponding methacrylate (methyl) acryloxy refers to acryloxy or metering system to acrylate Acyloxy.
In addition in the present specification, (poly-) oxygen ethylidene refers to that the ethylidene of oxygen ethylidene or 2 or more are connected with ehter bond Polyoxyethylene made of connecing it is at least one kind of, (poly-) oxygen propylidene refers to the propylidene of oxygen propylidene or 2 or more with ehter bond The polyoxypropylene being formed by connecting it is at least one kind of.Further " EO is modified " refers to the compound with (poly-) oxygen ethylidene, " PO It is modified " refer to the compound with (poly-) oxygen propylidene." EOPO is modified " refers to there is (poly-) oxygen ethylidene and/or (poly-) oxygen The compound of both propylidene.
< photosensitive polymer combination >
The photosensitive polymer combination of present embodiment (is only called " photosensitive polymer combination " below.) it is to contain (A) Ingredient: binder polymer, (B) ingredient: photopolymerizable compound, (C) ingredient: Photoepolymerizationinitiater initiater and (D) ingredient: silane is even Join the photosensitive polymer combination of agent, (D) ingredient includes the silane compound with mercaptoalkyl.
According to such photosensitive polymer combination, be capable of forming the excellent adhesion of the substrate high for flatness and With the excellent acid proof resist pattern for carrying out being difficult to generate removing etc. ITO is etched even if using hydrochloric acid.Therefore, this reality The photosensitive polymer combination for applying mode is suitable as the erosion of ITO etching use, particularly the transparency conducting layer comprising crystallinity ITO It carves and uses.
As one of the reasons why such effect can be achieved, it is believed that be the metal layer as possessed by the outmost surface of substrate with The mercaptoalkyl of silane coupling agent forms the chemical bonding such as complexing, therefore shows high adhesion.In addition, with regard to present embodiment For photosensitive polymer combination, it is believed that in photocuring reaction, silane compound and optical polymerism with mercaptoalkyl It closes object reaction and forms thioether bond.It can thus be assumed that due in the polymeric system of solidfied material silane coupling agent be fixed, into And the thioether bond influence with the chemical interaction of substrate, therefore the closely sealed sex expression of resist and metal surface obtain it is stronger.
(A) ingredient: binder polymer
Photosensitive polymer combination contains at least one kind of binder polymer and is used as (A) ingredient.As binder polymer, Such as can enumerate makes polymerizable monomer (monomer) to carry out polymer obtained from free radical polymerization.
As polymerizable monomer (monomer), (methyl) acrylic acid can be enumerated；(methyl) alkyl acrylate, (methyl) propylene Sour cycloalkyl ester, (methyl) benzyl acrylate, (methyl) benzyl acrylate derivative, (methyl) acrylic acid furfuryl group ester, (methyl) Tetrahydrofurfuryl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid Buddha's warrior attendant alkyl ester, two ring penta of (methyl) acrylic acid Ester, (methyl) acrylate, (methyl) acrylic acid diethylamino ethyl ester, (methyl) glycidyl Ester, 2,2,2- trifluoroethyl (methyl) acrylate, tetra- fluoropropyl of 2,2,3,3- (methyl) acrylate, alpha-brominated acrylic acid, α-chloro-acrylicacid, (methyl) acrylic acid dicyclopentenyl oxygroup ethyl ester, (methyl) acrylic acid bicyclopentyl oxygroup ethyl ester, (methyl) Isobomyl acrylate base oxygroup ethyl ester, (methyl) acrylate base oxygroup ethyl ester, (methyl) acrylic acid adamantyl oxygroup second Ester, (methyl) acrylic acid dicyclopentenyl oxygroup propyl oxygroup ethyl ester, (methyl) acrylic acid bicyclopentyl oxygroup propyl oxygroup ethyl ester, (methyl) acrylic acid dicyclopentenyl oxygroup propyl oxygroup ethyl ester, (methyl) acrylic acid adamantyl oxygroup propyl oxygroup ethyl ester, (first Base) (methyl) acrylate such as propenoic acid beta-furans ester, (methyl) propenoic acid beta-styrene esters；Styrene；Vinyltoluene, α- The substituted styrene derivative that can polymerize on the alpha-positions such as methyl styrene or aromatic ring；Diacetone acrylamide etc. Acrylamide；Acrylonitrile；The ether compound of the vinyl alcohols such as vinyl n-butyl ether；Maleic acid；Maleic anhydride；Maleic acid list The maleic acid monoesters such as methyl esters, ethyl maleate, maleic acid list isopropyl ester；Fumaric acid, cinnamic acid, alpha-cyano cinnamic acid, clothing health Olefinically unsaturated carboxylic acid derivatives such as acid, crotonic acid, lactic acid etc..They can be used alone or any combination of two or more uses.
(A) ingredient preferably has the structural unit from (methyl) acrylic acid.Have in (A) ingredient and derives from (methyl) When the structural unit of acrylic acid, from resolution ratio and fissility (the resist fissility after etching) excellent aspect, contain Rate (100 mass %, below equally) preferably on the basis of the total amount of (A) ingredient is the 10 mass % of mass %~60, more preferably The 15 mass % of mass %~50, further preferably 20 mass of mass %~35 %.
In addition, (A) ingredient, which preferably has, to be derived from from the viewpoint of further increasing from acrylic acid developability and fissility The structural unit of (methyl) alkyl acrylate.
As (methyl) alkyl acrylate, the preferably ester of the alkylol of (methyl) acrylic acid and carbon atom number 1~12. As such (methyl) alkyl acrylate, such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (first can be enumerated Base) propyl acrylate, (methyl) butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate and (methyl) propylene Sour 2- ethylhexyl, they can be used alone or any combination of two or more uses.
It is excellent from resolution ratio and adaptation when (A) ingredient has from the structural unit of (methyl) alkyl acrylate Different aspect is set out, and containing ratio is preferably 40 mass %~90 mass % using the total amount of (A) ingredient as benchmark, and more preferably 50 The mass % of quality %~85, further preferably 65 mass of mass %~80 %.
From the acid value of developability and excellent adhesion aspect, (A) ingredient be preferably 90mgKOH/g~250mgKOH/ G, more preferably 100mgKOH/g~240mgKOH/g, further preferably 120mgKOH/g~235mgKOH/g, particularly preferably For 130mgKOH/g~230mgKOH/g.
From shorten developing time aspect, acid value is preferably greater than or equal to 90mgKOH/g, more preferably higher than or Equal to 100mgKOH/g, further preferably greater than or it is equal to 120mgKOH/g, particularly preferably greater than or equal to 130mgKOH/ g。
In addition, further increasing aspect from the adaptation of the solidfied material of photosensitive polymer combination, acid value is preferred Further preferably less than or to be equal to less than or equal to 250mgKOH/g, more preferably less than or equal to 240mgKOH/g 235mgKOH/g is particularly preferably less than or equal to 230mgKOH/g.In addition, preferably will in the case where carrying out solvent development There is (methyl) acrylic acid etc. the polymerizable monomer (monomer) of carboxyl to be adjusted to a small amount of.
It is measured by gel permeation chromatography (GPC) (by using standard in the weight average molecular weight (Mw) of (A) ingredient The standard curve of polystyrene converts) in the case where, from developability and excellent adhesion aspect, preferably 10000 ~200000, more preferably 20000~100000, further preferably 25000~80000, particularly preferably 30000~ 60000.From the excellent aspect of developability, preferably less than or equal to 200000, more preferably less than or equal to 100000, into One step is preferably less than or equal to 80000, is particularly preferably less than or equal to 60000.From excellent adhesion aspect, preferably For more than or equal to 10000, more preferably greater than or equal to 20000, further preferably greater than or it is equal to 25000, it is especially excellent It is selected as being greater than or equal to 30000.
It is excellent from the dispersion degree (weight-average molecular weight/number-average molecular weight) of resolution ratio, excellent adhesion aspect, (A) ingredient It is selected as being less than or equal to 3.0, more preferably less than or equal to 2.8, further preferably less than or equal to 2.5.
As (A) ingredient, binder polymer can be used alone, it can also be poly- with any combination of two or more adhesive Object is closed to use.
From (A) component content in film formative, sensitivity and excellent in resolution aspect, photosensitive polymer combination It is preferred that being 30 mass parts~70 mass parts, more preferably 35 mass parts in 100 mass parts of total amount of (A) ingredient and (B) ingredient ~65 mass parts, particularly preferably 40 mass parts~60 mass parts.In terms of the formative of film (photosensitive polymer combination layer) It sets out, content is preferably greater than or equal to 30 mass parts, more preferably greater than or equal to 35 mass parts, particularly preferably greater than Or it is equal to 40 mass parts.In addition from sufficiently obtaining sensitivity and resolution ratio aspect, content is preferably less than or equal to 70 Mass parts, more preferably less than or equal to 65 mass parts, further preferably less than or equal to 60 mass parts.
(B) ingredient: photopolymerizable compound
Photosensitive polymer combination contains at least one kind of photopolymerizable compound and is used as (B) ingredient.Photopolymerizable compound is only It to be just not particularly limited to be capable of the compound of photopolymerization.
Photopolymerizable compound is preferably free-radical polymerised compound, more preferably with the change of ethylene unsaturated bond Close object.As the compound with ethylene unsaturated bond, the chemical combination that intramolecular has 1 ethylene unsaturated bond can be enumerated The chemical combination of compound, intramolecular with 3 or more ethylene unsaturated bonds of object, intramolecular with 2 ethylene unsaturated bonds Object etc..
(B) ingredient preferably comprises at least the compound that a kind of intramolecular has 2 ethylene unsaturated bonds.At (B) at subpackage In the case where the compound containing intramolecular with 2 ethylene unsaturated bonds, content is preferably in (A) ingredient and (B) ingredient It is 5 mass parts~60 mass parts, more preferably 5 mass parts~55 mass parts, further preferably 10 matter in 100 mass parts of total amount Measure part~50 mass parts.
There is the compound of 2 ethylene unsaturated bonds as intramolecular, such as bisphenol A-type two (methyl) propylene can be enumerated Ester compound, hydrogenated bisphenol A type two (methyl) acrylate compounds, intramolecular have two (methyl) of urethane bond Acrylate compounds, intramolecular have the polyalkylene glycol two (methyl) of both (poly-) oxygen ethylidene and (poly-) oxygen propylidene Acrylate and trimethylolpropane two (methyl) acrylate.
From the viewpoint of further increasing acid resistance, (B) ingredient is preferably comprised from by bisphenol A-type two (methyl) acrylic acid Ester compounds and carbamate two (methyl) the acrylate chemical combination with (poly-) oxygen ethylidene and/or (poly-) oxygen propylidene Object (hereinafter referred to as " EOPO modified urethane two (methyl) acrylate compounds ".) composed by select in group to It is a kind few.
As bisphenol A-type two (methyl) acrylate compounds, compound represented by following formula (1) can be enumerated.
[changing 1]
In formula (1), R1And R2Each independently represent hydrogen atom or methyl.XO and YO each independently represents oxygen Asia second Base or oxygen propylidene.m1、m2、n1And n2Each independently represent 0~40.Wherein, m1+n1And m2+n2It is all larger than or equal to 1.? XO is m in the case that oxygen ethylidene, YO are oxygen propylidene1+m2For 1~40, n1+n2It is 0~20.It is oxygen propylidene, YO in XO In the case where oxygen ethylidene, m1+m2For 0~20, n1+n2It is 1~40.m1、m2、n1And n2Indicate the structural unit of structural unit Number.Therefore integer value is indicated in individual molecule, the rational as average value is indicated in the aggregate of different kinds of molecules.Below Structural unit number about structural unit is same.
The m from the excellent aspect of acid resistance, formula (1)1+m2Preferably 8~40, more preferably 8~20, further preferably It is 8~10.
It include the case where (methyl) acrylate compounds of bisphenol A-type two are as (B) ingredient in photosensitive polymer combination Under, it is preferably 1 mass parts~50 mass parts in 100 mass parts of total amount of (A) ingredient and (B) ingredient as its content, it is more excellent It is selected as 5 mass parts~50 mass parts.
As EOPO modified urethane two (methyl) acrylate compounds, it is represented that following formula (2) can be enumerated Compound.
[changing 2]
In formula (2), R3Each independently represent hydrogen atom or methyl.OR4And OR5Each independently represent oxygen ethylidene Or oxygen propylidene.R6Indicate alkyl chain.M and n each independently represent 0~40.Wherein, m+n is greater than or equal to 1.In OR4For Oxygen ethylidene, OR5In the case where oxygen propylidene, the total amount that the total amount of m is 1~40, n is 0~20.In OR4For oxygen propylidene, OR5In the case where oxygen ethylidene, the total amount that the total amount of m is 0~20, n is 1~40.M and n indicates the structure list of structural unit First number.Therefore integer value is indicated in individual molecule, the rational as average value is indicated in the aggregate of different kinds of molecules.Under Face is same about the structural unit number of structural unit.
It include EOPO modified urethane two (methyl) acrylate compounds conduct in photosensitive polymer combination (B) in the case where ingredient, as its content, preferably in 100 mass parts of total amount of (A) ingredient and (B) ingredient for 1 mass parts~ 50 mass parts, more preferably 5 mass parts~50 mass parts.
In photosensitive polymer combination, as (B) ingredient, in addition to intramolecular has the chemical combination of 2 ethylene unsaturated bonds Other than object, can further have the compound of 1 ethylene unsaturated bond containing intramolecular.
There is the compound of 1 ethylene unsaturated bond as intramolecular, such as the poly- sub- ethoxy of Nonylphenoxy can be enumerated Base acrylate, phthalic acid based compound and (methyl) alkyl acrylate.In these substances, well from balance From the viewpoint of improving resolution ratio, adaptation, resist shape and peel property after solidify, preferably comprises Nonylphenoxy and gather Inferior ethoxyl acrylate or phthalic acid based compound.
There is the phthalic acid based compound of 1 ethylene unsaturated bond as intramolecular, such as can to enumerate γ-chloro- β-hydroxy propyl-Beta '-methacryloxyethyl-phthalic acid ester, 2- acryloyl-oxyethyl -2- ethoxy-neighbour's benzene two Formic acid and 2- acryloyl-oxyethyl-phthalic acid.
It include that there is intramolecular the compound of 1 ethylene unsaturated bond to be used as (B) ingredient in photosensitive polymer combination In the case where, content is preferably 1 mass parts~20 mass parts in 100 mass parts of total amount of (A) ingredient and (B) ingredient, more Preferably 3 mass parts~15 mass parts, further preferably 5 mass parts~12 mass parts.
Total amount of the content of (B) ingredient totality in photosensitive polymer combination preferably with respect to (A) ingredient and (B) ingredient 100 mass parts be 30 mass parts~70 mass parts, more preferably 35 mass parts~65 mass parts, particularly preferably 35 mass parts~ 50 mass parts.If its content is greater than or equal to 30 mass parts, have the tendency that being easy to get sufficient sensitivity and resolution ratio. If it is less than or equal to 70 mass parts, then have the tendency that film easy to form (photosensitive polymer combination layer), in addition there are also be easy Obtain the tendency of good resist shape.
(C) ingredient: Photoepolymerizationinitiater initiater
Photosensitive polymer combination contains at least one kind of Photoepolymerizationinitiater initiater and is used as (C) ingredient.As long as Photoepolymerizationinitiater initiater energy The polymerization of (B) ingredient is not particularly limited just, can suitably be selected from usually used Photoepolymerizationinitiater initiater.
As (C) ingredient, benzophenone, 2- benzyl -2- dimethylamino -1- (4- morphlinophenyl)-butanone-can be enumerated The equal aromatic ketones of 1,2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholino-acetone-1；The quinones such as alkyl-anthraquinone；Benzoin alkane The benzoin ethers compound such as base ether；The benzoins compounds such as benzoin, alkyl benzoin；The benzils such as benzil dimethyl ketal Derivative；2- (Chloro-O-Phenyl) -4,5- diphenyl-imidazole dimer, 2- (o-fluorophenyl) -4,5- diphenyl-imidazole dimer etc. 2,4,5- triarylimidazoles dimer；Acridine derivatives such as 9- phenylacridine, 1,7- (9,9 '-acridinyl) heptane etc..They can To be used singly or in combination of two or more thereof.
From the viewpoint of further increasing sensitivity and adaptation, (C) ingredient preferably comprises 2,4,5- triarylimidazoles Dimer it is at least one kind of, more preferably include 2- (Chloro-O-Phenyl) -4,5- diphenyl-imidazole dimer.With regard to 2,4,5- triaryl miaow For azoles dimer, structure can be symmetrically or asymmetric.
Total amount 100 of the content of (C) ingredient in photosensitive polymer combination preferably with respect to (A) ingredient and (B) ingredient Mass parts are 0.1 mass parts~10 mass parts, more preferably 1 mass parts~7 mass parts, further preferably 2 mass parts~6 matter Measure part, particularly preferably 3 mass parts~5 mass parts.It is easy to get if its content is greater than or equal to 0.1 mass parts good Sensitivity, resolution ratio or adaptation tendency, if it is less than or be equal to 10 mass parts, then be easy to get good against corrosion The tendency of dosage form shape.
(D) ingredient: silane coupling agent
Photosensitive polymer combination contains silane coupling agent and is used as (D) ingredient.As silane coupling agent, can enumerate (D1) at Point: silane compound, (D2) ingredient with mercaptoalkyl: the silane compound with amino is (preferably with the silicon of urea groups Hydride compounds), (D3) have (methyl) acryloxy silane compound.Photosensitive polymer combination contains in these substances At least (D1) ingredient.
Photosensitive polymer combination is used as (D) ingredient by containing (D1) ingredient, is capable of forming to realize for smooth Property high substrate excellent adhesion and have and carry out being difficult to generate the excellent resistance to of removing etc. ITO is etched even if using hydrochloric acid Excellent effect as acid resist pattern.
In addition, photosensitive polymer combination, which can contain the silane coupling agent in addition to (D1) ingredient, is used as (D) ingredient.
For example, (D1) ingredient can be used together for photosensitive polymer combination and (D3) ingredient is used as (D) ingredient.In photonasty tree Oil/fat composition only includes (D1) ingredient as in the case where (D) ingredient, can obtain the resist for showing excellent adaptation, but Have and is easy to produce the residual of the development for copper base etc. (that is, the resist being formed on copper base is difficult to remove after the etching) Tendency, there is the increased tendency of etching period.In contrast, contain (D1) ingredient and (D3) at being allocated as in photosensitive polymer combination In the case where for (D) ingredient, it is able to maintain that excellent adaptation and inhibits generation remaining for the development of copper base etc., realize The shortening of etching period.
In addition, photosensitive polymer combination can contain simultaneously (D1) ingredient, (D2) ingredient and (D3) ingredient as (D) at Point.According to such photosensitive polymer combination, it is able to suppress generation remaining for the development of copper base etc. and realization is higher Adaptation.
As (D1) ingredient, it is however preferred to have silane compound (the mercaptoalkyl alkoxy silicon of mercaptoalkyl and alkoxy Alkane), as such (D1) ingredient, mercapto propyl methyl dimethoxy silane, mercaptopropyi trimethoxy silane, mercapto can be enumerated Base propyl-triethoxysilicane etc..Wherein, it is easy to happen hydrolysis and is able to carry out the mercaptopropyi trimethoxy silicon of 3 points of crosslinkings Alkane due to the adaptation put up the best performance and it is preferred that.
As (D2) ingredient, preferably silane compound of the end with primary amino group, as such (D2) ingredient, such as 3- aminopropyl methoxysilane, aminopropyl Ethoxysilane, N-2- (amino-ethyl) -3- aminopropyl trimethoxy can be enumerated Base silane, 3- ureidopropyltriethoxysilane, 3- ureido-propyl trimethoxy silane, ureidomethy trimethoxy silane, urea Ylmethyl triethoxysilane, 2- ureidoethyltrimethoxsilane, 2- urea groups ethyl triethoxysilane, 4- urea groups butyl three Methoxy silane, 4- urea groups butyl triethoxysilane etc..Wherein, it is contemplated that the reactivity with binder polymer preferably has The silane compound for the functional group for having urea groups etc. low with the reactivity of carboxylic acid group, most preferably simultaneously used time development remains with (D1) ingredient The 3- ureidopropyltriethoxysilane that can observe especially significantly of inhibitory effect.
As (D3) ingredient, such as 3- methacryloxypropylmethyl dimethoxysilane, 3- methyl-prop can be enumerated Alkene acryloxypropylethoxysilane trimethoxy silane, 3- methacryloxypropyl methyl diethoxysilane, 3- methacryloxypropyl Base propyl-triethoxysilicane.Wherein, it is easy to happen hydrolysis and is able to carry out the mercaptopropyi trimethoxy silane of 3 points of crosslinkings Due to the adaptation put up the best performance and it is preferred that.It is easy to happen hydrolysis and is able to carry out the 3- methacryloxy third of 3 points of crosslinkings Base trimethoxy silane due to the adaptation put up the best performance and it is preferred that.
From the content of (D) ingredient in excellent adhesion aspect, photosensitive polymer combination preferably with respect to (A) at Point and (B) ingredient 100 mass parts of total amount be 0.01 mass parts~10 mass parts, more preferably 0.05 mass parts~5 mass parts, Further preferably 0.1 mass parts~3 mass parts.If the content of (D) ingredient is more than above range, it is easy to produce pair In the remaining tendency of the development of copper base etc., furthermore, it is possible to which generating is caused by the reduction of resolution ratio, being substantially increased for sensitivity The solidification deficiency of resist bottom etc..It in contrast, can be abundant if the content of (D) ingredient is located in above range Inhibit the development for copper base etc. to remain and realizes and to resist bottom also sufficiently cured appropriate curability.Due to and extremely The abundant effect of resist bottom, so as to obtain good resist shape and also become better to the patience of etching solution It is good.
(other ingredients)
Photosensitive polymer combination can according to need containing the ingredient other than above-mentioned (A)~(D) ingredient.For example, photosensitive Property resin combination can be containing from by sensitization pigment, bis- [4- (dimethylamino) phenyl] methane, bis- [4- (diethylamino) Phenyl] select in group composed by methane and colorless crystal violet it is at least one kind of.
As sensitization pigment, such as dialkyl amido benzophenone cpd, pyrazoline compounds, anthracene chemical combination can be enumerated Object, coumarin compound, xanthene ketone compound, thioxanthone compounds, oxazoline compound, benzoxazoles compound, thiazole chemical combination Object, benzothiazole compound, triazole compounds, stilbene compounds, triaizine compounds, thiophene compound, naphthalimide compound, three Novel arylamine compound and aminacrine compound.They can be used alone or combine two or more use.
In addition, the cyclic ether that photosensitive polymer combination can have at least one to be capable of cationic polymerization containing intramolecular The polymerizable compound (oxetane compound etc.) of base；Cationic polymerization initiators；Sparrow malachite green, Victoria pure blue, alkali The dyestuffs such as property brilliant green, crystal violet；Tribromo phenylsulfone, diphenylamine, benzyl amine, triphenylamine, diethylaniline, o-chloraniline etc. Light color developing agent；Heat colour developing preventing agent；The plasticizer such as para toluene sulfonamide；Pigment；Filler；Defoaming agent；Fire retardant；Stabilizer； Adaptation imparting agent；Levelling agent；Remove promotor；Antioxidant；Fragrance；Preparation；Thermal cross-linking agent；Deng.They can be independent Using or combine two or more use.
In the case where photosensitive polymer combination includes other ingredients (ingredient other than (A)~(D) ingredient), they Content is set to 0.01 mass parts~20 mass parts journeys preferably with respect to 100 mass parts of total amount of (A) ingredient He (B) ingredient Degree.
[solution of photosensitive polymer combination]
Photosensitive polymer combination can be the liquid composition for further including at least one kind of organic solvent.As organic Solvent can enumerate the alcoholic solvents such as methanol, ethyl alcohol；The ketone solvents such as acetone, methyl ethyl ketone；Methyl cellosolve, ethyl cellosolve, third The glycol ether solvents such as glycol monomethyl ether；The aromatic hydrocarbon solvents such as toluene；The aprotic polars such as N,N-dimethylformamide are molten Agent etc..They can be used alone, and can also mix two or more use.
The content of organic solvent contained by photosensitive polymer combination can suitably be selected according to purpose etc..Such as photonasty Resin combination can be used as the liquid composition that solid component is the 30 mass % degree of mass %~60 The photosensitive polymer combination of solvent is known as " coating fluid ".) use.
By the way that coating fluid is coated on the surface of aftermentioned support membrane, metal plate etc. and is dried, so as to shape At the photosensitive polymer combination layer of the film as photosensitive polymer combination.As metal plate, it is not particularly limited, it can be with It is suitably selected according to purpose etc..As metal plate, can enumerate comprising iron-based alloys such as copper, copper series alloy, nickel, chromium, iron, stainless steels The metal plate of equal metals.As preferred metal plate, the metal plate comprising metals such as copper, copper series alloy, iron-based alloys can be enumerated.
The thickness of the photosensitive polymer combination layer of formation is not particularly limited, and can suitably be selected according to its purposes.Sense The thickness (thickness after dry) of photosensitive resin composition layer is preferably 1 μm~100 μm degree.
In the case where foring photosensitive polymer combination layer on a metal plate, photoresist can be coated with protective film The surface with metal plate opposite side of composition layer.As protective film, polymer films such as polyethylene, polypropylene etc. can be enumerated.
< photosensitive element >
The photosensitive element of present embodiment (is only called " photosensitive element " below.) there is support membrane and be arranged in the branch Support the photosensitive polymer combination layer comprising above-mentioned photosensitive polymer combination in the one side of film.According to such photonasty member Part can be effectively formed i.e. due to having the photosensitive polymer combination layer comprising above-mentioned photosensitive polymer combination Make the substrate high for flatness that also there is sufficient adaptation and there is excellent acid proof resist pattern.Photonasty Element can according to need with other layers such as protective film.
Fig. 1 is the schematic section for indicating an embodiment of photosensitive element of the invention.Shown in Fig. 1 is photosensitive In property element 10, support membrane 2, the photosensitive polymer combination layer 4 comprising photosensitive polymer combination and protective film 6 successively layer It is folded.Photosensitive polymer combination layer 4 is referred to as the film of photosensitive polymer combination.In addition film is photoresist group Close the film that object is uncured state.
Photosensitive element 10 can for example operate acquisition as follows.Coating is as the sense comprising organic solvent on support membrane 2 The coating fluid of photosensitive resin composition and form coating layer, be dried and (remove at least one of organic solvent from coating layer Point), to form photosensitive polymer combination layer 4.Then, be coated photosensitive polymer combination layer 4 with protective film 6 with support The face of 2 opposite side of film, to obtain the photosensitive polymer combination layer 4 and layer that there is support membrane 2, be layered on the support membrane 2 It is stacked in the photosensitive element 10 of the protective film 6 on the photosensitive polymer combination layer 4.In addition, photosensitive element 10 can not also Centainly there is protective film 6.
As support membrane 2, can be used comprising polyester such as polyethylene terephthalate；The polyenes such as polypropylene, polyethylene Hydrocarbon etc. has the film of the polymer of heat resistance and solvent resistance.
The thickness of support membrane 2 is preferably 1 μm~100 μm, more preferably 5 μm~50 μm, further preferably 5 μm~30 μ m.By making the thickness of support membrane 2 be greater than or equal to 1 μm, it is damaged to be able to suppress the support membrane 2 when removing support membrane 2.In addition lead to Crossing makes it be less than or equal to 100 μm, is able to suppress the reduction of resolution ratio.
As protective film 6, it is less than support membrane 2 for photonasty preferably for the bonding force of photosensitive polymer combination layer 4 The bonding force of resin composition layer 4.Specifically, can be used poly- comprising polyethylene terephthalate etc. as protective film 6 Ester；Polyolefin such as polypropylene, polyethylene etc. have the film of the polymer of heat resistance and solvent resistance.As commercially available product, can enumerate ALPHANMA-410, E-200 of Oji Paper's manufacture, the polypropylene screen of film Co., Ltd., SHIN-ETSU HANTOTAI manufacture, Supreme Being people's strain The NF-15A of the polyethylene terephthalate film of the PS series such as PS-25 of formula commercial firm manufacture, Tamapoly.In addition, protective film 6 It can be identical as support membrane 2.
The thickness of protective film 6 is preferably 1 μm~100 μm, more preferably 5 μm~50 μm, further preferably 5 μm~30 μ M, particularly preferably 15 μm~30 μm.If the thickness of protective film 6 be greater than or equal to 1 μm. while removing protective film 6 When photosensitive polymer combination layer 4 and support membrane 2 are laminated on substrate, it is damaged to be able to suppress protective film 6.If it is less than or wait It is in 100 μm, then operational and cheapness excellent.
Photosensitive element 10 specifically can for example be operated as follows and be manufactured.It can be by the inclusion of the system of following process The method of making is manufactured: preparing the process of the coating fluid comprising photosensitive polymer combination；Above-mentioned coating fluid is coated on support The process and process that is above-mentioned coating layer is dry and forming photosensitive polymer combination layer 4 of coating layer are formed on film 2.
Coating of the coating fluid on support membrane 2 can pass through roller coating, the coating of unfilled corner wheel, intaglio plate coating, airblade coating, mould Method well known to painting, stick painting etc. carries out.
About the drying of coating layer, without special as long as it at least part of organic solvent can be removed from coating layer Limitation.Such as preferably in 70 DEG C~150 DEG C progress, 5 minutes~30 minutes degree.About photosensitive polymer combination layer 4 after drying In remaining organic solvent amount, from prevent in subsequent handling organic solvent diffusion from the viewpoint of, be preferably set to be less than or wait In 2 mass %.
The thickness of photosensitive polymer combination layer 4 in photosensitive element 10 can be selected suitably depending on the application.With drying Thickness gauge afterwards is preferably 1 μm~100 μm, more preferably 1 μm~50 μm, further preferably 5 μm~40 μm.It is photosensitive by making Property resin composition layer 4 thickness be greater than or equal to 1 μm, industrial coating becomes easy.If it is less than or be equal to 100 μm, then have It can fully obtain the tendency of adaptation and resolution ratio.
The form of photosensitive element 10 is not particularly limited.It for example, can be sheet, or can be to be wound in core At the shape of web-like.In the case where wound into rolls, preferably it is wound in such a way that support membrane 2 is outside.As core, Polyvinyl resin, acrylic resin, polystyrene resin, Corvic, ABS resin (acrylonitrile-butadiene-can be enumerated Styrol copolymer) etc. plastics etc..On the end face that the photosensitive element of the web-like obtained in this way is rolled up, from the viewpoint of end face protection It sets out and is preferably provided with end face diaphragm, damp proof end face diaphragm is preferably provided with from the viewpoint of resistance to edge-melting.As bundling method, preferably It is packed in the small black thin plate of penetrability and is packed.
Photosensitive element 10 can for example be suitably used for the forming method of aftermentioned resist pattern.
The forming method > of < resist pattern
The forming method of the resist pattern of present embodiment has following process: (i) is formed on substrate comprising photosensitive The lamination process of the photosensitive polymer combination layer of property resin combination；(ii) by the irradiation of active ray by photoresist Composition layer it is a part of regions curing, formed and solidify the exposure process of object area；(iii) by photosensitive polymer combination layer Solidify the region other than object area to remove from substrate, on substrate formed comprising photosensitive polymer combination solidfied material (Gu Compound region) resist pattern developing procedure.The forming method of resist pattern, which can according to need, further has it Its process.Each process is described in detail below.
(i) lamination process
In lamination process, the photosensitive polymer combination layer comprising photosensitive polymer combination is formed on substrate.
As the method for forming photosensitive polymer combination layer on substrate, such as the coating on substrate can be enumerated and include sense After the coating fluid of photosensitive resin composition, the method that is dried.
In addition, as the method for forming photosensitive polymer combination layer on substrate, such as can enumerate from photosensitive element After protective film is removed as needed, the photosensitive polymer combination of photosensitive element is pressed into method on base material layer by layer.Layer Pressure can be carried out by the way that the photosensitive polymer combination layer of photosensitive element is crimped on substrate while heating.By this Lamination, obtains laminated body made of substrate, photosensitive polymer combination layer and support membrane stack gradually.
Lamination is preferably carried out with such as 70 DEG C~130 DEG C of temperature, preferably with 0.1MPa~1.0MPa degree (1kgf/cm2 ~10kgf/cm2Degree) pressure crimping and carry out.These conditions can according to need carry out appropriate adjustment.It, can in lamination To carry out the pre-heat treatment to substrate, photosensitive polymer combination layer can also be heated to 70 DEG C~130 DEG C.
(ii) exposure process
In exposure process, to a part of area illumination active ray of photosensitive polymer combination layer, thus will irradiation The exposure portion photocuring of active ray forms sub-image.Here, when using photosensitive element in lamination process, in photonasty There are support membranes on resin composition layer, can be through support in the case where support membrane has permeability for active ray Film irradiates active ray.On the other hand, in the case where support membrane shows light-proofness for active ray, support membrane is removed Afterwards, active ray is irradiated to photosensitive polymer combination layer.
As exposure method, it can enumerate to irradiate through the minus or eurymeric mask pattern for being referred to as original image with image shape and live The method (mask exposure method) of property light.Pass through LDI (laser direct imaging, Laser Direct alternatively, it is also possible to use Imaging) exposure method, DLP (digital light processing, Digital Light Processing) exposure method etc. directly describe exposure method In the method for image shape irradiation active ray.
It is excellent from the viewpoint of more reliably obtaining effect of the invention as the wavelength (exposure wavelength) of active ray It is selected as within the scope of 340nm~430nm, within the scope of more preferably 350nm~420nm.
(iii) developing procedure
In developing procedure, by development treatment by the region of photosensitive polymer combination layer solidified other than object area (that is, uncured portion of photosensitive polymer combination layer) is removed from substrate, and being formed on substrate includes photoresist group Close the resist pattern of the solidfied material of nitride layer.In addition, there is support on the photosensitive polymer combination layer by exposure process In the case where film, developing procedure is carried out after support membrane is removed.For development treatment, there are wet developing and dry process development, but It is preferable to use wet developings.
In wet developing, using developer solution corresponding with photosensitive polymer combination, by well known developing method into Row development.As developing method, can enumerate impregnation method, sheathed submergence mode, spray pattern, using brushing, beating, scraping, The method for shaking impregnating, from the viewpoint of resolution ratio raising, high-pressure fog mode is most suitable for.Can also by this two or more Method combination develop.
Developer solution can suitably be selected according to the composition of photosensitive polymer combination.As developer solution, alkaline water can be enumerated Solution, water system developer solution, organic solvent system developer solution etc..
As the alkaline aqueous solution that development uses, the preferably 0.1 mass % of mass %~5 sodium carbonate liquor, 0.1 mass % ~5 mass % solution of potassium carbonate, the 0.1 mass % of mass %~5 sodium hydroxide solution, the 0.1 mass % sodium tetraborate of mass %~5 Solution etc..The pH of alkaline aqueous solution is preferably 9~11 range.In addition its temperature can be according to the alkali of photosensitive polymer combination layer Developability is adjusted.Surfactant, defoaming agent can be mixed into alkaline aqueous solution, for promoting a small amount of organic molten of development Agent etc..
The forming method of resist pattern can further have following process: after unexposed portion is removed, according to Need to carry out the heating and/or 0.2J/cm of 60 DEG C~250 DEG C degree2~10J/cm2The exposure of degree, thus by resist pattern Further solidification.
The manufacturing method > of < touch panel
The manufacturing method of the touch panel of present embodiment, which has, forms the forming method by above-mentioned resist pattern The process that the substrate of resist pattern is etched.About etching process, using the resist pattern of formation as mask, Conductor layer to substrate etc. carries out.The pattern for drawing wiring and transparent electrode is formed by etching process, to manufacture touch surface Plate.
Fig. 3 is the schematic section for indicating a form of manufacturing method for touch panel of the invention.The system of this form Method is made with following process: with supporting base material 22,24 and of transparency conducting layer that is arranged in the one side of supporting base material 22 It is arranged on the metal layer 26 of the laminated substrate of the metal layer 26 on transparency conducting layer 24, being formed includes photosensitive polymer combination Solidfied material resist pattern 29 the 1st process；Metal layer 26 and transparency conducting layer 24 are etched, formed comprising transparent 2nd process of the lamination pattern (24+26 in Fig. 3 (d)) of the remainder of the remainder and metal layer 26 of conductive layer 24；With And remove metal layer from a part of lamination pattern, form the transparent electrode and packet of the remainder comprising transparency conducting layer 24 3rd process of the metal wiring of metal-containing layer remainder.
In 1st process, first as shown in Fig. 3 (a), with supporting base material 22, be arranged in the one side of supporting base material 22 Transparency conducting layer 24 and the laminated substrate of metal layer 26 being arranged on transparency conducting layer 24 metal layer 26 on stacking include The photosensitive polymer combination layer 28 of photosensitive polymer combination.Photosensitive polymer combination layer 28 can also with metal layer 26 There is support membrane on the face of opposite side.
As metal layer 26, the conjunction of the alloy comprising copper, copper and nickel, molybdenum-aluminium-molybdenum layer stack, silver and palladium and copper can be enumerated The metal layer of gold etc..In these metal layers, from the viewpoint of obtaining effect of the invention more significantly, it can be suitble to use The metal layer of alloy comprising copper or copper and nickel.
Transparency conducting layer 24 contains tin indium oxide (ITO).From the viewpoint of never needing to annealing, transparency conducting layer 24 Preferably comprise crystalline ITO.
Then, a part of regions curing of photosensitive polymer combination layer 28 is formed solid by the irradiation of active ray Compound region removes in the region of photosensitive polymer combination layer solidified other than object area from laminated substrate.As a result, as schemed Shown in 3 (b), resist pattern 29 is formed in laminated substrate.
In the 2nd process, by etching process, by the metal layer 26 in the region that do not covered by resist pattern 29 and transparent Conductive layer 24 is removed from supporting base material 22.
The method of etching process is suitably selected according to the layer to be removed.For example, as the etching solution for removing metal layer, Copper chloride solution, ferric chloride solution, phosphoric acid solution etc. can be enumerated.In addition, as the etching solution for removing transparency conducting layer, it can Use oxalic acid, hydrochloric acid, chloroazotic acid etc..
In the case where transparency conducting layer 24 includes crystallinity ITO, as the etching solution for removing transparency conducting layer 24, The strong acid such as concentrated hydrochloric acid must be used, but in the manufacturing method of this form, since resist pattern includes above-mentioned photoresist The solidfied material of composition, therefore can sufficiently inhibit under the etching process carried out using strong acid the removing of resist pattern Deng.
Fig. 3 (c) is the figure after indicating etching process, in Fig. 3 (c), is formed in supporting base material 22 comprising metal layer The laminated body of the remainder of 26 remainder, the remainder of transparency conducting layer 24 and resist pattern 28.In this form Manufacturing method in, removed from the laminated body by resist pattern 28.
The removing of resist pattern 28 can be used for example than alkaline aqueous solution alkalinity used in above-mentioned developing procedure more Strong aqueous solution.As the aqueous solution of the strong basicity, 1~10 mass % sodium hydrate aqueous solution, 1~10 mass % hydrogen can be used Aoxidize aqueous solutions of potassium etc..Wherein, it is preferable to use 1~10 mass % sodium hydrate aqueous solution or potassium hydroxide aqueous solution, more excellent Choosing uses 1~5 mass % sodium hydrate aqueous solution or potassium hydroxide aqueous solution.It, can as the removing mode of resist pattern Impregnation method, spray pattern etc. are enumerated, they, which can be used alone, also can be used together.
Fig. 3 (d) is to indicate that the figure after resist pattern removing is formed in supporting base material 22 in Fig. 3 (d) and includes The lamination pattern of the remainder of the remainder and transparency conducting layer 24 of metal layer 26.
In the 3rd process, it will be used to form other than a part of metal wiring and remove in metal layer 26 from the lamination pattern, Form the metal wiring of the remainder comprising metal layer 26 and the transparent electrode of the remainder comprising transparency conducting layer 24.Separately Outside, in this form, as the method for removing metal layer 26 in the 3rd process, using the method being etched, but the 3rd The method that metal layer 26 removes is not necessarily limited to etch in process.
In the 3rd process, 30 (Fig. 3 of photosensitive polymer combination layer is formed first in the laminated substrate Jing Guo the 2nd process (e)).Then, it by the exposure and imaging of photosensitive polymer combination layer 30, is formed comprising photosensitive polymer combination layer 30 The resist 31 (Fig. 3 (f)) of solidfied material.In addition, photosensitive resin composition layer can be to include the photosensitive of above-mentioned present embodiment The layer of property resin combination, or the layer comprising previously known etching photosensitive polymer combination.
Then, by etching process, the part of not formed resist 31 removes metal layer 26 from lamination pattern.This When, as etching process liquid, etching solution same as removing the etching solution of above-mentioned metal layer can be used.
Fig. 3 (g) is the figure after indicating etching process, in Fig. 3 (g), is formed in supporting base material 22 and leads comprising transparent The transparent electrode of the remainder of electric layer 24, and be formed in a part of transparent electrode comprising metal layer 26 and resist 31 Laminated body.By being removed from the laminated body by resist 31, as shown in Fig. 3 (h), formed in supporting base material 22 comprising transparent The metal wiring of the transparent electrode of the remainder of conductive layer 24 and the remainder comprising metal layer 26.
Fig. 4 is the top view for indicating a form of the touch panel obtained using the present invention.In touch panel 100, X electrode 52 and Y electrode 54 as transparent electrode are alternately set side by side, and the X electrode 52 for being arranged to length direction same column leads to each other It crosses an extraction wiring 56 to be connected with each other, in addition, being arranged to the Y electrode 54 of width direction same column each other by an extraction wiring 57 interconnect.
The preferred embodiment of the present invention is illustrated above, but the present invention is not limited to the above embodiments.
Embodiment
It is further elaborated with the present invention below by embodiment, but the present invention is not limited to embodiments.
(Production Example 1: the manufacture of binder polymer (A-1))
It will be as the methacrylic acid 30g, methyl methacrylate 35g and methacrylic acid fourth of polymerizable monomer (monomer) The solution that ester 35g (mass ratio 30/35/35), azobis isobutyronitrile 0.5g and acetone 10g are mixed to get is used as " solution a ".It will be The solution that 0.6g azobis isobutyronitrile obtains is dissolved in 30g acetone is used as " solution b ".
Acetone is added in the flask with blender, reflux cooler, thermometer, dropping funel and nitrogen ingress pipe Mixed liquor (mass ratio 4:1) 100g of 80g and propylene glycol monomethyl ether 20g, is stirred while being blown into nitrogen into flask It mixes while being heated, be warming up to 80 DEG C.
After the above-mentioned solution a that drips in 4 hours above-mentioned mixed liquors into flask, exist 80 DEG C of guarantors while being stirred Temperature 2 hours.Then, with after the above-mentioned solution b that drips in the 10 minutes solution into flask. while stirring the solution in flask 3 hours are kept the temperature at 80 DEG C.Further, the solution in flask is warming up to 90 DEG C with 30 minutes, it is cold after keeping the temperature 2 hours at 90 DEG C But, the solution of binder polymer (A-1) is obtained.
The nonvolatile component (solid component) of binder polymer (A-1) is 42.8 mass %, and weight average molecular weight is 50000, acid value 195mgKOH/g, dispersion degree 2.58.
In addition, weight average molecular weight is measured by gel permeation chromatography (GPC), by using standard polystyren Standard curve is converted and is exported.The condition of following presentation GPC.
GPC condition
Pump: Hitachi/L-6000 type (Hitachi Co., Ltd's system)
Column: totally 3 below, column specification:
Gelpack GL-R440
Gelpack GL-R450
Gelpack GL-R400M (the above are Hitachi Chemical Co., Ltd.'s systems, trade name)
Elutriant: tetrahydrofuran (THF)
Sample solution concentration: taking 120mg solid component is the resin solution of 40 mass %, is dissolved in the THF of 5mL and modulates examination Sample.
Measuring temperature: 40 DEG C
Injection rate: 200 μ L
Pressure: 49Kgf/cm2(4.8MPa)
Flow: 2.05mL/ minutes
Detector: Hitachi L-3300 type RI (Hitachi Co., Ltd's system)
Embodiment and comparative example are carried out by the following method.
(modulation of photosensitive polymer combination (coating fluid))
By each ingredient shown in Tables 1 and 2 with use level shown in the table (mass parts) and 5 mass parts of methanol, toluene 12 Mass parts and the mixing of 5 mass parts of acetone, to modulate the coating fluid of the photosensitive polymer combination of embodiment and comparative example.In table (A) ingredient use level be nonvolatile component quality (solid content).The details of each ingredient shown in table 1 and 2 As described below.
((A) ingredient)
A-1: the binder polymer (A-1) obtained by Production Example 1.
((B) ingredient)
FA-321M:FA-321M (Hitachi Chemical Co., Ltd.'s system, trade name), the bis- (4- (methacryloxypropyls of 2,2- Five ethyoxyl of base) phenyl) propane；
UA-11:UA-11 (village Xin Zhong chemical industry Co. Ltd. system, trade name), polyoxyethylene carbamate diformazan Base acrylate；
UA-13:UA-13 (village Xin Zhong chemical industry Co. Ltd. system, trade name), polyoxyethylene polyoxypropylene amino Formic acid esters dimethylacrylate；
FA-MECH:FA-MECH (Hitachi Chemical Co., Ltd.'s system, trade name), γ-chloro- β-hydroxy propyl-Beta '-methyl Acryloyl-oxyethyl-phthalic acid ester.
((C) ingredient)
B-CIM:B-CIM (Hampford corporation, ProductName), 2,2 '-bis- (2- chlorphenyl) -4,4 ', 5,5 '-tetraphenyls Double imidazoles；
EAB:EAB (Baotugu Chemical Industrial Co., Ltd's system, ProductName), 4,4 '-bis- (diethylamino) benzophenone.
((D) ingredient)
(D1) ingredient
KBM-803:KBM-803 (SHIN-ETSU HANTOTAI's organosilicon corporation, ProductName), 3-mercaptopropyi trimethoxy silane.
(D2) ingredient
AY43-031:AY43-031 (Dong Li Dow Corning Corporation system, ProductName), 3- ureidopropyltriethoxysilane；
KBE-573:KBE-573 (SHIN-ETSU HANTOTAI's organosilicon corporation, ProductName), N- phenyl -3- aminopropyl trimethoxy silicon Alkane；
KBE-903:KBE-903 (SHIN-ETSU HANTOTAI's organosilicon corporation, ProductName), 3-aminopropyltriethoxysilane；
KBM-903:KBM-903 (SHIN-ETSU HANTOTAI's organosilicon corporation, trade name), 3- TSL 8330；
KBE-9103:KBE-9103 (SHIN-ETSU HANTOTAI's organosilicon corporation, ProductName), 3- triethoxysilyl-N- (1,3- Dimethyl-butylidene) propylamine；
Z-6032:Z-6032 (Dong Li Dow Corning Corporation system, ProductName), aminoethylaminopropyl trimethoxy silane.
(D3) ingredient
SZ-6030:SZ-6030 (Dong Li Dow Corning Corporation system, trade name), methacryloxypropyl trimethoxy silicon Alkane.
(D1)~(D3) silane coupling agent other than ingredient
KBE-846:KBE-846 (SHIN-ETSU HANTOTAI's organosilicon corporation, ProductName), bis- (triethoxysilylpropyltetrasulfide) four sulphur Compound；
KBE-9007:KBE-9007 (SHIN-ETSU HANTOTAI's organosilicon corporation, ProductName), 3- isocyanates propyl-triethoxysilicane Alkane；
KBE-403:KBE-403 (SHIN-ETSU HANTOTAI's organosilicon corporation, ProductName), 3- glycidoxypropyl group triethoxysilicane Alkane；
KBE-5103:KBE-5103 (SHIN-ETSU HANTOTAI's organosilicon corporation, ProductName), 3- acryloxypropyl trimethoxy silicon Alkane.
((E) ingredient: the ingredient other than (A)~(D) ingredient)
LCV:LCV (hillside plot Chemical Co., Ltd. system, ProductName), colorless crystal violet；
TBC:DIC-TBC-5P (Dainippon Ink. & Chemicals Inc's system, ProductName), 4- tert-butyl catechol；
F-806P: bis- (N, N-2- ethylhexyl) amino methyl -5- carboxyl-l, 2,3 triazoles；
AZCV-PW:AZCV-PW (Baotugu Chemical Industrial Co., Ltd's system, ProductName), [4- { bis- (4- dimethylaminos Phenyl) methylene } -2,5- cyclohexadiene -1- subunit].
[table 1]
[table 2]
The production > of < photosensitive element
The coating fluid of photosensitive polymer combination obtained above is uniformly coated to 16 μm of thickness poly- to benzene respectively On dioctyl phthalate second diester film (eastern beautiful (strain) system, ProductName " FB-40 "), 70 DEG C and 110 DEG C of hot wind convection type drier is used It is successively dried, the photosensitive polymer combination layer that the film thickness after forming drying is 15 μm.In the photoresist group It closes and is bonded protective film (Tamapoly (strain) system, ProductName " NF-15A ") in nitride layer, obtain polyethylene terephthalate film (branch Support film), photosensitive polymer combination layer and protective film stack gradually made of photosensitive element.
The production > of < laminated substrate
The transparency conducting layer comprising ITO is formed, further saturating using on the upper layer of polyethylene terephthalate materials The upper layer of bright conductive layer forms the metal layer comprising copper, carries out film base material made of antirust treatment to the outmost surface of metal layer. To the film base material (hereinafter referred to as " substrate ".) heated and be warming up to 80 DEG C after, the photosensitive element of above-mentioned production is laminated The layer on surface of metal of (stacking) in substrate.Lamination is following to be carried out: on one side being removed protective film, is made the photosensitive of photosensitive element on one side The property closely sealed layer on surface of metal in substrate of resin composition layer, in 110 DEG C of temperature, lamination pressure 4kgf/cm2The item of (0.4MPa) It is carried out under part.It obtains being laminated with photosensitive polymer combination layer and poly terephthalic acid on the layer on surface of metal of substrate as a result, The laminated substrate of second diester film.
The evaluation > of < sensitivity
The placement of obtained laminated substrate is cooled to 23 DEG C.Then, laminated substrate is divided into 3 regions, wherein one Closely sealed light tool in the polyethylene terephthalate film in a region, it is 0.00~2.00, concentration ladder that light tool, which has concentration range, Degree be 0.05, exposure meter size be 20mm × 187mm, 41 sections of stage exposure meters that the size in each stage is 3mm × 12mm. About exposure, the directional light with short arc UV lamp ((strain) ORC manufacturing company system, ProductName " AHD-5000R ") for light source is used Line exposing machine ((strain) ORC manufacturing company system, ProductName " EXM-1201 "), with 100mJ/cm2Energy (light exposure) across Light tool and polyethylene terephthalate film are exposed photosensitive polymer combination layer.At this moment, the other regions not used It is covered with black thin plate.In addition, to each region using same method respectively with 200mJ/cm2、400mJ/cm2Energy carry out Exposure.In addition, the measurement of illumination uses ultraviolet light illumination photometer (USHIO motor (strain) system, production that 405nm corresponds to probe of applying The name of an article " UIT-150 ").
It after exposure, is removed from laminated substrate by polyethylene terephthalate film, exposes photosensitive polymer combination layer, It is at 30 DEG C that 1 mass % aqueous sodium carbonate is 16 seconds spraying, so that unexposed portion be removed.As a result, in the metal of substrate The resist pattern comprising photosensitive polymer combination solidfied material is formed in layer surface.By being used as resist pattern under each light exposure The standard curve of remaining number of segment (number of stages) the production light exposure and number of stages of the stage exposure meter that (cured film) obtains, finds out The light exposure that number of stages is 20 sections, to evaluate the sensitivity of photosensitive polymer combination.Sensitivity from standard curve by finding out Number of stages be 20 sections light exposure indicate, the light exposure is fewer to mean that sensitivity is the better.Show the result in table 3 and table 4 In.
The evaluation > of < adaptation
(it is denoted as " L/S " below using line width (L)/interval wide (S).) be 8/400~47/400 (unit: μm) mask artwork Case, the energy for being 20 sections with the remaining number of segment of 41 sections of stage exposure meters is to the photosensitive polymer combination layer of above-mentioned laminated substrate It is exposed.After exposure, development treatment same as the evaluation of above-mentioned sensitivity is carried out.
After development, it is completely removed by compartment (unexposed portion) and line part (exposed portion) does not generate song Minimum value evaluation adaptation in the wide value in line width/interval of the resist pattern roll over, formed to notch.The smaller meaning of the numerical value Adaptation it is the better.It shows the result in table 3 and table 4.
The evaluation > of < resolution ratio
It is the mask pattern of 8/8~47/47 (unit: μm) using L/S, the remaining number of segment with 41 sections of stage exposure meters is 20 sections of energy is exposed the photosensitive polymer combination layer of above-mentioned laminated substrate.After exposure, carry out and above-mentioned sensitivity The same development treatment of evaluation.
After development, it is completely removed by compartment (unexposed portion) and line part (exposed portion) does not generate song Minimum value evaluation resolution ratio in the wide value in line width/interval of the resist pattern roll over, formed to notch.The smaller meaning of the numerical value Resolution ratio it is the better.It shows the result in table 3 and table 4.
The evaluation > of < corrosion liquid resistance
The elching resistant of following evaluation resist pattern.It is the mask artwork of 8/400~47/400 (unit: μm) using L/S Case, the energy for being 20 sections with the remaining number of segment of 41 sections of stage exposure meters is to the photosensitive polymer combination layer of above-mentioned laminated substrate It is exposed.After exposure, development treatment same as the evaluation of above-mentioned sensitivity is carried out, obtains forming figuratum substrate.
Obtained substrate is etched the metal layer disappearance until surface using chlorination copper system solution.Later, washed, It is dry.Further, the substrate for eliminating surface metal-layer is impregnated 1 minute or 2 points in 25 mass % hydrochloride aqueous solutions Clock is washed, is dried later.
After being removed transparency conducting layer by etching, by the metal layer and transparency conducting layer of compartment (unexposed portion) Be completely removed and line part (exposed portion) do not generate resist pattern that is tortuous, being formed to notch line width/interval it is wide Value in minimum value, evaluation etching after adaptation.The numerical value is smaller to mean that corrosion liquid resistance is higher, adaptation is better It is good.The case where by the etching period for being used to remove transparency conducting layer being 1 minute is denoted as (μm/1min), by 2 minutes the case where be denoted as (μm/2min), it shows the result in table 3 and table 4.
[table 3]
[table 4]
In addition, in comparative example 5 and comparative example 10, be coated with pension gelation and film forming made to become extremely difficult, from stability, From the viewpoint of yield rate, it is difficult to be used as product.The reason of as coating pension gelation, it is believed that be that each comparative example is used The amino of silane coupling agent and the carboxylic acid of binder polymer have occurred and act on.
Symbol description
2: support membrane, 4: photosensitive polymer combination layer, 6: protective film, 10: photosensitive element, 12: supporting base material, 14: Transparency conducting layer, 16: wiring, 22: supporting base material, 24: transparency conducting layer, 26 photosensitive polymer combination layer, 18: are drawn: gold Belong to layer, 28: photosensitive polymer combination layer, 29: resist, 30: photosensitive polymer combination layer, 31: resist, 52: transparent Electrode (X electrode), 54: wiring, 100: touch panel transparent electrode (Y electrode), 56,57: are drawn.

Claims (41)

1. a kind of ITO etching photosensitive polymer combination, contains:
Binder polymer,
Photopolymerizable compound,
Photoepolymerizationinitiater initiater and
Silane coupling agent,
Described adhesive polymer has from the structural unit of (methyl) acrylic acid and from (methyl) acrylic acid alkyl The structural unit of ester,
The photopolymerizable compound includes the compound that at least one kind of intramolecular has 2 ethylene unsaturated bonds,
The silane coupling agent includes the silane compound with mercaptoalkyl, the silane compound with amino and has The silane compound of (methyl) acryloxy,
Relative to 100 mass parts of total amount of described adhesive polymer and the photopolymerizable compound, the silane coupling agent Content be 0.01 mass parts~10 mass parts, the content of the photopolymerizable compound is 30 mass parts~70 mass parts, institute The content for stating Photoepolymerizationinitiater initiater is 0.1 mass parts~10 mass parts,
Total amount 100 mass of the content of described adhesive polymer in described adhesive polymer and the photopolymerizable compound It is 30 mass parts~70 mass parts in part.
2. photosensitive polymer combination according to claim 1, the silane compound with mercaptoalkyl be with The silane compound of mercaptoalkyl and alkoxy.
3. photosensitive polymer combination according to claim 2, the silane chemical combination with mercaptoalkyl and alkoxy Object is mercaptopropyi trimethoxy silane.
4. photosensitive polymer combination described in any one of claim 1 to 3, the silane compound with amino There is the silane compound of primary amino group for end.
5. photosensitive polymer combination according to claim 4, it is 3- that the end, which has the silane compound of primary amino group, Ureidopropyltriethoxysilane.
6. photosensitive polymer combination described in any one of claim 1 to 3, described to have (methyl) acryloxy Silane compound be 3- methacryloxypropyl trimethoxy silane.
7. the content of photosensitive polymer combination described in any one of claim 1 to 3, the silane coupling agent is opposite In 100 mass parts of total amount of described adhesive polymer and the photopolymerizable compound be 0.05 mass parts~5 mass parts.
8. the content of photosensitive polymer combination described in any one of claim 1 to 3, the silane coupling agent is opposite In 100 mass parts of total amount of described adhesive polymer and the photopolymerizable compound be 0.1 mass parts~3 mass parts.
9. photosensitive polymer combination described in any one of claim 1 to 3, the intramolecular has 2 ethylene The content of the compound of unsaturated bond is in 100 mass parts of total amount of described adhesive polymer and the photopolymerizable compound For 5 mass parts~60 mass parts.
10. photosensitive polymer combination described in any one of claim 1 to 3, the photopolymerizable compound include From by (methyl) acrylate compounds of bisphenol A-type two and the amino with (poly-) oxygen ethylidene and/or (poly-) oxygen propylidene It is selected in group composed by formic acid esters two (methyl) acrylate compounds at least one kind of.
11. photosensitive polymer combination described in any one of claim 1 to 3, the photopolymerizable compound contains Bisphenol A-type two (methyl) acrylate compounds.
12. photosensitive polymer combination according to claim 11, bisphenol A-type two (methyl) acrylate compounds For compound represented by following formula (1),
[changing 1]
In formula (1), R1And R2Each independently represent hydrogen atom or methyl；XO and YO each independently represent oxygen ethylidene or Person's oxygen propylidene；m1、m2、n1And n2Each independently represent 0~40；Wherein, m1+n1And m2+n2It is all larger than or equal to 1；It is in XO In the case that oxygen ethylidene, YO are oxygen propylidene, m1+m2For 1~40, n1+n2It is 0~20；XO is oxygen propylidene, YO is oxygen In the case where ethylidene, m1+m2For 0~20, n1+n2It is 1~40.
13. photosensitive polymer combination according to claim 12, in the formula (1), XO is oxygen ethylidene, and YO is that oxygen is sub- Propyl, m1+m2It is 8~40.
14. photosensitive polymer combination according to claim 12, in the formula (1), XO is oxygen ethylidene, and YO is that oxygen is sub- Propyl, m1+m2It is 8~20.
15. photosensitive polymer combination according to claim 12, in the formula (1), XO is oxygen ethylidene, and YO is that oxygen is sub- Propyl, m1+m2It is 8~10.
16. photosensitive polymer combination according to claim 11, bisphenol A-type two (methyl) acrylate compounds Content in 100 mass parts of total amount of described adhesive polymer and the photopolymerizable compound be 1 mass parts~50 matter Measure part.
17. photosensitive polymer combination described in any one of claim 1 to 3, the photopolymerizable compound contains Carbamate two (methyl) acrylate compounds with (poly-) oxygen ethylidene and/or (poly-) oxygen propylidene.
18. photosensitive polymer combination according to claim 17, described to have (poly-) oxygen ethylidene and/or (poly-) oxygen sub- The content of carbamate two (methyl) acrylate compounds of propyl is in described adhesive polymer and the optical polymerism It is 1 mass parts~50 mass parts in 100 mass parts of total amount of compound.
19. photosensitive polymer combination described in any one of claim 1 to 3, the photopolymerizable compound is into one Walk the compound that there is 1 ethylene unsaturated bond containing intramolecular.
20. photosensitive polymer combination according to claim 19, the intramolecular has 1 ethylene unsaturated bond Compound includes the poly- inferior ethoxyl acrylate of Nonylphenoxy or phthalic acid based compound.
21. photosensitive polymer combination according to claim 19, the intramolecular has 1 ethylene unsaturated bond The content of compound is 1 mass parts in 100 mass parts of total amount of described adhesive polymer and the photopolymerizable compound ~20 mass parts.
22. photosensitive polymer combination described in any one of claim 1 to 3, described in described adhesive polymer Containing ratio from the structural unit of (methyl) acrylic acid is 10 mass % on the basis of the total amount of described adhesive polymer ~60 mass %.
23. photosensitive polymer combination described in any one of claim 1 to 3, described in described adhesive polymer Containing ratio from the structural unit of (methyl) alkyl acrylate is 40 on the basis of the total amount of described adhesive polymer The mass of quality %~90 %.
24. photosensitive polymer combination described in any one of claim 1 to 3, the acid value of described adhesive polymer For 90mgKOH/g~250mgKOH/g.
25. the weight of photosensitive polymer combination described in any one of claim 1 to 3, described adhesive polymer is equal Molecular weight is 10000~200000.
26. photosensitive polymer combination described in any one of claim 1 to 3, the Photoepolymerizationinitiater initiater includes 2, 4,5- triarylimidazoles dimer it is at least one kind of.
27. photosensitive polymer combination described in any one of claim 1 to 3, the content of the Photoepolymerizationinitiater initiater It is 1 mass parts~7 mass parts relative to 100 mass parts of total amount of described adhesive polymer and the photopolymerizable compound.
28. photosensitive polymer combination described in any one of claim 1 to 3, the content of the Photoepolymerizationinitiater initiater It is 2 mass parts~6 mass parts relative to 100 mass parts of total amount of described adhesive polymer and the photopolymerizable compound.
29. photosensitive polymer combination described in any one of claim 1 to 3, the content of the Photoepolymerizationinitiater initiater It is 3 mass parts~5 mass parts relative to 100 mass parts of total amount of described adhesive polymer and the photopolymerizable compound.
30. a kind of photosensitive element, with support membrane and be arranged in the one side of the support membrane comprising claim 1~29 Any one of described in photosensitive polymer combination photosensitive polymer combination layer.
31. a kind of forming method of resist pattern, with following process:
The photoresist group comprising photosensitive polymer combination described in any one of claim 1~29 is formed on substrate Close the 1st process of nitride layer；
The a part of of the photosensitive polymer combination floor regions curing is formed into solidfied material area by the irradiation of active ray 2nd process in domain；With
Region other than the solidification object area of the photosensitive polymer combination layer is removed from the substrate, is wrapped The 3rd process containing the resist pattern for solidifying object area.
32. the forming method of resist pattern according to claim 31, the wavelength of the active ray be 340nm~ Within the scope of 430nm.
33. the forming method of resist pattern according to claim 31, the wavelength of the active ray be 350nm~ Within the scope of 420nm.
34. a kind of manufacturing method of touch panel has to by resist described in any one of claim 31~33 The forming method of pattern forms the process that the substrate of resist pattern is etched.
35. a kind of manufacturing method of touch panel, with following process:
With in supporting base material, the one side that the supporting base material is set the transparency conducting layer comprising tin indium oxide and setting exist On the metal layer of the laminated substrate of metal layer on the transparency conducting layer, formed comprising any one of claim 1~29 1st process of the resist pattern of the solidfied material of the photosensitive polymer combination；
The metal layer and the transparency conducting layer are etched, the remainder comprising the transparency conducting layer and institute are formed State the 2nd process of the lamination pattern of the remainder of metal layer；With
The metal layer is removed from a part of the lamination pattern, forms the remainder comprising the transparency conducting layer 3rd process of the metal wiring of transparent electrode and the remainder comprising the metal layer.
36. the manufacturing method of touch panel according to claim 35, the transparency conducting layer includes crystalline oxidation Indium tin,
The etching carried out using strong acid is etched in 2nd process.
37. the application that photosensitive polymer combination described in any one of claim 1~29 is used to etch ITO.
38. photosensitive polymer combination described in any one of claim 1~29 is used to form ITO etching resist pattern Application.
39. a kind of application of photosensitive polymer combination, for the formation side by resist pattern described in claim 31 Method forms resist pattern.
40. application according to claim 39, the wavelength of the active ray is within the scope of 340nm~430nm.
41. application according to claim 39, the wavelength of the active ray is within the scope of 350nm~420nm.
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