CN104541204A - Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing touch panel - Google Patents

Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing touch panel Download PDF

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Publication number
CN104541204A
CN104541204A CN201380042172.9A CN201380042172A CN104541204A CN 104541204 A CN104541204 A CN 104541204A CN 201380042172 A CN201380042172 A CN 201380042172A CN 104541204 A CN104541204 A CN 104541204A
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polymer combination
photosensitive polymer
composition
layer
methyl
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CN104541204B (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)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

A photosensitive resin composition for ITO etching use, which comprises a binder polymer, a photopolymerizable compound, a photopolymerization initiator and a silane coupling agent, wherein the silane coupling agent comprises a silane compound having a mercaptoalkyl group.

Description

The formation method of photosensitive polymer combination, photosensitive element, Resist patterns and the manufacture method of contact panel
Technical field
The present invention relates to photosensitive polymer combination, photosensitive element, the formation method of Resist patterns and the manufacture method of contact panel.
Background technology
The touch sensing position of contact panel comprises: in the scope (visible area) of visible picture, do not cover the sensor site of information of contact and the distributions (wiring lead position) for transmitting this information such as the finger of image information ground perception people.
The absorption that sensor site in this visible area forms visible ray less and have the transparent electrode pattern of electric conductivity.In addition, wiring lead uses the metal that resistance value is little.
These sensor site and wiring lead position such as operate as follows and manufacture.First, photosensitive polymer combination (lamination process) is folded at the polyethylene terephthalate or glass superstrate with transparent electrode layer.Then, active ray is irradiated to the established part of photosensitive polymer combination and exposed portion is solidified (or dissolving) (exposure process).Afterwards, by uncured portion (or dissolving part) from base material removing (development), thus on base material, the Resist patterns (developing procedure) comprising the solidfied material of photosensitive polymer combination is formed.Etch processes is implemented to the Resist patterns obtained, after base material is formed the sensor patterns of visible area, resist is peeled off removing (stripping process).Then, form the wiring lead of drawing from formed transparency electrode sensor by the serigraphy employing silver paste etc., thus manufacture the touch sensing position of contact panel.
In addition, Fig. 2 is the schematic section representing contact panel manufacture method in the past.In this manufacture method, as lamination process, stacked photosensitive polymer combination layer 16 (Fig. 2 (a)) on the transparent electrode layer 14 of laminated substrate comprising transparent electrode layer 14 and support base material 12.Then, active ray irradiated to the established part of photosensitive polymer combination layer 16 and exposure portion is solidified, uncured portion being removed from base material, forms the Resist patterns (Fig. 2 (b)) comprising cured portion.Then, etch processes is implemented to the laminated substrate being formed with Resist patterns, a part for transparent electrode layer 14 is removed (Fig. 2 (c)) from support base material 12, then, resist peeled off removing and on support base material 12, form the sensor patterns (Fig. 2 (d)) of visible area.Form the wiring lead 18 of drawing from formed sensor by the serigraphy employing silver paste etc., thus manufacture the touch sensing position of contact panel.
In lamination process, most by being coated with aqueous photosensitive polymer combination to carry out in the past.But, in recent years along with the slim lightweight of contact panel, wish that the requirement with film forms the base material at touch sensing position such uprises, and importing and manufactured by the photosensitive element good with the matching of film base material.
In addition, due to frame (video screen) narrowing of contact panel, therefore the narrowing of wiring lead spacing is also required.Employing in the serigraphy that silver sticks with paste, L/S (live width/interval is wide) (unit: μm) degree that is 70/70, but the wiring lead that L/S is less than or equal to 30/30 must formed.
Therefore, the new formation method at the touch sensing position that the L/S as wiring lead is little, has following method.Use the laminated substrate comprising metal level (wiring lead is formed and uses), transparent electrode layer (sensor of visible area is formed and uses), support base material (film) 3-tier architecture from top to bottom, stacked in this laminated substrate (lamination) photosensitive polymer combination layer (lamination process).Then, active ray is irradiated to the established part of photosensitive polymer combination layer and exposure portion is solidified (or dissolving) (exposure process).Afterwards, by uncured position (or dissolving part) from base material removing (development), thus on base material, the Resist patterns (developing procedure) comprising photosensitive polymer combination solidfied material is formed.For the Resist patterns obtained, by etch processes by metal level and transparent electrode layer removing (the 1st etching work procedure), form the transparent electrode pattern of wiring lead and formation visible area.Next, stacked photosensitive polymer combination layer again, and carry out exposing, developing, thus the metal level only visible area not wanted removing (the 2nd etching).By the touch sensing position (such as with reference to patent documentation 1) that the spacing of the method manufacture wiring lead is narrow and small.
With regard to the method, be less than or equal to 30/30 for L/S can be made in theory, the slim light-weighted technology of contact panel can be gone far towards.But, on the other hand, use the surface smoothness of base material very high, for use photosensitive element require high adhesion.
In addition, as middle photosensitive polymer combinations used such as the formation at Resist patterns, such as, the composition described in patent documentation 2 ~ 6 is disclosed.
Prior art document
Patent documentation
Patent documentation 1: No. 4855536th, Jap.P.
Patent documentation 2: Japanese Unexamined Patent Publication 07-146553 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2005-107121 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2008-112145 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2010-276631 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2011-128358 publication
Summary of the invention
The problem that invention will solve
When using glass baseplate as support base material, the most following formation of transparency electrode: use non-crystalline ITO (tin indium oxide) to carry out patterning, carries out heating (annealing) process thus the crystallization carrying out ITO to reduce resistance value afterwards.But, when using film base material as support base material, if carry out annealing in process, the contraction of base material can be there is, dimensional stability is deteriorated, therefore preferably use crystalline ITO to carry out patterning.
But non-crystalline ITO can fully be dissolved in the weak acid such as oxalic acid, but crystallinity ITO must use concentrated hydrochloric acid (> 20 quality %) to etch under heating condition (40 ~ 50 DEG C of degree).Therefore, the resist used for patterning requires highly-acidproof.
In addition, metal level uses the alloy etc. of the alloy of copper, copper and nickel, molybdenum-aluminium-molybdenum duplexer, silver-colored and palladium and copper, in recent years in order to antirust and become main flow at the metal level that outmost surface is configured with copper and nickel alloy.Therefore, for resist, require and the metal level comprising copper, the adaptation particularly comprising the metal level of copper and nickel alloy.
With regard to former photosensitive polymer combination, being difficult to be formed the Resist patterns fully meeting these acid resistances and adaptation, carrying out utilizing hydrochloric acid problems such as being peeling when ITO etches.
For the method for dealing with problems
The present inventor etc. further investigate repeatedly in order to solve the problem, and found that: have the silane compound of mercaptoalkyl as silane coupling agent by interpolation in photosensitive polymer combination, can expect the raising of acid resistance and adaptation.
That is, the first form of the present invention relates to a kind of ITO etching photosensitive polymer combination, and it contains binder polymer, photopolymerizable compound, Photoepolymerizationinitiater initiater and silane coupling agent, and described silane coupling agent comprises the silane compound with mercaptoalkyl.
Such photosensitive polymer combination can form the Resist patterns of acid resistance and excellent adhesion, uses, particularly comprises the etching of the transparency conducting layer of crystallinity ITO to use therefore, it is possible to be suitable as ITO etching.
Above-mentioned silane coupling agent can comprise the silane compound with amino further.According to such photosensitive polymer combination, resist development on the metal layer can be suppressed to remain, the shortening of etching period can be expected.
Above-mentioned silane coupling agent can comprise the silane compound with (methyl) acryloxy further.According to such photosensitive polymer combination, the further raising with the adaptation of metal level can be expected.
Above-mentioned photopolymerizable compound can contain bisphenol A-type two (methyl) acrylate compounds.According to such photosensitive polymer combination, the acid resistance of resist improves further, by the swelling stripping caused of resist when can ITO be suppressed further significantly to etch.
Above-mentioned photopolymerizable compound can containing carbamate two (methyl) acrylate compounds with (gathering) oxygen ethylidene and/or (gathering) oxygen propylidene.Thereby, it is possible to give flexibility to resist, the more excellent adaptation for the such flexible substrate of film base material can be guaranteed.
Second form of the present invention relates to the photosensitive element comprising the photosensitive polymer combination layer of the photosensitive polymer combination of above-mentioned first form having support membrane and be arranged in the one side of this support membrane.According to such photosensitive element, owing to having the photosensitive polymer combination layer of the photosensitive polymer combination comprising the first form, even if therefore, it is possible to effectively formed and for the substrate that flatness is high, also there is sufficient adaptation and there is excellent acid proof Resist patterns.
3rd form of the present invention relates to a kind of formation method of Resist patterns, has following operation: on base material, form the 1st operation comprising the photosensitive polymer combination layer of the photosensitive polymer combination of above-mentioned first form; By the irradiation of active ray by regions curing for a part for above-mentioned photosensitive polymer combination layer, form the 2nd operation in solidfied material region; And the region beyond the above-mentioned solidfied material region of above-mentioned photosensitive polymer combination layer is removed from above-mentioned base material, obtain the 3rd operation of the Resist patterns comprising above-mentioned solidfied material region.According to the formation method of such Resist patterns, for the substrate that flatness is high, also there is sufficient adaptation even if can be formed and there is excellent acid proof Resist patterns.
4th form of the present invention relates to a kind of manufacture method of contact panel, has the operation that the above-mentioned base material defining Resist patterns to the formation method of the Resist patterns by above-mentioned 3rd form carries out etch processes.In the manufacture method of such contact panel, because the photosensitive polymer combination layer of Resist patterns by the photosensitive polymer combination comprising above-mentioned first form is formed, therefore, it is possible to fully suppress the stripping etc. of Resist patterns in etch processes, even the contact panel of thin space (such as having the contact panel that L/S is less than or equal to the wiring lead of 30/30) also can manufacture efficiently.
5th form of the present invention relates to a kind of manufacture method of contact panel, it has following operation: have support base material, be arranged on the transparency conducting layer comprising tin indium oxide in the one side of this support base material and be arranged on the above-mentioned metal level of laminated substrate of the metal level on this transparency conducting layer, forms the 1st operation comprising the Resist patterns of the solidfied material of the photosensitive polymer combination of above-mentioned first form; Above-mentioned metal level and above-mentioned transparency conducting layer are etched, forms the 2nd operation comprising the lamination pattern of the remainder of above-mentioned transparency conducting layer and the remainder of above-mentioned metal level; And from a part for above-mentioned lamination pattern, above-mentioned metal level is removed, form the 3rd operation of the metal wiring of the transparency electrode comprising the remainder of above-mentioned transparency conducting layer and the remainder comprising above-mentioned metal level.
According to the manufacture method of such contact panel, the contact panel (such as, there is the contact panel that L/S is less than or equal to the wiring lead of 30/30) of thin space easily and efficiently can be manufactured.
Above-mentioned transparency conducting layer can comprise crystalline tin indium oxide, and the etching in above-mentioned 2nd operation can for the etching utilizing strong acid to carry out.In above-mentioned manufacture method, because the photosensitive polymer combination layer of Resist patterns by the photosensitive polymer combination comprising above-mentioned first form is formed, even if therefore utilize strong acid to carry out etching the stripping etc. that also fully can suppress Resist patterns.Therefore, above-mentioned manufacture method can be applicable to the manufacture of the contact panel being applicable to employ the laminated substrate with the transparency conducting layer comprising crystallinity tin indium oxide.
Invention effect
According to the present invention, the excellent adhesion for the high base material of flatness can be formed even if provide a kind of and there is the photosensitive polymer combination of the acid proof Resist patterns of excellence utilizing hydrochloric acid to carry out that ITO etching is also difficult to be peeling etc.In addition, according to the present invention, provide the photosensitive element, the formation method of Resist patterns and the manufacture method of contact panel that employ this photosensitive polymer combination.
Accompanying drawing explanation
Fig. 1 is the schematic section of the embodiment representing photosensitive element of the present invention.
Fig. 2 is the schematic section representing contact panel manufacture method in the past.
Fig. 3 is the schematic section of a form of the manufacture method representing contact panel of the present invention.
Fig. 4 is the vertical view of the form representing the contact panel utilizing the present invention to obtain.
Embodiment
Be described in detail to for implementing mode of the present invention below.But, the invention is not restricted to following embodiment.In addition, in this manual, (methyl) acrylic acid refers to acrylic acid or methacrylic acid, (methyl) acrylate refers to acrylate or the methacrylate corresponding with it, and (methyl) acryloxy refers to acryloxy or methacryloxy.
In addition in this manual, (gathering) oxygen ethylidene refers at least a kind of the polyoxyethylene that the ethylidene of oxygen ethylidene or more than 2 is formed by connecting with ehter bond, and (gathering) oxygen propylidene refers at least a kind of the polyoxypropylene that the propylidene of oxygen propylidene or more than 2 is formed by connecting with ehter bond.Further " EO modification " refer to the compound with (gathering) oxygen ethylidene, " PO modification " refers to the compound with (gathering) oxygen propylidene." EOPO modification " refers to have (gathering) oxygen ethylidene and/or the compound both (gathering) oxygen propylidene.
< photosensitive polymer combination >
The photosensitive polymer combination of present embodiment (is only called " photosensitive polymer combination " below.) for containing (A) composition: binder polymer, (B) composition: photopolymerizable compound, (C) composition: Photoepolymerizationinitiater initiater and (D) composition: the photosensitive polymer combination of silane coupling agent, (D) composition comprises the silane compound with mercaptoalkyl.
According to such photosensitive polymer combination, even if the acid proof Resist patterns of excellence that the excellent adhesion that can be formed for the high base material of flatness and having utilizes hydrochloric acid to carry out that ITO etching is also difficult to be peeling etc.Therefore, the photosensitive polymer combination of present embodiment is suitable as the etching use that the transparency conducting layer of crystallinity ITO was used, particularly comprised in ITO etching.
As one of reason that can realize such effect, think that the mercaptoalkyl of metal level because the outmost surface of base material has and silane coupling agent forms the chemical bond such as complexing, therefore show high adhesion.In addition, with regard to the photosensitive polymer combination of present embodiment, think when photocuring reaction, silane compound and the photopolymerizable compound with mercaptoalkyl react and form thioether bond.Therefore can think, because in the polymeric system of solidfied material, silane coupling agent is fixed, and then the chemical interaction of the impact of this thioether bond and base material, therefore the adaptation of resist and metal surface shows stronger.
(A) composition: binder polymer
Photosensitive polymer combination contains at least a kind of binder polymer as (A) composition.As binder polymer, include, for example and make polymerizable monomer (monomer) carry out free radical polymerization and the polymkeric substance obtained.
As polymerizable monomer (monomer), (methyl) acrylic acid can be enumerated, (methyl) alkyl acrylate, (methyl) acrylate base ester, (methyl) benzyl acrylate, (methyl) benzyl acrylate derivant, (methyl) acrylic acid furfuryl group ester, (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) isobornyl acrylate, (methyl) acrylic acid diamantane ester, (methyl) acrylic acid two ring pentyl ester, (methyl) acrylate, (methyl) acrylic acid diethylamino ethyl ester, (methyl) glycidyl acrylate, 2,2,2-trifluoroethyl (methyl) acrylate, 2,2,3,3-tetra-fluoropropyl (methyl) acrylate, alpha-brominated acrylic acid, α-chloro-acrylicacid, (methyl) acrylic acid dicyclopentenyl oxygen base ethyl ester, (methyl) acrylic acid bicyclopentyl oxygen base ethyl ester, (methyl) isobomyl acrylate base oxygen base ethyl ester, (methyl) acrylate base oxygen base ethyl ester, (methyl) acrylic acid adamantyl oxygen base ethyl ester, (methyl) acrylic acid dicyclopentenyl oxygen base propyl group oxygen base ethyl ester, (methyl) acrylic acid bicyclopentyl oxygen base propyl group oxygen base ethyl ester, (methyl) acrylic acid dicyclopentenyl oxygen base propyl group oxygen base ethyl ester, (methyl) acrylic acid adamantyl oxygen base propyl group oxygen base ethyl ester, (methyl) propenoic acid beta-furans ester, (methyl) acrylate such as (methyl) propenoic acid beta-styrene esters, styrene, the styrene derivative that can be polymerized that the alpha-position such as vinyltoluene, α-methyl styrene or aromatic ring are substituted, the acrylamides such as diacetone acrylamide, vinyl cyanide, the ether compound of the vinyl alcohol such as vinyl n-butyl ether, maleic acid, maleic anhydride, the maleic mono-ester such as monomethyl maleate, ethyl maleate, maleic acid list isopropyl ester, the olefinically unsaturated carboxylic acid derivatives etc. such as fumaric acid, cinnamic acid, alpha-cyano cinnamic acid, itaconic acid, crotonic acid, lactic acid.They can be used alone or two or more use of combination in any.
(A) composition preferably has and derives from (methyl) acrylic acid structural unit.(A) composition have derive from (methyl) acrylic acid structural unit time, from resolution and fissility (the resist fissility after etching) excellent aspect, its containing ratio is preferably benchmark (100 quality % with the total amount of (A) composition, same below) be 10 quality % ~ 60 quality %, be more preferably 15 quality % ~ 50 quality %, more preferably 20 quality % ~ 35 quality %.
In addition, improve further from the viewpoint of acrylic acid developability and fissility, (A) composition preferably has the structural unit deriving from (methyl) alkyl acrylate.
As (methyl) alkyl acrylate, be preferably the ester of the alkylol of (methyl) acrylic acid and carbon number 1 ~ 12.As such (methyl) alkyl acrylate, include, for example (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate and (methyl) 2-EHA, they can be used alone or two or more use of combination in any.
When (A) composition has the structural unit deriving from (methyl) alkyl acrylate, from resolution and excellent adhesion aspect, its containing ratio is preferably 40 quality % ~ 90 quality % using the total amount of (A) composition as benchmark, be more preferably 50 quality % ~ 85 quality %, more preferably 65 quality % ~ 80 quality %.
From developability and excellent adhesion aspect, (A) acid number of composition is preferably 90mgKOH/g ~ 250mgKOH/g, be more preferably 100mgKOH/g ~ 240mgKOH/g, more preferably 120mgKOH/g ~ 235mgKOH/g, be particularly preferably 130mgKOH/g ~ 230mgKOH/g.
From reducing developing time aspect, its acid number is preferably greater than or equal to 90mgKOH/g, is more preferably and is more than or equal to 100mgKOH/g, is more preferably more than or equal to 120mgKOH/g, is particularly preferably and is more than or equal to 130mgKOH/g.
In addition, from the adaptation raising aspect further of the solidfied material of photosensitive polymer combination, its acid number is preferably less than or equal to 250mgKOH/g, be more preferably and be less than or equal to 240mgKOH/g, more preferably be less than or equal to 235mgKOH/g, be particularly preferably and be less than or equal to 230mgKOH/g.In addition, when carrying out solvent development, the polymerizable monomer (monomer) preferably (methyl) acrylic acid etc. with carboxyl is adjusted to a small amount of.
When the weight-average molecular weight (Mw) of (A) composition is undertaken measuring (being converted by the typical curve employing polystyrene standard) by gel permeation chromatography (GPC), from developability and excellent adhesion aspect, be preferably 10000 ~ 200000, be more preferably 20000 ~ 100000, more preferably 25000 ~ 80000, be particularly preferably 30000 ~ 60000.From the excellent aspect of developability, be preferably less than or equal to 200000, be more preferably and be less than or equal to 100000, be more preferably less than or equal to 80000, be particularly preferably and be less than or equal to 60000.From excellent adhesion aspect, be preferably greater than or equal to 10000, be more preferably and be more than or equal to 20000, be more preferably more than or equal to 25000, be particularly preferably and be more than or equal to 30000.
From resolution, excellent adhesion aspect, the dispersion degree (weight-average molecular weight/number-average molecular weight) of (A) composition is preferably less than or equal to 3.0, is more preferably and is less than or equal to 2.8, be more preferably less than or equal to 2.5.
As (A) composition, can be used alone a kind of binder polymer, also can use by two or more binder polymer of combination in any.
From film formative, sensitivity and excellent in resolution aspect, (A) component content in photosensitive polymer combination is preferably 30 mass parts ~ 70 mass parts in total amount 100 mass parts of (A) composition with (B) composition, be more preferably 35 mass parts ~ 65 mass parts, be particularly preferably 40 mass parts ~ 60 mass parts.From the formative aspect of film (photosensitive polymer combination layer), its content is preferably greater than or equal to 30 mass parts, is more preferably and is more than or equal to 35 mass parts, is particularly preferably and is more than or equal to 40 mass parts.In addition from fully obtaining sensitivity and resolution aspect, its content is preferably less than or equal to 70 mass parts, is more preferably and is less than or equal to 65 mass parts, is more preferably less than or equal to 60 mass parts.
(B) composition: photopolymerizable compound
Photosensitive polymer combination contains at least a kind of photopolymerizable compound as (B) composition.As long as photopolymerizable compound is for can just be not particularly limited by photopolymerisable compound.
Photopolymerizable compound is preferably free-radical polymerised compound, is more preferably the compound with ethene unsaturated link.As the compound with ethene unsaturated link, the compound etc. in the compound with 1 ethene unsaturated link, the compound in molecule with 2 ethene unsaturated links, molecule with more than 3 ethene unsaturated links can be enumerated in molecule.
(B) composition preferably comprises the compound at least a kind of molecule with 2 ethene unsaturated links.When (B) composition comprises in molecule the compound with 2 ethene unsaturated links, its content is preferably 5 mass parts ~ 60 mass parts in total amount 100 mass parts of (A) composition with (B) composition, be more preferably 5 mass parts ~ 55 mass parts, more preferably 10 mass parts ~ 50 mass parts.
As the compound in molecule with 2 ethene unsaturated links, include, for example two (methyl) acrylate compounds in bisphenol A-type two (methyl) acrylate compounds, hydrogenated bisphenol A type two (methyl) acrylate compounds, molecule with amino-formate bond, poly alkylene glycol two (methyl) acrylate in molecule with (gathering) oxygen ethylidene and (gathering) oxygen propylidene and trimethylolpropane two (methyl) acrylate.
Consider from improving further acid proof viewpoint, (B) composition preferably comprise from by bisphenol A-type two (methyl) acrylate compounds and there is (gathering) oxygen ethylidene and/or (gathering) oxygen propylidene carbamate two (methyl) acrylate compounds (hereinafter referred to " EOPO modified urethane two (methyl) acrylate compounds ".) select in the group that forms at least a kind.
As bisphenol A-type two (methyl) acrylate compounds, the compound represented by following formula (1) can be enumerated.
[changing 1]
In formula (1), R 1and R 2represent hydrogen atom or methyl independently of one another.XO and YO represents oxygen ethylidene or oxygen propylidene independently of one another.M 1, m 2, n 1and n 2represent 0 ~ 40 independently of one another.Wherein, m 1+ n 1and m 2+ n 2all be more than or equal to 1.When XO be oxygen ethylidene, YO be oxygen propylidene, m 1+ m 2be 1 ~ 40, n 1+ n 2be 0 ~ 20.When XO be oxygen propylidene, YO be oxygen ethylidene, m 1+ m 2be 0 ~ 20, n 1+ n 2be 1 ~ 40.M 1, m 2, n 1and n 2represent the structural unit number of structural unit.Therefore in individual molecule, represent round values, in the aggregate of different kinds of molecules, represent the rational number as mean value.Structural unit number below about structural unit is same.
From the excellent aspect of acid resistance, m in formula (1) 1+ m 2be preferably 8 ~ 40, be more preferably 8 ~ 20, more preferably 8 ~ 10.
When photosensitive polymer combination comprises bisphenol A-type two (methyl) acrylate compounds as (B) composition, as its content, be preferably 1 mass parts ~ 50 mass parts in total amount 100 mass parts of (A) composition with (B) composition, be more preferably 5 mass parts ~ 50 mass parts.
As EOPO modified urethane two (methyl) acrylate compounds, the compound represented by following formula (2) can be enumerated.
[changing 2]
In formula (2), R 3represent hydrogen atom or methyl independently of one another.OR 4and OR 5represent oxygen ethylidene or oxygen propylidene independently of one another.R 6represent alkyl chain.M and n represents 0 ~ 40 independently of one another.Wherein, m+n is more than or equal to 1.At OR 4for oxygen ethylidene, OR 5when for oxygen propylidene, the total amount of m is the total amount of 1 ~ 40, n is 0 ~ 20.At OR 4for oxygen propylidene, OR 5when for oxygen ethylidene, the total amount of m is the total amount of 0 ~ 20, n is 1 ~ 40.M and n represents the structural unit number of structural unit.Therefore in individual molecule, represent round values, in the aggregate of different kinds of molecules, represent the rational number as mean value.Structural unit number below about structural unit is same.
When photosensitive polymer combination comprises EOPO modified urethane two (methyl) acrylate compounds as (B) composition, as its content, be preferably 1 mass parts ~ 50 mass parts in total amount 100 mass parts of (A) composition with (B) composition, be more preferably 5 mass parts ~ 50 mass parts.
In photosensitive polymer combination, as (B) composition, except there is in molecule the compound of 2 ethene unsaturated links, can further containing the compound in molecule with 1 ethene unsaturated link.
As the compound in molecule with 1 ethene unsaturated link, include, for example Nonylphenoxy and gather inferior ethoxyl acrylate, phthalic acid based compound and (methyl) alkyl acrylate.In these materials, improve the peel property after resolution, adaptation, resist shape and solidification well from the viewpoint of balance, preferably comprise Nonylphenoxy and gather inferior ethoxyl acrylate or phthalic acid based compound.
As the phthalic acid based compound in molecule with 1 ethene unsaturated link, include, for example γ-chloro-β-hydroxy propyl-Beta '-methacryloxyethyl-phthalic ester, 2-acryloyl-oxyethyl-2-hydroxyethyl-phthalic acid and 2-acryloyl-oxyethyl-phthalic acid.
When photosensitive polymer combination comprise in molecule there is 1 ethene unsaturated link compound as (B) composition, its content is preferably 1 mass parts ~ 20 mass parts in total amount 100 mass parts of (A) composition with (B) composition, be more preferably 3 mass parts ~ 15 mass parts, more preferably 5 mass parts ~ 12 mass parts.
The overall content of (B) composition in photosensitive polymer combination is preferably 30 mass parts ~ 70 mass parts relative to total amount 100 mass parts of (A) composition and (B) composition, be more preferably 35 mass parts ~ 65 mass parts, be particularly preferably 35 mass parts ~ 50 mass parts.If its content is more than or equal to 30 mass parts, then there is the tendency easily obtaining sufficient sensitivity and resolution.If be less than or equal to 70 mass parts, then there is the tendency easily forming film (photosensitive polymer combination layer), easily obtain the tendency of good resist shape in addition in addition.
(C) composition: Photoepolymerizationinitiater initiater
Photosensitive polymer combination contains at least a kind of Photoepolymerizationinitiater initiater as (C) composition.Just be not particularly limited as long as Photoepolymerizationinitiater initiater can make (B) composition be polymerized, suitably can select from normally used Photoepolymerizationinitiater initiater.
As (C) composition, benzophenone, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butanone-1,2-methyl isophthalic acid-aromatic ketone such as [4-(methyl mercapto) phenyl]-2-morpholino-acetone-1 grade can be enumerated; The quinones such as alkyl-anthraquinone; The benzoin ether compounds such as benzoin alkylether; The benzoin compounds such as benzoin, alkyl benzene acyloin; The benzil derivatives such as benzil dimethyl ketal; 2,4, the 5-triarylimidazoles dimers such as 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dimer, 2-(adjacent fluorophenyl)-4,5-diphenyl-imidazole dimer; The acridine derivatives etc. such as 9-phenylacridine, 1,7-(9,9 '-acridinyl) heptane.They can be used alone or combine two or more and use.
From the viewpoint of improving sensitivity and adaptation further, (C) composition preferably comprises dimeric at least a kind of 2,4,5-triarylimidazoles, more preferably comprises 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dimer.With regard to 2,4,5-triarylimidazoles dimer, its structure can symmetry also can be asymmetric.
The content of (C) composition in photosensitive polymer combination is preferably 0.1 mass parts ~ 10 mass parts relative to total amount 100 mass parts of (A) composition and (B) composition, be more preferably 1 mass parts ~ 7 mass parts, more preferably 2 mass parts ~ 6 mass parts, are particularly preferably 3 mass parts ~ 5 mass parts.If its content is more than or equal to 0.1 mass parts, there is the tendency easily obtaining good sensitivity, resolution or adaptation, if be less than or equal to 10 mass parts, then have the tendency easily obtaining good resist shape.
(D) composition: silane coupling agent
Photosensitive polymer combination contains silane coupling agent as (D) composition.As silane coupling agent, (D1) composition can be enumerated: there is the silane compound of mercaptoalkyl, (D2) composition: there is amino silane compound (preferably having the silane compound of urea groups), (D3) have the silane compound of (methyl) acryloxy.Photosensitive polymer combination contains at least (D1) composition in these materials.
Photosensitive polymer combination by containing (D1) composition as (D) composition, even if thus realize the excellent adhesion that can be formed for the high base material of flatness and there is the such excellent effect of the acid proof Resist patterns of excellence that utilizes hydrochloric acid to carry out that ITO etching is also difficult to be peeling etc.
In addition, photosensitive polymer combination can containing the silane coupling agent except (D1) composition as (D) composition.
Such as, photosensitive polymer combination can be used together (D1) composition with (D3) composition as (D) composition.When photosensitive polymer combination only comprises (D1) composition as (D) composition, the resist showing excellent adaptation can be obtained, but there is the development easily produced for copper base etc. residual (namely, the resist be formed on copper base be difficult to after the etching peel off) tendency, have the tendency that etching period increases.On the other hand, when photosensitive polymer combination contains (D1) composition and (D3) composition as (D) composition, excellent adaptation can be maintained and suppress, for residual generation such as the development of copper base etc., to realize the shortening of etching period.
In addition, photosensitive polymer combination can contain (D1) composition, (D2) composition and (D3) composition as (D) composition simultaneously.According to such photosensitive polymer combination, the generation that the development for copper base etc. can be suppressed to remain and realize higher adaptation.
As (D1) composition, preferably there is the silane compound (mercaptoalkyl alkoxy silane) of mercaptoalkyl and alkoxy, as such (D1) composition, mercaptopropyi methyl dimethoxysilane, mercaptopropyi trimethoxy silane, Mercaptopropyltriethoxysilane etc. can be enumerated.Wherein, be easily hydrolyzed and 3 crosslinked mercaptopropyi trimethoxy silanes can be carried out due to the adaptation of putting up the best performance preferably.
As (D2) composition, be preferably the silane compound that end has primary amino radical, as such (D2) composition, include, for example 3-aminopropyl methoxysilane, aminopropyl Ethoxysilane, N-2-(amino-ethyl)-3-TSL 8330, 3-ureidopropyltriethoxysilane, 3-ureido-propyl trimethoxy silane, ureidomethy trimethoxy silane, ureidomethy triethoxysilane, 2-ureidoethyltrimethoxsilane, 2-urea groups ethyl triethoxysilane, 4-urea groups butyl trimethoxy silane, 4-urea groups butyl triethoxysilane etc.Wherein, consider the reactivity with binder polymer, preferably there is the silane compound of the functional group low with the reactivity of carboxylic acid group such as urea groups, most preferably with (D1) composition and the used time develops the 3-ureidopropyltriethoxysilane that residual inhibition can be observed especially significantly.
As (D3) composition, include, for example 3-methacryloyloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloyloxypropyl methyl diethoxy silane, 3-methacryloxypropyl.Wherein, be easily hydrolyzed and 3 crosslinked mercaptopropyi trimethoxy silanes can be carried out due to the adaptation of putting up the best performance preferably.Easily be hydrolyzed and 3 crosslinked 3-methacryloxypropyl trimethoxy silane can be carried out due to the adaptation of putting up the best performance preferably.
From excellent adhesion aspect, the content of (D) composition in photosensitive polymer combination is preferably 0.01 mass parts ~ 10 mass parts relative to total amount 100 mass parts of (A) composition and (B) composition, be more preferably 0.05 mass parts ~ 5 mass parts, more preferably 0.1 mass parts ~ 3 mass parts.If (D) content of composition is more than above-mentioned scope, then has and easily produce for residual tendency such as the development of copper base etc., in addition, it is not enough etc. likely to produce solidification bottom by the resist that causes of significantly rising of the reduction of resolution, sensitivity.On the other hand, if the content of (D) composition is positioned at above-mentioned scope, then the development for copper base etc. can be fully suppressed to remain and the appropriate curability realizing and also fully solidify to resist.Due to and abundant effect to resist, thus good resist shape can be obtained and the patience of etching solution is also become better.
(other composition)
Photosensitive polymer combination can as required containing the composition beyond above-mentioned (A) ~ (D) composition.Such as, photosensitive polymer combination can containing at least a kind of selecting from the group be made up of sensitization pigment, two [4-(dimethylamino) phenyl] methane, two [4-(diethylamino) phenyl] methane and leuco crystal violet.
As sensitization pigment, include, for example dialkyl amido benzophenone cpd, pyrazoline compounds, anthracene compound, coumarin compound, xanthone compound, thioxanthone compounds, oxazole compounds, benzoazole compounds, thiazolium compounds, benzothiazole compound, triazole compounds, stilbene compounds, triaizine compounds, thiophene compound, naphthalimide compound, triarylamine compound and aminacrine compound.They can be used alone or combine two or more and use.
In addition, photosensitive polymer combination can the polymerizable compound (oxetane compound etc.) of cyclic ether group of cationic polymerization containing having at least 1 in molecule; Cationic polymerization initiators; The dyestuffs such as sparrow malachite green, Victoria pure blue, brilliant green, methyl violet; The light display toners such as tribromo phenylsulfone, diphenylamine, benzyl amine, triphenylamine, diethylaniline, o-chloraniline; Heat colour developing preventing agent; The plastifier such as para toluene sulfonamide; Pigment; Filling agent; Defoamer; Fire retardant; Stabilizing agent; Adaptation imparting agent; Levelling agent; Peel off promoter; Antioxidant; Spices; Preparation; Thermal cross-linking agent; Deng.They can be used alone or combine two or more and use.
When photosensitive polymer combination comprises other composition (composition beyond (A) ~ (D) composition), their content is preferably set to 0.01 mass parts ~ 20 mass parts degree respectively relative to total amount 100 mass parts of (A) composition and (B) composition.
[solution of photosensitive polymer combination]
Photosensitive polymer combination can for comprising the liquid composition of at least a kind of organic solvent further.As organic solvent, the alcoholic solvent such as methyl alcohol, ethanol can be enumerated; The ketone solvent such as acetone, methyl ethyl ketone; The glycol ether solvents such as methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether; The aromatic hydrocarbon solvents such as toluene; The aprotic polar solvent etc. such as DMF.They can be used alone, and also can mix two or more and use.
The content of the organic solvent contained by photosensitive polymer combination suitably can be selected according to object etc.The photosensitive polymer combination comprising organic solvent (is also called " coating fluid " by liquid composition that such as photosensitive polymer combination can be 30 quality % ~ 60 quality % degree as solid constituent below.) use.
By coating solution is carried out drying on the surface of support membrane described later, sheet metal etc., thus the photosensitive polymer combination layer of the film as photosensitive polymer combination can be formed.As sheet metal, be not particularly limited, suitably can select according to object etc.As sheet metal, the sheet metal comprising the metals such as iron-based alloy such as copper, copper series alloy, nickel, chromium, iron, stainless steel can be enumerated.As preferred sheet metal, the sheet metal comprising the metals such as copper, copper series alloy, iron-based alloy can be enumerated.
The thickness of the photosensitive polymer combination layer formed is not particularly limited, and suitably can select according to its purposes.The thickness (dried thickness) of photosensitive polymer combination layer is preferably 1 μm ~ 100 μm degree.
When defining photosensitive polymer combination layer on a metal plate, that photosensitive polymer combination layer can be coated to diaphragm with surface that is sheet metal opposition side.As diaphragm, the polymer film such as tygon, 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 on the photosensitive polymer combination layer comprising above-mentioned photosensitive polymer combination in the one side of this support membrane.According to such photosensitive element, owing to having the photosensitive polymer combination layer comprising above-mentioned photosensitive polymer combination, even if therefore, it is possible to effectively formed and for the substrate that flatness is high, also there is sufficient adaptation and there is excellent acid proof Resist patterns.Photosensitive element can have other layers such as diaphragm as required.
Fig. 1 is the schematic section of the embodiment representing photosensitive element of the present invention.In the photosensitive element 10 shown in Fig. 1, support membrane 2, the photosensitive polymer combination layer 4 comprising photosensitive polymer combination and diaphragm 6 stack gradually.Photosensitive polymer combination layer 4 also can be called the film of photosensitive polymer combination.The film of film to be photosensitive polymer combination be its uncured state in addition.
Photosensitive element 10 such as can operate acquisition as follows.Support membrane 2 be coated with the coating fluid as the photosensitive polymer combination comprising organic solvent and form coating layer, being dried (from coating layer removing organic solvent at least partially), thus forming photosensitive polymer combination layer 4.Then; that be coated to photosensitive polymer combination layer 4 with diaphragm 6 with face that is support membrane 2 opposition side, thus obtain that there is support membrane 2, be layered in the photosensitive polymer combination layer 4 on this support membrane 2 and be layered in the photosensitive element 10 of the diaphragm 6 on this photosensitive polymer combination layer 4.In addition, photosensitive element 10 also can not necessarily have diaphragm 6.
As support membrane 2, polyester such as comprising polyethylene terephthalate can be used; The polyolefin such as polypropylene, tygon etc. has the film of the polymkeric substance of thermotolerance and solvent resistance.
The thickness of support membrane 2 is preferably 1 μm ~ 100 μm, is more preferably 5 μm ~ 50 μm, more preferably 5 μm ~ 30 μm.By making the thickness of support membrane 2 be more than or equal to 1 μm, the support membrane 2 when peeling off support membrane 2 can be suppressed damaged.Additionally by making it be less than or equal to 100 μm, the reduction of resolution can be suppressed.
As diaphragm 6, the bonding force preferably for photosensitive polymer combination layer 4 is less than the bonding force of support membrane 2 for photosensitive polymer combination layer 4.Specifically, as diaphragm 6, polyester such as comprising polyethylene terephthalate can be used; The polyolefin such as polypropylene, tygon etc. has the film of the polymkeric substance of thermotolerance and solvent resistance.As commercially available product, the polyethylene terephthalate film of PS series, the NF-15A of Tamapoly such as ALPHANMA-410, E-200, the polypropylene screen of film Co., Ltd. of SHIN-ETSU HANTOTAI manufacture, the PS-25 of Teijin Ltd's manufacture that Oji Paper manufactures can be enumerated.In addition, diaphragm 6 can be identical with support membrane 2.
The thickness of diaphragm 6 is preferably 1 μm ~ 100 μm, is more preferably 5 μm ~ 50 μm, more preferably 5 μm ~ 30 μm, is particularly preferably 15 μm ~ 30 μm.If the thickness of diaphragm 6 is more than or equal to 1 μm, then when peeling off diaphragm 6 and photosensitive polymer combination layer 4 and support membrane 2 being laminated on base material, diaphragm 6 can be suppressed damaged.If be less than or equal to 100 μm, then operability and cheapness excellence.
Photosensitive element 10 specifically such as can operate as follows and manufacture.Can be manufactured by the manufacture method comprising following operation: the operation preparing to comprise the coating fluid of photosensitive polymer combination; Above-mentioned coating solution formed on support membrane 2 operation of coating layer and above-mentioned coating layer drying formed the operation of photosensitive polymer combination layer 4.
The coating of coating fluid on support membrane 2 can be undertaken by known methods such as roller coat, the coating of unfilled corner wheel, intaglio plate coating, airblade coating, mould painting, rod paintings.
About the drying of coating layer, as long as just can be not particularly limited from the removing at least partially of coating layer by organic solvent.Such as preferably carry out 5 minutes ~ 30 minutes degree at 70 DEG C ~ 150 DEG C.About the remaining organic solvent amount in photosensitive polymer combination layer 4 after drying, spread from the viewpoint of the organic solvent prevented in subsequent handling, be preferably set to and be less than or equal to 2 quality %.
The thickness of the photosensitive polymer combination layer 4 in photosensitive element 10 suitably can be selected according to purposes.Be preferably 1 μm ~ 100 μm with dried thickness gauge, be more preferably 1 μm ~ 50 μm, more preferably 5 μm ~ 40 μm.By making the thickness of photosensitive polymer combination layer 4 be more than or equal to 1 μm, industrial coating becomes easy.If be less than or equal to 100 μm, then there is the tendency that fully can obtain adaptation and resolution.
The form of photosensitive element 10 is not particularly limited.Such as, can be sheet, or can be the shape of wound into rolls in core.When wound into rolls, the mode being preferably outside with support membrane 2 reels.As core, the plastics etc. such as polyvinyl resin, acrylic resin, polystyrene resin, Corvic, ABS resin (acrylonitrile-butadiene-styrene copolymer) can be enumerated.On the end face that the photosensitive element of the web-like obtained like this is rolled up, end face barrier film is preferably set from the viewpoint of end face protection, damp proof end face barrier film is preferably set from the viewpoint of resistance to edge-melting.As bundling method, preferably wrap in the little black thin plate of moisture-penetrability and pack.
Photosensitive element 10 such as can be suitably used for the formation method of Resist patterns described later.
The formation method > of < Resist patterns
The formation method of the Resist patterns of present embodiment has following operation: (i) forms the lamination process of the photosensitive polymer combination layer comprising photosensitive polymer combination on base material; (ii) by the irradiation of active ray by regions curing for a part for photosensitive polymer combination layer, form the exposure process in solidfied material region; (iii) region beyond the solidfied material region of photosensitive polymer combination layer is removed from base material, base material is formed the developing procedure comprising the Resist patterns of the solidfied material (solidfied material region) of photosensitive polymer combination.The formation method of Resist patterns can have other operation as required further.Below each operation is described in detail.
(i) lamination process
In lamination process, base material forms the photosensitive polymer combination layer comprising photosensitive polymer combination.
As the method forming photosensitive polymer combination layer on base material, to include, for example on base material after coating comprises the coating fluid of photosensitive polymer combination, carry out dry method.
In addition, as the method forming photosensitive polymer combination layer on base material, include, for example after as required diaphragm being removed from photosensitive element, the photosensitive polymer combination of photosensitive element is pressed in layer by layer the method on base material.Lamination can by be heated by the photosensitive polymer combination layer of photosensitive element while be crimped on base material and carry out.By this lamination, obtain the duplexer that base material, photosensitive polymer combination layer and support membrane stack gradually.
Lamination preferably carries out with the temperature of such as 70 DEG C ~ 130 DEG C, preferably with 0.1MPa ~ 1.0MPa degree (1kgf/cm 2~ 10kgf/cm 2degree) pressure crimping and carry out.These conditions can suitably adjust as required.When lamination, thermal pretreatment can be carried out to base material, also photosensitive polymer combination layer can 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 the exposure portion photocuring of active ray be irradiated, form sub-image.Here, when using photosensitive element in lamination process, there is support membrane in photosensitive polymer combination layer, when support membrane has permeability for active ray, active ray can be irradiated through support membrane.On the other hand, when support membrane is for active ray display light-proofness, after being removed by support membrane, active ray is irradiated to photosensitive polymer combination layer.
As exposure method, the minus or eurymeric mask pattern can enumerated through being called as former figure irradiates the method (mask exposure method) of active ray with image shape.In addition, also can adopt by LDI (laser direct imaging, Laser Direct Imaging) exposure method, DLP (digital light process, Digital Light Processing) exposure method etc. directly describe exposure method and irradiate the method for active ray with image shape.
As the wavelength (exposure wavelength) of active ray, from the viewpoint of more positively obtaining effect of the present invention, being preferably within the scope of 340nm ~ 430nm, being more preferably within the scope of 350nm ~ 420nm.
(iii) developing procedure
In developing procedure, by development treatment by the region beyond the solidfied material region of photosensitive polymer combination layer (namely, the uncured portion of photosensitive polymer combination layer) remove from base material, base material is formed the Resist patterns comprising the solidfied material of photosensitive polymer combination layer.In addition, the photosensitive polymer combination layer through exposure process exists support membrane, after being removed by support membrane, carry out developing procedure.With regard to development treatment, there are wet developing and dry process development, but preferably use wet developing.
In wet developing, use the developer solution corresponding with photosensitive polymer combination, developed by known developing method.As developing method, impregnation method can be enumerated, revolve submergence mode of covering, spray pattern, use brush, pat, scraping, shake impregnating method, from the viewpoint of resolution improve, high-pressure fog mode is the most applicable.Also this Combination of Methods of more than two kinds can be developed.
Developer solution suitably can be selected according to the formation of photosensitive polymer combination.As developer solution, alkaline aqueous solution, water system developer solution, organic solvent system developer solution etc. can be enumerated.
As the alkaline aqueous solution that development uses, be preferably 0.1 quality % ~ 5 quality % sodium carbonate liquor, 0.1 quality % ~ 5 quality % solution of potassium carbonate, 0.1 quality % ~ 5 quality % sodium hydroxide solution, 0.1 quality % ~ 5 quality % sodium tetraborate solution etc.The pH of alkaline aqueous solution is preferably the scope of 9 ~ 11.Its temperature can regulate according to the alkali-developable of photosensitive polymer combination layer in addition.Can be mixed in alkaline aqueous solution surfactant, defoamer, for promote develop a small amount of organic solvent etc.
The formation method of Resist patterns can have following operation further: after being removed by unexposed portion, carry out heating and/or the 0.2J/cm of 60 DEG C ~ 250 DEG C of degree as required 2~ 10J/cm 2the exposure of degree, thus Resist patterns is solidified further.
The manufacture method > of < contact panel
The manufacture method of the contact panel of present embodiment has the operation that the base material defining Resist patterns to the formation method by above-mentioned Resist patterns carries out etch processes.About etch processes, using the Resist patterns of formation as mask, the conductor layer etc. of base material is carried out.Formed the pattern of wiring lead and transparency electrode by etch processes, thus manufacture contact panel.
Fig. 3 is the schematic section of a form of the manufacture method representing contact panel of the present invention.The manufacture method of this form has following operation: have support base material 22, be arranged on the transparency conducting layer 24 in the one side of support base material 22 and be arranged on the metal level 26 of laminated substrate of the metal level 26 on transparency conducting layer 24, forms the 1st operation comprising the Resist patterns 29 of the solidfied material of photosensitive polymer combination; Metal level 26 and transparency conducting layer 24 are etched, forms the 2nd operation comprising the lamination pattern (24+26 in Fig. 3 (d)) of the remainder of transparency conducting layer 24 and the remainder of metal level 26; And from a part for lamination pattern, metal level is removed, form the 3rd operation of the transparency electrode comprising the remainder of transparency conducting layer 24 and the metal wiring comprising metal level remainder.
In 1st operation, first, as shown in Fig. 3 (a), having support base material 22, the metal level 26 upper strata stacked package of laminated substrate that is arranged on the transparency conducting layer 24 in the one side of support base material 22 and is arranged on the metal level 26 on transparency conducting layer 24 is containing the photosensitive polymer combination layer 28 of photosensitive polymer combination.Photosensitive polymer combination layer 28 can also with the face of metal level 26 opposition side on there is support membrane.
As metal level 26, can enumerate comprise copper, copper and nickel alloy, molybdenum-aluminium-molybdenum duplexer, silver and palladium and copper the metal level of alloy etc.In these metal levels, from the viewpoint of obtaining effect of the present invention more significantly, the metal level using the alloy comprising copper or copper and nickel can be applicable to.
Transparency conducting layer 24 is containing tin indium oxide (ITO).Never need the viewpoint of annealing in process to consider, transparency conducting layer 24 preferably comprises crystalline ITO.
Then, by the irradiation of active ray by regions curing for a part for photosensitive polymer combination layer 28, form solidfied material region, the region beyond the solidfied material region of photosensitive polymer combination layer is removed from laminated substrate.Thus, as shown in Fig. 3 (b), laminated substrate forms Resist patterns 29.
In the 2nd operation, by etch processes, the metal level 26 in the region of not covered by Resist patterns 29 and transparency conducting layer 24 are removed from support base material 22.
The method of etch processes is suitably selected according to the layer that will remove.Such as, as the etching solution for removing metal level, copper chloride solution, ferric chloride solution, phosphoric acid solution etc. can be enumerated.In addition, as the etching solution for removing transparency conducting layer, oxalic acid, hydrochloric acid, chloroazotic acid etc. can be used.
When transparency conducting layer 24 comprises 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 manufacture method of this form, because Resist patterns comprises the solidfied material of above-mentioned photosensitive polymer combination, even if the stripping etc. of Resist patterns therefore also fully can be suppressed under the etch processes utilizing strong acid to carry out.
Fig. 3 (c) is the figure after representing etch processes, in Fig. 3 (c), support base material 22 is formed with the duplexer of remainder, the remainder of transparency conducting layer 24 and the remainder of Resist patterns 28 comprising metal level 26.In the manufacture method of this form, from this duplexer, Resist patterns 28 is removed.
The removing of Resist patterns 28, such as, can use the aqueous solution stronger than the alkaline aqueous solution alkalescence used in above-mentioned developing procedure.As this alkaline aqueous solution, 1 ~ 10 quality % sodium hydrate aqueous solution, 1 ~ 10 quality % potassium hydroxide aqueous solution etc. can be used.Wherein, preferably use 1 ~ 10 quality % sodium hydrate aqueous solution or potassium hydroxide aqueous solution, more preferably use 1 ~ 5 quality % sodium hydrate aqueous solution or potassium hydroxide aqueous solution.As the stripping mode of Resist patterns, can enumerate impregnation method, spray pattern etc., they can be used alone and also can be used together.
Fig. 3 (d) is the figure after representing Resist patterns stripping, in Fig. 3 (d), support base material 22 is formed with the lamination pattern of the remainder of the remainder comprising metal level 26 and transparency conducting layer 24.
In the 3rd operation, remove metal level 26 for the formation of beyond a part for metal wiring from this lamination pattern, form the transparency electrode of the metal wiring comprising the remainder of metal level 26 and the remainder comprising transparency conducting layer 24.In addition, in this form, as the method in the 3rd operation, metal level 26 removed, adopt and carry out etching method, but in the 3rd operation, the method that metal level 26 removes is not necessarily limited to etching.
In the 3rd operation, first in the laminated substrate through the 2nd operation, form photosensitive polymer combination layer 30 (Fig. 3 (e)).Then, through exposure and the development of photosensitive polymer combination layer 30, the resist 31 (Fig. 3 (f)) comprising the solidfied material of photosensitive polymer combination layer 30 is formed.In addition, photosensitive resin composition layer can for comprising the layer of the photosensitive polymer combination of above-mentioned present embodiment, also can be the layer of known etching photosensitive polymer combination before comprising.
Then, by etch processes, metal level 26 removes by the part not forming resist 31 from lamination pattern.At this moment, as etch processes liquid, the etching solution same with the etching solution for removing above-mentioned metal level can be used.
Fig. 3 (g) is the figure after representing etch processes, in Fig. 3 (g), support base material 22 is formed the transparency electrode of the remainder comprising transparency conducting layer 24, and in a part of transparency electrode, is formed with the duplexer comprising metal level 26 and resist 31.By being removed by resist 31 from this duplexer, as shown in Fig. 3 (h), support base material 22 forms the transparency electrode comprising the remainder of transparency conducting layer 24 and the metal wiring of remainder comprising metal level 26.
Fig. 4 is the vertical view of the form representing the contact panel utilizing the present invention to obtain.In contact panel 100, alternately be set up in parallel as the X electrode 52 of transparency electrode and Y electrode 54, the X electrode 52 being arranged to length direction same column is interconnected each other by a wiring lead 56, in addition, the Y electrode 54 being arranged to Width same column is connected to each other each other by a wiring lead 57.
Above the preferred embodiment of the present invention is illustrated, but the invention is not restricted to above-mentioned embodiment.
Embodiment
Illustrate the present invention further below by embodiment, but the invention is not restricted to embodiment.
(Production Example 1: the manufacture of binder polymer (A-1))
The solution be mixed to get by methacrylic acid 30g, methyl methacrylate 35g and butyl methacrylate 35g (mass ratio 30/35/35), azobis isobutyronitrile 0.5g and acetone 10g as polymerizable monomer (monomer) is as " solution a ".Solution that 0.6g azobis isobutyronitrile obtains will be dissolved as " solution b " in 30g acetone.
Mixed liquor (mass ratio 4:1) 100g of acetone 80g and propylene glycol monomethyl ether 20g is added in the flask with stirring machine, reflux cooler, thermometer, tap funnel and nitrogen ingress pipe, while be blown into nitrogen while carry out stirring heating simultaneously in flask, be warming up to 80 DEG C.
After 4 hours above-mentioned solution a that drip in the above-mentioned mixed liquor in flask, carry out stirring 80 DEG C of insulations 2 hours.Then, after the above-mentioned solution b that drips in the solution in 10 points of clockwise flasks, the solution in stirred flask is while 80 DEG C of insulations 3 hours.Further, with 30 minutes by the solution warms to 90 in flask DEG C, in 90 DEG C of insulations cooling after 2 hours, obtain the solution of binder polymer (A-1).
The nonvolatile component (solid constituent) of binder polymer (A-1) is 42.8 quality %, and weight-average molecular weight is 50000, and acid number is 195mgKOH/g, and dispersion degree is 2.58.
In addition, weight-average molecular weight is measured by gel permeation chromatography (GPC), derives by using the typical curve of polystyrene standard to carry out converting.Below represent the condition of GPC.
GPC condition
Pump: Hitachi/L-6000 type (Hitachi Co., Ltd's system)
Post: following totally 3, post specification:
Gelpack GL-R440
Gelpack GL-R450
Gelpack GL-R400M (being Hitachi Chemical Co., Ltd.'s system, trade name above)
Eluant: tetrahydrofuran (THF)
Sample solution concentration: get the resin solution that 120mg solid constituent is 40 quality %, be dissolved in the THF of 5mL and modulate sample.
Measure temperature: 40 DEG C
Injection rate IR: 200 μ L
Pressure: 49Kgf/cm 2(4.8MPa)
Flow: 2.05mL/ minute
Detecting device: Hitachi L-3300 type RI (Hitachi Co., Ltd's system)
Embodiment and comparative example are undertaken by following method.
(modulation of photosensitive polymer combination (coating fluid))
Each composition shown in table 1 and table 2 is mixed with methyl alcohol 5 mass parts, toluene 12 mass parts and acetone 5 mass parts with the use level (mass parts) shown in this table, thus the coating fluid of the photosensitive polymer combination of modulation embodiment and comparative example.The use level of (A) composition in table is the quality (solid constituent amount) of nonvolatile component.The details of each composition shown in table 1 and 2 is as described below.
((A) composition)
A-1: the binder polymer (A-1) obtained by Production Example 1.
((B) composition)
FA-321M:FA-321M (Hitachi Chemical Co., Ltd.'s system, trade name), 2,2-two (4-(methacryloxy five ethoxy) phenyl) propane;
UA-11:UA-11 (chemical industry Co., Ltd. of Xin Zhong village system, trade name), polyoxyethylene urethane dimethacrylate;
UA-13:UA-13 (chemical industry Co., Ltd. of Xin Zhong village system, trade name), polyoxyethylene polyoxypropylene urethane dimethacrylate;
FA-MECH:FA-MECH (Hitachi Chemical Co., Ltd.'s system, trade name), γ-chloro-β-hydroxy propyl-Beta '-methacryloxyethyl-phthalic ester.
((C) composition)
B-CIM:B-CIM (Hampford Inc., ProductName), 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole;
EAB:EAB (Baotugu Chemical Industrial Co., Ltd's system, ProductName), 4,4 '-bis-(diethylamino) benzophenone.
((D) composition)
(D1) composition
KBM-803:KBM-803 (organosilicon Inc. of SHIN-ETSU HANTOTAI, ProductName), 3-mercaptopropyi trimethoxy silane.
(D2) composition
AY43-031:AY43-031 (Dong Li Dow Corning Corporation system, ProductName), 3-ureido-propyl Ethoxysilane;
KBE-573:KBE-573 (organosilicon Inc. of SHIN-ETSU HANTOTAI, ProductName), N-phenyl-3-TSL 8330;
KBE-903:KBE-903 (organosilicon Inc. of SHIN-ETSU HANTOTAI, ProductName), APTES;
KBM-903:KBM-903 (organosilicon Inc. of SHIN-ETSU HANTOTAI, trade name), APTES;
KBE-9103:KBE-9103 (organosilicon Inc. of SHIN-ETSU HANTOTAI, ProductName), 3-triethoxysilyl-N-(1,3-dimethyl-butylidene) propylamine;
Z-6032:Z-6032 (Dong Li Dow Corning Corporation system, ProductName), aminoethylaminopropyl trimethoxy silane.
(D3) composition
SZ-6030:SZ-6030 (Dong Li Dow Corning Corporation system, trade name), methacryloxypropyl trimethoxy silane.
(D1) silane coupling agent ~ (D3) beyond composition
KBE-846:KBE-846 (organosilicon Inc. of SHIN-ETSU HANTOTAI, ProductName), two (triethoxysilylpropyltetrasulfide) tetrasulfide;
KBE-9007:KBE-9007 (organosilicon Inc. of SHIN-ETSU HANTOTAI, ProductName), 3-isocyanates propyl-triethoxysilicane;
KBE-403:KBE-403 (organosilicon Inc. of SHIN-ETSU HANTOTAI, ProductName), 3-glycidoxypropyl group triethoxysilane;
KBE-5103:KBE-5103 (organosilicon Inc. of SHIN-ETSU HANTOTAI, ProductName), 3-acryloxypropyl trimethoxy silane.
((E) composition: the composition beyond (A) ~ (D) composition)
LCV:LCV (hillside plot KCC system, ProductName), leuco crystal violet;
TBC:DIC-TBC-5P (Dainippon Ink. & Chemicals Inc's system, ProductName), 4-tert-butyl catechol;
F-806P: two (N, N-2-ethylhexyl) amino methyl-5-carboxyl-1,2,3-benzotriazole;
AZCV-PW:AZCV-PW (Baotugu Chemical Industrial Co., Ltd's system, ProductName), [two (4-dimethylaminophenyl) methylene of 4-{ }-2,5-cyclohexadiene-1-subunits].
[table 1]
[table 2]
The making > of < photosensitive element
The coating fluid of photosensitive polymer combination obtained above is coated on respectively equably in the polyethylene terephthalate film (east beautiful (strain) system, ProductName " FB-40 ") of thickness 16 μm, use the hot wind convection type exsiccator of 70 DEG C and 110 DEG C to carry out drying process successively, form the photosensitive polymer combination layer that dried thickness is 15 μm.This photosensitive polymer combination layer to be fitted diaphragm (Tamapoly (strain) system, ProductName " NF-15A "), obtain the photosensitive element that polyethylene terephthalate film (support membrane), photosensitive polymer combination layer and diaphragm stack gradually.
The making > of < laminated substrate
The upper strata being used in polyethylene terephthalate materials formed comprise ITO transparency conducting layer, formed on the upper strata of transparency conducting layer and comprise the metal level of copper, the outmost surface of metal level carried out to the film base material of antirust treatment further.To this film base material (hereinafter referred to as " base material ".) carry out heating and after being warming up to 80 DEG C, by the layer on surface of metal of the photosensitive element lamination (stacked) of above-mentioned making at base material.Lamination carries out as follows: remove, diaphragm while make the closely sealed layer on surface of metal at base material of the photosensitive polymer combination layer of photosensitive element, at temperature 110 DEG C, lamination pressure 4kgf/cm 2(0.4MPa) carry out under condition.Thus, the laminated substrate of stacked thoughts photosensitive resin composition layer and polyethylene terephthalate film on the layer on surface of metal of base material is obtained.
The evaluation > of < sensitivity
The laminated substrate obtained is placed and is cooled to 23 DEG C.Then, laminated substrate is divided into 3 regions, closely sealed smooth tool in the polyethylene terephthalate film in a region wherein, this light tool has 41 sections of stage metraster that concentration range is 0.00 ~ 2.00, concentration gradient is 0.05, the size of metraster is 20mm × 187mm, the size in each stage is 3mm × 12mm.About exposure, use the parallel rays exposure machine ((strain) ORC manufacturing company system, ProductName " EXM-1201 ") being light source with short arc UV lamp ((strain) ORC manufacturing company system, ProductName " AHD-5000R "), with 100mJ/cm 2energy (exposure) across light tool and polyethylene terephthalate film, photosensitive polymer combination layer is exposed.At this moment, other region do not used covers with black thin plate.In addition, make to use the same method respectively with 200mJ/cm to regional 2, 400mJ/cm 2energy expose.In addition, the mensuration of illumination uses the ultraviolet illuminometer (USHIO motor (strain) system, ProductName " UIT-150 ") applying the corresponding probe of 405nm.
After exposure, from laminated substrate, polyethylene terephthalate film is peeled off, photosensitive polymer combination layer is exposed, at 30 DEG C, 1 quality % aqueous sodium carbonate was sprayed for 16 seconds, thus unexposed portion is removed.Thus, the layer on surface of metal of base material is formed the Resist patterns comprising photosensitive polymer combination solidfied material.The typical curve of exposure and number of stages is made by the remaining hop count (number of stages) of the stage metraster obtained as Resist patterns (cured film) under each exposure, obtain the exposure that number of stages is 20 sections, thus evaluate the sensitivity of photosensitive polymer combination.The exposure that sensitivity is 20 sections by the number of stages obtained from typical curve represents, this exposure is fewer means that sensitivity is better.Show the result in table 3 and table 4.
The evaluation > of < adaptation
Live width (L)/interval wide (S) is used (to be designated as below " L/S ".) be 8/400 ~ 47/400 mask pattern of (unit: μm), be that the photosensitive polymer combination layer of energy to above-mentioned laminated substrate of 20 sections exposes with the remaining hop count of 41 sections of stage metraster.After exposure, carry out the development treatment same with the evaluation of above-mentioned sensitivity.
After development, to be completely removed by compartment (unexposed portion) and the minimum value that line part (exposed portion) does not produce in the wide value in complications, the live width/interval of Resist patterns that formed breach evaluates adaptation.This numerical value is less means that adaptation is better.Show the result in table 3 and table 4.
The evaluation > of < resolution
Use L/S to be 8/8 ~ 47/47 mask pattern of (unit: μm) is that the photosensitive polymer combination layer of energy to above-mentioned laminated substrate of 20 sections exposes with the remaining hop count of 41 sections of stage metraster.After exposure, carry out the development treatment same with the evaluation of above-mentioned sensitivity.
After development, to be completely removed by compartment (unexposed portion) and the minimum value that line part (exposed portion) does not produce in the wide value in complications, the live width/interval of Resist patterns that formed breach evaluates resolution.This numerical value is less means that resolution is better.Show the result in table 3 and table 4.
The evaluation > of < corrosion liquid resistance
The elching resistant of following evaluation Resist patterns.Use L/S to be 8/400 ~ 47/400 mask pattern of (unit: μm) is that the photosensitive polymer combination layer of energy to above-mentioned laminated substrate of 20 sections exposes with the remaining hop count of 41 sections of stage metraster.After exposure, carry out the development treatment same with the evaluation of above-mentioned sensitivity, obtain forming figuratum base material.
The base material obtained uses cupric chloride system solution to carry out etching until the metal level on surface disappears.Afterwards, carry out washing, dry.Further, the base material eliminating surface metal-layer is flooded 1 minute or 2 minutes in 25 quality % hydrochloride aqueous solutions, afterwards, carries out washing, dry.
After transparency conducting layer being removed by etching, to be completely removed by the metal level of compartment (unexposed portion) and transparency conducting layer and line part (exposed portion) does not produce the minimum value in the wide value in complications, the live width/interval of Resist patterns that formed breach, to evaluate the adaptation after etching.This numerical value is less means that corrosion liquid resistance is higher, adaptation is better.The situation being 1 minute by the etching period being used for removing transparency conducting layer is designated as (μm/1min), the situation of 2 minutes be designated as (μm/2min), show the result in table 3 and table 4.
[table 3]
[table 4]
In addition, in comparative example 5 and comparative example 10, coating fluid gelation and make film forming become very difficult, from the viewpoint of stability, yield rate, is difficult to use as product.As the reason of coating fluid gelation, think that the amino of the silane coupling agent that each comparative example uses and the carboxylic acid of binder polymer there occurs effect etc.
Symbol description
2: support membrane, 4: photosensitive polymer combination layer, 6: diaphragm, 10: photosensitive element, 12: support base material, 14: transparency conducting layer, 16: photosensitive polymer combination layer, 18: wiring lead, 22: support base material, 24: transparency conducting layer, 26: metal level, 28: photosensitive polymer combination layer, 29: resist, 30: photosensitive polymer combination layer, 31: resist, 52: transparency electrode (X electrode), 54: transparency electrode (Y electrode), 56,57: wiring lead, 100: contact panel.

Claims (10)

1. an ITO etching photosensitive polymer combination, it contains:
Binder polymer,
Photopolymerizable compound,
Photoepolymerizationinitiater initiater and
Silane coupling agent,
Described silane coupling agent comprises the silane compound with mercaptoalkyl.
2. photosensitive polymer combination according to claim 1, described silane coupling agent comprises the silane compound with amino further.
3. the photosensitive polymer combination according to claims 1 or 2, described silane coupling agent comprises the silane compound with (methyl) acryloxy further.
4. the photosensitive polymer combination according to any one of claims 1 to 3, described photopolymerizable compound contains bisphenol A-type two (methyl) acrylate compounds.
5. the photosensitive polymer combination according to any one of Claims 1 to 4, described photopolymerizable compound contains carbamate two (methyl) acrylate compounds with (gathering) oxygen ethylidene and/or (gathering) oxygen propylidene.
6. a photosensitive element, it has support membrane and is arranged on the photosensitive polymer combination layer comprising the photosensitive polymer combination according to any one of Claims 1 to 5 in the one side of this support membrane.
7. a formation method for Resist patterns, it has following operation:
Base material is formed the 1st operation of the photosensitive polymer combination layer of the photosensitive polymer combination comprised according to any one of Claims 1 to 5;
By the irradiation of active ray by regions curing for a part for described photosensitive polymer combination layer and form the 2nd operation in solidfied material region; With
Region beyond the described solidfied material region of described photosensitive polymer combination layer is removed from described base material, obtains the 3rd operation of the Resist patterns comprising described solidfied material region.
8. a manufacture method for contact panel, it has the operation that the described base material defining Resist patterns to the formation method by Resist patterns according to claim 7 carries out etch processes.
9. a manufacture method for contact panel, it has following operation:
There is support base material, be arranged on the transparency conducting layer comprising tin indium oxide in the one side of this support base material and be arranged on the described metal level of laminated substrate of the metal level on this transparency conducting layer, forming the 1st operation of the Resist patterns of the solidfied material of the photosensitive polymer combination comprised according to any one of Claims 1 to 5;
Described metal level and described transparency conducting layer are etched, forms the 2nd operation comprising the lamination pattern of the remainder of described transparency conducting layer and the remainder of described metal level; With
From a part for described lamination pattern, described metal level is removed, form the 3rd operation of the metal wiring of the transparency electrode comprising the remainder of described transparency conducting layer and the remainder comprising described metal level.
10. the manufacture method of contact panel according to claim 9, described transparency conducting layer comprises crystalline tin indium oxide,
The etching utilizing strong acid to carry out is etched in described 2nd operation.
CN201380042172.9A 2012-09-27 2013-09-11 The manufacturing method of photosensitive polymer combination, photosensitive element, the forming method of resist pattern and touch panel Active CN104541204B (en)

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