CN107407870A - Photosensitive polymer combination, the manufacture method of conductive pattern, substrate, touch panel and display - Google Patents
Photosensitive polymer combination, the manufacture method of conductive pattern, substrate, touch panel and display Download PDFInfo
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- CN107407870A CN107407870A CN201680014153.9A CN201680014153A CN107407870A CN 107407870 A CN107407870 A CN 107407870A CN 201680014153 A CN201680014153 A CN 201680014153A CN 107407870 A CN107407870 A CN 107407870A
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- Prior art keywords
- photosensitive polymer
- polymer combination
- methyl
- compound
- manufacture method
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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
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
Abstract
The present invention provides a kind of photosensitive polymer combination, can obtain the distinguishing of fine pattern, and can suppress the residue on substrate simultaneously.The photosensitive polymer combination contains electroconductive particle (A), alkali soluble resins (B) and organo-tin compound (C), and the primary particle size of above-mentioned electroconductive particle (A) is less than 0.7 μm.
Description
Technical field
The present invention relates to photosensitive polymer combination, the manufacture method of conductive pattern, substrate, touch panel and display
Device.
Background technology
In recent years, along with the High precision of display, the miniaturization of electronic unit or densification etc., to electronics wiring
The requirement of miniaturization improves.As the conduction made using the resin combination containing electroconductive particle for electronics wiring
Property pattern method, usually on substrate formed pattern after heated, thus contact electroconductive particle obtain electric conductivity figure
The method of case.As the method for the formation pattern on substrate, such as silk screen print method, ink-jet method or photoetching process can be enumerated.Its
In, silk screen print method, ink-jet method are not suitable for forming fine pattern, and photoetching process suitably forms fine pattern.
Photoetching process is as follows：After photosensitive composite is coated with and dried, there is the shape of fine wiring pattern case across description
Photomask irradiation ultraviolet etc., is thus formed exposure portion and unexposed portion on film, is developed using developer solution, thus existed
Fine pattern is formed on substrate.And then by conductive treatment afterwards, form fine conductive pattern.Make in this method
Photosensitive composite is made up of (patent document 1) electroconductive particle, emulsion and resin etc..
And then led to form less than 5 μm of submicroscopic patterns, it is necessary to use the particle with more small particle diameter to be used as
Conductive particles.Now, from the viewpoint of the surface smoothness of pattern and sided linear, for required wiring width,
The sufficiently small particulate of particle diameter must be used.Herein, as the photosensitive polymer combination for having used the sufficiently small particulate of particle diameter,
Knowing has the photosensitive polymer combination for having used the silver particles (patent document 2) being coated to through surface.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2000-199954 publications
Patent document 2：Japanese Unexamined Patent Publication 2013-196997 publications
The content of the invention
Invent problem to be solved
But in the photosensitive polymer combination using silver particles, it is easy to produce on substrate when forming pattern residual
The problems such as bad order or reliability reduction be present in slag, gained pattern.
The present invention be in view of make the defects of above-mentioned prior art, its object is to provide one kind can obtain it is fine
The distinguishing of pattern and the photosensitive polymer combination for suppressing the residue on substrate simultaneously.By using such photoresist
Composition, the extremely good and high reliability fine conductive pattern of outward appearance can be obtained.
Means for solving the problems
As a result present inventors have found by concentrating on studies, photosensitive polymer combination is contained organotin
Compound (C) is extremely effective to solving above-mentioned problem.
That is, the present invention provides photosensitive polymer combination, and it contains electroconductive particle (A), alkali soluble resins (B) and organic
Tin compound (C), the primary particle size of above-mentioned electroconductive particle (A) is less than 0.7 μm.
Invention effect
According to the photosensitive polymer combination of the present invention, the conduction that outward appearance is good and reliability is high, fine can be obtained
Pattern.In addition, it is not necessary according to the invention that form the solidification film figure of electric conductivity by etching method, therefore can be by operative employee
Sequence is simplified, and can avoid the deterioration of decoction during as etching, wiring portion caused by plasma.
Embodiment
The photosensitive polymer combination of the present invention is characterised by containing electroconductive particle (A), alkali soluble resins (B) and had
Machine tin compound (C), the primary particle size of above-mentioned electroconductive particle (A) is less than 0.7 μm.It should be noted that the photonasty tree
The photonasty of oil/fat composition can be that positive light sensitivity can also be negative-type photosensitive, but preferably negative-type photosensitive.
(electroconductive particle (A))
As electroconductive particle (A), such as golden (Au), silver-colored (Ag), copper (Cu), nickel (Ni), tin (Sn), bismuth can be enumerated
(Bi), the metal particle such as lead (Pb), zinc (Zn), palladium (Pd), platinum (Pt), aluminium (Al), tungsten (W) or molybdenum (Mo).Wherein, preferably contain
There is the metal particle selected from least one of gold, silver, copper, nickel, tin, bismuth, lead, zinc, palladium, platinum, aluminium and carbon element, more preferably
The metal particle of silver.
In order to form the fine conductive pattern with desired electric conductivity, it is necessary to make the once grain of electroconductive particle (A)
Footpath is less than 0.7 μm.Herein, the primary particle size of so-called electroconductive particle (A), can be by being selected at random using SEM
The average value of the particle diameter for 100 primary particles selected calculates.For the particle diameter of each primary particle, the length of primary particle can be determined
Footpath and minor axis, calculated by its average value.The primary particle size of electroconductive particle (A) is preferably 10~200nm, more preferably 10~
60nm。
Electroconductive particle (A) is preferably the particle that surface is coated with carbon simple substance and/or carbon compound.By existing by carbon list
The layer (hereinafter referred to as " surface coating ") on electroconductive particle (A) surface that matter and/or carbon compound are formed, coated, can press down
Electroconductive particle (A) is melting adhered each other during low temperature processed.
As the method with carbon simple substance and/or carbon compound coated particle surface, for example, can enumerate using heat etc. from
Daughter legal system makees method (the Japanese Unexamined Patent Publication 2007-138287 public affairs for making it be contacted with reactant gas during electroconductive particle (A)
Report).The surface of electroconductive particle (A) is preferably fully coated to, but as long as the object of the invention can be realized, is then allowed partly
In the presence of coated incomplete particle.
The average thickness of surface coating is preferably 0.1~10nm.When within the range, by suppressing electric conductivity microfine
Son is melting adhered each other, can improve fine pattern processability, and by being heat-treated in less than 300 DEG C of temperature,
Desired electric conductivity can be showed.
For the average thickness of surface coating, carbon simple substance and/or carbonization are coated with using thermobalance measure surface
The Mass lost of the electroconductive particle (A) of compound, it is assumed that the value all is from the burning of carbon, using the density of carbon as 2.0, so as to
The average thickness of surface coating is calculated by particle diameter.Known to particle diameter (Dp) on electroconductive particle (A) with average thickness A (μ
M) it is coated to carbon.The number for the particle being coated to through carbon is set to n.The quality initially weighed during thermobalance is determined is set to W1(g), will
Quality after carbon disperses completely is set to W2(g) density of electroconductive particle (A), is set to ρ, if it is known that Dp and W2, then can be under
Formula calculates n.
W2=π/6 × Dp3ρ×n
And then can be by the average thickness A of following formula gauging surface coating.
W1-W2={ 4/3 × π (Dp/2+A)3-π/6×Dp3}×2.0×n
As the content of the electroconductive particle (A) in photosensitive polymer combination, preferably 65~95 mass %, more preferably
For 70~95 mass %, more preferably 70~90 mass %., can by containing electroconductive particle (A) within the range
Take into account the presentation of pattern processability and electric conductivity.Herein, so-called whole solid state components, refer to what photosensitive polymer combination contained
Whole compositions outside solvent are removed in composition.
, can be by photosensitive resin composition for electroconductive particle (A) ratio shared in whole solid state components
Whole compositions of thing carry out quantitative analysis and calculated.It should be noted that the ratio of following each compositions can also use equally
Method calculate.
Whole component analyzing methods of photosensitive polymer combination are as follows.
(i) organic solvent diluting photosensitive polymer combination is used, is carried out1H-NMR measure, GC measure and GC/MS measure, are adjusted
Look into its rough idea.
(ii) it is centrifuged after photosensitive polymer combination is extracted with organic solvent, separates soluble ingredient and insoluble
Composition.
(iii) above-mentioned insoluble component is directed to, is centrifuged after being extracted with highly polar organic solvent, further separation can
Melt into point and insoluble component.
(iv) mixed liquor of the soluble ingredient obtained for passing through above-mentioned (ii) and (iii), progress IR measure,1H-NMR is surveyed
Fixed and GC/MS measure.And then GPC classifications are carried out to above-mentioned mixed liquor.For gained classification thing carry out IR measure and1H-NMR
Measure.In addition, being directed to the classification thing, GC measure, GC/MS measure, thermal decomposition GC/MS measure and MALDI/MS are carried out as needed
Measure.
(v) insoluble component obtained in above-mentioned (iii) is directed to, carries out IR measure or TOF-SIMS measure.Confirm presence
During organic matter, carry out thermally decomposing GC/MS or TPD/MS measure.
(vi) synthetically judged by the measurement result to above-mentioned (i), (iv) and (v), photoresist can be obtained
The containing ratio of each composition contained by composition.It is it should be noted that highly polar organic molten as what is used in above-mentioned (iii)
Agent, preferably chloroform or methanol etc..
(alkali soluble resins)
Alkali soluble resins (B) generally can be by making the compound containing carboxyl be obtained with other monomer copolymerizations.Alkali soluble
Property resin (B) be preferably (methyl) acrylic acid series copolymer.Herein, so-called (methyl) acrylic acid series copolymer, refers to be copolymerized into
At least contain the copolymer of (methyl) acrylic monomer in point.Herein, as (methyl) acrylic monomer, such as can lift
Go out (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (first
Base) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (first
Base) acrylic acid n-pentyl ester, (methyl) allyl acrylate, (methyl) benzyl acrylate, (methyl) acrylate, butoxy second
Base ester, butoxytriglycol (methyl) acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid bicyclopentyl
Ester, (methyl) acrylic acid dicyclopentenyl base ester, (methyl) 2-ethylhexyl acrylate, (methyl) glycerol acrylate, (first
Base) glycidyl acrylate, the fluorine decyl ester of (methyl) acrylic acid 17, (methyl) acrylic acid 2- hydroxyethyls ester, (first
Base) isobornyl acrylate, (methyl) acrylic acid 2- hydroxy-propyl esters, (methyl) Isodecyl base ester, (methyl) propylene
Sour isooctyl acrylate, (methyl) lauryl acrylate, (methyl) acrylic acid 2- methoxy ethyls ester, methoxy ethyl glycol (methyl)
Acrylate, methoxyl group diethylene glycol (methyl) acrylate, (methyl) acrylic acid octafluoro amyl group ester, (methyl) acrylic acid benzene oxygen
Base ethyl ester, (methyl) stearyl acrylate base ester, (methyl) acrylic acid trifluoroethyl ester, (methyl) acrylamide, (methyl) third
Olefin(e) acid amino-ethyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid 1- naphthyls ester, (methyl) acrylic acid 2- naphthyls ester,
Benzenethiol (methyl) acrylate or benzyl mercaptan (methyl) acrylate.
As the copolymer composition beyond (methyl) acrylic monomer, the compound with carbon-to-carbon double bond can be used.Make
For such compound, for example, can enumerate styrene, p-methylstyrene, o-methyl styrene, a methyl styrene or α-
The aromatic ethenyl compounds such as methyl styrene, (methyl) acrylamide, N- methylols (methyl) acrylamide or N- ethene
The acid amides such as base pyrrolidones system unsaturated compound, (methyl) acrylonitrile, allyl alcohol, vinyl acetate, cyclohexyl vinyl ether,
N-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether, IVE, 2- hydroxyethylvinyls
Ether or 4- hydroxybutyl vinyl ethers.
Alkali-soluble copolymer composition, the i.e. compound containing carboxyl are assigned as to alkali soluble resins (B), such as can be lifted
Go out (methyl) acrylic acid, itaconic acid, crotonic acid, maleic acid or fumaric acid or their acid anhydrides.
When using (methyl) acrylic acid series copolymer, solidify to increase photosensitive polymer combination because of caused by exposure
The speed of reaction, preferably there is (methyl) acrylic acid series copolymer of carbon-to-carbon double bond in side chain or molecular end.As with
The functional group of carbon-to-carbon double bond, such as vinyl, pi-allyl or (methyl) acrylic acid series group can be enumerated.In order to by above-mentioned official
It can roll into a ball and be added on (methyl) acrylic acid series copolymer, there are as below methods：Make with glycidyl (or NCO) and
The compound of carbon-to-carbon double bond or (methyl) acryloyl chloride or allyl chloride, with the sulfydryl in (methyl) acrylic acid series copolymer,
Amino, hydroxyl or carboxyl carry out addition reaction.
As the compound with glycidyl and carbon-to-carbon double bond, for example, can enumerate (methyl) acrylic acid shrink it is sweet
Oil base ester, allyl glycidyl ether or glycidyl base ethyl ester, crotyl glycidyl ether, crotonic acid contracting
Water glycerine base ester or iso-crotonic acid glycidyl esters.As the compound with NCO and carbon-to-carbon double bond, such as can
To enumerate (methyl) propenoyl isocyanate or (methyl) acryloyloxyethyl isocyanate.
Alkali soluble resins (B) is preferably the alkali soluble resins with acid dissociation group.For with acid dissociation group
Alkali soluble resins, generally can by make the compound containing carboxyl and with acid dissociation group copolymer compound and
Arrive.As more specifically example, can enumerate makes (methyl) acyclic compound containing carboxyl and has acid dissociation group
(methyl) acrylic ester copolymer.
In order that acid dissociation group decomposes, gasified after the decoupling, preferred acid dissociative group is carbon number 4~15
Organic group, more preferably 6~15 organic group.If the carbon number of acid dissociation group is less than 4, after disengaging
Gasify at low temperature, therefore following situations be present：Air pocket is produced in film and hinders electroconductive particle (A) is mutual to connect
Touch, electric conductivity deterioration.On the other hand, if the carbon number of acid dissociation group is more than 15, following situations be present：Departing from
Afterwards, dissociative group remains in film and hinders electroconductive particle (A) mutual contact, and electric conductivity still deteriorates.Need to illustrate
, when acid dissociation group is the organic group of carbon number 6~15, bubble is produced in film also easily by rear baking
It is roasting to make its disappearance, conductive pattern with good conductivity can be formed.
As acid dissociation group, for example, can enumerate the tert-butyl group, tert-butoxycarbonyl, benzyl, methyl adamantane base or
THP trtrahydropyranyl.
As (methyl) acrylate with acid dissociation group, such as (methyl) acrylic acid 1- methyl gold can be enumerated
Firm Arrcostab, (methyl) acrylate tert-buthyl, (methyl) benzyl acrylate or (methyl) acrylic acid oxinane base ester.
In the photosensitive polymer combination of the present invention, it is contemplated that when photonasty is presented, the content of alkali soluble resins (B) is relative
For whole solid state components preferably in the range of 5~30 mass %.
Alkali soluble resins (B) is preferably the free-radical polymerized compound for having 20~80 moles of % to have acid dissociation group
Alkali soluble resins.There is (methyl) propylene of acid dissociation group particularly preferably in alkali soluble resins containing 20~80 moles of %
Acid esters is as monomer component.It is easy by using such alkali soluble resins with acid dissociation group, acid dissociation group
Under air, 100~300 DEG C issue heat oxidation Decomposition and disengaging, and film significantly shrinks, so as to make in whole solid state components
Electroconductive particle (A) concentration easily improve.Moreover, as a result, readily available ratio resistance is 10~1,000 μ Ω
Cm desired electric conductivity.Now, it is and if more notable with following photoacid generators and/or thermal acid generator, its effect.
The carboxylate equivalent of alkali soluble resins (B) is preferably 200~Isosorbide-5-Nitrae 00g/mol, more preferably 400~1,000g/mol.
The carboxylate equivalent of acrylic resin can be calculated by determining acid number.In addition, in order to obtain hardness simultaneously with high level
With it is resistance to anti-thread breakage, the double bond equivalent of alkali soluble resins (B) is preferably 150~10,000g/mol.The double bond equivalent of acrylic resin
It can be calculated by determining iodine number.
For alkali soluble resins (B) weight average molecular weight (Mw), determined by gel permeation chromatography (GPC) with polyphenyl second
Alkene conversion meter, preferably 1,000~100,000.By making weight average molecular weight (Mw) be above range, good painting can be obtained
Cloth characteristic, dissolubility when forming pattern in developer solution also become good.
(organo-tin compound)
So-called organo-tin compound (C), refer to the change that at least one carbon atom is bonded with the acylate or tin atom of tin
Compound.As organo-tin compound, such as the acylate such as 2 ethyl hexanoic acid tin or tin dilaurate tin or oxalic acid can be enumerated
Dibutyl tin, dibutyl tin laurate, dibutyitin maleate, double (2-ethylhexyl mercaptoacetate) dibutyl tins, double (mercaptos
The different monooctyl ester of guanidine-acetic acid) dibutyl tin, dioctyl tin diacetate, tin dilaurate dioctyl tin, dioctyl tin maleate, oxalic acid two
Methyl tin, dilaurate, maleic acid stannous methide, oxalic acid stannous phenide, tin dilaurate stannous phenide, maleic acid
Stannous phenide, dichloro dibutyl tin, dichloro dipropyl tin, Dichlorodiethyl tin, dimethyl tin dichloride, trichlorine butyl tin, trichlorine
Methyl tin, dichlorophenyl tin, Dibutyltin oxide, dimethyl tin oxide, dioctyl tin oxide, tetrabutyltin, tetramethyl tin,
Tetraphenyltin, allene base (allenyl) tributyl tin, allyl tributyltin, pi-allyl triphenyltin or tin diethyl etc.
The compound of at least one carbon atom is bonded with tin atom.By making photosensitive polymer combination contain organo-tin compound
(C), the residue inhibition on substrate becomes notable.
Organo-tin compound (C) is preferably the compound that formula (1) represents.
[compound 1]
(in formula, R1And R2Separately represent organic group, X1And X2Separately represent the anion of 1 valency.X1And
X2It can also be connected with each other.)
As R1And R2In organic group, such as alkyl, alkenyl or aryl can be enumerated.As alkyl, such as can be with
Enumerate methyl, ethyl, n-propyl, normal-butyl or octyl group.As alkenyl, such as vinyl, acryloxy third can be enumerated
Base or methacryloxypropyl.As aryl, such as phenyl, tolyl or naphthyl can be enumerated.
As X1And X2In 1 valency anion, such as can enumerate fluoride ion, chloride ion, bromide ion,
Iodide ion, hydroxide ion, nitrate ion or Carboxylic Acid Ions.
The particular compound represented as formula (1), such as dibutyltin diacetate, di lauric dibutyl can be enumerated
Tin, dibutyitin maleate, double (2-ethylhexyl mercaptoacetate) dibutyl tins, double (isooctyl thioglycolate) dibutyl tins,
Dioctyl tin diacetate, tin dilaurate dioctyl tin, dioctyl tin maleate, dimethyltin diacetate, tin dilaurate dimethyl
Tin, maleic acid stannous methide, oxalic acid stannous phenide, tin dilaurate stannous phenide, maleic acid stannous phenide, dichloro dibutyl
Tin, dichloro dipropyl tin, Dichlorodiethyl tin, dimethyl tin dichloride or dichlorophenyl tin.Wherein, preferred oxalic acid dibutyl
Tin, dibutyl tin laurate, dibutyitin maleate, (2-ethylhexyl mercaptoacetate) dibutyl tin be double, double (TGAs
Different monooctyl ester) dibutyl tin, dioctyl tin diacetate, tin dilaurate dioctyl tin, dioctyl tin maleate, oxalic acid dimethyl
Tin, dilaurate, maleic acid stannous methide, oxalic acid stannous phenide, tin dilaurate stannous phenide, maleic acid hexichol
Ji Xi.
Organo-tin compound (C) ratio shared in whole solid state components is preferably 0.01~10 mass %, more preferably
For 0.05~5 mass %, more preferably 0.1~5 mass %.Organo-tin compound (C) content is more than 0.01 mass %
When, the residue inhibition on substrate is more notable.On the other hand, when organo-tin compound (C) content is below 10 mass %, energy
Enough form electric conductivity height and fine pattern.
(dispersant)
The photosensitive polymer combination of the present invention can also contain dispersant.By containing dispersant, electric conductivity can be made
Particle (A) is stably present in photosensitive polymer combination.
As dispersant, preferably amine system dispersant.As commercially available amine system dispersant, such as DISPERBYK can be enumerated
(registration mark) 106,108,112,116,142,145,166,180,2001,2008,2022,2150,6919 or 21116 (with
On, by BYK Japan systems) or Efka (registration mark) 4300,4400,4401,4403,4406,4510,4570,4800,
5054th, 5055 or 5207 (above by BASF systems).
In order to further improve dispersiveness, preferred dispersants have acrylic block copolymer structure.As with third
The commercially available amine system dispersant of olefin(e) acid based block copolymer structure, for example, can enumerate DISPERBYK (registration mark) 2001,
2008th, 2022,2150,6919 or 21116 or Efka (registration mark) 4300.
As the content of the dispersant in photosensitive polymer combination, relative to electroconductive particle (A) and following other grains
The mass parts of total 100 of son, preferably 1~7 mass parts, the reason is that well dispersed, the Ke Yijin of electroconductive particle (A)
The finer pattern processing of row, promote the contact of electroconductive particle (A) and melting adhered, the higher electric conductivity of acquisition.
(Photoepolymerizationinitiater initiater)
The photosensitive polymer combination of the present invention can contain Photoepolymerizationinitiater initiater.By containing Photoepolymerizationinitiater initiater, energy
It is enough to assign negative-type photosensitive to photosensitive polymer combination.
As Photoepolymerizationinitiater initiater, such as acetophenone based compound, benzophenone based compound, benzoin ether can be enumerated
Based compound, alpha-aminoalkyl Benzophenone based compound (α-aminoalkyl phenone), thioxanthones based compound, organic mistake
Oxide, imidazole compound, titanocenes (titanocene) based compound, triazine based compound, acylphosphine oxide compound,
Naphtoquinone compounds or oxime ester based compound, it is preferably even if adding its sensitivity also high oxime ester based compound on a small quantity, more preferably
Oxime ester based compound with carbazole skelton.As the oxime ester based compound without carbazole skelton, such as can enumerate
Irgacure (registration mark) OXE01 (BASF AG's system), as the oxime ester based compound with carbazole skelton, such as it can lift
Go out Irgacure (registration mark) OXE02 (BASF AG's system), ADEKA OPTOMER (registration mark) N1919 (Co., Ltd.
ADEKA systems) or ADEKA ARKLS (registration mark) NCI-831 (Asahi Denka Co., Ltd.'s system).
(solvent)
The photosensitive polymer combination of the present invention can contain solvent.
As solvent, such as propylene glycol monomethyl ether, glycol monobutyl ether, 2- enanthol, cyclohexanol, ring penta can be enumerated
Alcohol, 2- butanol, 2- amylalcohols, the tert-butyl alcohol, DAA, alpha-terpineol, 2- hydroxy-methyl isobutyl acids, 2- ethyl butyrate of hydroxyl iso,
Propylene glycol monoethyl acetic acid esters, ethyl acetoacetate, methyl acetoacetate, 3- methoxy methyl propionates, acetic acid 3- methyl -3-
Methoxybutyl, cyclopentanone, cyclohexanone, benzylisoeugenol, hexyl ether, acetonyl acetone, isophorone, acetic acid benzyl ester,
Ethyl benzoate, diethy-aceto oxalate, diethyl maleate, carbonic acid ethylidene ester, propylene carbonate, benzoic acid methyl ester, benzene
Carboxylate, diethyl malonate, beta-propiolactone, gamma-butyrolacton, gamma-valerolactone, δ-valerolactone, γ-own lactones, ε-oneself
Lactones, ethylene glycol monobutyl ether acetic acid esters, TC acetic acid esters, diethylene glycol monobutyl ether acetic acid esters, diethyl
Glycol dimethylether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol methyl ether acetic acid esters, dipropyl two
Alcohol dimethyl ether, propylene-glycol diacetate, 1,3-BDO diacetate esters, adnoral acetate, dimethyl sulfoxide (DMSO), Methylethyl
Ketone, Sucrose Acetate base ester, Sucrose Acetate base ester, acetic acid butyl ester, acetic acid propyl ester, isopropyl, acetylacetone,2,4-pentanedione, glycerine
Triacetate or 2-HEPTANONE.
(other particles)
The photosensitive polymer combination of the present invention can also contain except (A) is conductive to improve dispersiveness, control electric conductivity
Other particles beyond particulate.As other particles, such as the coated metal particle of surface free or metal oxidation can be enumerated
Thing particulate, organic pigment or inorganic pigment.
The particle diameter of these other particles is preferably 10~100nm.When particle diameter is less than 10nm, for the scattered of dispersion stability
Agent is difficult to obtain desired electric conductivity sometimes using becoming more.On the other hand, if particle diameter is more than 100nm, pattern sometimes
Resolution ratio reduction, the submicroscopic patterns for being difficult to be formed less than 5 μm.
As these other particles, preferably contribute to control the carbon black of electric conductivity.
As carbon black, such as MA77,7,8,11,100,100R, 100S, 230,220 or 14 can be enumerated (above by three
Water chestnut KCC system), #52,47,45,45L, 44,40,33,32,30,25,20,10,5,95,85 or 260 (above by
Mitsubishi chemical Co., Ltd's system), Special Black100,250,350 or 550 are (above by Evonik Degussa companies
System) or Printex95,90,55,45,40, P, 60, L6, L, 300,30, ES23,9, ES22,35,25,200, A or G are (above
By Evonik Degussa company systems).Wherein, preferable ph be less than 4 MA77,7,8,11,100,100R, 100S, 230,
220 or 14 or Special Black100,250,350 or 550.It should be noted that the pH value of carbon black is according to JIS K5101
It is measured.
(photoacid generator and thermal acid generator)
The photosensitive polymer combination of the present invention can also contain photoacid generator and/or thermal acid generator.Alkali soluble resins (B)
For alkali soluble resins with acid dissociation group when, acid dissociation radical decomposition can be promoted by caused acid, make sky
Heat treatment temperature under gas reduces.
Produced as Yin Re acid compound, i.e. thermal acid generator, such as can enumerate SI-60, SI-80, SI-100,
SI-110、SI-145、SI-150、SI-60L、SI-80L、SI-100L、SI-110L、SI-145L、SI-150L、SI-160L、
SI-180L or SI-200 (being made above by three new chemical industry (strain)), 4- hydroxy phenyls dimethyl sulfonium, benzyl -4- hydroxy benzenes
Ylmethyl sulfonium, 2- methyl-benzyl -4- hydroxyphenylmethyls sulfonium, 2- methyl-benzyl -4- acetylbenzene ylmethyl sulfoniums or 2- methyl benzyls
Base -4- benzoyls phenyl methyl sulfonium or their mesylate, fluoroform sulphonate, camsilate or to toluene sulphur
Hydrochlorate.Wherein, preferably using 4- hydroxy phenyls dimethyl sulfonium, benzyl -4- hydroxyphenylmethyls sulfonium, 2- methyl-benzyl -4- hydroxyls
Phenyl methyl sulfonium, 2- methyl-benzyl -4- acetylbenzene ylmethyl sulfoniums or 2- methyl-benzyl -4- benzoyl phenyl methyl sulfoniums
Or their mesylate, fluoroform sulphonate, camsilate or tosilate.
As the content of the thermal acid generator in photosensitive polymer combination, in order to promote the alkali soluble containing acid dissociation group
Property resin in acid dissociation group decomposition, without prejudice to electroconductive particle (A) it is mutual contact, obtain higher electric conductivity,
Relative to the mass parts of alkali soluble resins (B) 100, preferably 0.01~20 mass parts.
For the acid as caused by photoacid generator (it is that sour compound is produced under light action), in order to promote acid dissociation
The strong acid such as the decomposition of group, preferably perfluoro alkyl sulfonic acid or p-methyl benzenesulfonic acid.
As photoacid generator, for example, can enumerate SI-101, SI-105, SI-106, SI-109, PI-105, PI-106,
PI-109、NAI-100、NAI-1002、NAI-1003、NAI-1004、NAI-101、NAI-105、NAI-106、NAI-109、
NDI-101, NDI-105, NDI-106, NDI-109, PAI-01, PAI-101, PAI-106 or PAI-1001 (above by
Midori Kagaku (strain) make), SP-077 or SP-082 (above by (strain) ADEKA systems), (Japan synthesizes work to TPS-PFBS
Industry (strain) is made), CGI-MDT or CGI-NIT (more than, made by Ciba Japan (strain)) or WPAG-281, WPAG-336,
WPAG-339、WPAG-342、WPAG-344、WPAG-350、WPAG-370、WPAG-372、WPAG-449、WPAG-469、WPAG-
505 or WPAG-506 (makes) by with Wako Pure Chemical Industries (strain) above.
As the content of the photoacid generator in photosensitive polymer combination, in order to promote that there is the alkali soluble of acid dissociation group
Property resin in acid dissociation group decomposition, without prejudice to electroconductive particle (A) it is mutual contact, obtain higher electric conductivity,
Relative to the mass parts of alkali soluble resins (B) 100, preferably 0.01~20 mass parts.
In addition, in order to further promote the decomposition of acid dissociation group, can also and with thermal acid generator and photoacid generator.
(sensitizer)
When the photosensitive polymer combination of the present invention contains photoacid generator, photosensitive polymer combination can further contain
Sensitizer.Sensitizer is preferably the sensitizer that gasifies by heat treatment or also can be because of light irradiation even if when remaining in cured film
And the sensitizer to fade, from the viewpoint of the high-resolution of pattern processing, the sensitizer that is more preferably faded by light irradiation.
As the sensitizer for gasifying or being faded by light irradiation by heat treatment, such as 3 can be enumerated, 3 '-carbonyl is double
Anthraquinone, benzophenone, 4 such as cumarins such as (diethyl amino coumarins), 9,10- anthraquinones, 4 '-dimethoxy-benzophenone, benzene
The aromatic ketones such as ethyl ketone, 4- methoxyacetophenones or benzaldehyde or biphenyl, Isosorbide-5-Nitrae-dimethylnaphthalene, 9-Fluorenone, fluorenes, phenanthrene, benzo [9,
10] double (4- methoxyphenyls) anthracenes of phenanthrene, pyrene, anthracene, 9- phenylanthracenes, 9- methoxyl groups anthracene, 9,10- diphenylanthrancenes, 9,10-, 9,10- are double
(triphenyl-silyl) anthracene, 9,10- dimethoxys anthracene, 9,10- diethoxies anthracene, 9,10- dipropoxy anthracenes (DPA；Kawasaki
Into (strain) make), 9,10- dibutoxy anthracenes (DBA；Kawasaki chemical conversion (strain) system), the amoxy anthracenes of 9,10- bis-, 2- tert-butyl groups -9,10-
The fused aromatic such as dibutoxy anthracene or double (trimethylsilylacetylenyl) anthracenes of 9,10-.
As the sensitizer to gasify by heat treatment, preferably distil, evaporate or because obtained from thermal decomposition because of heat treatment
The material that pyrolysate can distil or evaporate.As the gasification temperature of sensitizer, in order to do not gasify at a temperature of prebake conditions and
During heat cure decompose and gasify, make electroconductive particle (A) contact and it is melting adhered, preferably 150~300 DEG C.
In addition, for sensitizer, from can realize high sensitivity and it is high-resolution in terms of and pass through light irradiation
And from the aspect of dimerization and colour fading, preferably anthracene based compound, preferably heat stable, 9,10- bis- substitutes anthracene based compound,
From the viewpoint of the reactivity that the dissolubility of sensitizer is improved and photodimerizationization is reacted, what further preferred formula (2) represented
9,10- dialkoxy anthracene based compounds.
[compound 2]
(R3~R10Separately represent hydrogen, the alkyl of carbon number 1~20, alkoxy, alkenyl, acetenyl, aryl
Or acyl group or their organic groups that are substituted and being formed, R11And R12Separately represent the alkoxy of carbon number 1~20
Or the alkoxy substituted by other organic groups.)
As R3~R10In alkyl, such as methyl, ethyl or n-propyl can be enumerated.As alkoxy, such as can be with
Enumerate methoxyl group, ethyoxyl, propoxyl group, butoxy or amoxy.As alkenyl, such as vinyl, acryloyl can be enumerated
Epoxide propyl group or methacryloxypropyl.As aryl, such as phenyl, tolyl or naphthyl can be enumerated.As acyl group,
Such as acetyl group can be enumerated.It should be noted that from the viewpoint of the reactivity of the gasification of compound and photodimerization,
R3~R10The preferably organic group of hydrogen or carbon number 1~6, R3、R6、R7And R10More preferably hydrogen.
As R11And R12In the substituent that is substituted to alkoxy, such as alkoxy or acyl group can be enumerated.It is used as this
When alkoxy, such as methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, methoxy ethoxy, 1- methoxies can be enumerated
Base -2- propoxyl group or 1- acetyl group -2- propoxyl group, from the viewpoint of color fading reaction caused by the dissolubility of compound and photodimerization
Consider, preferably propoxyl group or butoxy.
As the sensitizer concentration in photosensitive polymer combination, in order that must be used to imitate the photosensitive sensitizing of photoacid generator
Fruit becomes abundant, without prejudice to the mutual contact of electroconductive particle (A), higher electric conductivity is obtained, relative to alkali soluble resins (B)
100 mass parts, preferably 0.001~20 mass parts, more preferably 0.005~15 mass parts.
(there is the pigment and/or dyestuff that absorb to visible ray)
The photosensitive polymer combination of the present invention can be in contact with each other and melting adhered not damaging electroconductive particle (A)
In the range of contain to visible ray have absorb pigment and/or dyestuff.By making photosensitive polymer combination contain to visible ray
Pigment and/or dyestuff with absorption, the visible reflectance of the conductive pattern after being toasted after can suppressing.
There is the pigment absorbed as to visible ray, such as lactams series pigments, series pigments, phthalocyanine system face can be enumerated
Material, isoindoline series pigments, diaminoanthraquinone- quinone pigment, dioxazine series pigments, indanthrone series pigments, carbon black or inorganic pigment.
As the pigment of blueness, such as C.I. alizarol saphirols (hereinafter referred to as " PB ") 15, PB15 can be enumerated：1、PB15：2、
PB15：3、PB15：4、PB15：5、PB15：6th, PB16 or PB60.As the pigment of purple, such as C.I. pigment violets can be enumerated
(hereinafter referred to as " PV ") 19, PV23 or PV37.As the pigment of red, such as C.I. paratoneres can be enumerated (hereinafter referred to as
" PR ") 149, PR166, PR177, PR179, PR209 or PR254.As the pigment of green, such as C.I. naphthol greens can be enumerated
(hereinafter referred to as " PG ") 7, PG36 or PG58.As the pigment of yellow, such as C.I. pigment yellows can be enumerated (hereinafter referred to as
" PY ") 150, PY138, PY139 or PY185.As the pigment of black, for example, can enumerate HCF, MCF, LFF, RCF, SAF,
The hot tearings such as the furnace blacks such as ISAF, HAF, XCF, FEF, GPF or SRF (Furnace Black), FT or MT black (Thermal Black),
The carbon black such as channel black (Channel Black) or acetylene black or lactams series pigments (such as, " Irgaphor " (registration mark)
Black S0100CF；BASF AG's system).Wherein, the excellent carbon black of the absorbability of preferably heat resistance, light resistance and visible ray, from
From the viewpoint of electric conductivity and dispersiveness, more preferably furnace black or lactams series pigments.
As carbon black, such as MA77,7,8,11,100,100R, 100S, 230,220 or 14 can be enumerated (above by three
Water chestnut KCC system), #52,47,45,45L, 44,40,33,32,30,25,20,10,5,95,85 or 260 (above by
Mitsubishi chemical Co., Ltd's system), Special Black100,250,350 or 550 are (above by Evonik Degussa companies
System) or Printex95,90,55,45,40, P, 60, L6, L, 300,30, ES23,9, ES22,35,25,200, A or G.Wherein,
MA77 that preferable ph is less than 4,7,8,11,100,100R, 100S, 230,220 or 14 or Special Black100,
250th, 350 or 550.The pH value of carbon black can be measured according to JIS K5101.
As the addition to visible ray with the pigment absorbed in photosensitive polymer combination, relative in composition
Whole solid state components, preferably 0.1~10 mass %.
There is the dyestuff absorbed as to visible ray, such as ferrocene based dye, Fluorenone based dye can be enumerated, be dye
Material, triphenyl methane based dye, coumarin series dyestuff, diphenylamine based dye, quinacridone based dye, quinophthalone based dye,
Phthalocyanine based dye or xanthene based dye, the excellent black dyes of the absorbability of preferably heat resistance, light resistance and visible ray, preferably
VALIFAST (registration mark) Black 1888, VALIFAST (registration mark) Black 3830, NUBIAN (registration mark)
Black PA-2802 or OIL Black 860.
As the addition to visible ray with the dyestuff absorbed in photosensitive polymer combination, relative in composition
Whole solid state components, preferably 0.1~10 mass %.
(other compositions)
The photosensitive polymer combination of the present invention also may be used from the viewpoint of regulation photosensitive property, raising pattern processability
With do not damage electroconductive particle (A) be in contact with each other and melting adhered scope in contain acrylic monomer.
As acrylic monomer, such as trimethylolpropane tris (methyl) acrylate, pentaerythrite three can be enumerated
(methyl) acrylate, pentaerythrite five (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six
(methyl) acrylate or (methyl) acrylate of dipentaerythritol five or their alkyl-modified thing, alkyl oxide modified thing or alkane
Base ester modifier.
The photosensitive polymer combination of the present invention can also be as needed further containing closely sealed modifying agent, surfactant
Or polymerization inhibitor etc..
As closely sealed modifying agent, such as vinyltrimethoxy silane, VTES, ethene can be enumerated
Base three (2- methoxy ethoxies) silane, N- (2- amino-ethyls) -3- amino propyl methyls dimethoxysilane, N- (2- amino
Ethyl) -3- TSL 8330s, APTES, 3- glycidoxypropyl group trimethoxies
Silane, 3- glycidoxypropyls dimethoxysilane, 2- (3,4- expoxycyclohexyl) ethyl trimethoxy silane, 3-
Chloropropylmethyldimethoxysilane, 3- r-chloropropyl trimethoxyl silanes, 3- methacryloxypropyl trimethoxy silanes
Or the silane coupler such as 3-mercaptopropyi trimethoxy silane.
As surfactant, such as ammonium lauryl sulfate or polyoxyethylene alkyl ether sulfuric acid triethanolamine can be enumerated
Deng the cationic surfactants such as anion surfactant, octadecylamine acetic acid esters or DTAC,
The amphoteric surfactant such as DDAO or dodecyl carboxymethyl group hydroxyethyl imidazolinium betaine, gather
The non-ionic surface actives such as oxygen ethene lauryl ether, polyoxyethylene stearyl base ether or sorbitan monosterate
Agent, fluorine system surfactant or silicon systems surfactant.
As the addition of the surfactant in photosensitive polymer combination, in order that coating and film coated surface is equal
Even property is good, overall relative to composition, preferably 0.001~10 mass %, more preferably 0.01~1 mass %.Addition
During less than 0.001 mass %, the effect that the uniformity of coating and film coated surface be present becomes insufficient.The opposing party
Face, when addition is more than 10 mass %, there is a situation where to cause the paint film defects such as contraction, depression, particles aggregate.
As polymerization inhibitor, such as the chemical combination of quinhydrones system, catechol system, phosphorus system, sulphur system, amine system or hindered phenol series can be enumerated
Thing.Wherein, for the polymerization inhibitor of quinhydrones system and catechol system, the dissolubility preferably do not damaged into solvent and pigment it is scattered steady
Double (1,1,3, the 3- tetramethyl fourths of the qualitatively compound of quinhydrones system or catechol system, more preferably quinhydrones, tertiary butylated hydroquinone, 2,5-
Base) quinhydrones, double (1,1- dimethylbutyl) quinhydrones, catechol or the tert-butyl catechols of 2,5-.
(manufacture method of photosensitive polymer combination)
The photosensitive polymer combination of the present invention can use ball mill, sand mill, three-roll grinder, gentle (Mild) point
Dissipate machine, made without dispersal mechanisms such as medium dispersion machines (medialess dispersion machine).Want electroconductive particle
(A) when being uniformly dispersed, can also manufacture by the following method：It is previously prepared to make electroconductive particle (A) scattered using dispersant
The dispersion liquid formed into organic solvent, by the dispersion liquid with containing monomer, polymer, closely sealed modifying agent, surfactant and
The solution mixing of polymerization inhibitor etc..For electroconductive particle (A) dispersion liquid, in order to prevent surface coating from sustaining damage,
It is preferred that making it scattered using gentle dispersion machine or without medium dispersion machine, no medium dispersion machine is more preferably used to make it scattered.It is conductive
Property particle (A) dispersion liquid use for example gentle dispersion machine NANO GETTER (registration mark) (Ashizawa Finetech
(strain)) or high-voltage wet type without media particles makeup put the dispersion machines such as NANOMIZER (NANOMIZER (strain)), make electroconductive particle
(A) disperse to be manufactured in organic solvent.
(manufacture method of conductive pattern)
Next, the method for conductive pattern is manufactured by photoetching process for the photosensitive polymer combination using the present invention
Illustrate.
The manufacture method of the conductive pattern of the present invention is carried out by possessing the technique of following processes：By the sense of the present invention
Painting process that photosensitive resin composition is coated on real estate, the prebake conditions process being dried, by its it is exposed and developed and
The post-bake process for forming the process (exposure process, developing procedure) of pattern and being toasted after being carried out to it.
As the substrate used in painting process, such as silicon wafer, ceramic substrate or organic system substrate can be enumerated.As
Ceramic substrate, such as the glass bases such as soda-lime glass (soda glass), alkali-free glass, pyrex or quartz glass can be enumerated
Plate, aluminum oxide substrate, aluminium nitride substrate or silicon carbide substrate.As organic system substrate, such as epoxy substrate, polyethers can be enumerated
Sub- amide resin substrate, polyether ketone resin substrate, polysulfones system resin substrate, polyimide film or polyester film.
As the method being coated on the photosensitive polymer combination of the present invention on real estate, such as can enumerate using rotation
The painting that painting machine, bar coater, knife type coater, roll coater, mould coating machine, calender courter or meniscus coating machine are carried out
Cloth, silk-screen printing, spraying or dip coated.
As the drying means in prebake conditions process, such as it can enumerate by heating plate, air drier (baking oven), subtract
Press dry the drying that dry, vacuum drying or infrared radiation are carried out.
The temperature and time of prebake conditions can be according to the composition of photosensitive polymer combination, the thickness of the coated film to be dried
Suitably determine, heated 10 seconds~30 minutes preferably within the temperature range of 50~150 DEG C.
Wherein, the heating carried out using heating plate or air drier (baking oven) is used in combination with being dried under reduced pressure, can pressed down
Solvent seasoning is removed while the heat cure for the resin that coated film processed contains, so it is preferred that.As the arrival pressure being dried under reduced pressure
Power, preferably 10~200Pa, more preferably 30~100Pa.
As the light source used in exposure process, for example, it is preferable to be the j lines of mercury lamp, i lines, h lines or g lines.
As in developing procedure be used for alkaline-based developer alkaline matter, such as can enumerate sodium hydroxide, potassium hydroxide,
Primary amine class, the diethyl such as the inorganic bases such as sodium carbonate, potassium carbonate, sodium metasilicate, sodium metasilicate or ammoniacal liquor, ethylamine or n-propyl amine
The tertiary amines such as the secondary amine class such as amine or di-n-propyl amine, triethylamine or methyidiethylamine, TMAH (TMAH) etc.
The quaternary ammonium salts such as tetra-alkyl ammonium hydroxide class, choline, triethanolamine, diethanol amine, MEA, dimethylaminoethanol or diethyl
The alcamines such as base ethylaminoethanol or pyrroles, piperidines, the carbon -7- alkene of 1,8- diazabicyclos [5,4,0] 11,1,5- diazabicyclos
The organic bases such as the cyclic amine such as [4,3,0] -5- nonanes or morpholine, can also be properly joined into ethanol, γ-Ding Nei into them
The water-miscible organic solvents such as ester, dimethylformamide or METHYLPYRROLIDONE.
In addition, in order to obtain more preferable conductive pattern, the further addition 0.01 further preferably into these alkaline-based developers
The surfactants such as~1 mass % nonionic surfactants.
As the drying means in post-bake process, can enumerate and prebake conditions process identical method.The atmosphere toasted afterwards
Enclose, temperature and time can suitably determine according to the composition of photosensitive polymer combination, the thickness of the coated film to be dried,
It is preferred that heat 5~120 minutes in atmosphere, within the temperature range of 100~300 DEG C.
When forming conductive pattern on substrate with mesh-shape, the display such as touch panel, liquid crystal or organic EL can act as
The electrically conducting transparent wiring that device panel or wearable terminal etc. have.
Above-mentioned conductive pattern is opaque, so, if the width of pattern is big, the user of equipment can see wiring.
Therefore, the width of conductive pattern is preferably less than 5 μm.
Embodiment
Hereinafter, illustrated for embodiments of the invention.First, enter for the material used in embodiment and comparative example
Row explanation.
[electroconductive particle (A)]
(A-1) primary particle size is 0.7 μm of silver particles (Mitsui Metal Co., Ltd.'s (strain) system)
(A-2) primary particle size is 0.2 μm of silver particles (Mitsui Metal Co., Ltd.'s (strain) system)
(A-3) silver particles (Nisshin that the average thickness of surface carbon coating is 1nm, primary particle size is 40nm
Engineering Co. Ltd. systems).
[alkali soluble resins (B)]
(B-1)
2 are added into 500ml flasks, 2 '-azo two (isobutyronitrile) 2g, PGMEA 50g.Then, methacrylic acid is added
15.69g, styrene 37.45g, methacrylic acid bicyclopentyl ester 46.86g, it is stirred at room temperature a little while, will be burnt by blowing
After fully nitrogen displacement is carried out in bottle, in 70 DEG C of heating stirrings 5 hours.Next, add metering system into the solution of gained
Acid glycidyl base ester 10.46g, dimethyl benzyl amine 1g, p methoxy phenol 0.2g, PGMEA 100g, stirred in 90 DEG C of heating
Mix 4 hours, obtain acrylic resin (B-1) solution.PGMEA is added into the solution of obtained acrylic resin (B-1) to be made
Solid component concentration turns into 40 mass %.The weight average molecular weight (Mw) of acrylic resin (B-1) is 25,000.
(B-2)
2 are added into 500ml flask, 2 '-azo two (isobutyronitrile) 2g, PGMEA (methyl proxitol acetate)
50g.Then, methacrylic acid 23.26g, benzyl methacrylate 31.46g, methacrylic acid bicyclopentyl ester are added
32.80g, it is stirred at room temperature a little while, it is small in 70 DEG C of heating stirrings 5 after fully nitrogen displacement will be carried out in flask by air blowing
When.Next, methyl propenoic acid glycidyl base ester 12.69g, dimethyl benzyl amine 1g are added into the solution of gained, to first
Epoxide phenol 0.2g, PGMEA 100g, in 90 DEG C of heating stirrings 4 hours, obtain acrylic resin (B-2) solution.To gained
Acrylic resin (B-2) solution in add PGMEA solid component concentration is turned into 40 mass %.Acrylic resin (B-2)
Weight average molecular weight (Mw) be 24,000.
[organo-tin compound (C)]
(C-1) 2 ethyl hexanoic acid tin (and the pure medicine of light (strain) system)
(C-2) tetrabutyltin (Tokyo chemical conversion industry (strain) system)
(C-3) dibutyl tin laurate (Tokyo chemical conversion industry (strain) system)
(C-4) dibutyltin diacetate (Tokyo chemical conversion industry (strain) system).
[dispersant]
DISPERBYK (registration mark) 140 (BYKJapan Co. Ltd. systems) (amine value：146mgKOH/g).
[solvent]
PGMEA：Propylene glycol monomethyl ether (Tokyo chemical conversion industry (strain) system)
CA：TC acetic acid esters (Tokyo chemical conversion industry (strain) system).
[Photoepolymerizationinitiater initiater]
Irgacure (registration mark) OXE02 (oxime ester based compounds；BASF AG's system).
[acrylic monomer]
Light acrylate (registration mark) PE-4A (chemical company of common prosperity society system).
(embodiment 1)
Alkali soluble resins (B-1) 25.0g solution (40 mass %), 1.0g is added into clean bottle (Clean Bottle)
Organo-tin compound (C-1), 1.5g Photoepolymerizationinitiater initiaters, 5.5g acrylic monomers and 2.0g dispersants, are mixed with rotation-revolution
Clutch " de-soak stirring Taro " (registration mark) (ARE-310；SHINKI (strain) makes) mixing, obtain resin solution 1.
80.0g electroconductive particles (A-1) are added into the resin solution 1 of gained, and then add CA to make solid state component ratio
As 80 mass %, then mix, use triple-roller mill (EXAKT M-50；EXAKT company systems) it is kneaded, thus obtain photosensitive
Property resin combination 1.
In alkali-free glass substrate (OA-10；Nippon Electric Glass Co., Ltd's system) on, turn into 2 μm with the thickness of desciccator diaphragm
Mode photosensitive polymer combination 1 is subjected to silk-screen printing, by the coated film of gained in 100 DEG C of hot-air oven prebake conditions
5 minutes.Using PLA, using ultrahigh pressure mercury lamp as light source, across gray scale mask (the Gray scale of sensitivity determination
Mask) the prebake conditions film of gained is exposed with 50 μm of gap.Then, using automatic developing device (AD-2000；Long Ze
Industry (strain) is made), spray development 30 seconds is carried out with 0.2 mass % aqueous sodium carbonates, is then rinsed 30 seconds with water.Exposure, show
Movie queen, 5 μm of line and the light exposure (hereinafter referred to as " most suitable light exposure ") of intermittent pattern will be formed using 1 to 1 width and is used as spirit
Sensitivity.Light exposure is determined using I lines illumination photometer.And then the minimum pattern size after the development under optimum exposure is determined, as
Resolution ratio.
In addition, photosensitive polymer combination 1 is separately screen printed onto alkali-free in a manner of the thickness of desciccator diaphragm turns into 2 μm
On glass substrate, by the coated film of gained in 100 DEG C of hot-air oven prebake conditions 5 minutes.Using PLA, with ultrahigh pressure mercury lamp
As light source, the preliminary drying across the photomask with rectangular light-transparent pattern (10mm × 15mm) with 50 μm of gap to gained
Roasting film is exposed.Then, using automatic developing device, spray development 30 seconds is carried out with 0.2 mass % aqueous sodium carbonates, is connect
Get off, rinsed 30 seconds with water.Then, using baking oven (" IHPS-222 "；ESPEC (strain) makes) carry out 30 minutes (air in 230 DEG C
In) toast afterwards, thus obtain specific insulation evaluation pattern generating.
For the specific insulation evaluation pattern generating of gained, with sheet resistance measuring machine (Loresta (registration mark)-FP；Three
Water chestnut oiling Co. Ltd. system) measure sheet resistance value ρ s (Ω/), and use rough surface form measuring instrument (SURFCOM (notes
Volume trade mark) 1400D；Tokyo Seimitsu Co., Ltd's system) measure thickness t (cm), two values are multiplied, thus calculate specific insulation
(μΩ·cm)。
And then for the unexposed portion of the above-mentioned substrate formed with specific insulation evaluation pattern generating, commented using transmitance
Valency, the residue on substrate is evaluated.Specifically, for unexposed portion, spectrophotometer (U-3410 is used；Hitachi
Make institute's Co. Ltd. system) transmitance that film is formed at front and rear 400nm is determined, and then, the transmitance before film is formed is set to
T0, film formed after transmitance when being set to T, calculate by formula (T0-T)/T0The transmitance change of expression.Transmitance deficient change 1%
When, it can determine that residue inhibition is abundant.The resolution ratio measured and the specific insulation calculated and the result of transmitance change
As shown in table 1.
(embodiment 2)
Using homogenizer (homogenizer) by 160.0g electroconductive particles (A), 50.0g alkali soluble resins (B-2) it is molten
Liquid (40 mass %), 4.0g dispersants and 486.0g PGMEA in 1200rpm, mixed processing is carried out under conditions of 30 minutes, enter
And put NANOMIZER (NANOMIZER (strain)) without media particles makeup using high-voltage wet type and disperseed, obtain silver particles point
Granular media 2.By 350.0g silver granuels molecular dispersion 2,1.0g organo-tin compounds (C-1), 1.5g Photoepolymerizationinitiater initiaters, 5.5g acrylic acid
It is that monomer and 142.0g PGMEA are mixed and be stirred, thus obtains photosensitive polymer combination 2.
Using spin coater (Mikasa (strain) makes " 1H-360S (trade name) ") 10 seconds are being carried out with 500rpm, with 1000rpm
Under conditions of carrying out 4 seconds, photosensitive polymer combination 2 is spin-coated on alkali-free glass substrate, then, uses heating plate (SCW-
636；Big Japanese silk screen manufacture (strain) system) in 90 DEG C of prebake conditions 2 minutes, obtain the prebake conditions film that thickness is 1 μm.To the pre- of gained
Fired film is exposed, developed similarly to Example 1, determines resolution ratio.Evaluation result is shown in table 1.
In addition, it is that 500rpm carries out 10 seconds, under conditions of 1000rpm is carried out 4 seconds using spin coater, by photonasty tree
Oil/fat composition 2 is separately spin-coated on alkali-free glass substrate, then obtains thickness in 90 DEG C of prebake conditions 2 minutes as 1 using heating plate
μm prebake conditions film.The prebake conditions film of gained is exposed similarly to Example 1, developed, calculate specific insulation and
Transmitance changes.Evaluation result is as shown in table 1.
(embodiment 3~5 and 9 and comparative example 1)
Using method similarly to Example 1, the photosensitive polymer combination of the composition of the record of table 1 is obtained, for each
Photosensitive polymer combination carries out evaluation similarly to Example 1.Evaluation result is shown in table 1.
(embodiment 6~8 and 10~12 and comparative example 2)
Using method similarly to Example 2, the photosensitive polymer combination of the composition of the record of table 1 is obtained, for each
Photosensitive polymer combination carries out evaluation same as Example 2.Evaluation result is shown in table 1.
Embodiment 1~12 is by adding organo-tin compound and residue inhibition becomes abundant, also, resolution ratio
For less than 5 μm.
On the other hand, comparative example 1 and 2 is due to being not added with organo-tin compound, so residue inhibition is insufficient.
Industrial applicability
The photosensitive polymer combination of the present invention is applicable in touch panel, display, imaging sensor, organic electroluminescence
The formation of the conductive pattern used in luminous lighting or solar cell etc..
Claims (13)
1. photosensitive polymer combination, containing electroconductive particle (A), alkali soluble resins (B) and organo-tin compound (C),
The primary particle size of the electroconductive particle (A) is less than 0.7 μm.
2. photosensitive polymer combination as claimed in claim 1, wherein, the electroconductive particle (A) is silver particles.
3. photosensitive polymer combination as claimed in claim 1 or 2, wherein, the electroconductive particle (A) is that surface is coated with
The particle of carbon simple substance and/or carbon compound.
4. such as photosensitive polymer combination according to any one of claims 1 to 3, wherein, as the organo-tin compound
(C) compound, represented containing following formulas (1),
In formula, R1And R2Separately represent organic group, X1And X2Separately represent the anion of 1 valency, X1And X2
It can be connected with each other.
5. such as photosensitive polymer combination according to any one of claims 1 to 4, wherein, the alkali soluble resins (B) is tool
There is the alkali soluble resins of acid dissociation group.
6. the manufacture method of conductive pattern, including following process：
Painting process, photosensitive polymer combination according to any one of claims 1 to 5 is coated on substrate and is coated with
Film；
Drying process, the coated film is dried to obtain desciccator diaphragm；
Exposure imaging process, by the exposed and developed formation pattern of the desciccator diaphragm；With
Post-bake process, toasted after the pattern is carried out and obtain conductive pattern.
7. substrate, there is the conductive pattern described in claim 6.
8. manufacture method as claimed in claim 6, wherein, the width of the conductive pattern is less than 5 μm.
9. the manufacture method of touch panel, it is characterised in that the photoresist any one of usage right requirement 1~5
Composition, including at least developing procedure.
10. the manufacture method of display, it is characterised in that the photoresist group any one of usage right requirement 1~5
Compound, including at least developing procedure.
11. the manufacture method of imaging sensor, it is characterised in that the photonasty tree any one of usage right requirement 1~5
Oil/fat composition, including at least developing procedure.
12. organic electroluminescent luminous manufacture method, it is characterised in that the sense any one of usage right requirement 1~5
Photosensitive resin composition, including at least developing procedure.
13. the manufacture method of solar cell, it is characterised in that the photonasty tree any one of usage right requirement 1~5
Oil/fat composition, including at least developing procedure.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-074975 | 2015-04-01 | ||
| JP2015074975 | 2015-04-01 | ||
| PCT/JP2016/059937 WO2016158864A1 (en) | 2015-04-01 | 2016-03-28 | Photosensitive resin composition, method for producing conductive pattern, substrate, touch panel and display |
Publications (2)
| Publication Number | Publication Date |
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| CN107407870A true CN107407870A (en) | 2017-11-28 |
| CN107407870B CN107407870B (en) | 2018-12-14 |
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| Country | Link |
|---|---|
| JP (1) | JP6202228B2 (en) |
| KR (1) | KR20170132726A (en) |
| CN (1) | CN107407870B (en) |
| TW (1) | TWI648595B (en) |
| WO (1) | WO2016158864A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3521925B1 (en) | 2016-09-30 | 2021-08-25 | Toray Industries, Inc. | Photosensitive resin composition, method for producing electrically conductive pattern, substrate, touch panel, and display |
| CN109891375B (en) * | 2016-11-01 | 2022-04-12 | 东丽株式会社 | Touch panel and method for manufacturing touch panel |
| US11609494B2 (en) | 2019-04-30 | 2023-03-21 | Samsung Sdi Co., Ltd. | Semiconductor photoresist composition and method of forming patterns using the composition |
| KR102606844B1 (en) * | 2019-04-30 | 2023-11-27 | 삼성에스디아이 주식회사 | Semiconductor resist composition and method of forming patterns using the composition |
| KR102446459B1 (en) * | 2019-10-15 | 2022-09-21 | 삼성에스디아이 주식회사 | Semiconductor resist composition, and method of forming patterns using the composition |
| KR102586099B1 (en) * | 2020-09-14 | 2023-10-05 | 삼성에스디아이 주식회사 | Semiconductor photoresist composition and method of forming patterns using the composition |
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Also Published As
| Publication number | Publication date |
|---|---|
| TW201704861A (en) | 2017-02-01 |
| JP6202228B2 (en) | 2017-09-27 |
| KR20170132726A (en) | 2017-12-04 |
| CN107407870B (en) | 2018-12-14 |
| TWI648595B (en) | 2019-01-21 |
| JPWO2016158864A1 (en) | 2017-08-17 |
| WO2016158864A1 (en) | 2016-10-06 |
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