CN104737239A - Conductive composition, electrode, plasma display panel and touch panel - Google Patents
Conductive composition, electrode, plasma display panel and touch panel Download PDFInfo
- Publication number
- CN104737239A CN104737239A CN201380054894.6A CN201380054894A CN104737239A CN 104737239 A CN104737239 A CN 104737239A CN 201380054894 A CN201380054894 A CN 201380054894A CN 104737239 A CN104737239 A CN 104737239A
- Authority
- CN
- China
- Prior art keywords
- resin
- conductive composition
- acid
- composition
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- 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
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
- H01J11/20—Constructional details
- H01J11/22—Electrodes, e.g. special shape, material or configuration
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0812—Aluminium
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Plasma & Fusion (AREA)
- Health & Medical Sciences (AREA)
- Dispersion Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Chemistry (AREA)
- Conductive Materials (AREA)
- Materials For Photolithography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Non-Insulated Conductors (AREA)
- Gas-Filled Discharge Tubes (AREA)
Abstract
Provided are: a conductive composition which contains aluminum particles and exhibits excellent electrical conductivity, acid resistance and adhesion to a base after firing; and an electrode which uses this conductive composition. A conductive composition which is characterized by containing (A) aluminum particles and (B) a resin that has a thermal decomposition end temperature within the range of 500-650 DEG. It is preferable that the conductive composition additionally contains a photosensitive monomer and a photopolymerization initiator. It is also preferable that the resin (B) that has a thermal decomposition end temperature within the range of 500-650 DEG is a resin having a bisphenol structure, a polyvinyl acetal resin, a resin having a phenolic novolac structure, or a resin having a cresol novolac structure.
Description
Technical field
The present invention relates to conductive composition, electrode, plasma display (hereinafter also referred to " PDP ") and contact panel, specifically, relate to containing aluminum particulate and conductivity after calcining, acid resistance, with the conductive composition of the excellent adhesion of base material, employ the electrode of said composition and there is PDP, the contact panel of this electrode.
Background technology
Conductive composition containing aluminium and so-called conductive paste are used as the electrode material in PDP, solar cell, ceramic capacitor etc. always, from considerations such as cost aspects, the substitute as the conductive composition containing the such noble metal of gold, silver is studied it.
In solar cell, in order to extract the electric power of generation efficiently, the conductive composition of coating containing aluminium at the back side of silicon wafer, on whole of namely contrary with sensitive surface side.When it at high temperature being calcined, aluminium-silicon alloys layer can be formed, under this layer, form the p that diffusion has aluminium further
+layer.
In PDP, in order to form the bus electrode in the show electrode on face glass substrate and the addressing electrode on back glass substrate, employ the conductive composition containing aluminium.Bus electrode, addressing electrode on each glass substrate with striated and mutually orthogonal mode formed.In addition, often kind of electrode all with about hundreds of microns close distance and formed, particularly fine is required to addressing electrode.
In the electrode of PDP, conductivity is important characteristic for the reduction etc. of the miniaturization of electrode pattern, filming, power consumption.But with silver, metallographic ratio, the conductivity of aluminium is low.And aluminium is easily oxidized, there is the problem that conductivity is reduced due to the oxidation in calcining etc., therefore, up to now various scheme is proposed to its solution.Such as, in patent documentation 1, disclose the amount of glass powder more containing aluminium photoelectric sensitivity conductive thickener.
Prior art document
Patent documentation
Patent documentation 1: Japan Patent No. 4862962 publication
Summary of the invention
Invent problem to be solved
Aluminium is easily oxidized, and therefore the surface of aluminum particulate is coated by the overlay film of autoxidation institute.Therefore, although conductive composition is usually owing to showing conductivity by calcining by organic principle burning-off, but for the conductive resin composition containing aluminum particulate, also can not there is the fusion between aluminum particulate interface, bonding after calcining, sometimes cannot obtain desired conductivity.
On the other hand, in the manufacturing process of plasma display backplate, be coated with dielectric layer on the addressing electrode, after calcining, form interval insulant (barrier).This interval insulant is usually by utilizing the chemical etching of acid to carry out shape processing, and etchant may infiltrate into addressing electrode, therefore, requires highly-acidproof to the conductive composition used in addressing electrode.In addition, when the adaptation of electrode and base material is poor, the stripping etc. of meeting generating electrodes, may become the underproof reason of product, therefore, require the excellent adhesion of conductive composition and base material.
Therefore, the object of the present invention is to provide containing aluminum particulate and conductivity, acid resistance, the conductive composition with the excellent adhesion of base material, the electrode employing said composition, PDP and contact panel after calcining.
Solve the means of problem
The present inventor conducts in-depth research to solve above-mentioned problem, found that, by using the resin of thermal decomposition end point in specific temperature range can solve above-mentioned problem in containing the conductive composition of aluminum particulate, thus completes the present invention.
That is, the feature of conductive composition of the present invention is, is the resin in the scope of 500 ~ 650 DEG C containing (A) aluminum particulate and (B) thermal decomposition end point.
In conductive composition of the present invention, above-mentioned (B) thermal decomposition end point be resin in the scope of 500 ~ 650 DEG C preferably have the resin of bis-phenol structure, polyvinyl acetal resin, have phenol novolak structure resin and have in the resin of cresol novolac structure any one.
In addition, conductive composition of the present invention is preferably also containing photo-sensitive monomer and Photoepolymerizationinitiater initiater.
The feature of electrode of the present invention is, any one conductive composition above-mentioned is carried out calcining and forms.
The feature of plasma display of the present invention is, has above-mentioned electrode.
The feature of contact panel of the present invention is, has above-mentioned electrode.
The effect of invention
According to the present invention, can provide containing aluminum particulate and conductivity after calcining, acid resistance, with the conductive composition of the excellent adhesion of base material, employ the electrode of said composition and there is PDP, the contact panel of this electrode.
In addition, when using conductive composition of the present invention to form line, resistance value can be suppressed to change with the size of its live width.The conductive composition that such resistance value not easily changes with the size of live width is suitable for the electrode of large-scale PDP.
Accompanying drawing explanation
Fig. 1 is the figure of the TG-DTA measurement result representing the resin C used in embodiment.
Fig. 2 is the curve chart conductive composition of embodiment 15 ~ 19 being illustrated to the relation of live width and resistance value.
Fig. 3 is the curve chart conductive composition of comparative example 3 ~ 7 being illustrated to the relation of live width and resistance value.
Embodiment
The feature of conductive composition of the present invention is, is the resin in the scope of 500 ~ 650 DEG C containing aluminum particulate and thermal decomposition end point.Conductive composition containing metal powder, metallic is usually owing to passing through to calcine by resinous principle burning-off, making bond between metal and show conductivity.If the resinous principle of cull composition, carbonization after calcination process (hereinafter referred to as carbon residue), then can produce bubble, expansion, harmful effect may be produced to the characteristic of inorganic layer.Therefore, as the resin used in conductive composition, after optionally using the high resin of volatility, calcining, not easily produce the resin of carbon residue.On the other hand, be the resin that thermal decomposition end point is in 500 ~ 650 DEG C of such higher temperature ranges as the resin of (B) of the present invention composition.Think thus, the resin as (B) of the present invention composition has at least a part residual in the composition in the calcination process of such as about 600 DEG C.As mentioned above, carbon residue is regarded as not preferred character in existing conductive composition.But the present inventor finds, be in containing thermal decomposition end point the conductivity after the calcining of the conductive composition of the resin in the scope of 500 ~ 650 DEG C, acid resistance, with the excellent adhesion of base material.Detailed mechanism may not be clear, but think that one of reason that effect of the present invention is described is, for aluminum particulate, because particle surface is coated and protect aluminium from the impact of acid by carbon residue, makes acid resistance improve thus.Think in addition, carbon residue also contributes to the adaptation with base material.Think in addition, carbon residue inhibits the growth of the oxide-film of metallized aluminum particle, and therefore conductivity improves.
Below, each composition is described in detail.
[aluminum particulate]
(A) as long as the aluminum particulate used in aluminum particulate conductive composition is then not particularly limited, any one aluminum particulate known can be used.(A) average grain diameter (D50) of aluminum particulate is preferably 1 ~ 6 μm, is more preferably 2 ~ 5 μm.When the average grain diameter of aluminum particulate is in above-mentioned scope, the volumetric balance of aluminum particulate and resin can be obtained, utilize the fully coated of the carrying out of (B) composition, effect of the present invention can be obtained well.In addition, the specific area of aluminum particulate reaches suitable scope, can suppress the impact of the oxidation of aluminium.
The average grain diameter of aluminium such as can measure with the form of the D50 in the weight distribution curve utilizing laser diffraction formula particle size distribution device to measure.
When becoming to be divided into 100 mass parts by (B), the content of (A) aluminum particulate is preferably 70 ~ 520 mass parts, is more preferably 100 ~ 400 mass parts.
As (A) aluminum particulate, preferably utilize the aluminum particulate that nitrogen atomization method manufactures.About nitrogen atomization method, as long as in nitrogen atmosphere in the molten metal of metal (aluminium) with the form nitrogen-blow of fluid, pulverize fine for molten metal and form drop and make this droplet solidification and obtain the method for metal dust thus, be not particularly limited.
[thermal decomposition end point is the resin in the scope of 500 ~ 650 DEG C]
Resin involved by (B) of the present invention composition is the resin of thermal decomposition end point in the scope of 500 ~ 650 DEG C.Be preferably 550 ~ 650 DEG C.
Resin involved by (B) of the present invention composition is as adhesive acts.About thermal decomposition end point, use TG determinator (thermogravimetric determinator) or TG-DTA determinator (TG-DTA Simultaneously test device), measure the weight change of the resin samples caused by rising of temperature, make TG curve weight change obtained relative to time (temperature) mapping, the temperature that the weight no longer observed caused by heating reduces is defined as thermal decomposition end point.
In addition, the weight average molecular weight of resin is different because of resin matrix, but usually preferred in the scope of 2000 ~ 150000, preferred in the scope of 5000 ~ 100000 further.When weight average molecular weight is in above-mentioned scope, film decrement when can suppress the deterioration of the moisture-proof of the film after the deterioration of surface drying performance, exposure, development and the deterioration of resolution.In addition, the deterioration of developability and storage stability can be suppressed.
As the resin that can be used as (B) composition and use, such as, can enumerate: the epoxy resin such as the copoly type epoxy resin of the phenoxy group system resins such as the copoly type phenoxy resin of bisphenol A-type phenoxy resin, bisphenol-f type phenoxy resin, bisphenol-A/Bisphenol F, bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-A/Bisphenol F, acrylic acid modified and that obtain Pioloform, polyvinyl acetal system resin, polyester based resin, the block copolymer etc. such as epoxy acrylate system resin, polyvinyl butyral resin system resin are carried out to the end of above-mentioned epoxy resin.(B) resin involved by composition can be used alone one, also can be used together two or more.
As (B) composition, preferred main chain has in the resin of bis-phenol structure, polyvinyl acetal resin, phenol novolak type resin and cresol novolac type resin any one.In addition, from the view point of conductive composition being made Photocurable composition, preferably there is the resin of ethylenical unsaturated double bonds.In addition, in order to can alkali development be carried out, resin of the present invention can for offside chain carry out carboxyl acid modified and obtain containing carboxy resin.
Above-mentioned phenoxy resin is by the multi-hydroxy polyether be obtained by reacting of the phenolic compounds of divalence and epihalohydrins or the multi-hydroxy polyether making the phenolic compounds of the epoxy compounds of divalence and divalence react and obtain.As the phenolic compounds of divalence, bisphenols can be enumerated.As phenoxy resin, such as, can enumerate the phenoxy resin with structure of bisphenol A (skeleton), phenoxy resin etc. that the phenoxy resin with Bisphenol F structure, the phenoxy resin with bisphenol S structure, the phenoxy resin with bis-phenol M structure, the phenoxy resin with bis-phenol P-structure, the phenoxy resin etc. with bisphenol Z structure have bis-phenol structure.In addition, the phenoxy resin etc. with line style phenolic structure, anthracene structure, fluorene structured, the skeleton structure such as dicyclopentadiene structure, norborene structure, naphthalene structure, biphenyl structural, adamantane structure can also be enumerated.As above-mentioned skeleton structure, two or more skeleton structures can be had.In above-mentioned, preferably there is the phenoxy resin of bis-phenol structure.
Above-mentioned epoxy resin is the multi-functional epoxy compound of the epoxy radicals (oxirane ring) in 1 molecule with more than 2 or this multi-functional epoxy compound is polymerized and the resin that obtains.As above-mentioned multi-functional epoxy compound, can enumerate: epoxidized vegetable oil; Bisphenol A type epoxy resin; Hydroquinone type epoxy resin, bisphenol-type epoxy resin, thioether-type epoxy resin; Brominated epoxy resin; Novolac type epoxy resin; Xenol novolac type epoxy resin; Bisphenol f type epoxy resin; Bisphenol-A epoxy resin; Glycidyl amine type epoxy resin; Hydantoins type epoxy resin; Alicyclic epoxy resin; Trihydroxy benzene methylmethane type epoxy resin; Di-toluene phenolic or united phenol-type epoxy resin or their mixture; Bisphenol-s epoxy resin; Bisphenol A novolac type epoxy resin; Four hydroxy phenyl ethane type epoxy resin; Hetero ring type epoxy resin; Diglycidyl phthalate resin; Four glycidyl group dimethylbenzene acyl group ethane resin; Epoxy resin containing naphthyl; There is the epoxy resin of dicyclopentadiene skeleton; Glycidyl methacrylate copolymerization system epoxy resin; The copolymerization epoxy resin of N-cyclohexylmaleimide and glycidyl methacrylate; Epoxide modified polybutadiene rubber derivative, CTBN modified epoxy etc., but be not limited to these.These epoxy resin can be used alone or are used in combination of two or more.Wherein, particularly preferably bisphenol-type epoxy resin.
Above-mentioned epoxy acrylate system resin makes to have in above-mentioned epoxy resin and molecule the resin that ethylenically unsaturated group and carboxyl (methyl) acrylic acid or derivatives thereof react and obtain.In addition, also can for make multi-anhydride carry out reacting and addition carboxyl containing carboxy resin.Such as the epoxy resin with the such bis-phenol structure of bisphenol-A, Bisphenol F being carried out (methyl) acrylic acid modified and epoxy acrylate system resin with bis-phenol structure obtained.
As the concrete example containing carboxy resin, following compound (can be any one in oligomer and polymer) can be enumerated.
(1) make the monocarboxylic acid containing unsaturated group with the reaction of reacting and obtaining by the compound and the alkylene oxide such as oxirane, expoxy propane making the phenolic hydroxyl group in 1 molecule with more than 2 and make multi-anhydride and the reaction that obtains and obtain contain carboxyl photoresist.
(2) make multifunctional (solid-state) epoxy resin of more than (methyl) acrylic acid and two senses or two senses react and make hydroxyl addition that dibasic acid anhydride and side chain exist and obtain containing carboxyl photoresist.
(3) make (methyl) acrylic acid with the polyfunctional epoxy resin that the hydroxyl of two senses (solid-state) epoxy resin obtains with chloropropylene oxide epoxidation further reacted and make the hydroxyl addition of dibasic acid anhydride and generation and obtain contain carboxyl photoresist.
(4) make the dicarboxylic acids such as adipic acid, phthalic acid, hexahydrophthalic acid and two sense oxetane resins react and make the primary hydroxyl addition of the dibasic acid anhydrides such as phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride and generation and obtain containing carboxyl non-photosensitive mylar.
(5) make to have in 1 molecule the compound of (methyl) acryloyl group of 1 epoxy radicals and more than 1 and the further addition of resin of above-mentioned (1) ~ (4) and formed containing carboxyl photoresist.
It should be noted that, in this specification, (methyl) acrylate is the term be referred to as acrylate, methacrylate and their mixture, for the statement that other are similar too.
As above have multiple carboxyl containing carboxy resin on the side chain of skeleton, polymer, therefore, dilute alkaline aqueous solution can be utilized to develop.
In addition, the above-mentioned acid number containing carboxy resin is the scope of 40 ~ 200mgKOH/g is suitable, is more preferably the scope of 45 ~ 120mgKOH/g.When acid number containing carboxy resin is more than 40mgKOH/g, alkali-developable is good, on the other hand, for below 200mgKOH/g time, the dissolving in the exposure portion caused by developer solution is inhibited, be dissolved by the developing the generation of the phenomenon of stripping with can suppressing the excessive constriction of live width or exposure portion and unexposed portion indistinction, can easily describe normal electrode pattern.
Polyvinyl alcohol resin acetalation obtains by utilizing aldehyde by above-mentioned Pioloform, polyvinyl acetal system resin.As above-mentioned aldehyde, be not particularly limited, such as can enumerate: formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, hexanal, enanthaldehyde, 2-ethyl hexanal, hexamethylene aldehyde, furfural, benzaldehyde, 2-tolyl aldehyde, 3-tolyl aldehyde, 4-tolyl aldehyde, parahydroxyben-zaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, beta-phenyl propionic aldehyde etc., preferred butyraldehyde.These aldehyde can be used alone one, also can be used together two or more.As Pioloform, polyvinyl acetal system resin, preferably polyethylene butyral system resin.
The copolymerization aromatic polyester resins of the preferred polymer electrolyte of above-mentioned polyester based resin.
As above-mentioned block copolymer, preferred A-B-A or A-B-A ' type block copolymer.As A or A ', preferably comprise poly-(methyl) methyl acrylate (PMMA), polystyrene (PS) etc., as B, preferably comprise the positive butyl ester of polyacrylic acid (PBA), polybutadiene (PB) etc.
(B) composition preferably has the resin of aromatic rings, particularly preferably has the resin of bis-phenol structure, has the resin of phenol novolak structure and has the resin of cresol novolac structure.In addition, (B) composition preferred phenoxy group system resin, Pioloform, polyvinyl acetal system resin, polyester based resin, block copolymer.Wherein, more preferably phenoxy group system resin, Pioloform, polyvinyl acetal system resin, polyester based resin.
(other resins)
Conductive composition of the present invention can in the scope not damaging effect of the present invention, containing other resins except the resin involved by above-mentioned (B) composition.As other resins, such as, can enumerate in existing conductive composition and use and the resin of thermal decomposition end point outside the scope of 500 ~ 650 DEG C as organic binder bond.
As such organic binder bond, such as can enumerate: mylar, urethane-modified polyester, epoxy modified polyester resin, the various modified polyester resin such as acrylic acid modified polyester resin, polyether urethane resin, polycarbonate urethane resin, propenoic methyl carbamate resin, vinyl chloride vinyl acetate copolymer, epoxy resin, phenolic resins, acrylic resin, polyvinyl butyral resin, polyamidoimide, polyimides, polyamide, celluloid, cellulose acetate-butyrate (CAB), the modified cellulose classes etc. such as cellulose-acetate propionate (CAP).
(photo-sensitive monomer)
In order to give photo-curable to composition thus can form pattern by development, conductive composition of the present invention is preferably containing photo-sensitive monomer.Photo-sensitive monomer is the compound in molecule with ethylenic unsaturated bond, in order to adjusting viscosity, promotes photo-curable, raising developability and uses.As such compound, known usual polyester (methyl) acrylate, polyethers (methyl) acrylate, carbamate (methyl) acrylate, carbonic ester (methyl) acrylate, epoxy (methyl) acrylate, carbamate (methyl) acrylate can be used, specifically, can enumerate: the hydroxyalkyl acrylates classes such as acrylic acid 2-hydroxy methacrylate, acrylic acid 2-hydroxy propyl ester; The diacrylate class of the glycol such as ethylene glycol, methoxyl group TEG, polyethylene glycol, propylene glycol; The acrylic amides such as N,N-DMAA, N hydroxymethyl acrylamide, N, N-dimethylamino propyl acrylamide; The alkyl aminoacrylate classes such as N, N-dimethylamino ethyl acrylate, N, N-dimethylamino propyl acrylate; The multicomponent methacrylate classes such as the polyalcohols such as hexylene glycol, trimethylolpropane, pentaerythrite, dipentaerythritol, tris(2-hydroxy ethyl)isocyanurate or their ethylene oxide adduct, propylene oxide adduct or 6-caprolactone addition product; The multicomponent methacrylate classes such as the ethylene oxide adduct of acrylic acid phenoxy group ester, bisphenol a diacrylate and these phenol or propylene oxide adduct; The multicomponent methacrylate class of the glycidol ethers such as glycerin diglycidyl ether, T 55, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl group isocyanuric acid ester; Be not limited to above-mentioned, can also enumerate by direct for the polyalcohols such as PPG, PCDL, hydroxy terminated polybutadiene, PEPA acroleic acid esterification or the esters of acrylic acid utilizing vulcabond to carry out urethane acrylate and obtain and melamine acrylate and each methyl acrylic ester corresponding with aforesaid propylene acid esters at least any one etc.
Preferred blend amount during mixture is preferably 5 ~ 200 mass parts relative to every 100 mass parts (B) composition.
(Photoepolymerizationinitiater initiater)
In order to give photonasty to composition thus can form pattern by development, conductive composition of the present invention is preferably containing Photoepolymerizationinitiater initiater.As Photoepolymerizationinitiater initiater; known arbitrary Photoepolymerizationinitiater initiater can be used; wherein, preferably there are the oxime ester system Photoepolymerizationinitiater initiater of oxime ester base, alpha-aminoacetophenone system Photoepolymerizationinitiater initiater, acylphosphine oxide system Photoepolymerizationinitiater initiater, two luxuriant titanium system Photoepolymerizationinitiater initiaters.Photoepolymerizationinitiater initiater can be used alone one, also can be used together two or more.
The Photoepolymerizationinitiater initiater of part-structure (oxime ester base) of oxime ester system Photoepolymerizationinitiater initiater for there is following general formula (I) representing.
(in formula, R
1represent hydrogen atom, phenyl (alkyl, phenyl or the halogen atom that can be 1 ~ 6 by carbon number replace), carbon number be 1 ~ 20 alkyl (can be replaced by the hydroxyl of more than 1; alkyl middle-of-chain can have the oxygen atom of more than 1), the carbon number cycloalkyl that is 5 ~ 8, carbon number be 2 ~ 20 alkanoyl or benzoyl (alkyl or phenyl that can be 1 ~ 6 by carbon number replaces), R
2represent phenyl (alkyl, phenyl or the halogen atom that can be 1 ~ 6 by carbon number replace), cycloalkyl that alkyl (can be replaced by the hydroxyl of more than 1, alkyl middle-of-chain can have the oxygen atom of more than 1) that carbon number is 1 ~ 20, carbon number are 5 ~ 8, carbon number be 2 ~ 20 alkanoyl or benzoyl (alkyl or phenyl that can be 1 ~ 6 by carbon number replaces))
As oxime ester system Photoepolymerizationinitiater initiater, CGI-325, Irgacure (registered trade mark) OXE01, Irgacure OXE02 that the BASF Japanese firm as commercially available product manufactures can be enumerated, N-1919, ADEKA Arkls (registered trade mark) NCI-831 etc. that Chinese mugwort Dicon A/S manufactures.
Blend amount during oxime ester system's Photoepolymerizationinitiater initiater is used to be preferably set to 0.01 ~ 5 mass parts relative to (B) composition 100 mass parts.When being more than 0.01 mass parts, photo-curable is abundant, can suppress the reduction of the solidfied material characteristics such as the stripping of solidfied material, chemical proofing.On the other hand, when being below 5 mass parts, the light absorption on solidfied material surface can being avoided excessive, deep curability can be guaranteed.More preferably be 0.5 ~ 3 mass parts relative to (B) composition 100 mass parts.
As alpha-aminoacetophenone system Photoepolymerizationinitiater initiater, can enumerate particularly: 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-(morpholinyl)-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) butane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl)) phenyl]-1-butanone, N, N-dimethylamino acetophenone etc.As commercially available product, Irgacure 907, Irgacure 369, Irgacure 379 etc. that BASF Japanese firm manufactures can be enumerated.
As acylphosphine oxide system Photoepolymerizationinitiater initiater; can enumerate particularly: 2; 4; 6-trimethyl benzoyl diphenyl base phosphine oxide, two (2; 4,6-trimethylbenzoyl) phenyl phosphine oxide, two (2,6-Dimethoxybenzoyl)-2; 4,4-trimethylpentylphosphine oxide etc.As commercially available product, Lucirin (registered trade mark) TPO, Irgacure 819 etc. that BASF Japanese firm manufactures can be enumerated.
Respective blend amount when alpha-aminoacetophenone system Photoepolymerizationinitiater initiater or acylphosphine oxide system Photoepolymerizationinitiater initiater is used to be preferably 0.01 ~ 15 mass parts relative to (B) composition 100 mass parts.When being more than 0.01 mass parts, photo-curable is abundant, can suppress the reduction of the solidfied material characteristics such as the stripping of solidfied material, chemical proofing.On the other hand, when being below 15 mass parts, the effect reducing ease gas is abundant, and the light absorption on solidfied material surface can be avoided excessive, can guarantee deep curability.More preferably be 0.5 ~ 10 mass parts relative to (B) composition 100 mass parts.
In addition, as Photoepolymerizationinitiater initiater, the Irgacure 389 that also can suitably use BASF Japanese firm to manufacture, Irgacure 784 as two luxuriant titanium system Photoepolymerizationinitiater initiaters.
Except Photoepolymerizationinitiater initiater, can suitably use light-initiated auxiliary agent or sensitizer.As light-initiated auxiliary agent or sensitizer, benzoin compound, acetophenone compound, anthraquinone compounds, thioxanthone compounds, ketal compound, benzophenone cpd, tertiary amine compound and xanthone compound etc. can be enumerated.These compounds also use as Photoepolymerizationinitiater initiater sometimes, but preferably and Photoepolymerizationinitiater initiater using.In addition, light-initiated auxiliary agent or sensitizer can be used alone one, also can be used together two or more.
(frit)
Even if conductive composition of the present invention is not containing frit, also excellent to the adaptation of base material, therefore, the content of frit can be reduced.But, if be a small amount of, then also can contain frit.From the view point of obtaining high conductivity, preferably not containing frit.
As frit, be not particularly limited, the frit using lead oxide, bismuth oxide, zinc oxide, lithia or alkali borosilicate as main component can be used.
The average grain diameter (D50) of glass particle can be measured by laser diffraction-scattering method, is preferably 0.3 ~ 5.0 μm, is more preferably 0.5 ~ 3.0 μm.When average grain diameter is more than 0.3 μm, can yield be guaranteed, and can cost up be avoided, on the other hand, when being below 5.0 μm, the uniform shrinkage when formation of film, calcining can being made to become easy, the deterioration of wire shaped, compactness can be suppressed.
Be such as less than 550 DEG C, excellent electric conductivity by making the softening point of frit.
Be not particularly limited containing blend amount during frit, be preferably below 15 quality % in composition in its entirety, be more preferably below 4 quality %, most preferably be 0%.When the amount of the frit making softening point high is inexcessive, the reduction of adaptation can be suppressed.
In order to make frit evenly spread in conductive composition, dispersant can be added further.As long as the material that dispersant can make frit be distributed to equably in conductive composition is not particularly limited.As dispersant, can enumerate: polycarboxylic acid type high molecular surfactant, modified acroleic acid based block copolymer, the acrylic copolymer with pigment affinity groups, the block copolymer with the pigment adsorption group of alkalescence or acidity, the modification poly-alkoxylation thing with pigment affinity groups, polyaminoamide salt and the combination of polyester or the combination, the alkylammonium salt of acidic polymer, the high molecular weight block copolymer with pigment affinity groups, special modified urea etc. of polar acid ester and high molecular alcohol.Above-mentioned dispersant can be used alone one, also can be used together two or more.
(aliphatic acid)
Conductive composition of the present invention can contain aliphatic acid.By containing aliphatic acid, the raising of storage stability can be expected.As aliphatic acid, can be any one in saturated fatty acid, unrighted acid, preferably there is the unrighted acid of the unsaturated bond of more than 2.As the concrete example of aliphatic acid, behenic acid, oleic acid, leukotrienes, stearic acid, thiodiglycolic acid etc. can be enumerated.Blend amount during mixture aliphatic acid is preferably 0.1 ~ 5 mass parts relative to (B) composition 100 mass parts.
(stabilizer)
In conductive composition of the present invention, in order to improve the storage stability of composition, suppressing gelation, the deterioration of coating operations that the reduction of mobility causes, also can add the stabilizer except above-mentioned aliphatic acid.As stabilizer, the compound having and to form complex compound with the aluminium in conductive composition or form the effects such as salt can be used.Specifically, such as can enumerate: the various inorganic acids such as nitric acid, sulfuric acid, hydrochloric acid, boric acid; The various organic acids such as formic acid, acetic acid, acetoacetate, citric acid, phthalic acid, benzene sulfonic acid, sulfamic acid; The acid such as various phosphate cpd (inorganic phosphate, organic phosphoric acid) such as phosphoric acid, phosphorous acid, hypophosphorous acid, methyl orthophosphoric acid, etherophosphoric acid, butylphosphoric acid ester, phenyl phosphate, phosphorous acid ethyl ester, diphenyl phosphite, list (2-methacryloxyethyl) phosphate ester acid, two (2-methacryloxyethyl) phosphate ester acid, preferably phosphoric acid, phosphate, organic acid.As commercially available product, Light ester P-1M (manufacture of chemical company of common prosperity society) etc. can be enumerated.Aforementioned stable agent can be used alone one, also can be used together two or more.
The blend amount of stabilizer is preferably 0.05 ~ 10 mass parts relative to (B) composition 100 mass parts, is more preferably 0.1 ~ 5 mass parts.
(solvent)
In order to regulate the viscosity of composition, conductive composition of the present invention can contain organic solvent.As organic solvent, as long as by the organic solvent of the resin dissolves involved by (B) composition, then known usual organic solvent can be used.Such as can enumerate: toluene, dimethylbenzene, ethyl acetate, butyl acetate, methyl alcohol, ethanol, isopropyl alcohol, isobutanol, n-butyl alcohol, diacetone alcohol, ethylene glycol monobutyl ether, dihydroxypropane single-ether, propylene glycol methyl ether acetate, terpineol, methyl ethyl ketone, carbitol, carbitol acetate, butyl carbitol, acetate of butyl carbitol etc.Can two or more as required containing in these organic solvents.
(other additives)
In conductive composition of the present invention, only otherwise damage effect of the present invention, then can mixture electrode, electric wiring formation in the composition containing mixture usually in aluminium conductive composition that uses.As such composition, binding agent, colouring agent, surface conditioning agent, defoamer, levelling agent, surface tension reducer, diluent, plasticizer, filler, coupling agent, antioxidant, dispersant etc. can be enumerated.In addition, can containing the conductive powder beyond the aluminium such as silver particles, copper particle.
It should be noted that, photoelectric sensitivity conductive composition of the present invention can make thickener by utilizing three-roll mill etc. to carry out grinding.
< electrode >
Electrode of the present invention is the electrode using conductive composition of the present invention to be formed.The example of the formation method of electrode is as described below.But, be not limited thereto.
By conductive composition of the present invention by silk screen printing using predetermined pattern application to such as on the glass substrate of the front substrate of PDP, then calcine, PDP electrode can be formed.
In addition, under imparting photosensitive situation to conductive composition of the present invention, photoetching process also can be utilized to form pattern.Such as, utilized by conductive composition of the present invention suitable coating process such as silk screen print method, line rod coating machine, scraper-type coating machine etc. to be applied on glass substrate, form film.Then, in order to obtain surface drying, obtained film being utilized the drying about 5 ~ 40 minutes at such as about 70 ~ 120 DEG C such as heated air circulation type drying oven, far infrared drying stove, making organic solvent evaporation, forming the film (dry coating) of surface drying.Now, when in advance conductive composition to be applied on film and dry and form dry film, also photopolymer layer can be laminated on substrate.
Then, pattern exposure is carried out to obtained dry coating.As exposure method, can for using the contact exposure and noncontact exposure with the negative mask of predetermined exposure pattern.As exposure light source, Halogen lamp LED, high-pressure mercury lamp, laser, metal halide lamp, black light lamp, electrodeless lamp etc. can be used.As exposure, preferably about 100 ~ 800mJ/cm
2.In addition, maximum wavelength also can be used to be that the Drawing Directly device of the laser generation light source of 350 ~ 420nm exposes.
And then, the film exposed with predetermined pattern is developed.As developing method, spray-on process, infusion process etc. can be used.As developer solution, such as preferably use the amine aqueous solutions such as the metal base aqueous solution, monoethanolamine, diethanol amine, triethanolamine such as NaOH, potassium hydroxide, sodium carbonate, potash, sodium metasilicate, particularly preferably working concentration is the dilute alkaline aqueous solution of less than about 1.5 % by weight.In addition, in order to remove developer solution not after development, preferably carry out washing, acid neutralization.
In calcination process, the glass substrate making conductive composition of the present invention define pattern is carried out heat treated, the electrode desired by formation in air atmosphere or under nitrogen atmosphere, at preferably less than 650 DEG C, more preferably from about 400 ~ 650 DEG C, further preferred about 500 ~ 600 DEG C.It should be noted that, now, programming rate is preferably set to less than 20 DEG C/min.By making calcining heat be less than 650 DEG C, the disappearance of carbon residue can be prevented.
Electrode of the present invention can be suitable as PDP with or contact panel be used for using, but to be not limited thereto.As contact panel electrode, lead-in wire electrode can be enumerated.
Embodiment
Below, specifically describe the present invention by embodiment, but the present invention is not by the restriction of following embodiment, comparative example.
(TG-DTA)
For each resin recorded in following table 1, use TG-DTA determinator (manufacture of Seiko electronics corporation), measure the weight change that resin samples rises with temperature.
Mensuration temperature conditions is room temperature ~ 600 DEG C, keeps 30 minutes in arrival temperature.In addition, Elevated Temperature Conditions is set as 20 DEG C/min.To no longer observe the temperature of weight minimizing as thermal decomposition end point.Obtained result is shown in following table 1.In addition, for resin C, obtained is illustrated in Fig. 3.
[table 1]
※ 1: the THPA modification of triphenyl methane system epoxy acrylate is containing carboxy resin
※ 2: the carboxyl acid modified of bisphenol F type epoxy acrylate contains carboxy resin
※ 3: the carboxyl acid modified of bisphenol F type epoxy acrylate contains carboxy resin
※ 4: polyvinyl butyral resin
※ 5: bisphenol A-type phenoxy resin
※ 6: bisphenol A-type mylar
※ 7: the copolymer resins of butyl acrylate and methyl methacrylate
※ 8: addition HHPA (hexahydrophthalic anhydride) on the copolymer of methacrylate and BG methacrylate and obtain containing carboxy resin
(embodiment 1 ~ 10, comparative example 1)
(preparation of conductive composition)
According to the ratio shown in following table 2, each composition is mixed, use three-roll mill to grind, be made into conductive composition.The unit of the blend amount in table is mass parts.
[table 2]
※ 1: average grain diameter 2 μm, pass through N
2atomization manufactures
※ 2: average grain diameter 4 μm, pass through N
2atomization manufactures
※ 3: average grain diameter 6 μm, pass through N
2atomization manufactures
※ 4: average grain diameter 2 μm, to be manufactured by air atomizing method
※ 5: average grain diameter 2.5 μm
※ 6: THPA (1,2,3, the 6-tetrabydrophthalic anhydride) modification of triphenyl methane system epoxy acrylate is containing carboxy resin, thermal decomposition end temp=591 DEG C
※ 7: the carboxyl acid modified of bisphenol F type epoxy acrylate contains carboxy resin, thermal decomposition end temp=592 DEG C
※ 8: the carboxyl acid modified of bisphenol F type epoxy acrylate contains carboxy resin, thermal decomposition end temp=592 DEG C
※ 9: polyvinyl butyral resin, thermal decomposition end temp=595 DEG C
※ 10: bisphenol A-type phenoxy resin, thermal decomposition end temp=597 DEG C
※ 11: bisphenol A-type mylar, thermal decomposition end temp=603 DEG C
※ 12: the copolymer resins of butyl acrylate and methyl methacrylate, thermal decomposition end temp=594 DEG C
※ 13: addition HHPA (hexahydrophthalic anhydride) on the copolymer of methacrylate and BG (butyl glycidyl base) methacrylate and obtain containing carboxy resin, thermal decomposition end temp=474 DEG C
※ 14: aminoacetophenone system Photoepolymerizationinitiater initiater
※ 15: trifunctional EO modification trimethylolpropane triacrylate
※ 16: polyester acrylate
※ 17: hydrocarbon aromatic series kind solvent
(embodiment 1 ~ 3,8 ~ 10, the making of the test film of comparative example 1,2)
Use 200 object polyester nets to be coated with each conductive composition evaluated by entire surface on the glass substrate, then, utilize heated air circulation type drying oven at 80 DEG C dry 20 minutes, form the film that surface drying is good.Then, use metal halide lamp as light source, reach 300mJ/cm to make the accumulated light on composition
2mode expose.Finally, calcine 30 minutes at 580 ~ 600 DEG C, be made into the test film being formed with electrode.
(making of the test film of embodiment 4 ~ 7)
Use 200 object polyester nets to be coated with each conductive composition evaluated by entire surface on the glass substrate, then, utilize heated air circulation type drying oven at 80 DEG C dry 20 minutes, form the film that surface drying is good.Then, calcine 30 minutes at 580 ~ 600 DEG C, be made into the test film being formed with electrode.
Resistivity value:
For above-mentioned test film (0.1cm × 40cm), the low-resistivity instrument GP of Mitsubishi Chemical's analytical technology manufacture installs tiny sampler four point probe probe (PSP), utilizes four probe method to measure.The thickness of sample uses the digimatic micrometer (MDC-25MJ) of three rich manufactures to measure.
Adaptation:
For test film (2cm × 5cm), according to cross-cut method (JIS K-5600), film is cut into the clathrate that 25 are spaced apart 1mm.Continuous pressing device for stereo-pattern thereon, state during by peeling off carries out the evaluation of adaptation.It should be noted that, for comparative example 2, cannot acid resistance be obtained, therefore evaluate.
Do not peel off completely: ◎,
The part on top layer is peeled off: 〇,
Top layer entirety is peeled off: △,
Entirety is peeled off from substrate interface: ×
Acid resistance:
Test film is flooded 10 minutes in the aqueous solution of nitric acid of 0.3 quality %.Then, in the same manner as the evaluation of above-mentioned adaptation, acid resistance is evaluated.
Do not peel off completely: ◎,
The part on top layer is peeled off: 〇,
Top layer entirety is peeled off: △,
Entirety is peeled off from substrate interface: ×
Resolution:
(making of the test film of embodiment 1 ~ 3, embodiment 8 ~ 10, comparative example 1,2)
Use 200 object polyester nets to be coated with each conductive composition evaluated by entire surface on the glass substrate, then, utilize heated air circulation type drying oven at 80 DEG C dry 20 minutes, form the film that surface drying is good.Then, use metal halide lamp as light source, use the negative mask of live width 40 μm and 20 μm to reach 300mJ/cm to make the accumulated light on composition
2mode expose after, use liquid temperature to be 0.4 % by weight Na of 30 DEG C
2cO
3the aqueous solution, is set as developing time developing for 10 seconds or 20 seconds, through washing, utilizes air knife to carry out drying.Then, calcine 30 minutes at 580 ~ 600 DEG C.
For test film, can observation form 40 μm of lines and 20 μm of lines, selects minimum feature.It should be noted that, for comparative example 2, cannot acid resistance be obtained, therefore evaluate.
[table 3]
(embodiment 11,12)
Operate in the same manner as above-described embodiment, according to the record of following table 4, each composition is carried out mixture, make photoelectric sensitivity conductive resin combination, and evaluate.Obtained result is shown in following table 5.
[table 4]
※ 1: average grain diameter 2 μm, pass through N
2atomization manufactures
※ 2: the carboxyl acid modified of bisphenol F type epoxy acrylate contains carboxy resin, thermal decomposition end temp=592 DEG C
※ 3: aminoacetophenone system Photoepolymerizationinitiater initiater
※ 4: trifunctional EO modification trimethylolpropane triacrylate
※ 5: polyester acrylate
※ 6: softening point 515 DEG C, mixed organic solvents and thixotropic agent
※ 7: softening point 595 DEG C, mixed organic solvents and thixotropic agent
[table 5]
(embodiment 13,14)
Operate in the same manner as above-described embodiment, according to the record of following table 6, each composition is carried out mixture, make photoelectric sensitivity conductive composition, and evaluate.Obtained result is shown in following table 7.
[table 6]
※ 1: average grain diameter 2 μm, pass through N
2atomization manufactures
※ 2: the carboxyl acid modified of bisphenol F type epoxy acrylate contains carboxy resin, thermal decomposition end temp=592 DEG C
※ 3: softening point 515 DEG C, mixed organic solvents and thixotropic agent
※ 4: aminoacetophenone system Photoepolymerizationinitiater initiater
※ 5: trifunctional EO modification trimethylolpropane triacrylate
※ 6: polyester acrylate
※ 7: hydrocarbon aromatic series kind solvent
[table 7]
(assay method of resistance value during each live width)
(embodiment 15)
Use the conductive composition of 200 object polyester nets coating Examples 3 by entire surface on the glass substrate, then, utilize heated air circulation type drying oven at 80 DEG C dry 20 minutes, form the film that surface drying is good.Then, use metal halide lamp as light source, use live width is the negative mask of 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, reaches 300mJ/cm to make the accumulated light on composition
2mode expose after, use liquid temperature to be 0.4 % by weight Na of 30 DEG C
2cO
3the aqueous solution, is set as developing time developing for 10 seconds or 20 seconds, through washing, utilizes air knife to carry out drying.Then, calcine 30 minutes at 600 DEG C.
In the pattern of each live width, measure the resistance value of 100cm length.By shown in Figure 2 in the lump for the resistance value of resistance value now and following embodiment 16 ~ 19.
(embodiment 16)
Except preparing except conductive composition with the mode mixture frit A (softening point 515 DEG C, mixed organic solvents and thixotropic agent) of reach total composition 3% in the composition of embodiment 3, operate similarly to Example 15.
(embodiment 17)
Except the content of frit A is set as total composition 7%, operate similarly to Example 16.
(embodiment 18)
Except preparing except conductive composition with the mode mixture frit B (softening point 595 DEG C, mixed organic solvents and thixotropic agent) of reach total composition 3% in the composition of embodiment 3, operate similarly to Example 15.
(embodiment 19)
Except the content of frit B is set as total composition 7%, operate similarly to Example 18.
(comparative example 3)
Replace, except embodiment 3, measuring resistance value similarly to Example 15 except using the conductive composition of comparative example 1.By shown in Figure 3 in the lump for the resistance value of resistance value and following comparative example 4 ~ 7.
(comparative example 4)
Except preparing except conductive composition with the mode mixture frit A (softening point 515 DEG C, mixed organic solvents and thixotropic agent) of reach total composition 3% in the composition of comparative example 1, operate in the same manner as comparative example 3.
(comparative example 5)
Except the content of frit A is set as total composition 6%, operate in the same manner as comparative example 4.
(comparative example 6)
Except preparing except conductive composition with the mode mixture frit B (softening point 595 DEG C, mixed organic solvents and thixotropic agent) of reach total composition 3% in the composition of comparative example 1, operate in the same manner as comparative example 3.
(comparative example 7)
Except the content of frit B is set as total composition 6%, operate in the same manner as comparative example 6.
(comparative example 8 ~ 10, embodiment 20 ~ 22)
Operate in the same manner as above-described embodiment, according to the record of following table 8, each composition is carried out mixture, make photoelectric sensitivity conductive resin combination, use the test film of the pattern being formed with live width to evaluate acid resistance in the same manner as above-described embodiment 15.Obtained result is shown in following table 9.It should be noted that, the numerical value in the bracket of the blend amount of frit is the quality % relative to composition in its entirety.
[table 8]
※ 1: average grain diameter 2 μm, pass through N
2atomization manufactures
※ 2: average grain diameter 2.5 μm
※ 3: the carboxyl acid modified of bisphenol F type epoxy acrylate contains carboxy resin, thermal decomposition end temp=592 DEG C
※ 4: addition HHPA (hexahydrophthalic anhydride) on the copolymer of methacrylate and BG methacrylate and obtain containing carboxy resin, thermal decomposition end temp=474 DEG C
※ 5: aminoacetophenone system Photoepolymerizationinitiater initiater
※ 6: trifunctional EO modification trimethylolpropane triacrylate
※ 7: polyester acrylate
※ 8: softening point 515 DEG C, mixed organic solvents and thixotropic agent
※ 9: softening point 595 DEG C, mixed organic solvents and thixotropic agent
[table 9]
Claims (6)
1. a conductive composition, is characterized in that, contains:
(A) aluminum particulate and
(B) thermal decomposition end point is the resin in the scope of 500 ~ 650 DEG C.
2. conductive composition according to claim 1, wherein, described (B) thermal decomposition end point to be the resin in the scope of 500 ~ 650 DEG C be have the resin of bis-phenol structure, polyvinyl acetal resin, have phenol novolak structure resin and have in the resin of cresol novolac structure any one.
3. conductive composition according to claim 1 and 2, wherein, also containing photo-sensitive monomer and Photoepolymerizationinitiater initiater.
4. an electrode, is characterized in that, it the conductive composition according to any one of claims 1 to 3 is carried out calcining form.
5. a plasma display, is characterized in that, has electrode according to claim 4.
6. a contact panel, is characterized in that, has electrode according to claim 4.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-232903 | 2012-10-22 | ||
| JP2012232903 | 2012-10-22 | ||
| PCT/JP2013/077317 WO2014065112A1 (en) | 2012-10-22 | 2013-10-08 | Conductive composition, electrode, plasma display panel and touch panel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104737239A true CN104737239A (en) | 2015-06-24 |
| CN104737239B CN104737239B (en) | 2018-01-30 |
Family
ID=50544492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380054894.6A Active CN104737239B (en) | 2012-10-22 | 2013-10-08 | Conductive composition, electrode, plasma display and contact panel |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6324898B2 (en) |
| KR (1) | KR20150075096A (en) |
| CN (1) | CN104737239B (en) |
| TW (1) | TW201428773A (en) |
| WO (1) | WO2014065112A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6789193B2 (en) * | 2017-08-09 | 2020-11-25 | 太陽インキ製造株式会社 | Photosensitive resin compositions, dry films, cured products, and printed wiring boards |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101901844A (en) * | 2009-05-27 | 2010-12-01 | 比亚迪股份有限公司 | Solar cell conductive slurry and preparation method thereof |
| JP2011064864A (en) * | 2009-09-16 | 2011-03-31 | Jsr Corp | Photosensitive composition, method of forming pattern, and method of manufacturing electrode for fpd |
| JP2012038625A (en) * | 2010-08-09 | 2012-02-23 | Sekisui Chem Co Ltd | Conductive fine particle-dispersed paste |
-
2013
- 2013-10-08 CN CN201380054894.6A patent/CN104737239B/en active Active
- 2013-10-08 JP JP2014543218A patent/JP6324898B2/en not_active Expired - Fee Related
- 2013-10-08 WO PCT/JP2013/077317 patent/WO2014065112A1/en active Application Filing
- 2013-10-08 KR KR1020157012107A patent/KR20150075096A/en not_active Application Discontinuation
- 2013-10-17 TW TW102137491A patent/TW201428773A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101901844A (en) * | 2009-05-27 | 2010-12-01 | 比亚迪股份有限公司 | Solar cell conductive slurry and preparation method thereof |
| JP2011064864A (en) * | 2009-09-16 | 2011-03-31 | Jsr Corp | Photosensitive composition, method of forming pattern, and method of manufacturing electrode for fpd |
| JP2012038625A (en) * | 2010-08-09 | 2012-02-23 | Sekisui Chem Co Ltd | Conductive fine particle-dispersed paste |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6324898B2 (en) | 2018-05-16 |
| CN104737239B (en) | 2018-01-30 |
| WO2014065112A1 (en) | 2014-05-01 |
| JPWO2014065112A1 (en) | 2016-09-08 |
| KR20150075096A (en) | 2015-07-02 |
| TW201428773A (en) | 2014-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI326005B (en) | ||
| CN105778618B (en) | A kind of preparation method of liquid photocurable solder mask and its photosensitive resin | |
| CN103515025B (en) | A kind of low temperature curing type conductive photoreceptor slurry and the method with its making conducting wire | |
| JP5393402B2 (en) | Photosensitive conductive paste and method for producing the same | |
| CN104428322B (en) | Photocurable composition and its cured article | |
| TWI809000B (en) | Photosensitive conductive paste, film for forming conductive pattern, pressure sensor, and method of manufacturing substrate with wiring | |
| CN101003690A (en) | Heat radiation insulation resin composition and printing circuit board using same | |
| CN104428712B (en) | Photocurable resin composition, its solidfied material and printed circuit board (PCB) | |
| WO2007123270A1 (en) | Photocurable conductive paste and photocurable black paste used for forming bus electrode having two-layer structure, and plasma display panel | |
| WO2000040632A1 (en) | Curable resin composition, modified copolymer and resin composition, and alkali development type photocurable glass paste | |
| CN104737239A (en) | Conductive composition, electrode, plasma display panel and touch panel | |
| CN104345564A (en) | Photocurable composition for producing printed wiring board, cured product thereof, and printed wiring board | |
| JP4011885B2 (en) | Method for producing curable resin and composition containing curable resin | |
| CN104423160A (en) | Photosensitive Resin Composition, Dry Film, Cured Material And Printed Circuit Board | |
| CN106463199B (en) | The manufacturing method of conductive paste, touch panel and conductive pattern | |
| CN109679402B (en) | Hole plugging ink composition special for hole plugging and filling and printed circuit board | |
| US20170363958A1 (en) | Low dk/df solder resistant composition use for printed circuit board | |
| JP6076687B2 (en) | Conductive composition, electrode, plasma display panel and touch panel | |
| CN108700806A (en) | The manufacturing method of photosensitive conductive paste and substrate with conductive pattern | |
| JP5133104B2 (en) | Epoxy (meth) acrylate resin, photocurable / thermosetting resin composition containing the same, and cured product thereof | |
| TW202338017A (en) | Electroconductive paste | |
| JP5246808B2 (en) | Conductive paste and conductive pattern | |
| JP6230300B2 (en) | Photocurable composition and cured product thereof | |
| JP4916908B2 (en) | Epoxy resin and method for producing the same | |
| JP2008116525A (en) | Photosensitive paste |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |