CN103339685A - Electroconductive paste and method for manufacturing same - Google Patents
Electroconductive paste and method for manufacturing same Download PDFInfo
- Publication number
- CN103339685A CN103339685A CN2012800066510A CN201280006651A CN103339685A CN 103339685 A CN103339685 A CN 103339685A CN 2012800066510 A CN2012800066510 A CN 2012800066510A CN 201280006651 A CN201280006651 A CN 201280006651A CN 103339685 A CN103339685 A CN 103339685A
- Authority
- CN
- China
- Prior art keywords
- conductive paste
- acid
- silver powder
- resin
- aliphatic acid
- 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
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- 238000004519 manufacturing process Methods 0.000 title claims description 8
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- 239000003085 diluting agent Substances 0.000 claims abstract description 55
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- 239000002253 acid Substances 0.000 claims description 97
- 125000001931 aliphatic group Chemical group 0.000 claims description 93
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- 239000011347 resin Substances 0.000 claims description 63
- 238000013007 heat curing Methods 0.000 claims description 44
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 26
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- 239000005642 Oleic acid Substances 0.000 claims description 26
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 26
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- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 6
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- ZSAICLUIVSNXGW-UHFFFAOYSA-N 2-[[4-[4-(oxiran-2-ylmethyl)phenyl]phenyl]methyl]oxirane Chemical group C=1C=C(C=2C=CC(CC3OC3)=CC=2)C=CC=1CC1CO1 ZSAICLUIVSNXGW-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
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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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
- H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0545—Dispersions or suspensions of nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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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
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
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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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
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Abstract
Provided is an electroconductive paste with which heat treatment is possible at low temperature; i.e., at 200 C or below, and with which an electroconductive film having sufficiently low electrical resistance can be obtained. This electroconductive paste includes (A) silver powder that has been surface-treated using a liquid fatty acid, (B) a thermoset resin and/or a thermoplastic resin, and (C) a diluent. Alternatively, this electroconductive paste includes (A) silver powder surface-treated using a liquid fatty acid and a solid fatty acid, (B) a thermoset resin and/or a thermoplastic resin, and (C) a diluent. This electroconductive paste may also include (A') silver powder surface-treated using only a solid fatty acid.
Description
Technical field
The present invention relates to comprise and utilize aqueous aliphatic acid to carry out conductive paste and the manufacture method thereof of surface-treated silver powder.
Background technology
In recent years, silver-colored particulate uses as the raw material of the conductive paste of the electrode that is used to form electronic unit, circuit pattern.With regard to conductive paste, because it is easy to handle, therefore be used to test various uses such as purposes, electronic industry purposes.
In order to form circuit pattern, at first, utilize the conductive paste that for example silk screen printing will contain silver-colored particulate to be coated on the substrate.Then, the conductive paste of coating on the substrate is heated to burn till.Thus, for example can form the distribution width is circuit pattern about 50 μ m.
Conductive paste is broadly divided into " high temperature burns till type " and " heat-curing type " two types.High temperature burns till the conductive paste of type and can handle under the high temperature about 550～900 ℃.On the other hand, the conductive paste of heat-curing type can be handled under the lower temperature of room temperature (about 20 ℃)～about 200 ℃.Because the conductive paste of heat-curing type can form conductor at low temperatures, therefore, receive publicity from the viewpoint of saving the energy in recent years.
Because the conductive paste of heat-curing type can solidify at low temperatures, therefore can be applied to the material of poor heat resistance.
For example, in the field of mobile phone, use polyimides flexible circuit board processed.Perhaps, also use more cheap PET (PETG) film, PEN (PEN) film etc. sometimes.These substrates are because poor heat resistance and advantageous applications can be given birth to the conductive paste of the heat-curing type that solidifies in the occurs at low temperatures below 200 ℃.
In addition, be field of solar cells at touch panel, film, be formed with metal oxide film at substrate.Poor heat resistance and advantageous applications be formed with the substrate of metal oxide film owing to can be given birth to the conductive paste of the heat-curing type that solidifies in the occurs at low temperatures below 200 ℃.
But, usually exist the conducting film that obtains with using high temperature to burn till the conductive paste of type to compare, use the conductive paste of heat-curing type and the resistivity of the conducting film that the obtains problem of big (that is, conductivity is lower).
That is, heat and for the conducting film that obtains, be bonded to each other because heating makes metal powder with regard to the conductive paste that high temperature is burnt till type, therefore have the low-resistivity with the metal same degree of block.Relative therewith, heat and for the conducting film that obtains, form conductive path because metal powder contacts with each other with regard to the conductive paste to heat-curing type, therefore have than higher resistivity.
Like this, for the conducting film that two types conductive paste is heated and obtain, the mechanism that conducts is had nothing in common with each other.
In addition, the conductive paste that high temperature is burnt till type heats and the ratio resistance value of the conducting film that obtains is 1 * 10
-4Below the Ω m, relative therewith, the conductive paste of heat-curing type is heated and the ratio resistance value of the conducting film that obtains is 10 * 10
-4About Ω m, also do not claim enough low than resistance value.
In view of the situation, a kind of conductive paste that can under the low temperature below 200 ℃, heat-treat and can access the conducting film with low-resistivity of expectation.
As the method that is used for obtaining having the conducting film of low-resistivity, think the method that has the contact area that makes between the metal powder that comprises in the conductive paste to increase.
As the reason that the metal powder that comprises in the obstruction conductive paste effectively contacts each other, think for example following reason.
(1) the resin ratio height in the conductive paste.
The surface of the metal powder that (2) comprises in conductive paste is formed with oxide film thereon, and this oxide film thereon hinders the conducting of electricity.
(3) dispersiveness of the metal powder that comprises in the conductive paste is not good.
Put down in writing the technology that non-oxidizability that the coating that forms organic coating and inorganic matter by the surface at metal powder makes the surface of metal powder improves in the patent documentation 1.Organic coating comprises organic aliphatic acids such as oleic acid.But, with regard to the technology of record in the patent documentation 1, for the recrystallizationization of the metal that promotes the center, and need be under the high temperature more than 350 ℃ the heating of metal powder.Therefore, the technology of putting down in writing in the patent documentation 1 can't be applied to the materials such as PET film of poor heat resistance.
Having put down in writing in the patent documentation 2 and having accessed the low and thickness of sheet resistance is the silver-colored paste of the silver-colored film below 2.5 microns.This silver paste comprises organic acid silver such as oleic acid silver.But, with regard to the silver-colored paste of record in the patent documentation 2, decompose in order to make the organic substance that comprises in the paste, need under the high temperature about 500 ℃, burn till.Therefore, disclosed silver-colored paste can't be applied to the materials such as PET film of poor heat resistance in the patent documentation 2.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2005-133119 communique
Patent documentation 2:WO2006-035908 number
Summary of the invention
Invent problem to be solved
The objective of the invention is to, the conductive paste that can carry out the heat treatment under the low temperature below 200 ℃ and can access the conducting film with enough low-resistivities is provided.
Be used for solving the method for problem
The inventor finds, in order to obtain having the conducting film of enough low-resistivities, uses that to comprise the scheme that aqueous aliphatic acid such as utilizing oleic acid carried out the silver-colored paste of surface-treated silver powder be effective.The present invention is based on above-mentioned new discovery and the invention finished.
The present invention is as follows.
[1] a kind of conductive paste, it comprises: (A) utilize aqueous aliphatic acid to carry out surface-treated silver powder, (B) heat-curing resin and/or thermoplastic resin and (C) diluent.
[2] a kind of conductive paste, it comprises: (A) utilize aqueous aliphatic acid and solid-state aliphatic acid to carry out surface-treated silver powder, (B) heat-curing resin and/or thermoplastic resin and (C) diluent.
[3] according to [1] or [2] described conductive paste, it also comprises (A ') and only utilizes solid-state aliphatic acid to carry out surface-treated silver powder.
[4] according to any described conductive paste in [1]～[3], wherein, described aqueous aliphatic acid is that fusing point is-20 ℃～+ 20 ℃ aliphatic acid.
[5] according to any described conductive paste in [2]～[4], wherein, described solid-state aliphatic acid is that fusing point is higher than+20 ℃ aliphatic acid.
[6] according to any described conductive paste in [1]～[5], wherein, the amount of described aliphatic acid is 0.1～5 quality % with respect to the total amount of described silver powder and described aliphatic acid.
[7] according to any described conductive paste in [1]～[6], wherein, described aqueous aliphatic acid is to be selected from least a in butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, myristoleic acid, palmitoleic acid, castor oil acid, oleic acid, linoleic acid and the leukotrienes.
[8] according to [7] described conductive paste, wherein, described aqueous aliphatic acid is oleic acid and/or leukotrienes.
[9] according to any described conductive paste in [1]～[8], wherein, described heat-curing resin is epoxy resin and phenolic resins
[10] according to any described conductive paste in [1]～[9], wherein, described thermoplastic resin is to be selected from least a in phenoxy resin, butyral resin, celluosic resin, acrylic resin and the mylar.
[11] according to any described conductive paste in [1]～[10], wherein, described diluent is reactive diluent.
[12] according to [11] described conductive paste, wherein, described reactive diluent is 1,2-epoxy radicals-4-(2-methyl oxirane base)-1-hexahydrotoluene or 4-tert-butyl-phenyl glycidol ether.
[13] a kind of conducting film, it obtains by any described conductive paste in heating [1]～[12].
[14] a kind of electronic unit, it comprises [13] described conducting film.
[15] a kind of manufacture method of conductive paste, it comprises:
Utilize aqueous aliphatic acid that silver powder is carried out the surface-treated operation; With
Operation with described silver powder, heat-curing resin and/or thermoplastic resin and mixing diluents.
The invention effect
According to the present invention, can provide and to carry out the heat treatment under the low temperature below 200 ℃ and can access to have enough low-resistivities (for example, 0.50 * 10
-4Ω m is following) the conductive paste of conducting film.
Description of drawings
Fig. 1 heats the electron micrograph of the conducting film that obtains for the conductive paste to embodiment 1.
Fig. 2 heats the electron micrograph of the conducting film that obtains for the conductive paste to comparative example 1.
Embodiment
Conductive paste of the present invention comprises: (A) utilize aqueous aliphatic acid to carry out surface-treated silver powder, (B) heat-curing resin and/or thermoplastic resin and (C) diluent.
Perhaps, conductive paste of the present invention comprises: (A) utilize aqueous aliphatic acid and solid-state aliphatic acid to carry out surface-treated silver powder, (B) heat-curing resin and/or thermoplastic resin and (C) diluent.
The shape of the silver powder that comprises in the conductive paste of the present invention is not particularly limited.Silver powder can be arbitrary shape such as spherical, laminar, flakey, needle-like for example.Also multiple difform silver powder can be mixed and use.
The average grain diameter of silver powder is preferably 0.015～30 μ m.Under silver powder was spherical situation, the average grain diameter of silver powder is 0.2～5 μ m more preferably.Be under the laminar situation at silver powder, the average grain diameter of silver powder is 5～30 μ m more preferably.
Average grain diameter at silver powder is under the situation of above-mentioned scope, prints or the surface state that has been coated with the film behind the conductive paste becomes good.In addition, conductive paste is heated and the conductivity of the conducting film that obtains improves.
In this manual, " average grain diameter " of silver powder is defined as follows.
Under silver powder was spherical situation, average grain diameter referred to the mean value of the diameter of particle.
Be under the laminar or lepidiod situation at silver powder, average grain diameter refers to the mean value of the length of long portion of particle.
Be under the situation of needle-like at silver powder, average grain diameter refers to the mean value of the length of long portion of particle.
Average grain diameter, the form of the result's that can record with the particle diameter to the particle of specified quantity (for example 100) arithmetic mean is obtained.
The average grain diameter of silver powder for example can observe to measure to the particle of silver powder by using scanning electron microscope (SEM).Perhaps, the average grain diameter of silver powder can be measured by graphical analysis.
Conductive paste of the present invention comprises and utilizes aqueous aliphatic acid to carry out surface-treated silver powder.
Perhaps, conductive paste of the present invention comprises and utilizes aqueous aliphatic acid and solid-state aliphatic acid to carry out surface-treated silver powder.
Aqueous aliphatic acid refers to be aqueous aliphatic acid under room temperature (20 ℃).
Aqueous aliphatic acid be preferably fusing point more than-20 ℃ and+aliphatic acid below 20 ℃.
Solid-state aliphatic acid refers to be solid-state aliphatic acid under room temperature (20 ℃).
Solid-state aliphatic acid is preferably fusing point and is higher than+20 ℃ aliphatic acid.
The aliphatic acid that uses in the surface treatment of silver powder preferably dissolves in diluent.
The conducting film that obtains with existing conductive paste is heated is compared, and conductive paste of the present invention is heated and the conducting film that obtains has less resistivity.Think that its reason is as follows.
Conductive paste of the present invention comprises and utilizes aqueous aliphatic acid to carry out surface-treated silver powder and diluent.Aqueous aliphatic acid is dissolved in diluent easily.Therefore, when the electric conduction of heating paste, the aliphatic acid that is present in the silver powder surface evaporates with diluent easily.Consequently, conductive paste of the present invention is heated and in the conducting film that obtains, the area of the part of silver powder exposing surface increases, the contact area between the silver powder increases.And, conductive paste of the present invention is heated and in the conducting film that obtains, the contact condition between the silver powder is good, at least a portion of silver powder also can combine together sometimes.
Need to prove, as the silver powder that comprises in the conductive paste, also can consider to use and not utilize aliphatic acid to carry out surface-treated silver powder.But, because the wetability of such silver powder and resin is poor, therefore be not suitable as the raw material of conductive paste.
As the example of aqueous aliphatic acid, can list saturated fatty acids such as butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, unrighted acids such as myristoleic acid, palmitoleic acid, castor oil acid, oleic acid, linoleic acid, leukotrienes.These aliphatic acid can be used alone or two or more kinds may be used.Wherein, preferably use oleic acid, linoleic acid or their mixture.
Conductive paste of the present invention also can comprise and utilizes aqueous aliphatic acid and solid-state aliphatic acid to carry out surface-treated silver powder.
As the example of solid-state aliphatic acid, can list carbon numbers such as capric acid, palmitic acid, stearic acid and be the saturated fatty acid more than 10, unrighted acids such as crotonic acid, sorbic acid.
The boiling point of solid-state aliphatic acid is preferably below 200 ℃.Its reason is, is under the situation of the aliphatic acid below 200 ℃ having used boiling point, and when the electric conduction of heating paste, the aliphatic acid on silver powder surface can evaporate, so the area of the part of silver powder exposing surface further increases.As the example of such aliphatic acid, can list crotonic acid.
And situation with aqueous aliphatic acid and solid-state aliphatic acid under, preferably making aqueous aliphatic acid is more than the 20 quality % with respect to the ratio of fatty acid total amount.
Conductive paste of the present invention above-mentioned except comprising (A), (B) and (C) the composition, can also comprise (A ') only utilize solid-state aliphatic acid to carry out surface-treated silver powder.
The silver powder that comprises in the conductive paste of the present invention for example can prepare by the method for following (1)～(3).
(1) utilize aqueous aliphatic acid that silver powder is handled.
(2) aqueous aliphatic acid and solid-state aliphatic acid are mixed after, utilize this mixture that silver powder is handled.
(3) utilize aqueous aliphatic acid and solid-state aliphatic acid respectively silver powder to be handled.Then, the silver powder after utilizing the silver powder after the aqueous fatty acid treatment and utilizing solid-state fatty acid treatment is mixed.
Under the situation of above-mentioned (3), utilize the silver powder after the aqueous fatty acid treatment to be preferably more than the 20 quality % with respect to the ratio of silver powder total amount.
In order to utilize aliphatic acid that silver powder is handled, for example can use the method for following (1)～(3).
(1) silver powder be impregnated in the aqueous aliphatic acid.
(2) aqueous aliphatic acid, solid-state aliphatic acid and silver powder are mixed after, in solvent, stir this mixture.
(3) with behind the solid-state aliphatic acid and solvent, in this mixture, stir silver powder.
As above-mentioned solvent, for example can make organic solvents such as water, alcohol.As alcohol, for example can use ethanol.
With regard to silver powder, can use the silver powder that utilizes after jar shape material grinder (pot mill) carries out sheet.
When utilizing a jar shape material grinder that silver powder is carried out sheet, can in jar shape material grinder, drop into aliphatic acid.Thus, can in the silver powder sheet, utilize aliphatic acid that the surface of silver powder is handled.And be adsorbed in the surface of silver particles with thinking at least a portion aliphatic acid physical property.
The amount of the aliphatic acid that uses in the surface treatment procedure of silver powder is preferably 1～100 mass parts with respect to silver powder 100 mass parts, more preferably 1～20 mass parts.
Conductive paste of the present invention comprises and utilizes aliphatic acid to carry out surface-treated silver powder.The amount of the aliphatic acid that comprises in the conductive paste is preferably 0.1～5 quality % with respect to the total amount of silver powder and aliphatic acid, more preferably 0.2～2 quality %.Be adjusted to this scope by the amount with aliphatic acid, have the more conducting film of small resistor rate thereby can access.
The amount of the silver powder that comprises in the conductive paste is preferably 75～98 quality %, more preferably 80～97 quality %.
Conductive paste of the present invention comprises (B) heat-curing resin and/or thermoplastic resin as adhesive.
The heat-curing resin that uses among the present invention is preferably the heat-curing resin that curing takes place under the temperature below 200 ℃.
As heat-curing resin, for example can use epoxy resin, phenolic resins or their mixture.
As the example of heat-curing resin, can use the amino resins of urea resin, melmac, guanamine resin and so on; The epoxy resin of the biphenyl type epoxy resin of the bisphenol A type epoxy resin of HMW, diglycidyl biphenyl and so on, phenol aldehyde type epoxy resin, tetrabromobisphenol A type epoxy resin, three (hydroxy phenyl) methane type epoxy resin and so on; Oxetane resin; The phenolic resins of resol, alkyl resol, linear phenol-aldehyde resin, alkyl linear phenol-aldehyde resin, aralkyl linear phenol-aldehyde resin and so on; The silicone modified resin of silicone epoxy resin, the poly-resin of silicone and so on; Bismaleimides, polyimide resin etc.Also can use bismaleimide-triazine resin (BT resin).These resins can be used alone, also can be also with two or more.
The heat-curing resin that uses among the present invention is preferably at normal temperatures for aqueous.Here said " normal temperature " refers to+5 ℃～+ 35 ℃ temperature.By using aqueous heat-curing resin, thereby can reduce the use amount of diluent.
The heat-curing resin that uses among the present invention is preferably aqueous epoxy resin and/or aqueous phenolic resins.
In heat-curing resin, can add under the normal temperature to being the resin of superelevation viscosity under the resin of solid or the normal temperature.The resin that adds preferably has intermiscibility to heat-curing resin.In addition, preferably in that being had in the mobile scope, mixed resin in heat-curing resin, adds resin.As the example of such resin, can list biphenyl type epoxy resin, phenol aldehyde type epoxy resin, tetrabromobisphenol A type epoxy resin, resol, the aralkyl linear phenol-aldehyde resin of the bisphenol A type epoxy resin, diglycidyl biphenyl and so on of HMW.
As the example of thermoplastic resin, can list linear phenol-aldehyde resin, phenoxy resin, butyral resin, celluosic resin, acrylic resin, methacrylic resin, mylar, polyurethane resin, polyamide, thermoplastic xylene resin, hydroxy styrenes based polymer, cellulose derivative or the two or more mixture in them.Wherein, preferred phenoxy resin or butyral resin.
The heat-curing resin that comprises in the conductive paste and the amount of thermoplastic resin are preferably 1～12 quality %, more preferably 1.5～8 quality %.
In conductive paste, comprising under the situation of heat-curing resin and thermoplastic resin, the ratio of the quality of heat-curing resin and thermoplastic resin is preferably 1: 0.02～and 1: 0.42, more preferably 1: 0.05～1: 0.25.
Conductive paste of the present invention comprises (C) diluent.
Diluent is used for regulating the viscosity of conductive paste and makes the aliphatic acid dissolving that is present in the silver powder surface.
Diluent is preferably the material that can evaporate when the electric conduction of heating paste.That is, be preferably can be by the material removed from conductive paste of heating for diluent.
In addition, as diluent, also can use solvent.
When the electric conduction of heating paste, diluent is evaporated and does not react with other compositions.This can be by measuring to confirm to the reduction of the quality before and after the electric conduction of heating paste.
As the example of solvent, can list aromatic hydrocarbons such as toluene, dimethylbenzene, mesitylene, naphthane; Ethers such as oxolane; Ketones such as methylethylketone, methyl iso-butyl ketone (MIBK), cyclohexanone, isophorone; Lactams such as 2-Pyrrolidone, 1-Methyl-2-Pyrrolidone; Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), and the ether alcohol classes such as propanediol derivative corresponding with them; The ester classes such as acetate corresponding with them; The diester class of the methyl esters of dicarboxylic acids such as malonic acid, butanedioic acid or ethyl ester etc.Wherein, preferred butyl carbitol.
(C) diluent as comprising in the conductive paste also can use reactive diluent.Reactive diluent refers to have in the molecule for example diluent of functional group such as glycidyl.
As the example of reactive diluent, can list 1,2-epoxy radicals-4-(2-methyl oxirane base)-1-hexahydrotoluene, 4-tert-butyl-phenyl glycidol ether, 1,3-two (3-epoxypropoxy)-1,1,3,3-tetramethyl disiloxane, neodecanoic acid ethylene oxidic ester etc.Wherein, preferred 1,2-epoxy radicals-4-(2-methyl oxirane base)-1-hexahydrotoluene or 4-tert-butyl-phenyl glycidol ether.
The amount of the diluent that comprises in the conductive paste is preferably 1～25 quality %, more preferably 1～15 quality %.Under the situation of the amount of the diluent that in conductive paste, comprises less than 1 quality %, can't obtain having the conducting film of enough low-resistivities sometimes.Under the situation of the amount of the diluent that in conductive paste, comprises greater than 25 quality %, make the bad stability of conductive paste sometimes.
Reactive diluent has the viscosity that is higher than other diluents (for example, butyl carbitol, butyl carbitol acetate).Therefore, by in conductive paste, adding reactive diluent, thereby can easily conductive paste be adjusted to the viscosity that is suitable for printing.In addition, by in conductive paste, adding reactive diluent, thereby make conductive paste is heated and the ratio resistance decreasing of the conducting film that obtains.
Utilizing silk screen printing conductive paste to be coated under the situation of substrate, preferably utilize diluent that the apparent viscosity under the normal temperature of conductive paste is adjusted to 10～500Pas.The preferred apparent viscosity of conductive paste is 15～300Pas.
Conductive paste of the present invention can comprise known additive.
For example, conductive paste also can comprise dispersing aid.
As the example of dispersing aid, can list diisopropoxy (ethyl acetoacetate root) and close aluminium chelate compounds such as aluminium; Titanate esters such as isopropyl three isostearoyl base titanate esters; Aliphat multi-carboxylate; The unsaturated fat amine salt; Surfactants such as single oleic acid sorbitan ester; Macromolecular compounds such as polyester amine salt, polyamide etc.
Conductive paste of the present invention also can comprise be selected from inorganic pigment, organic pigment, silane coupler, levelling agent, thixotropic agent, and defoamer at least a.
The manufacture method of conductive paste of the present invention comprises:
(1) utilize aqueous aliphatic acid to silver powder carry out the surface-treated operation and
(2) with the operation of above-mentioned silver powder, heat-curing resin and/or thermoplastic resin and mixing diluents.
The manufacture method of conductive paste of the present invention comprises:
(1) utilize aqueous aliphatic acid and solid-state aliphatic acid to silver powder carry out the surface-treated operation and
(2) with the operation of above-mentioned silver powder, heat-curing resin and/or thermoplastic resin and mixing diluents.
In the operation of above-mentioned (2), can also mix (A ') only utilize solid-state aliphatic acid to carry out surface-treated silver powder.
Conductive paste of the present invention comprises silver powder, heat-curing resin and/or thermoplastic resin and diluent.These compositions can pass through devices such as mixing and kneading machine, propeller-type mixer, kneader, roller mill, jar shape material grinder to be mixed equably.Temperature when these compositions are mixed is preferably 10～40 ℃.
Conductive paste of the present invention can utilize known method such as silk screen printing to coat on the substrate.After coating conductive paste on the substrate, can the electric conduction of heating paste and form conducting film.
Comprise under the situation of heat-curing resin as adhesive at conductive paste, the heating-up temperature of conductive paste is preferably 60～200 ℃, more preferably 60～150 ℃.In this case, from the viewpoint of operability, be preferably 1～60 minute the heating time of conductive paste.
Comprise under the situation of heat-curing resin as adhesive at conductive paste, also can before the electric conduction of heating paste, make its drying.
The thickness of coating the conductive paste on the substrate is preferably 10～200 μ m, more preferably 20～100 μ m.
Comprise under the situation of thermoplastic resin as adhesive at conductive paste, can form conducting film at for example 80～160 ℃ of following electric conduction of heating pastes.Perhaps, also can make the conductive paste drying form conducting film at normal temperatures.
In addition, can be by conductive paste of the present invention being heated or making its drying form conducting film.Utilize this conducting film, can form electrode, the circuit pattern of electronic unit.
Conductive paste of the present invention not only can be applied to ceramic substrate, and can be applied to the substrate by the low material formation of PET thermal endurances such as (PETGs).
In addition, conductive paste of the present invention can also be applied to be formed with the substrate of the solar cell of the low metal oxide film of thermal endurance.
Embodiment
Below, embodiments of the invention and comparative example are described.
In embodiment 1～13 and comparative example 1～4, prepare conductive paste according to the proportioning shown in following table 1～table 3.
For this reason, as the raw material of conductive paste, silver powder a, silver powder b, silver powder c, silver powder d, six kinds of silver powder of silver powder e, silver powder f have been prepared.
(silver powder a)
Surface-treated method: utilize oleic acid to carry out surface treatment
The shape of particle: laminar
Average grain diameter: 7 μ m
BET specific area: 0.662m
2/ g
Tap density (tap density): 5.33g/cm
3
Loss on ignition value (heat-flash decrement): 0.56%
(silver powder b)
Surface-treated method: silver powder 1000g and oleic acid 20g are mixed with jar shape material grinder
The shape of particle: laminar
Average grain diameter: 10 μ m
BET specific area: 0.776m
2/ g
Tap density: 5.13g/cm
3
Loss on ignition value (heat-flash decrement): 0.53%
(silver powder c)
Surface-treated method: utilize the mixture of 1: 1 (mass ratio) of oleic acid and palmitic acid to carry out surface treatment
The shape of particle: laminar
Average grain diameter: 3 μ m
BET specific area: 0.708m
2/ g
Tap density: 4.88g/cm
3
Loss on ignition value (heat-flash decrement): 0.59%
(silver powder d)
Surface-treated method: stir with the mixture of jar shape material grinder to silver powder 1000g, stearic acid 20g and ethanol 100g, implement the surface treatment of silver powder thus.
The shape of particle: laminar
Average grain diameter: 3 μ m
BET specific area: 1.007m
2/ g
Tap density: 4.76g/cm
3
Loss on ignition value (heat-flash decrement): 0.48%
(silver powder e)
Surface-treated method: silver powder 1000g be impregnated in oleic acid 20g is dissolved in the solution of 100g ethanol gained, carry out the surface treatment of silver powder thus.
The shape of particle: spherical
Average grain diameter: 0.3 μ m
BET specific area: 0.635m
2/ g
Tap density: 1.32g/cm
3
Loss on ignition value (heat-flash decrement): 1.98%
(silver powder f)
Surface-treated method: make silver powder 1000g impregnated in the mixture of stearic acid 20g and ethanol 100g and use dissolvers (dissolver) to stir, implement the surface treatment of silver powder thus.
The shape of particle: spherical
Average grain diameter: 0.3 μ m
BET specific area: 1.095m
2/ g
Tap density: 1.13g/cm
3
Loss on ignition value (heat-flash decrement): 1.98%
The physics value of silver powder a～f shown in above-mentioned is measured according to following step.
The BET specific area uses commercially available analyzer (island Feng makes the Fruosobu II that company of institute makes) to measure.
Tap density uses rammer (Tibetan is held instruments for scientific research and made the manufacturing of company of institute) to measure.
Loss on ignition value (heat-flash decrement) is by the quality of the residual components of silver powder after burning till 30 minutes under 800 ℃ is calculated.
The loss on ignition value representation is present in the amount (quality %) of the aliphatic acid on silver powder surface.For example, with regard to silver powder a, the quality that is present in the oleic acid on silver powder surface is 0.56% with respect to the total amount of silver powder and oleic acid.With regard to silver powder c, the quality that is present in the oleic acid on silver powder surface and palmitic acid is 0.59% with respect to the total amount of silver powder, oleic acid and palmitic acid.
Next, the conductive paste of preparation embodiment 1～13 and comparative example 1～4.
(embodiment 1)
In reaction vessel, drop into silver powder a95 mass parts, phenolic resins 1.58 mass parts, epoxy resin 2.68 mass parts, butyral resin 0.24 mass parts, carboxyl terminal acrylonitrile-butadiene copolymer 0.40 mass parts, curing accelerator 0.10 mass parts, reach butyl carbitol 4.97 mass parts as diluent.Next, use mixing and blending machine (hybrid mixer) that these mixtures were stirred for 15 seconds down at 25 ℃.Thus, prepare the conductive paste of embodiment 1.
(embodiment 2)
Use silver powder b to replace silver powder a, in addition, prepare the conductive paste of embodiment 2 according to step similarly to Example 1.
(embodiment 3)
In reaction vessel, drop into silver powder a98 mass parts, phenolic resins 0.63 mass parts, epoxy resin 1.07 mass parts, butyral resin 0.10 mass parts, carboxyl terminal acrylonitrile-butadiene copolymer 0.16 mass parts, curing accelerator 0.04 mass parts, reach butyl carbitol 1.99 mass parts as diluent.Next, under 25 ℃, with mixing and blending machine these mixtures were stirred for 15 seconds.Thus, prepare the conductive paste of embodiment 3.
(embodiment 4)
Use silver powder b to replace silver powder a, in addition, prepare the conductive paste of embodiment 4 according to step similarly to Example 3.
(embodiment 5)
In reaction vessel, drop into silver powder a24.25 mass parts, silver powder f72.75 mass parts, phenolic resins 0.95 mass parts, epoxy resin 1.61 mass parts, butyral resin 0.15 mass parts, carboxyl terminal acrylonitrile-butadiene copolymer 0.23 mass parts, curing accelerator 0.06 mass parts, reach butyl carbitol 2.99 mass parts as diluent.Next, under 25 ℃, with mixing and blending machine these mixtures were stirred for 15 seconds.Thus, prepare the conductive paste of embodiment 5.
(embodiment 6)
Use silver powder e to replace silver powder f, in addition, prepare the conductive paste of embodiment 6 according to step similarly to Example 5.
(embodiment 7)
In reaction vessel, drop into silver powder a94.00 mass parts, phenoxy resin (number-average molecular weight is 1180) 6.00 mass parts, reach butyl carbitol 14.00 mass parts as diluent.Next, under 25 ℃, with mixing and blending machine these mixtures were stirred for 15 seconds.Thus, prepare the conductive paste of embodiment 7.
(embodiment 8)
In reaction vessel, drop into silver powder c95.00 mass parts, phenolic resins 1.58 mass parts, epoxy resin 2.68 mass parts, butyral resin 0.24 mass parts, carboxyl terminal acrylonitrile-butadiene copolymer 0.40 mass parts, curing accelerator 0.10 mass parts, reach butyl carbitol 4.97 mass parts as diluent.Next, under 25 ℃, with mixing and blending machine these mixtures were stirred for 15 seconds.Thus, prepare the conductive paste of embodiment 8.
(embodiment 9)
In reaction vessel, drop into silver powder a95 mass parts, phenolic resins 1.58 mass parts, epoxy resin 2.68 mass parts, butyral resin 0.24 mass parts, carboxyl terminal acrylonitrile-butadiene copolymer 0.40 mass parts, curing accelerator 0.10 mass parts, reach as 1 of diluent 2-epoxy radicals-4-(2-methyl oxirane base)-1-hexahydrotoluene 5.33 mass parts.Next, under 25 ℃, with mixing and blending machine these mixtures were stirred for 15 seconds.Thus, prepare the conductive paste of embodiment 9.
(embodiment 10)
In reaction vessel, drop into silver powder a95 mass parts, phenolic resins 1.58 mass parts, epoxy resin 2.68 mass parts, butyral resin 0.24 mass parts, carboxyl terminal acrylonitrile-butadiene copolymer 0.40 mass parts, curing accelerator 0.10 mass parts, reach 4-tert-butyl-phenyl glycidol ether 5.33 mass parts as diluent.Next, under 25 ℃, with mixing and blending machine these mixtures were stirred for 15 seconds.Thus, prepare the conductive paste of embodiment 10.
(embodiment 11)
In reaction vessel, drop into silver powder a95 mass parts, phenolic resins 1.58 mass parts, epoxy resin 2.68 mass parts, butyral resin 0.24 mass parts, carboxyl terminal acrylonitrile-butadiene copolymer 0.40 mass parts, curing accelerator 0.10 mass parts, reach as 1 of diluent, 3-two (3-epoxypropoxy)-1,1,3,3-tetramethyl disiloxane, 5.33 mass parts.Next, under 25 ℃, with mixing and blending machine these mixtures were stirred for 15 seconds.Thus, prepare the conductive paste of embodiment 11.
(embodiment 12)
In reaction vessel, drop into silver powder a95 mass parts, phenolic resins 1.58 mass parts, epoxy resin 2.68 mass parts, butyral resin 0.24 mass parts, carboxyl terminal acrylonitrile-butadiene copolymer 0.40 mass parts, curing accelerator 0.10 mass parts, reach neodecanoic acid ethylene oxidic ester 5.33 mass parts as diluent.Next, under 25 ℃, with mixing and blending machine these mixtures were stirred for 15 seconds.Thus, prepare the conductive paste of embodiment 12.
(embodiment 13)
In reaction vessel, drop into silver powder a95 mass parts, phenolic resins 1.58 mass parts, epoxy resin 2.68 mass parts, butyral resin 0.24 mass parts, carboxyl terminal acrylonitrile-butadiene copolymer 0.40 mass parts, curing accelerator 0.10 mass parts, reach butyl carbitol acetate 4.97 mass parts as diluent.Next, under 25 ℃, with mixing and blending machine these mixtures were stirred for 15 seconds.Thus, prepare the conductive paste of embodiment 13.
(comparative example 1)
Use silver powder d to replace silver powder a, in addition, prepare the conductive paste of comparative example 1 according to step similarly to Example 1.
(comparative example 2)
Use silver powder d to replace silver powder a, in addition, prepare the conductive paste of comparative example 2 according to step similarly to Example 3.
(comparative example 3)
Use silver powder d to replace silver powder a, in addition, prepare the conductive paste of comparative example 3 according to step similarly to Example 7.
(comparative example 4)
Behind the conductive paste of preparing comparative example 1, to wherein adding oleic acid 0.50 mass parts, thereby prepare the conductive paste of comparative example 4.
Concrete title and the physics value of the raw material that uses in embodiment 1～13 and the comparative example 1～4 are as follows.
Phenolic resins:
Softening point is that 98～102 ℃, hydroxyl (OH) equivalent are 104～106g/eq
Epoxy resin:
Three (hydroxy phenyl) methane type solid epoxy resin, epoxide equivalent are 169～179g/eq
Butyral resin:
Polyvinyl alcohol: polyvinyl butyral resin: polyvinyl acetate=83: 16: 1 (mass ratio), average degree of polymerization are 2400
The carboxyl terminal acrylonitrile-butadiene copolymer:
Number-average molecular weight is 10000
Curing accelerator:
2-ethyl-4-methylimidazole
(than the mensuration of resistance)
Next, the ratio resistance (resistivity) that uses the conducting film that the conductive paste obtained by embodiment 1～13 and comparative example 1～4 produces is measured.
Measure according to following step than resistance.
Be that 20mm, length are that 20mm, thickness are on the aluminum oxide substrate of 1mm at width, use the stainless steel web plate of 250 purposes, printing length is that 71mm, width are that 1mm, thickness are the zigzag pattern that is formed by conductive paste of 20 μ m.
Under 150 ℃ to embodiment 1～4,7～13 and the conductive paste of comparative example 1～4 heating 30 minutes.
Conductive paste to embodiment 5 and 6 under 200 ℃ heated 30 minutes.
With regard to the thickness of pattern, the surface roughness profile measuring machine (trade name SURFCOM1400) that uses Tokyo Micronics Inc. to make is tried to achieve according to the mean value of 6 the measured value of reporting to the leadship after accomplishing a task with pattern.
About conductive paste being heated or make it dry and conducting film that obtain uses the LCR tester, and compare resistance with 4 terminal methods mensuration.To be shown in table 1～table 3 than the measurement result of resistance.
Need to prove that unless otherwise specified, the numeral shown in table 1～table 3 is represented with mass parts.
In table 1～table 3,
" amount of resin (%) " refers to: the total amount of resin is with respect to the ratio of the total amount of silver powder, resin (curing agent, heat-curing resin, thermoplastic resin and acrylonitrile-butadiene copolymer) and curing accelerator.
" accounting for the amount of resin (%) of system integral body " refers to: the total amount of resin is with respect to the ratio of the total amount of silver powder, resin (curing agent, heat-curing resin, thermoplastic resin and acrylonitrile-butadiene copolymer), curing accelerator and diluent.
" accounting for the silver powder amount (%) of system integral body " refers to: the total amount of silver powder is with respect to the ratio of the total amount of silver powder, resin (curing agent, heat-curing resin, thermoplastic resin and acrylonitrile-butadiene copolymer), curing accelerator and diluent.
" ratio of heat-curing resin (%) " refers to: the total amount of curing agent and heat-curing resin is with respect to the ratio of the total amount of resin (curing agent, heat-curing resin, thermoplastic resin and acrylonitrile-butadiene copolymer).
By the result shown in the table 1 as can be known, the conductive paste of embodiment 1～13 has excellent characteristic.
The conductive paste of embodiment 1～13 comprises utilization, and to be aqueous aliphatic acid under room temperature (about 20 ℃) be that oleic acid has carried out surface-treated silver powder.
As seen: the conductive paste of relative comparative example 1～4 does not have excellent characteristic therewith.
The conductive paste of comparative example 1～4 comprises utilization, and to be solid-state aliphatic acid under room temperature (about 20 ℃) be that stearic acid has carried out surface-treated silver powder.
As seen: heat with conductive paste to comparative example 1～4 and the conducting film that obtains is compared, the conductive paste of embodiment 1～13 is heated and the ratio resistance of the conducting film that obtains significantly reduces.
As seen: by in laminar silver powder, mixing spherical silver powder, thereby make the further reduction of ratio resistance (embodiment 5,6) of conducting film.
As seen: to comprising that the conductive paste that utilizes oleic acid to carry out surface-treated silver powder and utilize the stearic acid to have carried out surface-treated silver powder heats and the conducting film that obtains has enough little ratio resistance (embodiment 5).
Oleic acid is aqueous aliphatic acid, and stearic acid is solid-state aliphatic acid.
As seen: to comprising that conductive paste that the mixture that utilizes oleic acid and palmitic acid carried out surface-treated silver powder heats and the conducting film that obtains has enough little ratio resistance (embodiment 8).
Oleic acid is aqueous aliphatic acid, and palmitic acid is solid-state aliphatic acid.
As seen: prepare comprise utilize stearic acid to carry out the conductive paste of surface-treated silver powder after to wherein adding oleic acid, more resulting conductive paste is heated and the conducting film that obtains, it does not reduce (comparative example 4) than resistance.
This expression: in order to obtain the conducting film littler than resistance, must use and utilize aqueous aliphatic acid (oleic acid) to carry out surface-treated silver powder.I.e. expression: even in conductive paste, add aqueous aliphatic acid (oleic acid) more afterwards, the ratio resistance of conducting film is reduced.
Fig. 1 heats the electron micrograph of the conducting film that obtains for the conductive paste to embodiment 1.As shown in Figure 1, heat with regard to the conductive paste to embodiment 1 and for the conducting film that obtains, the contact condition between its silver powder is good, seems the part that silver powder merges each other but also have.Think that thus the ratio resistance of conducting film becomes extremely low.
Fig. 2 heats the electron micrograph of the conducting film that obtains for the conductive paste to comparative example 1.As shown in Figure 2, heat with regard to the conductive paste to comparative example 1 and for the conducting film that obtains, the contact condition between the silver powder is not so good.Think that thus the ratio resistance of conducting film increases.
Utilizability on the industry
According to the present invention, can provide and to carry out the heat treatment under the low temperature below 200 ℃ and can access to have enough low-resistivities (for example, 0.50 * 10
-4Ω m is following) the conductive paste of conducting film.
According to the present invention, even owing to also can form electrode, circuit pattern for the low material of thermal endurance, therefore have the utilizability on the industry.
Claims (15)
1. conductive paste, it comprises: (A) utilize aqueous aliphatic acid to carry out surface-treated silver powder, (B) heat-curing resin and/or thermoplastic resin and (C) diluent.
2. conductive paste, it comprises: (A) utilize aqueous aliphatic acid and solid-state aliphatic acid to carry out surface-treated silver powder, (B) heat-curing resin and/or thermoplastic resin and (C) diluent.
3. conductive paste according to claim 1 and 2, it also comprises (A ') and only utilizes solid-state aliphatic acid to carry out surface-treated silver powder.
4. according to any described conductive paste in the claim 1～3, wherein, described aqueous aliphatic acid is that fusing point is-20 ℃～+ 20 ℃ aliphatic acid.
5. according to any described conductive paste in the claim 2～4, wherein, described solid-state aliphatic acid is that fusing point is higher than+20 ℃ aliphatic acid.
6. according to any described conductive paste in the claim 1～5, wherein, the amount of described aliphatic acid is 0.1～5 quality % with respect to the total amount of described silver powder and described aliphatic acid.
7. according to any described conductive paste in the claim 1～6, wherein, described aqueous aliphatic acid is to be selected from least a in butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, myristoleic acid, palmitoleic acid, castor oil acid, oleic acid, linoleic acid and the leukotrienes.
8. conductive paste according to claim 7, wherein, described aqueous aliphatic acid is oleic acid and/or leukotrienes.
9. according to any described conductive paste in the claim 1～8, wherein, described heat-curing resin is epoxy resin and phenolic resins.
10. according to any described conductive paste in the claim 1～9, wherein, described thermoplastic resin is to be selected from least a in phenoxy resin, butyral resin, celluosic resin, acrylic resin and the mylar.
11. according to any described conductive paste in the claim 1～10, wherein, described diluent is reactive diluent.
12. conductive paste according to claim 11, wherein, described reactive diluent is 1,2-epoxy radicals-4-(2-methyl oxirane base)-1-hexahydrotoluene or 4-tert-butyl-phenyl glycidol ether.
13. a conducting film, it obtains by any described conductive paste in the heating claim 1～12.
14. an electronic unit, it comprises the described conducting film of claim 13.
15. the manufacture method of a conductive paste, it comprises:
Utilize aqueous aliphatic acid that silver powder is carried out the surface-treated operation; With
Operation with described silver powder, heat-curing resin and/or thermoplastic resin and mixing diluents.
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| PCT/JP2012/051546 WO2012102304A1 (en) | 2011-01-26 | 2012-01-25 | Electroconductive paste and method for manufacturing same |
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| JP (2) | JP5916633B2 (en) |
| KR (1) | KR102007046B1 (en) |
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Also Published As
| Publication number | Publication date |
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| KR20140007862A (en) | 2014-01-20 |
| KR102007046B1 (en) | 2019-08-02 |
| JP5916633B2 (en) | 2016-05-11 |
| CN103339685B (en) | 2017-03-15 |
| JP6174106B2 (en) | 2017-08-02 |
| JPWO2012102304A1 (en) | 2014-06-30 |
| WO2012102304A1 (en) | 2012-08-02 |
| JP2016106356A (en) | 2016-06-16 |
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