CN103339685B - Conductive paste and its manufacture method - Google Patents
Conductive paste and its manufacture method Download PDFInfo
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- CN103339685B CN103339685B CN201280006651.0A CN201280006651A CN103339685B CN 103339685 B CN103339685 B CN 103339685B CN 201280006651 A CN201280006651 A CN 201280006651A CN 103339685 B CN103339685 B CN 103339685B
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- conductive paste
- resin
- argentum powder
- fatty acid
- diluent
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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
-
- 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
-
- 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
-
- 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
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- 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
-
- 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
- H05K2203/12—Using specific substances
- H05K2203/122—Organic non-polymeric compounds, e.g. oil, wax, thiol
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Nanotechnology (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Conductive Materials (AREA)
- Powder Metallurgy (AREA)
Abstract
The present invention provides the conductive paste that can be carried out the heat treatment in a low temperature of below 200 DEG C and can obtain conducting film with enough low-resistivities.The conductive paste of the present invention includes：(A) argentum powder, (B) heat-curing resin and/or the thermoplastic resin that are surface-treated using the fatty acid of liquid and (C) diluent.Or, the conductive paste of the present invention includes：(A) argentum powder, (B) heat-curing resin and/or the thermoplastic resin that are surface-treated using the fatty acid of liquid and the fatty acid of solid-state and (C) diluent.The conductive paste of the present invention can also comprising (A ') merely with solid-state the argentum powder that is surface-treated of fatty acid.
Description
Technical field
The present invention relates to the conductive paste of the argentum powder being surface-treated comprising the fatty acid using liquid and its system
Make method.
Background technology
In recent years, silver-colored microgranule as formed the electrode of electronic unit, the raw material of the conductive paste of circuit pattern and
Use.For conductive paste, as which is easily handled, the various use such as experimental use, electronic industry purposes are therefore used for
On the way.
In order to form circuit pattern, first, the conductive paste containing silver-colored microgranule is coated on using such as silk screen printing
On substrate.Then, burn till to coating the heating of the conductive paste on substrate.Thus, for example can be formed with live width
Spend the circuit pattern for 50 μm or so.
Conductive paste is broadly divided into " high temperature burns till type " and " heat-curing type " two types.High temperature burns till leading for type
Conductive paste can be processed at a high temperature of 550～900 DEG C or so.On the other hand, the conductive paste of heat-curing type
Can be processed at the relatively low temperature of the ratio of room temperature (about 20 DEG C)～200 DEG C or so.Electric conductivity due to heat-curing type
Paste can form conductor at low temperature, therefore, be received publicity in recent years from from the viewpoint of save energy.
As the conductive paste of heat-curing type can solidify at low temperature, therefore, it is possible to be applied to the material of poor heat resistance
Material.
For example, in the field of mobile phone, using polyimides flexible circuit board.Or, sometimes also using more honest and cleaner
PET (polyethylene terephthalate) film of valency, PEN (PEN) film etc..These substrates are due to heat-resisting
Property difference and advantageous applications can less than 200 DEG C in a low temperature of occur solidification heat-curing type conductive paste.
Additionally, in touch panel, the field of thin film system solaode, being formed with metal oxide film on substrate.Formed
Have the substrate of metal oxide film due to poor heat resistance advantageous applications can below 200 DEG C in a low temperature of there is the heating that solidifies
The conductive paste of curing type.
But, generally exist compared with conducting film obtained from the conductive paste for burning till type using high temperature, using heating
The problem of the resistivity of conducting film obtained from the conductive paste of curing type larger (that is, electric conductivity is relatively low).
That is, just high temperature is burnt till type conductive paste heat obtained from for conducting film, because heating makes metal
Powder is bonded to each other, and therefore there is the low-resistivity with the metal same degree of block.On the other hand, just heat-curing type is led
Conductive paste heated obtained from for conducting film, form conductive path because metal powder contacts with each other, therefore have than
Higher resistivity.
So, for conducting film obtained from just heating to two kinds of conductive paste, the machine for conducting is made
System is different.
Additionally, the conductive paste for burning till type to high temperature heat obtained from conducting film ratio resistance value be 1 × 10-4
Below Ω m, on the other hand, the ratio resistance value of conducting film obtained from heating to the conductive paste of heat-curing type is
10×10-4Ω m or so, ratio resistance value also do not claim sufficiently low.
In view of the situation, expect one kind can below 200 DEG C in a low temperature of carry out heat treatment and can be had
The conductive paste of the conducting film of low-resistivity.
As the method for obtaining the conducting film with low-resistivity, it is believed that there is the metal for making to include in conductive paste
The method of the contact area increase between powder.
As hinder in conductive paste the metal powder that includes each other effective contact the reason for, it is believed that be for example following original
Cause.
(1) resin ratio in conductive paste is high.
(2) oxide film thereon is formed with the surface of the metal powder included in conductive paste, the oxide film thereon hinders electricity
Conducting.
(3) dispersibility of the metal powder included in conductive paste is not good.
Recorded in patent documentation 1 by the coating of Organic substance and the coating of inorganic matters is formed on the surface of metal powder and made
The technology that the non-oxidizability on the surface of metal powder is improved.The coating of Organic substance includes the organic aliphatic acids such as Oleic acid.But, with regard to patent
For technology described in document 1, in order to promote the recrystallization of the metal at center, and at a high temperature of needing more than 350 DEG C
Heating metal powder.Therefore, the technology described in patent documentation 1 cannot be applied to the materials such as the PET film of poor heat resistance.
Recorded in patent documentation 2 can obtain that sheet resistance is low and thickness be less than 2.5 microns Ag films silver paste
Agent.The silver paste agent includes the organic acid such as Oleic acid silver silver.But, for the silver paste agent described in patent documentation 2, in order that paste
In the Organic substance that includes decompose, need to be burnt till at a high temperature of 500 DEG C or so.Therefore, the silver paste disclosed in patent documentation 2
Agent cannot be applied to the materials such as the PET film of poor heat resistance.
Prior art literature
Patent documentation
Patent documentation 1：Japanese Unexamined Patent Publication 2005-133119 publications
Patent documentation 2：No. WO2006-035908
Content of the invention
Invent problem to be solved
It is an object of the invention to, there is provided the heat treatment in a low temperature of below 200 DEG C can be carried out and can be had
There is the conductive paste of the conducting film of enough low-resistivities.
Method for solving problem
The inventors discovered that, in order to obtain the conducting film with enough low-resistivities, using comprising using liquids such as Oleic acid
The scheme of the silver paste agent of argentum powder that is surface-treated of fatty acid be effective.The present invention is complete based on above-mentioned new discovery
Into invention.
The present invention is as follows.
[1] a kind of conductive paste, which includes：(A) argentum powder that is surface-treated using the fatty acid of liquid, (B)
Heat-curing resin and/or thermoplastic resin and (C) diluent.
[2] a kind of conductive paste, which includes：(A) surface has been carried out using the fatty acid of liquid and the fatty acid of solid-state
The argentum powder of process, (B) heat-curing resin and/or thermoplastic resin and (C) diluent.
[3] conductive paste according to [1] or [2], which is also carried out merely with the fatty acid of solid-state comprising (A ')
The argentum powder of surface treatment.
[4] according to the conductive paste in [1]～[3] described in any one, wherein, the fatty acid of the liquid is fusing point
For -20 DEG C～+20 DEG C of fatty acid.
[5] according to the conductive paste in [2]～[4] described in any one, wherein, the fatty acid of the solid-state is fusing point
Fatty acid higher than+20 DEG C.
[6] according to the conductive paste in [1]～[5] described in any one, wherein, the amount of the fatty acid is relative to institute
The total amount for stating argentum powder and the fatty acid is 0.1～5 mass %.
[7] according to the conductive paste in [1]～[6] described in any one, wherein, the fatty acid of the liquid be selected from
Butanoic acid, valeric acid, caproic acid, enanthic acid, octanoic acid, n-nonanoic acid, myristoleic acid, palmitoleic acid, castor oil acid, Oleic acid, linoleic acid and Caulis et Folium Lini
At least one in acid.
[8] conductive paste according to [7], wherein, the fatty acid of the liquid is Oleic acid and/or linolenic acid.
[9] according to the conductive paste in [1]～[8] described in any one, wherein, the heat-curing resin is epoxy
Resin and phenolic resin
[10] according to the conductive paste in [1]～[9] described in any one, wherein, the thermoplastic resin be selected from
At least one in phenoxy resin, butyral resin, celluosic resin, acrylic resin and polyester resin.
[11] according to the conductive paste in [1]～[10] described in any one, wherein, the diluent is that reactivity is dilute
Release agent.
[12] conductive paste according to [11], wherein, the reactive diluent is 1,2- epoxy radicals -4- (2-
Methyl oxirane base) -1- hexahydrotoluenes or 4- tert-butyl-phenyl glycidyl ethers.
[13] a kind of conducting film, its are obtained by the conductive paste heated in [1]～[12] described in any one.
[14] a kind of electronic unit, which includes the conducting film described in [13].
[15] a kind of manufacture method of conductive paste, which includes：
Operation argentum powder being surface-treated using the fatty acid of liquid；With
The operation that the argentum powder, heat-curing resin and/or thermoplastic resin and diluent are mixed.
Invention effect
According to the present invention it is possible to provide the heat treatment that can be carried out in a low temperature of below 200 DEG C and can be had
Enough low-resistivities (for example, 0.50 × 10-4Below Ω m) conducting film conductive paste.
Description of the drawings
Fig. 1 is the electron micrograph of conducting film obtained from the conductive paste to embodiment 1 is heated.
Fig. 2 is the electron micrograph of conducting film obtained from the conductive paste to comparative example 1 is heated.
Specific embodiment
The conductive paste of the present invention includes：(A) argentum powder that is surface-treated using the fatty acid of liquid, (B) heat
Curable resin and/or thermoplastic resin and (C) diluent.
Or, the conductive paste of the present invention includes：(A) table has been carried out using the fatty acid of liquid and the fatty acid of solid-state
Argentum powder, (B) heat-curing resin and/or thermoplastic resin and (C) diluent that face is processed.
The shape of the argentum powder included in the conductive paste of the present invention is not particularly limited.Argentum powder can be for example spherical,
The arbitrary shapes such as flake, flakey, needle-like.Multiple argentum powder of different shapes can also be used in mixed way.
The mean diameter of argentum powder is preferably 0.015～30 μm.In the case where argentum powder is spherical, the mean diameter of argentum powder is more
Preferably 0.2～5 μm.In the case of argentum powder is laminar, more preferably 5～30 μm of the mean diameter of argentum powder.
In the case where the mean diameter of argentum powder is above range, the surface of the film after conductive paste is printed or is coated with
State becomes good.Additionally, the electric conductivity of conducting film obtained from heating to conductive paste is improved.
In this manual, " mean diameter " of argentum powder is defined as follows.
In the case where argentum powder is spherical, mean diameter refers to the meansigma methodss of the diameter of particle.
In the case of argentum powder is laminar or lepidiod, mean diameter refers to the average of the length in the most long portion of particle
Value.
In the case where argentum powder is needle-like, mean diameter refers to the meansigma methodss of the length in the most long portion of particle.
Mean diameter, the arithmetic average of the result that can be measured with the particle diameter to the particle of specified quantity (such as 100)
The form of value is obtained.
The mean diameter of argentum powder, for example, can be carried out to the particle of argentum powder by using scanning electron microscope (SEM)
Observe to determine.Or, the mean diameter of argentum powder can be determined by graphical analyses.
The argentum powder is surface-treated comprising the fatty acid using liquid by the conductive paste of the present invention.
Or, the conductive paste of the present invention includes have been carried out at surface using the fatty acid of liquid and the fatty acid of solid-state
The argentum powder of reason.
The fatty acid of liquid refers to the fatty acid under room temperature (20 DEG C) in liquid.
The fatty acid of liquid is preferably fusing point more than -20 DEG C and less than+20 DEG C of fatty acid.
The fatty acid of solid-state refers to the fatty acid under room temperature (20 DEG C) in solid-state.
The fatty acid of solid-state is preferably fatty acid of the fusing point higher than+20 DEG C.
Fatty acid used in the surface treatment of argentum powder is preferably soluble in diluent.
Compared with conducting film obtained from heating to existing conductive paste, the conductive paste of the present invention is entered
Conducting film obtained from row heating has less resistivity.Think that its reason is as follows.
Argentum powder and diluent that the conductive paste of the present invention is surface-treated comprising the fatty acid using liquid.Liquid
The fatty acid of shape is easily dissolved in diluent.Therefore, when conductive paste is heated, the fatty acid for being present in argentum powder surface is easy
Evaporate together with diluent.As a result, in conducting film obtained from heating to conductive paste of the invention, argentum powder
The area increase of the part of exposing surface, the contact area increase between argentum powder.And, the conductive paste of the present invention is carried out
In conducting film obtained from heating, the contact condition between argentum powder is good, and at least a portion of argentum powder can also permeate sometimes
Body.
It should be noted that as the argentum powder included in conductive paste, it is also possible to which consideration uses not enter using fatty acid
The argentum powder of row surface treatment.But, as such argentum powder is poor with the wettability of resin, therefore it is not suitable as conductive paste
Raw material.
As the example of the fatty acid of liquid, the saturations such as butanoic acid, valeric acid, caproic acid, enanthic acid, octanoic acid, n-nonanoic acid can be included
The unsaturated fatty acids such as fatty acid, myristoleic acid, palmitoleic acid, castor oil acid, Oleic acid, linoleic acid, linolenic acid.These fat
Acid can be used alone or two or more kinds may be used.Wherein, Oleic acid, linoleic acid or their mixture are preferably used.
The conductive paste of the present invention can also include has carried out surface using the fatty acid of liquid and the fatty acid of solid-state
The argentum powder of process.
As the example of the fatty acid of solid-state, the carbon numbers such as capric acid, Palmic acid, stearic acid can be included for more than 10
Satisfied fatty acid, the unsaturated fatty acid such as .beta.-methylacrylic acid, sorbic acid.
The boiling point of the fatty acid of solid-state is preferably less than 200 DEG C.Its reason is, is less than 200 DEG C boiling point has been used
Fatty acid in the case of, heat conductive paste when, the fatty acid on argentum powder surface can be evaporated, therefore argentum powder exposing surface
The area of part further increase.As the example of such fatty acid .beta.-methylacrylic acid can be included.
And the fatty acid of fatty acid with liquid and solid-state in the case of, preferably make the fatty acid of liquid relative to fat
The ratio of sour total amount is more than 20 mass %.
The conductive paste of the present invention can also include (A ') only profit in addition to comprising above-mentioned (A), (B) and (C) composition
The argentum powder being surface-treated with the fatty acid of solid-state.
The argentum powder included in the conductive paste of the present invention, for example, can be made by the method for following (1)～(3)
Standby.
(1) argentum powder is processed using the fatty acid of liquid.
(2), after by the fatty acid mixing of the fatty acid of liquid and solid-state, argentum powder is processed using the mixture.
(3) respectively argentum powder is processed using the fatty acid of liquid and the fatty acid of solid-state.Then, by using liquid
Argentum powder after fatty acid treatment and mixed using the argentum powder after the fatty acid treatment of solid-state.
In the case of above-mentioned (3), excellent relative to the ratio of argentum powder total amount using the argentum powder after the fatty acid treatment of liquid
Elect more than 20 mass % as.
In order to be processed to argentum powder using fatty acid, for example can be using the method for following (1)～(3).
(1) argentum powder is made to impregnated in the fatty acid of liquid.
(2), after by the mixing of the fatty acid of liquid, the fatty acid of solid-state and argentum powder, the mixture is stirred in a solvent.
(3), after by the fatty acid of solid-state and solvent mixing, argentum powder is stirred in the mixture.
As above-mentioned solvent, for example, can use the organic solvents such as water, alcohol.As alcohol, for example, can use ethanol.
For argentum powder, it is possible to use carry out the argentum powder after sheet using tank shape material grinder (pot mill).
When sheet being carried out using tank shape material grinder to argentum powder, can put into fatty acid in tank shape material grinder.Thus,
The surface of argentum powder can be processed using fatty acid while by argentum powder sheet.And think at least a portion fat
Fat acid is physically adsorbed in the surface of silver particles.
The amount of the fatty acid used in the surface treatment procedure of argentum powder is preferably 1～100 matter relative to 100 mass parts of argentum powder
Amount part, more preferably 1～20 mass parts.
The conductive paste of the present invention includes the argentum powder being surface-treated using fatty acid.Wrapped in conductive paste
The amount of the fatty acid for containing is preferably 0.1～5 mass %, more preferably 0.2～2 matter relative to the total amount of argentum powder and fatty acid
Amount %.By the amount of fatty acid is adjusted to the scope such that it is able to obtain the conducting film with more small resistor rate.
The amount of the argentum powder included in conductive paste is preferably 75～98 mass %, more preferably 80～97 mass %.
The conductive paste of the present invention is comprising (B) heat-curing resin and/or thermoplastic resin as binding agent.
Heat-curing resin used in the present invention is preferably at the temperature below 200 DEG C the Thermocurable for occurring to solidify
Resin.
As heat-curing resin, for example, can use epoxy resin, phenolic resin or their mixture.
As the example of heat-curing resin, it is possible to use the ammonia of urea resin, melmac, guanamine resin etc
Base resin；The biphenyl type epoxy resin of the bisphenol A type epoxy resin of high molecular, diglycidyl biphenyl etc, phenol aldehyde type
The epoxy resin of epoxy resin, tetrabromobisphenol A type epoxy resin, three (hydroxy phenyl) methane type epoxy resin etc；Oxa- ring
Butane resin；Resol, alkyl resol, linear phenol-aldehyde resin, alkyl linear phenol-aldehyde resin, aralkyl baseline
The phenolic resin of type phenolic resin etc；The silicone modified resin of silicone epoxy, silicone poly resin etc；Bismaleimide
Amine, polyimide resin etc..Bismaleimide-triazine resin (BT resins) can also be used.These resins can be used alone
A kind of, it is also possible to and with two or more.
Heat-curing resin used in the present invention is preferably liquid at normal temperatures." room temperature " mentioned here refers to+5 DEG C
～+35 DEG C of temperature.By using the heat-curing resin of liquid, such that it is able to reduce the usage amount of diluent.
Heat-curing resin used in the present invention is preferably the epoxy resin of liquid and/or the phenolic resin of liquid.
In heat-curing resin, can add under room temperature as the resin under the resin or room temperature of solid for Very High Bond.
The resin preferred pair heat-curing resin for being added has intermiscibility.Furthermore it is preferred that making mixed resin that there is mobility
In the range of in heat-curing resin add resin.As the example of such resin, the double of high molecular can be included
The biphenyl type epoxy resin of phenol A type epoxy resin, diglycidyl biphenyl etc, phenol aldehyde type epoxy resin, tetrabromobisphenol A type
Epoxy resin, resol, aralkyl linear phenol-aldehyde resin.
As the example of thermoplastic resin, linear phenol-aldehyde resin, phenoxy resin, butyral resin, fibre can be included
The plain resin of dimension, acrylic resin, methacrylic resin, polyester resin, polyurethane resin, polyamide, thermoplastic two
Toluene resin, hydroxy styrenes based polymer, cellulose derivative or the two or more mixture in them.Wherein, preferably
Phenoxy resin or butyral resin.
The heat-curing resin included in conductive paste and the amount of thermoplastic resin are preferably 1～12 mass %, more excellent
Elect 1.5～8 mass % as.
Comprising in the case of heat-curing resin and thermoplastic resin in conductive paste, heat-curing resin and
The ratio of the quality of thermoplastic resin is preferably 1: 0.02～1: 0.42, more preferably 1: 0.05～1: 0.25.
The conductive paste of the present invention includes (C) diluent.
Diluent is used for the fatty acid dissolving for adjusting the viscosity of conductive paste and making to be present in argentum powder surface.
Diluent is preferably the material that can be evaporated when conductive paste is heated.That is, diluent can preferably pass through to add
The material that heat is removed from conductive paste.
Additionally, as diluent, it is also possible to using solvent.
When conductive paste is heated, diluent is evaporated and is not reacted with other compositions.It is right that this can pass through
The decrement of the quality before and after heating conductive paste is measured to confirm.
As the example of solvent, the aromatic hydrocarbons such as toluene, dimethylbenzene, sym-trimethylbenzene., naphthane can be included；Tetrahydrochysene furan
The ethers such as mutter；The ketones such as butanone, methyl iso-butyl ketone (MIBK), Ketohexamethylene, isophorone；2-Pyrrolidone, 1- methyl -2- pyrrolidines
The lactams such as ketone；Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol list
The ether alcohol classes such as ether, diethylene glycol monobutyl ether (butyl carbitol) and the propanediol derivative corresponding with them；With their phases
The esters such as corresponding acetate；Two esters of the methyl ester or ethyl ester of the dicarboxylic acids such as malonic acid, succinic acid etc..Wherein, preferred butyl
Carbitol.
As (C) diluent included in conductive paste, it is also possible to using reactive diluent.Reactive diluent is
Refer to the diluent in molecule with functional groups such as such as glycidyls.
As the example of reactive diluent, 1,2- epoxy radicals -4- (2- methyl oxirane bases) -1- first can be included
Butylcyclohexane, 4- tert-butyl-phenyl glycidyl ethers, 1,3-, bis- (3- epoxypropoxies) -1,1,3,3- tetramethyl, two silica
Alkane, glycidyl neodecanoate etc..Wherein, preferably 1,2- epoxy radicals -4- (2- methyl oxirane bases) -1- hexahydrotoluenes,
Or 4- tert-butyl-phenyl glycidyl ethers.
The amount of the diluent included in conductive paste is preferably 1～25 mass %, more preferably 1～15 mass %.?
The amount of the diluent included in conductive paste cannot be obtained with enough low-resistivities sometimes less than in the case of 1 mass %
Conducting film.The amount of the diluent included in conductive paste makes conductive paste sometimes more than in the case of 25 mass %
Bad stability.
Reactive diluent has viscous higher than other diluent (for example, butyl carbitol, butyl carbitol acetate)
Degree.Therefore, by adding reactive diluent in conductive paste such that it is able to easily adjust conductive paste to suitable
Viscosity in printing.Additionally, pass through in conductive paste add reactive diluent so that conductive paste is carried out plus
The ratio resistance of conducting film obtained from heat diminishes.
In the case where conductive paste is coated substrate using silk screen printing, preferably by diluent by conductive paste
Apparent viscosity under the room temperature of agent is adjusted to 10～500Pa s.The preferred apparent viscosity of conductive paste be 15～
300Pa·s.
The conductive paste of the present invention can include known additive.
For example, conductive paste can also include dispersing aid.
As the example of dispersing aid, diisopropoxy (ethyl acetoacetate root) can be included and close the aluminum such as aluminum chelating
Thing；The titanate esters such as three isostearoyl base titanate esters of isopropyl；Aliphatic polycarboxylic acid's ester；Unsaturated fatty acidss amine salt；Single Oleic acid takes off
The surfactants such as water sorbitol ester；Macromolecular compounds such as polyester amine salt, polyamide etc..
The present invention conductive paste can also include selected from inorganic pigment, organic pigment, silane coupler, levelling agent,
At least one in thixotropic agent and defoamer.
The manufacture method of the conductive paste of the present invention includes：
(1) operation that argentum powder is surface-treated using the fatty acid of liquid and
(2) operation that above-mentioned argentum powder, heat-curing resin and/or thermoplastic resin and diluent are mixed.
The manufacture method of the conductive paste of the present invention includes：
(1) operation that argentum powder is surface-treated using the fatty acid of liquid and the fatty acid of solid-state and
(2) operation that above-mentioned argentum powder, heat-curing resin and/or thermoplastic resin and diluent are mixed.
In the operation of above-mentioned (2), the silver that is surface-treated of fatty acid of (A ') merely with solid-state can also be mixed
Powder.
The conductive paste of the present invention includes argentum powder, heat-curing resin and/or thermoplastic resin and diluent.This
A little compositions can equably be mixed by devices such as meat mill, propeller-type mixer, kneader, roller mill, tank shape material grinders.
Temperature when these compositions are mixed is preferably 10～40 DEG C.
The conductive paste of the present invention can be coated on substrate using the known method such as silk screen printing.By conductive paste
After agent is coated on substrate, conductive paste can be heated and form conducting film.
In the case where conductive paste includes heat-curing resin as binding agent, the heating-up temperature of conductive paste is excellent
Elect 60～200 DEG C as, more preferably 60～150 DEG C.In this case, from from the viewpoint of operability, conductive paste
Heat time heating time is preferably 1～60 minute.
In the case where conductive paste includes heat-curing resin as binding agent, it is also possible in heating conductive paste
Dry which before.
The thickness for coating the conductive paste on substrate is preferably 10～200 μm, more preferably 20～100 μm.
In the case where conductive paste includes thermoplastic resin as binding agent, can add at such as 80～160 DEG C
Electrical conductivity paste is forming conducting film.Or, it is also possible to make conductive paste dry to form conducting film at normal temperatures.
Furthermore, it is possible to be heated by the conductive paste to the present invention or made which dry to form conducting film.Profit
The conducting film is used, electrode, the circuit pattern of electronic unit can be formed.
The conductive paste of the present invention can not only be applied to ceramic substrate, and can be applied to (poly- to benzene two by PET
Formic acid glycol ester) etc. the substrate that constitutes of the low material of thermostability.
Additionally, the conductive paste of the present invention can also be applied to the solar energy for being formed with the low metal oxide film of thermostability
The substrate of battery.
Embodiment
Hereinafter, examples and comparative examples of the present invention are illustrated.
In embodiment 1～13 and comparative example 1～4, conductive paste is prepared according to the proportioning shown in table 1 below～table 3
Agent.
For this purpose, as the raw material of conductive paste, having prepared argentum powder a, argentum powder b, argentum powder c, argentum powder d, argentum powder e, argentum powder f six
Plant argentum powder.
(argentum powder a)
The method of surface treatment：It is surface-treated using Oleic acid
The shape of particle：Flake
Mean diameter：7μm
BET specific surface area：0.662m2/g
Tap density (tap density)：5.33g/cm3
Loss on ignition value (heat-flash decrement)：0.56%
(argentum powder b)
The method of surface treatment：Argentum powder 1000g and Oleic acid 20g are mixed with tank shape material grinder
The shape of particle：Flake
Mean diameter：10μm
BET specific surface area：0.776m2/g
Tap density：5.13g/cm3
Loss on ignition value (heat-flash decrement)：0.53%
(argentum powder c)
The method of surface treatment：It is surface-treated using the mixture of Oleic acid and 1: 1 (mass ratio) of Palmic acid
The shape of particle：Flake
Mean diameter：3μm
BET specific surface area：0.708m2/g
Tap density：4.88g/cm3
Loss on ignition value (heat-flash decrement)：0.59%
(argentum powder d)
The method of surface treatment：The mixture of argentum powder 1000g, stearic acid 20g and ethanol 100g is entered with tank shape material grinder
Row stirring, thus implementing the surface treatment of argentum powder.
The shape of particle：Flake
Mean diameter：3μm
BET specific surface area：1.007m2/g
Tap density：4.76g/cm3
Loss on ignition value (heat-flash decrement)：0.48%
(argentum powder e)
The method of surface treatment：Impregnated in argentum powder 1000g Oleic acid 20g is dissolved in the solution of 100g ethanol gained,
Thus the surface treatment of argentum powder is carried out.
The shape of particle：Spherical
Mean diameter：0.3μm
BET specific surface area：0.635m2/g
Tap density：1.32g/cm3
Loss on ignition value (heat-flash decrement)：1.98%
(argentum powder f)
The method of surface treatment：Argentum powder 1000g is made to impregnated in the mixture of stearic acid 20g and ethanol 100g and using molten
Solution device (dissolver) is stirred, thus implementing the surface treatment of argentum powder.
The shape of particle：Spherical
Mean diameter：0.3μm
BET specific surface area：1.095m2/g
Tap density：1.13g/cm3
Loss on ignition value (heat-flash decrement)：1.98%
The physics value of above-mentioned shown argentum powder a～f is measured according to below step.
BET specific surface area is measured using commercially available determinator (the Fruosobu II of island Feng manufacturing companies manufacture).
Tap density is measured using rammer (manufacture of Zang Chi instruments for scientific research manufacturing company).
Loss on ignition value (heat-flash decrement), is calculated by the quality of the residual componentss after argentum powder is burnt till 30 minutes at 800 DEG C.
Loss on ignition value represents the amount (quality %) of the fatty acid for being present in argentum powder surface.For example, for argentum powder a, exist
In argentum powder surface Oleic acid quality relative to argentum powder and Oleic acid total amount be 0.56%.For argentum powder c, it is present in argentum powder table
The quality of the Oleic acid in face and Palmic acid is 0.59% relative to the total amount of argentum powder, Oleic acid and Palmic acid.
Next, preparing the conductive paste of embodiment 1～13 and comparative example 1～4.
(embodiment 1)
In reaction vessel input argentum powder a95 mass parts, 1.58 mass parts of phenolic resin, 2.68 mass parts of epoxy resin,
0.24 mass parts of butyral resin, 0.40 mass parts of carboxyl terminal acrylonitrile-butadiene copolymer, 0.10 mass of curing accelerator
Part and 4.97 mass parts of butyl carbitol as diluent.Next, using mixing and blending machine (hybrid at 25 DEG C
Mixer) these mixture are stirred 15 seconds.Thus, the conductive paste of embodiment 1 is prepared.
(embodiment 2)
Using argentum powder b replace argentum powder a, in addition, according to similarly to Example 1 the step of prepare leading for embodiment 2
Conductive paste.
(embodiment 3)
In reaction vessel input argentum powder a98 mass parts, 0.63 mass parts of phenolic resin, 1.07 mass parts of epoxy resin,
0.10 mass parts of butyral resin, 0.16 mass parts of carboxyl terminal acrylonitrile-butadiene copolymer, 0.04 mass of curing accelerator
Part and 1.99 mass parts of butyl carbitol as diluent.Next, with mixing and blending machine by these mixture at 25 DEG C
Stirring 15 seconds.Thus, the conductive paste of embodiment 3 is prepared.
(embodiment 4)
Using argentum powder b replace argentum powder a, in addition, according to similarly to Example 3 the step of prepare leading for embodiment 4
Conductive paste.
(embodiment 5)
In reaction vessel input argentum powder a24.25 mass parts, argentum powder f72.75 mass parts, 0.95 mass parts of phenolic resin,
1.61 mass parts of epoxy resin, 0.15 mass parts of butyral resin, 0.23 mass of carboxyl terminal acrylonitrile-butadiene copolymer
Part, 0.06 mass parts of curing accelerator and 2.99 mass parts of butyl carbitol as diluent.Next, using at 25 DEG C
These mixture are stirred 15 seconds by mixing and blending machine.Thus, the conductive paste of embodiment 5 is prepared.
(embodiment 6)
Using argentum powder e replace argentum powder f, in addition, according to similarly to Example 5 the step of prepare leading for embodiment 6
Conductive paste.
(embodiment 7)
Input argentum powder a94.00 mass parts, phenoxy resin (number-average molecular weight is 1180) 6.00 mass in reaction vessel
Part and 14.00 mass parts of butyl carbitol as diluent.Next, these are mixed with mixing and blending machine at 25 DEG C
Thing is stirred 15 seconds.Thus, the conductive paste of embodiment 7 is prepared.
(embodiment 8)
Input argentum powder c95.00 mass parts, 1.58 mass parts of phenolic resin, 2.68 mass of epoxy resin in reaction vessel
Part, 0.24 mass parts of butyral resin, 0.40 mass parts of carboxyl terminal acrylonitrile-butadiene copolymer, curing accelerator 0.10
Mass parts and 4.97 mass parts of butyl carbitol as diluent.Next, these are mixed with mixing and blending machine at 25 DEG C
Compound is stirred 15 seconds.Thus, the conductive paste of embodiment 8 is prepared.
(embodiment 9)
In reaction vessel input argentum powder a95 mass parts, 1.58 mass parts of phenolic resin, 2.68 mass parts of epoxy resin,
0.24 mass parts of butyral resin, 0.40 mass parts of carboxyl terminal acrylonitrile-butadiene copolymer, 0.10 mass of curing accelerator
Part and 1,2- epoxy radicals -4- (2- methyl oxirane bases) 5.33 mass parts of -1- hexahydrotoluenes as diluent.Connect down
Come, these mixture are stirred 15 seconds with mixing and blending machine at 25 DEG C.Thus, the conductive paste of embodiment 9 is prepared.
(embodiment 10)
In reaction vessel input argentum powder a95 mass parts, 1.58 mass parts of phenolic resin, 2.68 mass parts of epoxy resin,
0.24 mass parts of butyral resin, 0.40 mass parts of carboxyl terminal acrylonitrile-butadiene copolymer, 0.10 mass of curing accelerator
Part and 5.33 mass parts of 4- tert-butyl-phenyls glycidyl ether as diluent.Next, using mixing and blending machine at 25 DEG C
These mixture are stirred 15 seconds.Thus, the conductive paste of embodiment 10 is prepared.
(embodiment 11)
In reaction vessel input argentum powder a95 mass parts, 1.58 mass parts of phenolic resin, 2.68 mass parts of epoxy resin,
0.24 mass parts of butyral resin, 0.40 mass parts of carboxyl terminal acrylonitrile-butadiene copolymer, 0.10 mass of curing accelerator
Part and 1,3-, bis- (the 3- epoxypropoxies) -1 as diluent, 1,3,3- tetramethyl disiloxane, 5.33 mass parts.Connect down
Come, these mixture are stirred 15 seconds with mixing and blending machine at 25 DEG C.Thus, the conductive paste of embodiment 11 is prepared
Agent.
(embodiment 12)
In reaction vessel input argentum powder a95 mass parts, 1.58 mass parts of phenolic resin, 2.68 mass parts of epoxy resin,
0.24 mass parts of butyral resin, 0.40 mass parts of carboxyl terminal acrylonitrile-butadiene copolymer, 0.10 mass of curing accelerator
Part and 5.33 mass parts of glycidyl neodecanoate as diluent.Next, at 25 DEG C with mixing and blending machine by these
Mixture is stirred 15 seconds.Thus, the conductive paste of embodiment 12 is prepared.
(embodiment 13)
In reaction vessel input argentum powder a95 mass parts, 1.58 mass parts of phenolic resin, 2.68 mass parts of epoxy resin,
0.24 mass parts of butyral resin, 0.40 mass parts of carboxyl terminal acrylonitrile-butadiene copolymer, 0.10 mass of curing accelerator
Part and 4.97 mass parts of butyl carbitol acetate as diluent.Next, at 25 DEG C with mixing and blending machine by these
Mixture is stirred 15 seconds.Thus, the conductive paste of embodiment 13 is prepared.
(comparative example 1)
Using argentum powder d replace argentum powder a, in addition, according to similarly to Example 1 the step of prepare leading for comparative example 1
Conductive paste.
(comparative example 2)
Using argentum powder d replace argentum powder a, in addition, according to similarly to Example 3 the step of prepare leading for comparative example 2
Conductive paste.
(comparative example 3)
Using argentum powder d replace argentum powder a, in addition, according to similarly to Example 7 the step of prepare leading for comparative example 3
Conductive paste.
(comparative example 4)
After the conductive paste for preparing comparative example 1,0.50 mass parts of Oleic acid are added to, are compared so as to prepare
The conductive paste of example 4.
The specific name of the raw material used in embodiment 1～13 and comparative example 1～4 and physics value are as follows.
Phenolic resin：
Softening point is 98～102 DEG C, hydroxyl (OH) equivalent is 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 ratioes), average degree of polymerization are
2400
Carboxyl terminal acrylonitrile-butadiene copolymer：
Number-average molecular weight is 10000
Curing accelerator：
2-ethyl-4-methylimidazole
(measure of ratio resistance)
Next, the conducting film produced by the conductive paste that use is obtained by embodiment 1～13 and comparative example 1～4
Ratio resistance (resistivity) be measured.
Ratio resistance is measured according to below step.
On the aluminum oxide substrate that width is 20mm, length is 20mm, thickness is 1mm, using the stainless steel net of 250 purposes
Plate, printing length is 71mm, width is 1mm, the zigzag pattern formed by conductive paste that thickness is 20 μm.
The conductive paste of embodiment 1～4,7～13 and comparative example 1～4 is heated 30 minutes at 150 DEG C.
The conductive paste of embodiment 5 and 6 is heated 30 minutes at 200 DEG C.
For the thickness of pattern, the surface roughness profile measuring machine (trade name that manufactured using Tokyo Micronics Inc.
SURFCOM1400), tried to achieve according to the meansigma methodss of the measured value of 6 points reported to the leadship after accomplishing a task with pattern.
Conducting film obtained from regard to being heated to conductive paste or drying which, using LCR testers, and uses 4
Terminal method determines ratio resistance.The measurement result of ratio resistance is shown in 1～table of table 3.
It should be noted that unless otherwise specified, the numeral shown in 1～table of table 3 is represented with mass parts.
In 1～table of table 3,
" amount of resin (%) " is referred to：The total amount of resin is relative to argentum powder, resin (firming agent, heat-curing resin, thermoplasticity
Resin and acrylonitrile-butadiene copolymer) and curing accelerator total amount ratio.
" accounting for the overall amount of resin (%) of system " refers to：The total amount of resin is relative to argentum powder, resin (firming agent, heat cure
Property resin, thermoplastic resin and acrylonitrile-butadiene copolymer), the ratio of the total amount of curing accelerator and diluent.
" accounting for the overall argentum powder amount (%) of system " refers to：The total amount of argentum powder is relative to argentum powder, resin (firming agent, heat cure
Property resin, thermoplastic resin and acrylonitrile-butadiene copolymer), the ratio of the total amount of curing accelerator and diluent.
" ratio (%) of heat-curing resin " is referred to：The total amount of firming agent and heat-curing resin relative to resin (Gu
Agent, heat-curing resin, thermoplastic resin and acrylonitrile-butadiene copolymer) total amount ratio.
Result as shown in Table 1 understands that the conductive paste of embodiment 1～13 has excellent characteristic.
The conductive paste of embodiment 1～13 is that Oleic acid is entered comprising the fatty acid in liquid under room temperature (about 20 DEG C) is utilized
Gone surface treatment argentum powder.
It can be seen that：The conductive paste of comparative example 1～4 does not have excellent characteristic on the other hand.
The conductive paste of comparative example 1～4 is stearic acid comprising the fatty acid in solid-state under room temperature (about 20 DEG C) is utilized
The argentum powder being surface-treated.
It can be seen that：Compared with conducting film obtained from heating with the conductive paste to comparative example 1～4, to embodiment 1～
The ratio resistance of conducting film obtained from 13 conductive paste is heated is greatly reduced.
It can be seen that：By mixing spherical argentum powder in laminar argentum powder, so that the ratio resistance of conducting film further drops
Low (embodiment 5,6).
It can be seen that：To the silver being surface-treated comprising the argentum powder being surface-treated using Oleic acid and using stearic acid
The conductive paste of powder heated obtained from conducting film, with sufficiently small ratio resistance (embodiment 5).
Oleic acid is the fatty acid of liquid, and stearic acid is the fatty acid of solid-state.
It can be seen that：The conductive paste of the argentum powder being surface-treated comprising the mixture using Oleic acid and Palmic acid is entered
Conducting film obtained from row heating, with sufficiently small ratio resistance (embodiment 8),.
Oleic acid is the fatty acid of liquid, and Palmic acid is the fatty acid of solid-state.
It can be seen that：Add after the conductive paste comprising the argentum powder being surface-treated using stearic acid is prepared thereto
Refuel acid, then conducting film obtained from heating to obtained conductive paste, and its ratio resistance does not reduce (comparative example
4).
This expression：The conducting film little in order to obtain ratio resistance, it is necessary to carried out using the fatty acid (Oleic acid) using liquid
The argentum powder of surface treatment.Represent：Even if adding the fatty acid (Oleic acid) of liquid afterwards again in conductive paste, will not also make
The ratio resistance of conducting film reduces.
Fig. 1 is the electron micrograph of conducting film obtained from the conductive paste to embodiment 1 is heated.As schemed
Contact condition shown in 1, for conducting film obtained from just heating to the conductive paste of embodiment 1, between its argentum powder
Well, but also the part fusion together with argentum powder is seemed.It is thus regarded that the ratio resistance of conducting film becomes extremely low.
Fig. 2 is the electron micrograph of conducting film obtained from the conductive paste to comparative example 1 is heated.As schemed
Shown in 2, for conducting film obtained from just heating to the conductive paste of comparative example 1, the contact condition between argentum powder is not
Very good.It is thus regarded that the ratio resistance of conducting film increases.
Industrial applicability
According to the present invention it is possible to provide the heat treatment that can be carried out in a low temperature of below 200 DEG C and can be had
Enough low-resistivities (for example, 0.50 × 10-4Below Ω m) conducting film conductive paste.
According to the present invention, as electrode, circuit pattern can be formed also even for the low material of thermostability, therefore have
Industrial applicability.
Claims (13)
1. a kind of conductive paste, which includes：(A) argentum powder that is surface-treated using the fatty acid of liquid, (B) heat cure
Property resin and/or thermoplastic resin and (C) diluent,
The fatty acid of the liquid is Oleic acid, and the argentum powder is by the argentum powder of laminar and spherical argentum powder mixing, the electric conductivity
The amount of the fatty acid included in paste is 0.1～5 mass % relative to the total amount of the argentum powder and the fatty acid.
2. conductive paste according to claim 1, which has also carried out surface comprising (A ') merely with the fatty acid of solid-state
The argentum powder of process.
3. conductive paste according to claim 1 and 2, wherein, the heat-curing resin is epoxy resin and phenolic aldehyde
Resin.
4. conductive paste according to claim 1 and 2, wherein, the thermoplastic resin is selected from phenoxy resin, fourth
At least one in acetal resin, celluosic resin, acrylic resin and polyester resin.
5. conductive paste according to claim 3, wherein, the thermoplastic resin is to contract selected from phenoxy resin, fourth
At least one in urea formaldehyde, celluosic resin, acrylic resin and polyester resin.
6. the conductive paste according to any one in claim 1,2,5, wherein, the diluent is reactive dilution
Agent.
7. conductive paste according to claim 3, wherein, the diluent is reactive diluent.
8. conductive paste according to claim 4, wherein, the diluent is reactive diluent.
9. conductive paste according to claim 6, wherein, the reactive diluent is 1,2- epoxy radicals -4-
(2- methyl oxirane bases) -1- hexahydrotoluenes or 4- tert-butyl-phenyl glycidyl ethers.
10. the conductive paste according to claim 7 or 8, wherein, the reactive diluent be 1,2- epoxy radicals-
4- (2- methyl oxirane bases) -1- hexahydrotoluenes or 4- tert-butyl-phenyl glycidyl ethers.
A kind of 11. conducting films, its are obtained by the conductive paste heated in claim 1～10 described in any one.
A kind of 12. electronic units, which includes the conducting film described in claim 11.
A kind of 13. manufacture methods of conductive paste, which includes：
The operation laminar and spherical argentum powder being surface-treated using Oleic acid；With
The operation that the argentum powder, heat-curing resin and/or thermoplastic resin and diluent are mixed, the conductive paste
The amount of the fatty acid included in agent is 0.1～5 mass % relative to the total amount of the argentum powder and the fatty acid.
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| JP2011014352 | 2011-01-26 | ||
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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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2012
- 2012-01-25 JP JP2012554817A patent/JP5916633B2/en active Active
- 2012-01-25 CN CN201280006651.0A patent/CN103339685B/en active Active
- 2012-01-25 WO PCT/JP2012/051546 patent/WO2012102304A1/en active Application Filing
- 2012-01-25 KR KR1020137022331A patent/KR102007046B1/en active IP Right Grant
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2015
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Also Published As
| Publication number | Publication date |
|---|---|
| JP6174106B2 (en) | 2017-08-02 |
| KR20140007862A (en) | 2014-01-20 |
| JPWO2012102304A1 (en) | 2014-06-30 |
| CN103339685A (en) | 2013-10-02 |
| KR102007046B1 (en) | 2019-08-02 |
| WO2012102304A1 (en) | 2012-08-02 |
| JP2016106356A (en) | 2016-06-16 |
| JP5916633B2 (en) | 2016-05-11 |
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