CN103946926A - Conductive paste and multilayer ceramic capacitor - Google Patents
Conductive paste and multilayer ceramic capacitor Download PDFInfo
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- CN103946926A CN103946926A CN201280058409.8A CN201280058409A CN103946926A CN 103946926 A CN103946926 A CN 103946926A CN 201280058409 A CN201280058409 A CN 201280058409A CN 103946926 A CN103946926 A CN 103946926A
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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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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
- C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
- C04B35/62655—Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/63416—Polyvinylalcohols [PVA]; Polyvinylacetates
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/005—Electrodes
- H01G4/008—Selection of materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
- C04B2237/32—Ceramic
- C04B2237/34—Oxidic
- C04B2237/345—Refractory metal oxides
- C04B2237/346—Titania or titanates
Abstract
One purpose of the present invention is to provide a conductive paste which has excellent thixotropy and excellent printability such as resistance to stringiness, bleeding resistance and resistance to sheet attack. Another purpose of the present invention is to provide a conductive paste which enables efficient production of a multilayer ceramic capacitor. The present invention is a conductive paste which contains: a modified vinyl alcohol polymer that contains a monomer unit (A) having a group with 5 or more carbon atoms; a conductive powder; and an aqueous solvent. This conductive paste is characterized in that the modified vinyl alcohol polymer has a viscosity-average polymerization degree of from 200 to 5,000 (inclusive), a saponification degree of from 20% by mole to 99.99% by mole (inclusive), and a content of the monomer unit (A) of from 0.05% by mole to 5% by mole (inclusive).
Description
Technical field
The present invention relates to a kind of conductive paste, its formation for the formation of the interior electrode layer of the laminated electronic components such as laminated ceramic capacitor or the conductive layer of solar cell etc., and relate to a kind of laminated ceramic capacitor that uses this conductive paste and ceramic green embryo sheet material to obtain.
Background technology
Laminated ceramic capacitor refers to the sheet type ceramic capacitor that the dielectric layer such as titanium oxide, barium titanate and interior electrode layer multiple-layer overlapped form.This laminated ceramic capacitor is for example manufactured by following method.First, the adhesive resins such as polyvinyl butyral resin and plasticizer are added in the organic solvent that is dispersed with ceramic powders, evenly mix by ball mill etc., thereby preparation ceramic green embryo sheet material paste compound, by preparation paste compound roll forming on the fissility supporters such as pet film, wait and remove after solvent etc. by heating, it is peeled off by support, manufacture ceramic green embryo sheet material.
The ceramic green embryo sheet material obtaining thus uses by peeling off on above-mentioned fissility supporter.First, multiple surfaces at ceramic green embryo sheet material are coated with as the sheet of the conductive paste of internal electrode alternately overlapping by silk screen printing etc., add thermo-compressed, obtain duplexer.And then, form duplexer by all operations, cut into regulation shape.Then, carry out thermal decomposition and remove after the processing of the adhesive ingredients that contains in this duplexer etc., i.e. so-called ungrease treatment, burn till, at the end face sintering outer electrode of the ceramic burned material obtaining, thereby manufacture laminated ceramic capacitor via these operations.
In recent years, in order to realize microminiaturization, the high capacity of laminated ceramic capacitor, ceramic green embryo sheet material is also constantly carrying out thin layer, multiple stratification.But, along with thin layer and the multiple stratification of ceramic green embryo sheet material, the Printing Department of conductive paste and the not difference in height between Printing Department increase, and produce following problem in the time adding thermo-compressed duplexer: produce splitting or the distortion of ceramic green embryo sheet material and interior electrode layer, electrical characteristics and the reliability decrease of laminated ceramic capacitor.In addition,, along with microminiaturization, the high capacity of laminated ceramic capacitor, current conductive paste is also with problems such as printability deficiencies.
For addressing these problems, a kind of conductive paste that contains specific modified polyvinyl acetal resin (referring to Patent Document 1) is proposed.But, in patent documentation 1, in the time conductive paste being printed on ceramic green embryo sheet material, the adhesives such as the polyvinyl butyral resin stripping due to the organic solvent containing in conductive paste in ceramic green embryo sheet material, therefore the sheet material corrosion resistance (ー of Nai シ ト ア タ ッ Network) deficiency.In addition, the thixotropy of conductive paste is also not enough.
Here, the thixotropy of conductive paste refers under the fast state of shear rate apparent reduced viscosity and in the slow state of shear rate and character that apparent viscosity does not raise under shearing condition.
On the other hand, manufacturing when electronic unit, use the danger etc. of the infringement of current organic solvent to human-body safety, environmental pollution, fire, blast to become a problem.In order to address this is that, propose to use the aqueous slurry that contains vinol series polymer (being sometimes called for short below " PVA ") to replace the scheme (refer to Patent Document 2) of organic system slurry as ceramic green embryo sheet material paste compound.But, in patent documentation 2, not record and use water solvent as the solvent that is printed in the conductive paste on ceramic green embryo sheet material, the thixotropy of conductive paste and sheet material corrosion resistance are still not enough.
For solving above-mentioned variety of issue, seeking can thixotropy and sheet material corrosion resistance excellent and the conductive paste to human body and Environmental security.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2008-143922 communique
Patent documentation 2: TOHKEMY 2002-284579 communique.
Summary of the invention
The problem that invention will solve
The object of the invention is to, the conductive paste of the printability excellences such as a kind of thixotropy and anti-stringiness, impermeability and sheet material corrosion resistance is provided.Object is also, a kind of conductive paste that can high efficiency manufacture laminated ceramic capacitor is provided.
For the means of dealing with problems
The invention of making for solving above-mentioned problem is:
[1] a kind of conductive paste, it is characterized in that, in fact contain: the conductive paste that contains modified vinyl alcohol based polymer, conductive powder and the water solvent with the monomeric unit that carbon number is more than 5 group (A), the viscometric degree of polymerization of above-mentioned modified vinyl alcohol based polymer is more than 200 5, below 000, saponification degree be 20 % by mole of above 99.99 % by mole of containing ratios following and monomeric unit (A) be 0.05 % by mole above below 5 % by mole.
[2] according to the conductive paste above-mentioned [1] Suo Shu, above-mentioned modified vinyl alcohol based polymer containing proportional be below above 10 % by weight of 0.1 % by weight.
[3] according to the conductive paste above-mentioned [1] Suo Shu, the containing ratio of the water in above-mentioned water solvent is more than 60 % by weight.
[4], according to the conductive paste above-mentioned [1] Suo Shu, monomeric unit (A) is that more than 5 group replaces (methyl) acrylamide unit as the substituent N-of nitrogen-atoms for having carbon number.
[5], according to the conductive paste above-mentioned [1] Suo Shu, the carbon number of monomeric unit (A) is that more than 5 groups is that carbon number is more than 5 alkyl below 29.
[6], according to the conductive paste above-mentioned [5] Suo Shu, the carbon number of abovementioned alkyl is more than 15 below 26.
[7], according to the conductive paste above-mentioned [1] Suo Shu, the carbon number of monomeric unit (A) is that more than 5 groups is polyoxyalkylene.
[8], according to the conductive paste above-mentioned [7] Suo Shu, the alkylidene oxide unit number of above-mentioned polyoxyalkylene is more than 2 below 50.
[9] according to the conductive paste above-mentioned [7] Suo Shu, above-mentioned polyoxyalkylene is at least one being selected from polyoxyethylene, polyoxygenated propylidene and polyoxybutylene.
[10] according to the conductive paste above-mentioned [7] Suo Shu, above-mentioned polyoxyalkylene is as shown in following formula (I):
(in formula (I), R
1for hydrogen atom or methyl.R
2for hydrogen atom or the carbon number alkyl that is 1 ~ 8.M and n represent respectively the number of repeat unit of alkylidene oxide unit, the integer that m is 1 ~ 30, the integer that n is 1 ~ 20." b " represents that two adjacent cells form by block copolymerization).
[11] laminated ceramic capacitor, the conductive paste of its use above-mentioned [1] and ceramic green embryo sheet material and obtain.
Invention effect
The printability excellences such as the thixotropy of conductive paste of the present invention and anti-stringiness, impermeability and sheet material corrosion resistance.Therefore, conductive paste of the present invention can be preferably used as the conductive paste using in the formation etc. of the conductive layer of formation, the solar cell of the interior electrode layer of the laminated electronic components such as laminated ceramic capacitor.In addition, laminated ceramic capacitor of the present invention is difficult for producing distortion, the splitting etc. of ceramic green embryo sheet material and interior electrode layer, the excellences such as electrical characteristics, reliability.
Above-mentioned anti-stringiness or impermeability refer to respectively and are difficult for producing wire drawing or oozing out.Here, wire drawing refers to upper intact the peeling off of version that conductive paste can not be used by printshop, and the state of wire drawing appears in printing surface, the apparent viscosity of its conductive paste under the fast state of shear rate is high, occurs.In addition, ooze out the conductive paste that refers to printing and flow on ceramic green embryo sheet material, a kind of phenomenon being printed with the state expanding than target printing shape, its in the case of the slow state of shear rate and not under shearing condition the apparent viscosity of conductive paste occur low.
Embodiment
, describe conductive paste of the present invention and manufacture method thereof in detail below, and utilize the execution mode of the laminated ceramic capacitor of this conductive paste acquisition.
< conductive paste >
Conductive paste of the present invention contains specific modified PVA, conductive powder and water solvent, as required, also can further contain other compositions.Below the each composition containing in conductive paste of the present invention is described.
[modified PVA]
The modified PVA using in the present invention contains and has the monomeric unit that carbon number is more than 5 group (A).By using such modified PVA that carbon number is more than 5 group that has, the thixotropy of the conductive paste of acquisition improves.Therefore, while printing this conductive paste, Printing Department is difficult for expanding, and the printabilities such as anti-stringiness and impermeability improve.Be more than 5 groups as above-mentioned carbon number, preferably carbon number is more than 5 alkyl below 29, polyoxyalkylene, also, above-mentioned modified PVA is preferably alkyl-modified PVA, polyoxyalkylene modified PVA (following, " polyoxyalkylene " is sometimes referred to as " POA ").
(alkyl-modified PVA)
The alkyl-modified PVA using in the present invention preferably contains and has the monomeric unit that carbon number is more than 5 29 following alkyl.Also, abovementioned alkyl modified PVA is preferably and contains above-mentioned monomeric unit and the vinyl alcohol units (CH that carbon number is more than 5 29 following alkyl that have
2-CHOH-) copolymer, also can further contain other monomeric units.In the time using this alkyl-modified PVA, interact by the hydrophobic grouping in this alkyl-modified PVA, the thixotropy of the conductive paste of acquisition improves.Therefore, while printing this conductive paste, Printing Department is difficult for expanding, and the printabilities such as anti-stringiness and impermeability also improve.The carbon number of abovementioned alkyl is less than in 5 situation, and the interaction between alkyl can fully not show, and therefore thixotropy declines.On the other hand, the carbon number of this alkyl is greater than in 29 situation, and the operability under the water-soluble and high temperature of abovementioned alkyl modified PVA declines.Wherein, from the thixotropic viewpoint of further raising, more preferably carbon number is more than 8 alkyl below 29, further preferably carbon number is more than 12 alkyl below 27, particularly preferably carbon number is more than 15 alkyl below 26, and most preferably carbon number is more than 17 alkyl below 24.
There is as above-mentioned the monomeric unit that carbon number is more than 5 29 following alkyl, preferably derive from the monomeric unit of the alpha-olefines such as 1-octene, 1-decene; Derive from the monomeric unit of the vinyl ethers such as amyl group vinyl ethers, octyl group vinyl ethers, nonyl vinyl ethers, dodecyl vinyl, octadecyl vinyl ether; (methyl) alkyl acrylate; N-alkyl (methyl) acrylamide unit shown in following formula (II), more preferably following R
3for N-alkyl (methyl) acrylamide unit of more than 8 alkyl below 29 of carbon number.
In formula (II), R
3represent that carbon number is the more than 5 straight or branched alkyl below 29.R
4represent hydrogen atom or methyl.In addition, not affecting in the scope of effect of the present invention, above-mentioned R
3and R
4also can there is the substituting groups such as halogen atom, but preferably not there are these substituting groups.
As above-mentioned R
3represented carbon number is more than 5 alkyl below 29, can enumerate such as amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, pentadecyl, nonadecyl etc.Wherein, from the thixotropic viewpoint of further raising, preferably carbon number is more than 8 alkyl below 29, and more preferably carbon number is more than 12 alkyl below 27, further preferably carbon number is more than 15 alkyl below 26, and particularly preferably carbon number is more than 17 alkyl below 24.
From the viewpoints such as synthetic easiness, above-mentioned R
4for hydrogen atom or methyl.
(POA modified PVA)
The POA modified PVA using in the present invention, has POA base on its side chain.As above-mentioned POA base, preferably there is carbon number and be the POA base of 1 ~ 8 alkylidene, be more preferably selected from least one the POA base in polyoxyethylene, polyoxygenated propylidene and polyoxybutylene.In addition, the effect of the performance of the POA modified PVA in conductive paste adhesive.
In the molecule of above-mentioned POA modified PVA, have in the situation of two or more alkylidene oxides, two or more alkylidene oxides can be any number of in random shape or block-wise.Wherein, from the viewpoint that the physical property of POA group is more easily showed, be preferably block-wise.
The alkylidene oxide unit number of the alkylidene oxide in above-mentioned POA base is preferably more than 2 below 50, more preferably more than 5 below 40, more preferably more than 8 below 30, is particularly preferably more than 10 below 25.By making like this alkylidene oxide unit number of alkylidene oxide in above-mentioned scope, the thixotropy of the conductive paste of acquisition further improves.In addition, in the situation that above-mentioned POA base comprises two or more alkylidene oxides, the total alkylidene oxide unit number of each alkylidene oxide is made as to the alkylidene oxide unit number of alkylidene oxide.In addition, POA modified PVA has in the situation of multiple POA bases, and unit number refers to the weighted average of the total alkylidene oxide unit number of the alkylidene oxide of each POA base.
Wherein, particularly preferably above-mentioned POA base is the POA base shown in above-mentioned formula (I).In above-mentioned formula (I), R
1for hydrogen atom or methyl, from the viewpoint of productivity ratio, be preferably hydrogen atom.
In above-mentioned formula (I), R
2for hydrogen atom or the carbon number alkyl that is 1 ~ 8.R
2be preferably hydrogen atom, methyl or butyl, more preferably hydrogen atom or methyl.
In above-mentioned formula (I), m and n represent the average number of repeat unit of each alkylidene oxide, the integer that m is 1 ~ 30, the integer that n is 1 ~ 20.Wherein, the unit that number of repeat unit is m is called unit 1, and the unit that number of repeat unit is n is called unit 2.
The integer that the number of repeat unit m of the unit 1 of the POA base shown in above-mentioned formula (I) is 1 ~ 30, is preferably 1 ~ 20 integer, more preferably 1 ~ 10 integer, more preferably 1 ~ 5 integer.By making number of repeat unit m in above-mentioned scope, the thixotropy of the conductive paste of acquisition further improves.
In addition, the integer that the number of repeat unit n of the unit 2 of the POA base shown in above-mentioned formula (I) is 1 ~ 20, is preferably 5 ~ 18 integer, more preferably 8 ~ 15 integer.By making above-mentioned number of repeat unit n in above-mentioned scope, the thixotropy of the conductive paste of acquisition further improves.
In above-mentioned formula (I), " b " represents that two adjacent cells form by block copolymerization.
[synthesizing of modified PVA]
Modified PVA is in the situation of alkyl-modified PVA, the manufacture method of abovementioned alkyl modified PVA is not particularly limited, preferably carry out shown in following formula (III) unsaturated monomer and vinyl esters be the copolymerization of monomer, to the alkyl-modified vinyl acetate polymer method of carrying out saponification obtaining.
In formula (III), R
3and R
4definition identical with above-mentioned formula (II).
As the unsaturated monomer shown in above-mentioned formula (III), can enumerate such as N-octyl acrylamide, N-decyl acrylamide, N-dodecyl acrylamide, N-octadecyl acrylamide, N-cerul acrylamide, N-octyl group Methacrylamide, N-decyl Methacrylamide, N-dodecyl methyl acrylamide, N-octadecyl methyl acrylamide, N-cerul Methacrylamide etc.Wherein, be preferably N-octadecyl acrylamide, N-octyl group Methacrylamide, N-decyl Methacrylamide, N-dodecyl methyl acrylamide, N-octadecyl methyl acrylamide, N-cerul Methacrylamide, more preferably N-octadecyl acrylamide, N-dodecyl methyl acrylamide, N-octadecyl methyl acrylamide, more preferably N-octadecyl acrylamide, N-octadecyl methyl acrylamide.
Modified PVA is in the situation of POA modified PVA, the manufacture method of this POA modified PVA is not particularly limited, the method that unsaturated monomer and the vinyl esters that preferably carries out having on side chain POA base be the copolymerization of monomer, carry out saponification to the POA modified vinyl ester based polymer obtaining.
As the unsaturated monomer on side chain with POA base, preferably on side chain, there is the unsaturated monomer of the POA base shown in above-mentioned formula (I), the unsaturated monomer shown in preferred following formula (IV).Also the method that, more preferably to have the unsaturated monomer shown in the following formula (IV) of the POA base shown in above-mentioned formula (I) and vinyl esters be the copolymerization of monomer, carry out saponification to the ethene improved ester polymer of POA obtaining.
In formula (IV), R
1, R
2, m, n be identical with above-mentioned formula (I).R
5represent hydrogen atom or COOM base, wherein M represents hydrogen atom, alkali metal or ammonium.R
6represent hydrogen atom, methyl or CH
2-COOM base, wherein M is as aforementioned definitions.Represent-O-of X ,-CH
2-O-,-CO-,-(CH
2) k-,-COO-,-CO-NR
7-or CO-NR
7-CH
2-.In addition, X is in asymmetrical situation, and it is towards not limiting.Wherein R
7represent the alkyl that hydrogen atom or carbon number are 1 ~ 4, the integer that k is 1 ~ 15.
In unsaturated monomer shown in above-mentioned formula (IV), R
1, R
2, the preferred exemplary of m, n and number range and formula (I) explanation in foregoing identical.In addition R,
5be preferably hydrogen atom, R
6be preferably hydrogen atom or methyl.In addition be preferably-CH of X,
2-O-,-CO-NR
7-or CO-NR
7-CH
2-, more preferably-CO-NR
7-or CO-NR
7-CH
2-.In addition R,
7be preferably hydrogen atom or methyl, more preferably hydrogen atom.
For example, the R of above-mentioned formula (IV)
2for hydrogen atom, R
5for hydrogen atom and R
6in situation for hydrogen atom or methyl, the unsaturated monomer shown in above-mentioned formula (IV) can be enumerated polyoxyalkylene list (methyl) acrylamide, polyoxyalkylene list (methyl) allyl ether, polyoxyalkylene mono vinyl ether, polyoxyalkylene list (methyl) acrylate, particularly, can enumerate polyoxyethylene polyoxy butylene list acrylamide, N-methylene polyoxyethylene polyoxy butylene list acrylamide, polyoxyethylene polyoxy butylene monomethyl acrylamide, N-methylene polyoxyethylene polyoxy butylene monomethyl acrylamide, polyoxyethylene polyoxy butylene mono allyl ether, polyoxyethylene polyoxy butylene monomethyl allyl ether, polyoxyethylene polyoxy butylene mono vinyl ether, polyoxyethylene polyoxy butylene mono acrylic ester, polyoxyethylene polyoxy butylene monomethacrylates, polyoxypropylene polyoxy butylene list acrylamide, N-methylene polyoxypropylene polyoxy butylene list acrylamide, polyoxypropylene polyoxy butylene monomethyl acrylamide, N-methylene polyoxypropylene polyoxy butylene monomethyl acrylamide, polyoxypropylene polyoxy butylene mono allyl ether, polyoxypropylene polyoxy butylene monomethyl allyl ether, polyoxypropylene polyoxy butylene mono vinyl ether, polyoxypropylene polyoxy butylene mono acrylic ester, polyoxypropylene polyoxy butylene monomethacrylates etc.Wherein, preferably use polyoxyethylene polyoxy butylene list acrylamide, N-methylene polyoxyethylene polyoxy butylene list acrylamide, polyoxyethylene polyoxy butylene monomethyl acrylamide, N-methylene polyoxyethylene polyoxy butylene monomethyl acrylamide, polyoxyethylene polyoxy butylene mono allyl ether, more preferably use polyoxyethylene polyoxy butylene monomethyl acrylamide, N-methylene polyoxyethylene polyoxy butylene monomethyl acrylamide, polyoxyethylene polyoxy butylene mono allyl ether, further preferably use polyoxyethylene polyoxy butylene monomethyl acrylamide, N-methylene polyoxyethylene polyoxy butylene monomethyl acrylamide.
The R of above-mentioned formula (IV)
2for carbon number be 1 ~ 8 alkyl, R
5for hydrogen atom and R
6in situation for hydrogen atom or methyl, the unsaturated monomer shown in above-mentioned formula (IV) can specifically be enumerated as the R of above-mentioned formula (IV)
2the product that alkoxyl replaced that in situation for hydrogen atom, the terminal hydroxyl of cited above-mentioned unsaturated monomer is 1 ~ 8 by carbon number.Wherein, preferably use the terminal hydroxyl of polyoxyethylene polyoxy butylene monomethyl acrylamide, N-methylene polyoxyethylene polyoxy butylene monomethyl acrylamide, polyoxyethylene polyoxy butylene mono allyl ether by the unsaturated monomer of methoxy substitution, particularly preferably use the terminal hydroxyl of polyoxyethylene polyoxy butylene monomethyl acrylamide, N-methylene polyoxyethylene polyoxy butylene monomethyl acrylamide by the unsaturated monomer of methoxy substitution.
Unsaturated monomer shown in above-mentioned formula (III) or above-mentioned formula (IV) and vinyl esters are that the temperature of monomer while carrying out copolymerization is not particularly limited, be preferably 0 DEG C above below 200 DEG C, more preferably 30 DEG C above below 140 DEG C.Carry out the temperature of copolymerization lower than in the situation of 0 DEG C, be difficult for obtaining sufficient polymerization speed.In addition, carry out the temperature of polymerization higher than in the situation of 200 DEG C, difficult acquisition has the modified PVA of the containing ratio (also claiming below " containing ratio S ") of the monomeric unit (A) specifying in the present invention.Be controlled at 0 DEG C of above 200 DEG C of following method as the temperature of use when carrying out copolymerization, for example can enumerate by controlling polymerization speed, the method for the heat release of equilibrium polymerization and the heat of reactor surface release; The method of controlling by the external jacket of the thermal medium with suitable etc., from the viewpoint of fail safe, preferably the latter's method.
Be that monomer carries out polymerization methods that copolymerization adopts and can select any in batchwise polymerization, semi-batch polymerization, continuous polymerization, semi-continuous polymerization as the unsaturated monomer shown in above-mentioned formula (III) or above-mentioned formula (IV) and vinyl esters.As polymerization, can adopt mass polymerization, solution polymerization process, be suspended any means in the known method such as polymerization, emulsion polymerization.Wherein, preferably adopt the mass polymerization and the solution polymerization process that under solvent-free or alcohols solvent exist, carry out polymerization.To manufacture the copolymer of high polymerization degree in the situation of object, adopt emulsion polymerization.As the alcohols solvent using in mass polymerization or solution polymerization process, can use methyl alcohol, ethanol, normal propyl alcohol etc., but be not limited only to these.In addition, these solvents can two kinds or are used in combination.
As the initator using in copolymerization, can be according to polymerization, suitably select current known azo initiator, peroxide initiator, redox series initiators etc.Azo initiator can enumerate 2,2 '-azodiisobutyronitrile, 2,2 '-azo two (2,4-methyl pentane nitrile), 2, two (4-methoxyl group-2 of 2 '-azo, 4-methyl pentane nitrile) etc., peroxide initiator can be enumerated the peroxocarbonate compounds (percarbonate) such as di-isopropyl peroxydicarbonate, peroxy dicarbonate two (2-ethylhexyl) ester, peroxy dicarbonate diethoxy ethyl ester; The perester compounds (peresters) such as new peroxide tert-butyl caprate, peroxidating neodecanoic acid α-cumyl ester, the peroxidating capric acid tert-butyl ester; Acetyl group cyclohexyl sulfonyl-peroxide; 2,4,4-tri-methyl-amyl-2-benzoyl peroxide ethoxyacetic acid ester etc.In addition, can also on the basis of above-mentioned initator, be used in combination potassium peroxydisulfate, ammonium persulfate, hydrogen peroxide etc. as initator.In addition, redox initiator can be enumerated the reducing agents such as above-mentioned peroxide and sodium hydrogensulfite, sodium acid carbonate, tartaric acid, L-AA, rongalite are combined to the product obtaining.
In addition, under higher temperature, carry out the unsaturated monomer shown in above-mentioned formula (III) or above-mentioned formula (IV) and vinyl esters while being the copolymerization of monomer, occur sometimes the phenomenons such as the PVA causing because of the decomposition that vinyl esters is monomer is painted.In this situation, painted for preventing, in polymer system, can add the antioxidants such as the tartaric acid about (being the weight of monomer with respect to vinyl esters) below the above 100ppm of 1ppm.
The vinyl esters using in copolymerization is that monomer can be enumerated vinyl formate, vinyl acetate, propionate, vinyl butyrate, isobutyric acid vinyl acetate, pivalic acid (Pivalic acid) vinyl acetate, versatic acid (Versatic acid) vinyl acetate, vinyl caproate, sad vinyl acetate, vinyl laurate, palmitic acid vinyl acetate, stearic acid vinyl ester, oleic acid vinyl acetate, vinyl benzoate etc.Wherein, most preferably be vinyl acetate.
When unsaturated monomer shown in above-mentioned formula (III) or above-mentioned formula (IV) and vinyl esters are monomer copolymerization, not departing from the scope of purport of the present invention, also can with other monomer copolymerizations.As the monomer that can use, can enumerate the alpha-olefins such as such as ethene, propylene, n-butene, isobutene; Acrylic acid and salt thereof; The esters of acrylic acids such as methyl acrylate, ethyl acrylate, acrylic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate; Methacrylic acid and salt thereof; The methyl acrylic esters such as methyl methacrylate, EMA, n propyl methacrylate, isopropyl methacrylate, n-BMA, isobutyl methacrylate, Tert-butyl Methacrylate; Acrylamide; The acrylamide derivatives such as N methacrylamide, N-ethyl acrylamide, N,N-DMAA, diacetone acrylamide, acrylamido propane sulfonic acid and salt thereof, acrylamide propyl dimethylamine and salt or its quaternary ammonium salt, N hydroxymethyl acrylamide and derivative thereof; Methacrylamide; The methacrylamide derivatives such as N-methyl acrylamide, N-ethyl-methyl acrylamide, Methacrylamide propane sulfonic acid and salt, Methacrylamide diemethylamine and salt thereof or its quaternary ammonium salt, N-methylol methacrylamide and derivative thereof; Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether, IVE, tert-Butyl vinyl ether, 2, the vinyl ethers such as 3-diacetoxy-1-ethyleneoxy propane; The nitrile such as acrylonitrile, methacrylonitrile; The ethylene halide such as vinyl chloride, PVF class; Vinylidene chloride, vinylidene isogonic ethylene halide class; Allyl acetate, 2, the allyl compounds such as 3-diacetoxy-1-allyloxy propane, allyl chloride; Unsaturated dicarboxylic and salt or its esters such as maleic acid, itaconic acid, fumaric acid; The vinyl silane compounds such as vinyltrimethoxy silane; Methylvinyl acetate etc.
In addition, when unsaturated monomer shown in above-mentioned formula (III) or above-mentioned formula (IV) and vinyl esters are monomer copolymerization, for regulating the degree of polymerization etc. of the modified vinyl ester based polymer obtaining, not departing from the scope of purport of the present invention, can under the existence of chain-transferring agent, carry out copolymerization.As chain-transferring agent, can enumerate the aldehydes such as acetaldehyde, propionic aldehyde; The ketone such as acetone, methyl ethyl ketone; The thio-alcohols such as 2-hydroxyl ethyl mercaptan; The halogenated hydrocarbon such as trichloroethylene, perchloroethylene; The phosphonates such as Alendronate monohydrate.Wherein, preferably use aldehydes and ketone.The addition of chain-transferring agent is determined according to the chain transfer constant of chain-transferring agent adding and the degree of polymerization of target vinyl acetate polymer.Generally speaking be preferably, that monomer is below above 10 % by weight of 0.1 % by weight with respect to vinyl esters.
The saponification of ethene improved ester polymer can be suitably by alcoholysis reaction and the hydrolysis of the acidic catalysts such as base catalyst or p-methyl benzenesulfonic acid such as current known NaOH, potassium hydroxide, sodium methoxide.The solvent that can use as this reaction, can enumerate the alcohols such as methyl alcohol, ethanol; The ester such as methyl acetate, ethyl acetate class; The ketone such as acetone, methyl ethyl ketone; Benzene, toluene etc. are aromatic hydrocarbon based etc.These solvents may be used singly or two or more in combination.Wherein, taking methyl alcohol or methanol/methyl acetate mixed solution as solvent, NaOH is carried out to saponification for catalyst easy, for preferably.
In the modified PVA using in the present invention, the containing ratio S with the monomeric unit that carbon number is more than 5 group (A) should be 0.05 % by mole above below 5 % by mole, be preferably 0.1 % by mole above below 2 % by mole, more preferably 0.2 % by mole above below 1 % by mole.In addition, in this specification, the containing ratio S of monomeric unit (A) refers to have molal quantity proportion in the molal quantity of the total unit of composition modified PVA that carbon number is the monomeric unit of more than 5 groups.
In the time that above-mentioned containing ratio S is greater than 5 % by mole, the shared ratio of modified group containing in the above-mentioned modified PVA of every a part raises, the water-soluble decline of this modified PVA.In addition, under containing ratio S is less than the situation of 0.05 % by mole, the water-soluble excellence of above-mentioned modified PVA, is more than 5 group quantity minimizings but contain carbon number in this modified PVA, and the thixotropy of the conductive paste based on modification, anti-stringiness and impermeability cannot fully manifest.
Above-mentioned containing ratio S can obtain according to this modified PVA, also can obtain according to the ethene improved ester polymer as its precursor, and both all can obtain according to proton N MR.For example, in situation about obtaining according to ethene improved ester polymer, particularly, first by n-hexane/acetone, ethene improved ester polymer is carried out, after 3 above purifications of precipitation fully again, under the reduced pressure of 50 DEG C, being dried two days, manufacture sample for analysis.By this sample dissolution in CDCl
3in, by proton N, MR at room temperature measures.
Now, when for example modified PVA is alkyl-modified PVA, not containing alkyl-modified monomeric unit and R except above-mentioned monomeric unit
3for straight chain, and R
4in situation for hydrogen atom, can calculate by the following method.Also, according to derive from alkyl-modified vinyl acetate polymer main chain methine α peak (4.7 ~ 5.2ppm) and derive from alkyl R
3the β peak (0.8 ~ 1.0ppm) of terminal methyl group, obtain alkyl-modified rate S by following formula.
Alkyl-modified rate S(% by mole)={ (proton number/3 of β)/(proton number+(proton number/3 of β) of α) } × 100.
In addition, when modified PVA is in the situation of POA modified PVA, can according to derive from above-mentioned vinyl esters be monomeric unit main chain methine protons α peak (4.7 ~ 5.2ppm) and derive from the β peak (0.8 ~ 1.0ppm) of the terminal methyl group proton of unit 2, use following formula to obtain POA base degree of modification S.In addition, the n in following formula represents the number of repeat unit of unit 2.
POA base degree of modification S(% by mole)={ (β peak area/3n)/(α peak area+(β peak area/3n)) } × 100.
The viscometric degree of polymerization of above-mentioned modified PVA (also claims " viscometric degree of polymerization P " below.In addition, also likely by viscometric degree of polymerization referred to as the degree of polymerization.) be necessary for more than 200 below 5,000, be preferably more than 500 below 4,000, more preferably more than 1,000 below 3,000.When the degree of polymerization of modified PVA is greater than at 5,000 o'clock, the productivity ratio of this modified PVA can decline to some extent, therefore impracticable.On the contrary, under the degree of polymerization of modified PVA is less than 200 situation, the thixotropy of the conductive paste of acquisition cannot fully manifest.
Above-mentioned viscometric degree of polymerization P measures according to JIS-K6726.Also,, by after above-mentioned modified PVA resaponifying, purification, be pursuant to limiting viscosity [the η] (unit: decilitre/g) obtain by following formula measuring in 30 DEG C of water.
Viscometric degree of polymerization P=([η] × 10
3/ 8.29)
(1/0.62).
The saponification degree of above-mentioned modified PVA be necessary for 20 % by mole above below 99.99 % by mole, be preferably 40 % by mole above below 99.9 % by mole, more preferably 60 % by mole above below 99.5 % by mole, more preferably 80 % by mole above below 99 % by mole.Under the saponification degree of modified PVA is less than the situation of 20 % by mole, the water-soluble meeting of modified PVA declines to some extent, is therefore difficult to prepare conductive paste.On the other hand, under the saponification degree of modified PVA is greater than the situation of 99.99 % by mole, be difficult to produce modified PVA, therefore impracticable.In addition, the saponification degree of above-mentioned modified PVA is to measure according to JIS-K6726 the value obtaining.
Thixotropic viewpoint of the conductive paste obtaining from further raising, above-mentioned modified PVA is preferably more than 0.1 % by weight below 10 % by weight containing proportional in conductive paste of the present invention.
(conductive powder)
The conductive powder using in the present invention is not particularly limited, as long as demonstrating the material of conductivity.For example can enumerate by nickel, palladium, platinum, gold, silver, copper, the powder etc. of alloy that comprises them.As above-mentioned conductive powder, it is the conductive powder of insoluble inorganic oxide that preferred use has at adsorption the oxide that comprises silicon, aluminium or zirconium.By using this conductive powder, can make conductive powder no longer condense, be dispersed in water paste with high-concentration stable, therefore can, preferably as burning till with conductive paste, use especially for the conductive paste that forms laminated ceramic capacitor.Above-mentioned conductive powder may be used singly or two or more in combination.
Thixotropic viewpoint of the conductive paste obtaining from further raising, above-mentioned conductive powder is preferably more than 30 % by weight below 80 % by weight containing proportional in conductive paste of the present invention.
(water solvent)
In conductive paste of the present invention, importantly use water solvent as solvent.As reason, can enumerate above-mentioned modified PVA and in molecule, there is great amount of hydroxy group, therefore polarity is high, is not soluble in organic solvent.Therefore,, by using water solvent, can easily manufacture conductive paste of the present invention.
In addition, by using water solvent to also have a benefit as described below as solvent, conductive paste being printed in while manufacturing laminated ceramic capacitor on ceramic green embryo sheet material, the resins such as the Pioloform, polyvinyl acetal containing in above-mentioned ceramic green embryo sheet material are difficult for stripping in conductive paste, and sheet material corrosion resistance is excellent especially.
Above-mentioned water solvent is not particularly limited, from the aspect such as possibility, the possibility of blast of the fail safe to human body, environmental pollution, fire, preferably water is made as to main body, particularly, more preferably the water containing ratio in water solvent is more than 60 % by weight, more than 70 % by weight, more than being particularly preferably 80 % by weight, can be more preferably also 100 % by weight.Above-mentioned water is preferably distillation and stays water or ion exchange water, more preferably ion exchange water.
Thixotropic viewpoint of the conductive paste obtaining from further raising, above-mentioned water solvent is preferably more than 20 % by weight below 70 % by weight containing proportional in conductive paste of the present invention.
(other compositions)
Not departing from the scope of purport of the present invention, conductive paste of the present invention can also contain the modified PVA that known various PVA(uses in the present invention), the water soluble polymer such as starch, carboxymethyl cellulose, methylcellulose, CMC; Plasticizer; Lubricant; Dispersant; Other compositions such as antistatic agent.
The method of manufacturing conductive paste of the present invention is not particularly limited, and can adopt the method for carrying out mixing manufacture conductive paste in the known mixer such as mixer grinder, three roller roller mills (Three-Rollers) that for example conductive powder, above-mentioned modified PVA, water solvent and other compositions is supplied to.
The viscosity of conductive paste of the present invention is not particularly limited, and is preferably shear rate (shear rate): the 1(1/sec) viscosities il under condition
1with shear rate (shear rate): the 100(1/sec) viscosities il under condition
2ratio of viscosities η
2/ η
1be below 0.8, more preferably, below 0.5, more preferably, below 0.3, be particularly preferably below 0.1.Above-mentioned ratio of viscosities η
2/ η
1in above-mentioned scope, can obtain thixotropy and further improve, anti-stringiness and impervious more excellent conductive paste, be therefore preferred.
(purposes)
Conductive paste of the present invention is preferred for forming the interior electrode layer of the laminated electronic components such as laminated ceramic capacitor or the conductive layer of formation solar cell etc.Therefore the laminated ceramic capacitor that, uses conductive paste of the present invention and ceramic green embryo sheet material to obtain is also one embodiment of the present invention.The printability excellences such as the thixotropy of conductive paste of the present invention and anti-stringiness, impermeability and sheet material corrosion resistance, therefore by being used this conductive paste can manufacture efficiently laminated ceramic capacitor.
The manufacture method of the paste compound using in above-mentioned ceramic green embryo sheet material is not particularly limited, the methods of the various various mixers mixing such as ball mill, mixer grinder, three roller roller mills additive for that for example, can adopt the adhesive resins such as polyvinyl acetal resin, ceramic powders, organic solvent and add as required.
The manufacture method of above-mentioned ceramic green embryo sheet material is not particularly limited, can be by current known manufacture method manufacture, for example can be by using paste compound roll forming on the fissility supporters such as polyethylene Polyethyleneglycol Terephthalate film ceramic green embryo sheet material, wait and remove after solvent etc. by heating, the method that it is peeled off by supporter etc.
The product that conductive paste printing of the present invention (coating) is obtained on the ceramic green embryo sheet material obtaining is like this stacked, can manufacture thus laminated ceramic capacitor.Particularly, for example can adopt following method, multiple are utilized in above-mentioned ceramic green embryo sheet surface silk screen printing etc. be coated with the sheet of conductive paste of the present invention alternately overlapping, add thermo-compressed, form duplexer, and add thermal decomposition and remove after (ungrease treatment) containing resin etc. in this duplexer, burnt till, in the method for the ceramic burned material end face sintering outer electrode obtaining etc.
< laminated ceramic capacitor >
Laminated ceramic capacitor of the present invention is by this conductive paste being printed to (coating) stacked obtaining of product on ceramic green embryo sheet material.Therefore, this laminated ceramic capacitor is difficult for producing distortion, the splitting etc. of ceramic green embryo sheet material and interior electrode layer, the excellences such as electrical characteristics, reliability.
Embodiment
Describe the present invention in detail below by embodiment and comparative example.In the following examples and comparative example, unless otherwise noted, " part " and " % " refers to weight standard.
By the following method to obtain the alkyl-modified PVA of PVA(, POA modified PVA and unmodified PVA according to following Production Example) evaluate.
[viscometric degree of polymerization P and the saponification degree of PVA]
The method that the viscometric degree of polymerization P of PVA and saponification degree are recorded according to JIS-K6726 is obtained.
[the POA base degree of modification of the alkyl-modified rate of the containing ratio S(PVA of monomeric unit (A) or PVA]
The containing ratio S of monomeric unit (A) obtains according to the method for above-mentioned use proton N MR.In addition, proton N MR utilizes the JEOL GX-500 of 500MHz.
The manufacture > of the alkyl-modified PVA of <
The manufacture of [Production Example 1] PVA1
To have that mixer, reflux condensing tube, nitrogen conduit, comonomer drip mouthful and 3L reactor that initator adds mouthful in supply with 750g vinyl acetate, 250g methyl alcohol and 1.1g N-octadecyl methyl acrylamide, on one side by nitrogen bubble (nitrogen bubbling), on one side to carrying out the nitrogen replacement of 30 minutes in system.In addition, using N-octadecyl methyl acrylamide be dissolved in Methanol for the comonomer solution of 5% concentration as postponing (delay) solution, and by nitrogen bubble, this comonomer solution is carried out to nitrogen replacement.Start reactor and heat up, when after interior temperature rise to 60 DEG C, add 0.25g 2,2 '-azodiisobutyronitrile (AIBN), initiated polymerization.On one side drip above-mentioned delay solution to above-mentioned reactor and makes the monomer composition in polymeric solution keep constant, on one side after 60 DEG C of polyase 13s hour, cooling, stop polymerization.Be 4.8g until stop the comonomer total amount that polymerization adds.In addition the solid component concentration while, stopping polymerization is 29.9%.Then, under 30 DEG C, reduced pressure, constantly add methyl alcohol on one side, remove unreacted vinyl-acetic ester monomer on one side, obtain the methanol solution (35% concentration) of alkyl-modified vinyl acetate based polymer (alkyl-modified PVAc).And then, carry out saponification (in saponification solution, the concentration of alkyl-modified PVAc is 25%, NaOH is 0.03 with respect to the mol ratio of vinyl acetate unit in alkyl-modified PVAc) to this being added to the alkaline solution (10% methanol solution of NaOH) that adds 27.9g in the methanol solution (the alkyl-modified PVAc in solution is 200.0g) of the alkyl-modified PVAc of 771.4g for preparing of methyl alcohol.Add alkaline solution and generate spawn after approximately one minute.This spawn is pulverized with grinder, and within 1 hour, carried out after saponification in 40 DEG C of placements, add in 500g methyl acetate and residual alkali.Use phenolphthalein indicator to confirm that in arrival and after terminal, isolated by filtration obtains white solid.Add 2,000g methyl alcohol to this white solid and place 3 hours to wash in room temperature.Repeat after 3 these washing operations.Centrifugal dewatering obtains white solid, is placed in drying machine and places and within two days, obtain alkyl-modified PVA(PVA1 in 65 DEG C).The viscometric degree of polymerization P of PVA1 is 1,700, saponification degree is that 98.5 % by mole, alkyl-modified rate S are 0.4 % by mole.
The manufacture of [Production Example 2 ~ 4] PVA2 ~ 4
When by the kind of N-alkyl (methyl) acrylamide unit and use amount thereof, the degree of polymerization, saponification the concentration of alkyl-modified PVAc and NaOH with respect to the mol ratio of vinyl acetate unit change to as shown in table 1, other have manufactured various PVA(PVA2 ~ 4 according to the method identical with Production Example 1).
The manufacture > of < POA modified PVA
The manufacture of [Production Example 5] PVA5
The unsaturated monomer that adds 750g vinyl acetate, 250g methyl alcohol, 3.3g to have POA base to the 3L reactor with mixer, reflux condensing tube, nitrogen conduit, monomer dropping mouth and initator interpolation mouth is that (monomer A is the unsaturated monomer shown in following formula (V) to monomer A.), on one side by nitrogen bubble, on one side to carrying out the nitrogen replacement of 30 minutes in system.In addition, using monomer A be dissolved in Methanol for the solution of 20% concentration as postponing solution, and carry out nitrogen replacement by nitrogen bubble.Start reactor and heat up, when after interior temperature rise to 60 DEG C, add 0.25g 2,2 '-azodiisobutyronitrile (AIBN), initiated polymerization.
Drip on one side and postpone solution and makes the monomer composition (ratio of vinyl acetate and monomer A) in polymeric solution keep constant, on one side after 60 DEG C of polyase 13s hour, cooling, stop polymerization.Be 17.6g until stop the monomer A total amount that polymerization adds.In addition the solid component concentration while, stopping polymerization is 24.4%.Then, under 30 DEG C, reduced pressure, constantly add methyl alcohol on one side, removing unreacted vinyl-acetic ester is on one side monomer, obtains the ethene improved ester polymer of POA (POA modified PVA methanol solution (concentration 35%) c).And then, in the methanol solution (the POA modified PVA c in solution is 100.0g) of the 453.4g POA modified PVA c for preparing of methyl alcohol, add 55.6g alkaline solution (10% methanol solution of NaOH) and carry out saponification (the POA modified PVA c concentration of saponification solution is 20%, NaOH be 0.1 with respect to the mol ratio of vinyl acetate unit in POA modified PVA c) to this is added.Add alkaline solution and generate spawn after approximately 1 minute, it is pulverized by grinder, within 1 hour, carry out after saponification in 40 DEG C of placements, add in 500g methyl acetate and residual alkali.Utilize phenolphthalein indicator to confirm that in arrival and after terminal, isolated by filtration obtains white solid, it is added to 2,000g methyl alcohol and place 3 hours to wash in room temperature.Repeat, after 3 these above-mentioned washing operations, to carry out centrifugal dewatering and obtain white solid, be placed in drying machine and obtain two days later POA modified PVA (PVA5) in 65 DEG C of placements.The viscometric degree of polymerization P of PVA5 is 1,700, saponification degree is that 98.7 % by mole, POA base degree of modification S are 0.4 % by mole.
The manufacture of [Production Example 6] PVA6
When the use amount of the unsaturated monomer with POA base using in during except polymerization, the degree of polymerization, saponification the concentration of POA modified PVA c and NaOH with respect to the mol ratio of vinyl acetate unit change to as shown in table 1, other manufacture PVA6 according to the method identical with Production Example 5.
[embodiment 1]
(manufacture of conductive paste)
Get PVA1 and the 98g ion exchange water that 2g obtains according to Production Example 1 and be supplied in the detachable flask (separable flask) with stirring vane, in 90 DEG C of water-baths, heat while stir the PVA1 aqueous solution of preparation 2% 2 hours.Then, the 2%PVA1 aqueous solution preparing is all supplied in three-roll grinder as the nickel powder (Mitsui Metal Co., Ltd.'s mining industry 2020SS processed) of conductive powder with 100g, makes conductive paste.
(evaluation)
According to following method, made conductive paste in embodiment 1 is evaluated.Its evaluation result is as shown in table 2.
(manufacture of ceramic green embryo sheet material)
By 10 parts of polyvinyl butyral resin (KURARAY systems; MOWITAL B60H) be added in the mixed solvent of 30 parts of toluene and 15 parts of ethanol stirring and dissolving.Then, add 3 parts of dibutyl phthalates as plasticizer, stirring and dissolving.In the solution obtaining, add 100 parts of barium titanates as ceramic powders (Sakai chemical industry system; BT-01(average grain diameter 0.1 μ is m)), after 48 hours, obtain ceramic size composition with ball mill mixing.After the ceramic size composition demoulding obtaining is processed, the mode that is about 1 μ m with dried thickness is coated on mylar, air-dry 1 hour of normal temperature, be dried 3 hours with air drier in 80 DEG C again, then in 120 DEG C after dry 2 hours, peel off from mylar, make ceramic green embryo sheet material.
(1) viscosity
Using the thixotropy index of the viscosity of conductive paste made conductive paste in embodiment 1, use rotational rheometer (TA INST RUMENT system; ARES G2) under following condition determination with FLOW SWEEP(traffic scanning) pattern measured shear rate (shear rate): the 1(1/sec) viscosity under condition and shear rate (shear rate): the 100(1/sec) viscosity under condition.Shear rate (shear rate): the 1(1/sec) viscosities il under condition
1for 25Pas, shear rate (shear rate): the 100(1/sec) viscosities il under condition
2for 1.5Pas, ratio of viscosities η
2/ η
1be 0.06.
< condition determination >
The diameter of rotating circular disk: 40mm
Rotating circular disk (upside): flat board
The coning angle of rotating circular disk (downside): 0.02rad
Block gap (Truncation gap): 0.0262mm.
(2) anti-stringiness
After made conductive paste in embodiment 1 being printed on above-mentioned ceramic green embryo sheet material by screen process press, use baking box to be dried 30 minutes in 100 DEG C.By the anti-stringiness of observation by light microscope printing, and according to following standard evaluate, thereafter.
Zero: without wire drawings more than length 20 μ m.
×: there is wire drawings more than length 20 μ m.
(3) impermeability
After made conductive paste in embodiment 1 being printed on above-mentioned ceramic green embryo sheet material by screen process press, use baking box to be dried 30 minutes in 100 DEG C.By the impermeability of observation by light microscope printing, and according to following standard evaluate, thereafter.
Zero: seepage discharge is less than 20 μ m.
×: more than seepage discharge 20 μ m.
(4) sheet material corrosion resistance
After made conductive paste in embodiment 1 being printed on above-mentioned ceramic green embryo sheet material by screen process press, use baking box to be dried 30 minutes in 100 DEG C.Thereafter, the aggressivity for ceramic green embryo sheet material to conductive paste, by expansion and the distortion at the printed sheet material back side of stereoscopic microscope observing, and evaluates by following standard.
Zero: almost do not expand or distortion.
×: have and expand or distortion.
[embodiment 2]
Use PVA2 to replace PVA1, in addition, all with embodiment 1, make conductive paste.By the method identical with embodiment 1, viscosity, anti-stringiness, impermeability and the sheet material corrosion resistance of the conductive paste obtaining are evaluated.Its evaluation result is as shown in table 2.
[embodiment 3]
Use PVA3 to replace PVA1, in addition, all with embodiment 1, make conductive paste.By the method identical with embodiment 1, viscosity, anti-stringiness, impermeability and the sheet material corrosion resistance of the conductive paste obtaining are evaluated.Its evaluation result is as shown in table 2.
[comparative example 1]
Use PVA4 to replace PVA, in addition, all with embodiment 1, make conductive paste.By the method identical with embodiment 1, viscosity, anti-stringiness, impermeability and the sheet material corrosion resistance of the conductive paste obtaining are evaluated.Its evaluation result is as shown in table 2.
[comparative example 2]
Use α-terpineol to replace the water using as the water solvent in conductive paste, in addition all with embodiment 1, to manufacture conductive paste, but because PVA1 does not dissolve completely, fail to make homogeneous solution.
[comparative example 4]
Use heater that 92g α-terpineol is heated to 60 DEG C of temperature, stir with stirring vane on one side, slowly add 8g ethyl cellulose (Dow Chemical system on one side; STD-200), preparation 8% ethyl cellulose solution.Then, using preparation 8% ethyl cellulose solution all with nickel powder (Mitsui Metal Co., Ltd. mining industry system of 100g as conductive powder; 2020SS) be supplied in three-roll grinder, make conductive paste.By the way identical with embodiment 1, viscosity, anti-stringiness, impermeability and the sheet material corrosion resistance of the conductive paste obtaining are evaluated.Its evaluation result is as shown in table 2.
[embodiment 4]
Get PVA5 and the 96g ion exchange water that 4g makes according to Production Example 5 and be supplied in the separable flask with stirring vane, in 90 DEG C of water-baths, heat while stir the preparation 4%PVA5 aqueous solution 2 hours.Then, using preparation the 4%PVA5 aqueous solution all with nickel powder (Mitsui Metal Co., Ltd. mining industry system of 100g as conductive powder; 2020SS) be supplied in three-roll grinder, make conductive paste.By the method identical with embodiment 1, viscosity, anti-stringiness, impermeability and the sheet material corrosion resistance of the conductive paste obtaining are evaluated.Its evaluation result is as shown in table 2.
[embodiment 5]
Use PVA6 to replace PVA5, in addition, all with embodiment 4, make conductive paste.By the method identical with embodiment 1, viscosity, anti-stringiness, impermeability and the sheet material corrosion resistance of the conductive paste obtaining are evaluated.Its evaluation result is as shown in table 2.
[comparative example 3]
Use α-terpineol to replace the water using as the water solvent in conductive paste, in addition all with embodiment 4, to manufacture conductive paste, but because PVA5 does not dissolve completely, fail to make homogeneous solution.
Industrial applicibility
The printability excellences such as the thixotropy of conductive paste of the present invention and anti-stringiness, impermeability and sheet material corrosion resistance.Therefore, conductive paste of the present invention can be preferably used as and form the conductive paste that the interior electrode layer of the laminated electronic components such as laminated ceramic capacitor or the conductive layer of formation solar cell etc. use.In addition, laminated ceramic capacitor of the present invention is difficult for producing distortion, the splitting etc. of ceramic green embryo sheet material and interior electrode layer, the excellences such as electrical characteristics, reliability.
Claims (11)
1. a conductive paste, is characterized in that, it is to contain:
Contain have the monomeric unit that carbon number is more than 5 group (A) modified vinyl alcohol based polymer,
Conductive powder and
The conductive paste of water solvent,
The viscometric degree of polymerization of above-mentioned modified vinyl alcohol based polymer is more than 200 below 5,000, saponification degree be 20 % by mole of above 99.99 % by mole of containing ratios following and monomeric unit (A) be 0.05 % by mole above below 5 % by mole.
2. conductive paste according to claim 1, above-mentioned modified vinyl alcohol based polymer containing proportional be below above 10 % by weight of 0.1 % by weight.
3. conductive paste according to claim 1, the containing ratio of the water in above-mentioned water solvent is more than 60 % by weight.
4. conductive paste according to claim 1, monomeric unit (A) is that more than 5 group replaces (methyl) acrylamide unit as the substituent N-of nitrogen-atoms for having carbon number.
5. conductive paste according to claim 1, the carbon number of monomeric unit (A) is that more than 5 groups is that carbon number is more than 5 alkyl below 29.
6. conductive paste according to claim 5, the carbon number of abovementioned alkyl is more than 15 below 26.
7. conductive paste according to claim 1, the carbon number of monomeric unit (A) is that more than 5 groups is polyoxyalkylene.
8. conductive paste according to claim 7, the alkylidene oxide unit number of above-mentioned polyoxyalkylene is more than 2 below 50.
9. conductive paste according to claim 7, above-mentioned polyoxyalkylene is at least one being selected from polyoxygenated ethylidene, polyoxygenated propylidene and polyoxybutylene.
10. conductive paste according to claim 7, above-mentioned polyoxyalkylene as shown in following formula (I),
[Chemical formula 1]
In formula (I), R
1for hydrogen atom or methyl, R
2for the alkyl that hydrogen atom or carbon number are 1 ~ 8, m and n represent respectively the number of repeat unit of alkylidene oxide unit, the integer that m is 1 ~ 30, and the integer that n is 1 ~ 20, " b " represents that two adjacent cells form by block copolymerization.
11. 1 kinds of laminated ceramic capacitors, its right to use requires conductive paste described in 1 and ceramic green embryo sheet material and obtains.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-259864 | 2011-11-29 | ||
| JP2011259864A JP2013114890A (en) | 2011-11-29 | 2011-11-29 | Conductive paste and multilayer ceramic capacitor |
| JP2011259865A JP2013114891A (en) | 2011-11-29 | 2011-11-29 | Conductive paste and multilayer ceramic capacitor |
| JP2011-259865 | 2011-11-29 | ||
| PCT/JP2012/080994 WO2013081077A1 (en) | 2011-11-29 | 2012-11-29 | Conductive paste and multilayer ceramic capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103946926A true CN103946926A (en) | 2014-07-23 |
Family
ID=48535525
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280058409.8A Pending CN103946926A (en) | 2011-11-29 | 2012-11-29 | Conductive paste and multilayer ceramic capacitor |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR20140106548A (en) |
| CN (1) | CN103946926A (en) |
| TW (1) | TW201331956A (en) |
| WO (1) | WO2013081077A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107871543A (en) * | 2016-09-28 | 2018-04-03 | 株式会社则武 | Conductive paste |
| CN109313955A (en) * | 2016-04-28 | 2019-02-05 | 夏普株式会社 | The manufacturing method of conductive paste, electrode connecting structure and electrode connecting structure |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3121829B1 (en) | 2014-03-20 | 2020-09-16 | Sekisui Chemical Co., Ltd. | Electroconductive paste |
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| JP2004303748A (en) * | 2003-03-28 | 2004-10-28 | Matsushita Electric Ind Co Ltd | Conductive water-base ink for rotogravure printing, and method for manufacturing multilayer ceramic electronic component using it |
| WO2010109562A1 (en) * | 2009-03-27 | 2010-09-30 | 株式会社村田製作所 | Method of producing multilayer ceramic electronic component |
| CN101910214A (en) * | 2008-08-27 | 2010-12-08 | 可乐丽股份有限公司 | Vinyl alcohol system polymer and film containing same |
| CN102117671A (en) * | 2009-12-30 | 2011-07-06 | 三星电机株式会社 | Conductive paste composition and method of manufacturing multilayer ceramic capacitor using the same |
| CN102169755A (en) * | 2010-02-26 | 2011-08-31 | 住友金属矿山株式会社 | Conductive paste for internal electrode of laminated ceramic capacitor |
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|---|---|---|---|---|
| JPS5374588A (en) * | 1976-12-14 | 1978-07-03 | Mitsui Petrochem Ind Ltd | Copolymer, its production and use |
| JP4136542B2 (en) * | 2002-08-27 | 2008-08-20 | 富士フイルム株式会社 | Thermal recording material |
| WO2010113567A1 (en) * | 2009-03-31 | 2010-10-07 | 株式会社クラレ | Coating agent containing vinyl alcohol polymer |
-
2012
- 2012-11-29 CN CN201280058409.8A patent/CN103946926A/en active Pending
- 2012-11-29 TW TW101144636A patent/TW201331956A/en unknown
- 2012-11-29 KR KR1020147015591A patent/KR20140106548A/en not_active Application Discontinuation
- 2012-11-29 WO PCT/JP2012/080994 patent/WO2013081077A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004303748A (en) * | 2003-03-28 | 2004-10-28 | Matsushita Electric Ind Co Ltd | Conductive water-base ink for rotogravure printing, and method for manufacturing multilayer ceramic electronic component using it |
| CN101910214A (en) * | 2008-08-27 | 2010-12-08 | 可乐丽股份有限公司 | Vinyl alcohol system polymer and film containing same |
| WO2010109562A1 (en) * | 2009-03-27 | 2010-09-30 | 株式会社村田製作所 | Method of producing multilayer ceramic electronic component |
| CN102117671A (en) * | 2009-12-30 | 2011-07-06 | 三星电机株式会社 | Conductive paste composition and method of manufacturing multilayer ceramic capacitor using the same |
| CN102169755A (en) * | 2010-02-26 | 2011-08-31 | 住友金属矿山株式会社 | Conductive paste for internal electrode of laminated ceramic capacitor |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109313955A (en) * | 2016-04-28 | 2019-02-05 | 夏普株式会社 | The manufacturing method of conductive paste, electrode connecting structure and electrode connecting structure |
| CN109313955B (en) * | 2016-04-28 | 2020-06-09 | 夏普株式会社 | Conductive paste, electrode connection structure, and method for manufacturing electrode connection structure |
| CN107871543A (en) * | 2016-09-28 | 2018-04-03 | 株式会社则武 | Conductive paste |
| CN107871543B (en) * | 2016-09-28 | 2020-12-11 | 株式会社则武 | Conductive paste |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201331956A (en) | 2013-08-01 |
| KR20140106548A (en) | 2014-09-03 |
| WO2013081077A1 (en) | 2013-06-06 |
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