CN110506083A - Conductive paste - Google Patents
Conductive paste Download PDFInfo
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- CN110506083A CN110506083A CN201880022499.2A CN201880022499A CN110506083A CN 110506083 A CN110506083 A CN 110506083A CN 201880022499 A CN201880022499 A CN 201880022499A CN 110506083 A CN110506083 A CN 110506083A
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- Prior art keywords
- conductive paste
- powder
- mass
- dispersing agent
- conductive
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/10—Intaglio printing ; Gravure printing
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- C—CHEMISTRY; METALLURGY
- 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
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01G4/228—Terminals
- H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
-
- 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
Abstract
The present invention provides a kind of conductive paste, it is useful for using especially for multilayer ceramic capacitor internal electrode, with the low viscosity for being suitable for intaglio printing, after printing, manufacture after keeping when can inhibit re-uniting for conductive metal powder, be unlikely to deform and be not susceptible to separate.A kind of multilayer ceramic capacitor conductive paste for internal electrode agent, it contains conductive powder (A), organic resin (B), organic solvent (C), additive (D) and dielectric medium powder (E), organic resin (B) is only made of ethyl cellulose, organic solvent (C) is only made of terpineol, additive (D) is made of the composition containing unsaturated carboxylic acid class dispersing agent and oleyl amine class dispersing agent, the containing ratio of unsaturated carboxylic acid class dispersing agent in aforementioned additive (D) is 0.2 mass % or more and 1.2 mass % or less relative to conductive paste total amount, and the content of oleyl amine class dispersing agent is 0.3 mass % or more and 2.0 mass % or less.
Description
Technical field
The present invention relates to conductive pastes, more specifically, are related to multilayer ceramic capacitor conductive paste for internal electrode agent, into
One step is in particular to intaglio printing conductive paste.
Background technique
With the frivolous miniaturization of the electronic equipments such as mobile phone, digital equipment, for the multi-layer ceramics electricity as chip part
Container (Multi-Layer Ceramic Capacitor, hereinafter referred to as " MLCC ") also minimized, high capacity and height
Performance-based.The most effective means for realizing these are that interior electrode layer and dielectric layer is thinned to realize multiple stratification.
The MLCC is generally manufactured as follows.In order to form dielectric layer, first with barium titanate (BaTiO3) etc. dielectrics conduct
Main component is dried, thus makes after being dispersed in the dielectric in the organic resins binder such as polyvinyl butyral
Dielectric blank.It is printed by predetermined pattern using conductive powder as main component in gained blank and is dispersed in it containing having
Conductive paste obtained by the excipient of machine resinoid bond and solvent, dry removal solvent, forms as the dry of internal electrode
Dry film.Then, it pressurizes in the state of being laminated with multilayer and being formed with the dielectric blank of desciccator diaphragm as internal electrode,
It is crimped and is cut off after integration, in oxidizing atmosphere or not reactive atmosphere, in order to remove organic resin binder, with
500 DEG C of temperature below are heat-treated to carry out de- binder and then restoring in such a way that internal electrode does not aoxidize
With 1300 DEG C or so progress heating and calcinings in atmosphere, integrated sintering is carried out to internal electrode and dielectric.Then, to calcining chip
Both ends ground, make internal electrode expose after, its end face be coated with external electrode paste and calcine form external electrode
Afterwards, implement nickel plating etc. on the external electrode to make MLCC.
However, the temperature that dielectric layer starts sintering is 1200 DEG C or so in the calcination process, it is higher than the conductions such as nickel
Powder starts sintering/contraction temperature, therefore generates the faults of construction such as layering (splitting), crackle sometimes.Especially companion
With small-sized/high capacity, stacking number increases or the thickness of dielectric layer is thinned, and thus the generation of fault of construction becomes aobvious therewith
It writes.
Therefore, usually in internal electrode nickel paste, in order to until dielectric layer starts near sintering/contraction temperature
Until control sintering/contraction of conductive powder, add similar with the composition of dielectric layer with barium titanate series or strontium zirconate system
Deng perofskite type oxide make ceramic powders as main component.By the sintering row for controlling nickel by powder by these ceramic powders
For the mismatch of the sintering shrinkage behavior of interior electrode layer and dielectric layer can be reduced.In addition, if addition and dielectric layer
The similar ceramic powders of composition, then have the effect of reducing dielectric loss sometimes, it is due to dielectric layer that foregoing dielectric, which is lost,
Main component constitution element and conductive paste for internal electrode agent in the constitution element of dielectric medium powder that contains it is different and produce
Raw.
However, above-mentioned MLCC is mostly used in silk-screen printing with conductive paste for internal electrode agent all the time.However, due to
It is required that cost cutting, productivity improve, therefore print speed printing speed than silk-screen printing higher speed and expectable mentions large-duty intaglio plate
Printing attracts attention, and more needing can be in conductive paste used in intaglio printing.
Since the print speed printing speed of intaglio printing is faster than silk-screen printing, is printed, needed to adapt to its speed
The viscosity when printing of intaglio printing paste is set to be lower than the viscosity of silk-screen printing paste.On the other hand, if after printing, protected
Viscosity when pipe reduces, then paste is easy flowing, is easy to produce the different conductive powder of specific gravity and the electricity as sintering regulator
The separation of medium powder.In order to obtain sufficient characteristic in intaglio printing, need printing in printing for low viscosity and having
It is unlikely to deform after brush, the conductive paste for the viscosity that conductive powder will not be separated with dielectric medium powder in keeping.
Such as a kind of intaglio plate electrode ink is disclosed in patent document 1, which is characterized in that containing using nickel as main component
Base metal powder intaglio plate electrode ink in, relative to 100 parts by weight of metal powder, resin is 1 parts by weight or more and 15 weight
Part is hereinafter, organic solvent is 20 parts by weight or more and 150 parts by weight hereinafter, viscosity is 10 pools hereinafter, eliminating 10 μm or more
Condensate.
In addition, disclosing a kind of intaglio printing conductive paste in patent document 2, which is characterized in that it is to contain conduction
Powder (A), organic resin (B), organic solvent (C), additive (D) and dielectric medium powder (E) multilayer ceramic capacitor in
Portion's electrode conductive paste, organic resin (B) by the degree of polymerization be 10000 or more and 50000 polyvinyl butyrals below with
And weight average molecular weight is that 10000 or more and 100000 ethyl celluloses below are constituted, organic solvent (C) is by propyleneglycol monobutyl
The mixed solvent or propylene glycol monobutyl ether of ether or propylene glycol monobutyl ether and propylene glycol methyl ether acetate and the mixing of mineral spirits
Any one of solvent is constituted, and additive (D) is made of separation inhibitor and dispersing agent, as the separation inhibitor, by containing
The composition of the salt of polycarboxylic acid polymers or polybasic carboxylic acid is constituted.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 10-335167 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2012-174797 bulletin
Summary of the invention
Problems to be solved by the invention
For low viscosity and the separation of metal powder will not occur when technology described in Patent Document 1 can be formed in printing
The conductive paste of intaglio printing, but since metal powder can not be made without the dielectric medium powder as sintering regulator
Sintering it is synchronous with dielectric sintering opportunity, generate fault of construction sometimes.
In addition, technology described in Patent Document 2 in the conductive paste containing dielectric medium powder by using specific aggregation
It spends, the organic resin of the mixing class of weight average molecular weight, the organic solvent for mixing class, is suitable for the low viscous of intaglio printing to have
Degree, but the separation of metal powder occurs because taking care of for a long time sometimes.
The present invention makes in view of the above-mentioned problems of the prior art, its purpose is to provide a kind of conductive paste,
Be for being used especially for multilayer ceramic capacitor internal electrode it is useful, in printing with being suitable for the low of intaglio printing
Viscosity, after printing, manufacture after keeping when can inhibit re-uniting, being unlikely to deform for conductive metal powder, be not susceptible to separate.
The solution to the problem
Therefore, to achieve the goals above, be characterized in that based on intaglio printing conductive paste of the invention, for containing
There is the multi-layer ceramics electricity of conductive powder (A), organic resin (B), organic solvent (C), additive (D) and dielectric medium powder (E)
Container conductive paste for internal electrode agent, organic resin (B) are only made of ethyl cellulose, and organic solvent (C) is only by terpineol group
At additive (D) is made of the composition containing unsaturated carboxylic acid class dispersing agent and oleyl amine class dispersing agent, aforementioned additive (D)
In unsaturated carboxylic acid class dispersing agent containing ratio relative to conductive paste total amount be 0.2 mass % or more and 1.2 mass % with
Under and oleyl amine class dispersing agent content be 0.3 mass % or more and 2.0 mass % or less.
In addition, in intaglio printing conductive paste of the invention, it is preferred that the containing ratio of conductive powder (A) is opposite
In paste total amount be 40 mass % or more and 60 mass % or less.
In addition, in intaglio printing conductive paste of the invention, it is preferred that organic resin (B) is relative to electroconductive paste
The containing ratio of agent entirety is 1.5 mass % or more and 6 mass % or less.
In addition, in intaglio printing conductive paste of the invention, it is preferred that dielectric medium powder (E) is BaTiO3。
In addition, in intaglio printing conductive paste of the invention, it is preferred that the containing ratio phase of dielectric medium powder (E)
It is 2 mass % or more and 15 mass % or less for paste total amount.
In addition, in intaglio printing conductive paste of the invention, it is preferred that the shearing rate 10000s under room temperature-1When
Viscosity be 0.05Pas or more and 10Pas or less, shearing rate 10s-1When viscosity be 0.5Pas or more.
The effect of invention
According to the present invention, by with the organic solvent of specified amount being only made of terpineol and only by ethyl cellulose group
At organic resin unsaturated carboxylic acid class dispersing agent and specified amount containing specified amount together oleyl amine class dispersing agent, can be obtained
Following intaglio printing conductive paste, passes through shearing rate 10000s-1High speed shear when viscosity come confirm printing when it is viscous
Degree is low viscosity, passes through shearing rate 10s-1Low velocity shear when viscosity come after the printing that confirms, keeping when viscosity also have
The value that can maintain dispersity for a long time, can prevent the separation of conductive powder and dielectric medium powder, even if after long-term keeping
It uses, the variation that also can be used normally without viscosity occurs, print film, which will not occur, becomes inhomogenous, film flatness change
Difference.
Specific embodiment
Hereinafter, intaglio printing of the invention is described in detail with conductive paste.
Organic resin that intaglio printing of the invention is formed with conductive paste by conductive powder, only by ethyl cellulose, only
The organic solvent that is made of terpineol, the additive being made of unsaturated carboxylic acid class dispersing agent and oleyl amine class dispersing agent and electricity are situated between
Matter powder is formed.
Present inventor has performed a large amount of in-depth studies, as a result, it has been found that, as organic resin be used only ethyl cellulose,
It is used only in terpineol, conductive paste with excellent dispersibility as organic solvent, if as so far in order to make to lead
Electro-powder disperses in organic resin binder and the acids dispersing agent, the amine alkaline dispersing agent that add, respectively containing specified amount
Unsaturated carboxylic acid class dispersing agent and oleyl amine class dispersing agent, then form the shearing rate 10000s under room temperature-1When conductive paste it is viscous
Degree is the shearing rate 10s under 0.05Pas or more and 10Pas viscosity below, room temperature-1When the viscosity of conductive paste be
The viscosity of 0.5Pas or more, print film when being suitable for the high speed printing of intaglio printing form the shape with the printed article after printing
Any one of shape maintenance, and can prevent conductive powder from separating in a short time with dielectric medium powder.Hereinafter, to of the invention
Intaglio printing conductive paste and its constituent material are further described.
<conductive powder>
As conductive powder used in intaglio printing conductive paste of the invention, other than nickel by powder, copper powders
Silver powder, palladium powder etc. can also be used, it is preferable to use nickel by powder.
With the miniaturization of the electronic components such as MLCC, the conductors such as smaller and thin internal electrode are formed, it is therefore desirable to mention
The flatness of high dry coating and dry film density.Therefore, the partial size of conductive powder be preferably 0.05 μm or more and 0.5 μm with
Under.
If the partial size of conductive powder is less than 0.05 μm, the specific surface area of particle becomes excessive, thus conductive powder
Surface-active excessively improves, and not only can generate adverse effect to drying, de- binder characteristic, but also be difficult to obtain appropriate viscous
Characteristic is spent, rotten worry occurs in the long-term preservation of conductive paste for generation, therefore not preferably.
In addition, if partial size is more than 0.5 μm, then film forming when carrying out thin layer to the coated film of paste is deteriorated, it is difficult to
The flatness of capacitor as defined in obtaining or desciccator diaphragm becomes inadequate, and the filling of conductive powder becomes inadequate, and is unable to ensure
Desired dry film density, it is thus not preferred therefore, it is difficult to form sufficiently small and thin uniform internal electrode.Conductive powder
Preferred partial size be 0.1 μm or more and 0.4 μm or less.
It should be noted that in the present invention, the partial size of conductive powder is in the case where no special declaration for according to base
In the partial size that the specific surface area value that BET method obtains calculates.Its calculating formula is shown in numerical expression 1.
(numerical expression 1)
Partial size=6/ (SA1 × ρ 1) of conductive powder
SA1: the specific surface area value (BET method) of conductive powder
ρ 1: the real density (example: nickel 8.9) of conductive powder
Conductive powder is preferably 40 mass % or more and 60 mass % or less relative to the content of conductive paste total amount.If
The content of conductive powder is less than 40%, then calcined thickness of electrode becomes too thin, or is unable to fully to form electrode film or resistance
Value rises or loses electric conductivity, can not obtain the capacitor of target sometimes.On the other hand, if the content of conductive powder is more than
60%, then it is difficult to carry out the thin layer of electrode film sometimes.
<organic resin>
Ethyl cellulose is used only in organic resin.Ethyl cellulose be all the time dissolubility in a solvent, printing,
Combustion decomposition etc. is excellent, is suitable for the organic resin constituent of conductive paste for internal electrode agent of MLCC etc..It is led existing
Other various organic resins are used in electric paste, and in intaglio printing conductive paste of the invention, it is wanted in its characteristic
Unbiased poorly even print in high speed printing is sought, ethyl cellulose is used only by organic resin, can be subtracted as far as possible
Deviation when few high speed printing.
It relative to the content of conductive paste total amount is preferably 1.5 mass % or more using only the organic resin of ethyl cellulose
And 6 below mass %.If it is less than 1.5 mass %, then the strength reduction of desciccator diaphragm sometimes, or the conduction formed by conductive paste
The adaptation of film and dielectric piece is deteriorated or conductive film is easy to remove from dielectric piece.If the content of organic resin increases,
De- binder can be deteriorated, and the present inventor's repetition test as a result, by being made by conductive powder, only by ethyl cellulose group
At organic resin, only be made of terpineol organic solvent, be made of unsaturated carboxylic acid class dispersing agent and oleyl amine class dispersing agent
Additive and dielectric medium powder formed conductive paste, even if export organic resin content be more than 5 mass %, unsticking knot
The conductive paste that agent will not be deteriorated.But, if the content of organic resin is more than 6 mass %, sometimes because of organic tree
The content of rouge, which increases, causes de- binder to be deteriorated.
<organic solvent>
Terpineol is used only in organic solvent.Terpineol is also with ethyl cellulose again it is what is used is organic molten all the time
Agent, it is good with the compatibility of conductive metal powder, conductive paste can be manufactured with the short time, and have and be easy to make conductive metal powder
Effect last, dielectric medium powder is evenly dispersed.Intaglio printing of the invention needs dispersibility than previous superior electroconductive paste
Terpineol must be used only in agent, organic solvent, and thus, it is possible to the excellent conductive paste of dispersibility is made.
Adjusting contains using only the content of the organic solvent of terpineol, when so that the viscosity of conductive paste being suitable for printing
Intaglio printing, and formation is able to maintain that the long-term dispersity when shape after printing, the keeping after manufacture and can prevent
The isolated viscosity of conductive powder and dielectric medium powder.
It is suitable for the shearing rate 10000s of the viscosity of the conductive paste of the high speed printing of intaglio printing at normal temperature-1Shi Wei
0.05Pas or more and 10Pas or less.
If the shearing rate 10000s under room temperature-1When conductive paste viscosity be less than 0.05Pas, then viscosity is too low,
The problems such as bleeding can be generated in high speed printing.On the other hand, if shearing rate 10000s under room temperature-1When conductive paste
The problems such as viscosity is more than 10Pas, then viscosity is excessively high, and the style of calligraphy characterized by hollow strokes can be generated in high speed printing.
Furthermore it is possible to maintain the long-term dispersity when shape after printing, keeping after manufacture and conduction can be prevented
The shearing rate 10s of the viscosity for the conductive paste that powder is separated with dielectric medium powder at normal temperature-1When be 0.5Pas or more.
If the shearing rate 10s under room temperature-1When conductive paste viscosity be less than 0.5Pas, then after being unable to maintain that printing
Shape, keeping after manufacture when long-term dispersity, conductive powder is easy to happen with dielectric medium powder and separates.
<additive>
Additive uses the composition containing unsaturated carboxylic acid class dispersing agent and oleyl amine class dispersing agent.Intaglio process of the invention
Brush conductive paste, which needs to be made due to high speed printing, reduces the excellent conductive paste of various deviations, dispersibility to the greatest extent, only leans on
It is insufficient by above-mentioned ethyl cellulose and the raising of terpineol bring dispersibility.However, the inventors discovered that, if conduct
The composition containing unsaturated carboxylic acid class dispersing agent and oleyl amine class dispersing agent is added in additive, then can further increase dispersion
Property, excellent intaglio printing conductive paste is made.
The content of unsaturated carboxylic acid class dispersing agent is 0.2 mass % or more and 1.2 mass % relative to conductive paste total amount
Below and the content of oleyl amine class dispersing agent is 0.3 mass % or more and 2.0 mass % or less.It is less than above-mentioned model in each dispersing agent
In the case where enclosing, the range of viscosities of long-term dispersity when deviateing the shape after being suitable for maintaining printing, keeping after manufacture
(the shearing rate 10s under room temperature-1When range of viscosities:
0.5Pas or more), it is unable to give full play dispersion effect, it may occur that the separation of conductive powder and dielectric powder is existing
As.In addition, the additive that can be played dispersion effect, but be present in excess can make in the case where each dispersing agent is more than above range
The tack of conductive paste deviates the range of viscosities for being suitable for high speed printing, the shearing under room temperature as intaglio printing purposes
Rate 10000s-1When viscosity can be less than 0.05Pas.
It should be noted that as additive, other than above-mentioned dispersing agent, conductive paste of the invention can also be can
Maintain the shearing rate 10000s under above-mentioned room temperature-1When viscosity characteristics and shearing rate 10s-1When viscosity characteristics in the range of plus
Enter to separate inhibitor etc..
<dielectric medium powder>
The BaTiO used in common conductive paste can be used in dielectric medium powder3Deng powder.In addition it is also possible to
It is containing the BaTiO3Oxide as main component and containing Mn, Cr, Si, Ca, Ba, Mg, V, W, Ta, Nb and rare earth element
Deng the powder as accessory ingredient, it is also possible to BaTiO3Ba atom, Ti atomic substitutions at other atoms, Sn, Pb, Zr etc. this
The powder of kind perofskite type oxide strong dielectric.In turn, if selection forms the powder i.e. ZnO (oxidation of the blank of MLCC
Zinc), ferrite, PZT (lead zirconate titanate), BaO (barium monoxide), Al2O3(aluminium oxide), Bi2O3(bismuth oxide), R2O3(rare earth oxygen
Compound: R=rare earth element), TiO2(titanium oxide), Nd2O3Oxides such as (neodymia) can then reduce dielectric loss sometimes, because
This is more preferably.
The partial size of dielectric medium powder is preferably 0.01 μm or more and 0.5 μm of range below.If the grain of dielectric medium powder
Diameter is less than 0.01 μm, then the specific surface area of particle excessively increases, thus the surface-active of dielectric medium powder excessively improves, and not only can
Are generated by adverse effect, but also is difficult to obtain viscosity characteristics appropriate for drying, de- binder characteristic, in the long-term of conductive paste
It is in preservation it some times happens that rotten, therefore not preferably.
In addition, if the partial size of dielectric medium powder is more than 0.5 μm, then film forming when carrying out thin layer to the coated film of paste
Property be deteriorated, the filling of dielectric medium powder becomes inadequate, and in desciccator diaphragm formation, flatness is become inadequate, and is unable to ensure institute's phase
The drying film density of prestige, it is difficult to form sufficiently small and thin uniform internal electrode, defined capacitor can not be obtained sometimes, therefore
Not preferably.The preferred partial size of dielectric medium powder is 0.01 μm or more and 0.3 μm or less.
The content of dielectric medium powder in conductive paste of the invention is preferably 2 mass % or more and 15 mass % or less.
When the content of dielectric medium powder is less than 2 mass %, it is unable to fully inhibit the contraction of electrode sometimes, on the other hand, if dielectric
The content of powder is more than 15 mass %, then electrode can become blocked up sometimes, or causes electrode to disconnect by tenor reduction.
<conductive paste>
Conductive paste of the invention prepares organic excipients by the way that organic resin is dissolved in organic solvent first, then adds
Add conductive powder, the dispersing agent as additive, dielectric medium powder and is dispersed in it in organic excipients to obtain.
Organic excipients pass through in being heated up to 50 DEG C or more the and 60 DEG C organic solvents below being only made of terpineol
The organic resin being only made of ethyl cellulose is added and is mixed to obtain.
Then, weigh the conductive powder of specified amount, dielectric medium powder, made organic excipients, by containing unsaturation
The additive that the composition of carboxylic acids dispersing agent and oleyl amine class dispersing agent is constituted is ground after putting into mixer and stirring by three rollers
Grinding machine makes the evenly dispersed mixing in organic excipients of conductive powder, additive and dielectric medium powder, obtains conductive paste.
The shearing rate 10000s of conductive paste of the invention at normal temperature-1When viscosity be 0.05Pas or more and
10Pas or less.Shearing rate 10000s under room temperature-1When conductive paste viscosity be less than 0.05Pas when, be unable to maintain that with
Printing width when high speed printing conductive paste occurs bleeding, is unable to ensure required film thickness after printing.On the other hand, such as
Shearing rate 10000s under fruit room temperature-1When the viscosity of conductive paste be more than 10Pas, then be unable to give full play to be carried out at high speed
Tracing ability when printing, it may occur that following rough sledding: conductive paste is unable to fully the roller of filling intaglio printing and is printing
Brush portion generates shortcoming, or can not all transfer conductive paste from the recess portion of roller in printing and pollute printed article or generate dense
Light deviation etc..It should be noted that if shearing rate 10000s under room temperature-1When conductive paste viscosity be 0.05Pas
Above and 0.3Pas is hereinafter, then viscosity is sufficiently low, can sufficiently cope with the printing of high speed, therefore preferably.
In addition, the shearing rate 10s of conductive paste of the invention at normal temperature-1When viscosity be 0.5Pas or more.Room temperature
Under shearing rate 10s-1When conductive paste viscosity be less than 0.5Pas when, print conductive paste after such as wiring print
The shape maintenance of object becomes difficult, and can not obtain required wiring width/thickness.It should be noted that if cutting under room temperature
Cut rate 10s-1When conductive paste viscosity be 1Pas or more, then will not occur substantially as printed article formed wiring shape
The deformation of shape, therefore preferably.
In addition, the separation of conductive powder and dielectric medium powder etc. does not occur after standing 30 days for conductive paste of the invention.
If conductive paste separates, separate and the conductive powder etc. assembled can agglomerate, only by being slightly kneaded before printing
It is unable to improve cohesion, bad dispersibility, the shape of print film, the flatness for printing film surface are deteriorated.
Embodiment
Hereinafter, based on more specific embodiment, the present invention is described in detail, and the present invention is not completely by the limit of embodiment
It is fixed.
(1) composition of conductive paste
As conductive powder (A), contain 0.3 μm of partial size of spherical Ni powder.Organic excipients contain will be as bonding
The ethyl cellulose of the organic resin (B) of agent and the terpineol as organic solvent (C) are heated to 60 DEG C and mixed substance.Make
For additive (D), contain acids dispersing agent and bases dispersing agent by type shown in table 1 and formula mixing.As dielectric powder
Last (E), the spherical barium titanate containing partial size 70nm.The composition of the conductive paste of each sample is shown in table 1.
It should be noted that the content of the organic resin (B) in organic excipients is with 1/10 amount of conductive powder (A)
Basis, and in order to confirm the effect of organic resin (B), about sample 22~25, the content of conductive powder (A) is made to keep certain,
Only make the changes of contents of organic resin (B).In addition, the content of organic solvent (C) relative to 100 mass % of conductive paste be containing
The surplus when other materials of specified amount.
(2) evaluation of separation property
The conductive paste of the sample is added in the evaluation of separation property about conductive paste in the container of 100ml respectively
100g, 25 DEG C at a temperature of place 30 days, with visual confirmation, whether there is or not the separation of conductive powder and dielectric medium powder.By electroconductive paste
The dielectric medium powder (E) that contains in agent occur separation, be able to confirm that the state of white supernatant fraction be determined as ×, will not deposit
It is determined as zero in white supernatant fraction, the isolated state for failing to confirm dielectric medium powder (E).Evaluation result is shown in table 1.
(3) measurement of viscosity
The measurement of the viscosity of conductive paste is carried out using rheometer.By shearing rate 10000s-1High speed shear when viscosity
Situation for 0.05Pas or more and 0.3Pas or less is determined as zero, will be more than 0.3Pas and be 10Pas feelings below
The case where condition is determined as △, will be more than 10Pas be determined as ×.In addition, by shearing rate 10s-1Low velocity shear when viscosity be
The situation of 1Pas or more is determined as zero, will be determined as △ more than and less than the case where 1Pas for 0.5Pas, will be less than
The case where 0.5Pas is determined as ×.Respective measurement result is shown in table 1.
[table 1]
By the result of above-mentioned table 1 it is found that within the scope of the invention containing conductive powder (A), dielectric medium powder (E) and
As the unsaturated carboxylic acid class dispersing agent of additive (D), oleyl amine class dispersing agent content within the scope of the invention and in this hair
Only contain ethyl cellulose in bright range and contains sample 3 of the terpineol as organic solvent (C) as organic resin (B), only
Even if~6,10~12,18~29 place 30 days in the state of being packed into container, conductive powder (A) and dielectric medium powder (E)
It does not separate, and there is the viscosity for being suitable for intaglio printing.
In these samples, contain conductive powder (A), organic resin (B), dielectric in preferred scope of the invention respectively
When the sample 3~6,10~12,19,20,23,24,27,28 of powder (E) has the high speed printing for being very suitable for intaglio printing
Print film formed and printing after printed article shape maintain viscosity.
In addition, the content about conductive powder (A) is lower than sample 18, the organic resin of the lower limit of preferred scope of the invention
(B) content is excellent lower than of the invention lower than the content of the sample 22 of lower limit of preferred scope of the invention, dielectric medium powder (E)
The sample 26 of the lower limit of range is selected, although for maintaining the viscosity when low velocity shear of printed article shape after the printing of intaglio printing
It is slightly lower compared with sample 3~6,10~12,19~21,23~25,27~29, but there is print film when being suitable for high speed printing
The viscosity of formation.
In addition, about conductive powder (A), organic resin (B) respective content be more than preferred scope of the invention the upper limit
Sample 21, organic resin (B) content be more than the sample 25 of the upper limit of preferred scope of the invention, dielectric medium powder (E)
Content is more than the sample 29 of the upper limit of preferred scope of the invention, although being used to form print film when the high speed printing of intaglio printing
High speed shear when viscosity it is slightly higher compared with sample 3~6,10~12,18~20,22~24,26~28, but have be suitable for
The viscosity that the shape of printed article after printing maintains.
In contrast, about the unsaturated carboxylic acid class dispersing agent as additive (D), at least one in oleyl amine class dispersing agent
The content of side lower than the scope of the present invention or without unsaturated carboxylic acid class dispersing agent, the sample 1 of oleyl amine class dispersing agent, 2,8,
9, conductive powder (A) is separated with dielectric medium powder (E) in keeping in 30 days.In addition, about as additive (D)
The content of unsaturated carboxylic acid class dispersing agent is more than the sample 7 of upper limit value (1.2 mass %) of the invention, as additive (D)
The content of oleyl amine class dispersing agent is more than the sample 13 of upper limit value (2.0 mass %) of the invention, although conductive powder (A) and electricity are situated between
Matter powder (E) does not separate, but shearing rate 10000s-1High speed shear when viscosity it is excessively high, in the high print duplication of intaglio printing
The style of calligraphy characterized by hollow strokes has occurred when brush.In addition, replacing unsaturated carboxylic acid class dispersing agent, in oleyl amine class dispersing agent about as additive (D)
At least any one party contain not unsaturated carboxylic acid class dispersing agent, oleyl amine class dispersing agent substance sample 14~17, be packed into
When placing 30 days in the state of container, fail the separation for inhibiting conductive powder (A) and dielectric medium powder (E).
Industrial availability
To sum up, conductive paste of the invention long-term preservability while having the low viscosity for being suitable for intaglio printing is excellent
It is different, it is particularly possible to be suitably used as the multilayer of the chip part of the electronic equipment minimized as propulsions such as mobile phone, digital equipments
The material of ceramic capacitor internal electrode use etc..
Claims (6)
1. a kind of intaglio printing conductive paste, which is characterized in that it is to contain conductive powder (A), organic resin (B), organic
The multilayer ceramic capacitor conductive paste for internal electrode agent of solvent (C), additive (D) and dielectric medium powder (E), organic resin
(B) it is only made of ethyl cellulose, organic solvent (C) is only made of terpineol, and additive (D) is by containing unsaturated carboxylic acid class point
The composition of powder and oleyl amine class dispersing agent is constituted, and the content of the unsaturated carboxylic acid class dispersing agent in the additive (D) is opposite
In conductive paste total amount be 0.2 mass % or more and the content of 1.2 mass % or less and oleyl amine class dispersing agent is 0.3 mass %
Above and 2.0 mass % or less.
2. intaglio printing conductive paste according to claim 1, which is characterized in that the content of the conductive powder (A)
It is 40 mass % or more and 60 mass % or less relative to paste total amount.
3. intaglio printing conductive paste according to claim 1 or 2, which is characterized in that the organic resin (B) is opposite
In conductive paste entirety content be 1.5 mass % or more and 6 mass % or less.
4. intaglio printing conductive paste according to any one of claims 1 to 4, which is characterized in that the dielectric
Powder (E) is BaTiO3。
5. intaglio printing conductive paste according to any one of claims 1 to 5, which is characterized in that the dielectric
The content of powder (E) is 2 mass % or more and 15 mass % or less relative to paste total amount.
6. intaglio printing conductive paste described according to claim 1~any one of 6, which is characterized in that cutting under room temperature
Cut rate 10000s-1When viscosity be 0.05Pas or more and 10Pas or less, shearing rate 10s-1When viscosity be 0.5Pas
More than.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-065321 | 2017-03-29 | ||
| JP2017065321A JP6939015B2 (en) | 2017-03-29 | 2017-03-29 | Conductive paste for gravure printing for internal electrodes of multilayer ceramic capacitors |
| PCT/JP2018/006313 WO2018180048A1 (en) | 2017-03-29 | 2018-02-21 | Electroconductive paste |
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| CN110506083A true CN110506083A (en) | 2019-11-26 |
| CN110506083B CN110506083B (en) | 2022-04-05 |
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| CN201880022499.2A Active CN110506083B (en) | 2017-03-29 | 2018-02-21 | Conductive paste |
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| JP (1) | JP6939015B2 (en) |
| KR (1) | KR102501339B1 (en) |
| CN (1) | CN110506083B (en) |
| TW (1) | TWI762596B (en) |
| WO (1) | WO2018180048A1 (en) |
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| CN112955980B (en) * | 2018-10-31 | 2023-01-10 | 昭荣化学工业株式会社 | Ni paste and multilayer ceramic capacitor |
| JP7405098B2 (en) * | 2018-12-25 | 2023-12-26 | 住友金属鉱山株式会社 | Conductive paste, electronic components, and multilayer ceramic capacitors |
| WO2021177420A1 (en) * | 2020-03-04 | 2021-09-10 | 住友金属鉱山株式会社 | Electroconductive paste, electronic component, and laminated ceramic capacitor |
| CN116745872A (en) | 2021-02-02 | 2023-09-12 | 株式会社村田制作所 | Paste containing inorganic particles, film containing inorganic particles, and laminate |
| KR20230125269A (en) | 2021-02-02 | 2023-08-29 | 가부시키가이샤 무라타 세이사쿠쇼 | Complex structure, multilayer ceramic electronic component precursor, method for manufacturing multilayer ceramic electronic component precursor, and method for manufacturing multilayer ceramic electronic component |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003187638A (en) * | 2001-12-20 | 2003-07-04 | Murata Mfg Co Ltd | Conductive paste for gravure printing and its manufacturing method as well as laminated ceramic electronic component |
| JP2003242835A (en) * | 2001-12-13 | 2003-08-29 | Murata Mfg Co Ltd | Conductive paste for photogravure printing and its producing method as well as laminated ceramic electronic component |
| JP2004182951A (en) * | 2002-12-06 | 2004-07-02 | Murata Mfg Co Ltd | Conductive ink for gravure printing, and laminated ceramic electronic component |
| JP2012046779A (en) * | 2010-08-25 | 2012-03-08 | Toyota Central R&D Labs Inc | Surface-coated metal nanoparticle, method for producing the same, and metal nanoparticle paste containing the same |
| JP2012174797A (en) * | 2011-02-18 | 2012-09-10 | Sumitomo Metal Mining Co Ltd | Conductive paste for photogravure used for multilayer ceramic capacitor internal electrode |
| CN103137243A (en) * | 2011-11-22 | 2013-06-05 | 旭硝子株式会社 | Conductive paste, and preparing method of conductive paste |
| US20130139873A1 (en) * | 2011-12-02 | 2013-06-06 | Young Wook Choi | Paste composition for a solar cell electrode, electrode fabricated using the same, and solar cell including the electrode |
| JP2013151753A (en) * | 2013-03-04 | 2013-08-08 | Dowa Electronics Materials Co Ltd | Silver micropowder excellent in affinity for polar medium, and silver ink |
| CN104769044A (en) * | 2012-11-06 | 2015-07-08 | 株式会社则武 | Conductive paste composition |
| WO2016204105A1 (en) * | 2015-06-15 | 2016-12-22 | 株式会社大阪ソーダ | Composition for manufacturing metal nanoparticles |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3180718B2 (en) | 1997-06-02 | 2001-06-25 | 松下電器産業株式会社 | Gravure electrode ink, method of manufacturing the same, and method of manufacturing multilayer ceramic electronic component |
| JP6613551B2 (en) * | 2014-07-31 | 2019-12-04 | 住友金属鉱山株式会社 | Multilayer ceramic capacitor internal electrode paste and multilayer ceramic capacitor |
-
2017
- 2017-03-29 JP JP2017065321A patent/JP6939015B2/en active Active
-
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- 2018-02-21 CN CN201880022499.2A patent/CN110506083B/en active Active
- 2018-02-21 KR KR1020197031008A patent/KR102501339B1/en active IP Right Grant
- 2018-02-21 WO PCT/JP2018/006313 patent/WO2018180048A1/en active Application Filing
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Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003242835A (en) * | 2001-12-13 | 2003-08-29 | Murata Mfg Co Ltd | Conductive paste for photogravure printing and its producing method as well as laminated ceramic electronic component |
| JP2003187638A (en) * | 2001-12-20 | 2003-07-04 | Murata Mfg Co Ltd | Conductive paste for gravure printing and its manufacturing method as well as laminated ceramic electronic component |
| JP2004182951A (en) * | 2002-12-06 | 2004-07-02 | Murata Mfg Co Ltd | Conductive ink for gravure printing, and laminated ceramic electronic component |
| JP2012046779A (en) * | 2010-08-25 | 2012-03-08 | Toyota Central R&D Labs Inc | Surface-coated metal nanoparticle, method for producing the same, and metal nanoparticle paste containing the same |
| JP2012174797A (en) * | 2011-02-18 | 2012-09-10 | Sumitomo Metal Mining Co Ltd | Conductive paste for photogravure used for multilayer ceramic capacitor internal electrode |
| CN103137243A (en) * | 2011-11-22 | 2013-06-05 | 旭硝子株式会社 | Conductive paste, and preparing method of conductive paste |
| US20130139873A1 (en) * | 2011-12-02 | 2013-06-06 | Young Wook Choi | Paste composition for a solar cell electrode, electrode fabricated using the same, and solar cell including the electrode |
| CN104769044A (en) * | 2012-11-06 | 2015-07-08 | 株式会社则武 | Conductive paste composition |
| JP2013151753A (en) * | 2013-03-04 | 2013-08-08 | Dowa Electronics Materials Co Ltd | Silver micropowder excellent in affinity for polar medium, and silver ink |
| WO2016204105A1 (en) * | 2015-06-15 | 2016-12-22 | 株式会社大阪ソーダ | Composition for manufacturing metal nanoparticles |
Non-Patent Citations (1)
| Title |
|---|
| 韩长日等: "《电子与信息化学品制造技术》", 31 October 2001, 科学技术文献出版社 * |
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| JP2018168238A (en) | 2018-11-01 |
| TWI762596B (en) | 2022-05-01 |
| KR20190129980A (en) | 2019-11-20 |
| KR102501339B1 (en) | 2023-02-17 |
| CN110506083B (en) | 2022-04-05 |
| JP6939015B2 (en) | 2021-09-22 |
| WO2018180048A1 (en) | 2018-10-04 |
| TW201840756A (en) | 2018-11-16 |
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