CN106653146A - Electrically conductive paste and method for forming conductive film - Google Patents
Electrically conductive paste and method for forming conductive film Download PDFInfo
- Publication number
- CN106653146A CN106653146A CN201610959190.9A CN201610959190A CN106653146A CN 106653146 A CN106653146 A CN 106653146A CN 201610959190 A CN201610959190 A CN 201610959190A CN 106653146 A CN106653146 A CN 106653146A
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- electroconductive paste
- face
- contact angle
- viscosity
- electroconductive
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000012360 testing method Methods 0.000 claims abstract description 24
- 238000012546 transfer Methods 0.000 claims abstract description 12
- 238000007639 printing Methods 0.000 claims description 68
- 238000007747 plating Methods 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 11
- 238000011156 evaluation Methods 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 2
- 239000004020 conductor Substances 0.000 abstract description 14
- 238000007646 gravure printing Methods 0.000 abstract description 4
- 229910052573 porcelain Inorganic materials 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 239000002904 solvent Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 230000003746 surface roughness Effects 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 8
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 7
- 229910002113 barium titanate Inorganic materials 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- UODXCYZDMHPIJE-UHFFFAOYSA-N menthanol Chemical group CC1CCC(C(C)(C)O)CC1 UODXCYZDMHPIJE-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WWJLCYHYLZZXBE-UHFFFAOYSA-N 5-chloro-1,3-dihydroindol-2-one Chemical compound ClC1=CC=C2NC(=O)CC2=C1 WWJLCYHYLZZXBE-UHFFFAOYSA-N 0.000 description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 3
- KGEKLUUHTZCSIP-UHFFFAOYSA-N Isobornyl acetate Natural products C1CC2(C)C(OC(=O)C)CC1C2(C)C KGEKLUUHTZCSIP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000001940 [(1R,4S,6R)-1,7,7-trimethyl-6-bicyclo[2.2.1]heptanyl] acetate Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 3
- 150000003505 terpenes Chemical class 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- -1 phenolic aldehyde Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 238000003854 Surface Print Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 210000003764 chromatophore Anatomy 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HJUFTIJOISQSKQ-UHFFFAOYSA-N fenoxycarb Chemical compound C1=CC(OCCNC(=O)OCC)=CC=C1OC1=CC=CC=C1 HJUFTIJOISQSKQ-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- ZWMHQTRHIXWILP-UHFFFAOYSA-N methyl propanoate 2-methylpropanoic acid Chemical compound C(C(C)C)(=O)O.COC(CC)=O ZWMHQTRHIXWILP-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G4/0085—Fried electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/005—Electrodes
- H01G4/012—Form of non-self-supporting electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Conductive Materials (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Ceramic Capacitors (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The present invention provides a conductive paste for gravure printing and a method for forming a conductor film capable of forming a continuous thin conductor film capable of forming an internal electrode suitable for a small high-capacity MLCC. The contact angle y degree of the test surface satisfies y<17.6x + 19.1, where x <=3.0, y <40, since the viscosity x Pa*s and the test surface y degree with respect to the arithmetic mean roughness Ra of 0.010 [mu]m or less , The conductive paste is rapidly and uniformly transferred from the gravure printing plate when gravure printing is carried out using the conductive paste on the green porcelain tape. As a result, since the conductive paste surface becomes a smooth surface from the time of the transfer, it is easy to maintain the film thickness continuously. Therefore, it is possible to form a continuous film thickness of a conductor film suitable for the internal electrode of the small-sized high-capacity MLCC.
Description
Technical field
The present invention relates to the electroconductive paste of photogravure (gravure printing) can be suitably used for and using photograph
The forming method of the electrically conductive film of phase woodburytype.
Background technology
For example, when manufacture schematically shows in FIG the laminated ceramic capacitor (MLCC) 10 of cross-sectional configuration, pass through
Contain in the surface printing coating of the green band (ceramic green sheet) not burnt till for being used to constitute its dielectric layer 12
Metal with heat resistance as conductive component electroconductive paste, stacking and implement to burn till behind the surface of pressure welding multiple green bands
Process, so as to generate the conductor layer 14 that internal electrode is made up of electroconductive paste while dielectric layer 12 are generated by green band.Separately
Outward, 16 it is in FIG outer electrode for being powered to the internal electrode (conductor layer 14).In the printing of such internal electrode
A kind of gravure processes as intaglio printing are suitable for during formation (for example, referring to patent document 1).Photogravure
Method is that electroconductive paste is filled in the recess for be arranged at printing plate and the printing plate is led so as to transfer from the printing plate by printed face
The continuous printing method of electricity paste, has the advantages that print speed printing speed is fast.
In the printing of the electroconductive paste of the internal electrode formation for MLCC etc., silk screen print method was generally used in the past, but
There is a problem of that producing the dimensional accuracy caused by plate elongation declines in silk screen print method.Particularly, in 0603 size (outward
Shape size 0.6mm × 0.3mm × 0.3mm), microminiature MLCC such as 0402 size (appearance and size 0.4mm × 0.2mm × 0.2mm)
In, it is more difficult to guarantee the dimensional accuracy of print film.In contrast, according to aforementioned gravure processes, plate elongation is not produced,
So requiring that the MLCC of high accuracy prints is used as being suitable for.
Prior art literature
Patent document
【Patent document 1】Japanese Unexamined Patent Publication 10-199331 publication
【Patent document 2】Japanese Unexamined Patent Publication 2003-249121 publications
【Patent document 3】Japanese Unexamined Patent Publication 2005-126505 publications
【Patent document 4】Japanese Unexamined Patent Publication 06-142579 publication
But, in miniaturized high capacity MLCC such as foregoing 0603 size and 0402 size, it is desirable to by internal electrode
Thickness be set to less than 1 μm.It is that continuous film is obtained with such film thickness, needs to form the smooth print film in surface.
Print speed printing speed is fast and in the short gravure processes of pitch time, from being printed to drying is entered in printing, drying process
The time of operation shortens, so the print film levelling time also shortens.Therefore, the print film excellent to obtain surface smoothness,
It is preferred that, the smooth print film in surface is thus formed after just transfer by equably transferring electroconductive paste from printing plate.
Since in the past, the motion of the improvement of the various electroconductive pastes for gravure processes has been carried out.For example, it is to incite somebody to action
When gravure processes are applied to MLCC, (band impacts (sheet- for the swelling of the green band that suppression solvent causes and re-dissolved
Attack)), it is proposed that using the scheme (for example, referring to the patent document 1) of oil series solvent or alcohol series solvent.In addition,
When suppressing band impact, it is considered to print the rate of drying of film, it is proposed that using 1-P- Meng's alkane, the scheme (example of P- Meng's alkane equal solvents
Such as, with reference to patent document 2).
In addition, it is proposed that following proposal：When the laminated ceramic parts such as MLCC are manufactured, on green band electroconductive paste is printed
Afterwards, the paste with ceramic raw material as principal component is printed in into the position beyond conductive pattern forming portion and makes the surface of green band flat
In the case of change, by making paste in addition to ethyl cellulose resin also containing number average molecular weight for 300～5,000 terpenes
(terpene) resin, is consequently formed the excellent print film of flexibility (for example, referring to patent document 3).In photogravure
In, using low viscosity and inhibit thixotropic electroconductive paste to make it easy to from printing plate be transferred to printed body, but by so
Electroconductive paste generate print film, if ceramics paste printing when contact with printing plate if easily generation conductive pattern breakage and fall
Fall.Therefore, the present invention will suppress the breakage and drop by improving the flexibility of print film.
In addition, for the purpose of to improve paste transferability by the change of printing plate side, it is proposed that with the contact angle relative to water
For the printing plate in more than 50 ° of cover layer capping unit groove (for example, referring to patent document 4).According to the printing plate, by with perfluor
The capping unit grooves such as alkane (Perfluoroalkoxy) resin, thus make to increase to more than 50 ° with the contact angle of water, so that
Wetability between paste and printing plate declines, and transferability is improved.
So, from the viewpoint grade for suppressing with impact and improving printing film-strength, it is proposed that various for heliogravure
The improvement of the electroconductive paste of print process and the improvement of printing plate.However, they cannot be used for forming continuous with less than 1 μm of film thickness
Film.In addition, according to supplementary test result, it is known that：Even if modulation electroconductive paste causes to become same contact angle, but if conductive
Property powder the different then transferability of the component of species and particle diameter etc. or chromatophore (vehicle) etc. it is different, also not necessarily can obtain
To good result.
The content of the invention
The present invention is carried out with above-mentioned situation as background, and its object is to offer can form suitable for small-sized Gao Rong
The electroconductive paste and the forming method of the electrically conductive film of the photogravure of the continuous thin conductor film of the internal electrode of amount MLCC.
In order to reach the purpose, the 1st invention is that the photogravure containing electroconductive powder, binding agent and organic solvent is used
Electroconductive paste, wherein：Viscosity when by 25 DEG C of down cut 40 1/s of speed be set to x Pas, will be flat to counting at 25 DEG C
Roughness Ra be 0.010 μm of level below test face drip 10 μ L when contact angle when being set to y °, x, y meet following formula
(1)。
Y ＜ 17.6x+19.1, wherein, x≤3.0, y ＜ 40 (1)
In addition, the purport of the 2nd invention for reaching the purpose is, a kind of forming method of electrically conductive film, including：Adjust
The operation of electroconductive paste of the system containing electroconductive powder, binding agent and organic solvent；The electroconductive paste is filled in into photogravure print
The recess of version and the printing process transferred to printed face；With by the print film to being formed carry out enforcement burn till process so as to
The firing process of electrically conductive film is generated in the printed face；In modulating the operation of the electroconductive paste, the electroconductive paste is modulated so that 25
Viscosity x Pas during DEG C down cut 40 1/s of speed and to the outermost side face identical with the photogravure printing plate
Material be set to be dripped with the state on the same surface of the outermost side face and the test face of horizontal arrangement 10 μ L when y ° of satisfaction of contact angle
(1) formula.
According to the 1st invention, the electroconductive paste of photogravure, viscosity x Pas and thick relative to arithmetic mean
Rugosity Ra is (1) formula described in y ° of the contact angle in less than 0.010 μm of test face meets, so working as using the electroconductive paste to printed
Face rapidly and uniformly can transfer electroconductive paste from photogravure printing plate when implementing photogravure to the printed face.By
This, from after just transfer, paste surface is just even surface, so the thinning thickness in continuity ground is easily kept, if so used
The electroconductive paste, then can form the thick electrically conductive film of the continuous film of the internal electrode for being suitable to miniaturized high capacity MLCC.
In addition, according to the 2nd invention, when electrically conductive film is formed using gravure processes, in modulation electroconductive paste
In operation, modulate electroconductive paste so that viscosity x Pas under the 1/s of shear rate 40 and to with photogravure printing plate
Outermost side face identical material be set to the state on the same surface of the outermost side face and the test face of horizontal arrangement drip 10 μ L when
Y ° of contact angle meet described in (1) formula.Therefore, in printing process, can when photogravure is implemented using the electroconductive paste
Electroconductive paste is rapidly and uniformly transferred to printed face.Thus, surface is pasted from after just transfer and is just changed into even surface, so holding
The thinning thickness in continuity ground is easily kept, it is possible to the continuous film for forming the internal electrode for being suitable to miniaturized high capacity MLCC is thick
Electrically conductive film.In addition, in this application, " outermost side face of printing plate " means to be located at the circle formed on printing plate before printed patterns
Face on cylinder face.
Thus, in the past since, for the purpose of the uniform transfer from photogravure printing plate to printed face, attempt conductive
The optimization of the organic component of paste and/or the optimization of rheological characteristic etc., but as it was previously stated, these trials are not obtained sufficiently yet
As a result.In contrast, the present application is the wetability i.e. size of contact angle, the electroconductive paste for finding not only printing plate and electroconductive paste
Viscosity also has relation and the invention that carries out with transferability.By be modulated so that viscosity and contact angle meet described in (1) formula, i.e.
By the way that contact angle is set to below certain value in the relation with viscosity, thus can be equal from photogravure printing plate by electroconductive paste
Printed face is needed on evenly, and it is just smoothened from skinning surface after just transfer.
In addition, in the 1st invention, test the arithmetic mean roughness Ra of the surface roughness in face need for 0.010 μm with
Under.The surface roughness of the outermost side face of photogravure printing plate, it is however generally that Ra is less than 0.010 μm, so using
The evaluation in above-mentioned test face can be considered as the evaluation of the outermost side face of the photogravure printing plate for having used general.
In addition, in this application, viscosity x Pas uses quiet viscosity during 25 DEG C of down cut 40 1/s of speed.The condition
It is to consider room temperature when carrying out photogravure and/or make when transferring electroconductive paste to printed face in photogravure
Stress for the electroconductive paste etc. and determine, so by using the value, the viscosity of electroconductive paste can be stably obtained and connect
Correlation between feeler and transferability.In addition, viscosimetric analysis can be carried out using commercially available viscosimeter.
In addition, in this application, y ° of use of contact angle to the drip drop of 10 μ L of horizontal plane at 25 DEG C to being measured
Obtained by be worth.The condition be consider room temperature when carrying out photogravure and/or, form when institute in the internal electrode of MLCC
Amount of the electroconductive paste of transfer etc. and determine, so by using the value, viscosity and the contact of electroconductive paste can be stably obtained
Correlation between angle and transferability.In addition, dripping for electroconductive paste can be carried out using for example miniature pipette, the survey of contact angle
Surely can be carried out using commercially available contact angle meter.
In addition, (1) formula is set up in the range of x≤3.0, y ＜ 40.In the viscosity more than these scopes and contact
In the scope at angle, even if meeting y ＜ 17.6x+19.1, good transferability can not be obtained.
According to the present application, viscosity and contact angle are determined with method determined as described above, modulation electroconductive paste is caused
(1) formula described in their value satisfaction, as it was previously stated, following effects are obtained：Can be equal from photogravure printing plate by electroconductive paste
Printed face is needed on evenly, and from after just transfer, film surface is just smoothened.That is, if being only with contact angle
Wetability more than certain value, then can not always obtain good transferability, and viscosity becomes more little more needs to reduce contact angle, i.e.
Wetting is set to become easy.
In addition, for contact angle and the relation of transferability, illustrating in the patent document 4：Transferability when contact angle is big
Good, contact angle is needed for more than 50 °, but if excessive, electroconductive paste becomes to be difficult to enter unit groove.However, according to present inventor
Deng result of study, to obtain good transferability, it is preferable that contact angle is little, and, as shown in (1) formula, electroconductive paste with
Need to be set to less than 40 ° when being measured between printing plate.The record of above-mentioned patent document 4 is preferably " for more than 50 ° and only
Greatly ", but by present inventor etc. opposite to that result is obtained.In addition, in above-mentioned patent document 4, with the value equivalent to water come
Contact angle is limited, but this is the surface state for limiting unit groove indirectly with the value of the contact angle relative to water, is not considered
Appropriate contact angle is different according to the physical property of actually used electroconductive paste.
Here, it is preferred that the test face in the 1st invention or, the photograph in the 2nd invention
The outermost side face of phase gravure plates and the test face are all the faces for implementing plating Cr or plating Ni.For raising and electroconductive paste
Wetability, it is preferable that photogravure printing plate be implement plating Cr or plating Ni printing plate.It is preferable therefore that test face also uses
Printing plate is copied to implement the test face of plating Cr or plating Ni.In addition, reducing contact angle to improve wetability, plating is preferable to carry out
Apply, test the plating species in face, it is preferably consistent with the species of photogravure printing plate plating.Even if however, plating species is not
With can also obtain same contact angle, so being not required to make its consistent.
It is further preferred, that in (1) formula, the scope of viscosity x Pas is 0.1≤x≤3.0.Such as (1)
Shown in formula, the higher limit that viscosity becomes lower allowed contact angle y is also lower, so being difficult to modulate electroconductive paste so that its satisfaction
(1) formula.Therefore, viscosity is preferably set to more than 0.1Pas.
It is further preferred, that in (1) formula, the scope of y ° of contact angle is 10 ＜ y ＜ 40.Contact angle y be 10 ° with
When lower, wetability becomes too high, so can not obtain good transferability on the contrary.
It is further preferred, that viscosity x meets y ＞ 8.8x+12.4 (2) with contact angle y.Contact angle y becomes to get over
It is poorer that little, wetability becomes more eminence rationality, but viscosity x becomes lower, and contact angle y just can allow for less value, so excellent
It is full the above-mentioned formula (2) of foot.
It is further preferred, that the electroconductive paste coats green band and forms electrically conductive film for printing.The conduction of the present invention
Paste does not limit purposes, but is adapted in use to form the situation of electrically conductive film on the insulator in ceramics system.Particularly, if to green
Band carries out printing coating, then can burn till process with enforcement and generate insulator simultaneously by burning till generation electrically conductive film, with system
Cause the advantage of present aspect.
It is further preferred, that the electroconductive paste is used to form the internal electrode of MLCC.As it was previously stated, of the invention
Electroconductive paste, easily keeps the thinning thickness in continuity ground, is suitable for the internal electrode of miniaturized high capacity MLCC.
It is further preferred, that the electroconductive powder is nickel by powder.In the internal electrode purposes of such as MLCC, pass through
The green band of electroconductive paste has been printed in stacking and processs is burnt till in enforcement, thus with using green band generate dielectric layer generate simultaneously it is interior
Portion's electrode, it requires that electroconductive powder has heat resistance.Accordingly, as the electroconductive powder of the electroconductive paste of the present invention, have
The metal of heat resistance such as Pt, Pd, Ag-Pd, Ag, Ni, Cu etc. are suitable, but from from the aspect of manufacturing cost, preferably cheap low-priced gold
Category material, from heat resistance, electric conductivity, in price, particularly preferred nickel.The average grain diameter of electroconductive powder be able to can obtained
Suitably determine in the range of the expected characteristic of electroconductive paste, but be preferably such as less than 1.0 μm and 0.01～0.50 μm of model
Enclose, more preferably 0.05～0.30 μm of scope.
It is further preferred, that the binding agent is polyvinyl butyral resin, polyvinylcarbazole, acrylic resin, epoxy
It is resin, phenolic aldehyde system resin, alkyd system resin, cellulose polymer, rosin series resin etc..As electroconductive paste of the invention
Binding agent, can suitably select from the binding agent generally used in the range of viscosity expected from being capable of achieving and contact angle,
But decomposability this respect of the above-mentioned binding agent because of film Forming ability (i.e. relative to the tack of substrate) and/or when burning till and
It is preferred that.
As long as it is further preferred, that the organic solvent can suitably dissolve or dispersed electro-conductive powder and bonding
The composition of agent resin is just not particularly limited.As one, the terpenes such as the alcohol series solvents such as terpinol, isobornyl acetate can be enumerated
Glycol ether series solvent, the esters such as the ethylene glycol series solvent such as series solvent, glycol ester, diethylene glycol monobutyl ether (butyl carbitol)
The hydrocarbon system solvents such as series solvent, toluene and dimethylbenzene, other mineral spirits etc. have high boiling organic solvent.These organic solvents
It is difficult to dissolve the binding agent of butyral system resin and acrylic resin in green band, it is difficult to produce so-called band impact, so
It is preferred that.
It is further preferred, that carry out as like that, comprising the green band for being suitable for the electroconductive paste in the electroconductive paste
Constituent (material altogether).For example, in the case where the dielectric layer of MLCC is made up of barium titanate, preferably containing barium titanate powder.This
The electroconductive paste of invention is able to easily form thin internal electrode, it is advantageous to altogether the average grain diameter of material is little, for example, 0.5 μm with
Under, preferably 0.005～0.2 μm of scope, more preferably 0.01～0.1 μm of scope.
In addition, the component ratio of the electroconductive paste is not particularly limited, suitably determine to meet (1) formula and (2)
Formula, but preferably for example in mass ratio comprising 30～60% the electroconductive powder, 1～5% binding agent, 35～65%
The organic solvent and 0～20% other common materials component.In addition, in the case of comprising material altogether, preferably 1～20%
Scope.
Description of the drawings
Fig. 1 is the figure in the section for illustrating the MLCC that the electroconductive paste of one embodiment of the present of invention is applied to internal electrode.
Fig. 2 is the chart of the viscosity with the relation of contact angle of the electroconductive paste for illustrating one embodiment of the present of invention.
Symbol description
10：MLCC 12：Dielectric layer 14：Conductor layer 16：Outer electrode
Specific embodiment
Hereinafter, one embodiment of the present of invention is described in detail.In addition, in embodiment explained below, as long as
The general structure for adopting since suitably can using in the past without especially negative.
The electroconductive paste of the present embodiment is used in MLCC10 as shown in Figure 1 described in manufacture, utilizes photogravure
Method is formed into the conductor layer 14 of its internal electrode.In the present embodiment, the thickness of one layer of dielectric layer 12 is such as 10 μ
Below m, such as in the range of 0.1～3 μm, such as 1 μm or so, the thickness of one layer of conductor layer 14 is such as less than 10 μm,
For example in the range of 0.1～3 μm, such as 0.5 μm or so.
Above-mentioned conductor layer 14 is made up of such as nickel, and above-mentioned dielectric layer 12 is made up of such as barium titanate.It is such in manufacture
During MLCC10, electroconductive powder, ceramic powders, binding agent and organic solvent are mixed according to predetermined blending specification and is adjusted
Make electroconductive paste, electroconductive paste printing is coated by photogravure separately prepare for constituting dielectric layer 12
The one side of green band.By laminating postwelding in the green belt for being coated with electroconductive paste, process is burnt till in enforcement, is thus given birth to utilizing
Porcelain band generates dielectric layer 12 and generates conductor layer 14 using electroconductive paste simultaneously, then, is formed by impregnating methods such as (dipping)
Outer electrode 16, thus obtains the MLCC10 shown in described Fig. 1.
Above-mentioned electroconductive powder be such as average grain diameter be less than 1 μm, the nickel powder in the range of such as 0.13～0.18 μm
End, is mixed in electroconductive paste with the ratio of such as 30～60wt% or so.In addition, above-mentioned ceramic powders are for such as average grain diameter
The common material of barium titanate powder, the i.e. barium titanate of composition dielectric layer 12 in the range of less than 0.1 μm such as 10～20nm is (common
Material), mixed with the ratio of such as 10～15wt% or so in electroconductive paste.In addition, above-mentioned binding agent is such as ethyl cellulose
(ethocel), polyvinyl butyral (polyvinyl butyral), above-mentioned organic solvent is dihydroterpineol as main solvent
(dihydroterpineol), isobornyl acetate (isobornyl acetate), methyl propionate (methyl
propionate).They are used respectively with 1～5%, 30～65% or so ratio.
In the present embodiment, modulate the component of above-mentioned electroconductive paste so that its viscosity with to with heliogravure printing plate most
Outer peripheral face identical material is modulated to contact angle when dripping with the test face of the same surface state of the outermost side face and meets following
(1) formula.Viscosity is the value using such as flow graph (HAAKE Rheostress6000) measure, using 25 DEG C and shear rate
Quiet viscosity under conditions of 40 1/s after 1 minute.In addition, contact angle is used at 5 DEG C using miniature pipette to horizontal arrangement
Test face drip 10 μ L, the contact angle that determined with such as FACE contact angle meters (republicanism surface chemistry Co. Ltd. system CA-DT).
Contact angle is for example to determine the mean value of 5 times.
Y ＜ 17.6x+19.1, wherein, x≤3.0, the ┅ of y ＜ 40 (1)
In addition, such as photogravure printing plate be plate Cr printing plates situation, above-mentioned test face be such as Cr plates, its table
Face is finished as the high state of flatness that arithmetic mean roughness Ra is less than 0.010 μm.Alternatively, it is also possible to replace Cr
Plate and use with printing plate equally implement plating Cr plate.In the present embodiment, using such as photogravure printing plate never
Material after having the part to form pattern to peel off its surface material.The size of the planar substrates of test is such as 5cm × 3cm.
The electroconductive paste for so modulating printing is coated green band by photogravure method, as a result, formed
Print film has the smooth surface that dry film thickness is 0.5 μm or so, surface roughness Ra is less than 0.020 μm, by entering to it
Row burns till and can obtain smooth continuous film.Obtain the flatness of the rank, it is thus possible to be more conducive to capacitor characteristic, can
By the raising of property.
Table 1 below be to electroconductive paste component carried out in the printing painting process of above-mentioned conductor layer 14 various changes and
Viscosity evaluates the table that the result of printing is summarized with various combination the down of contact angle.In table 1, " Ni mean particle dias ", " BT
Mean particle dia " is respectively the average grain diameter of nickel by powder, the average grain diameter of barium titanate powder.In addition, " BT amounts " is barium titanate powder
Relative to the mass ratio of Ni.In addition, " MC " is mass ratio of the nickel by powder relative to electroconductive paste entirety." viscosity of 40 1/s " are such as front
It is the quiet viscosity arrived with rheometer measurement to state like that.In addition, " contact angle with Cr plates ", " plating Cr printing plate block letter Ra " are respectively
Implement evaluating data during photogravure using plating Cr printing plates, the former is the measured value of electroconductive paste and the contact angle of Cr plates,
The latter is to carry out the dried surface roughness of print film obtained by printing coating on plating Cr printing plates using the electroconductive paste.With regard to
Surface roughness, using interference microscope (Nikon LV150 ECLIPSE) in 10 times of multiplication factor, the μ m of measurement range 50
1000 μm, determine number 12 under conditions of determine arithmetic mean roughness Ra.In addition, " contact angle with Ni plates ", " plating Ni prints
Version printing body Ra " respectively implements evaluating data during photogravure using plating Ni printing plates.
Table 1
In table 1 above, the surface roughness Ra of block letter be less than 0.020 μm of example be the good example of printing
That is embodiment.Figure 2 illustrates the chart of above-mentioned evaluation result.In fig. 2, " ◆ " is embodiment, and " " is comparative example.Implement
Example 1～11 than in Fig. 2 illustrate (1) formula on the lower, be meet (1) formula electroconductive paste.Comparative example 1～8 it is more upper than (1) formula or
Person's specific viscosity 3.0Pas on the right side, is unsatisfactory for (1) formula, is the electroconductive paste of the comparative example outside the scope of the present invention.
As shown in above-mentioned evaluation result, viscosity be 0.1～3.0Pas, contact angle be 14～39 ° in the range of, pass through
The combination of the viscosity and contact angle of (1) formula described in meeting is set to, the surface roughness that can obtain block letter is 0.003～
0.016 μm of fabulous result.Therefore, when internal electrode (conductor layer 14) of MLCC10 is formed using such electroconductive paste,
The good transferability from photogravure printing plate to printed face can be obtained, as a result, can be readily derived it is thin and
The smooth continuous film in surface, it is possible to the MLCC10 for obtaining miniaturized high capacity with high fabrication yield.In addition, embodiment 11 pairs
Plating Ni printing plates have been also carried out evaluating, the good result of same degree in the case of can obtaining with plating Cr printing plates.If modulation is led
Electricity paste causes to meet (1) formula, then plating the either of which in Cr printing plates and plating Ni printing plates, can equally to obtain thin and surface smooth
Continuous film.
In contrast, in comparative example 1～6, even if viscosity is the scope of 0.2～3.0Pas, but contact angle is greatly to 22
～72 °, thus become the combination for being unsatisfactory for the viscosity with contact angle of described (1) formula, so carrying out from photogravure printing plate
The transferability of transfer is poor, and the surface roughness Ra of block letter is changed into 0.021～0.194 μm of value larger like that.The rough surface
Degree Ra size represent print film surface concavo-convex size, but the thickness of conductor layer 14 be 0.5 μm or so, it is very thin,
So the big concavo-convex continuity for meaning that print film can not be obtained as described above.That is, in the electroconductive paste of comparative example, it is difficult to
Obtain the smooth continuous film in thin and surface.
In addition, in comparative example 7,8, viscosity is 5.3～6.9Pas, high, but contact angle is 51～61 °, positioned at described
(1) downside of formula.However, when photogravure is carried out using them, the surface roughness Ra of print film is for greatly to 0.036
～0.095 μm of larger value, with comparative example 1～6 continuous film is equally cannot get.Because even the downside of (1) formula of being located at, if
Then transferability is still poor more than 3.0Pas for viscosity.
As described above, according to the present embodiment, with regard to electroconductive paste, because viscosity x Pas and coarse relative to arithmetic mean
Degree Ra is (1) formula described in y ° of the contact angle in less than 0.010 μm of test face meets, so, when using the electroconductive paste in green band
Electroconductive paste is rapidly and uniformly transferred during upper enforcement photogravure from photogravure printing plate.Thus, it is transferred from just
After play electroconductive paste surface and be just changed into even surface, so easily keep the thinning thickness in continuity ground, therefore, it is possible to formed be suitable to it is small-sized
The thick electrically conductive film 14 of the continuous film of the internal electrode of high power capacity MLCC10.
In addition, the viscosity and contact angle of electroconductive paste can also be by change Ni mean particle dias, BT mean particle dias, Ni amounts, BT
The species of amount or change binding agent and organic solvent is suitably adjusted with measuring.
In addition, according to above-mentioned table 1 and Fig. 2, the lower limit of preferred viscosity is 0.1Pas.It is difficult to be set to electroconductive paste
Also low viscosity than this.In addition, the lower limit of contact angle is 10 °.When contact angle is less than 10 °, wetability becomes too high, on the contrary
Good transferability can not be obtained.
In addition, (2) formula of viscosity x with contact angle y preferably than Fig. 2 is top, that is, meet y ＞ 8.8x+12.4.Contact angle y becomes
Must be less, wetability just becomes higher, treatability is deteriorated, but viscosity x becomes lower, and contact angle y just can allow for less value.
More than, the present invention has been explained in detail with reference to the accompanying drawings, but the present invention can also be implemented by other schemes, not taken off
Can various changes in addition in the range of its purport.
Claims (4)
1. a kind of electroconductive paste, is the electroconductive paste of the photogravure containing electroconductive powder, binding agent and organic solvent, and it is special
Levy and be：
Viscosity when by 25 DEG C of down cut 40 1/s of speed be set to x Pas, will be to 80 μm of cutting quantity and evaluation length 1.0mm
When arithmetic mean roughness Ra be 0.010 μm of level below test face drip 10 μ L when contact angle when being set to y °, x, y are full
Foot formula：
Y ＜ 17.6x+19.1,
Wherein, x≤3.0, y ＜ 40.
2. electroconductive paste according to claim 1, wherein：
The test face is the test face for implementing plating Cr or plating Ni.
3. a kind of forming method of electrically conductive film, including：
The operation of electroconductive paste of the modulation containing electroconductive powder, binding agent and organic solvent；
The electroconductive paste is filled in into the recess of photogravure printing plate and to the printing process of printed face transfer；With
Implement to burn till by the print film to being formed and process so as to generate the firing process of electrically conductive film in the printed face,
The forming method of the electrically conductive film is characterised by：
In modulating the operation of the electroconductive paste,
Modulate the electroconductive paste so that viscosity x Pas during 25 DEG C of down cut 40 1/s of speed and to recessed with the photograph
The outermost side face identical material of version printing printing plate is set to the test of the state with the same surface of the outermost side face and horizontal arrangement
Face drip 10 μ L when y ° of contact angle meet y ＜ 17.6x+19.1, wherein, x≤3.0, y ＜ 40.
4. the forming method of electrically conductive film according to claim 3, wherein：
The outermost side face of the photogravure printing plate and the test face are the faces for implementing plating Cr or plating Ni.
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| JP2015217135A JP7023042B2 (en) | 2015-11-04 | 2015-11-04 | Method of forming conductive paste and conductor film |
| JP2015-217135 | 2015-11-04 |
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| JP (1) | JP7023042B2 (en) |
| KR (1) | KR102600208B1 (en) |
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|---|---|
| TW201729221A (en) | 2017-08-16 |
| KR102600208B1 (en) | 2023-11-08 |
| JP7023042B2 (en) | 2022-02-21 |
| KR20170052498A (en) | 2017-05-12 |
| CN106653146B (en) | 2020-01-10 |
| JP2017088668A (en) | 2017-05-25 |
| TWI700709B (en) | 2020-08-01 |
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