CA2043171A1 - Electrically conductive barium sulfate and process of producing it - Google Patents
Electrically conductive barium sulfate and process of producing itInfo
- Publication number
- CA2043171A1 CA2043171A1 CA002043171A CA2043171A CA2043171A1 CA 2043171 A1 CA2043171 A1 CA 2043171A1 CA 002043171 A CA002043171 A CA 002043171A CA 2043171 A CA2043171 A CA 2043171A CA 2043171 A1 CA2043171 A1 CA 2043171A1
- Authority
- CA
- Canada
- Prior art keywords
- electrically conductive
- solution
- barium sulfate
- added
- value
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/027—Barium sulfates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
- C09C3/063—Coating
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- 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
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
-
- 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
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/90—Other properties not specified above
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/54—Inorganic substances
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Paper (AREA)
- Artificial Filaments (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Manufacturing Of Electric Cables (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Electrically conductive barium sulfate and process of producing it. The electrically conductive barium sulfate consists of particles of BaSO4 which are covered by a coating of SnO2 that is doped with Sb2O3. A process of producing the electrically conductive barium sulfate is also described. The electrically conductive barium sulfate distinguishes by having a thermally stable electrical conductivity and a particularly high dispersibility in plastics.
Electrically conductive barium sulfate and process of producing it. The electrically conductive barium sulfate consists of particles of BaSO4 which are covered by a coating of SnO2 that is doped with Sb2O3. A process of producing the electrically conductive barium sulfate is also described. The electrically conductive barium sulfate distinguishes by having a thermally stable electrical conductivity and a particularly high dispersibility in plastics.
Description
~ ~3~ 71 This inventlon relates to electrically conduc-tive barium sulfate, to the use of the electrically conduc-tive barium sulFate, and to a Process of producing it.
In some applications of plastics, their electri-cally insulatins properties oive rise to technical problems.
The electrically insulating prooerties of Dlastics will be oarticularly undesirable, for instsnce, when electronic com-Donents must be shielded from relatively làrge electromag-netlc fields, such 39 is the caee with computer housings, or when electric charges are to be discharged from comoonents.
The electrically insulating proDerties of plastics give also rise to difficulties when hi~h exDlosives or IC comoonents are to be keot in storage, and in the manufacture of medical rubber articles or carpeting orovided with an anti~tatic finish or in the production of electrically conductive adhe-slves ~or metal. It i9 known that polymers can be rendered electrically conductive by an additlon of conductlv~ o~rtlcles.
In some applications of plastics, their electri-cally insulatins properties oive rise to technical problems.
The electrically insulating prooerties of Dlastics will be oarticularly undesirable, for instsnce, when electronic com-Donents must be shielded from relatively làrge electromag-netlc fields, such 39 is the caee with computer housings, or when electric charges are to be discharged from comoonents.
The electrically insulating proDerties of plastics give also rise to difficulties when hi~h exDlosives or IC comoonents are to be keot in storage, and in the manufacture of medical rubber articles or carpeting orovided with an anti~tatic finish or in the production of electrically conductive adhe-slves ~or metal. It i9 known that polymers can be rendered electrically conductive by an additlon of conductlv~ o~rtlcles.
2 ~
Such conductive particles may consist of metal or carbon black particles as well as o~ particles consis~in~ of semi-conductino oxides, such as zinc oxide, or iodides, such as coooer iodide. A disadvantage involved in the use of metal or carbon black Darticles resides in that the polymers con-taining the additives have a black color, which is not de-sired in numerous cases. The use of particles of zinc oxide will result in undesired temperature-dependent Fluctuations of the electrical conductivity. 52cause polymers which con-taln copper iodide have only a low chemical stability, they can be used only for a limited number of applications.
JP-56157436-A describes a process of producing a powder mixture which can be added to plastics in order tG
render them electrically conductive. ln that process a so-lution which contains SnCl4 and 5bCl3 is added to an aqueous diepersion of barium sulfate which has been heated. A preci-pitation is effected in an acid medium and results in mixed powders consisting of SnO2 powder and 5aS04 Dowder. ~ut the plastics to which ~aid mixed DoWders have Deen added have an electrical conductivity which i9 thermally unstable. ~esides, the mixed oowders have a relatively poor disoersibility in plastics so that problems arise in the production of a homo-~eneous mixture consistino of the mixed powders and Plastics.
For this reason it is an object of the inven-tion to provide an electrically conductive barium sulfate .
.
., - ~- 2~3~7~
which has a thermally stable electrical conductivity and a high dispersibility in plastics. an object underlying the invention resides also in the provision o~ a process by which the electrically conductive barium sulfate can be produced with the aid of simple technical means and at a high reaction rate.
The object underlyino the invention is accom-plished in that the electrically conductive barium sulfate consists of oarticles oF SaS04 which are covered by a coating of SnO2 that i9 dooed with Sbz03. The content of Sb203 in the coating of SnO2 amounts to from 1 to 15% by weioht. The coatino has a thickness from 2 to 80 nm. The ~aS04 has a sur-face area from 0.1 to 150 mZ/g. The electrical conductivity of the substance provided by the invention amounts to frnm 1.2 x 10 4 to 7 x 10 1 (ohm x cm) 1. It has surprisin~ly been found that the electrically conductive barium sulfate in accordance with the invention has a hioh dispersibility in plastics, particularly in resins. The olastics to which the electri-cally conductive barlum sulfate in accordance wlth the lnven-tlon has been added also distinquish by having a constant electrical conductivity even at Fluctuating temDeratures so that the plastics to whlch the electrically conductive barium sulfate in accordance with the inventlon has been added can be used for a large variety oF DurDoses.
In accordance with a preferred feature of the invention, the content of Sb~03 in the coating amounts to from . ,.. ' : '. '.~ :
, :,, - . .
_ 4 _ 2~ L~ ?~ 7~
6 to 12~ by weight. In that case the electrically conductive barium sulfate will have a relatively high electrical conduc-tivity so that the content of the coatin~ in the electrical-ly conductive barium sulFate may be relatively low on weight basis and, as a result, the cost of the electrically conduc-tive barium sulfate will be relatively low too.
In accordance with a further preferred feature of the invention the c03ting has a thickness from 10 to 30 nm.
In that case the strenath of the bond between the coating consisting of Sn~2 doped with Sb203 and the oarticles of 9aS04 will be relatively high. A coating having a thickness from 10 to 30 nm will ensure that the coating will not become detached from the oarticles of OaSU4 during the incorporation of tne electrically conductive barium sulfate in a matrix.
In accordance with a further preFerred feature of the invention the particles of ~aSU4 have a surface area from 0.1 to 15U m2/g. In that case the electrically conductive barium sulfate in accordance with the invention will be ùse-ful in numerous fields.
In accordance with a fùrther feature of the in-vention the Darticles of ~aS04 have a surface area from 0.1 to 4 or from 1~ to 15~ mZ/g. In that case the electrically conductive barium sulfate will oe transDarent so that it can desirably be Drocessed together with paints, which will then be electrically conductive whereas the covering power of ad-ditional pigments will not adversely be effected.
, ' ' ~ ., '' ' ,' ' :'.. ..
Such conductive particles may consist of metal or carbon black particles as well as o~ particles consis~in~ of semi-conductino oxides, such as zinc oxide, or iodides, such as coooer iodide. A disadvantage involved in the use of metal or carbon black Darticles resides in that the polymers con-taining the additives have a black color, which is not de-sired in numerous cases. The use of particles of zinc oxide will result in undesired temperature-dependent Fluctuations of the electrical conductivity. 52cause polymers which con-taln copper iodide have only a low chemical stability, they can be used only for a limited number of applications.
JP-56157436-A describes a process of producing a powder mixture which can be added to plastics in order tG
render them electrically conductive. ln that process a so-lution which contains SnCl4 and 5bCl3 is added to an aqueous diepersion of barium sulfate which has been heated. A preci-pitation is effected in an acid medium and results in mixed powders consisting of SnO2 powder and 5aS04 Dowder. ~ut the plastics to which ~aid mixed DoWders have Deen added have an electrical conductivity which i9 thermally unstable. ~esides, the mixed oowders have a relatively poor disoersibility in plastics so that problems arise in the production of a homo-~eneous mixture consistino of the mixed powders and Plastics.
For this reason it is an object of the inven-tion to provide an electrically conductive barium sulfate .
.
., - ~- 2~3~7~
which has a thermally stable electrical conductivity and a high dispersibility in plastics. an object underlying the invention resides also in the provision o~ a process by which the electrically conductive barium sulfate can be produced with the aid of simple technical means and at a high reaction rate.
The object underlyino the invention is accom-plished in that the electrically conductive barium sulfate consists of oarticles oF SaS04 which are covered by a coating of SnO2 that i9 dooed with Sbz03. The content of Sb203 in the coating of SnO2 amounts to from 1 to 15% by weioht. The coatino has a thickness from 2 to 80 nm. The ~aS04 has a sur-face area from 0.1 to 150 mZ/g. The electrical conductivity of the substance provided by the invention amounts to frnm 1.2 x 10 4 to 7 x 10 1 (ohm x cm) 1. It has surprisin~ly been found that the electrically conductive barium sulfate in accordance with the invention has a hioh dispersibility in plastics, particularly in resins. The olastics to which the electri-cally conductive barlum sulfate in accordance wlth the lnven-tlon has been added also distinquish by having a constant electrical conductivity even at Fluctuating temDeratures so that the plastics to whlch the electrically conductive barium sulfate in accordance with the inventlon has been added can be used for a large variety oF DurDoses.
In accordance with a preferred feature of the invention, the content of Sb~03 in the coating amounts to from . ,.. ' : '. '.~ :
, :,, - . .
_ 4 _ 2~ L~ ?~ 7~
6 to 12~ by weight. In that case the electrically conductive barium sulfate will have a relatively high electrical conduc-tivity so that the content of the coatin~ in the electrical-ly conductive barium sulFate may be relatively low on weight basis and, as a result, the cost of the electrically conduc-tive barium sulfate will be relatively low too.
In accordance with a further preferred feature of the invention the c03ting has a thickness from 10 to 30 nm.
In that case the strenath of the bond between the coating consisting of Sn~2 doped with Sb203 and the oarticles of 9aS04 will be relatively high. A coating having a thickness from 10 to 30 nm will ensure that the coating will not become detached from the oarticles of OaSU4 during the incorporation of tne electrically conductive barium sulfate in a matrix.
In accordance with a further preFerred feature of the invention the particles of ~aSU4 have a surface area from 0.1 to 15U m2/g. In that case the electrically conductive barium sulfate in accordance with the invention will be ùse-ful in numerous fields.
In accordance with a fùrther feature of the in-vention the Darticles of ~aS04 have a surface area from 0.1 to 4 or from 1~ to 15~ mZ/g. In that case the electrically conductive barium sulfate will oe transDarent so that it can desirably be Drocessed together with paints, which will then be electrically conductive whereas the covering power of ad-ditional pigments will not adversely be effected.
, ' ' ~ ., '' ' ,' ' :'.. ..
3 ~ 7 ~
The object underlying the invention is also accomplished by the orovision of a Process which serves to Droduce an electrically conductive barium sulfate and where-in a first solution which contains ~SnC14 is added to an aqueous disPersion of HaSD4 to orovide a mixture and the second solution which contains SbC13 is added to said mix-ture and which Droce~s is characterized in that an aqueous dispersion which contains OaS04 in a concentration from 5G
to BOO 9/l is used, the first acid solution contains SnC14 in a concentration from 1 to 95~ by weight, the second acid solution contains SbC13 in a concentration from 0.5 to 60%
by weight, a basic solution is added together with the first solution to the dispersion of ~aS04 to adjust its pH value to a value from 9 to 15, the pH value of the mixture is de-creased to a value between 4 and 1 by an addition of acid before the second solution is added, and the resulting elec-trically conductive barium sulfate is separated, dried and ignited at 300 to B00C. Qqueous solutions of NaOH or KOH
may be used, e.g., as the basic solution. That Drocess will afford the advantage that the oarticles of ~aS04 are entire-ly covered by a coating of SnO~ which i9 doped with Sbz03.
The process can easily be carried out within a short time and the electrically conductive barium sulfate which has been Droduced by the process has a hiqh dispersibility in Dlastics.
In accordance with a further Feature of the invention a third acid solution which has a pH value from .. . .,. ,: ,.. :.
,., ~
~". ~, , ": ,, .- . - -.: ., O to 3 and contains 5nC14 in a concentration from 1 to 95~
by weight is added to the suspension of ~aS04 beFore the first solution is added and the resulting starting mixture is stirred for 10 to 200 minutes before the first solution is added. This will afford the advantaoe that the surface of the particles of ~aS04 is etched by the SnC14 which is contained in the third solution before the first solution is added so that a stronger bond will be formed between the coating of SnU2 which is dooed with Sbz03 and particles of 9aS04.
In accordance with a further preferred feature of the invention the mixture is stirred for 10 to ZOO mi-nutes after the first solution and the basic colution have been added and the DH value of the mixture is subsequently decreased to a value from 4 to 1 by an addition of acid be-fore the second solution i5 added. This will afford the ad-vantage that the particles of 9aS04 will be entirely covered by a coating of SnO2 before the SnOz 19 doped with Sbz03. As a result, the 5b203 will be homogeneously distributed in the coating of SnO2.
In accordance with a further preferred feature of the invention the electrically conductive barium sulfate is separated, dried and ignited when 1 to 30 hours have pas-sed after the addition of the second solution has been com-pleted. This will result in an electrically conductive barium sulfate having a relatively high chemical stability.
. .
:
' :, - In accordance with a further Dreferred feature of the invention the electrically conductive barium sulfate is used in the production of electrically conductive adhesi-ves or electrically conductive oaints or electrically conduc-tive plastics or electrically conductive lsminated papers or electrically conductive synthetic fibers. The quality of said products can thus be improved.
The subject matter of the invention will be ex-plained more in detail with reference to the following Examples.
ExamDle 1 100 9 OaS04 having an average particle diameter of 10 um and a surface area of 0.1 m2/g are suspended in 400 ml water at a temperature of 7DC. The pH value is subsequently adjusted to Z by an addition of 1 ml concentrated hydro-chloric acid. Thereafter, 500 ml water at a temperature of 70C
and the third solution consisting of 1 ml SnC14 and 1 ml con-centrated hycrochloric acid are added to the acid dispersion of SaS04. The resulting starting mixture is stirred for 60 mi-nutes so that it assumes a pH value of 1.5. Thereafter, ~00 ml of a 10~ solution of NaOH and a first solution consistiny of 31 ml SnC14 dissolved in 100 ml 2-molar hydrocloric acid are added. The mixture is stirred for 30 minutes while its tempera-ture is kept at 70. During the next 90 minutes the pH value is decreased to Z.5 by an addition of 110 ml Z-molar hydro-chloric acid. Thereafter a second solution consisting of 100 ml 5.3 9 SbC13 in 100 ml Z-molar hydrochloric acid and 170 ml of , . -.. , . ~ :
,: - , : :
~ ,: ~ ,, - ~ - 2~ 71 10~ solution of NaOH are added in drops at the same time.
After further 20 hours the electrically conductive barium sulfate is separated and dried. ~hen the electrically con-ductive barium sulfate has been ionited at 600C for two hours, it has an electrical conductivity of 1.1 x 10 1 (ohm x cm) Example Z
100 9 OaS04 having an average Darticle dia-meter of 100 um and a surface area oF 30 m~/g are suspended in 900 ml distilled water. The third solution consisting of 1 ml SnCl and 1 ml concentrated hydrochloric acid is added to the resulting suspension to a~just its p~ value to 1.5.
The resulting startinq mixture is stirred for 1 hour. There-after, ~00 ml of a 10% solution of NaOH and a first solution containing 31 ml SnC14 dissolved in 100 ml 2-molar hydro-chloric acid are added at the same time. The mixture is then stirred for further 30 minutes while its temperature is kept at 70. During the next 90 minutes the oH value is decreased to 2.5 by an addition of 110 ml 2-molar hydrochlorlc acid, ThereaFter the second solution conslsting of 5.3 9 9bC13 in 100 ml Z-molar hydrochloric acid and 17D ml of a 10% solution of NaOH are added in drops at the same time. ~fter further 20 hours, the electrLcally conductive barium sulfate is sepa-rated and dried. It has a conductLvity of 2.3 x 10 4 (ohm x cm) 1 after having been ignited at 400C for two hours and of ` .: ; , , ,..:
.:
2 ~
1.7 x 10 Z (ohm x cm) 1 after having been ignited at 600C
for two hours.
Example 3 100 9 ~aS04 having an average particle diame-ter of 100 ~m and a surface area of 30 m2/g are susoended in 900 ml distilled water. 1 ml concentrated hydrochloric ecid are added to adjust the pH value to Z. The third 901u-tion consisting of 1 ml SnC14 and 1 ml concentrated hydro-chloric acid is then added to provide a starting mixture, which i9 stirred for 60 minutes to adjust its pH value to 1.5. Thereafter a first solution containing 7Z ml SnC14 dis-solved in 150 ml Z-molar hydrochloric acid and 1 liter of a 10% solution of NaOH are added at the same time. The mixture is subsequently stirred for 30 minutes while it is kept at a temDerature of 70C. In the next 90 minutes the pH value is decreased to Z.5 by an addition of 110 ml hydrochloric acid.
The second solution consisting of Bg SbC13 in 150 ml 2-molar hydrochloric acid and 150 ml of a 10% solution of NaOH are subsequently added in droDs at the same time. Rfter further ZO hours the electrically conductive barium sulfate i9 9eDa-rated and dried. When it has ignited at 60noc for two hours it hasa conductivity o~1.9 x 102 (ohm x cm) 1.
Exam~le 4 ZOO g ~aS04 havinq an average Darticle diameter of 0.5 um and a surface area o~ 4 m2/g are suspended in 800 ml water. 8y an addition of 1 ml concentrated hydrochloric acid : ' .
. .
',~
~.
- 10 - 2~3~ 71 the pH value is adjusted to 2. The third solution consisting of an acid sDlution of SnCl4 in a concentration of 50~ is then added and the solution is stirred for 1 hour to assume a pH value of 1.5. Thereafter, 1UOU ml oF a 10~ solution of NaOH are added to the starting mixture to initially adjust its pH value to 14. The first solution consisting of 6Z ml SnCl4 in 13B ml Z-molar hydrochloric acid is added at the same time whereby the pH value i5 decreased to 11.5. The mixture is subsequently stirred For 30 minutes while it is kept at a temperature of 70C. ~y an addition of 470 ml 2-molar hydrochloric acid during the next 90 minutes the pH
value is decreased to 2.5. Thereafter the second snlution consisting of 10.6 9 SbCl~ in 200 ml Z-molar hydrochloric acid is added. For an adjustment to a pH value of 2.5, a to-tal of 200 ml of a 10~ solution of NaOH must be added. After further ZO hours the electrically conductive barium sulfate is separated and dried. When it has been ignited at 600C for two hours it has a conductivity of a.o x 10 3 (ohm x cm) 1, Example 5 Thi5 Example diFfers from the preceding Exam-ples 1 to 4 in that the HaS04 is coated in an acid medium and an increase of the pH value to a value from 9 to 15 by a si-multaneous addition of a basic solution together with the SnCl4-containing first acid solution is intentionally omitted.
; .' , , ' .. , ' ~ :
..
ZOO g BaSD4 havinr an average particle diame-ter of 0.5 um and a surface area of 4 m2/g are suspended in BOO ml water. 1 ml concentrated hydroshloric acid is added to the suspension to adjust its pH velue to Z. Z ml SnC14 are subsequently added and the solution is stirred for 1 hour tD adjust its pH value to 1.5. The starting mixture is then heated to 70C and its pH value is increased only to Z.5 oy means of a 10' solution of NaOH. 6Z ml SnCl4 dissolved in 2-molar hydrochloric acid and 10.69 SbC13 dissolved in Z-mo-lar hydrochloric acid together with 1100 ml of a 10% solution of NaOH are added at the same time within YO minutes. After further ZO haurs the BaS04 is separated and dried and after having been ignited for two hours at 500C it has a conducti-vi-ty of Z x 10 (ohm x cm) . That relatively low resistivity and the results of investir~ations with a transmission elec-tron microscope prove that BaSD4 cannot be coated in an acid medium but mixed powders consisting of particles of SnOz doped with Sb203 and of pa:rticles of HaSOL will be obtained in that case .
The object underlying the invention is also accomplished by the orovision of a Process which serves to Droduce an electrically conductive barium sulfate and where-in a first solution which contains ~SnC14 is added to an aqueous disPersion of HaSD4 to orovide a mixture and the second solution which contains SbC13 is added to said mix-ture and which Droce~s is characterized in that an aqueous dispersion which contains OaS04 in a concentration from 5G
to BOO 9/l is used, the first acid solution contains SnC14 in a concentration from 1 to 95~ by weight, the second acid solution contains SbC13 in a concentration from 0.5 to 60%
by weight, a basic solution is added together with the first solution to the dispersion of ~aS04 to adjust its pH value to a value from 9 to 15, the pH value of the mixture is de-creased to a value between 4 and 1 by an addition of acid before the second solution is added, and the resulting elec-trically conductive barium sulfate is separated, dried and ignited at 300 to B00C. Qqueous solutions of NaOH or KOH
may be used, e.g., as the basic solution. That Drocess will afford the advantage that the oarticles of ~aS04 are entire-ly covered by a coating of SnO~ which i9 doped with Sbz03.
The process can easily be carried out within a short time and the electrically conductive barium sulfate which has been Droduced by the process has a hiqh dispersibility in Dlastics.
In accordance with a further Feature of the invention a third acid solution which has a pH value from .. . .,. ,: ,.. :.
,., ~
~". ~, , ": ,, .- . - -.: ., O to 3 and contains 5nC14 in a concentration from 1 to 95~
by weight is added to the suspension of ~aS04 beFore the first solution is added and the resulting starting mixture is stirred for 10 to 200 minutes before the first solution is added. This will afford the advantaoe that the surface of the particles of ~aS04 is etched by the SnC14 which is contained in the third solution before the first solution is added so that a stronger bond will be formed between the coating of SnU2 which is dooed with Sbz03 and particles of 9aS04.
In accordance with a further preferred feature of the invention the mixture is stirred for 10 to ZOO mi-nutes after the first solution and the basic colution have been added and the DH value of the mixture is subsequently decreased to a value from 4 to 1 by an addition of acid be-fore the second solution i5 added. This will afford the ad-vantage that the particles of 9aS04 will be entirely covered by a coating of SnO2 before the SnOz 19 doped with Sbz03. As a result, the 5b203 will be homogeneously distributed in the coating of SnO2.
In accordance with a further preferred feature of the invention the electrically conductive barium sulfate is separated, dried and ignited when 1 to 30 hours have pas-sed after the addition of the second solution has been com-pleted. This will result in an electrically conductive barium sulfate having a relatively high chemical stability.
. .
:
' :, - In accordance with a further Dreferred feature of the invention the electrically conductive barium sulfate is used in the production of electrically conductive adhesi-ves or electrically conductive oaints or electrically conduc-tive plastics or electrically conductive lsminated papers or electrically conductive synthetic fibers. The quality of said products can thus be improved.
The subject matter of the invention will be ex-plained more in detail with reference to the following Examples.
ExamDle 1 100 9 OaS04 having an average particle diameter of 10 um and a surface area of 0.1 m2/g are suspended in 400 ml water at a temperature of 7DC. The pH value is subsequently adjusted to Z by an addition of 1 ml concentrated hydro-chloric acid. Thereafter, 500 ml water at a temperature of 70C
and the third solution consisting of 1 ml SnC14 and 1 ml con-centrated hycrochloric acid are added to the acid dispersion of SaS04. The resulting starting mixture is stirred for 60 mi-nutes so that it assumes a pH value of 1.5. Thereafter, ~00 ml of a 10~ solution of NaOH and a first solution consistiny of 31 ml SnC14 dissolved in 100 ml 2-molar hydrocloric acid are added. The mixture is stirred for 30 minutes while its tempera-ture is kept at 70. During the next 90 minutes the pH value is decreased to Z.5 by an addition of 110 ml Z-molar hydro-chloric acid. Thereafter a second solution consisting of 100 ml 5.3 9 SbC13 in 100 ml Z-molar hydrochloric acid and 170 ml of , . -.. , . ~ :
,: - , : :
~ ,: ~ ,, - ~ - 2~ 71 10~ solution of NaOH are added in drops at the same time.
After further 20 hours the electrically conductive barium sulfate is separated and dried. ~hen the electrically con-ductive barium sulfate has been ionited at 600C for two hours, it has an electrical conductivity of 1.1 x 10 1 (ohm x cm) Example Z
100 9 OaS04 having an average Darticle dia-meter of 100 um and a surface area oF 30 m~/g are suspended in 900 ml distilled water. The third solution consisting of 1 ml SnCl and 1 ml concentrated hydrochloric acid is added to the resulting suspension to a~just its p~ value to 1.5.
The resulting startinq mixture is stirred for 1 hour. There-after, ~00 ml of a 10% solution of NaOH and a first solution containing 31 ml SnC14 dissolved in 100 ml 2-molar hydro-chloric acid are added at the same time. The mixture is then stirred for further 30 minutes while its temperature is kept at 70. During the next 90 minutes the oH value is decreased to 2.5 by an addition of 110 ml 2-molar hydrochlorlc acid, ThereaFter the second solution conslsting of 5.3 9 9bC13 in 100 ml Z-molar hydrochloric acid and 17D ml of a 10% solution of NaOH are added in drops at the same time. ~fter further 20 hours, the electrLcally conductive barium sulfate is sepa-rated and dried. It has a conductLvity of 2.3 x 10 4 (ohm x cm) 1 after having been ignited at 400C for two hours and of ` .: ; , , ,..:
.:
2 ~
1.7 x 10 Z (ohm x cm) 1 after having been ignited at 600C
for two hours.
Example 3 100 9 ~aS04 having an average particle diame-ter of 100 ~m and a surface area of 30 m2/g are susoended in 900 ml distilled water. 1 ml concentrated hydrochloric ecid are added to adjust the pH value to Z. The third 901u-tion consisting of 1 ml SnC14 and 1 ml concentrated hydro-chloric acid is then added to provide a starting mixture, which i9 stirred for 60 minutes to adjust its pH value to 1.5. Thereafter a first solution containing 7Z ml SnC14 dis-solved in 150 ml Z-molar hydrochloric acid and 1 liter of a 10% solution of NaOH are added at the same time. The mixture is subsequently stirred for 30 minutes while it is kept at a temDerature of 70C. In the next 90 minutes the pH value is decreased to Z.5 by an addition of 110 ml hydrochloric acid.
The second solution consisting of Bg SbC13 in 150 ml 2-molar hydrochloric acid and 150 ml of a 10% solution of NaOH are subsequently added in droDs at the same time. Rfter further ZO hours the electrically conductive barium sulfate i9 9eDa-rated and dried. When it has ignited at 60noc for two hours it hasa conductivity o~1.9 x 102 (ohm x cm) 1.
Exam~le 4 ZOO g ~aS04 havinq an average Darticle diameter of 0.5 um and a surface area o~ 4 m2/g are suspended in 800 ml water. 8y an addition of 1 ml concentrated hydrochloric acid : ' .
. .
',~
~.
- 10 - 2~3~ 71 the pH value is adjusted to 2. The third solution consisting of an acid sDlution of SnCl4 in a concentration of 50~ is then added and the solution is stirred for 1 hour to assume a pH value of 1.5. Thereafter, 1UOU ml oF a 10~ solution of NaOH are added to the starting mixture to initially adjust its pH value to 14. The first solution consisting of 6Z ml SnCl4 in 13B ml Z-molar hydrochloric acid is added at the same time whereby the pH value i5 decreased to 11.5. The mixture is subsequently stirred For 30 minutes while it is kept at a temperature of 70C. ~y an addition of 470 ml 2-molar hydrochloric acid during the next 90 minutes the pH
value is decreased to 2.5. Thereafter the second snlution consisting of 10.6 9 SbCl~ in 200 ml Z-molar hydrochloric acid is added. For an adjustment to a pH value of 2.5, a to-tal of 200 ml of a 10~ solution of NaOH must be added. After further ZO hours the electrically conductive barium sulfate is separated and dried. When it has been ignited at 600C for two hours it has a conductivity of a.o x 10 3 (ohm x cm) 1, Example 5 Thi5 Example diFfers from the preceding Exam-ples 1 to 4 in that the HaS04 is coated in an acid medium and an increase of the pH value to a value from 9 to 15 by a si-multaneous addition of a basic solution together with the SnCl4-containing first acid solution is intentionally omitted.
; .' , , ' .. , ' ~ :
..
ZOO g BaSD4 havinr an average particle diame-ter of 0.5 um and a surface area of 4 m2/g are suspended in BOO ml water. 1 ml concentrated hydroshloric acid is added to the suspension to adjust its pH velue to Z. Z ml SnC14 are subsequently added and the solution is stirred for 1 hour tD adjust its pH value to 1.5. The starting mixture is then heated to 70C and its pH value is increased only to Z.5 oy means of a 10' solution of NaOH. 6Z ml SnCl4 dissolved in 2-molar hydrochloric acid and 10.69 SbC13 dissolved in Z-mo-lar hydrochloric acid together with 1100 ml of a 10% solution of NaOH are added at the same time within YO minutes. After further ZO haurs the BaS04 is separated and dried and after having been ignited for two hours at 500C it has a conducti-vi-ty of Z x 10 (ohm x cm) . That relatively low resistivity and the results of investir~ations with a transmission elec-tron microscope prove that BaSD4 cannot be coated in an acid medium but mixed powders consisting of particles of SnOz doped with Sb203 and of pa:rticles of HaSOL will be obtained in that case .
Claims (11)
1. Electrically conductive barium sulfate, characterized in that it consists of particles of BasO4 which are covered by a coating of SnO2 doped with
2. Electrically conductive barium sulfate ac-cording to claim 1, characterized in that the coating con-tains from 6 to 12% by weight Sb2O3.
3. Electrically conductive barium sulfate according to claim l, characterized in that the coating has a thickness from 10 to 30 nm.
4. Electrically conductive barium sulfate according to claim l, 2 or 3, characterized in that the uncoated particles of BaSO4 have in an uncoated state a sur-face area from 0.1 to 150 m2/g.
5. Electrically conductive barium sulfate according to claim 4, characterized in that the Particles of BaSO4 have in an uncoated state a surface area from 0.1 to 3 m2/g or from 12 to 150 m2/g.
6. A process of producing an electrically con-ductive barium sulfate, wherein a first solution which con-tains SnCl4 is added to an aqueous dispersion of BaSO4 to provide a mixture and the second solution which contains SbCl3 is added to said mixture, characterized in that an aqueous dispersion which contains BaSO4 in a concentration from 50 to 800 g/l is used, the first acid solution contains SnCl4 in a concentration from 1 to 95% by weight, the second acid solution contains SbC13 in a concentration from 0.5 to 60% by weight, a basic solution is added together with the first solution to the dispersion ofBaS04 to adjust its pH value to a value from 9 to 15, the pH value of the mix-ture is decreased to a value between 4 and 1 by an addition of acid before the second solution is added, and the result-ing electrically conductive barium sulfate is separated, dried and ignited at 300 to 800°C.
7. A process according to claim 6, characte-rized in that a third acid solution which has a pH value from 0 to 3 and contains SnC14 in a concentration from 1 to 95% by weight is added to the suspension of BaS04 before the first solution is added and the resulting starting mixture is stirred for 10 to 200 minutes before the first solution is added.
8. A process according to claim 6 or 7, charac-terized in that the mixture is stirred for 10 to 200 minutes after the first solution and the basic solution have been added and the pH value of the mixture is subsequently de-creased to a value from 4 to 1 by an addition of acid before the second solution is added.
9. A process according to claim 6 or 7, characterized in that the electrically conductive barium sulfate is separated, dried and ignited after 1 to 30 hours have passed after the addition of the second solution has been completed.
10. A process according to claim 8, characterized in that the electrically conductive barium sulfate is separated, dried and ignited after 1 to 30 hours have passed after the addition of the second solution has been completed.
11. The use of an electrically conductive barium sulfate according to claim 1, 2, 3 or 5, in the production of electrically conductive adhesives, electrically conductive paints, electrically conductive plastics, electrically conductive laminated papers or electrically conductive synthetic fibers.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4017044A DE4017044A1 (en) | 1990-05-26 | 1990-05-26 | ELECTRICALLY CONDUCTIVE BARIUM SULFATE AND METHOD FOR THE PRODUCTION THEREOF |
| DEP4017044.6 | 1990-05-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2043171A1 true CA2043171A1 (en) | 1991-11-27 |
Family
ID=6407279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002043171A Abandoned CA2043171A1 (en) | 1990-05-26 | 1991-05-24 | Electrically conductive barium sulfate and process of producing it |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0459552B1 (en) |
| JP (2) | JPH0688785B2 (en) |
| KR (1) | KR950009165B1 (en) |
| AU (1) | AU643017B2 (en) |
| CA (1) | CA2043171A1 (en) |
| DE (2) | DE4017044A1 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0640719B2 (en) * | 1986-04-01 | 1994-05-25 | 株式会社三ツ葉電機製作所 | Motor frame mounting structure |
| DE4137002C2 (en) * | 1991-11-11 | 1996-12-19 | Thomas Waescher | Partial recovery of exhaust gases from vehicles |
| WO1994000852A1 (en) * | 1992-06-29 | 1994-01-06 | E.I. Du Pont De Nemours And Company | Electroconductive material and process |
| US5292551A (en) * | 1992-06-29 | 1994-03-08 | E. I. Du Pont De Nemours And Company | Process for producing electroconductive powders |
| DE69319289T2 (en) * | 1992-09-07 | 1998-12-17 | Mitsui Mining & Smelting Co | Electrically conductive barium sulfate filler and process for its manufacture |
| JP2959928B2 (en) * | 1993-06-23 | 1999-10-06 | チタン工業株式会社 | White conductive resin composition |
| DE19511012A1 (en) * | 1994-04-06 | 1995-10-12 | Merck Patent Gmbh | Surface-modified conductive pigment useful in coating, plastics and prints |
| DE4415802A1 (en) * | 1994-05-05 | 1995-11-09 | Merck Patent Gmbh | Laser-markable plastics |
| DE4431829A1 (en) | 1994-09-07 | 1996-03-14 | Merck Patent Gmbh | Conductive pigment preparation |
| EP0833862B1 (en) * | 1995-06-22 | 1999-08-11 | Itri Limited | Fire retardant products |
| DE69705709T2 (en) | 1996-05-01 | 2001-10-31 | Itri Ltd | FIRE-RETARDANT TREATMENT |
| WO1999023178A1 (en) * | 1997-10-31 | 1999-05-14 | Dynamit Nobel Kunststoff Gmbh | Electrically conductive covering paint |
| DE19939199B4 (en) * | 1999-08-18 | 2005-12-15 | Sachtleben Chemie Gmbh | Use of polymer-based paints |
| DE102007028349A1 (en) | 2007-06-20 | 2008-12-24 | Mitsubishi Polyester Film Gmbh | Transparent polyester film with BaSO4 particles |
| DE102010011127A1 (en) * | 2010-03-11 | 2011-09-15 | Bundesdruckerei Gmbh | Adhesive composition for a security and / or value document with a circuit |
| WO2016076230A1 (en) | 2014-11-10 | 2016-05-19 | 堺化学工業株式会社 | Barium sulfate powder production method and barium sulfate powder |
| CN114426780A (en) * | 2021-12-29 | 2022-05-03 | 浙江凯色丽科技发展有限公司 | Preparation method of barium sulfate-based conductive composite pearlescent pigment |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56157438A (en) * | 1980-05-06 | 1981-12-04 | Mitsubishi Metal Corp | Preparation of conductive composite powder |
| JPS57121063A (en) * | 1981-01-21 | 1982-07-28 | Ricoh Co Ltd | Electrically conductive pigment and its preparation |
| SE452280C (en) * | 1981-12-30 | 1990-03-12 | Bekaert Sa Nv | ELECTRIC LEADING PLASTIC ARTICLES AND PROCEDURES AND RESOURCES FOR PRODUCING THEREOF |
| JPS6111254A (en) * | 1984-06-27 | 1986-01-18 | Tokyo Takara Shokai:Kk | Method and apparatus for printing suspended curtain |
| JPS6116124A (en) * | 1984-06-29 | 1986-01-24 | Kinugawa Rubber Ind Co Ltd | Structure of corner piece glass run |
| US4857233A (en) * | 1988-05-26 | 1989-08-15 | Potters Industries, Inc. | Nickel particle plating system |
| EP0343496B1 (en) * | 1988-05-27 | 1994-08-31 | Kuraray Co., Ltd. | Conductive composite filament and process for producing the same |
-
1990
- 1990-05-26 DE DE4017044A patent/DE4017044A1/en active Granted
-
1991
- 1991-03-29 JP JP3091557A patent/JPH0688785B2/en not_active Expired - Lifetime
- 1991-05-01 DE DE59107373T patent/DE59107373D1/en not_active Expired - Fee Related
- 1991-05-01 EP EP91201032A patent/EP0459552B1/en not_active Expired - Lifetime
- 1991-05-22 AU AU77269/91A patent/AU643017B2/en not_active Ceased
- 1991-05-24 CA CA002043171A patent/CA2043171A1/en not_active Abandoned
- 1991-05-24 KR KR1019910008398A patent/KR950009165B1/en not_active IP Right Cessation
-
1998
- 1998-05-29 JP JP15030098A patent/JP3167119B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| KR910019908A (en) | 1991-12-19 |
| JPH1171110A (en) | 1999-03-16 |
| AU7726991A (en) | 1991-11-28 |
| EP0459552A1 (en) | 1991-12-04 |
| AU643017B2 (en) | 1993-11-04 |
| DE4017044C2 (en) | 1992-03-19 |
| DE59107373D1 (en) | 1996-03-21 |
| JP3167119B2 (en) | 2001-05-21 |
| KR950009165B1 (en) | 1995-08-16 |
| DE4017044A1 (en) | 1991-11-28 |
| JPH0688785B2 (en) | 1994-11-09 |
| EP0459552B1 (en) | 1996-02-07 |
| JPH0640719A (en) | 1994-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5997775A (en) | Electrically conductive barium sulfate-containing composition and process of producing | |
| CA2043171A1 (en) | Electrically conductive barium sulfate and process of producing it | |
| KR100394889B1 (en) | Needle-shaped electrically conductive tin oxide fine particles and preparation method thereof | |
| US4518524A (en) | Silver coating composition for use in electronic applications and the like | |
| JP2911429B2 (en) | Production method of copper fine powder | |
| EP0648371A1 (en) | Electroconductive material and process | |
| JP3935513B2 (en) | Method for producing conductive fine powder dispersion | |
| JP3609159B2 (en) | Acicular conductive antimony-containing tin oxide fine powder and method for producing the same | |
| DE10148055B4 (en) | Electrically conductive pigment | |
| CN1132885C (en) | Process for preparing conducting light colour flaky pigment | |
| EP1366124B1 (en) | Conductive coating composition | |
| JP3515625B2 (en) | Needle-like conductive tin oxide fine powder and method for producing the same | |
| JPS6052090B2 (en) | white conductive coated powder | |
| JP3394556B2 (en) | Conductive barium sulfate filler and method for producing the same | |
| JPH07133374A (en) | Electroconductive flaky barium sulfate filler and its production | |
| JPS6139686B2 (en) | ||
| JPH0832560B2 (en) | Composite conductive powder and method for producing the same | |
| JPH0370322B2 (en) | ||
| JPH11241035A (en) | Production of flaky copper powder for conductive coating material | |
| JP3140576B2 (en) | Conductive barium sulfate filler and method for producing the same | |
| JP2571222B2 (en) | Method for producing conductive filler | |
| JPS6021554B2 (en) | Manufacturing method of white conductive composite powder | |
| JPH05246710A (en) | Electroconductive powder and production therefor | |
| JPH11256208A (en) | Copper fine powder | |
| JPH08217446A (en) | Strip type (leaflet) electroconductive powder, production and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |