CA2368021A1 - Surface treated barium sulfate and method of preparing the same - Google Patents
Surface treated barium sulfate and method of preparing the same Download PDFInfo
- Publication number
- CA2368021A1 CA2368021A1 CA002368021A CA2368021A CA2368021A1 CA 2368021 A1 CA2368021 A1 CA 2368021A1 CA 002368021 A CA002368021 A CA 002368021A CA 2368021 A CA2368021 A CA 2368021A CA 2368021 A1 CA2368021 A1 CA 2368021A1
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- CA
- Canada
- Prior art keywords
- barium sulfate
- silicon
- surface treated
- polysiloxane
- sulfate particles
- 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
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 title claims abstract description 222
- 238000000034 method Methods 0.000 title claims abstract description 46
- -1 polysiloxane Polymers 0.000 claims abstract description 73
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 67
- 239000002245 particle Substances 0.000 claims abstract description 47
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052990 silicon hydride Inorganic materials 0.000 claims abstract description 28
- 239000000839 emulsion Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000004800 polyvinyl chloride Substances 0.000 claims description 21
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 7
- 238000010298 pulverizing process Methods 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002736 nonionic surfactant Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 229910007161 Si(CH3)3 Inorganic materials 0.000 claims 3
- 239000002952 polymeric resin Substances 0.000 claims 2
- 229920003002 synthetic resin Polymers 0.000 claims 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 238000009472 formulation Methods 0.000 abstract description 8
- 239000011369 resultant mixture Substances 0.000 abstract 1
- 229910052601 baryte Inorganic materials 0.000 description 49
- 239000010428 baryte Substances 0.000 description 49
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 23
- 238000012360 testing method Methods 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 12
- 239000000049 pigment Substances 0.000 description 12
- 239000012530 fluid Substances 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- 239000004408 titanium dioxide Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 238000004381 surface treatment Methods 0.000 description 7
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000002356 laser light scattering Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000006557 surface reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BKUSIKGSPSFQAC-RRKCRQDMSA-N 2'-deoxyinosine-5'-diphosphate Chemical compound O1[C@H](CO[P@@](O)(=O)OP(O)(O)=O)[C@@H](O)C[C@@H]1N1C(NC=NC2=O)=C2N=C1 BKUSIKGSPSFQAC-RRKCRQDMSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- SDGNNLQZAPXALR-UHFFFAOYSA-N 3-sulfophthalic acid Chemical compound OC(=O)C1=CC=CC(S(O)(=O)=O)=C1C(O)=O SDGNNLQZAPXALR-UHFFFAOYSA-N 0.000 description 1
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005376 alkyl siloxane group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- YCZJVRCZIPDYHH-UHFFFAOYSA-N ditridecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCCCC YCZJVRCZIPDYHH-UHFFFAOYSA-N 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- 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
- C01F11/462—Sulfates of Sr or Ba
-
- 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
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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
- C01P2006/10—Solid density
-
- 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
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
-
- 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
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—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
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
- Y10T428/2995—Silane, siloxane or silicone coating
Abstract
A method of preparing a surface treated barium sulfate product is disclosed which has improved dispersibility in end use applications such as polymeric formulations. The method includes mixing a silicon-hydride containing polysiloxane, in neat or in aqueous emulsion form, with a quantity of barium sulfate particles and then optionally drying the resultant mixture. The silicon-hydride containing polysiloxane is deposited on and chemically bonded to the surface of the barium sulfate particles.
Description
DESCRIPTION
SURFACE TREATED BARIUM SULFATE AND
METHOD OF PREPARING THE SAME
Technical Field This invention relates to surface treated barium sulfate and, more particularly, to a surface treated barium sulfate product that provides desirable performance properties and improved processing in polymeric end use applications. The invention also relates to a method of preparing such a surface treated barium sulfate product.
Background Art Natural barium sulfate (also commonly referred to as barite or barytes) is frequently used as an extender pigment and/or filler due to its chemical inertness (in both acid and alkali environments), high refractive index, low abrasiveness, low oil absorption, and resistance to corrosion. Barium sulfate is also known to promote flame retardancy and smoke suppression in polymeric end use applications. Given their high refractive index, barium sulfates of high brightness are desirable to use as a replacement for titanium dioxide (TiOz) in certain compositions such as pigmented polymeric compounds. Barite can be utilized to replace a portion of the more expensive TiOz pigment without having a deleterious impact on the compound's brightness and whiteness properties. Synthetic, precipitated barium sulfate pigments are used in a like fashion, but are typically available in finer particle size grades versus the mechanically ground, natural barites. Precipitated barium sulfate is commonly referred to as blanc fixe.
Despite barium sulfate's many end use advantages, it is not readily wetted or dispersed in organic based formulations such as polymeric compounds given its inert inorganic surface. Accordingly, lengthy processing times are typically required to obtain desired levels of dispersibility of the barite in such compounds.
Further, fine and ultrafine particle barites in dry form tend to cake when stored and/or transported. Caking creates processing problems when the barite particles are added to end use formulations via automated dry feeders and the like.
Disclosure of the Invention The present invention is designed to overcome the deficiencies discussed above. It is an object of the invention to provide a surface treated barium sulfate product that is adapted to be readily dispersed in end use applications such as polymeric formulations. Good wet out and dispersion in polymers is important to the inventive product yielding improved processability during compounding and improved extension/spacing of TiOz.
It is a further. object of the invention to provide such a treated barium sulfate product which when added to a polymeric compound does not have a deleterious impact on the physical properties of such compound.
It is another object of the invention to provide a method of treating a barium sulfate product with a hydrogen reactive polysiloxane that promotes improved manufacturing quality and consistency. Such hydrogen reactive polysiloxanes contain silicon-hydride groups as the reactive moiety.
In accordance with the illustrative embodiments and demonstrating features of the present invention, there is provided a surface treated barium sulfate product particularly suited for use in polymeric compositions such as those derived from a polyvinyl chloride or a polyolefin. The product comprises a plurality of barium sulfate particles and a silicon-hydride containing polysiloxane. This hydrogen reactive polysiloxane is deposited on the surface of the barium sulfate particles and bonds to this surface through means of a chemical reaction involving its reactive Si-H~ groups. The treatment level of the silicon-hydride containing polysiloxane can range from about 0.1 % to about 2.0% by weight, but is preferably from about 0.5% to about 1.5% by weight on an active weight basis.
Brief Description of the Drawings FIG. 1 is a graphical representation displaying the effect of replacing titanium dioxide with a surface treated barium sulfate product of the present invention on the whiteness index of a pigmented PVC compound, and FIG. 2 is a graphical representation displaying the effect of replacing titanium dioxide with a surface treated barium sulfate product of the present invention on the percent brightness of a pigmented PVC compound.
Best Mode of Carryin~ Out the Invention In accordance with the preceding summary, the present invention is directed toward a surface treated barium sulfate product that provides improved dispersibility in polymeric end use applications resulting in reduced processing times.
In the preferred embodiment a dry ground natural barite is subsequently surface treated in the manner more fully described below. However, it should be noted that precipitated barium sulfates or wet ground barites can also be surface treated by the inventive method to yield similar benefits. Table I sets forth some mineral properties of a typical dry ground barium sulfate. Table II sets forth some physical properties of four different, dry ground barite products available under the mark Huberbrite~ from J.M. Huber Corporation.
Table I
Mineral Properties Morphology Blocky Refractive Index 1.64 Specific Gravity 4.50 Mohs Hardness 3.0 - 3.5 Linear Coefficient of Expansion 10 (10-6/C) Solubility (g/100m1) 0.00025 Dielectric Constant 11.4 Bulking Value (gal/lb) 0.027 Table II
General Specifications Huberbrite Huberbrite Huberbrite Huberbrite Moisture, 105C0.20 0.10 0.10 0.10 (max), Screen residue,0.05 0.005 0.01 0.6 325 mesh (max),%
pH (100g/250m18.5-9.5 8.5-9.5 8.5-9.5 8.5-9.5 HZO) Dry brightness,94 94 94 93 reflectance Hegman Grind 6.5 6 4 3 Typical Physical .
Properties Form Fine PowderFine Powder Fine Powder Fine Powder Avg. Stokes 1.1 3.0 6.5 8.5 equiv. particle diameter, microns Median particle0.9 2.1 5.8 8.1 size, LLS, microns Surface area, 3.6 1.4 0.6 0.5 BET (m2/g) Oil absorption12 12 12 11 (g/1 OOg) Bulk density, 60 80 90 100 loose (lb/ft3) Bulk density, 90 110 120 130 tapped (lb/ft3) The physical and chemical data reported herein were determined as follows.
Specific gravities were determined by helium gas displacement using a Quantachrome 1000 automated pycnometer unit. The moisture content on the barite in wt. % was determined by drying test samples in a forced air oven at deg. C. for approximately 2 hours in accordance with the TAPPI Method T671 cm 85 procedure. Screen residue values for an untreated barite were measured by pouring a well-mixed slurry of the barite through a 325 mesh screen, rinsing, drying and weighing the residue, following the ASTM D-185 procedure. Barite pH values were determined using a standard pH meter on a 28% solids (by weight) mixture of the barite with deionized water in accordance with the ASTM D-1208, E-70 procedure. Dry pigment brightness values in Table II were measured at 530 nm with a magnesium oxide standard equal to 100%, following the ASTM C-110 procedure. The whiteness index and % brightness values shown in FIG. 1 and FIG. 2 are standard TAPPI brightness numbers as determined by reading the PVC
test plaques with a Technidyne Micro TB-1 C brightness meter in accordance with the TAPPI Method T646 om-86 procedure. Hegman grind values were determined following the standard ASTM D-1210 procedure. The average Stokes equivalent particle diameters in microns were determined by an x-ray sedimentation method based on Stokes Law using a Micromeritics 5100 Sedigraph particle size instrument. The average Stokes equivalent particle diameter is the median particle size (MPS) value determined by the x-ray Sedigraph. The median particle size values, measured by the laser light scattering (LLS) method and reported in microns, were determined using a Malvern Mastersizer/E instrument which is based on Fraunhofer diffraction as generally described in U.S. Pat. No.
5,167,707, incorporated herein by reference, and references cited therein. BET surface areas were determined by the nitrogen absorption method described by Brunauer, Emett, and Teller in the "Journal of the American Chemical Society," Volume 60, page 309, published in 1938. A mufti-point surface area determination was made on the barite test samples after outgassing them at 130 deg. C. using a Micromeritics Gemini III 2375 instrument. Oil absorbance values were determined from the grams of linseed oil absorbed per 100 grams of pigment by the rub-out method of ASTM-D.281. Loose and tapped bulk densities were determined by the procedures described in ASTM D-1895.
SURFACE TREATED BARIUM SULFATE AND
METHOD OF PREPARING THE SAME
Technical Field This invention relates to surface treated barium sulfate and, more particularly, to a surface treated barium sulfate product that provides desirable performance properties and improved processing in polymeric end use applications. The invention also relates to a method of preparing such a surface treated barium sulfate product.
Background Art Natural barium sulfate (also commonly referred to as barite or barytes) is frequently used as an extender pigment and/or filler due to its chemical inertness (in both acid and alkali environments), high refractive index, low abrasiveness, low oil absorption, and resistance to corrosion. Barium sulfate is also known to promote flame retardancy and smoke suppression in polymeric end use applications. Given their high refractive index, barium sulfates of high brightness are desirable to use as a replacement for titanium dioxide (TiOz) in certain compositions such as pigmented polymeric compounds. Barite can be utilized to replace a portion of the more expensive TiOz pigment without having a deleterious impact on the compound's brightness and whiteness properties. Synthetic, precipitated barium sulfate pigments are used in a like fashion, but are typically available in finer particle size grades versus the mechanically ground, natural barites. Precipitated barium sulfate is commonly referred to as blanc fixe.
Despite barium sulfate's many end use advantages, it is not readily wetted or dispersed in organic based formulations such as polymeric compounds given its inert inorganic surface. Accordingly, lengthy processing times are typically required to obtain desired levels of dispersibility of the barite in such compounds.
Further, fine and ultrafine particle barites in dry form tend to cake when stored and/or transported. Caking creates processing problems when the barite particles are added to end use formulations via automated dry feeders and the like.
Disclosure of the Invention The present invention is designed to overcome the deficiencies discussed above. It is an object of the invention to provide a surface treated barium sulfate product that is adapted to be readily dispersed in end use applications such as polymeric formulations. Good wet out and dispersion in polymers is important to the inventive product yielding improved processability during compounding and improved extension/spacing of TiOz.
It is a further. object of the invention to provide such a treated barium sulfate product which when added to a polymeric compound does not have a deleterious impact on the physical properties of such compound.
It is another object of the invention to provide a method of treating a barium sulfate product with a hydrogen reactive polysiloxane that promotes improved manufacturing quality and consistency. Such hydrogen reactive polysiloxanes contain silicon-hydride groups as the reactive moiety.
In accordance with the illustrative embodiments and demonstrating features of the present invention, there is provided a surface treated barium sulfate product particularly suited for use in polymeric compositions such as those derived from a polyvinyl chloride or a polyolefin. The product comprises a plurality of barium sulfate particles and a silicon-hydride containing polysiloxane. This hydrogen reactive polysiloxane is deposited on the surface of the barium sulfate particles and bonds to this surface through means of a chemical reaction involving its reactive Si-H~ groups. The treatment level of the silicon-hydride containing polysiloxane can range from about 0.1 % to about 2.0% by weight, but is preferably from about 0.5% to about 1.5% by weight on an active weight basis.
Brief Description of the Drawings FIG. 1 is a graphical representation displaying the effect of replacing titanium dioxide with a surface treated barium sulfate product of the present invention on the whiteness index of a pigmented PVC compound, and FIG. 2 is a graphical representation displaying the effect of replacing titanium dioxide with a surface treated barium sulfate product of the present invention on the percent brightness of a pigmented PVC compound.
Best Mode of Carryin~ Out the Invention In accordance with the preceding summary, the present invention is directed toward a surface treated barium sulfate product that provides improved dispersibility in polymeric end use applications resulting in reduced processing times.
In the preferred embodiment a dry ground natural barite is subsequently surface treated in the manner more fully described below. However, it should be noted that precipitated barium sulfates or wet ground barites can also be surface treated by the inventive method to yield similar benefits. Table I sets forth some mineral properties of a typical dry ground barium sulfate. Table II sets forth some physical properties of four different, dry ground barite products available under the mark Huberbrite~ from J.M. Huber Corporation.
Table I
Mineral Properties Morphology Blocky Refractive Index 1.64 Specific Gravity 4.50 Mohs Hardness 3.0 - 3.5 Linear Coefficient of Expansion 10 (10-6/C) Solubility (g/100m1) 0.00025 Dielectric Constant 11.4 Bulking Value (gal/lb) 0.027 Table II
General Specifications Huberbrite Huberbrite Huberbrite Huberbrite Moisture, 105C0.20 0.10 0.10 0.10 (max), Screen residue,0.05 0.005 0.01 0.6 325 mesh (max),%
pH (100g/250m18.5-9.5 8.5-9.5 8.5-9.5 8.5-9.5 HZO) Dry brightness,94 94 94 93 reflectance Hegman Grind 6.5 6 4 3 Typical Physical .
Properties Form Fine PowderFine Powder Fine Powder Fine Powder Avg. Stokes 1.1 3.0 6.5 8.5 equiv. particle diameter, microns Median particle0.9 2.1 5.8 8.1 size, LLS, microns Surface area, 3.6 1.4 0.6 0.5 BET (m2/g) Oil absorption12 12 12 11 (g/1 OOg) Bulk density, 60 80 90 100 loose (lb/ft3) Bulk density, 90 110 120 130 tapped (lb/ft3) The physical and chemical data reported herein were determined as follows.
Specific gravities were determined by helium gas displacement using a Quantachrome 1000 automated pycnometer unit. The moisture content on the barite in wt. % was determined by drying test samples in a forced air oven at deg. C. for approximately 2 hours in accordance with the TAPPI Method T671 cm 85 procedure. Screen residue values for an untreated barite were measured by pouring a well-mixed slurry of the barite through a 325 mesh screen, rinsing, drying and weighing the residue, following the ASTM D-185 procedure. Barite pH values were determined using a standard pH meter on a 28% solids (by weight) mixture of the barite with deionized water in accordance with the ASTM D-1208, E-70 procedure. Dry pigment brightness values in Table II were measured at 530 nm with a magnesium oxide standard equal to 100%, following the ASTM C-110 procedure. The whiteness index and % brightness values shown in FIG. 1 and FIG. 2 are standard TAPPI brightness numbers as determined by reading the PVC
test plaques with a Technidyne Micro TB-1 C brightness meter in accordance with the TAPPI Method T646 om-86 procedure. Hegman grind values were determined following the standard ASTM D-1210 procedure. The average Stokes equivalent particle diameters in microns were determined by an x-ray sedimentation method based on Stokes Law using a Micromeritics 5100 Sedigraph particle size instrument. The average Stokes equivalent particle diameter is the median particle size (MPS) value determined by the x-ray Sedigraph. The median particle size values, measured by the laser light scattering (LLS) method and reported in microns, were determined using a Malvern Mastersizer/E instrument which is based on Fraunhofer diffraction as generally described in U.S. Pat. No.
5,167,707, incorporated herein by reference, and references cited therein. BET surface areas were determined by the nitrogen absorption method described by Brunauer, Emett, and Teller in the "Journal of the American Chemical Society," Volume 60, page 309, published in 1938. A mufti-point surface area determination was made on the barite test samples after outgassing them at 130 deg. C. using a Micromeritics Gemini III 2375 instrument. Oil absorbance values were determined from the grams of linseed oil absorbed per 100 grams of pigment by the rub-out method of ASTM-D.281. Loose and tapped bulk densities were determined by the procedures described in ASTM D-1895.
In the preferred embodiment, Huberbrite~ 1 barium sulfate is surface treated in accordance with the method of the present invention. The fine particle size of Huberbrite~ 1 barium sulfate is well suited when utilized in thermoplastic compounds since the fineness of the particles is important to the resultant physical properties and/or effective spacing of the titanium dioxide pigment.
The ground barite is surface modified with a hydrogen reactive silicone fluid (commonly referred to as a H-siloxane, a hydrogen reactive polysiloxane, or a silicon-hydride containing polysiloxane). The presence of the reactive silicon-hydride (Si-H) groups is essential to the siloxane's effectiveness as a surface treatment agent for the barite. A preferred H-siloxane fluid utilized for surface modification of barium sulfate is a methyl hydrogen polysiloxane (denoted hereafter as Me H polysiloxane). Me H polysiloxanes of low molecular weight (MW < 10,000) are particularly preferred as treatment agents. It should be noted that other alkyl hydrogen polysiloxanes and siloxanes of lower reactive hydrogen content can also be utilized.
An illustrative example of the chemical structure of a silicon-hydride containing polysiloxane useful in preparing the surface treated barite products of this invention is set forth immediately below:
R
I
Y Si-O Z
I
X
n wherein n = an integer greater than 1;
X=HorR';
R or R' = an organic substituent comprising 1 to 20 carbon atoms whereby R and R' are not necessarily the same; and Y and Z = silicon-containing terminating end groups.
In the case where the silicon-hydride containing polysiloxane used for surface treatment is an alkyl hydrogen polysiloxane then in reference to the above chemical structure:
n = an integer greater than 1 ;
X=H;
R = a C, - CZ° alkyl ; and Y and Z = silicon-containing terminating end groups.
Finally, in the preferred embodiment where the silicon-hydride containing polysiloxane used for surface treatment is a Me H polysiloxane of low molecular weight, then in reference to the above chemical structure:
n = about 50-80 ;
X=H;
R = methyl ;
Y = (CH3)3SiO-Z = -Si(CH3)s .
The surface treated barite of the present invention is prepared by treating either dry, finely divided barite powder or a barite slurry with the H-reactive silicone fluid. Effective surface treatments on the barium sulfate particles can be carried out on either physical form (dry or slurry) by using a neat H-siloxane fluid or by adding an aqueous emulsion of the H-siloxane fluid as more fully described below. Initially, 98 to 99.9 parts by weight of a quantity of barium sulfate (e.g., Huberbrite~ 1 barium sulfate) is added to a solids/liquid batch blender. The blender is turned on and 0.1 to 2.0 parts by weight (on an active basis) of the Me H
polysiloxane is added respectively over approximately 0.1 to 3 minutes so as to yield a total of 100 parts by weight. The total mixing time is preferably 5 to minutes. The preferred treatment level of the Me H polysiloxane is from about 0.5% to about 1.5% by weight. Optionally, the barite may be heated during the dry treatment and subsequent mixing steps. In the case of surface treating a dry barite powder with Me H polysiloxane at room temperature, the treated barite _g_ product should be allowed to sit for a period of about 24 - 48 hours prior to its use to insure that the surface reaction is complete. Increasing treated product hydrophobicity and small amounts of HZ gas evolution are typically observed over this time period.
Alternatively, the dry treatment process can be carried out continuously by adding the H-siloxane (neat or as an aqueous emulsion) via a chemical metering pump that is used in combination with a pin mixer, a Bepex turbulizer unit or a similar continuous blending device. If a barite starting material is to be treated in slurry form, the Me H polysiloxane is added slowly to the slurry with good mixing and then mixed for an additional 5 to 30 minutes. The treated barite slurry is then vacuum filtered and subsequently oven dried or flash-dried under conventional drying conditions. Whether surface treated in dry particulate form or in slurry form followed by drying, the treated barite product can be optionally post-pulverized to reduce treated particle agglomeration thereby improving its Hegman grind properties.
In an alternative method, an aqueous emulsion of a Me H polysiloxane is used to surface treat the barium sulfate. The aqueous emulsion is preferably prepared from a high-speed dispersion of the Me H polysiloxane in water in the presence of a, surfactant. In a preferred embodiment, the aqueous emulsion comprises Me H polysiloxane in an amount of from about 30% to about 70%, and a nonionic surfactant in an amount of from about 1.0% to about 3.0% of the total formulation (percentages are on an active weight basis).
It has been found that the optimum amount of nonionic surfactant used in preparing the emulsion formulation described above is about 4.0% by weight of the H-siloxane component. Further, preferred nonionic surfactants have a hydrophilic lypophilic balance (HLB) value of greater than 9. A nonionic surfactant particularly suited for emulsifying the Me H polysiloxane is a polysorbitan monolaurate with 20 moles of ethoxylation available under the trade name Alkamuls PSML-20 from Rhodia. In order to obtain sufficient stability, the emulsions are optimally prepared at a 50% by weight concentration of Me H
polysiloxane whereby the corresponding weight concentration of Alkamuls PSML-20 utilized therein would optimally be 2%.
Table III sets forth some variable physical properties of the treated barium sulfate product that was produced by surface treating Huberbrite~ 1 barium sulfate with 1 % by weight of the preferred Me H polysiloxane.
Table III
General Specifications Treated Barium Sulfate Moisture, 105C (max), 0.5 %
Screen Residue*, 325 mesh0.1 (max),/
Hegman Grind 4 - 7 Typical Physical Properties Form Fine Powder bulk density, loose (lb/ft50 - 60 ) bulk density, tamped (lb/76 - 80 ) * Given their very hydrophobic nature, a modified test procedure was used for determining the % screen residue of a treated barite product, as follows:
Using 100.0 grams of pigment, a 38% solids dispersion in ethanol was produced and poured through a 325 mesh sieve screen. After washing with an additional 100 gm quantity of ethanol, the residue was dried, collected and then weighed.
Table IV lists a number of barite test samples and their corresponding descriptions.
Table IV
Sample Description A 1 micron MPS, dry ground barite' B 1 micron MPS, dry ground barite' treated with 1.0% Me H
polysiloxane" (neat addition) C 1 micron MPS, dry ground barite' treated with 1.0% Me H
polysiloxane" (added as an emulsion) D 1 micron MPS, dry ground barite treated with 1.0%
isostearic acid"' (neat addition) E 1 micron MPS, dry ground barite treated with 1.0% dimethyl siloxane, hydroxy terminated (neat addition)t F 1 micron MPS, dry ground barite' treated with 1.0% Si-H
functional alkyl siloxanett (neat addition) G 1 micron MPS, dry ground barite' treated with 1.0%
phenyltrimethoxysilanettt H 1 micron MPS, dry ground barite' treated with 1.0%
isobutyltrimethoxysilanetttt Huberbrite~ 1 barium sulfate available from J.M. Huber Corporation " Me H polysiloxane available from Dow Corning under the trade name Silicone Fluid 1107 "' Isostearic Acid available from Henkel Corporation under the trade name Emery 873 t Dimethyl siloxane available from Dow Corning under the trade name Silicone Fluid 4-2797 tt Alkyl siloxane available from Dow Corning under the trade name Silicone Fluid 2-5084 (has about 50% less Si-H content than Dow Corning Silicone Fluid No. 1107) ttt phenyltrimethoxysilane available from Sivento Inc.
trtt Isobutyltrimethoxysilane available from Sivento Inc.
PVC Test Recipe A polyvinyl chloride compound was prepared from 100 parts by weight of a polyvinyl chloride resin (Vista 5385 resin available from Vista Chemical Co.), 50 phr (parts per hundred resin) of a plasticizer (diisodecyl phthalate, Jayflex DIDP
available from Exxon Chemical Co.), 5 phr of a heat stabilizer (lead sulfophthalate, Lectro 90 available from Synthetic Products Co.), 1 phr of stearic acid (available from Synthetic Products Co.) and 15 phr of total pigment which consisted of either barite, titanium dioxide or a blend of barite and titanium dioxide. The PVC formulation was prepared in a Brabender mixer using the following mixing procedure.
The PVC formulation was prepared by adding the PVC resin to a Brabender Plasti-corder PL-2100 blender which was heated to 340 deg. F and stirred at 60 rpm. Once the PVC resin was heated, the plasticizer and heat stabilizer were added followed by stearic acid addition. Mixing and heating was continued until the mixture was uniform at which time either barite or titanium dioxide or a blend of these pigments was added. Torque measurements were taken after 3 minutes. The composite PVC material was then cooled and compression molded at 340 deg. F and 5,000 psi to form test plaques which were used for optical brightness and color measurements using a Technidyne Micro TB-1 C
brightness meter.
Table V compares the mixing characteristics of the PVC test recipe described in Example 1 using three sample pigments from Table IV. Table V sets forth the impact on mixing torque when the Ti02 pigment is replaced with various percentages of the barium sulfate test samples.
Table V
Mixing Torque (in meter-grams) at Various % Replacement levels for Ti02' Test TreatmentSurface Modifyin0% 25% 50% 75% 100%
Sample Level Agent A --- None 752 758 711 695 920 B 1 % Me H Polysiloxane752 711 700 685 697 (neat) C 1 % Me H Polysiloxane752 691 672 677 677 (emulsion) ' % values above indicate percent Ti02 replacement with barite; initial loading of Ti02 in PVC compound was 15 phr.
As can be seen in Table V, the processing viscosity of the PVC compounds containing treated barium sulfate (Samples B and C) is significantly lower than the viscosity of the PVC compounds containing untreated barium sulfate at various replacement levels (as represented by the mixing torque). The lower viscosity results in reduced processing times.
FIG. 1 is graphical representation displaying the effect of replacing titanium dioxide with a surface treated barium sulfate product of the present invention on the whiteness index of the pigmented PVC compound described in Example 1.
The samples in FIG. 1 correspond to samples A, B and C in Table IV. FIG. 2 displays a similar representation with respect to % brightness, measured as TAPPI
brightness. The whiteness index and % brightness values were both measured on PVC test plaques using the Technidyne Micro TB-1 C instrument as previously described.
As is readily apparent from the figures, the replacement of Ti02 (at various percentages) with barium sulfate treated in accordance with the present invention yields higher whiteness and brightness values as compared to Ti02 replaced with untreated barium sulfate in PVC compounds. The improvements in the PVC
compound's brightness and whiteness properties can likely be attributed to improved barite pigment dispersion wherein better extension/spacing of the Ti02 is achieved.
Table VI displays average % caking values for each of the test samples described in Table IV, all of which are based on a 1 micron barium sulfate (Huberbrite~ 1 ). For comparison, all the treated barite samples were tested for caking in a non post-pulverized form. Post-pulverization after surface treatment can affect a treated barite product's relative Hegman grind and caking properties.
The test procedure utilized for determining average % caking is as follows: A
gram test sample of barite powder was placed inside a 1 inch high by 1 5/8 inch inner diameter stainless steel ring which is located on a glass plate. Using a stainless steel plunger, the powder test sample was hand pressed into a firm plaque using 20 pounds of applied pressure for 10 seconds. The test plaque was then transferred onto the top of a 40 mesh US sieve screen that was then vibrated for about 2 minutes using a Sepor Inc. screen shaker unit. The sample was partially disintegrated by this vibrating action with the clumps of material still remaining on the screen representing the amount of product caking on a weight % basis. The screen residue retained was weighed and the % caking value was determined by the following formula:
caking = (wt. of residue material/original sample wt.) x 100 For a given powder sample, the % caking is determined three times and the average value was reported.
Table VI
Test Sample*% Treatment Surface Modifying AgentAverage Level Caking A --- None 64 B 1 % Me H Polysiloxane (neat)4.9 C 1 % Me H Polysiloxane (emulsion)3.3 D 1 % Isostearic Acid 60 E 1 % Dimethyl Siloxane, 63 hydroxy terminated F 1 % Si-H functional alkyl 62 Siloxane G 1 % PhTMO Silane 68 H 1% IBTMO Silane 62 * All treated barite samples were tested in non post=pulverized form at least hours after having been prepared.
Table VI demonstrates that the surface treatment of a barium sulfate with Me H polysiloxane in accordance with the methods of the present invention results in a product which exhibits a significant reduction in % caking as compared to either an untreated barium sulfate or barium sulfate treated with other surface-modifying materials. The noted reduction in caking reflects improved dry powder flow and bulk dry handling characteristics as well as improved dispersibility of the treated barium sulfate in polymeric end use applications.
In this example, the effect of post-pulverization on resultant Hegman grind properties and % caking values for the surface treated barite product of this invention is demonstrated. After surface treatment of a barite with a Me H
Polysiloxane, post-pulverization of the treated product is an optional process step that can be practiced to provide particle deagglomeration so as to improve the product's dispersibility in organic resin or polymer systems as reflected by an improved Hegman grind value. Treated barite test samples B and C of Table IV
were checked for Hegman grind and both were then subsequently pulverized through a micro-pulverizer unit twice using a 0.020 inch screen. The pulverized test samples are hereafter designated as samples B-P and C-P, respectively.
The resultant Hegman grind properties and % caking values of B-P and C-P were determined and the data are reported in Table VII.
Table VII
Barite Test Sample Description Average % CakingHegman Sample Grind B Per Table IV in 4.9 0-1 non-pulverized form.
C Per Table IV in 3.3 0-1 non-pulverized form.
B-P Sample B pulverized44 6.0 passes through a 0.020 inch screen.
C-P Sample C pulverized25 6.0 passes through a 0.020 inch screen.
Table VII clearly demonstrates that pulverization after surface treatment can significantly improve the Hegman grind properties of the treated barite products of this invention but this improvement often comes at the expense of decreasing dry flow properties some as reflected by an increase in the %
caking values.
In this example, barite test sample C of Table IV was prepared again except that the treatment process with Huberbrite~ 1 barium sulfate and the Me H
polysiloxane as a 50% active emulsion was carried out in a continuos fashion using a Bepex turbilizer unit rather than batch wise in a Henschel mixer. No heating was utilized. The treated barite product so produced at a 1 % treatment level by this continuous treatment process is designated hereafter as sample C-C.
Immediately after its production, sample C-C was evaluated in non-pulverized form for average caking and was re-checked again after 24 hours. The initial % caking value for C-C was determined to be 43%, while the same product tested 24 hours later yielded a % caking value of 9.4 . These data suggest that the surface reaction between the silicon-hydride containing polysiloxane and the barite particles continues over a period of about 24 hours. Optimum dry flow properties for a treated barite product of this invention are not achieved until this surface reaction is complete.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof and accordingly reference should be made to the appended claims rather than the foregoing specification as indicating the scope of the invention.
The ground barite is surface modified with a hydrogen reactive silicone fluid (commonly referred to as a H-siloxane, a hydrogen reactive polysiloxane, or a silicon-hydride containing polysiloxane). The presence of the reactive silicon-hydride (Si-H) groups is essential to the siloxane's effectiveness as a surface treatment agent for the barite. A preferred H-siloxane fluid utilized for surface modification of barium sulfate is a methyl hydrogen polysiloxane (denoted hereafter as Me H polysiloxane). Me H polysiloxanes of low molecular weight (MW < 10,000) are particularly preferred as treatment agents. It should be noted that other alkyl hydrogen polysiloxanes and siloxanes of lower reactive hydrogen content can also be utilized.
An illustrative example of the chemical structure of a silicon-hydride containing polysiloxane useful in preparing the surface treated barite products of this invention is set forth immediately below:
R
I
Y Si-O Z
I
X
n wherein n = an integer greater than 1;
X=HorR';
R or R' = an organic substituent comprising 1 to 20 carbon atoms whereby R and R' are not necessarily the same; and Y and Z = silicon-containing terminating end groups.
In the case where the silicon-hydride containing polysiloxane used for surface treatment is an alkyl hydrogen polysiloxane then in reference to the above chemical structure:
n = an integer greater than 1 ;
X=H;
R = a C, - CZ° alkyl ; and Y and Z = silicon-containing terminating end groups.
Finally, in the preferred embodiment where the silicon-hydride containing polysiloxane used for surface treatment is a Me H polysiloxane of low molecular weight, then in reference to the above chemical structure:
n = about 50-80 ;
X=H;
R = methyl ;
Y = (CH3)3SiO-Z = -Si(CH3)s .
The surface treated barite of the present invention is prepared by treating either dry, finely divided barite powder or a barite slurry with the H-reactive silicone fluid. Effective surface treatments on the barium sulfate particles can be carried out on either physical form (dry or slurry) by using a neat H-siloxane fluid or by adding an aqueous emulsion of the H-siloxane fluid as more fully described below. Initially, 98 to 99.9 parts by weight of a quantity of barium sulfate (e.g., Huberbrite~ 1 barium sulfate) is added to a solids/liquid batch blender. The blender is turned on and 0.1 to 2.0 parts by weight (on an active basis) of the Me H
polysiloxane is added respectively over approximately 0.1 to 3 minutes so as to yield a total of 100 parts by weight. The total mixing time is preferably 5 to minutes. The preferred treatment level of the Me H polysiloxane is from about 0.5% to about 1.5% by weight. Optionally, the barite may be heated during the dry treatment and subsequent mixing steps. In the case of surface treating a dry barite powder with Me H polysiloxane at room temperature, the treated barite _g_ product should be allowed to sit for a period of about 24 - 48 hours prior to its use to insure that the surface reaction is complete. Increasing treated product hydrophobicity and small amounts of HZ gas evolution are typically observed over this time period.
Alternatively, the dry treatment process can be carried out continuously by adding the H-siloxane (neat or as an aqueous emulsion) via a chemical metering pump that is used in combination with a pin mixer, a Bepex turbulizer unit or a similar continuous blending device. If a barite starting material is to be treated in slurry form, the Me H polysiloxane is added slowly to the slurry with good mixing and then mixed for an additional 5 to 30 minutes. The treated barite slurry is then vacuum filtered and subsequently oven dried or flash-dried under conventional drying conditions. Whether surface treated in dry particulate form or in slurry form followed by drying, the treated barite product can be optionally post-pulverized to reduce treated particle agglomeration thereby improving its Hegman grind properties.
In an alternative method, an aqueous emulsion of a Me H polysiloxane is used to surface treat the barium sulfate. The aqueous emulsion is preferably prepared from a high-speed dispersion of the Me H polysiloxane in water in the presence of a, surfactant. In a preferred embodiment, the aqueous emulsion comprises Me H polysiloxane in an amount of from about 30% to about 70%, and a nonionic surfactant in an amount of from about 1.0% to about 3.0% of the total formulation (percentages are on an active weight basis).
It has been found that the optimum amount of nonionic surfactant used in preparing the emulsion formulation described above is about 4.0% by weight of the H-siloxane component. Further, preferred nonionic surfactants have a hydrophilic lypophilic balance (HLB) value of greater than 9. A nonionic surfactant particularly suited for emulsifying the Me H polysiloxane is a polysorbitan monolaurate with 20 moles of ethoxylation available under the trade name Alkamuls PSML-20 from Rhodia. In order to obtain sufficient stability, the emulsions are optimally prepared at a 50% by weight concentration of Me H
polysiloxane whereby the corresponding weight concentration of Alkamuls PSML-20 utilized therein would optimally be 2%.
Table III sets forth some variable physical properties of the treated barium sulfate product that was produced by surface treating Huberbrite~ 1 barium sulfate with 1 % by weight of the preferred Me H polysiloxane.
Table III
General Specifications Treated Barium Sulfate Moisture, 105C (max), 0.5 %
Screen Residue*, 325 mesh0.1 (max),/
Hegman Grind 4 - 7 Typical Physical Properties Form Fine Powder bulk density, loose (lb/ft50 - 60 ) bulk density, tamped (lb/76 - 80 ) * Given their very hydrophobic nature, a modified test procedure was used for determining the % screen residue of a treated barite product, as follows:
Using 100.0 grams of pigment, a 38% solids dispersion in ethanol was produced and poured through a 325 mesh sieve screen. After washing with an additional 100 gm quantity of ethanol, the residue was dried, collected and then weighed.
Table IV lists a number of barite test samples and their corresponding descriptions.
Table IV
Sample Description A 1 micron MPS, dry ground barite' B 1 micron MPS, dry ground barite' treated with 1.0% Me H
polysiloxane" (neat addition) C 1 micron MPS, dry ground barite' treated with 1.0% Me H
polysiloxane" (added as an emulsion) D 1 micron MPS, dry ground barite treated with 1.0%
isostearic acid"' (neat addition) E 1 micron MPS, dry ground barite treated with 1.0% dimethyl siloxane, hydroxy terminated (neat addition)t F 1 micron MPS, dry ground barite' treated with 1.0% Si-H
functional alkyl siloxanett (neat addition) G 1 micron MPS, dry ground barite' treated with 1.0%
phenyltrimethoxysilanettt H 1 micron MPS, dry ground barite' treated with 1.0%
isobutyltrimethoxysilanetttt Huberbrite~ 1 barium sulfate available from J.M. Huber Corporation " Me H polysiloxane available from Dow Corning under the trade name Silicone Fluid 1107 "' Isostearic Acid available from Henkel Corporation under the trade name Emery 873 t Dimethyl siloxane available from Dow Corning under the trade name Silicone Fluid 4-2797 tt Alkyl siloxane available from Dow Corning under the trade name Silicone Fluid 2-5084 (has about 50% less Si-H content than Dow Corning Silicone Fluid No. 1107) ttt phenyltrimethoxysilane available from Sivento Inc.
trtt Isobutyltrimethoxysilane available from Sivento Inc.
PVC Test Recipe A polyvinyl chloride compound was prepared from 100 parts by weight of a polyvinyl chloride resin (Vista 5385 resin available from Vista Chemical Co.), 50 phr (parts per hundred resin) of a plasticizer (diisodecyl phthalate, Jayflex DIDP
available from Exxon Chemical Co.), 5 phr of a heat stabilizer (lead sulfophthalate, Lectro 90 available from Synthetic Products Co.), 1 phr of stearic acid (available from Synthetic Products Co.) and 15 phr of total pigment which consisted of either barite, titanium dioxide or a blend of barite and titanium dioxide. The PVC formulation was prepared in a Brabender mixer using the following mixing procedure.
The PVC formulation was prepared by adding the PVC resin to a Brabender Plasti-corder PL-2100 blender which was heated to 340 deg. F and stirred at 60 rpm. Once the PVC resin was heated, the plasticizer and heat stabilizer were added followed by stearic acid addition. Mixing and heating was continued until the mixture was uniform at which time either barite or titanium dioxide or a blend of these pigments was added. Torque measurements were taken after 3 minutes. The composite PVC material was then cooled and compression molded at 340 deg. F and 5,000 psi to form test plaques which were used for optical brightness and color measurements using a Technidyne Micro TB-1 C
brightness meter.
Table V compares the mixing characteristics of the PVC test recipe described in Example 1 using three sample pigments from Table IV. Table V sets forth the impact on mixing torque when the Ti02 pigment is replaced with various percentages of the barium sulfate test samples.
Table V
Mixing Torque (in meter-grams) at Various % Replacement levels for Ti02' Test TreatmentSurface Modifyin0% 25% 50% 75% 100%
Sample Level Agent A --- None 752 758 711 695 920 B 1 % Me H Polysiloxane752 711 700 685 697 (neat) C 1 % Me H Polysiloxane752 691 672 677 677 (emulsion) ' % values above indicate percent Ti02 replacement with barite; initial loading of Ti02 in PVC compound was 15 phr.
As can be seen in Table V, the processing viscosity of the PVC compounds containing treated barium sulfate (Samples B and C) is significantly lower than the viscosity of the PVC compounds containing untreated barium sulfate at various replacement levels (as represented by the mixing torque). The lower viscosity results in reduced processing times.
FIG. 1 is graphical representation displaying the effect of replacing titanium dioxide with a surface treated barium sulfate product of the present invention on the whiteness index of the pigmented PVC compound described in Example 1.
The samples in FIG. 1 correspond to samples A, B and C in Table IV. FIG. 2 displays a similar representation with respect to % brightness, measured as TAPPI
brightness. The whiteness index and % brightness values were both measured on PVC test plaques using the Technidyne Micro TB-1 C instrument as previously described.
As is readily apparent from the figures, the replacement of Ti02 (at various percentages) with barium sulfate treated in accordance with the present invention yields higher whiteness and brightness values as compared to Ti02 replaced with untreated barium sulfate in PVC compounds. The improvements in the PVC
compound's brightness and whiteness properties can likely be attributed to improved barite pigment dispersion wherein better extension/spacing of the Ti02 is achieved.
Table VI displays average % caking values for each of the test samples described in Table IV, all of which are based on a 1 micron barium sulfate (Huberbrite~ 1 ). For comparison, all the treated barite samples were tested for caking in a non post-pulverized form. Post-pulverization after surface treatment can affect a treated barite product's relative Hegman grind and caking properties.
The test procedure utilized for determining average % caking is as follows: A
gram test sample of barite powder was placed inside a 1 inch high by 1 5/8 inch inner diameter stainless steel ring which is located on a glass plate. Using a stainless steel plunger, the powder test sample was hand pressed into a firm plaque using 20 pounds of applied pressure for 10 seconds. The test plaque was then transferred onto the top of a 40 mesh US sieve screen that was then vibrated for about 2 minutes using a Sepor Inc. screen shaker unit. The sample was partially disintegrated by this vibrating action with the clumps of material still remaining on the screen representing the amount of product caking on a weight % basis. The screen residue retained was weighed and the % caking value was determined by the following formula:
caking = (wt. of residue material/original sample wt.) x 100 For a given powder sample, the % caking is determined three times and the average value was reported.
Table VI
Test Sample*% Treatment Surface Modifying AgentAverage Level Caking A --- None 64 B 1 % Me H Polysiloxane (neat)4.9 C 1 % Me H Polysiloxane (emulsion)3.3 D 1 % Isostearic Acid 60 E 1 % Dimethyl Siloxane, 63 hydroxy terminated F 1 % Si-H functional alkyl 62 Siloxane G 1 % PhTMO Silane 68 H 1% IBTMO Silane 62 * All treated barite samples were tested in non post=pulverized form at least hours after having been prepared.
Table VI demonstrates that the surface treatment of a barium sulfate with Me H polysiloxane in accordance with the methods of the present invention results in a product which exhibits a significant reduction in % caking as compared to either an untreated barium sulfate or barium sulfate treated with other surface-modifying materials. The noted reduction in caking reflects improved dry powder flow and bulk dry handling characteristics as well as improved dispersibility of the treated barium sulfate in polymeric end use applications.
In this example, the effect of post-pulverization on resultant Hegman grind properties and % caking values for the surface treated barite product of this invention is demonstrated. After surface treatment of a barite with a Me H
Polysiloxane, post-pulverization of the treated product is an optional process step that can be practiced to provide particle deagglomeration so as to improve the product's dispersibility in organic resin or polymer systems as reflected by an improved Hegman grind value. Treated barite test samples B and C of Table IV
were checked for Hegman grind and both were then subsequently pulverized through a micro-pulverizer unit twice using a 0.020 inch screen. The pulverized test samples are hereafter designated as samples B-P and C-P, respectively.
The resultant Hegman grind properties and % caking values of B-P and C-P were determined and the data are reported in Table VII.
Table VII
Barite Test Sample Description Average % CakingHegman Sample Grind B Per Table IV in 4.9 0-1 non-pulverized form.
C Per Table IV in 3.3 0-1 non-pulverized form.
B-P Sample B pulverized44 6.0 passes through a 0.020 inch screen.
C-P Sample C pulverized25 6.0 passes through a 0.020 inch screen.
Table VII clearly demonstrates that pulverization after surface treatment can significantly improve the Hegman grind properties of the treated barite products of this invention but this improvement often comes at the expense of decreasing dry flow properties some as reflected by an increase in the %
caking values.
In this example, barite test sample C of Table IV was prepared again except that the treatment process with Huberbrite~ 1 barium sulfate and the Me H
polysiloxane as a 50% active emulsion was carried out in a continuos fashion using a Bepex turbilizer unit rather than batch wise in a Henschel mixer. No heating was utilized. The treated barite product so produced at a 1 % treatment level by this continuous treatment process is designated hereafter as sample C-C.
Immediately after its production, sample C-C was evaluated in non-pulverized form for average caking and was re-checked again after 24 hours. The initial % caking value for C-C was determined to be 43%, while the same product tested 24 hours later yielded a % caking value of 9.4 . These data suggest that the surface reaction between the silicon-hydride containing polysiloxane and the barite particles continues over a period of about 24 hours. Optimum dry flow properties for a treated barite product of this invention are not achieved until this surface reaction is complete.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof and accordingly reference should be made to the appended claims rather than the foregoing specification as indicating the scope of the invention.
Claims (27)
1. A surface treated barium sulfate product comprising a plurality of barium sulfate particles and a silicon-hydride containing polysiloxane, said barium sulfate particles being surface treated by said silicon-hydride containing polysiloxane.
2. The surface treated barium sulfate product of claim 1 wherein said silicon-hydride containing polysiloxane is represented by the general formula wherein n = an integer greater than 1;
X=H or R';
R or R' = an organic substituent comprising 1 to 20 carbon atoms; and Y and Z = silicon-containing terminating end groups.
X=H or R';
R or R' = an organic substituent comprising 1 to 20 carbon atoms; and Y and Z = silicon-containing terminating end groups.
3. The surface treated barium sulfate product of claim 1 wherein said silicon-hydride containing polysiloxane is an alkyl hydrogen polysiloxane of the formula wherein n = an integer greater than 1;
X = H;
R = a C1 - C20 alkyl; and Y and Z = silicon-containing terminating end groups.
X = H;
R = a C1 - C20 alkyl; and Y and Z = silicon-containing terminating end groups.
4. The surface treated barium sulfate product of claim 1 wherein said silicon-hydride containing polysiloxane is a methyl hydrogen polysiloxane of the formula wherein n = about 50-80;
X = H;
R = methyl;
Y = (CH3)3SiO-;
Z = -Si(CH3)3.
X = H;
R = methyl;
Y = (CH3)3SiO-;
Z = -Si(CH3)3.
5. The surface treated barium sulfate product of claim 1 wherein said barium sulfate particles are selected from a group consisting of dry ground barium sulfate, a slurry of ground barium sulfate and precipitated barium sulfate.
6. The surface treated barium sulfate product of claim 1 wherein said barium sulfate particles have a median particle size of approximately 0.1 to microns.
7. The surface treated barium sulfate product of claim 1 wherein said barium sulfate particles have a median particle size of approximately 1 micron.
8. A method of preparing a surface treated barium sulfate product comprising the steps of:
a) providing a quantity of barium sulfate particles; and b) mixing a silicon-hydride containing polysiloxane with said barium sulfate particles in an amount of from about 0.1 % to about 2.0% by weight based on the weight of said barium sulfate particles in order to deposit said polysiloxane on the surface of said barium sulfate particles.
a) providing a quantity of barium sulfate particles; and b) mixing a silicon-hydride containing polysiloxane with said barium sulfate particles in an amount of from about 0.1 % to about 2.0% by weight based on the weight of said barium sulfate particles in order to deposit said polysiloxane on the surface of said barium sulfate particles.
9. The method of claim 8 further including the step of drying said surface treated barium sulfate particles.
10. The method of claim 8 further including the step of pulverizing said surface treated barium sulfate particles.
11. The method of claim 8 wherein said silicon-hydride containing polysiloxane is mixed with said barium sulfate particles in an amount from about 0.5% to about 1.5% by weight based on the weight of said barium sulfate particles.
12. The method of claim 9 further including the step of filtering said surface treated barium sulfate particles prior to the step of drying.
13. The method of claim 8 wherein said barium sulfate particles have an average particle size of from about 0.1 to about 10 microns.
14. The method of claim 8 wherein said silicon-hydride containing polysiloxane is an alkyl hydrogen polysiloxane of the formula wherein n = an integer greater than 1;
X = H;
R = a C1-C20 alkyl; and Y and Z = silicon-containing terminating end groups.
X = H;
R = a C1-C20 alkyl; and Y and Z = silicon-containing terminating end groups.
15. The method of claim 8 wherein said silicon-hydride containing polysiloxane is a methyl hydrogen polysiloxane of the formula wherein n = about 50-80;
X = H;
R = methyl;
Y = (CH3)3SiO-;
Z = -Si(CH3)3.
X = H;
R = methyl;
Y = (CH3)3SiO-;
Z = -Si(CH3)3.
16. A method of preparing a surface treated barium sulfate product comprising the steps of:
a) providing a quantity of barium sulfate particles; and b) mixing an aqueous emulsion of a silicon-hydride containing polysiloxane with said barium sulfate particles in an amount of from about 0.1% to about 2.0% (on an active weight basis of said polysiloxane) as based on the weight of said barium sulfate particles in order to deposit said polysiloxane on the surface of said barium sulfate particles.
a) providing a quantity of barium sulfate particles; and b) mixing an aqueous emulsion of a silicon-hydride containing polysiloxane with said barium sulfate particles in an amount of from about 0.1% to about 2.0% (on an active weight basis of said polysiloxane) as based on the weight of said barium sulfate particles in order to deposit said polysiloxane on the surface of said barium sulfate particles.
17. The method of claim 16 further including the step of drying said surface treated particles.
18. The method of claim 16 further including the step of pulverizing said surface treated particles.
19. The method of claim 16 wherein said aqueous emulsion includes a silicon-hydride containing polysiloxane in an active basis amount of from about 30 to about 70% by weight and a surfactant in an active basis amount of from about 1.0% to about 3.0% by weight.
20. The method of claim 19 wherein said silicon-hydride containing polysiloxane in said emulsion is a methyl hydrogen polysiloxane of the formula wherein n = about 50-80;
X = H;
R = methyl;
Y = (CH3)3SiO-;
Z = -Si(CH3)3.
X = H;
R = methyl;
Y = (CH3)3SiO-;
Z = -Si(CH3)3.
21. The method of claim 19 wherein said surfactant is nonionic.
22. The method of claim 21 wherein said nonionic surfactant has a hydrophilic lypophilic balance of at least about 9.
23. The method of claim 16 wherein said barium sulfate particles have a median particle size from about 0.1 to about 10 microns.
24. The method of claim 19 wherein said aqueous emulsion includes approximately 50% of a Me H polysiloxane on an active weight basis.
25. The method of claim 19 wherein said aqueous emulsion is mixed with said barium sulfate particles in an active basis amount of from about 0.5% to about 1.5% by weight of said silicon-hydride containing polysiloxane as based on the weight of said barium sulfate particles.
26. A polymeric composition comprising:
a polymeric resin;
a surface treated barium sulfate product including a plurality of barium sulfate particles and a silicon-hydride containing polysiloxane, said barium sulfate particles being surface treated by said silicon-hydride containing polysiloxane.
a polymeric resin;
a surface treated barium sulfate product including a plurality of barium sulfate particles and a silicon-hydride containing polysiloxane, said barium sulfate particles being surface treated by said silicon-hydride containing polysiloxane.
27. The polymeric composition of claim 26 wherein said polymeric resin is selected from the group consisting of a polyolefin and a polyvinyl chloride.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/288,903 US6194070B1 (en) | 1999-04-09 | 1999-04-09 | Surface treated barium sulfate and method of preparing the same |
US09/288,903 | 1999-04-09 | ||
PCT/US2000/009586 WO2000061361A1 (en) | 1999-04-09 | 2000-04-10 | Surface treated barium sulfate and method of preparing the same |
Publications (1)
Publication Number | Publication Date |
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CA2368021A1 true CA2368021A1 (en) | 2000-10-19 |
Family
ID=23109153
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA002368021A Abandoned CA2368021A1 (en) | 1999-04-09 | 2000-04-10 | Surface treated barium sulfate and method of preparing the same |
Country Status (8)
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US (1) | US6194070B1 (en) |
EP (1) | EP1177093B1 (en) |
JP (1) | JP2002541051A (en) |
KR (1) | KR20020006701A (en) |
AT (1) | ATE356173T1 (en) |
CA (1) | CA2368021A1 (en) |
DE (1) | DE60033798D1 (en) |
WO (1) | WO2000061361A1 (en) |
Families Citing this family (11)
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JP4211217B2 (en) * | 1999-12-01 | 2009-01-21 | 味の素株式会社 | Edible oil and fat substitute |
TWI227719B (en) * | 2002-11-22 | 2005-02-11 | Far Eastern Textile Ltd | Method of preparing a surface modifier for nanoparticles dispersion of inorganic oxide nanoparticles |
US6838495B2 (en) | 2003-01-17 | 2005-01-04 | Louis Frank Gatti | Rubber composition comprising composite pigment |
US6866711B2 (en) | 2003-01-17 | 2005-03-15 | Fitzgerald Alphanso Sinclair | Composite pigment composition containing silica |
US6849673B2 (en) * | 2003-07-02 | 2005-02-01 | J. M. Huber Corporation | Film forming coating composition containing surface treated barium sulfate, and methods of use |
US7645334B2 (en) * | 2006-02-21 | 2010-01-12 | Sachtleben Chemie Gmbh | Barium sulfate |
BRPI0717172A2 (en) * | 2006-08-25 | 2013-10-15 | Sachtleben Chemie Gmbh | COMPOSITE CONTAINING BARIUM SULFATE |
CN108473332B (en) * | 2015-12-25 | 2020-10-09 | 堺化学工业株式会社 | Barium sulfate particles with low alpha-ray dose, use thereof, and method for producing same |
KR102571368B1 (en) * | 2015-12-25 | 2023-08-25 | 사까이가가꾸고오교가부시끼가이샤 | Low α-dose barium sulfate particles and their use and manufacturing method |
JP6390756B2 (en) * | 2017-02-24 | 2018-09-19 | 堺化学工業株式会社 | Barium sulfate spherical composite powder and method for producing the same |
CN115350336B (en) * | 2022-08-12 | 2023-12-15 | 深圳市骏鼎达新材料股份有限公司 | Developing catheter |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
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US3944705A (en) * | 1973-07-26 | 1976-03-16 | Kanzaki Paper Manufacturing Company, Ltd. | Electrostatic recording material and manufacture thereof |
US4263051A (en) * | 1978-06-12 | 1981-04-21 | Ppg Industries, Inc. | Soft-settling silica flatting agent |
US4505755A (en) | 1982-12-28 | 1985-03-19 | Onahama Sakai Kagaku Kabushiki Kaisha | Method of producing surface-treated barium sulfate |
US4818614A (en) * | 1985-07-29 | 1989-04-04 | Shiseido Company Ltd. | Modified powder |
JPH05112430A (en) * | 1991-10-18 | 1993-05-07 | Kanebo Ltd | Cosmetic |
US5401570A (en) * | 1993-08-02 | 1995-03-28 | Xerox Corporation | Coated fuser members |
US5393437A (en) | 1994-05-31 | 1995-02-28 | Chemguard, Inc. | Fire extinguishing material |
FI956324A (en) * | 1995-02-01 | 1996-08-02 | Goldschmidt Ag Th | Use of organofunctional polysiloxanes to modify the surfaces of fine particles |
JPH08268840A (en) | 1995-03-30 | 1996-10-15 | Kao Corp | Covering powder and cosmetic containing the same |
JPH093211A (en) | 1995-04-18 | 1997-01-07 | Sakai Chem Ind Co Ltd | Resin composition |
JP3524281B2 (en) | 1996-08-06 | 2004-05-10 | カネボウ株式会社 | Cosmetics |
-
1999
- 1999-04-09 US US09/288,903 patent/US6194070B1/en not_active Expired - Fee Related
-
2000
- 2000-04-10 EP EP00923226A patent/EP1177093B1/en not_active Expired - Lifetime
- 2000-04-10 JP JP2000610670A patent/JP2002541051A/en active Pending
- 2000-04-10 WO PCT/US2000/009586 patent/WO2000061361A1/en active IP Right Grant
- 2000-04-10 KR KR1020017012905A patent/KR20020006701A/en not_active Application Discontinuation
- 2000-04-10 DE DE60033798T patent/DE60033798D1/en not_active Expired - Lifetime
- 2000-04-10 CA CA002368021A patent/CA2368021A1/en not_active Abandoned
- 2000-04-10 AT AT00923226T patent/ATE356173T1/en not_active IP Right Cessation
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EP1177093A4 (en) | 2002-06-12 |
JP2002541051A (en) | 2002-12-03 |
DE60033798D1 (en) | 2007-04-19 |
EP1177093A1 (en) | 2002-02-06 |
EP1177093B1 (en) | 2007-03-07 |
KR20020006701A (en) | 2002-01-24 |
US6194070B1 (en) | 2001-02-27 |
ATE356173T1 (en) | 2007-03-15 |
WO2000061361A1 (en) | 2000-10-19 |
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