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WO1992002587A1 - Carbonate de calcium traite avec des acides gras, sa fabrication et son utilisation - Google Patents

Carbonate de calcium traite avec des acides gras, sa fabrication et son utilisation Download PDF

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Publication number
WO1992002587A1
WO1992002587A1 PCT/US1991/004993 US9104993W WO9202587A1 WO 1992002587 A1 WO1992002587 A1 WO 1992002587A1 US 9104993 W US9104993 W US 9104993W WO 9202587 A1 WO9202587 A1 WO 9202587A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
fatty acid
high molecular
molecular weight
calcium carbonate
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.)
Ceased
Application number
PCT/US1991/004993
Other languages
English (en)
Inventor
Roger E. Bauer
Krishna K. Mathur
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Pfizer Corp Belgium
Pfizer Corp SRL
Original Assignee
Pfizer Corp Belgium
Pfizer Corp SRL
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Pfizer Corp Belgium, Pfizer Corp SRL filed Critical Pfizer Corp Belgium
Priority to KR1019930700359A priority Critical patent/KR930701526A/ko
Publication of WO1992002587A1 publication Critical patent/WO1992002587A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • C09C1/021—Calcium carbonates
    • 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
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • 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
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • 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
    • C01P2006/80—Compositional purity

Definitions

  • This invention broadly relates to treated filler materials, more particularly, to surface-treated calcium carbonate, and still more particularly to calcium carbonate surface-treated with a high molecular weight unsaturated fatty acid for use as filler in polyvinyl chloride plastisols to improve the baked adhesion to electrocoated metal surfaces at low bake temperatures.
  • Polyvinyl chloride (PVC) plastisols are generally composed of finely divided PVC resin, plasticizers and fillers; for particular application they may contain small amounts other additives such as stabilizer, pigments or colorants, and adhesion promoting compounds.
  • the components of a plastisol are combined and mixed to form a fluid which may be applied to a substrate (e.g. cloth or metal) or formed into shapes or articles (e.g. gloves) .
  • the plastisol is heated, which results in the complete diffusion of plasticizer into the resin particles (gelation) over the temperature range of from about 50°C to about 170°C, and in the melting of the polymer over the temperature range of from about 120°C to about 180°C.
  • the melted (fused) plastisol is then allowed to cool below about 50°C, it forms a flexible, tough and chemical- resistant solid.
  • PVC plastisols may be used as undercoatings, chip guards and as sealants for the seams of welded metal parts.
  • the body work and underside of autos are generally electrocoated primed sheet metal; plastisols for these applications must adhere well to the electrocoated metal and must have good abrasion and impact resistance to perform their protective and sealant functions. Since PVC homopoly er has relatively poor inherent adhesion to electrocoated metal, vinyl acetate copolymers which have fast gelation times and low fusion temperatures are substituted for a portion of the homopolymer resin.
  • copolymers undergo quicker viscosity aging (increase in viscosity) and develop lower ultimate impact strength properties than homopolymers, the amount of homopolymer they can replace is limited. Therefore organic adhesion promoting compounds are often added to automotive type plastisols.
  • Calcium carbonate is used in PVC plastisols in the forms of ground limestone and precipitated calcium carbonate (PCC) .
  • Ground limestone is added as a filler, primarily to reduce the volume cost of the plastisol.
  • Precipitated calcium carbonate is used to increase the low shear viscosity and thixotropy of the fluid plastisol and to increase the impact resistance of the baked product.
  • Surface treatment of the calcium carbonate with stearic acid or salts of stearic acid is widely practiced for decreasing the plasticizer absorption and increasing the compatibility of the calcium carbonate.
  • PCC treated with stearic acid or salts of stearic acid, manufactured by Pfizer Inc. , New York, and commercially available under the name Ultra-Pflex
  • a polyvinyl chloride plastisol of the type used in the automotive industry for performance with respect to rheology and adhesion.
  • the plastisols made with Ultra-Pflex had unacceptably poor baked adhesion to electrocoated metal when the bake temperature was around 120°C. It was then decided to experiment with different combinations of PCC treated with other materials to determine whether there would be improvement in baked adhesion at low baking temperature by using such other treated PCC's as a functional filler material in PVC plastisols.
  • the PCC for surface treatment has an average particle size of from about 0.01 to about 0.1 micron, and preferably about 0.07 micron.
  • the PCC has a specific surface area in the range of from about 10 m 2 /g to about 100 ⁇ r/g, depending on the corresponding average particle size.
  • the specific surface area is from about 18 m : /g to about 22 m 2 . ' .,.
  • the PCC is surface- treated with a combination of at least one high molecular weight unsaturated fatty acid at at least one high molecular weight saturated fatty acid
  • the high molecular weight unsaturated fatty acid when utilized alone, is selected from the group consisting of erucic acid (cis-13-docosenoic acid) , gadoleic acid (9 cis-eicosenoic acid) , brassidic acid (13 trans-docosenoic acid) , selacholeic acid (15 cis- tetrasenoic acid), ximenic acid (17 cis-hexacosenoic acid), lu egueic acid (21 cis-triacon-tenoic acid) , and combinations thereof.
  • a high molecular weight unsaturated fatty acid is used in combination with the unsaturated fatty acid
  • an unsaturated fatty acid selected from the above indicated group and further including oleic acid (C ⁇ ) it has been found, according to the present invention, that erucic acid (cis-13-docosenoic acid) is preferred as the unsaturated fatty acid when used alone.
  • the high molecular weight saturated fatty acid is selected from the group consisting of arachidic acid (C 20 ) , behenic acid (C 22 ) , lignoceric acid (C 24 ) , cerotic acid (C 26 ) , montanic acid (C 28 ) , and combinations thereof.
  • a preferred combination of a high molecular weight unsaturated fatty acid and a high molecular weight saturated fatty acid is oleic acid and behenic acid.
  • the PCC is surface-treated with the unsaturated fatty acid or acids or combination of unsaturated and saturated fatty acids to the extent of from about 1.0 weight percent to about 3.5 weight percent based on the weight of the calcium carbonate.
  • the fatty acid surface treatment is present in an amount of about 2.0 weight percent to about 2.5 weight percent, based on the weight of calcium carbonate.
  • ultrafine precipitated calcium carbonate at room temperature is first dry-mixed alone until the frictional heating produced by mixing causes an increase in the temperature of the PCC to about 80°C. At that point, a sufficient amount of at least one high molecular weight unsaturated fatty acid or a combination of at least one high molecular weight unsaturated fatty acid and at least one high molecular weight saturated fatty acid, is added to the PCC to produce a coating of the fatty acid on the PCC of from about 1.0 to about 3.5 weight percent based on the weight of PCC. Mixing of the PCC and the fatty acid is continued until the temperature rises to about 105°C due to frictional heating, or at least five minutes have elapsed since addition of the fatty acid. The coated ultrafine PCC is then ready for milling to any desired degree of fineness, using, for example, a Mikroato izer mill (Mikropul Division, Hosokawa Micron International, Inc., Summit, N.J.).
  • ultrafine precipitated calcium carbonate is first mixed with water to form a slurry.
  • the PCC is as a centrifuge paste containing about 40.1% by weight of calcium carbonate.
  • the PCC-water slurry is heated to 85°C and agitated for about one hour to produce a homogeneous mixture.
  • a sodium salt solution of a at least one high molecular weight unsaturated fatty acid or a combination of sodium salt solutions of at least one high molecular weight unsaturated fatty acid and at least one high molecular weight saturated fatty acid is then added to the slurry, with agitation, over a period of about 5 minutes.
  • the resulting new slurry is agitated for about one hour at a temperature around 85°C and is then dewatered, such as by filtration, dried at a temperature around 110°C and milled, such as with a Mikroatomizer mill.
  • the high molecular weight fatty acid is erucic acid.
  • a sodium erurate solution is prepared by saponifying erucic acid with an excess of sodium hydroxide.
  • Erucic acid is a solid at room temperature.
  • the PCC and the erucic acid are combined and homogenized in a high intensity mixer, such as a Henschel type mixer (Rheinstahl Henschel AG, Kassel, W. Germany) or a Welex type mixer (Gunther Pappen eier GmbH, Detmold, W. Germany) .
  • the components are mixed sufficiently long to allow complete melting of the erucic acid and its uniform adsorption by the calcium carbonate.
  • the calcium carbonate is then deagglomerated in a high speed mill such as a Mikroatomizer mill.
  • Addition of an effective amount of an erucic acid surface-treated PCC filler to a PVC plastisol namely, an amount of from about 10 weight percent to about 30 weight percent, based on the weight of the plastisol, and preferably, from about 15 weight percent to about 20 weight percent, based on the weight of the plastisol, has been found to greatly increase the baked adhesion of the filled plastisol to an electrocoated metal, particularly when the baking step is performed at a low temperature in the range of from about 110°C to about 140°C, and preferably at about 120°C.
  • An amine type adhesion promoter may also be added to the surface-treated PCC-PVC plastisol mixture to further improve the baked adhesion of the mixture to a metal surface.
  • an amine type adhesion promoter is used, it is added to the surface-treated PCC-PVC plastisol mixture in an amount of from about 0.8 weight percent to about 1.0 weight percent, based on the weight of the PCC-PVC plastisol mixture.
  • the amine type adhesion promoter is selected from the group consisting of amino-a ides, such as Euretek 550, 556, 580 and 600, manufactured by Sherex Corp., Dublin, OH, and amino functional silanes, as manufactured by Union Carbide Corp., Danbury, CT.
  • Samples of ultrafine PCC were surface treated with erucic acid in amounts of 1.5%, 2.0% 2.25%, and 2.5% by weight, based on the weight of PCC.
  • the samples were prepared by surface-treating ultrafine
  • PCC which had previously been synthesized, dewatered and dried.
  • the source of the PCC was from the Pfizer Inc. plant at Adams, MA.
  • the dried samples of Ultrafine PCC were surface-treated with the erucic acid at the various levels in a laboratory scale Welex high intensity mixer.
  • the Ultrafine PCC was first placed int he Welex mixer and mixed alone at a blade speed of 3800 rpm until the temperature reached 80°C.
  • erucic acid (Prifrac 2990, Unichema Chemicals Inc. , Chicago, IL) was added and mixing was continued at 3800 rpm until the temperature of the batch reached 105°C or five minutes had elapsed from the time of the erucic acid addition.
  • the amounts of each ingredient for the various samples are shown in Table I.
  • Example 2 Evaluation of Samples of Erucic Acid surface-treated PCC in PVC Plastisol
  • the samples of Ultra fine PCC surface-treated with various levels of erucic acid, prepared in Example 1 were added to a polyvinyl chloride plastisol of the type used in the automotive industry to evaluate the properties of the material as to adhesion and rheology.
  • Each of the surface treated PCC samples of Example 1 was evaluated in the PVC plastisol formulation shown in Table II. Table II
  • Plasticizer Santicizer 220 31.94 711 (Monsanto Co., St. Louis, MO)
  • the plastisol formulations were mixed using a Ross double planetary mixer (Charles Ross and Son Co. , Hauppauge,
  • each plastisol was measured.
  • a 0.050 ⁇ 0.002 inch thick film, of each sample of plastisol was applied to an ED 3060 (PPG Automotive Products Inc., Cleveland, OH) electrocoated metal test panel.
  • the film was applied to a 2-inch wide by 3 inch long rectangular area of the panel.
  • the panels were then placed in an oven at 120°C for 30 minutes. After removal from the oven, the panels were allowed to stand at room temperature for 30 minutes. At that time, two parallel slits were made in the plastisol film 0.5 inch apart and through the entire width of the film.
  • a spatula was used to lift a small piece of the strip thus formed and an attempt was made to slowly pull the test strip from the metal test panel. If the strip could be entirely removed leaving no residue on the panel, the adhesion was rated poor. If the strip tore before detaching from the panel, the adhesion was rated excellent
  • Table IV shows that although all of the erucic acid surface treated PCC containing PVC plastisol formulations according to the present invention demonstrated superior baked adhesion to an electrocoated metal surface, the adhesion increased with increasing amount of erucic acid on the PCC.
  • Example 3 Wet Coating Calcium Carbonate with Erucic Acid Three gallons of tap water and 5,095 grams of ultrafine precipitated calcium carbonate centrifuge paste containing 40.1% by weight of calcium carbonate were combined in a stainless steel container to form a first slurry. The components were heated to 85°C with agitation and further agitated for about 1 hour at 85°C after which a sodium erucate solution was added with agitation over a period of about 5 minutes, forming a second slurry.
  • the sodium erucate solution was prepared by saponifying erucic acid with an excess of sodium hydroxide. 53.12 grams of erucic acid (Prifrac 2990, Unichema Chemicals Inc., Chicago, 111.) were added with agitation to 3090 ml of tap water which had been heated to 85°C. 12.58 grams of 50% (weight/weight) sodium hydroxide aqueous solution, representing a 5% excess of NaOH was added. The resultant solution was agitated for one hour at 85°C before addition to the PCC slurry.
  • the second slurry was agitated for one hour at 85°C after which it was dewatered by filtration, dried at 110 °C and milled with a Mikroatomizer mill.

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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

On décrit du carbonate de calcium précipité, présentant une grosseur de particules moyenne comprise entre environ 0,01 micron et environ 0,1 micron, et une surface spécifique comprise entre environ 10 m2/g et environ 100 m2/g, superficiellement traitée au moyen d'au moins un acide gras insaturé de poids moléculaire élevé, tel que l'acide érucique, ou une combinaison d'au moins un acide gras insaturé de poids moléculaire élevé et d'au moins un acide gras saturé de poids moléculaire élevé, où la combinaison préférée d'un acide gras insaturé et d'un acide gras saturé, tous deux de poids moléculaire élevé, se compose respectivement d'acide oléique et d'acide érucique. Des procédés de préparation d'une telle matière sont aussi décrits, ainsi qu'un procédé consistant à ajouter un tel carbonate de calcium à traitement de surface à des plastisols de chlorure de polyvinyle pour augmenter l'adhérence sous cuisson du plastisol à une surface métallique et réduire la température de cuisson à laquelle la composition de plastisol est appliquée sous cuisson sur la surface métallique.
PCT/US1991/004993 1990-08-06 1991-07-19 Carbonate de calcium traite avec des acides gras, sa fabrication et son utilisation Ceased WO1992002587A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1019930700359A KR930701526A (ko) 1990-08-06 1991-07-19 지방산으로 처리된 칼슘카보네이트, 그의 제법과 용도

Applications Claiming Priority (2)

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US56322390A 1990-08-06 1990-08-06
US563,223 1990-08-06

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WO1992002587A1 true WO1992002587A1 (fr) 1992-02-20

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EP (1) EP0542870A1 (fr)
CA (1) CA2089004A1 (fr)
MX (1) MX9100514A (fr)
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WO2000001769A1 (fr) * 1998-07-02 2000-01-13 Oegretici Celalettin Enrobage de micro-mineraux avec un acide gras dans les broyeurs a marteaux
WO2001032787A1 (fr) 1999-11-03 2001-05-10 Imerys Minerals Limited Traitement de carbonates metalliques alcalino-terreux particulaires
EP1452489A4 (fr) * 2001-12-03 2006-03-15 Shiraishi Kogyo Kaisha Ltd Matiere conferant une thixotropie et composition de resine pateuse
US7341625B2 (en) 2002-03-06 2008-03-11 Sachtleben Chemie Gmbh Method for the production of coated, fine-particle, inorganic solids and use thereof
FR2907788A1 (fr) * 2006-10-31 2008-05-02 Coatex Sas Utilisation comme agent compatibilisant de charges minerales pour materiaux thermoplastiques chlores d'un polymere peigne avec au moins une fonction greffee oxyde de polyalkylene.
EP1980588A1 (fr) 2007-04-13 2008-10-15 Omya Development Ag Processus de préparation d'un produit de remplissage d'un minéral traité, le produit de remplissage d'un minéral traité obtenu et ses utilisations
EP2159258A1 (fr) 2008-08-26 2010-03-03 Omya Development AG Produits de remplissage à base de minerai traité, leur procédé de préparation et leurs utilisations
EP1457459A4 (fr) * 2001-11-16 2010-08-25 Maruo Calcium Carbonate de calcium traite en surface, procede permettant sa production et composition de resine comprenant ledit carbonate de calcium
EP2390285A1 (fr) 2010-05-28 2011-11-30 Omya Development AG Procédé de préparation de charges à base de minerai traité en surface et leurs utilisations
EP2390280A1 (fr) 2010-05-28 2011-11-30 Omya Development AG Produits de remplissage à base de minerai traité, leur procédé de préparation et leurs utilisations
EP2722368A1 (fr) 2012-10-16 2014-04-23 Omya International AG Procédé de réaction chimique contrôlée d'une surface de matériau de charge solide et additifs afin de produire un produit de matériau de charge traité en surface
EP2770017A1 (fr) 2013-02-22 2014-08-27 Omya International AG Nouveau traitement de surface de matériaux minéraux blancs pour application dans des matières plastiques
EP2843005A1 (fr) 2013-08-26 2015-03-04 Omya International AG Carbonate alcalino-terreux, surface modifiée par au moins un polyhydrogensiloxane
EP2821132A3 (fr) * 2013-07-03 2015-04-01 Fels-Werke GmbH Agent de séparation de coffrage et de moulage
WO2017116440A1 (fr) * 2015-12-30 2017-07-06 Halliburton Energy Services, Inc. Particules traitées pour l'hydrophobie destinées à la rhéologie améliorée d'un fluide
KR20180101423A (ko) * 2016-01-14 2018-09-12 옴야 인터내셔널 아게 O2 포집 CaCO3 처리
EP3415570A1 (fr) 2017-06-14 2018-12-19 Omya International AG Procédé de préparation d'un matériau de remplissage traité en surface au moyen d'anhydride(s) succinique(s) monosubstitué(s) et d'un mélange d'acides carboxyliques linéaire ou ramifié comprenant de l'acide stéarique
WO2019075021A1 (fr) * 2017-10-11 2019-04-18 Imerys Usa, Inc. Carbonate réactif pour articles élastomères
US10287407B2 (en) 2014-08-14 2019-05-14 Omya International Ag Surface-treated fillers for breathable films
EP2537806B1 (fr) 2010-02-15 2019-12-04 Shiraishi Kogyo Kaisha, Ltd. Carbonate de calcium traité en surface et composition de résine pâteuse contenant celui-ci
EP3628705A1 (fr) 2018-09-28 2020-04-01 Omya International AG Procédé de preparation d'un produit de matériau de remplissage grossier traité en surface
WO2022139418A1 (fr) * 2020-12-24 2022-06-30 (주)슈퍼노바 바이오 Nanoparticules de polymère modifiées par acide gras et leur utilisation
US11708478B2 (en) 2016-07-19 2023-07-25 Omya International Ag Use of mono-substituted succinic anhydride
EP3328944B1 (fr) 2015-07-30 2023-09-06 Imertech Sas Carbonate de calcium précipité, son procédé de fabrication et ses utilisations
US11753548B2 (en) 2016-01-14 2023-09-12 Omya International Ag Treatment of surface-reacted calcium carbonate

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TR201802411T4 (tr) * 2015-02-27 2018-03-21 Omya Int Ag Katyonik katkı maddesine sahip yüksek katı maddeli PCC.
JP6670298B2 (ja) * 2015-03-23 2020-03-18 丸尾カルシウム株式会社 硬化型樹脂組成物用表面処理炭酸カルシウム填料、及び該填料を含有してなる硬化型樹脂組成物

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EP0377149A2 (fr) * 1989-01-03 1990-07-11 Deutsche Solvay-Werke Gmbh Composition de protection de bas de caisse et son procédé de préparation

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Cited By (54)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000001769A1 (fr) * 1998-07-02 2000-01-13 Oegretici Celalettin Enrobage de micro-mineraux avec un acide gras dans les broyeurs a marteaux
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