WO2008109270A1 - Formulation abrasive contenant des particules polymères organiques - Google Patents

Formulation abrasive contenant des particules polymères organiques Download PDF

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Publication number
WO2008109270A1
WO2008109270A1 PCT/US2008/054714 US2008054714W WO2008109270A1 WO 2008109270 A1 WO2008109270 A1 WO 2008109270A1 US 2008054714 W US2008054714 W US 2008054714W WO 2008109270 A1 WO2008109270 A1 WO 2008109270A1
Authority
WO
WIPO (PCT)
Prior art keywords
formulation
abrasive
polymer particles
particles
organic polymer
Prior art date
Application number
PCT/US2008/054714
Other languages
English (en)
Inventor
Amy A. Lefebvre
Catherine Melahn
Original Assignee
Arkema France
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 Arkema France filed Critical Arkema France
Publication of WO2008109270A1 publication Critical patent/WO2008109270A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents

Definitions

  • the invention relates to an abrasive fluid formulation containing organic polymeric particles.
  • the formulation is useful in cleaning and polishing metals, plastic, glass, skin, ceramics and other materials.
  • the polymer particles can be round or irregular in shape.
  • the invention also relates to a method of adjusting polymer and particle characteristics including modulus, elasticity, morphology, molecular weight, Tg, degree of crosslinking, particle size and particle size distribution, to produce an abrasive fluid formulation having optimal cleaning and polishing properties for a given substrate.
  • abrasive media contain inorganic particles as the abrasive.
  • inorganic abrasive particles include metal oxide particles such as the oxides of titanium, zirconium, aluminum, silicon, magnesium, germanium, chromium, and iron; nitride particles; silicon carbide particles; diamond particles; ceramic particles; metal pieces, and combinations thereof.
  • metal oxide particles such as the oxides of titanium, zirconium, aluminum, silicon, magnesium, germanium, chromium, and iron
  • nitride particles silicon carbide particles
  • diamond particles ceramic particles
  • metal pieces metal pieces, and combinations thereof.
  • Polymeric particles offer many advantages over the very hard inorganic particles.
  • the hardness of the polymer can be adjusted by the selection of parameters, such as monomers, molecular weight, and crosslinking.
  • the modulus and elasticity can be varied by selection of monomers, glass transition of the polymer (Tg) and the degree of crosslinking.
  • Tg glass transition of the polymer
  • the particles are also easily recyclable, and are more environmentally friendly, especially when used in an aqueous-based formulation.
  • US 2001/0039322 describes the use of polymer particles in a chemical- mechanical polishing (CMP) process.
  • the polymer particles contain polyvalent metallic ions.
  • US 2002/0173243 describes the use of low levels of polymeric particles in an aqueous CMP process.
  • the polymeric polymers homo-, co- and ter-polymers; cross- linked or uncross-linked; homogeneous, core-shell or hollow sphere. They have average molecular weights of at least 500,000, and Tgs of at least 25 0 C. Particle size diameters are in the 5 to 5,000 nm range.
  • Organic polymer particles for use as abrasives in an fluid formulation must be strong enough to withstand multiple cleaning cycles. It is advantageous for the formulation to be recyclable.
  • the polymer particles perform the dual function of scouring and polishing.
  • fluid abrasive formulations can be produced using organic polymer particles as the abrasive, in which the polymer particle parameters are selected for optimum polishing and cleaning properties.
  • the particles will have an medium particle size of from 10 to 1000 microns.
  • the invention relates to an fluid abrasive formulation having organic polymer particles with a median particle diameter of from 10 to 1000 microns.
  • the polymer particles in the formulation are selected to have an effective Tg, degree of crosslinking, modulus, elasticity, morphology, and particle size distribution for optimal cleaning and polishing of a given substrate.
  • the organic polymer particles are preferably suspended in an aqueous media. The particles may be round or irregular in shape.
  • the invention also relates to a method for cleaning and polishing a substrate using a fluid abrasive formulation having organic polymer particles with a mean particle diameter of from 10 to 1000 microns as the abrasive agent.
  • the invention provides a fluid-based abrasive formulation having organic polymeric particles.
  • the particles are chosen to have a modulus, Tg, hardness, elasticity, particle size and particle size distribution to provide both good scrubbing and good polishing properties for a selected substrate.
  • the organic polymer particles of the invention can be made of a thermoplastic or thermoset polymer.
  • the particles may also be composed of a blend of two or more different polymer types and/or compositions.
  • the term "polymer” as used herein is used to mean homopolymers as well as copolymers in which "copolymers” means polymers formed from two or more monomers, including terpolymers, etc..
  • the copolymers can be random or block; heterogeneous or homogeneous, and may be of any morphology including but not limited to linear, branched, star, comb, and core- shell.
  • the polymer particles may be uncrosslinked or crosslinked. Preferably the particles are insoluble in water.
  • the polymer particles may also be impact modified by the addition of from 0 to 100% by weight, based on the weight of the polymer matrix material, of impact modifiers.
  • impact modifiers include copolymers having soft and hard segements, including both linear and core-shell morphologies.
  • the organic polymer particles are made up of polymer chains that generally have an average molecular weight of greater than 50,000 g/mol, and preferably greater than 100,000 g/mol.
  • the polymer particles are made of acrylic polymers.
  • “Acrylic” includes polymers formed from alkyl methacrylate and alkyl acrylate monomers, and mixtures thereof.
  • the alkyl methacrylate monomer is preferably methyl methacrylate, which may make up from 50 to 100 percent of the monomer mixture. 0 to 50 percent of other acrylate and methacrylate monomers or other ethylenically unsaturated monomers, included but not limited to, styrene, alpha methyl styrene, acrylonitrile, and crosslinkers may also be present in the monomer mixture.
  • methacrylate and acrylate monomers useful in the monomer mixture include, but are not limited to, methyl acrylate, 2-ethyl hexyl acrylate and methacrylate, ethyl acrylate and ethyl methacrylate, butyl acrylate and butyl methacrylate, iso-octyl methacrylate and acrylate, lauryl acrylate and lauryl methacrylate, stearyl acrylate and stearyl methacrylate, isobornyl acrylate and methacrylate, methoxy ethyl acrylate and methacrylate, 2-ethoxy ethyl acrylate and methacrylate, dimethylamino ethyl acrylate and methacrylate monomers.
  • Alkyl (meth) acrylic acids such as methyl acrylic acid and acrylic acid can be useful for the monomer mixture.
  • the polymers may be made by methods known in the art including emulsion polyerization, suspension polymerization, bulk polymerization, and solution polymerization.
  • the polymer particles may be formed by means known in the art, including but not limieted to: formed directly from the polymerization (suspension, emulsion); by coagulation of a polymer suspesension or emulsion; into a sheet or other shape from the polymerization process, and ground into particles; or may be extruded to form strands that can be cut into pellets, hi one embodiment the polymer sheet is made by a bulk, cast process.
  • the particles may be screened, or in other ways sorted to provide the desired particle sizes and particle size distribution.
  • One skilled in the art would be able from the description herein to adjust the monomer mixtures, feed levels and feed rates, initiator level, reaction temperature, reaction time, level of crosslinker, and other process conditions to achieve the desired level of hardness, modulus, elasticity, Tg, morphology, molecular weight, particle size and particle size distribution in a manner to produce particles with characteristics suited to the final application.
  • the particles produced can be of any shape - such as cylindrical or irregular, though they are generally round, having median diameters of from 10 to 1,000 microns and preferably 20 to 300 microns.
  • the particle size can be matched to the substrate to be cleaned and/or polished, wherein the smallest particles should be smaller than the smallest dimension of the substrate, to a particle size large enough for cleaning and polishing the larger surfaces. While not being bound by any particular theory, it is believed that a broad particle size distribution allows the small particles to effectively clean and polish small crevices in the substrate, while the larger particles would effectively clean and polish the larger surfaces of the substrate.
  • “broad” particle size distribution is meant that at least 50% of the particles are outside the range that is +/- 25% of the median particle size.
  • the polymer particles are made irregular, through grinding or other means, to provide a rougher particle surface to aid in cleaning of the substrate.
  • the organic polymer particles of the invention are formulated into a fluid- based formulation. More than one type/size of particles can be blended into the formulation.
  • the formulation could be organic-solvent based, provided the solvent does not significantly dissolve the polymer particles.
  • a preferred formulation of the invention is an aqueous-based formulation.
  • aqueous-based as used herein, is meant that the primary liquid is water. Small amounts of other miscible solvents, such as alcohols, could also be present.
  • the fluid-based abrasive formulation contains the polymer particles suspended in a liquid by means known in the art, such as by agitation, sonication, the use of suspending, gelling or thickening additives, or a combination thereof.
  • the abrasive formulation could be in the form of an emulsion or an aqueous gel.
  • the level of polymer particles in the liquid will vary, based on the final application, however the polymer particles are generally used at a level of from 1 to 75 weight percent, preferably from 5 to 60 weight percent, based on the total abrasive formulation. In some applications, as in fluid for cleaning hard metal surface, the formulation preferably contains 30 to 60 weight percent of the abrasive particles.
  • other adjuvants may be present in the media, including, but not limited, to UV absorbers, lubricants, antioxidants, pigments, dyes, buffers, thickeners, and biocides.
  • cosmetic additives such as emulsifiers, aloe, skin softeners, vitamins may also be present.
  • the abrasive formulation could also contain inorganic abrasive particles.
  • the abrasive formulation is adjusted to a low pH of from 1 to 5.
  • the acidic media aid in the cleaning and polishing by etching the surface of the substrates.
  • the etching by an acidic media is the prime cleaning method, with the abrasive polymer particles serving the role of cleaning up the residue of any etching, then further polishing the substrate.
  • the pH is adjusted to minimize irritation.
  • the abrasive formulation is used as a lapping solutions for the cleaning and polishing of stainless steel parts.
  • the aqueous-based abrasive media can be used to clean and polish substrates as hard as stainless steel, and as soft as a baby's skin.
  • Substrates and articles that can be cleaned and polished by using the abrasive formulation o the invention include, but are not limited to, any metal or metallic alloys, plastics, skin, glass and ceramic.
  • the abrasive media of the invention is used in a cosmetic formulation for the cleaning of skin, scalp, or teeth.
  • stainless steel parts are cleaned by an acidic formulation of the polymer abrasive media.
  • Some uses include: a cosmetic formulation for cleansing skin,
  • Organic polymer particles in the formulation, is the possibility of recycling the polymer particles.
  • the polymer particles cause extraneous material (dirt, grime, oils, hazardous materials, ect. from in-use substrates; extra substrate material from newly manufactured substrate pieces) to be removed from the substrate.
  • the used formulation containing a carrier fluid, organic polymer particles and extraneous material can then be separated and recycled.
  • Organic polymer particles can advantageously be separated based on their unique properties, including but not limited to thermal properties, specific gravities, size, and selective solubility in organic solvents. The organic polymer particles can then be reused in a new cleaning polishing formulation.
  • An acrylic polymer with a Rockwell hardness of M-100, as measured using ASTM Method D785 on a 0.236" thick sheet, and a flexural modulus of elasticity of 450 kpsi, as measured using ASTM Method D790, is made by a cast polymerization process and then ground.
  • the granulated acrylic particles have a median size of 75 microns, and 57% of the particles are outside of the range +/- 25% of the median particle size.
  • the particles are added to an aqueous solution with a pH between 2.8- 3.0 at a level of 50% by weight, and suspended in the solution with agitation.
  • Stainless steel articles to be cleaned are submerged in the solution and agitated until they are clean. The articles are then removed from the bath and rinsed to remove any of the residual cleaning solution. The cleaning solution can then be used to clean more parts.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne une formulation liquide abrasive contenant des particules polymères organiques. La formulation est utilisée pour nettoyer et polir des métaux, du plastique, du verre, la peau, des céramiques et d'autres matières. Les particules polymères peuvent être de forme arrondie ou irrégulière. Cette invention a aussi pour objet un procédé d'ajustement des caractéristiques de polymère et de particule, à savoir, le module, l'élasticité, la morphologie, le poids moléculaire, Tg, le degré de durcissement, la granulométrie et la distribution granulométrique, afin de produire une formulation liquide abrasive possédant des propriétés optimales de nettoyage et de polissage pour un substrat donné
PCT/US2008/054714 2007-03-06 2008-02-22 Formulation abrasive contenant des particules polymères organiques WO2008109270A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US89320607P 2007-03-06 2007-03-06
US60/893,206 2007-03-06

Publications (1)

Publication Number Publication Date
WO2008109270A1 true WO2008109270A1 (fr) 2008-09-12

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PCT/US2008/054714 WO2008109270A1 (fr) 2007-03-06 2008-02-22 Formulation abrasive contenant des particules polymères organiques

Country Status (1)

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WO (1) WO2008109270A1 (fr)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009141611A3 (fr) * 2008-05-21 2010-06-17 King's College London Agents abrasifs
US8440603B2 (en) 2011-06-20 2013-05-14 The Procter & Gamble Company Liquid cleaning and/or cleansing composition comprising a polylactic acid biodegradable abrasive
US8440604B2 (en) 2008-09-30 2013-05-14 The Procter & Gamble Company Liquid hard surface cleaning composition
US8440602B2 (en) 2009-12-22 2013-05-14 The Procter & Gamble Company Liquid cleaning and/or cleansing composition comprising a divinyl benzene cross-linked styrene polymer
US8445422B2 (en) 2010-09-21 2013-05-21 The Procter & Gamble Company Liquid cleaning composition
US8470759B2 (en) 2011-06-20 2013-06-25 The Procter & Gamble Company Liquid cleaning and/or cleansing composition comprising a polyhydroxy-alkanoate biodegradable abrasive
US8546316B2 (en) 2010-09-21 2013-10-01 The Procter & Gamble Company Liquid detergent composition with natural abrasive particles
US8551932B2 (en) 2008-09-30 2013-10-08 The Procter & Gamble Company Liquid hard surface cleaning composition
US8569223B2 (en) 2008-09-30 2013-10-29 The Procter & Gamble Company Liquid hard surface cleaning composition
US8629095B2 (en) 2010-04-21 2014-01-14 The Procter & Gamble Company Liquid cleaning and/or cleansing composition comprising polyurethane foam abrasive particles
US8680036B2 (en) 2009-12-22 2014-03-25 The Procter & Gamble Company Liquid cleaning composition comprising color-stable polyurethane abrasive particles
US8759270B2 (en) 2011-06-20 2014-06-24 The Procter & Gamble Company Liquid detergent composition with abrasive particles
US8852643B2 (en) 2011-06-20 2014-10-07 The Procter & Gamble Company Liquid cleaning and/or cleansing composition
US9163201B2 (en) 2012-10-15 2015-10-20 The Procter & Gamble Company Liquid detergent composition with abrasive particles
US9353337B2 (en) 2010-09-21 2016-05-31 The Procter & Gamble Company Liquid cleaning composition
WO2017027344A1 (fr) * 2015-08-12 2017-02-16 The Procter & Gamble Company Compositions de nettoyage de peau comprenant des particules abrasives biodégradables
US9957468B2 (en) 2015-11-06 2018-05-01 The Procter & Gamble Company Shaped particles
US10266793B2 (en) 2016-09-30 2019-04-23 Novaflux, Inc. Compositions for cleaning and decontamination
US10806692B2 (en) 2016-10-03 2020-10-20 The Procter & Gamble Company Skin cleansing compositions comprising color stable abrasive particles
US11345878B2 (en) 2018-04-03 2022-05-31 Novaflux Inc. Cleaning composition with superabsorbent polymer
US11918677B2 (en) 2019-10-03 2024-03-05 Protegera, Inc. Oral cavity cleaning composition method and apparatus
US12064495B2 (en) 2019-10-03 2024-08-20 Protegera, Inc. Oral cavity cleaning composition, method, and apparatus

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010039322A1 (en) * 1998-11-05 2001-11-08 Jsr Corporation Polymer particles and polishing material containing them
US20020042200A1 (en) * 2000-10-02 2002-04-11 Clyde Fawcett Method for conditioning polishing pads
US20020173243A1 (en) * 2001-04-05 2002-11-21 Costas Wesley D. Polishing composition having organic polymer particles

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010039322A1 (en) * 1998-11-05 2001-11-08 Jsr Corporation Polymer particles and polishing material containing them
US20020042200A1 (en) * 2000-10-02 2002-04-11 Clyde Fawcett Method for conditioning polishing pads
US20020173243A1 (en) * 2001-04-05 2002-11-21 Costas Wesley D. Polishing composition having organic polymer particles

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009141611A3 (fr) * 2008-05-21 2010-06-17 King's College London Agents abrasifs
US8569223B2 (en) 2008-09-30 2013-10-29 The Procter & Gamble Company Liquid hard surface cleaning composition
US8440604B2 (en) 2008-09-30 2013-05-14 The Procter & Gamble Company Liquid hard surface cleaning composition
US8551932B2 (en) 2008-09-30 2013-10-08 The Procter & Gamble Company Liquid hard surface cleaning composition
US9163200B2 (en) 2009-12-22 2015-10-20 The Procter & Gamble Company Liquid cleaning and/or cleansing composition
US8440602B2 (en) 2009-12-22 2013-05-14 The Procter & Gamble Company Liquid cleaning and/or cleansing composition comprising a divinyl benzene cross-linked styrene polymer
US8680036B2 (en) 2009-12-22 2014-03-25 The Procter & Gamble Company Liquid cleaning composition comprising color-stable polyurethane abrasive particles
US8629095B2 (en) 2010-04-21 2014-01-14 The Procter & Gamble Company Liquid cleaning and/or cleansing composition comprising polyurethane foam abrasive particles
US8445422B2 (en) 2010-09-21 2013-05-21 The Procter & Gamble Company Liquid cleaning composition
US8546316B2 (en) 2010-09-21 2013-10-01 The Procter & Gamble Company Liquid detergent composition with natural abrasive particles
US9353337B2 (en) 2010-09-21 2016-05-31 The Procter & Gamble Company Liquid cleaning composition
US8470759B2 (en) 2011-06-20 2013-06-25 The Procter & Gamble Company Liquid cleaning and/or cleansing composition comprising a polyhydroxy-alkanoate biodegradable abrasive
US8703685B2 (en) 2011-06-20 2014-04-22 The Procter & Gamble Company Liquid cleaning and/or cleansing composition comprising polylactic acid abrasives
US8759270B2 (en) 2011-06-20 2014-06-24 The Procter & Gamble Company Liquid detergent composition with abrasive particles
US8852643B2 (en) 2011-06-20 2014-10-07 The Procter & Gamble Company Liquid cleaning and/or cleansing composition
US8440603B2 (en) 2011-06-20 2013-05-14 The Procter & Gamble Company Liquid cleaning and/or cleansing composition comprising a polylactic acid biodegradable abrasive
US9163201B2 (en) 2012-10-15 2015-10-20 The Procter & Gamble Company Liquid detergent composition with abrasive particles
WO2017027344A1 (fr) * 2015-08-12 2017-02-16 The Procter & Gamble Company Compositions de nettoyage de peau comprenant des particules abrasives biodégradables
CN107847420A (zh) * 2015-08-12 2018-03-27 宝洁公司 包含生物可降解的磨粒的皮肤清洁组合物
JP2018522059A (ja) * 2015-08-12 2018-08-09 ザ プロクター アンド ギャンブル カンパニー 生分解性研磨材粒子を含む皮膚クレンジング組成物
US9957468B2 (en) 2015-11-06 2018-05-01 The Procter & Gamble Company Shaped particles
US11680226B2 (en) 2016-09-30 2023-06-20 Novaflux, Inc.. Compositions for cleaning and decontamination
US11326128B2 (en) 2016-09-30 2022-05-10 Novaflux, Inc. Compositions for cleaning and decontamination
US10266793B2 (en) 2016-09-30 2019-04-23 Novaflux, Inc. Compositions for cleaning and decontamination
US10806692B2 (en) 2016-10-03 2020-10-20 The Procter & Gamble Company Skin cleansing compositions comprising color stable abrasive particles
US11166905B2 (en) 2016-10-03 2021-11-09 The Procter & Gamble Company Skin cleansing compositions comprising color stable abrasive particles
US11345878B2 (en) 2018-04-03 2022-05-31 Novaflux Inc. Cleaning composition with superabsorbent polymer
US12060539B2 (en) 2018-04-03 2024-08-13 Novaflux Inc. Cleaning composition with superabsorbent polymer
US11918677B2 (en) 2019-10-03 2024-03-05 Protegera, Inc. Oral cavity cleaning composition method and apparatus
US12064495B2 (en) 2019-10-03 2024-08-20 Protegera, Inc. Oral cavity cleaning composition, method, and apparatus

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