EP2697416B1 - Nonwoven abrasive article containing elastomer bound agglomerates of shaped abrasive grain - Google Patents

Nonwoven abrasive article containing elastomer bound agglomerates of shaped abrasive grain Download PDF

Info

Publication number
EP2697416B1
EP2697416B1 EP12771150.5A EP12771150A EP2697416B1 EP 2697416 B1 EP2697416 B1 EP 2697416B1 EP 12771150 A EP12771150 A EP 12771150A EP 2697416 B1 EP2697416 B1 EP 2697416B1
Authority
EP
European Patent Office
Prior art keywords
abrasive
nonwoven
particles
agglomerates
binder
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.)
Active
Application number
EP12771150.5A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP2697416A2 (en
EP2697416A4 (en
Inventor
Bret W. Ludwig
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.)
3M Innovative Properties Co
Original Assignee
3M Innovative Properties Co
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 3M Innovative Properties Co filed Critical 3M Innovative Properties Co
Publication of EP2697416A2 publication Critical patent/EP2697416A2/en
Publication of EP2697416A4 publication Critical patent/EP2697416A4/en
Application granted granted Critical
Publication of EP2697416B1 publication Critical patent/EP2697416B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B24GRINDING; POLISHING
    • B24DTOOLS FOR GRINDING, BUFFING OR SHARPENING
    • B24D3/00Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
    • B24D3/02Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
    • B24D3/20Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially organic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B24GRINDING; POLISHING
    • B24DTOOLS FOR GRINDING, BUFFING OR SHARPENING
    • B24D3/00Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B24GRINDING; POLISHING
    • B24DTOOLS FOR GRINDING, BUFFING OR SHARPENING
    • B24D3/00Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
    • B24D3/02Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
    • B24D3/20Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially organic
    • B24D3/28Resins or natural or synthetic macromolecular compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B24GRINDING; POLISHING
    • B24DTOOLS FOR GRINDING, BUFFING OR SHARPENING
    • B24D11/00Constructional features of flexible abrasive materials; Special features in the manufacture of such materials
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/413Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties containing granules other than absorbent substances
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions

Definitions

  • Nonwoven abrasive articles generally have a nonwoven web (e.g., a lofty open fibrous web), abrasive particles, and a binder material (commonly termed a "binder") that bonds the fibers within the nonwoven web to each other and secures the abrasive particles to the nonwoven web.
  • a binder material commonly termed a "binder”
  • nonwoven abrasive articles include nonwoven abrasive hand pads such as those marketed by 3M Company of Saint Paul, Minnesota under the trade designation "SCOTCH-BRITE".
  • nonwoven abrasive articles include convolute abrasive wheels and unitized abrasive wheels.
  • Nonwoven abrasive wheels typically have abrasive particles distributed through the layers of nonwoven web bonded together with a binder that bonds layers of nonwoven webs together, and likewise bonds the abrasive particles to the nonwoven web.
  • Unitized abrasive wheels have individual discs of nonwoven web arranged in a parallel fashion to form a cylinder having a hollow axial core.
  • convolute abrasive wheels have a nonwoven web that is spirally wound about and affixed to a core member.
  • nonwoven abrasive articles while using them on a work piece are import performance attributes. For some applications, reducing the resulting surface roughness (finish) on the work piece while maintaining or even increasing the cut of the nonwoven abrasive article in use is very desirable. It was surprisingly found that nonwoven abrasive articles according to the present invention exhibit significant improvements in the surface finish, as evaluated according to the test methods disclosed, when compared to alternative nonwoven abrasive articles as shown in the Examples.
  • the flexible bound agglomerates of formed abrasive particles produced a finer finish than nonwoven abrasive articles made using the identical formed abrasive particles that were not agglomerated.
  • agglomerating the formed abrasive particles would only increase the life of the abrasive article, and the resulting finish would be identical to non-agglomerated abrasive particles having the identical size.
  • the invention resides in a nonwoven abrasive article comprising a nonwoven web; agglomerates comprising formed ceramic abrasive particles bound together by a first flexible binder; and a second binder binding the agglomerates to the nonwoven fiber web.
  • cur means hardening a material, either by drying (i.e., evaporation of solvent), polymerizing (e.g., providing a sufficient degree of chain extension of the curable polyurethane prepolymer), or cooling a molten material.
  • the term "flexible binder” means that the cured binder material has a modulus of elasticity such that the cured binder material is able to bend a significant amount without breaking unlike a phenolic binder which would break.
  • the modulus of elasticity is less than 28,000 psi (193,053 kPa).
  • the modulus of elasticity can be less than 25,000 psi (172,369 kPa) or less than 23,000 psi (158,579 kPa) as tested by ASTM D882.
  • Suitable flexible binders include those of polyurethane, polyurea, polyisoprene, polybutadiene, polychloroprene, butyl rubber, styrene-butadiene copolymer, and nitrile rubber.
  • formed ceramic abrasive particle means an abrasive particle having at least a partially replicated shape.
  • Non-limiting processes to make formed abrasive particles include shaping the precursor ceramic abrasive particle in a mold having a predetermined shape to make shaped ceramic abrasive particles, extruding the precursor ceramic abrasive particle through an orifice having a predetermined shape, printing the precursor ceramic abrasive particle though an opening in a printing screen having a predetermined shape, or embossing the precursor ceramic abrasive particle into a predetermined shape or pattern.
  • Non-limiting examples of formed ceramic abrasive particles include shaped ceramic abrasive particles, such as triangular plates as disclosed in U.S.
  • the term “mineral” means abrasive particles or a mixture of abrasive particles and filler.
  • exemplary abrasive articles according to the present invention including lofty open nonwoven abrasive articles (e.g., webs and sheets), unitized abrasive wheels, and convolute abrasive wheels, may be manufactured through processes that include steps such as, for example, coating a curable composition, typically in slurry form, on a nonwoven web.
  • the curable composition comprises: a curable polyurethane prepolymer; an effective amount of an amine curative; at least one of a cationic surfactant, anionic surfactant, fluorinated nonionic surfactant, or silicone-based nonionic surfactant; and a dipodal aminosilane.
  • the nonwoven web is typically compressed (i.e., densified) relative to nonwoven webs used in lofty open nonwoven fiber articles.
  • Nonwoven webs suitable for use in the aforementioned abrasive articles are well known in the abrasives art.
  • the nonwoven web comprises an entangled web of fibers.
  • the fibers may comprise continuous fiber, staple fiber, or a combination thereof.
  • the nonwoven web may comprise staple fibers having a length of at least about 20 millimeters (mm), at least about 30 mm, or at least about 40 mm, and less than about 110 mm, less than about 85 mm, or less than about 65 mm, although shorter and longer fibers (e.g., continuous filaments) may also be useful.
  • the fibers may have a fineness or linear density of at least about 1.7 decitex (dtex, i.e., grams/10000 meters), at least about 6 dtex, or at least about 17 dtex, and less than about 560 dtex, less than about 280 dtex, or less than about 120 dtex, although fibers having lesser and/or greater linear densities may also be useful. Mixtures of fibers with differing linear densities may be useful, for example, to provide an abrasive article that upon use will result in a specifically preferred surface finish. If a spunbond nonwoven is used, the filaments may be of substantially larger diameter, for example, up to 2 mm or more in diameter.
  • the nonwoven web may be manufactured, for example, by conventional air laid, carded, stitch bonded, spun bonded, wet laid, and/or melt blown procedures.
  • Air laid nonwoven webs may be prepared using equipment such as, for example, that available under the trade designation "RANDO WEBBER” commercially available from Rando Machine Company of Ard, New York.
  • Nonwoven webs are typically selected to be suitably compatible with adhering binders and abrasive particles while also being processable in combination with other components of the article, and typically can withstand processing conditions (e.g., temperatures) such as those employed during application and curing of the curable composition.
  • the fibers may be chosen to affect properties of the abrasive article such as, for example, flexibility, elasticity, durability or longevity, abrasiveness, and finishing properties.
  • Examples of fibers that may be suitable include natural fibers, synthetic fibers, and mixtures of natural and/or synthetic fibers.
  • Examples of synthetic fibers include those made from polyester (e.g., polyethylene terephthalate), nylon (e.g., hexamethylene adipamide, polycaprolactam), polypropylene, acrylonitrile (i.e., acrylic), rayon, cellulose acetate, polyvinylidene chloride-vinyl chloride copolymers, and vinyl chloride-acrylonitrile copolymers.
  • suitable natural fibers include cotton, wool, jute, and hemp.
  • the fiber may be of virgin material or of recycled or waste material, for example, reclaimed from garment cuttings, carpet manufacturing, fiber manufacturing, or textile processing.
  • the fiber may be homogenous or a composite such as a bicomponent fiber (e.g., a co-spun sheath-core fiber).
  • the fibers may be tensilized and crimped, but may also be continuous filaments such as those formed by an extrusion process. Combinations of fibers may also be used.
  • the nonwoven fiber web Prior to impregnation with the curable composition, the nonwoven fiber web typically has a weight per unit area (i.e., basis weight) of at least about 50 grams per square meter (gsm), at least about 100 gsm, or at least about 200 gsm; and/or less than about 400 gsm, less than about 350 gsm, or less than about 300 gsm, as measured prior to any coating (e.g., with the curable composition or optional pre-bond resin), although greater and lesser basis weights may also be used.
  • basis weight i.e., basis weight
  • the fiber web prior to impregnation with the curable composition, typically has a thickness of at least about 5 mm, at least about 6 mm, or at least about 10 mm; and/or less than about 200 mm, less than about 75 mm, or less than about 30 mm, although greater and lesser thicknesses may also be useful.
  • prebond resin serves, for example, to help maintain the nonwoven web integrity during handling, and may also facilitate bonding of a urethane binder to the nonwoven web.
  • prebond resins include phenolic resins, urethane resins, hide glue, acrylic resins, urea-formaldehyde resins, melamine-formaldehyde resins, epoxy resins, and combinations thereof.
  • the amount of prebond resin used in this manner is typically adjusted toward the minimum amount consistent with bonding the fibers together at their points of crossing contact. If the nonwoven web includes thermally bondable fibers, thermal bonding of the nonwoven web may also be helpful to maintain web integrity during processing.
  • Useful abrasive particles for incorporating into the agglomerates of the invention are formed ceramic abrasive particles and, in particular, shaped ceramic abrasive particles.
  • Shaped ceramic abrasive particles were prepared according to the disclosures of copending U.S. Patent Publication 2010/0151196 .
  • the shaped ceramic abrasive particles were prepared by shaping alumina sol gel from, for example, equilateral triangle-shaped polypropylene mold cavities of side length 0.054 inch (1.37 mm) and a mold depth of 0.012 inch (0.3 mm). After drying and firing, such resulting shaped ceramic abrasive particles comprised triangular plates that were about 570 micrometers (longest dimension) and would pass through a 30-mesh sieve.
  • inventive articles may also contain conventional (e.g., crushed) abrasive particles.
  • conventional abrasive particles for blending with the shaped ceramic abrasive particles include any abrasive particles known in the abrasive art.
  • Exemplary useful abrasive particles include fused aluminum oxide based materials such as aluminum oxide, ceramic aluminum oxide (which may include one or more metal oxide modifiers and/or seeding or nucleating agents), and heat-treated aluminum oxide, silicon carbide, co-fused alumina-zirconia, diamond, ceria, titanium diboride, cubic boron nitride, boron carbide, garnet, flint, emery, sol-gel derived abrasive particles, and mixtures thereof.
  • the abrasive particles may be in the form of, for example, individual particles, agglomerates, composite particles, and mixtures thereof.
  • the conventional abrasive particles may, for example, have an average diameter of at least about 0.1 micrometer, at least about 1 micrometer, or at least about 10 micrometers, and less than about 2000, less than about 1300 micrometers, or less than about 1000 micrometers, although larger and smaller abrasive particles may also be used.
  • the conventional abrasive particles may have an abrasives industry specified nominal grade.
  • Such abrasives industry accepted grading standards include those known as the American National Standards Institute, Inc. (ANSI) standards, Federation of European Producers of Abrasive Products (FEPA) standards, and Japanese Industrial Standard (JIS) standards.
  • Exemplary ANSI grade designations include: ANSI 4, ANSI 6, ANSI 8, ANSI 16, ANSI 24, ANSI 36, ANSI 40, ANSI 50, ANSI 60, ANSI 80, ANSI 100, ANSI 120, ANSI 150, ANSI 180, ANSI 220, ANSI 240, ANSI 280, ANSI 320, ANSI 360, ANSI 400, and ANSI 600.
  • Exemplary FEPA grade designations include P8, P12, P16, P24, P36, P40, P50, P60, P80, P100, P120, P150, P180, P220, P320, P400, P500, 600, P800, P1000, and P1200.
  • Exemplary JIS grade designations include HS8, JIS12, JIS16, JIS24, JIS36, JIS46, JIS54, JIS60, JIS80, JIS100, JIS 150, JIS 180, JIS220, JIS 240, JIS280, JIS320, JIS360, JIS400, JIS400, JIS600, JIS800, JIS1000, JIS1500, JIS2500, JIS4000, JIS6000, JIS8000, and JIS10000.
  • the inventive agglomerates comprise a first flexible binder.
  • suitable flexible binders include those of polyurethane, polyurea, polyisoprene, polybutadiene, polychloroprene, butyl rubber, styrene-butadiene copolymer, and nitrile rubber.
  • a typical flexible binder for preparation of agglomerates comprising formed ceramic abrasive particles is a polyurethane binder.
  • useful urethane prepolymers include polyisocyanates and blocked versions thereof.
  • blocked polyisocyanates are substantially unreactive to isocyanate reactive compounds (e.g., amines, alcohols, thiols, etc.) under ambient conditions (e.g., temperatures in a range of from about 20 °C to about 25 °C), but upon application of sufficient thermal energy the blocking agent is released, thereby generating isocyanate functionality that reacts with the amine curative to form a covalent bond.
  • Useful polyisocyanates include, for example, aliphatic polyisocyanates (e.g., hexamethylene diisocyanate or trimethylhexamethylene diisocyanate); alicyclic polyisocyanates (e.g., hydrogenated xylylene diisocyanate or isophorone diisocyanate); aromatic polyisocyanates (e.g., tolylene diisocyanate or 4,4'-diphenylmethane diisocyanate); adducts of any of the foregoing polyisocyanates with a polyhydric alcohol (e.g., a diol, low molecular weight hydroxyl group-containing polyester resin, water, etc.); adducts of the foregoing polyisocyanates (e.g., isocyanurates, biurets); and mixtures thereof.
  • aliphatic polyisocyanates e.g., hexamethylene diisocyanate or trimethylhexamethylene diis
  • polyisocyanates include, for example, those available under the trade designation "ADIPRENE” from Chemtura Corporation, Middlebury, Connecticut (e.g., “ADIPRENE L 0311”, “ADIPRENE L 100”, “ADIPRENE L 167", “ADIPRENE L 213", “ADIPRENE L 315", “ADIPRENE L 680”, “ADIPRENE LF 1800A”, “ADIPRENE LF 600D”, “ADIPRENE LFP 1950A”, “ADIPRENE LFP 2950A”, “ADIPRENE LFP 590D”, “ADIPRENE LW 520", and “ADIPRENE PP 1095”); polyisocyanates available under the trade designation "MONDUR” from Bayer Corporation, Pittsburgh, Pennsylvania (e.g., “MONDUR 1437”, “MONDUR MP-095", or “MONDUR 448”); and polyisocyanates available under the trade designations "AIRTHANE” and “VERSATHANE” from Air Products and Chemicals, Allentown, Pennsylvania (e.g., "AIRTH
  • polyisocyanates such as, for example, those mentioned above may be blocked with a blocking agent according to various techniques known in the art.
  • blocking agents include ketoximes (e.g., 2-butanone oxime); lactams (e.g., epsilon-caprolactam); malonic esters (e.g., dimethyl malonate and diethyl malonate); pyrazoles (e.g., 3,5-dimethylpyrazole); alcohols including tertiary alcohols (e.g., t-butanol or 2,2-dimethylpentanol), phenols (e.g., alkylated phenols), and mixtures of alcohols as described.
  • ketoximes e.g., 2-butanone oxime
  • lactams e.g., epsilon-caprolactam
  • malonic esters e.g., dimethyl malonate and diethyl malonate
  • pyrazoles
  • Exemplary useful commercially-available blocked polyisocyanates include those marketed by Chemtura Corporation under the trade designations "ADIPRENE BL 11", “ADIPRENE BL 16", “ADIPRENE BL 31”, and blocked polyisocyanates marketed by Baxenden Chemicals, Ltd., Accrington, England under the trade designation “TRIXENE” (e.g., "TRIXENE BL 7641”, “TRIXENE BL 7642”, “TRIXENE BL 7772", and “TRIXENE BL 7774").
  • the amount of urethane prepolymer present in the curable composition is in an amount of from 10 to 40 percent by weight, more typically in an amount of from 15 to 30 percent by weight, and even more typically in an amount of from 20 to 25 percent by weight based on the total weight of the curable composition, although amounts outside of these ranges may also be used.
  • Suitable amine curatives include aromatic, alkyl-aromatic, or alkyl polyfunctional amines, preferably primary amines.
  • useful amine curatives include 4,4'-methylenedianiline; polymeric methylene dianilines having a functionality of 2.1 to 4.0 which include those known under the trade designations "CURITHANE 103", commercially available from the Dow Chemical Company, and "MDA-85” from Bayer Corporation, Pittsburgh, Pennsylvania; 1,5-diamine-2-methylpentane; tris(2-aminoethyl) amine; 3-aminomethyl-3,5,5-trimethylcyclohexylamine (i.e., isophoronediamine), trimethylene glycol di-p-aminobenzoate, bis(o-aminophenylthio)ethane, 4,4'-methylenebis(dimethyl anthranilate), bis(4-amino-3-ethylphenyl)methane (e.g., as marketed under the trade
  • the amine curative should be present in an amount effective (i.e., an effective amount) to cure the blocked polyisocyanate to the degree required by the intended application; for example, the amine curative may be present in a stoichiometric ratio of curative to isocyanate (or blocked isocyanate) in a range of from 0.8 to 1.35; for example, in a range of from 0.85 to 1.20, or in a range of from 0.90 to 0.95, although stoichiometric ratios outside these ranges may also be used.
  • the curable composition will include at least one organic solvent (e.g., isopropyl alcohol or methyl ethyl ketone) to facilitate coating of the curable composition on the nonwoven fiber web, although this is not a requirement.
  • the curable composition may be mixed with and/or include one or more additives.
  • additives include fillers, plasticizers, surfactants, lubricants, colorants (e.g., pigments), bactericides, fungicides, grinding aids, and antistatic agents.
  • the curable composition (including any solvent that may be present) is coated onto the nonwoven fiber web in an amount of from 1120 to 2080 gsm, more typically 1280 - 1920 gsm, and even more typically 1440 - 1760 gsm, although values outside these ranges may also be used.
  • Filler materials other than conventional abrasive particles may be blended with shaped ceramic abrasive particles in the inventive agglomerates.
  • useful fillers for this invention include metal carbonates (such as calcium carbonate, calcium magnesium carbonate, sodium carbonate, magnesium carbonate), silica (such as quartz, glass beads, glass bubbles and glass fibers), silicates (such as talc, clays, montmorillonite, feldspar, mica, calcium silicate, calcium metasilicate, sodium aluminosilicate, sodium silicate), metal sulfates (such as calcium sulfate, barium sulfate, sodium sulfate, aluminum sodium sulfate, aluminum sulfate), gypsum, vermiculite, sugar, wood flour, aluminum trihydrate, carbon black, metal oxides (such as calcium oxide, aluminum oxide, tin oxide, titanium dioxide), metal sulfites (such as calcium sulfite), thermoplastic particles (such as polycarbonate, polyetherimide,
  • the filler may also be a salt such as a halide salt.
  • halide salts include sodium chloride, potassium cryolite, sodium cryolite, ammonium cryolite, potassium tetrafluoroborate, sodium tetrafluoroborate, silicon fluorides, potassium chloride, magnesium chloride.
  • metal fillers include, tin, lead, bismuth, cobalt, antimony, cadmium, iron and titanium.
  • Other miscellaneous fillers include sulfur, organic sulfur compounds, graphite, lithium stearate and metallic sulfides.
  • the size of the agglomerates have a maximum diameter (if generally spherical) or a maximum side edge length (if generally cylindrical, ovoid, or other geometric shape) ranging from 0.8 mm to 5 mm, or 1.4 mm to 4 mm, or 1.8 to 3 mm and may be spherical, ovoid, cylindrical, pyramidal, conical or any multi-sided Platonic solid (tetrahedron, octahedron, etc.).
  • the ratio of the formed abrasive particle size (measuring the edge length of the formed abrasive particles) divided by the agglomerate size (measuring the maximum diameter or maximum side edge length of the agglomerate) is 0.0033 to 0.5 (approximately 300 to 2 formed abrasive particles across the agglomerate), or 0.01 to 0.33 (approximately 100 to 3 formed abrasive particles across the agglomerate), or 0.05 to 0.25 (approximately 20 to 4 formed abrasive particles across the agglomerate).
  • filler particles conventional crushed abrasive particles or diluents
  • they have an average particle size less than that of the formed ceramic abrasive particles, or the ratio of the filler particle size (maximum diameter) divided by the formed abrasive particles size (measuring the maximum diameter or maximum side edge length of the agglomerate) is 0.001 to 1.0, or 0.003 to 0.5, or 0.01 to 0.1.
  • Typical inventive agglomerates can comprise no more than 30 weight percent (wt. %) first flexible binder, no more than 20 wt. % first flexible binder, no more than 15 wt. % first flexible binder, or even no more than 10 wt.
  • Typical inventive agglomerates comprise at least 50 wt. % formed ceramic abrasive particles.
  • the formed ceramic abrasive particle content is 50 wt. % to 98 wt. %, 75 wt. % to 96 wt. %, or 80 wt. % to 94 wt. %;
  • the resin content is 2 wt. % to 20 wt. %, 4 wt. % to 10 wt. %, or 5 wt. % to 8 wt. %;
  • the filler particle content is 0 wt. % to 40 wt. %, 10 wt. % to 35 wt. %, or 15 wt. % to 30 wt. %. It is understood the above ranges for the various properties can be combined or selected in any manner to specify the agglomerate's attributes.
  • the nonwoven abrasive web is prepared by adhering the agglomerates of the invention to a nonwoven web with a curable second binder.
  • the coating weight for the abrasive agglomerates may depend, for example, on the particular second binder used, the process for applying the abrasive agglomerates, and the size of the abrasive agglomerates.
  • the coating weight of the abrasive agglomerates on the nonwoven web may be at least 200 grams per square meter (g/m), at least 600 g/m, or at least 800 g/m; and/or less than 2000 g/m, less than about 1600 g/m, or less than about 1200 g/m, although greater or lesser coating weights may be also be used.
  • Second binders useful for adhering the agglomerates to the nonwoven fiber web are known in the art and are selected according to the final product requirements.
  • Typical binders include those comprising polyurethane, phenolic, acrylate, and blends of phenolic and acrylate.
  • Useful polyurethane binder materials and their precursors for adhering agglomerates to nonwoven web have been described herein above.
  • Phenolic materials are useful binder precursors because of their thermal properties, availability, cost, and ease of handling.
  • Resole phenolics have a molar ratio of formaldehyde to phenol of greater than or equal to one, typically between 1.5:1.0 to 3.0:1.0.
  • Novolac phenolics have a molar ratio of formaldehyde to phenol of less than 1.0:1.0.
  • Examples of commercially available phenolics include those known by the trade names DUREZ and VARCUM from Occidental Chemicals Corp.; RESINOX from Monsanto; AROFENE from Ashland Chemical Co. and AROTAP from Ashland Chemical Co.
  • Emulsions of crosslinked acrylic resin particles may also find utility in the present invention.
  • Some binder precursors include a phenolic mixed with a latex.
  • latexes include materials containing acrylonitrile butadiene, acrylics, butadiene, butadiene-styrene, and combinations thereof.
  • These latexes are commercially available from a variety of different sources and include those available under the trade designations RHOPLEX and ACRYLSOL commercially available from Rohm and Haas Company, FLEXCRYL and VALTAC commercially available from Air Products & Chemicals Inc., SYNTHEMUL, TYCRYL, and TYLAC commercially available from Reichold Chemical Co., HYCAR and GOODRITE commercially available from B. F. Goodrich, CHEMIGUM commercially available from Goodyear Tire and Rubber Co., NEOCRYL commercially available from ICI, BUTAFON commercially available from BASF, and RES commercially available from Union Carbide.
  • Nonwoven abrasive articles of the invention may take any of a variety of conventional forms.
  • FIG. 1 shows a nonwoven abrasive article 100 comprising a nonwoven web; agglomerates comprising formed ceramic abrasive particles bound together by a first flexible binder; and a second binder binding the agglomerates to the nonwoven fiber web.
  • FIGS. 4-6 show abrasive agglomerates comprising shaped ceramic abrasive particles and a first flexible binder.
  • the shaped ceramic abrasive particles comprises triangular plates as seen.
  • Nonwoven abrasive articles are in the form of wheels.
  • Nonwoven abrasive wheels are typically in the form of a disc or right cylinder having dimensions that may be very small, e.g., a cylinder height on the order of a few millimeters or very large, e.g., a meter or more, and a diameter which may be very small, e.g., on the order of a few centimeters, or very large, e.g., tens of centimeters.
  • Wheels typically have a central opening for support by an appropriate arbor or other mechanical holding means to enable the wheels to be rotated in use. Wheel dimensions, configurations, means of support, and means of rotation are all well known in the art.
  • Convolute abrasive wheels may be provided, for example, by winding the nonwoven web that has been impregnated with the curable composition under tension around a core member (e.g., a tubular or rod-shaped core member) such that the impregnated nonwoven layers become compressed, and then curing the curable composition to provide, in one embodiment, a polyurethane binder binding the abrasive agglomerates to the layered nonwoven web and binding layers of the layered nonwoven web to each other.
  • a core member e.g., a tubular or rod-shaped core member
  • layered nonwoven fiber web 210 coated with binder binding the abrasive agglomerates to the layered nonwoven fiber web and binding layers of the layered nonwoven fiber web to each other is spirally disposed around and affixed to core member 230.
  • convolute abrasive wheels may be dressed prior to use to remove surface irregularities, for example, using methods known in the abrasive arts.
  • An exemplary unitized abrasive wheel is shown in FIG. 3 , and can be provided, for example, by layering the impregnated above-provided nonwoven web 310 (e.g., as a layered continuous web or as a stack of sheets) compressing the nonwoven layers, curing the curable composition (e.g., using heat), and die cutting the resultant abrasive article to provide a unitized abrasive wheel having a hollow axial core 320.
  • the layers are typically compressed to form a bun having a density that is from 1 to 20 times that of the density of the layers in their non-compressed state.
  • the bun is then typically subjected to heat molding (e.g., for from 2 to 20 hours) at elevated temperature (e.g., at 135 °C), typically depending on the urethane prepolymer and bun size.
  • Agglomerated binder solutions for the Examples were prepared by mixing components as described below.
  • Binder AR1 was 72.3% BL16, 26.8% K-450S, and 0.9% D-1122.
  • Binder AR2 was 63.9% Phenolic, 27.7% tap water, 7.8% SR511, and 0.6% D-1122.
  • Binder AR3 was 87% of a free radical-cured resin selected from Acrylic1 through Acrylic7, inclusive, and 13% Initiator S.
  • Binder AR4 was 61.4% BL16, 22.7% K4-450S, 15.3% PMA, and 0.6% D-1122.
  • Agglomerate precursor compositions included mineral (abrasive particles with optional fillers) and binder mixed by hand with a spatula.
  • Agglomerates prepared with AR1, AR2, and AR4 were 94 wt. % mineral based on solids content.
  • Agglomerates prepared with AR3 were 90 wt. % mineral based on solids content.
  • a stainless steel putty knife was used to force an agglomerate precursor composition into the cavities of 15 cm by 86 cm sheets of microreplicated polypropylene tooling.
  • the tooling had total thickness of 2.2 mm, a plurality of precisely-shaped, microreplicated cavities 4.0 mm square and 1.6 mm deep separated by walls 1.5 mm thick.
  • the tooling was prepared from a corresponding master roll generally according to the procedure of U.S. Pat. No. 6,076,248 to Hoopman et al.
  • Filled sheets of polypropylene tooling were heated in a forced air oven to cure the agglomerates.
  • Urethane agglomerates were cured for 20 minutes at 260 °F (127 °C).
  • Phenolic agglomerates were cured at 200 °F (91 °C) for 90 minutes followed by 16 hours at 215 °F (102 °C).
  • Agglomerates containing free radical cured resins were cured for 30 minutes at 280°F (138 °C).
  • the cured agglomerates were removed from the tooling by ultrasonic energy. More particularly, the backside of the tooling was pulled, under tension, across the forward edge of an ultrasonic horn tapered to a single edge.
  • the horn was oscillated at a frequency of 19,100 HZ at amplitude of about 130 micrometers.
  • the horn was composed of 6-4 titanium and was driven with a 900 watt 184 V Branson power source coupled with a 2:1 Booster 802 piezoelectric converter. Examples of the resulting abrasive agglomerates are shown in FIG. 4 .
  • abrasive particles 3000 grams was thoroughly mixed with 250 grams of AR1 producing a friable, tacky agglomerate precursor composition.
  • the agglomerate precursor composition was processed into abrasive agglomerate particles with the aid of a size reduction machine obtained under the trade designation "QUADRO COMIL" ("Model #197", Quadro Engineering Incorporated, Waterloo, Ontario, Canada). Details of the operation of the size reduction machine can be found in WO 02/32832 A1 to Culler et.al.
  • the premix was forced through the 75 mil (1.9 mm) circular openings of a conical screen using an impeller driven at a range of 50 rpm to 3500 rpm.
  • the filamentary shaped agglomerate precursor particle separates and falls by gravity to an aluminum collection pan.
  • a mono- or bi-layer of precursor particles were collected in a pan, which was then placed in an oven set to 320 °F (160 °C) for 15 minutes in order to cure the binder resin.
  • the abrasive agglomerate particles were size-reduced by running them once through the size reduction machine ("QUADRO COMIL") set up with a conical screen pierced by 95 mil (2.4 mm) round holes. The size-reduced particles were sieved on a 14-mesh (1400 micron) screen. Those particles retained on the screen were used to produce unitized abrasive wheels.
  • FIG. 5 An example of the abrasive agglomerate is shown in FIG. 5 .
  • Agglomerates of abrasive grain, or abrasive grain and fillers were produced by applying drops of AR4 to beds of mineral one to two centimeters in thickness. Drops were produced by feeding the solution through a blunt-tipped 22-guage hypodermic needle supported in a vertical position approximately seven centimeters above the mineral bed. The resin droplets wicked into the mineral beds within 10 seconds of application, wetting a volume of material dependent upon the surface area of the mineral or mineral/filler blends. The agglomerates were cured at 302°F (150 °C) for 30 minutes and then sieved from the non-agglomerated mineral, which was recycled back into the agglomerate forming process.
  • AR2 was dripped onto the mineral or mineral/filler bed in a similar manner and cured at 200 °F (91 °C) for 90 minutes followed by 16 hours at 215 °F (102 °C).
  • Individual agglomerates weighed between 0.033 and 0.076 grams and contained from twelve to four percent resin by weight.
  • An example of the resulting abrasive agglomerate is show in FIG. 6 .
  • a nonwoven web was formed on an air laid fiber web forming machine, available under the trade designation "RANDO-WEBBER” from the Rando Machine Corporation of Ard, New York.
  • the fiber web was formed from 70 denier nylon crimp set fiber with a staple length of one and one-half inches (available from E. I. du Pont de Nemours & Company, Wilmington, Delaware).
  • the weight of the web was approximately 105 grams per square meter (gsm), and the thickness was approximately 0.4 inches (10 mm).
  • the web was conveyed to a horizontal, two-roll coater, where a pre-bond resin was applied at a wet add-on weight of 89 gsm.
  • the pre-bond resin had the following composition (all percentages relative to component weight): 54.1% BL16, 19.9% K450S, 26% PMA.
  • the pre-bond resin was cured to a non-tacky condition by passing the coated web through a convection oven at 330 °F (166 °C) for 4.5 minutes, yielding a pre-bonded, nonwoven web of approximately 6 mm thickness and having a basis weight of 168 gsm.
  • Unitized abrasive wheels were prepared from the pre-bonded nonwoven web as follows. A 9-inch (23-cm) square section was cut from the prebonded nonwoven web and saturated with one of two wheel adhesives. Wheel adhesive one (WA1) was 44% BL16, 16.4% K-450S, 15.8% PMA, 7% MP-22VF, 6% phenoxy, 9.9% kaolin, and 0.4% D-1122. Wheel adhesive two (WA2) was 60.8% Phenolic, 31.2% water, 7.4% SR511, and 0.6% D-1122.
  • Wheel adhesive one was 44% BL16, 16.4% K-450S, 15.8% PMA, 7% MP-22VF, 6% phenoxy, 9.9% kaolin, and 0.4% D-1122.
  • Wheel adhesive two (WA2) was 60.8% Phenolic, 31.2% water, 7.4% SR511, and 0.6% D-1122.
  • the saturated prebonded web was then passed through the nip of a roll coater having 4-inch (10-cm) diameter rubber rolls of 85-Shore A durometer hardness to remove excess resin until the desired resin add-on weight of 0.49 ⁇ 0.035 oz (14 ⁇ 1 g) for WA1 or 0.60 ⁇ 0.035 oz (17 ⁇ 1 g) for WA2 was obtained.
  • a roll coater having 4-inch (10-cm) diameter rubber rolls of 85-Shore A durometer hardness to remove excess resin until the desired resin add-on weight of 0.49 ⁇ 0.035 oz (14 ⁇ 1 g) for WA1 or 0.60 ⁇ 0.035 oz (17 ⁇ 1 g) for WA2 was obtained.
  • multiple passes through the nip at 11 fpm (3.35 mpm) under pressures of 10-21 psi (69-145 kPa) were required to reach the target weight.
  • seven sections of pre-bonded web were coated in the above manner.
  • the coated sections of prebonded web were placed in a forced air oven set at 260 °F (127 °C) for one minute to remove a majority of the solvent.
  • a forced air oven set at 260 °F (127 °C) for one minute to remove a majority of the solvent.
  • six sections of prebond were each covered with 42 grams of randomly, uniformly distributed mineral or mineral agglomerates.
  • the six coated sections were then stacked and covered with a seventh section of prebond.
  • a release liner was then applied to the top and bottom of the stack before it was placed in a hydraulic, heated platen press.
  • a pressure of 5,000 psi (34.5 MPa) was applied to the platens. Consistent thickness of the unitized slab was maintained by placing 0.25 inch (0.635 cm) thick metal spacers in each corner of the platen.
  • the slab After removal from the oven, the slab was cooled to room temperature, and an 8.0-inch (20-cm) diameter unitized abrasive wheel with a 1.25-inch (3.2-cm) center hole was die cut from it using a SAMCO SB-25 swing beam press manufactured by Deutsche vernier Schuhmaschinen GmbH & Co., Frankfurt, Germany.
  • a pre-weighed, 0.25 inch (6.4 mm)-thick unitized abrasive wheel to be tested was mounted in a vertical orientation on the arbor of a mechanically driven, variable speed lathe adjusted to generate a surface speed at the wheel's edge of approximately 3500 feet (1065 meters) per minute.
  • the edge of a 0.0625 inch (1.59 mm)-thick, two-inch by eleven-inch (5.08-cm by 27.9-cm) cold rolled carbon steel or T304 stainless steel panel held horizontally at the height of the arbor was plunged into the rotating edge of the wheel with approximately 5 pounds (22.2 Newtons) of force for 20 seconds.
  • the amount of material removed from the panel during the test sequence was designated as the "cut” and was defined as the difference between the weight of the panel before and after the test sequence.
  • the amount of material removed from the wheel during the test sequence was designated as the “wear” and was defined as the difference between the weight of the wheel before and after the test sequence.
  • Finish samples were produced by placing the 6.4 mm-thick wheels on a back stand and adjusting the speed to produce a surface speed of approximately 3500 feet (1065 meters) per minute.
  • the faces of 0.0625 inch (1.59 mm)-thick, two-inch by eleven-inch (5.08-cm by 27.94-cm) cold rolled carbon steel or T304 stainless steel panels were abraded while applying roughly five pounds (22.2 Newtons) of pressure.
  • a 4-inch (10.2-cm) length of panel was finished by passing the panel over the wheel eight times, stepping roughly 0.25 inch (6.4 mm) between passes and moving the panel approximately 2 inches (5.04 cm) per second. Finish was measured using a Perthometer PRK profilometer (Feinpruf GmbH; Gottingen, Germany). Ten measurements were taken on each surface. The high and low values were discarded and the remaining eight data points averaged.
  • Films for modulus measurements were prepared by placing 16 grams of AR1 on a circular stainless steel form with a diameter of 5.5 inches (14 cm) and a side wall 0.12 inch (3 mm) high. Samples were placed in a forced air oven set at 180 °F (82 °C) for one hour to drive off the majority of solvent. The oven was then set at 260 °F (127 °C) for two hours to complete curing. The resulting films, approximately 0.027 in (0.69 mm) thick, were removed from the steel form.
  • Urethane-bound unitized abrasive wheels were prepared according to the procedures set forth above in the sections on Preparation of Agglomerates and Unitized Abrasive Wheel Preparation, using the components reported in Table 1.
  • the unitized abrasive wheels were tested according to the Unitized Abrasive Wheel Performance Test and Unitized Abrasive Wheel Finish Testing. Results are reported in Table 2.
  • Comparative Examples G through L the cut and wear data were not collected because the smaller abrasive particle size resulted in very low cut. Comparative Examples G through L are presented to show the comparative finishes obtained.
  • Phenolic-bound unitized abrasive wheels were prepared according to the procedures set forth above in the sections Preparation of Agglomerates and Unitized Abrasive Wheel Preparation, using the ingredients reported in Table 3. The unitized abrasive wheels were tested according to the Unitized Abrasive Wheel Performance Test and Unitized Abrasive Wheel Finish Testing. Results are reported in Table 4.
  • the modulus of AR1 was measured according to the procedure in the section on Measurement of Resin Modulus above.
  • Urethane bound unitized wheels containing agglomerates bound by a variety of free radical cured resins were produced according to the procedures set forth above in the sections Preparation of Agglomerates and Unitized Abrasive Wheel Preparation, using the ingredients reported in Table 5.
  • the unitized abrasive wheels were tested according to the Unitized Abrasive Wheel Finish Testing. Results are reported in Table 6.
  • Examples 8 and 9 and examples Z and AA were prepared to demonstrate the effect of filler on the finish produced by agglomerates of precisely shaped grain.
  • Urethane bound unitized abrasive wheels were prepared according to the procedures set forth above in the sections Preparation of Agglomerates and Unitized Abrasive Wheel Preparation, using the ingredients reported in Table 7. The unitized abrasive wheels were tested according to the Unitized Abrasive Wheel Performance Test and Unitized Abrasive Wheel Finish Testing. Results are reported in Table 8.
  • Examples 10 and 11 were prepared to demonstrate that the unexpected improved finish result is independent of the method of agglomerate production.
  • Urethane bound unitized abrasive wheels were prepared according to the procedures set forth above in the sections Preparation of Agglomerates and Unitized Abrasive Wheel Preparation, using the variables reported in Table 9. The unitized abrasive wheels were tested according to the Unitized Abrasive Wheel Performance Test and Unitized Abrasive Wheel Finish Testing. Results are reported in Table 10.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
EP12771150.5A 2011-04-14 2012-03-29 Nonwoven abrasive article containing elastomer bound agglomerates of shaped abrasive grain Active EP2697416B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161475350P 2011-04-14 2011-04-14
PCT/US2012/031086 WO2012141905A2 (en) 2011-04-14 2012-03-29 Nonwoven abrasive article containing elastomer bound agglomerates of shaped abrasive grain

Publications (3)

Publication Number Publication Date
EP2697416A2 EP2697416A2 (en) 2014-02-19
EP2697416A4 EP2697416A4 (en) 2014-10-01
EP2697416B1 true EP2697416B1 (en) 2017-05-10

Family

ID=47009912

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12771150.5A Active EP2697416B1 (en) 2011-04-14 2012-03-29 Nonwoven abrasive article containing elastomer bound agglomerates of shaped abrasive grain

Country Status (10)

Country Link
US (1) US20140080393A1 (es)
EP (1) EP2697416B1 (es)
JP (1) JP6000333B2 (es)
KR (1) KR20140024884A (es)
CN (1) CN103476979B (es)
BR (1) BR112013026334A2 (es)
ES (1) ES2633316T3 (es)
PL (1) PL2697416T3 (es)
RU (1) RU2013145788A (es)
WO (1) WO2012141905A2 (es)

Families Citing this family (60)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104726063B (zh) 2010-11-01 2018-01-12 3M创新有限公司 成形陶瓷磨粒和成形陶瓷前体粒子
RU2013135445A (ru) 2010-12-31 2015-02-10 Сэнт-Гобэн Керамикс Энд Пластикс, Инк. Абразивное изделие (варианты) и способ его формования
EP2726248B1 (en) 2011-06-30 2019-06-19 Saint-Gobain Ceramics & Plastics, Inc. Liquid phase sintered silicon carbide abrasive particles
CN108262695A (zh) 2011-06-30 2018-07-10 圣戈本陶瓷及塑料股份有限公司 包括氮化硅磨粒的磨料制品
WO2013036402A1 (en) 2011-09-07 2013-03-14 3M Innovative Properties Company Method of abrading a workpiece
JP5802336B2 (ja) 2011-09-26 2015-10-28 サン−ゴバン セラミックス アンド プラスティクス,インコーポレイティド 研磨粒子材料を含む研磨製品、研磨粒子材料を使用する研磨布紙および形成方法
EP3517245B1 (en) 2011-12-30 2023-12-13 Saint-Gobain Ceramics & Plastics Inc. Shaped abrasive particle and method of forming same
BR112014016159A8 (pt) 2011-12-30 2017-07-04 Saint Gobain Ceramics formação de partículas abrasivas moldadas
EP2797716B1 (en) 2011-12-30 2021-02-17 Saint-Gobain Ceramics & Plastics, Inc. Composite shaped abrasive particles and method of forming same
US8840696B2 (en) 2012-01-10 2014-09-23 Saint-Gobain Ceramics & Plastics, Inc. Abrasive particles having particular shapes and methods of forming such particles
CA2860755C (en) 2012-01-10 2018-01-30 Saint-Gobain Ceramics & Plastics, Inc. Abrasive particles having complex shapes and methods of forming same
EP2830829B1 (en) 2012-03-30 2018-01-10 Saint-Gobain Abrasives, Inc. Abrasive products having fibrillated fibers
US9771504B2 (en) 2012-04-04 2017-09-26 3M Innovative Properties Company Abrasive particles, method of making abrasive particles, and abrasive articles
KR20150020199A (ko) 2012-05-23 2015-02-25 생-고뱅 세라믹스 앤드 플라스틱스, 인코포레이티드 형상화 연마입자들 및 이의 형성방법
EP2866977B8 (en) 2012-06-29 2023-01-18 Saint-Gobain Ceramics & Plastics, Inc. Abrasive particles having particular shapes and methods of forming such particles
CN104822494B (zh) 2012-10-15 2017-11-28 圣戈班磨料磨具有限公司 具有特定形状的磨粒以及形成这种粒子的方法
KR102146313B1 (ko) 2012-10-31 2020-08-21 쓰리엠 이노베이티브 프로퍼티즈 컴파니 성형 연마 입자, 그의 제조 방법, 및 그를 포함하는 연마 용품
JP2016503731A (ja) 2012-12-31 2016-02-08 サン−ゴバン セラミックス アンド プラスティクス,インコーポレイティド 粒子材料およびその形成方法
CA2903967A1 (en) * 2013-03-04 2014-09-12 3M Innovative Properties Company Nonwoven abrasive article containing formed abrasive particles
MX2015013566A (es) * 2013-03-29 2016-02-05 3M Innovative Properties Co Articulos abrasivos no tejidos y metodos para la elaboracion de los mismos.
CA2907372C (en) 2013-03-29 2017-12-12 Saint-Gobain Abrasives, Inc. Abrasive particles having particular shapes and methods of forming such particles
TW201502263A (zh) 2013-06-28 2015-01-16 Saint Gobain Ceramics 包含成形研磨粒子之研磨物品
WO2015048768A1 (en) 2013-09-30 2015-04-02 Saint-Gobain Ceramics & Plastics, Inc. Shaped abrasive particles and methods of forming same
JP6290428B2 (ja) 2013-12-31 2018-03-07 サンーゴバン アブレイシブズ,インコーポレイティド 成形研磨粒子を含む研磨物品
US9771507B2 (en) 2014-01-31 2017-09-26 Saint-Gobain Ceramics & Plastics, Inc. Shaped abrasive particle including dopant material and method of forming same
WO2015160854A1 (en) 2014-04-14 2015-10-22 Saint-Gobain Ceramics & Plastics, Inc. Abrasive article including shaped abrasive particles
JP6484647B2 (ja) 2014-04-14 2019-03-13 サン−ゴバン セラミックス アンド プラスティクス,インコーポレイティド 成形研磨粒子を含む研磨物品
US9902045B2 (en) 2014-05-30 2018-02-27 Saint-Gobain Abrasives, Inc. Method of using an abrasive article including shaped abrasive particles
CN106573361B (zh) * 2014-08-27 2019-07-09 3M创新有限公司 制备磨料制品的方法
JP6280292B2 (ja) * 2014-10-07 2018-02-14 スリーエム イノベイティブ プロパティズ カンパニー テクスチャー化研磨物品及び関連方法
US10668597B2 (en) 2014-12-01 2020-06-02 3M Innovative Properties Company Nonwoven abrasive wheel with moisture barrier layer
US9914864B2 (en) 2014-12-23 2018-03-13 Saint-Gobain Ceramics & Plastics, Inc. Shaped abrasive particles and method of forming same
US9707529B2 (en) 2014-12-23 2017-07-18 Saint-Gobain Ceramics & Plastics, Inc. Composite shaped abrasive particles and method of forming same
US9676981B2 (en) 2014-12-24 2017-06-13 Saint-Gobain Ceramics & Plastics, Inc. Shaped abrasive particle fractions and method of forming same
WO2016161157A1 (en) 2015-03-31 2016-10-06 Saint-Gobain Abrasives, Inc. Fixed abrasive articles and methods of forming same
TWI634200B (zh) 2015-03-31 2018-09-01 聖高拜磨料有限公司 固定磨料物品及其形成方法
CA3118239A1 (en) 2015-06-11 2016-12-15 Saint-Gobain Ceramics & Plastics, Inc. Abrasive article including shaped abrasive particles
CN109415615A (zh) 2016-05-10 2019-03-01 圣戈本陶瓷及塑料股份有限公司 磨料颗粒及其形成方法
US20170335155A1 (en) 2016-05-10 2017-11-23 Saint-Gobain Ceramics & Plastics, Inc. Abrasive particles and methods of forming same
CN106112836A (zh) * 2016-06-27 2016-11-16 宁夏中卫大河精工机械有限责任公司 一种超硬集聚粒磨料及由其制作而成的超硬珩磨油石
WO2018005111A1 (en) * 2016-07-01 2018-01-04 3M Innovative Properties Company Nonwoven abrasive article including abrasive particles
JP2019527148A (ja) 2016-07-20 2019-09-26 スリーエム イノベイティブ プロパティズ カンパニー 成形ガラス化研磨凝集体、研磨物品、及び研磨方法
EP4349896A3 (en) 2016-09-29 2024-06-12 Saint-Gobain Abrasives, Inc. Fixed abrasive articles and methods of forming same
US10655038B2 (en) 2016-10-25 2020-05-19 3M Innovative Properties Company Method of making magnetizable abrasive particles
WO2018080765A1 (en) 2016-10-25 2018-05-03 3M Innovative Properties Company Structured abrasive articles and methods of making the same
CN109890930B (zh) 2016-10-25 2021-03-16 3M创新有限公司 可磁化磨料颗粒及其制备方法
EP3532246B1 (en) * 2016-10-25 2022-11-30 3M Innovative Properties Company Shaped vitrified abrasive agglomerate with shaped abrasive particles, abrasive articles, and related methods
WO2018080703A1 (en) 2016-10-25 2018-05-03 3M Innovative Properties Company Magnetizable abrasive particles and abrasive articles including them
WO2018119275A1 (en) 2016-12-23 2018-06-28 Saint-Gobain Abrasives, Inc. Coated abrasives having a performance enhancing composition
US10563105B2 (en) 2017-01-31 2020-02-18 Saint-Gobain Ceramics & Plastics, Inc. Abrasive article including shaped abrasive particles
US10759024B2 (en) 2017-01-31 2020-09-01 Saint-Gobain Ceramics & Plastics, Inc. Abrasive article including shaped abrasive particles
CN106965101B (zh) * 2017-04-06 2019-01-08 湖北明仁研磨科技股份有限公司 一种砂纸基材抗裂处理方法
WO2018198004A1 (en) * 2017-04-28 2018-11-01 3M Innovative Properties Company Large denier nonwoven fiber webs
CN110719946B (zh) 2017-06-21 2022-07-15 圣戈本陶瓷及塑料股份有限公司 颗粒材料及其形成方法
EP3651934A1 (en) * 2017-07-14 2020-05-20 3M Innovative Properties Company Abrasive article with anionic water solubilizing material and method of making
US12006464B2 (en) * 2018-03-01 2024-06-11 3M Innovative Properties Company Shaped siliceous abrasive agglomerate with shaped abrasive particles, abrasive articles, and related methods
CN112512748A (zh) 2018-07-23 2021-03-16 3M创新有限公司 包括聚酯背衬和底漆层的制品及相关方法
WO2020026060A1 (en) * 2018-07-30 2020-02-06 3M Innovative Properties Company Self-contained buffing articles
EP4081609A4 (en) 2019-12-27 2024-06-05 Saint-Gobain Ceramics & Plastics Inc. ABRASIVE ARTICLES AND THEIR FORMATION PROCESSES
KR20220116556A (ko) 2019-12-27 2022-08-23 세인트-고바인 세라믹스 앤드 플라스틱스, 인크. 연마 물품 및 이의 형성 방법

Family Cites Families (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1953983A (en) * 1928-02-07 1934-04-10 Carborundum Co Manufacture of rubber bonded abrasive articles
DE1752612C2 (de) * 1968-06-21 1985-02-07 Roc AG, Zug Schleifkörper
US3982359A (en) * 1968-06-21 1976-09-28 Roc A.G. Abrasive member of bonded aggregates in an elastomeric matrix
DE2813258C2 (de) * 1978-03-28 1985-04-25 Sia Schweizer Schmirgel- & Schleifindustrie Ag, Frauenfeld Schleifkörper
US4459779A (en) * 1982-09-16 1984-07-17 International Business Machines Corporation Fixed abrasive grinding media
US5366523A (en) 1992-07-23 1994-11-22 Minnesota Mining And Manufacturing Company Abrasive article containing shaped abrasive particles
US5201916A (en) * 1992-07-23 1993-04-13 Minnesota Mining And Manufacturing Company Shaped abrasive particles and method of making same
US5372620A (en) 1993-12-13 1994-12-13 Saint Gobain/Norton Industrial Ceramics Corporation Modified sol-gel alumina abrasive filaments
US5562745A (en) * 1994-03-16 1996-10-08 Minnesota Mining And Manufacturing Company Abrasive articles, methods of making abrasive articles, and methods of using abrasive articles
US6478977B1 (en) * 1995-09-13 2002-11-12 Hitachi, Ltd. Polishing method and apparatus
DE69627538T2 (de) * 1996-05-03 2004-04-08 Minnesota Mining And Manufacturing Company, St. Paul Nichtgewebte schleifmittel
US5692950A (en) * 1996-08-08 1997-12-02 Minnesota Mining And Manufacturing Company Abrasive construction for semiconductor wafer modification
DE19727104C2 (de) * 1997-06-26 2000-07-20 Ver Schmirgel & Maschf Flexibler Schleifkörper und Verfahren zu seiner Herstellung
US5942015A (en) * 1997-09-16 1999-08-24 3M Innovative Properties Company Abrasive slurries and abrasive articles comprising multiple abrasive particle grades
US5984998A (en) 1997-11-14 1999-11-16 American Iron And Steel Institute Method and apparatus for off-gas composition sensing
US6186866B1 (en) * 1998-08-05 2001-02-13 3M Innovative Properties Company Abrasive article with separately formed front surface protrusions containing a grinding aid and methods of making and using
US6390890B1 (en) * 1999-02-06 2002-05-21 Charles J Molnar Finishing semiconductor wafers with a fixed abrasive finishing element
US6056794A (en) * 1999-03-05 2000-05-02 3M Innovative Properties Company Abrasive articles having bonding systems containing abrasive particles
JP2001138244A (ja) * 1999-08-17 2001-05-22 Mitsubishi Materials Corp レジンボンド砥石
US6352567B1 (en) * 2000-02-25 2002-03-05 3M Innovative Properties Company Nonwoven abrasive articles and methods
BR0109387B1 (pt) * 2000-03-23 2011-01-25 ferramenta abrasiva com liga vitrificada e processo para fabricação da mesma.
WO2002032832A1 (en) * 2000-10-16 2002-04-25 3M Innovative Properties Company Method of making abrasive agglomerate particles and abrasive articles therefrom
US7297170B2 (en) * 2002-07-26 2007-11-20 3M Innovative Properties Company Method of using abrasive product
CN1490347A (zh) * 2002-10-18 2004-04-21 廉长江 一种聚氨酯胶软体砂轮磨盘
GB0225913D0 (en) * 2002-11-06 2002-12-11 3M Innovative Properties Co Abrasive articles
US6951504B2 (en) * 2003-03-20 2005-10-04 3M Innovative Properties Company Abrasive article with agglomerates and method of use
US6802878B1 (en) * 2003-04-17 2004-10-12 3M Innovative Properties Company Abrasive particles, abrasive articles, and methods of making and using the same
US20070026754A1 (en) * 2003-04-25 2007-02-01 Carmen Martin Rivera Scouring material
CN1960835A (zh) * 2004-05-03 2007-05-09 3M创新有限公司 用于精密磨削的支撑底板及其方法
KR20070094811A (ko) * 2004-12-30 2007-09-21 쓰리엠 이노베이티브 프로퍼티즈 컴파니 연마성 물품 및 그의 제조 방법
US7883398B2 (en) * 2005-08-11 2011-02-08 Saint-Gobain Abrasives, Inc. Abrasive tool
US20070298240A1 (en) * 2006-06-22 2007-12-27 Gobena Feben T Compressible abrasive article
US7985269B2 (en) * 2006-12-04 2011-07-26 3M Innovative Properties Company Nonwoven abrasive articles and methods of making the same
US20090075547A1 (en) * 2007-09-19 2009-03-19 Rotter Matin J Cleaning pads with abrasive loaded filaments and anti-microbial agent
US8123828B2 (en) 2007-12-27 2012-02-28 3M Innovative Properties Company Method of making abrasive shards, shaped abrasive particles with an opening, or dish-shaped abrasive particles
EP2242618B1 (en) 2007-12-27 2020-09-23 3M Innovative Properties Company Shaped, fractured abrasive particle, abrasive article using same and method of making
PL2174751T3 (pl) * 2008-10-10 2014-12-31 Center For Abrasives And Refractories Res & Development C A R R D Gmbh Aglomeraty ziaren ściernych, sposób ich wytwarzania, jak również ich zastosowanie do produkcji materiałów ściernych
US20100092746A1 (en) * 2008-10-14 2010-04-15 Jean-Marie Coant Nonwoven material containing benefiting particles and method of making
US8142531B2 (en) * 2008-12-17 2012-03-27 3M Innovative Properties Company Shaped abrasive particles with a sloping sidewall
US8142891B2 (en) 2008-12-17 2012-03-27 3M Innovative Properties Company Dish-shaped abrasive particles with a recessed surface
US10137556B2 (en) 2009-06-22 2018-11-27 3M Innovative Properties Company Shaped abrasive particles with low roundness factor
US8764865B2 (en) 2008-12-17 2014-07-01 3M Innovative Properties Company Shaped abrasive particles with grooves
US8142532B2 (en) 2008-12-17 2012-03-27 3M Innovative Properties Company Shaped abrasive particles with an opening
BR112012013346B1 (pt) * 2009-12-02 2020-06-30 3M Innovative Properties Company partículas abrasivas com formato duplamente afunilado

Also Published As

Publication number Publication date
ES2633316T3 (es) 2017-09-20
WO2012141905A3 (en) 2012-12-27
PL2697416T3 (pl) 2017-09-29
EP2697416A2 (en) 2014-02-19
CN103476979A (zh) 2013-12-25
JP6000333B2 (ja) 2016-09-28
CN103476979B (zh) 2016-01-06
JP2014514173A (ja) 2014-06-19
US20140080393A1 (en) 2014-03-20
EP2697416A4 (en) 2014-10-01
BR112013026334A2 (pt) 2016-12-27
WO2012141905A2 (en) 2012-10-18
KR20140024884A (ko) 2014-03-03
RU2013145788A (ru) 2015-05-20

Similar Documents

Publication Publication Date Title
EP2697416B1 (en) Nonwoven abrasive article containing elastomer bound agglomerates of shaped abrasive grain
EP2106329B1 (en) Nonwoven abrasive articles and methods of making the same
EP3283258B1 (en) Nonwoven abrasive article and method of making the same
EP2964424B1 (en) Nonwoven abrasive article containing formed abrasive particles
US8888561B2 (en) Nonwoven abrasive wheel
US6352567B1 (en) Nonwoven abrasive articles and methods
US20200230783A1 (en) Nonwoven abrasive wheel with moisture barrier layer
JP2013530062A5 (es)
US20190202032A1 (en) Nonwoven abrasive article including abrasive particles

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20131021

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20140903

RIC1 Information provided on ipc code assigned before grant

Ipc: D04H 1/413 20120101AFI20140828BHEP

Ipc: D04H 1/64 20120101ALI20140828BHEP

Ipc: B24D 3/00 20060101ALI20140828BHEP

17Q First examination report despatched

Effective date: 20151201

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602012032300

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: D04H0001413000

Ipc: B24D0003200000

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: B24D 3/00 20060101ALI20161028BHEP

Ipc: D04H 1/413 20120101ALI20161028BHEP

Ipc: D04H 1/64 20120101ALI20161028BHEP

Ipc: B24D 11/00 20060101ALI20161028BHEP

Ipc: B24D 3/28 20060101ALI20161028BHEP

Ipc: B24D 3/20 20060101AFI20161028BHEP

INTG Intention to grant announced

Effective date: 20161116

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 891797

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170515

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602012032300

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20170510

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2633316

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20170920

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 891797

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170510

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170810

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170811

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170810

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170910

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602012032300

Country of ref document: DE

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20180213

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20180321

Year of fee payment: 7

Ref country code: PL

Payment date: 20180102

Year of fee payment: 7

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20180331

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180329

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180329

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180331

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180331

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180329

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190329

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20120329

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: MK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170510

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20210406

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190329

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20230602

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230530

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220330

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20240220

Year of fee payment: 13

Ref country code: GB

Payment date: 20240221

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20240221

Year of fee payment: 13