WO2013081790A1 - Abrasive filaments with improved stiffness and industrial brushes comprising the same and uses thereof - Google Patents

Abrasive filaments with improved stiffness and industrial brushes comprising the same and uses thereof Download PDF

Info

Publication number
WO2013081790A1
WO2013081790A1 PCT/US2012/063984 US2012063984W WO2013081790A1 WO 2013081790 A1 WO2013081790 A1 WO 2013081790A1 US 2012063984 W US2012063984 W US 2012063984W WO 2013081790 A1 WO2013081790 A1 WO 2013081790A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyamide
bis
abrasive
composition
oxazoline
Prior art date
Application number
PCT/US2012/063984
Other languages
French (fr)
Inventor
Xianqiao Liu
Haifeng Yu
Original Assignee
E. I. Du Pont De Nemours And Company
Dupont Xingda Filaments Company Limited
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 E. I. Du Pont De Nemours And Company, Dupont Xingda Filaments Company Limited filed Critical E. I. Du Pont De Nemours And Company
Priority to EP12791366.3A priority Critical patent/EP2785900B1/en
Priority to JP2014544748A priority patent/JP2015505737A/en
Priority to KR1020147017432A priority patent/KR20140096152A/en
Priority to ES12791366.3T priority patent/ES2557006T3/en
Publication of WO2013081790A1 publication Critical patent/WO2013081790A1/en

Links

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
    • B24D3/22Rubbers synthetic or natural
    • B24D3/24Rubbers synthetic or natural for close-grained structure
    • AHUMAN NECESSITIES
    • A46BRUSHWARE
    • A46DMANUFACTURE OF BRUSHES
    • A46D1/00Bristles; Selection of materials for bristles
    • A46D1/02Bristles details
    • A46D1/0207Bristles characterised by the choice of material, e.g. metal
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B24GRINDING; POLISHING
    • B24BMACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B29/00Machines or devices for polishing surfaces on work by means of tools made of soft or flexible material with or without the application of solid or liquid polishing agents
    • B24B29/005Machines or devices for polishing surfaces on work by means of tools made of soft or flexible material with or without the application of solid or liquid polishing agents using brushes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B24GRINDING; POLISHING
    • B24BMACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B7/00Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor
    • B24B7/20Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor characterised by a special design with respect to properties of the material of non-metallic articles to be ground
    • B24B7/22Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor characterised by a special design with respect to properties of the material of non-metallic articles to be ground for grinding inorganic material, e.g. stone, ceramics, porcelain
    • B24B7/228Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor characterised by a special design with respect to properties of the material of non-metallic articles to be ground for grinding inorganic material, e.g. stone, ceramics, porcelain for grinding thin, brittle parts, e.g. semiconductors, wafers
    • 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
    • B24D3/001Physical 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 supporting member
    • B24D3/002Flexible supporting members, e.g. paper, woven, plastic materials
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00Treatment of filament-forming or like material
    • D01D1/06Feeding liquid to the spinning head
    • D01D1/065Addition and mixing of substances to the spinning solution or to the melt; Homogenising
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/38Formation of filaments, threads, or the like during polymerisation
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • AHUMAN NECESSITIES
    • A46BRUSHWARE
    • A46BBRUSHES
    • A46B2200/00Brushes characterized by their functions, uses or applications
    • A46B2200/30Brushes for cleaning or polishing
    • A46B2200/3093Brush with abrasive properties, e.g. wire bristles

Definitions

  • the present disclosure is related to abrasive filaments with improved stiffness, industrial brushes comprising the abrasive filaments, and the uses of the industrial brushes.
  • Abrasive filaments made from polyamides filled with abrasive particles were developed in the late 1950's as a man made alternative to natural abrasive filaments. At about that time an extrusion process was developed for dispersing abrasive particles uniformly in a polyamide matrix in the form of a filament (U.S. Patent Nos. 3,522,342 and 3,947,169).
  • Some of the advantages of polyamide abrasive filaments are their safety, cleanliness, cutting speed, low cost, superior radius and finish control, adaptability, and ease to design.
  • a solar cell also called photovoltaic cell or photoelectric cell
  • a solar cell is a solid state electrical device that converts the energy of light directly into electricity by the photovoltaic effect.
  • silicon wafers are made by wire-sawing block- cast silicon ingots into very thin (180 to 350 ⁇ ) slices or wafers.
  • a typical process of manufacturing silicon wafers often includes pulling a crystal silicon ingot; grinding the ingot; sawing off the ingot ends; and sawing up the ingot into wafers. In certain processes, the ingot is further polished using industrial brushes after the ingot ends are sawn off.
  • One of the purpose of the present disclosure is to provide an abrasive filament with improved stiffness, wherein the abrasive filament is formed of a melt blended polyamide composition, and wherein the polyamide composition comprises: (a) at least one polyamide; (b) 0.1 -1 wt% of at least one linear chain extending compound having a molecular weight of 1000 Daltons or lower; (c) 0.1 -1 wt% of at least one antioxidant; and (d) 10-40 wt% of abrasive particles, with the total wt% of all components in the composition totaling to 100 wt%.
  • the at least one linear chain extending compound is selected from the group consisting of bis-lactam compounds, bis-oxazoline compounds, bis-oxazine compounds, and combinations of two or more thereof.
  • the bis-lactam compounds are selected from the group consisting of ⁇ , ⁇ '- isophthaloyl bis-caprolactam; ⁇ , ⁇ '-adipoyl bis-caprolactam; ⁇ , ⁇ '-terephthaloyl bis- laurolactam; ⁇ , ⁇ '-isophthaloyl bis-butyrolactam; carbonyl bis-caprolactam; and
  • the bis-oxazoline compounds and bis-oxazine compounds are selected from the group consisting of 2,2'-bis(2-oxazoline); 2,2-bis(4- methyl-2-oxazoline); 2,2'-bis(4-phenyl-2-oxazoline); 2,2'-bis(4-hexyloxazoline); 2,2'-p- phenylene bis(2-oxazoline); 2,2'-m-phenylene bis(2-oxazoline); 2,2'-tetramethylene bis(4,4'- dimethyl-2-oxazoline); the corresponding oxazines; and combinations or two or more thereof.
  • the at least one linear chain extending compound is carbonyl bis-caprolactam.
  • the at least one linear chain extending compound is present in the polyamide composition at a level of 0.2-0.7 wt%, based on the total weight of the polyamide composition.
  • the at least one antioxidant is selected from sterically hindered phenols.
  • the at least one antioxidant is selected from the group consisting of pentaerythritol tetrakis (3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate; 3,3',3',5,5',5'-hexa-tert-butyl-a,a',a'-(mesitylene-2,4-,6-triyl)tri-p- cresol; N,N'-hexane-1 ,6-diylbis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide));
  • the at least one antioxidant is N,N'-hexane-1 ,6-diylbis(3-(3,5-di-tert-butyl- 4-hydroxyphenylpropionamide)).
  • the at least one antioxidant is present in the polyamide composition at a level of 0.2-0.7 wt%, based on the total weight of the polyamide composition.
  • the abrasive particles are selected from the group consisting of organic abrasive particles, inorganic abrasive particles, and combinations thereof.
  • the abrasive particles are selected from the group consisting of particles based on aluminum oxides, alpha alumina, silicon carbides, titanium diborides, alumina zirconia, diamond, boron carbide, ceria, aluminum silicates, cubic boron nitride, garnet, silica, pumice, sand, emery, mica, corundum, quartz, and combinations of two or more thereof.
  • the at least one polyamide is selected from aliphatic polyamides.
  • the at least one polyamide is selected from the group consisting of polyamide 4,6; polyamide 6; polyamide 6,6;
  • polyamide 6,16 polyamide 9,10; polyamide 9,12; polyamide 9,13; polyamide 9,14; polyamide 9,15; polyamide 9,36; polyamide 10,10; polyamide 10,12; polyamide 10,13;
  • polyamide 12,13; polyamide 12,14; and combinations of two or more thereof, or the at least one aliphatic polyamide is selected from polyamide 6,10; polyamide 6,12; and
  • the at least one polyamide has a relative viscosity of 2.3-5, or 2.3-4, or 2.3-3.5.
  • the at least one polyamide is present in the polyamide composition at a level of 60-90 wt%, or 60-80 wt%, or 60-75 wt%, based on the total weight of the polyamide composition.
  • the abrasive filament is prepared by a continuous melt spinning process, and wherein the process comprises: (i) blending the at least one polyamide, the at least one linear chain extender compound, and the at least one antioxidant into a mixture; (ii) passing the mixture through an extruder while the abrasive particles are added into the extruder through one or more side feeders; and (iii) melt spinning the composition that comes out of the extruder into filaments.
  • the abrasive filament is prepared by a two-step melt spinning process, and wherein the process comprises: (i) melt compounding the at least one polyamide, the at least one linear chain extender compound, and the at least one antioxidant into resin pellets; (ii) passing the resin pellets through an extruder while the abrasive particles are added into the extruder through one or more side feeders; and (iii) melt spinning the composition that comes out of the extruder into filaments.
  • a further purpose of the present disclosure is to provide an industrial brush
  • a yet further purpose of the present disclosure is to provide the use of the industrial brush described above in grinding and/or polishing silicon ingots, stone, or metal parts.
  • a yet further purpose of the present disclosure is to provide the use of the industrial brush in grinding and/or polishing silicon ingots.
  • the range includes any value that is within the two particular end points and any value that is equal to or about equal to any of the two end points
  • abrasive filaments formed of a melt blended polyamide composition wherein the polyamide composition comprises: (a) at least one polyamide; (b) about 0.1 -1 wt% of at least one linear chain extending compound having a molecular weight of about 1000 Daltons or lower; (c) about 0.1 -1 wt% of at least one antioxidant, and (d) about 10-40 wt% of abrasive particles, with the total wt% of all components in the composition totaling to 100 wt%.
  • Polyamides are condensation copolymers formed by reacting equal parts of one or more diamines and one ore more dicarboxylic acids, so that amides are formed at both ends of each monomer in a process analogous to polypeptide biopolymers. It is
  • the polyamides used herein also include co-polyamides, which are copolymers formed by polymerizing two or more polyamide monomers or by reacting equal parts of two or more diamines and two or more dicarboxylic acids.
  • the at least one polyamide comprised in the melt blended polyamide composition also may be a blend of two or more polyamides.
  • the polyamides used herein may have a relative viscosity (RV) of about 2.3-5, or about 2.3-4, or about 2.3-3.5.
  • the polyamides used herein are aliphatic polyamides.
  • aliphatic polyamide is used to refer to a polyamide containing no aromatic ring in its molecular chain and is a condensation product of an aminocarboxylic acid, a lactam, or a diamine and a dicarboxylic acid.
  • aminocarboxylic acids used here may be aminocarboxylic acids having 6 to 12 carbon atoms, which include, but are not limited to, 6-aminocapronic acid, 7- aminoheptanoic acid, 9-aminononanoic acid, 1 1 -aminoundecanoic acid, 12- aminododecanoic acid, and the like.
  • the lactam used here may be lactams having 4 to 12 carbon atoms, which include, but are not limited to, a-pyrrolidone, ⁇ -caprolactam, ⁇ -laurolactam, ⁇ -enantholactam, and the like.
  • the diamines used here may be aliphatic or alicyclic diamines, including but not limited to, tetramethylenediamine; hexamethylenediamine; 2 methylpentamethylenediamine; nonamethylenediamine; undecamethylenediamine; dodeca-methylenediamine; 2,2,4- trimethylhexamethylenediamine; 2,4,4-trimethylhexamethylenediamine; 5- methylnonamethylene-diamine; 1 ,3-bis(aminomethyl)cyclohexane; 1 ,4- bis(aminomethyl)cyclohexane; 1 -amino-3 aminomethyl-3,5,5-trimethylcyclohexane; bis(4- aminocyclohexyl)methane; bis(3-methyl-4-aminocyclohexyl)methane; 2,2-bis(4- aminocyclohexyl)propane; bis(aminopropyl)piperazine; aminoethylpipe
  • the dicarboxylic acids used herein may be aliphatic or alicyclic dicarboxylic acids, including but not limited to, adipic acid; glutaric acid; pimelic acid; suberic acid; azelaic acid; sebacic acid; dodecanedioic acid; 1 ,4-cyclohexanedicarboxylic acid; and the like.
  • Examples of preferred aliphatic polyamides include, but are not limited to, polyamide 4,6; polyamide 6; polyamide 6,6; polyamide 6,10; polyamide 6,12; polyamide 6,13;
  • polyamide 6,14 polyamide 6,15; polyamide 6,16; polyamide 9,10; polyamide 9,12;
  • the at least one aliphatic polyamide comprised in the polyamide resin is selected from polyamide 6,10 ; polyamide 6,12; and combinations thereof.
  • the at least one polyamide may be present in the composition at a level of about 60-90 wt%, or about 60-80 wt%, or about 60-75 wt%.
  • the linear chain extending compounds used herein are low molecular weight ( ⁇ 1000 Daltons) compounds that have bi-functional end groups. Such linear chain extending compounds are reactive with the terminal groups of polyamides but are essentially non- crosslinking.
  • the at least one linear chain extending compound used herein may be selected from bis-lactam compounds, bis-oxazoline compounds, bis-oxazine compounds, and combinations of two or more thereof.
  • the bis-lactam compounds used herein may be represented by the following general formula (I):
  • n is an integer of 2-15.
  • R group in formula (I) may have a general formula (II):
  • A is a divalent organic group.
  • A is a hydrocarbon group of about 20 carbons or less or a (poly)ether group.
  • Exemplary A groups include, without limitation, alkylene groups (e.g., methylene; ethylene; 1 ,2 propylene; 1 ,3 propylene; or
  • arylene groups e.g., phenylene; methylphenylene; naphthylene; 4,4'- biphenylene; a bisphenol A residue; or a bisphenol S residue
  • alkarylene groups e.g., ethylenephenylene
  • ether interrupted hydrocarbon groups e.g., ethyleneoxyethylene; (polyethyleneoxy)ethylene; (polyethyleneoxy)propylene; or (polypropyleneoxy)ethylene).
  • R group in formula (I) may have a general formula (III):
  • R group in formula (I) may simply be a carbonyl group with a general formula (IV):
  • carbonyl bis-lactams Compounds employing such carbonyl linkages are designated as "carbonyl bis-lactams". Suitable carbonyl bis-lactam compounds may have the general formula (V):
  • n is an integer of 3-15, or preferably an integer of 5-12.
  • Bis-lactam compounds useful herein include those disclosed in U.S. Patent No. 6,228,980; PCT Patent Application No. WO 96/34909; and European Patent No. EP
  • 0288253 Specific examples include, without limitation, ⁇ , ⁇ '-isophthaloyl bis-caprolactam; ⁇ , ⁇ '-adipoyl bis-caprolactam; ⁇ , ⁇ '-terephthaloyl bis-laurolactam; ⁇ , ⁇ '-isophthaloyl bis- butyrolactam; carbonyl bis-caprolactam; and combinations of two or more thereof.
  • X may be an ethylene group, a substituted ethylene group, a trimethylene, or a substituted trimethylene group.
  • substituent for instance an alkyl group with 1 to 10 carbon atoms, an aryl group, a cycloalkyl group, or an aralkyl group may be present.
  • Exemplary alkyl groups include, without limitation, methyl, ethyl, hexyl, alkylhexyl, and nonyl groups; exemplary aryl groups include, without limitation, phenyl, naphthyl, and diphenyl groups; and exemplary cycloalkyl groups include, without limitation, cyclohexyl.
  • D may be suitably a hydrocarbon group, e.g., an alkylene group, an arylene group, a cycloalkylene group, or an aralkylene group.
  • bis-oxazolines and bis-oxazines examples include, without limitation, 2,2'-bis(2- oxazoline); 2,2-bis(4-methyl-2-oxazoline); 2,2'-bis(4-phenyl-2-oxazoline); 2,2'-bis(4- hexyloxazoline); 2,2'-p-phenylene bis(2-oxazoline); 2,2'-p-phenylene bis(2-oxazoline); 2,2'- tetramethylene bis(4,4'-dimethyl-2-oxazoline); and the corresponding oxazines.
  • linear chain extending compounds used herein also may be obtained
  • CBC biscaprolactam
  • ALLINCOTM 1 ,4-phenylene bisoxazoline
  • ALLINCOTM 1,4-phenylene bisoxazoline
  • ALLINCOTM 2,2'-m-phenylene bis(2-oxazoline)
  • the at least one linear chain extending compound may be present in the polyamide composition at a level of about 0.1 -1 wt% or about 0.2-0.7 wt%.
  • the process of incorporating the linear chain extending compounds can be carried out in a simple manner using the usual extruder melt-mixing techniques and equipment, for example by blending the terminally reactive polymer and the chain extender in a solid state.
  • a small quantity (preferably no more than about 0.2%) of an oily processing aid may be added to the dry mix to improve the uniformity of distribution of the chain extender in the dry mix.
  • the dry mix so obtained is then melted in a conventional melt- mixing apparatus, for example a single- or double-screw extruder.
  • the polymer composition may be prepared in another type of melt mixer and then subsequently provided to the extruder directly from the initial melt mixer.
  • the different components can also be fed to the extruder or other mixing apparatus separately.
  • Chain extenders, in any form, can be fed into an extruder separately from the polymer resin by continuous feeding equipments.
  • the antioxidants used herein are sterically hindered phenols.
  • the antioxidants used herein may be selected from pentaerythritol tetrakis (3-(3,5-d i-tert-butyl-4- hydroxyphenyl)propionate (CAS No. 6683-19-8, available from BASF (Germany) under the trade name IrganoxTM 1010); 3,3',3',5,5',5'-hexa-tert-butyl-a,a',a'-(mesitylene-2,4-,6-triyl)tri- p-cresol (CAS No.
  • the at least one antioxidant may be present in the polyamide composition at a level of about 0.1 -1 wt% or about 0.2-0.7 wt%.
  • the abrasive particles used herein may be organic or inorganic and may have a particle size of about 0.1 -1500 ⁇ , or about 1 -1000 ⁇ , or about 50-500 ⁇ .
  • Exemplary inorganic abrasive particles that are useful herein include, without limitation, aluminum oxides (e.g., fused aluminum oxides or heat treated aluminum oxides), alpha alumina, silicon carbides, titanium diborides, alumina zirconia, diamond, boron carbide, ceria, aluminum silicates, cubic boron nitride, garnet, silica, pumice, sand, emery, mica, corundum, quartz, and combinations of two or more thereof.
  • Exemplary fused aluminum oxide particles include those available commercially from Exolon ESK Company (U.S.A.) or Washington Mills Electro Minerals Corp. (U.S.A.).
  • Suitable ceramic aluminum oxide particles include those described in U.S. Patent Nos. 4,314,827; 4,623,364;
  • Suitable alpha alumina-based ceramic particles that comprise alpha alumina and rare earth oxide include those commercially available from 3M Company (U.S.A.) under the trade name
  • CUBITRONTM 321 is also suitable herein.
  • shaped abrasive particles such as those disclosed in U.S. Patent Nos. 5,009,676; 5,185,012; 5,244,477; and 5,372,620.
  • particles useful herein include solid glass spheres, hollow glass spheres, calcium carbonate, polymeric bubbles, silicates, aluminum trihydirate, and mullite.
  • abrasive particle also encompasses single abrasive particles which are bonded together to form an abrasive agglomerate.
  • the abrasive particles used herein may also contain a surface coating.
  • Organic abrasive particles useful herein include those formed from a thermoplastic polymer and/or a thermosetting polymer.
  • Organic abrasive particles useful herein may be individual particles or agglomerates of individual particles. The agglomerates may comprise a plurality of the organic abrasive particles bonded together by a binder to form a shaped mass.
  • the organic abrasive particles used herein may have any precise shape or may be irregularly or randomly shaped. Examples of such three dimensional shapes include, without limitation, pyramids, cylinders, cones, spheres, blocks, cubes, polygons, and the like. Alternatively, the organic abrasive particles may be relatively flat and have a cross sectional shape such as a diamond, cross, circle, triangle, rectangle, square, oval, octagon, pentagon, hexagon, polygon and the like.
  • the surface of the organic abrasive particles may be treated with coupling agents to enhance adhesion to and/or dispersibility in the molten thermoplastic matrix.
  • the organic abrasive particles are not required to be uniformly dispersed in the hardened composition, but a uniform dispersion may provide more consistent abrasion characteristics.
  • the organic abrasive particles may be formed from a thermoplastic material such as polycarbonate, polyetherimide, polyester, polyvinyl chloride, methacrylate, methylmethacrylate, polyethylene, polysulfone, polystyrene, acrylonitrile-butadiene-styrene block copolymer, polypropylene, acetal polymers, polyurethanes, polyamide, and
  • preferred thermoplastic material used herein as the organic abrasive particles are those having a high melting temperature, e.g. greater than 200°C or 300°C; or good heat resistance properties.
  • the organic abrasive particles need to have a higher melting or softening point than that of the thermoplastic matrix, so that the organic abrasive particles are not substantially affected by the filament manufacturing process.
  • the organic abrasive particle should be capable of maintaining a generally particulate state during filament or brush segment processing, and therefore should be selected so as not to substantially melt or soften during the filament
  • the organic particles are selected to provide greater abrasive properties than the thermoplastic matrix, if present. In this manner, the organic abrasive particles will perform the desired surface refinement, such as
  • thermoplastic matrix wears away during operation to continuously present fresh organic abrasive particles to the workpiece surface.
  • thermoplastic abrasive particle There are several ways to form a thermoplastic abrasive particle.
  • One such method is to extrude the thermoplastic polymer into elongate segments and then cut these
  • thermoplastic material can be molded into the desired shape and particle size. This molding process can be compression molding or injection molding.
  • the organic abrasive particles may be formed from a thermosetting polymer.
  • Thermosetting polymers may be selected from phenolic resins, aminoplast resins, urethane resins, epoxy resins, acrylate resins, acrylated isocyanurate resins, ureaformaldehyde resins, isocyanurate resins, acrylated urethane resins, melamine formaldehyde resins, acrylated epoxy resins, and combinations of two or more thereof.
  • the organic abrasive particles used herein also may be formed from a mixture of a thermoplastic polymer and a thermosetting polymer. Also in accordance to the present disclosure, the abrasive particles comprised in the composition may be a mixture of inorganic abrasive particles and organic particles.
  • the abrasive particles may be present in the composition at a level of about 10-40 wt%, or about 20-40 wt%, or about 25-40 wt%.
  • the abrasive filaments disclosed herein may be prepared by any suitable process, such as melt spinning processes.
  • the abrasive filaments may be prepared by a continuous melt spinning process, in which all components of the polyamide composition without the abrasive particles disclosed herein are blended together and then the blend is passed through an extruder (e.g., a twin-screw extruder) with the abrasive particles being added into the extruder through a side feeder and melt spun into filaments.
  • an extruder e.g., a twin-screw extruder
  • the abrasive filaments may be prepared by a two-step melt spinning process, in which all components of the polyamide composition without the abrasive particles are first melt compounded into resin pellets, and then the resin pellets are passed through an extruder (e.g., a twin-screw extruder), with the abrasive particles being added into the extruder through a side feeder, and melt spun into filaments.
  • an extruder e.g., a twin-screw extruder
  • the base polyamide e.g., polyamide 6,10
  • the base polyamide has a relatively low flexural modulus (e.g., 1548.8 MPa) (CE1 ).
  • the flexural modulus of the base polyamide composition is greatly improved (an about 25% improvement, see E1 ).
  • branched chain extending additive such as polycarbodiimide
  • the density of the base polyamide composition becomes too low to be processable and usable in practice (see CE2).
  • industrial brushes comprising the abrasive filaments disclosed hereabove.
  • the industrial brushes disclosed herein may be used for the grinding and/or polishing of silicon ingot, stone, or metal parts.
  • the industrial brushes disclosed herein are used for polishing silicon ingot.
  • industrial brushes comprising prior art abrasive filaments often cause severe end-rounding at the longitudinal end of the ingots and therefore decreases the production rate of silicon wafers.
  • the end-rounding effect could be reduced and therefore the production rate of silicon wafers could be improved.
  • PA610-1 a polyamide 6,10 having a relative viscosity (RV) of 2.73 and obtained from DuPont-Xingda Filaments Co. Ltd. (China) under trade name Herox ® ;
  • PA610-2 a polyamide 6,10 having a RV of 2.35 and obtained from DuPont-Xingd Filaments Co. Ltd. (China) under trade name Herox ® ;
  • PA612 a polyamide 6,12 having a RV of 2.5 and obtained from E.I. du Pont de Nemours and Company (U.S.A.) (hereafter "DuPont") under trade name Zytel ® ;
  • AO an antioxidant (N,N'-hexane-1 ,6-diylbis(3-(3,5-di-tert-butyl-4- hydroxyphenylpropionamide))) obtained from BASF (Germany) under trade name lrganox®1098;
  • LCEC a linear chain extending compound ( ⁇ , ⁇ '-carbonyl biscaprolactam)
  • BCEA a branched chain extending additive (polycarbodiimide) obtained from Rhein Chemie (Germany) under the trade name StabaxolTM P400;
  • AP abrasive particles: silicon carbide grits obtained from Jiangyan Dongyin Grinding Materials and Tools Co. Ltd. (China).
  • RV relative viscosity
  • Izod Izod impact strength
  • ⁇ Density was measured using an electronic densimeter SD-200L (purchased from Alfa Mirage Co. Ltd. (Japan)).
  • specimens used in these measurements were molded using a 180 ton injection molding machine purchased from Sumitomo Plastic Machinery (Japan) with a molding temperature set at about 250-260°C.
  • the resin pellets in each of CE1 -CE6 and E1 were fed into a twin-screw extrusion spinning line to form filaments.
  • the resin pellets were fed through the main feeder while the abrasive particles were fed through a side feed of the extruder and the extruder temperature was set at 240°-280°C.
  • the density of the filaments were then determined and the results are tabulated in Table 1 .
  • PA610-1 before adding Abrasive Particles, PA610-1 has a relatively low flexural modulus (e.g., 1548.8 MPa) (CE1 ).
  • flexural modulus e.g. 1548.8 MPa
  • the flexural modulus of the base polyamide composition is greatly improved (an about 25% improvement, see E1 ).
  • Branched Chain Extending Additive the density of the base polyamide composition becomes too low to be processable and usable in practice (see CE2).
  • the polyamide resin pellets used in E2-E4 and CE7- CE8 were prepared.
  • the RV for each of the resin pellets used in E2-E4 and CE7-CE8 were determined and the results are tabulated in Table 2.
  • the resin pellets used in E2-E4 and CE7-CE8 were molded into test specimens (as described above) and the tensile strength at break, elongation at break, flexural modulus, and Izod impact strength thereof were determined and tabulated in Table 2.

Abstract

Disclosed herein are abrasive filaments with improved stiffness and industrial brushes comprising the same, wherein the abrasive filaments are formed of polyamide compositions comprising, (a) at least one polyamide; (b) about 0.1-1 wt% of at least one linear chain extending compound that has a molecular weight of 1000 Daltons or lower; (c) about 0.1-1 wt% of at least one antioxidant; and (d) about 10-40 wt% of abrasive particles, with the total wt% of all components in the composition totaling to 100 wt%.

Description

ABRASIVE FILAMENTS WITH IMPROVED STIFFNESS AND INDUSTRIAL BRUSHES
COMPRISING THE SAME AND USES THEREOF
FIELD OF DISCLOSURE
The present disclosure is related to abrasive filaments with improved stiffness, industrial brushes comprising the abrasive filaments, and the uses of the industrial brushes.
BACKGROUND
Abrasive filaments made from polyamides filled with abrasive particles were developed in the late 1950's as a man made alternative to natural abrasive filaments. At about that time an extrusion process was developed for dispersing abrasive particles uniformly in a polyamide matrix in the form of a filament (U.S. Patent Nos. 3,522,342 and 3,947,169). Some of the advantages of polyamide abrasive filaments are their safety, cleanliness, cutting speed, low cost, superior radius and finish control, adaptability, and ease to design.
A solar cell (also called photovoltaic cell or photoelectric cell) is a solid state electrical device that converts the energy of light directly into electricity by the photovoltaic effect. In crystal silicon based solar cells, silicon wafers are made by wire-sawing block- cast silicon ingots into very thin (180 to 350 μιτι) slices or wafers. A typical process of manufacturing silicon wafers often includes pulling a crystal silicon ingot; grinding the ingot; sawing off the ingot ends; and sawing up the ingot into wafers. In certain processes, the ingot is further polished using industrial brushes after the ingot ends are sawn off.
Currently, polyamide based industrial brushes are often used in polishing the ingot.
However, it is found that the polyamide based industrial brushes, due to the relative softness of the filaments, often causes end-rounding at the two longitudinal ends of the ingot and therefore reduces the production rate of silicon wafers. Thus, there is still a need to develop polyamide based abrasive filaments with improved stiffness and therefore increase the production rate of silicon wafers. Various chain extending additives have been used in the prior art to improve the relative viscosity (RV) and other properties of polyamides. For example, U.S. Patent No. 7,005,097 discloses a polyamide composition in forming medical devices such as catheters or balloons. It is also disclosed that the addition of the bis-lactam compound, bis-oxazoline compound, or bis-oxazine compound based chain extending additive in the polyamide composition improves the RV of the composition and the wall strength of the medical device made therefrom. Further, PCT Patent Application No. WO2010033671 discloses the use of polycarbodiimide in polyamide based brush filaments to improve the hydrolysis resistance thereof. Yet, none of these references teaches that the addition of linear chain extending compounds may improve the flexural modulus or stiffness of polyamides.
SUMMARY
One of the purpose of the present disclosure is to provide an abrasive filament with improved stiffness, wherein the abrasive filament is formed of a melt blended polyamide composition, and wherein the polyamide composition comprises: (a) at least one polyamide; (b) 0.1 -1 wt% of at least one linear chain extending compound having a molecular weight of 1000 Daltons or lower; (c) 0.1 -1 wt% of at least one antioxidant; and (d) 10-40 wt% of abrasive particles, with the total wt% of all components in the composition totaling to 100 wt%.
In one embodiment of the abrasive filament, the at least one linear chain extending compound is selected from the group consisting of bis-lactam compounds, bis-oxazoline compounds, bis-oxazine compounds, and combinations of two or more thereof. In such embodiments, the bis-lactam compounds are selected from the group consisting of Ν,Ν'- isophthaloyl bis-caprolactam; Ν,Ν'-adipoyl bis-caprolactam; Ν,Ν'-terephthaloyl bis- laurolactam; Ν,Ν'-isophthaloyl bis-butyrolactam; carbonyl bis-caprolactam; and
combinations of two or more thereof, and the bis-oxazoline compounds and bis-oxazine compounds are selected from the group consisting of 2,2'-bis(2-oxazoline); 2,2-bis(4- methyl-2-oxazoline); 2,2'-bis(4-phenyl-2-oxazoline); 2,2'-bis(4-hexyloxazoline); 2,2'-p- phenylene bis(2-oxazoline); 2,2'-m-phenylene bis(2-oxazoline); 2,2'-tetramethylene bis(4,4'- dimethyl-2-oxazoline); the corresponding oxazines; and combinations or two or more thereof. Or, the at least one linear chain extending compound is carbonyl bis-caprolactam.
In a further embodiment of the abrasive filament, the at least one linear chain extending compound is present in the polyamide composition at a level of 0.2-0.7 wt%, based on the total weight of the polyamide composition.
In a yet further embodiment of the abrasive filament, the at least one antioxidant is selected from sterically hindered phenols. Or, the at least one antioxidant is selected from the group consisting of pentaerythritol tetrakis (3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate; 3,3',3',5,5',5'-hexa-tert-butyl-a,a',a'-(mesitylene-2,4-,6-triyl)tri-p- cresol; N,N'-hexane-1 ,6-diylbis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide));
octadecyl-3-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionate; and combinations of two or more thereof. Or, the at least one antioxidant is N,N'-hexane-1 ,6-diylbis(3-(3,5-di-tert-butyl- 4-hydroxyphenylpropionamide)).
In a yet further embodiment of the abrasive filament, the at least one antioxidant is present in the polyamide composition at a level of 0.2-0.7 wt%, based on the total weight of the polyamide composition.
In a yet further embodiment of the abrasive filament, the abrasive particles are selected from the group consisting of organic abrasive particles, inorganic abrasive particles, and combinations thereof. Or, the abrasive particles are selected from the group consisting of particles based on aluminum oxides, alpha alumina, silicon carbides, titanium diborides, alumina zirconia, diamond, boron carbide, ceria, aluminum silicates, cubic boron nitride, garnet, silica, pumice, sand, emery, mica, corundum, quartz, and combinations of two or more thereof.
In a yet further embodiment of the abrasive filament, the at least one polyamide is selected from aliphatic polyamides.
In a yet further embodiment of the abrasive filament, the at least one polyamide is selected from the group consisting of polyamide 4,6; polyamide 6; polyamide 6,6;
polyamide 6,10; polyamide 6,12; polyamide 6,13; polyamide 6,14; polyamide 6,15;
polyamide 6,16; polyamide 9,10; polyamide 9,12; polyamide 9,13; polyamide 9,14; polyamide 9,15; polyamide 9,36; polyamide 10,10; polyamide 10,12; polyamide 10,13;
polyamide 10,14; polyamide 1 1 ; polyamide 12; polyamide 12,10; polyamide 12,12;
polyamide 12,13; polyamide 12,14; and combinations of two or more thereof, or the at least one aliphatic polyamide is selected from polyamide 6,10; polyamide 6,12; and
combinations thereof.
In a yet further embodiment of the abrasive filament, the at least one polyamide has a relative viscosity of 2.3-5, or 2.3-4, or 2.3-3.5.
In a yet further embodiment of the abrasive filament, the at least one polyamide is present in the polyamide composition at a level of 60-90 wt%, or 60-80 wt%, or 60-75 wt%, based on the total weight of the polyamide composition.
In a yet further embodiment of the abrasive filament, the abrasive filament is prepared by a continuous melt spinning process, and wherein the process comprises: (i) blending the at least one polyamide, the at least one linear chain extender compound, and the at least one antioxidant into a mixture; (ii) passing the mixture through an extruder while the abrasive particles are added into the extruder through one or more side feeders; and (iii) melt spinning the composition that comes out of the extruder into filaments.
In a yet further embodiment of the abrasive filament, the abrasive filament is prepared by a two-step melt spinning process, and wherein the process comprises: (i) melt compounding the at least one polyamide, the at least one linear chain extender compound, and the at least one antioxidant into resin pellets; (ii) passing the resin pellets through an extruder while the abrasive particles are added into the extruder through one or more side feeders; and (iii) melt spinning the composition that comes out of the extruder into filaments.
A further purpose of the present disclosure is to provide an industrial brush
comprising a plurality of the abrasive filaments described above.
A yet further purpose of the present disclosure is to provide the use of the industrial brush described above in grinding and/or polishing silicon ingots, stone, or metal parts.
A yet further purpose of the present disclosure is to provide the use of the industrial brush in grinding and/or polishing silicon ingots. In accordance with the present disclosure, when a range is given with two particular end points, it is understood that the range includes any value that is within the two particular end points and any value that is equal to or about equal to any of the two end points
DETAILED DESCRIPTION
Disclosed herein are abrasive filaments formed of a melt blended polyamide composition, wherein the polyamide composition comprises: (a) at least one polyamide; (b) about 0.1 -1 wt% of at least one linear chain extending compound having a molecular weight of about 1000 Daltons or lower; (c) about 0.1 -1 wt% of at least one antioxidant, and (d) about 10-40 wt% of abrasive particles, with the total wt% of all components in the composition totaling to 100 wt%.
Polyamides are condensation copolymers formed by reacting equal parts of one or more diamines and one ore more dicarboxylic acids, so that amides are formed at both ends of each monomer in a process analogous to polypeptide biopolymers. It is
understood that the polyamides used herein also include co-polyamides, which are copolymers formed by polymerizing two or more polyamide monomers or by reacting equal parts of two or more diamines and two or more dicarboxylic acids. In addition, the at least one polyamide comprised in the melt blended polyamide composition also may be a blend of two or more polyamides. Moreover, the polyamides used herein may have a relative viscosity (RV) of about 2.3-5, or about 2.3-4, or about 2.3-3.5.
Preferably, the polyamides used herein are aliphatic polyamides. The term "aliphatic polyamide" is used to refer to a polyamide containing no aromatic ring in its molecular chain and is a condensation product of an aminocarboxylic acid, a lactam, or a diamine and a dicarboxylic acid.
The aminocarboxylic acids used here may be aminocarboxylic acids having 6 to 12 carbon atoms, which include, but are not limited to, 6-aminocapronic acid, 7- aminoheptanoic acid, 9-aminononanoic acid, 1 1 -aminoundecanoic acid, 12- aminododecanoic acid, and the like.
The lactam used here may be lactams having 4 to 12 carbon atoms, which include, but are not limited to, a-pyrrolidone, ε-caprolactam, ω-laurolactam, ε-enantholactam, and the like.
The diamines used here may be aliphatic or alicyclic diamines, including but not limited to, tetramethylenediamine; hexamethylenediamine; 2 methylpentamethylenediamine; nonamethylenediamine; undecamethylenediamine; dodeca-methylenediamine; 2,2,4- trimethylhexamethylenediamine; 2,4,4-trimethylhexamethylenediamine; 5- methylnonamethylene-diamine; 1 ,3-bis(aminomethyl)cyclohexane; 1 ,4- bis(aminomethyl)cyclohexane; 1 -amino-3 aminomethyl-3,5,5-trimethylcyclohexane; bis(4- aminocyclohexyl)methane; bis(3-methyl-4-aminocyclohexyl)methane; 2,2-bis(4- aminocyclohexyl)propane; bis(aminopropyl)piperazine; aminoethylpiperazine; bis(p- aminocyclohexyl)methane; 2-methyloctamethylenediamine;
trimethylhexamethylenediamine; 1 ,8-diaminooctane; 1 ,9-diaminononane; 1 ,10- diaminodecane; 1 ,12-diaminododecane; m-xylylenediamine; and the like.
The dicarboxylic acids used herein may be aliphatic or alicyclic dicarboxylic acids, including but not limited to, adipic acid; glutaric acid; pimelic acid; suberic acid; azelaic acid; sebacic acid; dodecanedioic acid; 1 ,4-cyclohexanedicarboxylic acid; and the like.
Examples of preferred aliphatic polyamides include, but are not limited to, polyamide 4,6; polyamide 6; polyamide 6,6; polyamide 6,10; polyamide 6,12; polyamide 6,13;
polyamide 6,14; polyamide 6,15; polyamide 6,16; polyamide 9,10; polyamide 9,12;
polyamide 9,13; polyamide 9,14; polyamide 9,15; polyamide 9,36; polyamide 10,10;
polyamide 10,12; polyamide 10,13; polyamide 10,14; polyamide 1 1 ; polyamide 12;
polyamide 12,10; polyamide 12,12; polyamide 12,13; polyamide 12,14; and combinations of two or more thereof. In one embodiment, the at least one aliphatic polyamide comprised in the polyamide resin is selected from polyamide 6,10 ; polyamide 6,12; and combinations thereof.
In accordance to the present disclosure, the at least one polyamide may be present in the composition at a level of about 60-90 wt%, or about 60-80 wt%, or about 60-75 wt%. The linear chain extending compounds used herein are low molecular weight (<1000 Daltons) compounds that have bi-functional end groups. Such linear chain extending compounds are reactive with the terminal groups of polyamides but are essentially non- crosslinking. The at least one linear chain extending compound used herein may be selected from bis-lactam compounds, bis-oxazoline compounds, bis-oxazine compounds, and combinations of two or more thereof.
The bis-lactam compounds used herein may be represented by the following general formula (I):
Figure imgf000008_0001
in which one or more of the methylene hydrogen atoms may alternatively be substituted by an alkyl or aryl radical; R represents a divalent organic radical; and n is an integer of 2-15.
In one embodiment, the R group in formula (I) may have a general formula (II):
(Π)
o o
II II wherein A is a divalent organic group. Suitably A is a hydrocarbon group of about 20 carbons or less or a (poly)ether group. Exemplary A groups include, without limitation, alkylene groups (e.g., methylene; ethylene; 1 ,2 propylene; 1 ,3 propylene; or
hexamethylene); arylene groups (e.g., phenylene; methylphenylene; naphthylene; 4,4'- biphenylene; a bisphenol A residue; or a bisphenol S residue); alkarylene groups (e.g., ethylenephenylene); and ether interrupted hydrocarbon groups (e.g., ethyleneoxyethylene; (polyethyleneoxy)ethylene; (polyethyleneoxy)propylene; or (polypropyleneoxy)ethylene).
In a further embodiment, the R group in formula (I) may have a general formula (III):
(III)
o o
II II C B C wherein B is -NH-A-NH, with A being as previously defined.
In a yet further embodiment, the R group in formula (I) may simply be a carbonyl group with a general formula (IV):
(IV)
o
II
Compounds employing such carbonyl linkages are designated as "carbonyl bis-lactams". Suitable carbonyl bis-lactam compounds may have the general formula (V):
Figure imgf000009_0001
in which n is an integer of 3-15, or preferably an integer of 5-12.
Bis-lactam compounds useful herein include those disclosed in U.S. Patent No. 6,228,980; PCT Patent Application No. WO 96/34909; and European Patent No. EP
0288253. Specific examples include, without limitation, Ν,Ν'-isophthaloyl bis-caprolactam; Ν,Ν'-adipoyl bis-caprolactam; Ν,Ν'-terephthaloyl bis-laurolactam; Ν,Ν'-isophthaloyl bis- butyrolactam; carbonyl bis-caprolactam; and combinations of two or more thereof.
The bis-oxazoline and bis-oxazine compounds used herein are both described by the formula (VI):
Figure imgf000009_0002
where X is a divalent hydrocarbon group and the ring is a 5-membered ring for the bis- oxazoline or a 6-membered ring for the bis-oxazine, respectively; n=0 or 1 ; and D is a divalent organic group. And X may be an ethylene group, a substituted ethylene group, a trimethylene, or a substituted trimethylene group. As substituent, for instance an alkyl group with 1 to 10 carbon atoms, an aryl group, a cycloalkyl group, or an aralkyl group may be present. Exemplary alkyl groups include, without limitation, methyl, ethyl, hexyl, alkylhexyl, and nonyl groups; exemplary aryl groups include, without limitation, phenyl, naphthyl, and diphenyl groups; and exemplary cycloalkyl groups include, without limitation, cyclohexyl. D may be suitably a hydrocarbon group, e.g., an alkylene group, an arylene group, a cycloalkylene group, or an aralkylene group.
Examples of bis-oxazolines and bis-oxazines include, without limitation, 2,2'-bis(2- oxazoline); 2,2-bis(4-methyl-2-oxazoline); 2,2'-bis(4-phenyl-2-oxazoline); 2,2'-bis(4- hexyloxazoline); 2,2'-p-phenylene bis(2-oxazoline); 2,2'-p-phenylene bis(2-oxazoline); 2,2'- tetramethylene bis(4,4'-dimethyl-2-oxazoline); and the corresponding oxazines. Preference is given to 2,2'-bis(2-oxazoline); 2,2'-p-phenylene bis(2-oxazoline) (1 ,4-PBO); 2,2'-m- phenylene bis(2-oxazoline) (1 ,3-PBO); and the corresponding oxazines.
The linear chain extending compounds used herein also may be obtained
commercially from various venders, which include, without limitation, carbonyl
biscaprolactam (CBC) available from DSM (the Netherlands) under trade name ALLINCO™ 1 ,4-phenylene bisoxazoline (1 ,4-PBO) available from DSM under trade name ALLINCO™; and 2,2'-m-phenylene bis(2-oxazoline) (1 ,3-PBO) available from Takeda Chemical
Industries (Japan) or from Mikuni Pharmaceutical Industrial Co., LTD. (Japan).
In accordance to the present disclosure, the at least one linear chain extending compound may be present in the polyamide composition at a level of about 0.1 -1 wt% or about 0.2-0.7 wt%.
The process of incorporating the linear chain extending compounds can be carried out in a simple manner using the usual extruder melt-mixing techniques and equipment, for example by blending the terminally reactive polymer and the chain extender in a solid state. In some cases a small quantity (preferably no more than about 0.2%) of an oily processing aid may be added to the dry mix to improve the uniformity of distribution of the chain extender in the dry mix. The dry mix so obtained, is then melted in a conventional melt- mixing apparatus, for example a single- or double-screw extruder. Alternatively the polymer composition may be prepared in another type of melt mixer and then subsequently provided to the extruder directly from the initial melt mixer. The different components can also be fed to the extruder or other mixing apparatus separately. Chain extenders, in any form, can be fed into an extruder separately from the polymer resin by continuous feeding equipments.
Any suitable type of antioxidants may be used herein. Preferably, the antioxidants used herein are sterically hindered phenols. For examples, the antioxidants used herein may be selected from pentaerythritol tetrakis (3-(3,5-d i-tert-butyl-4- hydroxyphenyl)propionate (CAS No. 6683-19-8, available from BASF (Germany) under the trade name Irganox™ 1010); 3,3',3',5,5',5'-hexa-tert-butyl-a,a',a'-(mesitylene-2,4-,6-triyl)tri- p-cresol (CAS No. 1709-70-2, available from BASF under the trade name Irganox™ 1330); N,N'-hexane-1 ,6-diylbis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)) (CAS No.
23128-74-7, available from BASF under the trade name Irganox™ 1098); octadecyl-3-(3,5- di-tert.butyl-4-hydroxyphenyl)-propionate (CAS No. 2082-79-3, available from BASF under the trade name Irganox™ 1076); and combinations of two or more thereof.
In accordance to the present disclosure, the at least one antioxidant may be present in the polyamide composition at a level of about 0.1 -1 wt% or about 0.2-0.7 wt%.
The abrasive particles used herein may be organic or inorganic and may have a particle size of about 0.1 -1500 μιτι, or about 1 -1000 μιτι, or about 50-500 μιτι.
Exemplary inorganic abrasive particles that are useful herein include, without limitation, aluminum oxides (e.g., fused aluminum oxides or heat treated aluminum oxides), alpha alumina, silicon carbides, titanium diborides, alumina zirconia, diamond, boron carbide, ceria, aluminum silicates, cubic boron nitride, garnet, silica, pumice, sand, emery, mica, corundum, quartz, and combinations of two or more thereof. Exemplary fused aluminum oxide particles include those available commercially from Exolon ESK Company (U.S.A.) or Washington Mills Electro Minerals Corp. (U.S.A.). Suitable ceramic aluminum oxide particles include those described in U.S. Patent Nos. 4,314,827; 4,623,364;
4,744,802; 4,770,671 ; 4,881 ,951 ; 4,964,883; 5,01 1 ,508; and 5,164,348. Suitable alpha alumina-based ceramic particles that comprise alpha alumina and rare earth oxide include those commercially available from 3M Company (U.S.A.) under the trade name
CUBITRON™ 321 . Also suitable herein are shaped abrasive particles, such as those disclosed in U.S. Patent Nos. 5,009,676; 5,185,012; 5,244,477; and 5,372,620. Other examples of particles useful herein include solid glass spheres, hollow glass spheres, calcium carbonate, polymeric bubbles, silicates, aluminum trihydirate, and mullite.
As used herein, the term abrasive particle also encompasses single abrasive particles which are bonded together to form an abrasive agglomerate. Abrasive
agglomerates are further described in U.S. Patent Nos. 4,31 1 ,489; 4,652,275; and
4,799,939. The abrasive particles used herein may also contain a surface coating.
Surface coatings are known to improve the adhesion between the abrasive particles and the binder. Suitable surface coatings are described in, e.g., U.S. Patent Nos. 5,01 1 ,508; 1 ,910,444; 3,041 ,156; 5,009,675; 4,997,461 ; 5,213,591 ; and 5,042,991 . In some instances, the addition of the coating improves the abrading and/or processing characteristics of the abrasive particles.
Organic abrasive particles useful herein include those formed from a thermoplastic polymer and/or a thermosetting polymer. Organic abrasive particles useful herein may be individual particles or agglomerates of individual particles. The agglomerates may comprise a plurality of the organic abrasive particles bonded together by a binder to form a shaped mass.
The organic abrasive particles used herein may have any precise shape or may be irregularly or randomly shaped. Examples of such three dimensional shapes include, without limitation, pyramids, cylinders, cones, spheres, blocks, cubes, polygons, and the like. Alternatively, the organic abrasive particles may be relatively flat and have a cross sectional shape such as a diamond, cross, circle, triangle, rectangle, square, oval, octagon, pentagon, hexagon, polygon and the like.
The surface of the organic abrasive particles (a portion of their surface, or the entire surface) may be treated with coupling agents to enhance adhesion to and/or dispersibility in the molten thermoplastic matrix. The organic abrasive particles are not required to be uniformly dispersed in the hardened composition, but a uniform dispersion may provide more consistent abrasion characteristics.
The organic abrasive particles may be formed from a thermoplastic material such as polycarbonate, polyetherimide, polyester, polyvinyl chloride, methacrylate, methylmethacrylate, polyethylene, polysulfone, polystyrene, acrylonitrile-butadiene-styrene block copolymer, polypropylene, acetal polymers, polyurethanes, polyamide, and
combinations thereof. In general, preferred thermoplastic material used herein as the organic abrasive particles are those having a high melting temperature, e.g. greater than 200°C or 300°C; or good heat resistance properties. Moreover, the organic abrasive particles need to have a higher melting or softening point than that of the thermoplastic matrix, so that the organic abrasive particles are not substantially affected by the filament manufacturing process. The organic abrasive particle should be capable of maintaining a generally particulate state during filament or brush segment processing, and therefore should be selected so as not to substantially melt or soften during the filament
manufacturing process. In one preferred embodiment, the organic particles are selected to provide greater abrasive properties than the thermoplastic matrix, if present. In this manner, the organic abrasive particles will perform the desired surface refinement, such as
removing foreign material from the workpiece or providing a fine surface finish, while the thermoplastic matrix wears away during operation to continuously present fresh organic abrasive particles to the workpiece surface.
There are several ways to form a thermoplastic abrasive particle. One such method is to extrude the thermoplastic polymer into elongate segments and then cut these
segments into the desired length. Alternatively, the thermoplastic material can be molded into the desired shape and particle size. This molding process can be compression molding or injection molding.
The organic abrasive particles may be formed from a thermosetting polymer.
Thermosetting polymers may be selected from phenolic resins, aminoplast resins, urethane resins, epoxy resins, acrylate resins, acrylated isocyanurate resins, ureaformaldehyde resins, isocyanurate resins, acrylated urethane resins, melamine formaldehyde resins, acrylated epoxy resins, and combinations of two or more thereof.
The organic abrasive particles used herein also may be formed from a mixture of a thermoplastic polymer and a thermosetting polymer. Also in accordance to the present disclosure, the abrasive particles comprised in the composition may be a mixture of inorganic abrasive particles and organic particles.
In accordance to the present disclosure, the abrasive particles may be present in the composition at a level of about 10-40 wt%, or about 20-40 wt%, or about 25-40 wt%.
The abrasive filaments disclosed herein may be prepared by any suitable process, such as melt spinning processes. For example, the abrasive filaments may be prepared by a continuous melt spinning process, in which all components of the polyamide composition without the abrasive particles disclosed herein are blended together and then the blend is passed through an extruder (e.g., a twin-screw extruder) with the abrasive particles being added into the extruder through a side feeder and melt spun into filaments. Or, the abrasive filaments may be prepared by a two-step melt spinning process, in which all components of the polyamide composition without the abrasive particles are first melt compounded into resin pellets, and then the resin pellets are passed through an extruder (e.g., a twin-screw extruder), with the abrasive particles being added into the extruder through a side feeder, and melt spun into filaments.
As demonstrated by the examples below, before adding the abrasive particles, the base polyamide (e.g., polyamide 6,10) has a relatively low flexural modulus (e.g., 1548.8 MPa) (CE1 ). However, with the addition of the linear chain extending compound, along with the antioxidant, the flexural modulus of the base polyamide composition is greatly improved (an about 25% improvement, see E1 ). However, by adding branched chain extending additive (such as polycarbodiimide), the density of the base polyamide composition becomes too low to be processable and usable in practice (see CE2).
Further disclosed herein are industrial brushes comprising the abrasive filaments disclosed hereabove. The industrial brushes disclosed herein may be used for the grinding and/or polishing of silicon ingot, stone, or metal parts. In one embodiment, the industrial brushes disclosed herein are used for polishing silicon ingot. When used in polishing silicon ingots, industrial brushes comprising prior art abrasive filaments often cause severe end-rounding at the longitudinal end of the ingots and therefore decreases the production rate of silicon wafers. However, due to the improved flexural modulus or stiffness of the base polyamide composition that is used in the abrasive filaments disclosed herein, the end-rounding effect could be reduced and therefore the production rate of silicon wafers could be improved.
EXAMPLES
Material:
• PA610-1 : a polyamide 6,10 having a relative viscosity (RV) of 2.73 and obtained from DuPont-Xingda Filaments Co. Ltd. (China) under trade name Herox®;
• PA610-2: a polyamide 6,10 having a RV of 2.35 and obtained from DuPont-Xingd Filaments Co. Ltd. (China) under trade name Herox®;
• PA612: a polyamide 6,12 having a RV of 2.5 and obtained from E.I. du Pont de Nemours and Company (U.S.A.) (hereafter "DuPont") under trade name Zytel®;
• AO: an antioxidant (N,N'-hexane-1 ,6-diylbis(3-(3,5-di-tert-butyl-4- hydroxyphenylpropionamide))) obtained from BASF (Germany) under trade name lrganox®1098;
• LCEC: a linear chain extending compound (Ν,Ν'-carbonyl biscaprolactam)
obtained from DSM (Netherland) under the trade name ALLINCO™;
• BCEA: a branched chain extending additive (polycarbodiimide) obtained from Rhein Chemie (Germany) under the trade name Stabaxol™ P400;
• AP (abrasive particles): silicon carbide grits obtained from Jiangyan Dongyin Grinding Materials and Tools Co. Ltd. (China).
Test Methods: · RV (relative viscosity) was measured using ViscoSystem™ AVS 370 viscometer purchased from SI Analytics GmbH (Germany), wherein the test sampled were dissolved in a 98% sulfuric acid solution;
• MT (melt temperature) was measured using a Q100 Differential Scanning
Calorimeter (DSC) (purchased from Texas Instruments (U.S.A.)) with the temperature ramp from 40°C to 280°C at a rate of 10°C/min; • Tensile (tensile strength at break) was measured in accordance to ISO 527-2;
• EAB (elongation at break) was measured in accordance to ISO 527-2;
• FM (flexural modulus) was measured in accordance to ISO 178;
• Izod (Izod impact strength) was measured in accordance to ISO 180;
· Density was measured using an electronic densimeter SD-200L (purchased from Alfa Mirage Co. Ltd. (Japan)).
Comparative Examples CE1 -CE6 and Example E1 :
All components contained in each of the polyamide compositions in Examples E1 and Comparative Examples CE1 -CE6 and the amounts present are listed in Table 1 below. First, in each of CE2-E6 and E1 , resin pellets comprising all components except abrasive particles were prepared by extrusion using a ZSK-30 twin-screw extruder (purchased from Coperion Werner & Pfleiderer GmbH & Co. (Germany)) with the extruder temperature set at 240-280°C, the extrusion speed at 300 rpm, and the throughput at 30 Ib/hr. The RV for each of the resin pellets used in CE2-CE6 and E1 and the PA610-1 pellets used in CE1 were determined and the results are tabulated in Table 1 . Thereafter, the resin pellets used in CE2-CE6 and E1 and the PA610-1 pellets used in CE1 were each molded into test specimens and the tensile strength at break, elongation at break, flexural modulus, and Izod impact strength thereof were determined and tabulated in Table 1 . The test
specimens used in these measurements were molded using a 180 ton injection molding machine purchased from Sumitomo Plastic Machinery (Japan) with a molding temperature set at about 250-260°C.
Finally, the resin pellets in each of CE1 -CE6 and E1 , along with 30 wt% of abrasive particles, were fed into a twin-screw extrusion spinning line to form filaments. The resin pellets were fed through the main feeder while the abrasive particles were fed through a side feed of the extruder and the extruder temperature was set at 240°-280°C. The density of the filaments were then determined and the results are tabulated in Table 1 .
As it is shown here, before adding Abrasive Particles, PA610-1 has a relatively low flexural modulus (e.g., 1548.8 MPa) (CE1 ). However, with the addition of Linear Chain Extending Compound, along with Antioxidant, the flexural modulus of the base polyamide composition is greatly improved (an about 25% improvement, see E1 ). However, by adding Branched Chain Extending Additive, the density of the base polyamide composition becomes too low to be processable and usable in practice (see CE2).
TABLE 1
Figure imgf000017_0001
Notes: The measurements of RV, MT, Tensile, EAB, FM, and Izod were obtained using the compositions without AP. Comparative Examples CE7-CE8 and Example E2-E4:
Similarly to E1 and CE2-CE6, the polyamide resin pellets used in E2-E4 and CE7- CE8 were prepared. The RV for each of the resin pellets used in E2-E4 and CE7-CE8 were determined and the results are tabulated in Table 2. Thereafter, the resin pellets used in E2-E4 and CE7-CE8 were molded into test specimens (as described above) and the tensile strength at break, elongation at break, flexural modulus, and Izod impact strength thereof were determined and tabulated in Table 2. Again, as demonstrated herein, by adding Linear Chain Extending Compound and Antioxidant simultaneously into PA612, the flexural modulus therefore (E2) is improved compared to that of the PA612 compositions containing the Antioxidant (CE7) alone or that of the PA612 composition containing the Linear Chain Extending Compound alone (CE8).
TABLE 2
Figure imgf000018_0001

Claims

WHAT IS CLAIMED IS:
1 . An abrasive filament formed of a melt blended polyamide composition, wherein the polyamide composition comprises:
(i) at least one polyamide;
(ii) 0.1 -1 wt% of at least one linear chain extending compound having a molecular weight of 1000 Daltons or lower;
(iii) 0.1 -1 wt% of at least one antioxidant; and
(iv) 10-40 wt% of abrasive particles,
with the total wt% of all components in the composition totaling to 100 wt%.
2. The abrasive filament of Claim 1 , wherein the at least one linear chain extending compound is selected from the group consisting of bis-lactam compounds, bis- oxazoline compounds, bis-oxazine compounds, and combinations of two or more thereof, or preferably, the bis-lactam compounds are selected from the group consisting of Ν,Ν'-isophthaloyl bis-caprolactam; Ν,Ν'-adipoyl bis-caprolactam; Ν,Ν'- terephthaloyl bis-laurolactam; Ν,Ν'-isophthaloyl bis-butyrolactam; carbonyl bis- caprolactam; and combinations of two or more thereof, and the bis-oxazoline compounds and bis-oxazine compounds are selected from the group consisting of 2,2'-bis(2-oxazoline); 2,2-bis(4-methyl-2-oxazoline); 2,2'-bis(4-phenyl-2-oxazoline); 2,2'-bis(4-hexyloxazoline); 2,2'-p-phenylene bis(2-oxazoline); 2,2'-m-phenylene bis(2-oxazoline); 2,2'-tetramethylene bis(4,4'-dimethyl-2-oxazoline); the
corresponding oxazines; and combinations of two or more thereof, or more preferably, the at least one linear chain extending compound is carbonyl bis- caprolactam.
3. The abrasive filament of Claim 1 or 2, wherein the at least one linear chain
extending compound is present in the polyamide composition at a level of 0.2-0.7 wt%, based on the total weight of the polyamide composition.
4. The abrasive filament of any of Claims 1 -3, wherein the at least one antioxidant is selected from sterically hindered phenols, or preferably, the at least one antioxidant is selected from the group consisting of pentaerythritol tetrakis (3-(3,5-d i-tert-butyl-4- hydroxyphenyl)propionate; 3,3',3',5,5',5'-hexa-tert-butyl-a,a',a'-(mesitylene-2,4-,6- triyl)tri-p-cresol; N,N'-hexane-1 ,6-diylbis(3-(3,5-di-tert-butyl-4- hydroxyphenylpropionamide)); octadecyl-3-(3,5-di-tert.butyl-4-hydroxyphenyl)- propionate; and combinations of two or more thereof, or more preferably, the at least one antioxidant is N,N'-hexane-1 ,6-diylbis(3-(3,5-di-tert-butyl-4- hydroxyphenylpropionamide)).
5. The abrasive filament of any of Claims 1 -4, wherein the at least one antioxidant is present in the polyamide composition at a level of 0.2-0.7 wt%, based on the total weight of the polyamide composition.
6. The abrasive filament of any of Claims 1 -5, wherein the abrasive particles are
selected from the group consisting of organic abrasive particles, inorganic abrasive particles, and combinations thereof, or preferably, the abrasive particles are selected from the group consisting of particles based on aluminum oxides, alpha alumina, silicon carbides, titanium diborides, alumina zirconia, diamond, boron carbide, ceria, aluminum silicates, cubic boron nitride, garnet, silica, pumice, sand, emery, mica, corundum, quartz, and combinations of two or more thereof.
7. The abrasive filament of any of Claims 1 -6, wherein the at least one polyamide is selected from aliphatic polyamides, or preferably, the at least one polyamide is selected from the group consisting of polyamide 4,6; polyamide 6; polyamide 6,6; polyamide 6,10; polyamide 6,12; polyamide 6,13; polyamide 6,14; polyamide 6,15; polyamide 6,16; polyamide 9,10; polyamide 9,12; polyamide 9,13; polyamide 9,14; polyamide 9,15; polyamide 9,36; polyamide 10,10; polyamide 10,12; polyamide 10,13; polyamide 10,14; polyamide 1 1 ; polyamide 12; polyamide 12,10; polyamide 12,12; polyamide 12,13; polyamide 12,14; and combinations of two or more thereof, or more preferably, the at least one aliphatic polyamide is selected from polyamide 6,10; polyamide 6,12; and combinations thereof.
8. The abrasive filaments of any of Claims 1 -7, wherein the at least one polyamide has a relative viscosity of 2.3-5, or preferably 2.3-4, or more preferably 2.3-3.5.
9. The abrasive filament of any of Claims 1 -8, wherein the at least one polyamide is present in the polyamide composition at a level of 60-90 wt%, or preferably 60-80 wt%, or more preferably 60-75 wt%, based on the total weight of the polyamide composition.
10. The abrasive filament of any of Claims 1 -9, wherein the abrasive filament is
prepared by a continuous melt spinning process, and wherein the process comprises:
(i) blending the at least one polyamide, the at least one linear chain extender compound, and the at least one antioxidant into a mixture;
(ii) passing the mixture through an extruder while the abrasive particles are
added into the extruder through one or more side feeders; and
(iii) melt spinning the composition that comes out of the extruder into filaments.
1 1 . The abrasive filament of any of Claims 1 -9, wherein the abrasive filament is
prepared by a two-step melt spinning process, and wherein the process comprises:
(i) melt compounding the at least one polyamide, the at least one linear chain extender compound, and the at least one antioxidant into resin pellets;
(ii) passing the resin pellets through an extruder while the abrasive particles are added into the extruder through one or more side feeders; and
(iii) melt spinning the composition that comes out of the extruder into filaments.
12. An industrial brush comprising a plurality of the abrasive filaments of any of Claims 1 -9.
13. The use of the industrial brush of Claim 12 in grinding and/or polishing silicon ingots, stone, or metal parts, or preferably the use in grinding and/or polishing silicon ingots.
PCT/US2012/063984 2011-11-29 2012-11-07 Abrasive filaments with improved stiffness and industrial brushes comprising the same and uses thereof WO2013081790A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP12791366.3A EP2785900B1 (en) 2011-11-29 2012-11-07 Abrasive filaments with improved stiffness and industrial brushes comprising the same and uses thereof
JP2014544748A JP2015505737A (en) 2011-11-29 2012-11-07 Abrasive filament with improved rigidity, an industrial brush containing the abrasive filament, and use of the industrial brush
KR1020147017432A KR20140096152A (en) 2011-11-29 2012-11-07 Abrasive filaments with improved stiffness and industrial brushes comprising the same and uses thereof
ES12791366.3T ES2557006T3 (en) 2011-11-29 2012-11-07 Abrasive filaments with improved stiffness and industrial brushes comprising them and their uses

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201110386805.0 2011-11-29
CN201110386805.0A CN103132172B (en) 2011-11-29 2011-11-29 Abrasive silk with improved rigidity, industrial brush with the same and purpose of industrial brush

Publications (1)

Publication Number Publication Date
WO2013081790A1 true WO2013081790A1 (en) 2013-06-06

Family

ID=47226449

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2012/063984 WO2013081790A1 (en) 2011-11-29 2012-11-07 Abrasive filaments with improved stiffness and industrial brushes comprising the same and uses thereof

Country Status (7)

Country Link
US (1) US20130137344A1 (en)
EP (1) EP2785900B1 (en)
JP (1) JP2015505737A (en)
KR (1) KR20140096152A (en)
CN (1) CN103132172B (en)
ES (1) ES2557006T3 (en)
WO (1) WO2013081790A1 (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104562286B (en) * 2013-10-11 2017-08-04 杜邦兴达(无锡)单丝有限公司 A kind of abrasive filaments and its manufacture method
CN104088031B (en) * 2014-01-02 2016-04-20 浙江美丝邦化纤有限公司 Multi-functional nylon-6 fiber and manufacture method thereof
GB201516679D0 (en) 2015-09-21 2015-11-04 Colormatrix Holdings Inc Polymeric materials
WO2017223225A1 (en) * 2016-06-22 2017-12-28 Cabot Microelectronics Corporation Polishing composition comprising an amine-containing surfactant
CN106400156B (en) * 2016-08-31 2019-04-23 义乌华鼎锦纶股份有限公司 A kind of preparation method of high-strength flatness nylon-6 fiber
CN107881594B (en) * 2016-09-30 2021-08-06 杜邦兴达(无锡)单丝有限公司 Acid-resistant and wear-resistant abrasive wire
CN108188947A (en) * 2018-01-29 2018-06-22 韶关威鸣研磨材料有限公司 A kind of special grinding apparatus of stainless steel plate wire drawing and preparation method thereof
CN109623638A (en) * 2018-12-27 2019-04-16 中车青岛四方机车车辆股份有限公司 Stainless steel surface grinding head and milling tools
CN110408205B (en) * 2019-07-26 2022-03-25 中车青岛四方机车车辆股份有限公司 Heat-resistant and wear-resistant composition and preparation method and application thereof
CN110423429B (en) * 2019-08-16 2022-01-14 安徽省恒昌刷业有限公司 Efficient wear-resistant brush roll material and preparation method thereof
KR20220080163A (en) 2019-10-24 2022-06-14 인비스타 텍스타일스 (유.케이.) 리미티드 Polyamide compositions and articles made therefrom
CN112301441B (en) * 2020-10-29 2022-05-27 厦门安踏体育用品有限公司 Preparation method of superfine denier nylon fiber and ultralight fabric and ultralight jacket

Citations (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1910444A (en) 1931-02-13 1933-05-23 Carborundum Co Process of making abrasive materials
US3041156A (en) 1959-07-22 1962-06-26 Norton Co Phenolic resin bonded grinding wheels
US3522342A (en) 1967-07-03 1970-07-28 Nypel Inc Apparatus and method for making bristles having a filler
US3947169A (en) 1966-07-29 1976-03-30 Allied Chemical Corporation Apparatus for making rods or tubes having a filter
US4311489A (en) 1978-08-04 1982-01-19 Norton Company Coated abrasive having brittle agglomerates of abrasive grain
US4314827A (en) 1979-06-29 1982-02-09 Minnesota Mining And Manufacturing Company Non-fused aluminum oxide-based abrasive mineral
US4623364A (en) 1984-03-23 1986-11-18 Norton Company Abrasive material and method for preparing the same
US4652275A (en) 1985-08-07 1987-03-24 Minnesota Mining And Manufacturing Company Erodable agglomerates and abrasive products containing the same
US4744802A (en) 1985-04-30 1988-05-17 Minnesota Mining And Manufacturing Company Process for durable sol-gel produced alumina-based ceramics, abrasive grain and abrasive products
US4770671A (en) 1985-12-30 1988-09-13 Minnesota Mining And Manufacturing Company Abrasive grits formed of ceramic containing oxides of aluminum and yttrium, method of making and using the same and products made therewith
EP0288253A2 (en) 1987-04-24 1988-10-26 Polyplastics Co. Ltd. Resin compositions
US4799939A (en) 1987-02-26 1989-01-24 Minnesota Mining And Manufacturing Company Erodable agglomerates and abrasive products containing the same
US4881951A (en) 1987-05-27 1989-11-21 Minnesota Mining And Manufacturing Co. Abrasive grits formed of ceramic containing oxides of aluminum and rare earth metal, method of making and products made therewith
US4964883A (en) 1988-12-12 1990-10-23 Minnesota Mining And Manufacturing Company Ceramic alumina abrasive grains seeded with iron oxide
US4997461A (en) 1989-09-11 1991-03-05 Norton Company Nitrified bonded sol gel sintered aluminous abrasive bodies
US5009675A (en) 1988-06-17 1991-04-23 Lonza Ltd Coated silicon carbide abrasive grain
US5009676A (en) 1989-04-28 1991-04-23 Norton Company Sintered sol gel alumina abrasive filaments
US5011508A (en) 1988-10-14 1991-04-30 Minnesota Mining And Manufacturing Company Shelling-resistant abrasive grain, a method of making the same, and abrasive products
US5042991A (en) 1989-03-13 1991-08-27 Lonza Ltd. Hydrophobically coated abrasive grain
US5164348A (en) 1987-05-27 1992-11-17 Minnesota Mining And Manufacturing Company Abrasive grits formed by ceramic impregnation method of making the same, and products made therewith
US5185012A (en) 1989-04-28 1993-02-09 Norton Company Coated abrasive material containing abrasive filaments
US5213591A (en) 1992-07-28 1993-05-25 Ahmet Celikkaya Abrasive grain, method of making same and abrasive products
US5244477A (en) 1989-04-28 1993-09-14 Norton Company Sintered sol gel alumina abrasive filaments
JPH05279916A (en) * 1992-03-27 1993-10-26 Asahi Chem Ind Co Ltd Monofilament for abrasion
US5372620A (en) 1993-12-13 1994-12-13 Saint Gobain/Norton Industrial Ceramics Corporation Modified sol-gel alumina abrasive filaments
WO1996034909A1 (en) 1995-05-04 1996-11-07 Dsm N.V. High-molecular polyamide
US6228980B1 (en) 1997-04-22 2001-05-08 Dsm N.V. High-molecular polyamide
DE10042176A1 (en) * 2000-03-09 2001-09-13 Bayer Ag Thermoplastic molding composition based on an aliphatic polyamide of copolyamide useful for making articles with high resistance to engine coolants
US7005097B2 (en) 2002-01-23 2006-02-28 Boston Scientific Scimed, Inc. Medical devices employing chain extended polymers
WO2010033671A1 (en) 2008-09-18 2010-03-25 E. I. Du Pont De Nemours And Company Acid-resistant filament for industrial application and brush (made) with same
CN101994167A (en) * 2009-08-11 2011-03-30 慈溪市洁达纳米复合材料有限公司 Method for preparing grinding silk

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0632908B2 (en) * 1985-08-12 1994-05-02 東レ・モノフィラメント株式会社 Bristles for polishing brush
TW307801B (en) * 1992-03-19 1997-06-11 Minnesota Mining & Mfg
TW222668B (en) * 1992-03-19 1994-04-21 Minnesota Mining & Mfg
US5679067A (en) * 1995-04-28 1997-10-21 Minnesota Mining And Manufacturing Company Molded abrasive brush
JP4047926B2 (en) * 1995-04-28 2008-02-13 スリーエム カンパニー Abrasive products having a bond system containing polysiloxane
US6179887B1 (en) * 1999-02-17 2001-01-30 3M Innovative Properties Company Method for making an abrasive article and abrasive articles thereof
US20070099549A1 (en) * 2004-05-21 2007-05-03 Simon Palushaj Abrasive cleaning and honing device and method of honing concrete surfaces
WO2006038507A1 (en) * 2004-10-06 2006-04-13 Mitsubishi Engineering-Plastics Corporation Polyamide resin molding material for film and process for producing the same
US20090211218A1 (en) * 2005-07-15 2009-08-27 Dsm Ip Assets B.V. Polycondensate fibers
WO2008140929A1 (en) * 2007-05-10 2008-11-20 3M Innovative Properties Company Abrasive filament and brush
CA2811216C (en) * 2010-09-15 2015-08-25 Saint-Gobain Abrasives, Inc. Abrasive impregnated brush

Patent Citations (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1910444A (en) 1931-02-13 1933-05-23 Carborundum Co Process of making abrasive materials
US3041156A (en) 1959-07-22 1962-06-26 Norton Co Phenolic resin bonded grinding wheels
US3947169A (en) 1966-07-29 1976-03-30 Allied Chemical Corporation Apparatus for making rods or tubes having a filter
US3522342A (en) 1967-07-03 1970-07-28 Nypel Inc Apparatus and method for making bristles having a filler
US4311489A (en) 1978-08-04 1982-01-19 Norton Company Coated abrasive having brittle agglomerates of abrasive grain
US4314827A (en) 1979-06-29 1982-02-09 Minnesota Mining And Manufacturing Company Non-fused aluminum oxide-based abrasive mineral
US4623364A (en) 1984-03-23 1986-11-18 Norton Company Abrasive material and method for preparing the same
US4744802A (en) 1985-04-30 1988-05-17 Minnesota Mining And Manufacturing Company Process for durable sol-gel produced alumina-based ceramics, abrasive grain and abrasive products
US4652275A (en) 1985-08-07 1987-03-24 Minnesota Mining And Manufacturing Company Erodable agglomerates and abrasive products containing the same
US4770671A (en) 1985-12-30 1988-09-13 Minnesota Mining And Manufacturing Company Abrasive grits formed of ceramic containing oxides of aluminum and yttrium, method of making and using the same and products made therewith
US4799939A (en) 1987-02-26 1989-01-24 Minnesota Mining And Manufacturing Company Erodable agglomerates and abrasive products containing the same
EP0288253A2 (en) 1987-04-24 1988-10-26 Polyplastics Co. Ltd. Resin compositions
US4881951A (en) 1987-05-27 1989-11-21 Minnesota Mining And Manufacturing Co. Abrasive grits formed of ceramic containing oxides of aluminum and rare earth metal, method of making and products made therewith
US5164348A (en) 1987-05-27 1992-11-17 Minnesota Mining And Manufacturing Company Abrasive grits formed by ceramic impregnation method of making the same, and products made therewith
US5009675A (en) 1988-06-17 1991-04-23 Lonza Ltd Coated silicon carbide abrasive grain
US5011508A (en) 1988-10-14 1991-04-30 Minnesota Mining And Manufacturing Company Shelling-resistant abrasive grain, a method of making the same, and abrasive products
US4964883A (en) 1988-12-12 1990-10-23 Minnesota Mining And Manufacturing Company Ceramic alumina abrasive grains seeded with iron oxide
US5042991A (en) 1989-03-13 1991-08-27 Lonza Ltd. Hydrophobically coated abrasive grain
US5244477A (en) 1989-04-28 1993-09-14 Norton Company Sintered sol gel alumina abrasive filaments
US5009676A (en) 1989-04-28 1991-04-23 Norton Company Sintered sol gel alumina abrasive filaments
US5185012A (en) 1989-04-28 1993-02-09 Norton Company Coated abrasive material containing abrasive filaments
US4997461A (en) 1989-09-11 1991-03-05 Norton Company Nitrified bonded sol gel sintered aluminous abrasive bodies
JPH05279916A (en) * 1992-03-27 1993-10-26 Asahi Chem Ind Co Ltd Monofilament for abrasion
US5213591A (en) 1992-07-28 1993-05-25 Ahmet Celikkaya Abrasive grain, method of making same and abrasive products
US5372620A (en) 1993-12-13 1994-12-13 Saint Gobain/Norton Industrial Ceramics Corporation Modified sol-gel alumina abrasive filaments
WO1996034909A1 (en) 1995-05-04 1996-11-07 Dsm N.V. High-molecular polyamide
US6228980B1 (en) 1997-04-22 2001-05-08 Dsm N.V. High-molecular polyamide
DE10042176A1 (en) * 2000-03-09 2001-09-13 Bayer Ag Thermoplastic molding composition based on an aliphatic polyamide of copolyamide useful for making articles with high resistance to engine coolants
US7005097B2 (en) 2002-01-23 2006-02-28 Boston Scientific Scimed, Inc. Medical devices employing chain extended polymers
WO2010033671A1 (en) 2008-09-18 2010-03-25 E. I. Du Pont De Nemours And Company Acid-resistant filament for industrial application and brush (made) with same
CN101994167A (en) * 2009-08-11 2011-03-30 慈溪市洁达纳米复合材料有限公司 Method for preparing grinding silk

Also Published As

Publication number Publication date
ES2557006T3 (en) 2016-01-21
CN103132172A (en) 2013-06-05
EP2785900A1 (en) 2014-10-08
EP2785900B1 (en) 2015-11-04
KR20140096152A (en) 2014-08-04
US20130137344A1 (en) 2013-05-30
JP2015505737A (en) 2015-02-26
CN103132172B (en) 2015-07-22

Similar Documents

Publication Publication Date Title
EP2785900B1 (en) Abrasive filaments with improved stiffness and industrial brushes comprising the same and uses thereof
JP3676804B2 (en) Abrasive filaments containing an abrasive-filled thermoplastic abrasive elastomer, method for producing the same, and products containing the same
JP4047926B2 (en) Abrasive products having a bond system containing polysiloxane
JP3078020B2 (en) Wire saw and manufacturing method thereof
JP3683581B2 (en) Composite abrasive filament, method for producing the same, and article incorporating the same
US5669941A (en) Coated abrasive article
JPH0790719A (en) Monofilament for abrasion
EP2128215B1 (en) Cement compositions including polymer particles
EP2329068A1 (en) Acid-resistant filament for industrial application and brush (made) with same
JP2002537493A (en) Abrasive filaments of plasticized polyamide
TW201412830A (en) Hollow polymeric-alkaline earth metal oxide composite
US20210206051A1 (en) Feed Material For Three-Dimensional Printing Containing A Polyoxymethylene Polymer
JP2012101353A5 (en)
WO2019195689A1 (en) Additive manufacturing compositions
CN107881594B (en) Acid-resistant and wear-resistant abrasive wire
CN110564144B (en) Nylon sand and preparation method thereof
WO2021127106A1 (en) Powder composition for three-dimensional printing containing a polyoxymethylene polymer
KR20010110199A (en) Moldable abrasive pellets, their production and use
US10086498B2 (en) Coated abrasives having a supersize layer including an active filler
JP3272832B2 (en) Polishing monofilament
JPH05279916A (en) Monofilament for abrasion
JPH0441182A (en) Monofilament for polishing
JPH0493178A (en) Projection member for wet blast
CN101443174A (en) Coloured rotomoulded articles
EP4229133A1 (en) Magnetic composition comprising a resin consisting of copolymers containing polyamide blocks and polyether blocks

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12791366

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014544748

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20147017432

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2012791366

Country of ref document: EP