CN1882418A - Abrasive article and methods of making the same - Google Patents
Abrasive article and methods of making the same Download PDFInfo
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- CN1882418A CN1882418A CNA2004800343646A CN200480034364A CN1882418A CN 1882418 A CN1882418 A CN 1882418A CN A2004800343646 A CNA2004800343646 A CN A2004800343646A CN 200480034364 A CN200480034364 A CN 200480034364A CN 1882418 A CN1882418 A CN 1882418A
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- abrasive
- abrasive product
- concave portion
- characteristic body
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
- B24D3/02—Physical 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
- B24D3/20—Physical 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D11/00—Constructional features of flexible abrasive materials; Special features in the manufacture of such materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
- B24D3/02—Physical 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
- B24D3/20—Physical 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
- B24D3/28—Resins or natural or synthetic macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D2203/00—Tool surfaces formed with a pattern
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- Mechanical Engineering (AREA)
- Polishing Bodies And Polishing Tools (AREA)
Abstract
An abrasive article and methods of making the same are disclosed. The abrasive article (100) includes a backing (130) and an array (110) of features (120) on the backing. Each feature includes a base and a body. The body includes a face having an undercut (125). In one embodiment, the feature also includes a planar top portion having abrasive particles disposed thereon. In another embodiment, the feature also includes a radiused portion on the undercut sidewall (124) adjacent the base.
Description
Technical field
The present invention relates to a kind of abrasive product, more particularly, the present invention relates to a kind of structured abrasive article and manufacture method thereof and using method.
Background technology
With abrasive product surface of the work was carried out grinding and buffing existing more than 100 year.Degree of depth grinding, high-pressure metal polishing processing have been contained in these application, and even for example meticulous polishing of lens.Usually, abrasive product is made (for example, bonding material or emery wheel) by a plurality of abrasive particles that are adhered to one another, or makes (for example, sand paper) by a plurality of abrasive particles that are bonded on the substrate.Sand paper has single layer of abrasive particles usually or has two-layer abrasive particle sometimes.In case these abrasive wears, sand paper has has just worn and torn basically, can only throw away usually.
The latest developments of three-dimensional coated grits provide a kind of abrasive product that is referred to as " structured abrasives " usually.For example United States Patent (USP) 5,152, and 917 (people such as Pieper) have disclosed the structure of various structured abrasive articles, incorporate this paper at this into way of reference.Pieper has instructed a kind of structured abrasives, and this abrasive material can obtain higher grinding speed and form meticulousr polished surface on surface of the work.This structured abrasives comprises the nonrandomness that is bonded on the substrate, the abrasive composites of Accurate Shaping.
Other lists of references that relate to structured abrasive article and manufacture method thereof comprise United States Patent (USP) 5.855,632 (people such as Stoetzel), 5,681,217 (people such as Hoopman), 5,435,816 (people such as Spurgeon), 5,378,251 (people such as Culler), 5,304,223 (people such as Pieper) and 5,014,468 (people such as Ravipati), above-mentioned all patents are incorporated this paper at this into way of reference.
Pieper and other people structured abrasives patent are the major progress of abrasive material technical field, but still also have improved space.
Summary of the invention
One aspect of the present invention relates to the characteristic body that is used for abrasive product.This characteristic body comprises substrate and body.Body is a polyhedron, is the pyramidal polyhedron with four sidewalls that limit body in one embodiment.A sidewall has the side concave portion that forms anterior angle.In one embodiment, the recessed sidewall of side comprises near the part that is cut into fillet that substrate is.In another embodiment, body also comprises planar top, and this planar top comprises abrasive particle.
Another aspect of the present invention relates to the abrasive product with the characteristic body array that is positioned on the substrate.Described array comprises a plurality of characteristic bodies, and each characteristic body comprises substrate and body.Each body all is a polyhedron, is the pyramid polyhedron with four sidewalls that limit body in one embodiment.A sidewall has the side concave portion that forms anterior angle.In one embodiment, the recessed sidewall of side comprises near the part that is cut into circle that substrate is.In another embodiment, body also comprises planar top, and this planar top comprises abrasive particle.
Description of drawings
Fig. 1 is the perspective view according to the part of abrasive product example embodiment of the present invention;
Figure 1A is the side view of Fig. 1 goods of A-A along the line;
Figure 1B is the front view of Fig. 1 goods of B-B along the line;
Fig. 2 is the example embodiment that is used to make according to the system of abrasive product of the present invention;
Fig. 3 is another example embodiment that is used to make according to the system of abrasive product of the present invention.
The specific embodiment
The present invention relates generally to abrasive product and production and preparation method thereof.In one embodiment, abrasive product comprises the characteristic body (feature) that a plurality of microcosmic repeat.In the context of the present invention, term characteristics thing and composition are interchangeable.
Characteristic body comprises substrate and body.Body comprises the face with side concave portion.This face also comprises near the arch section the substrate.Characteristic body also comprises planar top.This planar top substrate relatively tilts.
In another example embodiment, abrasive product is a band.Described band comprises substrate and layout a plurality of characteristic bodies on tape.In an example embodiment, characteristic body is arranged as and makes all similar orientation of whole side concave surfaces.In another example embodiment, the relative substrate tilting of planar top.Other embodiment can comprise one of above-mentioned characteristic or their combination.
With reference to figure 1, abrasive product 100 comprises the abrasive composites 120 that is separated by gap or border.Abrasive composites adheres on the surface of substrate 130.The border relevant with the composition shape or a plurality of border are separated into to a certain degree an abrasive composites and other adjacent abrasive composites.For forming single abrasive composites, a part that forms the border of abrasive composites shapes of substrates must be spaced from each other.In certain embodiments, the abrasive composites substrate of close substrate or the part abrasive composites adjacency that can be adjacent.Abrasive composites 120 comprises a plurality of abrasive particles and the grinding aid that is dispersed in the adhesive.Scope of the present invention also comprises the combination that is bonded at the abrasive composites on the substrate, and wherein some abrasive composites adjacency has open space between other the abrasive composites.
Substrate
Substrate of the present invention has front and rear surfaces, and can be the abrasive material substrate of any routine.Available substrate example comprises thin polymer film, goes up thin polymer film, cloth, paper, sclerotic fiber, non-weaving cloth and the above-mentioned composition of primer.Other available substrates comprise as United States Patent (USP) 5,316, the fiber reinforced thermolplastic substrate disclosed in 812, and at the bottom of the ring-type seamless lining disclosed in world patent application WO93/12911.Substrate also can comprise one or more seal substrate and/or some physical property of substrate be carried out the processing of modification.These are handled in the present technique field is known.
Substrate also can have attachment arrangement on its back side, so that resulting coated abrasives can be fixed on supporting pad or the support pad.As above-mentioned United States Patent (USP) 5,316, disclosed in 812, this attachment arrangement can be that pressure sensitive adhesives, one side are the attachment system or the threaded ridge of hook and ring.Perhaps can be the United States Patent (USP) 5,201 as the assignee, the intermeshing attachment system described in 101 be incorporated this paper at this into way of reference.
Non-skid coating or friction coating can also be contained in the back side of abrasive product.The example of this class coating comprises the inorganic particles (for example, calcium carbonate or quartz) that is dispersed in the binding agent.
Abrasive coating
Abrasive particle
The particle size range of abrasive particle is generally about 0.1～1500 micron, between about 0.1～400 micron, is preferably between 0.1～100 micron usually, is preferably between 0.1～50 micron.In one embodiment, the Morse hardness of abrasive particle is at least about 8, more preferably greater than 9.The example of this class abrasive particle comprises aluminium oxide (comprising brown aluminium oxide, heat treatment aluminium oxide and white alumina), ceramic alumina, green silicon carbide, carborundum, chromium oxide, alumina zirconia abrasive, diamond, iron oxide, ceria, cubic boron nitride, boron carbide, garnet and the above-mentioned composition of fusion.
Term " abrasive particle " also comprises by single abrasive particle and bonding together to form abrasive agglomerate.United States Patent (USP) 4,311,489,4,652,275 and 4,799,939 have further described abrasive agglomerate, and above-mentioned all patents are incorporated this paper at this into way of reference.
The present invention also is included in has face coat on the abrasive particle.Face coat can have multiple difference in functionality.In some cases, face coat can improve abrasive particle to the adhesion of binding agent, the abrasive characteristic of change abrasive particle etc.The example of face coat comprises coupling agent, halide salt, comprises siliceous metal oxide, fire-resistant metal nitride, fire-resistant metal carbides etc.
In the abrasive composites particulate that mixes can also be arranged.These granularities of mixing particulate can be in the same order of magnitude with abrasive particle.The example that this class is mixed particulate comprises gypsum, marble, lime stone, flint, silica, glass envelope, bead, alumina silicate etc.
Binding agent
Abrasive particle is dispersed in the organic binder bond to form abrasive composites.Binding agent is derived by binder precursor and is got, and contains polymerisable organic resin in the binder precursor.In abrasive particle manufacture process of the present invention, binder precursor is exposed to energy source, and this energy source helps initiated polymerization process or solidification process.The example of energy source comprises heat energy and radiant energy, and the latter comprises electron beam, ultraviolet light and visible light.In polymerization process, resin polymerization and binder precursor change into solid binder.After binder precursor is solidified, form abrasive coating.Binding agent in the abrasive coating also plays usually abrasive coating is bonded to effect on the substrate.
There are two class preferred resins to can be used among the present invention, promptly curable condensation resin and polymerisable addition resin.Preferred binder precursor comprises polymerisable addition resin, because this resinoid solidifies by being exposed to radiant energy easily.Polymerisable addition resin can the polymerization by cationic mechanism or free radical mechanism.The chemical property that depends on employed energy source and binder precursor is preferably helped initiated polymerization with curing agent, initator or catalyst sometimes.
Commonly used and preferred organic resin example comprises phenolic resins, urea formaldehyde resin, melamine formaldehyde resin, acroleic acid polyurethane, acrylic acid epoxy resin, ethylenically unsaturated compounds, has the aminoplast derivative of side chain unsaturated carbonyl, has the acrylate-based isocyanurate derivative of at least one side chain, has the acrylate-based isocyanate derivates of at least one side chain, vinyl ethers, epoxy resin and above-mentioned mixture and composition.Term " acrylate " comprises acrylate and methacrylate.
Phenolic resins because of its thermal property, obtain easily and cost is low is widely used in the abrasive product binding agent.Two class phenolic resins, resol and novolac resins are arranged.The mol ratio of formaldehyde and phenol is more than or equal to 1: 1, usually between 1.5: 1.0～3.0: 1.0 in the resol.The mol ratio of formaldehyde and phenol was less than 1: 1 in the novolac resin.Commercially available phenolic resins example comprises following product: commodity are called " Durez " and " Varcum ", and OccidentalChemicals company produces; " Resinox ", Monsanto produces; " Aerofene ", Ashland Chemical Co. produces; " Aerotap ", Ashland Chemical Co. produces.
The polyurethane of propylene acidifying is with the polyester hydroxy-end capped, that isocyanates NCO stretches or the diacrylate of polyethers.Commercially available acroleic acid polyurethane product example comprises that commodity " UVITHANE 782 " Morton Thiokol Chemical by name produces, and " CMD6600 ", " CMD 8400 " and " CMD 8805 " Radcure Specialties product.
Acrylic acid epoxy ester is the diacrylate of epoxy resin, for example the diacrylate of bisphenol A epoxide resin.Commercially available acrylic acid epoxy ester product example comprises that commodity are called " CMD3500 ", " CMD 3600 " and " CMD 3700 ", and Radcure Specialties produces.
The ethylenic unsaturated-resin had both comprised that monomeric compound also comprised polymerizable compound, and this monomeric compound and polymerizable compound contain carbon atom, hydrogen atom and oxygen atom, and contained nitrogen-atoms and halogen atom alternatively.Oxygen atom or nitrogen-atoms or the two appear in ether, ester group, urethane ester group, amide groups and the urea groups usually.
Ethylenically unsaturated compounds is preferably molecular weight less than about 4,000, and be preferably the ester that generates by containing the reaction of polyhydric compound of aliphatic monohydroxy or aliphatic and unsaturated carboxylic acid, unsaturated carboxylic acid is acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid and maleic acid etc. for example.The representative instance of acrylate comprises methyl methacrylate, EMA styrene, divinylbenzene, vinyltoluene, ethylene glycol diacrylate, methacrylic acid glycol ester, diacrylate adipate ester, diacrylate triethyleneglycol ester, trimethyol propane triacrylate, three acrylic acid glyceride, pentaerythritol triacrylate, methacrylic acid pentaerythritol ester, pentaerythritol tetracrylate and pentaerythritol tetracrylate.Other ethylenic unsaturated-resins comprise monoene propyl diester, polyenoid propyl diester and many methylallyls ester and carboxylic acid amide, for example diallyl phthalate, diallyl adipate and N, N-diallyl adipamide.Other nitrogen-containing compounds also comprise three (2-acryloyl ethyoxyl) isocyanuric acid ester, 1,3,5-three (2-methacryl ethyoxyl)-triazine, acrylamide, Methacrylamide, N methacrylamide, N,N-DMAA, N-vinyl pyrrolidone and N-vinyl piperidones.
Has at least one α on each molecule of amino resin or the oligomer, β side chain unsaturated carbonyl.These unsaturated carbonyls can be acrylate, methacrylate or acid/acrylic amide type group.The example of this class material comprises N-(methylol) acrylamide, N, N '-oxygen ethanetetrayl bisacrylamide, ortho position and contraposition acrylamide methylate phenolic aldehyde, acrylamide methylate novolac resin and above-mentioned composition.United States Patent (USP) 4,903,440 and 5,236,472 have further described these materials, and above-mentioned patent is incorporated this paper at this into way of reference.
United States Patent (USP) 4,652,274 have further described and have the acrylate-based isocyanurate derivative of at least one side chain and have the acrylate-based isocyanate derivates of at least one side chain, and this patent is incorporated this paper at this into way of reference.Preferred isocyurnate material is the triacrylate of three (ethoxy) isocyanuric acid ester.
Epoxy resin has oxirane, and forms by ring-opening polymerisation.This based epoxy resin comprises monomeric epoxy resins and epoxy resin oligomer.Some preferred epoxy resin examples comprise 2, [4-(2 for 2-two, the 3-glycidoxy)-and phenyl-propane] (diphenol diglycidyl ether) and commercially available proprietary concentrate, these materials can be following products, commodity are called " Epon 828 ", " Epon1004 " and " Epon 1001F " produced by Shell Chemical Co., and commodity " DER-331 ", " DER-332 " and " DER-334 " by name, produce by Dow Chemical Co..Other suitable epoxy resin comprise the glycidol ether (for example, can available from " DEN-431 " and " DEN-428 " of Dow chemical Co.) of phenolic resin varinish.
Epoxy resin of the present invention can carry out polymerization with cationic mechanism by adding suitable cation curing agent.Cation curing agent produces acid source, to cause polymerization of epoxy resins.These cation curing agents can comprise the salt with complex cation and halogen, and this salt contains metal or nonmetal coordination anion.United States Patent (USP) 4,751,138 (the 6th hurdle the 65th row is to the 9th hurdle the 45th row) have also been described other cation curing agents, comprise the salt with organic metal coordination cation and halogen, this salt contains metal or nonmetal complex anion, and this patent is incorporated this paper at this into way of reference.United States Patent (USP) 4,985,340 (the 4th hurdle the 65th row is to the 14th hurdle the 50th row) and on March 8th, 1989 disclosed european patent application 306,161 and 306,162 examples of having described another kind of organic metal salt and salt, above-mentioned patent is all incorporated this paper into way of reference.In addition, November 21 nineteen eighty-three disclosed european patent application 109,581 have described other cation curing agents, this cation curing agent includes the ion salt of organic metal complex, wherein metal is selected from IVB, VB, VIB, VIIB and the VIIIB family element of the periodic table of elements, and this patent is incorporated this paper into way of reference.
About the free radical curable resin, be preferably in some cases and also comprise free radical curing agent in the abrasive material slurry.But under the situation of electron beam, because electron beam itself just produces free radical, so not necessarily always need curing agent as energy source.
The example of free radical thermal initiator comprises peroxide, for example benzoyl peroxide, azo-compound, benzophenone and quinone.For ultraviolet light or visible light energy source, this curing agent is called as light trigger sometimes.Be exposed to the initator example that can produce the free radical source under the ultraviolet light, include but not limited to be selected from the group that constitutes by following material: organic peroxide, azo-compound, quinone, benzophenone, nitroso compound, acryloyl halogenation thing, hydrazone, sulfhydryl compound, pyrylium compound, three propylene imidazoles (triacrylimdazoles), diimidazole, chlorine alkyl triazine, benzoin ether, dibenzoyl ketal, thioxanthones and acetophenone derivs and above-mentioned mixture.At the United States Patent (USP) 4 that is entitled as " Coated Abrasive Binder Containing Ternary PhotoinitiatorSystem (the coated abrasives binding agent that contains triple photoinitiator systems) ", 735, in 632, can find to be exposed to the initator example that visible radiation can produce the free radical source, this patent is incorporated this paper at this into way of reference.The preferred initator that uses together with visible light is can be from " Irgacure 369 " that Ciba Geigy Corporation buys.
Grinding aid
Grinding aid is defined as a kind of like this material, is preferably microparticle material, this material is added in the abrasive product and can produce remarkable result to the chemistry and the physical process of grinding, thereby improve performance.Common and preferable methods is that grinding aid is added in the slurry as particulate, adds in the slurry but grinding aid can be used as liquid, perhaps can be used as external coating and adds to reduce the filler of product.Compare with the abrasive product that does not comprise grinding aid, use grinding aid can improve the grinding efficiency or the cutting speed (being defined as the workpiece weight that loss Unit Weight abrasive product is removed) of corresponding abrasive product.Specifically, in this area, believe that grinding aid can reach following effect: 1) reduce abrasive grain and the workpiece that ground between friction, 2) prevent " block " of abrasive grain, that is, prevent that metallic (under the situation of metal works) is heat fused to the top of abrasive grain, 3) reduce the interface temperature between abrasive grain and the workpiece, 4) reduce required abrasive power, perhaps 5) stop the metal works oxidation.Usually, add the service life that grinding aid can prolong abrasive product.
The present invention can with grinding aid contain various material, and can be material based on inorganic matter or organic matter.The example of grinding aid chemical race comprises wax, soap, organohalogen compounds, halide salt and metal and alloy thereof.Organohalogen compounds can decompose and discharge hydracid or gaseous halide usually in process of lapping.The example of this class material comprises chlorinated wax such as Tetrachloronaphthalene, Pentachloronaphthalene and polyvinyl chloride.The example of soap comprises lithium stearate and zinc stearate.The example of halide salt comprises sodium chloride, elpasolite, sodium cryolite, ammonium ice crystal, potassium tetrafluoroborate, sodium tetrafluoroborate, silicon fluoride, potassium chloride, magnesium chloride.The example of metal comprises tin, lead, bismuth, cobalt, antimony, cadmium, iron, titanium, and other various grinding aids comprise sulphur, organic sulfur compound, graphite and metal sulfide.The combination of using different grinding aids and can produce cooperative effect also within the scope of the present invention in some cases.
The example of above-mentioned grinding aid is only as representative.The grinding aid that the present invention better uses is an ice crystal, preferably potassium tetrafluoroborate (KBF
4).
It is non-abrasive material that grinding aid is considered to, that is, the Morse hardness of grinding aid is less than 8.Can also contain impurity in the grinding aid; These impurity should not can obviously reduce the performance of abrasive product.
The preferable range of grinding aid granularity is about 0.1～100 micron, more preferably between 10～70 microns.Usually, the granularity of grinding aid is preferably and is equal to or less than wear particle size.
Usually, abrasive coating comprise at least about 1% (percentage by weight), usually at least about 2.5% (percentage by weight), be preferably at least about 5% (percentage by weight), more preferably at least about the grinding aid of 10% (percentage by weight), but be preferably the grinding aid that comprises at least about 20% (percentage by weight).It can be disadvantageous that grinding aid surpasses about 50% (percentage by weight), because nonferromagnetic substance is descended (because only having less abrasive particle).Along with the raising of grinding aid content, the relative nonferromagnetic substance of estimating with cutting speed also can improve thereupon but unexpectedly.This is beat all, because along with the raising of grinding aid content in the abrasive coating, the relative amount of abrasive particle can descend.And abrasive particle is to be responsible for as-machined workpiece surface, and grinding aid does not have this effect.Usually, abrasive coating contains abrasive particle 5～90% (percentage by weight), is preferably 20～80% (percentage by weights), contain binding agent 5～80% (percentage by weight), be preferably 5～40% (percentage by weights), contain grinding aid 5～60% (percentage by weight), be preferably 10～40% (percentage by weights).
Optional additive
The present invention can with slurry can also contain optional additive, for example filler, fiber, lubricant, wetting agent, thixotropic materials, surfactant, pigment, dyestuff, antistatic additive, coupling agent, plasticizer and suspending agent.Content to these materials is selected, so that desired properties to be provided.Use these materials can influence the erosion property of abrasive composites.In some cases, have a mind to add additive, so that the easier abrasion of abrasive composites, thereby remove the abrasive particle of blunt and expose the abrasive particle that makes new advances.
The present invention can with the example of antistatic additive comprise graphite, carbon black, vanadium oxide and wetting agent etc.These antistatic additive are disclosed in United States Patent (USP) 5,061, and 294,5,137,542 and 5,203,884, above-mentioned patent is incorporated this paper at this into way of reference.
Coupling agent can form related bridge joint between binder precursor and filler grain or abrasive particle.Available coupling agent example comprises silane, titanate esters and zirconium aluminate (zirconium aluminium is coupling agent).Available slurry preferably contains the coupling agent of have an appointment 0.01～3% (percentage by weight).
The present invention can with the suspending agent example be amorphous silica particles, its surface area is less than 150 meters squared per gram, the commercially available prod has commodity to be called " OX-50 ", DeGussa company produces.
The abrasive coating that contains abrasive composites
A preferred aspect of the present invention is: abrasive coating is the form that a plurality of abrasive composites are bonded to substrate.Usually preferably, each abrasive composites has accurate shape.The accurate shape of each compound is determined by clear and legible boundary line.When microscope is for example observed the cross section of abrasive product under the SEM, these clear and legible boundary lines are easy to see and are very clear.Comparatively speaking, in the abrasive coating of forming by the compound that does not have accurate shape, the uncertain and very difficult identification in boundary line.Above-mentioned these clear and legible boundary lines form the profile or the profile of accurate shape.These boundary lines are separated from each other to a certain degree abrasive composites, also abrasive composites are distinguished each other.
With reference to Fig. 1-1B, wherein show example embodiment according to abrasive product 100 of the present invention.Abrasive product 100 comprises abrasive composites 122.In certain embodiments, one or more relevant with composite shape boundary line to a certain degree separates an abrasive composites abrasive composites adjacent with another piece.In order to form independent abrasive composites, the part in the boundary line of formation abrasive composites shape must be separated from each other.Notice in Figure 1A substrate or the abrasive composites part of the close substrate abrasive composites adjacency that can be adjacent.Abrasive composites 122 comprises a plurality of abrasive particles, and abrasive particle is dispersed in binding agent and the grinding aid.The present invention also comprises and obtains a kind of abrasive composites assembly that is bonded on the substrate, part abrasive composites adjacency wherein, and have open area between other abrasive composites.
In some cases, the border of formation shape is the plane.For the shape with plane, it has at least three planes.The number of planes of given shape changes according to required geometry, and for example number of planes can be from 3 to more than 20.Be generally 3～10 planes, be preferably 3～6 planes.These Plane intersects form required shape and angle, and the angle of cut on these planes will determine geomery.
Another aspect of the present invention is: the part abrasive composites has the adjacent abrasive composites different with its size.In this invention scheme, at least 10%, be preferably at least 30%, more preferably at least 50%, be preferably at least 60% abrasive composites and have the adjacent abrasive composites different with its size.The size of these different sizes and the shape of abrasive composites, the angle between the flat edge boundary line or abrasive composites is relevant.Adjacent abrasive composites has these different sizes, makes the abrasive product that obtains produce meticulousr surface finish relatively on the workpiece that is ground or make with extra care.
The shape of abrasive composites can be an Any shape, but is preferably geometry for example rectangle, taper, semicircle, circle, triangle, square, hexagon, pyramid and octagon etc.The embodiment of preferable shape appears in the part that hereinafter is called " geometry ".Can call " projection unit " to the shape of single abrasive composites at this.Preferable shape is a pyramid, and this pyramidal bottom can be three limits or four edges.In addition, long-pending being preferably from substrate of the cross-sectional surface of abrasive composites successively decreased or reduced along its height.In use, along with the wearing and tearing of abrasive composites, the surface area of this variation causes uneven pressure.In addition, in making the abrasive product process, the surface area of this variation makes that abrasive composites is easier and breaks away from from the tool of production.Usually, every square centimeter has at least 5 independent abrasive composites.In some cases, every square centimeter has at least 500 independent abrasive composites.
The manufacture method of abrasive product
The basic step of making arbitrary abrasive product of the present invention is to prepare slurry.Make slurry by binder precursor, grinding aid, abrasive particle and optional additive being combined with any suitable hybrid technology.The example of hybrid technology comprises low shear-mixed and high shear mixing, and high shear mixing is preferred.Can also be used in combination ultrasonic energy with blend step, to reduce the viscosity of abrasive material slurry.Usually, gradually abrasive particle and grinding aid are added in the binder precursor.In the blend step process, vacuumize and to make in the slurry air bubble content reduce to minimum.In some cases, the preferred usually slurry that heats in 30～70 ℃ scope is to reduce viscosity.Importantly, slurry should have make it can be well applied rheological property, wherein abrasive particle and grinding aid can not settle from slurry.
Energy source
After slurry is coated on the substrate, for example, slurry is exposed to energy source to cause the polymerization of resin in the binder precursor by after the tool of production (hereinafter describing) is transferred on the substrate.The example of energy source comprises heat energy and radiant energy.The consumption of energy depends on Several Factors, for example the content of the granularity of the chemical property of binder precursor, abrasive material slurry, abrasive particle and type and selected content of additive and type.For heat energy, temperature can be in about 30～150 ℃ scope, is generally in 40～120 ℃ the scope.Open-assembly time can arrive above 24 hours at about 5 minutes.
Suitable radiation source comprises electron beam, ultraviolet light or visible light.Electron beam irradiation is also referred to as ionising radiation, can be used in the about 0.1～about 10Mrad of energy rank, be preferably in the occasion of the about 1～about 10Mrad of energy rank.Ultraviolet radiation refer to wavelength in about 200～about 400 nanometer range, be preferably the non-particle radiation in about 250～400 nanometer range.Visible radiation refer to wavelength in about 400～about 800 nanometer range, be preferably the non-particle radiation in about 400～about 550 nanometer range.The preferred visible light that uses 300～600 watts/inch.
After polymerization process finished, binder precursor changed into binding agent, and slurry changes into abrasive coating.Usually, made abrasive product can use.But in some cases, also can need other processing for example wetting or crooked.Before using abrasive product, can change into any required form to abrasive product, for example taper, endless belt shape, sheet and plate-like etc.
The tool of production
About third and fourth aspect of the present invention, in some cases, be preferably the abrasive composites that abrasive coating is become have accurate shape.In order to make this class abrasive product, need the tool of production usually.
The tool of production contains a plurality of cavitys.These cavitys are essentially the negative shape of abrasive composites, and are used to form the shape of abrasive composites.The size of selecting cavity is to provide required abrasive composites shape and size.If the shape of cavity or size are made improperly, the then made tool of production just can not provide required size for abrasive composites.
Cavity can be dot pattern, has between the adjacent pocket at interval, perhaps the mutual butt of cavity.Be preferably the mutual butt of cavity.In addition, select the shape of cavity that the cross-sectional area of abrasive composites is successively decreased from substrate.
The tool of production can be band, sheet, continuous sheet or net, applicator roll (for example gravure roll), be installed in sleeve pipe or mould on the coating roll.The tool of production can be made of metal (for example, nickel), metal alloy or plastics.Available any routine techniques for example engraving method, polishing method (bobbing), electrocasting, diamond turning etc. is made the Metal Production instrument.A kind of technology of preferred manufacturing Metal Production instrument is diamond turning.
Thermoplasticity instrument available metal mother-tool duplicates and forms.Mother-tool has and the opposite pattern of the required pattern of the tool of production.Mother-tool can adopt the mode identical with the tool of production to make.Mother-tool preferably with metal for example nickel make and by diamond turning.But heating thermoplastic sheet material, and can select to heat together with mother-tool, thereby by the two is forced together, and make thermoplastic impress out the pattern of mother-tool.Also thermoplastic can be extruded or is cast on the master metal instrument, then pressurization.The thermoplastic cooling curing has been made the tool of production.The example of preferred thermoplasticity tool of production material comprises polyester, Merlon, polyvinyl chloride, polypropylene, polyethylene and combination thereof.If use the thermoplasticity tool of production, it is overheated then must carefully not produce, and overheated meeting makes the distortion of the thermoplasticity tool of production.
The tool of production can also contain release coating, so that the easier disengaging tool of production of abrasive product.This metalloid comprises hard carbide, nitride or boride coating with the example of release coating.The example of the used release coating of thermoplastic comprises silicones and fluorochemical.
Fig. 2 illustrates a kind of method, is used to prepare abrasive product of the present invention as shown in Figure 1.Substrate 41 leaves unreel station 42, and the tool of production 46 leaves unreel station 45 simultaneously.By applying station 44 slurry is coated on the tool of production 46.Before applying,, can heat slurry and/or slurry is applied ultrasonic wave in order to reduce the viscosity of slurry.Applying the station can be any conventional coated tool, and for example squash type point gum machine (drop die coater), knife type coater, curtain formula coating machine, vacuum are coated with mould machine or extrusion coater (die coater).Coating procedure should reduce the formation of bubble.Preferred paint-on technique is a United States Patent (USP) 3,594,865,4,959,265 and 5,077 for example, the directed cladding process (vacuum fluid bearing die) of the vacuum fluid disclosed in 870, and above-mentioned all patents are incorporated this paper at this into way of reference.After applying the tool of production, adopt any method that makes slurry soak the substrate front, substrate is contacted with slurry.In Fig. 2, slurry contacts with substrate by contact mip rolls 47.Next, contact mip rolls 47 also makes the resulting structures thing near support drum 43.Energy source 48 (being preferably visible light source) sends sufficient energy in slurry, make binder precursor partly solidified at least.Term " partly solidified " is meant that the binder precursor polymerization reaches slurry can be from being inverted the state that test tube flows down.In case binder precursor breaks away from the tool of production, makes it to solidify fully with regard to available any energy source.Subsequently, around on axle 49, the tool of production just can reuse the tool of production so again.Alternatively, before precursor is a bit all uncured, make binder precursor break away from the tool of production.After the disengaging, can make precursor cures, and the tool of production can be again around on axle 49 to reuse.In addition, abrasive product 120 is around on axle 121.If binder precursor is solidified as yet fully, then binder precursor can be through solidifying after a while fully, and/or place under the energy source it is solidified fully.United States Patent (USP) 5,152,917 (people such as Pieper) and 6,129,540 (people such as Hoopman) have further described the additional step for preparing abrasive product according to this paper first method, and above-mentioned document is incorporated this paper at this into way of reference.Use above-mentioned United States Patent (USP) 6,129,540 (people such as Hoopman) described instrument and technology to can be made into the abrasive composites of random shape.
The preferred radiant energy cured binders precursor that uses.As long as the not obvious absorbed radiation energy of the tool of production, radiant energy just can penetrate the tool of production.In addition, radiation source should not can make tool of production obvious degradation.The preferred thermoplasticity tool of production and ultraviolet light or the visible light of using.
Can be coated onto slurry on the substrate rather than be coated onto in the cavity of the tool of production.The substrate that scribbles slurry is contacted with the tool of production, thereby slurry is flow in the cavity of the tool of production.All the other steps of preparation abrasive product are with that step above is described in detail in detail is identical.
Fig. 3 illustrates another kind of method.Substrate 51 leaves unreel station 52, applies station 53 slurry 54 is coated onto in the cavity of the tool of production 55.Can be coated onto on the instrument with any slurry in the following multiple technologies, for example push that dotting glue method, rolling method, knife coating, curtain are coated with method, vacuum is coated with modulus method or extrusion coated method (die coating).Equally, before applying,, can heat slurry and/or slurry is applied ultrasonic wave in order to reduce the viscosity of slurry.Coating procedure should reduce the formation of bubble.Subsequently, substrate is contacted with the tool of production that contains the abrasive material slurry, make slurry soak the front of substrate with mip rolls 56.Next, be exposed to energy source 57, make it partly solidified at least by making the binder precursor in the slurry.After this was partly solidified at least, slurry changed into abrasive composites 59, and this compound is bonded to or adheres on the substrate.Mip rolls 58 makes the gained abrasive product break away from the tool of production and around to recoiling on the station 60.Alternatively, before precursor is a bit all uncured, make binder precursor break away from the tool of production.Break away from after the tool of production, can make precursor cures.In either case, energy source can be heat energy or radiant energy.If energy source is ultraviolet light or visible light, then substrate is preferably and can sees through ultraviolet light or visible light.The example of this class substrate is a polyester substrate.
Can directly be coated onto slurry the front of substrate.The substrate that scribbles slurry is contacted with the tool of production, thereby slurry is dipped in the cavity of the tool of production.All the other steps of preparation abrasive product are identical with the step that above describes in detail.
The repair method of surface of the work
Another aspect of the present invention relates to the Ginding process on metal or wooden surface.This method comprises that making abrasive product of the present invention and the workpiece that metal or wooden surfaces are arranged produce friction contacts.Term " grinding " is meant the part of cutting or removing metal works with abrasive product.In addition, handle, can reduce the surface roughness (surface roughness relevant usually with surface of the work through such trimming.A kind of surface finish measurement commonly used is Ra; Ra is normally with the surface roughness on microinch or micron arithmetic mean that records.Surface roughness can for example Perthometer or Surtronic measure with talysurf.
Workpiece
Metal works can be the metal of any kind, for example mild steel, stainless steel, titanium, metal alloy and particulate metal alloy etc.Workpiece can be flat or have shape related with it or section.
According to purposes, the power of grinding at the interface can arrive above 1000 kilograms at about 0.1 kilogram.Usually grinding at the interface, this scope is 1 kilogram～500 kilograms a power.In addition, according to purposes, can there be liquid to exist in the process of lapping.This liquid can be water and/or organic compound.The example of using organic compound always comprises the organic compound of lubricant, oil, emulsification, cutting fluid, soap or the like.These liquid can also contain other additives, for example defoamer, degreasing agent, corrosion inhibiter or the like.In the use, abrasive product can grind vibration at the interface.In some cases, this vibration meeting forms meticulousr surface on polished workpiece.
Abrasive product of the present invention can use or be used in combination with machine by hand.In process of lapping, at least one or two move with respect to the other side in abrasive product and the workpiece.Abrasive product can be converted to band shape, winding shape, plate-like and sheet etc.When using, two free ends of abrasive sheet are connected together to form joint with band shape.The present invention also comprises and uses jointless band, as the assignee's that proposed on July 24th, 1992 U.S. Patent application 07/919,541 to be examined jointly, incorporates this paper at this into way of reference.Usually, the ring-type abrasive belts is through at least one idle pulley and pressing plate or contact wheel.Regulate the hardness of pressing plate or contact wheel, to obtain required cutting speed and workpiece surface roughness.The speed of abrasive belts depends on required cutting speed and surface roughness.The size range of band can be about 5mm～1, wide, the about 5mm of 000mm～10, and 000mm is long.The abrasive material winding is the abrasive product of continuous length.Its width range can be about 1mm～1, and 000mm is usually between 5mm～250mm.The abrasive material winding is uncoiled usually, and process is used for making winding to be close to the supporting pad of workpiece (support pad), and then twines.Can feed the abrasive material winding continuously by grinding the interface, and can be to the winding mark.The diameter range of mill can be about 50mm～1,000mm.Usually, with jockey mill is fixed on the support pad (back-up pad).These mills can be 100～20, and 000 rev/min, usually 1,000～15, the speed rotation between 000 rev/min.
Geometry
With reference to Fig. 1-1B, this illustrates the part of abrasive product 100 embodiment.Abrasive product 100 comprises substrate 130.Substrate 130 is normally banded, but also can be other shapes and form.If substrate 130 is banded, then it generally includes machine direction and cross-machine-direction, and the two is arranged vertically mutually.
The array 110 of the characteristic body 120 that substrate 130 and microcosmic repeat is adjacent and link to each other.Usually, characteristic body 120 is arranged on the substrate 120 with the array 110 that comprises skew.Usually, array 110 is angled with respect to the machine direction of goods 100, or with respect to the machine direction deflection.
Array 110 comprises a plurality of characteristic bodies 120.In the embodiment shown, each characteristic body comprises substrate 122 and body 123.In one embodiment, substrate 122 is preferably parallelogram, and perhaps requiring according to concrete purposes also can be other shapes.Substrate 122 and substrate 130 in abutting connection with or adjacent, and connect or be attached on the substrate 130.In the embodiment shown, each characteristic body comprises four sidewalls 127 or the surface of stretching out from substrate, thereby forms polyhedron.Though shown in the characteristic body example comprise four sidewalls, also more or less sidewall can be arranged according to concrete purposes.Polyhedron can be an arbitrary shape, but pyramid or prismatic normally.
Each characteristic body 120 comprises at least one sidewall 124, and the relative substrate 122 of this sidewall forms positive rake angle (positive rake) γ.Anterior angle on the sidewall 124 (inclination angle) γ forms side concave portion 125 on sidewall 124.In the time will being timber with the material that abrasive product 100 grinds, side recessed 125 is particularly useful.
In the woodenware processed and applied, wood chip or other fragment trend towards gathering and block abrasive product 100.By on sidewall 124, comprising the part R that is cut into fillet with side recessed 125, can easier removal wood chip or other fragment.The part R that is cut into fillet is positioned near the substrate 130.Comprise that between adjacent characteristic body a gap or grooved area also assist in removing the material that gathers.
Usually, when abrasive product 100 engaged workpiece with the removal material, side concave surface 125 was front edges 124 of abrasive product.As mentioned above, front edge 124 can engage workpiece, and wherein front edge is orientated or directly engages or engages with certain drift angle.Comprise that very little drift angle can preferentially be shifted on the limit of abrasive product 100 to be removed onto wood chip or other fragment.And, in one embodiment, do not project in the periphery that limits by substrate 122 from the point of substrate 122 body 123 farthest.This is illustrated among Figure 1A, and wherein the vertical line that extends from substrate 130 shows, the spot projection farthest on the body 123 of leftmost characteristic body 120 is outside the zone that the periphery by substrate 122 limits.
Each characteristic body 120 also can comprise top plan part 128, the substrate 122 cant angle theta angles of described top plan part relative characteristic thing 120.In one embodiment, top 128 scribbles abrasive particle 140.Abrasive particle 140 is auxiliary from workpiece removal material and further refine workpiece.The characteristic body 120 of array 100 is arranged as usually on machine direction (direction of the recessed surface engagement workpiece of side) has pitch P, and upward has gap M in the direction vertical with machine direction (laterally) between adjacent feature thing 120.Pitch P between the characteristic body 120 that engages on (or machine) direction can change so that the front edge of recessed 125 sidewalls of side with directly be close to or the substrate 122 of adjacent characteristic body overlapping.Pitch P can be constant or change.
And in one embodiment, rear edge (relative with the recessed sidewall of side) is spent less than 90 with the inclination alpha of substrate.And, add the part R2 that is cut into fillet in the bottom of each lateral sidewalls and also assist in removing material.And opposing sidewalls transversely can be from vertically becoming angle of inclination beta.
Example 1
Make and tested according to abrasive product of the present invention.These goods comprise the characteristic body array that is arranged on the backing material.Characteristic body is arranged as and makes characteristic body last skew be arranged.The height with substrate point farthest of each characteristic body is about 20mil (1mil equals 0.001 inch), and machine direction pitch P is about 32mil, and lateral clearance is about 2mil.Radius in the sidewall on the recessed sidewall of side is about 4mil, and each lateral sidewalls radius is about 1.3mil.The positive rake angle of the recessed sidewall of side is about 5 degree.The sidewall relative substrate relative with the recessed sidewall of side tilt about 45 the degree, the planar top opposing parallel tilt in the plane of substrate about 10 the degree.
The inventor has been found that above-mentioned abrasive product is particularly suitable for removing material from the timber workpiece.Most of material is removed and is finished by the recessed sidewall of side.Then, the abrasive particle on the planar top is gently scraped the surface of workpiece, make workpiece further preprocessing just can be easy to painted.
Above-mentioned abrasive product is made by tools at first, and described instrument is the negative-appearing image of the image that formed by array.With intermediate abrasive mineral, the alumina coated instrument that can obtain from Washingon Mills.Then will be with Tatheic/TMPTA acrylic resin, KBF
4, the slurry made of Irgacure 369, OX-50 silica and A174 silane and mineral is coated on the substrate.When slurry is on the substrate, with tool applications in slurry.The substrate that uses is can be from the polyester/cotton textile substrate of Milliken acquisition.Goods are solidified and separate with instrument.These those skilled in the art can understand, according to the concrete application of desirable abrasive article, can use the multiple various combination of abrasive mineral or particle, slurry, backing material.And, can be used in combination being cut into the fillet part and having the planar top of abrasive particle near the one or more sidewalls the recessed sidewall of side, substrate in every way, because concrete application can have benefited from any combination of above-mentioned characteristic.
Disclosed manufacturing of the present invention and use have been described above-mentioned specification, example and data integrity.Because under situation without departing from the spirit and scope of the present invention, can make various embodiments, so the present invention is limited by the appended claim book.
Claims (38)
1. abrasive product comprises:
Substrate; With
A plurality of characteristic bodies, described characteristic body also comprises adhesive and abrasive particle, and wherein said characteristic body has substrate and at least three sides, and the angle between one of described substrate and described side forms positive rake angle.
2. abrasive product according to claim 1, one of wherein described at least characteristic body also comprise described relatively substrate plane inclined top.
3. abrasive product according to claim 2 also comprises the abrasive particle on the planar top that is positioned at described abrasive material characteristic body.
4. abrasive product according to claim 1, wherein said body comprise from described substrate zone or point farthest, and wherein said zone or spot projection are beyond described substrate periphery.
5. abrasive product according to claim 4, one of wherein described at least abrasive material characteristic body also comprise the top plan part that described relatively substrate is tilted.
6. make the method for abrasive product, comprising:
Instrument is provided, and this instrument comprises the pattern that is used to form the abrasive material characteristic body;
Abrasive particle is placed in the instrument;
Use the slurry fill tool;
Slurry is contacted with substrate; With
Slurry is solidified to form the abrasive material characteristic body, and this abrasive material characteristic body comprises top that adheres on the described abrasive particle and the bottom that adheres on the described substrate.
7. method according to claim 6, the wherein said instrument that provides instrument to comprise to be provided for forming the abrasive material characteristic body that comprises planar top.
8. method according to claim 7, wherein said planar top are tilted by the reference planes that substrate limits relatively.
9. method according to claim 7, wherein said abrasive particle is an aluminium oxide.
10. abrasive product comprises:
Substrate;
Be positioned at a plurality of abrasive material characteristic bodies on the described substrate, each abrasive material characteristic body comprises substrate and body, and wherein body is limited by four surfaces, and wherein one of described at least surface comprises the side concave portion.
11. abrasive product according to claim 10 also comprises the plane surface relative with substrate.
12. abrasive product according to claim 11 also comprises the abrasive particle that is arranged on the described plane surface.
13. abrasive product according to claim 12, the relative substrate of wherein said plane surface is tilted.
14. abrasive product according to claim 12, wherein said side concave portion comprise near the part that is cut into fillet the substrate.
15. abrasive product according to claim 10, wherein said side concave portion comprise near the part that is cut into fillet the substrate.
16. abrasive product according to claim 10, wherein said a plurality of characteristic bodies are arranged to array, and wherein each side concave portion is with identical direction orientation.
17. abrasive product according to claim 16, wherein said array on abrasive product with certain drift angle orientation.
18. be used for the characteristic body of abrasive product, comprise:
Substrate and body, described body comprise four sidewalls, and wherein at least one sidewall forms the surface with positive rake angle.
19. characteristic body according to claim 18 also comprises the planar top that is arranged as away from substrate.
20. characteristic body according to claim 19, wherein said planar top is orientated substantially parallel with described substrate.
21. characteristic body according to claim 19, wherein said planar top are orientated the angle of described relatively substrate greater than 2 degree, and wherein said plane napex tilts away from the surface with negative rake.
22. characteristic body according to claim 19 also comprises the abrasive particle that is arranged on the planar top.
23. characteristic body according to claim 18, wherein said surface comprise near the part that is cut into fillet the substrate.
24. characteristic body according to claim 22, wherein said surface comprise near the part that is cut into fillet the substrate.
25. be used for making the instrument of arbitrary abrasive product of claim 1-17.
26. a band that is used for removing material comprises:
Substrate, this substrate limits belt shape; With
A plurality of abrasive composites are positioned on the described substrate, and each abrasive composites all comprises substrate and body, and wherein said body is limited by four surfaces, and wherein at least one surface comprises the side concave portion.
27. band according to claim 26 also comprises the plane surface relative with described substrate.
28. band according to claim 27 also comprises the abrasive particle that is arranged on the described plane surface.
29. band according to claim 28, the described relatively substrate of wherein said plane surface is tilted.
30. band according to claim 28, wherein said side concave portion comprise near the part that is cut into fillet the described substrate.
31. band according to claim 26, wherein said side concave portion comprise near the part that is cut into fillet the described substrate.
32. band according to claim 26, wherein said a plurality of compositions are arranged to array, and wherein each side concave portion is with identical direction orientation.
33. band according to claim 32, wherein said array on abrasive product with certain drift angle orientation.
34. the method for grinding timber workpiece, this method comprises:
Abrasive product is contacted with workpiece, and wherein said abrasive product comprises:
Substrate;
Be positioned at a plurality of abrasive composites on the described substrate, each abrasive composites all comprises substrate and body, wherein said body is limited by four surfaces, and wherein at least one surface comprises the side concave portion, and the part of wherein said side concave portion engaged with workpiece before any other surface of described body.
35. method according to claim 34, wherein said contact abrasive product also comprises: contact comprises the abrasive product of planar top, and wherein is furnished with abrasive particle on described top.
36. method according to claim 34, wherein said contact abrasive product also comprises: contact following abrasive product, this abrasive product is included in and is positioned near the part that is cut into fillet of substrate on the side concave portion.
37. method according to claim 36 also comprises by the part that is cut into fillet and removes wood chip.
38. method according to claim 34, wherein substrate is a band.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/668,735 | 2003-09-23 | ||
| US10/668,735 US20050060941A1 (en) | 2003-09-23 | 2003-09-23 | Abrasive article and methods of making the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1882418A true CN1882418A (en) | 2006-12-20 |
Family
ID=34313558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004800343646A Pending CN1882418A (en) | 2003-09-23 | 2004-07-29 | Abrasive article and methods of making the same |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20050060941A1 (en) |
| EP (1) | EP1663579A1 (en) |
| JP (1) | JP2007505758A (en) |
| KR (1) | KR20060087582A (en) |
| CN (1) | CN1882418A (en) |
| BR (1) | BRPI0414610A (en) |
| WO (1) | WO2005035198A1 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| US20050060941A1 (en) | 2005-03-24 |
| JP2007505758A (en) | 2007-03-15 |
| WO2005035198A1 (en) | 2005-04-21 |
| KR20060087582A (en) | 2006-08-02 |
| EP1663579A1 (en) | 2006-06-07 |
| BRPI0414610A (en) | 2006-11-07 |
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