EP0940224B1 - Bande abrasive - Google Patents

Bande abrasive Download PDF

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Publication number
EP0940224B1
EP0940224B1 EP99105024A EP99105024A EP0940224B1 EP 0940224 B1 EP0940224 B1 EP 0940224B1 EP 99105024 A EP99105024 A EP 99105024A EP 99105024 A EP99105024 A EP 99105024A EP 0940224 B1 EP0940224 B1 EP 0940224B1
Authority
EP
European Patent Office
Prior art keywords
polishing
formplate
roll
abrasive
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP99105024A
Other languages
German (de)
English (en)
Other versions
EP0940224A3 (fr
EP0940224A2 (fr
Inventor
Toshikazu Nishio
Hiroyuki Amemiya
Yasuo Nakai
Taiji Ishii
Masahisa Yamaguchi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dai Nippon Printing Co Ltd
Original Assignee
Dai Nippon Printing Co Ltd
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 Dai Nippon Printing Co Ltd filed Critical Dai Nippon Printing Co Ltd
Priority to DE1993632281 priority Critical patent/DE69332281T2/de
Priority claimed from EP93913473A external-priority patent/EP0664187B1/fr
Publication of EP0940224A2 publication Critical patent/EP0940224A2/fr
Publication of EP0940224A3 publication Critical patent/EP0940224A3/fr
Application granted granted Critical
Publication of EP0940224B1 publication Critical patent/EP0940224B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
    • B24D18/00—Manufacture of grinding tools or other grinding devices, e.g. wheels, not otherwise provided for
    • B24D18/009—Tools not otherwise provided for
    • 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
    • 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
    • B24D11/001—Manufacture of flexible abrasive materials
    • 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
    • B24D11/001—Manufacture of flexible abrasive materials
    • B24D11/005—Making abrasive webs
    • B24D11/006—Making abrasive webs without embedded abrasive particles
    • 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
    • B24D11/08—Equipment for after-treatment of the coated backings, e.g. for flexing the coating
    • 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
    • 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

Definitions

  • the present invention relates to an abrasive tape for finish lapping or polishing with high precision to a mirror-surface finish such surfaces as those of floppy disks, magnetic heads, precision electronic components, and end surfaces of optical fibers.
  • abrasive tapes of the above stated kind in general, there are those of a structural organization wherein, on a substrate material, a coating comprising a polishing abrasive material and a binder component is applied to form a polishing film.
  • An abrasive tape of this character has a simple structural organization and can be readily produced. During its use, however, debris formed from the workpiece being polished tends to infiltrate between the abrasive polishing film of the abrasive tape and the workpiece. If the polishing process is continued in this state, the surface of the workpiece will be damaged by this polishing debris, or the polishing debris will adhere to the film surface and cause its pores or recesses to become clogged. As a result, the polishing capacity of the abrasive tape has dropped considerably heretofore.
  • an abrasive tape provided with grooves in its polishing layer has been proposed.
  • a paint containing a large quantity of an inorganic ingredient in a coating compound is applied.
  • the concavities and convexities of the Bernard cell due a "convection cell phenomenon" which occurs in the coating layer at the time when the solvent is dried are utilized as groove forms of the polishing layer.
  • this abrasive tape In the case of this abrasive tape, however, the shape as viewed in plan view of the grooved parts thus formed becomes restricted to an approximately hexagonal shape for reasons due to the production method.
  • sparking may occur between the abrasive tape and the workpiece and damage the surface of the workpiece in some cases.
  • US-A-5,152,917 describes a coated abrasive article comprising a backing bearing on at least one major surface thereof abrasive composites comprising a plurality of abrasive grains dispersed in a binder.
  • the binder serves as a medium for dispersing abrasive grains, and it may also bond the abrasive composites to the backing.
  • the abrasive composites have a predetermined shape, e.g. pyramidal. The dimensions of a given shape can be made substantially uniform.
  • the composites are disposed in a predetermined array.
  • a predetermined array can exhibit some degree of repetitiveness.
  • a repeating pattern of a predetermined array can be in linear form or in the form of a matrix.
  • the coated abrasive article can be prepared by a method comprising the steps of: (1) introducing a slurry containing a mixture of a binder and a plurality of abrasive grains onto the production tool, (2) introducing a backing to the outer surface of the production tool such that the slurry wets one major surface of the backing to form an intermediate article, (3) at least partially curing or gelling the binder before the intermediate article departs from the outer surface of the production tool to form a coated abrasive article, and (4) removing said coated abrasive article from the production tool.
  • the present invention provides an abrasive tape having a film substrate (2) and an abrasive layer (10) laminated on one surface of said film substrate (2), said abrasive layer (10) having on the outer surface thereof a plurality of recessed parts (9) and comprises a binder of a crosslinked type cured resin (3) and polishing abrasive material particles dispersed therewithin, wherein the density of said abrasive material particles increases in the direction away from the film substrate (2).
  • a preferred embodiment of the present invention is an abrasive tape, wherein said crosslinked type cured resin (3) has a three-dimensional network molecular structure in which surface-active agent molecules are chemically bonded.
  • a further preferred embodiment of the present application is an abrasive tape, wherein said abrasive layer (10)contains an antistatic agent.
  • the present invention further provides an abrasive tape, wherein said polishing abrasive material particles in said abrasive layer (10) are in the form of either flaky fish scales or short fibers.
  • FIG. 1 is a view for describing a process for producing an abrasive tape.
  • 1 is a roll formplate (intaglio printing plate).
  • a film substrate 2 is partially wrapped and is fed in the arrow direction.
  • a pan 4 containing an ionizing radiation curable resin containing an abrasive material is provided below the roll formplate 1.
  • Plate concavities 5 having a shape for imparting shapes of recessed parts to the polishing layer of the abrasive tape are formed on the outer surface of the roll formplate 1.
  • the film substrate 2 is sent from a supply roll 2a, past a pressing roll 6a, to the outer surface of the roll formplate 1 and, passing around a feed-out roll 6b, is fed out. Clearance adjustments, etc., of both rolls with the roll formplate 1 are made possible.
  • the ionizing radiation curable resin 3 containing an abrasive material is supplied from within the pan 4 by coating rolls 7 so as to fill at least the plate concavities 5. Then, while the substrate 2 is contacting the formplate 1, ionizing radiation rays R are irradiated toward the substrate 2 by an ionizing radiation irradiating device 8 thereby curing the above mentioned resin 3 interposed between the substrate 2 and the formplate 1 and simultaneously causing the same to adhere securely to the side of the substrate 2. Finally, at a feed-out roll 6b, the substrate 2 is peeled off from the formplate 1.
  • an abrasive tape 11 having on the substrate 2 a polishing abrasive layer 10 provided with recesses 9 formed by the roll formplate 1 as shown in FIG. 2 is obtained. Since the forming of the layer 10 having the recesses 9 is carried out by a production method as described above, sharp and clear shapes of the recesses 9 that are faithful reproductions of the shapes profiled on the roll formplate 1 are obtained. Particularly, even in the case where the recesses are of complex and delicate shapes, they can be obtained simply and positively.
  • abrasive layers 10 of the same kind can be formed on both surfaces of the substrate.
  • abrasive layers 10 are to provided on both surfaces of the substrate, furthermore, by installing a second roll formplate on the downstream side in the feed direction of the substrate, and feeding the substrate 2 after it has been peeled off from the first roll formplate directly, as it is, to the second roll formplate, continuous production can be carried out.
  • the abrasive polishing layer 10 of the instant example is of a configuration in which a resin layer part 9a of the polishing layer exists at the bottom of each recess 9. This configuration is so formed that the ionizing radiation curable resin 3 supplied to the plate concavities 5 of the roll formplate 1 will not only be supplied into the plate concavities 5 but will also be interposed between the peripheral surface of the formplate 1 and the substrate 2.
  • the forming of the plate concavities 5 in the roll formplate 1 can be carried out by a method such as electronic engraving, etching, machining on a lathe, milling machine, or the like, electroforming, and sand-blasting. Furthermore, the shape of each plate concavity 5 is a complementary shape of the shape of each recess 9 of the polishing layer, and in actuality, the convex-shaped parts impart recessed shapes.
  • the recesses in the abrasive tape carry out the function of accommodating and thereby collecting the polishing debris produced from the workpiece during polishing.
  • the recess 9 in general, have an opening width of 0.1 to 200 ⁇ m, a depth of 0.1 to 100 ⁇ m, and a pitch (spacing of the center parts of adjacent recesses) of 10 to 500 ⁇ m.
  • the capability of accommodating polishing debris of recesses which do not satisfy simultaneously these dimension conditions becomes inadequate.
  • the forming of recesses of conditions other than those recited above is of course possible.
  • the recesses 9 are arranged uniformly and regularly over the entire surface of the abrasive layer 10 as illustrated by one example in FIG. 3.
  • the recesses can be so formed that the shape of each in planar view (in horizontal section) is quadrilateral, hexagonal, circular, elliptical, or some other shape and in vertical section is the shape of an inverted triangle, a rectangle, a semicircle, a trapezoid, or some other figure. That is, the plate concavities 5 are provided with a shape such as to form recesses possessing simultaneously various structural requirements as described above.
  • ionizing radiation curable resin known resins of the type which are cured by irradiation with ultraviolet rays or an electron beam can be used.
  • resins a resin of the type to which no solvent is added
  • undesirable results such as volumetric contraction, deformation, and generation of bubbles due to setting do not occur, and, in addition to a process step of predrying this resin becoming unnecessary, it becomes easier to obtain positively recesses of good reproducibility.
  • ultraviolet rays can be used in the case where the film substrate 2 is transparent. However, in the case where the substrate is opaque, it is necessary to use an electron beam.
  • the roll formplate is constructed of a material through which ionizing radiation rays can be transmitted, irradiation from an irradiating device installed in the interior of this formplate will become possible.
  • the quantity of irradiation thereof depends on factors such as the thickness and material of the sheet substrate, but ordinarily (an irradiation quantity of) the order of 0.5 to 30 Mrad is desirable.
  • the shape of the recesses is so designed that, in addition to the requirement for polishing performance of the polishing adhesive layer, the recesses will fulfill also the requirement of suitability for separating of the polishing layer from the roll formplate together with the film substrate.
  • a suitable shape of the plate concavities on the roll formplate is such that, as shown in FIGS. 4 and 5, the sectional area of each plate concavity 5 cut by the horizontal sectional plane indicated by line X-X becomes smaller progressively and continuously towards the bottom thereof.
  • a shape of a recess as shown in FIG. 4 is obtained.
  • plate concavities 5 of a shape as shown in FIG. 4 can also be formed by the aforedescribed machining, and plate concavities 5 of the shape shown in FIG. 4 can also be formed by forming concavities by the aforedescribed etching method and thereafter carrying out sand-blasting.
  • Plate concavities 5 of the shape shown in FIG. 4 can be formed by known photoetching (or photolithographic) methods other than the aforedescribed gravure plate processing method. That is, it is also possible to: lay a photosensitive resist film 16 on a surface of a metal plate 15 as shown in FIG. 6; next, through an original plate (photomask) having the desired concavity shape (whether to be used as a negative or whether to be used as a positive of the concave part pattern, selection is made according to whether the resist is of the negative type or whether it is of the positive type), expose the resist film 16 to light to develop the same; open windows 18 of the desired shape of opening part by leaving a resist pattern 16a; etch the metal within the windows 18 as indicated at 20 in FIG.
  • photoetching or photolithographic
  • etching solution 19 such as an aqueous solution of ferric chloride (Fe 2 Cl 3 ); thereafter cause side etching with the etching solution in the concave parts 20 as indicated at 21 in FIG. 8; and cause side etching to proceed further, whereby, through the state indicated in FIG. 9, plate concavities 5 as shown in FIG. 10 are obtained.
  • the polishing layer (cured resin layer) can be so formed that it can be peeled off from the formplate and have concavities in which side etching is negligible as shown in FIG. 7 in the following manner.
  • a copper cylinder is used for the roll formplate.
  • An aqueous solution of ferric chloride (of a concentration of 39 to 42 Baumé degrees as measured with a Baumé hydrometer) is used for the etching solution.
  • This etching solution is supplied onto the copper surface by a shower method or an air-agitation method.
  • the depth of the plate concavities is made less than 150 ⁇ m.
  • the extent of the side etching 21 shown in FIG. 8 is excessively great, the resin which has filled the plate concavities and has set cannot be easily dislodged from the plate concavities, and peeling off becomes difficult.
  • peeling off becomes possible.
  • the cumulative frequency distribution curve (ogive) of the surface roughness of the roll formplate 1 is also important. More specifically, when the steps of: obtaining statistical data of the heights of the hills (concavities/convexities) of the surface of the roll formplate by means of a measuring and curve-plotting instrument for surface roughness of an electric tactometric type, optical type, or the like; and plotting cumulative frequency distribution function f (R) curves with surface roughness, that is, height of the hills, R, as abscissa and cumulative frequency distribution function of the surface roughness (where P(R) is the probability density function of the surface roughness R) as ordinate are taken, curves as shown in FIG.
  • FIG. 12 A specific example of the shape of the formplate surface in the case of a function such as is indicated by curve f A (R) is as shown in FIG. 12.
  • a function such as is indicated by curve f B (R)
  • the shape becomes as shown in FIG. 13, for example.
  • the cumulative frequency distribution curve of the height of the concavities/convexities is as indicated by curve f B in FIG. 11, that is, the curve has a downward convexity over the entire region from 0% to 100% of the cumulative frequency
  • good mold separability results.
  • the point at which the cumulative frequency distribution of the cumulative frequency distribution curve becomes 50% passes on the right-hand side of the middle value of the height, that is, average value ⁇ middle value
  • amply satisfactory mold separability of the set resin layer from the formplate can be obtained.
  • FIGS. 15 and 16 illustrate actual examples of such a case.
  • the relationship of "average value ⁇ middle value" of the concavities/convexities height in these cases is satisfied, and the shapes of the concavities/convexities are respectively as shown in FIGS. 15B and 16B.
  • the mold separabilities of the set resin layers from the formplate were good.
  • the section of the formplate surface of FIG. 15B was obtained by sand-blasting the surface of a smooth copper cylinder with #80 sand
  • the section of the formplate surface of FIG. 16B was obtained by sand-blasting the surface of a smooth copper cylinder with #200 sand.
  • the average value is 52% of the maximum value, and moreover the cumulative frequency distribution curve comprises a portion of downward convexity and a portion of upward convexity.
  • the cumulative frequency distribution curve comprises a portion of downward convexity and a portion of upward convexity.
  • FIG. 17B shows the formplate surface corresponding to FIG. 17A. This sectional shape was obtained by lightly etching the surface of a smooth copper cylinder, sand-blasting this surface with #200 sand, and further plating the surface with lustrous chromium plating as indicated at 1a.
  • FIG. 18A illustrates a case where the cumulative frequency distribution is linear. In this case, good mold separation was obtained. This is also a case of borderline conditions between f A (R) and f B (R) of FIG. 11.
  • FIG. 18B shows the formplate surface corresponding to FIG. 18A. This formplate surface was obtained by forming ridges of a section of a right-angled isosceles triangle on the surface of a smooth copper cylinder by means of a lathe.
  • FIG. 19A indicates a case wherein the cumulative frequency distribution curve has a portion of upward convexity and a portion of downward convexity and a relationship of average value ⁇ middle value.
  • the mold separability in this case was poor.
  • FIG. 19B shows the formplate surface corresponding to FIG. 19A. In this case, the surface of a smooth copper cylinder was plated with a plating layer 1b of a chromium matte (delustering particulate state).
  • FIG. 20A illustrates a case where the cumulative frequency distribution curve becomes a curve of downward convexity over the entire scope of concavity/convexity height.
  • the peeling characteristic from the roll formplate in this case was good.
  • FIG. 20B shows the sectional shape of the formplate surface corresponding to FIG. 20A. This formplate surface shape was produced by carrying out molding from a polyethylene terephthalate film obtained by kneading thereinto calcium carbonate of particle size of 1 to 10 ⁇ m and fabricating the plate by the electroforming method.
  • the depressions are formed by grooves 9A, which are connected to form a pattern of hexagons, the entire assembly resembling a tortoise-shell.
  • the grooves form hexagonal lands (islands) 23.
  • a recess 9B of pin-hole shape is formed in the middle of each island.
  • the depressions comprise linear grooves 9c mutually intersecting at substantially right angles.
  • Square lands 24 are thus formed by these grooves 9c.
  • lands 25 of a convex curved surface shape such as a semisphere or semiellipsoid are formed instead of the square lands 24 of the polishing layer of FIG. 22. Depressions 9d are provided around these lands 25.
  • a land 26 is further formed in the middle of each depression 9 in the polishing layer of FIG. 3.
  • curvilinear ribbon form In the polishing layer 10 shown in FIG. 25, parallel lands 27 of curvilinear ribbon form are formed by depressions 9e of curvilinear groove form lying therebetween.
  • the curves of these curvilinear shapes are curves of bounded periodic functions such as a sinusoidal curve, a hyperbolic curve, an elliptic function curve, a Bessel function curve, a cycloidal curve, or an involute curve.
  • the shape of concavities of the polishing layer is suitably selected in accordance with conditions such as the kind of workpiece to be polished, the degree of precision of the polishing, and the object.
  • the working surface of the polishing layer 10 may take a configuration wherein the recesses 9 are mutually isolated as in the examples shown in FIGS. 3 and 24. Furthermore, in order to attain a high uniformity of finish, it is preferable that the angles formed by the edges of the recesses and the lands therebetween relative to the polishing direction be numerous and that, moreover, the symmetry of the configuration thereof be good. For example, the configuration of the example shown in FIG. 21 is better than that shown in FIG. 24 for this purpose.
  • the dimensions of the various configurations of the polishing layers shown in FIGS. 21 through 25 are also selected suitably in accordance with the application, the finishing precision, and the material of the article to be polished.
  • the dimension of the recesses (the width in the case of groove-shaped recesses; the length of one side of each recess in the case of isolated polygonal recesses; and the diameter of each recess in the case of isolated circular recesses), is ordinarily approximated 0.1 to 200 ⁇ m and the depth of each recess is approximately 1 to 100 ⁇ m, as stated hereinbefore.
  • the forward relief angle ⁇ and the rearward relief angle ⁇ between the front and rear parts of the land, i.e., the convexity, of the polishing layer 10 and the workpiece 30 undergoing polishing, as shown in FIG. 26, are also selected at suitable values in accordance with factors such as the application, the material of the workpiece 30, and the polishing speed.
  • the relief angles ⁇ and ⁇ contribute to the performances of discharging and intercepting the polishing debris. That is, as indicated in FIG. 27, the polishing debris 31 is discharged through the range of the relief angles ⁇ and ⁇ and is intercepted and accumulated in recesses of the polishing layer 10.
  • the contact area ratio R can be expressed by the following equation.
  • Sc is the area of contact between the polishing layer 10 and the workpiece 30;
  • Sg is the projected area of the portion of the polishing layer 10 that is not in contact with the surface of the workpiece (i.e., the portion with a space gap therebetween) which area is projected onto the surface of the film substrate 2;
  • Sp is the area of the flat portion of the top parts of the lands of the polishing layer 10;
  • Sr is the area of the other portions (corresponding to the concave portions) projected onto the surface of the film substrate 2.
  • the plate concavities 5 of the roll copper plate 1 can be supplied and filled with an ionizing radiation setting resin by a roll-coating method with the use of coating rolls 7.
  • This supplying and filling process can be carried out alternatively also by other methods.
  • this process can be carried out by supplying the resin from a die such as a T die as described hereinafter.
  • Another possible method comprises coating and forming the resin by a method such as roll coating beforehand on the film substrate 2 before the substrate 2 contacts the roll formplate 1.
  • the resin can be applied as a coating on the surface of the film substrate 2 in the following manner.
  • the film substrate 2 stock is supplied from a supply roll 2a to a roll-coating section 36 comprising guide rolls 32 and 33, pressing roll 34, and a coating roll 35 as essential parts.
  • the ionizing radiation curable resin 3 in liquid form is applied as a coating on the substrate 2 thus supplied.
  • the substrate 2 is passed through a drying device 37, where the dilute solvent is evaporated off by a method such blowing warm air. Thereafter, by means of a pressing roll 6a, the coated surface of the film substrate 2 is pressed into contact with the surface of the roll formplate 1.
  • a portion of the coated resin layer 3 is thereby forced to fill the interior of the plate concavities 5.
  • Reference numerals 38 and 39 designate a liquid accumulation and an ink pan, respectively.
  • this coating process can be accomplished by suitably applying any of various methods such as gravure roll coating and flow coating.
  • the resin liquid can be applied onto the surface of the roll formplate also by another method as follows. As shown in FIG. 29, as the roll formplate 1 is rotated, liquid resin 3 is ejected through a T-dye type nozzle 41 and applied on the surface of the formplate 1. Thus the resin 3 is caused to fill the interiors of the plate concavities 5. Separately, but simultaneously, uncoated film substrate 2 is supplied in the arrow direction and is pressed into forceful contact with the coated surface of the roll formplate 1 by a pressing roll 6a.
  • FIG. 30 is a view from the left side of FIG. 29. In this connection, it is possible to use also another method of coating the surface of the formplate 1.
  • One example of an alternative method is dipping of the roll formplate 1 directly in the liquid resin in an ink pan.
  • a specific preventive measure for this purpose is as follows. As shown in FIGS. 29 and 30, surplus resin liquid 3 is supplied beforehand through the nozzle 41. Then, surplus resin liquid is squeezed out by rubbing action due to the compression by the pressing roll 6a, thereby to form a liquid accumulation 42. As a result, air is also squeezed out by the rubbing action.
  • the method of coating onto the side of the film substrate 2 as indicated in FIG. 28 is used in the case where the depth of the plate concavities 5 of the roll formplate 1 is relatively shallow, and where the fluidity of the resin liquid is also good, or where a dilute solvent is used.
  • Still another case where the method of coating onto the film substrate side of FIG. 28 is used is the case where, as a consequence of the addition of the abrasive polishing material, the fluidity of the ionizing radiation curable resin 3 becomes poor, and an increase in its viscosity and thixotropy, dilatancy, and the like occur. Consequently, coating and supplying the resin cannot be carried out without dilution of the solvent.
  • a roll formplate of a rigid material such as a metal or glass is used. Furthermore, the film substrate is pressed by a pressing roll over the resin liquid, and moreover a tension is applied to the film substrate.
  • the particles P of the polishing material in the vicinity of the surface of the polishing layer 10 are blocked and prevented from protruding outward by the plate surface of the roll formplate 1. Furthermore, the resin liquid (binder), aided by the pressing pressure, amply flows into and fills also the interface between the polishing material particles or grains P and the plate surface. As a result, the surface of the polishing layer 10 after being thus molded becomes a smooth surface as indicated in FIG. 32.
  • Such a polishing layer 10 can be obtained by measures such as reducing the pressing pressure or the fluidity of the resin liquid or by selecting somewhat high values of the curing shrinkage rate of the liquid of the resin 3 of ionizing radiation curing type. In comparison with the case illustrated in FIG. 32, that shown in FIG. 33 has a greater polishing capacity.
  • FIGS. 28, 29, 34, 35, and 36 The mode of practice of the resin curing method for obtaining an abrasive tape according to this invention is illustrated in FIGS. 28, 29, 34, 35, and 36.
  • the polishing particles or grains in the polishing layer are caused to be more densely distributed in vicinity of the surface of the polishing layer.
  • a plural number of ionizing radiation devices 8a, 8b, and 8c are installed at positions to confront and irradiate the surface of the roll formplate 1, being spaced at suitable intervals in the circumferential direction of the formplate 1.
  • the relationships between the respective energies of the radiation devices are approximately as follows.
  • E 1 ⁇ E 2 ⁇ E 3 ⁇ ⁇ E N E N
  • the relative distribution of these energies E 1 , E 2 , E 3 , ..., E N is suitably adjusted in accordance with factors such as the desired distribution of the polishing particles in the thickness direction of the polishing layer, the kind of resin to be set, and type of irradiation.
  • FIGS. 34 through 37 The stages of an example of the multistage setting process of this character are shown in FIGS. 34 through 37.
  • a film substrate 2 is pressed against the surface of the roll formplate 1 over the yet to be cured resin liquid 3 interposed therebetween.
  • the resin liquid 3 is thereby covered and caused to adhere intimately.
  • ionizing radiation rays are projected onto the coated film 3 (polishing layer 10).
  • the resin 3 closer to the side of the film substrate 2 sets.
  • the distance between the molecules in the resin liquid 3 in this region is narrowed by the cross-linking reaction, and the resin 3 shrinks in volume.
  • the polishing material particles P which had been dispersed, are squeezed out from the spaces between the molecules and migrate from the side of the film substrate 2 toward the yet not cured resin on the formplate side.
  • the multistage setting of the resin is carried out with the surface of the coated film in a state of being fixed to the surface of the formplate. For this reason, an excellent polishing layer 10 as shown in FIG. 37 is obtained. Thus, protrusion of particles or grains outward through the surface due to the high density of the polishing particles in the vicinity of the surface as shown in FIG. 38 is prevented.
  • abrasive tape 11 is in intimate contact with the back-up roller 43 and is irradiated in wrapped state by the irradiation device 8d.
  • a particularly effective method of increasing the cross-linking density of the surface comprises, first, setting with ultraviolet rays the polishing layer at the roll formplate surface and then, after separation from the formplate, irradiating the outer surface side of the polishing layer with an electron beam.
  • Control of the temperatures of the roll formplate 1 and the back-up roller 43 is also important.
  • infrared rays are also radiated from sources such as mercury lamps and carbon-arc lamps.
  • the ionizing radiation is by ultraviolet rays, an electron beam, or the like, a part of the absorbed radiation energy changes into heat. Consequently, if this heating becomes excessive, defects such as deformation and heat deterioration will occur in the cured resin layer or film substrate.
  • a measure for preventing this, in the case of a mercury lamp or a carbon-arc lamp, is to insert a filter which transmits ultraviolet rays but shuts off infrared rays.
  • a specific example of practicing this method comprises using a roll formplate or/and back-up roller of hollow construction and passing cooling water through the interior thereof. In some cases, good results are obtained by heating the roll formplate or/and back-up roller to an appropriate temperature. This is a useful method for solving the problem of internal stress and/or residual strain remaining in the coated film (polishing layer) which has been cross-linked and cured by ionizing radiation.
  • a suitable surface temperature of the roll formplate and the back-up roller is ordinarily of the order of 30 to 80°C.
  • heat generation accompanies ionizing irradiation, it is necessary to take precautionary measures for preventing the temperature of the roll from rising above a limiting temperature with the passage of time.
  • a specific measure is to use a hollow roll formplate and back-up roller and to pass therethrough warm water at a specific temperature. By this measure, absorption of heat by the heat capacity of the water itself and discharging of heating by the flow of the water are accomplished.
  • FIG. 39 an arrangement as shown in FIG. 39 is suitable.
  • two irradiating devices 8A and 8B are provided around the roll formplate 1 at spaced apart positions. These spaced apart positions are such that the angle ⁇ between the lines respectively joining the two irradiating devices 8A and 8B to the center O of the formplate 1 is 90 degrees.
  • the points (lines) at which lines that radiate from the irradiating device 8A and are tangent to the outer surface of the formplate 1 respectively at opposite sides thereof are designated A1 and A2.
  • the points (lines) at which lines that radiate from the irradiating device 8B and are tangent to the outer surface of the formplate 1 respectively at opposite sides thereof are designated B1 and B2. Then, in the case where a uniform irradiation intensity (W/m 2 ) within the irradiated region A1-B1-A2-B2 on the circumferential surface of the roll formplate 1 is desired, portions of the irradiation regions of the irradiating devices 8A and 8B are caused to overlap (as at B1-A2).
  • the irradiation intensity of the arc B1-A2 is caused to be zero (0). This is a case where, for example, the internal stress of the polishing layer due to irradiation by the irradiating device 8A is once reduced, or the polishing layer whose temperature has been raised is once cooled, and thereafter the remaining irradiation is carried out.
  • the quantity of ionizing radiation rays that have been irradiated can be used effectively without waste by either of the following methods.
  • the radiation rays emerging with maximum diverging angle from the irradiating devices 8A and 8B are caused to become tangents of the outer surface of the roll formplate 1 as shown in FIG. 39.
  • the irradiating devices are positioned even closer to the roll formplate 1. However, if they are brought excessively near the roll formplate, the irradiation quantity will become excessively great.
  • FIG. 39 Advantages obtainable from the arrangement of FIG. 39 are as follows.
  • the region ATB used for irradiation out of one circumference of the roll formplate 1 is a limited range.
  • the irradiated region even at its maximum limit is up to one half of one circumference (as in the case shown in FIG. 41).
  • the irradiating device is at an infinitely remote point, and furthermore a parallel radiation flux of amply large area is used.
  • the temperature of the coated film rises to a high value, whereby heat deterioration occurs therein in some cases, and it is difficult to carry out satisfactory setting of the coating film and forming of the concavities and convexities.
  • the ratio 270/360 is that for the case where the irradiating device is infinitely remote (at a far distance of an order which can be thus stated) or for the case where a surface irradiating device radiating a flux of parallel rays is used; ordinarily it is less.
  • 210/360 of the entire circumference becomes the irradiated region.
  • the optimum process is to use two irradiation sources and a center angle formed thereby of 90 degrees.
  • a large irradiation region area of a maximum of 270/360 out of the entire circumferential surface of the roll formplate required in practice can be obtained.
  • deformation, cracking, or thermal deterioration of the coated film due to rapid curing can be prevented.
  • the polishing material or agent used in the present invention is not particularly limited provided that it is one that is used for the purpose of carrying out precision polishing. It can be selected from a wide variety of materials according to the purpose of the polishing process.
  • a polishing material such as green silicon carbide (SiC) or diamond is suitable.
  • SiC green silicon carbide
  • ferric oxide (Fe 2 O 3 ) is suitable. Polishing materials of a grain or particle size of 0.1 to 20 ⁇ m are suitable.
  • polishing materials silicon nitride, zirconium oxide, boron nitride, and emery. Furthermore, it is also possible to use particles and flakes of synthetic resins as polishing materials. Examples of such resins are:
  • Polishing materials produced from these synthetic resins are suitable for polishing the surfaces of relatively soft articles such as synthetic resin products. Furthermore, such polishing materials can be used also for precision polishing requiring fine degrees of roughness.
  • these synthetic resin polishing materials are superior to metals in their transmittances with respect to ultraviolet rays and visible light rays. Furthermore, their indices of refraction are close to those of ionizing radiation curable resins. For these reasons, they are suitable for setting by radiation with ultraviolet rays and visible light rays.
  • This method has already been disclosed in Japanese Patent Publication No. 16002/1993 as a process method with the object, in the production of light-diffusing plates (or films) by dispersing particles of a delusterant or delustering agent in a transparent synthetic resin, of obtaining uniformity of dispersion of the delusterant thereby to obtain uniformity of delustering and high light transmittance.
  • this process method is effective also for preventing peeling off of the polishing material and for improving the polishing performance.
  • Japanese Patent Publication No. 16002/1993 discloses a process wherein, with the use of particles of a silicone resin (polysiloxane) comprising a three-dimensional-network high polymer as polishing (abrasive) particles, an alkyl group such as an ethyl group, a methyl group, a propyl group, or a butyl group, or an organic group such as a carboxyl group, a carbonyl group, an ester group, or an ether group is caused to bond to at least silicon atoms in the vicinity of the outer surfaces of the silicon resin particles, thereby exposing a portion of the organic group at the surfaces of the silicone resin particles.
  • a silicone resin polysiloxane
  • an alkyl group such as an ethyl group, a methyl group, a propyl group, or a butyl group
  • an organic group such as a carboxyl group, a carbonyl group, an ester group, or an ether group
  • the number of this organic group is desirably 0.5 or more and less than 1.5 per 1 silicon atom. If this number is less than 0.5, the dispersibility and the effect of preventing peeling with be inadequate. If it exceeds 1.5, the density of the mesh of the polysiloxane bond will become coarse, and the capacity of the material as a polishing agent will be insufficient.
  • silane coupling agent is applied as a coating on the surfaces of polishing particles of silica, alumina, etc.
  • An even more desirable mode of procedure is that of dispersing, in an ionizing radiation curable resin, particles obtained by subjecting the surfaces of polishing material particles to a coating process with a silane coupling agent comprising alkoxysilane having a radical-polymerizable unsaturated group.
  • This processing method also has already been disclosed in Japanese Patent Application Laid-Open Publn. No. 293099/1988 with the object stated therein of preventing blocking (preventing tackiness) of yet uncured coating film of resin of ionizing radiation curing type. According to the present invention, however, it was discovered that the instant processing method is effective in preventing the peeling off of the abrasive tape during polishing and in improving the polishing performance thereof.
  • the silane coupling agent is an alkoxysilane having a radical-polymerizable unsaturated group, such as for example,
  • alumina Al 2 O 3
  • silica SiO 2
  • a method in which particles or grains of the polishing material are dispersed in a solvent such as toluene, and thereafter a specific quantity of the silane coupling agent is added to cause a reaction is desirable for carrying out the process uniformly.
  • the radical polymerizable unsaturated group in the silane coupling agent molecule cross links with a monomer, prepolymer, and/or oligomer in the solution of the ionizing radiation curable resin, polymerizes, and chemically bonds to the polishing material particles and the cured resin of the ionizing radiation curable resin, adhering strongly thereto.
  • polishing layer a material produced by forming desired irregularities of concavities and convexities on the surface of the cross-linked cured material of the ionizing radiation curable resin solution without adding any polishing material whatsoever.
  • This polishing layer without a polishing material is suitable for surface polishing and precision polishing of soft substances such as, for example, synthetic resins.
  • the content of the polishing material in the coating for forming the polishing layer be 50 to 1,400 parts by weight relative to 100 parts by weight of the binder component.
  • the thickness of the polishing layer 10 is suitably set in accordance with the use, a thickness of the order of 0.5 to 500 ⁇ m is ordinarily suitable. Furthermore, in the case where the polishing layer 10 is required to have a high flexibility or resistance to shrinkage, the requirement can be met by adding into the above mentioned curing type resin a suitable quantity of a thermosetting resin such as, for example, non-reactive acrylic resin or various waxes. In addition, additives such as an antistatic agent can also be added as necessary to the polishing layer.
  • a thermosetting resin such as, for example, non-reactive acrylic resin or various waxes.
  • additives such as an antistatic agent can also be added as necessary to the polishing layer.
  • a material containing as a predominant component a monomer, prepolymer, or oligomer having within its molecule two or more ethylenically unsaturated groups such as acryloyl groups or methacrylol groups or thiol groups as a binder is used.
  • acrylates such as urethane acrylate, polyester acrylate, epoxy acrylate, trimethylolpropane triacrylate, and dipentaerythritol hexaacrylate
  • methacrylates such as urethane methacrylate, polyester methacrylate, epoxy methacrylate, trimethylolpropane trimethacrylate, and dipentaerythritol hexamethacrylate
  • thiols such as trimethylolpropane trithiopropylate and pentaerythritol tetrathioglycol; and unsaturated polyesters.
  • a monomer, prepolymer, or oligomer having one or more of groups such as ethylenically unsaturated groups and thiol groups within the molecule can also be added.
  • groups such as ethylenically unsaturated groups and thiol groups within the molecule
  • examples are acrylates and methacrylates.
  • the cross-link density of the set substance and further physical properties such as flexibility and heat resistance are adjusted by selecting the numbers of the functional groups, the molecular weights, the kinds, and other characteristics of the compounds to be compounded.
  • an acetophenone, a benzophenone, or the like is added as a photopolymerization initiator.
  • An example of an ionizing radiation curing type resin solution composition which will produce a crosslink cured substance that is relatively flexible, pliant, yet tough is a composition obtained by mixing a substance having a hard segment and a soft segment in the monomer, prepolymer, or oligomer to become the polymerization unit. Upon being irradiated with ionizing radiation rays, these polymerization units mutually cross link and form a set substance.
  • a specific example is a monomer, prepolymer, or oligomer of urethane acrylate. To this, for adjusting the crosslinking density and hardness of the set substance, acryl monomer is admixed.
  • urethane acrylate that of an average molecular weight of 500 to 50,000 is selected from those known heretofore.
  • an oligomer or a prepolymer of an urethane acrylate having an urethane group and a radical polymerizable unsaturated group in the molecule can be obtained by causing an isocyanate having two or more isocyanate groups, a polyester prepolymer of a weight average molecular weight of 200 to 3,000 having 1 to 4 hydroxyl groups in one molecule, and an acrylate compound having a hydroxyl group as a terminal group and moreover having a radical polymerizable unsaturated group to react in a solvent or not in a solvent in the presence of a reaction catalyst such as an amino or an organic tin compound and a polymerization inhibitor such as hydroquinone.
  • a reaction catalyst such as an amino or an organic tin compound
  • a polymerization inhibitor such as hydroquinone.
  • isocyanates for constituting the above mentioned urethane acrylate there are aliphatic or aromatic isocyanate compounds. Examples are isophoronediisocyanate and hexamethylenediisocyanate.
  • polyester prepolymer having 1 to 4 hydroxyl groups in one molecule which constitutes the above mentioned urethane acrylate are: addition reaction products of diol compounds having aromatic or spiro-ring skeletons and lactone compounds or derivatives thereof or epoxy compounds; condensation products of polybasic acids such as phthalic acid and polyols such as ethylene glycol; polyester diols such as polyester compounds obtained by cleaving cyclic ester compounds; polyether diols such as polytetramethylene ether glycol, polyethylene glycol, and polypropylene glycol; and polycarbonate diols. These compounds are used singly or in a mixture of two or more members.
  • the weight average molecular weight of the polyester polymer having 1 to 4 hydroxyl groups in one molecule is desirably within a range of 200 to 3,000 from the standpoint of wear resistance and hardness, a range of 500 to 1,500 being particularly desirable.
  • acrylate compounds having a hydroxyl group at the end of each molecule and, moreover, having one or more radical polymerizable unsaturated groups are hydroxylation derivatives of (meth)acrylic acid ester such as hydroxyethyl acrylate and hydroxypropyl methacrylate and epoxy acrylate. Monomers of these (acrylates) are used.
  • the binder is made relatively hard.
  • the hardness and flexibility are made to be of the same order as those of a thermoplastic polyester of a Tg of 50°C or higher.
  • an antistatic agent is added.
  • a good result can be obtained by causing a preparation resulting from the addition of a surface active agent (anionic or nonionic) molecule to a monomer, prepolymer, or oligomer having an ethylenically unsaturated bond (acryloyl group, methacryloyl group, or the like) to undergo crosslinking together with the aforementioned ionizing radiation setting resin composition.
  • a surface active agent anionic or nonionic
  • the crosslinkable surface active agent undergoes crosslinking and curing together with the binder resin and, in the three-dimensional network macropolymer structure, chemically bonds by covalent bonding or the like, thereby to form an integral structure.
  • a composition as disclosed in Japanese Patent Laid-Open Publication No. Heisei 5-98049 may be used.
  • This is a composition of a resin of ultraviolet-ray setting type comprising principally the following members (A), (B), (C), and (D) and used singly by itself or is a substance formed by dispersing particles of the polishing material in said composition.
  • graphite or metals such as, silver, copper, platinum, nickel, chromium, iron or ferrous alloys such as carbon steel and stainless steel, and aluminum or aluminum alloys such as duralumin in the form of powder or thin flakes are added to the polishing layer.
  • these (metal powders or flakes) can be added to the film substrate material.
  • any kind of film can be used as long as it has been used from the past for polishing tapes and, moreover, has a suitable flexibility for its smooth passage of also rolls, etc., in the production process.
  • polyester film, polyethylene film, polypropylene film, polyvinyl chloride film, polyvinylidene chloride film, polycarbonate film, polyamide (nylon) film, polystyrene film, ethylene-vinyl acetate copolymer film, etc. can be used.
  • polyester films such as those of particularly biaxial orientated polyethylene terephthalate, polyethylene naphthalate, etc., are desirable.
  • the surfaces of these films to form the polishing layer can be processed according to necessity by corona discharge treatment or by easily adhesive primer treatment with polyester resin, etc.
  • paper, fabric, non-woven fabric, synthetic paper, etc. which have been treated with a filler may be used.
  • the thickness of this substrate 2 is desirably of the order of 12 to 100 ⁇ m. Further, these substrates may be of a single layer or be laminated with two or more layers.
  • an abrasive tape of constantly uniform and precise recessed part shape is obtained. At least the initial polishing capacity of this abrasive tape is stable. Furthermore, since the recessed parts are of specific shapes as described hereinbefore, the polishing debris produced from the article being polished during polishing is efficiently accommodated in these recessed parts. As a result, there is little risk of damaging the surface of the article being polished due to infiltration of polishing debris in between the abrasive tape and the article being polished. Furthermore, there is also no lowering of the polishing capacity due to clogging of the pores of the polishing layer.
  • the abrasive tape is particularly optimally suitable for precision polishing such as that requiring mirror finishing.
  • the polishing layer is constituted of an ionizing radiation curing type resin which has been set, it has excellent physical properties such as wear resistance, whereby polishing by the polishing material is positively carried out, and there is little possibility of defective polishing of the article being polished, polishing of high precision becoming possible.
  • a double-liquid curable type polyester primer was applied by the gravure coating method so as to form a coating of a thickness of 0.3 ⁇ m upon drying thereby to carry out mold release (lubrication) processing.
  • a polishing layer was formed with the following constituent materials and under the following conditions by employing the production mode indicated in FIG. 1, thereby fabricating an abrasive tape.
  • the abrasive tape thus obtained had a polishing layer with recessed parts formed in accordance with the plate, of desired sharp shape, moreover with good reproducibility.
  • polishing of stainless steel (SUS-45C, JIS) of a centerline average roughness (JIS-B-0601, JIS) of 0.5 ⁇ m was carried out, whereupon a polishing finish of a centerline average roughness of 0.1 ⁇ m was obtained.
  • the polishing debris was accommodated in the above mentioned recessed parts, and damaging (scoring, abrading, etc.) of the surface of the article being polished did not occur.
  • a double-liquid curing type polyester primer was applied by the gravure coating method so as to form a coating of a thickness of 0.3 ⁇ m upon drying thereby to carry out mold release (lubrication) processing.
  • a polishing layer was formed with the following constituent materials and under the following conditions by employing the production mode indicated in FIG. 29, thus fabricating an abrasive tape.
  • the abrasive tape thus obtained had a polishing layer having recessed parts formed in accordance with the plate, of desired sharp shape, moreover with good reproducibility.
  • polishing of the surface of a 5.25-inch magnetic floppy disc of a centerline average roughness of 0.5 ⁇ m was carried out, whereupon a polishing finish of a centerline average roughness of 0.05 ⁇ m was obtained.
  • the polishing debris at this time was accommodated in the above mentioned recessed parts, and damaging of the surface of the article being polished due to the polishing debris did not occur.
  • a double-liquid curing type polyester primer was applied by the gravure coating so as to form a coating of a thickness of 0.3 ⁇ m upon drying thereby to carry out mold release processing.
  • a polishing layer was formed with the following constituent materials and under the following conditions by employing the production mode indicated in FIG. 1, thus fabricating an abrasive tape.
  • the abrasive tape thus obtained had a polishing layer having recessed parts formed in accordance with the plate, of desired sharp shape, moreover with good reproducibility.
  • polishing of the surface of a 5.25-inch magnetic floppy disc of a centerline average roughness of 0.40 ⁇ m was carried out, whereupon a polishing finish of a centerline average roughness of 0.09 ⁇ m was obtained.
  • polishing debris at this time was accommodated in the above mentioned recessed parts, and damaging of the surface of the article being polished due to the polishing debris did not occur.
  • the present invention is applicable to polishing for the purpose of high precision finishing of surfaces of articles such as floppy discs and magnetic heads and end faces of optical fibers.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Laminated Bodies (AREA)

Claims (4)

  1. Bande abrasive ayant un support de film (2) et une couche abrasive (10) laminée sur une face dudit support de film (2), ladite couche abrasive (10) ayant sur sa face extérieure une pluralité de parties en creux (9), et qui comprend un liant d'une résine durcie (3) de type réticulé, des particules d'un matériau abrasif de polissage étant dispersées dans la couche abrasive, caractérisée en ce que la densité desdites particules de matériau abrasif augmente dans la direction s'éloignant du support de film (2).
  2. Bande abrasive selon la revendication 1, où ladite résine durcie (3) de type réticulé a une structure moléculaire à réseau tridimensionnel, structure dans laquelle sont chimiquement combinées des molécules d'un agent tensio-actif.
  3. Bande abrasive selon la revendication 1 ou 2, où ladite couche abrasive (10) contient un agent antistatique.
  4. Bande abrasive selon l'une quelconque des revendications 1, 2 ou 3, où lesdites particules de matériau abrasif de polissage contenues dans ladite couche abrasive (10) sont sous la forme d'écailles de poisson en lamelles ou sous la forme de fibres courtes.
EP99105024A 1993-06-02 1993-06-02 Bande abrasive Expired - Lifetime EP0940224B1 (fr)

Priority Applications (1)

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EP99105025A Expired - Lifetime EP0938951B1 (fr) 1993-06-02 1993-06-02 Procédé de fabrication d'une bande adhésive

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JP2003071731A (ja) * 2001-09-03 2003-03-12 Three M Innovative Properties Co ディンプル構造の研磨材料
US7267700B2 (en) 2003-09-23 2007-09-11 3M Innovative Properties Company Structured abrasive with parabolic sides
US20050060944A1 (en) * 2003-09-23 2005-03-24 3M Innovative Properties Company Method of making a coated abrasive
US7300479B2 (en) 2003-09-23 2007-11-27 3M Innovative Properties Company Compositions for abrasive articles

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US3689187A (en) * 1971-04-28 1972-09-05 Kuretoishi Kk Belt-mold forming apparatus grinding wheels
SE451687B (sv) * 1980-12-29 1987-10-26 Norton Co Agglomererade slipmedelspartiklar
US5152917B1 (en) * 1991-02-06 1998-01-13 Minnesota Mining & Mfg Structured abrasive article
JP3133402B2 (ja) * 1991-07-19 2001-02-05 大日本印刷株式会社 研磨テープ及びその製造方法

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EP0938950B1 (fr) 2003-03-19
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EP0938950A2 (fr) 1999-09-01
EP0938951A2 (fr) 1999-09-01
EP0938951A3 (fr) 2000-04-05
EP0940224A2 (fr) 1999-09-08
EP0938951B1 (fr) 2002-09-04

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