WO2002055264A1 - Pastille de meule, meule, et leurs procedes de production, procede de production d'elements optiques a l'aide la meule et procede de production d'aligneurs de projection - Google Patents
Pastille de meule, meule, et leurs procedes de production, procede de production d'elements optiques a l'aide la meule et procede de production d'aligneurs de projection Download PDFInfo
- Publication number
- WO2002055264A1 WO2002055264A1 PCT/JP2002/000180 JP0200180W WO02055264A1 WO 2002055264 A1 WO2002055264 A1 WO 2002055264A1 JP 0200180 W JP0200180 W JP 0200180W WO 02055264 A1 WO02055264 A1 WO 02055264A1
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- WIPO (PCT)
- Prior art keywords
- base
- plate
- grinding wheel
- grinding
- layer
- Prior art date
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D7/00—Bonded abrasive wheels, or wheels with inserted abrasive blocks, designed for acting otherwise than only by their periphery, e.g. by the front face; Bushings or mountings therefor
- B24D7/18—Wheels of special form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B13/00—Machines or devices designed for grinding or polishing optical surfaces on lenses or surfaces of similar shape on other work; Accessories therefor
- B24B13/01—Specific tools, e.g. bowl-like; Production, dressing or fastening of these tools
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B13/00—Machines or devices designed for grinding or polishing optical surfaces on lenses or surfaces of similar shape on other work; Accessories therefor
- B24B13/02—Machines or devices designed for grinding or polishing optical surfaces on lenses or surfaces of similar shape on other work; Accessories therefor by means of tools with abrading surfaces corresponding in shape with the lenses to be made
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D7/00—Bonded abrasive wheels, or wheels with inserted abrasive blocks, designed for acting otherwise than only by their periphery, e.g. by the front face; Bushings or mountings therefor
- B24D7/06—Bonded abrasive wheels, or wheels with inserted abrasive blocks, designed for acting otherwise than only by their periphery, e.g. by the front face; Bushings or mountings therefor with inserted abrasive blocks, e.g. segmental
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D7/00—Bonded abrasive wheels, or wheels with inserted abrasive blocks, designed for acting otherwise than only by their periphery, e.g. by the front face; Bushings or mountings therefor
- B24D7/06—Bonded abrasive wheels, or wheels with inserted abrasive blocks, designed for acting otherwise than only by their periphery, e.g. by the front face; Bushings or mountings therefor with inserted abrasive blocks, e.g. segmental
- B24D7/066—Grinding blocks; their mountings or supports
Definitions
- the present invention relates to a grindstone pellet, a grindstone, a method of manufacturing these, and a method of manufacturing an optical element using the grindstone, which are fixed to a base plate and used for glass or metal grinding or polishing. And a method of manufacturing the projection exposure apparatus.
- the grindstone pellet is fixed on the platen with an adhesive, and this is used as a grindstone.
- the grinding wheel pellet is made of a material such as metal bond, resin bond, or vitrified bond, and hardened by putting abrasive grains into it. There is.
- the present invention has been made in view of such conventional problems, and therefore has a grinding wheel pellet, a grinding wheel, and a grinding wheel capable of achieving a uniform distribution of abrasive grains.
- An object of the present invention is to provide a manufacturing method, a method for manufacturing an optical element using the grinding wheel, and a method for manufacturing a projection exposure apparatus.
- the grinding wheel pellets for achieving the above-mentioned purpose are: In a whetstone pellet that is fixed to a plate to form a whetstone,
- a column-shaped base fixed to the base plate
- a metal layer containing abrasive grains and formed on the surface of the substrate is a metal layer containing abrasive grains and formed on the surface of the substrate.
- the plating layer may be an electrolytic plating layer or an electroless plating layer, but the electroless plating layer is more preferable from the viewpoint of the manufacturing process and the like.
- the base may be a metal that acts as a catalyst when forming the electroless plating layer.
- a method of manufacturing a grinding wheel pellet includes a method of manufacturing a grinding wheel pellet in which a plurality of grinding wheels are fixed to a base plate to form a grinding wheel.
- a columnar base body fixed to the base plate is prepared, and a plating solution containing abrasive grains is provided on an end surface of the columnar base body opposite to the end surface fixed to the base plate.
- the abrasive layer is formed by the above method.
- the substrate is formed of a conductive material, and the plurality of substrates are interconnected. Are electrically connected by a conductor, and the plurality of electrically connected bases are placed in an electrolytic plating solution containing abrasive grains, and the abrasive layer is applied to the end faces of the plurality of bases. Forming is preferred.
- the abrasive layer is formed by electrolytic plating, the abrasive layer is thereafter formed so that the thickness of the abrasive layer becomes uniform. It is good to process the abrasive layer.
- a plurality of electroless plating solutions are provided on a fixed plate prepared in advance. Before or after fixing the plurality of substrates to the fixing plate, on an end surface of the substrate, the end surface being opposite to the end surface fixed to the fixing plate. Forming a catalyst layer for the electroless plating, placing the plurality of substrates fixed on the fixing plate in an electroless plating solution containing abrasive grains, and placing the plurality of substrates on the catalyst layer of each substrate. It is preferable to form the abrasive layer.
- the abrasive layer formed of the electroless plating solution is entirely amorphous.
- a whetstone having a plurality of abrasive layers scattered on a base plate, a plurality of columnar substrates fixed on the base plate, and formed only on the surface of the substrate including abrasive grains and including an end surface of the base Further, it is characterized by having a plating layer forming the abrasive layer.
- a whetstone having a plurality of abrasive layers scattered on a plate, a plurality of columnar substrates fixed on the plate, including abrasive grains, and being formed on an end surface of the substrate, A plating layer forming an abrasive layer, and a plurality of bases disposed on the base plate and between the plurality of bases to fix the bases to the base plate; And a masking layer that plays a role as a masking agent when forming the masking layer.
- the above-mentioned grinding layer of the grinding wheel is preferably an amorphous plating layer formed by electroless plating, similarly to the grinding wheel pellet described above. .
- a method for producing a grinding wheel for achieving the above-mentioned object is as follows.
- a catalyst layer is formed, and an abrasive grain layer is formed on the catalyst layer by electroless plating including abrasive grains.
- an adhesive is applied to the entire surface of the base plate on the base fixing surface side, and the plurality of bases are placed on the adhesive.
- the base may be fixed to the plate.
- the adhesive also serves as a masking agent for the electroless plating.
- the end faces of the plurality of bases are fixed after the plurality of bases are fixed on the base plate and before the end faces of the bases are plated.
- the surface may be curved so that the continuous surface shape becomes a desired inverted shape of the processed surface.
- Another method for producing a grinding stone for achieving the above-mentioned object is a method for producing a grinding stone in which a plurality of abrasive layers are scattered on a base plate.
- At least a surface plate on the side on which the abrasive layer is formed has conductivity, and a plurality of pillar-shaped, conductive substrates fixed to the plate.
- a body is prepared, and a plurality of bases are fixed to a surface of the base plate on a side on which the abrasive grain layer is to be formed so as to be mutually conductive via the base plate.
- a plurality of the bases fixed to the base plate are put in a cleaning solution, and the abrasive layer is formed on an end face of the base by electrolytic plating including the abrasives. It is assumed that.
- a non-conductive adhesive is used, and the adhesive is applied between the plurality of substrates on the plate, and the adhesive is It may be a masking agent for the electrolytic plating.
- the abrasive layer is formed by electrolytic plating, after the abrasive layer is formed, the surface shape obtained by connecting the surfaces of the plurality of abrasive layers is a desired coating. It is preferable to process a plurality of the abrasive layers so as to have an inverted shape of the processed surface.
- a grindstone in which a plurality of substrates are fixed on a plate and a plating layer containing a large number of abrasive grains is formed only on the surface of the substrate including the end surface of the substrate is prepared.
- the element material is processed to form the optical element or an intermediate product of the optical element.
- the optical projection exposure apparatus provided by the present application is:
- a grindstone having a plurality of substrates fixed on a plate and having a plating layer containing abrasive grains formed only on the surface of the substrate including an end surface of the substrate is prepared.
- the lens material is processed using the whetstone to form the lens or an intermediate product of the lens, and the lens obtained by processing the lens material is applied to the optical system.
- the feature is to incorporate it.
- the abrasive grains are mixed in the plating solution, which is a liquid, and the abrasive layer is formed by the plating layer containing the abrasive grains. Since the abrasive grains are formed, the abrasive grains can be uniformly dispersed. For this reason, it is preferable to use the grindstone of the present invention for ultra-precision machining where abrasive grains having a small particle size are required.
- the metal layer is used as a binder for the abrasive grains, so that the holding power of the abrasive grains is increased, and the binder itself is basically hard, so that the life of the grinding wheel is extended. can do.
- the outer peripheral plating layer is formed like an electrolytic plating. Since the thickness of the abrasive grains does not increase, the thickness of the abrasive grains can be made uniform.
- the grinding wheel pellet since the abrasive grains are formed on the substrate, a grinding wheel pellet of a certain size can be secured, and the grinding wheel pellet is used. The handleability when fixing it on the plate can be improved. Furthermore, when trying to obtain a grinding wheel pellet of a predetermined height, the plating time is shortened compared to making a grinding wheel pellet with no plating layer. be able to.
- FIG. 1 shows a grindstone and a grindstone pellet according to an embodiment of the present invention.
- FIG. 2 is an explanatory view showing a procedure for manufacturing a grinding wheel pellet in Example 1 of the present invention.
- FIG. 3 is an explanatory view showing a procedure for manufacturing a grindstone in Embodiment 2 of the present invention.
- FIG. 4 is an explanatory view showing a procedure for manufacturing a grindstone in a modification of the second embodiment of the present invention.
- FIG. 5 is an explanatory view showing a process of manufacturing an optical element.
- FIG. 6 is an explanatory diagram showing a surface state when fluorite is ground with a conventional resin-bonded grindstone.
- FIG. 5 is an explanatory view (No. 1) showing a procedure for manufacturing a grindstone of Embodiment 3 of the present invention.
- FIG. 8 is an explanatory view (No. 2) showing a procedure for manufacturing the grindstone according to the third embodiment of the present invention.
- FIG. 9 is a configuration diagram of a projection exposure apparatus according to an embodiment of the present invention.
- a plurality of grindstone pellets 1 of the present embodiment are fixed on a platen 9 and used as a grindstone 10.
- the base 2 has an abrasive portion 5 formed on one end surface 3 side.
- the abrasive grains 5 are formed of an amorphous plating layer containing abrasive grains by an electroless plating method.
- the material of the base 2 is preferably a material that is not easily eroded by the electroless plating solution and can obtain good adhesion to the electroless plating solution. Further, the material of the base 2 preferably has good adhesiveness to the adhesive used for sticking to the plate 9 of the grinding wheel 1 and has good mechanical rigidity. Metal is most suitable for Among them, a metal having a catalytic action to promote a plating reaction, or a catalyst which can be easily formed on the surface of the substrate 2 before plating, is suitable for the metal. Iron and nickel are good, and stainless steel, aluminum and brass are good for the latter.
- stainless steel and aluminum are suitable because the remaining abrasive grains can be easily peeled off when the substrate 2 is reused.
- the electroless plating since the surface shape of the substrate 2 is faithfully transferred, it is preferable that the surface of the substrate 2 be smoothed in advance.
- a plurality of substrates 2, 2,... are manufactured in order to manufacture a plurality of grinding wheel pellets 1, 1,. It is preferable to use a fixing plate that can fix the plate. The dimensions of the fixing plate are determined according to the quantity of the wheel pellet 1 to be manufactured.
- the material of the fixing plate is not easily eroded by the pretreatment of the electroless plating and the electroless plating solution because it is used repeatedly, and is not used by a masking agent described later. Select one that does not dissolve. If the masking process described below is to be simplified, a resin is suitable for the fixing plate. If a large number of bases are fixed, the fixing plate must be able to withstand the weight of the fixing plate. PTFE (Polytetrafluoroethylene) is good.
- a plurality of bases 2, 2,... are attached to the fixing plate with an adhesive, and a region where no plating is applied on the surface of the base 2, that is, a region where the abrasive portion 5 is not formed, is formed. King.
- the fixing plate and the base 2 are degreased with a solvent.
- the base 2 can be held during the process from the pretreatment of the electroless plating to the electroless plating, and the masking is performed. It is suitable that the substrate 2 can be easily peeled off from the fixing plate after electroless plating. That is, such an adhesive is used for both the fixing of the base 2 and the masking.
- the contact used to fix the base 2 The adhesive and the masking agent used for the masking of the base 2 need not be the same, and may be different. From the point of view, it is preferable that they are the same.
- the fixing plate is made of metal, the plating will precipitate out of the fixing plate itself, so all exposed metal parts immersed in the plating liquid must be masked. This is not necessary when the fixing plate is made of resin. Even if the thickness of the masking film is not uniform, there is no problem with the electroless plating layer deposited on the substrate because the uniform thickness can be obtained from its characteristics. .
- a catalyst layer for the electroless plating is formed in a region of the surface of the base 2 where the masking film is not formed. If the substrate itself has a catalytic property, the oxide film on the surface of the substrate where the masking film is not formed is subjected to a predetermined degreasing and activation treatment. Etc., and this is used as a catalyst layer. On the other hand, if the substrate itself does not have catalytic properties, a catalyst layer is formed on the surface of the substrate after performing a predetermined degreasing and activation treatment.
- the catalyst layer is formed when the material of the base 2 is brass or stainless steel, for example, when the base 2 is immersed in an aqueous solution containing palladium chloride as a main component, the palladium serving as a catalyst is formed. Is deposited on the substrate surface.
- the material of the substrate 2 is aluminum
- the substrate 2 is immersed in a zinc-substituted solution, and a zinc layer serving as a catalyst is deposited on the surface of the substrate.
- Catalysts that promote the reaction of electroless plating include metals belonging to Group 8 such as iron and ruthenium, and Group 10 metals such as nickel and noradium. Metal element is there .
- the catalyst layer is formed on the base after the base is fixed to the fixed plate.
- the base may be fixed on the fixed plate after the catalyst layer is formed on the base. .
- an electroless plating solution characterized by good uniform precipitation is used.
- the electroless plating solution for example, a nickel-lin plating solution is used.
- Abrasive grains are mixed into this electroless plating solution.
- the abrasive grains commercially available diamond powder or cubic boron nitride (CBN) can be used, and the grain size is not limited, but is generally about 0.1 /. i II! Up to 200 ⁇ m is often used.
- the plating solution is stirred with a stirrer or the like to uniformly disperse the abrasive grains while the catalyst layer is formed on the substrate.
- a plating layer having a uniform thickness including abrasive grains is formed in a certain area of the catalyst layer.
- the thickness of the abrasive grains 5 is controlled mainly by the plating solution temperature and plating time.
- the substrate is removed from the fixing plate, and the masking film is removed to obtain a grinding wheel pellet 1.
- the electrolytic plating layer is concentrated and deposited on the convex portions to make the layer thickness uniform. I can't do this.
- the electroless plating method according to the present embodiment since the electroless plating is used, a large number of plating layers are not deposited on the convex portion and the outer peripheral portion.
- the force S can be made uniform in thickness.
- the abrasive grains are mixed into the plating liquid, which is a liquid, and the abrasive grains are mixed during the precipitation of the plating layer serving as the abrasive grains 5.
- the abrasive grains are uniformly dispersed in the deposited plating layer ⁇ . For this reason, for example, when a grinding wheel containing very small grain size is required for finishing, even if the size of the grain size is small, the distribution of the grain size is uniform. It is very effective because it can be used for the purpose.
- the amorphous plating layer formed by the electroless plating method acts as a binder for the abrasive grains, the holding power of the abrasive grains is increased, and the life of the grinding stone is extended. can do .
- the amorphous metal layer, which is a binder is basically hard, the surface change of the abrasive layer due to grinding or polishing is small, and the frequency of repair work on the ground or polished surface is small. Can be reduced.
- the grinding wheel pellet having a certain height can be obtained without taking much time for forming the plating layer. 1 can be secured. Therefore, since the size of the grinding wheel pellet 1 is easily secured, it is possible to enhance the handling property when the grinding wheel pellet 1 is fixed on the base plate 9.
- a plate 9 having an inverted shape of a desired work surface is prepared, and a plurality of grindstone pellets 1 are prepared. Is fixed using an adhesive or the like. Then, grinding or cutting using a grinding plate or the like is performed so that the surface shape connecting the end faces of the plurality of grinding wheel pellets 1 becomes the inverted shape of the desired workpiece. Process and finish.
- the base 2 is made of stainless steel (SUS304) and is formed in a cylindrical shape having a diameter of 14.4 mm and a height of 3 mm. Of the two end faces of the substrate 2, the end face 3 on which the abrasive layer 5 is formed has been smoothed to Ra 0.2 by machining.
- the masking agent is a commercially available masking agent that serves as an adhesive used for fixing the base 2 and a masking agent used for masking the base 2.
- Use turquoise 590--1A (trade name of Art Chemicals, Inc., USA), which is a sticking agent.
- the plurality of substrates 2, 2, ... placed on this together with the fixing plate 11 are placed in an oven heated to 100 ° C, and baked for 1 hour to make the masking film 1 2 Is cured.
- the bases 2, 2, ... on the fixing plate 11 are subjected to degreasing and acid activation, and then to hydrochloric acid and chloride. It was immersed in an aqueous solution containing palladium as a main component for 60 seconds, and as shown in Fig. 2 (b), a palladium layer was formed on the surface of the substrate 2 on which the masking film 12 was not applied. To form This This becomes the catalyst layer 4 that promotes the reaction of the electroless plating.
- a metal that can become the catalyst layer 4 for example, iron is used as a base, there is no need to separately form the catalyst layer, and the surface on which the catalyst layer is formed can be activated with an acid. In this case, the surface becomes a catalyst layer.
- the substrate 2 placed on the fixed plate 11 was washed with water and pressed, as shown in FIG. 2 (c), to remove the base 2 containing abrasive grains 15.
- Mesh liquid 16 contains diamond particles with a particle size of 2 to 4 ⁇ m.
- the content of the abrasive grains 15 in the plating layer can be adjusted by changing the stirring amount such as the amount of the diamond powder and the rotation speed of the stirrer 17. .
- the temperature of the plating solution 16 was 90 ° C.
- the substrate 2 was put into the plating solution for 16 hours, and an electroless plating layer having a thickness of 0.3 mm was deposited. Let This becomes the abrasive grains 5 formed of the amorphous black layer.
- the fixing plate 11 When the electroless plating layer is deposited to a predetermined thickness, the fixing plate 11 is taken out of the plating tank, and the fixing plate 11 and the base 2 are washed with water and then dried. You Then, as shown in FIG. 2 (d), the base 2 is removed from the fixing plate 11, and the masking film 12 is removed, whereby the abrasive grains 5 are removed. A wheel pellet 1 with a diameter of 15 mm and an overall height of 3.3 mm is completed. When removing the grinding wheel pallet 1 from the fixing plate 11, the base 2 and the fixing plate 11 after plating are placed in a solvent for diluting the masking film 12. When immersed, the masking film 12 dissolves, and the fixed plate 11 is easily polished. Stone pellet 1 can be removed.
- the schematic configuration of the grindstone of this embodiment is the same as that of the grindstone 10 described above with reference to FIG. That is, a plurality of bases 2 are fixed on the plate 9, and the abrasive grains 5 are formed on one end face 3 side of each base 2. However, in the first embodiment, after the grinding wheel pellet 1 is completed, it is fixed to the base plate 9 to produce the grinding wheel 10. However, in this embodiment, the grinding wheel pellet 1 is manufactured. The grindstone 10 is manufactured without going through the process of completing the let 1.
- a plate 9 having an inverted shape of a desired surface to be processed is manufactured.
- Metal is most suitable for the material of the plate 9 because it has good adhesiveness to an adhesive described later and can maintain mechanical rigidity.
- aluminum which can be easily manufactured by the manufacturing method or cutting and is lightweight
- iron which can be manufactured by the manufacturing method, are suitable.
- the surface of the plate 9 on which the abrasive grains are to be formed may be rough-finished in order to enhance the adhesiveness with the adhesive, and may be subjected to a blast treatment as necessary. Roughening force such as may be applied. As described above, since the abrasive grain forming side surface of the plate 9 does not need to be smooth-finished, the force B cost of the plate 9 can be suppressed.
- the shape of the base 2 may be any of various shapes such as a prism, a column, and the like. In addition, it is formed into a shape as required. As with resin-bonded and metal-bonded pellets, if you want to obtain a cylindrical object, you can cut the round bar at regular intervals to process it. Cost can be reduced and it can be obtained easily.
- the end face to be attached to the plate 9 may be rough-finished in order to strengthen the adhesiveness with the adhesive, similarly to the plate 9, and The other end face on which the abrasive grains 5 are formed can be rough-finished because it is separately finished in a later step.
- the end face on the side attached to the base plate 9 may be subjected to a roughening process such as blasting as in the case of the base plate 9.
- the base plate 9 and the plurality of bases 2 described above are obtained, the base plate 9 is degreased with a solvent, and then the entire surface of the base plate 9 on which the abrasive grains are formed is coated with an adhesive.
- the substrate 2 is placed.
- the adhesive used in this case since the surface of the base plate 9 is not a flat surface but a curved surface, the base 2 is difficult to move along the curved surface due to gravity. This is preferred, and high viscosity epoxy adhesives are preferred.
- a projection or a recess is formed on the end surface of the base 2, and a recess or a projection is formed at a position of the base 9 where the base 2 is to be fixed, and You may make it fit the convex part or concave part of 2 into the concave part or convex part of a base plate. In this case, since the base 2 does not shift with respect to the base plate 9, a low-viscosity adhesive may be used.
- a weight or the like is placed on the base 2 so that the base 2 is not lifted from the force of the plate 9 by the adhesive.
- the plurality of bases 2 are placed on a surface plate having a flat surface, and the plate 9 with the adhesive is placed thereon, and Plate 9 It is good to weigh yourself. Also, plate
- a plurality of bases 2 may be placed on a base plate 9 with an adhesive, and a sliding plate described later may be placed as a weight.
- the plurality of bases 2 are placed on the plate 9 with the adhesive, and after the weight is placed thereon, the substrate 2 is left until the adhesive is cured. If the adhesive is a thermosetting adhesive, it is preferable to put the above adhesives in an oven or the like to shorten the curing time.
- the end face of the base 2 is ground or cut so that the surface shape formed by connecting the end faces of the plurality of bases 2 becomes a desired inverted shape of the work surface.
- masking for the electroless plating is performed on the base plate 9 with the base.
- An adhesive is applied to the side of the plate 9 where the abrasive grains are formed, and since this adhesive acts as a masking agent, no masking is applied here. Mask the back side.
- the base plate 9 with the substrate is put into the electroless plating solution containing the abrasive particles, and the abrasive particles are placed on the catalyst layer of each substrate 2.
- an electroless plating layer that is, an abrasive grain portion 5. This electroless plating is performed in the same manner as in the first embodiment.
- the base plate 9 with the base is taken out of the electroless plating solution, washed with water, and then washed on the back side of the base plate 9.
- the masking film 12 is removed, and the grindstone 10 is completed.
- the grindstone pellet 1 of the first embodiment is basically formed. The same effect can be obtained.
- the abrasive grains 5 are provided on the base 2 so that the shape of the end faces of all the bases 2 fixed to the base plate 9 is a reverse shape of the desired work surface. Since the end face of the base body 2 was machined before forming, the completed grindstone pellet 1 was fixed on the platen 9 as in the first embodiment, and then the grindstone pellet was fixed. The machining can be performed in a shorter time and more easily than when machining the abrasive grain portion 5 of the let 1 by machining. This is because the object of machining is not an extremely hard metal layer containing abrasive grains as in the first embodiment.
- the adhesive applied to the entire side surface of the base plate on which the abrasive grains are formed serves as a masking agent, so that the consumption of the plating liquid and the abrasive grains is suppressed. In addition to this, there is no need to separately mask the side of the platen where the abrasive grains are formed.
- a specific method for manufacturing the grindstone 10 described in the second embodiment will be described with reference to FIG. It is assumed that the grindstone 10 to be finally obtained in the second embodiment is a spherical grindstone having a radius of curvature of 197 mm.
- the plate 9 is made of an aluminum material and is formed in a disk shape having a diameter of 3 O Om m, and the surface on which the abrasive grains are formed is formed as a spherical surface having a radius of curvature of 200 mm. This surface is not particularly roughened.
- the substrate 2 is made of aluminum (A5506), and has a cylindrical shape with a diameter of 10 mm and a height of 3 mm. The surface of the substrate 2 is shot-processed with glass beads having a particle size of # 100.
- the epoxy adhesive 12a is applied to the entire spherical surface of the base plate 9 where the abrasive grains are formed. Is applied.
- SC507 A / B (trade name of Sony Chemicals) having a relatively high viscosity is suitable.
- the amount of the adhesive 12a to be applied is preferably about half the height of the substrate 2.
- a sliding plate described later is used. 1 9 is placed on top of it, and the adhesive 12 a is cured. In this way, by placing the sliding plate 19 as a weight on the base 2, it is possible to prevent the base 2 from shifting during the curing of the adhesive 12a. .
- the surface shape connecting the end faces 3 of the plurality of bases 2 is a reverse shape of the desired processing surface, that is, a spherical surface, as shown in FIG. 3 (b). Then, the end face 3 of the base body 2 is shaved using a sliding plate 19. In this rubbing, a mixture of water and silicon carbide-based grinding sand having a grain size of # 600 is applied to the rubbed surface. At this stage, the radius of curvature of the spherical surface to be obtained is 197.3 mm, taking into account the thickness of the plating layer (0.3 mm).
- the masking film 13 (see FIG. 3) is applied to the surface of the plate 9 other than the spherical surface, in other words, the back surface of the plate 9 using a masking tape or a coating type masking agent. (shown in (c)). Then, after the base plate 9 with the base was subjected to alkaline degreasing and activation with an acid in order, the base plate 9 was immersed in a zinc replacement solution for 30 seconds, and the side surfaces of the bases 2 and the end faces of the bases 2 were placed on the bases 2. Form a zinc layer (not shown). This zinc layer becomes a catalyst layer that promotes the reaction of the electroless plating.
- the base plate 9 with the base was washed with water, and then, as shown in FIG. 3 (c), the electroless nickel-rinse-mesh solution 16 containing abrasive grains 15 was used. Then, a 0.3 mm electroless plating layer is deposited on the end face 3 of the substrate 2. This becomes the abrasive grains 5 formed of the amorphous plating layer. Note that various conditions in this electroless plating step are the same as in Example 1. After the above electroless plating, take out the plate 9 on which the abrasive layer 5 has been formed from the plating tank, wash it with water, dry it, and attach it to the back of the plate 9. When the masking film 13 is removed, a spherical grindstone 10 having a radius of curvature of 197 mm is completed.
- the spherical plate 9 is used in accordance with the surface shape of the surface to be processed.
- the plate does not necessarily need to be adapted to the surface shape of the surface to be processed.
- a flat disk-shaped plate 9a may be used.
- a method of manufacturing a grinding wheel using such a plate 9a will be briefly described below.
- a plurality of bases 2 having the same height are placed on the adhesive 12 a and the adhesive 1 2 Cure a.
- a plurality of bases 2 are placed on a surface plate having a flat surface, a base plate 9a with an adhesive is placed thereon, and the base plate 9a itself is weighed.
- the end face 3 of the base 2 is scraped using a sliding plate 19, and as shown in FIG. 4 (c), A surface shape obtained by connecting the end faces 3 of the plurality of bases 2 is made to be a desired inverted shape of the processed surface.
- a grinding process is performed to complete the grindstone.
- a base having a reduced height that is, this practice was carried out.
- the base attached to the vicinity of the center of the plate 9a is one that is lower than other bases. You may do so.
- test objects are the grindstone 10 of the second embodiment, a conventional metal-bonded grindstone, and a conventional resin-bonded grindstone.
- FIG. 5 a procedure as shown in FIG. 5 is performed. Specifically, first, as shown in FIGS. 3A and 3B, the shape of the optical element material 25a is made closer to the desired shape of the optical element 25 by using the material 25a. Create a in shape. Next, as shown in FIG. 3 (c), the surface of the shaped material 25b is roughly ground using a rough grinding wheel 26c. Subsequently, as shown in FIG. 3 (d), the surface of the roughly ground material 25 c is finely ground using a fine grinding wheel 26 d. Finally, as shown in FIG. 11E, the surface of the finely ground material 25d is polished to obtain an optical element 25 having a desired processed surface shape.
- the surface roughness is drawn extremely to clarify the change in the surface roughness of the material.
- only one surface of the material 25 a is drawn so as to apply a force, but when the optical element is a lens, the same applies to the other surface.
- an optical element which is the final product, is obtained through a polishing process.However, even if the surface roughness is somewhat large, if the product is within the specification range, fine grinding is required. There is no need to go through a polishing step after the step. Therefore, at the stage after the fine grinding process, it may be an intermediate product or a final product.
- test conditions of the performance test are as follows.
- Abrasive grain size 2 to 4 / im (equivalent to mesh size of 350)
- Abrasive grain size No. 1500 mesh size
- Optical element shape Spherical convex lens with outer diameter of 238 mm and R22Omm
- the whetstone of the second embodiment used in this test was one in which the base was fixed on a base plate with a pitch of 5 mm.
- the area of the entire ground surface is 30% of the area of the abrasive grain forming side surface of the base plate. In the following, the discharge of processing waste is improved.
- the average grinding speed of the grinding wheel of the second embodiment is 28 mZ, which is equivalent to that of a conventional metal grinding wheel for rough grinding. It is far superior to the conventional precision grinding whetstone, resin-bonded whetstone.
- Second The average grinding speed of the grindstone of the present embodiment is equivalent to that of the conventional coarse grinding wheel, though the diameter of the abrasive grains is much smaller than that of the conventional coarse grinding wheel. The reason for this is thought to be that the holding force of the abrasive grains S is extremely high because the paint layer is used as a binder for the abrasive grain layers.
- the surface roughness after grinding was 0.47 ⁇ m for the grindstone of the second embodiment, which was equivalent to that of the conventional precision grinding grindstone, resin bone r stone 4 mm. It is far superior to the metal grinding wheel ⁇ ⁇ , a rough grinding wheel. As described above, the surface roughness after the grinding is the same as that of the grinding wheel of the second embodiment and the resin-bonded grinding wheel of the conventional precision grinding wheel. The time required for polishing in the polishing step is also equivalent to that of the grindstone of the second embodiment and the conventional resin grindstone which is a fine grinding wheel.
- the grinding wheel of the second embodiment has the same average grinding speed as the conventional rough grinding wheel and the excellent metal bond grinding wheel, and the surface roughness and the required polishing time are the conventional fine grinding wheels. It is equivalent to a whetstone.
- different grinding wheels are used for the rough grinding process and the fine grinding process, respectively.
- the rough grinding process and the fine grinding process are performed separately. Even if the grinding wheel is not changed in the fine grinding process, the result is basically the same as that of the conventional technology, that is, the surface roughness and the polishing time can be made equal to those of the conventional technology.
- the conventional technology requires about 5 minutes in the rough grinding process (amount of grinding: 150 ⁇ m ⁇ 28 ⁇ m / min) and 5 minutes in the fine grinding process. In addition to this, it takes several minutes to replace the grinding wheel, and more than 10 minutes to complete the entire grinding process.
- the grinding wheel of the second embodiment since there is no need to change the grinding wheel in the rough grinding process and the fine grinding process, there is no time to replace the grinding wheel, and the rough grinding process and the fine grinding process are not performed.
- the time required for the entire grinding process, including the grinding process, can be reduced to about 5 minutes ( ⁇ grinding amount 1550 ⁇ ⁇ 28 zm Z minutes).
- it takes about 5 minutes to perform the grinding in the fine grinding process because the rough grinding is performed after the target of about 150 m, and then the crack layer on the material surface generated by the rough grinding ( This is because it is necessary to remove the part where the material has changed due to processing strain) by precision grinding.
- the grain size of the abrasive grains contained therein is about the same as or smaller than the grain size of the abrasive grains contained in the grinding wheel for fine grinding. No crack layer is generated as in the case of rough grinding in the conventional technology.
- the time required to expose the grindstone of the second embodiment is broken down into 10 minutes as the time required to process the end face of the base 2 before forming the abrasive grains 5, and the abrasive grains 5 are formed. After finishing, the time for finishing the surface of the abrasive grains 5 is 25 minutes, a total of 35 minutes.
- fluorite (CaF 2 ) having a crystal structure was pressed by using the grindstone of the second embodiment and a resin bond grindstone which is a conventional fine grinding wheel. In this process, the grinding speed and grinding accuracy are required.
- Fluorite which is an optical element material, is known to have difficulty in obtaining a uniformly good surface as the surface to be processed (optical surface) because its processing characteristics depend on the crystal orientation. Therefore, in this test, the fluorite faces 111, 110, and 100 The object whose shape has been created is to be ground so that the surface emerges as a surface perpendicular to the optical axis.
- test conditions of the performance test are as follows.
- Abrasive grain size 1 to 3 ⁇ ⁇ (corresponding to the mesh size of 4000)
- Optical element shape R 5 O mm spherical convex lens with an outer diameter of 39 mm
- the whetstone of the second embodiment used in this test has a base fixed on a base plate with a 3 mm pitch.
- the area of the entire ground surface is 30% of the area of the abrasive grain forming side surface of the base plate. It has been improved to improve the discharge of processing waste.
- Table 3 when grinding the optical element material, the average grinding speed of each grinding wheel, the surface condition of the material, the surface roughness of the material, the required polishing time in the polishing process performed after the grinding process, the surface of the grinding wheel The required time is shown in Table 3 below. Table 3
- the whetstone of the second embodiment is smaller than the whetstone of the conventional resin-bonded whetstone and is smaller than the whetstone of the conventional resin-bonded whetstone. Somewhat better. This is thought to be because, as described in the performance test example 1, the grindstone of the second embodiment has a larger abrasive grain holding force.
- the condition of the surface to be processed after grinding is such that the cloudy surface 28 and the glossy surface 29 have the same crystal orientation in any crystal orientation, as shown in Fig. 6.
- the optical axis was changed. Center as 1 A cloudy surface 28 appears every 20 °, and as shown in Figure (b), if the 110 surface of the fluorite is ground perpendicular to the planned optical axis, Every 180 ° as the center of the optical axis (this cloudy surface 28 appears, and as shown in Figure (c), the 100 surface of the fluorite is perpendicular to the planned optical axis.
- a cloudy surface 28 appears every 90 ° around the optical axis, which tends to appear even if the same grinding is performed many times.
- the opaque surface 28 is formed by the force of forming the above-mentioned black layer on the opaque surface layer.
- the glossy surface was 0.19 ni and the cloudiness surface force was S i. Ll / xm.
- the whetstone of the second embodiment overturns the conventional wisdom that it is difficult to obtain a uniformly good surface as a work surface as described above.
- a glossy surface was obtained on all surfaces to be processed.
- the surface roughness after grinding is 0.13 m, which is superior to conventional resin-bonded grinding wheels.
- the exact reason why the grinding wheel of the second embodiment is superior to the conventional resin-bonded grinding wheel in terms of the surface condition and surface roughness after grinding as described above is as follows. Although it is unknown, it is considered that the force of the grindstone of the second embodiment is not due to smaller abrasive grains and uniform abrasive grain distribution.
- the grinding wheel of the second embodiment is superior in terms of the surface condition and surface roughness after grinding, and the time required for grinding after the grinding process is smaller than that of the conventional resin. 1 when using a bonded whetstone This is 120 minutes of Z4.
- the polishing time is extremely long, at least 480 minutes, because the cracks that make the surface to be processed cloudy It is necessary to remove the layer by polishing.
- the time required to expose the grindstone is 15 minutes for the grindstone of the second embodiment and 60 minutes for the conventional resin-bonded grindstone.
- the grinding performance of the grinding wheel of the second embodiment is basically the same grinding performance can be obtained with the grinding wheel of the first embodiment.
- the grinding wheel pellet 1 on which the grinding layer has been formed is fixed to the base plate 9, and therefore, in the work of grinding the grinding wheel, a hard grinding layer is formed.
- the whetstone of this embodiment has an abrasive grain layer formed by electrolysis instead of electroless plating, and the other basic configuration is the same as that of the second embodiment.
- a plate and a plurality of bases are prepared.
- the material of the base plate and the base must be a conductive material because of performing electroplating.
- iron, stainless steel, aluminum, etc. are preferable. .
- a required number of bases are placed on the side of the base plate where the abrasive grains are formed, and then the base base and the base are interposed between the bases.
- Apply epoxy adhesive That is, an adhesive is not attached to the end surface of the base, and an adhesive is applied to the side peripheral surface of the base, and the base is fixed to the base while ensuring conductivity between the base and the base. It should be noted that the adhesive is not attached to the end face of the base in order to secure conductivity between the base and the plate, and therefore, the adhesive may be applied to a part of the end face of the base. Absent.
- a protrusion or a recess is formed on an end face of the base, and a recess or a protrusion is formed at a position where the base of the plate is to be fixed. Then, the bottom or the recess of the base may be fitted into the recess or the projection of the base plate.
- the end faces of the base are connected to the end faces of all the bases fixed to the base plate in a reverse shape of the desired processing surface, similarly to the second embodiment. Grinding or cutting.
- a negative electrode for electrolytic plating was attached to the back surface of the base plate with the base, and a force was applied to the reverse side of the base plate.
- a pre-treatment for electrolytic plating is performed on an area where the king is not applied, that is, on an end face of the base.
- a positive electrode is put into the electrolytic plating solution, and abrasive grains are mixed.
- the abrasive grains may be diamond powder, cubic boron nitride, or the like, as in the first embodiment.
- the base plate with the base is placed in the electrolytic plating solution containing the abrasive grains, and the positive electrode in the electrolytic plating and the plate are attached to the plate while the electrolytic plating solution is stirred.
- an electrolytic plating layer containing abrasive grains that is, an abrasive grain portion, is formed on the end face of the substrate.
- the plate on which the abrasive grains have been formed is taken out of the electrolytic plating solution, washed with water, and then the masking agent on the back side of the plate is removed. Remove. After the masking agent is removed, the surfaces of the abrasive grains formed on the end faces of the plurality of bases are rubbed with a rubbing plate or the like so as to have a predetermined surface shape. Is completed. As described in the first embodiment, in the electromechanical plating, a large amount of the electrolytic plating layer is deposited on the convex portion and the outer peripheral portion, and the thickness of the plating layer is increased. This is due to the inability to achieve uniformity.
- the abrasive grains are mixed in the plating solution, which is a liquid, the abrasive grains in the deposited plating layer can be uniformly dispersed. . Furthermore, since the plating layer formed by the electrolytic plating method is used as a binder for the abrasive grains, the holding power of the abrasive grains is increased, and the life of the grinding wheel can be extended. You. In addition, since the plating layer, which is a binder, is hard, the surface change of the abrasive layer due to grinding or polishing is small, and the frequency of the work of modifying the ground or polished surface is reduced. And can be.
- this adhesive since an adhesive was applied between the plurality of bases on the side of the base plate where the abrasive grains were formed, this adhesive also functioned as a masking agent. Even without performing the king, it is possible to prevent the formation of the plating layer between the plurality of substrates.
- the grinding performance of the grinding wheel of the present embodiment is basically the same as the grinding performance of the grinding wheel of the second embodiment described above.
- the book As described above the grindstone of the present embodiment is longer than the second embodiment in terms of the time required for exposing the grindstone because the thickness of the abrasive layer cannot be made uniform, as described above. In other words, there is not much difference from the conventional technology.
- the method of manufacturing a grinding wheel has been described.
- the electrolytic plating layer containing the abrasive grains can be used as the abrasive grains. It goes without saying that a grinding wheel pellet can be formed.
- the plate 9b is made of steel and has a disk shape.
- the base 2b is made of stainless steel (SUS304) and has a cylindrical shape. However, the surfaces of the plate 9b and the base 2b are glass beads having a particle size of # 100. Shot processing is applied.
- Examples of the adhesive 12b include EP-1380 (trade name of Semedin Co., Ltd.) and SC 507 used in Example 2.
- a / (Sony Chemicals' product name) is suitable.
- the coating amount of the adhesive 12b is preferably about half the height of the base 2b. After applying the adhesive 12b, a weight is placed on the plurality of substrates 2b to cure the adhesive 12b.
- the base plate 9b with the base was subjected to alkaline degreasing and activation with acid in this order, and then, as shown in FIG.
- a masking film 13b is formed on the back surface of the plate 9b using a masking tape or a coating type masking agent.
- the base plate 9b with the base is subjected to a nickel-free trailer plating 4b.
- a current of about 10 A per 100 cm 2 of surface area is applied for about 2 minutes to form a very thin plating film on the end face 3 b of the base 2 b.
- This electrolytic plating process is a process performed for the purpose of electrochemically activating the stainless steel surface because the material of the base 2b is stainless steel. is there.
- the positive electrode 21 is put into the electrolytic plating solution 16 b, and the abrasive grains 15 are further added.
- a nickel sulphamate solution of PH 4 at 50 ° C. was used as the electrolytic plating solution 16 b, and the abrasive grains 15 were used.
- the base plate 9b with the base is put into the electrolytic plating solution 16b containing the abrasive grains 15 and the electrolytic plating solution 16b is stirred by the stirrer 17.
- an electric current is applied between the positive electrode 21 and the negative electrode 20 attached to the base plate 9b, so that an electrolytic plating layer containing abrasive grains 15, that is, an abrasive, is applied to the end face of the base 2b.
- a grain 5b is formed.
- a current of 5 A is applied for a surface area of 100 cm 2 for about 4 hours to form an abrasive grain portion 5 b having a thickness of 0.24 mm.
- the plate 9b on which the abrasive grains 5b are formed is taken out from the inside of the electrolytic plating solution 16b, washed, and then washed. Remove the masking film 13b on the back side of 9b. Then, as shown in FIG. 8 (e), the surface shape connecting the surfaces of the abrasive grains 5 b formed on the end faces of all the substrates 2 b fixed to the plate 9 b is The surface is rubbed with a sliding plate 19c so that the desired shape of the work surface is inverted, thereby completing the grinding wheel 10b.
- a grinding wheel pellet is formed by using a fixing plate instead of a plate, it is used as an adhesive to be used when the base is temporarily fixed to the fixing plate.
- the turquoise 598-0-1A used in Example 1 (trade name of Fatfin Chemicals, USA) may be used.
- the projection exposure apparatus performs pattern projection on a silicon wafer 30, and includes a light source 31, a condensing lens 32, and an illumination optical system 33. , A projection optical system 34, and a stage 35 on which a silicon antenna 30 is placed. Illumination light A reticle 36 having a pattern corresponding to the processing content of the silicon wafer 30 is appropriately disposed between the scientific system 33 and the projection optical system 34. . And a light source 3 1, in the embodiment of this, Rere Ru extremely A r F lasers for outputting light of a short wavelength, or Is et to be F 2 laser is used for outputting a light of a short wavelength.
- the illumination optical system 33 has the function of equalizing the luminous intensity distribution in the optical path, and the projection optical system 34 forms the image of the reticle 36 on the silicon wafer 30. It has the function of imaging.
- a projection exposure apparatus projects a fine pattern onto a silicon wafer 30, and as described above, uses a light having a shorter wavelength to form a reticle 36. No ,. There is a need to project turns. Therefore, in the present embodiment, in order to cope with light having a short wavelength, various lenses in the focusing lens 32, the illumination optical system 33, and various lenses in the projection optical system 34 are used. All lenses use quartz and fluorite as lens materials.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Polishing Bodies And Polishing Tools (AREA)
- Grinding And Polishing Of Tertiary Curved Surfaces And Surfaces With Complex Shapes (AREA)
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02729571A EP1369201B1 (en) | 2001-01-16 | 2002-01-15 | Grinding stone pellet, grinding stone, and method of producing them, and method of producing optical elements using grinding stone and method of producing projection aligners |
JP2002555978A JP3956048B2 (ja) | 2001-01-16 | 2002-01-15 | 砥石ペレット、砥石、これらの製造方法、砥石を用いた光学素子の製造方法、及び投影露光装置の製造方法 |
DE60222100T DE60222100T2 (de) | 2001-01-16 | 2002-01-15 | "schleifsteinkorn, schleifstein und verfahren zu ihrer herstellung sowie verfahren zur herstellung optischer elemente unter verwendung des schleifsteins und verfahren zur herstellung von projektionsausrichtern" |
US10/618,706 US6933018B2 (en) | 2001-01-16 | 2003-07-15 | Processes for producing a whetstone and whetstone pellets with uniform abrasion layers |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001007794 | 2001-01-16 | ||
JP2001-7794 | 2001-01-16 | ||
JP2001200383 | 2001-07-02 | ||
JP2001-200383 | 2001-07-02 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/618,706 Continuation US6933018B2 (en) | 2001-01-16 | 2003-07-15 | Processes for producing a whetstone and whetstone pellets with uniform abrasion layers |
Publications (1)
Publication Number | Publication Date |
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WO2002055264A1 true WO2002055264A1 (fr) | 2002-07-18 |
Family
ID=26607768
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2002/000180 WO2002055264A1 (fr) | 2001-01-16 | 2002-01-15 | Pastille de meule, meule, et leurs procedes de production, procede de production d'elements optiques a l'aide la meule et procede de production d'aligneurs de projection |
Country Status (5)
Country | Link |
---|---|
US (2) | US6933018B2 (ja) |
EP (3) | EP1618994B1 (ja) |
JP (1) | JP3956048B2 (ja) |
DE (2) | DE60236766D1 (ja) |
WO (1) | WO2002055264A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6933018B2 (en) | 2001-01-16 | 2005-08-23 | Nikon Corporation | Processes for producing a whetstone and whetstone pellets with uniform abrasion layers |
JP2011235424A (ja) * | 2010-05-13 | 2011-11-24 | Haruchika Seimitsu:Kk | ダイヤモンド皿型砥石および球面レンズの研削方法 |
CN110744390A (zh) * | 2019-10-25 | 2020-02-04 | 天津津航技术物理研究所 | 高精度锥台平面结构类光学元件抛光工艺和抛光装置 |
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DE102009053954A1 (de) * | 2009-11-19 | 2011-06-09 | Siemens Aktiengesellschaft | Labyrinthdichtung und Verfahren zum Herstellen einer Labyrinthdichtung |
KR20150004931A (ko) * | 2012-06-15 | 2015-01-13 | 가부시키가이샤 토쿄 세이미쯔 | 다이싱 장치 및 다이싱 방법 |
JP5988898B2 (ja) * | 2013-03-06 | 2016-09-07 | オリンパス株式会社 | 砥石及びその製造方法 |
EP3200954B1 (en) * | 2014-10-03 | 2020-12-09 | Zeeko Innovations Limited | Tool and method for shaping and finishing a workpiece |
USD763932S1 (en) * | 2014-12-04 | 2016-08-16 | Georgi M Popov | Grinding tool |
JP6378626B2 (ja) * | 2014-12-17 | 2018-08-22 | オリンパス株式会社 | 光学素子の加工用工具および光学素子の製造方法 |
GB2557952B (en) * | 2016-12-16 | 2022-06-15 | Zeeko Innovations Ltd | Methods and apparatus for shaping workpieces |
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JP2011235424A (ja) * | 2010-05-13 | 2011-11-24 | Haruchika Seimitsu:Kk | ダイヤモンド皿型砥石および球面レンズの研削方法 |
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Also Published As
Publication number | Publication date |
---|---|
DE60222100T2 (de) | 2008-05-21 |
JPWO2002055264A1 (ja) | 2004-05-13 |
US20050191415A1 (en) | 2005-09-01 |
EP1618994B1 (en) | 2010-06-16 |
US7220168B2 (en) | 2007-05-22 |
JP3956048B2 (ja) | 2007-08-08 |
EP1369201A1 (en) | 2003-12-10 |
EP1369201B1 (en) | 2007-08-29 |
US6933018B2 (en) | 2005-08-23 |
DE60236766D1 (de) | 2010-07-29 |
DE60222100D1 (de) | 2007-10-11 |
EP1618994A1 (en) | 2006-01-25 |
US20040058062A1 (en) | 2004-03-25 |
EP1616666A1 (en) | 2006-01-18 |
EP1369201A4 (en) | 2004-11-03 |
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