WO2015040796A1 - 耐熱ロール、その製造方法及びこれを使用した板ガラスの製造方法 - Google Patents
耐熱ロール、その製造方法及びこれを使用した板ガラスの製造方法 Download PDFInfo
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- WO2015040796A1 WO2015040796A1 PCT/JP2014/004331 JP2014004331W WO2015040796A1 WO 2015040796 A1 WO2015040796 A1 WO 2015040796A1 JP 2014004331 W JP2014004331 W JP 2014004331W WO 2015040796 A1 WO2015040796 A1 WO 2015040796A1
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- Prior art keywords
- roll
- heat
- clay
- resistant
- producing
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 55
- 239000005357 flat glass Substances 0.000 title claims description 21
- 239000004927 clay Substances 0.000 claims abstract description 46
- 239000002734 clay mineral Substances 0.000 claims abstract description 44
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 23
- 238000000227 grinding Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims description 70
- 238000004381 surface treatment Methods 0.000 claims description 52
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 19
- 239000011707 mineral Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 238000003825 pressing Methods 0.000 claims description 12
- 239000000440 bentonite Substances 0.000 claims description 10
- 229910000278 bentonite Inorganic materials 0.000 claims description 10
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 10
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 238000009499 grossing Methods 0.000 claims description 7
- 239000005995 Aluminium silicate Substances 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 230000008961 swelling Effects 0.000 claims description 5
- 238000012545 processing Methods 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 22
- 238000010304 firing Methods 0.000 description 21
- 239000012784 inorganic fiber Substances 0.000 description 20
- 239000000835 fiber Substances 0.000 description 14
- 239000011521 glass Substances 0.000 description 13
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- 238000001035 drying Methods 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
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- 230000008569 process Effects 0.000 description 7
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
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- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- 230000001680 brushing effect Effects 0.000 description 2
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- 238000006297 dehydration reaction Methods 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
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- 239000011490 mineral wool Substances 0.000 description 1
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- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B35/00—Transporting of glass products during their manufacture, e.g. hot glass lenses, prisms
- C03B35/14—Transporting hot glass sheets or ribbons, e.g. by heat-resistant conveyor belts or bands
- C03B35/16—Transporting hot glass sheets or ribbons, e.g. by heat-resistant conveyor belts or bands by roller conveyors
- C03B35/18—Construction of the conveyor rollers ; Materials, coatings or coverings thereof
- C03B35/181—Materials, coatings, loose coverings or sleeves thereof
-
- 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
- B24B7/00—Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor
- B24B7/20—Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor characterised by a special design with respect to properties of the material of non-metallic articles to be ground
- B24B7/22—Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor characterised by a special design with respect to properties of the material of non-metallic articles to be ground for grinding inorganic material, e.g. stone, ceramics, porcelain
- B24B7/24—Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor characterised by a special design with respect to properties of the material of non-metallic articles to be ground for grinding inorganic material, e.g. stone, ceramics, porcelain for grinding or polishing glass
- B24B7/241—Methods
-
- 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
- B24B7/00—Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor
- B24B7/20—Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor characterised by a special design with respect to properties of the material of non-metallic articles to be ground
- B24B7/22—Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor characterised by a special design with respect to properties of the material of non-metallic articles to be ground for grinding inorganic material, e.g. stone, ceramics, porcelain
- B24B7/24—Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor characterised by a special design with respect to properties of the material of non-metallic articles to be ground for grinding inorganic material, e.g. stone, ceramics, porcelain for grinding or polishing glass
- B24B7/242—Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor characterised by a special design with respect to properties of the material of non-metallic articles to be ground for grinding inorganic material, e.g. stone, ceramics, porcelain for grinding or polishing glass for plate glass
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
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- C04B33/36—Reinforced clay-wares
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
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- C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5037—Clay, Kaolin
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
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- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
- F16C13/00—Rolls, drums, discs, or the like; Bearings or mountings therefor
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- C—CHEMISTRY; METALLURGY
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
- C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
- C04B2235/3472—Alkali metal alumino-silicates other than clay, e.g. spodumene, alkali feldspars such as albite or orthoclase, micas such as muscovite, zeolites such as natrolite
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
- C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
- C04B2235/3481—Alkaline earth metal alumino-silicates other than clay, e.g. cordierite, beryl, micas such as margarite, plagioclase feldspars such as anorthite, zeolites such as chabazite
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
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- C—CHEMISTRY; METALLURGY
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5208—Fibers
- C04B2235/5216—Inorganic
- C04B2235/522—Oxidic
- C04B2235/5228—Silica and alumina, including aluminosilicates, e.g. mullite
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/94—Products characterised by their shape
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/963—Surface properties, e.g. surface roughness
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49544—Roller making
- Y10T29/4956—Fabricating and shaping roller work contacting surface element
- Y10T29/49563—Fabricating and shaping roller work contacting surface element with coating or casting about a core
Definitions
- the present invention relates to a heat-resistant roll, a method for producing the heat-resistant roll, and a method for producing a plate glass using the heat-resistant roll, and particularly relates to an improvement in heat-resistant roll characteristics such as low dust generation.
- a heat-resistant roll provided with a roll part is used to convey a molten glass ribbon.
- a heat-resistant roll provided with a roll part is used to convey a molten glass ribbon.
- it is necessary to reduce as much as possible the undesirable effect of the heat-resistant roll on the glass ribbon.
- Patent Documents 1 to 3 propose to grind the surface of the roll portion for finishing the heat-resistant roll. Further, Patent Document 4 describes that the surface is ground and then smoothed with water.
- JP 2004-299980 A JP 2007-269604 A JP 2005-520774 A JP 2010-095437 A
- This invention was made in view of the said subject, Comprising: To provide the heat-resistant roll by which the dust generation property from the surface of a roll part was reduced, its manufacturing method, and the manufacturing method of plate glass using this One of its purposes.
- a roll part production step for producing a roll part containing 5% by weight or more of a clay mineral for producing a roll part containing 5% by weight or more of a clay mineral
- a grinding step of grinding the roll surface of the roll part for grinding the roll surface of the roll part
- a surface treatment step of performing a surface treatment to smooth the ground roll surface in a wet state for performing a surface treatment to smooth the ground roll surface in a wet state
- a clay coating step of forming a clay-based mineral coating on the surface-treated roll surface A method for producing a heat-resistant roll.
- a roll part production step for producing a roll part containing 5% by weight or more of a clay mineral for producing a roll part containing 5% by weight or more of a clay mineral;
- the surface treatment smoothing in the wet state of the surface treatment step the first step of moistening the ground roll surface, and then the second step of smoothing the wet roll surface,
- the surface treatment step the surface treatment is performed by pressing a wet base material against the roll surface of the rotating roll unit.
- a heat-resistant roll in which a surface part of a roll part containing 5% by weight or more of a clay mineral is coated with a clay mineral. 11.
- the heat-resistant roll according to 10 wherein a surface portion of the roll portion is densified as compared to the inside of the roll portion.
- a heat-resistant roll produced by the method according to any one of 12.1 to 9. 13 The heat-resistant roll according to any one of 10 to 12, wherein the amount of the clay mineral coating is 0.1 g or more in terms of solid content per 1 m 2 of the average surface area. 14.
- the present invention it is possible to provide a heat-resistant roll having reduced dust generation from the surface of the roll part, a method for producing the heat-resistant roll, and a method for producing a plate glass using the heat-resistant roll.
- FIG. 1 shows an example of a disk roll 1.
- the disk roll 1 includes a cylindrical roll portion 10 extending in the longitudinal direction.
- the roll part 10 is configured by laminating a plurality of disk members 11 containing 5% by weight or more of clay mineral (hereinafter also simply referred to as clay) in the longitudinal direction of the roll part 10. That is, the plurality of disk members 11 constituting the roll unit 10 are fitted and inserted into the shaft unit 20 that serves as the rotation axis of the disk roll 1.
- the surface of the roll unit 10 is further coated with a clay mineral.
- the clay mineral that is formed by uniformly dispersing the entire roll unit 10 and the clay mineral that covers the surface may be the same or different.
- the plurality of stacked disk members 11 are fixed in a compressed state in the longitudinal direction of the shaft portion 20 by flanges 21 and nuts 22 respectively provided at both end portions of the shaft portion 20. Therefore, the surface of the roll unit 10 (hereinafter referred to as “roll surface 12”) is constituted by the outer peripheral surfaces of the plurality of disk members 11 stacked in a compressed state.
- the structure of the disk roll is not limited to the structure in which the entire shaft is covered with a disk material as shown in FIG. 1.
- the structure in which the shaft is covered with the disk material only at the portion where the glass contacts There are specifications with a single shaft and those with a removable disk part.
- This disc roll 1 can be used as a transport roll in the production of plate glass.
- FIG. 2 an example of the disk roll 1 used as a conveyance roll in manufacture of plate glass is shown.
- a pair of disk rolls 1 arranged in parallel are installed so as to be rotatable around a shaft portion 20.
- the disk roll 1 may be connected to a power generation device (not shown). In this case, the disk roll 1 can rotate based on the power generated by the power generation device.
- the glass ribbon 30 sent in a melted state from the upstream side of the transport path is transported to the downstream side while being sandwiched between the pair of rotating roll portions 10. That is, in the example shown in FIG. 2, the glass ribbon 30 is conveyed vertically downward (the direction indicated by the arrow D shown in FIG. 2).
- the flat glass can be produced by a float method, a roll-out method, a Colburn method, etc. in addition to the above-described downdraw method.
- the glass ribbon 30 is gradually cooled by being conveyed by the disc roll 1. Although only a pair of disk rolls 1 is shown in FIG. 2, two or more pairs of disk rolls 1 can be installed along the conveyance path.
- the disc roll 1 can also be used as a pulling roll that applies tension to the glass ribbon 30 in order to adjust the nominal thickness of the plate glass to be produced.
- the nominal plate thickness of the plate glass to be manufactured can be adjusted by the pulling speed of the glass ribbon 30 by the pulling roll.
- the roll surface 12 in contact with the glass ribbon 30 is in contact with the heat resistance to withstand a high temperature above the melting temperature of the glass, the spalling resistance for taking out the roll immediately in case of line trouble, etc. It is desirable to have characteristics such as flexibility that does not damage the glass ribbon 30, durability that can withstand high temperatures for a long time, and low dust generation that does not contaminate the glass ribbon 30.
- the heat-resistant roll of the present invention refers to a roll having a heat shrinkage of 1% or less as measured by the method described in Examples.
- the disk roll 1 having such excellent characteristics and a manufacturing method thereof (hereinafter referred to as “the present manufacturing method”) will be described.
- the disk roll 1 is first assembled using a plurality of disk materials 11.
- a aqueous slurry is prepared, and a plate-like body (so-called millboard) having a predetermined thickness is manufactured from the aqueous slurry.
- the aqueous slurry is prepared with a composition corresponding to the composition that the disk material 11 to be finally produced should have. That is, for example, this aqueous slurry contains an amount of clay mineral necessary to achieve a content of 5 wt% or more in the disk material 11 mounted on the disk roll 1.
- the clay mineral those having the characteristic of being sintered by heating can be preferably used.
- One type can be used alone or two or more types can be used in combination.
- refractory clay such as Kibushi clay and Sasame clay, bentonite and kaolin can be used, and the refractory clay can be preferably used.
- Kibushi clay is preferable because it has a high binder effect by sintering and has few impurities.
- the aqueous slurry can further contain inorganic fibers and fillers.
- the inorganic fiber is not particularly limited as long as it is a reinforcing material that enhances the strength of the disk material 11, and any kind of inorganic fiber can be appropriately selected and used. One kind can be used alone, or two or more kinds can be used in combination. Can be used.
- artificial inorganic fibers such as ceramic fibers, glass fibers, and rock wool fibers can be preferably used. More specifically, for example, alumina fibers, mullite fibers, silica / alumina fibers, and silica fibers excellent in heat resistance can be particularly preferably used.
- the filler is not particularly limited as long as it contributes to improvement in characteristics such as heat resistance and strength of the disk material 11, and any kind of filler can be appropriately selected and used. More than one type can be used in combination. That is, for example, inorganic fillers such as mica, wollastonite, sepiolite, silica, alumina, cordierite, and calcined kaolin can be used. Mica can be preferably used. Moreover, scaly silica and scaly alumina can be used, and scaly silica is particularly preferred because of its high wear resistance.
- inorganic fillers such as mica, wollastonite, sepiolite, silica, alumina, cordierite, and calcined kaolin can be used. Mica can be preferably used.
- scaly silica and scaly alumina can be used, and scaly silica is particularly preferred because of its high wear resistance.
- the scaly silica is preferably a secondary aggregate formed by overlapping the scaly silica in parallel, or a tertiary aggregate formed by collecting a plurality of the secondary aggregates.
- flake primary particles of scaly silica are leaf-like silica secondary particles formed by overlapping a plurality of sheets, with the planes oriented in parallel with each other.
- the leaf-like silica secondary particles may be further three-dimensionally aggregated to form tertiary particles.
- the leaf-like silica secondary particles and tertiary particles are described in JP-A-2006-143666, Patent Publication 3795671 and the like.
- the aqueous slurry can further contain an auxiliary agent for improving the properties such as moldability.
- an auxiliary agent for example, an organic material or an inorganic material that can be eliminated from the disk material 11 by firing the disk material 11 can be used.
- an organic material an organic binder such as pulp, starch, synthetic resin fibers or particles can be used.
- a millboard can be produced by forming an aqueous slurry prepared as a mixture of such raw materials into a plate shape and drying it.
- the forming of the millboard can be preferably performed by a papermaking method using a papermaking machine.
- the thickness of the mill board can be set to a desired value corresponding to the thickness of the disk material 11, and can be set in the range of 2 to 30 mm, for example.
- the disk material 11 can be obtained by firing a disk punched from a millboard, or can be a disk itself obtained by punching a millboard without firing.
- the roll unit 10 including the plurality of disk materials 11 can also be fired.
- the said roll part 10 can also be baked.
- the firing conditions are not particularly limited, and can be appropriately changed according to the specifications of the firing furnace, the bulk density and size of the disk material 11, and the like.
- the firing temperature is not particularly limited, but can be, for example, in the range of 300 to 1000 ° C., preferably in the range of 400 to 900 ° C., and more preferably in the range of 500 to 800 ° C. it can.
- the firing time is not particularly limited, but can be, for example, in the range of 1 to 24 hours.
- assistant such as the organic material contained in the mill board, can be lose
- a disk material 11 made of a sintered inorganic material is obtained. Further, in the disc material 11 after firing, voids derived from the burning of some of the materials accompanying the firing are formed.
- the disk material 11 can be manufactured by molding. That is, the disk material 11 can be manufactured, for example, by pouring a slurry prepared as a mixture of raw materials as described above into a mold having a predetermined shape corresponding to the shape of the disk material 11 and performing suction dehydration molding. it can. Moreover, the disk material 11 containing the said clay-type mineral can also be manufactured by impregnating the surface of the molded disk with a clay slurry and drying it.
- the molded disc material 11 can also be fired. Firing conditions such as the firing method, firing time, firing temperature, firing time are the same as described above.
- the disc material 11 thus obtained contains 5% by weight or more of a clay mineral.
- the content of the clay mineral is preferably 10% by weight or more, and more preferably 15% by weight or more.
- the upper limit of the content of the clay mineral can be appropriately set according to the characteristics required for the disk roll 1. That is, the content of the clay mineral is preferably 50% by weight or less, and more preferably 45% by weight or less. When the content of the clay mineral is large, problems such as generation of cracks, formation of cracks, and separation of a plurality of disk members 11 are likely to occur in the roll unit 10, and the disk roll 1 cannot sufficiently exhibit its performance. There is.
- the content of the clay mineral in the disk material 11 can be, for example, in the range of 5 to 50% by weight, preferably in the range of 10 to 30% by weight, and in the range of 10 to 43% by weight. More preferably.
- clay minerals kibushi clay and bentonite are preferably included. Each of these contents is preferably 5 to 30% by weight, more preferably 7 to 25% by weight, and still more preferably 8 to 23% by weight.
- the amount of the inorganic fiber and filler contained in the disk material 11 can be appropriately set according to the types of these materials and the characteristics required for the disk roll 1. That is, the content of inorganic fiber is, for example, preferably 20 to 50% by weight, more preferably 25 to 45% by weight, and further preferably 30 to 43% by weight.
- the filler content is preferably in the range of 5 to 50% by weight, more preferably in the range of 7 to 40% by weight, and more preferably in the range of 10 to 35% by weight. preferable.
- Clay-based minerals, inorganic fibers, fillers and organic binders can occupy 90% or more, 95% or more, 98% or more, or 100% of the disc roll.
- the plurality of disc members 11 manufactured in this way are sequentially fitted into the shaft portion 20. Further, the plurality of disk members 11 stacked along the shaft portion 20 are tightened in the longitudinal direction of the shaft portion 20 by a hydraulic press or the like. The plurality of disk members 11 in a compressed state are sandwiched by a pair of flanges 21 provided at both end portions of the shaft portion 20, and further fixed by a pair of nuts 22. In addition, after inserting the several disc material 11 in the axial part 20, these can also be fixed with the flange 21 and the nut 22 without compressing.
- the disk roll 1 including the roll unit 10 composed of a plurality of stacked disk members 11 can be assembled.
- the roll unit 10 can be hardened and densified as compared to the respective disk members 11 before assembly.
- the roll part 10 is not restricted to what has the several disk material 11 laminated
- Such a cylindrical molded body can be manufactured by, for example, molding using a raw material mainly composed of the inorganic material as described above.
- the roll unit 10 is a cylindrical molded body by pouring the slurry prepared as a mixture of raw materials as described above into a mold having a predetermined shape corresponding to the shape of the roll unit 10 and performing suction dehydration molding.
- a clay mineral may be previously contained in the slurry before molding.
- the roll part 10 containing the said clay type mineral can also be manufactured by impregnating the surface of the molded cylindrical molded body with a clay slurry and drying it.
- the roll part 10 can also be made into the inorganic fiber molded object containing a clay-type mineral between fibers. That is, the roll part 10 can be formed by, for example, winding a sheet-like inorganic fiber molded body containing a clay mineral between fibers around the shaft part 20 once or a plurality of times.
- the roll unit 10 can be manufactured, for example, by impregnating a clay slurry into an inorganic fiber molded body.
- the roll part 10 can be manufactured by impregnating an inorganic fiber paper with clay slurry and then winding the inorganic fiber paper around the shaft part 20.
- the inorganic fiber paper containing the said clay mineral can be manufactured by making the slurry containing a clay mineral, and the roll part 10 can also be manufactured then using the said inorganic fiber paper.
- the roll part 10 can also be manufactured by winding an inorganic fiber blanket around the shaft part 20 and then impregnating the inorganic fiber blanket with a clay slurry and drying it.
- cylindrical molded bodies and inorganic fiber molded bodies can also be fired.
- the said roll part 10 after assembling the heat-resistant roll provided with the roll part 10 which has the above several disc materials 11, a cylindrical molded object, or an inorganic fiber molded object, the said roll part 10 can also be baked.
- the firing conditions are not particularly limited, and can be appropriately changed according to the specifications of the firing furnace, the conditions such as the bulk density and size of the cylindrical molded body and the inorganic fiber molded body.
- the firing temperature and firing time are the same as described above.
- FIG. 3 shows the main steps included in the first embodiment of the manufacturing method. At the right end, the outline of the surface is shown.
- the roll surface 12 of the disc roll 1 assembled in the assembly step is ground. That is, by removing a part of the roll surface 12 in a dry state, the roll surface 12 is smoothed and the diameter of the roll part 10 is adjusted. For example, as shown in FIG. 1, the diameter of the roll part 10 in the longitudinal direction can be adjusted to be constant.
- the grinding step S10 includes a cutting step S12 and a polishing step S14.
- a cutting device such as a lathe
- fine irregularities still remain on the surface.
- the roll surface 12 is further polished and flattened by a polishing tool such as sandpaper (polishing step S14).
- polishing step S14 fine particles generated by polishing enter the recess.
- the grinding and polishing may be performed in one step without separating the grinding step S10 from the cutting step S12 and the polishing step S14, or one of them may be omitted depending on the surface state.
- a surface treatment is performed in which the roll surface 12 ground in the grinding step S10 is wetted.
- water is applied to the dried roll surface 12 after grinding (water application step S22).
- water is used in the present embodiment, it is not particularly limited as long as it is a liquid that does not contain a solute and can be impregnated into the roll surface 12, and any type can be appropriately selected and used. Can be used alone or in combination of two or more. That is, for example, polar solvents such as water, ethanol, and acetone can be preferably used. Among them, water is particularly preferably used because it is easy to handle and can effectively plasticize the clay mineral. Moreover, it is not restricted to application
- the roll surface 12 can be plasticized by wetting. That is, the fine particles constituting the roll surface 12 are hardened and strongly constrained in the dry state, but soften in the wet state and become relatively easy to deform and move.
- an external force is further applied to the wet roll surface 12 to smooth the roll surface 12 (a smoothing step S24). That is, for example, the wet roll surface 12 is rubbed to apply a shearing force in a direction along the roll surface 12.
- the fine particles constituting the convex portion of the roll surface 12 are moved along the roll surface 12 and embedded in the concave portion of the roll surface 12, thereby 12 can be smoothed.
- the fine particles constituting the roll surface 12 can be filled more densely. That is, since the fine particles can move while being shifted from each other on the wet roll surface 12, the fine particles can be rearranged and refilled so as to be in a more uniform dispersed state under a load of an appropriate pressing force. As a result, the roll surface 12 can be densified.
- water application step S22 and the leveling step S24 may be performed while rotating the roll unit 10.
- the surface treatment step S20 may be performed in one step of simultaneously moistening with water without being separated from the water application step S22 and the leveling step S24.
- FIG. 4 shows an example of a preferred embodiment for realizing the surface treatment described above.
- FIG. 4 shows a cross section of the roll part 10 cut along the line IV-IV in the disk roll 1 shown in FIG. 1 and a cross section of the base material 40 used for the surface treatment on the roll part 10.
- the above-described surface treatment is performed by pressing the substrate 40 against the rotating roll surface 12. That is, the roll unit 10 is first rotated in the direction indicated by the arrow R shown in FIG.
- the base material 40 is pressed against the rotating roll surface 12, and the state is maintained. At this time, as shown in FIG. 4, the base material 40 is preferably disposed along the roll surface 12.
- FIG. 4 shows only the state in which the base material 40 is disposed along the circumferential direction of the roll surface 12, but the base material 40 is also along the longitudinal direction of the roll surface 12. Can be arranged. Thus, the roll surface 12 is rotated while being in contact with the base material 40.
- a sheet-like substrate 40 can be preferably used.
- maintained the liquid contact the roll surface 12 can be used.
- the leveling step S24 by rotating the roll unit 10 while placing the base material 40 along the circumferential direction of the roll surface 12 by pressing the sheet-like base material 40 against the wet roll surface 12, The roll surface 12 is leveled.
- a sheet-like base material 40 in which irregularities for polishing are formed on the surface that contacts the roll surface 12, such as sandpaper, can be preferably used.
- the base material 40 having such a polishing ability movement and refilling of the fine particles constituting the roll surface 12 can be realized as described above.
- a base material 40 having flexibility that can be arranged along the roll surface 12 can be preferably used.
- a sheet-like fiber substrate such as a woven fabric or a non-woven fabric, or a sheet-like porous substrate made of a synthetic polymer having flexibility (for example, a foam-molded product) can be preferably used.
- the sheet-like base material 40 for example, sandpaper in which the unevenness
- the surface treatment is performed on the roll surface 12 of the roll unit 10 that rotates in one circumferential direction, and the surface treatment is performed by switching the rotation direction of the roll unit 10 to the opposite direction. Iterative processing can be performed once or more.
- a surface treatment is performed in which the roll surface 12 is wetted while rotating the roll portion 10 in one circumferential direction (for example, the direction indicated by the arrow R shown in FIG. 4).
- this surface treatment may be carried out in two stages: first moistening and then smoothing.
- the rotation direction of the roll unit 10 is switched to the opposite direction, and the treatment is repeated. That is, in the repetitive processing, a surface treatment is performed in which the roll surface 12 is wetted while rotating the roll portion 10 in the other circumferential direction (for example, the direction opposite to the direction indicated by the arrow R shown in FIG. 4). Do.
- the second repetitive treatment is performed by switching the rotation direction of the roll unit 10 to the opposite direction again without drying the roll surface 12 after the first repetitive treatment. I do. That is, in the second repeated treatment, a surface treatment is performed in which the roll surface 12 is wetted while the roll portion 10 is rotated again in the circumferential direction.
- the surface treatment in the repetitive treatment may also be performed in two stages as described above.
- the pressing force applied to the roll surface 12 for leveling the roll surface 12 is not particularly limited, and is arbitrarily set within a range where the above-described smoothing and densification of the roll surface 12 can be achieved. be able to.
- a pressing force in the range of 100 to 2000 N per unit length (1 mm) in the width direction (longitudinal direction of the shaft portion 20) of the substrate 40 (that is, a pressing force in the range of 100 to 2000 N / mm). Can be loaded.
- the speed at which the roll surface 12 is rotated when the roll surface 12 is leveled is not particularly limited, and is arbitrarily set within a range in which the roll surface 12 can be smoothed and densified as described above. can do.
- the rotation speed of the roll unit 10 can be set in the range of 10 to 1500 rpm, for example. Further, the peripheral speed of the roll surface 12 can be set, for example, in the range of 1 to 1000 m / min.
- the roll surface 12 is smoothed using a previously wetted base material, and the surface treatment is performed.
- a fiber base material or a porous base material that can hold a liquid such as water can be used.
- a water-containing fiber base material or porous base material made of a hydrophilic material can be preferably used.
- the wet base material 40 covers a part of the roll surface 12.
- the roll surface 12 can be efficiently moistened, and the once wet roll surface 12 can be effectively prevented from drying again.
- clay water is applied to the roll surface 12 subjected to the surface treatment (clay water application step S32). Then, it dries (drying process S34). Drying may be natural drying, but a dryer can also be used. By doing so, a clay mineral film is formed, and unevenness that cannot be sufficiently flattened only by the surface treatment step S20 can be flattened. As a result, dust generation is suppressed.
- the clay mineral those having a swelling power of 15 ml / 2 g or more can be used, preferably those having 20 ml / 2 g or more, more preferably those having 30 ml / 2 g or more.
- refractory clay such as Kibushi clay and Sasame clay, bentonite and kaolin can be used.
- the swelling force may be measured according to the Japan Bentonite Industry Association standard test method (JBAS-104-77). Specifically, the measurement may be performed as follows. Weigh accurately 2 g of sample and add to a 100 ml stoppered graduated cylinder containing 100 ml of purified water. At this time, care should be taken that the added sample does not adhere to the inner wall.
- the sample is added in several times so that the sample is sufficiently absorbed and dispersed, and the next sample is added after most of the previously added sample has settled.
- the cap is closed, and after standing for 24 hours, the volume A (ml) deposited at the bottom of the graduated cylinder is read.
- the value read is the swelling power (ml / 2g).
- clay water used for coating for example, 1 to 1000 g of clay mineral dissolved or dispersed in 10 L of water can be used.
- water is used in the present embodiment, any type can be appropriately selected and used as long as it can appropriately dissolve or disperse the clay mineral, and one type can be used alone. Alternatively, two or more types can be used in combination. From the viewpoint of ease of handling, water is preferred.
- the amount to be coated is preferably an average film thickness of about 0.01 mm to 5 mm, and can be further increased.
- the solid content per 1 m 2 of the average surface area is about 0.1 to 1000 g, preferably 0.1 to 100 g, more preferably 0.3 to 50 g.
- the coating may not cover the entire surface. Preferably it is 80% or more, More preferably, it is 90% or more, Most preferably, it is 100%.
- the clay mineral liquid is deposited on the roll surface 12 by, for example, spraying, dipping, brushing, or dropping.
- FIG. 5 shows main steps included in the second embodiment of the present invention. At the right end, the outline of the surface is shown.
- the clay-containing water used in the first embodiment is applied (surface treatment step S40).
- surface treatment step S40 since grinding process S10 is the same as 1st Embodiment, description is abbreviate
- clay-containing water is applied (clay water application step S42) and then dried (leveling step S44, drying step S46), and then a clay mineral film is applied as in the first embodiment. Form.
- a shearing force is applied to the wet roll surface 12 in the direction along the surface 12, and a part of the fine particles constituting the roll surface 12 are applied to the roll surface 12. It moves along, and the unevenness
- clay minerals contained in the clay water also enter and fill the recesses on the surface 12, and further form a clay film on the surface. Therefore, unevenness that cannot be sufficiently flattened only by the surface treatment step S20 with only water as in the first embodiment can be flattened. As a result, dust generation is suppressed.
- the roll surface 12 is densified as compared to the inside 13 of the roll unit 10. That is, in the roll part 10, the surface part of predetermined thickness including the outer surface of the said roll part 10 and its vicinity part is locally densified.
- the thickness may be increased by further forming a clay-based mineral film (performing the clay film coating step S30) as in the first embodiment.
- the surface 12 of the heat-resistant roll of the present invention is smoothed with dust generation suppressed.
- the strength is high because of the coating of clay mineral.
- the arithmetic average roughness Ra of the roll surface 12 measured by the method specified in JIS B 0601-1994 can be 5.0 ⁇ m or less, more preferably 3.0 ⁇ m or less, and 1.0 ⁇ m or less. It is particularly preferred that
- the maximum height Ry of the roll surface 12 measured by the method specified in JIS B 0601-1994 can be 25.0 ⁇ m or less, more preferably 15.0 ⁇ m or less, and 10.0 ⁇ m. It is particularly preferred that
- the ten-point average roughness Rz of the roll surface 12 measured by the method defined in JIS B 0601-1994 can be 25.0 ⁇ m or less, more preferably 15.0 ⁇ m or less. It is particularly preferable that the thickness is 0.0 ⁇ m or less.
- the roll surface 12 preferably has at least one of the arithmetic average roughness Ra, the maximum height Ry, and the ten-point average roughness Rz within the above range, and particularly preferably all the three are within the above ranges. preferable.
- the roll part 10 of the heat-resistant roll obtained in the present invention can maintain the same characteristics such as heat resistance before and after the above surface finishing.
- Example 1 and Comparative Example 1 A disk material having an outer diameter of 60 mm and an inner diameter of 20 mm is punched from the disk roll base material, and roll-built to a length of 100 mm and a packing density of 1.35 g / cm 3 on a stainless steel shaft having a diameter of 20 mm, as shown in FIG. A disc roll 1 was prepared.
- This disc material 11 contained 10% by weight of xylem clay as clay mineral, 10% by weight bentonite, 40% by weight mullite fiber as inorganic fiber, and 32% by weight mica as filler.
- the disk roll substrate contained 6% by weight of pulp and 2% by weight of organic binder as auxiliary agents.
- the assembled disc roll 1 was fired.
- the pulp and organic binder contained in the disk material 11 were burned off by this firing.
- the roll surface 12 of the disk roll 1 was ground. Grinding was performed by placing the disk roll 1 in a predetermined drive device, rotating the shaft 20 around the shaft 20, and bringing sandpaper into contact with the rotating roll surface 12.
- the rotating roll surface 12 is pressed with dust-free paper (Kimwipe, Nippon Paper Crecia Co., Ltd.) previously impregnated with water and held for a predetermined time, thereby holding the roll surface.
- a surface treatment was performed in which 12 was moistened.
- the roll surface 12 after the surface treatment was heated and dried.
- a bentonite aqueous solution was applied to the roll surface 12 subjected to the above surface treatment by spraying and brushing to carry out a coating treatment.
- the bentonite aqueous solution was prepared by dissolving 50 g of bentonite in 10 L of water. Thereafter, the roll surface 12 was naturally dried to produce the disc roll 1.
- Comparative Example 1 a disk roll that was subjected to the surface treatment but not subjected to the coating treatment was prepared. The following characteristics were evaluated for each of the disk roll 1 and the disk roll that was not subjected to coating treatment. The results are shown in Table 1.
- a disk material having an outer diameter of 80 mm and an inner diameter of 30 mm is punched from the ceramic fiber-containing disk roll base material, and a stainless steel shaft having a diameter of 30 mm is provided with a length of 100 mm and a packing density of 1.
- a roll build was made so as to be 25 g / cm 3 to produce a disk roll.
- the diameter of the disk roll is 30 mm, and 5 grooves with a width of 2 mm are provided at intervals of 2 mm.
- the room temperature is 25 After cooling to 0 ° C., the depth of the groove formed on the roll surface of the disk roll was measured.
- Dust generation property was evaluated by rubbing the roll surface against black drawing paper, thereby measuring the weight of the powder adhering to the drawing paper, and measuring the lightness of the drawing paper with a color difference meter. When a plate glass was actually produced using the above disk roll, there was a significant difference in dust generation.
- the disc roll obtained by the production method of the present invention can be used for production of plate glass, particularly glass for liquid crystal and glass for plasma display.
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Abstract
Description
本発明によれば、以下の耐熱ロールの製造方法等が提供される。
1. 粘土系鉱物を5重量%以上含有するロール部を作製するロール部作製工程と、
前記ロール部のロール表面を研削する研削工程と、
研削された前記ロール表面を湿らせた状態でならす表面処理を行う表面処理工程と、
前記表面処理されたロール表面に粘土系鉱物の被膜を形成する粘土被膜工程と、
を含む
耐熱ロールの製造方法。
2.前記表面を被覆する粘土系鉱物の膨潤力が、15ml/2g以上である1に記載の耐熱ロールの製造方法。
3.前記表面を被覆する粘土系鉱物が、ベントナイト、木節粘土、カオリンから選択される1以上である1又は2に記載の耐熱ロールの製造方法。
4.前記粘土被膜工程において、前記表面処理されたロール表面に、粘土系鉱物含有液を付着し、乾燥させて粘土系鉱物の被膜を形成する1~3のいずれかに記載の耐熱ロールの製造方法。
5.粘土系鉱物を5重量%以上含有するロール部を作製するロール部作製工程と、
前記ロール部のロール表面を研削する研削工程と、
研削された前記ロール表面を、粘土系鉱物含有液によって湿らせた状態でならす表面処理をし、ロール表面に前記粘土系鉱物の被膜を形成する表面処理工程と、
を含む、耐熱ロールの製造方法。
6.前記表面処理工程の湿らせた状態でならす表面処理において、研削された前記ロール表面を湿らせる第一工程と、次いで、湿った前記ロール表面をならす第二工程と、を実施することにより、前記表面処理を行う
1~5のいずれかに記載の耐熱ロールの製造方法。
7.前記第二工程において、湿った前記ロール表面に基材を押し付けつつ前記ロール部を回転させることにより、前記ロール表面をならす
6に記載の耐熱ロールの製造方法。
8.前記表面処理工程において、回転する前記ロール部の前記ロール表面に、湿らせた基材を押し付けることにより、前記表面処理を行う
1~7のいずれかに記載の耐熱ロールの製造方法。
9.前記粘土系鉱物の被膜する量が平均表面積1m2当たり固形分量で0.1g以上である1~8のいずれかに記載の耐熱ロールの製造方法。
10.粘土系鉱物を5重量%以上含有するロール部の表面部分が、粘土系鉱物で被覆されている、耐熱ロール。
11.前記ロール部の表面部分が、前記ロール部の内部に比べて緻密化されている
10に記載の耐熱ロール。
12.1~9のいずれかに記載の方法で製造された耐熱ロール。
13.前記粘土系鉱物の被膜する量が平均表面積1m2当たり固形分量で0.1g以上である10~12のいずれかに記載の耐熱ロール。
14.10~13のいずれかに記載の耐熱ロールを搬送用ロールとして使用する
板ガラスの製造方法。
本発明において、ロール部10は、さらに表面が粘土系鉱物で被覆されている。ロール部10全体を均一に分散して構成する粘土系鉱物と、表面を被覆する粘土系鉱物は同一でも異なってもよい。
粘土系鉱物として、木節粘土とベントナイトを含むことが好ましい。これらの含有量はそれぞれ好ましくは5~30重量%、より好ましくは7~25重量%、さらに好ましくは8~23重量%である。
また、充填材の含有量は、たとえば、5~50重量%の範囲とすることが好ましく、7~40重量%の範囲とすることがより好ましく、10~35重量%の範囲とすることがより好ましい。
まず、ロール表面12を旋盤等の切削装置によって切削することにより、ロール表面12上の比較的大きな凹凸を解消する(切削工程S12)。しかしながら、図の右欄に示すように、表面には依然として微小な凹凸は残っている。
次に、サンドペーパー等の研磨具によってロール表面12をさらに研磨して平坦化する(研磨工程S14)。このとき、図の右欄に示すように、研磨により生じた微粒子が凹に入り込む。
また、研削工程S10を、切削工程S12及び研磨工程S14と分けずに、切削及び研磨を一工程で行ってもよく、または、表面状態によっては、どちらかを省略してもよい。
また、塗布に限られず、霧吹き等の噴霧器具を用いてもよい。
図4は、上述の表面処理を実現する上で好ましい態様の一例を示す。図4には、図1に示すディスクロール1のうち、IV-IV線で切断したロール部10の断面と、当該ロール部10に対する表面処理に使用される基材40の断面を示している。
図4に示すように、この例では、回転するロール表面12に基材40を押し付けることにより、上述の表面処理を行う。即ち、まず軸部20を中心にして、ロール部10を図4に示す矢印Rの指す方向に回転させる。
水塗布工程S22においては、予め液体を保持した基材40をロール表面12に接触させる方法を使用できる。
ならし工程S24においては、湿ったロール表面12にシート状の基材40を押し付けることにより当該基材40を当該ロール表面12の周方向に沿って配置しつつロール部10を回転させることにより、当該ロール表面12をならす。
膨潤力は日本ベントナイト工業会標準試験方法(JBAS-104-77)に準じて測定すればよい。具体的には以下のように測定すればよい。試料2gを正確に量り、精製水100mlを入れた100mlの共栓付きメスシリンダーに加える。このとき、加えた試料が内壁に付着しないように注意する。また、試料が十分吸水及び分散するように試料を数回に分けて加えるようにするとともに、前に加えた試料のほとんどが沈降してから次の試料を加える。すべての試料を加えたら栓をし、24時間静置後、メスシリンダーの下部に堆積した容積A(ml)を読み取る。読み取った値が膨潤力(ml/2g)となる。
尚、本実施形態では水を使用したが、粘土系鉱物を適当に溶解又は分散できるものであれば、特に限られず任意の種類のものを適宜選択して用いることができ、1種類を単独で又は2種類以上を組み合わせて用いることができる。取り扱い易さ等の点から、水が好ましい。
尚、被覆は表面の全てを被覆していなくてもよい。好ましくは80%以上、より好ましくは90%以上、最も好ましくは100%である。
この実施形態では、研削工程S10の後、水を塗布する代わりに、第1の実施形態において使用した粘土含有水を塗布する(表面処理工程S40)。尚、研削工程S10は第1の実施形態と同じであるため説明を省略する。
この実施形態では、粘土含有水を塗布し(粘土水塗布工程S42)、ならして乾燥した後(ならし工程S44、乾燥工程S46)、第1の実施形態と同様に粘土系鉱物の被膜を形成する。この工程では、図の右欄に示すように、湿らせたロール表面12に、表面12に沿った方向にせん断力をかけ、ロール表面12を構成する微粒子の一部を、当該ロール表面12に沿って移動させて、ロール表面12の凹凸を低減させる。これと共に、粘土水に含まれる粘土系鉱物も表面12の凹部に入り込みこれを埋め、さらに、表面の上に粘土被膜を形成する。従って、第1の実施形態のような水だけの表面処理工程S20だけでは十分に平坦化できなかった凹凸も、平坦化できるようになる。その結果、発塵が抑制される。
ディスクロール用基材から外径60mm内径20mmのディスク材を打ち抜き、直径20mmのステンレス製シャフトに長さ100mm、充填密度が1.35g/cm3になるようにロールビルドし、図1に示すようなディスクロール1を作製した。
表面処理後のロール表面12を加熱して乾燥させた。
ディスクロール1及び被膜処理を行っていないディスクロールそれぞれについて、以下の特性を評価した。結果を表1に示す。
ディスクロールを900℃で3時間加熱した後、ロールの長さ方向の長さを測定し、下記式に基づいて加熱収縮率を評価した。
[(加熱前の測定値-加熱後の測定値)/加熱前の測定値]×100
ディスクロールを、900℃に保持した電気炉に投入し、15時間後に取り出して室温25℃まで急冷した。そして、この加熱及び急冷のサイクルをディスクロールのクラック又はディスクセパレーションが発生するまで繰り返し、クラック又はディスクセパレーションが発生したサイクル数をカウントした。
ディスクロールをシャフトの両端を架台で支持し、ディスク材からなるロール面に圧縮子により8.82N/mmで加圧し、そのときの荷重変形量を測定した。
セラミック繊維含有ディスクロール用基材から外径80mm内径30mmのディスク材
を打ち抜き、直径30mmのステンレス製シャフトに、長さ100mm、充填密度が1.
25g/cm3になるようにロールビルドし、ディスクロールを作製した。
このディスクロールのロール面に2mm間隔で幅2mmの溝加工を5本施した直径30
mmのステンレス製の軸を接触させた状態で、900℃で5時間回転させた後、室温25
℃まで冷却し、ディスクロールのロール表面にできた溝の深さを測定した。
発塵性は、ロール表面を黒色の画用紙に擦り付け、これにより当該画用紙に付着した粉の重量を測定するとともに、当該画用紙の明度を色差計で測定することにより評価した。
上記のディスクロールを用いて、実際に板ガラスを製造したところ、発塵性に有意な差があった。
触針式表面粗さ測定機(JIS B 0651)を使用して、JIS B 0601-1994で規定された方法により測定し、算術平均粗さRa、最大高さRy及び十点平均粗さRzを測定した。
この明細書に記載の文献及び本願のパリ優先の基礎となる日本出願明細書の内容を全てここに援用する。
Claims (14)
- 粘土系鉱物を5重量%以上含有するロール部を作製するロール部作製工程と、
前記ロール部のロール表面を研削する研削工程と、
研削された前記ロール表面を湿らせた状態でならす表面処理を行う表面処理工程と、
前記表面処理されたロール表面に粘土系鉱物の被膜を形成する粘土被膜工程と、
を含む
耐熱ロールの製造方法。 - 前記表面を被覆する粘土系鉱物の膨潤力が、15ml/2g以上である請求項1に記載の耐熱ロールの製造方法。
- 前記表面を被覆する粘土系鉱物が、ベントナイト、木節粘土、カオリンから選択される1以上である請求項1又は2に記載の耐熱ロールの製造方法。
- 前記粘土被膜工程において、前記表面処理されたロール表面に、粘土系鉱物含有液を付着し、乾燥させて粘土系鉱物の被膜を形成する請求項1~3のいずれかに記載の耐熱ロールの製造方法。
- 粘土系鉱物を5重量%以上含有するロール部を作製するロール部作製工程と、
前記ロール部のロール表面を研削する研削工程と、
研削された前記ロール表面を、粘土系鉱物含有液によって湿らせた状態でならす表面処理をし、ロール表面に前記粘土系鉱物の被膜を形成する表面処理工程と、
を含む、耐熱ロールの製造方法。 - 前記表面処理工程の湿らせた状態でならす表面処理において、研削された前記ロール表面を湿らせる第一工程と、次いで、湿った前記ロール表面をならす第二工程と、を実施することにより、前記表面処理を行う
請求項1~5のいずれかに記載の耐熱ロールの製造方法。 - 前記第二工程において、湿った前記ロール表面に基材を押し付けつつ前記ロール部を回転させることにより、前記ロール表面をならす
請求項6に記載の耐熱ロールの製造方法。 - 前記表面処理工程において、回転する前記ロール部の前記ロール表面に、湿らせた基材を押し付けることにより、前記表面処理を行う
請求項1~7のいずれかに記載の耐熱ロールの製造方法。 - 前記粘土系鉱物の被膜する量が平均表面積1m2当たり固形分量で0.1g以上である請求項1~8のいずれかに記載の耐熱ロールの製造方法。
- 粘土系鉱物を5重量%以上含有するロール部の表面部分が、粘土系鉱物で被覆されている、耐熱ロール。
- 前記ロール部の表面部分が、前記ロール部の内部に比べて緻密化されている
請求項10に記載の耐熱ロール。 - 請求項1~9のいずれかに記載の方法で製造された耐熱ロール。
- 前記粘土系鉱物の被膜する量が平均表面積1m2当たり固形分量で0.1g以上である請求項10~12のいずれかに記載の耐熱ロール。
- 請求項10~13のいずれかに記載の耐熱ロールを搬送用ロールとして使用する
板ガラスの製造方法。
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001287823A (ja) * | 2000-04-07 | 2001-10-16 | Nichias Corp | ディスクロールおよびその作製方法 |
JP2010095437A (ja) * | 2008-09-17 | 2010-04-30 | Nichias Corp | 耐熱ロール、その製造方法及びこれを使用した板ガラスの製造方法 |
WO2012070650A1 (ja) * | 2010-11-25 | 2012-05-31 | ニチアス株式会社 | ディスクロール及びその製造方法、並びに該ディスクロールを用いた金属板の搬送方法及び板ガラスの製造方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
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KR20040102050A (ko) | 2002-03-22 | 2004-12-03 | 코닝 인코포레이티드 | 판유리 제조용 사출 로울러 |
JP4393781B2 (ja) | 2003-03-31 | 2010-01-06 | ニチアス株式会社 | ディスクロール及びその製造方法 |
US8636633B2 (en) | 2003-03-31 | 2014-01-28 | Nichias Corporation | Disc roll |
JP5219059B2 (ja) * | 2004-08-10 | 2013-06-26 | 独立行政法人産業技術総合研究所 | 粘土配向膜からなる保護膜 |
JP2006143666A (ja) | 2004-11-22 | 2006-06-08 | Asahi Glass Si-Tech Co Ltd | 水性ゲル状組成物及びこれを含有する水性ゲル状化粧料。 |
JP4731381B2 (ja) | 2006-03-31 | 2011-07-20 | ニチアス株式会社 | ディスクロール及びディスクロール用基材 |
US7507194B2 (en) * | 2006-11-29 | 2009-03-24 | Corning Incorporated | Pulling roll material for manufacture of sheet glass |
-
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001287823A (ja) * | 2000-04-07 | 2001-10-16 | Nichias Corp | ディスクロールおよびその作製方法 |
JP2010095437A (ja) * | 2008-09-17 | 2010-04-30 | Nichias Corp | 耐熱ロール、その製造方法及びこれを使用した板ガラスの製造方法 |
WO2012070650A1 (ja) * | 2010-11-25 | 2012-05-31 | ニチアス株式会社 | ディスクロール及びその製造方法、並びに該ディスクロールを用いた金属板の搬送方法及び板ガラスの製造方法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11613493B2 (en) * | 2016-07-26 | 2023-03-28 | Corning Incorporated | Method of making high quality heat-resistant rolls |
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