Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
  • B21B—ROLLING OF METAL
  • B21B27/00—Rolls, roll alloys or roll fabrication; Lubricating, cooling or heating rolls while in use
  • B21B27/005—Rolls with a roughened or textured surface; Methods for making same
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F1/00—Etching metallic material by chemical means
  • C23F1/02—Local etching

Definitions

• a predetermined portion of the surface of a rolling roll is coated with a cured product of a photosensitive resin composition to form a pattern, and the uncoated portion is chemically corroded, and then the cured product is released. It relates to a method for processing the surface of a roll. Background technology.
• the present invention solves the above-mentioned problems, and when processing the surface of a rolling roll in order to improve the surface properties of the steel sheet, the rolling roll processing time is shortened, and the surface processing of the rolling roll is inexpensive. It is an object of the present invention to provide a method capable of performing the above using a low-cost roll processing device.
• a pattern coated with the cured product of the photosensitive resin composition is formed only on a predetermined portion of the surface of the rolling roll, and the uncoated portion is chemically corroded.
• the present invention provides a method of surface treating a metal.
• a visible light curable photosensitive resin composition comprising an ethylenically unsaturated compound, a radical generator and a sensitizer, and optionally containing a binder polymer is used.
• FIGS. 1 (a), (b), (c) and (d) are explanatory views showing an example of the unevenness imparting processing step of the present invention.
• FIG. 2 is a drawing schematically showing an example of the concavo-convex pattern formed on the roll surface of the present invention.
• roll roll refers to a roll that rolls a flat material such as a steel plate and has a cylindrical roll shape.
• the visible light curable photosensitive resin composition used in the present invention comprises a binder polymer, an ethylenically unsaturated compound, a radical generator and a sensitizer, or an ethylenically unsaturated compound, a radical generator and a sensitizer.
• a binder polymer an ethylenically unsaturated compound
• a radical generator and a sensitizer an ethylenically unsaturated compound
• a radical generator and a sensitizer ethylenically unsaturated compound
• a radical generator and a sensitizer ethylenically unsaturated compound, a radical generator and a sensitizer.
• Binder polymers include (meta) acrylate (hereinafter, (meta) acrylate means both aggregate and metaacrylate) and other ethylene. Copolymers with unsaturated compounds, polyvinyl alcohol, butyral resin, formal resin, partially genated polyvinyl acetate, polyester resin, polyurethane resin, polyamide, phenoxy resin and phenol Resins. Particularly preferred are copolymers of (meth) acrylate with other ethylenically unsaturated compounds.
• the chemical resistance can be improved by mixing or copolymerizing a binder polymer with a crosslinkable component.
• a cross-linkable component include a melamine resin, an epoxy resin, an isocyanate, and a mask dysocyanate. Particularly preferred is a melamine resin. It is.
• the cross-linkable copolysynthetic component include vinyl monomers having a glycidyl group, a furfuryl group, an N-methylol group or an N-alkoxymethyl group. 'Particularly preferred is N-methylol. Is a vinyl monomer having a group
• Examples of the ethylenically unsaturated compound include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate.
• G Hydroxyshetil (Meta) Atari Polyvalent, such as latex, neopentyl glycol di (meth) acrylate, trimethylol propane tri (meth) acrylate, tetraethylene glycol di (meth) acrylate (Meth) acrylate of alkylene oxide adduct of alcohol or polyhydric alcohol; trade name: Aronix M-110, M-120, M-610 Polyester (meth) acrylate having an acrylate group at the end of a polyester resin from a polybasic acid and a polyhydric alcohol such as 0, M-7100 (manufactured by Toa Gosei Co., Ltd.); It has polyvalent compounds such as tolylene diisocyanate, isophorone
• Urethane (meth) acrylate which is a reaction product with tallylate; bisphenol A diglycidyl ether, isocyanuric acid triglycidyl ether, pen erythritol triglycidyl ether Epoxy (meth) acrylate, which is a reaction product of a polyfunctional epoxy resin such as, for example, and (meth) acrylate; styrenes, and unsaturated polyester resin. Further, a mixture of the above-mentioned ethylenically unsaturated compounds is also included. Particularly preferred are the (meth) acrylate, urethane (meth) acrylate and epoxy (meth) acrylate of polyhydric alcohols or alkylenoxyside adducts of polyhydric alcohols. It is.
• Radical generators include benzophenones such as benzophenone, 4,4'-bis (dimethylamino) benzophenone, and benzophenones such as 4-morpholinobenzophenone, benzyldimethylketal, and 2,2— Alkyl aryl ketones, such as diethoxydiacetophenone, 2-hydroxy 2-phenoxyphenone, 1-hydroxycyclohexyl phenyl ketone, and isopropyl benzoisoether; 2,4,6—tris S-triol such as trichloroazine) N-phenylglycines such as gins, N-phenylglycine, N- (p-cloth) -phenylglycine, 3, 3 ', 4, 4'-tetra (t-butyl peroxy force) Organic peroxides such as (rubonyl) benzophenone and g- (t-butyl veroxy) phthalate. Further, a mixture of the above radical generators is also included.
• sensitizers examples include coumarins such as 3,3'-luponylbis (7-getylaminocoumaline), 3-acetyl-7-dimethylmethylaminocoumarin, and 1,1bis (3— Ethyl-2, a mono-naphthothiazol) methine cyanine, 1, 1-bis (3-ethylu-3, benzothiabour) methine cyanine and other cyanine dyes, 2-methylthioxanthone , 2,4-dimethylthioxanthone and other xanthone dyes. Also, a mixture of the above sensitizers can be mentioned. Particularly preferred are coumarins.
• the visible light-curable photosensitive resin composition used in the present invention is preferably (a) 5 to 80% by weight of a binder polymer, more preferably 15 to 60% by weight, and (b) ethylenic resin. 5 to 80% by weight of a saturated compound, more preferably 15 to 60% by weight, (c) 0.1 to 15% by weight of a radical generator, more preferably 2.0 to 10.0% by weight, and (a) a sensitizer 0.1 -15% by weight, more preferably 0.2-10.0% by weight, or (a ') 100% by weight of an ethylenically unsaturated compound, (b') a radical raw material 0.1-15% by weight, furthermore Preferably, it can be used in the range of 2.0 to 10.0% by weight, and (c ') the sensitizer can be used in the range of 0.1 to 15% by weight, and more preferably in the range of 0.2 to 10.0% by weight.
• FIG. 1 shows an example of a surface processing step of a rolling roll according to the present invention
• FIG. 2 is a schematic view showing a concavo-convex pattern 2 formed on the surface of a roll 1 by the roll surface processing.
• the formation of the concavo-convex pattern 2 on the surface of the roll I can be performed, for example, by a method as shown in FIGS. 1 (a) to 1 (d). That is, first, the visible light curing type photosensitive resin composition 4 is supplied to the photosensitive resin composition supply 6 from the hopper 3 installed above the photosensitive resin composition supply 6, and the rear of the supply 6. The visible light-curable photosensitive resin composition 4 is coated on the surface of the roll 1 while adjusting the thickness to a predetermined value with the air 5, and the visible light-curable photosensitive resin composition layer 7 is formed on the surface of the roll 1. I do. Next, as shown in FIG.
• a laser beam 9 having a wavelength in the visible region emitted from a laser light source 8 is intermittently applied to the visible light curable photosensitive resin composition layer 7 at a predetermined regular pitch.
• the reference to Cho wrapper 11 having a Sri Tsu bets 10 while rotating it are performed intermittently irradiating the beam 9
• the method of intermittent irradiation is not limited to this, and may be, for example, a deflection control of a continuous irradiation laser beam, a pulse laser, or the like.
• etching is used as a method of forming the concavo-convex pattern on the roll surface.
• the treatment is performed, the present invention is not limited to this treatment method.
• a treatment method such as plating, vapor deposition, and dry etching may be used.
• a compound of the following composition is blended, and the visible light curable photosensitive resin composition No.
• Rate copolymer 85Z15 weight ratio, number average molecular weight 100,000 55 weight: part trimethylolpropane triacrylate 20 weight: part tetraethylene glycol glycol diacrylate 10 weight: part butoxylated methylol methyla Min 10 parts by weight Radical generator 2.5 parts by weight Sensitizer
• BTTB 3, 3 ', 4, 4' tetra (t-butyl peroxycarbonyl) benzopentanone
• Coumarin 3,3'-carbonylbis (7-
• Cyanine 1, 1 bis-one (3—ethyl-3—benzothiazole) methine cyanine
• Triazine 2, 4, 6—tris (trichloromethyl)
• FIG. 1 (a) a nozzle that blows visible light curable photosensitive resin composition 4 housed in hopper 13 and compressed air 5 while rotating the rolling roll 1 Spray coating with 6 is performed to form a visible and photocurable photosensitive resin composition film 7 having a uniform thickness.
• a chopper 11 having a slit 10 is placed between the laser light source 8 and the rolling roll 1, and the visible light laser having a wavelength of 488 nm is rotated while rotating. 9 is irradiated intermittently to form a cured product 12 of a visible light-curable photosensitive resin composition on the irradiated portion.
• 1, 1, 1-trichloromethane 14 is sprayed from the sprayer 13 to wash and remove the unirradiated portion of the visible light-curable photosensitive resin composition to expose the surface 15 of the roll 1.
• the roll surface 15 exposed by the above operation is corroded to a predetermined depth by the etching agent.
• the cured visible light-curable photosensitive resin composition 12 is removed by spraying methylene chloride from a sprayer 13. By the above operation, a rolling roll having a regular uneven pattern was produced.
• Irgacure 651 Benzyldimethyl ketal (manufactured by Ciba Geigy Corporation)
• Darocure 1 1 7 3 2 — Hydroxy 2 — Methylpropionophenone (manufactured by Merck)
• a visible light laser with a surface treatment wavelength of 488 nm of the rolling roll an ultraviolet light laser of 351 nm and 363 ⁇ m was used.
• the surface treatment of the rolling roll was performed in the same manner as in Example 1 except that photosensitive resin compositions Nos. 1 to 6 were used.
• Table 3 shows the evaluation results of the surface treatment method for the rolling rolls. As is clear from Table 3, the method of the present invention can obtain good surface properties in a short time.
• the protrusions on the roll surface after processing were observed with a microscope, and judged according to the following evaluation criteria.
• ⁇ A convex portion of a predetermined size is formed, but it looks double.
• the irradiation time of the laser beam required to cure the visible light-curable photosensitive resin composition having a thickness of 7 / zm was measured and defined as the curing time.
• the present invention forms a pattern covered with the cured product of the photosensitive resin composition only on a predetermined portion of the surface of the rolling roll, chemically corrodes a non-covered portion, and then removes the cured product. ⁇
• a visible light curable photosensitive resin composition that cures by irradiation with light in the visible region is used to reduce the rolling roll processing time and roll processing equipment.
• the visible light curable photosensitive resin composition cures with an energy of 0.2 to 0.5 mJZ cnf for light in the visible region, the minimum photosensitive energy is 0.2 mJ.
• the exposure time of 0.1 msec is sufficient as compared with the ultraviolet-curable photosensitive resin composition.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• General Chemical & Material Sciences (AREA)
• Materials Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Reduction Rolling/Reduction Stand/Operation Of Reduction Machine (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Macromonomer-Based Addition Polymer (AREA)
• ing And Chemical Polishing (AREA)
• Polymerisation Methods In General (AREA)

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Publications (1)

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Citations (3)

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• 1991
  • 1991-07-30 JP JP3190397A patent/JP2961159B2/ja not_active Expired - Fee Related
• 1992
  • 1992-07-30 US US08/039,015 patent/US5294297A/en not_active Expired - Fee Related
  • 1992-07-30 EP EP92916142A patent/EP0559900B1/en not_active Expired - Lifetime
  • 1992-07-30 WO PCT/JP1992/000964 patent/WO1993003199A1/ja not_active Ceased
  • 1992-07-30 DE DE69223762T patent/DE69223762T2/de not_active Expired - Fee Related
  • 1992-07-30 KR KR1019930700843A patent/KR950014639B1/ko not_active Expired - Fee Related
  • 1992-07-30 CA CA002092545A patent/CA2092545A1/en not_active Abandoned

Patent Citations (3)

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