WO2005071052A1 - 潤滑性水系ポリウレタン樹脂組成物、それを用いる亜鉛系メッキ鋼板の表面潤滑処理方法及びその表面処理鋼板 - Google Patents
潤滑性水系ポリウレタン樹脂組成物、それを用いる亜鉛系メッキ鋼板の表面潤滑処理方法及びその表面処理鋼板 Download PDFInfo
- Publication number
- WO2005071052A1 WO2005071052A1 PCT/JP2005/001287 JP2005001287W WO2005071052A1 WO 2005071052 A1 WO2005071052 A1 WO 2005071052A1 JP 2005001287 W JP2005001287 W JP 2005001287W WO 2005071052 A1 WO2005071052 A1 WO 2005071052A1
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- WO
- WIPO (PCT)
- Prior art keywords
- polyurethane resin
- steel sheet
- resin composition
- lubricating
- mass
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 52
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- 230000001050 lubricating effect Effects 0.000 title claims description 29
- 238000000034 method Methods 0.000 title claims description 21
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- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 5
- 239000001361 adipic acid Substances 0.000 description 5
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- 238000009864 tensile test Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
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- XDRLAGOBLZATBG-UHFFFAOYSA-N 1-phenylpenta-1,4-dien-3-one Chemical compound C=CC(=O)C=CC1=CC=CC=C1 XDRLAGOBLZATBG-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M173/00—Lubricating compositions containing more than 10% water
- C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/10—Compounds containing silicon
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/041—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds involving a condensation reaction
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/045—Polyureas; Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/055—Particles related characteristics
- C10N2020/06—Particles of special shape or size
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/079—Liquid crystals
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/14—Electric or magnetic purposes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/01—Emulsions, colloids, or micelles
Definitions
- the present invention is used for press processing of home appliances, building materials, etc.
- the present invention relates to a lubricating aqueous polyurethane resin composition for a surface lubricated steel sheet, a surface treatment method using the same, and a product thereof.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2001-214182
- Patent Document 2 Japanese Patent Application Laid-Open No. 08-270702
- Patent Document 3 Japanese Patent Application Laid-Open No. H06-145559
- Patent Document 1 discloses that an acryl-styrene resin (a) having an acid value of less than 10 is converted to a solid content of 30%.
- Patent Document 2 discloses that, on both sides of a zinc or zinc-based steel sheet, 10 to 200 mg per one side in terms of metal mouthpiece. has a click Rome bets coating Z m 2, thereon, the following mixed resin, curing agent
- Resin composition containing 5 to 40 parts by weight, 1 to 40 parts by weight of a lubricant having a melting point of 80 ° C. to 130 ° C., and 5 to 80 parts by weight of an organic silicon compound
- a method is disclosed in which a material layer is formed at an application amount of 0.1 to 1.0 g Zm 2 by dry weight.
- the mixed resin has two or more kinds of resins having a glass transition temperature of from 130 ° C. to 90 ° C. having a plurality of hydroxyl groups, that is, a glass transition temperature of from 130 ° C. to 30 ° C.
- Patent Document 3 discloses a method having a bisphenol-type skeleton, an ester skeleton, and a lipoxyl group.
- the solids weight ratio with respect to e) is 0.33: 1 to 0.30: 1, and the solids weight ratio of (d) with respect to (e) is 0.10: 1 to 0.40:
- the technology relating to the water-based lubricating coating composition, which is 1, is disclosed.
- Patent Document 3 In the technique of Patent Document 3, the desired performance is obtained by adding a crosslinking agent to a specific polyurethane resin.
- Patent Document 3 does not disclose any means for using a polyurethane resin composition containing no cross-linking agent to obtain the same or better performance.
- Patent Literature 1 Japanese Patent Application Laid-Open No. 2000-2-1024182, Claim 1
- Patent Literature 2 Japanese Patent Application Laid-Open No. 08-266700, Claim 1
- Patent Document 3 Japanese Patent Application Laid-Open No. 06-145550, Claim 1, Disclosure of the Invention
- An object of the present invention is to solve the problem of the prior art of performance degradation due to non-uniformity of a film, and to use an aqueous polyurethane resin composition having excellent lubricity, solvent resistance, and corrosion resistance, and use of the same.
- Another object of the present invention is to provide a method of lubricating the surface of a zinc-based coated steel sheet and a surface-treated steel sheet obtained by the method.
- the present inventors have intensively studied an aqueous chemical which simultaneously satisfies the properties of lubricity, solvent resistance and corrosion resistance, and a surface-treated steel sheet using the same. As a result of the repeated studies, they have found that the above problem can be solved mainly by specifying the urethane resin, and have completed the present invention.
- the lubricating aqueous polyurethane resin composition of the present invention comprises the following components (a), (b) and (c):
- a colloidal silica having a particle diameter of 5 to 50 nm, and an aqueous resin composition comprising:
- the solid content (( a ) / (a + b + c)) of the component (a) is 5O to 93% by mass
- the solid content ((b) / (a + b + c)) of the component (b) is 2 to 20% by mass
- the solid content ((c) / (a + b + c)) of the component (c) is 5 to 40% by mass.
- the mass ratio of the polyester skeleton to the polyether skeleton in the polyurethane resin (a) is preferably in the range of 1 Z 9 to 5/5.
- the method for lubricating a zinc-based plated steel sheet according to the present invention comprises: Applying a treatment solution containing a sex aqueous poly urethane resin composition to the surface of the zinc-based main Tsu key steel and dried to form a lubricating layer having a dry solid weight of 0. l ⁇ 5 g _ m 2 that It is characterized by the following.
- the surface-lubricated zinc-coated steel sheet of the present invention is manufactured by the method of lubricating a zinc-based plated steel sheet of the present invention.
- a film having excellent corrosion resistance, alkali resistance, coating adhesion, and lubricity can be formed.
- aqueous polyurethane resin composition in the present invention means “a polyurethane resin composition that can be dissolved, dispersed or emulsified in a medium containing water”.
- the (a) polyurethane resin contained in the resin composition of the present invention has a tensile rupture strength of at least 3.9 N / cm 2 (400 kgf / cm 2 ), preferably at least 4.9. 9.9.8 N / cm 2 , tensile elongation at break is 50% or less, preferably 1 140%, and its thermal transition temperature (T g) is 80 ⁇ 150 °. C (measured according to JISK 7121).
- T g thermal transition temperature
- the present inventors have found that the tensile strength of the resin film itself is 3.92 kN / cm 2 (400 K gf Z cm 2 ) or more, and the tensile elongation at break is 5%. It has been found that the target lubricity can be obtained when it is 0% or less and T g is 80 to 150 ° C.
- a dry film was placed on the polyester sheet. The resin is applied to a thickness of 50 ⁇ m, dried at room temperature for 24 hours, baked at 150 ° C for 30 minutes to produce a film, and the film is gently removed from the polyester sheet.
- the tensile test was performed in accordance with JISK6732. Further, the glass transition temperature of the polyurethane resin was measured using a commercially available dynamic viscoelasticity measuring device (Leoguchi Graph Solid S-1 manufactured by Toyo Seiki Seisaku-sho, Ltd.). At this time, a test piece with a thickness of 100 ⁇ , a width of 8 mm, and a length of 30 mm was dried at 100 ° C for 30 minutes and used at a measurement frequency of 100 Hz. Yes, the glass transition temperature was determined from the inflection point of the elastic loss rate.
- the solid content of the component (a) is 50 to 93% with respect to the total solid mass (a + b + c) of the components (a), (b) and (c). Preferably, it is 55 to 90%, more preferably 50 to 85%.
- the solid content of the component (a) is the same as that of the components (a), (b) and
- the polyurethane resin for the component (a) used in the present invention has a polyester skeleton and a polyether skeleton.
- the polyester skeleton is obtained from a polyester polyol compound
- the polyether skeleton is obtained from a polyether polyol.
- polyester polyol compound for forming a polyester skeleton F, low molecular weight polyols, ethylene glycol, ethylene glycol cornole, triethylene glycol, 1, 2 — propylene glycol cornole, 1, 3 — propylene glycol cornole, neopentinole glycolonele, 1, 2 Butylene glycol, 1,3—butylene glycol, 1,4—butylene glycol, 3-methylpentanediol, hexamethylenglycol, hydrogenated bisphenanol A, trimethylolpropane, glycerin, etc., and polybasic acids, For example, succinic acid, dalta / leic acid, adipic acid, sepatic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, tetrahydrophthalic acid, endmethylene trahydrophthalic acid, and By reaction with hexahydrophtalic acid, etc.
- polyether polyol for forming a polyether skeleton examples include glycols having a bisphenol skeleton, for example, methylenebisphenol, ethylidenebisphenol, butylidenebisphenol, and isopropylidenebis.
- phenols and the like phenols containing 24 carbon atoms (for example, ethylenoxide, propylene oxide, etc.)
- the number of additional monoles of the alkylene oxide is preferably 1 to 10.
- the mass ratio of the polyester skeleton to the polyether skeleton is less than 1 Z9, the content ratio of the relatively rigid polyether skeleton is high, and the extensibility of the film itself is low.
- the resulting coating is brittle and may have insufficient tensile fracture strength.
- the fine particles of (b) the polyolefin resin contained in the polyurethane resin composition of the present invention have a melting point of 70 to 160 ° C. and a particle size of 0.5 to 5 ⁇ . Generally, during press molding, the temperature of the molded product can reach 80 ° C.
- the melting point of the polyolefin resin fine particles is less than 70 ° C, all of the polyolefin resin fine particles in the film formed from this polyurethane resin composition will melt during molding. Therefore, it is not possible to obtain a film having sufficient lubricity in the forming process.
- the melting point of the polyolefin resin fine particles exceeds 160 ° C, melting of the polyolefin resin fine particles due to sliding frictional heat becomes difficult to occur, and the resulting film has poor lubrication during sliding. Will be enough.
- the polyolefin resin fine particles have a particle size of less than 0.5 ⁇ , the resulting resin film has insufficient lubricity.
- the polyolefin resin fine particles are likely to fall off from the obtained resin film.
- a true spherical shape is preferable in order to obtain a polyurethane resin composition having high workability.
- the solid content of the component (b) is 2 to 20% based on the total solid mass (a + b + c) of the components (a), (b) and (c). , Preferably 3 to 20%, more preferably 3 to 18%.
- the solid content of the component (b) is less than 2% based on the total solid mass (a + b + c) of the components (a), (b) and (c)
- a component is obtained.
- the lubricity of the polyurethane resin composition becomes insufficient.
- the particle diameter of the component (c) colloidal silica is 5 to 50 nm, preferably 5 to 40 nm, more preferably 5 to 30 nm.
- Component (c) If the particle diameter of the colloidal silicide exceeds 50 nm, the uniformity of the film formed from the obtained polyurethane resin composition will be insufficient, and therefore, the corrosion resistance and adhesion of the film will be insufficient. Etc. become insufficient.
- the particle diameter of the component (c) colloidal silica is less than 5 nm, production on an industrial basis becomes difficult, and it is economically disadvantageous.
- the solid content of the component (c) is 5 to 40%, preferably 5 to 40%, based on the total solid mass (a + b + c) of the components (a), (b) and (c). 335%, more preferably 5-30%. If the solids content of component (c) is less than 5% of the total solids mass (a + b + c) of components (a), (b) and (c), the resulting poly The effect of improving the corrosion resistance of the urethane resin composition becomes insufficient.
- the aqueous polyurethane resin composition for metal surface treatment of the present invention includes a surfactant called a wettability improver for forming a uniform film on the surface to be coated with a metal material, and a thickener for adjusting viscosity. It may contain one or more of an agent, a conductive substance for improving the weldability, a coloring pigment for improving the design, a metal additive having an inhibitory effect, and a metal compound.
- the surface is treated with the lubricating aqueous polyurethane resin composition of the present invention.
- the amount of the film formed on the surface of the zinc-based medic steel sheet is 0.1 to 5.0 Og / m 2 , preferably 0.2 to 4.0 g Zm 2 , more preferably, dry mass. Is 0.3 to 4 g / m 2 . If the dry weight of the coating formed on the surface of the zinc-based plating steel sheet is less than 0.1 g Zm 2 , the effect of improving the lubricity of the polyurethane resin composition is insufficient. Further, when the dry weight of the film formed on the surface of the zinc-based plated steel sheet exceeds 5. OgZm 2 , the lubricating effect is saturated, so that there is an economic disadvantage.
- Examples of a method for applying the treatment liquid containing the polyurethane resin composition of the present invention include a roll coater method, a dipping method, and an electrostatic coating method, but the method of the present invention is not particularly limited thereto.
- the treatment temperature for the applied treatment liquid layer or its dried film is not particularly limited, but it is preferable to control the ultimate plate temperature within the range of 100 to 200 ° C.
- the surface-treated steel sheet of the present invention there is no limitation on the type and conditions of the pretreatment step performed on the zinc-based steel sheet before the lubrication step by the method of the present invention, but the Pretreatment includes degreasing to maintain cleanliness, chromate treatment to improve corrosion resistance, phosphate treatment, and nonchromate treatment that does not contain chrome-based compounds that have excellent anti-dust effect.
- the lubricating polyurethane resin composition film formed thereon can exhibit excellent lubricity and adhesion.
- aqueous polyurethane resin compositions used in the following Examples and Comparative Examples were prepared as follows. Manufactured.
- the mixture of 3 parts of adduct of 3 moles and 100 parts of 2,2-bis (hydroxymethyl) propionic acid in 100 parts of N-methyl-2-pyrrolidone was mixed at 80 ° C. To dissolve. Thereafter, 120 parts of dicyclohexylmethandiocyanate was added to the solution, the mixture was heated to 110 ° C and reacted for 2 hours, and the reaction product was treated with triethylamine 10%. Neutralized.
- the resulting solution was added dropwise to an aqueous solution prepared by mixing 5 parts of ethylenediamine and 570 parts of deionized water under vigorous stirring to produce an aqueous polyurethane resin.
- This resin has a tensile fracture strength of 7.35 kN / cm 2 (750 kgf / cm 2 ), a tensile elongation at break of 10%, and a T g of 105 ° C.
- Bisphenol A propylene having an average molecular weight of 600 and an average molecular weight of 600, synthesized from adipic acid having a hydroxyl group at the terminal and 1,6-hexanediol 1.
- This solution was added dropwise to an aqueous solution prepared by mixing 5 parts of ethylenediamine and 570 parts of deionized water with vigorous stirring to produce an aqueous polyurethane resin.
- the tensile fracture strength of this resin was 7.84 kNZcm 2 (80 OK gf / cm 2 ), and the tensile elongation at break was 5%. Its T g was 125 ° C.
- 120 parts of the 3-molar adduct and 12 parts of 2,2-bis (hydroxymethyl) propionic acid are added to 100 parts of N-methyl-12-pyrrolidone, and the mixture is added to the mixture. It was dissolved by heating to 80 ° C. To this solution was added 100 parts of dicyclohexylmethanediisocyanate, the mixture was heated to 110 ° C. and reacted for 2 hours, and 11 parts of triethylamine was added to the obtained reaction product.
- This solution was added dropwise to an aqueous solution prepared by mixing 5 parts of ethylenediamine and 570 parts of deionized water under vigorous stirring to produce an aqueous urethane resin.
- the tensile rupture strength of this resin is 3.92 kN / cm 2 (400 kgf / cm 2 ), the tensile rupture elongation is 400%, and its T g is 30 °. C.
- Bisphenol A propylene oxide having an average molecular weight of 660, 3-mol adduct of 200 parts, and 15 parts of 2,2-bis (hydroxymethyl) propionic acid were combined with N-methyl-1-pyrrolidine.
- the mixture was mixed in 100 parts of Don and the mixture was dissolved by heating to 80 ° C.
- This solution was mixed with 120 parts of dicyclohexylmethanediacid, the mixture was heated to 110 ° C and reacted for 2 hours, and the resulting reaction product was treated with triethynoleamine 15 Neutralized. Add this solution to ethylenediamine 5 parts of deionized water and 570 parts of deionized water were mixed, and the mixture was dropped under strong stirring to produce an aqueous polyurethane resin.
- the chromium adhesion amount by this treatment was 1 O mg / m 2 .
- PARCOAT 384 1 (trademark, manufactured by Nippon Parkerizing Co., Ltd., containing silane compound) was applied to the degreased steel sheet using a roll coater.
- Table 2 shows the trademark, solid content concentration, and particle size of the colloidal sily force used in Examples and Comparative Examples. These were all made by Nissan Chemical.
- compositions of the lubricating aqueous polyurethane resin compositions d1 to (! 9 used in Examples are shown in Table 3.
- compositions of the resin compositions d10 to d15 used in Comparative Examples are shown in Table 3.
- the results are shown in Table 4.
- the numbers in parentheses in Tables 3 and 4 The value indicates the ratio (%) of the solid content mass of each component to the total solid content mass of the aqueous polyurethane resin composition.
- composition of aqueous polyurethane resin composition for Examples
- composition of aqueous resin composition for comparative example Composition of aqueous resin composition for comparative example
- the coating liquid containing the lubricating aqueous resin composition shown in Tables 3 and 4 was applied to the surface of the steel material using a per coater, and the coating liquid layer was dried at an ambient temperature of 320 ° C for 12 seconds. . At this time, the temperature reached by the steel material was 100 to 200 ° C. (preferably 120 ° C.), and the coating weight was 1.0 g Zm ”.
- the heating atmosphere temperature and heating time were as follows. '
- a salt spray test using JIS—Z—2731 was performed for 200 hours, and the occurrence of whitening was observed.
- Performance degradation occurs when the generated area is 10% or more of the total area
- a melamine-based paint (trademark: Amirac # 100, manufactured by Kansai Paint Co., Ltd.) is applied so that the film thickness after baking and drying is 25 / m. After baking for 24 minutes, 24 hours later, it was immersed in boiling water for 2 hours, and 24 hours later, an evaluation test was performed.
- the paint adhesion was evaluated according to JISK 540 by performing an evaluation of adhesion and a blister evaluation by the Goban-Erichsen test, and an overall evaluation of these. ⁇ Evaluation criteria>
- the lubricating water-based polyurethane resin composition of the present invention forms a surface film having excellent corrosion resistance, alkali resistance, paint adhesion and lubricity by coating it on the surface of a zinc-coated steel sheet. Therefore, it has high practicality.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
- Lubricants (AREA)
- Polyurethanes Or Polyureas (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Applications Claiming Priority (2)
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JP2004-017313 | 2004-01-26 | ||
JP2004017313A JP4671609B2 (ja) | 2004-01-26 | 2004-01-26 | 潤滑性水系ポリウレタン樹脂組成物、それを用いる亜鉛系メッキ鋼板の表面潤滑処理方法及びその表面処理鋼板 |
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JP (1) | JP4671609B2 (zh) |
KR (1) | KR100744094B1 (zh) |
CN (1) | CN100554389C (zh) |
MY (1) | MY148579A (zh) |
TW (1) | TWI300094B (zh) |
WO (1) | WO2005071052A1 (zh) |
Cited By (3)
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WO2010131756A1 (ja) * | 2009-05-11 | 2010-11-18 | 新日本製鐵株式会社 | 表面処理金属材及びその製造方法 |
US8895153B2 (en) | 2010-06-18 | 2014-11-25 | Nisshin Steel Co., Ltd. | Chemical conversion coated plated steel sheet and method for producing same |
US9260786B2 (en) | 2010-06-18 | 2016-02-16 | Nisshin Steel Co., Ltd. | Chemical conversion coated plated steel sheet and method for producing same |
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JP5135669B2 (ja) * | 2005-09-16 | 2013-02-06 | 新日鐵住金株式会社 | 塗装金属材の製造方法 |
AR082749A1 (es) | 2009-04-15 | 2013-01-09 | Bayer Materialscience Ag | Dispersiones de poliuretano para la pasivacion organica |
CN102575352B (zh) | 2009-09-15 | 2016-01-20 | 新日铁住金株式会社 | 电磁钢板及其制造方法 |
JP5659685B2 (ja) * | 2010-10-18 | 2015-01-28 | 新日鐵住金株式会社 | 塗装金属材 |
CN103102790B (zh) * | 2013-01-30 | 2016-02-10 | 马鞍山钢铁股份有限公司 | 一种镀锌钢板用润滑涂料、自润滑镀锌钢板及其生产方法 |
JP5836986B2 (ja) * | 2013-02-22 | 2015-12-24 | 日本写真印刷株式会社 | 金属加飾板に使用する保護シート |
CN103911031B (zh) * | 2014-04-10 | 2016-04-06 | 攀钢集团攀枝花钢铁研究院有限公司 | 一种热镀锌自润滑处理剂组合物和自润滑镀锌板及其制备方法 |
CN104497841B (zh) * | 2014-12-15 | 2016-08-24 | 中国钢研科技集团有限公司 | 一种镀锌钢板表面水性无铬润滑处理剂及其使用方法 |
EP4337730A1 (en) | 2021-05-10 | 2024-03-20 | Chemetall GmbH | Aqueous composition for metallic surface treatment and the application thereof |
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WO2010131756A1 (ja) * | 2009-05-11 | 2010-11-18 | 新日本製鐵株式会社 | 表面処理金属材及びその製造方法 |
JP4980470B2 (ja) * | 2009-05-11 | 2012-07-18 | 新日本製鐵株式会社 | 表面処理金属材及びその製造方法 |
US8956729B2 (en) | 2009-05-11 | 2015-02-17 | Nippon Steel & Sumitomo Metal Corporation | Surface-treated metal material and process for producing the same |
US8895153B2 (en) | 2010-06-18 | 2014-11-25 | Nisshin Steel Co., Ltd. | Chemical conversion coated plated steel sheet and method for producing same |
US9260786B2 (en) | 2010-06-18 | 2016-02-16 | Nisshin Steel Co., Ltd. | Chemical conversion coated plated steel sheet and method for producing same |
US9890461B2 (en) | 2010-06-18 | 2018-02-13 | Nisshin Steel Co., Ltd. | Chemical conversion coated plated steel sheet and method for producing same |
Also Published As
Publication number | Publication date |
---|---|
CN100554389C (zh) | 2009-10-28 |
TWI300094B (en) | 2008-08-21 |
JP2005206764A (ja) | 2005-08-04 |
KR100744094B1 (ko) | 2007-08-01 |
TW200536932A (en) | 2005-11-16 |
CN1934232A (zh) | 2007-03-21 |
JP4671609B2 (ja) | 2011-04-20 |
MY148579A (en) | 2013-04-30 |
KR20060126748A (ko) | 2006-12-08 |
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