WO2003027188A1 - Treating agent for forming protective coating and metallic material having protective coating - Google Patents

Treating agent for forming protective coating and metallic material having protective coating Download PDF

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Publication number
WO2003027188A1
WO2003027188A1 PCT/JP2002/007380 JP0207380W WO03027188A1 WO 2003027188 A1 WO2003027188 A1 WO 2003027188A1 JP 0207380 W JP0207380 W JP 0207380W WO 03027188 A1 WO03027188 A1 WO 03027188A1
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WO
WIPO (PCT)
Prior art keywords
protective film
treating agent
agent according
metal material
wax
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2002/007380
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
Shinobu Komiyama
Yugo Tsuiki
Akihiro Seo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Nihon Parkerizing Co Ltd
Original Assignee
Henkel AG and Co KGaA
Nihon Parkerizing Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA, Nihon Parkerizing Co Ltd filed Critical Henkel AG and Co KGaA
Priority to EP02747703.3A priority Critical patent/EP1454965B1/en
Priority to ES02747703.3T priority patent/ES2463472T3/es
Priority to CA002457984A priority patent/CA2457984A1/en
Priority to KR1020047002355A priority patent/KR100675537B1/ko
Publication of WO2003027188A1 publication Critical patent/WO2003027188A1/ja
Priority to US10/765,322 priority patent/US7651556B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • 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
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26—Silicates of the alkali metals
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
    • C09D1/04—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates with organic additives
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00215—Mortar or concrete mixtures defined by their oxide composition
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00482—Coating or impregnation materials
    • C04B2111/00525—Coating or impregnation materials for metallic surfaces
    • 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
    • C10M2201/102—Silicates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/10—Compounds containing silicon
    • C10M2201/102—Silicates
    • C10M2201/1023—Silicates used as base material
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/10—Compounds containing silicon
    • C10M2201/102—Silicates
    • C10M2201/1026—Silicates used as thickening agents
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    • 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
    • C10M2201/102—Silicates
    • C10M2201/103—Clays; Mica; Zeolites
    • C10M2201/1036—Clays; Mica; Zeolites used as thickening agents
    • 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
    • C10M2201/18—Ammonia
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • 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
    • C10M2205/14—Synthetic waxes, e.g. polythene waxes
    • C10M2205/143—Synthetic waxes, e.g. polythene waxes used as base material
    • 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
    • C10M2205/16—Paraffin waxes; Petrolatum, e.g. slack wax
    • C10M2205/163—Paraffin waxes; Petrolatum, e.g. slack wax used as base material
    • 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
    • C10M2205/18—Natural waxes, e.g. ceresin, ozocerite, bees wax, carnauba; Degras
    • C10M2205/183—Natural waxes, e.g. ceresin, ozocerite, bees wax, carnauba; Degras used as base material
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
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    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/401—Fatty vegetable or animal oils used as base material
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    • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2213/06—Perfluoro polymers
    • C10M2213/062—Polytetrafluoroethylene [PTFE]
    • C10M2213/0623—Polytetrafluoroethylene [PTFE] used as base material
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2010/00—Metal present as such or in compounds
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    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/06—Groups 3 or 13
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    • 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
    • C10N2040/20—Metal working
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    • 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
    • C10N2050/015—Dispersions of solid lubricants
    • C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
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    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/023—Multi-layer lubricant coatings
    • 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
    • C10N2050/10—Form in which the lubricant is applied to the material being lubricated semi-solid; greasy

Definitions

  • the present invention relates to a protective film treating agent, a metal material having a protective film, and a method for forming a protective film. More specifically, the present invention is intended to form a protective film having excellent workability and anti-seizure resistance on a metal material surface requiring cold plasticity, and also having excellent heat resistance and heat resistance to processing heat.
  • the present invention relates to a treatment agent, a metal material having a protective film, and a method for forming a protective film, which is used by applying a lubricating component to the surface of the film or by including the lubricating component in the film to impart the necessary lubricity to the coating. . Background art
  • a protective coating layer is applied to the surface of the impeached material to prevent seizure between the tool and the tool.
  • the main function of this protective film layer is to avoid direct metal contact between the surface of the workpiece and the tool surface, such as strong adhesion between the metal material surface and the protective film, The ability to follow the increase in surface area is particularly important.
  • a force to apply a lubricating component to the protective film layer the number of frictions with the tool surface is reduced, and the processing energy is reduced by reducing the load on the film layer itself and the generation of processing heat. Has been realized.
  • a film mainly composed of a lubricating component such as an oil film, a soap film, a metal soap film, and a wax film.
  • a method of forming a lubricant, a method of forming a reactive chemical conversion film such as a phosphate / oxalate film on a metal surface, and then forming a lubricant component film have been mainly used.
  • the former is a film obtained by applying the lubricating component alone or, if necessary, together with a binder component to the surface of the adhering material and drying it.
  • the latter has a strong reactivity with the material surface by forming a dense reactive conversion coating layer on the surface of the material, and it is also effective against the surface area increase when 3 It shows sufficient followability.
  • the metal soap layer formed by the reaction with the surface layer of the conversion coating layer and the sodium soap layer, which is the lubricating component of the uppermost layer are secured by the surface roughness to ensure adhesion and retention.
  • the processing energy has been dramatically reduced.
  • the conversion film since the conversion film is formed by a chemical reaction, it requires a large amount of power, including the need for proper treatment liquid management and many steps, and wastewater treatment and capital investment. You.
  • a lubricant composition for plastics of a metal material containing a synthetic resin and a water-soluble inorganic salt in a specific ratio Japanese Patent Application Laid-Open No. 2000-63080
  • This is to prevent the direct metal contact with the tool by forming a film in which the synthetic resin and the water-soluble inorganic salt are uniformly deposited on the surface of the roe material, and further to coat the lubricating component at an arbitrary ratio. It is said that by containing the compound in the composition, performance equivalent to or higher than that obtained when a lubricating component layer is formed on the phosphate film is obtained.
  • the present invention is to solve the above-mentioned problems of the prior art.
  • it can greatly reduce the load on power such as complicated treatment liquid management and many processes, wastewater treatment and industrial waste, and after being attached by an immersion method or spray method, drying
  • It is possible to form a film with excellent seizure resistance and excellent heat resistance equal to or higher than that of the chemical conversion treatment method by a simple method, and to apply a lubricating component on this protective film.
  • An object of the present invention is to provide a protective film treating agent capable of imparting excellent self-lubricating performance to a film obtained by including the same, a metal material having a protective film, and a method for forming a protective film.
  • the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, a simple method of applying a protective film treating agent obtained by blending a specific alkaline silicate with water to a metal material and drying it. As a result, it has been found that a film having excellent seizure resistance and excellent heat resistance equal to or higher than that of the ligating method can be formed. Further, they have found that by applying a lubricating component onto the protective film and by including the lubricating component in the film, it is possible to impart excellent self-lubricating performance to the obtained film, and have completed the present invention.
  • the present invention relates to Formula M: O ⁇ n S i 0 2 (where n is a number from 2 to 9 and M is Na, K, Li and NR 4 (wherein R independently represents a hydrogen atom or an alkyl group for each R)
  • the present invention relates to a protective film treating agent which is blended in the above.
  • a film obtained from a strong treating agent exhibits excellent seizure resistance and excellent heat resistance as a base for a conventional lubricating film composed of oil, soap, metal soap, wax and the like.
  • at least one lubricating component selected from oil, soap, metallic soap, wax and polytetrafluoroethylene is further blended as a lubricating component.
  • the present invention relates to a metal material having a protective film, characterized in that a protective film formed from the above protective film treating agent is formed.
  • the present invention further relates to a method for forming a protective film, which comprises applying the protective film treating agent to a surface of a metal material.
  • the calcium acid salt represented by the above formula used in the protective film treating agent of the present invention is an essential component of the skin B in the treatment lj of the present invention, and forms a strong continuous film on the metal surface.
  • it also provides excellent corrosion protection.
  • the melting point of the coating made of phenolic acid is much higher than the temperature reached by the material during cold plastic working, so that the lubricating coating layer based on this is hardly affected by the Karoe heat. Function can be stably exhibited.
  • R is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group.
  • the alkaline silicate used in the protective film treating agent of the present invention is usually used in the form of an aqueous solution consisting of silicon dioxide, alkali metal oxides, and copper.
  • the These Kei acid Al force Li can exist stably in a liquid, the hydration M + is believed to interfere with the condensation of Kei acid ions with a OH, dissolved in water as M 2 0 minutes often It is easily prepared and stable as an aqueous solution.
  • the present invention in order to form a glassy coating according Kei alkali, must be in the range of 2-9 molar ratio of S i 0 2 / M 2 O , than this is 2 If it is too small, sufficient strength as a protective film cannot be obtained, and if it is more than 9, the stability as an aqueous solution will be extremely poor, and it will be difficult to produce an aqueous protective film treating agent.
  • the S i 0 2 / M 2 0 mole ratio is not limited to an integer, it may be a numerical value, including the following figures point insofar as they come within the scope of 2-9.
  • Kei acid Al force Li to be used in the present invention
  • S i 0 2 / M 2 O Kei acid Natoriumu and potassium Kei acid molar ratio is 2 to 4
  • S i 0 2 ZM 2 0 of mode Forces such as lithium silicate having a nodding ratio of 3.5 to 8.5 and ammonium silicate having a molar ratio of SiO 2 / M 2 O of 3 to 9 etc. Stability of aqueous solution, film forming property, etc.
  • sodium silicate and potassium silicate are particularly preferred, and the molar ratio of S i. ⁇ 2 / M 2 O is preferably 2 to 4.
  • Kei alkali used in the present invention as long as the S i 0 2 ZM 2 0 molar ratio is satisfactory as a whole, can be used in combination each alone or two or more kinds.
  • the aqueous protective film treating agent of the present invention may contain a lubricating component as required, and it is usually preferable to include it in the treating agent.
  • the strong lubricating component is desirably one that is stable in a 7K liquid and does not reduce the film strength, and examples thereof include soap, metal soap, wax, polytetrafluoroethylene, and oil. Specific examples of the soap include sodium stearate and potassium stearate.
  • Examples of the metallic soap include calcium stearate, aluminum stearate, barium stearate, lithium stearate, and lithium stearate.
  • Examples of the wax include polyethylene wax, polypropylene wax, carnauba wax, beeswax, paraffin wax, and the like.
  • Examples of the fluoroethylene include polytetrafluoroethylene having a degree of polymerization of, for example, about 100,000 to 10,000.
  • vegetable oils, mineral oils, synthetic oils, etc. can be used as oils.For example, vegetable oils include palm oil, castor oil, rapeseed oil, etc., mineral oils include machine oil, turbine oil, spin-drain oil, and synthetic oils. Examples thereof include ester oil and silicone oil.
  • the lubricating component is usually dispersed or emulsified in the aqueous protective film treating agent of the present invention.
  • the lubricating components used in the present invention can be used alone or in combination of two or more.
  • the compounding amount of the lubricating component is 1 to 90% by mass (based on the total mass of the alkali silicate and the lubricating component). 1 0-9 9 mass 0 / o) and it is preferred to, 5-8 5% (Kei acid Al Chikarari 1 5-9 5 mass 0/0) and more preferably to Rere.
  • the blending amount is 1 mass 0 /.
  • the alkali silicate is usually used in the form of an aqueous solution
  • the lubricating component is preferably used in the form of a water dispersion and a water emulsion.
  • the values are for the power and the lubricating components themselves. In this case, water is excluded. The same applies to the amount of the viscosity modifier described later.
  • the aqueous protective film treating agent of the present invention may contain a viscosity modifier for the purpose of improving coatability.
  • the compounding amount of the viscosity modifier is preferably 1 to 30% by mass based on the total mass of the alkali silicate and the lubricating component (the mass of the alkaline silicate when no lubricating component is mixed). 0 mass% is more preferred And 2 to 5% by mass is still more preferable. If the amount is more than 30% by mass, the strength of the film is remarkably reduced. If the amount is less than 1% by mass, the compounding effect cannot be obtained.
  • viscosity modifier besides merely increasing the viscosity of the treating agent, those which impart thixotropic properties to the treating solution to promote uniform film formation are used. Specifically, organic polymer thickeners such as hydroxyethylcellulose, carboxymethylcellulose, polyacrylamide, sodium polyacrylate, polybutylpyrrolidone, and polyvinyl alcohol, finely divided silica, bentonite, kaolin, and synthetic hectorite Inorganic thickeners and the like are used. These viscosity modifiers can be used alone or in combination of two or more.
  • solid lubricants such as graphite, molybdenum disulfide, boron nitride, graphite fluoride, mica, ore sulfide, sulfide ester, sulfite, and thiocarbonate are included in the protective coating agent of the present invention.
  • Extreme pressure additives such as chlorinated fatty acids, phosphate esters, phosphites, molybdenum dithiocarbamate (Mo DTC), molybdenum dithiophosphate (Mo DTP), zinc dithiophosphate (Zn DTP) It can also be contained.
  • the total concentration of components other than the solvent or dispersion medium, which is usually water, in the protective film treating agent of the present invention is not particularly limited, but generally about 1 to 35% by mass is appropriate.
  • the metal material having a protective film of the present invention can be obtained by applying the above-mentioned aqueous protective film treating agent to the surface of a metal material such as iron or steel, copper or a copper alloy, aluminum or an aluminum alloy, titanium or a titanium alloy, and drying.
  • the protective coating of the present invention greatly improves the workability and seizure resistance of a metal material during cold plastic forming (drawing, drawing, forging, etc.), and the material after processing. It also has excellent protection against water.
  • the shape of the metal material having the protective film of the present invention is not particularly limited, since not only materials such as wood and block materials but also processing of shapes (gears, shafts, etc.) after hot forging can be considered.
  • the metal material to be processed Prior to applying the aqueous protective film treating agent of the present invention, the metal material to be processed is degreased (usually an alkali degreasing agent can be used), washed with water, and pickled (to remove the oxidized scale of the metal material, High film adhesion
  • the protective film treating agent of the present invention is applied to a metal material by an ordinary method such as dipping, spraying, pouring, electrostatic application and the like.
  • the application may be performed as long as the metal surface is sufficiently covered with the aqueous protective film treating agent, and the application time is not particularly limited.
  • the aqueous protective coating treatment must be dried. Drying may be carried out at room temperature, but it is usually preferable to carry out drying at 60 to 150 ° C for 1 to 30 minutes.
  • the mass of the protective coating of the present invention after application and drying is preferably 0.3 g / m 2 or more from the viewpoint of preventing seizure and imparting corrosion resistance, and is preferably 50 g / m 2 or less from the cost surface. Preferably, there is. Further, in order to stably exhibit the effects of the present invention, the coating weight is more preferably from 1 to 30 g / m 2 .
  • the metal material surface has excellent lubricating properties in addition to excellent seizure resistance and excellent heat resistance. Can be given to.
  • the agent does not contain a lubricating component, excellent seizure resistance and excellent heat resistance can be imparted to the metal material surface.
  • at least one lubricating component selected from the above-described soaps, metallic soaps, waxes, polytetrafluoroethylene and oils is applied onto the dried coating film to further improve the lubricity.
  • the application of the lubricating component can be usually carried out by melting the lubricating component and applying it on a dry coating film.
  • test piece After the oil adhering to the surface of the test piece subjected to the spike test processing was wiped off with a jet chiller, the test piece was exposed indoors for 6 months, and the degree of occurrence of ⁇ was visually evaluated. The evaluation criteria are shown below.
  • the processing was performed in the following processing steps.
  • the processing was performed in the following processing steps.
  • Table 1 shows the test results. As is evident from Table 1, Examples 1 to 7 using the aqueous composition for forming a protective film of the present invention exhibit excellent workability by simple steps and therefore have a good seizure resistance function. It was presumed that they had even better anticorrosion properties. On the other hand, Comparative Example 1 in which the molar ratio of SiO 2 ZM 20 is out of the range of the present invention, and Comparative Example 2 in which the mass ratio of the alkali silicate in the film is out of the range of the present invention follow the caroe. Comparative Examples 3 and 4 using only inorganic salts other than alkali acid were inferior in anticorrosion properties.
  • the phosphate film of Comparative Example 5 which had been subjected to a reaction soap treatment showed almost the same lubrication performance as the present invention, but required wastewater treatment and liquid management and could not be used with simple equipment, and was not disposed of due to the reaction. This is not the intention of the present invention because of the large environmental load caused by the product.
  • composition amount indicates the mass ratio of the alkaline silicate to the lubricating component in the film.
  • the aqueous protective film treating agent of the present invention can coat the protective film on the surface of the metal material by a simple method of adhering to the surface of the target metal and then drying.
  • the metal material having this protective film is at a practical level and has seizure resistance and good heat resistance equivalent to those of conventional phosphate-treated steel. In addition, there is little waste and the work environment is good, so the industrial utility value is extremely large

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  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
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PCT/JP2002/007380 2001-08-17 2002-07-22 Treating agent for forming protective coating and metallic material having protective coating Ceased WO2003027188A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP02747703.3A EP1454965B1 (en) 2001-08-17 2002-07-22 Treating agent for forming protective coating and metallic material having protective coating
ES02747703.3T ES2463472T3 (es) 2001-08-17 2002-07-22 Agente de tratamiento para formar una capa protectora y material metálico con capa protectora
CA002457984A CA2457984A1 (en) 2001-08-17 2002-07-22 Treating agent for forming protective coating and metallic materials with a protective coating
KR1020047002355A KR100675537B1 (ko) 2001-08-17 2002-07-22 보호피막 처리제, 보호피막을 가지는 금속재료 및보호피막 형성방법
US10/765,322 US7651556B2 (en) 2001-08-17 2004-01-26 Treating agent for forming a protective coating and metallic materials with a protective coating

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JP2001248288A JP2003055682A (ja) 2001-08-17 2001-08-17 保護皮膜処理剤および保護皮膜を有する金属材料
JP2001-248288 2001-08-17

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US7651556B2 (en) 2010-01-26
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KR20040030155A (ko) 2004-04-08
ES2463472T3 (es) 2014-05-28
JP2003055682A (ja) 2003-02-26
EP1454965A1 (en) 2004-09-08
US20040156995A1 (en) 2004-08-12
EP1454965B1 (en) 2014-03-05
CN1260310C (zh) 2006-06-21
KR100675537B1 (ko) 2007-01-29
CN1543489A (zh) 2004-11-03

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