WO2001036714A1 - Rust preventive - Google Patents

Rust preventive Download PDF

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Publication number
WO2001036714A1
WO2001036714A1 PCT/JP2000/007985 JP0007985W WO0136714A1 WO 2001036714 A1 WO2001036714 A1 WO 2001036714A1 JP 0007985 W JP0007985 W JP 0007985W WO 0136714 A1 WO0136714 A1 WO 0136714A1
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WO
WIPO (PCT)
Prior art keywords
acid
weight
fatty acid
salt
protective agent
Prior art date
Application number
PCT/JP2000/007985
Other languages
English (en)
French (fr)
Inventor
Yasuo Fukutani
Kikuko Fukutani
Yukio Wada
Yoshiki Ueno
Shinya Fukushima
Eiichiro Nakayama
Original Assignee
Yasuo Fukutani
Kikuko Fukutani
Yukio Wada
Yoshiki Ueno
Shinya Fukushima
Eiichiro Nakayama
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 Yasuo Fukutani, Kikuko Fukutani, Yukio Wada, Yoshiki Ueno, Shinya Fukushima, Eiichiro Nakayama filed Critical Yasuo Fukutani
Priority to KR10-2001-7008767A priority Critical patent/KR100539189B1/ko
Priority to US09/869,965 priority patent/US6488749B1/en
Priority to EP00974954A priority patent/EP1152068A4/en
Priority to JP2001538588A priority patent/JP3427071B2/ja
Publication of WO2001036714A1 publication Critical patent/WO2001036714A1/ja

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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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • 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
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/10—Liquid materials
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
    • C10M129/40—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
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    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
    • C10M129/42—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms polycarboxylic
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    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
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    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/38—Heterocyclic nitrogen compounds
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    • C10M173/00—Lubricating compositions containing more than 10% water
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
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    • 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
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
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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
    • C10M2201/02—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
    • 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
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • 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
    • 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
    • C10M2207/127—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 polycarboxylic
    • 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
    • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
    • 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
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/221—Six-membered rings containing nitrogen and carbon only
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
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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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C10M2215/226—Morpholines
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/26—Amines
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/30—Heterocyclic compounds
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    • C10N2010/00—Metal present as such or in compounds
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    • 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
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
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    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles

Definitions

  • the present invention relates to a metal-based antioxidant, and more particularly, to a water-soluble antioxidant used for storage of metal working fluids or metal parts.
  • Cutting fluids or lubricants are used when cutting metals, including iron, aluminum, and various alloys.
  • a water-insoluble cutting oil, a water-soluble cutting oil, or an aqueous solution type composition developed by the present inventors is used.
  • these cutting fluids and lubricants are added with an anti-corrosion agent to prevent metal corrosion.
  • An object of the present invention is to provide a protective agent which has low toxicity and does not adversely affect the environment.
  • Another object of the present invention is to provide a protective agent prepared as a composition having a high protective effect. Disclosure of the invention
  • the present inventors have repeatedly studied to develop a protective agent having a high protective effect without adversely affecting the environment, and as a result, the present invention has been achieved.
  • the antibacterial agent of the present invention is an aqueous solution containing a saturated fatty acid, a saturated dicarboxylic acid and a salt thereof, a chelating agent, tolyltriazole or benzotriazole, and a metal salt of a fatty acid.
  • the antioxidant of the present invention may further contain a hydroxide and a metasilicate such as Z or sodium metasilicate.
  • the protective agent of the present invention comprises 0.1% to 5% by weight of a saturated fatty acid, 0.01% to 1% by weight of a saturated dicarboxylic acid and a salt thereof, and 0.1% to 1% by weight of a chelating agent.
  • % may be an aqueous solution containing Torirutoriazo Ichiru or benzotriazole 5 X 1 0 one 3 wt% to 1 wt%, and metal salts of fatty acids 0. 0 1% to 1 by weight%.
  • the saturated fatty acid may be at least one selected from the group consisting of caprylic acid, caproic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, and stearic acid.
  • the saturated dicarboxylic acid can be dodecane diacid or sebacic acid.
  • the chelating agent can be a derivative of ethylenediaminetetraacetic acid or a derivative of nitrile triacetic acid.
  • the hydroxide may be potassium hydroxide. Also, the concentration of hydroxide may be from 0.1% to 5% by weight.
  • the metal salt of the fatty acid may be a potassium salt of a fatty acid.
  • the aqueous solution containing the saturated fatty acid, the saturated dicarboxylic acid and its salt, the chelating agent, the tolyltriazole or benzotriazole, and the metal salt of the fatty acid according to the present invention is at least used in ordinary distilled water, deionized water, tap water, etc. It is an aqueous solution in which saturated fatty acids, saturated dicarboxylic acids and salts thereof, chelating agents, tolyltriazole or benzotriazol, and metal salts of fatty acids are dissolved.
  • the antioxidant of the present invention can be further prepared by adding a hydroxide and Z or metasilicate.
  • Saturated fatty acids, saturated dicarboxylic acids and salts thereof in the antibacterial agent of the present invention The content of each of the chelating agent, tritriazole or benzotriabool, and the metal salt of the fatty acid is not particularly limited, but the saturated fatty acid may be 0.1% by weight to 5% by weight, preferably 0.3% by weight or less. 1% by weight, saturated dicarboxylic acid and its salt are 0.01% to 1% by weight, preferably 0.03% to 0.1% by weight, and a chelating agent such as a derivative of ethylenediaminetetraacetic acid is used. 0.01 wt% to 1 wt%, preferably 0.02 wt% to 0.
  • tolyl ⁇ tetrazole or benzotriazole is 5 X 1 0 one 3 wt% to 1 wt%, preferably 0. It is preferably an aqueous solution comprising from 0.01% to 0.1% by weight, and from 0.01% to 1%, preferably from 0.02% to 0.1% by weight of the metal salt of the fatty acid.
  • the saturated fatty acid used for preparing the antibacterial agent of the present invention is not particularly limited, and may be any saturated fatty acid known to those skilled in the art. Preferably, it is at least one selected from the group consisting of caprylic acid, caproic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, and stearic acid.
  • the saturated dicarboxylic acid used for preparing the antioxidant of the present invention is not particularly limited, and may be any saturated dicarboxylic acid known to those skilled in the art. Preferably, it is dodecane diacid or sebacic acid.
  • the chelating agent used for preparing the anti-oxidant of the present invention is not particularly limited, and may be any chelating agent known to those skilled in the art.
  • Such protective preparations include, for example, derivatives of ethylenediaminetetraacetic acid or tritriacetic acid.
  • it may be complex, such as tetrasodium salt of Echirenjiamin tetraacetic acid (E DTA- 4 N a 4H 2 ⁇ ).
  • the metal salt of a fatty acid used in the preparation of the antibacterial agent of the present invention is not particularly limited, and may be any fatty acid metal salt known to those skilled in the art. Particularly preferred are fatty acid potassium and fatty acid sodium.
  • aqueous solution prepared from a chelating agent such as a derivative of tritolylazole or benzotriazole, and a metal salt of a fatty acid can be used for various applications as it is as an alternative to a conventional antioxidant.
  • a hydroxide or a metasilicate having a pH adjusting action is not particularly limited, and may be any hydroxide known to those skilled in the art, such as sodium hydroxide, potassium hydroxide, and calcium hydroxide.
  • the metasilicate is not particularly limited, but a common salt known to those skilled in the art, such as sodium metasilicate, is used.
  • a stabilizer and the like can be appropriately added to the antioxidant of the present invention.
  • the anticorrosive agent of the present invention effectively acts on various metals such as iron, copper, stainless steel, and aluminum, and can be added to a metal cutting fluid used in metal cutting or used as an anticorrosive paint. In addition, it is used for circulating water for air conditioners and other vehicles, as well as for circulating fluid for floor heating, etc., and in various other applications.
  • the protective agent of the present invention also has lower toxicity than the conventional protective agent containing chromamine. In addition, they are well adapted to the metal working agents developed by the present inventors and exhibit excellent effects.
  • the present invention is not limited to the following examples, which shows examples using the anti-oxidant of the present invention.
  • the present invention can be carried out in various modified, modified, and modified embodiments based on the knowledge of those skilled in the art without departing from the spirit of the present invention.
  • a concentrated solution of the antioxidant of the present invention was prepared.
  • Example 1 Using the protective agent of the present invention (Test No. 1) obtained in Example 1 and a 50-fold diluted solution of the commercial protective agent (Test No. 3), the test was performed by the accelerated test method for half-immersion of the protective agent. The effect was studied. Stand one test piece (iron, copper alloy, aluminum alloy) of 25 mm x 5 Omm x 3.0 to 0.8 mm in a glass bottle, and use either the fire retardant of Example 1 or a diluted solution of a commercially available fire retardant. Soak about half of the test piece. After that, place the bottle on its side with the lid on, and leave it for about 1 minute so that the whole test piece is immersed. After that, place the glass bottle in a thermostat set at 50, and let the test pieces immerse on the surface (liquid phase, interface, gas phase) of the protective agent for 24 hours.
  • the surface condition of the test piece was observed for 48 hours, 72 hours, and 138 hours. The results are shown in Tables 1 and 2.
  • Example 1 when the dilution ratio of the concentrated solution obtained in Example 1 was kept low, the generation was better suppressed in any of the materials.
  • the waterproofing effect of the waterproofing agent of the present invention was tested.
  • a concentrated solution of the protective agent obtained in Example 1 was applied to Shinma paper (20 OmmX 275 mm) and filter paper (5C, 11 Omm) with a brush, dried with a dryer, and then dropped one drop of tap water. The time for complete absorption was measured. Judgment is based on visual observation.
  • the chemical inhibitor according to the present invention is actually used in companies in various fields such as production of semiconductors, production of plant machines, production of automobile parts and the like. Specifically, at the Tokyo Ikebukuro Mint, manufacturing medal medals, Toyoyu Motor R & D Center, Toyoyu Motor Co., Ltd., Hyundai Motor Co., Ltd., Nissan Motor Co., Ltd. and Suzuki Motor Co., Ltd. Manufacture of parts, manufacturing of semiconductors at Toshiba R & D Center Co., Ltd. Manufacture of brand machinery at New Nippon Steel Co., Ltd. Manufacture of billboard parts such as bulldozers at Topy Industries, Ltd. Power shovel at Komatsu Manufacturing Co., Ltd.
  • the heatproofing agent for adding to the metalworking fluid normally used at the time of metalworking is obtained.
  • This protective agent has little adverse effect on the environment, and its protective effect is not inferior to amine-based protective agents.
  • the fireproofing agent of the present invention is used in a wide range of applications where it is desired to suppress the generation of metal, such as being added to circulating fluids such as air conditioners and the like, in addition to metalworking.
  • the water-proofing agent of the present invention has a water-repelling effect, and thus has an effect as a water-proofing agent.

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Description

明細書
防鍺剤
技術分野
本発明は、 金属材用の防錡剤に関し、 より詳しくは、 金属加工液ある いは金属部品の保管等に使用される水溶性の防鍺剤に関する。 背景技術
鉄、 アルミニウム、 各種合金をはじめとする金属の切削加工の際には、 切削液あるいは潤滑剤が用いられている。 切削液や潤滑剤には、 水不溶 性切削油、 水溶性切削油、 あるいは本発明者らが開発した水溶液タイプ の組成物が用いられている。 通常、 これらの切削液や潤滑剤には、 金属 腐食を防ぐための防鍺剤が添加されている。
さらに、 防鐯剤は、 金属加工の用途の他、 ラジェ一夕用冷却液等に使 用されるなど、 種々のニーズがある。
しかし、 これまで防锖剤は、 毒性の問題や、 毒性と防鲭効果とのバラ ンスで効果が劣るなどの欠点があった。
本発明の目的は、 低毒性で環境に悪影響を与えない防鲭剤を提供する ことにある。
本発明の別の目的は、 防鍺効果の高い組成物として調製された防鐯剤 を提供することにある。 発明の開示
そこで、 本発明者等は、 環境に悪影響を与えず、 防鑌効果の高い防鍺 剤を開発するために検討を重ねた結果、 本発明に至ったのである。
本発明の防錡剤は、 飽和脂肪酸、 飽和ジカルボン酸及びその塩、 キレ —ト剤、 トリルトリァゾ一ルまたはべンゾトリァゾール、 および脂肪酸 の金属塩を含む水溶液である。 本発明の防鲭剤は、 さらに水酸化物および Zまたはメタ珪酸ナトリゥ ムなどのメタ珪酸塩を含む場合がある。
本発明の防锖剤は、 飽和脂肪酸 0 . 1重量％〜5重量％、 飽和ジカル ボン酸及びその塩 0 . 0 1重量％〜 1重量％、 キレート剤 0 . 0 1重 量％〜 1重量％、 トリルトリァゾ一ルまたはべンゾトリアゾール 5 X 1 0一3重量％〜 1重量％、 および脂肪酸の金属塩 0 . 0 1重量％〜 1重 量％を含む水溶液であり得る。
上記飽和脂肪酸は、 力プリル酸、 カブロン酸、 デカン酸、 ラウリン酸、 ミリスチン酸、 パルミチン酸、 ステアリン酸からなる群より選択される 少なくとも 1つであり得る。
上記飽和ジカルボン酸は、 ドデカン二酸またはセバチン酸であり得る。 上記キレート剤は、 エチレンジァミン四酢酸の誘導体又は二トリ口三 酢酸の誘導体であり得る。
上記水酸化物は、 水酸化カリウムであり得る。 また、 水酸化物の濃度 は、 0 . 1重量％〜5重量％であり得る。
上記脂肪酸の金属塩は、 脂肪酸のカリウム塩であり得る。 発明を実施するための最良の形態
本発明の飽和脂肪酸、 飽和ジカルボン酸及びその塩、 キレート剤、 ト リルトリァゾ一ルまたはべンゾトリァゾール、 および脂肪酸の金属塩を 含む水溶液は、 通常の蒸留水、 脱イオン水、 水道水等に、 少なくとも、 飽和脂肪酸、 飽和ジカルボン酸及びその塩、 キレート剤、 トリルトリァ ゾールまたはべンゾトリアゾ一ル、 および脂肪酸の金属塩を溶解させた 水溶液である。
本発明の防鑌剤は、 さらに、 水酸化物および Zまたはメタ珪酸塩を加 えて調製することもできる。
本発明の防鍺剤中の飽和脂肪酸、 飽和ジカルボン酸及びその塩、 キレ ート剤、 トリルトリァゾ一ルまたはべンゾトリアブール、 および脂肪酸 の金属塩のそれぞれの含有量は、 特に限定されないが、 飽和脂肪酸が 0. 1重量％〜5重量％、 好ましくは、 0. 3重量％〜1重量％、 飽和ジカ ルボン酸及びその塩が 0. 01重量％〜 1重量％、 好ましくは、 0. 0 3重量％〜0. 1重量％、 エチレンジァミン四酢酸の誘導体などのキレ —ト剤が 0. 01重量％〜1重量％、 好ましくは 0. 02重量％〜0. 1重量％、 トリルトリァゾールまたはべンゾトリアゾールが 5 X 1 0一3 重量％〜 1重量％、 好ましくは 0. 01重量％〜0. 1重量％、 および 脂肪酸の金属塩が 0 . 0 1重量％〜 1重量％、 好ましくは 0. 02重 量％〜0. 1重量％を含む水溶液であることが好ましい。
本発明の防鐯剤の調製に用いられる飽和脂肪酸は、 特に限定されず、 当業者に公知のいずれの飽和脂肪酸でもあり得る。 好ましくは、 カプリ ル酸、 カプロン酸、 デカン酸、 ラウリン酸、 ミリスチン酸、 パルミチン 酸、 およびステアリン酸からなる群より選択される少なくとも 1つであ る。
本発明の防鍺剤の調製に用いられる飽和ジカルボン酸は、 特に限定さ れず、 当業者に公知のいずれの飽和ジカルボン酸でもあり得る。 好まし くは、 ドデカン二酸またはセバチン酸である。
本発明の防鍺剤の調製に用いられるキレート剤は、 特に限定されず、 当業者に公知のいずれのキレート剤でもあり得る。 このような防製剤に は、 例えば、 エチレンジァミン四酢酸の誘導体または二トリ口三酢酸な どがある。 好ましくは、 エチレンジァミン四酢酸の四ナトリウム塩 （E DTA- 4 N a 4H2 〇） 等の錯体であり得る。
本発明の防锖剤の調製に用いられる脂肪酸の金属塩は、 特に限定され ず、 当業者に公知のいずれの脂肪酸金属塩でもあり得る。 特に好ましく は、 脂肪酸カリウム、 脂肪酸ナトリウムなどである。
飽和脂肪酸、 飽和ジカルボン酸及びその塩、 エチレンジァミン四酢酸 の誘導体などのキレート剤、 卜リルトリァゾ一ルまたはべンゾトリァゾ —ル、 および脂肪酸の金属塩から調製した水溶液は、 そのまま、 従来の 防鲭剤の代替として様々な用途に用いることができるが、 さらに防錡効 果を高めるために、 p H調整作用を有する水酸化物、 あるいはメタ珪酸 塩を加えることが好ましい。 この場合に用いられる水酸化物は、 特に限 定されず、 水酸化ナトリウム、 水酸化カリウム、 水酸化カルシウムなど、 当業者に公知のいずれの水酸化物でもあり得る。 また、 メタ珪酸塩も特 に限定されないが、 メ夕珪酸ナトリウムなど、 当業者に公知の一般的な 塩が用いられる。
その他にも、 本発明の防鐯剤には、 さらに安定剤等を適宜加えること ができる。
本発明の防錡剤は、 鉄、 銅、 ステンレス、 アルミニウムなど様々な金 属に対して有効に作用し、 金属切削の際に用いられる金属切削液に添加 されたり、 防食塗料として用いられ得る。 さらに、 自動車のラジェ一夕、 エアコン等の循環水、 床暖房等の為の循環液に用いられる他、 様々な用 途がある。
本発明の防鐯剤はまた、 従来のクロムゃァミンを含有する防鲭剤に比 ベて毒性が低い。 また、 本発明者らが開発した金属加工剤に良好になじ み、 優れた効果を発揮する。
本発明の防鑌剤を用いた実施例を示すが、 本発明は、 以下の実施例に 限定されるものではない。 本発明はその趣旨を逸脱しない範囲内で、 当 業者の知識に基づき種々なる改良、 修正、 変形を加えた態様で実施し得 るものである。 実施例
次に、 本発明に係る防鍺剤の製造方法、 およびそれを用いた防鐯作用 の試験についての実施例を説明する。 01/
5
(実施例 1 )
本発明の防锖剤の濃縮液を調製した。 蒸留水 440 gに、 市販の水酸 化カリウム （旭硝子株式会社製） 270 g、 カブリル酸 （日本油脂株式 会社製） 180 g、 EDTA-4N a - 4H2 O (クレワット S 2、 帝 国化学産業株式会社製） 20 g、 ドデカン二酸 （岡村製油株式会社製）
30 g、 トリルトリァゾール （城北化学工業株式会社製） 、 脂肪酸カリ ゥム 14 gを添加し、 混合した。 次に、 この濃縮液を、 蒸留水で 50倍 希釈して、 防鲭剤を調製した。
(実施例 2)
実施例 1で得られた本発明の防錡剤 （試番 1) と市販の防銪剤の 50 倍希釈液 （試番 3) を用いて、 防鍺剤半浸漬加速試験方法により、 防锖 作用を検討した。 ガラス瓶に 25mmx 5 Ommx 3. 0〜0. 8 mm の試験片 （铸鉄、 銅合金、 アルミ合金） を 1枚立て、 実施例 1の防鐯剤 または市販の防錡剤の希釈液のいずれかを試験片の半分程度浸す。 その 後、 蓋をしてビンを横にし、 試験片の全体が浸漬するようにして約 1分 間放置する。 その後、 50でにセットした恒温槽にガラス瓶を設置し、 各試験片の防锖剤浸漬表面 （液相、 界面、 気相） 部における、 24時間、
48時間、 72時間、 および 138時間の試験片表面状態を観察した。 その結果を表 1および表 2に示す。
【表 1】
Figure imgf000007_0001
替换页 (细则第 26糸） ここで、 判定結果を表す数値は、 0 ：発鍺なし、 1 ：発銪 10 %未満、 2 ：発鍺 10 %〜40 %未満、 3 ：発銪 40 %〜70 %未満、 4 ：発鍺 70%〜90%未満、 5 ：発錡 90%以上を意味する。
この結果、 実施例 1で得られた防锖剤を使用した場合、 铸鉄の FC— 200試験片、 は、 138時間後においても全く鍺の発生が見られなか つた。
一方、 市販の防鍺剤の場合、 24時間後に 10%程度、 138時間後 に 30%程度の鍺が見られた。
その他の材質の試験片に対しては、 本発明の防鍺剤を使用しても、 多 少の変色や発鲭は見られたが、 いずれも市販の防鍺剤に劣るものではな かった。
また、 実施例 1で得られる濃縮液の希釈割合を低く抑えれば、 いずれ の材質においても、 発鍺がよりよく抑えられた。
(実施例 3 )
本発明の防鍺剤の防水効果を試験した。 新間紙 （20 OmmX 275 mm) および濾紙 （5C、 1 1 Omm) に実施例 1の中で得られた防鍺 剤の濃縮液を刷毛で塗り、 ドライヤーで乾燥後、 水道水を 1滴落として 完全に吸収される時間を計測した。 判定は目視観察による。
その結果を表 3に示す。
【表 3】 吸収されるまでの時間
新聞紙ブランク A (無地） 2分 02秒
新聞紙: Γランク B (印刷） 2分 38秒
新聞紙 A (防鐫剤 5 17分 42秒
新聞紙 B (防鲭剤 10¾_) 17分 37秒
減紙ブランク 6, 7秒
濾紙 A (未乾燥） 1分 28秒
丽 B (鶴） 14分46 、カ、ら1フ分 本発明の防錡剤は、 防水作用も有することが分かった。
また、 本発明にかかる防錡剤は、 半導体の製造、 プラント機械の製造、 自動車部品の製造等種々の分野における企業において、 実際に用いられ ている。 具体的には、 東京池袋造幣局において、 勲章メダルの製造、 卜 ョ夕自動車研究開発センタ一、 トヨ夕自動車株式会社、 本田技研工業 (株） 、 日産自動車株式会社、 スズキ株式会社の各社において、 自動車 部品の製造、 株式会社東芝研究開発センターにおいて半導体の製造、 新 日本製鉄株式会社においてブラント機械製造、 トピー工業株式会社にお いてブルドーザ等のキヤ夕ビラ部品の製造、 小松製作所 （株） において パワーシャベル 'ブルドーザ等の部品の製造、 アイシン精機株式会社に おいて自動車部品の製造、 立命館大学工作センターにおいて種々の分野 における学生の実習研究に、 用いられている。 マシ一二ングセンタ、 L Cセンタ、 専用機等の駆動と共に用いられているが、 防鍺効果が認めら れている。
産業上の利用可能性
本発明によれば、 金属加工の際に通常用いられている金属加工液に添 加する為の防鐯剤が得られる。
この防鍺剤は、 環境に与える悪影響が少なく、 防鐯効果はアミン系防 錡剤に劣らない。
本発明の防鐯剤は、 金属加工の他、 ラジェ一夕、 エアコン等の循環液 にも加えられるなど、 金属の鍺の発生を抑えたい場合の幅広い用途に使 用される。
また、 本発明の防鲭剤は、 浼水作用もある為、 防水剤としての効果も ある。

Claims

請求の範囲
1 . 飽和脂肪酸、 飽和ジカルボン酸およびその塩、 キレート剤、 トリ ルトリアゾ一ルまたはべンゾトリァゾール、 および脂肪酸の金属塩を含 む水溶液であることを特徴とする防鍺剤。
2 . さらに水酸化物および またはメ夕珪酸塩を含むことを特徴とす る請求項 1に記載の防锖剤。
3 . 前記メ夕珪酸塩がメ夕珪酸ナトリウムであることを特徴とする請 求項 2に記載の防锖剤。
4 . 飽和脂肪酸 0 . 1重量％〜5重量％、 飽和ジカルボン酸及びその 塩 0 . 0 1重量％〜 1重量％、 キレート剤 0 . 0 1重量％〜 1重量％、 トリルトリァゾ一ルまたはべンゾトリアゾ一ル 5 X 1 0— 3重量％〜 1 重量％、 および脂肪酸の金属塩 0 . 0 1重量％〜1重量％を含む水溶 液であることを特徴とする請求項 1から 3までのいずれかに記載の防鍺 剤。
5 . 前記飽和脂肪酸が力プリル酸、 カブロン酸、 デカン酸、 ラウリン 酸、 ミリスチン酸、 パルミチン酸、 およびステアリン酸からなる群より 選択される少なくとも 1つであることを特徴とする請求項 1から 4まで のいずれかに記載の防锖剤。
6 . 前記飽和ジカルボン酸がドデカンニ酸またはセバチン酸であるこ とを特徴とする請求項 1から 5までのいずれかに記載の防鍺剤。
7 . 前記キレート剤が、 エチレンジァミン四酢酸の誘導体または二卜 リ口三酢酸の誘導体であることを特徴とする請求項 1から 6までのいず れかに記載の防鍺剤。
8 . 前記脂肪酸の金属塩が脂肪酸のカリウム塩であることを特徴とす る請求項 1から 7までのいずれかに記載の防錡剤。
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EP00974954A EP1152068A4 (en) 1999-11-12 2000-11-10 RUST
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JP3427071B2 (ja) 2003-07-14
KR20010089813A (ko) 2001-10-08
EP1152068A4 (en) 2006-12-27
KR100539189B1 (ko) 2005-12-27
EP1152068A1 (en) 2001-11-07
US6488749B1 (en) 2002-12-03

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