WO2018230313A1 - Treatment liquid for forming film having corrosion-resistance and insulating performance - Google Patents

Treatment liquid for forming film having corrosion-resistance and insulating performance Download PDF

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Publication number
WO2018230313A1
WO2018230313A1 PCT/JP2018/020266 JP2018020266W WO2018230313A1 WO 2018230313 A1 WO2018230313 A1 WO 2018230313A1 JP 2018020266 W JP2018020266 W JP 2018020266W WO 2018230313 A1 WO2018230313 A1 WO 2018230313A1
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Prior art keywords
group
mass
treatment liquid
film
parts
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PCT/JP2018/020266
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French (fr)
Japanese (ja)
Inventor
匡文 野崎
克将 嶋橋
隆 加東
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奥野製薬工業株式会社
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Priority to JP2019525268A priority Critical patent/JPWO2018230313A1/en
Publication of WO2018230313A1 publication Critical patent/WO2018230313A1/en

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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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • 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
    • C23F11/173—Macromolecular compounds

Definitions

  • the present invention relates to a processing solution for forming a film, a method for forming a film, and the like.
  • Patent Document 1 discloses a rust prevention treatment method by forming a siliceous film after chemical conversion treatment with trivalent chromium.
  • Patent Document 1 does not discuss insulation.
  • the requirements for the corrosion resistance and insulation performance for the metal materials described above are increasing, and there is a problem that the above-described methods cannot satisfy the required corrosion resistance and insulation performance.
  • An object of the present invention is to provide a treatment liquid and a treatment method capable of further enhancing both the rust prevention performance and insulation of a metal material.
  • the present invention provides a treatment liquid and a treatment method capable of further enhancing both the rust prevention performance and the insulating property of the metal material while the film formed by the treatment is thinner.
  • the present inventor contains a silicon compound having at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond, an organometallic compound, and water. It has been found that the above-mentioned problems can be solved by using a treatment liquid for forming a film having corrosion resistance and insulation performance. As a result of further research based on this knowledge, the present inventor completed the present invention.
  • this invention includes the following aspects as one aspect: Item 1.
  • a treatment liquid for forming a film having corrosion resistance and insulation performance comprising a silicon compound having at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond, an organometallic compound, and water.
  • Item 2. Item 2. The treatment liquid according to Item 1, wherein the silicon compound contains a resin.
  • Item 3. Item 3.
  • the treatment liquid according to Item 1 or 2 wherein the organometallic compound is at least one selected from the group consisting of an organometallic chelate compound and a metal alkoxide.
  • Item 4. Item 4.
  • Item 5. The treatment liquid according to any one of Items 1 to 4, wherein the content of the organometallic compound is 0.01 to 50 parts by mass with respect to 100 parts by mass of the silicon compound.
  • Item 6. The treatment liquid according to any one of Items 1 to 5, wherein the water content is 1 to 100 parts by mass with respect to 100 parts by mass of the silicon compound.
  • Item 8 The method according to Item 7, further comprising (Step 2) a step of curing after Step 1.
  • Step 2 a step of curing after Step 1.
  • Item 9. Item 9.
  • Item 10. A crosslinked structure of a silicon compound comprising a metal material and a film on the surface of the metal material, wherein the film has at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond; And containing an organometallic compound, Film-containing metal material.
  • the present invention it is possible to provide a treatment liquid and a treatment method that can further improve both the rust prevention performance and the insulating property of a metal material. Moreover, according to this invention, the metal material containing a rust preventive film which can be obtained by this processing method can also be provided.
  • the present invention includes a silicon compound having at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond, an organometallic compound, and water, and has corrosion resistance and insulation performance.
  • the treatment liquid for forming a film having the above in the present specification, it may be referred to as “the treatment liquid of the present invention”
  • the film formation method using the treatment liquid of the present invention, and the treatment liquid of the present invention relates to a film-containing metal material that can be obtained. These will be described below.
  • the alkoxysilyl group is not particularly limited as long as it is an alkoxysilyl group having at least one alkoxy group.
  • Examples of the alkoxysilyl group include, for example, the general formula (1): (R 1 ) m (R 2 O) 3-m Si— (wherein R 1 is a functional group and R 2 is a lower alkyl group. And an integer of 0 to 2).
  • Examples of the functional group represented by R 1 include methyl, dimethyl, phenyl, diphenyl, hexyl, decyl, 1,6-bis (trimethoxysilyl), trifluoropropyl, vinyl, 3-glycidoxypropyl, 3-glycid Xylpropylmethyl, 2- (3,4-epoxycyclohexyl) ethyl, p-styryl, 3-methacryloxypropyl, 3-methacryloxypropylmethyl, 3-acryloxypropyl, 3-aminopropyl, N-2- (amino Ethyl) -3-aminopropyl, N-2- (aminoethyl) -3-aminopropylmethyl, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3- Aminopropyl, N- (vinylbenzyl) -2-aminoethyl-3
  • lower alkyl group represented by R 2 examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, 1-ethylpropyl, isopentyl.
  • linear or branched alkyl groups having about 1 to 6 carbon atoms such as neopentyl.
  • the alkoxysilylene group is not particularly limited as long as it is an alkoxysilylene group having at least one alkoxy group.
  • Examples of the functional group represented by R 3 include the same functional groups represented by R 1 .
  • Examples of the lower alkyl group represented by R 4 include the same as the lower alkyl group represented by R 2 .
  • the silicon compound is not particularly limited as long as it is a silicon compound having at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond as a partial structure.
  • the silicon compound include resins, alkoxysilane oligomers, and alkoxysilanes. Among these, Preferably resin is mentioned.
  • the resin examples include not only silicone resins but also various resins into which alkoxysilyl groups are introduced (for example, acrylic resins, urethane resins, epoxy resins, polyester resins, melamine resins, etc.).
  • acrylic resins, urethane resins, epoxy resins, polyester resins, melamine resins, etc. examples include acrylic resins, urethane resins, epoxy resins, polyester resins, melamine resins, etc.
  • an acrylic resin and a silicone resin into which an alkoxysilyl group is introduced are preferable, and an acrylic resin into which an alkoxysilyl group is introduced is more preferable.
  • the weight average molecular weight of the resin is not particularly limited, but is, for example, 11000 to 200000, preferably 11000 to 100,000, more preferably 11000 to 70000, and still more preferably 11000 to 50000.
  • the content of the alkoxysilyl group is, for example, 1 to 70% by mass, preferably 2 to 60% by mass, more preferably 3 to 50% by mass, and still more preferably It is 4 to 45% by mass, more preferably 5 to 40% by mass.
  • alkoxysilane examples include Si (OCH 3 ) 4 , Si (OC 2 H 5 ) 4 , CH 3 Si (OCH 3 ) 3 , CH 3 Si (OC 2 H 5 ) 3 , C 2 H 5 Si (OCH 3).
  • the alkoxysilane oligomer is obtained by hydrolyzing and polycondensing alkoxysilane.
  • the alkoxysilane oligomer for example, an alkoxysilane oligomer having a weight average molecular weight of about 500 to 10,000 can be used.
  • the silicon compound may be used alone or in combination of two or more. Good.
  • the content of the silicon compound is, for example, 3 to 70% by mass, preferably 5 to 30% by mass, and more preferably 8 to 25% by mass with respect to 100% by mass of the treatment liquid of the present invention.
  • the treatment liquid of the present invention may contain an alkoxysilyl group, an alkoxysilylene group, and a resin having no siloxane bond (non-silicon resin).
  • non-silicon resin examples include an epoxy resin, an acrylic resin, a urethane resin, a polyester resin, and a melamine resin.
  • an epoxy resin is mentioned, More preferably, a bisphenol A type epoxy resin is mentioned.
  • Component A is preferably an acrylic resin or silicone resin into which an alkoxysilyl group is introduced, and more preferably an acrylic resin into which an alkoxysilyl group is introduced.
  • Component B is preferably a non-silicon resin, more preferably an epoxy resin, and still more preferably a bisphenol A type epoxy resin.
  • component B is, for example, 30 to 200 parts by mass, preferably 60 to 150 parts by mass, more preferably 80 to 120 parts per 100 parts by mass of component A. Part by mass, more preferably 90 to 110 parts by mass.
  • the organometallic compound is not particularly limited as long as it can function as a catalyst for the condensation reaction.
  • a metal compound for example, a water-soluble organometallic chelate compound containing titanium, zirconium, aluminum, tin or the like, a metal alkoxide, or the like can be used as a metal component.
  • examples of the organic titanium compound include titanium alkoxide compounds such as tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra tertiary butyl titanate, and tetraoctyl titanate; titanium diisopropoxybisacetylacetonate, titanium tetra Titanium chelates such as acetylacetonate, titanium dioctyloxybisethylacetoacetonate, titanium octylene glycolate, titanium diisopropoxybisethylacetylacetonate, titanium lactate, titanium lactate ammonium salt, titanium diisopropoxybistriethanolaminate
  • examples of the organic zirconium compound include dipropyl compounds such as normal propyl zirconate and normal butyl zirconate.
  • zirconium oxide compound examples include zirconium tetraacetylacetonate, zirconium tributoxymonoacetylacetonate, zirconium dibutoxybisethylacetoacetate, zirconium tributoxymonostearate and the like.
  • Aluminum alkoxide compounds such as aluminum butyl acetate, monobutoxy aluminum diisopropylate, aluminum butyrate; ethyl acetoacetate aluminum diisopropylate, aluminum trisethyl acetate, alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bisethylacetoacetate, etc.
  • aluminum chelate compounds That.
  • the organometallic compound may be a single type or a combination of two or more types.
  • the content of the organometallic compound is not particularly limited, but is usually about 0.01 to 50 parts by mass and about 0.1 to 30 parts by mass with respect to 100 parts by mass of the silicon compound. 1 to 30 parts by mass is more preferable, 5 to 30 parts by mass is further preferable, 10 to 25 parts by mass is still more preferable, and 15 to 25 parts by mass is even more preferable.
  • the treatment liquid of the present invention may contain a catalyst other than the organometallic compound. However, preferably, the treatment liquid of the present invention does not contain a catalyst other than the organometallic compound.
  • the content of water is not particularly limited, but is, for example, 1 to 100 parts by mass, preferably 10 to 100 parts by mass, and more preferably 20 to 100 parts by mass with respect to 100 parts by mass of the silicon compound.
  • the treatment liquid of the present invention preferably contains a solvent.
  • the solvent is not particularly limited as long as it is a hydrophilic solvent.
  • an organic solvent such as an alcohol, glycol, glycol ether, ether, ether alcohol, or ketone is used alone or as necessary. They can be used in appropriate combinations. Among these, glycol ether solvents are more preferable.
  • glycol ether solvent examples include a solvent represented by the general formula (3): HO—R 5 —O—R 6 (wherein R 5 represents a lower alkylene group and R 5 represents an alkyl group). Is mentioned.
  • the lower alkylene group represented by R 5 is not particularly limited, and includes any linear or branched (preferably branched) group.
  • the number of carbon atoms of the alkylene group is, for example, 1 to 6, preferably 1 to 5, more preferably 2 to 4, and still more preferably 3.
  • Specific examples of the alkylene group include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, and an isobutylene group.
  • the alkyl group represented by R 6 is not particularly limited, and includes any of linear or branched (preferably linear).
  • the number of carbon atoms of the alkyl group is, for example, 1 to 6, preferably 1 to 4, more preferably 1 to 2, and still more preferably 1.
  • Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group and the like.
  • the treatment liquid of the present invention may contain other components in addition to the above components.
  • the content of other components is, for example, 0 to 20% by mass, preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and further preferably 0 to 1% with respect to 100% by mass of the treatment liquid of the present invention. % By mass, more preferably 0% by mass.
  • the method for producing the treatment liquid of the present invention is not particularly limited, and can be obtained by appropriately mixing each component.
  • the treatment liquid of the present invention is preferably obtained by mixing a silicon compound and, if necessary, a solvent, and adding and mixing water and an organometallic compound thereto.
  • the intermolecular and / or intramolecular molecules of the film forming component may be partially crosslinked.
  • a coating having corrosion resistance and insulation performance can be formed on the surface of the metal material.
  • the metal material is not particularly limited as long as at least a part of the surface is made of metal.
  • the metal include various metals such as zinc, aluminum, magnesium, cobalt, nickel, iron, copper, tin, gold, and alloys thereof, and preferably zinc. More specifically, as a metal material, an article made only of metal, a composite article in which other articles other than metal (for example, ceramic material, plastics material, etc.) and metal are combined, and has a metal plating film on the surface Examples thereof include plating products (for example, steel plating products having a zinc plating film or a zinc alloy plating film on the surface).
  • the metal constituting the surface of the metal material may be an untreated metal or a metal that has been subjected to a pretreatment such as a degreasing treatment or an acid activation treatment.
  • coating method for example, known methods such as dip coating, spray coating, roll coating, spin coating, and bar coating can be employed.
  • the curing treatment is not particularly limited as long as it is a treatment capable of curing the film forming component in the treatment liquid of the present invention.
  • the curing treatment is preferably heat treatment.
  • the temperature of the heat treatment is not particularly limited, but is, for example, 20 ° C. or higher, preferably 50 to 300 ° C., more preferably 100 to 250 ° C., and further preferably 150 to 250 ° C.
  • the time for the heat treatment is not particularly limited, but is, for example, 5 minutes to 2 hours, preferably 10 minutes to 1 hour, more preferably 20 minutes to 40 minutes.
  • the silicon compound includes a metal material and a film on the surface of the metal material, and the film has at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond.
  • a film-containing metal material containing a crosslinked structure and an organometallic compound can be obtained.
  • Having corrosion resistance means performing a salt spray test (JIS Z2371), and the time until the generation area ratio of red rust to the sample surface area becomes 10% is, for example, 30 hours or more, preferably 40 hours or more, more preferably 100 Time or more, more preferably 150 hours or more, even more preferably 200 hours or more, and even more preferably 250 hours or more.
  • the maximum voltage at which dielectric breakdown does not occur when a voltage is applied by a withstand voltage test is, for example, 1200 V or more, preferably 1500 V or more.
  • the thickness of the coating is preferably thinner, for example, 0.1 to 100 ⁇ m, preferably 0.5 to 50 ⁇ m, more preferably 1 to 30 ⁇ m.
  • Example 1 A liquid mixture comprising 20% by mass of a silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight: about 11,000 to 100,000), 10% by mass of methyltrimethoxysilane oligomer, and 70% by mass of propylene glycol monomethyl ether was prepared. . Next, 10 parts by mass of water and 5 parts by mass of titanium diisopropoxybisethyl acetylacetonate were added to 100 parts by mass of the mixed solution to prepare a film forming treatment liquid.
  • a silicone resin manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight: about 11,000 to 100,000
  • propylene glycol monomethyl ether propylene glycol monomethyl ether
  • a nickel-plated steel plate (size 100 ⁇ 60 ⁇ 0.3 mm) was used as a metal material, and after alkaline degreasing treatment, the treatment liquid prepared above was spray-coated, and 200 times using a dryer. A film having a siloxane bond was formed by heat treatment at 30 ° C. for 30 minutes.
  • Example 2 A mixture comprising 15% by mass of acrylic silicone resin (produced by Taisei Fine Chemical Co., Ltd., weight average molecular weight: about 20,000, alkoxysilyl group content 40% by mass), 15% by mass of tetramethoxysilane, and 70% by mass of propylene glycol monoethyl ether A liquid was prepared. Next, 30 parts by mass of water and 5 parts by mass of titanium diisopropoxybisethyl acetylacetonate were added to 100 parts by mass of the mixed liquid to prepare a film forming treatment liquid.
  • acrylic silicone resin produced by Taisei Fine Chemical Co., Ltd., weight average molecular weight: about 20,000, alkoxysilyl group content 40% by mass
  • propylene glycol monoethyl ether A liquid was prepared.
  • 30 parts by mass of water and 5 parts by mass of titanium diisopropoxybisethyl acetylacetonate were added to 100 parts by mass of the mixed liquid to prepare a film forming treatment liquid.
  • Example 2 a nickel-plated steel plate (size 100 ⁇ 60 ⁇ 0.3 mm) was used as a metal material, and after alkaline degreasing treatment, the treatment liquid prepared above was spray-coated. Then, a heat treatment was performed at 200 ° C. for 30 minutes using a dryer to form a film having a siloxane bond.
  • Example 3 Acrylic silicone resin (produced by Taisei Fine Chemical Co., Ltd., weight average molecular weight: about 20,000, alkoxysilyl group content 40 mass%) 10 mass%, bisphenol A type epoxy resin 10 mass%, and propylene glycol monoethyl ether 80 mass% A mixed solution was prepared. Next, 3 parts by mass of water and 2 parts by mass of aluminum monoacetylacetonate bisethylacetoacetate were added to 100 parts by mass of the mixed solution to prepare a film forming treatment liquid.
  • Example 2 a nickel-plated steel plate (size 100 ⁇ 60 ⁇ 0.3 mm) was used as a metal material, and after alkaline degreasing treatment, the treatment liquid prepared above was spray-coated. Then, a heat treatment was performed at 200 ° C. for 30 minutes using a dryer to form a film having a siloxane bond.
  • Comparative Example 1 A mixture comprising 15% by mass of acrylic silicone resin (produced by Taisei Fine Chemical Co., Ltd., weight average molecular weight: about 20,000, alkoxysilyl group content 40% by mass), 15% by mass of tetramethoxysilane, and 70% by mass of propylene glycol monoethyl ether A liquid was prepared. Next, 0.1 part by mass of water and 3 parts by mass of titanium diisopropoxybisethyl acetylacetonate were added to 100 parts by mass of the mixed solution to prepare a film forming treatment liquid.
  • acrylic silicone resin produced by Taisei Fine Chemical Co., Ltd., weight average molecular weight: about 20,000, alkoxysilyl group content 40% by mass
  • propylene glycol monoethyl ether A liquid was prepared. Next, 0.1 part by mass of water and 3 parts by mass of titanium diisopropoxybisethyl acetylacetonate were added to 100 parts by mass of the mixed solution to prepare a film
  • Example 2 a nickel-plated steel plate (size 100 ⁇ 60 ⁇ 0.3 mm) was used as a metal material, and after alkaline degreasing treatment, the treatment liquid prepared above was spray-coated. Then, a heat treatment was performed at 200 ° C. for 30 minutes using a dryer to form a film having a siloxane bond.
  • Comparative Example 2 A mixed liquid consisting of 20% by mass of a bisphenol A type epoxy resin and 80% by mass of propylene glycol monoethyl ether was prepared. Next, 0.1 parts by mass of water and 2 parts by mass of aluminum monoacetylacetonate bisethylacetoacetate were added to 100 parts by mass of the mixed solution to prepare a film forming treatment liquid.
  • Example 2 a nickel-plated steel plate (size 100 ⁇ 60 ⁇ 0.3 mm) was used as a metal material, and after alkaline degreasing treatment, the treatment liquid prepared above was spray-coated. Then, heat treatment was performed at 200 ° C. for 30 minutes using a dryer to form a film.
  • Test Example 1 Corrosion Resistance Test A salt spray test (JIS Z2371) was performed on the nickel steel sheets on which the films obtained in Examples 1 to 3 and Comparative Examples 1 and 2 described above were formed. The time until the ratio reached 10% was measured. The results of the test are shown in Table 1 below.
  • Test Example 2 Insulation test Maximum voltage that does not cause dielectric breakdown by applying a voltage in a withstand voltage test to the nickel steel sheets on which the films obtained in Examples 1 to 3 and Comparative Examples 1 and 2 are formed. Was measured. The results of the test are shown in Table 1 below.
  • the film having a siloxane bond formed using the treatment liquid of the present invention has excellent corrosion resistance and insulation.

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Abstract

Provided are a treatment liquid and a treatment method capable of improving both anti-rust performance and the insulating properties of a metal material. The treatment liquid for forming a film having corrosion-resistance performance and insulating performance contains water, an organic metal compound, and a silicon compound having at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond.

Description

耐食性能及び絶縁性能を有する皮膜の形成用処理液Treatment liquid for film formation with corrosion resistance and insulation performance
　本発明は、皮膜の形成用処理液、皮膜の形成方法等に関する。 The present invention relates to a processing solution for forming a film, a method for forming a film, and the like.
　亜鉛、アルミニウム、マグネシウム、コバルト、ニッケル、鉄、銅、錫、金、これらの合金などの各種の金属材料の耐食性を有する絶縁性付与の方法として、クロムによる化成処理や陽極酸化処理、トップコート等の表面処理が施されている。 As a method of imparting insulation having corrosion resistance of various metal materials such as zinc, aluminum, magnesium, cobalt, nickel, iron, copper, tin, gold, and alloys thereof, chemical conversion treatment with chrome, anodizing treatment, top coat, etc. Surface treatment is applied.
　例えば、特許文献１においては、３価クロムによる化成処理後にシリカ質皮膜を形成することによる、防錆処理方法が開示されている。 For example, Patent Document 1 discloses a rust prevention treatment method by forming a siliceous film after chemical conversion treatment with trivalent chromium.
　しかしながら、特許文献１では絶縁性については検討されていない。上記した金属材料に対する耐食性能および絶縁性能の要求はますます高くなってきており、上記した方法では要求される耐食性能および絶縁性能を満足できないという問題点がある。 However, Patent Document 1 does not discuss insulation. The requirements for the corrosion resistance and insulation performance for the metal materials described above are increasing, and there is a problem that the above-described methods cannot satisfy the required corrosion resistance and insulation performance.
特開２０１５－１３４９４２号公報JP2015-134942A
　本発明は、金属材料の防錆性能及び絶縁性の両方をより高めることができる、処理液及び処理方法を提供することを課題とする。好ましくは、本発明は、処理により形成される皮膜がより薄膜でありながらも、金属材料の防錆性能及び絶縁性の両方をより高めることができる、処理液及び処理方法を提供することを課題とする。 An object of the present invention is to provide a treatment liquid and a treatment method capable of further enhancing both the rust prevention performance and insulation of a metal material. Preferably, the present invention provides a treatment liquid and a treatment method capable of further enhancing both the rust prevention performance and the insulating property of the metal material while the film formed by the treatment is thinner. And
　本発明者は上記課題に鑑みて鋭意研究を進めた結果、アルコキシシリル基、アルコキシシリレン基、及びシロキサン結合からなる群より選択される少なくとも１種を有するケイ素化合物、有機金属化合物、及び水を含有する、耐食性能及び絶縁性能を有する皮膜の形成用処理液を用いることによって、上記課題を解決できることを見出した。本発明者は、この知見に基づいてさらに研究を進めた結果、本発明を完成させた。 As a result of diligent research in view of the above problems, the present inventor contains a silicon compound having at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond, an organometallic compound, and water. It has been found that the above-mentioned problems can be solved by using a treatment liquid for forming a film having corrosion resistance and insulation performance. As a result of further research based on this knowledge, the present inventor completed the present invention.
　即ち、本発明は、一態様として下記の態様を包含する：
　項１．　アルコキシシリル基、アルコキシシリレン基、及びシロキサン結合からなる群より選択される少なくとも１種を有するケイ素化合物、有機金属化合物、及び水を含有する、耐食性能及び絶縁性能を有する皮膜の形成用処理液．
　項２．　前記ケイ素化合物が樹脂を含む、項１に記載の処理液．
　項３．　前記有機金属化合物が、有機金属キレート化合物及び金属アルコキシドからなる群より選択される少なくとも１種である、項１又は２に記載の処理液．
　項４．　前記有機金属化合物を構成する金属が、チタン、ジルコニウム、アルミニウム、及び錫からなる群より選択される少なくとも１種である、項１～３のいずれかに記載の処理液．
　項５．　前記有機金属化合物の含有量が、前記ケイ素化合物１００質量部に対して０．０１～５０質量部である、項１～４のいずれかに記載の処理液．
　項６．　前記水の含有量が、前記ケイ素化合物１００質量部に対して１～１００質量部である、項１～５のいずれかに記載の処理液．
　項７．　（工程１）項１～６のいずれかに記載の処理液を金属材料に塗布する工程を含む、耐食性能及び絶縁性能を有する皮膜の形成方法．
　項８．　さらに、（工程２）工程１後に硬化処理する工程を含む、項７に記載の形成方法．
　項９．　前記硬化処理が熱処理である、項８に記載の形成方法．
　項１０．　金属材料、及び前記金属材料の表面上の皮膜を含み、且つ
前記皮膜が、アルコキシシリル基、アルコキシシリレン基、及びシロキサン結合からなる群より選択される少なくとも１種を有するケイ素化合物の架橋構造体、及び有機金属化合物を含有する、
皮膜含有金属材料． That is, this invention includes the following aspects as one aspect:
Item 1. A treatment liquid for forming a film having corrosion resistance and insulation performance, comprising a silicon compound having at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond, an organometallic compound, and water.
Item 2. Item 2. The treatment liquid according to Item 1, wherein the silicon compound contains a resin.
Item 3. Item 3. The treatment liquid according to Item 1 or 2, wherein the organometallic compound is at least one selected from the group consisting of an organometallic chelate compound and a metal alkoxide.
Item 4. Item 4. The treatment liquid according to any one of Items 1 to 3, wherein the metal constituting the organometallic compound is at least one selected from the group consisting of titanium, zirconium, aluminum, and tin.
Item 5. Item 5. The treatment liquid according to any one of Items 1 to 4, wherein the content of the organometallic compound is 0.01 to 50 parts by mass with respect to 100 parts by mass of the silicon compound.
Item 6. Item 6. The treatment liquid according to any one of Items 1 to 5, wherein the water content is 1 to 100 parts by mass with respect to 100 parts by mass of the silicon compound.
Item 7. (Step 1) A method for forming a film having corrosion resistance and insulation performance, comprising a step of applying the treatment liquid according to any one of Items 1 to 6 to a metal material.
Item 8. Item 8. The method according to Item 7, further comprising (Step 2) a step of curing after Step 1.
Item 9. Item 9. The forming method according to Item 8, wherein the curing treatment is a heat treatment.
Item 10. A crosslinked structure of a silicon compound comprising a metal material and a film on the surface of the metal material, wherein the film has at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond; And containing an organometallic compound,
Film-containing metal material.
　本発明によれば、金属材料の防錆性能及び絶縁性の両方をより高めることができる、処理液及び処理方法を提供することができる。また、本発明によれば、該処理方法により得られ得る防錆皮膜含有金属材料を提供することもできる。 According to the present invention, it is possible to provide a treatment liquid and a treatment method that can further improve both the rust prevention performance and the insulating property of a metal material. Moreover, according to this invention, the metal material containing a rust preventive film which can be obtained by this processing method can also be provided.
　本明細書中において、「含有」及び「含む」なる表現については、「含有」、「含む」、「実質的にからなる」及び「のみからなる」という概念を含む。 In this specification, the expressions “containing” and “including” include the concepts of “containing”, “including”, “consisting essentially of”, and “consisting only of”.
　本発明は、その一態様において、アルコキシシリル基、アルコキシシリレン基、及びシロキサン結合からなる群より選択される少なくとも１種を有するケイ素化合物、有機金属化合物、及び水を含有する、耐食性能及び絶縁性能を有する皮膜の形成用処理液（本明細書において、「本発明の処理液」と示すこともある。）、本発明の処理液を用いた皮膜形成方法、及び本発明の処理液を用いて得られ得る皮膜含有金属材料に関する。以下に、これらについて説明する。 In one aspect, the present invention includes a silicon compound having at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond, an organometallic compound, and water, and has corrosion resistance and insulation performance. Using the treatment liquid for forming a film having the above (in the present specification, it may be referred to as “the treatment liquid of the present invention”), the film formation method using the treatment liquid of the present invention, and the treatment liquid of the present invention. The present invention relates to a film-containing metal material that can be obtained. These will be described below.
　アルコキシシリル基は、少なくとも１つのアルコキシ基を有するアルコキシシリル基である限り特に制限されない。アルコキシシリル基としては、例えば、一般式（１）：（Ｒ１）ｍ（Ｒ２Ｏ）３－ｍＳｉ－（式中、Ｒ１は官能基、Ｒ２は低級アルキル基である。ｍは０～２の整数である）で表される基が挙げられる。 The alkoxysilyl group is not particularly limited as long as it is an alkoxysilyl group having at least one alkoxy group. Examples of the alkoxysilyl group include, for example, the general formula (1): (R 1 ) m (R 2 O) 3-m Si— (wherein R 1 is a functional group and R 2 is a lower alkyl group. And an integer of 0 to 2).
　Ｒ１で示される官能基としては、メチル、ジメチル、フェニル、ジフェニル、ヘキシル、デシル、１、６－ビス（トリメトキシシリル）、トリフルオロプロピル、ビニル、３－グリシドキシプロピル、３－グリシドキシプロピルメチル、２－（３、４－エポキシシクロヘキシル）エチル、ｐ－スチリル、３－メタクリロキシプロピル、３－メタクリロキシプロピルメチル、３－アクリロキシプロピル、３－アミノプロピル、Ｎ－２－（アミノエチル）－３－アミノプロピル、Ｎ－２－（アミノエチル）－３－アミノプロピルメチル、３－トリエトキシシリル―Ｎ－（１、３－ジメチルーブチリデン）プロピルアミン、Ｎ―フェニル―３－アミノプロピル、Ｎ－（ビニルベンジル）－２－アミノエチル―３－アミノプロピル、トリス―（トリメトキシシリルプロピル）イソシアヌレート、３－ウレイドプロピル、３－メルカプトプロピル、３－メルカプトプロピルメチル、ビス（トリエトキシシリルプロピル）テトラスルフィド、３－イソシアネートプロピル、３―プロピルコハク酸無水物等を例示できる。 Examples of the functional group represented by R 1 include methyl, dimethyl, phenyl, diphenyl, hexyl, decyl, 1,6-bis (trimethoxysilyl), trifluoropropyl, vinyl, 3-glycidoxypropyl, 3-glycid Xylpropylmethyl, 2- (3,4-epoxycyclohexyl) ethyl, p-styryl, 3-methacryloxypropyl, 3-methacryloxypropylmethyl, 3-acryloxypropyl, 3-aminopropyl, N-2- (amino Ethyl) -3-aminopropyl, N-2- (aminoethyl) -3-aminopropylmethyl, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3- Aminopropyl, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyl, tris- (trime Toxisilylpropyl) isocyanurate, 3-ureidopropyl, 3-mercaptopropyl, 3-mercaptopropylmethyl, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyl, 3-propylsuccinic anhydride and the like can be exemplified.
　Ｒ２で示される低級アルキル基としては、具体的には、メチル、エチル、ｎ－プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｔｅｒｔ－ブチル、ｓｅｃ－ブチル、ｎ－ペンチル、１－エチルプロピル、イソペンチル、ネオペンチル等の炭素数１～６程度の直鎖状又は分岐鎖状のアルキル基を挙げることができる。 Specific examples of the lower alkyl group represented by R 2 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, 1-ethylpropyl, isopentyl. And linear or branched alkyl groups having about 1 to 6 carbon atoms such as neopentyl.
　アルコキシシリレン基は、少なくとも１つのアルコキシ基を有するアルコキシシリレン基である限り特に制限されない。アルコキシシリレン基としては、例えば、一般式（２）：（Ｒ３）ｎ（Ｒ４Ｏ）２－ｎＳｉ＝（式中、Ｒ３は官能基、Ｒ４は低級アルキル基である。ｎは０～１の整数である）で表される基が挙げられる。 The alkoxysilylene group is not particularly limited as long as it is an alkoxysilylene group having at least one alkoxy group. Examples of the alkoxysilylene group include, for example, the general formula (2): (R 3 ) n (R 4 O) 2-n Si = (wherein R 3 is a functional group, R 4 is a lower alkyl group, and n is And a group represented by an integer of 0 to 1.
　Ｒ３で示される官能基としては、Ｒ１で示される官能基と同様のものが挙げられる。 Examples of the functional group represented by R 3 include the same functional groups represented by R 1 .
　Ｒ４で示される低級アルキル基としては、Ｒ２で示される低級アルキル基と同様のものが挙げられる。 Examples of the lower alkyl group represented by R 4 include the same as the lower alkyl group represented by R 2 .
　ケイ素化合物としては、部分構造として、アルコキシシリル基、アルコキシシリレン基、及びシロキサン結合からなる群より選択される少なくとも１種を有するケイ素化合物である限り、特に制限されない。ケイ素化合物としては、例えば、樹脂、アルコキシシランオリゴマー、アルコキシシラン等が挙げられる。これらの中でも、好ましくは樹脂が挙げられる。 The silicon compound is not particularly limited as long as it is a silicon compound having at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond as a partial structure. Examples of the silicon compound include resins, alkoxysilane oligomers, and alkoxysilanes. Among these, Preferably resin is mentioned.
　樹脂としては、例えば、シリコーン樹脂のみならず、アルコキシシリル基が導入された各種樹脂（例えばアクリル樹脂、ウレタン樹脂、エポキシ樹脂、ポリエステル樹脂、メラミン樹脂等）等が挙げられる。これらの中でも、好ましくはアルコキシシリル基が導入されたアクリル樹脂、シリコーン樹脂等が挙げられ、より好ましくはアルコキシシリル基が導入されたアクリル樹脂が挙げられる。 Examples of the resin include not only silicone resins but also various resins into which alkoxysilyl groups are introduced (for example, acrylic resins, urethane resins, epoxy resins, polyester resins, melamine resins, etc.). Among these, an acrylic resin and a silicone resin into which an alkoxysilyl group is introduced are preferable, and an acrylic resin into which an alkoxysilyl group is introduced is more preferable.
　樹脂の重量平均分子量は、特に制限されないが、例えば１１０００～２０００００、好ましくは１１０００～１０００００、より好ましくは１１０００～７００００、更に好ましくは１１０００～５００００である。 The weight average molecular weight of the resin is not particularly limited, but is, for example, 11000 to 200000, preferably 11000 to 100,000, more preferably 11000 to 70000, and still more preferably 11000 to 50000.
　樹脂が、アルコキシシリル基が導入された樹脂である場合、アルコキシシリル基の含有量は、例えば１～７０質量％、好ましくは２～６０質量％、より好ましくは３～５０質量％、さらに好ましくは４～４５質量％、よりさらに好ましくは５～４０質量％である。 When the resin is a resin having an alkoxysilyl group introduced, the content of the alkoxysilyl group is, for example, 1 to 70% by mass, preferably 2 to 60% by mass, more preferably 3 to 50% by mass, and still more preferably It is 4 to 45% by mass, more preferably 5 to 40% by mass.
　アルコキシシランとしては、例えばＳｉ（ＯＣＨ３）４、Ｓｉ（ＯＣ２Ｈ５）４、ＣＨ３Ｓｉ（ＯＣＨ３）３、ＣＨ３Ｓｉ（ＯＣ２Ｈ５）３、Ｃ２Ｈ５Ｓｉ（ＯＣＨ３）３、Ｃ２Ｈ５Ｓｉ（ＯＣ２Ｈ５）４、ＣＨＣＨ２Ｓｉ（ＯＣＨ３）３、ＣＨ２ＣＨＯＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、ＣＨ２Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、ＣＨ２ＣＨＣＯＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、ＮＨ２（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、ＳＨ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、ＮＣＯ（ＣＨ２）３Ｓｉ（ＯＣ２Ｈ５）３を挙げることができる。 Examples of the alkoxysilane include Si (OCH 3 ) 4 , Si (OC 2 H 5 ) 4 , CH 3 Si (OCH 3 ) 3 , CH 3 Si (OC 2 H 5 ) 3 , C 2 H 5 Si (OCH 3). ) 3 , C 2 H 5 Si (OC 2 H 5 ) 4 , CHCH 2 Si (OCH 3 ) 3 , CH 2 CHOCH 2 O (CH 2 ) 3 Si (OCH 3 ) 3 , CH 2 C (CH 3 ) COO (CH 2 ) 3 Si (OCH 3 ) 3 , CH 2 CHCOO (CH 2 ) 3 Si (OCH 3 ) 3 , NH 2 (CH 2 ) 3 Si (OCH 3 ) 3 , SH (CH 2 ) 3 Si (OCH 3 ) 3 and NCO (CH 2 ) 3 Si (OC 2 H 5 ) 3 .
　アルコキシシランオリゴマーは、アルコキシシランを加水分解し、縮重合させたものである。アルコキシシランオリゴマーとしては、例えば、アルコキシシランオリゴマーの重量平均分子量として、５００～１００００程度のものを用いることができる
　ケイ素化合物は、１種単独であってもよく、２種以上の組み合わせであってもよい。 The alkoxysilane oligomer is obtained by hydrolyzing and polycondensing alkoxysilane. As the alkoxysilane oligomer, for example, an alkoxysilane oligomer having a weight average molecular weight of about 500 to 10,000 can be used. The silicon compound may be used alone or in combination of two or more. Good.
　ケイ素化合物の含有量は、本発明の処理液１００質量％に対して、例えば３～７０質量％、好ましくは５～３０質量％、より好ましくは８～２５質量％である。 The content of the silicon compound is, for example, 3 to 70% by mass, preferably 5 to 30% by mass, and more preferably 8 to 25% by mass with respect to 100% by mass of the treatment liquid of the present invention.
　本発明の処理液においては、アルコキシシリル基、アルコキシシリレン基、及びシロキサン結合を有しない樹脂（非ケイ素系樹脂）を含んでいてもよい。非ケイ素系樹脂としては、例えばエポキシ樹脂、アクリル樹脂、ウレタン樹脂、ポリエステル樹脂、メラミン樹脂等が挙げられる。これらの中でも、好ましくはエポキシ樹脂が挙げられ、より好ましくはビスフェノールＡ型エポキシ樹脂が挙げられる。 The treatment liquid of the present invention may contain an alkoxysilyl group, an alkoxysilylene group, and a resin having no siloxane bond (non-silicon resin). Examples of the non-silicon-based resin include an epoxy resin, an acrylic resin, a urethane resin, a polyester resin, and a melamine resin. Among these, Preferably an epoxy resin is mentioned, More preferably, a bisphenol A type epoxy resin is mentioned.
　本発明の処理液においては、皮膜形成成分として、アルコキシシリル基、アルコキシシリレン基、及びシロキサン結合からなる群より選択される少なくとも１種を有する樹脂（成分Ａ）と、アルコキシシラン、アルコキシシランオリゴマー、及び非ケイ素系樹脂からなる群より選択される少なくとも１種の成分（成分Ｂ）との組み合わせを含有することが好ましい。 In the treatment liquid of the present invention, as a film forming component, a resin (component A) having at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond, an alkoxysilane, an alkoxysilane oligomer, And a combination with at least one component (component B) selected from the group consisting of non-silicon-based resins.
　成分Ａとしては、好ましくはアルコキシシリル基が導入されたアクリル樹脂、シリコーン樹脂等が挙げられ、より好ましくはアルコキシシリル基が導入されたアクリル樹脂が挙げられる。 Component A is preferably an acrylic resin or silicone resin into which an alkoxysilyl group is introduced, and more preferably an acrylic resin into which an alkoxysilyl group is introduced.
　成分Ｂとしては、好ましくは非ケイ素系樹脂が挙げられ、より好ましくはエポキシ樹脂が挙げられ、さらに好ましくはビスフェノールＡ型エポキシ樹脂が挙げられる。 Component B is preferably a non-silicon resin, more preferably an epoxy resin, and still more preferably a bisphenol A type epoxy resin.
　成分Ａと成分Ｂとの含有比は、特に制限されないが、例えば成分Ａ１００質量部に対して、成分Ｂが、例えば３０～２００質量部、好ましくは６０～１５０質量部、より好ましくは８０～１２０質量部、よりさらに好ましくは９０～１１０質量部である。 The content ratio of component A and component B is not particularly limited, but for example, component B is, for example, 30 to 200 parts by mass, preferably 60 to 150 parts by mass, more preferably 80 to 120 parts per 100 parts by mass of component A. Part by mass, more preferably 90 to 110 parts by mass.
　有機金属化合物としては、縮合反応の触媒として機能し得るものである限り特に制限されない。有金属化合物としては、例えば、金属成分として、チタン、ジルコニウム、アルミニウム、錫などを含む水溶性の有機金属キレート化合物、金属アルコキシド等を用いることができる。これらの内で、有機チタン化合物としては、テトライソプロピルチタネート、テトラノルマルブチルチタネート、ブチルチタネートダイマー、テトラターシャリーブチルチタネート、テトラオクチルチタネート等のチタンアルコキシド化合物；チタンジイソプロポキシビスアセチルアセトネート、チタンテトラアセチルアセトネート、チタンジオクチロキシビスエチルアセトアセトネート、チタンオクチレングリコレート、チタンジイソプロポキシビスエチルアセチルアセトネート、チタンラクテート、チタンラクテートアンモニウム塩、チタンジイソプロポキシビストリエタノールアミネート等のチタンキレート化合物等を例示でき、有機ジルコニウム化合物としては、ノルマルプロピルジルコネート、ノルマルブチルジルコネート等のジルコニウムアルコキシド化合物；ジルコニウムテトラアセチルアセトネート、ジルコニウムトリブトキシモノアセチルアセトネート、ジルコニウムジブトキシビスエチルアセトアセテート、ジルコニウムトリブトキシモノステアレート等のジルコニウムキレート化合物を例示でき、有機アルミニウム化合物としては、アルミニウムイソプロピレート、モノブトキシアルミニウムジイソプロピレート、アルミニウムブチレート等のアルミニウムアルコキシド化合物；、エチルアセトアセテートアルミニウムジイソプロピレート、アルミニウムトリスエチルアセテート、アルキルアセトアセテートアルミニウムジイソプロピレート、アルミニウムモノアセチルアセトネートビスエチルアセトアセテート等のアルミニウムキレート化合物等を例示できる。 The organometallic compound is not particularly limited as long as it can function as a catalyst for the condensation reaction. As the metal compound, for example, a water-soluble organometallic chelate compound containing titanium, zirconium, aluminum, tin or the like, a metal alkoxide, or the like can be used as a metal component. Among these, examples of the organic titanium compound include titanium alkoxide compounds such as tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra tertiary butyl titanate, and tetraoctyl titanate; titanium diisopropoxybisacetylacetonate, titanium tetra Titanium chelates such as acetylacetonate, titanium dioctyloxybisethylacetoacetonate, titanium octylene glycolate, titanium diisopropoxybisethylacetylacetonate, titanium lactate, titanium lactate ammonium salt, titanium diisopropoxybistriethanolaminate Examples of the organic zirconium compound include dipropyl compounds such as normal propyl zirconate and normal butyl zirconate. Examples of the zirconium oxide compound include zirconium tetraacetylacetonate, zirconium tributoxymonoacetylacetonate, zirconium dibutoxybisethylacetoacetate, zirconium tributoxymonostearate and the like. Aluminum alkoxide compounds such as aluminum butyl acetate, monobutoxy aluminum diisopropylate, aluminum butyrate; ethyl acetoacetate aluminum diisopropylate, aluminum trisethyl acetate, alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bisethylacetoacetate, etc. Examples of aluminum chelate compounds That.
　有機金属化合物は、１種単独であってもよく、２種以上の組み合わせであってもよい。 The organometallic compound may be a single type or a combination of two or more types.
　有機金属化合物の含有量は、特に限定的ではないが、ケイ素化合物１００質量部に対して、通常、０．０１～５０質量部程度とすればよく、０．１～３０質量部程度とすることが好ましく、１～３０質量部がより好ましく、５～３０質量部がさらに好ましく、１０～２５質量部がよりさらに好ましく、１５～２５質量部がよりさらに好ましい。 The content of the organometallic compound is not particularly limited, but is usually about 0.01 to 50 parts by mass and about 0.1 to 30 parts by mass with respect to 100 parts by mass of the silicon compound. 1 to 30 parts by mass is more preferable, 5 to 30 parts by mass is further preferable, 10 to 25 parts by mass is still more preferable, and 15 to 25 parts by mass is even more preferable.
　本発明の処理液においては、有機金属化合物以外の触媒を含有することも許容される。ただ、好ましくは、本発明の処理液は、有機金属化合物以外の触媒を含有しない。 The treatment liquid of the present invention may contain a catalyst other than the organometallic compound. However, preferably, the treatment liquid of the present invention does not contain a catalyst other than the organometallic compound.
　水の含有量は、特に限定的ではないが、ケイ素化合物１００質量部に対して、例えば１～１００質量部、好ましくは１０～１００質量部、より好ましくは２０～１００質量部である。 The content of water is not particularly limited, but is, for example, 1 to 100 parts by mass, preferably 10 to 100 parts by mass, and more preferably 20 to 100 parts by mass with respect to 100 parts by mass of the silicon compound.
　本発明の処理液には、上記成分以外に、溶媒を含有することが好ましい。溶媒としては、親水性を有する溶媒である限り特に制限されず、例えばアルコール系、グリコール系、グリコールエーテル系、エーテル系、エーテルアルコール系、ケトン系などの有機溶剤を単独で、或いは必要に応じて適宜組み合わせて用いることができる。これらの中でもグリコールエーテル系溶媒がより好ましい。 In addition to the above components, the treatment liquid of the present invention preferably contains a solvent. The solvent is not particularly limited as long as it is a hydrophilic solvent. For example, an organic solvent such as an alcohol, glycol, glycol ether, ether, ether alcohol, or ketone is used alone or as necessary. They can be used in appropriate combinations. Among these, glycol ether solvents are more preferable.
　グリコールエーテル系溶媒としては、例えば一般式（３）：ＨＯ－Ｒ５－Ｏ－Ｒ６（式中、Ｒ５は低級アルキレン基を示す。Ｒ５はアルキル基を示す。）で表される溶媒が挙げられる。 Examples of the glycol ether solvent include a solvent represented by the general formula (3): HO—R 5 —O—R 6 (wherein R 5 represents a lower alkylene group and R 5 represents an alkyl group). Is mentioned.
　Ｒ５で示される低級アルキレン基は、特に制限されず、直鎖状又は分岐鎖状（好ましくは分岐鎖状）のいずれのものも包含する。該アルキレン基の炭素原子数は、例えば１～６、好ましくは１～５、より好ましくは２～４、さらに好ましくは３である。該アルキレン基の具体例としては、メチレン基、エチレン基、ｎ－プロピレン基、イソプロピレン基、ｎ－ブチレン基、イソブチレン基等が挙げられる。 The lower alkylene group represented by R 5 is not particularly limited, and includes any linear or branched (preferably branched) group. The number of carbon atoms of the alkylene group is, for example, 1 to 6, preferably 1 to 5, more preferably 2 to 4, and still more preferably 3. Specific examples of the alkylene group include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, and an isobutylene group.
　Ｒ６で示されるアルキル基は、特に制限されず、直鎖状又は分岐鎖状（好ましくは直鎖状）のいずれのものも包含する。該アルキル基の炭素原子数は、例えば１～６、好ましくは１～４、より好ましくは１～２、さらに好ましくは１である。該アルキル基の具体例としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ｓｅｃ－ブチル基等が挙げられる。 The alkyl group represented by R 6 is not particularly limited, and includes any of linear or branched (preferably linear). The number of carbon atoms of the alkyl group is, for example, 1 to 6, preferably 1 to 4, more preferably 1 to 2, and still more preferably 1. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group and the like.
　本発明の処理液は、上記成分以外に、他の成分を含有していてもよい。他の成分の含有量は、本発明の処理液１００質量％に対して、例えば０～２０質量％、好ましくは０～１０質量％、より好ましくは０～５質量％、さらに好ましくは０～１質量％、よりさらに好ましくは０質量％である。 The treatment liquid of the present invention may contain other components in addition to the above components. The content of other components is, for example, 0 to 20% by mass, preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and further preferably 0 to 1% with respect to 100% by mass of the treatment liquid of the present invention. % By mass, more preferably 0% by mass.
　本発明の処理液の製造方法は、特に限定されず、各成分を適宜混合して得ることができる。本発明の処理液は、好ましくは、ケイ素化合物及び必要に応じて溶媒を混合した後、そこへ水及び有機金属化合物を添加及び混合することにより得られる。 The method for producing the treatment liquid of the present invention is not particularly limited, and can be obtained by appropriately mixing each component. The treatment liquid of the present invention is preferably obtained by mixing a silicon compound and, if necessary, a solvent, and adding and mixing water and an organometallic compound thereto.
　本発明の処理液においては、皮膜形成成分の分子間及び／又は分子内が、一部架橋された状態であってもよい。 In the treatment liquid of the present invention, the intermolecular and / or intramolecular molecules of the film forming component may be partially crosslinked.
　本発明の処理液を金属材料に塗布することにより、金属材料表面に、耐食性能及び絶縁性能を有する皮膜を形成することができる。 By applying the treatment liquid of the present invention to a metal material, a coating having corrosion resistance and insulation performance can be formed on the surface of the metal material.
　金属材料は、その少なくとも一部の表面が金属で構成されている材料である限り特に制限されない。金属としては、例えば、亜鉛、アルミニウム、マグネシウム、コバルト、ニッケル、鉄、銅、錫、金、これらの合金などの各種の金属が挙げられ、好ましくは亜鉛が挙げられる。金属材料として、より具体的には、金属のみからなる物品、金属以外のその他の物品（例えば、セラミックス材料、プラスチックス材料等）と金属とが組み合わされた複合品、表面に金属めっき皮膜を有するめっき処理品（例えば、表面に亜鉛めっき皮膜又は亜鉛合金めっき皮膜を有する鋼のめっき処理品）等が挙げられる。また、金属材料の表面を構成している金属は、未処理の金属であってもよく、脱脂処理や酸活性処理等の前処理が施された金属であってもよい。 The metal material is not particularly limited as long as at least a part of the surface is made of metal. Examples of the metal include various metals such as zinc, aluminum, magnesium, cobalt, nickel, iron, copper, tin, gold, and alloys thereof, and preferably zinc. More specifically, as a metal material, an article made only of metal, a composite article in which other articles other than metal (for example, ceramic material, plastics material, etc.) and metal are combined, and has a metal plating film on the surface Examples thereof include plating products (for example, steel plating products having a zinc plating film or a zinc alloy plating film on the surface). In addition, the metal constituting the surface of the metal material may be an untreated metal or a metal that has been subjected to a pretreatment such as a degreasing treatment or an acid activation treatment.
　塗布方法としては、例えばディップコート、スプレーコート、ロールコート、スピンコート、バーコート等の公知の方法を採用することができる。 As the coating method, for example, known methods such as dip coating, spray coating, roll coating, spin coating, and bar coating can be employed.
　塗布後は、さらに硬化処理を行うことが好ましい。硬化処理は、本発明の処理液中の皮膜形成成分を硬化させ得る処理である限り特に制限されない。硬化処理として、好ましくは熱処理が挙げられる。 After coating, it is preferable to further perform a curing process. The curing treatment is not particularly limited as long as it is a treatment capable of curing the film forming component in the treatment liquid of the present invention. The curing treatment is preferably heat treatment.
　熱処理の温度は、特に制限されないが、例えば２０℃以上、好ましくは５０～３００℃、より好ましくは１００～２５０℃、さらに好ましくは１５０～２５０℃である。 The temperature of the heat treatment is not particularly limited, but is, for example, 20 ° C. or higher, preferably 50 to 300 ° C., more preferably 100 to 250 ° C., and further preferably 150 to 250 ° C.
　熱処理の時間は、特に制限されないが、例えば５分間～２時間、好ましくは１０分間～１時間、より好ましくは２０分間～４０分間である。 The time for the heat treatment is not particularly limited, but is, for example, 5 minutes to 2 hours, preferably 10 minutes to 1 hour, more preferably 20 minutes to 40 minutes.
　斯かる処理により、金属材料表面に、耐食性能及び絶縁性能を有する皮膜を形成することができる。換言すれば、金属材料、及び前記金属材料の表面上の皮膜を含み、且つ前記皮膜が、アルコキシシリル基、アルコキシシリレン基、及びシロキサン結合からなる群より選択される少なくとも１種を有するケイ素化合物の架橋構造体、及び有機金属化合物を含有する、皮膜含有金属材料を得ることができる。 By such treatment, a film having corrosion resistance and insulation performance can be formed on the surface of the metal material. In other words, the silicon compound includes a metal material and a film on the surface of the metal material, and the film has at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond. A film-containing metal material containing a crosslinked structure and an organometallic compound can be obtained.
　耐食性能を有するとは、塩水噴霧試験（ＪＩＳ　Ｚ２３７１）を行い、試料表面積に対する赤錆の発生面積比率が１０％となるまでの時間が、例えば３０時間以上、好ましくは４０時間以上、より好ましくは１００時間以上、さらに好ましくは１５０時間以上、よりさらに好ましくは２００時間以上、よりさらに好ましくは２５０時間以上である。 Having corrosion resistance means performing a salt spray test (JIS Z2371), and the time until the generation area ratio of red rust to the sample surface area becomes 10% is, for example, 30 hours or more, preferably 40 hours or more, more preferably 100 Time or more, more preferably 150 hours or more, even more preferably 200 hours or more, and even more preferably 250 hours or more.
　絶縁性能を有するとは、耐電圧試験により電圧を印加して絶縁破壊を起こさない最大電圧が、例えば１２００Ｖ以上、好ましくは１５００Ｖ以上である。 Having insulation performance means that the maximum voltage at which dielectric breakdown does not occur when a voltage is applied by a withstand voltage test is, for example, 1200 V or more, preferably 1500 V or more.
　皮膜の厚みは、より薄いことが好ましく、例えば０．１～１００μｍ、好ましくは０．５～５０μｍ、より好ましくは１～３０μｍである。 The thickness of the coating is preferably thinner, for example, 0.1 to 100 μm, preferably 0.5 to 50 μm, more preferably 1 to 30 μm.
　以下に、実施例に基づいて本発明を詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。 Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to these examples.
　実施例１
　シリコーン樹脂（信越化学工業社製、重量平均分子量：約１．１万～１０万）２０質量％、メチルトリメトキシシランオリゴマー１０質量％、及びプロピレングリコールモノメチルエーテル７０質量％からなる混合液を調製した。次に、該混合液１００質量部に対して水を１０質量部、チタンジイソプロポキシビスエチルアセチルアセトネート５質量部加えて、皮膜形成用処理液を調製した。 Example 1
A liquid mixture comprising 20% by mass of a silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight: about 11,000 to 100,000), 10% by mass of methyltrimethoxysilane oligomer, and 70% by mass of propylene glycol monomethyl ether was prepared. . Next, 10 parts by mass of water and 5 parts by mass of titanium diisopropoxybisethyl acetylacetonate were added to 100 parts by mass of the mixed solution to prepare a film forming treatment liquid.
　次いで、ニッケルめっきを施した鋼板（大きさ１００×６０×０．３ｍｍ）を金属材料として用い、アルカリ脱脂処理を行なった後、上記において調製した処理液をスプレー塗布し、乾燥機を用いて２００℃で３０分間熱処理を行ってシロキサン結合を有する皮膜を形成した。 Next, a nickel-plated steel plate (size 100 × 60 × 0.3 mm) was used as a metal material, and after alkaline degreasing treatment, the treatment liquid prepared above was spray-coated, and 200 times using a dryer. A film having a siloxane bond was formed by heat treatment at 30 ° C. for 30 minutes.
　実施例２
　アクリルシリコーン樹脂（大成ファインケミカル株式会社製、重量平均分子量：約２万、アルコキシシリル基含有量４０質量％）１５質量％、テトラメトキシシラン１５質量％、及びプロピレングリコールモノエチルエーテル７０質量％からなる混合液を調製した。次に、該混合液１００質量部に対して水を３０質量部、チタンジイソプロポキシビスエチルアセチルアセトネート５質量部加えて、皮膜形成用処理液を調製した。 Example 2
A mixture comprising 15% by mass of acrylic silicone resin (produced by Taisei Fine Chemical Co., Ltd., weight average molecular weight: about 20,000, alkoxysilyl group content 40% by mass), 15% by mass of tetramethoxysilane, and 70% by mass of propylene glycol monoethyl ether A liquid was prepared. Next, 30 parts by mass of water and 5 parts by mass of titanium diisopropoxybisethyl acetylacetonate were added to 100 parts by mass of the mixed liquid to prepare a film forming treatment liquid.
　次いで、実施例１と同様にして、ニッケルめっきを施した鋼板（大きさ１００×６０×０．３ｍｍ）を金属材料として用い、アルカリ脱脂処理を行なった後、上記において調製した処理液をスプレー塗布し、乾燥機を用いて２００℃で３０分間熱処理を行ってシロキサン結合を有する皮膜を形成した。 Subsequently, in the same manner as in Example 1, a nickel-plated steel plate (size 100 × 60 × 0.3 mm) was used as a metal material, and after alkaline degreasing treatment, the treatment liquid prepared above was spray-coated. Then, a heat treatment was performed at 200 ° C. for 30 minutes using a dryer to form a film having a siloxane bond.
　実施例３
　アクリルシリコーン樹脂（大成ファインケミカル株式会社製、重量平均分子量：約２万、アルコキシシリル基含有量４０質量％）１０質量％、ビスフェノールＡ型エポキシ樹脂１０質量％、及びプロピレングリコールモノエチルエーテル８０質量％からなる混合液を調製した。次に、該混合液１００質量部に対して水を３質量部、アルミニウムモノアセチルアセトネートビスエチルアセトアセテート２質量部加えて、皮膜形成用処理液を調製した。 Example 3
Acrylic silicone resin (produced by Taisei Fine Chemical Co., Ltd., weight average molecular weight: about 20,000, alkoxysilyl group content 40 mass%) 10 mass%, bisphenol A type epoxy resin 10 mass%, and propylene glycol monoethyl ether 80 mass% A mixed solution was prepared. Next, 3 parts by mass of water and 2 parts by mass of aluminum monoacetylacetonate bisethylacetoacetate were added to 100 parts by mass of the mixed solution to prepare a film forming treatment liquid.
　次いで、実施例１と同様にして、ニッケルめっきを施した鋼板（大きさ１００×６０×０．３ｍｍ）を金属材料として用い、アルカリ脱脂処理を行なった後、上記において調製した処理液をスプレー塗布し、乾燥機を用いて２００℃で３０分間熱処理を行ってシロキサン結合を有する皮膜を形成した。 Subsequently, in the same manner as in Example 1, a nickel-plated steel plate (size 100 × 60 × 0.3 mm) was used as a metal material, and after alkaline degreasing treatment, the treatment liquid prepared above was spray-coated. Then, a heat treatment was performed at 200 ° C. for 30 minutes using a dryer to form a film having a siloxane bond.
　比較例１
　アクリルシリコーン樹脂（大成ファインケミカル株式会社製、重量平均分子量：約２万、アルコキシシリル基含有量４０質量％）１５質量％、テトラメトキシシラン１５質量％、及びプロピレングリコールモノエチルエーテル７０質量％からなる混合液を調製した。次に、該混合液１００質量部に対して水を０．１質量部、チタンジイソプロポキシビスエチルアセチルアセトネート３質量部加えて、皮膜形成用処理液を調製した。 Comparative Example 1
A mixture comprising 15% by mass of acrylic silicone resin (produced by Taisei Fine Chemical Co., Ltd., weight average molecular weight: about 20,000, alkoxysilyl group content 40% by mass), 15% by mass of tetramethoxysilane, and 70% by mass of propylene glycol monoethyl ether A liquid was prepared. Next, 0.1 part by mass of water and 3 parts by mass of titanium diisopropoxybisethyl acetylacetonate were added to 100 parts by mass of the mixed solution to prepare a film forming treatment liquid.
　次いで、実施例１と同様にして、ニッケルめっきを施した鋼板（大きさ１００×６０×０．３ｍｍ）を金属材料として用い、アルカリ脱脂処理を行なった後、上記において調製した処理液をスプレー塗布し、乾燥機を用いて２００℃で３０分間熱処理を行ってシロキサン結合を有する皮膜を形成した。 Subsequently, in the same manner as in Example 1, a nickel-plated steel plate (size 100 × 60 × 0.3 mm) was used as a metal material, and after alkaline degreasing treatment, the treatment liquid prepared above was spray-coated. Then, a heat treatment was performed at 200 ° C. for 30 minutes using a dryer to form a film having a siloxane bond.
　比較例２
　ビスフェノールＡ型エポキシ樹脂２０質量％、及びプロピレングリコールモノエチルエーテル８０質量％からなる混合液を調製した。次に、該混合液１００質量部に対して水を０．１質量部、アルミニウムモノアセチルアセトネートビスエチルアセトアセテート２質量部加えて、皮膜形成用処理液を調製した。 Comparative Example 2
A mixed liquid consisting of 20% by mass of a bisphenol A type epoxy resin and 80% by mass of propylene glycol monoethyl ether was prepared. Next, 0.1 parts by mass of water and 2 parts by mass of aluminum monoacetylacetonate bisethylacetoacetate were added to 100 parts by mass of the mixed solution to prepare a film forming treatment liquid.
　次いで、実施例１と同様にして、ニッケルめっきを施した鋼板（大きさ１００×６０×０．３ｍｍ）を金属材料として用い、アルカリ脱脂処理を行なった後、上記において調製した処理液をスプレー塗布し、乾燥機を用いて２００℃で３０分間熱処理を行って皮膜を形成した。 Subsequently, in the same manner as in Example 1, a nickel-plated steel plate (size 100 × 60 × 0.3 mm) was used as a metal material, and after alkaline degreasing treatment, the treatment liquid prepared above was spray-coated. Then, heat treatment was performed at 200 ° C. for 30 minutes using a dryer to form a film.
　試験例１：耐食性試験
　上記した実施例１～３及び比較例１～２において得られた皮膜を形成したニッケル鋼板に対して、塩水噴霧試験（ＪＩＳ　Ｚ２３７１）を行い、試料表面積に対する赤錆の発生面積比率が１０％となるまでの時間を測定した。当該試験の結果を下記表１に示す。 Test Example 1: Corrosion Resistance Test A salt spray test (JIS Z2371) was performed on the nickel steel sheets on which the films obtained in Examples 1 to 3 and Comparative Examples 1 and 2 described above were formed. The time until the ratio reached 10% was measured. The results of the test are shown in Table 1 below.
　試験例２：絶縁性試験
　上記した実施例１～３及び比較例１～２において得られた皮膜を形成したニッケル鋼板に対して、耐電圧試験により電圧を印加して絶縁破壊を起こさない最大電圧を測定した。当該試験の結果を下記表１に示す。 Test Example 2: Insulation test Maximum voltage that does not cause dielectric breakdown by applying a voltage in a withstand voltage test to the nickel steel sheets on which the films obtained in Examples 1 to 3 and Comparative Examples 1 and 2 are formed. Was measured. The results of the test are shown in Table 1 below.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　以上の結果から明らかなように、本発明の処理液を用いて形成したシロキサン結合を有する皮膜は、優れた耐食性能及び絶縁性を有していることが分かった。 As is clear from the above results, it was found that the film having a siloxane bond formed using the treatment liquid of the present invention has excellent corrosion resistance and insulation.

Claims (10)

  1. アルコキシシリル基、アルコキシシリレン基、及びシロキサン結合からなる群より選択される少なくとも１種を有するケイ素化合物、有機金属化合物、及び水を含有する、耐食性能及び絶縁性能を有する皮膜の形成用処理液。 A treatment liquid for forming a film having corrosion resistance and insulation performance, comprising a silicon compound having at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond, an organometallic compound, and water.
  2. 前記ケイ素化合物が樹脂を含む、請求項１に記載の処理液。 The treatment liquid according to claim 1, wherein the silicon compound contains a resin.
  3. 前記有機金属化合物が、有機金属キレート化合物及び金属アルコキシドからなる群より選択される少なくとも１種である、請求項１又は２に記載の処理液。 The processing liquid according to claim 1 or 2, wherein the organometallic compound is at least one selected from the group consisting of an organometallic chelate compound and a metal alkoxide.
  4. 前記有機金属化合物を構成する金属が、チタン、ジルコニウム、アルミニウム、及び錫からなる群より選択される少なくとも１種である、請求項１～３のいずれかに記載の処理液。 The treatment liquid according to any one of claims 1 to 3, wherein the metal constituting the organometallic compound is at least one selected from the group consisting of titanium, zirconium, aluminum, and tin.
  5. 前記有機金属化合物の含有量が、前記ケイ素化合物１００質量部に対して０．０１～５０質量部である、請求項１～４のいずれかに記載の処理液。 The treatment liquid according to any one of claims 1 to 4, wherein the content of the organometallic compound is 0.01 to 50 parts by mass with respect to 100 parts by mass of the silicon compound.
  6. 前記水の含有量が、前記ケイ素化合物１００質量部に対して１～１００質量部である、請求項１～５のいずれかに記載の処理液。 The treatment liquid according to any one of claims 1 to 5, wherein a content of the water is 1 to 100 parts by mass with respect to 100 parts by mass of the silicon compound.
  7. （工程１）請求項１～６のいずれかに記載の処理液を金属材料に塗布する工程
    を含む、耐食性能及び絶縁性能を有する皮膜の形成方法。     (Step 1) A method of forming a film having corrosion resistance and insulation performance, comprising a step of applying the treatment liquid according to any one of claims 1 to 6 to a metal material.
  8. さらに、
    （工程２）工程１後に硬化処理する工程
    を含む、請求項７に記載の形成方法。     further,
    (Process 2) The formation method of Claim 7 including the process of carrying out the hardening process after the process 1.
  9. 前記硬化処理が熱処理である、請求項８に記載の形成方法。 The forming method according to claim 8, wherein the curing treatment is a heat treatment.
  10. 金属材料、及び前記金属材料の表面上の皮膜を含み、且つ
    前記皮膜が、アルコキシシリル基、アルコキシシリレン基、及びシロキサン結合からなる群より選択される少なくとも１種を有するケイ素化合物の架橋構造体、及び有機金属化合物を含有する、
    皮膜含有金属材料。     A crosslinked structure of a silicon compound comprising a metal material and a film on the surface of the metal material, wherein the film has at least one selected from the group consisting of an alkoxysilyl group, an alkoxysilylene group, and a siloxane bond; And containing an organometallic compound,
    Film-containing metal material.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7467866B2 (en) 2019-10-02 2024-04-16 住友ゴム工業株式会社 Hydrophilic substrate and method for producing hydrophilic substrate

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Publication number Priority date Publication date Assignee Title
JP2003193263A (en) * 2001-10-05 2003-07-09 Nippon Steel Corp Iron core having excellent insulation property of edge face and insulation film treatment method for edge face of iron core
JP2009190369A (en) * 2008-02-18 2009-08-27 Jfe Steel Corp Magnetic steel sheet having insulating film
JP2013112837A (en) * 2011-11-25 2013-06-10 Jfe Steel Corp Insulating-film-coated electrical steel sheet
JP2014009371A (en) * 2012-06-28 2014-01-20 Jfe Steel Corp Electromagnetic steel sheet having insulation film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003193263A (en) * 2001-10-05 2003-07-09 Nippon Steel Corp Iron core having excellent insulation property of edge face and insulation film treatment method for edge face of iron core
JP2009190369A (en) * 2008-02-18 2009-08-27 Jfe Steel Corp Magnetic steel sheet having insulating film
JP2013112837A (en) * 2011-11-25 2013-06-10 Jfe Steel Corp Insulating-film-coated electrical steel sheet
JP2014009371A (en) * 2012-06-28 2014-01-20 Jfe Steel Corp Electromagnetic steel sheet having insulation film

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7467866B2 (en) 2019-10-02 2024-04-16 住友ゴム工業株式会社 Hydrophilic substrate and method for producing hydrophilic substrate

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