Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • 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
  • C23C22/06—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 acidic solutions with pH less than 6
  • C23C22/34—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 acidic solutions with pH less than 6 containing fluorides or complex fluorides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
• • 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
  • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
  • C09D143/04—Homopolymers or copolymers of monomers containing silicon
• • 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
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• • 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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
  • C09D5/4407—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained by polymerisation reactions involving only carbon-to-carbon unsaturated bonds
  • C09D5/4415—Copolymers wherein one of the monomers is based on an epoxy resin
• • 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
  • C23C22/06—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 acidic solutions with pH less than 6
  • C23C22/40—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 acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
  • C23C22/44—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 acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
• • 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
  • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
  • C23C2222/20—Use of solutions containing silanes

Definitions

• the present invention is a chromate-free surface-treated metal that does not contain hexavalent chromium with high environmental impact, is relatively easy to manufacture, and is extremely excellent in water and oil repellency, contamination resistance, solvent resistance, alkali resistance, and corrosion resistance Regarding materials.
• the present invention relates to a chromate-free surface-treated metal material that can simultaneously satisfy water / oil repellency and adhesion.
• Contamination resistance in the present invention refers to dripping pollution (attachment of dust, carbon, etc. in the air outdoors), food contamination (attachment of foodstuffs, food oil, seasonings, soft drinks, etc.), etc. (tobacco , Fingerprints, machine oils, oil-based inks, etc.), or the like.
• a metal material is formed and processed through a cleaning process using an organic solvent or an alkaline degreasing solution before being processed into a final product. It is important that the stain resistance is maintained even after such a cleaning process, and depending on the application, durability that can withstand repeated cleaning is required.
• Patent Document 1 discloses a chemical conversion treatment film containing a composite compound of manganese and titanium
• Patent Document 2 discloses a vanadium compound, zirconium, titanium, molybdenum, tungsten, manganese
• a metal surface treatment agent containing at least one metal compound selected from cerium is disclosed.
• Patent Document 4 discloses a resin-coated metal plate in which a surface-treated steel sheet is provided with a resin film obtained from an emulsion composition containing a specific ethylene-unsaturated carboxylic acid copolymer as a main component.
• Patent Document 5 discloses a fluorine-clear coated stainless steel sheet obtained from an organic solvent-based thermosetting resin including a specific fluorine resin, blocked isocyanate resin and amino resin. Has been.
• the corrosion resistance has not been sufficiently studied, and since an organic solvent is used as a solvent, there is a problem that the conventional chromate coating equipment cannot be manufactured for safety and health.
• high-temperature baking is necessary to cure the resin film, and there are problems in terms of productivity and energy efficiency.
• the present invention does not include highly environmentally friendly hexavalent chromium, is relatively easy to manufacture, and has extremely excellent water and oil repellency, stain resistance, solvent resistance, alkali resistance, and corrosion resistance. It aims at providing the surface treatment metal material which combines.
• another object of the present invention is to provide a chromate-free surface-treated metal material that can simultaneously satisfy water / oil repellency and adhesiveness.
• the main point of the present invention is that (1) Contains an organosilicon compound (A) having an alkylene group, a siloxane bond and a crosslinkable functional group represented by the following general formula [X], and an organofluorine compound (B) having a perfluoroalkyl group.
• Chromate-free surface-treated metal material-SiR 1 R 2 R 3 [X] characterized in that it has a film formed by applying an aqueous treatment agent to the surface of the metal material and drying or baking.
• R 1 , R 2 and R 3 each independently represent an alkoxy group or a hydroxy group.
• the solid content mass ratio [(A) / (B)] of the organosilicon compound (A) and the organofluorine compound (B) is 4 to 200, described in (1) Chromate-free surface-treated metal material (3)
• the organosilicon compound (A) is at least one selected from an amino group, an epoxy group, and a hydroxy group (separate from those that can be included in the general formula [X])
• the chromate-free surface-treated metal material according to (13), wherein the crosslinkable functional group (b) is an amino group, an isocyanate group, an epoxy group, a functional group represented by the following general formula [Y] and a hydroxy group (the following general formula The chromate-free surface-treated metal material -SiR 6 R 7 R according to (11) or (12), characterized in that it is at least one selected from those that can be included in [Y].
• R 6 , R 7 and R 8 each independently represent an alkoxy group or a hydroxy group. (Including the case where any one of R 6 , R 7 and R 8 is substituted with a methyl group) .))
• the chromate-free surface-treated metal material (15) according to any one of (1) to (13), wherein the organic fluorine compound (B) has an alkyl group.
• the organic fluorine compound (B) The chromate-free surface according to any one of (9), (10) and (12), wherein the polymer comprises a polymer unit based on (meth) acrylate (B3) having an alkyl group Treated metal material (16) The chromate-free surface-treated metal material (17) according to (14) or (15), wherein the alkyl group has an alkyl group having 16 or more carbon atoms.
• the chromate-free surface-treated metal material (23) according to any one of (1) to (21), wherein the drying or baking temperature of the aqueous treatment agent is 60 ° C. to 150 ° C. at an ultimate temperature.
• °C Characterized characterized in that (1) the amount of deposition of the chromate-free coated metal material (24) the formed film described in any one of - (22) is 0.2 ⁇ 2.0 g / m 2
• the chromate-free surface-treated metal material of the present invention does not contain hexavalent chromium with high environmental impact, is relatively easy to manufacture, and has all of water / oil repellency, contamination resistance, solvent resistance, alkali resistance, and corrosion resistance. It is extremely excellent. In addition, it is possible to satisfy water / oil repellency and adhesiveness at the same time. For this reason, it is very promising as a future high-value-added environment-friendly material, and the contribution to each industrial field is very large.
• the chromate-free surface-treated metal material of the present invention is an organic silicon compound (A) containing an alkylene group, a siloxane bond and a crosslinkable functional group represented by the following general formula [X], and an organic containing a perfluoroalkyl group. It has the film formed by apply
• R 1 , R 2 and R 3 each independently represent an alkoxy group or a hydroxy group, and any one of R 1 , R 2 and R 3 may be substituted with a methyl group.
• the treating agent for forming the film is an aqueous treating agent containing an organosilicon compound (A) and an organofluorine compound (B) in an aqueous medium mainly composed of water.
• “Mainly containing water” means that water exceeds 50% by mass with respect to the total mass of the aqueous medium.
• the aqueous medium can contain an organic solvent, but the amount of the organic solvent contained in the aqueous medium is preferably 15% by mass or less with respect to the total mass of the aqueous medium. Since the aqueous treatment agent of the present invention can form a film only by applying it to the surface of a metal material and drying it, it can be produced relatively easily as in the conventional chromate treatment.
• the film thus formed is a film in which an organic silicon compound (A) is used as a binder component and an organic fluorine compound (B) is combined therewith.
• the alkylene group contained in the organosilicon compound (A) plays a role of imparting film forming properties, flexibility, water resistance, alkali resistance, corrosion factor barrier properties, etc. to the film, and the siloxane bond is tough to the film, It plays a role of imparting durability and solvent resistance.
• the crosslinkable functional group represented by the formula —SiR 1 R 2 R 3 contained in the organosilicon compound (A) has self-crosslinkability, and the crosslinkable functional groups are formed between the crosslinkable functional groups in the film formation stage.
• a siloxane bond plays a role of improving the crosslink density of the film and imparting denseness, toughness, durability and solvent resistance to the film.
• the crosslinkable functional group plays a role of improving adhesion to the base metal material, a role of enhancing the film retention of the combined organic fluorine compound (B), and adding hydrophilicity to the organosilicon compound (A). Also, it plays a role of facilitating dissolution or dispersion in an aqueous medium.
• R 1 , R 2 and R 3 in the crosslinkable functional group it is considered that a hydroxy group (silanol group) generated by hydrolysis of an alkoxy group is preferentially generated in an aqueous medium.
• this binder film By combining this binder film with an organic fluorine compound (B) containing a perfluoroalkyl group, it is possible to impart high water / oil repellency and stain resistance. This is because the organic fluorine compound (B) containing a perfluoroalkyl group composed of a C—F bond can form a low free energy surface due to the low polarizability of the C—F bond. Because.
• a perfluoroalkyl group is formed on the surface of the film by forming a film from an aqueous treatment agent containing an aqueous medium containing water as a main component and using an organosilicon compound (A) as a binder component of the film.
• the surface free energy of the coating can be efficiently reduced.
• a film whose surface is covered with a perfluoroalkyl group and has a low surface free energy is excellent in water and oil repellency, hardly adheres to various contaminants, and exhibits extremely excellent contamination resistance.
• the stain resistance is maintained over a long period of time, and the durability of the water / oil repellency and stain resistance does not decrease even after cleaning with an organic solvent or an alkaline cleaning solution. A certain highly water- and oil-repellent and stain-resistant film is formed.
• a chromate-free film that is extremely excellent in all of water / oil repellency, contamination resistance, solvent resistance, alkali resistance, and corrosion resistance (including after molding) is formed.
• the solid content mass ratio [(A) / (B)] of the organosilicon compound (A) and the organofluorine compound (B) is preferably 4 to 200, more preferably 10 to 100.
• the solid content mass ratio [(A) / (B)] is smaller than 4, not only the corrosion resistance may be lowered due to a decrease in film forming property, but also economically disadvantageous. If it is larger than 200, the water / oil repellency and stain resistance may be lowered.
• the organosilicon compound (A) contains an alkylene group, a siloxane bond and a crosslinkable functional group represented by the following general formula [X], and can be stably present in an aqueous medium containing water as a main component. Although there is no particular limitation, it may further contain at least one crosslinkable functional group selected from an amino group, an epoxy group, and a hydroxy group (separate from those that can be included in the general formula [X]). It is preferable for forming a dense film having a higher crosslink density and enhancing the film retention of the organic fluorine compound (B). That is, contamination resistance, solvent resistance, alkali resistance, and corrosion resistance can be further improved.
• crosslinkable functional groups exhibit hydrophilicity, they are advantageous in increasing the stability of the organosilicon compound (A) in an aqueous medium.
• the stability in an aqueous medium in the present specification indicates that agglomerates and precipitates are less likely to be generated in an aqueous medium over time, and that thickening and gelation are less likely to occur.
• organosilicon compounds (A) include hydrolysis condensates of silane coupling agents.
• silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldimethoxy.
• Silane 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl Methyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2 (amino Til) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, bis (trimethoxysilylpropyl) amine, 3 -Trieth
• the organosilicon compound (A) is obtained by a reaction of an amino group-containing silane coupling agent (A1) and an epoxy group-containing silane coupling agent (A2). It is possible to form a dense film with high crosslink density by reaction between amino group and epoxy group, and reaction between alkoxysilyl groups contained in each or partial hydrolysis products. Further, alkali resistance and corrosion resistance can be further improved.
• silane coupling agent (A1) containing an amino group 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 ( Aminoethyl) 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, bis (trimethoxysilylpropyl) amine is an epoxy group-containing silane coupling agent (A2).
• 3-glycidoxypropyltrimethoxysilane 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane.
• the molar ratio [(A1) / (A2)] of the silane coupling agent (A1) containing an amino group and the silane coupling agent (A2) containing an epoxy group is 0.5 to 2.5. Preferably, it is 0.7 to 1.6. If the molar ratio [(A1) / (A2)] is less than 0.5, the film-forming property may be deteriorated and the stain resistance may be deteriorated. Alkalinity and corrosion resistance may decrease.
• the number average molecular weight of the organosilicon compound (A) is preferably 1000 to 10,000, more preferably 2000 to 10,000.
• the measuring method of molecular weight here is not particularly limited, but either direct measurement by TOF-MS method or conversion measurement by chromatography method may be used.
• the number average molecular weight is less than 1000, the water resistance of the formed film is lowered, and the alkali resistance and corrosion resistance may be lowered.
• the number average molecular weight is greater than 10,000, it may be difficult to stably dissolve or disperse the organosilicon compound (A) in an aqueous medium containing water as a main component, and storage stability may be lowered.
• the method for producing the organosilicon compound (A) is not particularly limited.
• a method of dissolving or dispersing a silane coupling agent in water and stirring it at a predetermined temperature for a predetermined time to obtain an aqueous solution of a hydrolysis condensate examples thereof include a method of obtaining an aqueous liquid by dissolving or dispersing an organosilicon compound such as a silane coupling agent hydrolysis condensate in water.
• an acid, alkali, organic solvent, surfactant or the like may be added as appropriate in order to dissolve or disperse, and particularly an organic acid is added to adjust the pH.
• the solid content concentration of the aqueous liquid of the organosilicon compound (A) is preferably 25% by mass or less. When it exceeds 25% by mass, the storage stability of the aqueous treatment agent may decrease.
• the organic fluorine compound (B) is not particularly limited as long as it contains a perfluoroalkyl group in the molecule and can stably exist in an aqueous medium containing water as a main component, but the carbon atom of the perfluoroalkyl group is not limited.
• the number is preferably 6 or less. The more carbon atoms, the easier it is to align on the coating surface, and the greater the effect of reducing surface free energy and improving antifouling properties.
• perfluorooctane sulfonic acid or its derivative or perfluorooctanoic acid or its derivative which is an environmentally hazardous substance and is partially restricted in use, is not preferable as the impurity derived from the raw material.
• the number of carbon atoms is less than 2, the water / oil repellency and stain resistance may not be sufficient, the environmental load reduction, easy availability, low cost, etc.
• it is 4-6.
• the organic fluorine compound (B) is preferably a polymer containing a polymer unit based on (meth) acrylate (B1) containing a perfluoroalkyl group.
• (meth) acrylate means acrylate or methacrylate. Since (meth) acrylate is excellent in solubility in various solvents and is easily emulsion-polymerized, using (meth) acrylate (B1) containing a perfluoroalkyl group as a monomer It is suitable for synthesizing the organic fluorine compound (B) to be contained.
• the polymer thus obtained is also excellent in stability in an aqueous solvent containing water as a main component. Since copolymerization with (meth) acrylates, vinyl ethers, vinyl esters, and the like that do not contain a perfluoroalkyl group is easy, the polymer has a great degree of freedom in design.
• the (meth) acrylate (B1) containing a perfluoroalkyl group is more preferably a structure represented by the following general formula [B-1].
• CH 2 C (R 4) COO (CH 2) n R 5 [B-1]
• R 4 represents H or CH 3
• R 5 represents a perfluoroalkyl group
• n represents an integer of 0 to 4.
• the structure represented by the general formula [B-1] is particularly effective in preferentially orienting the perfluoroalkyl group on the surface of the film, and with the organosilicon compound (A) that is a binder component of the film. Since the affinity is high, the film retention of the organic fluorine compound (B) is also high. In other words, high stain resistance is obtained, and water / oil repellency and stain resistance are maintained over a long period of time, and water / oil repellency and stain resistance are reduced even after washing with an organic solvent or an alkaline cleaning solution. It is possible to obtain a highly water- and oil-repellent and stain-resistant coating film that is durable.
• Examples of the (meth) acrylate (B1) containing a perfluoroalkyl group having a structure represented by the following general formula [B-1] include CH 2 ⁇ CHCOOC 2 H 4 C 4 F 9 and CH 2 ⁇ C.
• CH 2 CHCOOC 2 H 4 C 4 F 9
• CH 2 C (CH 3) COOC 2 H 4 C 4 F 9
• CH 2 CHCOOC 2 H 4 C 6 F 13
• CH 2 C (CH 3) COOC 2 H 4 C 6 F 13
• CH 2 C (CH 3) COOC is 3 H 6 C 6 F 13.
• the organic fluorine compound (B) preferably contains 60 to 98% by mass of a polymer unit based on the (meth) acrylate (B1) containing a perfluoroalkyl group. If it is less than 60% by mass, the stain resistance may decrease. If it exceeds 98% by mass, the film retention of the organic fluorine compound (B) may decrease, and the durability of water repellency / oil repellency and stain resistance may decrease. In addition, the stability of the organic fluorine compound (B) in an aqueous medium containing water as a main component may be reduced.
• the organic fluorine compound (B) preferably contains a crosslinkable functional group (b) in the molecule. It is considered that the crosslinkable functional group (b) forms a crosslinked structure by a chemical bond with the crosslinkable functional group contained in the silicon compound (A) as a binder component in the film formation process, and while increasing the crosslink density, the organic fluorine compound The film retention of (B) can be improved. That is, durable stain resistance can be imparted. In addition, since the crosslinkable functional group (b) exhibits hydrophilicity, the stability of the organic fluorine compound (B) in an aqueous medium containing water as a main component can be enhanced.
• the organic fluorine compound (B) is a polymer containing a polymer unit based on the (meth) acrylate (B1) containing a perfluoroalkyl group
• the (meth) acrylate (B2) further containing a crosslinkable functional group (b)
• the polymer can be produced relatively easily by copolymerization of (meth) acrylate (B1) containing a perfluoroalkyl group and (meth) acrylate (B2) containing a crosslinkable functional group (b).
• the copolymer thus obtained exhibits excellent stability in an aqueous medium containing water as a main component, and the obtained film has excellent water / oil repellency and stain resistance with extremely durability. Show.
• the crosslinkable functional group (b) is not particularly limited as long as it is a functional group capable of undergoing a crosslinking reaction.
• a functional group capable of undergoing a crosslinking reaction for example, an amino group, an isocyanate group, an alkoxysilyl group, a silanol group, an alkoxymethylamide group, an ammonium group, an amide group, Examples thereof include an epoxy group, a hydroxy group, an oxazoline group, a carboxyl group, an alkenyl group, and a sulfonic acid group.
• At least one selected from an amino group, an isocyanate group, an epoxy group, a functional group represented by the following general formula [Y], and a hydroxy group is particularly preferable from the viewpoints of stability in an aqueous solvent containing water as a main component and durability of water and oil repellency and stain resistance.
• R 6 , R 7 and R 8 each independently represent an alkoxy group or a hydroxy group, and any one of R 6 , R 7 and R 8 may be substituted with a methyl group.
• Isocyanate groups also include blocked isocyanate groups.
• (meth) acrylate (B2) containing a crosslinkable functional group (b) For example, 2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, 4- 3 of isocyanatobutyl (meth) acrylate, 2-butanone oxime adduct of 2-isocyanatoethyl (meth) acrylate, pyrazole adduct of 2-isocyanatoethyl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate , 5-dimethylpyrazole adduct, 3-methylpyrazole adduct of 2-isocyanatoethyl (meth) acrylate, ⁇ -caprolactam adduct of 2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate 2-butan
• the organic fluorine compound (B) preferably contains 1 to 30% by mass of a polymer unit based on the (meth) acrylate (B2) containing the crosslinkable functional group (b). If it is less than 1% by mass, the effect of improving the durability of water / oil repellency and stain resistance may not be obtained. If it exceeds 30% by mass, the stability of the organic fluorine compound (B) in an aqueous medium containing water as a main component may be lowered.
• the organic fluorine compound (B) preferably contains an alkyl group in the molecule. By containing an alkyl group, water / oil repellency and stain resistance can be further improved.
• the organic fluorine compound (B) more preferably contains an alkyl group having 16 or more carbon atoms in the molecule. A long-chain alkyl group having 16 or more carbon atoms can be easily oriented on the surface of the film like the perfluoroalkyl group and can reduce the free energy of the surface, thereby further improving the water / oil repellency and stain resistance. it can.
• the organic fluorine compound (B) is a polymer containing a polymer unit based on the (meth) acrylate (B1) containing a perfluoroalkyl group
• the polymer also contains.
• the polymer can be produced relatively easily by copolymerization of a (meth) acrylate (B1) containing a perfluoroalkyl group and a (meth) acrylate (B3) containing an alkyl group.
• the film obtained from the copolymer thus obtained exhibits excellent water / oil repellency and stain resistance with extremely high durability.
• organic fluorine compound (B) is a polymer containing a polymer unit based on (meth) acrylate (B1) containing a perfluoroalkyl group, polymerization based on (meth) acrylate (B3) containing an alkyl group In addition to the units, it may further contain polymerized units based on (meth) acrylate (B2) containing a crosslinkable functional group (b).
• the (meth) acrylate (B3) containing an alkyl group is not particularly limited.
• methyl acrylate, ethyl acrylate, propyl acrylate, butyl methacrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) ) Acrylate and behenyl (meth) acrylate may be used alone or in combination of two or more.
• (Meth) acrylate containing an alkyl group having 16 or more carbon atoms can improve the water / oil repellency and stain resistance as described above, but there is a concern that the film-forming property of the film is lowered.
• (meth) acrylate containing an alkyl group having 6 or less carbon atoms has an effect of improving the film forming property of the film. Therefore, water / oil repellency and contamination resistance are improved while using a (meth) acrylate containing an alkyl group having 16 or more carbon atoms and a (meth) acrylate containing an alkyl group having 6 or less carbon atoms in combination. Therefore, more durable water / oil repellency and stain resistance can be imparted, which is more preferable.
• the organic fluorine compound (B) preferably contains 1 to 25% by mass of polymerized units based on the (meth) acrylate (B3) containing an alkyl group. If the amount is less than 1% by mass, the effect of improving water / oil repellency and stain resistance may not be obtained. When it exceeds 25 mass%, the stability of the organic fluorine compound (B) in an aqueous medium containing water as a main component may be lowered.
• the surface-treated metal material of the present invention requires adhesion, it is preferable to contain an alkylene oxide group in the molecule of the organic fluorine compound (B). Since the alkylene oxide group exhibits excellent adhesiveness, it can satisfy water / oil repellency and adhesiveness simultaneously when used in combination with a perfluoroalkyl group. In particular, the shorter the alkylene chain of the alkylene oxide group and the greater the number of repeating units of the alkylene oxide group, the more highly flexible flexible functional group, when an adhesive (adhesive, adhesive, etc.) comes into contact with the surface-treated metal material , It becomes easy to preferentially orient to the adhesive side, and excellent adhesiveness can be ensured. In addition, the alkylene oxide group has an effect of increasing the stability of the organic fluorine compound (B) in the aqueous medium by exhibiting hydrophilicity and an effect of increasing the film retention of the organic fluorine compound (B).
• the organic fluorine compound (B) is a polymer containing a polymer unit based on the (meth) acrylate (B1) containing a perfluoroalkyl group
• the (meth) acrylate (B4) further containing an alkylene oxide group for the reasons described above. It is preferable that it is a polymer which also contains the polymer unit based on.
• the (meth) acrylate (B4) containing an alkylene oxide group is more preferably a structure represented by the following general formula [B-4].
• CH 2 C (R 9) COO (CH 2) p - (R 10 O) q -R 11 [B-4]
• R 9 is H or CH 3
• R 10 is an alkylene group having 2 to 4 carbon atoms
• R 11 is a hydrogen atom, a methyl group or a (meth) acryloyl group
• p is 0 to 4
• Q is an integer of 1-30.
• R 9 is H or CH 3
• R 10 is an alkylene group having 2 to 3 carbon atoms
• R 11 is a hydrogen atom or a methyl group
• p is 0 to 4 and q are preferably integers of 4 to 30.
• the organic fluorine compound (B) is a polymer containing a polymer unit based on the (meth) acrylate (B1) containing a perfluoroalkyl group, it is based on the (meth) acrylate (B4) containing an alkylene oxide group.
• the polymer unit at least one of a polymer unit based on (meth) acrylate (B3) containing an alkyl group and a polymer unit based on (meth) acrylate (B2) containing a crosslinkable functional group (b) One may be included.
• the structure represented by the general formula [B-4] is most effective in improving the film retention and stain resistance of the organic fluorine compound (B), and is mainly composed of water of the organic fluorine compound (B). It is most effective in increasing the stability in an aqueous medium.
• R 11 is a (meth) acryloyl group
• the organic fluorine compound (B) can easily form a three-dimensional cross-linked structure, so that durable water / oil repellency and stain resistance can be obtained.
• a compound in which R 11 is a (meth) acryloyl group and a compound in which R 11 is a hydrogen atom or a methyl group are used in combination.
• the (meth) acrylate (B4) containing an alkylene oxide group is not particularly limited, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate.
• the organic fluorine compound (B) preferably contains 1 to 20% by mass of a polymer unit based on the (meth) acrylate (B4) containing an alkylene oxide group. If it is less than 1% by mass, the effect of improving the water and oil repellency, the durability of stain resistance and the adhesion may not be obtained. If it exceeds 20% by mass, the water / oil repellency and stain resistance may decrease.
• another monomer may be further contained in the organic fluorine compound (B) in order to improve the durability of contamination resistance.
• the proportion of polymerized units based on the other monomers is preferably 30% by mass or less, and more preferably 15% by mass or less.
• Examples of other monomers include ethylene, vinylidene chloride, vinyl chloride, vinylidene fluoride, vinyl acetate, vinyl propionate, vinyl isobutanoate, vinyl isodecanoate, vinyl stearate, cetyl vinyl ether, dodecyl vinyl ether, isobutyl vinyl ether, Ethyl vinyl ether, 2-chloroethyl vinyl ether, styrene, ⁇ -methyl styrene, p-methyl styrene, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, diacetone (meth) acrylamide, methylolated diacetone (meth) acrylamide, Vinyl alkyl ketone, butadiene, isoprene, chloroprene, benzyl (meth) acrylate, (meth) acrylate having polysiloxane, allyl acetate, N-vinylcarbazole Maleimi
• an organic fluorine compound (B) For example, after copolymerizing the various monomers containing the monomer containing a perfluoroalkyl group in an organic solvent, water is made into a main component.
• An organic fluorine compound (B) is prepared by a method of emulsifying and dispersing in an aqueous medium, a method of dispersing various monomers including a monomer containing a perfluoroalkyl group in an aqueous medium containing water as a main component, and emulsion polymerization. ) For producing an aqueous liquid.
• the obtained solution, dispersion, and emulsion may be used as they are, or may be used after diluting with water. Further, the organic solvent contained in the solvent may be distilled off and used.
• ketone acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.
• alcohol isopropyl alcohol, etc.
• ester ethyl acetate, butyl acetate, etc.
• Ether such as diisopropyl ether
• aliphatic hydrocarbon or aromatic hydrocarbon halogenated hydrocarbon (such as perchloroethylene, trichloro-1,1,1-ethane, trichlorotrifluoroethane, dichloropentafluoropropane), Dimethylformamide, N-methyl-pyrrolidone-2, butyroacetone, DMSO (dimethyl sulfoxide), glycol ether and derivatives thereof can be used.
• an organic solvent having a relatively low boiling point or an azeotropic mixture with water is preferable, and acetone, 2-propyl alcohol, methyl isobutyl ketone, methyl ethyl ketone, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether or These mixed solvents are preferred.
• the total concentration of the monomers in the organic solvent is preferably 5 to 60% by mass, and more preferably 10 to 40% by mass.
• the polymerization initiator In the polymerization reaction for obtaining the organic fluorine compound (B), it is preferable to use a polymerization initiator.
• a polymerization initiator peroxides such as benzyl peroxide, lauryl peroxide, succinyl peroxide, tert-butyl perpivalate, azo compounds, azoamidine compounds, and the like are preferable.
• the concentration of the initiator in the solvent is preferably 0.1 to 1.5% by mass with respect to the total amount of monomers.
• polymerization initiator among the above polymerization initiators, the following polymerization initiators are preferable because they are excellent in polymerizability and excellent in safety.
• polymerization initiator examples include 2,2′-azobis-2-methylbutyronitrile (LD50: 1316 mg / kg, 10 hour half-life temperature: 67 ° C.), dimethyl-2,2′-azo. Bisisobutyrate (LD50: 2369 mg / kg, 10 hour half-life temperature: 65 ° C.), 2,2′-azobis [2- (2-imidazolin-2-yl) propane] (LD50: 2000 mg / kg or more, 10 Time half-life temperature: 61 ° C., 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (LD50: 2900 mg / kg, 10-hour half-life temperature: 30 ° C.), 1,1′- Azobis (2-cyclohexane-1-carbonitrile) (LD50: 11800 mg / kg or more, 10 hour half-life temperature: 88 ° C.), 2,2′-azobis (2,4-di Tylvaleronitrile) (LD50: 13
• a chain transfer agent in the polymerization reaction.
• alkyl mercaptans such as tert-dodecyl mercaptan, n-dodecyl mercaptan, stearyl mercaptan, aminoethanethiol, mercaptoethanol, 2,4-diphenyl-4-methyl-1-pentene, carbon tetrachloride and the like are preferable.
• the amount of the chain transfer agent used is preferably 0.05 to 1% by mass with respect to the total amount of monomers in the polymerization reaction.
• the reaction temperature in the polymerization reaction is preferably in the range from room temperature to the boiling point of the reaction mixture. From the viewpoint of efficiently using the polymerization initiator, it is preferably at least the half-life temperature of the polymerization initiator, more preferably from 30 to 90 ° C.
• a surfactant may be used when the monomer for synthesizing the organic fluorine compound (B) or the organic fluorine compound (B) is dispersed in an aqueous medium.
• a hydrocarbon-based or fluorine-based surfactant can be used, and an anionic, nonionic, cationic or amphoteric surfactant can be used.
• a nonionic surfactant is preferable, and a combination of a nonionic surfactant and another ionic surfactant is particularly preferable.
• a cationic surfactant or an amphoteric surfactant is preferable.
• a combination of a nonionic surfactant and a cationic surfactant is preferable. It is more preferable to use a nonionic surfactant and a cationic surfactant in combination from the viewpoint of water / oil repellency and stain resistance.
• nonionic surfactant one or more nonionic surfactants selected from the group consisting of the following surfactants (a) to (f) are preferable.
• surfactant (b) a nonionic surfactant comprising a compound having one or more carbon-carbon triple bonds and one or more hydroxyl groups in the molecule.
• Surfactant (c) A polyoxyethylene chain (hereinafter referred to as POE) in which two or more oxyethylenes are continuously linked to a chain in which two or more oxyalkylenes having 3 or more carbon atoms are continuously linked. And a nonionic surfactant comprising a compound having both hydroxyl groups at the ends.
• Surfactant (d) a nonionic surfactant having an amine oxide moiety in the molecule.
• Surfactant (f) Nonionic surfactant comprising a fatty acid ester of polyol.
• the surfactant contains a cationic surfactant (g), it is preferable to use a substituted ammonium salt type cationic surfactant.
• the substituted ammonium salt type cationic surfactant include ammonium salts in which one or more hydrogen atoms bonded to a nitrogen atom are substituted with an alkyl group, an alkenyl group, or POA (polyoxyalkylene) having a terminal hydroxyl group. preferable.
• amphoteric surfactant h
• amphoteric surfactants such as alanines, imidazolinium betaines, amide betaines or betaine acetate are preferred.
• the content of the surfactant is preferably 1 to 10% by mass, particularly preferably 3 to 8% by mass with respect to 100% by mass of the organic fluorine compound (B).
• the content of the surfactant is within this range, the stability of the organic fluorine compound (B) in an aqueous medium containing water as a main component is good, and durability of water repellency / oil repellency and stain resistance is good. It is preferable because it is excellent.
• the cationic surfactant (g) and / or the amphoteric surfactant (h) it is preferable to use nonionic surfactants (a) to (f) in combination.
• the amount of the surfactant (g) and / or the amphoteric surfactant (h) is preferably 0.1 to 2% by mass with respect to 100% by mass of the organic fluorine compound (B).
• the organic fluorine compound (B) is dissolved or dispersed in an aqueous medium containing water as a main component.
• the number average particle diameter is preferably 300 nm or less, more preferably 100 nm or less, and particularly preferably 30 nm or less.
• the number average particle diameter is 300 nm or less, the uniformity in the film increases, and more excellent stain resistance can be obtained.
• the number average particle diameter can be measured by a particle diameter measuring apparatus using a dynamic light scattering method, for example, FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.).
• aqueous medium from the viewpoint of handling and safety and health, water or a mixture containing water as a main component and a small amount of an aqueous organic solvent added can be used.
• aqueous organic solvent propylene glycol monomethyl ether and dipropylene glycol monomethyl ether are preferable.
• the aqueous treatment agent for forming a film in the present invention is not particularly limited as long as it contains the organosilicon compound (A) and the organofluorine compound (B), but the organosilicon compound (A) and / or Or when the said organic fluorine compound (B) contains an amino group, it is preferable to contain an organic acid.
• the storage stability of the aqueous treatment agent is improved by subjecting the amino group to amine chloride.
• An acid or the like is preferably used for amine chloride, and an organic acid is particularly preferably used.
• the organic acid is not particularly limited, and examples include formic acid, acetic acid, butyric acid, succinic acid, succinic acid, lactic acid, ascorbic acid, tartaric acid, citric acid, malic acid, malonic acid, maleic acid, phthalic acid, and the like. Among these, those having volatility such as acetic acid and lactic acid hardly remain in the film, and are more preferable from the viewpoint of not reducing the corrosion resistance and durability of the film.
• the organic acid may be added at the stage of producing the organic silicon compound (A) aqueous liquid and / or the organic fluorine compound (B) aqueous liquid.
• the aqueous treatment agent for forming a film in the present invention preferably further contains at least one corrosion inhibitor of a phosphoric acid compound, a fluoro metal complex, a vanadium compound, and a cobalt compound for the purpose of improving the corrosion resistance.
• These corrosion inhibitors mainly improve the corrosion resistance by reacting with the base metal surface to form a passive film.
• the organic fluorine compound (B) contained in the film has a function of enhancing the barrier property against the corrosion factor of the film and improving the corrosion resistance. By allowing the corrosion inhibitor having these different functions and the organic fluorine compound (B) to coexist in the film, the corrosion resistance is dramatically improved.
• the coating film according to the present invention has excellent corrosion resistance just by being processed on a metal material in a single layer, it also has an advantage of eliminating the need for a base treatment or a primer. From the viewpoint of improving corrosion resistance, it is more preferable to use a phosphoric acid compound and a fluorometal complex or a phosphoric acid compound and a vanadium compound in combination, and it is particularly preferable to use a phosphoric acid compound, a fluorometal complex and a vanadium compound in combination. In addition to the effect of improving the corrosion resistance, the cobalt compound has an effect of improving the blackening resistance of the surface of the metal material or the plated metal material.
• the content thereof is preferably 1 to 15% by mass in the solid content of the film to be formed. If it is less than 1% by mass, the effect of improving the corrosion resistance may not be obtained, and if it exceeds 15% by mass, the stain resistance may be lowered.
• the phosphoric acid compound is not particularly limited.
• phosphoric acids such as orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid and tetraphosphoric acid, ammonium salts such as triammonium phosphate and diammonium hydrogen phosphate, Metal salts with Na, Mg, Al, K, Ca, Mn, Ni, Zn, Fe, etc., aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), Examples thereof include phosphonic acids such as diethylenetriaminepenta (methylenephosphonic acid) and salts thereof, organic phosphoric acids such as phytic acid and salts thereof, and the like. These may be used alone or in combination of two or more.
• the fluoro metal complex is not particularly limited.
• hexafluorophosphoric acid, hexafluorotitanic acid, hexafluorozirconic acid, hexafluorosilicic acid, hexafluoroniobic acid, hexafluoroantimonic acid and ammonium salts thereof potassium Examples thereof include salts, sodium salts, calcium salts, and magnesium salts. These may be used alone or in combination of two or more.
• the vanadium compound is not particularly limited, for example, vanadium pentoxide, metavanadate, ammonium metavanadate, sodium metavanadate, vanadium oxytrichloride, vanadium trioxide, vanadium dioxide, vanadium oxysulfate, vanadium oxyacetylacetonate, Examples thereof include vanadium acetylacetonate, vanadium trichloride, and phosphorus vanadomolybdic acid.
• a pentavalent vanadium compound is formed by an organic compound having at least one functional group selected from the group consisting of a hydroxyl group, a carbonyl group, a carboxyl group, a primary to tertiary amino group, an amide group, a phosphoric acid group, and a phosphonic acid group.
• Those reduced to tetravalent to divalent can also be used. These may be used alone or in combination of two or more.
• cobalt compound for example, cobalt sulfate, cobalt nitrate, cobalt carbonate, those ammonium salts, potassium salt, sodium salt, calcium salt, magnesium salt etc. are mentioned. These may be used alone or in combination of two or more.
• the aqueous treatment agent for forming a film in the present invention is a leveling agent, a water-soluble solvent, a metal stabilizer, an etching inhibitor, and a pH adjuster for improving coating properties within the range not impairing the effects of the present invention. It is possible to use an agent or the like.
• leveling agents include nonionic or cationic surfactants such as polyethylene oxide or polypropylene oxide adducts and acetylene glycol compounds
• examples of water-soluble solvents include alcohols such as ethanol, isopropyl alcohol, t-butyl alcohol, and propylene glycol.
• Cellosolves such as ethylene glycol monobutyl ether and ethylene glycol monoethyl ether, esters such as ethyl acetate and butyl acetate, and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone.
• metal stabilizers include chelate compounds such as EDTA (ethylenediaminetetraacetic acid) and DTPA (diethylenetriaminepentaacetic acid).
• etching inhibitors include amine compounds such as ethylenediamine, triethylenepentamine, guanidine, and pyrimidine. Can be mentioned.
• those having two or more amino groups in one molecule are more preferable because they are effective as metal stabilizers.
• the pH adjuster include organic acids such as acetic acid and lactic acid, inorganic acids such as hydrofluoric acid, ammonium salts and amines.
• the said organic silicon compound (A) containing aqueous liquid, the said organic fluorine compound (B) containing aqueous liquid, arbitrary additives can be sequentially mixed and stirred at a predetermined ratio. If necessary, it may be diluted with an aqueous medium such as water.
• the total solid content of the organosilicon compound (A) and the organofluorine compound (B) is preferably 5 to 25% by mass. When the amount is less than 5% by mass, a predetermined coating amount may not be obtained. When the amount exceeds 25% by mass, the storage stability of the aqueous treatment agent may be deteriorated.
• the content of the organic solvent contained in the aqueous treatment agent for forming a film in the present invention is preferably 15% by mass or less based on the total mass of the aqueous medium.
• the organic solvent is contained in an aqueous medium in an amount of more than 15% by mass, it inhibits the self-crosslinking of the crosslinkable functional group contained in the organosilicon compound (A) or is contained in the organic fluorine compound (B). There is a risk of inhibiting the orientation of the fluoroalkyl group on the surface of the film.
• an organic solvent having a boiling point higher than that of water is contained, the film may remain in the film even after the film is dried, and the film forming property of the film may be lowered.
• the content of the organic solvent contained in the aqueous treatment agent is preferably 5% by mass or less with respect to the total mass of the aqueous treatment agent.
• the surface-treated metal material of the present invention has a film formed by applying the aqueous treatment agent on the surface of the metal material and drying or baking.
• aqueous treatment agent there is no restriction
• the drying or baking method is not particularly limited, but the metal material may be heated in advance or the metal material may be heated after application.
• the drying or baking temperature is preferably 60 ° C. to 150 ° C.
• the ultimate temperature more preferably 70 ° C. to 150 ° C., and most preferably 100 ° C. to 150 ° C. If the ultimate temperature is less than 60 ° C., the stain resistance may decrease. Even if it exceeds 150 ° C., no further improvement in performance can be expected, which is disadvantageous in terms of productivity and energy efficiency.
• the adhesion amount of the formed film is preferably 0.2 to 2.0 g / m 2 , more preferably 0.3 to 1.0 g / m 2 , and 0.3 to 0.7 g / m 2. 2 is most preferred.
• the film mass is less than 0.1 g / m 2 , the surface of the metal material cannot be coated, and the corrosion resistance and contamination resistance may be lowered.
• it exceeds 2.0 g / m 2 the film-forming property is lowered and the stain resistance may be lowered.
• the contact angle of the formed film with water at 20 ° C. is preferably 100 ° or more. If the angle is less than 100 °, sufficient contamination resistance may not be obtained.
• the contact angle of the formed film with n-hexadecane at 20 ° C. is preferably 55 ° or more. Since the contact angle with n-hexadecane is an indicator of wettability with various oily substances, the coating design with an increased contact angle with n-hexadecane is very effective in increasing the resistance to contamination with oily contaminants. is there. If the angle is less than 55 °, the stain resistance particularly against oily soil may not be sufficient.
• the upper limit value of the contact angle with n-hexadecane at 20 ° C. are not particularly limited.
• the upper limit value of the contact angle with water at 20 ° C. is substantially about 120 °
• the upper limit value of the contact angle with n-hexadecane at 20 ° C. is 75.
• the metal material used in the present invention is not particularly limited.
• various metals such as steel, aluminum, copper, and titanium, or alloy materials (plate material, pipe material, wire material, shape material, etc., and , Molded or joined them), and metal materials plated with any metal or alloy such as zinc, aluminum, nickel, chromium, copper, cobalt, silicon, iron, magnesium, calcium, manganese, etc.
• steel plates, plated steel plates, aluminum plates, and stainless steel plates are preferable as the metal material used in the present invention, and zinc-based plated steel plates and aluminum-based plated steel plates are more preferable from the viewpoint of the balance between corrosion resistance and cost.
• Zinc-coated steel sheets include galvanized steel sheets, zinc-nickel plated steel sheets, zinc-iron plated steel sheets, zinc-chromium plated steel sheets, zinc-aluminum plated steel sheets, zinc-titanium plated steel sheets, zinc-magnesium plated steel sheets, zinc-manganese.
• Galvanized steel sheets such as plated steel sheets, zinc-aluminum-magnesium plated steel sheets, zinc-aluminum-magnesium-silicon-plated steel sheets, and cobalt, molybdenum, tungsten, nickel as a small amount of different metal elements or impurities in these plated layers
• Examples include those containing titanium, chromium, aluminum, manganese, iron, magnesium, lead, bismuth, antimony, tin, copper, cadmium, arsenic and the like, and those in which inorganic substances such as silica, alumina, and titania are dispersed.
• the aluminum-based plated steel sheet examples include aluminum or an alloy composed of aluminum and at least one of silicon, zinc, and magnesium, such as an aluminum-silicon plated steel sheet, an aluminum-zinc plated steel sheet, and an aluminum-silicon-magnesium plated steel sheet.
• the present invention can also be applied to multilayer plating in combination with the above plating and other types of plating such as iron plating, iron-phosphorus plating, nickel plating, cobalt plating and the like.
• the plating method is not particularly limited, and any known method such as an electroplating method, a hot dipping method, a vapor deposition plating method, a dispersion plating method, and a vacuum plating method may be used.
• a coating was formed by applying the aqueous treatment agent produced in Production Example 4 on a surface of various metal plates having a thickness of 0.8 mm with a bar coater and drying to obtain a surface-treated metal plate (test plate) used in an evaluation test.
• Table 6 shows the metal plate type, the coating amount, and the temperature reached during drying. The abbreviations in Table 6 have the following meanings.
• EG electrogalvanized steel sheet (plating adhesion amount 20 g / m 2 )
• GI Hot-dip galvanized steel sheet (plating adhesion amount 60 g / m 2 )
• GA Alloyed hot-dip galvanized steel sheet (plating adhesion amount 45 g / m 2 )
• ZL Electro-zinc-12% Ni alloy-plated steel sheet (plating adhesion amount 20 g / m 2 ) SD: Hot-dip zinc-11% Al-3% Mg-0.2% Si-plated steel sheet (plating adhesion amount 60 g / m 2 )
• AL Molten Al-9% Si plated steel sheet (plating adhesion amount 40 g / m 2 )
• SUS Ferritic stainless steel sheet (steel component: C; 0.008 mass%, Si; 0.07 mass%, Mn; 0.15 mass%, P; 0.011 mass%, S; 0.009 mass%, Al; 0.067% by mass, Cr; 17.3% by
• Fingerprint contamination resistance A fingerprint was attached by pressing a finger against the test plate, and after left at room temperature for 1 hour, the fingerprint was wiped off with absorbent cotton, and the remaining trace of the fingerprint was evaluated according to the following evaluation criteria. ⁇ : No fingerprint traces ⁇ : Fingerprint traces remain slightly (level that allows you to distinguish fingerprint traces with your eyes closed) ⁇ : Fingerprint traces remain (the fingerprint traces can be identified instantly, but there is no clear change in the part and color tone where there are no fingerprint traces) ⁇ : Fingerprint traces remain clearly (the fingerprint traces can be identified instantly, and there is a clear change in the part and color tone where there are no fingerprint traces)
• Adhesive strength of 15 N / 20 mm or more Adhesive strength of 10 N / 20 mm or more and less than 15 N / 20 mm
• Examples of the present invention are excellent in solvent resistance, alkali resistance, contact angle with water, contact angle with n-hexadecane, corrosion resistance, solvent resistance test in any evaluation test (excluding adhesiveness). Before and after and before and after the alkali resistance test, fingerprint stain resistance, oil resistance ink stain resistance, and scum stain resistance were exhibited.
• the aqueous processing agent used for the Example of this invention was left still at 40 degreeC for 1 month, and storage stability was investigated, w3, w13, w24, and w34 were gelatinized. That is, the organic silicon compound (A) aqueous liquid containing no organic acid and the molecular weight of 12,000 were slightly poor in storage stability compared to other aqueous treatment agents.
• Surface treated metal example 156 in which organic fluorine compound (B) is replaced with silane-based water repellent treatment agent is anti-fingerprint stain resistance after solvent / alkali test and oil-resistant ink stain resistance before and after solvent / alkali test Was inferior.
• the surface-treated metal example 157 using the chromate treatment solution was inferior in various stain resistances.
• the surface-treated metal example 158 using the inorganic chromate-free treatment solution was inferior in alkali resistance, processed part corrosion resistance, and various stain resistances.
• Surface-treated metal examples 159 and 160 using a resin-based chromate-free treatment liquid are alkali resistance, corrosion resistance, fingerprint contamination resistance after solvent / alkaline test, oil resistance ink stain resistance, solvent at a coating weight of 0.5 g / m 2 -Poor stain resistance before and after alkali test, and with coating coverage of 2.0 g / m 2 , alkali resistance, solvent resistance, fingerprint stain resistance after alkali test, oil resistance ink stain resistance before and after solvent / alkali test Soil resistance was poor after solvent / alkali tests.
• the surface-treated metal examples 44, 49, 161 to 169 containing an alkylene oxide group in the molecule of the organic fluorine compound (B) contain an alkylene oxide group.
• the surface-treated metal examples 29 and 58 which did not show adhesion better than those shown above.
• the shorter the alkylene chain of the alkylene oxide group and the greater the number of repeating units of the alkylene oxide group the better the adhesion.

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