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
  • C23C22/36—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 containing also phosphates
  • C23C22/361—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 containing also phosphates containing titanium, zirconium or hafnium compounds
• • 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
  • B05D7/14—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 to metal, e.g. car bodies
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
  • B32B15/095—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
  • C08G18/0809—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups
  • C08G18/0814—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups containing ammonium groups or groups forming them
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3203—Polyhydroxy compounds
  • C08G18/3206—Polyhydroxy compounds aliphatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3271—Hydroxyamines
  • C08G18/3275—Hydroxyamines containing two hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/487—Polyethers containing cyclic groups
  • C08G18/4875—Polyethers containing cyclic groups containing cycloaliphatic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
  • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
  • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
  • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
  • C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/68—Unsaturated polyesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
  • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
  • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
  • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/08—Polyurethanes from polyethers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
• • 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
  • C23C22/36—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 containing also phosphates
• • 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
  • C23C22/36—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 containing also phosphates
  • C23C22/368—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 containing also phosphates containing magnesium cations
• • 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 surface treatment with a cationic chromium-free surface treatment agent, such as corrosion resistance, alkali resistance, solvent resistance, and other detergent resistance, sweat resistance, film adhesion, paint adhesion, and print adhesion.
• a cationic chromium-free surface treatment agent such as corrosion resistance, alkali resistance, solvent resistance, and other detergent resistance, sweat resistance, film adhesion, paint adhesion, and print adhesion.
• the present invention relates to a zinc-based plated steel sheet having a chromium-free surface treatment which is excellent in water resistance such as adhesion, moisture discoloration resistance and dew condensation resistance, and also excellent in workability and slidability.
• the metal material surface contains chromic acid, dichromic acid or a salt thereof as a main component.
• a method of performing a chromate treatment with a treatment solution, a method of performing a phosphate treatment, a method of carrying out an organic resin film treatment, and the like are known and put into practical use.
• the metal surface is brought into contact with a treatment liquid containing chromium such as chromate chromate to deposit the chromate film, or coated and dried. And a method of forming a chromate film.
• a treatment liquid containing chromium such as chromate chromate to deposit the chromate film, or coated and dried.
• a method of forming a chromate film In the conventional chromate treatment, the metal surface is brought into contact with a treatment liquid containing chromium such as chromate chromate to deposit the chromate film, or coated and dried. And a method of forming a chromate film.
• these inorganic chromate coatings alone are hard, brittle and poor in lubricity, so that not only the coating will fall off and the appearance will be impaired, but also sufficient processing will not be possible, and the material will crack and crack. The problem that occurs.
• the operator's fingerprint is attached during the work, and the trace remains even after degreasing and cleaning.
• a chromate film is formed on the surface of the metal material, and the chromate film is formed on the formed chromate film. Further, a two-layer process for providing a resin film is performed.
• Patent Document 1 discloses a specific method on the surface of an aluminum-galvanized steel sheet.
• the chromate treatment has a property that the hexavalent chromium contained in the film gradually dissolves, and has problems in terms of environment and safety.
• Patent Document 3 discloses a polymer composition for surface treatment of a metal material containing a phenol resin polymer having a specific structure and an acidic compound, and a surface treatment method.
• Patent Document 4 discloses a metal surface treatment agent and a treatment method excellent in fingerprint resistance and the like, containing two or more silane coupling agents having reactive functional groups having specific structures that are different from each other and capable of reacting with each other, Patent Document 5
• a metal surface treatment agent and treatment method containing a silane coupling agent having a specific structure and a phenol resin polymer having a specific structure
• Patent Document 6 an epoxy resin having at least one nitrogen atom, an acrylic resin, and a urethane Metal surface treatment agent, treatment method and treatment metal material containing organic polymer such as resin and specific polyvalent anion
• Patent Document 7 (1) Bis with specific structure Rust inhibitor containing an enol A epoxy resin, (2) Rust inhibitor containing a specific resin such as a phenolic resin and other polyester, and a treatment using (1) and (2) Methods and treated metal materials are disclosed.
• chromium-free technologies are resistant to cleaning, such as corrosion resistance, alkali resistance and solvent resistance, film adhesion, adhesion such as paint adhesion and printing adhesion, moisture discoloration resistance and condensation resistance. It is excellent in water resistance and does not satisfy all the workability and slidability.
• the surface treatment agent that can be used as an alternative to the chromate film has not been obtained by any of these methods, and there is a strong demand for the development of a surface treatment agent and a treatment method that can satisfy these conditions comprehensively. It is.
• Japanese Patent Publication No.4-2672 Japanese Patent Publication No. 7-6070 JP 7-278410 A JP-A-8-73775 JP-A-9-241576 Japanese Patent Laid-Open No. 10-1789 Japanese Patent Laid-Open No. 10-60233
• the present invention solves the above-mentioned problems of the prior art, and has anti-corrosion, alkali resistance, solvent resistance and other cleaning resistance, sweat resistance, film adhesion, paint adhesion and printing adhesion,
• An object of the present invention is to provide a chromium-free surface-treated galvanized steel sheet having excellent water resistance such as moisture discoloration resistance and dew condensation resistance, and excellent workability and slidability.
• an organosilicon compound (C) having two or more specific functional groups and one or more specific hydrophilic functional groups, a specific molecular weight and a specific structure in the molecule, and a specific structural unit
• An inhibitor component (d) containing, as an essential component, a film-forming component (c) containing an aqueous polyurethane resin (E) having a specific ratio and a fluorometal complex compound (H) having at least one selected from titanium and zirconium )
• a water-based metal surface treatment agent containing an aqueous medium, and by drying, a composite film containing each component is formed, thereby providing a cleaning agent such as corrosion resistance, alkali resistance and solvent resistance.
• Chrome-free surface-treated zinc with excellent water resistance such as anti-sweat, film adhesion, paint adhesion and printing adhesion, moisture discoloration resistance and dew condensation resistance, and excellent workability and slidability It discovered that a system plating steel plate was obtained and came to complete this invention.
• the present invention relates to (1) a solid content mass ratio of a silane coupling agent (A) containing one amino group in the molecule and a silane coupling agent (B) containing one glycidyl group in the molecule [ (A) / (B)] obtained by blending at a ratio of 0.50 to 0.75, and having two or more functional groups (a) represented by the following general formula [1] in the molecule, and a hydroxyl group Containing at least one hydrophilic functional group (b) selected from an amino group (separate from those that can be included in the functional group (a)) and an average molecular weight of 1,000 to 10,000
• a polyether polyurethane resin (E) having a structural unit derived from a polyether
• the abundance ratio of the cyclic siloxane bond and the chain siloxane bond is 1090 to 1100 cm ⁇ 1 indicating the cyclic siloxane bond by FT-IR reflection method (C1) and 1030 indicating the chain siloxane bond.
• the ratio [C1 / (C1 + C2)] of absorbance (C2) at ⁇ 1040 cm ⁇ 1 is preferably 1.0 to 2.0.
• the polyether polyurethane resin (E) of the present invention preferably has an aromatic ring and / or an alicyclic structure having 4 to 6 carbon atoms in the molecule, and the polyether polyurethane resin (E) has an amino acid in the molecule. It is preferable that the ratio of the quaternary ammonium salt to the total amount of the amino group is 0.7 to 1.0 in terms of molar ratio. Moreover, it is preferable that the said polyether polyurethane resin (E) has a structural unit (D) represented by following General formula [2] in a molecule
• R9 is a monovalent organic residue selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group and an aralkyl group, and R10 and R11 are independently of each other an alkoxyl group, an acyloxy group, a hydroxyl group and a halogen atom.
• m represents an integer of 1 to 5.
• the film-forming component (c) of the present invention further contains a cationic phenol resin (F) having a bisphenol A skeleton, and the solid content mass ratio between the polyether polyurethane resin (E) and the cationic phenol resin (F). [(F) / (E)] is preferably 0.010 to 0.030.
• the inhibitor component (d) is (6) Phosphate compound (J) It is preferable to further contain (6) Phosphate compound (J) and (7) Vanadium (IV) compound (K) It is more preferable to further contain both, (8) Mass ratio of metal component (M) of Si (Si) derived from organosilicon compound (C) and fluorometal complex compound (H) having at least one selected from titanium and zirconium [(M) / (Si)] is 0.08 to 0.20, (9) The solid content mass ratio [(J) / (C)] of the organosilicon compound (C) and the phosphoric acid compound (J) is 0.02 to 0.11; (10) The solid content mass ratio [(K) / (C)] of the organosilicon compound (C) and the vanadium (IV) compound (K) is preferably 0.02 to 0.06.
• the metal component (M) of the fluorometal complex compound (H) of the present invention contains both titanium (M T ) and zirconium (M Z ), and each metal component ratio [(M T ) / (M Z ]] Is preferably 0.50 to 0.80, and the inhibitor component (d) preferably further contains at least one metal component selected from Mg, Co and W.
• the aqueous metal surface treatment agent further contains a polyethylene wax (L), and the solid content mass ratio [(L) / (C)] of the organosilicon compound (C) and the polyethylene wax (L) is 0.05 to It is preferably 0.30.
• the surface-treated galvanized steel sheet is coated with the aqueous metal surface treatment agent on the surface of the galvanized steel sheet, and dried at an ultimate temperature of 50 ° C. to 250 ° C., and the coating weight after drying is 0.2 to It is preferably 5.0 g / m 2 .
• the surface-treated zinc-based plated steel sheet of the present invention has corrosion resistance, alkali resistance, solvent resistance and other detergent resistance, sweat resistance, film adhesion, paint adhesion and printing adhesion, moisture discoloration resistance, In addition to excellent water resistance such as condensation resistance, it is extremely excellent in workability and slidability.
• the aqueous metal surface treatment agent for the chromium-free surface-treated zinc-based plated steel sheet according to the present invention contains two components, ie, an organosilicon compound (C) and a polyether polyurethane resin (E) as the film-forming component (c).
• the organosilicon compound (C) includes a silane coupling agent (A) containing one amino group in the molecule and a silane coupling agent (B) containing one glycidyl group in the molecule.
• [(A) / (B)] is blended at a ratio of 0.50 to 0.75.
• the solid content mass ratio [(A) / (B)] is a ratio of 0.50 to 0.75, It is preferably 0.50 to 0.65, and most preferably 0.55 to 0.65.
• the solid content mass ratio [(A) / (B)] is less than 0.50, the hydrophobicity and the self-crosslinking property of the organosilicon compound (C) are increased, so that the stability of the treating agent is remarkably lowered, which is not preferable. .
• the solid content mass ratio [(A) / (B)] exceeds 0.75, the hydrophilicity and cationicity of the organosilicon compound (C) become too high, and the water resistance and sweat resistance of the resulting film are increased. Is not preferable because of drastically lowering.
• the organosilicon compound (C) needs to have a cyclic siloxane bond in the skeleton. If the skeleton does not have a cyclic structure containing Si, the barrier property and adhesion of the film-forming component (c) are lowered, and all the performances such as corrosion resistance, detergent resistance, and film adhesion are lowered.
• the silane coupling agent (A) containing one amino group in the molecule is not particularly limited, but 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane.
• Examples of the silane coupling agent (B) containing one glycidyl group in the molecule include 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane. can do.
• the number of functional groups (a) in the organosilicon compound (C) needs to be 2 or more.
• the number of functional groups (a) is one, the adhesion to the surface of the zinc-based plated steel sheet, the self-crosslinking property of the organosilicon compound (C), and the binding property to the polyether polyurethane resin (E) described later And the film is not sufficiently formed, so that all the effects of the present invention cannot be obtained.
• the number of carbon atoms of the alkyl group and alkoxy group in the definition of R1, R2, and R3 of the functional group (a) is not particularly limited, but is preferably 1 to 6, more preferably 1 to 4, and 1 or 2 is most preferred.
• the abundance ratio of the functional group (b) in the organosilicon compound (C) may be one or more in one molecule, and the average molecular weight must be 1000 to 10,000, and 1300 to 6000. It is preferable that Although molecular weight here is not specifically limited, either direct measurement by TOF-MS method or conversion measurement by chromatography method may be used, and molecular weight standard substance using GFC (gel filtration chromatography). It is preferable to use ethylene glycol. When the average molecular weight determined by the same method is less than 1000, the water solubility of the organosilicon compound is increased, so that the water resistance of the formed film is significantly reduced. On the other hand, when the average molecular weight exceeds 10,000, it is difficult to stably dissolve or disperse the organosilicon compound (C) in water.
• the organosilicon compound (C) needs to have a cyclic siloxane structure, and the abundance ratio of the organic silicon compound (C) is an absorbance (C1) of 1090 to 1100 cm ⁇ 1 indicating a cyclic siloxane bond by the FT-IR reflection method and a chain siloxane bond.
• the ratio [C1 / C2] of the absorbance (C2) of 1030 to 1040 cm ⁇ 1 shown is most preferably 1.0 to 2.0.
• the ratio [C1 / C1] is 1.0 to 2.0, both the barrier property due to the cyclic structure and the flexibility due to the chain structure can be provided in a well-balanced manner, corrosion resistance, detergent resistance, and film adhesion. All the performances are improved.
• a tougher and denser film is formed by the entanglement between the resin molecule and the cyclic siloxane bond.
• the manufacturing method of the organosilicon compound (C) of the present invention is not particularly limited, but the silane coupling agent (A) and the silane coupling agent (B) are added to water adjusted to pH 4.
• the method of adding sequentially and stirring for predetermined time is mentioned.
• the organosilicon compound is prepared by cooling the water in advance, continuing to cool for a predetermined time, and producing in a certain temperature range.
• the abundance ratio of the cyclic siloxane bond and the chain siloxane bond in (C) can be controlled.
• the polyether polyurethane resin (E) which is an essential component of the present invention needs to be a polyether type.
• Polyester polyurethane resin is not preferable because it is hydrolyzed by acid or alkali, and polycarbonate polyurethane is not preferable because it is easy to form a hard and brittle film and is inferior in adhesion during processing and corrosion resistance of processed parts.
• the polyether polyurethane resin (E) preferably has an aromatic ring and / or an alicyclic structure having 4 to 6 carbon atoms in the molecule. By having an aromatic ring or an alicyclic structure, entanglement with the cyclic structure of the organosilicon compound (C) described above occurs, so that the barrier property of the film is improved.
• the polyether polyurethane resin (E) preferably contains an amino group in the molecule, and the ratio of the quaternary ammonium salt to the total amount of the amino group is preferably 0.7 to 1.0 in terms of molar ratio. When the ratio of the quaternary ammonium salt to the total amount of the amino groups is within this range, both the dispersion stability of the polyether polyurethane resin (E) and the water resistance after film formation can be satisfied.
• the polyether polyurethane resin (E) preferably has a structural unit (D) represented by the following general formula [2] in the molecule.
• a structural unit (D) represented by the following general formula [2] in the molecule.
• R9, R10, and R11 in the structural unit (D) are not particularly limited, but R9 is a monovalent organic residue selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an aralkyl group.
• R10 and R11 are each independently a functional group selected from the group consisting of an alkoxyl group, an acyloxy group, a hydroxyl group and a halogen atom, R9 is most preferably an alkyl group, and R10 and R11 are hydroxyl groups. Most preferably it is. Further, the number of ethylene chains m in the structural unit (D) is not particularly limited, but is preferably 1 to 5, and most preferably 2 or 3.
• the polyether polyurethane resin (E) of the present invention is a polyurethane resin that is a polycondensation product of a polyether polyol and an aliphatic, alicyclic or aromatic polyisocyanate, although not particularly limited, It is a polyurethane obtained by using a polyol having a (substituted) amino group as a part of the polyol to be used.
• polyether polyols ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, (aliphatic diol) as initiators Obtained by addition polymerization of one or more compounds such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrohydrofuran, and cyclohexylene using saccharose, methylene glycol, glycerin, etc.
• Polyisocyanates include tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, dicyclohexyl Tan diisocyanate, cyclohexylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, and the like.
• the organosilicon compound (C) and the polyether polyurethane resin (E) in the film-forming component (c) of the present invention the organosilicon compound (C) and the polyether polyurethane resin (E).
• the solid content mass ratio of [(E) / (C)] must be 0.33 to 0.90, more preferably 0.33 to 0.80, and 0.35 to 0.70. Most preferably it is. If the solid content mass ratio [(E) / (C)] is less than 0.33, it is not preferable because the barrier property of the film-forming component (c) is lowered. Conversely, if it exceeds 0.90, organosilicon Adhesiveness with the material resulting from the compound (C) is remarkably lowered, and various performances are lowered, which is not preferable.
• the film-forming component (c) of the present invention further contains a cationic phenol resin (F) having a bisphenol A skeleton in order to improve corrosion resistance and solvent resistance.
• a cationic phenol resin (F) having a bisphenol A skeleton in order to improve corrosion resistance and solvent resistance.
• the solid content mass ratio of the polyether polyurethane resin (E) and the cationic phenol resin (F) [(F ) / (E)] must be 0.010 to 0.030, more preferably 0.010 to 0.025, and most preferably 0.010 to 0.022.
• the mass ratio [(F) / (E)] is less than 0.010, the addition effect of the cationic phenol resin (F) is not exhibited, and the corrosion resistance and solvent resistance are lowered. If it exceeds 030, the film is colored slightly yellow with the cationic phenol resin, and it is not preferable because significant yellowing occurs in a high-humidity environment or an ultraviolet exposure environment.
• the aqueous metal surface treatment agent for the chromium-free surface-treated zinc-based plated steel sheet according to the present invention contains, as an essential component, a fluoro metal complex compound (H) having at least one selected from titanium and zirconium as an inhibitor component (d). There is a need.
• the fluorometal complex compound (H) having at least one selected from titanium and zirconium is not particularly limited, but includes titanium hydrofluoric acid, zircon hydrofluoric acid, ammonium salts thereof, and alkali metal salts. It can be illustrated.
• the compounding ratio of the organosilicon compound (C) and the fluorometal complex compound (H) having at least one selected from titanium and zirconium in the inhibitor component (d) of the present invention it is derived from the organosilicon compound (C).
• the mass ratio [(Si) / (M)] of the metal component (M) of the fluorometal complex compound (H) having at least one selected from Si (Si) and titanium and zirconium is 0.08 to 0.20. Is preferable, 0.12 to 0.20 is more preferable, and 0.14 to 0.18 is most preferable.
• the mass ratio [(Si) / (M)] of the metal component (M) is less than 0.08, the amount of oxide film formed from the metal component during film formation is reduced, and the corrosion resistance is improved. Since it becomes low, it is not preferable, and when it exceeds 0.20, the material surface coverage of the oxide film formed from the metal component increases, and the reaction point with the material of the organosilicon compound (C) decreases, The adhesion imparting effect by the organosilicon compound (C) is reduced, and the overall effect of the present invention is lowered, which is not preferable.
• the metal component (M) of the said fluoro metal complex compound (H) contains both titanium (M T ) and zirconium (M Z ) in order to achieve both corrosion resistance and alkali resistance.
• Each metal component mass ratio [(M T ) / (M Z )] is preferably 0.50 to 0.80, more preferably 0.60 to 0.80, and 0.60 to 0. Most preferred is .70. If the metal component mass ratio [(M T ) / (M Z )] is less than 0.50, the titanium oxide film decreases, and the abundance ratio of the relatively hard zirconium oxide increases.
• the inhibitor component (d) of the present invention preferably further contains a phosphoric acid compound (J) in order to improve corrosion resistance.
• a phosphoric acid compound (J) Phosphoric acid, the ammonium salt of phosphoric acid, the alkali metal salt of phosphoric acid, the alkaline-earth metal salt of phosphoric acid, etc. are mentioned. These are mainly effective in imparting corrosion resistance, and the elution property of phosphoric acid can be controlled and the corrosion resistance retention time can be extended depending on the type of salt of the phosphoric acid compound (J).
• phosphoric acid or magnesium diphosphate is preferable because a larger effect of improving corrosion resistance is obtained, and it is more preferable to use phosphoric acid and magnesium magnesium phosphate in combination.
• the solid content mass ratio of the organosilicon compound (C) and the phosphate compound (J) [(J ) / (C)] is preferably 0.020 to 0.110, more preferably 0.030 to 0.110, and most preferably 0.040 to 0.100. If the solid content mass ratio [(J) / (C)] is less than 0.020, the effects of addition of the phosphoric acid compound (J), such as alkali resistance and corrosion resistance, are not preferable. Exceeding 110 is not preferable because the stability of the metal surface treatment agent is lowered.
• Vanadium (IV) compound as a (K) is not particularly limited, vanadium pentoxide [V 2 O 5], metavanadate [HVO 3], ammonium metavanadate [NH 4 VO 3] sodium metavanadate [NaVO 3 ], vanadium (V) of a compound such as vanadium oxytrichloride [VOCl 3 ], etc.
• vanadium (IV) reduced to vanadium (IV) using a reducing agent such as alcohols and organic acids, vanadium dioxide [VO 2 ], vanadium oxy Vanadium (IV) -containing compounds such as acetylacetonate [VO (C 5 H 7 O 2 ) 2 ], vanadium oxysulfate [VOSO 4 ], vanadium acetylacetonate [V (C 5 H 7 O 2 ) 3 ] trioxide Compounds of vanadium [V 2 O 3 ], vanadium trichloride [VCl 3 ], etc. Examples thereof include those obtained by oxidizing nadium (III) to vanadium (IV) with an arbitrary oxidizing agent.
• the solid content mass ratio of the organosilicon compound (C) and the vanadium compound (K) [(K) / (C)] is preferably 0.020 to 0.060, more preferably 0.025 to 0.060, and most preferably 0.030 to 0.055.
• the solid content mass ratio [(K) / (C)] is less than 0.020, an inhibitor effect due to the vanadium (IV) compound (K) cannot be obtained, and when it exceeds 0.060.
• a complex compound of a vanadium (IV) compound and an organic substance contained in the film is not preferable because the film is likely to be colored yellow at high humidity.
• the aqueous metal surface treatment agent of the present invention preferably further contains polyethylene wax (L) in order to improve workability and slidability.
• the mass ratio [(L) / (C)] of the organosilicon compound (C) and the solid content of the polyethylene wax (L) is 0.05 to 0.30. It is necessary to be 0.07 to 0.30, and most preferably 0.10 to 0.25. If the mass ratio [(L) / (C)] is less than 0.05, it is not preferable because sufficient lubricity is not expressed, and if it exceeds 0.30, the continuity of the film is inhibited by the polyethylene wax, It is not preferable because the film is easily broken and the corrosion resistance is lowered.
• the surface-treated metal material of the present invention is coated with the aqueous metal surface-treating agent, dried at an ultimate temperature of 50 to 250 ° C., and the coating weight after drying is 0.2 to 5.0 g / m 2.
• the drying temperature is preferably 50 ° C. to 250 ° C., more preferably 70 ° C. to 150 ° C., and most preferably 100 ° C. to 140 ° C. at the ultimate temperature.
• An ultimate temperature of less than 50 ° C. is not preferable because the solvent of the aqueous metal surface treatment agent does not volatilize completely.
• the film weight is preferably 0.2 to 5.0 g / m 2 , more preferably 0.5 to 3.0 g / m 2 , and 0.8 to 2.0 g / m 2 . Most preferred. If the coating weight is less than 0.2 g / m 2 , the surface of the metal material cannot be coated and the corrosion resistance is remarkably lowered. On the other hand, if it exceeds 5.0 g / m 2 , the film adhesion deteriorates, which is not preferable.
• the aqueous metal surface treatment agent used in the present invention may use a leveling agent, a water-soluble solvent, a metal stabilizer, an etching inhibitor, etc. for improving the coating property within the range not impairing the effects of the present invention.
• leveling agents include nonionic or cationic surfactants such as polyethylene oxide or polypropylene oxide adducts and acetylene glycol compounds
• 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.
• the metal stabilizer include chelate compounds such as EDTA and DTPA
• the etching inhibitor include amine compounds such as ethylenediamine, triethylenepentamine, guanidine and pyrimidine. In particular, those having two or more amino groups in one molecule are more preferable because they are effective as metal stabilizers.
• the surface-treated zinc-based plated steel sheet of the present invention has corrosion resistance, alkali resistance, solvent resistance and other cleaning resistance, film adhesion, paint adhesion and printing adhesion, moisture discoloration resistance, and condensation resistance. It is excellent in water resistance and excellent in workability and slidability. The reason is presumed as follows, but the present invention is not limited to such presumption.
• the film formed using the aqueous metal surface treatment agent used in the present invention contains an organosilicon compound (C) and a polyether polyurethane resin (E) as film-forming components.
• the corrosion resistance is such that when one part of the organosilicon compound is concentrated by drying or the like, the organosilicon compound reacts with each other to form a continuous film, and one part of the organosilicon compound hydrolyzes. It is presumed that the generated —OR group exhibits a significant barrier effect by forming a Si—OM bond (M: metal element on the surface of the object to be coated) with the metal surface.
• the organosilicon compound (C) contains a specific structure, that is, a cyclic siloxane bond and a chain siloxane bond in a specific ratio.
• the organosilicon compound (C) forms a dense film that is firmly bonded to the material by its own condensation and reaction with the material. An original siloxane-bonded film is formed, and resistance to intrusion of oxygen, moisture and the like is increased, so that an extremely excellent barrier property is exhibited.
• the cyclic siloxane bond does not have a degree of freedom of deformation for skeleton reasons, and becomes a hard but brittle film.
• a chain siloxane bond does not form a three-dimensional structure like a cyclic siloxane bond, and has a lower barrier property than a cyclic siloxane bond, but has a high degree of freedom in deformation.
• Such siloxane bonds having different properties coexist at a certain ratio, whereby a film having excellent barrier properties and adhesion can be formed.
• a polyether polyurethane resin having a structural unit (D) that is entangled with the polyether urethane resin at the time of film formation and having reactivity with the organosilicon compound the organosilicon compound and the polyether polyurethane resin are bonded to each other. , Exhibit extremely high barrier properties.
• the cationic phenol resin (F) is a compound having a resonance stabilizing structure, and the coating containing the cationic phenol resin (F) reacts with and adheres to the metal surface. Because it is close enough to overlap with the orbit, it has the effect of delocalizing electrons generated by corrosion using ⁇ orbit, which keeps the surface potential uniform and provides excellent corrosion resistance.
• the effect of the inhibitor component (d) is the effect of removing the oxide film by etching the surface of the material, the precipitation and film formation due to the pH increase accompanying the etching, the formation of a hardly soluble salt with the metal ions derived from the eluted material, Examples include relaxation of pH increase due to corrosion, and uniform surface potential.
• the fluoro metal complex compound having at least one selected from titanium and zirconium has an effect of removing the oxide film by etching the material surface, and at the same time, as the pH increases, the fluorine dissociates and becomes an oxide or hydroxide. It is presumed that corrosion resistance is imparted by precipitation and film formation.
• the vanadium compound has an effect of consuming electrons generated by corrosion due to the oxidation-reduction reaction of vanadium and suppressing the progress of corrosion.
• the inhibitor component having such an effect and the adhesion and barrier properties caused by the above-mentioned film-forming component, it is resistant to detergents such as corrosion resistance, alkali resistance and solvent resistance, film adhesion, and paint adhesion. It is presumed that it is possible to form a film having excellent water resistance such as adhesion and print adhesion, moisture discoloration resistance and dew condensation resistance, and extremely excellent workability and slidability.
• Table 1 shows silane coupling agents used in Examples and Comparative Examples
• Table 2 shows urethane resins
• Table 3 shows phosphoric acid compounds
• Table 4 shows vanadium compounds
• Table 5 shows polyethylene waxes
• Formulation Examples Table 6 shows the coating amount and the drying temperature.
• Polyester polyol (synthesis component: condensate of maleic acid and 1,4-butanediol, molecular weight 1500): 150 parts by mass, trimethylolpropane: 6 parts by mass, N-methyl-N, N-diethanolamine: 24 parts by mass, 94 parts by mass of isophorone diisocyanate and 135 parts by mass of methyl ethyl ketone were placed in a reaction vessel and reacted for 1 hour while maintaining at 70 to 75 ° C. to produce a urethane prepolymer. Next, 15 parts by mass of dimethyl sulfuric acid was placed in the reaction vessel and reacted at 50 to 60 ° C.
• Polyester polyol synthetic component: poly (hexamethylene carbonate) diol, molecular weight 1500): 150 parts by mass, trimethylolpropane: 6 parts by mass, N-methyl-N, N-diethanolamine: 24 parts by mass, isophorone diisocyanate: 94 parts by mass Then, 135 parts by mass of methyl ethyl ketone was put into a reaction vessel and reacted for 1 hour while maintaining at 70 to 75 ° C. to produce a urethane prepolymer. Next, 15 parts by mass of dimethyl sulfuric acid was placed in the reaction vessel and reacted at 50 to 60 ° C.
• the FT-IR apparatus was used with an infrared total reflection absorption spectrum apparatus.
• an absorbance (C1) of 1090 to 1100 cm ⁇ 1 indicating a cyclic siloxane bond and 1030 to 1040 cm ⁇ 1 indicating a chain siloxane bond are determined by a baseline method (900 cm ⁇ 1 and 1200 cm ⁇ 1 ).
• the absorbance (C2) of was determined.
• Paint adhesion Melamine alkyd paint is applied by bar coating, baked at 120 ° C for 20 minutes, then cut into 1mm grids, and the adhesion evaluation is based on the remaining number ratio (remaining number / cut number: 100) went.
• Example 4 and Comparative Examples 8 to 9 when the urethane resin (E) does not have an ether structure, it is easy to hydrolyze if it is an ester system, so that it is resistant to degreasing, moisture and condensation. Inferior, the carbonate system is too rigid, so the film adhesion and workability are inferior. From the evaluation results of Examples 13, 16 to 19 and Comparative Examples 10 to 11, when the ratio of the organosilicon compound (C) and the urethane resin (E) is outside the scope of the claims, that is, when the urethane resin is small, the film forming component Since the barrier property of (c) is lowered, the corrosion resistance and the wet resistance are inferior.
• the urethane resin having a suitable structure with respect to the skeleton of the urethane resin is excellent in overall performance, particularly the structural unit (D1). When it contains, the performance is extremely excellent.
• the amount of quaternary ammonium salt in all amino groups is 0 or when there is no amino group, the stability of the treatment agent is inferior, and particularly when there is no amino group, the stability of the treatment agent is low. It can be seen that the overall performance is inferior due to the lack.

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