Classifications

• • 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
  • B32B15/082—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 vinyl resins; comprising acrylic resins
• • 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
  • C09D133/00—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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00

Definitions

• the present invention relates to a surface treatment agent and a metal material.
• a technique of laminating the surface of a metal material in order to protect and design a metal material such as aluminum or an aluminum alloy has been known.
• the laminated film adhered to the surface of the metal material in the laminating process is excellent in processability, corrosion resistance, barrier property of the contents, and the like. Further, unlike paints, it does not generate volatile organic compounds in the manufacturing process, so it is also excellent in terms of the environment, and is widely used as a surface protective material in food cans, condenser cases, battery members and the like.
• Patent Document 1 improves adhesion by having an amide ester moiety formed by the reaction of an oxazoline group and a carboxyl group in the base treatment layer. There was still room for improvement in terms of obtaining favorable adhesion. Further, since the condition is that a resin containing an oxazoline group is used, there is room for improvement in terms of manufacturing cost.
• the present invention has been made in view of the above, and an object of the present invention is to provide a base treatment agent capable of imparting preferable adhesion to a laminated film to a metal material.
• the present invention is a surface treatment agent containing a water-soluble metal compound which is at least one of a water-soluble zirconium compound and a water-soluble titanium compound, and a water-soluble or water-dispersible acrylic resin.
• concentration of the water-soluble metal compound is 500 to 200,000 mass ppm in terms of metal atom
• the water-soluble or water-dispersible acrylic resin has a molecular weight of 15,000 to 500,000 and a solid acid value. Is 150 to 740 mgKOH / g, the solid content hydroxyl value is 24 to 350 mgKOH / g, and the concentration of the water-soluble or water-dispersible acrylic resin is 500 to 200,000 mass ppm in terms of solid content.
• the ratio of the concentration of the water-soluble metal compound in terms of metal element to the concentration of the water-soluble or water-dispersible acrylic resin is 3/97 to 91/9, and the present invention relates to a surface treatment agent used for producing a laminated metal material. ..
• the water-soluble or water-dispersible acrylic resin is a copolymer of the monomer (A), and at least a part of the monomer (A) contains a glycidyl group, an amide group, a silanol group, a phosphoric acid group, and the like.
• the surface treatment agent according to (1) which contains a monomer containing at least one of the imide group and the imide group.
• the present invention relates to a metal material in which at least one surface is treated with the surface treatment agent according to (1) or (2).
• the water-soluble metal compound is 0.8 to 3200 mg / m2 in terms of metal atom, and the water-soluble or water-dispersible acrylic resin is converted into solid content in terms of the mass of the film after drying per one surface.
• the surface treatment agent according to the present embodiment forms a film on the surface of the metal material to improve the adhesion to the laminated film.
• the metal material laminated by the above-mentioned film and the laminated film (hereinafter, may be referred to as “laminated metal material”) is not particularly limited, but is not particularly limited, but is a food can body or lid material, a beverage can body or lid material.
• Heat exchanger exterior material for batteries, battery separator, condenser case, vehicle body, engine parts or chassis parts, aircraft body, main wings, frame, fuel tank, engine turbine, engine fan or parts, railroad vehicle body, Carts or parts, ships, rocket parts, bicycle parts, vending machines, elevator car side plates, speed regulators or hoisting machines, escalator steps or interior panels, machine tools, injection molding machines, industrial robot structural members or Drive components, semiconductor manufacturing equipment, displays, submarines, signals, automatic loom, tunnel excavators, pipelines, road signs, generators, waste incinerators, exhaust gas treatment equipment, motors, transformers, electronic circuits, light bulbs, photoelectron multipliers , Golf clubs, antennas, bolts, nuts, screws and the like.
• the surface treatment agent according to the present embodiment is used for applications that require adhesion between a metal material and a laminated film in a moist heat environment, for example, a soft packaging material for food such as an aluminum pouch, or a surface protective material. Can also be used as.
• the surface treatment agent according to this embodiment contains a water-soluble metal compound and a water-soluble or water-dispersible acrylic resin.
• the water-soluble metal compound is at least one of a water-soluble zirconium compound and a water-soluble titanium compound.
• a film containing at least one of a zirconium compound and a titanium compound is formed on the surface of the metal material.
• the water-soluble zirconium compound is not particularly limited, but is zirconium fluoride hydride (H 2 ZrF 6 ), ammonium hexafluoride zirconium ((NH 4 ) 2 ZrF 6 ), ammonium zirconium carbonate ((NH 4 ) 2 ZrO).
• the water-soluble titanium compound is not particularly limited, and examples thereof include a titanium fluoride ammonium salt, an alkoxytitanium, and a titanium lactate ammonium salt.
• the water-soluble zirconium compound and the water-soluble titanium compound also include an aqueous dispersion of the zirconium compound or the titanium compound.
• Examples of the aqueous dispersion of the zirconium compound or the titanium compound include zirconia (ZrO 2 ) as a zirconium compound and zirconia sol and titania sol having zirconia (TIO 2 ) as a titanium compound as a dispersoid and water as a dispersion medium.
• ZrO 2 zirconia
• Tia sol having zirconia (TIO 2 ) zirconia
• TiO 2 titania sol having zirconia
• water-soluble metal compounds may be used alone or in combination of two or more. That is, as one embodiment of the water-soluble metal compound, a water-soluble zirconium compound and a water-soluble titanium compound can be used in combination.
• the concentration of the water-soluble metal compound in the base treatment agent is 500 to 200,000 mass ppm in terms of metal atoms. If the concentration is less than 500 ppm, the adhesion and corrosion resistance of the laminated metal material are lowered. If the concentration exceeds 200,000 ppm, the adhesion is lowered and the cost of the surface treatment agent is increased. From the above viewpoint, the concentration of the water-soluble metal compound is preferably 500 to 60,000 mass ppm in terms of metal atoms.
• the water-soluble or water-dispersible acrylic resin is a copolymer of the monomer (A), and the monomer (A) is a polymerizable monomer such as a radically polymerizable monomer.
• the water-soluble or water-dispersible acrylic resin can be obtained by a known method using a polymerization reaction using the monomer (A) as a raw material component.
• the radically polymerizable monomer is not particularly limited, and for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.
• Hydroxyl group-containing radically polymerizable monomers such as allyl alcohol, methacrylic alcohol, adduct of 2-hydroxyethyl (meth) acrylate and ⁇ -caprolactone, methyl (meth) acrylate, ethyl (meth) acrylate, methoxypolyethylene methacrylate, acrylic acid, (Meta) acrylic acid such as methacrylic acid, crotonic acid, isocrotonic acid, acrylic acid dimer, ⁇ -caprolactone adduct of acrylic acid and its derivatives, unsaturated dibasic acid such as maleic acid, fumaric acid, itaconic acid and the like. Examples thereof include radically polymerizable monomers having a carboxyl group such as the half ester, half amide, and half thioester.
• examples of the monomer (A) that can be used to obtain a water-soluble or water-dispersible acrylic resin include n-butyl (meth) acrylate, isobutyl acrylate, t-butyl acrylate, and 2-ethylhexyl (meth).
• the monomer (A) used for obtaining the water-soluble or water-dispersible acrylic resin includes a glycidyl group and an amide group (specific examples of the amide group are -CONR- (R is a hydrogen atom or 1 or more carbon atoms 4). These are the following alkyl groups, and the alkyl group may be a linear group or a branched chain)), and at least one of a silanol group, a phosphoric acid group, and an imide group. It is preferable that the monomer containing the above is contained as a modifier. This makes it possible to improve the adhesion between the film formed by the surface treatment agent and the metal material.
• the monomer (A) containing the glycidyl group, the amide group, the silanol group, the phosphoric acid group, and the imide group may be used in combination of a plurality of types.
• Examples of the monomer that can be used as the modifier include glycidyl (meth) acrylate, glycidyl group-containing monomer such as (meth) allyl glycidyl ether, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl.
• Amide group-containing monomers such as (meth) acrylamide, N, N-dibutyl (meth) acrylamide, N, N-dioctyl (meth) acrylamide, N-monobutyl (meth) acrylamide, N-monooctyl (meth) acrylamide, acid phospho Phosphoric acid group-containing monomers such as oxyethyl methacrylate and acid phosphooxypolyoxyethylene glycol monomethacrylate, vinylmethoxysilane, vinyltrimethoxysilane, vinylethoxysilane, vinyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-methacry
• a silanol group-containing monomer such as loxypropyltriethoxysilane, an imide group-containing monomer such as amideimide, a hydroxyl group-containing monomer and the like can be used.
• the above monomer (A) is used by mixing two or more kinds.
• the polymerization initiator is not particularly limited, but is, for example, 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis.
• 2,2'-azobis. 2,2-Imidazoline-2-yl) propane hydrochloride, ammonium peroxodisulfate, sodium peroxodisulfate, potassium peroxodisulfate and the like can be mentioned.
• the polymerization method for obtaining the acrylic resin is not particularly limited, and can be synthesized by a known method such as a solution radical polymerization method, an emulsion polymerization method, or a suspension polymerization method.
• the acrylic resin is obtained by stirring a mixed solution of a known radical polymerization initiator and the above-mentioned monomer in a suitable solvent while dropping the mixture at a polymerization temperature of 60 to 160 ° C. for 2 to 10 hours. be able to.
• the molecular weight of the acrylic resin has a number average molecular weight of 15,000 to 500,000.
• the number average molecular weight is less than 15,000, the adhesion of the formed film to the preferable metal material and the laminated film cannot be obtained.
• the number average molecular weight exceeds 500,000, the viscosity of the obtained surface treatment agent increases, and the coating workability and storage stability deteriorate.
• the number average molecular weight of the acrylic resin is preferably 55,000 to 200,000.
• the number average molecular weight of the acrylic resin may be 10,000 to 800,000 depending on the required performance and other conditions.
• the number average molecular weight is determined by the GPC method using polyethylene oxide as a standard.
• the solid content hydroxyl value of the acrylic resin is 24-350 mgKOH / g. If it is less than 24 mgKOH / g, the adhesion and corrosion resistance of the laminated metal material are lowered. If it exceeds 350 mgKOH / g, the storage stability of the obtained acrylic resin is lowered.
• the "solid content hydroxyl value" of the acrylic resin in the present specification and the scope of the patent claim is the free content contained in 1 g of the solid content of the acrylic resin based on the charging ratio of each monomer used for the polymerization of the acrylic resin. It means the theoretical value of the solid content hydroxyl value calculated by calculating the amount of potassium hydroxide (unit: mg) required to neutralize the acrylic required for acetylating the amount of hydroxyl groups. The solid content hydroxyl value of the acrylic resin is adjusted within the above numerical range by adjusting the ratio of each monomer used for polymerization.
• the solid acid value of the acrylic resin is 150 to 740 mgKOH / g. If it is less than 150 mgKOH / g, the water solubility is lowered, the appearance of the film is deteriorated, and the adhesion of the laminated metal material is also lowered. If it exceeds 740 mgKOH / g, the above-mentioned required hydroxyl value cannot be obtained.
• the "solid acid value" of the acrylic resin in the present specification and the scope of the patent claim is the acid contained in 1 g of the solid content of the acrylic resin based on the charging ratio of each monomer used for the polymerization of the acrylic resin. It means the theoretical value of solid acid value calculated by calculation of the amount of potassium hydroxide (unit: mg) required to neutralize the group.
• the solid acid value of the acrylic resin is adjusted within the above numerical range by adjusting the ratio of each monomer used for polymerization.
• the concentration of the acrylic resin in the base treatment agent is 500 to 200,000 mass ppm in terms of solid content. If it is less than 500 mass ppm, the adhesion and corrosion resistance of the laminated metal material are lowered. If it exceeds 200,000 mass ppm, the viscosity of the obtained surface treatment agent increases and handling becomes difficult. In addition, the performance improvement corresponding to the increase in the blending amount cannot be obtained, and the cost increases. From the above viewpoint, the concentration of the acrylic resin in the base treatment agent is preferably 500 to 60,000 mass ppm in terms of solid content.
• the ratio of the mass concentration of the water-soluble metal compound in terms of metal atom to the mass concentration of the acrylic resin in terms of solid content is 3/97 to 91/9 in terms of the water-soluble metal compound concentration / acrylic resin concentration.
• the ratio of the water-soluble metal compound is higher than 91/9 in the above concentration ratio, the adhesion of the film formed by the base treatment agent to the metal material such as the aluminum material and the laminate film is lowered.
• the ratio of the water-soluble metal compound is lower than 3/97 in the concentration ratio, the adhesion to a metal material such as an aluminum material is lowered.
• the base treatment agent according to the present embodiment may contain other resins in addition to the above-mentioned water-soluble metal compound and acrylic resin.
• it may contain a polyester resin, an alkyd resin, an epoxy resin, a urethane resin, or the like. These resins can be used alone or in combination of two or more.
• the acrylic resin is preferably 70 to 100% by mass, more preferably 90 to 100% by mass, based on the total amount of the resin solid content.
• the base treatment agent according to this embodiment does not have to contain a cross-linking agent. Even if the base treatment agent according to the present embodiment does not contain a cross-linking agent, preferable adhesion and corrosion resistance of the laminated metal material can be obtained. However, the base treatment agent according to the present embodiment may contain a cross-linking agent.
• the cross-linking agent is not particularly limited, and examples thereof include water-soluble thermosetting cross-linking agents such as water-soluble melamine resin and water-soluble phenol resin.
• the surface treatment agent according to the present embodiment may contain known additives such as stabilizers, antioxidants, surface conditioners, antifoaming agents, and antibacterial agents, if necessary.
• antioxidant examples include a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like.
• the surface conditioner examples include a nonionic or cationic surfactant, a polyethylene oxide of polyacetylene glycol or an adduct of polypropylene oxide, an acetylene glycol compound and the like.
• defoaming agent examples include mineral oil-based defoaming agents, fatty acid-based defoaming agents, silicone-based defoaming agents, and the like.
• antibacterial agent examples include zincpyrythion, 2- (4-thiazolyl) -benzimidazole, 1,2-benzisothiazolin, 2-n-octyl-4-isothiazolin-3-one, N- (fluorodichloromethylthio) phthalimide, and the like.
• the method for producing the base treatment agent according to the present embodiment is not particularly limited, and the above-mentioned water-soluble metal compound, water-soluble or water-dispersible acrylic resin, and, if necessary, other components are mixed with water as a solvent. It can be produced by a known method such as stirring.
• the base treatment agent according to the present embodiment is prepared as an aqueous solution or an aqueous dispersion of the water-soluble metal compound and the water-soluble or water-dispersible acrylic resin. As a result, it is not necessary to include an organic solvent in the surface treatment agent, which is excellent in terms of environment and workability.
• the base treatment agent according to the present embodiment is used for producing a laminated metal material produced by forming a film on at least one surface of a metal material and adhering the laminated film.
• the method for manufacturing the laminated metal material is not particularly limited. For example, after degreasing a metal material such as a thin plate material, washing with water, pickling, surface adjusting, etc. as necessary, the surface treatment agent according to the present embodiment is applied, and the metal material is heated and dried. Examples thereof include a method of forming a film on the surface and further adhering a laminated film made of a thermoplastic resin or the like.
• Examples of the metal material to be treated of the surface treatment agent according to the present embodiment include aluminum or an aluminum alloy, iron, iron alloy, copper, copper alloy, SUS and the like.
• aluminum or an aluminum alloy is preferably used as the metal material from the viewpoint of processability and adhesion.
• aluminum alloy 3004 material, 3104 material, aluminum alloy 3005 material, etc. for beverage / food can body aluminum alloy 5052 material, aluminum alloy 5182 material, etc. for beverage / food can lid material, aluminum alloy 1050 material, aluminum as dry battery container.
• Alloy 1100 material, 1200 material, 8079 material as an aluminum alloy for a battery packaging material, 8021 material as an electrode material, and the like are preferably used.
• Aluminum alloys include Al—Cu alloys, Al—Mn alloys, Al—Si alloys, Al—Mg alloys, Al—Mg—Si alloys, Al—Zn—Mg alloys, and aluminum die casts (ADC materials). ) May be used.
• the copper alloy for example, oxygen-free copper such as brass and C1020P and commercially available copper foil are used, and as SUS, for example, austenite stainless steel such as SUS304 and SUS301, SUS430 and the like are used. Examples thereof include ferrite-based stainless steels such as SUS410 and martensite-based stainless steels such as SUS410.
• the nickel alloy include Ni-P alloy and the like.
• a plated metal material such as a Ni-plated steel sheet, a Zn-plated steel sheet, or a Zn—Ni-plated steel sheet may be used.
• a plated metal material such as a Ni-plated steel sheet, a Zn-plated steel sheet, or a Zn—Ni-plated steel sheet may be used.
• the above examples include Ni-plated steel sheets, Zn-plated steel sheets, Zn—Ni-plated steel sheets, etc., which use SPCC, SPCD, SPCE, or the like as a base steel sheet.
• the shape of the metal is not particularly limited, and examples thereof include a foil shape and a plate shape.
• only one surface may be surface-treated with the surface-treating agent according to the present embodiment, or both surfaces may be surface-treated with the surface-treating agent. You may.
• both sides may be surface-treated with a single surface treatment agent, or each side may be surface-treated with a surface treatment agent having a different composition.
• the degreasing treatment is not particularly limited, and for example, a known method such as alkaline degreasing cleaning can be used.
• the degreasing treatment is usually performed by a spray method.
• the moisture on the surface of the base material is subjected to a method such as draining with a roll, air blowing, or hot air drying. To remove.
• the film formed on at least one surface of the metal material preferably contains 0.8 to 3200 mg / m 2 of the water-soluble metal compound in terms of metal atom, based on the mass of the film after drying per surface.
• the water-soluble or water-dispersible acrylic resin is contained in an amount of 1.0 to 4000 mg / m 2 in terms of solid content in terms of the mass of the film after drying per surface.
• the film may be formed on any one surface of the metal material, and for example, the film may be formed on both sides of the thin plate material. When the mass of the film after drying per surface of the water-soluble metal compound is less than 0.8 mg / m 2 in terms of metal atoms, sufficient adhesion between the film and the laminated film cannot be obtained.
• the method of applying the surface treatment agent according to the present embodiment is not particularly limited as long as the weight of each component of the formed film is within the above range.
• roll coater paint gravure coater paint, reverse coater paint, slot die coater paint, lip coater paint, knife coater paint, blade coater paint, chamber doctor coater paint, air knife coater paint, curtain coat paint, spin coat paint, brush paint.
• Examples thereof include painting, roller painting, bar coater painting, dip painting, applicator painting, spray painting, sink painting, and combinations thereof.
• the method for heating and drying the surface treatment agent according to the present embodiment is not particularly limited, and examples thereof include oven drying, a method by forced circulation of hot air, a method of drying by an electromagnetic induction heating furnace using an IH heater, and the like. Can be mentioned.
• the conditions for heat drying can be, for example, 40 to 160 ° C. for 2 to 60 seconds.
• the air volume, wind speed, etc. set by the drying method can be set arbitrarily.
• the method of adhering the laminated film to the metal material having a film formed on the surface by the above-mentioned surface treatment agent is not particularly limited, and known methods such as a dry laminating method, a heat laminating method, and an extrusion laminating method can be used. can.
• the laminating film is not particularly limited, and a known laminating film can be used.
• Examples of the laminated film include polypropylene resin, polyethylene terephthalate resin, nylon resin, polyethylene naphthalate resin, polyester resin, polycarbonate resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyvinylidene chloride resin, polyvinyl acetate resin, and polyethylene isophthalate.
• Resin copolymerized polyester resin, polyester resin, polyamide resin, polyimide resin, polyetherimide resin, polyphenylene sulfide resin, fluororesin, silicone resin, nylon resin, phenol resin, (meth) acrylic resin, epoxy resin, polymethoxylylen adiba
• resin obtained by mixing two or more kinds of resins containing these resins and the like.
• the laminated film made of these materials may be uniaxially or biaxially stretched.
• the laminating metal material according to the present embodiment may have a film formed by the surface treatment agent and a layer other than the laminating film.
• it may have an adhesive layer arranged between the film formed by the surface treatment agent and the laminated film.
• the adhesive layer is not particularly limited, and may be formed by a one-component adhesive or a two-component adhesive.
• the resin component of the adhesive that can be used to form the adhesive layer is not particularly limited, and is, for example, a polyolefin resin, a polyester resin, a polyether resin, a polyurethane resin, a polycarbonate resin, an epoxy resin, or a phenol resin.
• Resin polyamide resin, polyvinyl acetate resin, cellulose resin, (meth) acrylic resin, polyimide resin, amino resin, chloroprene rubber, nitrile rubber, styrene-butadiene rubber, silicone resin, ethylene fluorinated propylene
• copolymers One of these resin components may be used alone, or two or more thereof may be used in combination.
• examples of the combination of two or more kinds of resin components include polyurethane resin and modified polyolefin resin, polyamide resin and acid-modified polyolefin resin, polyamide resin and metal modified polyolefin resin, polyamide resin and polyester resin, and the like.
• the method for forming the adhesive layer is not particularly limited, and examples thereof include an extrusion molding method and a dispersion method.
• the base treatment agent according to the present embodiment contains the above-mentioned water-soluble metal compound and acrylic resin in a specific amount, it is excellent in coating workability and stability, and the obtained laminated metal material has sufficient adhesion.
• the surface treatment agent simply containing the acrylic resin and the zirconium compound has corrosion resistance, but the surface treatment agent according to the present embodiment has an advantage that the adhesion to the laminated film is improved and the corrosion resistance is also obtained. Therefore, the surface treatment agent according to the present embodiment is particularly preferably used for producing a laminated metal material that is required to have high adhesion and corrosion resistance after high processing.
• the obtained acrylic resin had a number average molecular weight of 50,000, a solid content acid value of 620 mgKOH / g, and a solid content hydroxyl value of 82 mgKOH / g.
• the unit of the numerical value for which the unit is not described is the mass part.
• Example 1 Ion-exchanged water is charged into a corben equipped with a heating / stirring device, and while stirring at room temperature, the acrylic resin aqueous solution obtained in Synthesis Example 1 is gradually added so as to have a solid content of 7,500 mass ppm, and the mixture is stirred.
• the water-soluble zirconium compound (ammonium carbonate, manufactured by Daiichi Rare Element Chemical Industry Co., Ltd., trade name, zircozol AC-7, containing 13% in Zr atomic equivalent) is 2,500 mass ppm in terms of zirconium metal atom. Gradually added, stirring was continued for 20 minutes to prepare the surface treatment agent of Example 1.
• Examples 2 to 31, Comparative Examples 1 to 9 The surface treatment agents of Examples 2 to 31 and Comparative Examples 1 to 9 were prepared in the same manner as in Example 1 except that the types and concentrations of the acrylic resin and the water-soluble metal compound were shown in Table 2.
• a cross-linking agent a melamine resin (“Simel 370N” manufactured by Nippon Cytec Co., Ltd. (nonvolatile content 80%)) or a phenol resin (“Shonol BRL-204” manufactured by Aica Kogyo Co., Ltd. (nonvolatile content)). Minutes 70%)) were used in the amounts shown in Table 2.
• Example 21 tetraalkylammonium-modified zirconium (manufactured by Matsumoto Fine Chemical Co., Ltd., “Organotics ZC700” (nonvolatile component 20%)) was used as the water-soluble zirconium compound.
• Examples 22 and 23 were zirconium fluoride, respectively. Titanium triethanol aminate was used.
• Example 30 ammonium carbonate zirconium ammonium carbonate (2250 mass ppm in terms of Zr) and titanium triethanol aminate (250 mass ppm in terms of Ti) were used in combination as a water-soluble metal compound.
• Example 31 a polyester resin (“Vironal MD1245” (500 mass ppm) manufactured by Toyo Boseki Co., Ltd.) was used as another resin.
• Aluminum alloy 3004 plate (Al) as a metal material was degreased (treated at 65 ° C for 3 seconds) with a 2% diluted solution of "Surf Cleaner 330" manufactured by Nippon Paint Surf Chemicals Co., Ltd. to obtain the obtained aluminum material.
• the surface treatment agents of the above Examples and Comparative Examples were applied with a bar coater and dried in a hot air oven at a material temperature of 100 ° C. or higher to obtain a metal material having a film formed on the surface by the surface treatment agent. ..
• the film weight (mg / m 2 ) after drying the solid content weight of the acrylic resin and the weight in terms of metal atoms in the water-soluble metal compound are shown in Table 3, respectively.
• the metal material copper (NC-WS manufactured by Furukawa Electric Co., Ltd.) in Example 14, SUS (SUS304) in Example 15, Ni-plated steel sheet using SPCC as a base steel sheet in Example 16, and Example 17 Then, aluminum die casting (ADC-12) was used respectively.
• the base treatment agents according to the above Examples and Comparative Examples were coated, and the laminated metal material was prepared by the following three methods for producing the laminated metal material on the metal material having a film formed on the surface.
• the laminating method 1 a polyester-based two-component adhesive was used as the adhesive, and coating was applied on the film formed on the surface of the metal material so as to be 3 g / m 2 when dried.
• a PP film was pressure-bonded to the coated surface at 100 ° C. and 0.38 MPa, and then stored at 60 ° C. for 6 days to obtain a laminated metal material.
• the laminating method 2 acid-modified polypropylene was used as an adhesive, and a coating was applied on the film formed on the surface of the metal material so as to be 3 g / m 2 when dried, and dried at 200 ° C. for 30 seconds. Next, a PP film was attached to the coated surface and pressure-bonded at 180 ° C. and 0.38 MPa to obtain a laminated metal material. In the laminating method 3, a PET film was pressure-bonded on a film formed on the surface of the metal material at 180 ° C. and 0.38 MPa, and then dried at 240 ° C. for 60 seconds to obtain a laminated metal material.
• Adhesion test after retort treatment A test piece obtained by cutting the crimped metal plate into a size of 150 mm ⁇ 15 mm was placed in an autoclave and heat-treated in pressurized steam at 125 ° C. for 30 minutes (retort treatment). The retort-treated test piece was measured for peel strength (kgf / 15 mm width) when the film surface was peeled off using a "Tencilon tensile tester" (manufactured by LST-200N-S Minerva). The measurement result was evaluated as the adhesion after the retort treatment according to the same evaluation criteria as the initial adhesion, and the evaluation of 4 or more was passed. The results are shown in Table 4.

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