Substrate treatment agent and metal material

Abstract

The present invention provides a base treatment agent that can impart preferred adhesion, acid resistance, and alkali resistance to a laminated film to a metal material. The concentration of a water-soluble metal compound in the base treatment agent is 500 to 200,000 mass ppm in terms of metal atom conversion, the number average molecular weight of a water-soluble or water-dispersible acrylic resin is 70,000 to 500,000, the solid content acid value is 150 to 740 mgKOH / g, the solid content hydroxyl value is 40 to 350 mgKOH / g, the glass transition temperature of the water-soluble or water-dispersible acrylic resin is in the range of 63 to 100°C, the concentration of the water-soluble or water-dispersible acrylic resin is 500 to 200,000 mass ppm in terms of solid content conversion, and the ratio of the metal atom conversion concentration of the water-soluble metal compound to the concentration of the water-soluble or water-dispersible acrylic resin is 3 / 97 to 91 / 9. The base treatment agent is used for the manufacture of laminated metal materials.

Description

Technical Field

[0001] The invention relates to a substrate treating agent and a metal material. Background Art

[0002] In the past, it is known that there is a technology for laminating the surface of metal materials in order to protect metal materials such as aluminum and aluminum alloys and implement design. The laminated film bonded to the surface of the metal material in the lamination process has excellent processability, corrosion resistance, and barrier properties of the contents. In addition, unlike coatings, no volatile organic compounds are generated during the manufacturing process, so it is also excellent in terms of the environment and is widely used as a surface protection material for food cans, capacitor housings, battery components, etc.

[0003] When applying lamination processing, it is important to improve the adhesion of laminated film and metal material from the viewpoint of aesthetics and maintaining corrosion resistance. Therefore, it is known to use oxazoline-containing resin and acrylic resin as the base treatment layer of metal material to improve the adhesion of metal material and laminated film (refer to patent document 1).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2011-187386 Summary of the invention

[0007] Problems to be solved by the invention

[0008] In the technology of patent documentation 1 record, the base treatment layer has the amide ester position formed by oxazoline group and carboxyl reaction, improves adhesion thus, but from the viewpoint of obtaining preferred adhesion, still has room for improvement.In addition, owing to be condition with the resin containing oxazoline group, therefore aspect manufacturing cost, also has room for improvement.

[0009] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a surface treatment agent capable of imparting to a metal material favorable adhesion to a laminate film, acid resistance, alkali resistance, and water resistance of a film.

[0010] Methods for solving problems

[0011] In order to solve the above-mentioned problems, the present invention provides the following aspects.

[0012] [1] A substrate treatment agent for use in the manufacture of a laminated metal material, comprising a water-soluble metal compound and a water-soluble or water-dispersible acrylic resin, wherein the water-soluble metal compound is at least one of a water-soluble zirconium compound and a water-soluble titanium compound; the concentration of the water-soluble metal compound is 500 to 200,000 ppm by mass in terms of metal atom conversion; the water-soluble or water-dispersible acrylic resin has a number average molecular weight of 70,000 to 500,000, a solid content acid value of 150 to 740 mgKOH / g, a solid content hydroxyl value of 40 to 350 mgKOH / g, and a glass transition temperature of 63 to 100°C; the concentration of the water-soluble or water-dispersible acrylic resin is 500 to 200,000 ppm by mass in terms of solid content conversion; and the ratio of the metal atom conversion concentration of the water-soluble metal compound to the concentration of the water-soluble or water-dispersible acrylic resin is 3 / 97 to 91 / 9.

[0013] [2] The surface treatment agent according to [1], wherein the surface treatment agent is applied to an aluminum substrate and dried to form a film having a weight of 50 to 100 mg / m 2 The surface free energy of the dry film is 52~74mJ / m 2 .

[0014] [3] The substrate treatment agent according to [1] or [2], wherein the water-soluble or water-dispersible acrylic resin is a copolymer of a monomer (A), wherein the monomer (A) comprises one or more monomers having a glycidyl group, an amide group, a silanol group, a phosphoric acid group, a nitrile group or an imide group.

[0015] [4] The substrate treatment agent according to [3], wherein the equivalent ratio (i) / (ii) of the total equivalent weight of one or more functional groups selected from the group consisting of glycidyl group, amide group, silanol group, phosphoric acid group, nitrile group and imide group possessed by the above-mentioned water-soluble or water-dispersible acrylic resin to the equivalent weight of hydroxyl group possessed by the above-mentioned water-soluble or water-dispersible acrylic resin (ii) is in the range of 0.03 to 0.20.

[0016] [5] A metal material, at least one surface of which is treated with the surface treatment agent according to any one of [1] to [4].

[0017] [6] The metal material according to [5], wherein the formed film contains 0.8 to 3200 mg / m 2 in terms of metal atoms in the mass of the film after drying on each of the above-mentioned surfaces. 2 The water-soluble metal compound contains 1.0 to 4000 mg / m 2 The above-mentioned water-soluble or water-dispersible acrylic resin.

[0018] Effects of the Invention

[0019] According to the present invention, it is possible to provide a surface treatment agent capable of imparting to a metal material favorable adhesion to a laminate film, acid resistance, alkali resistance, and water resistance of a film. DETAILED DESCRIPTION

[0020] Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the description of the following embodiments.

[0021] <Substrate treatment agent>

[0022] The surface treatment agent of the present embodiment forms a film on the surface of the metal material that improves adhesion with the laminate film. The metal material laminated with the above-mentioned film and laminated film (hereinafter sometimes described as "laminated metal material") is not particularly limited, and can be used for the main body or cover material of food cans, the main body or cover material of beverage cans, heat exchangers, battery outer packaging materials, battery separators, capacitor cases, vehicle bodies, engine parts or chassis parts, aircraft bodies, main wings, frames, fuel tanks, engine turbines, engine fans or parts, railway vehicle bodies, trolleys or parts, ships, rocket parts, bicycle parts, vending machines, elevator car side panels, speed governors or traction machines, escalator pedals or interior panels, machine tools, injection molding machines, structural parts or drive parts of industrial robots, semiconductor manufacturing equipment, displays, submarines, signals, automatic looms, tunnel boring machines, pipelines, road signs, generators, garbage incinerators, exhaust gas treatment equipment, motors, transformers, electronic circuits, light bulbs, photomultiplier tubes, golf clubs, antennas, bolts, nuts, screws and other various uses. The surface treatment agent of the present embodiment can be used for purposes other than the above-mentioned purposes, and also for purposes requiring close adhesion between a metal material and a laminate film under a hot and humid environment, for example, for flexible packaging materials for food such as aluminum bags or surface protection materials.

[0023] The surface treatment agent of the present embodiment contains a water-soluble metal compound and a water-soluble or water-dispersible acrylic resin.

[0024] (Water-soluble metal compounds)

[0025] The water-soluble metal compound is at least one of a water-soluble zirconium compound and a water-soluble titanium compound. By including a water-soluble metal compound in the substrate treatment agent, a film containing at least one of a zirconium compound and a titanium compound is formed on the surface of the metal material. As a water-soluble zirconium compound, there is no particular limitation, and examples include fluorinated zirconic acid (H2ZrF6), ammonium hexafluorozirconate ((NH4)2ZrF6), ammonium zirconium carbonate ((NH4)2ZrO(CO3)2), tetraalkylammonium modified zirconium, monoacetoacetic zirconium, tetraacetoacetic zirconium, etc. In addition, as a water-soluble titanium compound, there is no particular limitation, and examples include ammonium fluoride titanium salt or alkoxy titanium, ammonium lactate titanium salt, etc. In addition to the above, in this specification, water-soluble zirconium compounds and water-soluble titanium compounds also include aqueous dispersions of zirconium compounds or titanium compounds. As an aqueous dispersion of a zirconium compound or a titanium compound, for example, zirconium oxide (ZrO2) as a zirconium compound, titanium dioxide (TiO2) as a titanium compound, zirconium oxide sol, titanium dioxide sol, etc., which use water as a dispersion medium, can be cited. The above-mentioned water-soluble metal compound can be used alone or in combination of two or more. That is, as an embodiment of the water-soluble metal compound, a water-soluble zirconium compound and a water-soluble titanium compound can be used in combination. The above-mentioned water-soluble metal compound is more preferably a water-soluble zirconium compound.

[0026] 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 above concentration is less than 500 ppm, the adhesion and corrosion resistance of the laminated metal material are reduced. If the above concentration exceeds 200,000 ppm, the adhesion is reduced and the cost of the base treatment agent increases. From the above viewpoints, the concentration of the water-soluble metal compound is preferably 500 to 60,000 mass ppm in terms of metal atoms, and more preferably 1,000 to 60,000 mass ppm.

[0027] (Water-soluble or water-dispersible acrylic resin)

[0028] The water-soluble or water-dispersible acrylic resin is a copolymer of a monomer (A), wherein the monomer (A) is a polymerizable monomer such as a radical polymerizable monomer. The water-soluble or water-dispersible acrylic resin can be obtained by a known method utilizing a polymerization reaction using the monomer (A) as a raw material component. The radical polymerizable monomer is not particularly limited, and examples thereof include hydroxyl-containing radical polymerizable monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, allyl alcohol, methallyl alcohol, and adducts of 2-hydroxyethyl (meth)acrylate and ε-caprolactone, and (meth)acrylic acid and its derivatives such as methyl (meth)acrylate, ethyl (meth)acrylate, methoxypolyethylene methacrylate, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, acrylic acid dimer, and ε-caprolactone adducts of acrylic acid, and unsaturated dibasic acids such as maleic acid, fumaric acid, and itaconic acid, and free radical polymerizable monomers having carboxyl groups such as half esters, half amides, and half thioesters thereof. In this specification, the description of "(meth)acrylic acid" refers to acrylic acid and / or methacrylic acid.

[0029] In addition to the above, examples of the monomer (A) that can be used when obtaining a water-soluble or water-dispersible acrylic resin include propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, dihydrodicyclopentadienyl (meth)acrylate and the like (meth)acrylates, styrene, α-methylstyrene, vinyl ketone, tert-butylstyrene, p-chlorostyrene, and polymerizable aromatic compounds such as vinylnaphthalene, α-olefins such as ethylene and propylene, vinyl esters such as vinyl acetate and vinyl propionate, and dienes such as butadiene and isoprene.

[0030] The monomer (A) used when obtaining a water-soluble or water-dispersible acrylic resin may contain a monomer having a glycidyl group, an amide group (as a specific example of an amide group, -CONR- (R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be a straight chain or a branched chain)), a silanol group, a phosphoric acid group, a nitrile group or an imide group as required. The monomer having the above functional groups can be used as a modifier for acrylic resin, for example, thereby having the advantage of being able to improve the adhesion between the film formed by the base treatment agent and the metal material. The monomer having a glycidyl group, an amide group, a silanol group, a phosphoric acid group, a nitrile group or an imide group that may be contained in the above monomer (A) may be one type or a combination of two or more types. The above monomer (A) included as required preferably contains a monomer containing at least any one of a glycidyl group, an amide group and a nitrile group.

[0031] In the preparation of the acrylic resin, when a monomer having a functional group selected from the group consisting of a glycidyl group, an amide group, a silanol group, a phosphoric acid group, a nitrile group or an imide group is included, the equivalent ratio (i) / (ii) of the total equivalent weight (i) of one or more functional groups selected from the group consisting of a glycidyl group, an amide group, a silanol group, a phosphoric acid group, a nitrile group and an imide group possessed by the acrylic resin obtained in the preparation and the equivalent weight (ii) of the hydroxyl group possessed by the water-soluble or water-dispersible acrylic resin is preferably in the range of 0.03 to 0.20, and more preferably in the range of 0.04 to 0.15. By making the equivalent ratio (i) / (ii) in the above range, there is an advantage that a good balance between the adhesion and the properties of the substrate treatment agent can be maintained.

[0032] Specific examples of monomers that can be used as the above-mentioned modifier include: glycidyl (meth)acrylate, (meth)allyl glycidyl ether and other glycidyl group-containing monomers; (meth)acrylamide, N-methylol (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-dibutyl (meth)acrylamide, N,N-dioctyl (meth)acrylamide, N-monobutyl (meth)acrylamide, N-monooctyl (meth)acrylamide, hydroxyethyl acrylamide and other amide group-containing monomers; acid phosphoxy (hoshooxy) (ii) phosphoric acid group-containing monomers such as ethyl methacrylate and acidic phosphoxy polyethylene glycol monomethacrylate, silanol group-containing monomers such as vinyl methoxysilane, vinyl trimethoxysilane, vinyl ethoxysilane, vinyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-methacryloxypropyl trimethoxysilane, nitrile group-containing monomers such as acrylonitrile, methacrylonitrile, and a monomer in which the methyl group of methacrylonitrile is substituted with an alkyl group having 2 to 16 carbon atoms, and imide group-containing monomers such as amide imide.

[0033] The monomer (A) used for preparing the acrylic resin contains at least two or more of the above-mentioned monomers.

[0034] The polymerization initiator used in the preparation of the acrylic resin is not particularly limited, and examples thereof include 4,4′-azobis(4-cyanovaleric acid), 2,2′-azobis(2-methylpropionamidine) dihydrochloride, 2,2′-azobis-2-(2-imidazolin-2-yl)propane hydrochloride, ammonium peroxodisulfate, sodium peroxodisulfate, potassium peroxodisulfate, and the like.

[0035] The polymerization method for obtaining the acrylic resin is not particularly limited, and the acrylic resin can be synthesized by known methods such as solution free radical polymerization, emulsion polymerization, and suspension polymerization. For example, a mixed solution of a known free radical polymerization initiator and the monomers is added dropwise to a suitable solvent while stirring at a polymerization temperature of 60 to 160° C. for 2 to 10 hours to obtain the acrylic resin. In the preparation of the acrylic resin, neutralization can be performed after polymerization as needed.

[0036] The molecular weight of the acrylic resin is a number average molecular weight of 70,000 to 500,000. When the number average molecular weight is less than 70,000, good water resistance of the film may not be obtained. When the number average molecular weight exceeds 500,000, the viscosity of the obtained base treatment agent increases, and the coating workability and storage stability may deteriorate. From the above viewpoints, the number average molecular weight of the acrylic resin is preferably 70,000 to 200,000, and more preferably 80,000 to 200,000. The number average molecular weight is determined by a GPC method using polyethylene oxide as a standard.

[0037] The solid content hydroxyl value of the acrylic resin is 40 to 350 mgKOH / g. If the solid content hydroxyl value is less than 40 mgKOH / g, the adhesion and corrosion resistance of the laminated metal material are reduced. If the solid content hydroxyl value exceeds 350 mgKOH / g, the storage stability of the obtained acrylic resin is reduced. The solid content hydroxyl value is preferably in the range of 50 to 250 mgKOH / g, more preferably in the range of 55 to 210 mgKOH / g, and particularly preferably in the range of 60 to 150 mgKOH / g.

[0038] The "solid content hydroxyl value" of the acrylic resin in the present specification and claims refers to a theoretical value of the solid content hydroxyl value calculated by calculating the amount of free hydroxyl groups contained in 1 g of the solid content of the acrylic resin (unit: mg) required to neutralize the acetic acid required for acetylation based on the charging ratio of each monomer used in the polymerization of the acrylic resin. The solid content hydroxyl value of the acrylic resin is adjusted to the above numerical range by adjusting the ratio of each monomer used for polymerization.

[0039] The solid acid value of the acrylic resin is 150 to 740 mgKOH / g. If the solid acid value is less than 150 mgKOH / g, the water solubility is reduced, resulting in a reduction in the appearance of the film, and the adhesion of the laminated metal material is also reduced. If the solid acid value exceeds 740 mgKOH / g, the required hydroxyl value cannot be obtained. The solid acid value is preferably in the range of 200 to 700 mgKOH / g, and more preferably in the range of 400 to 680 mgKOH / g.

[0040] The "solid content acid value" of the acrylic resin in this specification and claims refers to a theoretical value of the solid content acid value calculated by calculating the amount of potassium hydroxide (unit: mg) required to neutralize the acid groups contained in 1 g of the solid content of the acrylic resin based on the charging ratio of each monomer used in the polymerization of the acrylic resin. The solid content acid value of the acrylic resin is adjusted to the above numerical range by adjusting the ratio of each monomer used for polymerization.

[0041] The glass transition temperature of the acrylic resin is in the range of 63 to 100°C. If the glass transition temperature is lower than 63°C, the adhesion to the laminated metal material after heat treatment may be deteriorated. On the other hand, when the glass transition temperature exceeds 100°C, the manufacturing stability of the acrylic resin may be deteriorated, and the processing stability of the film formed by the base treatment agent may be deteriorated. The glass transition temperature is preferably in the range of 65 to 95°C, and more preferably in the range of 70 to 90°C.

[0042] The glass transition temperature (Tg) of the acrylic resin in the present specification and claims can be calculated as the reciprocal of the sum of quotients obtained by dividing the mass fraction of each monomer constituting the acrylic resin by the Tg (K: Kelvin) value of a homopolymer derived from each monomer.

[0043] More specifically, in the present disclosure, the glass transition temperature (Tg) can be calculated by the Fox equation (TGFox, Bull. Am. Phys. Soc. (Journal of the American Physical Society), 1 (3), 123 (1956)).

[0044] For example, when the resin is a polymer of a plurality of monomers, the Tg represented by the following general formula is taken as the Tg of the resin:

[0045] 1 / Tg=wa / Tga+wb / Tgb+...+wn / Tgn

[0046] in,

[0047] Tga: glass transition temperature of the homopolymer of monomer A (K), wa: mass fraction of monomer A,

[0048] Tgb: glass transition temperature of the homopolymer of monomer B (K), wb: mass fraction of monomer B,

[0049] Tgn: glass transition temperature of the homopolymer of monomer N (K), wn: mass fraction of monomer N,

[0050] wa+wb+…+wn=1.

[0051] The glass transition temperature of the acrylic resin can be adjusted to fall within the above numerical range by adjusting the types and ratios of the monomers used for polymerization.

[0052] The concentration of the acrylic resin in the base treatment agent is 500 to 200,000 mass ppm in terms of solid content. When it is less than 500 mass ppm, the adhesion and corrosion resistance of the laminated metal material are reduced, and the acid resistance and alkali resistance may deteriorate. When it exceeds 200,000 mass ppm, the viscosity of the obtained base treatment agent increases, and the operation becomes difficult. In addition, the performance improvement corresponding to the increase in the amount of compounding cannot be obtained, and the cost increases. The lower limit of the concentration of the acrylic resin in the base treatment agent can be 1000 mass ppm, 1400 mass ppm or 1500 mass ppm. The upper limit of the above concentration can be 100,000 mass ppm, 80,000 mass ppm or 70,000 mass ppm.

[0053] The ratio of the mass concentration of the water-soluble metal compound converted to metal atoms to the mass concentration of the acrylic resin converted to solid content is 3 / 97 to 91 / 9 in terms of water-soluble metal compound concentration / acrylic resin concentration. If the ratio of the water-soluble metal compound in the above concentration ratio is greater than 91 / 9, the adhesion between the film formed by the base treatment agent and the metal material such as aluminum material and the laminated film is reduced. If the ratio of the water-soluble metal compound in the above concentration ratio is less than 3 / 97, the adhesion with the metal material such as aluminum material is reduced. The above ratio is preferably 10 / 90 to 85 / 15, and more preferably 15 / 85 to 80 / 20.

[0054] (Other ingredients)

[0055] The substrate treatment agent of the present embodiment may contain other resins as required in addition to the above-mentioned water-soluble metal compound and acrylic resin. For example, it may contain polyester resin, alkyd resin, epoxy resin, urethane resin, etc. These resins can be used in one kind or in combination of two or more kinds. In the substrate treatment agent of the present embodiment, the above-mentioned acrylic resin is preferably 70 to 100% by mass, more preferably 90 to 100% by mass, relative to the total amount of the resin solids.

[0056] The substrate treatment agent of the present embodiment may not contain a crosslinking agent. Even if the substrate treatment agent of the present embodiment does not contain a crosslinking agent, excellent laminated metal material adhesion and corrosion resistance can be obtained. The substrate treatment agent of the present embodiment preferably does not substantially contain a resin containing oxazoline groups. Thus, the manufacturing cost of the substrate treatment agent can be reduced. It should be noted that substantially not containing the above-mentioned resin containing oxazoline groups refers to that the ratio of the solid content of the resin containing oxazoline groups relative to the solid content of the above-mentioned acrylic resin in the substrate treatment agent and the total amount of the solid content of the resin containing oxazoline groups is less than 2 mass %. The above-mentioned ratio of the resin containing oxazoline groups can be less than 1 mass %, or less than 0.1 mass %. Alternatively, it can also be that the substrate treatment agent does not contain a resin containing oxazoline groups at all. But the substrate treatment agent of the present embodiment may also contain a crosslinking agent. As a crosslinking agent, there is no particular limitation, and water-dispersible thermosetting crosslinking agents such as water-soluble melamine resins and water-soluble phenolic resins can be cited.

[0057] In addition to the above, the surface treatment agent of the present embodiment may contain additives such as a known stabilizer, an antioxidant, a surface conditioner, a defoaming agent, and an antibacterial agent as needed.

[0058] Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, and sulfur antioxidants.

[0059] Examples of the surface conditioner include nonionic or cationic surfactants, polyethylene oxide or polypropylene oxide adducts of polyacetylene glycol, and acetylene glycol compounds.

[0060] Examples of the defoaming agent include mineral oil-based defoaming agents, fatty acid-based defoaming agents, and silicone-based defoaming agents.

[0061] Examples of the antibacterial agent include zinc pyrithione, 2-(4-thiazolyl)-benzimidazole, 1,2-benzisothiazolin, 2-n-octyl-4-isothiazoline-3-one, N-(fluorodichloromethylthio)phthalimide, N,N-dimethyl-N′-phenyl-N′-(fluorodichloromethylthio)-sulfonamide, methyl 2-benzimidazolecarbamate, bis(dimethylthiocarbamoyl)disulfide, N-(trichloromethylthio)-4-cyclohexane-1,2-dicarboximide, barium metaborate, allyl isothiocyanate, quaternary ammonium salts such as polyoxyalkylene trialkylammonium, organosilicon quaternary ammonium salts, hexamethylenebiguanide hydrochloride, quaternary phosphonium salts such as tri-n-butyltetradecylphosphonium chloride, polyphenol-based antibacterial agents, phenylamide-based antibacterial agents, and biguanide-based antibacterial agents.

[0062] <Method for producing substrate treatment agent>

[0063] The method for producing the surface treatment agent of the present embodiment is not particularly limited, and the surface treatment agent can be produced by a known method such as mixing and stirring the water-soluble metal compound, the water-soluble or water-dispersible acrylic resin, and other components as required with water as a solvent.

[0064] For example, when the water-soluble metal compound is an alkaline metal compound such as ammonium zirconium carbonate, it is more preferable to adjust the pH of the base treatment agent to 7 to 10 in consideration of the stability of the base treatment agent. In the base treatment agent of this embodiment, the use of an alkaline metal compound as the water-soluble metal compound has the advantage of being able to make the bond between the resins stronger through metal cross-linking, and is more preferable.

[0065] The surface treatment agent of this embodiment is prepared as an aqueous solution or aqueous dispersion of the water-soluble metal compound and a water-soluble or water-dispersible acrylic resin. This eliminates the need for the surface treatment agent to contain an organic solvent, and is excellent in terms of environmental protection and workability.

[0066] <Laminated Metal Materials>

[0067] The base treatment agent of the present embodiment is used to manufacture a laminated metal material manufactured by forming a film on at least one surface of a metal material and bonding the laminated film. There is no particular limitation on the method for manufacturing the above-mentioned laminated metal material. For example, the following method can be cited: a metal material such as a thin plate material is subjected to a degreasing treatment, and after washing, pickling, surface adjustment, etc. as needed, the base treatment agent of the present embodiment is applied, and the film is formed on the surface of the metal material by heating and drying, and then a laminated film composed of a thermoplastic resin, etc. is bonded.

[0068] As the metal material of the treated object of the substrate treatment agent of this embodiment, aluminum or aluminum alloy, iron, iron alloy, copper, copper alloy, SUS, etc. can be listed. Among them, from the viewpoint of processability and adhesion, aluminum or aluminum alloy is preferably used as the metal material. For example, when used as a beverage or food can body, aluminum alloy 3004 material, 3104 material, aluminum alloy 3005 material, etc. are preferably used; as a beverage or food can lid material, aluminum alloy 5052 material, aluminum alloy 5182 material, etc. are preferably used; as a dry cell container, aluminum alloy 1050 material, aluminum alloy 1100 material, 1200 material are preferably used; as an aluminum alloy for battery packaging materials, 8079 material is preferably used; as an electrode material, 8021 material, etc. are preferably used. As an aluminum alloy, Al-Cu alloy, Al-Mn alloy, Al-Si alloy, Al-Mg alloy, Al-Mg-Si alloy, Al-Zn-Mg alloy, aluminum die casting (ADC material) can be used. In addition to the above, as a metal material, for example, brass as a copper alloy can be used; as SUS, for example, austenitic stainless steels such as SUS 304 and SUS 301, ferritic stainless steels such as SUS 430, and martensitic stainless steels such as SUS 410 can be cited. As a nickel alloy, for example, Ni-P alloy can be cited. In addition to the above, as a metal material, a metal material that has been plated, such as a Ni-plated steel sheet, a Zn-plated steel sheet, and a Zn-Ni-plated steel sheet can also be used. As the above example, for example, a Ni-plated steel sheet, a Zn-plated steel sheet, and a Zn-Ni-plated steel sheet using SPCC, SPCD, SPCE, etc. as a base steel sheet can be cited.

[0069] The shape of the metal is not particularly limited, and for example, a foil or plate shape can be cited. When a metal having a foil or plate shape is subjected to surface treatment, only one surface can be subjected to surface treatment using the base treatment agent of this embodiment, or both surfaces can be subjected to surface treatment using the base treatment agent. In addition, when two surfaces are subjected to surface treatment, both surfaces can be subjected to surface treatment using a single base treatment agent, or each single surface can be subjected to surface treatment using base treatment agents of different compositions.

[0070] 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. After the degreasing treatment, in order to remove the degreasing agent remaining on the surface of the substrate, after the water washing treatment, the moisture on the surface of the substrate is removed by a method such as roller dewatering, air blowing, hot air drying, etc.

[0071] The film formed on at least one surface of the metal material preferably contains 0.8 to 3200 mg / m 2 in terms of metal atoms per surface after drying. 2The water-soluble metal compound is added to the film mass after drying on each surface in terms of metal atoms to a concentration of 0.8 mg / m 2 The above has the advantage of being able to ensure sufficient adhesion between the film and the laminate film. In addition, the mass of the film after the above drying is calculated as 3200 mg / m 2 The following has the advantage of being able to ensure good adhesion between the film and the metal material as the treated object. Similarly, it is preferred that the film mass after drying per surface contains 1.0 to 4000 mg / m 2 The water-soluble or water-dispersible acrylic resin is used. The water-soluble or water-dispersible acrylic resin is used to make the solid content of the film mass after drying on each side 1.0 mg / m 2 The above has the advantage of being able to ensure sufficient adhesion between the film and the laminate film. In addition, the acrylic resin is made to have a solid content of 4000 mg / m2 in the film mass after drying on each side. 2 The following has the advantage of being able to ensure good adhesion between the film and the metal material as the object to be processed. The film may be formed on any one surface of the metal material, for example, the film may be formed on both surfaces of a thin plate.

[0072] In this embodiment, the weight of the film formed by applying the above-mentioned surface treatment agent on the aluminum substrate and drying it is preferably 50 to 100 mg / m 2 The surface free energy of the dry film is 52~74mJ / m 2 By making the surface free energy of the dried film within the above range, it is possible to design the water resistance of the film formed by the base treatment agent within a better range. The surface free energy is more preferably 52 to 68 mJ / m 2 within the range.

[0073] In this specification, the surface free energy of the dry film can be measured according to the Owens-Wendt theoretical formula for calculating the surface free energy of a substance. Specifically, the contact angle of the sample substance can be measured using a liquid (water, iodomethane) with a known surface free energy value, and the surface free energy of the sample substance can be calculated using the theoretical formula of DK Owens and RC Wendt, J. Appl. Polym. Sci. (Journal of Applied Polymer Science), 13, 1741 (1969).

[0074] For example, 2 μl of pure water and 2 μl of diiodomethane are dropped onto the surface of the coating layer of a glass test piece, the contact angle (θ) is measured using a contact angle meter, and the surface free energy value γs is calculated using the following Owens equation.

[0075] 1+cosθ=2[(γs d γl d ) 1 / 2 / γl+(γs p γl p ) 1 / 2 / γl]

[0076] Where γs represents the surface free energy of the solid, γl represents the surface free energy of the liquid, the superscript d represents the dispersion force component, and the superscript p represents the polar force component.

[0077] The coating method of the substrate treatment agent of the present embodiment is not particularly limited as long as the weight of each component of the formed film is within the above range. For example, roller coater coating, gravure coater coating, reverse coater coating, slot die coater coating, lip coater coating, knife coater coating, blade coater coating, cavity blade coater coating, air knife coater coating, curtain coating, spin coating, brush coating, roller coating, rod coater coating, dip coating, applicator coating, spray coating, flow coating, and combinations thereof can be cited.

[0078] The heating and drying method of the substrate treatment agent of the present embodiment is not particularly limited, and examples thereof include oven drying, a method utilizing forced circulation of hot air, and a method utilizing an electromagnetic induction heating furnace utilizing an IH heater, etc. The heating and drying conditions may be, for example, set at 40 to 160° C. for 2 to 60 seconds. The air volume, wind speed, etc. set in the drying method may be set arbitrarily.

[0079] As a method for bonding a laminated film to a metal material having a film formed on the surface by the above-mentioned base treatment agent, it is not particularly limited, and known methods such as dry lamination, hot lamination, and extrusion lamination can be used. As the above-mentioned laminated film, it is not particularly limited, and known laminated films can be used. As the above-mentioned laminated film, for example, 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, polyethylene isophthalate resin, copolyester resin, polyester resin, polyamide resin, polyimide resin, polyetherimide resin, polyphenylene sulfide resin, fluororesin, silicone resin, nylon resin, phenolic resin, (meth) acrylic resin, epoxy resin, poly(m-xylene adipamide), etc. and resins containing two or more resins mixed in these resins, etc. can be listed. Laminated films composed of these materials may be stretched uniaxially or biaxially.

[0080] The laminated metal material of the present embodiment may also have a layer other than the film and the laminated film formed by the base treatment agent. For example, it may also have an adhesive layer disposed between the film and the laminated film formed by the base treatment agent. As the above-mentioned adhesive layer, it is not particularly limited, and it can be formed by a single-liquid adhesive or a two-liquid adhesive. As the resin component of the adhesive that can be used in the formation of the above-mentioned adhesive layer, it is not particularly limited, and for example, polyolefin resins, polyester resins, polyether resins, polyurethane resins, polycarbonate resins, epoxy resins, phenol resins, polyamide resins, polyvinyl acetate resins, cellulose resins, (methyl) acrylic resins, polyimide resins, amino resins, chloroprene rubber, nitrile rubber, styrene-butadiene rubber, silicone resins, fluorinated ethylene propylene copolymers, etc. These resin components can be used alone or in combination. Examples of the combination of two or more resin components include a polyurethane resin and a modified polyolefin resin, a polyamide resin and an acid-modified polyolefin resin, a polyamide resin and a metal-modified polyolefin resin, a polyamide resin and a polyester resin, a polyester resin and an acid-modified polyolefin resin, and a polyester resin and a metal-modified polyolefin resin.

[0081] The method for forming the adhesive layer is not particularly limited, and examples thereof include an extrusion molding method and a dispersion method.

[0082] The substrate treatment agent of the present embodiment contains a specific amount of the above-mentioned water-soluble metal compound and acrylic resin, so the coating workability and stability are excellent, and the obtained laminated metal material has sufficient adhesion. Although the substrate treatment agent containing only acrylic resin and zirconium compound also has corrosion resistance, the substrate treatment agent of the present embodiment has the advantages of improving the adhesion with the laminated film and also being able to obtain corrosion resistance. Therefore, the substrate treatment agent of the present embodiment is particularly preferably used for the manufacture of laminated metal materials requiring high post-processing adhesion and corrosion resistance.

[0083] In addition, by having the above-mentioned structure, the substrate treatment agent of this embodiment has the advantage of being able to manufacture a laminated metal material having good water resistance, acid resistance, and alkali resistance. Furthermore, the substrate treatment agent of this embodiment also has the advantages of good dispersibility during the manufacture of the treatment agent and excellent manufacturing stability.

[0084] Example

[0085] The present invention will be described in more detail below based on examples. The present invention is not limited to the following examples. In the examples, "parts" and "%" are based on mass unless otherwise specified.

[0086] (Synthesis Example 1 of Acrylic Resin)

[0087] 95.13 parts by mass of ion exchange water were put into a flask equipped with a heating-stirring device, and heated to 80°C while stirring and refluxing nitrogen. Next, a mixed monomer solution of the monomer types shown in Table 1, ACVA (4,4'-azobis(4-cyanovaleric acid)) as a polymerization initiator, and a mixed solution of 25% ammonia solution were added dropwise using a dropping funnel over 3 hours while heating, stirring, and refluxing nitrogen. After the addition was completed, heating, stirring, and refluxing nitrogen were continued for 2 hours. Then, the heating and nitrogen refluxing were stopped, and the solution was cooled to 30°C while stirring, neutralized to pH 9 with 25% ammonia water, and filtered with 200 mesh to obtain a colorless and transparent water-soluble acrylic resin. As shown in Table 1, the solid acid value of the acrylic resin was 603 mgKOH / g, the solid hydroxyl value was 84 mgKOH / g, and the glass transition temperature was 94°C. In addition, the number average molecular weight was measured by GPC method, and the result was 100,000.

[0088] In Table 1, the units of the numerical values ​​without units are parts by mass. The amount of 25% ammonia water used in the neutralization is not included in the amount of ammonia water in Table 1, but is an amount used separately as a neutralizing agent.

[0089] (Synthesis Examples 2 to 20 of Acrylic Resin)

[0090] Acrylic resins of Synthesis Examples 2 to 20 were obtained in the same manner as Synthesis Example 1 except that the raw material blending amounts were set as shown in Table 1. The number average molecular weight, solid content acid value, solid content hydroxyl value, and glass transition temperature are shown in Table 1, respectively.

[0091] It should be noted that the various abbreviations described in Table 1 are as follows.

[0092] APS: polymerization initiator, ammonium persulfate

[0093] [Table 1]

[0094]

[0095] (Preparation of substrate treatment agent)

[0096] (Example 1)

[0097] Ion exchange water is poured into a flask equipped with a heating-stirring device. While stirring at room temperature, the acrylic resin aqueous solution obtained in Synthesis Example 1 is slowly added in a manner such that the solid content becomes 7,500 mass ppm. While stirring, a water-soluble zirconium compound (ammonium zirconium carbonate, manufactured by Daiichi Kizenso Chemical Industry Co., Ltd., trade name, Zircosol AC-7, containing 13% in terms of Zr atoms) is slowly added in a manner such that the solid content becomes 2,500 mass ppm in terms of zirconium metal atoms. Stirring is continued for 20 minutes to prepare the substrate treatment agent of Example 1.

[0098] (Examples 2 to 29, Comparative Examples 1 to 11)

[0099] Except having made the kind and concentration of an acrylic resin and a water-soluble metal compound into what is shown in Table 2, it carried out similarly to Example 1, and prepared the surface treatment agent of Examples 2-29 and Comparative Examples 1-11.

[0100] In Examples 15, 16 and Comparative Example 3, melamine resin ("CYMEL 370N" manufactured by Cytec Co., Ltd. (non-volatile content 80%)) or phenolic resin ("Shonol BRL-204" manufactured by AICA Industries Co., Ltd. (non-volatile content 70%)) was used as a crosslinking agent in the amount shown in Table 2. In Example 17, a polyester resin ("Vylonal MD1245" manufactured by Toyobo Co., Ltd. (500 mass ppm)) was used as another resin.

[0101] In Example 26, tetraalkylammonium-modified zirconium (Orgatix ZC 700 manufactured by Matsumoto Fine Chemical Co., Ltd.) (non-volatile content 20%) was used as the water-soluble zirconium compound. Ammonium zirconium fluoride and triethanolamine titanium were used in Examples 27 and 28, respectively. In Example 29, ammonium zirconium carbonate (2250 mass ppm in terms of Zr) and triethanolamine titanium (250 mass ppm in terms of Ti) were used together as the water-soluble metal compound. In Comparative Example 1, "Jurymer AC-10L" manufactured by Toagosei Co., Ltd. was used as the polyacrylic acid.

[0102] [Table 2]

[0103]

[0104] [Measurement of surface free energy of dry film of substrate treatment agent]

[0105] The aluminum alloy 3004 plate (Al) was degreased with a 2% dilution of "Surfcleaner 330" manufactured by Paint Surf Chemicals Co., Ltd. of Japan (65°C x 3 seconds), and the obtained base treatment agent was applied to the obtained aluminum material by a rod coater, and dried in a hot air oven at a raw material temperature of 100°C or above to obtain a film with a weight of 70 mg / m 2 Metal materials with dry films.

[0106] The contact angle between the obtained dry film and DIW (ion exchange water) and the contact angle between the dry film and iodomethane were measured under the conditions of 20°C to 23°C and 30 seconds after the droplet was added using an automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., PD-X model). The surface free energy of the dry film was calculated based on the above formula from the obtained measured values. The values ​​of the surface free energy of the dry film on the aluminum material are shown in Table 3 below.

[0107] 《Coating of base treatment agent》

[0108] Aluminum alloy 3004 plate (Al) as a metal material was degreased with a 2% dilution of "Surfcleaner 330" manufactured by Paint Surf Chemicals Co., Ltd. of Japan (treatment at 65°C for 3 seconds), and the base treatment agent of the above-mentioned embodiment and comparative example was applied to the obtained aluminum material by a rod coater, and dried in a hot air oven at a raw material temperature of 100°C or above to obtain a metal material having a film formed on the surface by the base treatment agent. The film weight after drying (mg / m 2 ), the solid content weight of the acrylic resin and the metal atom conversion weight in the water-soluble metal compound are shown in Table 3. In addition, as the metal material, copper (NC-WS manufactured by Furukawa Electric Co., Ltd.) was used in Example 11, SUS (SUS 304) was used in Example 12, Ni-plated steel plates using SPCC as the base steel plate were used in Example 13, and aluminum die castings (ADC-12) were used in Example 14.

[0109] [Table 3]

[0110]

[0111] 《Manufacturing of laminated metal materials》

[0112] The surface treatment agents of the above-mentioned examples and comparative examples were applied to the metal materials having a film formed on the surface, and a laminated metal material was produced by the following laminated metal material production method.

[0113] A polyester two-component adhesive was used as the adhesive and applied to the film formed on the surface of the metal material so that the adhesive density was 3 g / m 2 Next, a PP film was pressure-bonded to the coated surface at 100° C. and 0.2 mPa, and then stored at 40° C. for 4 days to obtain a laminated metal material.

[0114] [Initial fit test]

[0115] The laminated metal materials of the embodiments and comparative examples manufactured in the above order were cut into a size of 150 mm × 15 mm. The peel strength (N / 15 mm width) when the film surface of the test piece was peeled off was measured using a "Tensilon tensile tester" (LST-200N-S, manufactured by Minerva). The measurement results were used as initial adhesion and evaluated according to the following evaluation criteria, with an evaluation of 4 or above being considered qualified. The results are shown in Table 4.

[0116] (Evaluation Criteria)

[0117] 5: 8.0N / 15mm width or more

[0118] 4: 6.0N / 15mm width or more and less than 8.0N / 15mm width

[0119] 3: 4.0N / 15mm width or more and less than 6.0N / 15mm width

[0120] 2: 2.0N / 15mm width or more and less than 4.0N / 15mm width

[0121] 1: Less than 2.0N / 15mm width

[0122] [Adhesion test after retort treatment]

[0123] The above-mentioned crimped metal plate was cut into 150mm×15mm test pieces, which were placed in an autoclave and heated in pressurized steam at 125°C for 45 minutes (retorting). The peel strength (N / 15mm width) when the film surface of the retorting test piece was peeled off was measured using a "Tensilon tensile tester" (LST-200N-S, manufactured by Minerva). The measurement results were used as the adhesion after retorting, and the same evaluation criteria as the initial adhesion were used for evaluation, and an evaluation of 4 or more was considered acceptable. The results are shown in Table 4.

[0124] [Water resistance test]

[0125] The test plate prepared in the above "Coating of the base treatment agent" was immersed in running tap water (flow rate: 15 kg / hour) for 24 hours. Then, the test plate was lifted and the residual rate of the film after drying was visually evaluated. The evaluation criteria are as follows. The evaluation results are shown in Table 4.

[0126] (Evaluation Criteria)

[0127] 3: The film residual rate is more than 80%

[0128] 2: The film residual rate is 50% or more and less than 85%

[0129] 1: The film residual rate is less than 50%

[0130] [Acid resistance test]

[0131] The laminated metal material produced according to the procedure of the above-mentioned "Production of Laminated Metal Material" was cut into a size of 150 mm x 15 mm. The obtained test piece was immersed in an acetic acid aqueous solution (pH 2) at 23°C for 7 days.

[0132] The test piece removed from the immersion was washed with water and dried, and then the peel strength (N / 15 mm width) when the film surface of the test piece was peeled off was measured using a "Tensilon tensile tester" (LST-200N-S, manufactured by Minerva). The measurement results were evaluated according to the following evaluation criteria. The results are shown in Table 4.

[0133] (Evaluation Criteria)

[0134] 3: 6.0N / 15mm width or more

[0135] 2: 3.0N / 15mm width or more and less than 6.0N / 15mm width

[0136] 1: Less than 3.0N / 15mm width

[0137] [Alkali resistance test]

[0138] The laminated metal material produced according to the procedure of the above-mentioned "Production of Laminated Metal Material" was cut into a size of 150 mm x 15 mm. The obtained test piece was immersed in a 2% sodium hydroxide aqueous solution at 40°C for 7 days.

[0139] The test piece removed from the immersion was washed with water and dried, and then the peel strength (N / 15 mm width) when the film surface of the test piece was peeled off was measured using a "Tensilon tensile tester" (LST-200N-S, manufactured by Minerva). The measurement results were evaluated according to the following evaluation criteria. The results are shown in Table 4.

[0140] (Evaluation Criteria)

[0141] 3: 6.0N / 15mm width or more

[0142] 2: 3.0N / 15mm width or more and less than 6.0N / 15mm width

[0143] 1: Less than 3.0N / 15mm width

[0144] It should be noted that in the manufacture of the laminated metal material in the above evaluation test, an adhesive is used to manufacture the laminated metal material, but even if a PET film is pressed at 180°C and 0.2MPa on the film formed by applying the above-mentioned base treatment agent on the surface of the metal material, the laminated metal material can be well manufactured. In addition, by applying a polyester-based adhesive on the film formed by applying the above-mentioned base treatment agent on the surface of the metal material, pressing the PE film at 100°C and 0.2MPa, and storing it at 40°C for 4 days, the laminated metal material can also be well manufactured.

[0145] [Table 4]

[0146]

[0147] The above results confirm that the laminated metal materials of each example have excellent adhesion compared to the laminated metal materials of the comparative examples. Furthermore, the water resistance test results, acid resistance test results, and alkali resistance test results of the examples are also good.

[0148] Comparative Example 1 is an example in which polyacrylic acid was used and the acid value and hydroxyl value of the resin were outside the range of the present invention. In this example, it was confirmed that the adhesion after the retort treatment was poor.

[0149] Comparative Examples 2, 3, and 7 are examples in which the number average molecular weight of the acrylic resin is outside the range of the present invention. In these examples, it was confirmed that the adhesion after the retort treatment was poor.

[0150] Comparative Example 4 is an example in which the surface treatment agent does not contain an acrylic resin. In this example, it was confirmed that the initial adhesion, the adhesion after the retort treatment, the water resistance, the acid resistance, and the alkali resistance were all poor.

[0151] Comparative Example 5 is an example in which the content of the acrylic resin is outside the range of the present invention. In this example, it was confirmed that the initial adhesion, the adhesion after the retort treatment, the acid resistance, and the alkali resistance were poor.

[0152] Comparative Example 6 is an example in which no metal compound is contained. In this example, it was confirmed that the adhesion, water resistance, acid resistance, and alkali resistance after the retort treatment were poor.

[0153] Comparative Examples 8 and 9 are examples in which the acid value and / or hydroxyl value of the acrylic resin is outside the range of the present invention. In each of these examples, it was confirmed that the adhesion after the retort treatment was poor.

[0154] Comparative Example 10 is an example in which the number average molecular weight of the acrylic resin is outside the range of the present invention and the glass transition temperature is outside the range of the present invention. It was confirmed that this example has poor water resistance.

[0155] Comparative Example 11 is an example in which the glass transition temperature of the acrylic resin is outside the range of the present invention. It was confirmed that this example is inferior in acid resistance, alkali resistance, etc.

Claims

1. A substrate treatment agent for the manufacture of laminated metal materials, comprising 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. The concentration of the water-soluble metal compound is 500 to 200,000 ppm by mass in terms of metal atoms. The water-soluble or water-dispersible acrylic resin has a number average molecular weight of 70,000 to 500,000, a solid acid value of 150 to 740 mgKOH / g, a solid hydroxyl value of 40 to 350 mgKOH / g, and a glass transition temperature of 63 to 100° C. The concentration of the water-soluble or water-dispersible acrylic resin is 500 to 200,000 ppm by mass in terms of solid content. The ratio of the metal atom conversion concentration of the water-soluble metal compound to the concentration of the water-soluble or water-dispersible acrylic resin is 3 / 97 to 91 / 9, The substrate treatment agent does not contain a cross-linking agent.

2. The substrate treatment agent according to claim 1, wherein The base treatment agent is applied on an aluminum substrate and dried to form a film with a weight of 50 to 100 mg / m 2 The surface free energy of the dry film is 52~74mJ / m 2 .

3. The substrate treatment agent according to claim 1 or 2, wherein The water-soluble or water-dispersible acrylic resin is a copolymer of monomer (A), The monomer (A) includes one or more monomers having a glycidyl group, an amide group, a silanol group, a phosphoric acid group, a nitrile group or an imide group.

4. The substrate treatment agent according to claim 3, wherein The equivalent ratio (i) / (ii) of the total equivalent weight (i) of one or more functional groups selected from the group consisting of a glycidyl group, an amide group, a silanol group, a phosphoric acid group, a nitrile group and an imide group possessed by the water-soluble or water-dispersible acrylic resin to the equivalent weight (ii) of a hydroxyl group possessed by the water-soluble or water-dispersible acrylic resin is in the range of 0.03 to 0.

20.

5. A metal material having a coating formed of the surface treatment agent according to any one of claims 1 to 4 on at least one surface.

6. The metal material according to claim 5, wherein: The film contains 0.8 to 3200 mg / m2 of the metal atom in terms of the mass of the film after drying on each of the surfaces. 2 The water-soluble metal compound is 1.0 to 4000 mg / m 2 The water-soluble or water-dispersible acrylic resin.

Images