WO2017038251A1 - Surface treatment agent, film production method, and film-equipped metal material - Google Patents

Surface treatment agent, film production method, and film-equipped metal material Download PDF

Info

Publication number
WO2017038251A1
WO2017038251A1 PCT/JP2016/070195 JP2016070195W WO2017038251A1 WO 2017038251 A1 WO2017038251 A1 WO 2017038251A1 JP 2016070195 W JP2016070195 W JP 2016070195W WO 2017038251 A1 WO2017038251 A1 WO 2017038251A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
meth
acid
treatment agent
surface treatment
Prior art date
Application number
PCT/JP2016/070195
Other languages
French (fr)
Japanese (ja)
Inventor
祐補 山本
Original Assignee
日本パーカライジング株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本パーカライジング株式会社 filed Critical 日本パーカライジング株式会社
Priority to CN201680045656.2A priority Critical patent/CN107922779A/en
Priority to KR1020187003999A priority patent/KR20180036984A/en
Publication of WO2017038251A1 publication Critical patent/WO2017038251A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—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
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • 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 capable of forming a film having a predetermined performance on the surface of a metal material, a method for producing the film, and a metal material with a film having the film.
  • Patent Document 1 proposes a technique relating to an aqueous liquid containing poly (meth) acrylamide, polyalkylene glycol, and a compound having at least two aldehyde groups in the molecule as essential components.
  • this technology has excellent hydrophilicity, remarkably promotes water film formation, reliably prevents the deposition of water droplets over a long period of time, has good moldability as a coating forming material, and also wears molds. It is possible to form a hydrophilic film having an excellent performance that does not adversely affect corrosion resistance and the like.
  • the present invention is not only hydrophilic, but also excellent in water drainage (drying property), a surface treatment agent capable of forming a hydrophilic film that can further suppress the formation of frost, a method for producing the film, and It aims at providing the metal material with a film
  • a surface treatment agent in which amphoteric poly (meth) acrylamide and a compound having at least two aldehyde groups are blended in a solvent is used as a metal material.
  • a surface treatment agent in which amphoteric poly (meth) acrylamide and a compound having at least two aldehyde groups are blended in a solvent is used as a metal material.
  • the present invention (1) a surface treatment agent containing amphoteric poly (meth) acrylamide and a compound having at least two aldehyde groups; (2) A method for producing a film, comprising: a step of bringing the surface treatment agent according to (1) into contact with a surface of a metal material; and a step of baking the surface brought into contact with the surface treatment agent; (3) A metal material with a film having a film formed by the method for producing a film according to (2) above; Etc.
  • hydrophilicity not only hydrophilicity but also water drainage (drying property), a surface treatment agent capable of forming a hydrophilic film capable of further suppressing the formation of frost, a method for producing the film, and A coated metal material having the coating can be provided.
  • the surface treating agent according to the present invention contains amphoteric poly (meth) acrylamide and a compound having at least two aldehyde groups.
  • the surface treatment agent of the present invention is not only hydrophilic but also has excellent water drainage (dryability), and a hydrophilic film that can further suppress the formation of frost, It can be formed on the surface.
  • the surface treatment agent of the present invention may contain other components as long as the performance of the hydrophilic film is not impaired. Hereinafter, the components of the surface treatment agent will be described.
  • amphoteric poly (meth) acrylamide is not particularly limited as long as it has a cationic group and an anionic group, but a primary amino group, a secondary amino group, a tertiary amino group, and a Specific examples include those having at least a cationic group having a functional group selected from a quaternary ammonium group and an anionic group having a functional group selected from a carboxyl group, a phosphate group and a sulfo group. it can.
  • amphoteric poly (meth) acrylamide can be appropriately polymerized by a known method.
  • amphoteric poly (meth) acrylamide is referred to as (meth) acrylamide (hereinafter referred to as “(a) component”) and a cationic monomer having the cationic group (hereinafter referred to as “(b) component”).
  • component (c) An anionic monomer having an anionic group
  • component (d) an anionic group
  • component (d) another monomer
  • the polymerization reaction is carried out by blending (a) component, (b) component, (c) component, and (d) component, if necessary, with water in a predetermined amount in water, and various known radical polymerization initiators, if necessary.
  • the chain transfer agent can be further added.
  • the temperature and time of the polymerization reaction are not particularly limited, and examples thereof include a reaction temperature of 20 to 140 ° C. and a reaction time of 2 to 12 hours.
  • radical polymerization initiator examples include organic peroxides such as benzoyl peroxide, dicumyl peroxide, and lauryl peroxide; inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate; 2 , 2′-azobisisobutyronitrile, azo compounds such as dimethyl-2,2′-azobisisobutyrate, and the like. These may be used alone, You may use combining a seed
  • chain transfer agent examples include ethyl alcohol, methyl alcohol, isopropyl alcohol and the like.
  • the component is acrylamide and / or methacrylamide.
  • the component (b) is not particularly limited as long as it is a vinyl monomer having the above cationic group.
  • allylamine, aminoethyl (meth) acrylate, 4-aminostyrene or a salt thereof for example, hydrochloride Sulfate, formate, acetate, etc.]
  • N-alkylallylamine eg, N-methylallylamine, N-ethylallylamine, etc.
  • N-alkylaminoalkyl (meth) acrylamide eg, N-methylaminoethyl (meth) ) Acrylamide, N-ethylaminoethyl (meth) acrylamide, etc.] or diallylamine or a salt thereof [eg, hydrochloride, sulfate, formate, acetate, etc.]
  • N, N-dialkylaminoalkyl (meth) acrylate eg, N, N-dimethylaminoethyl
  • Examples of the quaternizing agent include alkyl halides such as methyl chloride and methyl bromide; aralkyl halides such as benzyl chloride and benzyl bromide; dimethyl sulfate; epichlorohydrin; 3-chloro-2-hydroxypropyltrimethylammonium chloride; glycidyl. Trialkylammonium chloride and the like can be used.
  • the component (c) is not particularly limited as long as it is a vinyl monomer having the above anionic group.
  • component (D) A well-known thing can be used as a component.
  • the component (d) include hydrophobic monomers such as acrylonitrile, vinyl acetate, vinyl propionate, styrene, ⁇ -methylstyrene, vinyltoluene, ⁇ -olefin; dialkyl itaconate having an alkyl group having 1 to 4 carbon atoms. Itaconic acid diesters such as esters; vinyl monomers having an allyl group; monomers having a polyalkylene glycol group; vinyl monomers having an N-substituted amide group such as diacetone acrylamide; crosslinkable monomers; One kind may be used alone, or two or more kinds may be used in combination.
  • Examples of the vinyl monomer having an allyl group include allyl (meth) acrylate, N-allyl (meth) acrylamide, N, N-diallyl (meth) acrylamide and the like.
  • the monomer having a polyalkylene glycol group is not particularly limited as long as it has at least two repeating units of oxyalkylene group in the molecule. For example, it has 2 to 10 repeating units. Things can be mentioned.
  • polyethylene glycol mono (meth) acrylate eg, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, etc.
  • polypropylene glycol mono (meth) acrylate For example, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, etc.], methoxypolyethylene glycol mono (meth) acrylate, polytrimethylene glycol mono (meth) acrylate, Polytetramethylene glycol mono (meth) acrylate, polyethylene glycol propylene glycol mono (meth) acryl
  • the crosslinkable monomer is not particularly limited as long as it is a monomer having at least two vinyl groups, and known monomers can be used.
  • amphoteric poly (meth) acrylamides used in the present invention include, for example, Hermide EX-200 series, Hermide EX-300 series, Hermide EX-400 series, Hermide RB-200 series, manufactured by Harima Chemical Group Co., Ltd. Hermide RB-300 series, Hermide RB-400 series, etc .; manufactured by Arakawa Chemical Industries, Ltd.
  • the weight average molecular weight of the amphoteric poly (meth) acrylamide used in the present invention is not particularly limited, but is, for example, from 10 to 20 million.
  • the weight average molecular weight described in this specification is a value measured from the weight average molecular weight obtained by the polyethylene oxide conversion value by the gel permeation chromatography (GPC) method.
  • Examples of compounds having at least two aldehyde groups include, but are not limited to, glyoxal, oxalic acid dialdehyde, and dialdehyde starch.
  • the said compound which has at least 2 aldehyde groups may be used individually by 1 type, but may be used in combination of 2 or more type.
  • the blending ratio [A / B] of the amphoteric poly (meth) acrylamide (A) and the compound (B) having at least two aldehyde groups in the surface treatment agent of the present invention is preferably 0.1 in terms of solid content mass ratio. It is more than less than 3.0, more preferably from 0.15 to 2.5, and particularly preferably from 0.2 to 1.0.
  • the surface treatment agent comprising only amphoteric poly (meth) acrylamide and a compound having at least two aldehyde groups in addition to the solvent has been described.
  • the surface treatment agent of the present invention can be used as needed.
  • a resin other than amphoteric poly (meth) acrylamide, a surfactant, an organic acid, a metal compound, a silicic acid compound, an additive for a surface treatment agent, and the like may further be included.
  • the resin may be any resin such as cationic, anionic, amphoteric, and nonionic other than amphoteric poly (meth) acrylamide.
  • the resin include urethane resin, epoxy resin, (meth) acrylic resin, (meth) acrylamide resin, phenol resin, polyester resin, polyvinyl resin, polyolefin resin, polyimide resin, sulfonic acid Examples thereof include known resins such as a series resin and natural polymers (cellulose, starch, gelatin, etc.), which may be a polymer or a copolymer. These resin may be used individually by 1 type, and may be used in combination of 2 or more type.
  • surfactants such as cationic, anionic, amphoteric, and nonionic can be used.
  • cationic surfactants such as alkylamine salts and alkyltrimethylammonium halides; alkylsulfonic acid esters, Anionic surfactants such as polyoxyethylene alkylphenyl ether sulfate, sodium dodecyl diphenyl ether disulfonate and sodium dodecyl sulfate; amphoteric surfactants such as alkylaminopropionate and alkyldimethylbetaine; polyoxyethylene alkylphenyl ether, poly Nonio such as oxyalkylene fatty acid ester, fatty acid glycerin ester, sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid, polyoxyethylene propylene glycol fatty acid ester Sex surfactant; can be exemplified, and these may be used alone or may be used in combination
  • organic acids include oxalic acid, malonic acid, maleic acid, fumaric acid, succinic acid, malic acid, citric acid, glutamic acid, aspartic acid, tartaric acid, phthalic acid, itaconic acid, melittic acid, trimellitic acid, trimesic acid, Pyromellitic acid, naphthalenetetracarboxylic acid, propanedicarboxylic acid, butanedicarboxylic acid, pentanedicarboxylic acid, hexanedicarboxylic acid, heptanedicarboxylic acid, butanetricarboxylic acid, butanetetracarboxylic acid (for example, 1,2,3,4-butanetetracarboxylic acid) Acid), cyclohexanetetracarboxylic acid, hexanetricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxy
  • Examples of the cationic counter ion that forms the salt of the above compound include metal ions such as alkali metal (sodium, potassium, lithium, etc.) ions, alkaline earth metal (magnesium, calcium, barium, etc.) ions, ammonium ions, and the like. Can be mentioned. These organic acids may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the metal compound examples include a zirconium compound (eg, hexafluorozirconic acid, ammonium zirconium carbonate, zirconyl acetate, zirconyl sulfate, zirconyl nitrate, etc.), a titanium compound (eg, hexafluorotitanic acid, titanium oxide, etc.), a cerium compound ( For example, cerium oxide, cerium carbonate, cerium fluoride, etc.), vanadium compounds (eg, metavanadate, vanadyl sulfate, vanadium acetylacetonate, etc.), chromium compounds (eg, chromium (III) sulfate, chromium (III) fluoride) Etc.), but is not limited thereto.
  • these metal compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
  • silicic acid compounds include alkali metal silicates such as sodium silicate, potassium silicate, and lithium silicate; polymer silica; water-dispersible silica such as colloidal silica, chain silica, pendant silica, plate silica, and hollow silica; However, it is not limited to these. In addition, these silicic acid compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
  • additives for surface treatment agents include known additives such as antifoaming agents, leveling agents, stabilizers, rust inhibitors, antibacterial agents, antifungal agents, wetting agents, thickeners, colorants, and the like. Of these, one or more of them can be used.
  • the pH of the surface treatment agent according to the present invention is preferably 2 or more or more than 12 or less, more preferably 2.5 or more or more than 10 or less, particularly preferably 2.5 or more or more than 6. 0 or less.
  • pH in this specification is a value obtained using a commercially available pH meter for the agent at 25 ° C.
  • the surface treating agent of the present invention can be produced by mixing amphoteric poly (meth) acrylamide, a compound having at least two aldehyde groups, and, if necessary, the above-mentioned other components in a solvent.
  • the solvent is not particularly limited, but an aqueous solvent is preferable.
  • the aqueous solvent means a solvent containing 50% by mass or more of water based on the mass of all the solvents.
  • the “solvent” does not mean a narrowly-defined solvent that dissolves all components, but a concept that includes a dispersion medium that may be in a dispersed state for some components.
  • Examples of the solvent other than water contained in the aqueous solvent include alkane solvents such as hexane and pentane; aromatic solvents such as benzene and toluene; alcohol solvents such as ethanol, 1-butanol and ethyl cellosolve; tetrahydrofuran, dioxane Ether solvents such as ethyl acetate, butoxyethyl acetate, etc .; amide solvents such as dimethylformamide and N-methylpyrrolidone; sulfone solvents such as dimethyl sulfoxide; phosphate amides such as hexamethylphosphate triamide Solvent; and the like. These solvents other than water may be mixed alone or in combination of two or more. In addition, it is preferable to use only water from an environmental and economic viewpoint.
  • the film formed by the surface treatment agent of the present invention is a hydrophilic film.
  • the method for producing the coating includes a contact step in which the surface treatment agent of the present invention is brought into contact with, for example, the surface of a metal material, and a baking step in which the surface, that is, the surface in contact with the surface treatment agent is baked after the contact step. And have.
  • pre-processing processes such as a degreasing
  • the contact step can be performed by a conventional contact method such as a spray coating method, a dip coating method, a roll coating method, a curtain coating method, a spin coating method, or a combination thereof, but is not limited thereto. It is not something.
  • the conditions for using the surface treatment agent are not particularly limited.
  • the temperature of the surface treatment agent and the metal material when contacting the surface treatment agent is preferably 5 ° C. or more and 50 ° C. or less, and more preferably 20 ° C. or more and 40 ° C. or less. It is not limited to.
  • the contact time can be appropriately set, but is usually 2 seconds or more and 180 seconds or less.
  • the baking step is preferably performed under a temperature condition in which the maximum reached temperature (PMT) of the metal material is in a range of 150 ° C. or higher and 230 ° C. or lower, more preferably in a temperature condition in a range of 170 ° C. or higher and 200 ° C. or lower. It is particularly preferable to carry out under a temperature condition within the range of 180 ° C. or higher and 190 ° C. or lower.
  • the baking time is not particularly limited, but is preferably in the range of 2 seconds to 300 seconds.
  • the baking method is not particularly limited, and examples thereof include a baking drying method using an electric hot air dryer, a gas hot air dryer, and the like.
  • the chemical conversion film forming step is a step of forming a chemical conversion film.
  • the method for forming the chemical conversion film include a chemical conversion treatment method such as a phosphate chemical conversion treatment method, a zirconium chemical conversion treatment method, a titanium chemical conversion treatment method, a hafnium chemical conversion treatment method, and a vanadium chemical conversion treatment method.
  • a chemical conversion treatment method such as a phosphate chemical conversion treatment method, a zirconium chemical conversion treatment method, a titanium chemical conversion treatment method, a hafnium chemical conversion treatment method, and a vanadium chemical conversion treatment method.
  • one chemical conversion treatment method may be performed, or two chemical conversion treatment methods may be combined.
  • phosphate chemical conversion treatment known ones such as a zinc phosphate chemical conversion treatment agent and a phosphate chromate chemical conversion treatment agent can be used.
  • a known zirconium chemical conversion treatment agent is used for zirconium chemical conversion treatment, a known titanium chemical conversion treatment agent for titanium chemical conversion treatment, a known hafnium chemical conversion treatment agent for hafnium chemical conversion treatment, and a known vanadium chemical conversion treatment for vanadium chemical conversion treatment.
  • Each treatment agent can be used.
  • Metal material examples of the metal material to which the surface treatment agent is applied include a pure aluminum material, an aluminum alloy material (these are also referred to as “aluminum materials”); a pure copper material, a copper alloy material (these are also referred to as “copper materials”), and the like. Although alloy steel materials etc. can be mentioned, it is not restrict
  • the shape and structure of the metal material are not particularly limited, and examples thereof include a plate shape and a foil shape.
  • the metal material is formed on a base material such as a metal material, a ceramic material, or an organic material different from the metal material, for example, by the method such as plating, vapor deposition, or clad, as described above, copper material, aluminum material, alloy steel material. Etc. may be coated.
  • the copper alloy material preferably contains 50% by mass or more of copper based on the total mass of the material, and examples thereof include a brass material.
  • alloy components other than copper in the copper alloy material include Zn, P, Al, Fe, and Ni.
  • the aluminum alloy material preferably contains 50% by mass or more of aluminum based on the total mass of the material, and examples thereof include an Al—Mg alloy material.
  • alloy components other than aluminum in the aluminum alloy material include Si, Fe, Cu, Mn, Cr, Zn, and Ti.
  • the alloy steel material preferably contains 50% by mass or more of iron on the basis of the total mass of the material, and examples thereof include a stainless steel material. Examples of alloy components other than iron in the alloy steel include C, Si, Mn, P, S, Ni, Cr, and Mo.
  • the metal material with a film according to the present invention includes a metal material and the hydrophilic film formed on the surface of the metal material by the surface treatment agent.
  • the metal material with a film according to the present invention includes a phosphate chemical conversion film, a zirconium chemical conversion film, a titanium chemical conversion film, a hafnium chemical conversion film, and a vanadium chemical conversion film between the surface of the metal material and the hydrophilic film. Etc. may be included.
  • the hydrophilic film may be an organic film made of an organic component, or an organic inorganic film made of an organic component and an inorganic component.
  • the coating weight of the hydrophilic coating is preferably dried mass at 0.05 g / m 2 or more, or an ultra, more preferably 0.1 g / m 2 or more, or an ultra, 0.2 g / m 2 Although it is especially preferable that it is more or more than this, it is not limited to these. In addition, although it does not limit about an upper limit, it is desirable that it is 1.0 g / m ⁇ 2 > or less from a cost surface.
  • Polystron 372 (amphoteric polyacrylamide; solid content 15.4%), Polystron 1228 (amphoteric polyacrylamide; solid content 20.4%), Polystron 1280 (amphoteric polyacrylamide; solid content 20.7%) and Polystron 1407 (amphoteric polyacrylamide; solid content 20.4%) manufactured by Arakawa Chemical Industries, Ltd., Haricoat 1057 (nonionic polyacrylamide; solid content 20.3%), Haliffix UF-570 (cationic) Polyacrylamide (solid content: 12.7%) and Hermide C-10 (anionic polyacrylamide; solid content: 10.3%) are those manufactured by Harima Kasei Group. Glyoxal (solid content: 40%) is Amzole India pvt. . Ltd .. Each of the products made was used. The solid content of nitrilotrismethylenephosphonic acid is 50.0%.
  • Degreasing is performed by spraying a degreasing agent (20% aqueous solution of fine cleaner 4377KN; manufactured by Nihon Parkerizing Co., Ltd.) at 50 ° C. for 10 seconds on a metal material (aluminum material: A1050; thickness 0.8 mm; manufactured by Partec Co., Ltd.). After the cleaning, the surface was cleaned by washing with water. Subsequently, the phosphoric acid chromate chemical conversion treatment [alchrome K702SKN: 21 g / L and Alchrome K702ACN: 4 g / L; both manufactured by Nihon Parkerizing Co., Ltd.] was performed at 50 ° C. for 15 seconds to perform the phosphoric acid chromate chemical conversion treatment. A chemical conversion film was formed on the surface of the material.

Abstract

[Problem] To provide a surface treatment agent capable of forming a hydrophilic film, the agent having excellent hydrophilicity as well as draining performance (drying performance) and which can further suppress the formation of frost; a method for producing the film; and a film-equipped metal material having the film. [Solution] The problem is solved by a surface treatment agent in which an amphoteric poly(meth)acrylamide and a compound having at least two aldehyde groups are combined in a solvent.

Description

表面処理剤、皮膜の製造方法及び皮膜付き金属材料Surface treatment agent, method for producing film, and metal material with film
　本発明は、金属材料の表面に所定の性能を有する皮膜を形成することができる表面処理剤、該皮膜の製造方法、及び該皮膜を有する皮膜付き金属材料に関する。 The present invention relates to a surface treatment agent capable of forming a film having a predetermined performance on the surface of a metal material, a method for producing the film, and a metal material with a film having the film.
　エアコン、ラジエータ、インタークーラー等の熱交換器には、フィン、チューブ、プレート、ヘッダー等を構成するアルミニウム材、アルミニウム合金材、銅材、銅合金材、ステンレス等の金属材料が用いられている。この金属材料に親水性等の各性能を付与するために、従来様々な技術が提案されている。例えば、特許文献１には、ポリ（メタ）アクリルアミドと、ポリアルキレングリコールと、分子内に少なくとも２個のアルデヒド基を有する化合物とを必須成分として含有する水性液に関する技術が提案されている。この技術によれば、優れた親水性を有し、水膜形成を著しく助長して水滴の付着を長期間にわたって確実に阻止し、かつ被覆形成素材としての成形加工性が良好で金型摩耗も少なく、更には耐食性等に悪影響を及ぼすこともない、優れた性能の親水性皮膜を形成することができる。 For heat exchangers such as air conditioners, radiators, and intercoolers, metal materials such as fins, tubes, plates, headers, etc., such as aluminum materials, aluminum alloy materials, copper materials, copper alloy materials, and stainless steel are used. Various techniques have been proposed in the past for imparting each performance such as hydrophilicity to the metal material. For example, Patent Document 1 proposes a technique relating to an aqueous liquid containing poly (meth) acrylamide, polyalkylene glycol, and a compound having at least two aldehyde groups in the molecule as essential components. According to this technology, it has excellent hydrophilicity, remarkably promotes water film formation, reliably prevents the deposition of water droplets over a long period of time, has good moldability as a coating forming material, and also wears molds. It is possible to form a hydrophilic film having an excellent performance that does not adversely affect corrosion resistance and the like.
特開平９－７７９９９号公報Japanese Patent Laid-Open No. 9-77999
　上記特許文献１に記載の技術では、親水性皮膜上に凝集付着した結露水などが水膜を形成して下方に流下し、これにより水滴状態での滞留を阻止することができるが、水切れ性（乾燥性）が悪く、霜が形成される場合がある。そこで、本発明は、親水性だけでなく、水切れ性（乾燥性）にも優れ、霜の形成をより抑制することができる親水性皮膜を形成可能な表面処理剤、該皮膜の製造方法、及び該皮膜を有する皮膜付き金属材料を提供することを目的とする。 In the technique described in Patent Document 1, condensed water and the like that clumps and adheres on the hydrophilic film forms a water film and flows downward, thereby preventing water from staying in the water droplet state. (Dryness) is poor and frost may be formed. Therefore, the present invention is not only hydrophilic, but also excellent in water drainage (drying property), a surface treatment agent capable of forming a hydrophilic film that can further suppress the formation of frost, a method for producing the film, and It aims at providing the metal material with a film | membrane which has this film | membrane.
　本発明者らは前記課題を解決するための手段について鋭意検討した結果、両性ポリ（メタ）アクリルアミドと、アルデヒド基を少なくとも２個有する化合物とを溶媒に配合させた表面処理剤を、金属材料の表面に接触させることにより、親水性だけでなく、水切れ性（乾燥性）にも優れ、霜の形成をより抑制することができる親水性皮膜を形成できることを見出し、本発明を完成するに至った。 As a result of intensive studies on means for solving the above problems, the present inventors have found that a surface treatment agent in which amphoteric poly (meth) acrylamide and a compound having at least two aldehyde groups are blended in a solvent is used as a metal material. By contacting the surface, it was found that not only hydrophilicity but also water drainage (drying property) can be formed and a hydrophilic film capable of further suppressing frost formation can be formed, and the present invention has been completed. .
　すなわち、本発明は、
（１）両性ポリ（メタ）アクリルアミドと、アルデヒド基を少なくとも２個有する化合物とを含有する表面処理剤；
（２）上記（１）に記載の表面処理剤を金属材料の表面に接触させる工程と、前記表面処理剤を接触させた前記表面を焼き付ける工程と、を含む皮膜の製造方法；
（３）上記（２）に記載の皮膜の製造方法により形成された皮膜を有する皮膜付き金属材料；
などである。 That is, the present invention
(1) a surface treatment agent containing amphoteric poly (meth) acrylamide and a compound having at least two aldehyde groups;
(2) A method for producing a film, comprising: a step of bringing the surface treatment agent according to (1) into contact with a surface of a metal material; and a step of baking the surface brought into contact with the surface treatment agent;
(3) A metal material with a film having a film formed by the method for producing a film according to (2) above;
Etc.
　本発明によれば、親水性だけでなく、水切れ性（乾燥性）にも優れ、霜の形成をより抑制することができる親水性皮膜を形成可能な表面処理剤、該皮膜の製造方法、及び該皮膜を有する皮膜付き金属材料を提供することができる。 According to the present invention, not only hydrophilicity but also water drainage (drying property), a surface treatment agent capable of forming a hydrophilic film capable of further suppressing the formation of frost, a method for producing the film, and A coated metal material having the coating can be provided.
　以下、本発明に係る金属表面処理剤、皮膜の製造方法、及び皮膜付き金属材料について詳細に説明する。なお、本発明は、その要旨を含む範囲で任意に変更可能であり、下記の実施形態のみに限定されない。 Hereinafter, the metal surface treatment agent, the method for producing a film, and the metal material with a film according to the present invention will be described in detail. In addition, this invention can be arbitrarily changed in the range including the summary, and is not limited only to the following embodiment.
（表面処理剤）
　本発明に係る表面処理剤は、両性ポリ（メタ）アクリルアミドと、アルデヒド基を少なくとも２個有する化合物とを含有する。本発明の表面処理剤は、これらの成分を含むことにより、親水性だけでなく、水切れ性（乾燥性）にも優れ、霜の形成をより抑制することができる親水性皮膜を、金属材料の表面に形成することができるようになる。なお、本発明の表面処理剤は、上記親水性皮膜の性能を損なわない限り、他の成分を含んでいてもよい。以下、表面処理剤の成分について説明する。 (Surface treatment agent)
The surface treating agent according to the present invention contains amphoteric poly (meth) acrylamide and a compound having at least two aldehyde groups. By including these components, the surface treatment agent of the present invention is not only hydrophilic but also has excellent water drainage (dryability), and a hydrophilic film that can further suppress the formation of frost, It can be formed on the surface. The surface treatment agent of the present invention may contain other components as long as the performance of the hydrophilic film is not impaired. Hereinafter, the components of the surface treatment agent will be described.
（両性ポリ（メタ）アクリルアミド）
　両性ポリ（メタ）アクリルアミドは、カチオン性基とアニオン性基とを有するものであれば特に限定されるものではないが、第１級アミノ基、第２級アミノ基、第３級アミノ基及び第４級アンモニウム基から選択される官能基を有するカチオン性基と、カルボキシル基、リン酸基及びスルホ基から選択される官能基を有するアニオン性基とを、少なくとも有するものを具体的に挙げることができる。 (Amotropic poly (meth) acrylamide)
The amphoteric poly (meth) acrylamide is not particularly limited as long as it has a cationic group and an anionic group, but a primary amino group, a secondary amino group, a tertiary amino group, and a Specific examples include those having at least a cationic group having a functional group selected from a quaternary ammonium group and an anionic group having a functional group selected from a carboxyl group, a phosphate group and a sulfo group. it can.
　上記両性ポリ（メタ）アクリルアミドは、公知の方法により適宜重合することができる。例えば、両性ポリ（メタ）アクリルアミドは、（メタ）アクリルアミド（以下、「（ａ）成分」と称する。）と、上記カチオン性基を有するカチオン性モノマー（以下、「（ｂ）成分」と称する。）と、上記アニオン性基を有するアニオン性モノマー（以下、「（ｃ）成分」と称する。）と、必要に応じて他のモノマー（以下、「（ｄ）成分」と称する。）と、の重合反応により得ることができる。重合反応は、（ａ）成分、（ｂ）成分、（ｃ）成分、必要に応じて（ｄ）成分等を所定量で水に配合した後、各種公知のラジカル重合開始剤と、必要に応じて連鎖移動剤と、をさらに添加することにより行うことができる。重合反応の温度及び時間は、特に制限されるものではないが、２０～１４０℃の反応温度及び２～１２時間の反応時間を例示することができる。 The amphoteric poly (meth) acrylamide can be appropriately polymerized by a known method. For example, amphoteric poly (meth) acrylamide is referred to as (meth) acrylamide (hereinafter referred to as “(a) component”) and a cationic monomer having the cationic group (hereinafter referred to as “(b) component”). ), An anionic monomer having an anionic group (hereinafter referred to as “component (c)”), and, if necessary, another monomer (hereinafter referred to as “component (d)”). It can be obtained by a polymerization reaction. The polymerization reaction is carried out by blending (a) component, (b) component, (c) component, and (d) component, if necessary, with water in a predetermined amount in water, and various known radical polymerization initiators, if necessary. The chain transfer agent can be further added. The temperature and time of the polymerization reaction are not particularly limited, and examples thereof include a reaction temperature of 20 to 140 ° C. and a reaction time of 2 to 12 hours.
　ラジカル重合開始剤としては、例えば、ベンゾイルパーオキサイド、ジクミルパーオキサイド、ラウリルパーオキサイド等の有機過酸化物；過酸化水素、過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウム等の無機過酸化物；２，２’－アゾビスイソブチロニトリル、ジメチル－２，２’－アゾビスイソブチレイト等のアゾ系化合物などを挙げることができ、これらは１種を単独で使用してもよいが、２種以上を組み合わせて使用してもよい。連鎖移動剤としては、例えば、エチルアルコール、メチルアルコール、イソプロピルアルコール等を挙げることができる。 Examples of the radical polymerization initiator include organic peroxides such as benzoyl peroxide, dicumyl peroxide, and lauryl peroxide; inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate; 2 , 2′-azobisisobutyronitrile, azo compounds such as dimethyl-2,2′-azobisisobutyrate, and the like. These may be used alone, You may use combining a seed | species or more. Examples of the chain transfer agent include ethyl alcohol, methyl alcohol, isopropyl alcohol and the like.
　（ａ）成分は、アクリルアミド及び／又はメタクリルアミドである。 (A) The component is acrylamide and / or methacrylamide.
　（ｂ）成分としては、上記カチオン性基を有するビニルモノマーであれば特に制限されるものではないが、例えば、アリルアミン、アミノエチル（メタ）アクリレート若しくは４－アミノスチレン又はその塩［例えば、塩酸塩、硫酸塩、ギ酸塩、酢酸塩等］；Ｎ－アルキルアリルアミン［例えば、Ｎ－メチルアリルアミン、Ｎ－エチルアリルアミン等］、Ｎ－アルキルアミノアルキル（メタ）アクリルアミド［例えば、Ｎ－メチルアミノエチル(メタ)アクリルアミド、Ｎ－エチルアミノエチル(メタ)アクリルアミド等］若しくはジアリルアミン又はその塩［例えば、塩酸塩、硫酸塩、ギ酸塩、酢酸塩等］；Ｎ，Ｎ－ジアルキルアミノアルキル（メタ）アクリレート［例えば、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノプロピル（メタ）アクリレート等］、若しくはＮ，Ｎ－ジアルキルアミノアルキル（メタ）アクリルアミド［例えば、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチルアミノプロピル（メタ）アクリルアミド等］又はその塩［例えば、塩酸塩、硫酸塩、ギ酸塩、酢酸塩等］；Ｎ，Ｎ－ジアルキル（メタ）アクリルアミド［例えば、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド等］、上記Ｎ，Ｎ－ジアルキルアミノアルキル（メタ）アクリレート又は上記Ｎ，Ｎ－ジアルキルアミノアルキル（メタ）アクリルアミドと、四級化剤との反応によって得られる第４級アンモニウム塩を含有するモノマー；等を挙げることができ、これらは１種を単独で使用してもよいが、２種以上を組み合わせて使用してもよい。なお、上記四級化剤としては、例えば、メチルクロライド、メチルブロマイド等のアルキルハライド；ベンジルクロライド、ベンジルブロマイド等のアラルキルハライド；ジメチル硫酸；エピクロルヒドリン；３－クロロ－２－ヒドロキシプロピルトリメチルアンモニウムクロライド；グリシジルトリアルキルアンモニウムクロライド等を用いることができる。 The component (b) is not particularly limited as long as it is a vinyl monomer having the above cationic group. For example, allylamine, aminoethyl (meth) acrylate, 4-aminostyrene or a salt thereof [for example, hydrochloride Sulfate, formate, acetate, etc.]; N-alkylallylamine [eg, N-methylallylamine, N-ethylallylamine, etc.], N-alkylaminoalkyl (meth) acrylamide [eg, N-methylaminoethyl (meth) ) Acrylamide, N-ethylaminoethyl (meth) acrylamide, etc.] or diallylamine or a salt thereof [eg, hydrochloride, sulfate, formate, acetate, etc.]; N, N-dialkylaminoalkyl (meth) acrylate [eg, N, N-dimethylaminoethyl (meth) acrylate, N, N-di Ethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, etc.], or N, N-dialkylaminoalkyl (meth) acrylamide [for example, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, etc.] or a salt thereof [eg, hydrochloride, sulfate, formate, acetate, etc.]; N, N-dialkyl (meth) Acrylamide [eg, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, etc.], the above N, N-dialkylaminoalkyl (meth) acrylate or the above N, N-dialkylaminoalkyl (meth) By reaction of acrylamide with quaternizing agent Quaternary ammonium salt monomer containing which is; there may be mentioned, and these may be used alone or may be used in combination of two or more thereof. Examples of the quaternizing agent include alkyl halides such as methyl chloride and methyl bromide; aralkyl halides such as benzyl chloride and benzyl bromide; dimethyl sulfate; epichlorohydrin; 3-chloro-2-hydroxypropyltrimethylammonium chloride; glycidyl. Trialkylammonium chloride and the like can be used.
　（ｃ）成分としては、上記アニオン性基を有するビニルモノマーであれば特に制限されるものではないが、例えば、（メタ）アクリル酸、クロトン酸、２－アクリルアミド－２－メチルプロパンカルボン酸、マレイン酸、フマル酸、イタコン酸、ムコン酸、シトラコン酸等のカルボキシル基含有ビニルモノマー；ビニルアルコール、アリルアルコール、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート等のヒドロキシル基含有ビニルモノマー；アシッドホスホオキシエチルメタクリレート、３－クロロ－２－アシッドホスホオキシプロピルメタクリレート等のリン酸基含有ビニルモノマー；ビニルスルホン酸、スチレンスルホン酸、（メタ）アリルスルホン酸、２－アクリルアミド－２－メチルプロパンスルホン酸等のスルホ基含有ビニルモノマー；又はこれらの各種モノマーの塩（例えば、ナトリウム塩、カリウム塩、アンモニウム塩等）；等を挙げることができ、これらは１種を単独で使用してもよいが、２種以上を組み合わせて使用してもよい。 The component (c) is not particularly limited as long as it is a vinyl monomer having the above anionic group. For example, (meth) acrylic acid, crotonic acid, 2-acrylamido-2-methylpropanecarboxylic acid, malein Carboxyl group-containing vinyl monomers such as acid, fumaric acid, itaconic acid, muconic acid, citraconic acid; vinyl alcohol, allyl alcohol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl ( Hydroxyl group-containing vinyl monomers such as meth) acrylate and hydroxypropyl (meth) acrylate; phosphate group-containing vinyl monomers such as acid phosphooxyethyl methacrylate and 3-chloro-2-acid phosphooxypropyl methacrylate; Sulfo group-containing vinyl monomers such as acid, styrene sulfonic acid, (meth) allyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid; or salts of these various monomers (for example, sodium salt, potassium salt, ammonium salt) Etc.), etc., and these may be used alone or in combination of two or more.
　（ｄ）成分としては、公知のものを用いることができる。（ｄ）成分としては、例えば、アクリロニトリル、酢酸ビニル、プロピオン酸ビニル、スチレン、α－メチルスチレン、ビニルトルエン、α－オレフィン等の疎水性モノマー；炭素数１～４のアルキル基を有するイタコン酸ジアルキルエステル等のイタコン酸ジエステル；アリル基を有するビニルモノマー；ポリアルキレングリコール基を有するモノマー；ダイアセトンアクリルアミド等のＮ－置換アミド基を有するビニルモノマー；架橋性モノマー；等を挙げることができ、これらは１種を単独で使用してもよいが、２種以上を組み合わせて使用してもよい。 (D) A well-known thing can be used as a component. Examples of the component (d) include hydrophobic monomers such as acrylonitrile, vinyl acetate, vinyl propionate, styrene, α-methylstyrene, vinyltoluene, α-olefin; dialkyl itaconate having an alkyl group having 1 to 4 carbon atoms. Itaconic acid diesters such as esters; vinyl monomers having an allyl group; monomers having a polyalkylene glycol group; vinyl monomers having an N-substituted amide group such as diacetone acrylamide; crosslinkable monomers; One kind may be used alone, or two or more kinds may be used in combination.
　アリル基を有するビニルモノマーとしては、アリル（メタ）アクリレート、Ｎ－アリル（メタ）アクリルアミド、Ｎ，Ｎ－ジアリル（メタ）アクリルアミド等を挙げることができる。 Examples of the vinyl monomer having an allyl group include allyl (meth) acrylate, N-allyl (meth) acrylamide, N, N-diallyl (meth) acrylamide and the like.
　ポリアルキレングリコール基を有するモノマーとしては、分子中に少なくとも２個のオキシアルキレン基の繰り返し単位を有するものであれば特に制限されるものではなく、例えば、２個以上１０個以下の繰り返し単位を有するものを挙げることができる。具体的には、ポリエチレングリコールモノ（メタ）アクリレート［例えば、ジエチレングリコールモノ（メタ）アクリレート、トリエチレングリコールモノ（メタ）アクリレート、テトラエチレングリコールモノ（メタ）アクリレート等］、ポリプロピレングリコールモノ（メタ）アクリレート［例えば、ジプロピレングリコールモノ（メタ）アクリレート、トリプロピレングリコールモノ（メタ）アクリレート、テトラプロピレングリコールモノ（メタ）アクリレート等］、メトキシポリエチレングリコールモノ（メタ）アクリレート、ポリトリメチレングリコールモノ（メタ）アクリレート、ポリテトラメチレングリコールモノ（メタ）アクリレート、ポリエチレングリコールプロピレングリコールモノ（メタ）アクリレート等を挙げることができる。 The monomer having a polyalkylene glycol group is not particularly limited as long as it has at least two repeating units of oxyalkylene group in the molecule. For example, it has 2 to 10 repeating units. Things can be mentioned. Specifically, polyethylene glycol mono (meth) acrylate [eg, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, etc.], polypropylene glycol mono (meth) acrylate [ For example, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, etc.], methoxypolyethylene glycol mono (meth) acrylate, polytrimethylene glycol mono (meth) acrylate, Polytetramethylene glycol mono (meth) acrylate, polyethylene glycol propylene glycol mono (meth) acrylate, etc. Door can be.
　架橋性モノマーとしては、例えば、ビニル基を少なくとも２つ有するモノマーであれば特に限定されず、公知のものを用いることができる。例えば、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ヘキサエチレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ジシクロペンタニルジ（メタ）アクリレート等のジ（メタ）アクリレート類；メチレンビス（メタ）アクリルアミド、エチレンビス（メタ）アクリルアミド、ヘキサメチレンビス（メタ）アクリルアミド等のビス（メタ）アクリルアミド類；アジピン酸ジビニル、セバシン酸ジビニル等のジビニルエステル類；エポキシアクリレート類；ウレタンアクリレート類；Ｎ－メチロールアクリルアミド、ジアリルアミン、ジアリルジメチルアンモニウム、ジアリルフタレート、ジアリルクロレンデート、ジビニルベンゼン等の２官能性モノマー；１，３，５－トリアクリロイルヘキサヒドロ－１，３，５－トリアジン、トリアリルイソシアヌレート、トリアリルアミン、トリアリルトリメリテート、Ｎ，Ｎ－ジアリルアクリルアミド等の３官能性モノマー；テトラメチロールメタンテトラアクリレート、テトラアリルピロメリテート、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラアリル－１，４－ジアミノブタン、テトラアリルアミン塩、テトラアリルオキシエタン等の４官能性モノマー等を挙げることができ、これらは１種を単独で使用してもよいが、２種以上を組み合わせて使用してもよい。 The crosslinkable monomer is not particularly limited as long as it is a monomer having at least two vinyl groups, and known monomers can be used. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di Di (meth) acrylates such as (meth) acrylate, hexaethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate; methylene bis (meth) acrylamide, ethylene bis ( Bis (meth) acrylamides such as meth) acrylamide and hexamethylenebis (meth) acrylamide; Divinyl esters such as divinyl adipate and divinyl sebacate; Epoxy acrylate Urethane acrylates; bifunctional monomers such as N-methylolacrylamide, diallylamine, diallyldimethylammonium, diallylphthalate, diallylchlorendate, divinylbenzene; 1,3,5-triacryloylhexahydro-1,3,5 -Trifunctional monomers such as triazine, triallyl isocyanurate, triallylamine, triallyl trimellitate, N, N-diallylacrylamide; tetramethylolmethane tetraacrylate, tetraallyl pyromellitate, N, N, N ', N Examples include tetrafunctional monomers such as' -tetraallyl-1,4-diaminobutane, tetraallylamine salts, tetraallyloxyethane, and the like. These may be used alone, but two or more may be used. Can be used in combination .
　なお、本発明において用いられる両性ポリ（メタ）アクリルアミドとしては、例えば、ハリマ化成グループ株式会社製の、ハーマイドＥＸ－２００シリーズ、ハーマイドＥＸ－３００シリーズ、ハーマイドＥＸ－４００シリーズ、ハーマイドＲＢ－２００シリーズ、ハーマイドＲＢ－３００シリーズ、ハーマイドＲＢ－４００シリーズ等；荒川化学工業株式会社製の、ポリストロン３７２、ポリストロン３７９、ポリストロン３８７－２０、ポリストロン５０３、ポリストロン５０４、ポリストロン１２２２、ポリストロン１２２８、ポリストロン１２５４、ポリストロン１２５７、ポリストロン１２５９、ポリストロン１２６７、ポリストロン１２８０、ポリストロン１４０７、ポリストロン１４１３、ポリストロン１８１０、ポリテンション１０００、ポリテンション１００１等；の既知のものを用いてもよい。 Examples of amphoteric poly (meth) acrylamides used in the present invention include, for example, Hermide EX-200 series, Hermide EX-300 series, Hermide EX-400 series, Hermide RB-200 series, manufactured by Harima Chemical Group Co., Ltd. Hermide RB-300 series, Hermide RB-400 series, etc .; manufactured by Arakawa Chemical Industries, Ltd. Polystron 372, Polystron 379, Polystron 387-20, Polystron 503, Polystron 504, Polystron 1222, Polystron 1228 , Polystron 1254, Polystron 1257, Polystron 1259, Polystron 1267, Polystron 1280, Polystron 1407, Polystron 1413, Polystron 1810, Polyten ® down 1000, poly tension 1001, and the like; may be used as known.
　本発明において用いられる両性ポリ（メタ）アクリルアミドの重量平均分子量は、特に限定されないが、例えば、１０～２０００万である。尚、本明細書に記載されている重量平均分子量は、ゲルパーメーションクロマトグラフィー（ＧＰＣ）法によるポリエチレンオキサイド換算値で得られた重量平均分子量から測定した値である。 The weight average molecular weight of the amphoteric poly (meth) acrylamide used in the present invention is not particularly limited, but is, for example, from 10 to 20 million. In addition, the weight average molecular weight described in this specification is a value measured from the weight average molecular weight obtained by the polyethylene oxide conversion value by the gel permeation chromatography (GPC) method.
（アルデヒド基を少なくとも２個有する化合物）
　アルデヒド基を少なくとも２個有する化合物としては、グリオキザール、琥珀酸ジアルデヒド、ジアルデヒド澱粉等を挙げることができるが、これらに限定されるものではない。なお、アルデヒド基を少なくとも２個有する上記化合物は、１種を単独で使用してもよいが、２種以上を組み合わせて使用してもよい。 (Compound having at least two aldehyde groups)
Examples of compounds having at least two aldehyde groups include, but are not limited to, glyoxal, oxalic acid dialdehyde, and dialdehyde starch. In addition, the said compound which has at least 2 aldehyde groups may be used individually by 1 type, but may be used in combination of 2 or more type.
（成分比率）
　本発明の表面処理剤における、両性ポリ（メタ）アクリルアミド（Ａ）と、アルデヒド基を少なくとも２個有する化合物（Ｂ）の配合比率［Ａ／Ｂ］は、好ましくは固形分質量割合で０．１超３．０未満であり、より好ましくは０．１５以上２．５以下であり、特に好ましくは０．２以上１．０以下である。 (Ingredient ratio)
The blending ratio [A / B] of the amphoteric poly (meth) acrylamide (A) and the compound (B) having at least two aldehyde groups in the surface treatment agent of the present invention is preferably 0.1 in terms of solid content mass ratio. It is more than less than 3.0, more preferably from 0.15 to 2.5, and particularly preferably from 0.2 to 1.0.
（他の成分）
　上述においては、溶媒以外に、両性ポリ（メタ）アクリルアミドと、アルデヒド基を少なくとも２個有する化合物とのみからなる表面処理剤について説明したが、本発明の表面処理剤は、必要に応じて、本発明の趣旨及び皮膜性能を損なわない範囲で、両性ポリ（メタ）アクリルアミド以外の樹脂、界面活性剤、有機酸、金属化合物、珪酸化合物、表面処理剤用添加剤等をさらに含んでいてもよい。 (Other ingredients)
In the above description, the surface treatment agent comprising only amphoteric poly (meth) acrylamide and a compound having at least two aldehyde groups in addition to the solvent has been described. However, the surface treatment agent of the present invention can be used as needed. As long as the gist of the invention and the film performance are not impaired, a resin other than amphoteric poly (meth) acrylamide, a surfactant, an organic acid, a metal compound, a silicic acid compound, an additive for a surface treatment agent, and the like may further be included.
　上記樹脂は、両性ポリ（メタ）アクリルアミド以外であれば、カチオン性、アニオン性、両性、ノニオン性等のいずれの樹脂であってもよい。樹脂としては、例えば、ウレタン系樹脂、エポキシ系樹脂、（メタ）アクリル系樹脂、（メタ）アクリルアミド系樹脂、フェノール系樹脂、ポリエステル系樹脂、ポリビニル系樹脂、ポリオレフィン系樹脂、ポリイミド系樹脂、スルホン酸系樹脂、天然高分子（セルロース、澱粉、ゼラチン等）等の公知のものを挙げることができ、それらは重合体であっても共重合体であってもよい。これらの樹脂は、１種を単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 The resin may be any resin such as cationic, anionic, amphoteric, and nonionic other than amphoteric poly (meth) acrylamide. Examples of the resin include urethane resin, epoxy resin, (meth) acrylic resin, (meth) acrylamide resin, phenol resin, polyester resin, polyvinyl resin, polyolefin resin, polyimide resin, sulfonic acid Examples thereof include known resins such as a series resin and natural polymers (cellulose, starch, gelatin, etc.), which may be a polymer or a copolymer. These resin may be used individually by 1 type, and may be used in combination of 2 or more type.
　界面活性剤としては、カチオン性、アニオン性、両性、ノニオン性等の界面活性剤を用いることができ、例えば、アルキルアミン塩、アルキルトリメチルアンモニウムハライド等のカチオン性界面活性剤；アルキルスルホン酸エステル、ポリオキシエチレンアルキルフェニルエーテル硫酸塩、ドデシルジフェニルエーテルジスルホン酸ナトリウム、ドデシル硫酸ナトリウム等のアニオン性界面活性剤；アルキルアミノプロピオン酸塩、アルキルジメチルベタイン等の両性界面活性剤；ポリオキシエチレンアルキルフェニルエーテル、ポリオキシアルキレン脂肪酸エステル、脂肪酸グリセリンエステル、ソルビタン脂肪酸エステル、ポリオキシエチレングリセリン脂肪酸、ポリオキシエチレンプロピレングリコール脂肪酸エステル等のノニオン性界面活性剤；等を挙げることができ、これらは、１種を単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 As the surfactant, surfactants such as cationic, anionic, amphoteric, and nonionic can be used. For example, cationic surfactants such as alkylamine salts and alkyltrimethylammonium halides; alkylsulfonic acid esters, Anionic surfactants such as polyoxyethylene alkylphenyl ether sulfate, sodium dodecyl diphenyl ether disulfonate and sodium dodecyl sulfate; amphoteric surfactants such as alkylaminopropionate and alkyldimethylbetaine; polyoxyethylene alkylphenyl ether, poly Nonio such as oxyalkylene fatty acid ester, fatty acid glycerin ester, sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid, polyoxyethylene propylene glycol fatty acid ester Sex surfactant; can be exemplified, and these may be used alone or may be used in combination of two or more thereof.
　有機酸としては、例えば、シュウ酸、マロン酸、マレイン酸、フマル酸、コハク酸、リンゴ酸、クエン酸、グルタミン酸、アスパラギン酸、酒石酸、フタル酸、イタコン酸、メリト酸、トリメリト酸、トリメシン酸、ピロメリト酸、ナフタレンテトラカルボン酸、プロパンジカルボン酸、ブタンジカルボン酸、ペンタンジカルボン酸、ヘキサンジカルボン酸、ヘプタンジカルボン酸、ブタントリカルボン酸、ブタンテトラカルボン酸（例えば、１，２，３，４－ブタンテトラカルボン酸）、シクロヘキサンテトラカルボン酸、ヘキサントリカルボン酸、１－ヒドロキシエチリデン－１，１－ジホスホン酸、２－ホスホノブタン－１，２，４－トリカルボン酸、ニトリロトリスメチレンホスホン酸、若しくはエチレンジアミンテトラ（メチレンホスホン酸）、又はこれらの化合物の塩等を挙げることができるが、これらに限定されるものではない。上記化合物の塩を形成するカチオン性対イオンとしては、例えば、アルカリ金属（ナトリウム、カリウム、リチウム等）イオン、アルカリ土類金属（マグネシウム、カルシウム、バリウム等）イオン等の金属イオン、アンモニウムイオン等を挙げることができる。これらの有機酸は、１種を単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 Examples of organic acids include oxalic acid, malonic acid, maleic acid, fumaric acid, succinic acid, malic acid, citric acid, glutamic acid, aspartic acid, tartaric acid, phthalic acid, itaconic acid, melittic acid, trimellitic acid, trimesic acid, Pyromellitic acid, naphthalenetetracarboxylic acid, propanedicarboxylic acid, butanedicarboxylic acid, pentanedicarboxylic acid, hexanedicarboxylic acid, heptanedicarboxylic acid, butanetricarboxylic acid, butanetetracarboxylic acid (for example, 1,2,3,4-butanetetracarboxylic acid) Acid), cyclohexanetetracarboxylic acid, hexanetricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, nitrilotrismethylenephosphonic acid, or ethylenediaminetetra (methyle) Phosphonic acid), or there may be mentioned salts of these compounds, but is not limited thereto. Examples of the cationic counter ion that forms the salt of the above compound include metal ions such as alkali metal (sodium, potassium, lithium, etc.) ions, alkaline earth metal (magnesium, calcium, barium, etc.) ions, ammonium ions, and the like. Can be mentioned. These organic acids may be used individually by 1 type, and may be used in combination of 2 or more type.
　金属化合物としては、例えば、ジルコニウム化合物（例えば、ヘキサフルオロジルコニウム酸、炭酸ジルコニウムアンモニウム、酢酸ジルコニル、硫酸ジルコニル、硝酸ジルコニル等）、チタン化合物（例えば、ヘキサフルオロチタン酸、酸化チタン等）、セリウム化合物（例えば、酸化セリウム、炭酸セリウム、フッ化セリウム等）、バナジウム化合物（例えば、メタバナジン酸塩、硫酸バナジル、バナジウムアセチルアセトネート等）、クロム化合物（例えば、硫酸クロム（III）、フッ化クロム（III）等）等を挙げることができるが、これらに制限されるものではない。なお、これらの金属化合物は、１種を単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 Examples of the metal compound include a zirconium compound (eg, hexafluorozirconic acid, ammonium zirconium carbonate, zirconyl acetate, zirconyl sulfate, zirconyl nitrate, etc.), a titanium compound (eg, hexafluorotitanic acid, titanium oxide, etc.), a cerium compound ( For example, cerium oxide, cerium carbonate, cerium fluoride, etc.), vanadium compounds (eg, metavanadate, vanadyl sulfate, vanadium acetylacetonate, etc.), chromium compounds (eg, chromium (III) sulfate, chromium (III) fluoride) Etc.), but is not limited thereto. In addition, these metal compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
　珪酸化合物としては、例えば、珪酸ナトリウム、珪酸カリウム、珪酸リチウム等の珪酸アルカリ金属塩；高分子シリカ；コロイダルシリカ、鎖状シリカ、ペンダント状シリカ、板状シリカ、中空シリカ等の水分散性シリカ；等を挙げることができるが、これらに制限されるものではない。なお、これらの珪酸化合物は、１種を単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 Examples of silicic acid compounds include alkali metal silicates such as sodium silicate, potassium silicate, and lithium silicate; polymer silica; water-dispersible silica such as colloidal silica, chain silica, pendant silica, plate silica, and hollow silica; However, it is not limited to these. In addition, these silicic acid compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
　表面処理剤用添加剤としては、例えば、公知の添加剤である、消泡剤、レベリング剤、安定化剤、防錆剤、抗菌剤、抗かび剤、濡れ剤、増粘剤、着色剤等を挙げることができ、これらのうち１種又は２種以上を用いることができる。 Examples of additives for surface treatment agents include known additives such as antifoaming agents, leveling agents, stabilizers, rust inhibitors, antibacterial agents, antifungal agents, wetting agents, thickeners, colorants, and the like. Of these, one or more of them can be used.
（液性）
　本発明に係る表面処理剤のｐＨは、好適には２以上又は超１２以下又は未満、より好適には２．５以上又は超１０以下又は未満、特に好適には２．５以上又は超６．０以下又は未満である。表面処理剤が当該ｐＨ範囲であると、当該表面処理剤は、本発明のより高い効果及びより優れた液安定性を有する。ここで、本明細書におけるｐＨは、２５℃の剤について、市販のｐＨメーターを用いて得られた値である。 (liquid)
The pH of the surface treatment agent according to the present invention is preferably 2 or more or more than 12 or less, more preferably 2.5 or more or more than 10 or less, particularly preferably 2.5 or more or more than 6. 0 or less. When the surface treatment agent is in the pH range, the surface treatment agent has the higher effect of the present invention and better liquid stability. Here, pH in this specification is a value obtained using a commercially available pH meter for the agent at 25 ° C.
（表面処理剤の製造）
　本発明の表面処理剤は、溶媒に、両性ポリ（メタ）アクリルアミドと、アルデヒド基を少なくとも２個有する化合物と、必要に応じて上記他の成分とを混合することにより製造することができる。 (Manufacture of surface treatment agents)
The surface treating agent of the present invention can be produced by mixing amphoteric poly (meth) acrylamide, a compound having at least two aldehyde groups, and, if necessary, the above-mentioned other components in a solvent.
　溶媒としては、特に限定されないが、水性溶媒が好ましい。水性溶媒とは、全溶媒の質量を基準とした際、水を５０質量％以上含有するものを意味する。尚、「溶媒」は、すべての成分を溶解するという狭義の溶媒を意味するものではなく、一部の成分については分散状態でもよい分散媒をも含む概念である。水性溶媒に含まれる水以外の溶媒としては、例えば、ヘキサン、ペンタン等のアルカン系溶媒；ベンゼン、トルエン等の芳香族系溶媒；エタノール、１－ブタノール、エチルセロソルブ等のアルコール系溶媒；テトラヒドロフラン、ジオキサン等のエーテル系溶媒；酢酸エチル、酢酸ブトキシエチル等のエステル系溶媒；ジメチルホルムアミド、Ｎ－メチルピロリドン等のアミド系溶媒；ジメチルスルホキシド等のスルホン系溶媒；ヘキサメチルリン酸トリアミド等のリン酸アミド系溶媒；等を挙げることができる。これらの水以外の溶媒は、１種を混合してもよいが、２種以上を組み合わせて混合してもよい。なお、環境上及び経済上の観点から、水のみを用いることが好ましい。 The solvent is not particularly limited, but an aqueous solvent is preferable. The aqueous solvent means a solvent containing 50% by mass or more of water based on the mass of all the solvents. The “solvent” does not mean a narrowly-defined solvent that dissolves all components, but a concept that includes a dispersion medium that may be in a dispersed state for some components. Examples of the solvent other than water contained in the aqueous solvent include alkane solvents such as hexane and pentane; aromatic solvents such as benzene and toluene; alcohol solvents such as ethanol, 1-butanol and ethyl cellosolve; tetrahydrofuran, dioxane Ether solvents such as ethyl acetate, butoxyethyl acetate, etc .; amide solvents such as dimethylformamide and N-methylpyrrolidone; sulfone solvents such as dimethyl sulfoxide; phosphate amides such as hexamethylphosphate triamide Solvent; and the like. These solvents other than water may be mixed alone or in combination of two or more. In addition, it is preferable to use only water from an environmental and economic viewpoint.
（皮膜の製造方法）
　本発明の表面処理剤によって形成される皮膜は、親水性皮膜である。その皮膜の製造方法は、本発明の表面処理剤を、例えば、金属材料の表面に接触させる接触工程と、接触工程後に、前記表面、すなわち、表面処理剤を接触させた表面を、焼き付ける焼付工程とを有する。なお、上記接触工程の前に、金属材料の表面に対して、脱脂、酸洗浄、アルカリ洗浄等の前処理工程を行ってもよい。また、前処理工程と接触工程との間に、化成皮膜を形成する化成皮膜形成工程、又は有機被覆処理を行ってもよい。また、上記焼付工程の後に潤滑性を有する潤滑皮膜処理を行ってもよい。さらに、上記接触工程と焼付工程との間に、表面処理剤を接触させた金属材料の表面を水洗する水洗工程を行ってもよい。 (Method for producing film)
The film formed by the surface treatment agent of the present invention is a hydrophilic film. The method for producing the coating includes a contact step in which the surface treatment agent of the present invention is brought into contact with, for example, the surface of a metal material, and a baking step in which the surface, that is, the surface in contact with the surface treatment agent is baked after the contact step. And have. In addition, you may perform pre-processing processes, such as a degreasing | defatting, an acid cleaning, and an alkali cleaning, with respect to the surface of a metal material before the said contact process. Moreover, you may perform the chemical conversion film formation process which forms a chemical conversion film, or an organic coating process between a pre-processing process and a contact process. Moreover, you may perform the lubricating film process which has lubricity after the said baking process. Furthermore, you may perform the water washing process of washing the surface of the metal material which contacted the surface treating agent between the said contact process and the baking process.
（接触工程）
　上記接触工程は、従来の接触方法、例えば、スプレーコート法、ディップコート法、ロールコート法、カーテンコート法、スピンコート法、又はこれらの組み合わせ等の方法によって行うことができるが、これらに限定されるものではない。 (Contact process)
The contact step can be performed by a conventional contact method such as a spray coating method, a dip coating method, a roll coating method, a curtain coating method, a spin coating method, or a combination thereof, but is not limited thereto. It is not something.
　この接触工程では、表面処理剤の使用条件は特に限定されない。例えば、表面処理剤を接触する際の該表面処理剤および金属材料の温度は、５℃以上５０℃以下であることが好ましく、２０℃以上４０℃以下であることがより好ましいが、これらの温度に制限されるものではない。なお、接触時間は適宜設定することができるが、通常、２秒以上１８０秒以内である。 In this contact step, the conditions for using the surface treatment agent are not particularly limited. For example, the temperature of the surface treatment agent and the metal material when contacting the surface treatment agent is preferably 5 ° C. or more and 50 ° C. or less, and more preferably 20 ° C. or more and 40 ° C. or less. It is not limited to. The contact time can be appropriately set, but is usually 2 seconds or more and 180 seconds or less.
（焼付工程）
　焼付工程は、金属材料の最高到達温度（ＰＭＴ）が１５０℃以上２３０℃以下の範囲内の温度条件で行うことが好ましく、１７０℃以上２００℃以下の範囲内の温度条件で行うことがより好ましく、１８０℃以上１９０℃以下の範囲内の温度条件で行うことが特に好ましい。また、焼付時間は、特に制限されるものではないが、２秒以上３００秒以下の範囲内であることが好ましい。焼付方法は特に制限されず、例えば、電気熱風乾燥機、ガス熱風乾燥機等を用いた焼付乾燥方法等を挙げることができる。 (Baking process)
The baking step is preferably performed under a temperature condition in which the maximum reached temperature (PMT) of the metal material is in a range of 150 ° C. or higher and 230 ° C. or lower, more preferably in a temperature condition in a range of 170 ° C. or higher and 200 ° C. or lower. It is particularly preferable to carry out under a temperature condition within the range of 180 ° C. or higher and 190 ° C. or lower. The baking time is not particularly limited, but is preferably in the range of 2 seconds to 300 seconds. The baking method is not particularly limited, and examples thereof include a baking drying method using an electric hot air dryer, a gas hot air dryer, and the like.
（化成皮膜形成工程）
　上述のように、化成皮膜形成工程は、化成皮膜を形成させる工程である。化成皮膜を形成させる方法としては、例えば、リン酸塩化成処理方法、ジルコニウム化成処理方法、チタン化成処理方法、ハフニウム化成処理方法、バナジウム化成処理方法等の化成処理方法を挙げることができる。化成皮膜形成工程では、１つの化成処理方法を行ってもよいし、２つの化成処理方法を組み合わせて行ってもよい。 (Chemical conversion film formation process)
As described above, the chemical conversion film forming step is a step of forming a chemical conversion film. Examples of the method for forming the chemical conversion film include a chemical conversion treatment method such as a phosphate chemical conversion treatment method, a zirconium chemical conversion treatment method, a titanium chemical conversion treatment method, a hafnium chemical conversion treatment method, and a vanadium chemical conversion treatment method. In the chemical conversion film forming step, one chemical conversion treatment method may be performed, or two chemical conversion treatment methods may be combined.
　リン酸塩化成処理には、リン酸亜鉛化成処理剤、リン酸クロメート化成処理剤等の、公知のものを用いることができる。また、ジルコニウム化成処理には公知のジルコニウム化成処理剤を、チタン化成処理には公知のチタン化成処理剤を、ハフニウム化成処理には公知のハフニウム化成処理剤を、バナジウム化成処理には公知のバナジウム化成処理剤を、それぞれ用いることができる。 For the phosphate chemical conversion treatment, known ones such as a zinc phosphate chemical conversion treatment agent and a phosphate chromate chemical conversion treatment agent can be used. In addition, a known zirconium chemical conversion treatment agent is used for zirconium chemical conversion treatment, a known titanium chemical conversion treatment agent for titanium chemical conversion treatment, a known hafnium chemical conversion treatment agent for hafnium chemical conversion treatment, and a known vanadium chemical conversion treatment for vanadium chemical conversion treatment. Each treatment agent can be used.
（金属材料）
　表面処理剤を適用する金属材料としては、例えば、純アルミニウム材、アルミニウム合金材（これらを「アルミニウム材料」ともいう。）；純銅材、銅合金材（これらを「銅材料」ともいう。）、合金鋼材等を挙げることができるが、これらに制限されるものではない。 (Metal material)
Examples of the metal material to which the surface treatment agent is applied include a pure aluminum material, an aluminum alloy material (these are also referred to as “aluminum materials”); a pure copper material, a copper alloy material (these are also referred to as “copper materials”), and the like. Although alloy steel materials etc. can be mentioned, it is not restrict | limited to these.
　金属材料の形状や構造等は特に限定されず、例えば、板状、箔状等を挙げることができる。更に、金属材料は、該金属材料とは異なる金属材料、セラミックス材料、有機材料等の基材上に、例えば、めっき、蒸着、クラッドなどの手法によって、上記の、銅材料、アルミニウム材料、合金鋼材等を被覆したものであってもよい。 The shape and structure of the metal material are not particularly limited, and examples thereof include a plate shape and a foil shape. Further, the metal material is formed on a base material such as a metal material, a ceramic material, or an organic material different from the metal material, for example, by the method such as plating, vapor deposition, or clad, as described above, copper material, aluminum material, alloy steel material. Etc. may be coated.
　銅合金材は、当該材の全質量を基準として、銅を５０質量％以上含有するものが好ましく、例えば、黄銅材等を挙げることができる。銅合金材における銅以外の合金成分としては、例えば、Ｚｎ、Ｐ、Ａｌ、Ｆｅ、Ｎｉ等を挙げることができる。アルミニウム合金材は、当該材の全質量を基準として、アルミニウムを５０質量％以上含有するものが好ましく、例えば、Ａｌ－Ｍｇ系合金材等を挙げることができる。アルミニウム合金材におけるアルミニウム以外の合金成分としては、例えば、Ｓｉ、Ｆｅ、Ｃｕ、Ｍｎ、Ｃｒ、Ｚｎ、Ｔｉ等を挙げることができる。合金鋼材は、当該材の全質量を基準として、鉄を５０質量％以上含有するものが好ましく、例えば、ステンレス鋼材等を挙げることができる。合金鋼材における鉄以外の合金成分としては、例えば、Ｃ、Ｓｉ、Ｍｎ、Ｐ、Ｓ、Ｎｉ、Ｃｒ、Ｍｏ等を挙げることができる。 The copper alloy material preferably contains 50% by mass or more of copper based on the total mass of the material, and examples thereof include a brass material. Examples of alloy components other than copper in the copper alloy material include Zn, P, Al, Fe, and Ni. The aluminum alloy material preferably contains 50% by mass or more of aluminum based on the total mass of the material, and examples thereof include an Al—Mg alloy material. Examples of alloy components other than aluminum in the aluminum alloy material include Si, Fe, Cu, Mn, Cr, Zn, and Ti. The alloy steel material preferably contains 50% by mass or more of iron on the basis of the total mass of the material, and examples thereof include a stainless steel material. Examples of alloy components other than iron in the alloy steel include C, Si, Mn, P, S, Ni, Cr, and Mo.
（皮膜付き金属材料）
　本発明に係る皮膜付き金属材料は、金属材料と、上記表面処理剤によって該金属材料の表面上に形成された上記親水性皮膜と、を有する。本発明に係る皮膜付き金属材料は、金属材料の表面と、親水性皮膜との間に、リン酸塩化成処理皮膜、ジルコニウム化成処理皮膜、チタン化成処理皮膜、ハフニウム化成処理皮膜、バナジウム化成処理皮膜等を有していてもよい。なお、親水性皮膜は、有機成分からなる有機皮膜であってもよいし、有機成分と無機成分とからなる有機無機皮膜であってもよい。また、親水性皮膜の付着量は、乾燥質量で０．０５ｇ／ｍ２以上又は超であることが好ましく、０．１ｇ／ｍ２以上又は超であることがより好ましく、０．２ｇ／ｍ２以上又は超であることが特に好ましいが、これらに限定されるものではない。尚、上限値については限定されるものではないが、コスト面から１．０ｇ／ｍ２以下であることが望ましい。 (Metal material with film)
The metal material with a film according to the present invention includes a metal material and the hydrophilic film formed on the surface of the metal material by the surface treatment agent. The metal material with a film according to the present invention includes a phosphate chemical conversion film, a zirconium chemical conversion film, a titanium chemical conversion film, a hafnium chemical conversion film, and a vanadium chemical conversion film between the surface of the metal material and the hydrophilic film. Etc. may be included. The hydrophilic film may be an organic film made of an organic component, or an organic inorganic film made of an organic component and an inorganic component. The coating weight of the hydrophilic coating is preferably dried mass at 0.05 g / m 2 or more, or an ultra, more preferably 0.1 g / m 2 or more, or an ultra, 0.2 g / m 2 Although it is especially preferable that it is more or more than this, it is not limited to these. In addition, although it does not limit about an upper limit, it is desirable that it is 1.0 g / m < 2 > or less from a cost surface.
　以下、実施例及び比較例により、本発明を更に詳しく説明する。なお、本発明は以下の実施例により限定されるものではない。尚、特に特記しない限り、％は「質量％」を意味する。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to the following examples. Unless otherwise specified, “%” means “mass%”.
＜表面処理剤の調製＞
　表１に示す質量割合で各成分を配合した後、攪拌混合して実施例１～１７及び比較例１～８の表面処理剤を調製した。なお、実施例１４～１７の表面処理剤については、希硫酸又はアンモニア水を用いてｐＨを調整した。また、ポリストロン３７２（両性ポリアクリルアミド；固形分１５．４％）、ポリストロン１２２８（両性ポリアクリルアミド；固形分２０．４％）、ポリストロン１２８０（両性ポリアクリルアミド；固形分２０．７％）及びポリストロン１４０７（両性ポリアクリルアミド；固形分２０．４％）は荒川化学工業株式会社製のものを、ハリコート１０５７（ノニオン性ポリアクリルアミド；固形分２０．３％）、ハリフィックスＵＦ－５７０（カチオン性ポリアクリルアミド；固形分１２．７％）、ハーマイドＣ－１０（アニオン性ポリアクリルアミド；固形分１０．３％）はハリマ化成グループ株式会社製のものを、グリオキザール（固形分４０％）はＡｍｚｏｌｅ　Ｉｎｄｉａ　ｐｖｔ．Ｌｔｄ．製のものを、それぞれ使用した。尚、ニトリロトリスメチレンホスホン酸の固形分は５０．０％である。 <Preparation of surface treatment agent>
After blending each component at a mass ratio shown in Table 1, stirring and mixing were performed to prepare surface treatment agents of Examples 1 to 17 and Comparative Examples 1 to 8. For the surface treatment agents of Examples 14 to 17, the pH was adjusted using dilute sulfuric acid or aqueous ammonia. Polystron 372 (amphoteric polyacrylamide; solid content 15.4%), Polystron 1228 (amphoteric polyacrylamide; solid content 20.4%), Polystron 1280 (amphoteric polyacrylamide; solid content 20.7%) and Polystron 1407 (amphoteric polyacrylamide; solid content 20.4%) manufactured by Arakawa Chemical Industries, Ltd., Haricoat 1057 (nonionic polyacrylamide; solid content 20.3%), Haliffix UF-570 (cationic) Polyacrylamide (solid content: 12.7%) and Hermide C-10 (anionic polyacrylamide; solid content: 10.3%) are those manufactured by Harima Kasei Group. Glyoxal (solid content: 40%) is Amzole India pvt. . Ltd .. Each of the products made was used. The solid content of nitrilotrismethylenephosphonic acid is 50.0%.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
＜皮膜の製造＞
　金属材料（アルミニウム材：Ａ１０５０；厚さ０．８ｍｍ；株式会社パルテック製）に、脱脂剤（ファインクリーナー４３７７ＫＮの２０％水溶液；日本パーカライジング株式会社製）を５０℃で１０秒間スプレーすることにより脱脂を行った後、水洗して表面を清浄化した。続いて、リン酸クロメート化成処理液［アルクロムＫ７０２ＳＫＮ：２１ｇ／Ｌ及びアルクロムＫ７０２ＡＣＮ：４ｇ／Ｌ；いずれも日本パーカライジング株式会社製］に５０℃で１５秒間浸漬してリン酸クロメート化成処理を行い、金属材料の表面に化成皮膜を形成させた。 <Manufacture of film>
Degreasing is performed by spraying a degreasing agent (20% aqueous solution of fine cleaner 4377KN; manufactured by Nihon Parkerizing Co., Ltd.) at 50 ° C. for 10 seconds on a metal material (aluminum material: A1050; thickness 0.8 mm; manufactured by Partec Co., Ltd.). After the cleaning, the surface was cleaned by washing with water. Subsequently, the phosphoric acid chromate chemical conversion treatment [alchrome K702SKN: 21 g / L and Alchrome K702ACN: 4 g / L; both manufactured by Nihon Parkerizing Co., Ltd.] was performed at 50 ° C. for 15 seconds to perform the phosphoric acid chromate chemical conversion treatment. A chemical conversion film was formed on the surface of the material.
　化成皮膜を形成させた各金属材料、あるいは、上記脱脂と水洗を行い、化成皮膜を形成させていない金属材料の表面に、バーコーター(番線Ｎｏ．４；第一理化株式会社製)を用いて実施例１～１７及び比較例１～８の表面処理剤をそれぞれ塗布した後、自動排出オーブン(株式会社東上熱学社製、ＡＴＯ－１０１Ｈ型)を用いて１７０℃（ＰＭＴ）で１０秒間焼付けを行い、親水性皮膜を形成させた。 Using a bar coater (No. 4; manufactured by Daiichi Rika Co., Ltd.) on the surface of each metal material on which a chemical conversion film has been formed, or on the surface of a metal material that has been degreased and washed with water and has not been formed with a chemical conversion film After coating the surface treatment agents of Examples 1 to 17 and Comparative Examples 1 to 8, respectively, baking was performed at 170 ° C. (PMT) for 10 seconds using an automatic discharge oven (ATO-101H type, manufactured by Tojo Thermal Co., Ltd.). And a hydrophilic film was formed.
＜性能評価＞
　化成皮膜及び親水性皮膜を有する各金属材料に対して、水切れ性及び親水性を以下のように評価した。 <Performance evaluation>
With respect to each metal material having a chemical conversion film and a hydrophilic film, drainage and hydrophilicity were evaluated as follows.
（１）水切れ性
　化成皮膜及び親水性皮膜を有する各金属材料を１０ｃｍ×８ｃｍに切り出し、水道水に２０℃で５分間浸漬した。浸漬後、水面に対して垂直に金属材料を引き揚げ、その際に付着した水が９５％以上乾くまでの時間を測定し、以下の評価基準に従って水切れ性を評価した。その結果を表２に示す。
（評価基準）
◎：４０秒未満
○：４０秒以上６０秒未満
×：６０秒以上 (1) Drainability Each metal material having a chemical conversion film and a hydrophilic film was cut into 10 cm × 8 cm and immersed in tap water at 20 ° C. for 5 minutes. After immersion, the metal material was pulled up perpendicularly to the water surface, and the time until the water adhering to that time was 95% or more was measured. The results are shown in Table 2.
(Evaluation criteria)
◎: Less than 40 seconds ○: More than 40 seconds and less than 60 seconds ×: More than 60 seconds
（２）親水性
　化成皮膜及び親水性皮膜を有する各金属材料の表面に１μＬの純水を滴下し、水滴の接触角（対水接触角；初期）を協和界面科学株式会社製の接触角計「ＤＭ－３００」を用いて測定した。また、化成皮膜及び親水性皮膜を有する各金属材料の表面に水道水（１Ｌ／分の流水量）を１０分間流水させた後、８０℃で５分間乾燥させ、上記と同様に対水接触角（流水後）を測定した。測定後、以下の評価基準に従って親水性を評価した。それらの結果を表２に示す。
（評価基準）
◎：２０°未満
○：２０°以上４０°未満
×：４０°以上 (2) Hydrophilic 1 μL of pure water is dropped onto the surface of each metal material having a chemical conversion film and a hydrophilic film, and the contact angle of the water droplet (water contact angle; initial) is a contact angle meter manufactured by Kyowa Interface Science Co., Ltd. Measurement was performed using “DM-300”. Further, tap water (flowing water amount of 1 L / min) was allowed to flow on the surface of each metal material having a chemical conversion film and a hydrophilic film for 10 minutes, and then dried at 80 ° C. for 5 minutes. (After running water) was measured. After the measurement, the hydrophilicity was evaluated according to the following evaluation criteria. The results are shown in Table 2.
(Evaluation criteria)
◎: Less than 20 ° ○: 20 ° or more and less than 40 ° ×: 40 ° or more
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002

Claims (3)

  1. 　両性ポリ（メタ）アクリルアミドと、アルデヒド基を少なくとも２個有する化合物とを含有する表面処理剤。 A surface treatment agent containing amphoteric poly (meth) acrylamide and a compound having at least two aldehyde groups.
  2. 　請求項１に記載の表面処理剤を金属材料の表面に接触させる工程と、
    　前記表面処理剤を接触させた前記表面を焼き付ける工程と、
    を含む皮膜の製造方法。     Contacting the surface treatment agent according to claim 1 with the surface of the metal material;
    Baking the surface in contact with the surface treatment agent;
    The manufacturing method of the film | membrane containing this.
  3. 　請求項２に記載の皮膜の製造方法により形成された皮膜を有する皮膜付き金属材料。 A metal material with a film having a film formed by the method for producing a film according to claim 2.
PCT/JP2016/070195 2015-08-28 2016-07-07 Surface treatment agent, film production method, and film-equipped metal material WO2017038251A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201680045656.2A CN107922779A (en) 2015-08-28 2016-07-07 Surface conditioning agent, the manufacture method of overlay film and the metal material with overlay film
KR1020187003999A KR20180036984A (en) 2015-08-28 2016-07-07 Surface treatment agent, method for producing a film, and metal material with film

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-169478 2015-08-28
JP2015169478A JP2017043744A (en) 2015-08-28 2015-08-28 Surface treatment agent, manufacturing method of coated film and metal material with coated film

Publications (1)

Publication Number Publication Date
WO2017038251A1 true WO2017038251A1 (en) 2017-03-09

Family

ID=58187360

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/070195 WO2017038251A1 (en) 2015-08-28 2016-07-07 Surface treatment agent, film production method, and film-equipped metal material

Country Status (4)

Country Link
JP (1) JP2017043744A (en)
KR (1) KR20180036984A (en)
CN (1) CN107922779A (en)
WO (1) WO2017038251A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023282112A1 (en) * 2021-07-08 2023-01-12 株式会社Uacj Precoated fin material and manufacturing method therefor
WO2023282111A1 (en) * 2021-07-08 2023-01-12 株式会社Uacj Pre-coated fin material and manufacturing method therefor

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111560203B (en) * 2020-04-23 2022-02-15 乐凯胶片股份有限公司 Aluminum foil treatment fluid and application thereof
JP2022187419A (en) * 2021-06-07 2022-12-19 株式会社神戸製鋼所 Aluminum fin material and icing/frosting inhibitor

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63171684A (en) * 1986-12-29 1988-07-15 Nippon Parkerizing Co Ltd Method for imparting hydrophilicity of aluminum
JPH02219876A (en) * 1989-02-21 1990-09-03 Sumitomo Light Metal Ind Ltd Hydrophilic coating agent, aluminum or aluminum alloy sheet for fin and heat exchanger
JPH06300482A (en) * 1991-06-19 1994-10-28 Nippon Parkerizing Co Ltd Heat exchanger
JPH0977999A (en) * 1995-09-13 1997-03-25 Kobe Steel Ltd Hydrophilic-film-forming coating agent and heat exchanger member coated therewith

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63171684A (en) * 1986-12-29 1988-07-15 Nippon Parkerizing Co Ltd Method for imparting hydrophilicity of aluminum
JPH02219876A (en) * 1989-02-21 1990-09-03 Sumitomo Light Metal Ind Ltd Hydrophilic coating agent, aluminum or aluminum alloy sheet for fin and heat exchanger
JPH06300482A (en) * 1991-06-19 1994-10-28 Nippon Parkerizing Co Ltd Heat exchanger
JPH0977999A (en) * 1995-09-13 1997-03-25 Kobe Steel Ltd Hydrophilic-film-forming coating agent and heat exchanger member coated therewith

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023282112A1 (en) * 2021-07-08 2023-01-12 株式会社Uacj Precoated fin material and manufacturing method therefor
WO2023282111A1 (en) * 2021-07-08 2023-01-12 株式会社Uacj Pre-coated fin material and manufacturing method therefor

Also Published As

Publication number Publication date
CN107922779A (en) 2018-04-17
KR20180036984A (en) 2018-04-10
JP2017043744A (en) 2017-03-02

Similar Documents

Publication Publication Date Title
CN104884177B (en) Hydrophilic coating film method, aluminum fin material and the aluminum-made heat exchanger of aluminum fin material
WO2017038251A1 (en) Surface treatment agent, film production method, and film-equipped metal material
JP6618903B2 (en) Method for coating hydrophilic film on aluminum fin material, aluminum fin material and aluminum heat exchanger
JP5503556B2 (en) Hydrophilic treatment agent for aluminum-containing metal material, hydrophilic treatment method, and hydrophilized aluminum-containing metal material
JP2013540202A (en) Method for passivating metal surfaces
WO2000022188A1 (en) Hydrophilizing agent for metallic material, hydrophilizing fluid, method of hydrophilizing, metallic material, and heat exchanger
KR20180015155A (en) A hydrophilic treatment agent, a method for forming a hydrophilic film, and a hydrophilic film
JP4464076B2 (en) Crosslinkable fine particles, hydrophilic treatment agent, hydrophilic film coating method and hydrophilic film
US6987143B2 (en) Hydrophilizing agent, hydrophilizing fluid, and method of hydrophilizing
WO2018101355A1 (en) Heat exchanger and method for hydrophilizing heat exchanger
JP6230118B2 (en) Hydrophilic coating composition and aluminum fin material for heat exchange
CN113993637B (en) Hydrophilizing agent and method for forming hydrophilic coating film
JP5180145B2 (en) Crosslinkable fine particles, hydrophilic treatment agent, hydrophilic film coating method and hydrophilic film
TWI662152B (en) Water-based metal surface treatment agent, metal surface treatment method and surface-treated metal plate
JP2009179811A5 (en)
JP6233886B2 (en) Hydrophilic coating composition and aluminum fin material for heat exchanger
JP2021095475A (en) Antifreezing coated film material, coating method using the same, and application of the same
JP4467264B2 (en) Fin coating composition and fin material
JP6574973B1 (en) RESIN EMULSION FOR METAL SURFACE TREATMENT, METAL SURFACE TREATING AGENT, SURFACE TREATED METAL MATERIAL AND ITS MANUFACTURING METHOD, AND RESIN EMULSION MANUFACTURING METHOD
JPH05222334A (en) Agent, bath, and method for hydrophilic surface treatment

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16841283

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20187003999

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16841283

Country of ref document: EP

Kind code of ref document: A1