KR20180100216A - A surface treatment agent, a method for producing a surface treatment film, and a method for producing an aluminum material or an aluminum alloy material - Google Patents

Abstract

It has excellent adhesion to an aluminum material or the like and an upper layer coating without using one or more kinds of iron compounds such as oxides of iron, nickel or cobalt, their hydroxides or oxyhydroxides thereof, and has excellent corrosion resistance A non-chromate surface treatment agent capable of forming a surface treated film between an aluminum material and an upper layer film, a method of producing a surface treated film using the surface treatment agent, and a method of producing a surface treated film using an aluminum material or an aluminum alloy material .
The above problem can be solved by a surface treatment agent containing a water-soluble or water-dispersible organic polymer (A) having a carbonyl group and / or a hydroxyl group in a unit structure and an organic compound (B) having a phosphon group.

Description

A surface treatment agent, a method for producing a surface treatment film, and a method for producing an aluminum material or an aluminum alloy material

The present invention relates to a surface treatment agent for treating the surface of an aluminum material or an aluminum alloy material (hereinafter simply referred to as " aluminum material "), a method for producing a surface treatment film using the surface treatment agent, And so on.

Recently, from the viewpoint of preserving the global environment, aluminum materials having excellent lightweight and recyclability have been used in various products such as automobiles, motorcycles, bicycles, various household appliances, beverage cans and airplanes. Aluminum materials and the like used in these products are subjected to various surface treatments for the purpose of imparting corrosion resistance to the aluminum materials and the like and for improving the adhesion between the aluminum material and the upper layer coating films such as coating films and laminated films .

As a medicament to be used in the surface treatment, various surface treating agents not containing hexavalent chromium have been recently developed. For example, Patent Document 1 proposes an aqueous metal surface treatment agent containing one or more iron compounds selected from oxides of iron, nickel or cobalt, hydroxides thereof, and oxyhydroxides thereof.

Japanese Laid-Open Patent Publication No. 2014-80639

The present invention relates to a method of forming a surface-treated film having excellent adhesion to an aluminum material or the like and an upper layer coating film, which imparts excellent corrosion resistance to an aluminum material or the like, without using the iron family compound and the like, A method for producing a surface treated film using the surface treatment agent, and an aluminum material having the surface treated film, etc., for the purpose of providing a non-chromate (meaning that the non-chromate means not containing hexavalent chromium) .

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above problems, the present inventors have found that a water-soluble or water-dispersible organic polymer (A) having a carbonyl group and / or a hydroxyl group in a unit structure and an organic compound It has been found out that a surface treated film having excellent adhesiveness to a treating agent, an aluminum material and the like and an upper layer coating film and also giving excellent corrosion resistance to an aluminum material and the like can be formed between an aluminum material and the upper layer coating film and completes the present invention It came to the following.

That is,

(1) A surface treatment agent for treating the surface of an aluminum material or an aluminum alloy material, wherein a water-soluble or water-dispersible organic polymer (A) having a carbonyl group and / or a hydroxyl group in a unit structure and an organic compound (B) Of the metal compound (C) relative to the phosphorus mass (M _P ) in the organic compound (B) in the case of containing the metal compound (C) A surface treating agent having a ratio (M _M / M _P ) of metal mass (M _M ) of not more than 0.30 (provided that at least one of iron, nickel, cobalt or hexavalent chromium, Or more of the amine compound);

(2) The surface treatment agent according to (1), wherein the organic polymer (A) has a carboxyl group or a carboxylic acid ester group in the unit structure;

(3) The surface treatment agent according to the above (1) or (2), wherein the organic compound (B) has three or more carbons and two or more phosphone groups in one molecule.

(4) The surface treatment agent according to any one of (1) to (3), wherein the metal compound (C) contains at least one transition metal;

(5) The surface treatment agent according to any one of (1) to (3), wherein the metal compound (C) contains at least one transition metal selected from titanium, tungsten, manganese, zirconium and cerium;

(6) The surface treatment agent according to any one of (1) to (5), wherein the weight average molecular weight of the organic polymer (A) is in the range of 2,000 to 1,000,000.

(7) A method for producing a surface treated film, which comprises the step of bringing the surface treatment agent according to any one of (1) to (6) above into contact with the surface of an aluminum material or an aluminum alloy material;

(8) A process for producing a surface-treated film, which comprises obtaining a surface-treated film by contacting the surface of an aluminum material or an aluminum alloy material with the surface treatment agent described in any one of (1) to (6) Aluminum material or aluminum alloy material;

(9) A positive resist composition comprising a water-soluble or water-dispersible organic polymer (A) having a carbonyl group and / or a hydroxyl group in a unit structure and an organic compound (B) having a phosphon group, (M _M / M _P ) of the metal mass (M _M ) of the metal compound (C) to the phosphorus mass (M _P ) in the organic compound (B) (Excluding those containing iron, nickel, cobalt or hexavalent chromium, or a compound containing such a metal, or an amine compound containing three or more hydroxyl groups in one molecule), which is not more than 0.30, An aluminum material or an aluminum alloy material;

.

According to the present invention, it is possible to form a surface-treated film having excellent adhesion to an aluminum material or the like and an upper-layer film without using the iron family compound or the like and also giving excellent corrosion resistance to an aluminum material or the like, A method for producing a surface treated film using the surface treatment agent, an aluminum material having the surface treated film, and the like can be provided.

Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the following embodiments.

(Surface treatment agent)

The surface treatment agent of the present invention is a medicament for treating the surface of an aluminum material or the like. The surface treatment agent is brought into contact with the surface of an aluminum material or the like to form a surface treatment film. The surface treatment agent contains a water-soluble or water-dispersible organic polymer (A) having a carbonyl group and / or a hydroxyl group in a unit structure and an organic compound (B) having a phosphon group. By using such a surface treatment agent to form a surface treated film between an aluminum material and an upper layer coating (for example, a coating film or a laminate layer), excellent adhesion to an aluminum material and the upper layer coating can be exhibited, Excellent corrosion resistance can be imparted to the aluminum material and the like. The surface-treated film formed on an aluminum material or the like has excellent retroreflectivity. Therefore, an aluminum material or the like having a surface treated film is useful for packaging containers such as foods, food cans, beverage cans, lids for containers or cans thereof. Herein, the retortability refers to a property of the coating film of an aluminum material or the like which is in contact with a liquid component (for example, an aqueous solution) contained in a retort food or the like, for the sterilization treatment or the heat treatment of retort food or the like, Quot;), peeling of the film, breakage of the film, and the like. The aqueous solution includes, for example, pure water; tap water ; Saline solution; Acidic aqueous solutions such as citric acid and acetic acid; An aqueous alkaline solution such as an aqueous ammonia solution; , But the present invention is not limited thereto.

The surface treatment agent according to the present invention may be composed of an organic material, for example, the organic polymer (A) and the organic compound (B) in addition to the solvent to be described later. However, (C) or the like may be contained as long as it does not impair the adhesion (adhesion, corrosion resistance, retort resistance) of the metal. However, the surface treatment agent of the present invention does not contain iron, nickel, cobalt, hexavalent chromium, a compound containing these metals, or an amine compound containing three or more hydroxyl groups in one molecule.

Here, the amine compound means a compound in which all or a part of hydrogen atoms in ammonia are replaced with other functional groups, that is, a nitrogen-containing compound. Thus, an amine compound containing three or more hydroxyl groups in one molecule means a nitrogen-containing compound having three or more hydroxyl groups in one molecule. As described above, the surface treatment agent of the present invention does not contain an amine compound containing three or more hydroxyl groups in one molecule, but preferably does not contain an amine compound.

Further, the surface treatment agent of the present invention is characterized in that it does not contain iron, nickel, or cobalt, or a compound containing these metals, but inevitable incorporation of these components is allowed. When these components are incorporated in the surface treatment agent, the mass concentrations of the various components allowed are not more than 5 ppm.

(Organic polymer (A))

The organic polymer (A) is a water-soluble or water-dispersible polymer having a carbonyl group or a hydroxyl group in the unit structure. The organic polymer (A) contained in the surface treatment agent for forming a surface treatment film contains a carbonyl group or a hydroxyl group which is a polar region to improve the adhesion between the surface treatment film and the upper layer film, . The organic polymer (A) preferably has a carboxyl group or a carboxylic acid ester group in the unit structure.

The organic polymer (A) may have other substituents or functional groups, provided that the organic polymer (A) has a carbonyl group or a hydroxyl group in the unit structure. The organic polymer (A) may be an ionic organic polymer or a nonionic organic polymer. The ionic character may be amphoteric, anionic, or cationic.

Specific examples of the organic polymer (A) include known ones such as a polyester-based copolymer, a (meth) acrylic-based polymer or copolymer, a polyvinyl-based polymer or a copolymer. These organic polymers may be used alone or in combination of two or more.

Examples of the polyester-based copolymer include a copolymer of maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, trimellitic acid, There may be mentioned a polycarboxylic acid such as mesacic acid, pyromellitic acid and naphthalene dicarboxylic acid, and a polycarboxylic acid such as ethylene glycol, diethylene glycol, trimethylol propane, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,6- A polyester polyol in which a polyol is condensed; A condensation reaction product of the polyvalent carboxylic acid with a polyol such as a polymer polyol, polycarbonate diol, polybutadiene polyol, polycaprolactone polyol, neopentyl glycol or methylpentadiol; And the like. Other examples of the polyester polyol or the copolymer of the condensation reactant and other polymers may be mentioned. Examples of other polymers include, for example, (meth) acrylic polymers, polyvinyl polymers, and the like, but are not limited thereto. Here, the polyvalent carboxylic acid means a compound having two or more carboxyl groups. As the polyvalent carboxylic acid, a dimeric acid or a trimeric acid of an unsaturated fatty acid may be used in addition to the above-mentioned materials.

Alternatively, an unreacted carboxyl group contained in a copolymer of a monomer having three or more carboxyl groups such as trimellitic acid and pyromellitic acid may be neutralized with an alkali, or a copolymer obtained by sulfonating the copolymer with sulfophthalic acid or the like may be used . Further, by using these alkali neutralized products, sulfonated products and the like, it becomes easy to dissolve or disperse in water.

Examples of (meth) acrylic polymers or copolymers include copolymers of polymers or copolymers of (meth) acrylic monomers, and polymers or copolymers of (meth) acrylic monomers, . The (meth) acrylic polymer or copolymer is not particularly limited as long as it is water-soluble and water-dispersible. (Meth) acrylic copolymers include, for example, block copolymers, graft copolymers, random copolymers, and alternating copolymers. Examples of the sequential polymerizable monomer include monomers used in the production of a polyester-based copolymer.

Examples of the (meth) acrylic monomer include acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2- (Meth) acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl (Meth) acrylate, N, N-diallyl (meth) acrylamide, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene Glycol mono (meth) (Meth) acrylate, polytetramethylene glycol mono (meth) acrylate, polytetramethylene glycol (meth) acrylate, dipropylene glycol mono Mono (meth) acrylate, and polyethylene glycol mono (meth) acrylate.

The (meth) acrylic monomer can be appropriately polymerized by a known method. Specific polymerization methods include, for example, a method of polymerizing various (meth) acrylic monomers in the presence of various known radical polymerization initiators and, if necessary, chain transfer agents, in a solvent or an inert gas. The temperature and time of the polymerization reaction are not particularly limited, but the reaction temperature is, for example, in the range of 20 ° C to 140 ° C, and the reaction time is, for example, within a range of 1 hour to 24 hours Respectively.

Examples of the radical polymerization initiator which can be used for the polymerization of the (meth) acrylic monomer 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; Azo compounds such as 2,2'-azobisisobutyronitrile and dimethyl-2,2'-azobisisobutylate; And the like. These may be used alone or in combination of two or more. Examples of the chain transfer agent usable for polymerization of the (meth) acrylic monomer include ethyl alcohol, methyl alcohol, isopropyl alcohol and the like.

Examples of (meth) acrylic copolymers include copolymers of acrylic acid and maleic acid; Copolymers of methacrylic acid and a copolymer of maleic acid and trimethylol propane; Copolymers of polyvinyl acetate and fumaric acid; And the like.

Examples of the polyvinyl polymer include polyvinyl alcohol and the like.

Examples of polyvinyl alcohols include, for example, partially saponified and fully saponified polyvinyl acetate and partially saponified and fully saponified copolymers of vinyl acetate and other monomers. There is no upper limit to the saponification degree of the partially saponified product of the copolymer of vinyl acetate and vinyl acetate and other monomers, but it is preferably 60% or more. Examples of the monomer forming the copolymer with vinyl acetate include the above (meth) acrylic monomers and the like.

As the polyvinyl-based copolymer, for example, a copolymer of an acrylic acid polymer and vinyl acetate; Copolymers of glutaric acid and ethylene glycol, and vinyl acetate; And the like.

The weight average molecular weight of the organic polymer (A) is preferably 2,000 or more and 1,000,000 or less, and more preferably 4,000 or more and 800,000 or less. The weight average molecular weight is measured by Gel Permeation Chromatography (GPC method) and converted into polystyrene.

(Organic compound (B))

The organic compound (B) is not particularly limited as long as it is an organic compound having a phosphonic group (-PO ₃ H ₂ ).

Examples of the organic compound (B) include, for example, aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 2-phosphobutanone-1,2,4-tricarboxylic acid, Citrin diphosphoric acid, cytidine-5'-phosphate, adenosine-3'-phosphate, phosphocerine, ethylenediaminetetra (methylenephosphonic acid), N-phosphonomethyl N, N ', N'-tetra (methylenephosphonic acid), cyclohexane-1,2-diamine-N (methylenephosphonic acid), ethylenediamine- , N, N ', N'-tetra (methylenephosphonic acid), N, N'-bis (2-hydroxybenzyl) ethylenediamine- Inositol bisphosphoric acid, inositol monophosphoric acid, dibenzyl phosphate, phosphoric acid 1-benzyl-3-methylphosphoric acid (hereinafter, referred to as " tetrakis (methylene)]] tetrakisphosphonic acid, inositol hexaphosphoric acid, inositol pentaphosphoric acid, inositol tetraphosphoric acid, Midazolium, phosphorus Butyl-3-methylimidazolium, erythrose-6-phosphate, erythrose-4-phosphate, phosphoenolpyruvic acid, fructose-6-phosphate, fructose- Phosphoric acid, glucose-6-phosphate, glucose-4-phosphate, glucose-3-phosphate, glucose-2-phosphate and glucose-1-phosphate. These organic compounds may be used alone or in combination of two or more.

As the organic compound (B), it is preferable to use a phosphonic group-containing compound having three or more carbon atoms and two or more phosphonic groups in one molecule. In this case, although there is no upper limit on the number of the phosphphone groups, the number of the phosphphone groups is preferably 3 or more. The number of carbon atoms is preferably 30 or less, more preferably 10 or less. A surface treatment agent containing a phosphonic group-containing compound having two or more phosphone groups in one molecule can form a surface treatment film having better adhesion to the upper layer coating.

Preferred combinations of the organic polymer (A) and the organic compound (B) include a combination of the polyester-based copolymer as the organic polymer (A) and the organic compound (B); A combination of a (meth) acrylic polymer or copolymer and an organic compound (B) as the organic polymer (A); . By containing the organic polymer (A) and the organic compound (B) in the combination of the above surface treatment agent, a surface treated film excellent in acid resistance and alkali resistance can be formed.

Examples of the combination of the polyester-based copolymer as the organic polymer (A) and the organic compound (B) include a copolymer of maleic acid and a polyol, 1-hydroxyethylidene-1,1-diphosphonic acid, (Hexamethylenebis (nitrilo) tetrakis (methylene)] tetrakisphosphonic acid, 2-phosphobutanone-1,2,4-tricarboxylic acid or ethylenediamine-N, N'-di (methylenephosphonic acid) ; A copolymer of fumaric acid and a polyol and a copolymer of ethylene diamine N, N, N ', N'-tetra (methylenephosphonic acid) or cyclohexane-1,2-diamine-N, N, N' Phosphonic acid); A combination of a copolymer of itaconic acid and a polyol and N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-bis (methylenephosphonic acid); A combination of a copolymer of isophthalic acid and polyol, and inositol hexaphosphoric acid; A combination of a copolymer of terephthalic acid and polyol, and inositol pentaphosphoric acid; .

Examples of the combination of the (meth) acrylic polymer or copolymer and the organic compound (B) as the organic polymer (A) include a polymer or copolymer of acrylic acid and a 1-hydroxyethylidene- (Methylenephosphonic acid), ethylenediamine-N, N, N ', N'-tetra (methylenephosphonic acid), cyclohexane-1,2-diamine-N, A combination of N, N ', N'-tetra (methylenephosphonic acid), inositol hexaphosphoric acid, inositol pentaphosphoric acid, inositol tetraphosphoric acid, inositol trisphosphoric acid or inositol bisphosphoric acid; N, N ', N'-tetra (methylenephosphonic acid), cyclohexane-1, methylenephosphonic acid, ethylenediamine-N, A combination of 2-diamine-N, N, N ', N'-tetra (methylenephosphonic acid), inositol pentaphosphoric acid, inositol tetraphosphoric acid, inositol trisphosphoric acid or inositol bisphosphoric acid; N, N ', N'-tetra (methylenephosphonic acid), cyclohexane-1,2 (methylenephosphonic acid), ethylenediamine-N, - a combination of diamine-N, N, N ', N'-tetra (methylenephosphonic acid), inositol tetra phosphate, inositol tris phosphate or inositol bisphosphate; (Methylenephosphonic acid), ethylenediamine-N, N, N ', N'-tetra (methylenephosphonic acid), cyclohexane-1,2-dicarboxylic acid, Diamine-N, N, N ', N'-tetra (methylenephosphonic acid), inositol trisphosphoric acid, or inositol bisphosphoric acid; N, N ', N'-tetra (methylenephosphonic acid), ethylenediamine-N, N'-di (methylenephosphonic acid), ethylenediamine- , Fructose-6-phosphate, fructose-2,6-bisphosphate, or fructose-1,6-bisphosphate; A combination of a polymer or copolymer of triethylene glycol mono (meth) acrylate and fructose-2,6-bisphosphoric acid; .

The organic polymer (A) with the organic compound (B), the organic compound (B), phosphorus (P) and the mass ratio of the organic polymer (A) (M _P / M _A) is, at least 0.001 the range of 0.70 or less is blended so that I of More preferably 0.001 or more and 0.60 or less. By using the surface treatment agent having a mass ratio (M _P / M _A ) within this range, it is possible to form a surface treatment film having improved adhesion with an aluminum material or the like and adhesion with the upper layer coating.

(Metal compound (C))

The surface treatment agent of the present invention may contain a metal compound (C), if necessary. Examples of the metal compound (C) include metal compounds containing at least one transition metal. However, from the metal compound (C), a compound containing a metal such as iron, nickel, cobalt or hexavalent chromium, and preferably further contains a metal such as vanadium or trivalent chromium is excluded . It is more preferable that the surface treatment agent of the present invention not only contain these compounds but also contain no metals such as iron, nickel, cobalt, hexavalent chromium, vanadium, and trivalent chromium. The surface treatment agent of the present invention is a surface treatment agent comprising a metal compound containing at least one transition metal selected from Ti, W, Mn, Zr, Ce and the like (excluding compounds containing a transition metal other than these five metals) Is particularly preferable. In addition, for metals such as iron, nickel, cobalt and the like, or compounds containing these metals, inevitable incorporation into the surface treatment agent is allowed, and the mass concentrations of the various components allowed are not more than 5 ppm.

Examples of the metal compound (C) include oxides, hydroxides, complex compounds, inorganic acids and organic acids of the transition metal. More specifically, examples thereof include titanyl sulfate, titanium lactate, titanium fluoride, titanium ammonium fluoride, titanium hydrofluoric acid, ammonium metatungstate, ammonium tungstate, paratungstic acid, ammonium paratungstate, permanganic acid, Manganese sulfate, manganese sulfate, manganese acetate, zirconium acetate, zirconium fluoride, zirconium hydrofluoric acid, ammonium zirconium fluoride, zirconium sulfate, zirconium fluoro zirconium, zirconium oxonitrate, zirconium zirconium carbonate, cerium acetate, cerium nitrate, cerium fluoride, Cerium ammonium, and the like. The metal compound (C) is coordinatively bonded to the organic compound (B) and the organic polymer (A), and by this bonding, a surface treatment film with higher corrosion resistance can be formed.

(M) of the metal mass (M _M ) of the metal compound (C) to the phosphorus mass (M _P ) in the organic compound (B) when the surface treatment agent of the present invention contains the metal compound _M / M _P ) is 0.30 or less.

The surface treatment agent of the present invention may or may not contain a compound having a benzenetriol structure as a component other than the metal compound (C).

The surface treatment agent of the present invention may contain various solvents, if necessary, from the viewpoint of workability in contact with an aluminum material or the like. As the solvent, for example, water; Alkane-based solvents such as hexane and pentane; Aromatic solvents such as benzene and toluene; Alcohol solvents such as ethanol, 1-butanol and ethyl cellosolve; Ether solvents such as tetrahydrofuran and dioxane; Ester solvents such as ethyl acetate and butoxyethyl acetate; Amide solvents such as dimethylformamide and N-methylpyrrolidone; Sulfone solvents such as dimethyl sulfoxide; Phosphoric acid amide type solvents such as hexamethylphosphoric triamide; And the like. One of these solvents may be used alone, or two or more of them may be used in combination. Further, from the viewpoints of environment and economy, it is preferable to use water as a solvent.

(Method for preparing surface treating agent)

The method of preparing the surface treatment agent is not particularly limited. For example, the surface treatment agent can be prepared by thoroughly mixing the organic polymer (A), the organic compound (B), and the solvent, and if necessary, further mixing the metal compound (C) and other components. The pH of the surface treatment agent is preferably in the range of 1.5 to 6.5. Further, the adjustment of the pH may be carried out using various acids; Alkaline agents such as ammonia; And the like can be used.

(Method for producing surface-treated film)

The surface treated film according to the present invention can be produced by bringing the above-mentioned surface treating agent into contact with an aluminum material or the like. More specifically, the method for producing a surface treated film has a contacting step of bringing the surface treating agent into contact with the surface of an aluminum material or the like, and a drying step of drying the surface treating agent brought into contact with the surface of the aluminum material or the like after the contacting step. In the method for producing a surface treated film, before the contacting step, a surface of an aluminum material or the like may be subjected to a degreasing step for degreasing, a pickling step for pickling, a chemical conversion treatment for chemical conversion, and the like. Between the contacting step and the drying step, the surface of an aluminum material or the like in contact with the surface treating agent may be washed, or may not be carried out.

(Such as aluminum)

The aluminum material or the like to be brought into contact with the surface treatment agent is a metal material containing aluminum such as aluminum material or aluminum alloy material. Examples of the aluminum material include a pure aluminum material of 1000 series specified in JIS 2014 H4000. As the aluminum alloy material, when a metallic material containing aluminum as a main component, that is, a metallic material is composed of a metal component different from aluminum, it is preferable that the aluminum alloy contains at least 50% by weight of aluminum; In the case where the metal material is composed of aluminum and at least two metal components, it is preferable that the metal contains the most aluminum; . More specifically, it may be an aluminum alloy material of 3000 series or 5000 series specified in JIS 2014 H4000, but is not limited thereto.

(Contact process)

The contacting step can be carried out by a known method such as a spraying method, a dipping method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, or a combination thereof. .

In the contacting step, the use conditions of the surface treatment agent are not particularly limited. For example, when the surface treating agent is brought into contact, the temperature of the surface treating agent or aluminum material is preferably in the range of 10 占 폚 to 70 占 폚, and more preferably in the range of 20 占 폚 to 60 占 폚. The contact time is preferably within a range of 1 second or more and 300 seconds or less.

(Drying step)

The drying step is preferably carried out under a temperature condition in which the maximum reachable temperature (PMT) of an aluminum material or the like is in the range of 20 占 폚 to 300 占 폚. The drying time is preferably within a range of 2 seconds to 150 seconds. The drying method is not particularly limited, and a known drying apparatus such as a batch drying apparatus, a continuous hot-air circulating drying apparatus, a conveyer-type hot-air drying apparatus, an electromagnetic induction heating apparatus using an IH heater, Drying method and the like. The air flow rate and the wind speed when these furnaces are used are set appropriately.

(Degreasing process)

The degreasing step is a step of removing oils and fouling adhering to the surface of an aluminum material or the like. The degreasing step is not particularly limited as long as it can remove the fuels and contaminants so as not to cause any adverse effect on the subsequent surface treatment or chemical treatment after the crater ring For example, a known degreasing treatment method using an alkaline- or acid-based degreasing agent or the like.

(Pickling process)

The pickling process is a process of cleaning the surface of an aluminum material or the like with an acidic aqueous solution. As the acidic aqueous solution, for example, an aqueous nitric acid solution, an aqueous sulfuric acid solution, and the like can be used, but the present invention is not limited thereto. Further, the pickling temperature and time are appropriately set.

(Chemical conversion process)

The chemical conversion treatment step is a step of bringing a chemical conversion agent into contact with the surface of an aluminum material or the like to form a chemical conversion coating. The corrosion resistance of an aluminum material or the like can be increased by the chemical conversion treatment. Thus, a multilayer coating film including a chemical conversion coating film and a surface treatment coating film can be formed on the surface of an aluminum material or the like by carrying out a contact process after a chemical conversion process is performed on the surface of an aluminum material or the like.

(Chemical conversion agent)

Examples of the chemical conversion treatment agent include, but are not limited to, a zirconium conversion treatment agent, a phosphate chemical conversion treatment agent, a titanium conversion treatment agent, and a chromate treatment agent. It is also preferable that the chemical conversion agent does not contain chromate (including trivalent chromium). The chemical treatment agent can be contacted by a known method such as a spraying method, a dipping method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, or a combination thereof. But are not limited thereto. The temperature of the chemical conversion treatment agent, the aluminum material, and the like at the time of chemical conversion treatment is preferably within the range of 5 占 폚 or higher and 70 占 폚 or lower. It is preferable that the conversion treatment time is within a range of 1 second or more and 300 seconds or less.

After the chemical conversion treatment, it is preferable to carry out a washing step of washing the surface of the aluminum material or the like, that is, the surface of the chemical conversion coating, before the contacting step of the surface treatment agent. Further, after the washing step before the contacting step of the surface treating agent, the drying step of drying the surface of the aluminum material or the like having the chemical conversion coating may or may not be carried out. The drying temperature of this drying step is preferably in the range of 20 ° C to 300 ° C, more preferably 80 ° C to 180 ° C. The drying time is preferably within a range of 2 seconds to 300 seconds, and more preferably within a range of 30 seconds to 150 seconds.

(Surface treated film)

The surface treated film can be obtained by the above-described production method. The mass (dry film mass) of the surface treated film after the drying step is preferably within the range of 1 mg / m 2 to 5,000 mg / m 2, and more preferably within the range of 3 mg / m 2 to 2,000 mg / m 2. The dry film mass is determined by measuring the amount of carbon in the surface treated film with the total organic carbon system (Total Organic Carbon (TOC) Analyzer) and using the calibration curve method. On the other hand, when the surface-treated film contains the metal compound (C), the metal compound (C) in the surface-treated film is measured by fluorescent X-ray and the value is calculated using the calibration curve method.

(Such as an aluminum material having a surface treated film)

The aluminum material or the like having a surface treatment film according to the present invention is not particularly limited as long as it has a surface treatment film on the surface of an aluminum material or the like and may have an upper layer film on the surface treatment film.

(Upper layer coating)

The upper layer coating is a coating formed on the surface treatment coating. Examples of the upper layer coating include a coating layer and a laminate layer. The coating film is composed of a layer containing an organic resin. The laminate layer is formed by laminating two or more layers containing an organic resin. The organic resin contained in each layer of the laminate layer may be the same or different.

The coating film can be produced, for example, by bringing a coating liquid containing an organic resin into contact with the surface treated film and then drying it. Examples of the method of bringing into contact with each other are methods such as spraying, dipping, roll coating, bar coating, curtain coating, spin coating, electrodeposition coating, powder coating, electrostatic coating, But are not limited to these. The drying method is not particularly limited, but a known drying apparatus such as a batch drying apparatus, a continuous hot-air circulating drying apparatus, a conveyer-type hot-air drying apparatus, an electromagnetic induction heating apparatus using an IH heater And a drying method using a furnace or the like. It is preferable that the drying temperature is a temperature condition within a range of 20 占 폚 or more and 300 占 폚 or less at the maximum reaching temperature (PMT) of an aluminum material or the like. The drying time is preferably within a range of 2 seconds to 150 seconds.

The laminate layer can be formed by, for example, a dry lamination method, an extrusion lamination method, or a combination thereof, but is not limited thereto. More specifically, an aluminum material or the like having a laminated film can be produced by superimposing a laminate film (which may have an adhesive layer) on a surface treated film formed on the surface of an aluminum material or the like and thermally bonding.

(PET), polyethylene naphthalate (PEN), polypropylene (PP), polycarbonate (PC), polyphenylene sulfide (PC), and the like can be used as the organic resin contained in each layer of the coating film and the laminate layer. PPS), triacetylcellulose (TAC), polyvinyl chloride (PVC), polyvinyl alcohol (PVA), polyester, polyolefin, polyurethane, nylon, acrylic, epoxy resin coatings and vinylorganozole resins , But are not limited thereto.

Example

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.

(Preparation of surface treatment agent)

The compositions of the surface treating agents of Examples 1 to 35 and the surface treating agents of Comparative Examples 1 to 2 are shown in Table 1. In Table 1, the symbols shown in the column of " type " of the organic polymer, the organic compound and the metal compound refer to the substances shown in Tables 2 to 4, respectively. The " mass% " of each component in Table 1 indicates the mass ratio (%) with respect to the solid mass of the surface treating agent. Various surface treatment agents were prepared by mixing each component with water as a solvent.

(Manufacture of Public Material)

Degreasing was carried out by spraying an degreasing agent (Fine Cleaner 4477, manufactured by Nihon Parkerizing Co., Ltd., concentration of the agent: 2%) at 60 캜 for 5 seconds on an aluminum alloy plate (JIS 2014 H4000 A5182 material). Subsequently, 2% sulfuric acid was pickled by spraying at 50 DEG C for 3 seconds, and then the surface was cleaned by washing with water. Next, surface treatment was performed by spraying various surface treatment agents (surface treatment agents of Examples 1 to 29 and Comparative Examples 1 and 2) on the surface of the degreased and pickled aluminum alloy material for 2 seconds, and then, in the hot air circulation type drying furnace, And dried at 100 DEG C for 7 seconds to form various surface-treated films on the surface of the aluminum alloy material.

The surface of the degreased and pickled aluminum alloy material was subjected to chemical conversion treatment by spraying a zirconium phosphate forming agent (Aldyn N405, manufactured by Nihon Parkerizing Co., Ltd.) at 55 캜 for 4 seconds, and then rinsed in a hot air circulating type drying furnace Lt; 0 > C for 10 seconds to form a chemical conversion coating film on the surface of the aluminum alloy material. Subsequently, the surface treatment agents of Examples 30 to 35 were sprayed on the chemical conversion coating film for 2 seconds to perform surface treatment, and then dried in a hot air circulation type drying furnace at 100 占 폚 for 10 seconds, whereby the surface of the aluminum alloy material To form various surface-treated films.

An epoxy-based solvent paint was applied to an aluminum alloy material having a surface-treated coating formed on the surface of an aluminum alloy material using various surface-treating agents so as to have a dry film thickness of 10 mu m with a bar coater # 26. After the application, the substrates were dried in a hot-air circulation type drying oven at 300 ° C for 15 seconds to prepare Samples Nos. 1 to 37 in which a coating film was formed on various surface-treated films. As a comparative control, a chemical conversion coating film similar to that described above was formed on the surface of the degreased and pickled aluminum alloy material, and then a visible material (No. 38) having a coating film formed in the same manner as described above on the chemical conversion coating film Prepared. The solid content concentration of each surface treatment agent was appropriately adjusted so that the amount (coating amount) of the surface treated film in each of the specimens was as shown in Tables 6 and 7.

(Assessment Methods)

The corrosion resistance, adhesion, and retort resistance of each of the seal materials Nos. 1 to 38 were evaluated by the following methods and evaluation criteria. Also, the evaluation results of? (Undesirable) and? (Unavailable) indicate that they are out of the practical range.

(Corrosion resistance, flat part)

The cross-cut blank was immersed in an aqueous solution of 1% citric acid and 0.5% sodium chloride at 70 캜 for 72 hours. After immersion, the maximum expansion width on one side of the cross cut portion and the maximum expansion width on the general portion (the portion on which no crosscut was performed) were measured, and the corrosion resistance was evaluated according to the following evaluation criteria. The results are shown in Tables 6 and 7.

(Evaluation Criteria of Crosscut Part)

◎ (Excellent): Maximum expansion width on one side is 0 ㎜ or more and less than 0.5 ㎜

(Good): The maximum expansion width on one side is 0.5 mm or more and less than 1 mm

× (not allowed): Maximum expansion width on one side is 1 mm or more

(Evaluation standard of general department)

◎ (excellent): The maximum expansion width is 0 mm or more and less than 0.5 mm

(Good): The maximum expansion width is 0.5 mm or more and less than 1 mm

× (impossible): Maximum expansion width is 1 mm or more

(Corrosion resistance, machining)

(1/2 inch, weight: 1000 g, height: 100 mm) was applied to an aqueous solution of 1% citric acid and 0.5% sodium chloride at 70 DEG C for 72 hours Lt; / RTI > After immersion, the rust area of the processed portion was measured and the corrosion resistance was evaluated according to the following evaluation criteria. The results are shown in Tables 6 and 7.

(Evaluation standard)

◎ (Excellent): Rust area is 0% to less than 5%

○ (Good): Rust area is 5% or more and less than 10%

× (Not applicable): Rust area is over 10%

(Coating film adhesion)

A cross-cut tape peel test according to JIS K 5400 was performed. A cross cut was made with a checkerboard gold pattern on the side having the coating of the sealing material with an NT cutter, the cellophane tape was affixed to the cross cut portion, and the tape was peeled off. The crosscuts on the checkerboard scale were made so that 11 parallel lines spaced at 1 mm were crossed at right angles to produce 100 cells. After peeling off the tape, the remaining cells were measured, and the coating film adhesion was evaluated according to the following evaluation criteria. The results are shown in Tables 6 and 7.

(Evaluation standard)

◎ (Excellent): No peeling

○ (Good): There was no peeling, but the periphery of the chamber was not bonded

DELTA (undesirable): 95 to less than 100 cells remained

× (not allowed): Less than 95 cells remained

(Retort resistance, retort test)

The entire test specimens were immersed in the test liquids 1 to 4 shown in Table 5, pressed at 15 MPaG, and heat-treated at 125 DEG C for 30 minutes. Thereafter, various retortability (whitening resistance, adhesion, workability, adhesiveness, etc.) was evaluated as described later. The evaluation of the machining adhesion was carried out by dipping the entire test specimen in which DuPont processing (1/2 inch, weight: 1000 g, height: 100 mm) was performed on the surface opposite to the surface on which the coating was formed, . The evaluation of the adhesiveness was carried out by forming a triangular inclination having a vertex of 30 占 on the surface opposite to the surface on which the film was formed and measuring a part of the specimen having the incision so as not to immerse the incision in at least various test liquids Which was immersed in a test solution and subjected to heat treatment.

(White Mars)

The appearance of the sealant was observed, and whitening resistance was evaluated according to the following evaluation criteria. The results are shown in Tables 6 and 7.

(Evaluation standard)

◎ (excellent): No change in the coating surface of the sealant, or very slight haze could be confirmed

○ (Good): It was possible to confirm a slight haze on the coated surface of the disclosed material, or to confirm a little haze

× (not applicable): Significant whiteness was observed on the surface of the coating material

(Adhesion)

After the heat treatment, a cross-cut tape peel test according to JIS K 5400 was carried out, and the adhesiveness was evaluated according to the following evaluation criteria. The results are shown in Tables 6 and 7.

(Evaluation standard)

◎ (Excellent): No peeling

○ (Good): There was no peeling, but the periphery of the chamber was not bonded

DELTA (undesirable): 95 to less than 100 cells remained

× (not allowed): Less than 95 cells remained

(Processing Adhesion)

After the heat treatment, a cellophane tape was attached to the DuPont processed portion (convex portion), and the tape was peeled off. The area of the peeled film was measured, and the processing adhesion was evaluated according to the following evaluation criteria. The results are shown in Tables 6 and 7.

(Evaluation standard)

⊚ (excellent): the area of the peeled film is 0% or more and less than 5%

(Good): The area of the peeled film is 5% or more and less than 10%

× (not applicable): The area of the peeled film is 10% or more

(Adhesive property)

After the heat treatment, the notched portion was pulled up to 200 mm / min by a tensile tester, and the notched portion was broken from the blank. The width of the film remaining on the cross section after the fracture was measured, and the adhesiveness was evaluated according to the following evaluation criteria. The results are shown in Tables 6 and 7.

(Evaluation standard)

? (Excellent): The width of the remaining film is 0 mm or more and less than 0.2 mm

(Good): The width of the remaining film is 0.2 mm or more and less than 1 mm

× (not possible): The remaining film thickness is 1 mm or more

As shown in Tables 6 and 7, the sealing materials Nos. 1 to 35 having the surface treated coatings formed of the surface treating agents of Examples 1 to 35 were excellent in corrosion resistance and adhesion, and also excellent in retort resistance. As shown in Tables 6 and 7, the specimens 30 through 35 subjected to the chemical conversion treatment and the surface treatment were particularly excellent in corrosion resistance.

On the other hand, in Samples Nos. 36 and 37 having surface-treated coatings formed of the surface treatment agents (Comparative Examples 1 and 2) of the organic polymer (A) or the organic compound (B) alone, practical retroreflectivity and corrosion resistance It was not.

In addition, M _M / M _P disclosure material (No.4 to 6, 22 to 29, and 33 to 35) having a surface treated film formed of the surface treatment agent containing a metal compound (C) is less than or equal to 0.30, the high Corrosion resistance.

Industrial availability

The surface treatment agent of the present invention is useful for production of a coating film having excellent retort resistance, adhesion and corrosion resistance, and for producing an aluminum material having the coating film. The aluminum material or the like having a coating thus obtained is useful for packaging containers such as foods, food cans, beverage cans, lids for containers or cans thereof.

Claims (9)

A surface treatment agent for treating the surface of an aluminum material or an aluminum alloy material, which comprises a water-soluble or water-dispersible organic polymer (A) having a carbonyl group and / or a hydroxyl group in a unit structure and an organic compound (B) containing a metal compound (C) as necessary, and the case of containing the metal compound (C), the metal mass of the weight, the metallic compound (C) to (M _P) in the organic compound (B) ( M _M) ratio (M _M / M _P) containing 0.30 or less, the surface treatment agent (where, iron, nickel, cobalt or a compound of hexavalent chromium, or their metal, or a hydroxyl group for at least 3 per molecule of Containing an amine compound). The method according to claim 1,
Wherein the organic polymer (A) has a carboxyl group or a carboxylic acid ester group in the unit structure. 3. The method according to claim 1 or 2,
Wherein the organic compound (B) has three or more carbons and two or more phosphon groups in one molecule. 4. The method according to any one of claims 1 to 3,
Wherein the metal compound (C) contains at least one transition metal. 4. The method according to any one of claims 1 to 3,
Wherein the metal compound (C) contains at least one transition metal selected from titanium, tungsten, manganese, zirconium and cerium. 6. The method according to any one of claims 1 to 5,
Wherein the weight average molecular weight of the organic polymer (A) is in the range of 2,000 to 1,000,000. A method for producing a surface treatment film, comprising the step of bringing the surface treatment agent according to any one of claims 1 to 6 into contact with the surface of an aluminum material or an aluminum alloy material. Comprising the step of forming a surface treatment film by bringing the surface treatment agent according to any one of claims 1 to 6 into contact with the surface of an aluminum material or an aluminum alloy material, Aluminum alloy material. (A) containing a water-soluble or water-dispersible organic polymer having a carbonyl group and / or a hydroxyl group in a unit structure and an organic compound (B) having a phosphon group, and optionally containing a metal compound (C) (M _M / M _P ) of the metal mass (M _M ) of the metal compound (C) to the phosphorus mass (M _P ) in the organic compound (B) is 0.30 (Excluding those containing iron, nickel, cobalt or hexavalent chromium, or a compound containing such a metal, or an amine compound containing three or more hydroxyl groups in one molecule) Ash or aluminum alloy material.