TW202020227A - Chemical polishing liquid and surface treatment method using same - Google Patents

Abstract

The present invention provides a chemical polishing liquid which is used for aluminum or an aluminum alloy, and which contains (A) hydrogen peroxide, (B) a fluorine compound, (C) an inorganic acid that is not the fluorine compound (B), and (D) a hydroxyl group-containing hydrocarbon compound. The content of the hydrogen peroxide (A) is 2-20% by mass based on the total amount of the chemical polishing liquid; the content of the fluorine compound (B) in terms of fluorine atoms is 3-17% by mass based on the total amount of the chemical polishing liquid; the content of the inorganic acid (C) is 20-55% by mass based on the total amount of the chemical polishing liquid; and the content of the hydroxyl group-containing hydrocarbon compound (D) is 2-15% by mass based on the total amount of the chemical polishing liquid.

Description

Chemical polishing liquid and surface treatment method using the chemical polishing liquid

The invention relates to a chemical polishing liquid and a surface treatment method of aluminum or aluminum alloy using the chemical polishing liquid.

Conventionally, as for the chemical polishing liquid for smoothing the surface of aluminum or its alloy while giving gloss, it is common to use a mixture of phosphoric acid and nitric acid. However, when using such a chemical polishing liquid containing nitric acid, there may be cases where toxic nitrogen oxides are generated due to the decomposition of nitric acid during the chemical polishing. In addition, the temperature of the chemical polishing liquid due to the exothermic heat during the decomposition of nitric acid Will become a high temperature of about 90 ~ 100 ℃. Therefore, for example, when using a chemical polishing solution containing nitric acid for the metal fittings of aluminum fasteners fixed to the fabric of the polyester material, the polyester material may be deteriorated due to the above heat and the fabric may be discolored. In order to improve such a problem, for example, Patent Document 1 discloses a chemical polishing liquid in which a specific amount of tungsten compound is blended. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 3629218

[Problems to be solved by the invention]

The chemical polishing liquid disclosed in Patent Document 1 contains a tungsten compound, so the cost is high, and there is still room for improvement in economic terms. In addition, the demand is more suitable for chemical polishing liquids for surface treatment of aluminum or aluminum alloys. [Means to solve the problem]

The inventors conducted intensive studies and found that chemical polishing liquids containing hydrogen peroxide, fluorine compounds, inorganic acids that are not fluorine compounds, and hydroxyl-containing hydrocarbon compounds can solve the above-mentioned problems. That is, the present invention provides the following [1] to [12]. [1] A chemical polishing liquid used for aluminum or aluminum alloy; Contains hydrogen peroxide (A), fluorine compound (B), inorganic acid (C) which is not the fluorine compound (B), and hydrocarbon compound (D) containing hydroxyl group; Based on the total amount of the chemical polishing liquid, the content of the hydrogen peroxide (A) is 2-20% by mass; Based on the total amount of the chemical polishing liquid, the content of the fluorine compound (B) in terms of fluorine atoms is 3 to 17% by mass; Based on the total amount of the chemical polishing liquid, the content of the inorganic acid (C) is 20 to 55% by mass; Based on the total amount of the chemical polishing liquid, the content of the hydroxyl-containing hydrocarbon compound (D) is 2 to 15% by mass [2] The chemical polishing liquid as described in [1] above, the pH of the chemical polishing liquid is 4 or less. [3] The chemical polishing liquid according to [1] or [2], wherein the fluorine compound (B) is selected from the group consisting of acidic ammonium fluoride, acidic potassium fluoride, ammonium fluoride, and hydrogen fluoride More than one species. [4] The chemical polishing liquid according to any one of [1] to [3], wherein the inorganic acid (C) contains phosphoric acid. [5] The chemical polishing liquid according to any one of [1] to [4], wherein the hydroxyl group-containing hydrocarbon compound (D) is selected from monovalent alcohols having a carbon number of 2 or more, polyhydric alcohols, and glycol ether compounds One or more of the groups formed. [6] The chemical polishing liquid according to any one of [1] to [5], wherein the content ratio of the inorganic acid (C) to the hydroxyl-containing hydrocarbon compound (D) [(C)/(D)] , In terms of mass ratio is 2~25. [7] A surface treatment method of aluminum or aluminum alloy, which uses the chemical polishing liquid as described in any one of [1] to [6] to perform the surface treatment of aluminum or aluminum alloy. [8] The surface treatment method of aluminum or aluminum alloy according to [7], wherein the temperature of the chemical polishing liquid during the surface treatment of aluminum or aluminum alloy is 40 to 80°C. [9] The aluminum or aluminum alloy surface treatment method according to [7] or [8], wherein the time for performing the aluminum or aluminum alloy surface treatment is 1 second or more and 10 minutes or less. [10] A manufacturing method of surface-treated aluminum or aluminum alloy, including the following steps: The surface treatment of aluminum or aluminum alloy is performed using the chemical polishing liquid as described in any one of [1] to [6]. [11] A surface-treated aluminum or aluminum alloy using the chemical polishing liquid as described in any one of [1] to [6], the arithmetic mean height (Sa) measured according to ISO 25178 before the surface treatment is 150-250nm aluminum or aluminum alloy described in JIS H4140 is surface-treated, the arithmetic average height (Sa) of the aluminum or aluminum alloy after surface treatment is 200nm or less, and the arithmetic average height after surface treatment is before surface treatment The arithmetic mean height (Sa) is below. [12] A surface-treated aluminum or aluminum alloy, using a chemical polishing liquid as described in any one of [1] to [6], before the surface treatment, the gloss measured according to ISO 2813 is 200 to 350 Aluminum or the aluminum alloy described in JIS H4140 is subjected to surface treatment. The gloss of the aluminum or aluminum alloy after surface treatment is 150 or more, and the gloss after surface treatment is more than the gloss before surface treatment. [Effect of invention]

When the surface of aluminum or aluminum alloy is treated with the chemical polishing liquid which is an ideal aspect of the present invention, the surface of aluminum or the like can be polished and smoothed, while giving excellent gloss. In addition, the ideal chemical polishing liquid of the present invention is excellent in operation safety.

[Chemical polishing liquid] The chemical polishing liquid of the present invention is a chemical polishing liquid for aluminum or aluminum alloy (also collectively referred to as "aluminum, etc." in this specification), which contains hydrogen peroxide (A), a fluorine compound (B), and is not a fluorine compound (B ) Inorganic acid (C), and hydroxyl-containing hydrocarbon compound (D) (hereinafter, in this specification, hydrogen peroxide (A), fluorine compound (B), inorganic acid that is not a fluorine compound (B) ( C), the hydroxyl-containing hydrocarbon compound (D) is called component (A), component (B), component (C), component (D)). It is considered that when the chemical polishing liquid of the present invention oxidizes the surface of aluminum or the like with hydrogen peroxide (A), and the fluorine compound (B) acts on the oxidized surface to smooth the surface, the inorganic acid (C ) And the hydroxyl-containing hydrocarbon compound (D) contribute to improving the smoothness of the surface of aluminum and the like and imparting excellent gloss, while also suppressing the violent reaction during surface treatment and improving the safety of work. In addition, the mechanism of action in the present invention is not limited to this.

The pH of the chemical polishing liquid according to one aspect of the present invention is preferably 4 or less, preferably 3.5 or less, more preferably 3 or less, particularly preferably 2.5 or less, and the lower limit can be set appropriately, and is preferably 1.1 or more . By adjusting the chemical polishing liquid to a pH of 4 or less, when performing surface treatment of aluminum or aluminum alloy (hereinafter, also referred to as "polishing" in this specification), aluminum will dissolve into aluminum ions and promote the treatment of these surfaces The surface treatment further improves the smoothness of the polished surface. In addition, in this specification, the pH of the chemical polishing liquid means a value measured under the condition of 25°C according to JIS Z8802.

The chemical polishing liquid according to one aspect of the present invention may further contain a dilution solvent such as water or an organic solvent (excluding those belonging to component (D)). In addition, the chemical polishing liquid according to one aspect of the present invention may contain active ingredients other than the components (A) to (D) as long as the effects of the present invention are not impaired. In addition, in this specification, "effective ingredient" is meant to exclude the components of the dilution solvent such as water in the chemical polishing liquid.

In the chemical polishing liquid according to one aspect of the present invention, in terms of the content of the active ingredient (effective component concentration), based on the total amount of the chemical polishing liquid (100% by mass), it is ideally 20 to 95% by mass, which is It is preferably 35 to 85% by mass, more preferably 45 to 80% by mass, further preferably 47 to 77% by mass, and particularly preferably 50 to 75% by mass.

In one aspect of the chemical polishing liquid of the present invention, based on the total amount of active ingredients (100% by mass) in the chemical polishing liquid, the components (A), (B), (C), and (D) The total content is desirably 60 to 100% by mass, preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass.

Hereinafter, each component will be described. >Hydrogen peroxide (A): Composition (A)> Based on the total amount of the chemical polishing liquid (100% by mass), the chemical polishing liquid of the present invention contains 2 to 20% by mass of hydrogen peroxide (A). If the content of hydrogen peroxide (A) is less than 2% by mass, it is easy to cause insufficient oxidation of the surface of the surface treatment object, that is, aluminum, and it is difficult to form a smooth surface. On the other hand, if the content of hydrogen peroxide (A) exceeds 20% by mass, the surface of aluminum or the like will be excessively oxidized, making it difficult to form a smooth surface.

Based on the above point of view, in the chemical polishing liquid of one aspect of the present invention, based on the total amount of chemical polishing liquid (100% by mass), the content of hydrogen peroxide (A) is preferably 3 to 18% by mass, preferably It is 4 to 16% by mass, more preferably 4 to 15% by mass, particularly preferably 5 to 15% by mass, or 5 to 12% by mass.

Furthermore, in one aspect of the present invention, hydrogen peroxide (A) may be mixed with other components in the form of an aqueous solution, that is, in the form of hydrogen peroxide, to further prepare a chemical polishing liquid. At this time, the blending amount of hydrogen peroxide in the chemical polishing liquid is to consider and adjust the hydrogen peroxide concentration in such a manner that the content of hydrogen peroxide (A) falls within the above range.

>Fluorine compound (B): Ingredient (B)> Based on the total amount (100% by mass) of the chemical polishing liquid, the chemical polishing liquid of the present invention contains 3 to 17% by mass of fluorine compound (B) in terms of fluorine atoms. If the content of the fluorine compound (B) in terms of fluorine atoms is less than 3% by mass, it is easy to cause insufficient smoothing of the surface of aluminum or the like oxidized by hydrogen oxide (A). In addition, the gloss imparted to the surface of aluminum or the like may be insufficient. On the other hand, if the content of the fluorine compound (B) in terms of fluorine atoms exceeds 17% by mass, the load on the drainage treatment of the obtained chemical polishing liquid tends to increase.

From the above viewpoint, in the chemical polishing liquid of one aspect of the present invention, based on the total amount (100% by mass) of the chemical polishing liquid, the content of the fluorine compound (B) in terms of fluorine atoms is preferably 5 ~15% by mass, preferably 7-13% by mass, more preferably 8-12% by mass, even more preferably 8-11% by mass, and particularly preferably 8-10% by mass. In addition, the content of the component (B) in terms of fluorine atoms can be calculated by multiplying the actual blending amount of the component (B) by the content fraction of the fluorine atoms in the component (B).

In the chemical polishing liquid according to one aspect of the present invention, the content of the fluorine compound (B) may be appropriately set so that the content in terms of fluorine atoms falls within the above range, for example, the total amount of the chemical polishing liquid (100% by mass) as a standard, ideally 5-25% by mass, preferably 8-22% by mass, more preferably 10-20% by mass, even more preferably 12-18% by mass, particularly preferably 12~ 15% by mass.

The fluorine compound (B) may be any compound containing a fluorine atom, and examples include ammonium fluoride, acidic ammonium fluoride, cerium fluoride, silicon tetrafluoride, and fluorinated silicic acid (hexafluorosilicic acid Etc.), nitrogen fluoride (nitrogen trifluoride, etc.), phosphorus fluoride (phosphorus trifluoride, phosphorus pentafluoride, etc.), vinylidene fluoride, boron trifluoride, fluoroboric acid (tetrafluoroboric acid, etc.), fluorine Ammonium borate, monoethanolamine hydrogen fluoride, methylamine hydrogen fluoride, ethylamine hydrogen fluoride, propylamine hydrogen fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, triethylmethylammonium fluoride, tris Non-metallic fluorine compounds such as methylhydroxyethylammonium fluoride, tetraethoxyammonium fluoride, methyltriethoxyammonium fluoride, hydrogen fluoride; lithium fluoride, sodium fluoride, acidic sodium fluoride, potassium fluoride , Acidic potassium fluoride, potassium fluoride silicate, potassium hexafluorophosphate, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, zinc fluoride, aluminum fluoride, stannous fluoride, lead fluoride, Metal fluoride compounds such as antimony trifluoride; etc. These fluorine compounds (B) may be used alone or in combination of two or more. In this specification, fluorine-containing inorganic acids such as hydrogen fluoride are classified as component (B).

Among these, the fluorine compound (B) used in one aspect of the present invention is preferably a fluoride. Furthermore, the present specification, "fluoride" can be a fluorine atom intention anion (F ^-) state of the compound, and more specifically, when the intention to become blended chemical polishing solution, dissolved and produce fluorine in the chemical polishing solution ion (F ^-) of the compound. Examples of such fluorides include ammonium fluoride, acidic ammonium fluoride, cerium fluoride, fluorinated silicic acid (hexafluorosilicic acid), and phosphorus fluoride (phosphorus trifluoride, phosphorus pentafluoride) , Fluoroboric acid (tetrafluoroborate), ammonium fluoroborate, monoethanolamine hydrogen fluoride, methylamine hydrogen fluoride, ethylamine hydrogen fluoride, propylamine hydrogen fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, Triethylmethylammonium fluoride, trimethylhydroxyethylammonium fluoride, tetraethoxyammonium fluoride, methyltriethoxyammonium fluoride, hydrogen fluoride, lithium fluoride, sodium fluoride, acid fluoride Sodium, potassium fluoride, acidic potassium fluoride, potassium fluoride silicate, potassium hexafluorophosphate, etc.

The fluorine compound (B) used in one aspect of the present invention is preferably a fluoride, and the fluoride is preferably selected from the group consisting of acidic ammonium fluoride, acidic potassium fluoride, ammonium fluoride, and hydrogen fluoride More than one species in the group, particularly preferred is acidic ammonium fluoride.

>Inorganic acid (C): composition (C)> Based on the total amount of the chemical polishing liquid (100% by mass), the chemical polishing liquid of the present invention contains 20 to 55% by mass of inorganic acid (C) that is not a fluorine compound (B). Chemical polishing liquids with an inorganic acid (C) content of less than 20% by mass or more than 55% by mass are likely to cause a decrease in the smoothness of the surface of aluminum or the like, or it is difficult to impart the desired gloss and other adverse effects. In addition, such a chemical polishing liquid tends to violently react with aluminum and the like, which may cause adverse effects such as deterioration in work safety and roughness of the surface after polishing.

Based on the above point of view, in the chemical polishing liquid of one aspect of the present invention, based on the total amount of the chemical polishing liquid (100% by mass), the content of the inorganic acid (C) is preferably 20-50% by mass, preferably It is 22 to 45% by mass, more preferably 25 to 45% by mass, particularly preferably 30 to 45% by mass, or 35 to 40% by mass.

Examples of the inorganic acid (C) used in one aspect of the present invention include one or more selected from the group consisting of phosphoric acid, sulfuric acid, hydrochloric acid, and nitric acid. From the viewpoint of the smoothness of the surface and the chemical polishing liquid that imparts excellent gloss, it is desirable to contain phosphoric acid. The content of phosphoric acid in the inorganic acid (C) used in one aspect of the present invention is preferably 70 to 100% by mass based on the total amount of inorganic acid (C) (100% by mass). It is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, even more preferably 95 to 100% by mass, and particularly preferably 100% by mass.

In addition, the chemical polishing liquid containing nitric acid has a problem in the environmental surface where nitric acid decomposes during the surface treatment of aluminum and the like and produces toxic nitrogen oxides. In addition, since nitric acid decomposes, it will release heat, so for example, when using chemical polishing liquid containing nitric acid on metal parts of aluminum fasteners fixed on polyester material fabric, the polyester material will be deteriorated due to heat release, and the fabric will be discolored Situation. In view of suppressing such adverse effects, in the chemical polishing liquid according to one aspect of the present invention, the smaller the content of nitric acid, the better. In terms of the content of nitric acid in the inorganic acid (C) used in one aspect of the present invention, based on the total amount of inorganic acid (C) (100% by mass), it is ideally 0 to 10% by mass. It is preferably 0 to 5% by mass, more preferably 0 to 1% by mass, and particularly preferably 0% by mass.

>Hydroxy-containing hydrocarbon compound (D): component (D)> Based on the total amount of the chemical polishing liquid (100% by mass), the chemical polishing liquid of the present invention contains 2 to 15% by mass of the hydroxyl-containing hydrocarbon compound (D). If the content of the hydroxyl-containing hydrocarbon compound (D) is less than 2% by mass or more than 15% by mass, the chemical polishing liquid is likely to reduce the smoothness of the surface of aluminum after polishing, and it is difficult to give the desired gloss, etc. Adverse effects. In addition, in such a chemical polishing liquid, since the reaction of aluminum or the like easily progresses violently, the work safety is also likely to be deteriorated, and the surface after polishing is likely to be adversely affected.

Based on the above point of view, in the chemical polishing liquid of one aspect of the present invention, based on the total amount of the chemical polishing liquid (100% by mass), the content of the hydroxyl-containing hydrocarbon compound (D) is preferably 3 to 12% by mass. It is preferably 4 to 10% by mass, and particularly preferably 5 to 8% by mass.

In the chemical polishing liquid according to one aspect of the present invention, the content ratio of component (C) to component (D) [(C)/(D)], based on the mass ratio, is preferably 2 to 25, preferably 2.5 to 20, more preferably 3-20, even more preferably 3-16, particularly preferably 3.5-12, 4-12, and 5-12. As long as the content ratio is 2 or more, it can become a chemical polishing liquid that can improve the smoothness of the surface of aluminum and the like after polishing and impart excellent gloss. On the other hand, as long as the content ratio is 25 or less, it becomes a chemical polishing liquid that maintains these good characteristics and has excellent work stability.

The hydroxyl-containing hydrocarbon compound (D) used in one aspect of the present invention may be a compound containing at least one hydroxyl group in the main chain and/or side chain of a hydrocarbon composed of carbon atoms and oxygen atoms. From the viewpoint of making a chemical polishing liquid that improves the surface smoothness of polished aluminum and the like, imparts excellent gloss, and makes a chemical polishing liquid with excellent work safety, it is preferably selected from the group consisting of a carbon number of 2 or more One or more of the group consisting of alcohol, polyol, and glycol ether compound.

In addition, from the same viewpoint as described above, the hydroxyl-containing hydrocarbon compound (D) is preferably a compound having an alcoholic hydroxyl group. In addition, in this specification, "alcoholic hydroxyl group" means a hydroxyl group directly bonded to a carbon atom constituting a chain hydrocarbon structure or an alicyclic hydrocarbon structure, and a hydroxyl group directly bonded to a carbon atom of an aromatic ring is "phenolic hydroxyl group" Other than hydroxyl. Therefore, the hydrocarbon compound (D) containing a hydroxyl group is desirably free of phenolic hydroxyl groups.

Examples of monohydric alcohols having a carbon number of 2 or more include ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, pentanol, hexanol, dodecanol, and stearyl alcohol. , Benzyl alcohol, etc. In addition, the carbon number of the monohydric alcohol is preferably 2-20, preferably 2-16.

Examples of polyols include polyalkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, 1,3-propanediol, and 1,2-butane. Glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, 1 ,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 1,2-hexane Glycol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, 2,2,4-trimethyl-1 , 3-pentanediol, benzenediol and other glycols; glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanetriol, ethyl-1, Triols such as 2,4-butanetriol, 1,2,3-butanetriol, 3-methyl-1,3,5-pentanetriol; hexavalent alcohol (sorbitol) and other tetravalents Of alcohol.

Examples of the polyglycol ether compound include ethylene glycol monoalkyl ether (ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, etc.), ethylene glycol monophenyl ether, and ethylene glycol. Alcohol monobenzyl ether, diethylene glycol monoalkyl ether (diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, etc.), triethylene glycol monoalkyl Ether (triethylene glycol monobutyl ether, etc.), tetraethylene glycol monoalkyl ether (tetraethylene glycol monomethyl ether, etc.), propylene glycol monoalkyl ether (propylene glycol monomethyl ether, propylene glycol monoethyl ether) Ether, etc.), dipropylene glycol monoalkyl ether (dipropylene glycol monomethyl ether, etc.), etc.

Among these, considering the viewpoint of making a chemical polishing liquid that can improve the smoothness of the surface of aluminum and the like after polishing and imparting excellent gloss, and a chemical polishing liquid with excellent work safety, the hydroxyl-containing hydrocarbon compound (D ) Is desirably one or more kinds selected from the group consisting of a hydroxyl-containing aliphatic hydrocarbon compound and a hydroxyl-containing alicyclic hydrocarbon compound.

In one aspect of the chemical polishing liquid of the present invention, it is considered that a chemical polishing liquid that can improve the smoothness of the surface of aluminum and the like after polishing and impart excellent gloss, and a chemical polishing liquid that is excellent in production safety In view of this, the hydroxyl group-containing hydrocarbon compound (D) is preferably one or more kinds selected from the group consisting of diols and glycol ether compounds, preferably selected from the group consisting of diols and glycol ether compounds One or more aliphatic hydrocarbon compounds or alicyclic hydrocarbon compounds, more preferably one or more selected from the group consisting of (poly) alkylene glycols and ethylene glycol monoalkyl ethers, still more preferably It is (poly) alkylene glycol, especially preferably polyethylene glycol. In this specification, the term "(poly)alkylene glycol" is used to indicate both "alkylene glycol" and "polyalkylene glycol."

The number average molecular weight (Mn) of polyalkylene glycols such as polyethylene glycol or polypropylene glycol is preferably 100 to 8,000, preferably 200 to 5,000, more preferably 300 to 3,000, and particularly preferably 400 ~1,500. In addition, in this specification, the number average molecular weight (Mn) is a value converted from a polystyrene standard product measured by a colloidal permeation chromatography (GPC) method.

>Dilution solvent> The chemical polishing liquid according to one aspect of the present invention may further contain water, an organic solvent (excluding those belonging to component (D)), and other diluent solvents. From the viewpoint of the dilution solvent, considering the solubility of the components (A) to (D), it is preferably water. With regard to water, there is no particular limitation, and it is desirable to use distillation, ion exchange treatment, filtration treatment, various adsorption treatments, etc. to remove metal ions, organic impurities, particles, etc., preferably pure water, particularly preferably super Pure water. In one aspect of the chemical polishing liquid of the present invention, based on the total amount of the chemical polishing liquid (100% by mass), the water content is preferably 5 to 80% by mass, preferably 15 to 65% by mass, and more It is preferably 20 to 55% by mass, further preferably 23 to 53% by mass, and particularly preferably 25 to 50% by mass.

>Other active ingredients except ingredients (A)~(D)> To the extent that the effects of the present invention are not compromised, the chemical polishing liquid according to one aspect of the present invention may further contain other effective ingredients than components (A) to (D). Examples of other active ingredients include surfactants and hydrogen peroxide stabilizers.

However, the chemical polishing liquid of one aspect of the present invention is selected from the group consisting of aminophenols and benzamide in consideration of making a chemical polishing liquid that can impart excellent gloss to surfaces such as aluminum and form a smooth surface. The less the content of amine compounds in the class, the better. In the present specification, aminophenols refer to compounds having an aminophenol skeleton, for example, compounds containing at least one hydrogen in aminophenol substituted with an arbitrary substituent. In addition, benzamides also mean compounds having a benzamide skeleton, for example, compounds containing at least one hydrogen in benzamide being substituted with an arbitrary substituent. Based on the above viewpoint, based on the total amount of 100 parts by mass of the components (A) to (D) in the chemical polishing liquid, the content of the aforementioned amine compound is preferably less than 0.15 parts by mass, preferably not At least 0.10 parts by mass, more preferably less than 0.05 parts by mass, still more preferably less than 0.01 parts by mass, and particularly preferably less than 0.001 parts by mass. In addition, based on the total amount of the chemical polishing liquid (100% by mass), the content of the aforementioned amine compound is desirably less than 0.1% by mass, preferably less than 0.01% by mass, and more preferably less than 0.005 parts by mass, Even more preferably, it is less than 0.001% by mass, and particularly preferably less than 0.0001% by mass.

In addition, the chemical polishing liquid according to one aspect of the present invention is considered to be a chemical polishing liquid that can smooth the surface of aluminum or the like, and the smaller the content of azoles, the better. In the present specification, azoles are compounds having a 5-cyclic heterocyclic 5-membered ring containing at least one nitrogen atom. Examples include triazole, benzotriazole, tetrazole, imidazole, benzimidazole, Thiazole, etc. From the above viewpoint, regarding the content of the aforementioned azoles, based on the total amount of 100 parts by mass of the components (A) to (D) in the chemical polishing liquid, it is preferably less than 1 part by mass, preferably not At least 0.1 parts by mass, more preferably less than 0.01 parts by mass, particularly preferably less than 0.001 parts by mass. In addition, the content of the aforementioned azoles, based on the total amount of the chemical polishing liquid (100% by mass), is preferably less than 0.1% by mass, preferably less than 0.01% by mass, and more preferably less than 0.001% by mass , Especially good is less than 0.0001% by mass.

The chemical polishing liquid according to one aspect of the present invention is preferably a dissolving liquid, that is, it is ideally substantially free of solid particles such as polishing particles. In this specification, "solid particles" means particles that have a particle diameter of 0.01 μm or more and do not dissolve in the chemical polishing liquid. In addition, "substantially free of solid particles" is intended to exclude the situation in which solid particles are blended in the chemical polishing liquid for a specific purpose, and it is not even excluded that the chemical polishing liquid contains unavoidable solid particles Regulations. However, even if it contains unavoidable solid particles, the content of solid particles should be as small as possible. As for the specific solid particle content, based on the total amount of the aforementioned chemical polishing liquid (100% by mass), it is preferably less than 0.1% by mass, preferably less than 0.01% by mass, and more preferably less than 0.001 Mass%, particularly preferably less than 0.0001 mass%.

In addition, the chemical polishing liquid of one aspect of the present invention can be reused for surface treatment after being used in the surface treatment of aluminum or aluminum alloy. Therefore, the chemical polishing liquid according to one aspect of the present invention may contain metal atoms eluted from aluminum or the like, which is a surface treatment object, and the metal atoms are metal atoms other than aluminum contained in aluminum or aluminum alloys.

On the other hand, in the chemical polishing liquid according to one aspect of the present invention, the smaller the content of the metal-containing compound, the better. Here, the metal-containing compound is a metal-containing additive (for example, a tungsten compound) blended for a specific purpose, and there is a difference from the metal component eluted from aluminum or the like which is a surface treatment object. In terms of the specific content of the metal-containing compound, based on the total of 100 parts by mass of the components (A) to (D) in the chemical polishing liquid, it is ideally less than 10 parts by mass, preferably less than 5 The part by mass is more preferably less than 1 part by mass, and particularly preferably less than 0.1 part by mass.

>Aluminum, aluminum alloy> The chemical polishing liquid of the present invention can be ideally used for surface treatment of aluminum or aluminum alloy. As for the aluminum alloy which is a surface treatment object, for example, a pure aluminum-based aluminum alloy having an aluminum content of 99% by mass or more; an aluminum-copper-based aluminum alloy mainly containing copper in addition to aluminum; mainly other than aluminum Aluminum-manganese aluminum alloys containing manganese; and aluminum-magnesium alloys mainly containing magnesium in addition to aluminum.

As for the more specific aluminum alloys, for example, the aluminum alloys for extensions specified in JIS H4140 are pure aluminum-based A1100 alloy, A1085 alloy, and A1050 alloy; aluminum-copper-based A2024 alloy; aluminum-manganese-based alloy A3003 alloy; A5052 alloy of aluminum-magnesium series; all alloys of A1000 series to 7000 series (corrosion-resistant aluminum alloy, high-strength aluminum alloy, heat-resistant aluminum alloy, etc.), and ADC1~12 types (aluminum alloy for die casting) Aluminum alloy for casting.

As for the composition of the aluminum alloy, for example, the content of each metal atom is adjusted to the following range relative to the total amount of the aluminum alloy (100% by mass). ･Si (Si): 1.5% by mass or less ･Iron (Fe): 1.0% by mass or less ･Copper (Cu): 8.0% by mass or less ･Manganese (Mn): 2.0% by mass or less ･Magnesium (Mg): 6.0% by mass or less ･Chromium (Cr): 0.50% by mass or less ･Zinc (Zn): 8.0% by mass or less ･Ti (Ti): 0.30% by mass or less ･Vanadium (V): 0.25 mass% or less ･Bismuth (Bi): 1.0% by mass or less ･Lead (Pb): 1.0% by mass or less ･The rest is aluminum (Al) and unavoidable impurities. In addition, Table 1 illustrates the composition of the aluminum alloy, but the composition is not limited thereto.

[Table 1]

In addition, the aluminum alloy may be an aluminum alloy for casting or an aluminum alloy for spreading, a member formed into a predetermined shape by a die casting method, a member formed into a predetermined shape by machining, or a laminated aluminum alloy. The aluminum alloy for extension may be an intermediate material, that is, a plate or the like, or a member formed into a predetermined shape by mechanical processing such as hot pressing. The shape of the laminated aluminum alloy is not particularly limited. For example, it may be a plate shape or a column shape, and any shape suitable for its use. In addition, aluminum or aluminum alloys, which are objects to be surface-treated, can also exist in the form of articles equipped with aluminum or aluminum alloys and non-metallic materials, such as metal fittings of aluminum fasteners fixed to polyester material cloth.

[Aluminum or aluminum alloy surface treatment method and manufacturing method] The present invention also provides the following [1] surface treatment method of aluminum or aluminum alloy (hereinafter also referred to as "surface treatment method") and the following [2] surface-treated aluminum or aluminum alloy manufacturing method (hereinafter also (Referred to as "manufacturing method"). [1] A surface treatment method of aluminum or aluminum alloy, which uses the chemical polishing liquid of the present invention described above to perform surface treatment of aluminum or aluminum alloy. [2] A method for manufacturing a surface-treated aluminum or aluminum alloy, including the following steps: the surface treatment of aluminum or aluminum alloy is performed using the chemical polishing liquid of the present invention described above. The details of the chemical polishing liquid used in the surface treatment method and manufacturing method of the present invention, and the surface treatment object, that is, aluminum or aluminum alloy are as described above. In addition, in the surface treatment method and manufacturing method of one aspect of the present invention, the surface treatment object, that is, aluminum, etc., for example, can also be provided as a metal fitting of an aluminum fastener fixed to a polyester material cloth The form of aluminum or aluminum alloy and non-metallic materials exist.

The above-mentioned steps of the surface treatment method and manufacturing method of one aspect of the present invention are preferably performed by bringing the chemical polishing liquid into contact with aluminum or aluminum alloy, which is the surface treatment object. The method of contacting the chemical polishing liquid with aluminum or aluminum alloy is preferably performed by immersing the aluminum or aluminum alloy, which is the surface treatment object, in the chemical polishing liquid. Other methods include aluminum or aluminum. A method of coating or spreading (eg spraying) chemical polishing liquid on the surface of the alloy. At this time, the aluminum or aluminum alloy may be mechanically polished in advance, and may be heated as necessary to contact the chemical polishing liquid (ideally immersed in the chemical polishing liquid).

As for the temperature of the aforementioned chemical polishing liquid during the surface treatment of aluminum or aluminum alloy, it is preferably 40 to 80°C, preferably 45 to 75°C, and more preferably 50 to 70°C. As long as the temperature of the chemical polishing liquid is above 40°C, it can promote surface treatment and further improve productivity. On the other hand, as long as the temperature of the chemical polishing liquid is 80°C or lower, for example, when the metal fittings of aluminum fasteners fixed on the fabric of the polyester material are surface-treated, the deterioration of the polyester material can be suppressed.

In addition, as for the surface treatment time of aluminum or aluminum alloy, it can be appropriately set according to the composition, size, presence or absence of preheating of the surface treatment object, that is, aluminum or aluminum alloy, and the temperature of the chemical polishing liquid, which is preferably 1 second or more And 10 minutes or less, preferably 30 seconds or more and 7 minutes or less, more preferably 60 seconds or more and 5 minutes or less.

In addition, in the surface treatment method and manufacturing method of one aspect of the present invention, the surface treatment object, that is, aluminum or aluminum alloy, can be contacted with the chemical polishing liquid (ideally immersed in the chemical polishing liquid) only once, or For many times.

The surface-treated aluminum or aluminum alloy obtained by using the surface treatment method and manufacturing method of one aspect of the present invention has a smooth surface and excellent gloss. The arithmetic average height (Sa) of the surface-treated aluminum or aluminum alloy is affected by the arithmetic average height (Sa) of the aluminum or aluminum alloy before treatment, or the type of aluminum alloy, so there is no particular limitation. However, for example, for the arithmetic average height (Sa) of aluminum before the surface treatment with an arithmetic average height (Sa) of 150 to 250 nm or the aluminum alloy described in JIS H4140 after surface treatment, it is ideally the arithmetic before the surface treatment The average height (Sa) or less, preferably 200 nm or less, and the arithmetic average height after surface treatment is the arithmetic average height (Sa) or less before surface treatment, more preferably 140 nm or less, even more preferably 110 nm or less, and still more It is preferably 90 nm or less, and particularly preferably 70 nm or less. In addition, the lower limit of the arithmetic mean height (Sa) after the surface treatment at this time is not particularly limited, but it is usually 1 nm or more, and ideally 5 nm or more. In addition, in this specification, the arithmetic mean height (Sa) is the value measured based on ISO 25178, specifically, the value measured according to the method described in the Examples.

In addition, the gloss of the surface-treated aluminum or aluminum alloy is affected by the gloss of the aluminum or aluminum alloy before the treatment, so there is no particular limitation. However, for example, in terms of the gloss after the surface treatment of aluminum having a gloss of 200 to 350 before the surface treatment or the aluminum alloy described in JIS H4140, it is preferably at least the gloss before the surface treatment, preferably 200 or more , And the gloss after surface treatment is the gloss before surface treatment is more than, more preferably 300 or more, further more preferably 360 or more, still more preferably 400 or more, particularly preferably 500 or more, and usually 1000 or less . In addition, in this specification, glossiness is the value measured based on ISO 2813, specifically, the value measured according to the method described in the Example. [Example]

Next, the present invention will be described in more detail by examples, but the present invention is not limited by these examples.

The physical properties of the chemical polishing liquid and the physical properties of the aluminum alloy in Examples and Comparative Examples were measured as follows. (1) pH of chemical polishing liquid Using a pH meter (Horiba Manufacturing Co., Ltd., product name "D-53"), the pH of the chemical polishing liquid at 25°C was measured in accordance with JIS Z8802. (2) The arithmetic mean height of aluminum alloy sheet (Sa) Using a laser microscope (Keynes Co., Ltd., product name "VK-X250"), the arithmetic mean height (Sa) of the aluminum alloy sheet was measured according to ISO 25178. (3)Glossiness of aluminum alloy sheet Using a gloss meter (Murakami Color Technology Research Institute Co., Ltd., product name "TrueGloss GM-26 PRO/Touch"), the gloss of the aluminum alloy sheet was measured according to ISO 2813.

Example 1 (1) Preparation of chemical polishing liquid 5 parts by mass of hydrogen peroxide (Mitsubishi Gas Chemical Co., Ltd., 60% by mass aqueous solution) (effective component ratio of hydrogen peroxide), ammonium hydrogen fluoride (Daiwa Chemical Co., Ltd.) 15 parts by mass (10 parts by mass in terms of fluorine atom), 40 parts by mass of phosphoric acid (85% by mass aqueous solution manufactured by Rasa Industries, Ltd.) (effective component ratio of H ₃ PO ₄ ), and polyethylene glycol ( It is manufactured by Daiichi Pharmaceutical Co., Ltd., with the product name "PEG600") 7 parts by mass, and then diluted with water to prepare a chemical polishing liquid (1) with an active ingredient concentration of 67% by mass. The pH of the prepared chemical polishing liquid (1) is 2.0.

(2) Surface treatment of aluminum alloy sheet As the surface treatment, an aluminum alloy sheet (I) (JIS A5052P-H34, arithmetic mean height (Sa) = 150 nm, gloss = 304, composition equivalent to alloy number A5052 in Table 1) with a thickness of 1.5 mm and a length of 20×50 mm is used as the surface treatment Object. The aluminum alloy sheet (I) was immersed in the chemical polishing liquid (1) prepared as described above, and immersed for 2 minutes at a liquid temperature of 60°C. Next, the impregnated aluminum alloy sheet (I) was taken out from the chemical polishing liquid (1), washed thoroughly with ion-exchanged water, and then sufficiently dried to obtain a surface-treated alloy. The arithmetic mean height (Sa) of the resulting surface-treated alloy = 65 nm, and gloss = 390.

Comparative example 1 The chemical polishing liquid (2) was prepared in the same manner as in Example 1 except that the phosphoric acid was not added and 40 parts by mass of water was substituted for the blending amount of the effective component ratio of phosphoric acid. The pH of the prepared chemical polishing liquid (2) is 2.0. Then, the aluminum alloy sheet (I) similar to Example 1 was surface-treated using the above-mentioned chemical polishing liquid (2) in the same manner as Example 1, to obtain a surface-treated alloy. The arithmetic mean height (Sa) of the resulting surface-treated alloy = 224 nm, and gloss = 40.

Example 2 As the surface treatment, an aluminum alloy sheet (II) (JIS A1100P-H14, arithmetic average height (Sa) = 94 nm, gloss = 463, composition equivalent to the alloy number A1100 in Table 1) with a thickness of 0.4 mm and a length of 30 mm and a width of 50 mm is used as the surface treatment Except for this, surface treatment was performed using the same chemical polishing liquid (1) as prepared in Example 1 to obtain a surface-treated alloy. The arithmetic mean height (Sa) of the resulting surface-treated alloy = 20 nm, and gloss = 745.

Comparative example 2 Using the same chemical polishing liquid (2) as prepared in Comparative Example 1, the same aluminum alloy sheet (II) as in Example 2 above was subjected to surface treatment in the same manner as Example 2 to obtain a surface-treated alloy. The arithmetic mean height (Sa) of the resulting surface-treated alloy = 233 nm and gloss = 120.

Comparative Example 3 The chemical polishing liquid (3) was prepared in the same manner as in Example 1 except that polyethylene glycol was not added, and the effective component ratio of polyethylene glycol was replaced with 7 parts by mass of water. The pH of the prepared chemical polishing liquid is 4.5. Then, to use the above-mentioned chemical polishing liquid (3), the aluminum alloy sheet (II) similar to the above-mentioned Example 2 was subjected to the surface treatment at the liquid temperature of 60° C. in the same time as in Example 2, but due to the reaction The process was vigorously carried out, and the chemical polishing liquid (3) overflowed from the container, so the treatment time of 1 minute ended, and a surface-treated alloy was obtained. The arithmetic mean height (Sa) of the resulting surface-treated alloy = 42 nm, and gloss = 607.

Table 2 shows the results of Examples 1 to 2 and Comparative Examples 1 to 3 as above. [Table 2]

According to Table 2, it was confirmed that in Examples 1 and 2, when the prepared chemical polishing liquid (1) was used for the surface treatment of the aluminum alloy, the surface of the aluminum alloy was polished and smoothed, and became a surface with high gloss. On the other hand, in Comparative Examples 1 and 2, when the surface treatment of the aluminum alloy was performed using the prepared chemical polishing liquid (2), the reaction proceeded violently, so the surface of the aluminum alloy was compared with that before the surface treatment The arithmetic mean height (Sa) increases and the surface gloss decreases. In addition, when the chemical polishing liquid (3) prepared in Comparative Example 3 was used for surface treatment of aluminum alloys, the reaction proceeded excessively violently, and as a result, the treatment time had to be ended within 1 minute, and the work safety was problematic.

Example 3 The blending amount of hydrogen peroxide is set to "15 parts by mass (as an effective component ratio of hydrogen peroxide)", and the blending amount of water is set to "23 parts by mass". In the same manner, a chemical polishing liquid (4) having an active ingredient concentration of 77% by mass was prepared. The pH of the prepared chemical polishing liquid (4) is 1.60. Then, the same aluminum alloy sheet (I) as in Example 1 was surface-treated using the above-mentioned chemical polishing liquid (4) to obtain a surface-treated alloy. The arithmetic mean height (Sa) of the resulting surface-treated alloy = 61 nm, and gloss = 520.

Example 4 Except that the blending amount of phosphoric acid was set to "25 parts by mass" and the blending amount of water was set to "48 parts by mass", it was carried out in the same manner as in Example 1 to prepare an effective component concentration of 52 mass% The chemical polishing liquid (5). The pH of the prepared chemical polishing liquid (5) was 2.90. Then, the same aluminum alloy sheet (I) as Example 1 was surface-treated using the above-mentioned chemical polishing liquid (5) to obtain a surface-treated alloy. The arithmetic average height (Sa) of the resulting surface-treated alloy = 51 nm, and gloss = 520.

Example 5 Except that the blending amount of polyethylene glycol was set to "2 parts by mass" and the blending amount of water was set to "38 parts by mass", it was carried out in the same manner as in Example 1 to prepare the effective ingredient concentration 62% by mass of chemical polishing liquid (6). The pH of the prepared chemical polishing liquid (6) is 2.20. Then, the same aluminum alloy sheet (I) as in Example 1 was surface-treated using the above-described chemical polishing liquid (6) to obtain a surface-treated alloy. The arithmetic average height (Sa) of the resulting surface-treated alloy = 104 nm, and gloss = 350.

Example 6 Except for blending 7 parts by mass of "ethylene glycol monobutyl ether" instead of "polyethylene glycol", the same procedure as in Example 1 was carried out to prepare a chemical polishing solution having an effective ingredient concentration of 67% by mass (7 ). The pH of the prepared chemical polishing liquid (7) is 2.20. Then, using the above chemical polishing liquid (7), the same aluminum alloy sheet (I) as in Example 1 was surface-treated in the same manner as in Example 1 to obtain a surface-treated alloy. The arithmetic mean height (Sa) of the resulting surface-treated alloy = 130 nm and gloss = 300.

Example 7 Except having mixed 7 mass parts of "propylene glycol" instead of "polyethylene glycol", it carried out similarly to Example 1, and prepared the chemical polishing liquid (8) with an active ingredient concentration of 67 mass %. The pH of the prepared chemical polishing liquid (8) is 2.20. Then, the same aluminum alloy sheet (I) as Example 1 was surface-treated using the above-mentioned chemical polishing liquid (8) to obtain a surface-treated alloy. The arithmetic average height (Sa) of the resulting surface-treated alloy = 105 nm, and gloss = 300.

Example 8 The blending amount of ammonium bifluoride was set to "5 parts by mass (converted fluorine atom is 3 parts by mass)", and the blending amount of water was set to "43 parts by mass", except that it was the same as Example 1. In this way, a chemical polishing liquid (9) having an active ingredient concentration of 57% by mass was prepared. The pH of the prepared chemical polishing liquid (9) was 1.90. Then, the same aluminum alloy sheet (I) as in Example 1 was surface-treated using the above-mentioned chemical polishing liquid (9) to obtain a surface-treated alloy. The arithmetic average height (Sa) of the resulting surface-treated alloy = 100 nm and gloss = 240.

Example 9 Except that the blending amount of polyethylene glycol was set to "15 parts by mass" and the blending amount of water was set to "25 parts by mass", the same as in Example 1, the active ingredient concentration was 75% by mass. Of chemical polishing fluid (10). The pH of the prepared chemical polishing liquid (10) is 2.10. Then, the aluminum alloy sheet (I) similar to Example 1 was surface-treated using the above-mentioned chemical polishing liquid (10) in the same manner as Example 1 to obtain a surface-treated alloy. The arithmetic average height (Sa) of the resulting surface-treated alloy = 109 nm and gloss = 280.

The results of Examples 3 to 9 above are shown in Table 3 together. [table 3]

According to Table 3, it can be confirmed that when the surface treatment of aluminum alloy is performed using the chemical polishing liquids (4) to (10) prepared in Examples 3 to 9, the surface of the aluminum alloy is smoothed by polishing and becomes a surface with high gloss .

Claims (12)

A chemical polishing liquid used for aluminum or aluminum alloy; Contains hydrogen peroxide (A), fluorine compound (B), inorganic acid (C) which is not the fluorine compound (B), and hydrocarbon compound (D) containing hydroxyl group; Based on the total amount of the chemical polishing liquid, the content of the hydrogen peroxide (A) is 2-20% by mass; Based on the total amount of the chemical polishing liquid, the content of the fluorine compound (B) in terms of fluorine atoms is 3 to 17% by mass; Based on the total amount of the chemical polishing liquid, the content of the inorganic acid (C) is 20 to 55% by mass; Based on the total amount of the chemical polishing liquid, the content of the hydroxyl-containing hydrocarbon compound (D) is 2 to 15% by mass. For example, if the chemical polishing liquid of patent application item 1 is used, the pH of the chemical polishing liquid is 4 or less. The chemical polishing liquid as claimed in item 1 or 2 of the patent application, wherein the fluorine compound (B) is at least one selected from the group consisting of acidic ammonium fluoride, acidic potassium fluoride, ammonium fluoride, and hydrogen fluoride . The chemical polishing liquid according to any one of claims 1 to 3, wherein the inorganic acid (C) contains phosphoric acid. The chemical polishing liquid according to any one of items 1 to 4 of the patent application scope, wherein the hydroxyl-containing hydrocarbon compound (D) is selected from the group consisting of monovalent alcohols with a carbon number of 2 or more, polyhydric alcohols, and glycol ether compounds More than one type in the group. For example, the chemical polishing liquid according to any one of claims 1 to 5, wherein the content ratio of the inorganic acid (C) to the hydroxyl-containing hydrocarbon compound (D) [(C)/(D)], to The mass ratio is 2~25. A surface treatment method for aluminum or aluminum alloy is to use a chemical polishing liquid as described in any one of patent application items 1 to 6 to perform surface treatment for aluminum or aluminum alloy. For example, the surface treatment method of aluminum or aluminum alloy according to item 7 of the patent application scope, wherein the temperature of the chemical polishing liquid during the surface treatment of aluminum or aluminum alloy is 40 to 80°C. For example, the surface treatment method of aluminum or aluminum alloy according to item 7 or 8 of the patent application scope, wherein the surface treatment time of aluminum or aluminum alloy is 1 second or more and 10 minutes or less. A method for manufacturing surface-treated aluminum or aluminum alloy includes the following steps: The surface treatment of aluminum or aluminum alloy is carried out using the chemical polishing liquid according to any one of items 1 to 6 of the patent application. A surface-treated aluminum or aluminum alloy that uses a chemical polishing liquid as described in any of items 1 to 6 of the patent application. The arithmetic average height (Sa) measured according to ISO 25178 before surface treatment is 150~ 250nm aluminum or aluminum alloy described in JIS H4140 is surface-treated, the arithmetic average height (Sa) of the aluminum or aluminum alloy after surface treatment is 200nm or less, and the arithmetic average height after surface treatment is the arithmetic before surface treatment Below average height (Sa). A surface-treated aluminum or aluminum alloy, which uses a chemical polishing liquid as described in any one of the patent application items 1 to 6, before the surface treatment, according to ISO 2813, the gloss of 200-350 aluminum or The aluminum alloy described in JIS H4140 is subjected to surface treatment. The gloss of the aluminum or aluminum alloy after the surface treatment is 150 or more, and the gloss after the surface treatment is more than the gloss before the surface treatment.