JP2016020522A - Aqueous metal surface treatment composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous metal surface treatment agent that is excellent in painting ability and storage stability and capable of forming a chromate-free surface treatment film excellent in corrosion resistance, electric conductivity, fingerprint resistance and top coating adhesion before and after degreasing.SOLUTION: An aqueous metal surface treatment composition contains an organopolysiloxane (A) as a binder principal component, and a compound (B) of a molecular weight of 100-800 having a propargyl group, a hydroxy group and a mono- or poly-oxyalkylene group. The mono- or poly-oxyalkylene group in the compound (B) is at least one kind selected from an oxyethylene group, a polyoxyethylene group, an oxypropylene group, a polyoxypropylene group, and a bivalent copolymer chain of ethylene oxide and propylene oxide.SELECTED DRAWING: None

Description

  The present invention is excellent in paintability and storage stability, and has excellent corrosion resistance before and after degreasing treatment, electrical conductivity, fingerprint resistance and adhesion to the top coat, and is free of chromate free of pollution-controlling substances such as hexavalent chromium in the film. The present invention relates to an aqueous metal surface treatment composition capable of forming a surface treatment film, a surface treatment method for a metal material using the surface treatment composition, and a surface treatment metal material on which a film is formed from the surface treatment composition.

  In general, as a technology that provides excellent adhesion to the metal material surface and imparts corrosion resistance to the metal material surface, chromate is applied to the metal material surface with a treatment liquid containing chromic acid, dichromic acid or a salt thereof as a main component. A method for performing treatment, a method for performing phosphate treatment, a method for performing treatment mainly with inorganic components, a method for performing treatment with a silane coupling agent, a method for performing organic resin film treatment, and the like are known and are practically used. Has been.

  Patent Document 1 discloses a metal surface treatment agent containing a vanadium compound and a metal compound containing at least one metal selected from zirconium, titanium, molybdenum, tungsten, manganese, and cerium as a technique for performing a treatment with an inorganic component. Are listed.

  As a technique using a silane coupling agent, a surface treatment agent containing an organofunctional silane and polysiloxane is taught. Patent Document 2 discloses a method for forming a siloxane film having improved adhesion to a substrate from an organofunctional silane and polysiloxane.

  As a technology for performing the organic resin film treatment, a specific resin compound (A) and a cationic urethane resin having at least one cationic functional group selected from a primary to tertiary amino group and a quaternary ammonium base ( B), one or more silane coupling agents (C) having a specific reactive functional group, and a specific acid compound (E), and a cationic urethane resin (B) and a silane coupling agent Patent Document 3 discloses a non-chromium surface-treated steel sheet using a surface treating agent having a content of (C) within a predetermined range and having excellent corrosion resistance, fingerprint resistance, blackening resistance and paint adhesion. ing.

  Patent Document 4 includes a water-soluble zirconium compound, a compound having an epoxy group, a chelating agent, a vanadic acid compound, and a metal compound containing a metal such as Ti, and is converted into Zr of the water-soluble zirconium compound. It is disclosed that a galvanized steel sheet having a surface treatment film with a surface treatment agent having a weight / tetraalkoxysilane mass ratio of 1.0 to 6.0 is excellent in corrosion resistance and electromagnetic shielding properties.

  However, these conventional techniques are excellent in paintability and storage stability, and form a film excellent in corrosion resistance before and after degreasing, conductivity, fingerprint resistance and topcoat adhesion, and are chromate-free. There is a need for further improvements rather than an aqueous metal surface treatment that satisfies all.

JP 2002-30460 A JP 11-43647 A JP 2003-105562 A JP 2010-255105 A

  The present invention solves the above-mentioned problems of the prior art, is excellent in paintability and storage stability, and is excellent in corrosion resistance before and after degreasing treatment, conductivity, fingerprint resistance, and topcoat adhesion. An object of the present invention is to provide an aqueous metal surface treatment agent capable of forming a chromate-free surface treatment film that does not contain a pollution control substance such as chromium. It is another object of the present invention to provide a surface treatment method for a metal material such as a zinc-based plated steel sheet using the surface treatment agent, and a surface treatment metal material on which a film is formed by the surface treatment agent.

  As a result of intensive studies to solve these problems, the inventors of the present invention have identified a specific composition having a propargyl group, a hydroxyl group and a polyoxyalkylene chain in an aqueous metal surface treatment composition containing organopolysiloxane as a main component of the binder. The present invention was completed by finding that the above-mentioned problems can be solved by containing the above compound.

  That is, the present invention contains an organopolysiloxane (A) as a binder main component and a compound (B) having a propargyl group and a hydroxyl group and having a mono- or poly-oxyalkylene group and having a molecular weight of 100 to 800. A mono- or poly-oxyalkylene group in the compound (B) is an oxyethylene group, a polyoxyethylene group, an oxypropylene group, a polyoxypropylene group, and a divalent copolymer of ethylene oxide and propylene oxide. The present invention provides an aqueous metal surface treatment composition characterized in that it is at least one selected from a combined chain.

Further, the present invention is characterized in that the aqueous metal surface treatment composition is applied on the surface of a metal material so as to have a dry film mass of 0.05 to 3.0 g / m ² and dried. A surface treatment method for a metal material is provided.

Furthermore, the present invention provides a surface-treated metal material in which a film of the aqueous metal surface treatment composition is formed on the surface of the metal material at a dry film mass of 0.05 to 3.0 g / m ² . It is.

  The aqueous metal surface treatment composition of the present invention is a chromate-free surface treatment composition that does not contain pollution-controlling substances such as hexavalent chromium, and is excellent in paintability and storage stability. From the metal surface treatment composition of the present invention, The formed film can satisfy all of the corrosion resistance before and after the degreasing treatment, the electrical conductivity, the fingerprint resistance, and the top coat adhesion. In addition, a metal material such as a zinc-based plated steel sheet on which the surface treatment film is formed is excellent in corrosion resistance even when the surface treatment film is thin. Is.

Aqueous Metal Surface Treatment Composition The aqueous metal surface treatment composition of the present invention comprises an aqueous metal containing an organopolysiloxane (A) as a binder main component and a compound (B) having a propargyl group, a hydroxyl group and a polyoxyalkylene chain. A surface treatment composition in which the component (A) and the component (B) are stably dissolved or dispersed in an aqueous medium. In the present invention, the “aqueous medium” means a uniform liquid or water at 20 ° C. containing water and an organic solvent and having a water content of 80% by mass or more. The organic solvent species that can constitute the “aqueous medium” is not particularly limited as long as it is a water-soluble or water-dispersible solvent, and examples thereof include methanol, ethanol, isopropyl alcohol, t-butyl alcohol, and propylene glycol. Examples include alcohols; glycol ethers such as ethylene glycol monobutyl ether and ethylene glycol monoethyl ether; esters such as ethyl acetate and butyl acetate; ketones such as acetone.

Organopolysiloxane (A)
The organopolysiloxane (A) as a binder component in the aqueous metal surface treatment composition of the present invention is a compound having a plurality of siloxane bonds condensed with an organosilane. The organopolysiloxane (A) is not limited as long as it is a compound having a plurality of siloxane bonds condensed with an organosilane.

  Representative examples of the organopolysiloxane (A) include, for example, at least one silane coupling agent (a) selected from an epoxy group-containing silane coupling agent and an amino group-containing silane coupling agent, and mono-, di- And a reaction product of at least one alkoxysilane selected from tri- and tetra-alkoxysilanes or a low condensate (b) of the alkoxysilanes.

  Among them, the organopolysiloxane (A) is based on the total amount of the silane coupling agent (a) and the alkoxysilane or the low-condensate (b) of the alkoxysilane, based on the silane coupling agent (a) 100. It is preferable that it is a reaction product of -30 mass parts and 0-70 mass parts of alkoxysilane or the low condensate (b) of this alkoxysilane.

  In particular, the organopolysiloxane (A) is an epoxy group-containing silane coupling agent 10 to 10 based on the total amount of the silane coupling agent (a) and the alkoxysilane or the low-condensate (b) of the alkoxysilane. The reaction product is more preferably 50 parts by mass, 10 to 50 parts by mass of an amino group-containing silane coupling agent, and 10 to 60 parts by mass of the alkoxysilane or the low-condensate (b) of the alkoxysilane.

Silane coupling agent (a)
The epoxy group-containing silane coupling agent in the silane coupling agent (a) is not particularly limited as long as it is an epoxy group-containing silane coupling agent, and typical examples thereof include, for example, γ-glycol. Sidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- And epoxy cyclohexyl) ethyltriethoxysilane.

  The amino group-containing silane coupling agent in the silane coupling agent (a) is not particularly limited as long as it is a silane coupling agent containing an amino group, and representative examples thereof include, for example, 3-amino Examples include propyltriethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, and N- (2-aminoethyl) 3-aminopropyltrimethoxysilane.

  When the epoxy group-containing silane coupling agent and the amino group-containing silane coupling agent are used in combination as the silane coupling agent (a), the organopolysiloxane (A) is bonded to the polysiloxane bond by hydrolysis / condensation reaction. In addition, it can have a chemical bond by addition reaction between the epoxy group in the epoxy group-containing silane coupling agent and the amino group in the amino group-containing silane coupling agent.

Alkoxysilane or low-condensate of alkoxysilane (b)
The component (b) is at least one alkoxysilane selected from mono-, di-, tri- and tetra-alkoxysilanes or a low condensate of the alkoxysilanes.

  Examples of the monoalkoxysilane include methoxytrimethylsilane, methoxytriethylsilane, methoxymethyldiethylsilane, ethoxytrimethylsilane, ethoxytriethylsilane, ethoxytriphenylsilane, propoxytrimethylsilane, propoxytripropylsilane, and butoxytributylsilane. It is done.

  Examples of the dialkoxysilane include dimethoxydimethylsilane, dimethoxydiethylsilane, dimethoxydiphenylsilane, diethoxydimethylsilane, diethoxydiethylsilane, diethoxydiphenylsilane, dipropoxydimethylsilane, dipropoxydiethylsilane, and dipropoxydipropyl. Examples thereof include silane, dipropoxydiphenylsilane, dibutoxydimethylsilane, dibutoxydiethylsilane, dibutoxydibutylsilane, and dibutoxydiphenylsilane.

  Examples of the trialkoxysilane include trimethoxymethylsilane, trimethoxyethylsilane, trimethoxypropylsilane, trimethoxybutylsilane, trimethoxyphenylsilane, triethoxymethylsilane, triethoxyethylsilane, triethoxybutylsilane, trimethoxybutylsilane, Examples include ethoxyphenylsilane, tripropoxymethylsilane, tripropoxypropylsilane, tripropoxyphenylsilane, and tributoxyphenylsilane.

  Examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and dimethoxydiethoxysilane.

  Of the alkoxysilanes, trialkoxysilane and tetraalkoxysilane are preferable from the viewpoint of crosslinkability.

  The alkoxy group of these alkoxysilanes is not particularly limited, and examples thereof include an alkoxy group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms.

  At least one low condensate of mono-, di-, tri-, and tetra-alkoxysilanes is a low condensate of a single alkoxysilane of mono-, di-, tri-, and tetra-alkoxysilanes. May also be a low condensate of two or more alkoxysilanes. The low condensate preferably has a degree of polymerization of 10 or less, particularly about 2 to 6.

  A typical example of a preferable production method of the organopolysiloxane (A) will be described below.

  The organopolysiloxane (A) is a hydrolysis condensate obtained by hydrolytic condensation reaction of organosilane. When the organosilane contains both an epoxy group-containing silane coupling agent and an amino group-containing silane coupling agent, the organopolysiloxane (A) contains an epoxy group in addition to the polysiloxane bond by hydrolysis condensation. It can have a bond by an addition reaction between an epoxy group in the silane coupling agent and an amino group in the amino group-containing silane coupling agent.

  The hydrolysis condensation reaction for obtaining the organopolysiloxane (A) can be carried out in the presence of water and an acid catalyst. The acid catalyst is not particularly limited as long as it is an acid used as a catalyst for the hydrolysis reaction of organosilane such as alkoxysilane. For example, inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid; formic acid, acetic acid Organic acids such as lactic acid and tartaric acid. In the hydrolysis condensation reaction, an organic solvent may be used as appropriate, and a water-soluble organic solvent (for example, an alcohol solvent or a glycol ether solvent) that dissolves the organosilane can be used. . As the water-soluble solvent, alcohol solvents such as, for example, methanol, ethanol and propanol are preferable.

  The reaction conditions for this hydrolysis reaction are usually pH 7 or less, preferably pH 1.5 to 7.0, more preferably pH 3.0 to 6.5, about 20 ° C. to 100 ° C., about 30 minutes to 20 hours. It can be performed by stirring, and the condensation reaction proceeds together with the hydrolysis reaction. The molecular weight of the organopolysiloxane (A) obtained by this reaction can be appropriately adjusted depending on the amount of water used, the type and amount of the catalyst, the reaction temperature and the reaction time.

  When both the epoxy group-containing silane coupling agent and the amino group-containing silane coupling agent are contained as raw materials for producing the organopolysiloxane (A), it is based on the hydrolysis reaction and the epoxy group and amino group. The addition reaction is carried out by a method of reacting in an aqueous medium or a method of further reacting in an aqueous medium after partially reacting in an alcohol solvent or without a solvent. The reaction sequence is not particularly limited, but the epoxy group-containing silane coupling agent and the amino group-containing silane coupling agent are kept separate, and one silane coupling agent and component (b) as necessary Is then hydrolyzed, and then the remaining silane coupling agent is added to cause hydrolysis / condensation reaction and addition reaction. The above addition reaction can occur simultaneously with the hydrolysis / condensation reaction.

  By the reaction described above, an aqueous medium in which the organopolysiloxane (A) as the binder component is dissolved or dispersed can be obtained.

  The aqueous medium in which the organopolysiloxane (A) is dissolved or dispersed contains an organic solvent such as an alcohol component produced by hydrolysis. From the viewpoint of safety and hygiene, for example, the organic solvent is distilled off by heating and decompression. This can be a non-hazardous material in the Fire Service Act that does not have a flash point.

  The weight average molecular weight of the organopolysiloxane (A) is preferably in the range of 400 to 20000, and more preferably in the range of 1000 to 10,000. The weight average molecular weight of the organopolysiloxane (A) is the retention time (retention capacity) of a standard polystyrene having a known molecular weight measured under the same conditions as the retention time (retention capacity) measured using a gel permeation chromatograph (GPC). Is a value obtained by converting to a molecular weight of polystyrene. As a gel permeation chromatograph apparatus, "HLC-8120GPC" (trade name, manufactured by Tosoh Corporation) is used, and as a column, "TSKgel GMHHR-L" (trade name, manufactured by Tosoh Corporation) is used as a detector. As a mobile phase: dimethylformamide (including 0.5% by mass of triethanolamine), measurement temperature: 25 ° C., and flow rate: 1 mL / min.

Moreover, the siloxane bond by condensation in organopolysiloxane (A) can be confirmed by ²⁹ Si NMR (nuclear magnetic resonance spectrum) measurement.

Compound (B)
Component (B) in the composition of the present invention is a compound having a propargyl group and a hydroxyl group and having a mono- or poly-oxyalkylene group and having a molecular weight of 100 to 800, wherein the mono- or poly-oxyalkylene group is It is at least one selected from an oxyethylene group, a polyoxyethylene group, an oxypropylene group, a polyoxypropylene group, and a divalent copolymer chain of ethylene oxide and propylene oxide.

  Compound (B), together with organopolysiloxane (A), can form a film on the metal surface that satisfies all of the corrosion resistance before and after the degreasing treatment, the electrical conductivity, the fingerprint resistance, and the topcoat adhesion. In the compound (B), the propargyl group is oriented on the metal surface, the hydroxyl group generates a hydrogen bond, or reacts with the silanol group in the organopolysiloxane (A) when the film is cured, and the mono- or poly-oxyalkylene described above. The group is considered to contribute to the affinity with the binder component, the dispersion stability, and the like.

  Examples of compound (B) include adducts of acetylene alcohols having 3 to 6 carbon atoms and ethylene oxide and / or propylene oxide. This adduct is preferably an adduct obtained by adding 1 to 12 mol, preferably 1 to 6 mol, of ethylene oxide and / or propylene oxide to 1 mol of acetylene alcohol.

  Examples of the acetylene alcohol include 2-propyn-1-ol, 3-butyn-1-ol, 1-hexyn-3-ol, 3-methyl-1-butyn-3-ol, and 3-methyl-1- Examples include pentyn-3-ol, and 2-propyn-1-ol is particularly preferable.

  As a typical example of a suitable thing of a compound (B), the compound represented by the following formula (1) which added the said alkylene oxide to 2-propyn-1-ol can be mentioned, for example.

(In the formula, X represents at least one oxyalkylene group selected from an oxyethylene group and an oxypropylene group, the repeating number n represents an integer of 1 to 12, preferably 1 to 6, and n is 2 or more. Sometimes each X in the repeating unit may be the same or different.)
The compound (B) may be a commercially available product, and suitable examples include, for example, Korantin PM and Korantin PP manufactured by BASF. Korantin is a registered trademark.

  In the composition of the present invention, the amount of compound (B) is determined in terms of the solid content of the organopolysiloxane (A) from the viewpoint of the stability of the surface treatment composition, the corrosion resistance of the resulting surface treatment film, particularly the corrosion resistance after degreasing. Based on 100 parts by mass, 0.1 to 10 parts by mass is preferable, 1 to 5 parts by mass is more preferable, and 2 to 5 parts by mass is particularly preferable.

Phosphoric acid compound (C)
In the metal surface treatment composition of the present invention, it is preferable to add a phosphoric acid compound (C) as necessary for the purpose of improving storage stability. Mixing the phosphoric acid compound (C) in the metal surface treatment composition is effective in improving the stability of the metal surface treatment composition, and the silanol groups in the polyorganosiloxane (A) as the binder component react. It is presumed that high molecular weight can be suppressed.

  The type of the phosphoric acid compound (C) is not particularly limited, and may be either an organic phosphoric acid compound or an inorganic phosphoric acid compound. Typical examples of the organic phosphate compound include 1-hydroxymethane-1, 1-diphosphonic acid, 1-hydroxyethane-1, 1-diphosphonic acid, 1-hydroxypropane-1, 1-diphosphonic acid, and the like. Suitable examples include hydroxyl group-containing organic phosphorous acid; carboxyl group-containing organic phosphorous acid such as 2-hydroxyphosphonoacetic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid, and salts thereof. Representative examples of inorganic phosphoric acid compounds include orthophosphoric acid, metaphosphoric acid, phosphorous acid, metaphosphorous acid, hypophosphoric acid, hypophosphorous acid, pyrophosphoric acid, tripolyphosphoric acid, tetraphosphoric acid, hexaphosphoric acid, and trimetalin. Examples include acids, pyrophosphorous acid, and phosphoric acid derivatives; alkali metal salts or ammonium salts of these phosphoric acid compounds.

  Among the phosphoric acid compounds, orthophosphoric acid is particularly preferable because it has a large effect of improving the storage stability of the metal surface treatment composition.

  When the phosphoric acid compound (C) is blended in the composition of the present invention, the blending amount is preferably 0.5 to 10 parts by mass based on 100 parts by mass of the solid content of the organopolysiloxane (A). . Phosphoric acid compound (C) can also be mix | blended at the time of manufacture of organopolysiloxane (A).

Antirust metal compound (D)
In the metal surface treatment composition of the present invention, a rust preventive metal compound (D) can be blended as necessary for the purpose of improving the rust preventive property of the resulting treated film.

  Examples of the anticorrosive metal compound (D) include metal compounds of metals such as titanium, zirconium, hafnium, manganese, cobalt, zinc, magnesium, nickel, vanadium, tin, calcium, silicon, tungsten, molybdenum and aluminum. It is preferably water-soluble or water-dispersible. Examples of such metal compounds include carbonates, phosphates, nitrates, sulfates, acetates, fluoro acids and salts thereof, oxides, and the like. These metal compounds may be anhydrides or hydrates when present.

  The metal compound (D) is preferably a metal compound of titanium, zirconium and / or hafnium.

Representative examples of the metal compound (D) include, for example, titanyl sulfate, titanyl nitrate, titanium nitrate, titanyl chloride, titanium chloride, titania sol, titanium oxide, potassium oxalate titanate, hexafluorotitanic acid (H ₂ TiF ₆ ). , Salts of hexafluorotitanic acid (for example, sodium salt, potassium salt, lithium salt, ammonium salt, amine salt, zinc salt, etc.), titanium lactate, titanium tetraisopropoxide, titanium acetylacetonate, diisopropyltitanium bisacetylacetone, Titanium compounds such as metatitanic acid, metatitanate, orthotitanic acid, orthotitanate; basic zirconium carbonate (ZrCO ₄ .ZrO ₂ .8H ₂ O), ammonium zirconium carbonate, zirconium nitrate, zirconium sulfate, zirconium acetate, six Fluoride Rukoniumu acid (H 2 _{ZrF 6),} salts of hexafluoro zirconate (such as sodium salts, potassium salts, lithium salts, ammonium salts, amine salts, zinc salts, etc.) zirconium compounds, such as hexafluoro hafnium acid (H ₂ HfF ₆ ), hafnium compounds such as a salt of hexafluorohafnium acid (for example, sodium salt, potassium salt, lithium salt, ammonium salt, amine salt, zinc salt, etc.).

Specific examples of metal compounds other than titanium, zirconium, and hafnium compounds include, for example, nickel sulfate, aluminum sulfate, vanadyl sulfate, zinc sulfate, zinc nitrate, aluminum nitrate, nickel acetate, aluminum oxide, vanadium oxide, zinc carbonate, and oxide. Zinc, aluminum hydroxide, zinc hydroxide, aluminum phosphate, aluminum chloride, zinc chloride, zinc phosphate, ammonium metavanadate, hexafluorosilicate (H ₂ SiF ₆ ), hexafluoroaluminate (H ₃ AlF ₆₎ ), Tetrafluoroboric acid (HBF ₄ ) and the like.

  The rust preventive metal compound (D) is a component blended as necessary, and the blending amount is preferably 100 parts by mass or less based on 100 parts by mass of the solid content of the organopolysiloxane (A). Yes, more preferably 2 to 40 parts by mass, still more preferably 5 to 30 parts by mass. The amount of the rust-preventive metal compound (D) within the above range is the corrosion resistance of the resulting coating film, particularly the corrosion resistance after alkaline degreasing treatment, conductivity, and the coating properties and storage stability of the surface treatment agent. From the viewpoint of

  The aqueous metal surface treatment composition of the present invention comprises the above-mentioned organopolysiloxane (A), compound (B), aqueous medium, phosphate compound (C) and rust-preventive metal compound (D) blended as necessary. In addition, leveling agents, antifoaming agents, surfactants, coloring agents, antibacterial and antifungal agents; etching inhibitors that are amine compounds such as ethylenediamine, triethylenepentamine, guanidine, pyrimidine; acetic acid, lactic acid, ammonium salts, PH adjusting agents such as amines; hydroxycarboxylic acids such as tartaric acid and malic acid, polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, citric acid, and adipic acid such as adipic acid, and aminocarboxylic acids such as glycine, EDTA Chelating agents such as DTPA; fillers such as zirconia sol, alumina sol, silica sol (colloidal silica aqueous dispersion); Aqueous organic resin having a water-dispersible; can contain a wax component and the like.

  The chelating agent can have a function of stably dissolving the rust preventive metal compound (D) in the surface treatment composition.

  The aqueous organic resin that can be blended in the aqueous metal surface treatment composition of the present invention as needed is an organic resin that can be stably dissolved or dispersed in the aqueous metal surface treatment composition of the present invention. Includes a nonionic or anionic group containing a functional group (for example, an acid group such as a hydroxyl group, a polyoxyalkylene group, or a carboxyl group) that can be water-soluble or water-dispersed singly or with a basic compound. An organic resin; an organic resin emulsion emulsified with a nonionic surfactant (emulsifier) can be used.

  Examples of the resin type of the aqueous organic resin include an epoxy resin, a phenol resin, an acrylic resin, a urethane resin, an olefin-carboxylic acid resin, a nylon resin, a resin having a polyoxyalkylene chain, polyvinyl alcohol, Examples include polyglycerin, carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, and the like. These aqueous organic resins can be used alone or in combination of two or more.

  Among these, acrylic resin emulsions and urethane resin emulsions are particularly preferable from the viewpoint of the balance between the storage stability of the surface treatment agent and the surface treatment film performance. By mix | blending aqueous organic resin in this invention composition, it may contribute to the improvement of the wettability to a base material, topcoat adhesiveness, and corrosion resistance. When the aqueous organic resin is blended, the blended amount is 70% by mass or less, preferably 5 to 50% by mass, based on the solid content of the organopolysiloxane (A). From the viewpoints of electrical conductivity, corrosion resistance, and the like.

  The wax component is a component that imparts lubricity to the surface of the resulting film. For example, a fatty acid ester wax that is an esterified product of a polyol compound and a fatty acid, a silicon wax, a fluorine wax, a polyolefin wax such as polyethylene or polypropylene Lanolin wax, montan wax, microcrystalline wax, carnauba wax and the like. These can be used alone or in combination of two or more. When the wax is blended, the blending amount is 0.1 to 10% by mass, preferably 0. 0% as the solid content with respect to the total solid content of the metal surface treatment composition in terms of molding processability and corrosion resistance. It is suitable to be in the range of 3-5% by mass.

  The aqueous metal surface treatment composition of the present invention is preferably in the range of pH 2-7, preferably pH 3-6, more preferably 3.5-5.5. When the pH of the surface treatment liquid composition is less than 2, the storage stability of the surface treatment liquid composition is likely to be reduced, and the metal material as the raw material is remarkably dissolved, and formed on the surface of a metal material such as a zinc-based plated steel sheet. Corrosion resistance of the surface treatment film to be applied and adhesion to the metal material surface tend to decrease. On the other hand, when the pH exceeds 7, the stability of the polyorganosiloxane is deteriorated, causing problems such as gelation.

  In the present invention, examples of the alkali compound used for pH adjustment include ammonia, amines, amine derivatives and aminopolycarboxylic acids, sodium hydroxide, potassium hydroxide, and the like, and acid compounds used for pH adjustment. Examples thereof include organic acids such as formic acid, acetic acid, lactic acid and tartaric acid; inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid.

  The solid content concentration of the aqueous metal surface treatment composition of the present invention is not particularly limited, but the viscosity of the surface treatment composition, the amount of the surface treatment film obtained by coating, flowability, paintability, etc. In view of the above, it is usually suitable that the content is in the range of 1 to 40% by mass, preferably 5 to 30% by mass.

  The aqueous metal surface treatment composition of the present invention has a viscosity measured at a measurement temperature of 20 ° C. and a B-type rotational viscometer at 60 rpm, which is 2.5 mPa · s or less. From the viewpoint of

Surface treatment method of metal material The surface treatment method of the metal material of the present invention is a method of coating the aqueous metal surface treatment composition of the present invention on the surface of the metal material, and drying the aqueous metal surface on the surface of the metal material. It is a method of forming a surface treatment film by a treatment composition.

  The metal material to which the surface treatment method of the present invention can be applied is not particularly limited. For example, iron, iron-base alloy, aluminum, aluminum-base alloy, copper, copper-base alloy, plating plated on the metal material A metal material can be mentioned, and among these, a zinc-based plated steel sheet can be most suitably applied as the metal material. Zinc-plated steel sheet: zinc-plated steel sheet; zinc-nickel-plated steel sheet, zinc-iron-plated steel sheet, zinc-chromium-plated steel sheet, zinc-aluminum-plated steel sheet, zinc-titanium-plated steel sheet, zinc-magnesium-plated steel sheet, zinc-manganese Zinc alloy plated steel sheets such as plated steel sheets, zinc-aluminum-magnesium plated steel sheets, zinc-aluminum-magnesium-silicon plated steel sheets; and cobalt, molybdenum, tungsten, nickel as a small amount of different metal elements or impurities in these plated layers. Examples include titanium, chromium, aluminum, manganese, iron, magnesium, lead, bismuth, antimony, tin, copper, cadmium, arsenic and the like, silica, alumina, titania and other inorganic materials dispersed. . Furthermore, multi-layer plating in which two or more of the above platings are combined is also applicable. The plating method is not particularly limited, and any known method such as an electroplating method, a hot dipping method, a vapor deposition plating method, a dispersion plating method, and a vacuum plating method may be used. As the metal material to be surface-treated with the metal surface treating agent of the present invention, among others, a galvanized steel plate and a zinc alloy plated steel plate can be suitably used.

  On the surface of the metal material, the aqueous metal surface treatment composition of the present invention is applied by various coating methods such as dip coating, spray coating, roll coating, and dried, and then dried on the surface of the metal material by the aqueous metal surface treatment composition. A surface treatment film can be formed. Before applying the surface treatment composition, the surface of the metal material is subjected to pretreatment such as hot water washing, solvent washing, and alkaline degreasing washing for the purpose of removing oil and dirt on the metal material surface as necessary. You may give it.

  The drying condition of the surface treatment film is usually preferably about 2 seconds to about 30 seconds under the condition that the material arrival temperature is about 50 to about 250 ° C.

The adhesion amount of the surface treatment film on the metal material surface is 0.05 to 3.0 g / m ² , preferably 0.2 to 2.0 g / m ² , more preferably 0.4 to 1. The range of 5 g / m ² is preferable from the viewpoints of the corrosion resistance, topcoat adhesion, conductivity, fingerprint resistance, etc. of the coating on the surface of the metal material on which the surface treatment coating is formed.

Surface-treated metal material The surface-treated metal material of the present invention can be obtained by forming a film of the aqueous metal surface treatment composition of the present invention on the surface of the metal material. Formation of the film by the aqueous metal surface treatment composition of the present invention can be carried out by the surface treatment method for a metal material.

  The surface-treated film formed on the surface of the surface-treated metal material of the present invention is excellent in corrosion resistance before and after the degreasing treatment, conductivity, fingerprint resistance, and top coating adhesion, and the film appearance can also be good. The reason for this is presumed as follows, but the present invention is not limited to this presumption.

  In the film formed using the aqueous metal surface treatment composition used in the present invention, the binder component is mainly composed of polyorganosiloxane, and the polyorganosiloxane is concentrated when the polyorganosiloxane is concentrated by drying or the like. The hydrolyzed silanol groups based on the above react with each other to form a continuous film, the silanol groups form bonds with the metal surface, and the compound (B) is oriented on the metal material surface and binds to the metal material surface. Moreover, it is presumed that the coating film by the aqueous metal surface treatment composition of the present invention exhibits a remarkable barrier effect due to the bonding of the hydroxyl group in the compound (B) with the silanol group of the polyorganosiloxane. As a result, it has excellent adhesion, is difficult to remove even after degreasing, can improve the corrosion resistance before and after degreasing, and can form a dense film. It can be considered that the conductivity is excellent.

  By using the aqueous metal surface treatment agent of the present invention, it has various performances such as corrosion resistance, conductivity, fingerprint resistance, and top coating adhesion, and is particularly excellent in conductivity without deteriorating corrosion resistance even when degreased. A surface-treated metal material such as a plated steel sheet can be provided.

The adhesion amount of the surface treatment film on the metal material surface is 0.05 to 3.0 g / m ² , preferably 0.2 to 2.0 g / m ² , more preferably 0.4 to 1. The range of 5 g / m ² is preferable from the viewpoint of the corrosion resistance, conductivity, fingerprint resistance, and top coating adhesion of the film on the surface of the metal material on which the surface treatment film is formed.

  The surface-treated metal material such as a galvanized steel sheet on which the aqueous metal surface-treating agent film of the present invention is formed can be applied to various applications. For example, as it is, a lubricating metal plate, a corrosion-resistant metal plate, a housing of an electrical product. It can be used as a body.

  Moreover, the said surface treatment metal material can also be used as a coating metal material which applied the coating material on it and formed the coating film. In this case, an alkali degreasing process is performed before paint coating in order to remove dirt, oils and fats attached to the surface-treated metal material as necessary. The film of the surface-treated metal material according to the present invention exhibits excellent corrosion resistance both before and after the degreasing treatment, and also has excellent adhesion with a paint coating film coated thereon.

  The paint applied on the surface-treated metal film of the present invention is not particularly limited, and may be either a clear paint or a colored paint. Examples of the paint resin include polyester, acrylic, and silicon polyester. Various resins such as alkyd, urethane, and epoxy resin can be used in combination with a crosslinking agent such as melamine resin and polyisocyanate compound, if necessary.

  The surface-treated metal material and the coated metal material having a coating film formed on the surface-treated metal material can be suitably used as materials used in various fields such as architecture, electricity, and automobiles.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples of the present invention. The present invention is not limited to these examples. Hereinafter, “parts” and “%” represent “parts by mass” and “% by mass” unless otherwise specified.

Production Production Example 1 of Organopolysiloxane (A)
A separable flask equipped with a reflux condenser, a thermometer, and a stirrer was mixed with 850 parts of deionized water and 23 parts of acetic acid, and then cooled in an ice bath and 61 parts of γ-glycidoxypropyltrimethoxysilane and methyltril. A mixture with 35 parts of methoxysilane was added and dissolved by stirring for 30 minutes. Next, 29 parts of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was gradually added and dissolved therein, and reacted at 80 ° C. for 5 hours to obtain an aqueous organopolysiloxane medium. From the result of 1H-NMR measurement, it was confirmed that no epoxy group remained in this organopolysiloxane. Subsequently, the aqueous medium of this organopolysiloxane was distilled under reduced pressure at 60 to 70 ° C. until the solid content concentration became 15% by mass. After the alcohol produced by hydrolysis was distilled off together with the water in this way, it was filtered through a 200 mesh filter to obtain an organopolysiloxane A1 aqueous solution. The organopolysiloxane A1 aqueous solution had a pH of 4.5. The alcohol concentration measured by gas chromatography was less than 1.5%, and no flash point was observed. The resin solid content of the organopolysiloxane A1 did not have an alkoxysilyl group, and the alkoxysilyl group was hydrolyzed. The amount of active hydrogen of the amino group of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane is 3.0 equivalents relative to 1 equivalent of the epoxy group of γ-glycidoxypropyltriethoxysilane used. . The acid neutralization equivalent for this amino group is 1.0.

The following ²⁹ Si NMR measurement method confirmed the reduction of each raw material and the formation of hydrolysis condensate.
²⁹ Si NMR measurement method: FT-NMR EX-400 (trade name, manufactured by JEOL) was used, and measurement was performed using heavy water as a solvent and tetramethylsilane as an internal standard substance. With respect to the silane coupling agent, a signal near −55 to −35 ppm and a tetraalkoxysilane with a signal around −100 to −80 ppm confirmed the decrease in raw material-derived alkoxy groups and the formation of hydrolysis condensates.

Production Examples 2-9
In Production Example 1, organopolysiloxane A2-A9 aqueous solutions were prepared in the same manner as in Production Example 1 except that the formulation was changed as shown in Table 1. In all of the organopolysiloxane A2 to A9 aqueous solutions, the alcohol concentration measured by gas chromatography was less than 1.5%, and no flash point was observed.

Production Example 10
A separable flask equipped with a reflux condenser, a thermometer, and a stirrer was mixed with 850 parts of deionized water, 1 part of 60% nitric acid and 5 parts of acetic acid, and then 93 parts of γ-glycidoxypropyltriethoxysilane and tetra 93 parts of ethoxysilane was added, dissolved by stirring for 30 minutes, and hydrolyzed to obtain an aqueous organopolysiloxane medium. Subsequently, the aqueous medium of this organopolysiloxane was distilled under reduced pressure at 60 to 70 ° C. until the solid content concentration became 15% by mass. After the alcohol produced by hydrolysis was distilled off together with the water in this way, it was filtered through a 200 mesh filter to obtain an organopolysiloxane A10 aqueous solution.
The organopolysiloxane A1 to A10 aqueous solutions obtained in Production Examples 1 to 10 each had an alcohol concentration of less than 1.5% measured by gas chromatography, and no flash point was observed. Table 1 shows special values such as equivalent of active hydrogen of amino group, solid content, pH, and weight average molecular weight with respect to 1 equivalent of epoxy group of organopolysiloxane A1 to A10 aqueous solution.

Preparation of metal surface treatment compositions Examples 1 to 26 and Comparative Examples 1 to 7
The formulation and liquid stability of the metal surface treatment composition are shown in Table 2 below. Each component was blended so as to have the blending composition shown in Table 2 below, and adjusted to pH 4.5 using acetic acid or aqueous ammonia to obtain each metal surface treatment composition. The compounding amount of each component in Table 2 is a display based on the solid content or the effective component amount excluding water and organic solvent.

  (Note) in Table 2 has the following meaning.

(Note 1) Compound B-1: trade name “Korantin PM” (manufactured by BASF, registered trademark), propargyl group, hydroxyl group and polyoxyethylene group, having a peak molecular weight of about 230, represented by the formula (1) The compound
(Note 2) Compound B-2: trade name “Korantin PP” (manufactured by BASF, registered trademark), propargyl group, hydroxyl group and oxypropylene group, having a peak molecular weight of about 260, and represented by the formula (1) Compounds,
(Note 3) Acrylic resin emulsion: manufactured by Henkel Technologies Japan Co., Ltd., trade name “Yodosol AD123”, anionic aqueous acrylic resin dispersion,
(Note 4) Urethane resin emulsion: manufactured by ADEKA Corporation, trade name “Adekabon titer HUX540”, anionic aqueous urethane resin dispersion,
(Note 5) Polyethylene wax: a product name “Chemical W-700” manufactured by Mitsui Chemicals, Inc., a polyethylene wax having a softening point of 132 ° C. and a particle diameter of about 1 μm.

  The initial liquid state in the above Table 2 was observed visually, and there were no precipitates or suspended solids and no problem in fluidity was evaluated as ◯.

The storage stability in Table 2 was evaluated according to the following criteria based on the liquid state and liquid viscosity after 30 days storage at 30 ° C. The liquid viscosity was measured with a measurement temperature of 20 ° C. and a B-type rotational viscometer at 60 rpm.
○: There is no precipitate or suspended matter in the liquid and the liquid viscosity is 2.5 mPa · s or less. Δ: Slightly precipitated or suspended matter is seen in the liquid, or the liquid viscosity exceeds 2.5 mPa · s, but it is significantly increased. There is no stickiness or gelation.
X: A considerable precipitate or suspended matter is observed in the liquid, or significant thickening or gelation is observed.

Production Examples 27-56 and Comparative Examples 8-14 of Surface Treatment Plate
Concentration 2 in which the surface of a 0.6 mm-thick double-sided electrogalvanized steel sheet (EG material, basis weight 20 g / m ^{2 on} one side) was dissolved with an alkaline degreasing agent (trade name “Chem Cleaner 561B”, manufactured by Nippon CB Chemical Co., Ltd.) Using a 2% aqueous solution, dust and oil adhering to the surface were removed by spraying at a temperature of 60 ° C. for 2 minutes for degreasing, followed by washing with water and drying. As shown in Table 3 below, each metal surface treatment composition obtained in the above Examples and Comparative Examples is applied to the obtained degreased galvanized steel sheet by the roll coating method so that the material arrival temperature becomes 100 ° C. Were baked for 20 seconds to obtain a surface-treated plate.

  Each surface-treated plate thus obtained was tested for corrosion resistance, post-degreasing corrosion resistance, fingerprint resistance, conductivity, and top coat adhesion based on the following test methods. The test results are shown in Table 3 below.

Test method:
Corrosion resistance: About each obtained surface treatment board, the end surface part and the back surface part of each surface treatment board were sealed, and the salt spray test (SST) by JISZ2371 was done. The degree of rust generation at the test time of 72 hours and 120 hours was evaluated according to the following criteria.
a: Rust generation is not recognized.
b: Rust generation is less than 5% of the total area.
c: Rust generation is 5% or more and less than 10% of the total area.
d: Rust generation is 10% or more and less than 50% of the total area.
e: Rust generation is 50% or more of the total area.

  Corrosion resistance after degreasing treatment: Each surface-treated plate obtained was treated at 65 ° C. for 2 minutes using an aqueous solution with a concentration of 2% in which an alkaline degreasing agent (“CLN-364” manufactured by Nihon Parker Lines Co., Ltd.) was dissolved. Degreasing was carried out under spraying conditions, followed by washing with water and drying to obtain a surface-treated plate after degreasing. After the degreasing, the end surface portion and the back surface portion of the surface treatment plate were sealed, and a salt spray test (SST) according to JIS Z 2371 was performed. The degree of rust generation at the test time of 72 hours and 120 hours was evaluated according to the same criteria as in the above corrosion resistance.

Fingerprint resistance: A fingerprint was attached to the film of the surface treatment plate, and the visibility of the fingerprint was judged visually.
A: The fingerprint mark is not visible.
○: Very few fingerprint marks are visible.
□: Slight fingerprint marks are visible.
Δ: Fingerprint marks are conspicuous.
X: The fingerprint mark is very conspicuous.

Conductivity: Using a Loresta GP and an ASP terminal manufactured by Mitsubishi Chemical Analytech Co., Ltd., surface resistance values at 10 arbitrary positions of the surface treatment plate were measured and evaluated by the number of times of 10 ⁻⁴ Ω or less.
a: 10 times all b: 6-9 times c: 1-5 times d: 0 times.

Top coat film adhesion: “Magiclon 1000 White” (manufactured by Kansai Paint Co., Ltd., acrylic-melamine resin paint, white) was applied to the surface-treated plate so that the dry film thickness was 25 μm, and 20 ° C. at 20 ° C. A top coat was obtained after baking for a minute. On the coating surface of the top coat plate, 11 scratches reaching the substrate with a knife were placed in a grid pattern to create 100 1 mm square cells. Extruding 5 mm from the opposite side of the cross section of the coating film surface by an Erichsen Extrusion Tester (manufactured by Eriksen Co., Ltd.). From the peeled state of the eye coat, the adhesion of the top coat film was evaluated according to the following criteria.
A: No peeling of the top coat film is observed,
○: Peeling of one or two top coat films is observed,
(Triangle | delta): Peeling of 3-10 top coat films is recognized,
X: Peeling of 11 or more top coat films is recognized.

  In addition, all the metal surface treatment compositions had good paintability, and the obtained surface treatment plate had a good treatment film free from film defects such as repellency.

  As is apparent from the above test results, the surface treatment composition of the present invention has excellent paintability and storage stability, and can satisfy all of the corrosion resistance before and after the degreasing treatment, fingerprint resistance, conductivity, and topcoat adhesion. Met.

Claims (10)

A composition containing an organopolysiloxane (A) as a binder main component, and a compound (B) having a propargyl group and a hydroxyl group and having a mono- or poly-oxyalkylene group and having a molecular weight of 100 to 800, The mono- or poly-oxyalkylene group in the compound (B) is at least selected from an oxyethylene group, a polyoxyethylene group, an oxypropylene group, a polyoxypropylene group and a divalent copolymer chain of ethylene oxide and propylene oxide. An aqueous metal surface treatment composition characterized by being one type. 100 to 30 parts by mass of at least one silane coupling agent (a) selected from the group consisting of an epoxy group-containing silane coupling agent and an amino group-containing silane coupling agent, and mono-, di-, The aqueous product according to claim 1, which is a reaction product with 0 to 70 parts by mass of at least one alkoxysilane selected from tri- and tetra-alkoxysilanes or a low condensate (b) of the alkoxysilanes. Metal surface treatment composition. 10 to 50 parts by mass of an epoxy group-containing silane coupling agent, 10 to 50 parts by mass of an amino group-containing silane coupling agent, and the alkoxysilane or the low-condensate of the alkoxysilane (b) 10 to 10 The aqueous metal surface treatment composition according to claim 2, which is a reaction product with 60 parts by mass. The aqueous metal surface treatment composition according to any one of claims 1 to 3, wherein the compound (B) is a compound represented by the following formula (1).

(In the formula, X represents at least one oxyalkylene group selected from an oxyethylene group and an oxypropylene group, the repeating number n represents an integer of 1 to 12, and when n is 2 or more, Each X may be the same or different.) The aqueous solution according to any one of claims 1 to 4, wherein the amount of the compound (B) is in the range of 0.1 to 10 parts by mass based on 100 parts by mass of the solid content of the organopolysiloxane (A). Metal surface treatment composition. Furthermore, a phosphoric acid compound (C) is contained, The aqueous metal surface treatment composition as described in any one of Claims 1-5 characterized by the above-mentioned. Furthermore, an antirust metal compound (D) is contained, The aqueous metal surface treatment composition as described in any one of Claims 1-6 characterized by the above-mentioned. The aqueous metal surface treatment composition according to claim 1, further comprising an aqueous organic resin and / or a wax. On the surface of a metal material, the aqueous metal surface treatment composition according to any one of claims 1 to 8 is applied so as to have a dry film mass of 0.05 to 3.0 g / m ² and dried. A surface treatment method for a metal material. The surface treatment by which the film | membrane by the aqueous | water-based metal surface treatment composition as described in any one of Claims 1-8 is formed on the surface of a metal material with the dry film | membrane mass of 0.05-3.0 g / m < ² >. Metal material.