TW200934891A - Aqueous surface treatment composition - Google Patents

Abstract

The purpose of this invention is to provide an aqueous surface treatment composition, which may improve corrosion resistance of zinc, alloy containing 20% or more of zinc, or electroplating bodies thereof. The present invention is related to an aqueous surface treatment composition, an aqueous surface treatment composition for corrosion resistance and zinc, alloy containing 20% or more of zinc, or electroplating bodies thereof. The feature of the aqueous surface treatment composition is that it at least has a chemical structure formed by reacting a silicon compound (d) containing at least one alkoxy group in the molecule with a titanium composite composition and/ or formed by mixing them, wherein the aforementioned titanium composite composition has a chemical structure formed by reacting oligomers of titanium compound (a), amine compounds (b) and diol compounds (c) and /or a composition formed by mixing them. The aforementioned zinc, alloy containing 20% or more of zinc, or electroplating bodies of thereof are characterized by using the aforementioned aqueous surface treatment composition to prevent corrosion.

Description

200934891 VI. Description of the Invention: [Technical Field] The present invention relates to a water-based surface treatment composition for use in the surface of an electroplated body containing or containing more than 20% of zinc alloy or the like; more specifically The present invention relates to a water-based surface treatment composition using a titanium compound oligomer as a raw material, or a composition containing at least one selected from the group consisting of a phosphoric acid compound, a vanadium compound, and a wrong compound in the above composition, particularly for 0 zinc or The surface of the alloy containing more than 20% zinc or its electro- ore body can improve the adhesion of the substrate, corrosion resistance, heat resistance, coating adhesion, alkali resistance and solvent resistance. Composition. [Prior Art] As a steel material excellent in corrosion resistance, a galvanized steel material which has been subjected to galvanization or a galvanized alloy is used. Such a plated steel is oxidized by contact of the zinc layer with air or water to produce white rust. Therefore, the industry prevents oxidation by surface treatment, that is, imparts corrosion resistance to steel. © In addition, steels that have been subjected to such surface treatments are also required to have heat resistance and damage resistance due to the need to use them under high temperature conditions or to damage the surface during transportation. Further, there is a case where the steel material subjected to the surface treatment is processed or coated, and therefore it is also required to have excellent corrosion resistance or coating adhesion after the processing. Further, the degreasing step of the press oil (presSQil) which is usually used in the processing is carried out by using an alkali-based degreaser, and therefore it is also required to have alkali resistance. As such a treatment, it is known that chromate treatment using a chromium compound can be carried out in the case of chromate treatment, and white rust can be prevented from being produced, thereby obtaining a very good galvanized steel sheet. However, in recent years, from the viewpoint of environmental issues, the method of chemical conversion treatment using a chromate-free treatment agent without using chromium has been considered. Patent Document 1 discloses a metal surface treatment agent containing a phthalic acid ester, an inorganic salt of aluminum, and a decane coupling agent. However, the metal surface treatment agent described in the patent document 无法 cannot achieve a stable and sufficient crosslinking reaction using a ruthenium oxygen bond, and therefore the metal surface treatment plate obtained by the treatment thereof has poor solvent resistance or testability. The possibility. Patent Document 2 discloses a metal surface treatment agent containing a vanadium compound and a metal compound. The metal compound contains at least one metal selected from the group consisting of cobalt, nickel, zinc, aluminum, calcium, strontium, barium, and lithium. However, when the metal surface-treated metal sheet obtained by the treatment with the metal surface treatment agent described in Patent Document 2 is left for a long period of time under high temperature and high humidity, there is a problem that the adhesion between the film and the substrate is lowered. Patent Document 3 discloses a metal surface treatment containing a diluted hydrolyzate and/or a decane coupling agent obtained by hydrolyzing ethyl phthalate (Ethy) Polysilicate and having a hydrolysis rate of at most 1% by weight. Agent. However, the metal surface treatment plate obtained by treating with the metal surface treatment agent described in Patent Document 3 forms a hard film which lacks flexibility, and since the processed film is easily broken, there is a margin of the processed portion or The adhesion between the skin and the substrate is not sufficient. Further, there is a possibility that the storage stability of the diluted hydrolyzate or the corrosion resistance of the film and the testability are inferior. 200934891 Patent Document 4 discloses a metal surface treatment composition containing a divalent or higher metal ion such as titanium ion, vanadium ion or zirconium ion, and a hydrofluoric acid having at least four fluorine atoms and elements such as titanium and zirconium. A decane coupling agent having an active hydrogen group, an epoxy group or the like, and an aqueous emulsion resin. However, the metal surface treatment composition described in Patent Document 4 contains a resin. Therefore, if the metal surface treatment plate obtained by the treatment is placed in a high temperature environment, there is a problem that the heat resistance of the film is poor. Patent Document 5 discloses a water-dispersible resin and/or a water-soluble resin, a decane coupling agent, phosphoric acid and/or a hexafluorometal acid, and a cationic species is a water-soluble solution of manganese, magnesium, aluminum or nickel. A metal surface treatment composition of a caustic acid salt. However, the metal surface treatment agent described in Patent Document 5 contains a resin. Therefore, if the metal surface treatment plate obtained by the treatment using the metal surface treatment plate is placed in a high temperature environment, the heat resistance of the film is inferior. Patent Document 6 discloses a water-based rust-preventing coating agent containing a decane coupling agent having an epoxy group, a decane coupling agent having an amine group, a decane coupling agent having a vinyl group, and an acid, and coating the same. The rust-preventing treatment method' and the rust-preventing metal material coated with the above coating agent. However, although the rust-preventing metal agent described in Patent Document 6 has good silver resistance, it has a problem of poor durability. Patent Document 1: Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. 2004-183015. Patent Document 3: Japanese Patent Laid-Open No. Hei. No. 2005418635. Patent Document 4: Japanese Patent Laid-Open No. 2〇〇5_12〇469 Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The purpose of the invention is to provide a water-based surface treatment composition which can satisfy the substrate hardness, the processing part, the heat resistance, the coating adhesion, which is difficult to achieve by the coating of the prior chromate-free treatment agent. All properties of alkali resistance and solvent resistance. [Means for Solving the Problems] The present inventors have made intensive studies to solve the above problems, and as a result, have found that a chemical structure formed by reacting a specific ruthenium compound with a titanium composite composition and/or mixing thereof is formed. a surface treatment composition comprising a composition in which a titanium compound oligomer, an amine compound, a diol compound is formed by reacting a chemical structure and/or a mixture thereof, or the like, or a composition Further, the composition further contains a surface treatment composition of at least one selected from the group consisting of a disc acid compound, a vanadium compound, and a zirconium compound, and the like is present in the form of a water-based compound (that is, it exists as a water-soluble compound), and is dissolved or The surface treatment composition dispersed in water is coated, fired, dried, hardened, etc., whereby the substrate adhesion of zinc or a surface containing an alloy of 20% or more or an electroplated body thereof can be obtained. The corrosion resistance, heat resistance, coating adhesion, alkali resistance and solvent resistance of the processed portion are remarkably improved, thereby Cost inventions. That is, the present invention provides a water-based surface treatment composition characterized by having at least a chemical structure formed by reacting a compound of the cerium compound (d) having one or more alkoxy groups in a molecule with a titanium composite composition, and 6 200934891 Or a composition formed by mixing or the like. The titanium composite composition has a chemical structure formed by reacting a titanium compound oligomer (a), an amine compound (b), and a diol compound (c), and/or And a composition formed by mixing; or having a composition comprising at least one selected from the group consisting of a scaly acid compound, a hunger compound, and a wrong compound. Further, the present invention provides a rust-preventing film which is formed by forming a surface of a zinc or a alloy containing 20% or more zinc or an electroplated body thereof using the water-based surface treatment composition described above. Further, the present invention provides a zinc or an alloy containing 20% or more of zinc, or an ore body thereof, which is characterized in that the above-mentioned water-based surface treatment composition is used to form a rust-preventing layer. [Efficacy] By the water-based surface treatment composition of the present invention, a composite film of a highly dense titanium compound and a bismuth compound can be formed on the surface of zinc or an alloy containing 2% by mass or more, or the surface of the electroplated body thereof. Thus, a film which satisfies all the characteristics of the substrate adhesion, the corrosion resistance of the processed portion, the heat resistance, the coating adhesion, the alkali resistance, and the solvent resistance is obtained. [Embodiment] The present invention will be described below, but the present invention is not limited to the following embodiments, and can be carried out arbitrarily. [Titanium composite composition] 7 200934891 The water-based surface treatment composition of the present invention has a chemical structure formed by reacting a "ruthenium compound (d) having one or more alkoxy groups in a molecule with a titanium composite composition) and/or The titanium composite composition has a chemical structure formed by reacting the "titanium compound oligomer (a) 'amine compound (b) and the diol compound (c)" and/or a composition formed by mixing them. The composition formed by mixing.

(Titanium compound oligomer (a)) The titanium compound polymer (a) is not particularly limited, and preferably has a titanium alkoxide represented by the following formula (1) or has the following formula (1) A structure in which a titanium chelate compound having a structure in which a chelating agent is coordinated by a chelating agent is formed by condensation. Chemical formula 1 OR1 (1) R2. Ti·—〇R4

OR3 or more and 18 formulas (1) t ′R1 to R4 each independently represent a luminescent group having a carbon number of 丄 or less. The starting material before the condensation is a titanium alkoxide of an alkyl group in which R1 to R4 in the formula (1) are independently a carbon alkoxide, and preferably Ri~R4 L More than one or more than 18 or more of the bases are particularly good. (1) The number of carbon atoms is 1 and 疋R1 to R4 are independently 200934891. The number of breaks is 1 or more and 5 or less. Specific examples of the "titanium alkoxide represented by the formula (1)" include tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxy-C, and B. n-Butoxy 35, tetraisobutoxy a, diisopropoxy di-n-butoxytitanium-second butoxide diisopropoxytitanium, tetra-butoxy-octyl, tetraisooctyloxy Titanium and tetra-hard titanium. These may be used singly or in combination of two or more.

In addition to the above-mentioned "titanium alkoxide represented by the formula (1)", it is also possible to form a S-position chelating agent in "the alkoxide represented by the formula (1)". The titanium nucleating compound having a structure is preferably a starting material. The chelating agent is not particularly limited. From the viewpoint of stability of hydrolysis of a titanium compound or the like, it is preferably selected from the group consisting of 10,000-diketone and 10,000. At least one of the group consisting of a ketoester, a polyol, an alkanolamine, and a hydroxycarboxylic acid. The diketone compound is not particularly limited as long as it is a point of coordination as a chelating agent, and specific examples thereof include 2,4-pentanedione, 2,4-hexanedione, and 2,4. - heptanedione, dibenzoylmethane, thiophenetrifluoroacetone, 1,3-cyclohexanedipine, and phenylidene- 13 butanedione. They may be used singly or in combination of two or more. The ketone ester is not particularly limited as long as it is a chelating agent, and specific examples thereof include acetamidine acetate, acetonitrile acetate, and acetoacetic acid. Ethyl acetoacetate, butyl acetoacetate, methyl isobutyl decyl acetate, decyl hexyl decanoate, and methyl laurate. These may be used singly or in combination of two or more. 200934891 As the polyol, it is not limited, and the polyol which is coordinated by the (4) mixture is not particularly 1,2-pentanediol, 2 3,2' ethylene glycol, U-propylene glycol, U-butylene glycol, alcohol And hexanediol, etc.'. The following: alcohol, 2'3-pentanediol, glycerin, and diethylene glycol are used as the alcoholic amine, and if it is used as a hydrazine or in combination of two or more. Unless otherwise limited, Ν, Ν Λ 5 agents and coordination of (4) amines are not special ... ethyl) ethanol::: ethanolamine, hydrazine, hydrazine-diethylethanolamine, alcohol oxime-methylethanolamine, ν —甲美- _ N methyl-B

First Dingqi 7 # n-butylethanolamine, N-n-butyltriethanolamine, N-ethanolamine, N-t-butyldiethanolamine, triethanolamine, -ethanolamine, and monoethanol-faced Gangu sigh one (4). These may be used singly or in combination of two or more. The sulfhydric acid is not particularly limited, and may be exemplified by a ruthenium acid which is coordinated with an acid and gluconic acid. These may be used singly or in combination of two to obtain a titanium compound by condensing the above-mentioned "titanium alkoxide represented by the formula (1)" or a titanium chelate compound having a structure formed by coordinating a chelating agent in the titanium alkoxide. Concentrate the polymer (a). Here, as the side of the condensation: it is not particularly limited. Preferably, the titanium alkoxide or the titanium-based compound is reacted with water in an alcohol solution to carry out condensation, or an amine in the alcohol solution is as follows. A method in which the compound (b) is allowed to react with water. The amount of water used to condense the compounds to condense is preferably from the viewpoint of stability to water, film formability, coatability, etc., with respect to titanium alkoxide and/or titanium chelate compound.摩尔摩尔, ie, relative to the titanium atom 1 mole, the water molar number is more than 莫 2 moles, less than 2 moles, 10 200934891 is more preferably 0. 3 moles above, 1.7 moles Hereinafter, it is particularly preferably 〇. 5 摩尔 or more, 1.6 摩尔 or less, and more preferably 1. 〇 Moule or more, 1. 5 mA or less. In addition, the manufacturing method of the titanium compound oligomer (a) in the present invention is not limited to the chemical structure such as the degree of condensation of the titanium compound oligomer (a) by a production method such as a condensation method. The titanium compound polymer (a) sometimes has a two-dimensional or three-dimensional chemical structure and its chemical structure Ο

It is only possible to determine by the manufacturing method that the titanium compound (a) having the same chemical structure which is manufactured by using various manufacturing methods can also be used in the present invention. When the titanium compound oligomer (a)' is represented by a composition formula, when the number of moles of water participating in the reaction is χmol with respect to 2 mol of titanium atoms, it is represented by the following formula (2). The titanium compound oligomer (a) is usually obtained by shrinking a person. ° (2)

Ti0x/2(0R)4- In the formula (2), 'R' represents a formula (dR to R4 in d). In contrast to a 1 molar atom, the molar water participates in the reaction. In the case where 2 moles of titanium atoms participate in the opposite of 2 moles of water: x = 2' and thus equation (2) becomes,

Ti0i(0R)2 Μ, . , when 1.5 moles of water is involved in the reaction with respect to 1 mole of titanium atoms, that is, when 3 moles are used with respect to 2 moles of titanium atoms... 3, so the formula (1) becomes, , and

Ti〇3/2(〇R), (4). In the case of the degree of condensation of the compound oligomer (a), it is preferred to obtain the X value corresponding to the above-mentioned "amount of water which is preferably condensed and concentrated" to be substituted into the formula (2). The composition. The titanium compound polymer (a) in the present invention is not particularly limited as long as it is an oligo, and is preferably a polymer of 1 or more and 2 or less, more preferably 2 or less. It is more preferably a tetramer or more and a 13-mer or less, and more preferably a 5-mer or more and a 12-mer or less. From the viewpoints of water stability, film formability, coating properties, etc., a preferred ® is a titanium compound oligomer having a large degree of condensation. The above formula (3) represents a titanium compound oligomer (a) which is one-dimensional in principle and has an infinite degree of condensation, but the titanium compound oligomer (a) actually produced has a limited degree of condensation. The titanium compound polymer (a) in the present invention is more preferably a chemical structure produced by using an amount of water having an infinite degree of condensation in principle. In the condensation, the titanium alkoxide or the titanium chelate compound may be formed into an alcohol solution using a solvent such as an alcohol, and a titanium compound Q oligomer (a) may be obtained by heat treatment such as reflow. The alcohol to be used at this time is not particularly limited, but it is preferable from the viewpoint of not changing the reactivity of the titanium compound condensate (a).

The concentration of 0.5% by mass or more and 20% by mass or less, and the total amount of the alcohol of K Xing is more preferably diluted to 〇. 7 12 200934891 The concentration of 罝% or more and 15% by mass or less is particularly preferably diluted. u The concentration of % by mass or more and 10% by mass or less. From the viewpoint of more easily suppressing the generation of white turbid substances or white precipitates in chemicals, it is preferred that the above condensation is carried out in the amine compound (b); in the alcohol/cold solution, the titanium alkoxide or the titanium chelate compound is The water reacts and enters the lamp. The amine compound & (b) used in this product may be the same as or different from the amine compound (b) used in the reaction and/or mixing of the following compound oligomer (a) to prepare a titanium composite composition. . The titanium compound oligomer (a) is preferably a titanium compound oligomer having a structure formed by coordinating a chelating agent in the above-mentioned titanium compound oligomer. That is, a titanium compound condensed polymer having a structure in which a titanium alkoxide represented by the above formula (1) or a titanium alkoxide represented by the above formula (^) is used as a chelating agent is preferred. In the compound having a structure in which the titanium chelate compound of the structure is formed to be condensed, a chelating agent is further coordinated to form a structure. In other words, from the viewpoint of improving the stability of hydrolysis of the titanium compound oligomer Q and the like, a titanium compound condensate having a structure in which a chelating agent is reacted before condensation and/or after condensation is preferred. The chelating agent to be used after the condensation is not particularly limited, and the above chelating agent can be suitably used. Particularly preferred are stone diketones, ketone esters or alkanolamines. (Amine compound (b)) The amine compound (b) which is reacted with and/or mixed with the above-mentioned titanium compound polymer (a) for obtaining a titanium composite composition is not particularly limited, and self-lifting is for a compound ( a) The stability of hydrolysis and the like, and considering the dissolution of water 13 200934891, it is preferred that the substituted or unsubstituted aliphatic amine or quaternary ammonium hydroxide. As the substituent in the "substituted or unsubstituted aliphatic amine", an alcoholic hydroxyl group is preferred. As the substituted aliphatic amine, an alkanolamine is particularly preferred.

Specific examples of the unsubstituted aliphatic amine include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, and isobutyl group as the aliphatic alkylamine. Amine, second butylamine, tert-butylamine, amylamine, second amylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-thylamine , trimethylamine, triethylamine 'tripropylamine and tributylamine, and piperidine and pyrrolidine as aliphatic cyclic amines. These may be used singly or in combination of two or more. Specific examples of the alkanoylamine include N,N-dimethylethanolamine, N,N-diethylethanolamine, N-(non-amineethyl)ethanolamine, N-f-ethanolamine, and N-fluorenyl group. Diethanolamine, N-ethylethanolamine, n-butylethanolamine, N-n-butyldiethanolamine, N-tert-butylethanolamine, N_t-butyldiethanolamine, trihexylamine, diethanolamine, and monoethanolamine Wait. These may be used singly or in combination of two or more. Specific examples of the quaternary ammonium hydroxide include tetramethyl oxynitride, tetraethyl ruthenium oxide, tetrapropyl oxyhydrogen (tetra), tetrabutyl hydride, and trimethyl hydrazine. Oxidation money and 2, propylethyltrimethylhydroquinone recording. These may be used singly or in combination of two or more. (diol compound (c)) 14 200934891 There is no particular diol (glyc〇1) compound (^) which is reacted and/or mixed with the above-mentioned titanium compound polymer (a) to obtain a titanium composite composition. The diol compound having a hydroxyl group respectively on the adjacent carbon atoms is preferably defined, and specific examples thereof include hydrazine, 2 ethylene glycol, hydrazine, 2-propylene glycol, and 1,2-butanediol. 1,2-pentanediol, 2,3-butanediol, 2,3-pentanediol, and glycerin. Among them, from the viewpoint of the stability of the hydrolysis of the titanium oligomer compound and the like, and the water solubility thereof, particularly preferred are hydrazine, 2-ethoxydiol, 1,2-propanediol or 2,3-butanediol. By using the diol compound (c), the stability to the hydrolysis of the titanium oligomeric compound (a) and the like can be improved, and the water can be dissolved. (The ratio of each component in the titanium composite composition) The ratio of the use of the "titanium compound oligomer (a)", the "amine compound (b)", and the "diol compound (c)" is not particularly limited, and (b) (a) The molar is better (b) / (a) = 〇.1/1 〇 ~ system, and more preferably (1) ❹ / (&) - (). 3 / 1 () ~ 1 () / (). 3, particularly good is 〇. 5 / 1 () ~ 1 〇 / 〇. 5. ;«· (a) Relatively small amount of (a) XI (b) is a cause of deterioration in crosslinkability, film formability, adhesion, etc. On the other hand, if (1) is excessive, there is water Stability such as solubility or hydrolysis is not; i. (C) is better than (a) Mo (C) / U) =0. "1〇 or more, 10/0·1 or less, ® cup recognition B, 疋(c) / (a) = 0.5/10 or more, 10/0.5 or less 'Specially good 岐 1/1Q or more. If (4) is too small compared to (a) and (c), the amount of a is too small, and the reason for the decrease in crosslinkability, film formation, and adhesion is m. If (4) is excessive, 15 200934891 exists for water. Insufficient solubility, insufficient stability such as hydrolysis. Chemical structure of a compound having a structure obtained by reacting a titanium compound oligomer (a), an amine compound (b), and a diol compound (c) (hereinafter referred to as "compound A") in a titanium composite composition The compound having the structure obtained by the above production method is not limited to those produced by a specific production method. As the chemical structure of the compound A, a glycol chelate or amine of a titanium compound valence formed by reacting the titanium compound oligomer (a), the amine compound (b) and the diol (c) is preferred. The structure is based on titanium. Particularly preferred is a chelate structure formed by reacting a terminal alkoxy group of the titanium compound oligomer (a) with an amine compound and/or a diol compound (c), or an amine group present in the amine compound or present in the second The structure in which the hydroxyl group in the alcohol compound is coordinated to the titanium atom. The titanium composite composition of the present invention contains the above compound A, the titanium compound oligomer (a), the amine compound (b), and/or the diol (c) e compound composition may have an oligomer for a titanium compound ( a) a titanium composite composition having a composition formed by mixing an amine compound (b) with a diol compound (c) at room temperature, or may have an amine compound (b) for a titanium compound polymer (a) A titanium composite composition having a composition obtained by heating under reflux with a diol compound (c). The above-mentioned "composition formed by mixing" includes a case where not all of the reactions are mixed and left unreacted, and only a part of the reaction is carried out. The titanium composite composition of the present invention is not particularly limited as long as it has the composition obtained by the above method, and is preferably the following eight types of bears: 16 200934891 (1) Compound A; (2) Compound A and a mixture of the titanium compound polymer (a); (3) a mixture of the compound A and the amine compound (b); (4) a mixture of the compound A and the diol compound (c); (5) compound A, titanium compound aggregation a mixture of the compound (a) and the amine compound (b); (6) a mixture of the compound A, the titanium compound oligomer (a) and the diol compound (c); (7) the compound A, the amine compound (b) and the second a mixture of the alcohol compound (c); (8) a mixture of the titanium compound polymer (a), the amine compound (b) and the diol compound (c). Among them, the form (1) and the form (8) are preferable in terms of the fact that the effects of the present invention described above can be favorably obtained. [矽 compound (d)] The water-based surface treatment composition of the present invention has the above-described titanium composite composition 'and further "an oxime compound (d) having one or more alkoxy groups in the molecule" (hereinafter referred to as "anthracene compound" (d)") A water-based surface treatment composition having a chemical structure formed by the reaction and/or a composition formed by mixing. The ruthenium compound (d) is not particularly limited, and from the viewpoint of improving the film formability, it is preferably a crushing agent or a coupling agent or an alkyl decanoate having four alkoxy groups bonded to the shixi atom. . Among them, from the viewpoint of further improving the coating adhesion and the viewpoint of heat generation, it is preferred that the compound is a compound containing an amine group, a mercapto group or an epoxy group. Further, from the viewpoint of improving the adhesion of the coating and the heat and the heat, it is also preferable to have a structure in which a structure formed by direct bonding of a base on a hard atom is formed. As the alkyl group at this time, a methyl group or an ethyl group is preferred. Further, a partially hydrolyzed condensate of the above compound can also be suitably used. Specific examples of the hydrazine compound (d) include monomethyltrimethoxydecane, dimethyldimethoxyoxydecane, methyl methoxy decane, tetraethoxy cerium, and tetra-n-propoxy group. Wei, m-aminopropyltrimethoxy zeoxime, r-amine-aminoamine ethyldimethoxy; ^ hospital, r-aminopropylamine ethylmethyldimethoxydecane, r-aminopropyl Amine ethyl triethoxy decane, r-aminopropylamine ethyl f-diethoxy decane, r-aminopropyl trimethoxy decane, r-aminopropyl triethoxy decane, double _ (triple Oxidylalkylpropyl)amine, bis-(triethoxydecylpropyl)ethylenediamine, r-ureidopropyltrimethoxydecane, r-ureidopropyltriethoxydecane, N- Phenylaminopropyltriethoxydecane, r-glycidoxypropyltrimethoxydecane, glycidoxypropylmethyldimethoxyacetate, r-glycidoxypropyltris-Q-ethoxylate Basear, 7-glycidoxypropyl decyl diethoxy decane, bis-(3,4-epoxycyclohexyl)ethyltriethoxy decane, hydrazinopropyltriethoxy decane, 7-mercaptopropyltrimethoxydecane, Mercaptopropylmethyldiethoxydecane, r-sulfopropyldecyldimethoxydecane, ^-methacryloxypropyldimethoxydecane, 7-mercaptopropenyloxypropane Methyl dimethoxy decane, 7-methacryloxypropyl trimethoxy decane, etc. can be used individually or in mixture of 2 or more types. In the case where the aqueous titanium oligomer composition is obtained by using the ruthenium compound in combination with the above titanium composite composition, it is preferred to have a structure obtained by reacting the ruthenium compound (d) 18 200934891 with the above titanium composite composition and/or Or a water-based titanium oligomer composition having a composition obtained by mixing them. In particular, the reaction method is not particularly limited, and it is preferred to carry out the reaction by mixing the titanium composite composition with the ruthenium compound (d) and refluxing at the boiling point of the solvent to be used. Furthermore, there is no provision for the order of deployment. The ratio of use of the above titanium composite composition to the above-mentioned ruthenium compound (d) is not particularly limited, and the quality of the titanium composite composition and the ruthenium compound (d) is preferably 1·1/10 or more, sen/0.1 or less, more preferably It is 0.5/10 or more and ° 1G/G.5 or less, and particularly preferably 1/10 or more and 1 G/1 or less. When the titanium composite composition is too small in comparison with the titanium composite composition and the ruthenium compound (d), the film formability is lowered. On the other hand, if the titanium composite yarn is excessively 彡, the film formation property is saved. The case where the stability of H hydrolysis property or the like is insufficient. The water-based surface treatment composition of the present invention is not limited to the water-based surface treatment composition produced by the above-described production method, and is a composition having a chemical structure and composition produced by the above-described production method, even if the water-based surface Different manufacturing methods for treating the composition are also included in the present invention. Among them, the water-based oligomer composition of the present invention is preferably a water-based oligomer composition produced by the above-described production method. That is, as a method for producing the composition of the compound and a method for producing the aqueous titanium oligomer composition, it is preferred to react and/or mix the titanium compound oligomer (a), the amine compound (1) and the diol compound (7). Further, as a method for producing a water-based titanium oligomer composition, it is preferred to react and/or mix the Si-based compound (d) having i or more alkoxy groups in the molecule with the titanium composite composition. 19 200934891 The content ratio of the cerium composite composition in the water-based surface treatment composition of the present invention is not particularly limited, and it is preferably 3 〇·1 mass 〇/0 or more in 1% by mass of the surface treatment agent. It is particularly preferable that it is 0.3% by mass or more and 2% by mass or less, and more preferably 0.5% by mass or more and 1% by mass or less. The aqueous surface treatment composition of the present invention may further contain at least one selected from the group consisting of phosphoric acid ruthenium, vanadium compounds and ruthenium compounds. This gives you superior marginality. ^ The compound (10) may, for example, be a phosphoric acid such as n- 4 acid, partial linonic acid, pyrophosphate monophosphate or tetraphosphoric acid, triammonium phosphate, diammonium phosphate, monosodium phosphate, disodium hydrogen phosphate or aluminum phosphate. Phosphates and the like. These may be used singly or in combination of two or more. When the above-mentioned disc acid compound is used, the cinnamate ion forms a disc acid salt layer on the surface of the metal green chain to be purely formed, and white rust or the like can be effectively prevented, thereby improving corrosion resistance. When the surface treatment composition of the aqueous system of the present invention contains a ruthenium surface treatment composition of a phosphoric acid compound, the content of the upper (tetra) acid compound is preferably 100% by mass or less by mass% or less by mass% or less of the surface treatment agent. The acid compound of the dish. When the amount is less than 001% by mass, the rhythm resistance is insufficient. When the amount exceeds 1Q% by mass, the water-based titanium oligomer composition used is gelled, resulting in failure to apply. More preferably, it is 0.05% by mass or more and 5% by mass or less. Examples of the above-mentioned compound include: (4), partial (four) nano, potassium metavanadate, diethyl acetonide oxide, vanadium, acetonide, vanadium, and the like.苴, etc. can be used alone or in combination of two or more. When the above-mentioned compound is used, it is similar to the chromium compound previously used for imparting corrosion resistance to 20 200934891, and a vanadium layer is formed on the surface of the green metal to be passivated, and in particular, white rust or the like of the zinc steel plate or the like can be effectively prevented. Improves corrosion resistance. In the case where the water-based surface treatment composition of the present invention contains the above-mentioned vanadium compound, it is preferred that the vanadium compound is contained in an amount of 5 mass% or more and 10 mass% or less in 100% by mass of the surface treatment agent. When the amount is less than 5% by mass, the corrosion resistance is insufficient. When the amount is more than 1% by mass, the corrosion resistance is saturated and becomes uneconomical, and gelation occurs due to the aqueous titanium oligofine composition used. This results in failure to coat. More preferably, it is 1% by mass or more and 5% by mass or less. Examples of the above-mentioned wrong compound include ammonium hexafluoroantimonate, sodium hexafluoroantimonate, potassium hexafluorozirconate, nitric acid, zirconium acetate, ammonium zirconium carbonate, and acetonium acetonide. These may be used singly or in combination of two or more. When the above-mentioned vanadium compound is used, the vanadium layer is formed on the surface of the metal green body to be passive, and the white rust or the like of the zinc steel sheet can be effectively prevented. Can improve the financial property. In the case where the water-based surface treatment composition of the present invention contains the above-mentioned ruthenium compound, it is preferred that the surface treatment agent contains 〇·05 mass% or more and 10 mass% or less in 1% by mass. When the amount is less than 0.05% by mass, the corrosion resistance is insufficient. When the amount is more than 10% by mass, the corrosion resistance is saturated and becomes uneconomical, and gelation occurs due to the aqueous titanium oligomer composition used. , resulting in failure to coat. More preferably, it is 01% by mass or more and 5% by mass or less. For the & anti-recording effect, the water-based surface treatment composition of the present invention may be used as required. 21 200934891 To further use an anti-scaling agent. Specific examples thereof include: i 2 bis(2-ethylhexyl)amine acetaminophen, and do not open diazole, 1-indole, decyl benzene oxime and ruthenium. Molybdenum, such as ortho molybdate, secondary molybdate and metamolybdate: and yttrium compounds such as carbon lanthanum, propylene sputum and water simmering yttrium, etc. ^. The surface treatment composition m to be used in the surface treatment composition of the present invention in an amount of from 1 to 1% by mass is used in the form of U1 to 1Q f or after the reaction. ‘mixable

The 2〇m-based surface treatment composition can be suitably used for zinc or contains a special::: ground; gold, or the like. If it is used, it can be used without particular limitation. Specifically, for example, it can be applied to a mirror zinc-based steel sheet such as a steel sheet, a key-recording steel sheet, a galvanized-iron steel sheet, or a bell-shaped steel sheet. The method of electrowinning is not particularly limited, and may be any of a known method such as a key method, a hot dip key method, a vapor deposition method, a dispersion plating method, or a vacuum plating method. In order to form a more uniform and smooth film, the water-based surface treatment composition of the present invention may also use an antifoaming agent, an organic solvent, a leveling agent, and a pH adjusting agent. The organic solvent which is usually used in the coating material is not particularly limited, and examples thereof include hydrophilic solvents such as an anthraquinone, a ketone, an ester or an ether. Examples of the leveling agent include compounds such as polyoxymethylene, acetylene glycol, and fluorine. Further, examples of the pH adjuster include inorganic acids such as hydrofluoric acid, sulfuric acid, and nitric acid; organic acids such as acetic acid, lactic acid, and phosphonic acid; ammonium salts or amines. The coating method in the case where the water-based surface treatment composition of the present invention is applied to zinc or an alloy containing 2% by mass or more, or an adherend such as an electroplated body thereof, is not particularly limited, and can be suitably used. Roll coating method, 22 200934891

Air spray method, airless spray method and dipping method. In order to improve the hardenability of the rust-preventing film, it is preferred to preheat the object to be coated or to thermally dry the object to be coated after coating. "The heating temperature of the object to be coated is 5 (rc or more, 25 Å < 5 (: The following is preferably 70 C or more and 220. (The following "If the heating temperature is less than 50 C, the evaporation rate of water is slow, and sufficient film formation property cannot be obtained, resulting in solvent resistance or alkali resistance. On the other hand, if it exceeds 250 C, the corrosion resistance will fall. The drying time in the case of performing thermal drying after coating is preferably 1 second or more and 5 minutes or less. The coating amount in the case where the composition is applied to an adherend such as zinc or an alloy containing 2% by weight or more of zinc or an electroplated body such as the like, is not particularly limited, and is preferably used as a coating amount after drying. The amount of the film is 0.5 g/m2 or more and 3 g/m2 or less. If it is less than 5 _2, the corrosion resistance or the alkali resistance may be lowered. On the other hand, if the amount of the film is too large, the substrate is not only dense. The decline is not economical. More preferably 0.5 g/m2 or more, 2 g/m Further, the anti-rust film of the present invention may be used by applying a top coat to a film to form a coating film, and as a top coat, for example, an acrylic resin, an acrylic modified alkyd resin, or an epoxy resin may be used. a coating formed by an amine ester resin, a melamine resin, a phthalic acid resin, an amine resin, a polyester resin, a vinyl chloride resin, etc. The thickness of the coating film of the top coat coating is based on the use of the rustproof metal product, The type of the top coat to be used is appropriately determined, and there is no (4) restriction. Usually it is about 5...300", more preferably about 1〇(4)~_P. The formation of the coating film of the top coat can be achieved by Applying a topcoat paint 23 200934891 to a film formed by the surface treatment composition of the above water system, heating, drying, and hardening. The drying temperature and time are according to the type of the top coat applied, and the coating film. The film thickness is suitably adjusted, and in general, the drying temperature is preferably 5 (rc or more, 25 〇t > c or less, and preferably 5 minutes to hrs as the drying time. Coating side According to the form of the coating, it can be carried out by a conventionally known method. In order to improve the performance of zinc or an alloy containing 20% or more of zinc, or the like, it is preferable to use the water-based surface treatment composition of the present invention. The surface is treated. That is, it is preferred to use the aqueous surface treatment composition of the present invention to prevent the surface from being recorded. The rust-preventing film formed by forming the film by using the aqueous surface treatment composition of the present invention can be improved. Anti-recording performance of the surface of the surface. The rust-proof zinc bite containing the water-based surface treatment composition of the present invention contains 20% or more of the alloy, or the electroplated body thereof, which maintains the substrate adhesion even under severe conditions. Sexuality, processing part resistance, heat resistance, adhesion, adhesion, alkali resistance and solvent resistance. The principle of the surface treatment composition of the present invention exhibiting an excellent rust preventive effect is not clear, and the present invention is not limited to the scope of the following functions and principles, and can be considered as the following reasons. In other words, it is considered that the formed film is densified by using a titanium oligomeric compound, and the pancreas and the metal plate as a substrate are improved by using the ruthenium compound (d) having one or more alkoxy groups in the molecule. The continuity of the. Due to such phenomena, the possibility that the substance causing rust, such as water or air, is in direct contact with the metal plate is lowered, thereby improving the anti-performance. Homogeneous rust 24 200934891 [Examples] Next, the production examples of the titanium composite composition and the titanium compound will be described, and the present invention will be more specifically described using the examples and comparative examples of the production examples. Further, % in each example represents mass%. <Production Example 1 >

After dissolving 28.4 g (0.10 mol) of titanium tetraisopropoxide in 5 g of 2-propanol, 2·7 g (G 15 mol) of water and 5 g of 2 were added dropwise. - a mixture of propanol. After completion of the dropwise addition, the mixture was stirred for a while to obtain 1,2-propanediol (titanium compound composition A) of "titanium compound oligomer (a) A N, N-dimethylethanolamine, ear). &lt;Production Example 2 &gt;&quot;. Then, after adding 8.9 g (〇.1〇莫耳) to the mixture for 1 hour, 30.4 g of the mixture was added, and the mixture was stirred for 1 hour, and further refluxed for 1 hour to obtain 28.4 g of 28.4 g (0.1 Torr molar). After the oxetine was dissolved in 2-propanol of μ′g, 2.7 g (〇15 mol) of water, 5 〇々 of 2-propanol and 5.9 g (0. 〇5 mol) were added dropwise. A mixture of N-n-butylethanolamine of Ganzidou). After the completion of the dropwise addition, the "titanium compound oligomer (a) B" was obtained by giving 1 hour of 13⁄4 g |A w + 授. Then, 36.8 g (〇.4〇笪, • 4U mole) of glycerin was added, and the mixture was mixed for an hour, and then refluxed for 1 hour to obtain "Qin Composite Composition B". &lt;Production Example 3 &gt; Dissolution of titanium tetraisopropoxide in 50. 〇g 0.05 mol of water, and mixing of 50.0 g of N,N-dimethylethanolamine to make 28.4 g (0.1 Torr) After 2-propanol, 〇·9 g (2-propanol and 4.5 g (〇. 〇5 mol) 25 200934891 solution was added dropwise. After the completion of the dropwise addition, the mixture was stirred for 1 hour to obtain "titanium compound oligo. Polymer (a) C". After further stirring for 1 hour, 36. Og (0.40 mol) of hydrazine and 2-butanediol were added, and the mixture was stirred for 1 hour, and further refluxed for 1 hour to further obtain 87 g of 2-propanol. The solvent was removed to obtain "titanium composite composition c". &lt;Production Example 4 &gt; After dissolving 34.0 g (0.10 mol) of tetra-n-butoxytitanium in 3 g of butanol, A mixture of 2.7 g (0.15 m) of water and 60 g of 1-butanol was added. After the completion of the dropwise addition, the mixture was stirred for 1 hour to obtain "titanium compound oligomer (a) D". 8. After 9 g (〇. 1〇mol) of N,N-dimethylethanolamine, stir for 1 hour, then add 36 〇g (〇4〇莫耳) of 2, 3-butanediol, stir 1 After an hour, the mixture was further refluxed for 1 hour to obtain "Qin Composite Composition D". Example 5 &gt; In the same manner as in Production Example 4, except that the amount of water of titanium tetraisopropoxide was 28.2 g (0.12 mol) with respect to 28.4 g (〇_1〇mol), Compound oligomer (a) E" and "titanium composite composition E". [Production Example 6 &gt; 36.4 g (0.1 mol) of diisopropoxy acetophenone was dissolved in 50. After 〇g of 2-propanol, a mixture of 27 g (〇15 mol) of water and 100.0 g of 2-propanol was added dropwise. After the completion of the dropwise addition, the mixture was stirred for 1 hour and further refluxed for 1 hour. "Titanium compound condensate (a) F". Then add 5. 1 g (0.05 mol) of triethylamine, stir for 1 hour, then add 30.4 g (〇.40 mol) of propylene glycol After stirring for 1 hour and further refluxing for 1 hour, "titanium composite composition F" was obtained. 26 200934891 &lt;Production Example 7 &gt; 28·4 g (0.10 mol) of titanium tetraisopropoxide was dissolved in 50.0 g of 2 In the case of propanol, a mixture of 2. 7 g (〇·15 mol) of water and 50.0 g of 2 propanol was added dropwise. After the completion of the dropwise addition, the mixture was stirred for 1 hour to obtain a "titanium compound oligomer ( a) G". Then add 8.9 g (0.1〇莫耳After 'N-methylethanolamine', the mixture was stirred for 1 hour, and then 1,4 propylene glycol (4 hydrazine) was added, and the mixture was stirred for 1 hour, and further refluxed for 1 hour. Thereafter, 13.6 g (〇.1) was further added. The methyltrimethoxy decane of 〇mole was further refluxed for 1 hour to obtain "titanium composite composition G". &lt;Production Example 8 &gt; 8.9 g (〇.1〇mol) of N,N-dimercaptoethanolamine was added to tetraisopropoxytitanium 28.4 g (〇.1〇莫耳). Stir for 1 hour after the addition. Further, 30.4 g (〇·40 mol) of 1,2-propanediol was added, and the mixture was stirred for 1 hour, and further refluxed for 1 hour to obtain "titanium compound a". &lt;Production Example 9 &gt; 5.1 g (0.05 mol) of triethylamine was added to tetramethylbutyrate 34.0 g (〇.1〇mol), and stirred for 1 hour. Thereafter, 3 〇 4 g (0.40 mol) of 1,2-propanediol was added for 1 hour, and further refluxed for 1 hour to obtain "chin compound b". &lt;Production Example 10 &gt; Triethylamine of 10 g of lgCO.l mole was added to 28.4 g (0.1 mol) of titanium tetraisopropoxide in 30 minutes. Then, 52.9 g (〇2 mol) of 2-(2-aminoethyl)amine propylmethyldiethoxydecane was added, followed by the addition of 49.6 g (0.8 mol) of 1,2-ethanediol. The mixture was stirred for 1 hour, and further refluxed for 27 hours at 27,2009,891 to obtain "titanium compound c"e. <Examples 1 to 84, Comparative Examples 1 to 24, Preparation of surface-coated steel sheet> Preparation of test plate Using 60 C alkali degreasing agent A 2% aqueous solution (SURFCLEANER 155, manufactured by Nippon Paint Co., Ltd.) was subjected to a 6-second spray treatment of an electrogalvanized steel sheet (zinc adhesion amount: 20 g/m2) having a thickness of 〇8 mm to degrease it. Then, the titanium composite composition obtained in the above production examples and the materials shown in Tables 1 to 4 were prepared as an aqueous coating agent in the formulation shown in Tables 5 and 6, and the aqueous coating was applied using a bar coater. The test agent was prepared so that the dry film amount became 〇. 5 g/m2, and it was calcined to a plate temperature of 8 &&gt;c using a hot air drying oven having an ambient temperature of 500 C. &lt;Evaluation method&gt; The substrate adhesion, the corrosion resistance of the processed portion, the heat resistance, the coating adhesion, the alkali resistance, and the solvent resistance were evaluated. The results are shown in Tables 5 and 6. The evaluation was carried out in accordance with the method described below. [Substrate adhesion] After the test plate was extruded to 8 mm using an Erichsen tester, a cell 〇 e e tape (registered trademark, manufactured by Nichiban Co., Ltd.) was adhered to the extrusion portion. Stripped. The test plate was immersed in the methyl violet staining solution to observe the film state and evaluated on the basis of the following criteria. 28 200934891 △: Partial peeling X: Complete peeling [Processing part resistance to surname]

The test panels were extruded to 7 mm using an Aristotle test machine, and the salt spray test SST (JIS-Z-2371) was carried out by tape sealing the edges and the back of the jaws. The occurrence of white rust after 120 hours was observed and evaluated based on the following criteria. ◎: No white rust generation 〇: White rust generation area is less than 1% △: White rust generation area is 103⁄4 or more and less than 30% X: White rust generation area is 30% or more [Heat resistance] The test plate is at 250° After heating for 1 hour at C, the edges and the back side were sealed with a tape to carry out a salt spray test SST (JIS-Z-2371). The occurrence of white rust after 72 hours was observed and evaluated on the basis of the following criteria. 〇 ◎ : No white rust is generated 〇: The area of white rust is less than 10% △ : The area of white rust is 10% or more, less than 30% X : The area of white rust is 30% or more [Coating adhesion] Using the rod type The coater was coated with a melamine alkyd paint (manufactured by SUPERLAC 100 'Nippon Paint) on the surface of the test plate to have a dry film thickness of 20 Ad m, and calcined at 120 ° C for 25 minutes to prepare a coated plate. After being placed for a day and night, it was immersed in boiling water for 30 minutes, taken out and placed for 1 day, and then extruded into a 7 mm film using an Aristotle test 29 200934891, and a transparent tape was applied to the extruded portion (Sellotape). (registered trademark, manufactured by Nichiban) The film state after forced peeling was evaluated on the basis of the following evaluation criteria. ◎: not peeled off 〇: slightly peeled △: partially peeled off X: completely peeled off [testability].

皮 The state of the film after the test piece was immersed for 30 minutes in a 2% aqueous solution of a degreasing agent (SURFCLEANER, manufactured by Nippon Paint Co., Ltd.) at 55 °C for 30 minutes on the basis of the following ef. price. ◎: unpeeled 〇: slightly peeled Δ: partially peeled off X: completely peeled off [solvent resistance] After the test panel was placed on a friction tester, the absorbent cotton impregnated with ethanol was applied under a load of 0.5 Kgf/on2 under the following evaluation criteria. Friction u times (round trip), and under the load of 0.5 Kgf/cm2, the state of the skin after rubbing with a cotton immersed in an o-pres. ◎: There is no friction trace on the friction surface 〇: a slight friction trace on the friction surface △: white trace on the friction surface χ: the film disappears on the friction surface 30 200934891 will be evaluated and measured by the above test The results are shown in Table 5 below. Table 1 矽 compound symbol substance name I τ - glycidoxypropyl trimethoxy dream Π r-amine ethylamine propyl trimethoxy sane m bis-(trimethoxy propyl propyl) amine

Table 3 Phosphoric acid (P) compounds Symbol Substance name IV Ammonium phosphate V Disodium hydrogen phosphate VI Aluminum phosphate

Vanadium (V) compound symbolic substance name W 偏 酸 酸 偏 偏 偏 酸 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 六 六 六 六 六 六 六 六 六 六 六 六 六 六 六 六 六 六结31 200934891 表 Example of electrogalvanized copper plate, comparative example Example Comparative film composition (mass ratio) Film properties Titanium composite composition 矽 Compound P Compound V Compound Zr compound Water substrate Adhesive processing part Corrosion resistance Heat resistance Coating adhesion, alkali resistance, solvent resistance, type, quantity, type, quantity, type, quantity, type, quantity, amount 2 A 52.9 I 7.1 Π 3.2 in 1.1 IV 0.2 35.6 〇 ◎ 〇〇〇 ◎ ◎ 3 A 52.9 I 7.1 U 3.2 m 1.1 VH 0.2 35.6 ◎ 〇〇 ◎ 〇 ◎ ◎ 4 A 52.9 I 7.1 Π 3.3 XI 0.2 36.7 ◎ 〇 ◎ ◎ ◎ ◎ 5 A 52.1 I 7.0 Π 3.1 IQ 1.0 VII 0.2 36.5 ◎ ◎ 〇 ◎ ◎ ◎ ◎ 6 A . 51.3 r 7.0 Π 3.1 V 0.2 VI 0.2 X 0.2 38.0 ◎ ◎ ◎ ◎ ◎ ◎ 7 B 56.0 I 7.5 VI 3.4 κ 0.2 Μ 0.2 32.7 〇〇〇〇〇 ◎ ◎ 8 B 52.9 I 7.1 Π 3.2 M 1.1 IV 0.2 35.6 〇〇〇〇〇 ◎ ◎ 9 B 52.9 I 7.1 Π 3.2 Melon 1.1 VE 0.2 35.6 ◎ 〇〇 ◎ 〇 ◎ ◎ 10 B 52.9 I 7.1 Π 3.3 XI 0.2 36.7 ◎ ◎ 〇 ◎ ◎ ◎ ◎ 11 B 52.1 I 7.0 Π 3.1 M 1.0 VH 0.2 36.5 ◎ 〇〇 ◎ ◎ ◎ ◎ 12 B 51.3 I 7.0 Π 3.1 V 0.2 V1Q 0.2 X 0.2 38.0 ◎ ◎ 〇 ◎ ◎ ◎ 13 C 8.0 I 7.5 VI 3.4 K 0.2 χ α 0.2 80.7 〇〇〇〇 ◎ ◎ ◎ 14 C 7.5 I 7.1 Π 3.2 m 1.1 ιν' 0.2 80.9 〇 ◎ 〇〇 ◎ ◎ ◎ 15 C 7.5 I 7.1 Π 3.2 m 1.1 vn 0.2 80.9 ◎ 〇〇 ◎ 〇 ◎ ◎ 16 C 8.0 I 7.1 Π 3.3 Vi 0.2 XI 0.2 8L2 ◎ 〇〇 ◎ ◎ ◎ ◎ 17 C 7.3 I 7.0 H 3.1 M 1.0 VB 0.2 81.4 ◎ 〇〇 ◎ ◎ ◎ ◎ 18 C 8.0 I 7.0 Π 3.1 V 0.2 Yi 0.2 X 0.2 81.7 ◎ ◎ 〇 ◎ ◎ ◎ ◎ 19 D 56.0 I 7.5 VI 3.4 IX 0.2 Μ 0.2 32.7 〇 ◎ 〇 〇〇◎ ◎ 20 D 52.9 I 7.1 Ε 3.2 IH 1.1 IV 0.2 35*6 〇〇〇〇〇 ◎ ◎ 21 D 52.9 I 7.1 Π 3.2 M 1.1 \E 0.2 35.6 ◎ 〇〇 ◎ ◎ ◎ ◎ 22 D 52.9 I 7.1 Π 3.3 XI 0.2 36.7 ◎ ◎ 〇 ◎ ◎ ◎ ◎ 23 D 52.1 I 7.0 Ε 3.1 Melon 1.0 VII 0.2 36.5 ◎ 〇〇 ◎ ◎ ◎ ◎ 24 D 51.3 I 7.0 Π 3.1 V 0.2 vm 0.2 X 0.2 38.0 ◎ ◎ 〇 ◎ ◎ ◎ ◎ 25 E 56.0 I 7.5 VI 3.4 IX 0.2 Μ 0.2 32.7 〇〇〇〇〇 ◎ ◎ 26 E 52.9 I 7.1 Π 3.2 in 1.1 IV 0.2 35.6 〇〇〇〇〇 ◎ ◎ 27 E 52.9 I 7.1 Π 3.2 HI 1.1 vn 0.2 35.6 ◎ ◎ 〇 ◎ 〇 ◎ ◎ 28 E 52.9 I 7.1 Π 3.3 XI 0.2 36.7 ◎ 〇〇 ◎ ◎ ◎ ◎ 29 E 52.1 I 7.0 Π 3.1 M 1.0 VH 0.2 36.5 ◎ 〇〇 ◎ ◎ ◎ ◎ 30 E 51.3 I 7.0 H 3.1 V 0.2 m 0.2 X 0.2 38.0 ◎ ◎ 〇 ◎ ◎ ◎ ◎ 31 F 56.0 I 7.5 VI 3.4 K 0.2 Μ 0.2 32.7 〇 ◎ 〇〇 ◎ ◎ ◎ 32 F 52.9 I 7.1 Π 3.2 in 1.1 IV 0.2 35.6 〇〇〇〇〇 ◎ ◎ 33 F 52.9 I 7.1 Π 3.2 m 1.1 va 0.2 35.6 〇〇 ◎ 〇 ◎ ◎ 34 F 52.9 I 7.1 Π 3.3 XI 0.2 36,7 ◎ 〇〇 ◎ ◎ ◎ ◎ 35 F 52.1 I 7.0 Π 3.1 Melon 1.0 vn 0.2 36.5 ◎ ◎ 〇 ◎ ◎ ◎ ◎ 36 F 51.3 I 7.0 Π 3.1 V 0.2 VHI 0.2 X 0.2 38.0 ◎ ◎ 〇 ◎ ◎ ◎ ◎ 37 G 56.0 I 7.5 VI 3.4 K 0.2 Μ 0.2 32.7 〇〇〇〇〇 ◎ ◎ 38 G 52.9 I 7.1 η 3.2 M 1.1 IV 0.2 35.6 〇〇〇〇 ◎ ◎ ◎ 39 G 52.9 I 7.1 n 3.2 m 1.1 VH 0.2 35.6 ◎ ◎ 〇 ◎ ◎ ◎ ◎ 40 G 52.9 I 7.1 n 3.3 XI 0.2 36.7 ◎ 〇〇 ◎ ◎ ◎ ◎ 41 G 52.1 I 7.0 π 3.1 IQ 1.0 VE 0.2 36.5 ◎ 〇〇 ◎ ◎ ◎ ◎ 42 G 51.3 I 7.0 n 3.1 V 0.2 vm 0.2 X 0.2 38.0 ◎ ◎ 〇 ◎ ◎ ◎ ◎ 1 a 25.2 IV 0.2 74.6 〇 △ △ △ X ◎ ◎ 2 b 19.8 w 0.2 80.0 〇 △ △ △ X ◎ ◎ 3 c 30.2 X 0.2 6 Θ.6 〇Δ △ △ X ◎ ◎ 4 A 64.5 IV 0.2 35.5 〇〇〇 △ X ◎ ◎ 5 E 64.5 vn 0.2 35.5 〇〇〇Δ X ◎ ◎ 6 G 64.5 X 0.2 35.5 〇〇〇Δ X ◎ ◎ 7 a 25.0 I 7.0 IV 0.2 67.8 〇 △ Δ Δ X ◎ ◎ 8 b 20.0 I 7.1 π 3.2 w 0.2 69.5 〇Δ Δ Δ X ◎ ◎ 9 c 30.0 I 7.0 π 3.1 M 1.0 X 0.2 58.7 〇Δ △ △ △ ◎ ◎ 10 I 50.0 IV 0.2 49.8 〇Δ △ 〇. X ◎ ◎ 11 I 35.0 n 15.0 VH 0.2 49.8 〇Δ Δ 〇X ◎ ◎ 12 I 35.0 π 15.0 in 5.0 X 0.2 44.8 〇△ △ 〇△ ◎ ◎ 32 200934891 Table 6 Example of hot-dip galvanized copper plate 皮 Film composition (mass ratio) __ Film performance comparison example Example comparison example compound composition 矽 compound P compound V compound Zr compound water Substrate Adhesive Processing Section Corrosion Resistance Heat Resistance Coating Adhesive Resistance Alkali Resistance Solubility Type Species Type Species Type Species Type Species Type Species Quantity M£K 43 A 56.0 I 7.5 VI 3.4 K 0.2 Μ 0.2 32.7 〇〇〇〇〇 ◎ ◎ 44 A 52.9 I 7.1 Π 3.2 ΙΠ 1.1 IV 0.2 35.6 〇 ◎ 〇〇〇 ◎ ◎ 45 A 52.9 ϊ 7.1 π 3.2 in 1.1 W 0.2 35.6 ◎ 〇〇 ◎ 〇 ◎ ◎ 46 A 52.9 I 7.1 H 3.3 XI 0.2 36.7 ◎ 〇〇 ◎ ◎ ◎ ◎ 47 A 52.1 I 7.0 H 3.1 Μ 1.0 va 0.2 36.5 ◎ ◎ 〇 ◎ ◎ ◎ ◎ 48 A 51.3 I 7.0 Π 3.1 V 0.2 vm 0.2 X 0.2 38.0 ◎ ◎ 〇 ◎ ◎ ◎ ◎ 49 B 56.0 I 7.5 VI 3.4 κ 0.2 Μ 0.2 32.7 〇〇〇〇〇 ◎ ◎ 50 B 52.9 I 7.1 Π 3.2 Μ 1.1 IV 0.2 35.6 〇〇〇〇 〇 ◎ ◎ 51 B 52.9 I 7.1 Π 3.2 m 1.1 YU 0.2 35.6 ◎ 〇〇 ◎ 〇 ◎ ◎ 52 B 52.9 I 7.1 Π 3.3 XI 0.2 36.7 ◎ ◎ 〇 ◎ ◎ ◎ ◎ 53 B 52.1 I 7.0 Π 3.1 m 1.0 vn 0.2 36.5 ◎ 〇〇 ◎ ◎ ◎ ◎ 54 B 51.3 I 7.0 Π 3.1 V 0.2 m 0.2 X 0.2 38.0 ◎ ◎ 〇 ◎ ◎ ◎ ◎ 55 C 8.0 I 7.5 VI 3.4 IX 0.2 ΎΆ 0.2 80.7 〇〇〇〇 ◎ ◎ ◎ 56 C 7.5 I 7.1 Π 3.2 m 1.1 IV 0.2 80.9 〇 ◎ 〇〇 ◎ ◎ ◎ 57 C 7.5 I 7.1 Π 3.2 m 1.1 w 0.2 80.9 ◎ 〇〇 ◎ 〇 ◎ ◎ 58 C 8.0 I 7.1 H 3.3 Yff 0.2 XI 0.2 81.2 ◎ 〇 〇◎ ◎ ◎ ◎ 59 C 7.3 I 7.0 Π 3.1 m 1.0 Vff 0.2 81.4 ◎ 〇〇 ◎ ◎ ◎ ◎ 60 C 8.0 I 7.0 Π 3.1 V 0.2 m 0.2 X 0.2 81.7 ◎ ◎ 〇 ◎ ◎ ◎ ◎ 61 D 56.0 I 7.5 VI 3.4 DC 0.2 XD 0.2 32.7 〇 ◎ 〇〇〇 ◎ ◎ 62 D 52.9 I 7.1 Π 3.2 m 1.1 IV 0.2 35.6 〇〇〇〇〇 ◎ ◎ 63 D 52.9 I 7.1 Π 3.2 M 1.1 va 0.2 35.6 ◎ 〇〇 ◎ ◎ ◎ ◎ 64 D 52.9 I 7.1 Π 3.3 XI 0.2 36.7 ◎ ◎ 〇 ◎ ◎ ◎ ◎ 65 D 52.1 I 7.0 Π 3.1 M 1.0 va 0.2 36.5 ◎ 〇〇 ◎ ◎ ◎ ◎ 66 D 51.3 I 7.0 Π 3.1 V 0.2 m 0.2 X 0.2 38.0 ◎ ◎ 〇 ◎ ◎ ◎ ◎ 67 £ 56.0 I 7.5 VI 3.4 ΊΧ 0.2 Μ 0.2 32.7 〇〇〇〇〇 ◎ ◎ 68 E 52.9 I 7.1 Η 3.2 Melon 1.1 IV 0.2 35.6 〇〇〇〇〇 ◎ ◎ 69 E 52.9 I 7.1 H 3.2 m 1.1 Vn 0.2 35.6 ◎ ◎ 〇 ◎ 〇 ◎ ◎ 70 E 52.9 I 7.1 H 3.3 η 0.2 36.7 ◎ 〇〇 ◎ ◎ ◎ ◎ 71 E 52.1 I 7.0 Π 3.1 M 1.0 w 0.2 36.5 ◎ 〇〇 ◎ ◎ ◎ ◎ 72 E 51.3 I 7.0 Π 3.1 V 0.2 m 0.2 X 0.2 38.0 ◎ ◎ 〇 ◎ ◎ ◎ ◎ 73 F 56.0 I 7.5 VI 3.4 K 0.2 μ 0.2 32.7 〇 ◎ 〇〇 ◎ ◎ ◎ 74 F 52.9 I 7.1 Π 3.2 M 1.1 IV 0.2 35.6 〇〇〇〇〇 ◎ ◎ 75 F 52.9 I 7.1 Π 3.2 M 1.1 w 0.2 35.6 ◎ 〇〇 ◎ 〇 ◎ ◎ 76 F 52.9 I 7.1 Π 3.3 XI 0.2 36.7 ◎ 〇〇 ◎ ◎ ◎ ◎ 77 F 52.1 I 7.0 Π 3.1 M 1.0 vs 0.2 36.5 ◎ ◎ 〇 ◎ ◎ ◎ ◎ 78 F 51.3 I 7.0 Π 3.1 V 0.2 m 0.2 X 0.2 38.0 ◎ ◎ 〇 ◎ ◎ ◎ 79 G 56.0 I 7.5 VI 3.4 K 0.2 ΧΠ 0.2 32.7 〇〇〇〇〇 ◎ ◎ 80 G 52.9 I 7.1 Π 3.2 M 1.1 IV 0.2 35.6 〇〇〇〇 ◎ ◎ ◎ 81 G 52.9 I 7.1 Π 3.2 m 1.1 VB 0.2 35.6 ◎ ◎ 〇 ◎ ◎ ◎ ◎ 82 G 52.9 I 7.1 U 3.3 XI 0.2 36.7 ◎ 〇〇 ◎ ◎ ◎ ◎ 83 G 52.1 I 7.0 Π 3.1 1 1.0 vn 0.2 36.5 ◎ 〇〇 ◎ ◎ ◎ 84 G 51.3 I 7.0 Π 3.1 V 0.2 vm 0.2 X 0.2 38.0 ◎ ◎ 〇 ◎ ◎ ◎ ◎ 13 a 25.2 IV 0.2 74.6 〇Δ Δ Δ X ◎ ◎ 14 b 19.8 v n 0.2 80.0 〇Δ Δ Δ X ◎ ◎ 15 c 30.2 X 0.2 69.6 〇Δ Δ Δ X ◎ ◎ 16 A 64.5 IV 0.2 35.5 〇〇〇Δ X ◎ ◎ 17 E 64.5 YE 0.2 35.5 〇〇〇△ X ◎ ◎ 18 G 64.5 X 0.2 35.5 〇〇〇Δ X ◎ ◎ 19 a 25.0 I 7.0 IV 0.2 67.8 〇Δ Λ Δ X ◎ ◎ 20 b 20.0 I 7.1 n 3.2 vn 0.2 69.5 〇△ Δ △ X ◎ ◎ 21 c 30.0 I 7.0 Π 3.1 m 1.0 X 0.2 58.7 〇Δ Δ Δ △ ◎ ◎ 22 I 50.0 IV 0.2 49.8 〇△ Δ 〇X ◎ ◎ 23 I 35.0 Π 15.0 vn 0.2 49.8 〇△ Δ 〇X ◎ ◎ 24 I 35.0 Π 15.0 m 5.0 X 0.2 44.8 〇Δ Δ 〇Δ ◎ ◎ 33 200934891 It can be seen from the results of Tables 4 and 5 that the adhesion of the substrate to be adhered to the surface of the water-based surface treatment composition of the example is good, and the processing portion is resistant to money and resistant. Adhesive body excellent in solvent, coating adhesion, alkali resistance, and heat resistance. On the other hand, the aqueous surface treatment composition (Comparative Examples 1 to 3) obtained from the titanium compounds a to c was used, and the ruthenium compound (d) was not reacted (mixed) with the titanium composite compositions a, e, and G. The formed aqueous surface treatment composition (Comparative Examples 4 to 6) and the aqueous surface treatment composition (Comparative Examples 7 to 9) formed by reacting (mixing) the ruthenium compound with the compound a to c, and the ruthenium compound (d) The obtained water-based surface treatment composition (Comparative Example 1 〇 to 12) was subjected to surface treatment, and any of the adherends was not excellent in all of the above properties. The water-based surface treatment composition of the present invention can remarkably improve the adhesion of the substrate of the adhered body such as zinc or an alloy containing 20% or more of zinc or the electroplated body such as the electroplated body, the corrosion resistance of the processed portion, the heat resistance, and the coating density. It is suitable for household appliances, office machines, building materials, automobiles and other industrial fields. [Simple diagram description] None [Main component symbol description] None 34

Claims (1)

200934891 VII. Patent Application Range: 1. A water-based surface treatment composition characterized by having a chemical structure formed by reacting a ruthenium compound (d) having one or more alkoxy groups in a molecule with a titanium composite composition and/or Or a composition formed by mixing or the like, the titanium composite composition having a chemical structure formed by reacting a titanium compound oligomer (a), an amine compound (b), and a diol compound (c), and/or the like The composition formed by mixing 'and the above aqueous surface treatment composition is used for the surface of zinc or an alloy containing 20% or more of the alloy, or the like. The aqueous surface treatment composition according to claim 1, which further comprises at least one selected from the group consisting of a phosphoric acid compound, a vanadium compound and a cerium compound. 3. The water-based surface treatment composition according to the first aspect of the invention, wherein the titanium compound polymer (a) has a condensation of a titanium alkoxide or a chelate compound represented by the following formula (1). In the structure, the titanium chelate compound has a structure in which a chelating agent is coordinated to a titanium alkoxide represented by the following formula (1), ® [Chemical Formula 1] OR1 R20-Ti-OR4 (\) I 3 OR3 [Formula In (1), R1 to R4 each independently represent an alkyl group having 1 or more carbon atoms and 18 or less carbon atoms. 4. The aqueous surface treatment composition according to claim 1, wherein the titanium compound oligomer (a) has a condensation with a titanium alkoxide or a titanium chelate compound represented by the following formula (1). In the structure of the chelating agent, the titanium chelate compound has a structure in which a chelating agent is coordinated in a titanium alkoxide represented by the following formula (1) = [Chemical Formula 2] OR1 R20—Τί—OR4 (1) Q 0R3 [In the formula (1), Ri to R4 independently represent an alkyl group having a carbon number of 丄 or more and i8 or less]. 5. The water-based surface treatment composition according to the third or fourth aspect of the invention, wherein the condensation of the titanium alkoxide or the titanium chelate compound is carried out by using a titanium alkoxide or a titanium chelate compound in an alcohol The solution is reacted with water to carry out. 6' The water-based surface treatment composition according to the third or fourth aspect of the invention, wherein the condensation of the titanium alkoxide or the titanium chelate compound is carried out by using Ο 1 mol a titanium alkoxide and/or a titanium chelate The compound is reacted in an alcohol solution with water of 2 mol or more and 2 mol or less. The water-based surface treatment composition as described in claim 3 or 4, wherein the condensation of the above titanium alkoxide or the above titanium chelate compound is carried out by using a chelate or a titanium compound as an amine compound It is carried out in the presence of (1) and reacted with water in an alcohol solution. The aqueous surface treatment composition of claim 1, wherein the amine compound (b) is a substituted or unsubstituted aliphatic amine or a quaternary ammonium 36 200934891 hydroxide. 9. The aqueous surface treatment composition according to claim 1, wherein the diol compound (c) is at least selected from the group consisting of U-ethylene glycol, U2 propylene glycol and 23-butanediol. - kind. 10. The water-based surface treatment composition as described in claim 3 or 4, wherein the chelating agent is selected from the group consisting of ketone ketone, polyol, alkaloid and hydroxycarboxylic acid. At least one of the groups. 11. The surface treatment composition of the water system as described in claim 3 or 4 of the patent scope, wherein R] in the formula (1) is "independently a carbon number of 8 carbon." The water-based surface treatment composition according to the above aspect, wherein the polymer (4) having one or more alkoxy groups in the molecule has a structure in which a group is directly bonded to a group on the stone atom. The water-based surface treatment composition according to the above aspect of the invention, wherein the compound (4) having at least one alkoxy group in the molecular group contains an amine group, a sulfhydryl group, an epoxy group, an ethylene group or a (fluorenyl) propylene group.氧基 · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · The surface of the body is formed by film formation. 15. A type of zinc or an alloy containing more than 2% by weight, or an electroplated body thereof, characterized in that: the surface treatment composition of the water system as described in the scope of the patent application is used. The object forms a rustproof layer. 37 200934891 IV FIG designated representative: (a) designated representative case Pictured: None (b) of FIG element symbols representative of this briefly described: None 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 2