TWI433898B - Chromium - free surface treatment of zinc - plated steel sheet - Google Patents

Description

Chrome-free surface treatment zinc-coated plate Field of invention

The present invention relates to a zinc-based plated steel sheet which has been subjected to a chromium-free surface treatment, which is subjected to a surface treatment with a cationic chromium-free surface treatment agent to impart corrosion resistance, resistance to corrosion resistance, alkali resistance and solvent resistance. The water resistance, the film adhesion, the coating adhesion, the printing adhesion, and the like are excellent in water resistance such as adhesion, moisture discoloration resistance, and dew condensation resistance, and also excellent in workability and slidability.

Background of the invention

Generally, it is excellent in adhesion to the surface of a metal material, and imparts corrosion resistance and fingerprint resistance to the surface of the metal material, and a treatment liquid containing chromic acid, dichromic acid or the like as a main component. The method of performing chromate treatment on the surface of the material, the method of performing phosphate treatment, the method of performing the treatment of the organic resin film, and the like are known and practically applied.

In the past, in the chromate treatment for practical use, the metal surface may be contacted with a chromium-containing treatment liquid such as chromate chromate to precipitate a chromate film, or coated and dried. A method of forming a chromate film on a metal surface. However, under these conditions, the inorganic chromate film is hard and brittle and lacks lubricity, so that the film will fall off and damage the appearance, and it will not be fully processed, causing cracks in the raw material, which may result in A defect such as cracking occurs. Further, there is a problem that the fingerprint of the operator adheres during the work, and even if the residue is degreased, the mark remains, and the appearance is impaired. Therefore, in general, in order to satisfy all the properties of high corrosion resistance, fingerprint resistance, scratch resistance, lubricity, coating adhesion, etc., a chromate film is formed on the surface of the metal material, and chromate is formed. A resin film was further provided on the film to perform two-layer treatment.

An attempt to satisfy all the performances by one layer treatment has been reviewed together with a resin chromate which forms a chromate and a resin film. In Patent Document 1, it is disclosed that a resin composition is coated on the surface of an aluminum-zinc plated steel sheet. In the treatment method, the resin composition is mixed with a specific aqueous dispersion or water-soluble resin and a specific amount of hexavalent chromium. In Patent Document 2, a metal surface treatment composition containing hexavalent chromium of an inorganic compound is disclosed. An ionic or hexavalent chromium ion with a trivalent chromium ion, and an acrylic latex polymerized under specific emulsion polymerization conditions.

However, the hexavalent chromium contained in the chromate treatment film has a property of being gradually decomposed, and has problems in terms of environment and safety.

In the method of using a chromium-free chromate-free treatment liquid, Patent Document 3 discloses a polymer composition for surface treatment of a metal material containing a specific structure of a phenol resin-based polymer and an acidic compound, and a surface treatment method, Patent Document 4 A metal surface treatment agent and a treatment method which are excellent in fingerprint resistance and the like which contain two or more kinds of decane coupling agents having mutually different kinds of reactive functional groups which can react with each other, and patent documents are disclosed. 5 discloses a metal surface treatment agent containing a specific structure of a decane coupling agent and a phenol resin-based polymer having a specific structure, and a treatment method, and Patent Document 6 discloses a metal surface treatment agent, a treatment method, and a treatment metal material, which contain An organic polymer having at least one nitrogen atom, an acrylic resin, an urethane resin, or the like, and a specific polyvalent anion, and Patent Document 7 discloses a treatment method and treatment using (1) and (2). a metal material, wherein (1) is a rust inhibitor containing a specific structure of bisphenol A epoxy resin, and (2) is a specific ratio The specific polyester resin, a rust inhibitor, etc. other than the phenolic resin thereto.

However, these chrome-free technologies do not fully satisfy the adhesion resistance, moisture resistance, such as corrosion resistance, alkali resistance, and solvent resistance, such as cleaning agent resistance, film adhesion, paint adhesion, and printing adhesion. It is excellent in water resistance such as discoloration and dew resistance, and in particular, workability and slidability are still problematic in practical use.

In the current state, no surface treatment agent which can be used in place of the chromate film is obtained in any of these methods, and development of a surface treatment agent and a treatment method which can comprehensively satisfy such requirements is strongly demanded.

Prior technical literature Patent literature

Patent Document 1: Special Fair 4-2672

Patent Document 2: Special Fair 7-6070

Patent Document 3: Japanese Patent Publication No. 7-278410

Patent Document 4: Japanese Patent Publication No. 8-73775

Patent Document 5: Japanese Patent Publication No. 9-241576

Patent Document 6: Japanese Patent Publication No. 10-1789

Patent Document 7: Japanese Patent Publication No. 10-60233

The object of the present invention is to solve the above problems of the prior art, and to provide a chromium-free surface-treated zinc-based plated steel sheet which has corrosion resistance, alkali resistance and solvent resistance, such as detergent resistance, sweat resistance and film adhesion. It is excellent in water resistance, such as adhesiveness, the adhesiveness of a coating, and printing adhesiveness, the moisture-resistant discoloration property, and the decondensation resistance, and is excellent in workability and slidability.

The inventors of the present invention have found a chromium-free surface-treated zinc-based plated steel sheet by applying a water-based metal surface treatment agent and drying it to form a composite film containing the respective components in order to solve the above problems. The adhesion resistance and wet color resistance of the steel sheet such as corrosion resistance, alkali resistance, and solvent resistance such as detergent resistance, sweat resistance, film adhesion, paint adhesion, and printing adhesion are obtained. The present invention is excellent in water resistance such as properties and resistance to condensation, and also excellent in workability and slidability, wherein the aqueous metal surface treatment agent contains a film-forming component (c), an inhibitor component (d) and an aqueous medium. The film-forming component (c) contains an organic cerium compound (C) and an aqueous polyurethane resin (E) in a specific ratio, and the organic cerium compound (C) is a specific ratio of two kinds of decane couples. The mixture is mixed and controlled by a specific method to control the reaction, and contains two or more specific functional groups and one or more specific hydrophilic functional groups in the molecule, and has a specific molecular weight and a specific structure. Organic hydrazine The aqueous polyurethane resin (E) has a specific structural unit, and the inhibitor component (d) has a fluorine metal complex (H) as an essential component, and the fluorine metal complex (H) has an optional composition. From at least one element of titanium and zirconium.

In other words, the present invention relates to a surface-treated zinc-based plated steel sheet which is obtained by applying a water-based metal surface treatment agent and drying it to form a composite film containing each component. The metal surface treatment agent contains the film-forming component (c) comprising the following (1) and (2), and the following materials (3) and (4):

(1) The organic hydrazine compound (C) is obtained by mixing a decane coupling agent (A) and a decane coupling agent (B) in a ratio of a solid content mass ratio [(A)/(B)] in a ratio of 0.50 to 0.75, The functional group (a) represented by the following general formula [1] is contained in the molecule, and at least one or more selected from the group consisting of a hydroxyl group (different from the functional group (a)) and an amine group a hydrophilic functional group (b) having an average molecular weight of from 1,000 to 10,000 and having a cyclic oxirane bond in the skeleton, the decane coupling agent (A) having one amine group in the molecule, the decane coupling agent ( B) contains one epoxy propyl group in the molecule,

[Chemical 1]

(wherein R1, R2 and R3 independently of each other represent an alkoxy group or a hydroxyl group, and at least one represents an alkoxy group);

(2) a polyether polyurethane resin (E), which is a structural unit derived from a polyether polyol in a molecule;

(3) an inhibitor component (d) having a fluorine metal complex (H) having at least one element selected from the group consisting of titanium and zirconium as an essential component;

(4) an aqueous medium; and, in the film-forming component (c) of the aqueous treatment agent,

(5) The solid content mass ratio [(E)/(C)] of the organic hydrazine compound (C) and the polyether polyurethane resin (E) is from 0.33 to 0.90.

The ratio of the presence of the cyclic oxime bond and the chain siloxane bond in the organic ruthenium compound (C) is based on the absorbance (C1) of the cyclic oxirane bond of 1090 to 1100 cm ^-1 according to the FT-IR reflection method. The ratio [C1/(C1+C2)] to the absorbance (C2) of 1030 to 1040 cm ^{-1 which} exhibits a chain-type decane bond is preferably 1.0 to 2.0.

Further, the polyether polyurethane resin (E) of the present invention preferably has an aromatic ring and/or an alicyclic structure having a carbon number of 4 to 6 in the molecule, and the above polyether polyurethane resin (E) is The molecule contains an amine group, and for the total amount of the amine group, the ratio of the grade 4 ammonium salt is preferably from 0.7 to 1.0 in terms of a molar ratio. Further, the polyether polyurethane resin (E) preferably has a structural unit (D) represented by the following general formula [2] in the molecule.

[Chemical 2]

(wherein R9 represents a monovalent organic residue selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an aralkyl group, and R10 and R11 each independently represent an alkoxy group, a decyloxy group, A functional group in a group consisting of a hydroxyl group and a halogen atom, and m represents an integer of 1 to 5.)

Further, the film-forming component (c) of the present invention further contains a cationic phenol resin (F), and the solid content mass ratio of the above-mentioned polyether polyurethane resin (E) to the cationic phenol resin (F) [ F)/(E)] is preferably 0.010 to 0.030, and the cationic phenol resin (F) has a bisphenol A skeleton.

The inhibitor component (d) preferably further contains (6) a phosphoric acid compound (J), and further preferably (6) a phosphoric acid compound (J) and (7) a vanadium (IV) compound (K), and preferably ,

(8) a mass ratio of the above-mentioned organic cerium compound (C)-derived Si(Si) to the aforementioned metal component (M) having at least one fluorine metal complex (H) selected from titanium and zirconium [() M)/(Si)] is 0.08 to 0.20,

(9) The solid content mass ratio [(J)/(C)] of the organic hydrazine compound (C) and the phosphoric acid compound (J) is 0.02 to 0.11,

(10) The solid content mass ratio [(K)/(C)] of the organic hydrazine compound (C) and the vanadium (IV) compound (K) is 0.02 to 0.06.

Further, the metal component (M) of the fluorometal complex (H) of the present invention contains both titanium (M _T ) and zirconium (M _Z ), and the respective metal composition ratio [(M _T )/(M _Z )] is preferably 0.50 to 0.80, and the inhibitor component (d) is preferably at least one metal component selected from the group consisting of Mg, Co, and W.

The aqueous metal surface treatment agent further contains a polyethylene wax (L), and the solid content mass ratio [(L)/(C)] of the organic cerium compound (C) and the polyethylene wax (L) is 0.05 to 0.30. good.

Preferably, the surface-treated zinc-based plated steel sheet is coated with the aqueous metal surface treatment agent on the surface of the zinc-based plated steel sheet, and dried at a temperature of 50 ° C to 250 ° C, and the weight of the dried film is 0.2 to 5.0 g / m ² .

The surface-treated zinc-based plated steel sheet of the present invention is resistant to cleaning agents, sweat resistance, film adhesion, paint adhesion, and printing adhesion, such as corrosion resistance, alkali resistance, and solvent resistance. It is excellent in water resistance such as wetness, moisture discoloration resistance, and dew condensation resistance, and is excellent in workability and slidability.

Form for implementing the invention

The water-based metal surface treatment agent for the chromium-free surface-treated zinc-based plated steel sheet of the present invention, as the film-forming component (c), is an organic cerium compound (C) and a polyether polyurethane resin (E). As an essential component.

The organic ruthenium compound (C) is a solid content mass ratio [(A)/) of a decane coupling agent (A) having one amine group in the molecule and a decane coupling agent (B) containing one epoxy propyl group in the molecule. (B)] It is prepared by mixing in a ratio of 0.50 to 0.75. The mixing ratio of the decane coupling agent (A) to the decane coupling agent (B) must be in the ratio of the solid content mass ratio [(A)/(B)] of 0.50 to 0.75, preferably 0.50 to 0.65, and 0.55 to 0.65. good. When the solid content mass ratio [(A)/(B)] is less than 0.50, since the hydrophobicity and self-crosslinkability of the organic hydrazine compound (C) are increased, the stability of the treating agent is remarkably lowered and is not suitable. On the other hand, if the solid content mass ratio [(A)/(B)] exceeds 0.75, since the hydrophilicity and cationicity of the organic hydrazine compound (C) are too high, the water resistance and sweat resistance of the obtained film will be high. Significantly lower and not suitable.

Further, the above organic hydrazine compound (C) must have a cyclic decane bond in the skeleton. If there is no ring structure containing Si in the skeleton, the barrier property and adhesion of the film-forming component (c) are lowered, and all properties such as corrosion resistance, detergent resistance, and film adhesion are lowered.

Further, in the present invention, the decane coupling agent (A) having one amine group in the molecule is not particularly limited, and examples thereof include 3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, and the like. Examples of the decane coupling agent (B) containing one epoxy propyl group include 3-glycidyloxypropyltrimethoxydecane, 3-glycidyloxypropyltriethoxydecane, and the like.

Further, the number of the functional groups (a) in the organic hydrazine compound (C) must be two or more. When the number of the functional groups (a) is one, the adhesion to the surface of the zinc-based plated steel sheet, the self-crosslinking property of the organic cerium compound (C), and the polyether polyurethane resin (E) described later The bonding property is lowered, and the film may not be sufficiently formed, so that the effects of the present invention are not obtained at all. In the definition of R1, R2 and R3 of the functional group (a), the carbon number of the alkyl group and the alkoxy group is not particularly limited, but preferably 1 to 6 is preferable, 1 to 4 is preferable, and 1 or 2 is most preferable.

Further, in the organic hydrazine compound (C), the functional group (b) may be present in an amount of one or more in one molecule, and the average molecular weight must be from 1,000 to 10,000, preferably from 1300 to 6,000. The molecular weight described herein is not particularly limited, and any one of the direct measurement by the TOF-MS method and the conversion according to the chromatographic method may be used to use GFC (gel filtration chromatography), and the molecular weight standard substance is B. A diol is preferred. If the average molecular weight obtained by the same method is less than 1,000, the water solubility of the organic hydrazine compound will increase, and the water resistance of the formed film will be remarkably lowered. On the other hand, when the average molecular weight exceeds 10,000, the organic hydrazine compound (C) is difficult to be dissolved or dispersed stably in water.

The organic ruthenium compound (C) must have a cyclic oxime structure, and the ratio of the presence thereof is based on the FT-IR reflection method showing the absorbance (C1) of the cyclic oxirane bond of 1090 to 1100 cm ^-1 and the display of the chain enthalpy. The ratio [C1/C2] of the absorbance (C2) of the oxyalkylene bond of 1030 to 1040 cm ^-1 is preferably 1.0 to 2.0. The ratio [C1/C1] is 1.0 to 2.0, and the barrier properties caused by the cyclic structure and the flexibility caused by the chain structure can be balanced, and the properties such as corrosion resistance, detergent resistance, and film adhesion can be improved. improve. In addition, due to the complexation of the resin molecules with the cyclic siloxane coupling, a tough and dense film is formed.

Further, the method for producing the organic hydrazine compound (C) of the present invention is not particularly limited, and the decane coupling agent (A) and the decane coupling agent (B) are sequentially added in water having a pH adjusted to 4, and stirring is specified. The method of time. Here, since the aqueous solution of the decane coupling agent (A) is added, heat is generated, so that the water is cooled in advance, and further cooling is performed for a predetermined period of time, and it is produced in a certain temperature range, whereby the ring of the above organic hydrazine compound (C) can be controlled. The ratio of the siloxane linkage to the chain siloxane linkage.

The above-mentioned polyether polyurethane resin (E) which is an essential component of the present invention must be a polyether system. The polyester polyurethane resin is not suitable for hydrolysis by acid or alkali, and the polycarbonate polyurethane is easy to form a crisp film due to being hard, and the adhesion during processing and the corrosion resistance of the processed portion are poor. Not suitable.

Further, the polyether polyurethane resin (E) preferably has an aromatic ring and/or an alicyclic structure having 4 to 6 carbon atoms in the molecule. By having an aromatic ring or an alicyclic structure, it will complex with the cyclic structure of the above-mentioned organic cerium compound (C), thereby improving the barrier property of the film. Further, the polyether polyurethane resin (E) contains an amine group in the molecule, and the ratio of the grade 4 ammonium salt is preferably from 0.7 to 1.0 in terms of a molar ratio with respect to the total amount of the amine group. The ratio of the quaternary ammonium salt to the total amount of the amine group satisfies both the dispersion stability of the polyether polyurethane resin (E) and the water resistance after film formation in this range.

Further, the above polyether polyurethane resin (E) preferably has a structural unit (D) represented by the following general formula [2] in the molecule. Since the structural unit (D) is contained, since it has a reaction point with the above-mentioned organic hydrazine compound (C) and a self-crosslinking point, the degree of crosslinking increases, and the corrosion resistance and the detergent resistance are remarkably improved. Further, R9, R10 and R11 in the above structural unit (D) are not particularly limited, but R9 is a monovalent organic residue selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group and an aralkyl group, R10 R11 is preferably one independently selected from the group consisting of an alkoxy group, a decyloxy group, a hydroxyl group and a halogen atom, and R9 is an alkyl group, and R10 and R11 are preferably a hydroxyl group. Further, the number of stretching ethyl groups of the structural unit (D) is not particularly limited, but preferably 1 to 5 is preferable, and 2 or 3 is most preferable.

Further, the polyether polyurethane resin (E) of the present invention is not particularly limited, and is a polyurethane resin of a polycondensate of a polyether polyol and an aliphatic, alicyclic or aromatic polyisocyanate. One part of the polyol is a polyurethane obtained by using a polyol having a (substituted) amine group. As the polyether polyol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, hexamethylene diene can be used. Alcohol, (addition of aliphatic diol), sucrose, propylene glycol, glycerin, etc. as initiators, through ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran And one or more kinds of compounds such as cyclohexene are added and polymerized to obtain a polyisocyanate: toluene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, dicyclohexylmethane diisocyanate, cyclohexyl diisocyanate. , hexamethylene diisocyanate, diazonic acid diisocyanate, and the like.

Further, in the film-forming component (c) of the present invention, the mixing ratio of the solid content of the organic cerium compound (C) and the polyether polyurethane resin (E) is an organic cerium compound (C) and a polyether. The solid content mass ratio [(E)/(C)] of the polyurethane resin (E) must be 0.33 to 0.90, preferably 0.33 to 0.80, and most preferably 0.35 to 0.70. When the solid content mass ratio [(E)/(C)] is less than 0.33, the barrier property of the film-forming component (c) may be lowered, and conversely, if it exceeds 0.90, it is caused by the organic cerium compound (C). The adhesion to the raw material is remarkably lowered, and the properties are all lowered and thus inappropriate.

Further, in the film-forming component (c) of the present invention, it is preferable to further contain a cationic phenol resin (F) having a bisphenol A skeleton in order to improve corrosion resistance and solvent resistance. With respect to the mixing ratio of the solid content of the aforementioned polyether polyurethane resin (E) and the aforementioned cationic phenol resin (F), the polyether polyurethane resin (E) and the cationic phenol resin (F) The solid content mass ratio [(F)/(E)] must be 0.010 to 0.030, preferably 0.010 to 0.025, and preferably 0.010 to 0.022. When the mass ratio [(F)/(E)] is less than 0.010, the addition effect of the cationic phenol resin (F) is not exhibited, and the corrosion resistance and the solvent resistance are lowered, which is not suitable. If it exceeds 0.030, the film will be It is colored yellowish due to the cationic phenol resin, and it is not suitable for causing significant yellowing in a high-humidity environment or an ultraviolet-exposed environment.

The water-based metal surface treatment agent for the chromium-free surface-treated zinc-based plated steel sheet of the present invention, as the inhibitor component (d), must contain a fluorine metal complex (H) as an essential component, and the fluorine metal complex ( H) has at least one selected from the group consisting of titanium and zirconium.

The fluorine metal complex (H) having at least one selected from the group consisting of titanium and zirconium is not particularly limited, and examples thereof include titanium hydrofluoride, zirconium hydrofluoride, or an ammonium salt or an alkali metal salt.

In the inhibitor component (d) of the present invention, the organic ruthenium compound (C) and the fluorometal complex (H) having at least one selected from the group consisting of titanium and zirconium, the organic ruthenium compound ( C) a mass ratio [(Si)/(M)] of the derived Si(Si) to the metal component (M) having at least one fluorine metal complex (H) selected from the foregoing titanium and zirconium is 0.08 ～0.20 is preferred, 0.12 to 0.20 is preferred, and 0.14 to 0.18 is most preferred. When the mass ratio [(Si)/(M)] of the metal component (M) is less than 0.08, the amount of the oxide film formed from the metal component is reduced when the film is formed, and the corrosion resistance is lowered, which is not suitable. When the content exceeds 0.20, the surface coverage of the raw material of the oxide film formed from the metal component increases, and the reaction point with the raw material of the organic cerium compound (C) decreases, so that the organic cerium compound (C) is brought into close contact. The sexual imparting effect is reduced, and the effect of the present invention is generally lowered and is not suitable.

Further, the metal component (M) of the fluorine metal complex (H) contains both titanium (M _T ) and zirconium (M _Z ), and is suitable for both corrosion resistance and alkali resistance. The metal component mass ratio [(M _T )/(M _Z )] is preferably 0.50 to 0.80, preferably 0.60 to 0.80, and most preferably 0.60 to 0.70. If the metal component mass ratio [(M _T ) / (M _Z )] is less than 0.50, the titanium oxide film is reduced, and the ratio of the hard zirconium oxide is relatively increased, so that the accompanying raw materials are The deformation of the plastically deformed film becomes brittle, and the film defect occurs, and the corrosion resistance is lowered, which is not suitable. On the contrary, if it exceeds 0.80, the proportion of the titanium oxide film having a low alkali resistance is relatively increased. Therefore, the alkali resistance of the film is lowered, and the corrosion resistance after the alkali test is lowered, which is not suitable.

Further, in order to improve the corrosion resistance, the inhibitor component (d) of the present invention preferably further contains a phosphoric acid compound (J), and further preferably contains both the phosphoric acid compound (J) and the vanadium (IV) compound (K). The phosphoric acid compound (J) is not particularly limited, and examples thereof include phosphoric acid, an ammonium phosphate salt, an alkali metal salt of phosphoric acid, and an alkaline earth metal salt of phosphoric acid. These mainly have an effect of imparting corrosion resistance, and the elution property of phosphoric acid can be controlled depending on the kind of the salt of the phosphoric acid compound (J), and the corrosion retention time can be increased. Among them, phosphoric acid or magnesium diphosphate is suitable for obtaining a large corrosion-improving effect, and it is preferable to use phosphoric acid and magnesium phosphate.

Further, in the inhibitor component (d) of the present invention, the mixing ratio of the organic cerium compound (C) to the phosphoric acid compound (J), the solid content ratio of the organic cerium compound (C) to the phosphoric acid compound (J) [(J) ) / (C)] is preferably from 0.020 to 0.110, more preferably from 0.030 to 0.110, and most preferably from 0.040 to 0.100. When the solid content mass ratio [(J)/(C)] is less than 0.020, the effect of alkali resistance and corrosion resistance of the addition effect of the phosphoric acid compound (J) is not exhibited, and thus it is not suitable, and if it exceeds 0.110 It is not suitable due to the decrease in the stability of the metal surface treatment agent.

The vanadium (IV) compound (K) is not particularly limited, and vanadium pentoxide [V ₂ O ₅ ], metavanadic acid [HVO ₃ ], ammonium metavanadate [NH] may be used as a reducing agent such as an alcohol or an organic acid. ₄ VO _3], sodium metavanadate [NaVO _3], vanadyl trichloride [VOCl _3] like the vanadium compound (V) is reduced to vanadium (IV) by using an oxidizing agent of any of vanadium dioxide [VO _2], a vanadium-containing (IV) compound such as acetonitrile, vanadyloxyvana [VO(C ₅ H ₇ O ₂ ) ₂ ], vanadyl sulfate [VOSO ₄ ], or vanadylacetate [V(C ₅ H ₇ O ₂ ) ₃ ] The vanadium (III) of a compound such as vanadium trioxide [V ₂ O ₃ ] or vanadium trichloride [VCl ₃ ] is oxidized to vanadium (IV).

Further, regarding the inhibitor component (d) of the present invention, the mixing ratio of the organic cerium compound (C) to the vanadium compound (K), the solid content ratio of the organic cerium compound (C) to the vanadium compound (K) [(K) ) / (C)] is preferably from 0.020 to 0.060, more preferably from 0.025 to 0.060, and most preferably from 0.030 to 0.055. If the solid content mass ratio [(K)/(C)] is less than 0.020, it is not suitable because the effect of the inhibitor of the vanadium (IV) compound (K) is not obtained, and if it exceeds 0.060, vanadium (IV) The complex of the compound and the organic matter contained in the film is liable to cause yellow coloration under high humidification conditions, which is not suitable.

The water-based metal surface treatment agent of the present invention preferably further contains a polyethylene wax (L) in terms of improving workability and slidability. Regarding the mixing ratio of the polyethylene wax (L), the mass ratio [(L)/(C)] of the solid content of the organic cerium compound (C) to the polyethylene wax (L) must be 0.05 to 0.30, to 0.07. ～0.30 is better, and 0.10～0.25 is the best. If the mass ratio [(L)/(C)] is less than 0.05, it is not suitable because it does not exhibit sufficient lubricity. If it exceeds 0.30, the continuity of the film is hindered by the polyethylene wax, and the film is easy. Cracking, corrosion resistance is reduced and is not suitable.

The surface-treated metal material of the present invention is preferably coated with the aqueous metal surface treatment agent and dried at a temperature of 50 to 250 ° C, and the weight of the film after drying is 0.2 to 5.0 g/m ² . The drying temperature is preferably from 50 ° C to 250 ° C, preferably from 70 ° C to 150 ° C, and most preferably from 100 ° C to 140 ° C. If the reaching temperature is lower than 50 ° C, the solvent of the aqueous metal surface treating agent is not completely volatilized and is not suitable. On the other hand, if it exceeds 250 ° C, a part of the organic chain of the film formed by the aqueous metal surface treating agent is decomposed and is not suitable. The film weight is preferably 0.2 to 5.0 g/m ^{2 , more} preferably 0.5 to 3.0 g/m ^{2 , and most} preferably 0.8 to 2.0 g/m ² . If the film weight is less than 0.2 g/m ² , the surface of the metal material cannot be coated, so that the corrosion resistance is remarkably lowered, which is not suitable. On the other hand, if it exceeds 5.0 g/m ² , the film adhesion is lowered and it is not suitable.

The aqueous metal surface treatment agent used in the present invention can be used as a leveling agent or a water-soluble solvent, a metal stabilizer, an etching inhibitor or the like for improving coatability without impairing the effects of the present invention. The leveling agent is a nonionic or cationic surfactant, and examples thereof include a polyethylene oxide or a polyoxypropylene adduct or an acetylene glycol compound, and the water-soluble solvent may be ethanol, isopropanol or t-butyl. Alcohols such as alcohols and propylene glycol, celecoxibs such as ethylene glycol monobutyl ether and ethylene glycol monoethyl ether, esters such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone, and methyl isobutyl ketone. Ketones. The metal stabilizer may be a chelate compound such as EDTA or DTPA, and the etching inhibitor may be an amine compound such as ethylenediamine, triethylenepentamine, hydrazine or pyrimidine. In particular, a compound having two or more amine groups in one molecule is effective as a metal stabilizer and thus is suitable.

The surface-treated zinc-based plated steel sheet of the present invention has excellent adhesion to wettability, alkali resistance, solvent resistance, film adhesion, paint adhesion, and printing adhesion, and moisture resistance. It is excellent in water resistance such as discoloration and condensation resistance, and is excellent in workability and slidability. The reason is presumed to be as follows, but the present invention is not limited by this speculation.

The film formed using the aqueous metal surface treatment agent used in the present invention contains an organic cerium compound (C) and a polyether polyurethane resin (E) as a film-forming component. First, it is presumed that the corrosion resistance is such that when one part of the organic ruthenium compound is concentrated by drying or the like, the organic ruthenium compound reacts with each other to form a continuous film, and one part of the organic ruthenium compound is hydrolyzed, and the -OR group formed and the surface of the metal form Si. - OM key (M: metal element on the surface of the object to be coated), thereby exerting a significant barrier effect. In addition to this, various effects are obtained by the organic ruthenium compound (C) having a specific structure in a specific ratio, that is, a cyclic siloxane chain bond and a chain siloxane chain bond. As described above, the organic ruthenium compound (C) forms a dense film which is strongly bonded to the raw material due to its own condensation and reaction with the raw material. If the oxime is ring-shaped, it will form a three-dimensional element when dried. The oxygen-bonded film has an increased resistance to intrusion of oxygen and moisture, and thus exhibits extremely excellent barrier properties. However, the cyclic siloxane chain has no deformation degree of freedom from the viewpoint of the skeleton, and forms a hard and brittle film. On the other hand, the chain-like decane bond does not form a three-dimensional structure like a cyclic siloxane chain, and has a lower barrier property than a cyclic siloxane, but has a high degree of freedom of deformation. By allowing such a different nature of the decane bond to coexist in a certain ratio, a film excellent in barrier properties and adhesion can be formed. The polyether urethane resin is complexed thereon when the film is formed, further, in the polyether polyurethane resin having the structural unit (D), and the structural unit (D) is reactive with the organic hydrazine compound In the case where the above organic hydrazine compound is combined with the polyether polyurethane, it exhibits extremely high barrier properties. In addition, the cationic phenol resin (F) is a compound having a structure that is resonantly stable, and the film containing the cationic phenol resin (F) is transmitted and fixed to the surface of the metal, and is sufficiently close to the outer shell of the raw material metal. The distance, and thus the use of the Φ orbital, has the effect of delocalizing the electrons generated by the corrosion, by which the surface potential is kept uniform, giving excellent corrosion resistance.

On the other hand, the effect of the inhibitor component (d) is an effect of removing the oxide film by etching of the surface of the raw material, precipitation due to an increase in pH of the etching, film formation, and poor solubility of metal ions caused by the eluted raw material. Formation of salt, relaxation of pH rise accompanying corrosion of raw materials, uniformity of surface potential, and the like. The fluorine metal complex having at least one selected from the group consisting of titanium and zirconium is presumed to have an effect of removing the oxide film by etching of the surface of the raw material, and at the same time, the fluorine is dissociated and oxide or hydroxide is caused by the pH rise accompanying the process. The form of the material precipitates, and the corrosion resistance is imparted by the film formation. Further, since corrosion forms a poorly soluble salt of a metal ion which is a source of the eluted material, it has an effect of slowing down the progress of corrosion. On the other hand, the phosphoric acid compound has a relaxing effect of an increase in pH accompanying corrosion of the raw material, and particularly has an effect as a dissolution inhibitor. It is speculated that the vanadium compound consumes electrons generated by corrosion by utilizing the redox reaction of vanadium, and has an effect of suppressing corrosion. By suppressing the adhesion between the inhibitor component having such an effect and the barrier property of the film-forming component described above, it is possible to form a detergent-resistant property such as corrosion resistance, alkali resistance, and solvent resistance. A film which is excellent in water resistance such as adhesion of film adhesion, paint adhesion, and printing adhesion, moisture resistance, and dew condensation resistance, and is excellent in workability and slidability.

Example

Hereinafter, the present invention will be specifically described by way of examples and comparative examples of the invention, but the invention is not limited thereto. The preparation of the test plate, the examples and comparative examples, and the coating method of the surface treatment agent for metal materials will be described below.

Preparation of test plates (1) Test materials

The commercially available raw materials shown below were used.

‧ Galvanized steel sheet (EG): sheet thickness = 0.8mm, coating amount = 20/20 (g/m ² )

‧ Hot-dip galvanized steel sheet (GI): plate thickness = 0.8mm, coating amount = 90/90 (g/m ² )

‧ Alloyed hot-dip galvanized steel sheet (GA): sheet thickness = 0.8mm, coating amount = 90/90 (g/m ² )

‧ Hot-dip galvanizing -11% aluminum-3% magnesium-0.2% bismuth steel plate (SD): plate thickness = 0.8 mm, coating amount = 60/60 (g/m ² )

(2) Degreasing treatment

The raw material was spray-treated at a concentration of 20 g/L and a temperature of 60 ° C for 2 minutes using FINE CLEANER 4336 (registered trademark: manufactured by Paka Co., Ltd., Japan). After washing for 3 seconds, the dryer was used as a test plate.

The decane coupling agents used in the examples and comparative examples are shown in Table 1, the urethane resin is shown in Table 2, the phosphoric acid compound is shown in Table 3, the vanadium compound is shown in Table 4, and the polyethylene wax is shown in Table 5, mixed. Examples, film amount and drying temperature are shown in Table 6.

[Preparation method of organic hydrazine compound C]

The decane coupling agent shown in Table 1 was reacted in ethanol in the combination shown in Table 6 and the mixing ratio, and then mixed with water adjusted to pH 4 to 4.5 with acetic acid to adjust the solid content to 20%. The number of functional groups (a) of the obtained organic hydrazine compound and the molecular weight of each of the hydrophilic groups (b), and the absorbance of 1090 to 1100 cm ^-1 of the cyclic siloxane coupling according to the FT-IR reflection method ( The ratio (C1/C2) of the absorbance (C2) of C1) to 1030 to 1040 cm ^-1 showing a chain-like decane bond is shown in Table 6.

[Synthesis method of urethane resin (E1)]

Polyether polyol (synthetic component: butanediol and ethylene glycol, molecular weight 1500): 150 parts by mass, trimethylolpropane: 6 parts by mass, N-methyl-N, N-diethanolamine: 24 mass Parts, isophorone diisocyanate: 94 parts by mass and 135 parts by mass of methyl ethyl ketone were placed in a reaction vessel, and kept at 70 ° C to 75 ° C for 1 hour to form an urethane prepolymer. Next, 10 parts by mass of 3-aminopropyltrimethoxydecane was added, and the reaction was maintained at 80 ° C to 85 ° C for 1 hour to form a structural unit (D1). Next, 15 parts by mass of dimethyl sulfate was added to the reaction vessel, and the reaction was carried out at 50 to 60 ° C for 30 minutes to 60 minutes to form a cationic urethane prepolymer. Next, 576 parts by mass of water was added to the reaction vessel, and the mixture was uniformly emulsified, and then methyl ethyl ketone and residual 3-aminopropyltrimethoxy decane were recovered to obtain a water-soluble cationic urethane resin. The Si content for the resin solid content was 0.5% by mass.

[Synthesis method of urethane resin (E2)]

Polyether polyol (synthetic component: butanediol and ethylene glycol, molecular weight 1500): 150 parts by mass, trimethylolpropane: 6 parts by mass, N-methyl-N, N-diethanolamine: 24 mass Parts, isophorone diisocyanate: 94 parts by mass and 135 parts by mass of methyl ethyl ketone were placed in a reaction vessel, and kept at 70 ° C to 75 ° C for 1 hour to form an urethane prepolymer. Next, 15 parts by mass of dimethyl sulfate was added to the reaction vessel, and the reaction was carried out at 50 to 60 ° C for 30 minutes to 60 minutes to form a cationic urethane prepolymer. Next, 576 parts by mass of water was added to the reaction vessel, and the mixture was uniformly emulsified, and then methyl ethyl ketone was recovered to obtain a water-soluble cationic urethane resin.

[Synthesis method of urethane resin (E3)]

Polyester polyol (synthetic component: condensate of maleic acid and 1,4-butanediol, molecular weight 1500): 150 parts by mass, trimethylolpropane: 6 parts by mass, N-methyl-N N-diethanolamine: 24 parts by mass, isophorone diisocyanate: 94 parts by mass and 135 parts by mass of methyl ethyl ketone were placed in a reaction vessel, and kept at 70 ° C to 75 ° C for 1 hour to form an urethane prepolymer. Next, 15 parts by mass of dimethyl sulfate was added to the reaction vessel, and the reaction was carried out at 50 to 60 ° C for 30 minutes to 60 minutes to form a cationic urethane prepolymer. Next, 576 parts by mass of water was added to the reaction vessel, and the mixture was uniformly emulsified, and then methyl ethyl ketone and residual 3-aminopropyltrimethoxy decane were recovered to obtain a water-soluble cationic urethane resin.

[Synthesis method of urethane resin (E4)]

Polyester polyol (synthetic component: poly(hexamethylene carbonate) diol, molecular weight 1500): 150 parts by mass, trimethylolpropane: 6 parts by mass, N-methyl-N,N-diethanolamine 24 parts by mass of isophorone diisocyanate: 94 parts by mass and 135 parts by mass of methyl ethyl ketone were added to the reaction vessel, and the reaction was maintained at 70 ° C to 75 ° C for 1 hour to form an urethane prepolymer. Next, 15 parts by mass of dimethyl sulfate was added to the reaction vessel, and the reaction was carried out at 50 to 60 ° C for 30 minutes to 60 minutes to form a cationic urethane prepolymer. Next, 576 parts by mass of water was added to the reaction vessel, and the mixture was uniformly emulsified, and then methyl ethyl ketone and residual 3-aminopropyltrimethoxy decane were recovered to obtain a water-soluble cationic urethane resin.

[Synthesis method of urethane resin (E5)]

Polyether polyol (synthetic component: butanediol and 1,4-cyclohexanedimethanol, molecular weight 1500): 150 parts by mass, trimethylolpropane: 6 parts by mass, N-methyl-N, N - Diethanolamine: 24 parts by mass, isophorone diisocyanate: 94 parts by mass and 135 parts by mass of methyl ethyl ketone were placed in a reaction vessel, and kept at 70 ° C to 75 ° C for 1 hour to form an urethane prepolymer. Next, 10 parts by mass of 3-aminopropyltrimethoxydecane was added, and the reaction was maintained at 80 ° C to 85 ° C for 1 hour to form a structural unit (D1). Next, 15 parts by mass of dimethyl sulfate was added to the reaction vessel, and the reaction was carried out at 50 to 60 ° C for 30 minutes to 60 minutes to form a cationic urethane prepolymer. Next, 576 parts by mass of water was added to the reaction vessel, and the mixture was uniformly emulsified, and then methyl ethyl ketone and residual 3-aminopropyltrimethoxy decane were recovered to obtain a water-soluble cationic urethane resin. The Si content for the resin solid content was 0.5% by mass.

[Synthesis method of urethane resin (E6)]

Polyether polyol (synthetic component: butylene glycol and propylene oxide 2 molar addition of bisphenol A, molecular weight 1500): 150 parts by mass, trimethylolpropane: 6 parts by mass, N-methyl -N,N-diethanolamine: 24 parts by mass, isophorone diisocyanate: 94 parts by mass and 135 parts by mass of methyl ethyl ketone are added to the reaction vessel, and kept at 70 ° C to 75 ° C for 1 hour to form a urethane prepolymer. Things. Next, 10 parts by mass of 3-aminopropyltrimethoxydecane was added, and the reaction was maintained at 80 ° C to 85 ° C for 1 hour to form a structural unit (D1). Next, 15 parts by mass of dimethyl sulfate was added to the reaction vessel, and the reaction was carried out at 50 to 60 ° C for 30 minutes to 60 minutes to form a cationic urethane prepolymer. Next, 576 parts by mass of water was added to the reaction vessel, and the mixture was uniformly emulsified, and then methyl ethyl ketone and residual 3-aminopropyltrimethoxy decane were recovered to obtain a water-soluble cationic urethane resin. The Si content for the resin solid content was 0.5% by mass.

[Synthesis method of urethane resin (E7)]

Polyether polyol (synthetic component: butanediol and 1,4-cyclohexanedimethanol, molecular weight 1500): 150 parts by mass, trimethylolpropane: 6 parts by mass, N-methyl-N, N - Diethanolamine: 24 parts by mass, isophorone diisocyanate: 94 parts by mass and 135 parts by mass of methyl ethyl ketone were placed in a reaction vessel, and kept at 70 ° C to 75 ° C for 1 hour to form an urethane prepolymer. Next, 15 parts by mass of dimethyl sulfate was added to the reaction vessel, and the reaction was carried out at 50 to 60 ° C for 30 minutes to 60 minutes to form a cationic urethane prepolymer. Next, 576 parts by mass of water was added to the reaction vessel, and the mixture was uniformly emulsified, and then methyl ethyl ketone was recovered to obtain a water-soluble cationic urethane resin.

[Synthesis method of urethane resin (E8)]

Polyether polyol (synthetic component: butylene glycol and propylene oxide 2 molar addition of bisphenol A, molecular weight 1500): 150 parts by mass, trimethylolpropane: 6 parts by mass, N-methyl -N,N-diethanolamine: 24 parts by mass, isophorone diisocyanate: 94 parts by mass and 135 parts by mass of methyl ethyl ketone are added to the reaction vessel, and kept at 70 ° C to 75 ° C for 1 hour to form a urethane prepolymer. Things. Next, 15 parts by mass of dimethyl sulfate was added to the reaction vessel, and the reaction was carried out at 50 to 60 ° C for 30 minutes to 60 minutes to form a cationic urethane prepolymer. Next, 576 parts by mass of water was added to the reaction vessel, and the mixture was uniformly emulsified, and then methyl ethyl ketone was recovered to obtain a water-soluble cationic urethane resin.

[Synthesis method of urethane resin (E9)]

Polyether polyol (synthetic component: butanediol and 1,4-cyclohexanedimethanol, molecular weight 1500): 150 parts by mass, trimethylolpropane: 6 parts by mass, N-methyl-N, N - Diethanolamine: 24 parts by mass, isophorone diisocyanate: 94 parts by mass and 135 parts by mass of methyl ethyl ketone were placed in a reaction vessel, and kept at 70 ° C to 75 ° C for 1 hour to form an urethane prepolymer. Next, 13 parts by mass of dimethyl sulfate was added to the reaction vessel, and the reaction was carried out at 50 to 60 ° C for 30 minutes to 60 minutes to form a cationic urethane prepolymer. Next, 576 parts by mass of water was added to the reaction vessel, and the mixture was uniformly emulsified, and then methyl ethyl ketone was recovered to obtain a water-soluble cationic urethane resin.

[Synthesis method of urethane resin (E10)]

Polyether polyol (synthetic component: butanediol and 1,4-cyclohexanedimethanol, molecular weight 1500): 150 parts by mass, trimethylolpropane: 6 parts by mass, N-methyl-N, N - Diethanolamine: 24 parts by mass, isophorone diisocyanate: 94 parts by mass and 135 parts by mass of methyl ethyl ketone were placed in a reaction vessel, and kept at 70 ° C to 75 ° C for 1 hour to form an urethane prepolymer. Next, 20 parts by mass of dimethyl sulfate was added to the reaction vessel, and the reaction was carried out at 50 to 60 ° C for 30 minutes to 60 minutes to form a cationic urethane prepolymer. Next, 576 parts by mass of water was added to the reaction vessel, and the mixture was uniformly emulsified, and then methyl ethyl ketone was recovered to obtain a water-soluble cationic urethane resin.

[Synthesis method of urethane resin (E11)]

Polyether polyol (synthetic component: butanediol and 1,4-cyclohexanedimethanol, molecular weight 1500): 150 parts by mass, trimethylolpropane: 6 parts by mass, N-methyl-N, N - Diethanolamine: 24 parts by mass, isophorone diisocyanate: 94 parts by mass and 135 parts by mass of methyl ethyl ketone were placed in a reaction vessel, and kept at 70 ° C to 75 ° C for 1 hour to form an urethane prepolymer. Next, 576 parts by mass of water and 30 parts by mass of acetic acid were added to the reaction vessel to uniformly emulsifie the mixture, and then methyl ethyl ketone was recovered to obtain a water-soluble cationic urethane resin.

[Synthesis method of urethane resin (E12)]

Polyether polyol (synthetic component: butanediol and 1,4-cyclohexanedimethanol, molecular weight 1500): 150 parts by mass, trimethylolpropane: 6 parts by mass, isophorone diisocyanate: 94 The mass fraction and 135 parts by mass of methyl ethyl ketone were added to the reaction vessel, and the reaction was maintained at 70 ° C to 75 ° C for 1 hour to form an urethane prepolymer. Next, 576 parts by mass of water was added to the reaction vessel, and the mixture was uniformly emulsified by a nonionic emulsifier, and then methyl ethyl ketone was recovered to obtain a water-soluble cationic urethane resin.

[Molecular weight determination method]

The molecular weight was measured by a gel filtration chromatography method at a column temperature of 40 ° C and a component concentration of 5% by weight to determine the molecular weight of the organic cerium compound (C). Further, it is converted into polyethylene glycol (molecular weight: 600 to 12,000).

[FT-IR]

The FT-IR device is equipped with an infrared total reflection spectroscopy device. Further, the measurement was carried out at a wave number range of 650 to 4000 cm ^-1 , a decomposition energy of 4 cm ^-1 , a cumulative number of times of 16 times, and a temperature of 25 °C. Method using baseline (900cm ^-1, 1200cm ^-1) of infrared absorption spectrum of the resulting display is obtained cyclic siloxane bonds of silicon absorbance at 1090 ~ 1100cm ^-1 (C1) of the display 1030 of chain siloxane bond Si ~ 1040cm ^-1 absorbance (C2).

Surface treatment stability

The pharmaceutical agent was added to a closed container, and the stability of the drug at 40 ° C was observed.

◎=No change in liquid traits during 3 months

○=1 months, there is no change in liquid traits

Increased viscosity or precipitation within △=1 months

×=1 weeks of viscosity increase or precipitation

[evaluation test] Corrosion resistance

A 240-hour salt spray test was conducted in accordance with JIS-Z-2371 to observe the occurrence of white rust.

<Evaluation Benchmark>

◎=The rust is less than 3% of the total area

○=The rust is generated in 3% or more of the entire area and less than 10%.

△=The rust is generated in 10% or more of the entire area and less than 30%.

×=rust is produced in more than 30% of the total area

Degreasing resistance

After forming a film, PALCLEAN N364S (registered trademark: manufactured by Paccarat, Japan) was spray-treated for 2 minutes at a concentration of 20 g/L and a temperature of 60 ° C using a citrate-based alkali degreaser. Z-2371 was subjected to a 240-hour salt spray test to observe the occurrence of white rust.

<Evaluation Benchmark>

◎=The rust is less than 3% of the total area

○=The rust is generated in 3% or more of the entire area and less than 10%.

△=The rust is generated in 10% or more of the entire area and less than 30%.

×=rust is produced in more than 30% of the total area

Sweat resistance

After the formation of the film, one drop of artificial sweat (JIS-L-0848 D method) was dropped, and then allowed to stand at 65 ° C and 93% RH for 48 hours and evaluated on the following basis.

<Evaluation Benchmark>

◎=The appearance has not changed

○=The appearance is almost unchanged

△=The area under the drop has an area change of less than 30%

×=30% or more area change in the lower part of the drop

Solvent resistance

MEK (methyl ethyl ketone) was infiltrated into the tissue and rubbed repeatedly for 5 times at a load of 500 g, and the marks formed were evaluated by the increase or decrease of the L value before and after the test.

<Evaluation Benchmark>

◎=△L is less than 0.5

○=△L is 0.5 or more and less than 1.0

△=△L is 1.0 or higher and lower than 2.0

×=△L is above 2.0

Membrane adhesion

The portion cut with a 1 mm grid was pressed by a concave pressure tester (Erichsen Tester) to a thickness of 7 mm, and the tape was peeled off, and the adhesion ratio was evaluated by the remaining number ratio (the remaining number/the number of cuts: 100).

<Evaluation Benchmark>

◎=100%

○= below 20% and 95%

△=90% or more, less than 95%

×= below 90%

Coating adhesion

The melamine alkyd-based paint was applied by a bar coater, and after baking at 120 ° C for 20 minutes, a 1 mm grid was cut, and the adhesion was evaluated by the remaining number (the remaining number / the number of cuts: 100).

<Evaluation Benchmark>

◎=100%

○=95% or more

△=90% or more, less than 95%

×= below 90%

Printing adhesion

The screen printing ink was solid-printed, and after baking at 120 ° C for 20 minutes, the 1 mm grid was cut, and the adhesion was evaluated by the remaining number (the remaining number / the number of cuts: 100).

<Evaluation Benchmark>

◎=100%

○=95% or more

△=90% or more, less than 95%

×= below 90%

Moisture resistance

The mixture was allowed to stand in a high-temperature and high-humidity environment at a temperature of 65 ° C and a humidity of 95% for 72 hours, and evaluated by the change in color tone ΔE before and after the test.

◎=△E is lower than 1.0

○=△E is 1.0 or higher and lower than 2.0

△=△E is above 2.0 and less than 3.0

×=△E is above 3.0

Condensation resistance

1 cc of pure water was dropped on the standing test piece under the environment of a temperature of 25 ° C and a humidity of 60%, and the color change ΔE before and after the test at the time of natural drying was evaluated.

◎=△E is lower than 0.5

○=△E is above 0.5 and less than 1.0

△=△E is above 1.0 and below 2.0

×=△E is above 2.0

A high-speed cylindrical deep-extension test was carried out using a blind plate of 115 mm Φ diameter under the conditions of punching hole diameter = 50 mm Φ , blanking force of 1 ton, deep drawing speed of 30 m/min, and no oiling.

<Evaluation Benchmark>

◎=The limit extension ratio is 2.50 or more

○=The limit extension ratio is 2.40 or more and less than 2.50

△=limit extension ratio is 2.30 or more and less than 2.40

×=The limit extension ratio is less than 2.30

[Results of evaluation test]

From the evaluation results of Examples 1 to 4 and Comparative Examples 1 and 2, when the decane coupling agents (A) and (B) used in the organic hydrazine compound (C) are separated from the scope of the patent application, that is, if decane If the coupling agent (B) is too much, the molecular structure of the upper surface film becomes hard, and the film adhesion is poor, so that the performance of all the evaluation items is lowered. On the other hand, if the decane coupling agent (A) is too much, the amine group imparts excessive hydrophilicity or the chromonic structure caused by the amine group, and the condensation resistance and the wet tarnish resistance are inferior. Conversely, it is understood that all of the performance is satisfied if it is a further suitable range within the scope of the patent application.

From the observation of Examples 2, 5 to 7, and Comparative Examples 3 to 5, since only one functional group (a) is not the organic hydrazine compound (C) of the present invention, only the same effect as the general decane coupling agent is obtained. The effect, so all performance will be significantly reduced.

From the evaluation results of Examples 2, 8 to 9, and Comparative Examples 5 to 6, the molecular weight of each of the functional groups (b), if it is 500 film components, is degreased, solvent resistant, and dew condensation due to easy dissolution. The properties and the moisture-resistant discoloration property are inferior, and if it exceeds 15,000, the film adhesion is insufficient, and the film adhesion is poor, so that the performance is all lowered.

It can be seen from Examples 10 to 15 and Comparative Example 7 that corrosion resistance and wettability are poor when there is no cyclic oxirane, and all evaluation items have a case where a cyclic siloxane is contained in a suitable range. Extremely excellent performance.

From the evaluation structure of Example 4 and Comparative Examples 8 to 9, when the urethane resin (E) does not have an ether structure, if it is an ester system, it is easily hydrolyzed and thus is resistant to degreasing, moisture resistance, and resistance. The dew condensation is poor, and the carbonate is too rigid to make the film adhesion and workability poor.

From the evaluation results of Examples 13, 16 to 19 and Comparative Examples 10 to 11, it is understood that when the ratio of the organic cerium compound (C) to the urethane resin (E) deviates from the scope of the patent application, that is, urethane When the amount of the resin is small, the barrier property of the film-forming component (c) is lowered to deteriorate the corrosion resistance and the wettability. Conversely, when the urethane resin is used for a long time, the adhesion to the raw material is remarkably lowered to improve the film adhesion. Poor adhesion to coating.

From the evaluation results of Examples 20 to 21 and Comparative Examples 12 to 19, the corrosion resistance and the wettability of the fluorometal complex (H) which does not contain Ti or Zr as the inhibitor component are extremely poor, even if The addition of the phosphoric acid compound (J) or the vanadium (IV) compound is equivalent to the decrease in performance, and the effect of the fluorine metal complex of Ti or Zr as an inhibitor component is known.

From the evaluation results of Examples 22 to 29 and Comparative Examples 20 to 21, regarding the skeleton of the urethane resin, the urethane resin having a suitable structure is excellent in overall performance, particularly containing structural units (D1). The performance of the situation will be extremely excellent. On the other hand, when the amount of the 4-grade ammonium salt in the entire amine group is 0 or does not have an amine group, the stability of the treating agent is poor, and particularly when the amine group is not present, the stability of the treating agent is insufficient, and the performance is all difference.

From the evaluation results of Examples 30 to 90, the content of the phenol resin, the type and content of the fluorometal complex, the type and content of the phosphoric acid compound, the type and content of the vanadium compound (K), and the polyethylene wax were observed. The types and contents are adjusted to the appropriate range, and it is known that the evaluation items all have practical levels of performance. In addition, it is understood that W, Co, and Mg have the same effect of improving the corrosion resistance without impairing the balance of the evaluation items as a whole. It is clearly known that these properties are dried at a temperature of 50 to 250 ° C, and the weight of the film after drying is 0.2 to 5.0 g/m ² , especially at a temperature of 100 to 200 ° C. The amount of 1.2 to 1.5 g/m ² has extremely excellent performance.

From the above evaluation results, it is understood that the water-based metal surface treatment agent of the present invention is applied and dried to form a composite film containing the respective components, thereby obtaining a detergent-resistant property such as corrosion resistance, alkali resistance, and solvent resistance. Excellent in water resistance, such as adhesion resistance, film adhesion, print adhesion, and printing adhesion, moisture resistance, and dew condensation resistance, and excellent chrome-free workability and slidability. Surface treated zinc-based plated steel.

Claims (17)

A surface-treated zinc-based plated steel sheet obtained by applying a water-based metal surface treatment agent and drying it to form a composite film containing each component, the water-based metal surface treatment agent containing The film-forming component (c) of the following (1) and (2), and the following substances (3) and (4): (1) the organic cerium compound (C) is a solid content mass ratio [(A) /(B)] obtained by mixing a decane coupling agent (A) and a decane coupling agent (B) in a ratio of 0.50 to 0.75, and containing two or more functional groups represented by the following general formula [1] in the molecule (a) And at least one hydrophilic functional group (b) selected from the group consisting of a hydroxyl group (other than the functional group (a)) and an amine group, and having an average molecular weight of from 1,000 to 10,000, in the skeleton In the case of a cyclic decane coupling agent, the decane coupling agent (A) contains one amine group in the molecule, and the decane coupling agent (B) contains one epoxy propyl group in the molecule. (wherein R1, R2 and R3 independently of each other represent an alkoxy group or a hydroxyl group, and at least one represents an alkoxy group); (2) a polyether polyurethane resin (E) having a poly group in a molecule a structural unit derived from an ether polyol; (3) an inhibitor component (d) having a fluorine metal complex (H) having an essential component selected from the group consisting of titanium and zirconium. At least one of the elements; (4) an aqueous medium; and, in the film-forming component (c) of the aqueous treatment agent, (5) an organic cerium compound (C) and a polyether polyurethane resin (E) The solid content mass ratio [(E)/(C)] is 0.33 to 0.90. The surface-treated zinc-based plated steel sheet according to the first aspect of the invention, wherein the ratio of the cyclic siloxane coupling and the chain siloxane coupling in the organic hydrazine compound (C) is based on the FT-IR reflection method. shows the absorbance (C1) cyclic siloxane bonds of silicon 1090 ~ 1100cm ^-1 absorbance ratio of the display silicon chain siloxane bond of the 1030 ~ 1040cm ^-1 (C2) of [C1 / C2] of 1.0 to 2.0. The surface-treated zinc-based plated steel sheet according to the first or second aspect of the invention, wherein the polyether polyurethane resin (E) has an aromatic ring and an alicyclic structure having a carbon number of 4 to 6 in the molecule. Or an aromatic ring and an alicyclic structure with a carbon number of 4-6. The surface-treated zinc-based plated steel sheet according to the first or second aspect of the invention, wherein the polyether polyurethane resin (E) contains an amine group in the molecule, and the total amount of the amine group is 4 The ratio of ammonium salt is 0.7 to 1.0 in terms of molar ratio. The surface-treated zinc-based plated steel sheet according to the first or second aspect of the invention, wherein the polyether polyurethane resin (E) has a structural unit represented by the following general formula [2] in the molecule (D) : (wherein R9 represents a monovalent organic residue selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an aralkyl group, and R10 and R11 each independently represent an alkoxy group, a decyloxy group, A functional group in a group consisting of a hydroxyl group and a halogen atom, and m represents an integer of 1 to 5). The surface-treated zinc-based plated steel sheet according to the fourth aspect of the invention, wherein the polyether polyurethane resin (E) has a structural unit (D) represented by the following general formula [2] in a molecule: (wherein R9 represents a monovalent organic residue selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an aralkyl group, and R10 and R11 each independently represent an alkoxy group, a decyloxy group, A functional group in a group consisting of a hydroxyl group and a halogen atom, and m represents an integer of 1 to 5). The surface-treated zinc-based plated steel sheet according to the first or second aspect of the invention, wherein the film-forming component (c) further contains a cationic phenol resin (F) having a bisphenol A skeleton, and the polyether polyamine The solid content mass ratio [(F)/(E)] of the ethyl formate resin (E) and the cationic phenol resin (F) is from 0.010 to 0.030. The surface-treated zinc-based plated steel sheet according to the sixth aspect of the invention, wherein the film-forming component (c) further contains a cationic phenol resin (F) having a bisphenol A skeleton, and the polyether polyurethane The solid content mass ratio [(F)/(E)] of the ester resin (F) and the cationic phenol resin (F) is 0.010 to 0.030. The surface-treated zinc-based plated steel sheet according to the first or second aspect of the invention, wherein the inhibitor component (d) further contains (6) a phosphoric acid compound (J). The surface-treated zinc-based plated steel sheet according to claim 9, wherein the inhibitor component (d) further contains (7) a vanadium (IV) compound (K). The surface-treated zinc-based plated steel sheet according to claim 10, wherein (8) Si (Si) derived from the organic cerium compound (C) and at least one selected from the group consisting of titanium and zirconium The mass ratio [(M)/(Si)] of the metal component (M) of the elemental fluorine metal complex (H) is 0.08 to 0.20; (9) the aforementioned organic cerium compound (C) and the aforementioned phosphoric acid compound (J) The solid content mass ratio [(J)/(C)] is 0.02 to 0.11, (10) the solid content mass ratio of the aforementioned organic cerium compound (C) to the aforementioned vanadium (IV) compound (K) [(K)/( C)] is 0.02~0.06. The surface-treated zinc-based plated steel sheet according to the first or second aspect of the invention, wherein the metal component (M) of the fluorine metal complex (H) contains both titanium (M _T ) and zirconium (M _Z ). And the metal component mass ratio [(M _T ) / (M _Z )] of each is 0.50 to 0.80. The surface-treated zinc-based plated steel sheet according to claim 11, wherein the metal component (M) of the fluorine metal complex (H) contains both titanium (M _T ) and zirconium (M _Z ), and The metal component mass ratio [(M _T )/(M _Z )] is 0.50 to 0.80. Surface treated zinc-based plated steel as described in claim 1 or 2 The plate wherein the inhibitor component (D) further contains at least one metal component selected from the group consisting of Mg, Co, and W. The surface-treated zinc-based plated steel sheet according to the first or second aspect of the invention, wherein the aqueous metal surface treatment agent further contains a polyethylene wax (L), and the organic cerium compound (C) and the polyethylene wax (L) The solid content mass ratio [(L)/(C)] is 0.05 to 0.30. A surface-treated zinc-based plated steel sheet characterized in that the surface of the zinc-based plated steel sheet is coated with an aqueous metal surface treatment agent as described in claim 1 or 2, and is subjected to an arrival temperature of 50 ° C to 250 ° C. The weight of the film after drying and drying is 0.2 to 5.0 g/m ² . A surface-treated zinc-based plated steel sheet characterized in that the surface of the zinc-based plated steel sheet is coated with an aqueous metal surface treatment agent as disclosed in claim 15 and dried at a temperature of from 50 ° C to 250 ° C. The weight of the film after drying is 0.2 to 5.0 g/m ² .