JP5642082B2 - Chrome-free surface-treated galvanized steel sheet - Google Patents

Description

  The present invention is a surface treatment with a cationic chromium-free surface treatment agent, such as corrosion resistance, alkali resistance, solvent resistance, and other detergent resistance, sweat resistance, film adhesion, paint adhesion, and print adhesion. The present invention relates to a zinc-based plated steel sheet having a chromium-free surface treatment which is excellent in water resistance such as adhesion, moisture discoloration resistance and dew condensation resistance, and also excellent in workability and slidability.

  In general, it has excellent adhesion to the metal material surface, and as a technology for imparting corrosion resistance, fingerprint resistance, etc. to the metal material surface, the metal material surface contains chromic acid, dichromic acid or a salt thereof as a main component. A method of performing a chromate treatment with a treatment solution, a method of performing a phosphate treatment, a method of carrying out an organic resin film treatment, and the like are known and put into practical use.

  In the conventional chromate treatment, the metal surface is brought into contact with a treatment liquid containing chromium such as chromate chromate to deposit the chromate film, or coated and dried. And a method of forming a chromate film. However, these inorganic chromate coatings alone are hard, brittle and poor in lubricity, so that not only the coating will fall off and the appearance will be impaired, but also sufficient processing will not be possible, and the material will crack and crack. The problem that occurs. In addition, the operator's fingerprint is attached during the work, and the trace remains even after degreasing and cleaning. Therefore, in general, in order to satisfy all performances such as high corrosion resistance, fingerprint resistance, scratch resistance, lubricity, and paint adhesion, a chromate film is formed on the surface of the metal material, and the chromate film is formed on the formed chromate film. Further, a two-layer process for providing a resin film is performed.

  As an attempt to satisfy all the performances by one-layer treatment, resin chromate that forms chromate and a resin film at the same time has been studied. Patent Document 1 discloses a specific method on the surface of an aluminum-galvanized steel sheet. A treatment method for applying a water dispersion or a resin composition containing a water-soluble resin and a specific amount of hexavalent chromium, Patent Document 2, includes hexavalent chromium ions of inorganic compounds or hexavalent chromium ions and trivalent chromium ions, And a metal surface treatment composition containing an acrylic emulsion polymerized under specific emulsion polymerization conditions.

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

  As a method of using a non-chromate treatment liquid that does not have chromium, Patent Document 3 discloses a polymer composition for surface treatment of a metal material containing a phenol resin polymer having a specific structure and an acidic compound, and a surface treatment method. Document 4 discloses a metal surface treatment agent and a treatment method excellent in fingerprint resistance and the like, containing two or more silane coupling agents having reactive functional groups having specific structures that are different from each other and capable of reacting with each other, Patent Document 5 In addition, a metal surface treatment agent and treatment method containing a silane coupling agent having a specific structure and a phenol resin polymer having a specific structure, Patent Document 6, an epoxy resin having at least one nitrogen atom, an acrylic resin, and a urethane Metal surface treatment agent containing organic polymer such as resin and specific polyvalent anion, treatment method and treated metal material, Patent Document 7, (1) Bisph having a specific structure Treatment using rust inhibitor containing Nord A epoxy-based resin, (2) rust inhibitor containing specific resin such as phenolic resin and other polyester, and (1) and (2) Methods and treated metal materials are disclosed.

  However, these chromium-free technologies are resistant to cleaning, such as corrosion resistance, alkali resistance and solvent resistance, film adhesion, adhesion such as paint adhesion and printing adhesion, moisture discoloration resistance and condensation resistance. It is excellent in water resistance and does not satisfy all the workability and slidability.

  As described above, the surface treatment agent that can be used as an alternative to the chromate film has not been obtained by any of these methods, and there is a strong demand for the development of a surface treatment agent and a treatment method that can satisfy these conditions comprehensively. It is.

Japanese Patent Publication No.4-2672 Japanese Patent Publication No. 7-6070 JP 7-278410 A JP-A-8-73775 JP-A-9-241576 Japanese Patent Laid-Open No. 10-1789 Japanese Patent Laid-Open No. 10-60233

  The present invention solves the above-mentioned problems of the prior art, and has anti-corrosion, alkali resistance, solvent resistance and other cleaning resistance, sweat resistance, film adhesion, paint adhesion and printing adhesion, An object of the present invention is to provide a chromium-free surface-treated galvanized steel sheet having excellent water resistance such as moisture discoloration resistance and dew condensation resistance, and excellent workability and slidability.

（式中、Ｒ１、Ｒ２及びＲ３は互いに独立に、アルコキシ基又は水酸基を表し、少なくとも１つはアルコキシ基を表す）
（２）分子中にポリエーテルポリオールに由来する構造単位を有すポリエーテルポリウレタン樹脂（Ｅ）と、
を含有する造膜成分（ｃ）と、
（３）チタンおよびジルコニウムから選ばれる少なくとも１種を有するフルオロ金属錯化合物（Ｈ）を必須成分とするインヒビター成分（ｄ）と、
（４）水性媒体、
を含有する水系金属表面処理剤を塗布し乾燥することにより各成分を含有する複合皮膜を形成した亜鉛系めっき鋼板であり、且つ、該水系処理剤の造膜成分（ｃ）における
（５）有機ケイ素化合物（Ｃ）とポリエーテルポリウレタン樹脂（Ｅ）の固形分質量比〔（Ｅ）／（Ｃ）〕が０．３３〜０．９０であることを特徴とする、表面処理亜鉛系めっき鋼板に関する。 That is, the present invention comprises (1) a silane coupling agent (A) containing one amino group in the molecule and a silane coupling agent (B) containing one glycidyl group in the molecule. Two or more functional groups (a) represented by the following general formula [1] in the molecule, obtained by blending at a ratio of 0.50 to 0.75 in [(A) / (B)], It contains at least one hydrophilic functional group (b) selected from a hydroxyl group (separate from those which can be included in the functional group (a)) and an amino group, and has an average molecular weight of 1,000 to 10,000. There, in the backbone have a cyclic siloxane bonds, cyclic siloxane bond and the presence proportion of chain siloxane bond, the absorbance of 1090～1100Cm ^-1 indicating the cyclic siloxane bond by FT-IR reflection method (C1) and chain siloxane 1030 indicating binding The ratio [C1 / C2] is 1.0 to 2.0 der Ru organosilicon compound in absorbance 1040 cm ^-1 (C2) (C), and

(Wherein R1, R2 and R3 each independently represent an alkoxy group or a hydroxyl group, and at least one represents an alkoxy group)
(2) a polyether polyurethane resin (E) having a structural unit derived from a polyether polyol in the molecule;
A film-forming component (c) containing:
(3) an inhibitor component (d) having a fluoro metal complex compound (H) having at least one selected from titanium and zirconium as an essential component;
(4) an aqueous medium,
(5) Organic in the film-forming component (c) of the water-based treatment agent, which is a zinc-based plated steel sheet in which a composite film containing each component is formed by applying and drying a water-based metal surface treatment agent containing The present invention relates to a surface-treated zinc-based plated steel sheet, wherein the solid content mass ratio [(E) / (C)] of the silicon compound (C) and the polyether polyurethane resin (E) is 0.33 to 0.90. .

The ratio of the cyclic siloxane bond and the chain siloxane bond in the organosilicon compound (C) is 1030 indicating the absorbance (C1) of 1090 to 1100 cm ⁻¹ indicating the cyclic siloxane bond by the FT-IR reflection method and the chain siloxane bond. The ratio [C1 / (C1 + C2)] of absorbance (C2) at 1040 cm ⁻¹ is preferably 1.0 to 2.0.

（式中、Ｒ９は水素原子、アルキル基、アリール基およびアラルキル基からなる群より選ばれる一価の有機残基、Ｒ１０、Ｒ１１は互いに独立に、アルコキシル基、アシロキシ基、水酸基およびハロゲン原子からなる群から選ばれる官能基を、ｍは１〜５の整数を表す。）Moreover, it is preferable that the polyether polyurethane resin (E) of the present invention has an aromatic ring and / or an alicyclic structure having 4 to 6 carbon atoms in the molecule, and the polyether polyurethane resin (E) has an amino acid in the molecule. It is preferable that the ratio of the quaternary ammonium salt to the total amount of the amino group is 0.7 to 1.0 in terms of molar ratio. Moreover, it is preferable that the said polyether polyurethane resin (E) has a structural unit (D) represented by following General formula [2] in a molecule | numerator.

(Wherein 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, and R10 and R11 are independently of each other an alkoxyl group, an acyloxy group, a hydroxyl group and a halogen atom. (In the functional group selected from the group, m represents an integer of 1 to 5.)

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

The inhibitor component (d) is
(6) Phosphate compound (J)
It is preferable to further contain
(6) Phosphate compound (J) and (7) Vanadium (IV) compound (K)
It is more preferable to further contain both,
(8) Mass ratio of metal component (M) of Si (Si) derived from organosilicon compound (C) and fluorometal complex compound (H) having at least one selected from titanium and zirconium [(M) / (Si)] is 0.08-0.20,
(9) The solid content mass ratio [(J) / (C)] of the organosilicon compound (C) and the phosphate compound (J) is 0.02 to 0.11;
(10) The solid content mass ratio [(K) / (C)] of the organosilicon compound (C) and the vanadium (IV) compound (K) is preferably 0.02 to 0.06.

In addition, the metal component (M) of the fluorometal complex compound (H) of the present invention contains both titanium (M _T ) and zirconium (M _Z ), and each metal component ratio [(M _T ) / (M _Z ]] Is preferably 0.50 to 0.80, and the inhibitor component (d) preferably further contains at least one metal component selected from Mg, Co and W.

  The water-based metal surface treatment agent further contains a polyethylene wax (L), and the solid content mass ratio [(L) / (C)] of the organosilicon compound (C) and the polyethylene wax (L) is 0.05 to It is preferably 0.30.

The surface-treated galvanized steel sheet is coated with the aqueous metal surface treatment agent on the surface of the galvanized steel sheet, dried at an ultimate temperature of 50 ° C. to 250 ° C., and the coating weight after drying is 0.2 to It is preferably 5.0 g / m ² .

  The surface-treated zinc-based plated steel sheet of the present invention has corrosion resistance, alkali resistance, solvent resistance and other detergent resistance, sweat resistance, film adhesion, paint adhesion and printing adhesion, moisture discoloration resistance, In addition to excellent water resistance such as condensation resistance, it is extremely excellent in workability and slidability.

  The water-based metal surface treating agent for the chromium-free surface-treated zinc-based plated steel sheet according to the present invention contains two components, ie, the organosilicon compound (C) and the polyether polyurethane resin (E) as the film-forming component (c).

  The organosilicon compound (C) includes a silane coupling agent (A) containing one amino group in the molecule and a silane coupling agent (B) containing one glycidyl group in the molecule. [(A) / (B)] is blended at a ratio of 0.50 to 0.75. As a compounding ratio of the silane coupling agent (A) and the silane coupling agent (B), it is necessary that the solid content mass ratio [(A) / (B)] is a ratio of 0.50 to 0.75, It is preferably 0.50 to 0.65, and most preferably 0.55 to 0.65. When the solid content mass ratio [(A) / (B)] is less than 0.50, the hydrophobicity and the self-crosslinking property of the organosilicon compound (C) are increased, so that the stability of the treating agent is remarkably lowered, which is not preferable. . On the other hand, if the solid content mass ratio [(A) / (B)] exceeds 0.75, the hydrophilicity and cationicity of the organosilicon compound (C) become too high, and the water resistance and sweat resistance of the resulting film are increased. Is not preferable because of drastically lowering.

  The organosilicon compound (C) needs to have a cyclic siloxane bond in the skeleton. If the skeleton does not have a cyclic structure containing Si, the barrier property and adhesion of the film-forming component (c) are lowered, and all the performances such as corrosion resistance, detergent resistance, and film adhesion are lowered.

  In the present invention, the silane coupling agent (A) containing one amino group in the molecule is not particularly limited, but 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane. Examples of the silane coupling agent (B) containing one glycidyl group in the molecule include 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane. can do.

  The number of functional groups (a) in the organosilicon compound (C) needs to be 2 or more. When the number of functional groups (a) is one, the adhesion to the surface of the zinc-based plated steel sheet, the self-crosslinking property of the organosilicon compound (C), and the binding property to the polyether polyurethane resin (E) described later And the film is not sufficiently formed, so that all the effects of the present invention cannot be obtained. The number of carbon atoms of the alkyl group and alkoxy group in the definition of R1, R2, and R3 of the functional group (a) is not particularly limited, but is preferably 1 to 6, more preferably 1 to 4, and 1 or 2 is most preferred.

  Furthermore, the abundance ratio of the functional group (b) in the organosilicon compound (C) may be one or more in one molecule, and the average molecular weight needs to be 1000 to 10,000, and 1300 to 6000. It is preferable that Although molecular weight here is not specifically limited, either direct measurement by TOF-MS method or conversion measurement by chromatography method may be used, and molecular weight standard substance using GFC (gel filtration chromatography). It is preferable to use ethylene glycol. When the average molecular weight determined by the same method is less than 1000, the water solubility of the organosilicon compound is increased, so that the water resistance of the formed film is significantly reduced. On the other hand, when the average molecular weight exceeds 10,000, it is difficult to stably dissolve or disperse the organosilicon compound (C) in water.

The organosilicon compound (C) needs to have a cyclic siloxane structure, and the abundance ratio of the organic silicon compound (C) is an absorbance (C1) of 1090 to 1100 cm ⁻¹ showing a cyclic siloxane bond by FT-IR reflection method and a chain siloxane bond. It is most preferable that the ratio [C1 / C2] of the absorbance (C2) of 1030 to 1040 cm ⁻¹ shown is 1.0 to 2.0. When the ratio [C1 / C1] is 1.0 to 2.0, both the barrier property due to the cyclic structure and the flexibility due to the chain structure can be provided in a well-balanced manner, and the corrosion resistance, the detergent resistance, and the film adhesion All the performances are improved. Moreover, a tougher and denser film is formed by the entanglement between the resin molecule and the cyclic siloxane bond.

  Moreover, the manufacturing method of the organosilicon compound (C) of the present invention is not particularly limited, but the silane coupling agent (A) and the silane coupling agent (B) are added to water adjusted to pH 4. The method of adding sequentially and stirring for predetermined time is mentioned. Here, since the aqueous solution generates heat when the silane coupling agent (A) is added, the organosilicon compound is prepared by cooling the water in advance, continuing to cool for a predetermined time, and producing in a certain temperature range. The abundance ratio of the cyclic siloxane bond and the chain siloxane bond in (C) can be controlled.

  The polyether polyurethane resin (E) which is an essential component of the present invention needs to be a polyether. Polyester polyurethane resin is not preferable because it is hydrolyzed by acid or alkali, and polycarbonate polyurethane is not preferable because it is easy to form a hard and brittle film and is inferior in adhesion during processing and corrosion resistance of processed parts.

  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, entanglement with the cyclic structure of the organosilicon compound (C) described above occurs, so that the barrier property of the film is improved. Moreover, it is preferable that the said polyether polyurethane resin (E) contains an amino group in a molecule | numerator, and the ratio of the quaternary ammonium salt with respect to the total amount of this amino group is 0.7-1.0 by molar ratio. When the ratio of the quaternary ammonium salt to the total amount of the amino groups is within this range, both the dispersion stability of the polyether polyurethane resin (E) and the water resistance after film formation can be satisfied.

  Furthermore, the polyether polyurethane resin (E) preferably has a structural unit (D) represented by the following general formula [2] in the molecule. By containing the structural unit (D), since it has a reaction point with the organosilicon compound (C) and a self-crosslinking point, the degree of crosslinking is increased and the corrosion resistance and the detergent resistance are remarkably improved. R9, R10, and R11 in the 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 and R11 are each independently a functional group selected from the group consisting of an alkoxyl group, an acyloxy group, a hydroxyl group and a halogen atom, R9 is most preferably an alkyl group, and R10 and R11 are hydroxyl groups. Most preferably it is. The number of ethylene chains m in the structural unit (D) is not particularly limited, but is preferably 1 to 5, and most preferably 2 or 3.

  The polyether polyurethane resin (E) of the present invention is a polyurethane resin that is a polycondensation product of a polyether polyol and an aliphatic, alicyclic or aromatic polyisocyanate, although not particularly limited, It is a polyurethane obtained by using a polyol having a (substituted) amino group as a part of the polyol to be used. As polyether polyols, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, (aliphatic diol) as initiators Obtained by addition polymerization of one or more compounds such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrohydrofuran, and cyclohexylene using saccharose, methylene glycol, glycerin, etc. Polyisocyanates include tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, dicyclohexyl Tan diisocyanate, cyclohexylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, and the like.

  Moreover, regarding the compounding ratio with respect to solid content of the organosilicon compound (C) and the polyether polyurethane resin (E) in the film-forming component (c) of the present invention, the organosilicon compound (C) and the polyether polyurethane resin (E). The solid content mass ratio [(E) / (C)] must be 0.33 to 0.90, more preferably 0.33 to 0.80, and 0.35 to 0.70. Most preferably it is. If the solid content mass ratio [(E) / (C)] is less than 0.33, it is not preferable because the barrier property of the film-forming component (c) is lowered. Conversely, if it exceeds 0.90, organosilicon Adhesiveness with the material resulting from the compound (C) is remarkably lowered, and various performances are lowered, which is not preferable.

  Moreover, it is preferable that the film-forming component (c) of the present invention further contains a cationic phenol resin (F) having a bisphenol A skeleton in order to improve corrosion resistance and solvent resistance. Regarding the blending ratio of the polyether polyurethane resin (E) and the cationic phenol resin (F) to the solid content, the solid content mass ratio of the polyether polyurethane resin (E) and the cationic phenol resin (F) [(F ) / (E)] must be 0.010 to 0.030, more preferably 0.010 to 0.025, and most preferably 0.010 to 0.022. If 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 solvent resistance are lowered. If it exceeds 030, the film is colored slightly yellow with the cationic phenol resin, and it is not preferable because significant yellowing occurs in a high-humidity environment or an ultraviolet exposure environment.

  The aqueous metal surface treatment agent for the chromium-free surface-treated zinc-based plated steel sheet according to the present invention contains, as an essential component, a fluoro metal complex compound (H) having at least one selected from titanium and zirconium as an inhibitor component (d). There is a need.

  The fluorometal complex compound (H) having at least one selected from titanium and zirconium is not particularly limited, but includes titanium hydrofluoric acid, zircon hydrofluoric acid, ammonium salts thereof, and alkali metal salts. It can be illustrated.

  Regarding the compounding ratio of the organosilicon compound (C) and the fluorometal complex compound (H) having at least one selected from titanium and zirconium in the inhibitor component (d) of the present invention, it is derived from the organosilicon compound (C). The mass ratio [(Si) / (M)] of the metal component (M) of the fluorometal complex compound (H) having at least one selected from Si (Si) and titanium and zirconium is 0.08 to 0.20. It is preferable that it is 0.12-0.20, and it is most preferable that it is 0.14-0.18. When the mass ratio [(Si) / (M)] of the metal component (M) is less than 0.08, the amount of oxide film formed from the metal component during film formation is reduced, and the corrosion resistance is improved. Since it becomes low, it is not preferable, and when it exceeds 0.20, the material surface coverage of the oxide film formed from the metal component increases, and the reaction point with the material of the organosilicon compound (C) decreases, The adhesion imparting effect by the organosilicon compound (C) is reduced, and the overall effect of the present invention is lowered, which is not preferable.

Moreover, it is preferable that the metal component (M) of the said fluoro metal complex compound (H) contains both titanium (M _T ) and zirconium (M _Z ) in order to achieve both corrosion resistance and alkali resistance. Each metal component mass ratio [(M _T ) / (M _Z )] is preferably 0.50 to 0.80, more preferably 0.60 to 0.80, and 0.60 to 0. Most preferred is .70. If the metal component mass ratio [(M _T ) / (M _Z )] is less than 0.50, the titanium oxide film decreases, and the abundance ratio of the relatively hard zirconium oxide increases. It is not preferable because it becomes brittle with respect to the deformation of the film accompanying the plastic deformation of the film, resulting in film defects and a decrease in corrosion resistance. Conversely, when it exceeds 0.80, there is a relatively low alkali resistance titanium oxide film. Since the ratio becomes high, the alkali resistance of the film is lowered, and the corrosion resistance after the alkali test is lowered.

  In addition, the inhibitor component (d) of the present invention preferably further contains a phosphoric acid compound (J) in order to improve corrosion resistance. Both the phosphoric acid compound (J) and the vanadium (IV) compound (K) It is more preferable to contain further. Although it does not specifically limit as a phosphoric acid compound (J), Phosphoric acid, the ammonium salt of phosphoric acid, the alkali metal salt of phosphoric acid, the alkaline-earth metal salt of phosphoric acid, etc. are mentioned. These are mainly effective in imparting corrosion resistance, and the elution property of phosphoric acid can be controlled and the corrosion resistance retention time can be extended depending on the type of salt of the phosphoric acid compound (J). Among these, phosphoric acid or magnesium diphosphate is preferable because a larger effect of improving corrosion resistance is obtained, and it is more preferable to use phosphoric acid and magnesium magnesium phosphate in combination.

  Moreover, regarding the compounding ratio of the organosilicon compound (C) and the phosphate compound (J) in the inhibitor component (d) of the present invention, the solid content mass ratio of the organosilicon compound (C) and the phosphate compound (J) [(J ) / (C)] is preferably 0.020 to 0.110, more preferably 0.030 to 0.110, and most preferably 0.040 to 0.100. If the solid content mass ratio [(J) / (C)] is less than 0.020, the effects of addition of the phosphoric acid compound (J), such as alkali resistance and corrosion resistance, are not preferable. Exceeding 110 is not preferable because the stability of the metal surface treatment agent is lowered.

Vanadium (IV) compound as a (K) is not particularly limited, vanadium pentoxide _{[V 2 O} 5], metavanadate _[HVO 3], ammonium metavanadate _[NH 4 VO _3] sodium metavanadate [NaVO ₃ ], vanadium (V) of a compound such as vanadium oxytrichloride [VOCl ₃ ], etc. reduced to vanadium (IV) using a reducing agent such as alcohols and organic acids, vanadium dioxide [VO ₂ ], vanadium oxy Vanadium (IV) -containing compounds such as acetylacetonate [VO (C ₅ H ₇ O ₂ ) ₂ ], vanadium oxysulfate [VOSO ₄ ], vanadium acetylacetonate [V (C ₅ H ₇ O ₂ ) ₃ ] trioxide Compounds of vanadium [V ₂ O ₃ ], vanadium trichloride [VCl ₃ ], etc. Examples thereof include those obtained by oxidizing nadium (III) to vanadium (IV) with an arbitrary oxidizing agent.

  Moreover, regarding the compounding ratio of the organosilicon compound (C) and the vanadium compound (K) in the inhibitor component (d) of the present invention, the solid content mass ratio of the organosilicon compound (C) and the vanadium compound (K) [(K) / (C)] is preferably 0.020 to 0.060, more preferably 0.025 to 0.060, and most preferably 0.030 to 0.055. When the solid content mass ratio [(K) / (C)] is less than 0.020, an inhibitor effect due to the vanadium (IV) compound (K) cannot be obtained, and when it exceeds 0.060. A complex compound of a vanadium (IV) compound and an organic substance contained in the film is not preferable because the film is likely to be colored yellow at high humidity.

  The aqueous metal surface treatment agent of the present invention preferably further contains polyethylene wax (L) in order to improve processability and slidability. Regarding the blending ratio of the polyethylene wax (L), the mass ratio [(L) / (C)] of the organosilicon compound (C) and the solid content of the polyethylene wax (L) is 0.05 to 0.30. It is necessary to be 0.07 to 0.30, and most preferably 0.10 to 0.25. If the mass ratio [(L) / (C)] is less than 0.05, it is not preferable because sufficient lubricity is not expressed, and if it exceeds 0.30, the continuity of the film is inhibited by the polyethylene wax, It is not preferable because the film is easily broken and the corrosion resistance is lowered.

The surface-treated metal material of the present invention is coated with the aqueous metal surface-treating agent, dried at an ultimate temperature of 50 to 250 ° C., and the film weight after drying is 0.2 to 5.0 g / m ^2. Is preferred. About drying temperature, it is preferable that it is 50 to 250 degreeC in ultimate temperature, It is more preferable that it is 70 to 150 degreeC, It is most preferable that it is 100 to 140 degreeC. An ultimate temperature of less than 50 ° C. is not preferable because the solvent of the aqueous metal surface treatment agent does not volatilize completely. On the other hand, if it exceeds 250 ° C., part of the organic chain of the film formed with the aqueous metal surface treatment agent is decomposed, which is not preferable. For the coating weight is preferably 0.2~5.0g / ^{m 2,} more preferably from 0.5 to 3.0 g / ^{m 2,} is 0.8 to 2.0 g / ^{m 2} Most preferred. If the coating weight is less than 0.2 g / m ² , the surface of the metal material cannot be coated and the corrosion resistance is remarkably lowered. On the other hand, if it exceeds 5.0 g / m ² , the film adhesion deteriorates, which is not preferable.

  The aqueous metal surface treatment agent used in the present invention may use a leveling agent, a water-soluble solvent, a metal stabilizer, an etching inhibitor, etc. for improving the coating property within the range not impairing the effects of the present invention. Is possible. Examples of leveling agents include nonionic or cationic surfactants such as polyethylene oxide or polypropylene oxide adducts and acetylene glycol compounds, and examples of water-soluble solvents include alcohols such as ethanol, isopropyl alcohol, t-butyl alcohol, and propylene glycol. , Cellosolves such as ethylene glycol monobutyl ether and ethylene glycol monoethyl ether, esters such as ethyl acetate and butyl acetate, and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. Examples of the metal stabilizer include chelate compounds such as EDTA and DTPA, and examples of the etching inhibitor include amine compounds such as ethylenediamine, triethylenepentamine, guanidine and pyrimidine. In particular, those having two or more amino groups in one molecule are more preferable because they are effective as metal stabilizers.

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

  The film formed using the water-based metal surface treatment agent used in the present invention contains an organosilicon compound (C) and a polyether polyurethane resin (E) as film-forming components. First, the corrosion resistance is such that when one part of the organosilicon compound is concentrated by drying or the like, the organosilicon compound reacts with each other to form a continuous film, and one part of the organosilicon compound hydrolyzes. It is presumed that the generated —OR group exhibits a significant barrier effect by forming a Si—OM bond (M: metal element on the surface of the object to be coated) with the metal surface. In addition, various effects can be obtained when the organosilicon compound (C) contains a specific structure, that is, a cyclic siloxane bond and a chain siloxane bond in a specific ratio. As described above, the organosilicon compound (C) forms a dense film that is firmly bonded to the material by its own condensation and reaction with the material. An original siloxane-bonded film is formed, and resistance to intrusion of oxygen, moisture and the like is increased, so that an extremely excellent barrier property is exhibited. However, the cyclic siloxane bond does not have a degree of freedom of deformation for skeleton reasons, and becomes a hard but brittle film. On the other hand, a chain siloxane bond does not form a three-dimensional structure like a cyclic siloxane bond, and has a lower barrier property than a cyclic siloxane bond, but has a high degree of freedom in deformation. Such siloxane bonds having different properties coexist at a certain ratio, whereby a film having excellent barrier properties and adhesion can be formed. In the case of a polyether polyurethane resin having a structural unit (D) that is entangled with the polyether urethane resin at the time of film formation and having reactivity with the organosilicon compound, the organosilicon compound and the polyether polyurethane resin are bonded to each other. , Exhibit extremely high barrier properties. In addition, the cationic phenol resin (F) is a compound having a resonance stabilizing structure, and the coating containing the cationic phenol resin (F) reacts with and adheres to the metal surface. Because it is close enough to overlap with the orbit, it has the effect of delocalizing electrons generated by corrosion using φ orbit, which keeps the surface potential uniform and provides excellent corrosion resistance. The

  On the other hand, the effect of the inhibitor component (d) is the effect of removing the oxide film by etching the surface of the material, the precipitation and film formation due to the pH increase accompanying the etching, the formation of a hardly soluble salt with the metal ions derived from the eluted material, Examples include relaxation of pH increase due to corrosion, and uniform surface potential. The fluoro metal complex compound having at least one selected from titanium and zirconium has an effect of removing the oxide film by etching the material surface, and at the same time, as the pH increases, the fluorine dissociates and becomes an oxide or hydroxide. It is presumed that corrosion resistance is imparted by precipitation and film formation. In addition, it has the effect of delaying the progress of corrosion by forming slightly soluble salts with metal ions derived from the material eluted by corrosion. On the other hand, phosphoric acid compounds have a pH increase mitigating effect associated with material corrosion, and particularly have an effect as an elution inhibitor. It is estimated that the vanadium compound has an effect of consuming electrons generated by corrosion due to the oxidation-reduction reaction of vanadium and suppressing the progress of corrosion. By exhibiting a good balance between the inhibitor component having such an effect and the adhesion and barrier properties caused by the above-mentioned film-forming component, it is resistant to detergents such as corrosion resistance, alkali resistance and solvent resistance, film adhesion, and paint adhesion. It is presumed that it is possible to form a film having excellent water resistance such as adhesion and print adhesion, moisture discoloration resistance and dew condensation resistance, and extremely excellent workability and slidability.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples of the present invention, but the present invention is not limited thereto. Preparation of the test plate, examples and comparative examples, and a method of applying the surface treatment agent for metal material will be described below.

Preparation of test plate (1) Test material Commercially available materials shown below were used.
Electrogalvanized steel sheet (EG): plate thickness = 0.8 mm, basis weight = 20/20 (g / m ² )
Hot-dip galvanized steel sheet (GI): plate thickness = 0.8 mm, basis weight = 90/90 (g / m ² )
Alloyed hot-dip galvanized steel sheet (GA): plate thickness = 0.8 mm, basis weight = 90/90 (g / m ² )
Hot-dip zinc-11% aluminum-3% magnesium-0.2% silicon-plated steel sheet (SD): plate thickness = 0.8 mm, basis weight = 60/60 (g / m ² )
(2) Degreasing treatment The material was sprayed for 2 minutes under the conditions of a concentration of 20 g / L and a temperature of 60 ° C. using a fine silicate alkali degreasing agent 4336 (registered trademark: manufactured by Nihon Parkerizing Co., Ltd.). The test plate was washed with water for 30 seconds and then dried.

  Table 1 shows silane coupling agents used in Examples and Comparative Examples, Table 2 shows urethane resins, Table 3 shows phosphoric acid compounds, Table 4 shows vanadium compounds, Table 5 shows polyethylene waxes, Formulation Examples, Table 6 shows the coating amount and the drying temperature.

[Method for preparing organosilicon compound C]
With the combinations and blending ratios shown in Table 6, the silane coupling agent shown in Table 1 was reacted in ethanol, and then mixed with water adjusted to pH 4 to 4.5 with acetic acid, and the solid content was 20%. It adjusted so that it might become. The number of functional groups (a) and the molecular weight per hydrophilic group (b) of the obtained organosilicon compound, the absorbance (C1) of 1090 to 1100 cm ⁻¹ showing the chain siloxane bond by FT-IR reflection method, and the chain siloxane Table 6 shows the ratio [C1 / C2] of absorbance (C2) of 1030 to 1040 cm ⁻¹ indicating the binding.

[Method of synthesizing urethane resin (E1)]
Polyether polyol (synthesis components: tetramethylene glycol and ethylene glycol, 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 mass parts of methyl ethyl ketone was put into reaction container, it was made to react for 1 hour, keeping at 70 to 75 degreeC, and the urethane prepolymer was produced | generated. Then, 10 parts by mass of 3aminopropyltrimethoxysilane was added and reacted for 1 hour while maintaining at 80 to 85 ° C. to form the structural unit (D1). Subsequently, 15 mass parts of dimethyl sulfuric acid was put into this reaction container, and it was made to react at 50-60 degreeC for 30 minutes-60 minutes, and the cationic urethane prepolymer was produced | generated. Subsequently, 576 parts by mass of water was placed in the reaction vessel, and the mixture was uniformly emulsified. Then, methyl ethyl ketone and remaining 3 aminopropyltrimethoxysilane were recovered to obtain a water-soluble cationic urethane resin. Si content with respect to resin solid content was 0.5 mass%.

[Synthesis Method of Urethane Resin (E2)]
Polyether polyol (synthesis components: tetramethylene glycol and ethylene glycol, 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 mass parts of methyl ethyl ketone was put into reaction container, it was made to react for 1 hour, keeping at 70 to 75 degreeC, and the urethane prepolymer was produced | generated. Subsequently, 15 mass parts of dimethyl sulfuric acid was put into this reaction container, and it was made to react at 50-60 degreeC for 30 minutes-60 minutes, and the cationic urethane prepolymer was produced | generated. Next, 576 parts by mass of water was placed in the reaction vessel to uniformly emulsify the mixture, and then methyl ethyl ketone was recovered to obtain a water-soluble cationic urethane resin.

[Method of synthesizing urethane resin (E3)]
Polyester polyol (synthesis 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 reacted for 1 hour while maintaining at 70 to 75 ° C. to produce a urethane prepolymer. Subsequently, 15 mass parts of dimethyl sulfuric acid was put into this reaction container, and it was made to react at 50-60 degreeC for 30 minutes-60 minutes, and the cationic urethane prepolymer was produced | generated. Subsequently, 576 parts by mass of water was placed in the reaction vessel, and the mixture was uniformly emulsified. Then, methyl ethyl ketone and remaining 3 aminopropyltrimethoxysilane were recovered to obtain a water-soluble cationic urethane resin.

[Method of synthesizing 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, isophorone diisocyanate: 94 parts by mass And 135 mass parts of methyl ethyl ketone was put into reaction container, it was made to react for 1 hour, keeping at 70 to 75 degreeC, and the urethane prepolymer was produced | generated. Subsequently, 15 mass parts of dimethyl sulfuric acid was put into this reaction container, and it was made to react at 50-60 degreeC for 30 minutes-60 minutes, and the cationic urethane prepolymer was produced | generated. Subsequently, 576 parts by mass of water was placed in the reaction vessel, and the mixture was uniformly emulsified. Then, methyl ethyl ketone and remaining 3 aminopropyltrimethoxysilane were recovered to obtain a water-soluble cationic urethane resin.

[Method of synthesizing urethane resin (E5)]
Polyether polyol (synthesis component: tetramethylene glycol and 1,4-cyclohexane-dimethanol, 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 reacted for 1 hour while maintaining at 70 to 75 ° C. to produce a urethane prepolymer. Subsequently, 10 mass parts of 3 aminopropyl trimethoxysilane was added, and it was made to react for 1 hour, keeping at 80 to 85 degreeC, and the structural unit (D1) was formed. Subsequently, 15 mass parts of dimethyl sulfuric acid was put into this reaction container, and it was made to react at 50-60 degreeC for 30 minutes-60 minutes, and the cationic urethane prepolymer was produced | generated. Subsequently, 576 parts by mass of water was placed in the reaction vessel, and the mixture was uniformly emulsified. Then, methyl ethyl ketone and remaining 3 aminopropyltrimethoxysilane were recovered to obtain a water-soluble cationic urethane resin. Si content with respect to resin solid content was 0.5 mass%.

[Method of synthesizing urethane resin (E6)]
Polyether polyol (synthesis component: PO2 molar adduct of tetramethylene glycol and 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 were placed in a reaction vessel and reacted for 1 hour while maintaining at 70 to 75 ° C. to produce a urethane prepolymer. Subsequently, 10 mass parts of 3 aminopropyl trimethoxysilane was added, and it was made to react for 1 hour, keeping at 80 to 85 degreeC, and the structural unit (D1) was formed. Subsequently, 15 mass parts of dimethyl sulfuric acid was put into this reaction container, and it was made to react at 50-60 degreeC for 30 minutes-60 minutes, and the cationic urethane prepolymer was produced | generated. Subsequently, 576 parts by mass of water was placed in the reaction vessel, and the mixture was uniformly emulsified. Then, methyl ethyl ketone and remaining 3 aminopropyltrimethoxysilane were recovered to obtain a water-soluble cationic urethane resin. Si content with respect to resin solid content was 0.5 mass%.

[Method of synthesizing urethane resin (E7)]
Polyether polyol (synthesis component: tetramethylene glycol and 1,4-cyclohexane-dimethanol, 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 reacted for 1 hour while maintaining at 70 to 75 ° C. to produce a urethane prepolymer. Subsequently, 15 mass parts of dimethyl sulfuric acid was put into this reaction container, and it was made to react at 50-60 degreeC for 30 minutes-60 minutes, and the cationic urethane prepolymer was produced | generated. Next, 576 parts by mass of water was placed in the reaction vessel to uniformly emulsify the mixture, and then methyl ethyl ketone was recovered to obtain a water-soluble cationic urethane resin.

[Synthesis Method of Urethane Resin (E8)]
Polyether polyol (synthesis component: PO2 molar adduct of tetramethylene glycol and 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 were placed in a reaction vessel and reacted for 1 hour while maintaining at 70 to 75 ° C. to produce a urethane prepolymer. Subsequently, 15 mass parts of dimethyl sulfuric acid was put into this reaction container, and it was made to react at 50-60 degreeC for 30 minutes-60 minutes, and the cationic urethane prepolymer was produced | generated. Next, 576 parts by mass of water was placed in the reaction vessel to uniformly emulsify the mixture, and then methyl ethyl ketone was recovered to obtain a water-soluble cationic urethane resin.

[Method of synthesizing urethane resin (E9)]
Polyether polyol (synthesis component: tetramethylene glycol and 1,4-cyclohexane-dimethanol, 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 reacted for 1 hour while maintaining at 70 to 75 ° C. to produce a urethane prepolymer. Next, 13 parts by mass of dimethyl sulfate was placed in the reaction vessel and reacted at 50 to 60 ° C. for 30 to 60 minutes to produce a cationic urethane prepolymer. Next, 576 parts by mass of water was placed in the reaction vessel to uniformly emulsify the mixture, and then methyl ethyl ketone was recovered to obtain a water-soluble cationic urethane resin.

[Synthesis Method of Urethane Resin (E10)]
Polyether polyol (synthesis component: tetramethylene glycol and 1,4-cyclohexane-dimethanol, 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 reacted for 1 hour while maintaining at 70 to 75 ° C. to produce a urethane prepolymer. Subsequently, 20 mass parts of dimethyl sulfuric acid was put into this reaction container, and it was made to react at 50-60 degreeC for 30 minutes-60 minutes, and the cationic urethane prepolymer was produced | generated. Next, 576 parts by mass of water was placed in the reaction vessel to uniformly emulsify the mixture, and then methyl ethyl ketone was recovered to obtain a water-soluble cationic urethane resin.

[Synthesis Method of Urethane Resin (E11)]
Polyether polyol (synthesis component: tetramethylene glycol and 1,4-cyclohexane-dimethanol, 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 reacted for 1 hour while maintaining at 70 to 75 ° C. to produce a 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 emulsify 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 (synthesis component: tetramethylene glycol and 1,4-cyclohexane-dimethanol, molecular weight 1500): 150 parts by mass, trimethylolpropane: 6 parts by mass, isophorone diisocyanate: 94 parts by mass and methyl ethyl ketone 135 parts by mass And was allowed to react for 1 hour while maintaining the temperature at 70 ° C. to 75 ° C. to produce a urethane prepolymer. Subsequently, 576 parts by mass of water was placed in the reaction vessel, and the mixture was uniformly emulsified using a nonionic emulsifier, and then methyl ethyl ketone was recovered to obtain a water-soluble urethane resin.

[Molecular weight measurement method]
The molecular weight was measured by gel filtration chromatography, the component concentration was diluted to 5% by weight at a column temperature of 40 ° C., and the molecular weight of the organosilicon compound (C) was determined. In addition, it was set as polyethylene glycol (molecular weight: 600-12000) conversion.

[FT-IR]
The FT-IR apparatus was used with an infrared total reflection absorption spectrum apparatus. The measurement wavenumber range 650～4000Cm ^-1, resolution ^{4 cm -1,} cumulated number 16 times, was carried out at a temperature of 25 ° C. From the obtained infrared absorption spectrum, baseline method ^{(900cm -1, 1200cm} -1) by, 1030～1040Cm ^-1 indicating the chain siloxane bond and absorbance 1090～1100Cm ^-1 indicating the cyclic siloxane bond (C1) The absorbance (C2) of was determined.

Surface treatment agent stability The drug after the pharmaceutical was placed in a sealed container, and the drug stability at 40 ° C was observed.
◎ = No liquid property change for 3 months ○ = No liquid property change for 1 month △ = Viscosity increase or precipitation occurred within 1 month × = Viscosity increase or precipitation occurred within 1 week

〔Evaluation test〕
Corrosion resistance A salt spray test according to JIS-Z-2371 was conducted for 240 hours, and the occurrence of white rust was observed.
<Evaluation criteria>
◎ = Rust generation is less than 3% of the total area ○ = Rust generation is 3% or more and less than 10% of the total area △ = Rust generation is 10% or more and less than 30% of the total area × = Rust generation is 30% or more of the total area

After alkali resistance film formed by using a pulse clean N364S silicate-based alkali degreasing agent (manufactured by Japan Parkerizing Co.) was sprayed for 2 minutes under conditions of a concentration 20 g / L, temperature 60 ℃, JIS-Z-2371 A salt spray test was conducted for 120 hours, and the occurrence of white rust was observed.
<Evaluation criteria>
◎◎ = Rust generation is 0% of the total area
◎ = Rust generation exceeds 0% of total area and less than 3% ○ = Rust generation is 3% or more and less than 10% of total area △ = Rust generation is 10% or more and less than 30% of total area × = Rust generation is all More than 30% of the area

After the formation of the sweat- resistant film, one drop of artificial sweat (JIS-L-0848 D method) was dropped and then left at 65 ° C. and 93% RH for 48 hours, and evaluated according to the following criteria.
<Evaluation criteria>
◎ = No change in appearance ○ = No change in appearance △ = Change in area of less than 30% of dripping part × = Change in area of 30% or more of dripping part

Solvent-resistant MEK (methyl ethyl ketone) was soaked in gauze, and a trace that was rubbed 5 times with a load of 500 g was evaluated by an increase or decrease in L value before and after the test.
<Evaluation criteria>
◎ = △ L is less than 0.5 ○ = △ L is 0.5 or more and less than 1.0 △ = △ L is 1.0 or more and less than 2.0 × = △ L is 2.0 or more

Film adhesiveness 1 mm A portion cut into a 1 mm grid was extruded 7 mm with an Erichsen tester, and then the tape was peeled off. The adhesiveness was evaluated at the remaining number ratio (remaining number / number of cuts: 100).
<Evaluation criteria>
◎ = 100%
○ = less than 20% 95% or more △ = 90% or more, less than 95% × = less than 90%

Paint adhesion Melamine alkyd paint is applied by bar coating, baked at 120 ° C for 20 minutes, then cut into 1mm grids, and the adhesion evaluation is based on the remaining number ratio (remaining number / cut number: 100) went.
<Evaluation criteria>
◎ = 100%
○ = 95% or more △ = 90% or more, less than 95% × = less than 90%

Printing adhesion Screen printing ink was solid-printed, baked at 120 ° C. for 20 minutes, then cut into 1 mm grids, and the adhesion was evaluated by the remaining number ratio (remaining number / cut number: 100). .
<Evaluation criteria>
◎ = 100%
○ = 95% or more △ = 90% or more, less than 95% × = less than 90%

The sample was allowed to stand for 72 hours in a high-temperature and high-humidity environment having a humidity discoloration resistance temperature of 65 ° C. and a humidity of 95%, and the color change ΔE before and after the test was evaluated.
◎ = △ E is less than 1.0 ○ = △ E is 1.0 or more and less than 2.0 △ = △ E is 2.0 or more and less than 3.0 × = △ E is 3.0 or more

1 cc of pure water was dropped onto a test piece that was allowed to stand in an environment with a condensation resistance temperature of 25 ° C. and a humidity of 60%, and the color change ΔE before and after the test when it was naturally dried was evaluated.
◎ = △ E is less than 0.5 ○ = △ E is 0.5 or more and less than 1.0 △ = △ E is 1.0 or more and less than 2.0 × = △ E is 2.0 or more

A blank plate having a diameter of 115 mmφ was used, and a high-speed cylindrical deep drawing test was performed under the conditions of punch diameter = 50 mmφ, wrinkle presser pressure 1 Ton, deep drawing speed 30 m / min, and no oil coating.
<Evaluation criteria>
◎ = Limit drawing ratio is 2.50 or more ○ = Limit drawing ratio is 2.40 or more and less than 2.50 Δ = Limit drawing ratio is 2.30 or more and less than 2.40 × = Limit drawing 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 silane coupling agents (A) and (B) used in the organosilicon compound (C) are outside the scope of the claims, that is, the silane coupling agent If the amount of (B) is too large, the film becomes hard due to its molecular structure, so that the film adhesion is inferior, and the performance deteriorates in all evaluation items. On the other hand, when the amount of the silane coupling agent (A) is too large, condensation resistance and moisture discoloration resistance are inferior due to excessive hydrophilicity imparted by amino groups or color formation structure due to amino groups. On the contrary, it is understood that all the performances are satisfied within the more preferable range within the scope of the claims.
From Examples 2, 5 to 7 and Comparative Examples 3 to 5, when there is only one functional group (a), it is not an organosilicon compound (C) of the present invention, but an action equivalent to a general silane coupling agent. Since only an effect can be obtained, all the performances are significantly reduced.

From the evaluation results of Examples 2, 8 to 9 and Comparative Examples 5 to 6, since the film component is easily solubilized when the molecular weight per functional group (b) is 500, degreasing resistance, solvent resistance, Condensation and moisture discoloration resistance are inferior, and if it exceeds 15000, the film-forming property is insufficient and the film adhesion is inferior, so the overall performance is lowered.
From Examples 10 to 15 and Comparative Example 7, when the cyclic siloxane bond is not present, the corrosion resistance and the wet resistance are inferior. It can be seen that it has excellent performance.
From the evaluation results of Example 4 and Comparative Examples 8-9, when the urethane resin (E) does not have an ether structure, it is easily dehydrolyzed if it is an ester system, so that it is resistant to degreasing, moisture, and condensation. Inferior, the carbonate system is too rigid, so the film adhesion and workability are inferior.
From the evaluation results of Examples 13, 16 to 19 and Comparative Examples 10 to 11, when the ratio of the organosilicon compound (C) and the urethane resin (E) is outside the scope of the claims, that is, when the urethane resin is small, the film forming component Since the barrier property of (c) is lowered, the corrosion resistance and the wet resistance are inferior. On the contrary, when there are many urethane resins, the adhesion to the material is remarkably lowered, so that it is inferior to the film adhesion and the coating adhesion.
From the evaluation results of Examples 20 to 21 and Comparative Examples 12 to 19, when Ti or Zr fluorometal complex compound (H) is not contained as an inhibitor component, the corrosion resistance and the wet resistance are extremely inferior, Even if a phosphoric acid compound (J) or a vanadium (IV) compound is added, it is the same, and the effect of a fluoro metal complex compound of Ti or Zr as an inhibitor component can be seen.
From the evaluation results of Examples 22 to 29 and Comparative Examples 20 to 21, the urethane resin having a suitable structure with respect to the skeleton of the urethane resin is excellent in overall performance, particularly the structural unit (D1). When it contains, the performance is extremely excellent. On the other hand, when the amount of quaternary ammonium salt in all amino groups is 0 or when there is no amino group, the stability of the treatment agent is inferior, and particularly when there is no amino group, the stability of the treatment agent is low. It can be seen that the overall performance is inferior due to the lack.

From the evaluation results of Examples 30 to 90, the content of the phenol resin, the type and content of the fluorometal complex compound, the type and content of the phosphate compound, the type and content of the vanadium compound (K), the type of polyethylene wax As for the content, by adjusting it to a suitable range, it can be seen that it has performance of a practically usable level in all evaluation items. Similarly, it was found that W, Co, and Mg have the effect of improving the corrosion resistance without losing the balance that is generally taken in the evaluation items. These performances can be achieved if the drying is performed at a temperature of 50 to 250 ° C., and the film weight after drying is 0.2 to 5.0 g / m ² . It was revealed that the film has extremely excellent performance when the coating amount is 1.2 to 1.5 g / m ² .

  From the above evaluation results, by forming a composite film containing each component by applying and drying the aqueous metal surface treatment agent of the present invention, it is resistant to detergents such as corrosion resistance, alkali resistance, solvent resistance, and the like. Chrome-free surface-treated zinc system with excellent water resistance such as sweat, film adhesion, paint adhesion and printing adhesion, moisture discoloration resistance and dew condensation resistance, and extremely excellent workability and slidability It turns out that a plated steel plate is obtained.

Claims (12)

(1) A silane coupling agent (A) containing one amino group in the molecule and a silane coupling agent (B) containing one glycidyl group in the molecule are mixed in a mass ratio [(A) / ( B)] in a ratio of 0.50 to 0.75, and two or more functional groups (a) represented by the following general formula [1] in the molecule and a hydroxyl group (functional group (a ) And at least one hydrophilic functional group (b) selected from amino groups, an average molecular weight of 1000 to 10,000, and cyclic in the skeleton have a siloxane bond, the presence ratio of cyclic siloxane bond and chain siloxane bond, the absorbance of 1090～1100Cm ^-1 indicating the cyclic siloxane bond by FT-IR reflection method and the chain siloxane bond (C1) 1030~1040cm ^-1 The ratio [C1 / C2] is 1.0 to 2.0 der Ru organosilicon compound luminosity (C2) (C), and

(Wherein R1, R2 and R3 each independently represent an alkoxy group or a hydroxyl group, and at least one represents an alkoxy group)
(2) a polyether polyurethane resin (E) having a structural unit derived from a polyether polyol in the molecule;
A film-forming component (c) containing:
(3) an inhibitor component (d) having a fluoro metal complex compound (H) having at least one selected from titanium and zirconium as an essential component;
(4) an aqueous medium,
(5) Organic in the film-forming component (c) of the water-based treatment agent, which is a zinc-based plated steel sheet in which a composite film containing each component is formed by applying and drying a water-based metal surface treatment agent containing A surface-treated zinc-based plated steel sheet, wherein the solid content mass ratio [(E) / (C)] of the silicon compound (C) and the polyether polyurethane resin (E) is 0.33 to 0.90. The surface-treated zinc-based plated steel sheet according to claim 1 , wherein the polyether polyurethane resin (E) has an aromatic ring and / or an alicyclic structure having 4 to 6 carbon atoms in the molecule. The polyether polyurethane resin (E) contains an amino group in the molecule, and the ratio of the quaternary ammonium salt to the total amount of the amino group is 0.7 to 1.0 in a molar ratio. Item 3. The surface-treated galvanized steel sheet according to item 1 or 2 . The polyether polyurethane resin (E) is characterized by having a structural unit (D) represented by the following general formula [2] in the molecule, a surface treatment according to any one of claims 1 to 3 Galvanized steel sheet.

(Wherein 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, and R10 and R11 are independently of each other an alkoxyl group, an acyloxy group, a hydroxyl group and a halogen atom. (In the functional group selected from the group, m represents an integer of 1 to 5.) The film-forming component (c) further contains a cationic phenol resin (F) having a bisphenol A skeleton, and the solid content mass ratio of the polyether polyurethane resin (E) and the cationic phenol resin (F) [(F) / (E)] is 0.010 to 0.030, The surface-treated zinc-based plated steel sheet according to any one of claims 1 to 4 . The inhibitor component (d) is
(6) Phosphate compound (J)
The surface-treated galvanized steel sheet according to any one of claims 1 to 5 , further comprising: The inhibitor component (d) is
(7) Vanadium (IV) compound (K)
The surface-treated galvanized steel sheet according to claim 6 , further comprising: (8) Mass ratio of metal component (M) of Si (Si) derived from organosilicon compound (C) and fluorometal complex compound (H) having at least one selected from titanium and zirconium [(M) / (Si)] is 0.08-0.20,
(9) The solid content mass ratio [(J) / (C)] of the organosilicon compound (C) and the phosphate compound (J) is 0.02 to 0.11;
(10) The solid content mass ratio [(K) / (C)] of the organosilicon compound (C) and the vanadium (IV) compound (K) is 0.02 to 0.06.
The surface-treated zinc-based plated steel sheet according to claim 7 , wherein The metal component (M) of the fluoro metal complex compound (H) contains both titanium (M _T ) and zirconium (M _Z ), and each metal component mass ratio [(M _T ) / (M _Z )] is The surface-treated galvanized steel sheet according to any one of claims 1 to 8 , wherein the surface-treated galvanized steel sheet is 0.50 to 0.80. The surface-treated zinc-based plating according to any one of claims 1 to 9 , wherein the inhibitor component (d) further contains at least one metal component selected from Mg, Co, and W. steel sheet. The water-based metal surface treatment agent further contains a polyethylene wax (L), and the solid content mass ratio [(L) / (C)] of the organosilicon compound (C) and the polyethylene wax (L) is 0.05 to The surface-treated zinc-based plated steel sheet according to any one of claims 1 to 10 , wherein the surface-treated zinc-based steel sheet is 0.30. The aqueous metal surface treatment agent according to any one of claims 1 to 11 is applied to the surface of a galvanized steel sheet, and dried at an ultimate temperature of 50 to 250 ° C. A surface-treated galvanized steel sheet, characterized by being -5.0 g / m ² .