KR101379135B1 - Chromium-free surface-treated galvanized steel sheet - Google Patents

Abstract

Polyurethane resin (E) which contains two or more specific functional groups in a molecule, one or more specific hydrophilic functional groups, has a specific molecular weight, has a cyclic siloxane bond in a skeleton, and has a specific structural unit. An inhibitor component (d) containing a film forming component (c) containing at a specific ratio, a fluorometal complex compound (H) having at least one selected from titanium and zirconium as a non-aqueous component, and an aqueous medium The composite film containing each component is formed by apply | coating and drying the aqueous metal surface treating agent containing a. A zinc-based plated steel sheet provided with a chromium-free surface treatment having excellent detergent resistance, sweat resistance, film adhesion, adhesion, and water resistance, and also having excellent workability and sliding mobility is provided.

Description

CHROMIUM-FREE SURFACE-TREATED GALVANIZED STEEL SHEET}

INDUSTRIAL APPLICABILITY The present invention has been subjected to surface treatment with a cationic chromium-free surface treatment agent, and has excellent adhesiveness such as corrosion resistance, alkali resistance and solvent resistance, sweat resistance, film adhesion, paint adhesion and printing adhesion, moisture discoloration resistance and resistance. The present invention relates to a zinc-based plated steel sheet which has been subjected to a chromium-free surface treatment having excellent water resistance such as dew condensation and excellent workability and sliding mobility.

Generally, it is excellent in adhesiveness to the surface of a metal material and gives a corrosion resistance, fingerprint resistance, etc. to the surface of a metal material, and it chromates-processes with the processing liquid which contains chromic acid, dichromic acid, or their salt as a main component in the metal material surface. The method of performing the process, the method of performing a phosphate treatment, the method of performing an organic resin film process, etc. are known, and contribute to practical use.

Conventionally, in the chromate treatment which has been contributed to practical use, the surface of the metal material is brought into contact with a treatment solution containing chromium such as chromic acid chromate to precipitate the chromate coating or to apply the coating to dry the surface to form a chromate coating on the metal surface. The method can be mentioned. However, these inorganic chromate coatings alone have a problem that the coating is hard and receding, and thus lacks in lubricity. Thus, the coating is dropped and the appearance is not damaged, and sufficient processing cannot be performed, resulting in cracking and breaking of the material. In addition, there is a problem that damages the appearance since the traces remain even when the worker's fingerprints are smeared and cleaned during operation. Therefore, in general, in order to satisfy all the performances such as high corrosion resistance, fingerprint resistance, damage resistance, lubricity, paint adhesion, etc., a two-layer layer is formed on the surface of the metal material and a resin film is formed again on the formed chromate film. The process is performed.

As an attempt to satisfy all the performances in a single layer treatment, a resin chromate for forming a chromate and a resin film at one time is examined. Patent Document 1 describes a surface of an aluminum-zinc plated steel sheet with a specific water dispersion system or a water-soluble resin and a specific amount of 6 A treatment method for applying a resin composition containing valent chromium, and Patent Document 2 discloses a metal surface treatment containing a hexavalent chromium ion or a hexavalent chromium ion and a trivalent chromium ion of an inorganic compound and an acrylic emulsion polymerized under specific emulsion polymerization conditions. A composition is disclosed.

However, the chromate treatment has a property that the hexavalent chromium contained in the film gradually starts to dissolve and has a problem in terms of environment and safety.

As a method of using the non-chromate treatment liquid which does not have chromium, Patent document 3 is a polymer composition for surface treatment of metal materials and a surface treatment method containing a phenolic resin polymer and an acidic compound of a specific structure, and the patent document 4 is different from each other. In addition, a metal surface treatment agent and a method excellent in anti-fingerprint containing two or more kinds of silane coupling agents having a reactive functional group having a specific structure capable of reacting with each other, Patent Document 5 in the silane coupling agent of a specific structure and a phenolic resin system of a specific structure Metal surface treatment agent and treatment method containing a polymer, Metal surface treatment agent, treatment method and treatment metal containing an organic polymer such as epoxy resin, acrylic resin, urethane resin having at least one nitrogen atom and specific polyvalent anion in Patent Document 6 (1) Bisphenol A epoxy-type number of a specific structure to material, patent document 7 The antirust agent containing paper, (2) Antirust agent containing specific resin, such as phenolic resin and other polyesters at specific ratio, The processing method and processing metal material using (1) and (2) are disclosed.

However, these chromium-free technologies are excellent in corrosion resistance, cleaning resistance such as alkali resistance and solvent resistance, adhesion such as film adhesion, paint adhesion and printing adhesion, water resistance such as moisture discoloration resistance and dew condensation resistance, Both workability and sliding mobility are not very satisfactory and still have problems in practical use.

As described above, there is no surface treatment agent that can be used as a substitute for the chromate coating by any method, and development of a surface treatment agent and a treatment method that can satisfactorily satisfy these is strongly required.

[Patent Document 1]: Japanese Patent Application Laid-Open No. 4-2672 [Patent Document 2]: Japanese Patent Application Laid-Open No. 7-6070 [Patent Document 3] Japanese Patent Application Laid-open No. Hei 7-278410 [Patent Document 4] Japanese Unexamined Patent Application Publication No. Hei 8-73775 [Patent Document 5] Japanese Patent Application Laid-open No. Hei 9-241576 [Patent Document 6] Japanese Unexamined Patent Application Publication No. Hei 10-1789 Patent Document 7: Japanese Unexamined Patent Application Publication No. Hei 10-60233

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

The present inventors have diligently studied to solve these problems, and as a result, two specific functional groups in a molecule are obtained by combining two kinds of specific silane coupling agents at specific ratios and controlling their reaction by specific methods. The film-forming component which contains the above-mentioned, one or more specific hydrophilic functional group, the specific molecular weight, the organosilicon compound (C) which has a specific structure, and the water-based polyurethane resin (E) which has a specific structural unit in a specific ratio ( c) and each component by apply | coating and drying the inhibitor component (d) which makes an essential component the fluoro metal complex compound (H) which has at least 1 sort (s) chosen from titanium and zirconium, and the aqueous metal surface treating agent containing an aqueous medium. By forming a composite film containing the coating agent, detergent resistance such as corrosion resistance, alkali resistance and solvent resistance, sweat resistance, film adhesion, paint mill The present inventors have found that a chromium-free surface-treated zinc-based plated steel sheet is obtained that is excellent in adhesiveness such as adhesion and printing adhesion, water resistance such as moisture discoloration resistance and dew condensation resistance, and also excellent in workability and sliding mobility, and has completed the present invention. .

That is, in this invention, (1) the silane coupling agent (A) containing one amino group in a molecule | numerator, and the silane coupling agent (B) containing one glycidyl group in a molecule | numerator are solid content mass ratio [(A) / (B )] And two or more functional groups (a) represented by the following general formula [1] in a molecule | numerator obtained by mix | blending in the ratio of 0.50 to 0.75, and a hydroxyl group [separate from what can be contained in a functional group (a)], and an amino group. An organosilicon compound (C) containing at least one hydrophilic functional group (b) selected from the group having an average molecular weight of 1000 to 10,000 and having a cyclic siloxane bond in the skeleton;

[Formula 1]

(Wherein R 1, R 2 and R 3 independently of one another represent an alkoxy group or a hydroxyl group, and at least one represents an alkoxy group)

(2) the film-forming component (c) containing the polyether polyurethane resin (E) which has a structural unit derived from a polyether polyol in a molecule | numerator,

(3) an inhibitor component (d) having as an essential component a fluoro metal complex (H) having at least one member selected from titanium and zirconium;

(4) A zinc-based plated steel sheet in which a composite film containing each component is formed by applying and drying an aqueous metal surface treatment agent containing an aqueous medium, and further, in the film-forming component (c) of the aqueous treatment agent.

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

1030 which shows the absorbance (C1) and chain siloxane bond of 1090-1100cm <^-1> in which the ratio of cyclic siloxane bond and chain | strand siloxane bond in the said organosilicon compound (C) shows cyclic siloxane bond by FT-IR reflection method It is preferable that ratio [C1 / (C1 + C2)] of the absorbance C2 of -1040cm <^-1> is 1.0-2.0.

Moreover, it is preferable that the polyether polyurethane resin (E) of this invention has an aromatic ring and / or alicyclic structure of 4-6 carbon atoms in a molecule | numerator, and the said polyether polyurethane resin (E) contains an amino group in a molecule | numerator And it is preferable that the ratio of quaternary ammonium salt with respect to the total amount of the said amino group is 0.7-1.0 in 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.

(2)

Wherein R 9 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 R 10 and R 11 are each independently selected from the group consisting of an alkoxyl group, an acyloxy group, a hydroxyl group and a halogen atom M represents an integer of 1 to 5)

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

The inhibitor component (d) is

(6) It is preferable to further contain a phosphoric acid compound (J),

(6) It is more preferable to further contain both a phosphoric acid compound (J) and (7) a vanadium (IV) compound (K),

(8) The mass ratio of the metal component (M) of Si (Si) derived from the organosilicon compound (C) and the fluorometal complex compound (H) having at least one selected from the titanium and zirconium [(M) / ( Si)] is 0.08 to 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) It is preferable that solid content mass ratio [(K) / (C)] of the said organosilicon compound (C) and the said vanadium (IV) compound (K) is 0.02-0.06.

In addition, the metal component (M) of the fluoro metal complex (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 it is preferable that the inhibitor component (d) further contains at least one metal component selected from Mg, Co and W.

It is preferable that the said water-based metal surface treating agent further contains polyethylene wax (L), and solid content mass ratio [(L) / (C)] of the said organosilicon compound (C) and polyethylene wax (L) is 0.05-0.30. .

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

The surface-treated galvanized steel sheet of the present invention has water resistance such as corrosion resistance, cleaning resistance such as alkali resistance and solvent resistance, sweat resistance, film adhesion, paint adhesion and printing adhesion, and water resistance such as moisture discoloration resistance and dew condensation resistance. At the same time, workability and sliding mobility are also very good.

The aqueous metal surface treating agent of the chromium-free surface-treated zinc-based plated steel sheet of the present invention contains two of an organic silicon compound (C) and a polyether polyurethane resin (E) as essential components as the film forming component (c).

The organosilicon compound (C) comprises a silane coupling agent (A) containing one amino group in a molecule and a silane coupling agent (B) containing one glycidyl group in a molecule, wherein the solid content mass ratio [(A) / (B It is obtained by mix | blending in the ratio of 0.50-0.75 in the]. As a compounding ratio of a silane coupling agent (A) and a silane coupling agent (B), it is necessary to be 0.50-0.75 in solid content mass ratio [(A) / (B)], It is preferable that it is 0.50-0.65, It is 0.55-0.55 Most preferred is 0.65. If the solid content mass ratio [(A) / (B)] is less than 0.50, the hydrophobicity and the self-crosslinking property of the organosilicon compound (C) become high, and thus the treatment agent stability is markedly lowered, which is not preferable. On the contrary, when solid content mass ratio [(A) / (B)] exceeds 0.75, the hydrophilicity and cationic property of an organosilicon compound (C) will become high too much, and the water resistance and sweat resistance of the film obtained will fall remarkably, and it is unpreferable.

In addition, the organosilicon compound (C) needs to have a cyclic siloxane bond in the skeleton. If it does not have a cyclic structure containing Si in frame | skeleton, the barrier property and adhesiveness of a film-forming component (c) will become low, and all the performances, such as corrosion resistance, detergent resistance, and film adhesiveness, will fall.

Moreover, although it does not specifically limit as a silane coupling agent (A) which contains one amino group in the said molecule in this invention, 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, etc. are illustrated. As a silane coupling agent (B) which contains one glycidyl group in a molecule | numerator, 3-glycidoxy propyl trimethoxysilane, 3-glycidoxy propyl triethoxysilane, etc. can be illustrated.

In addition, the number of functional groups (a) in the said organosilicon compound (C) needs to be two or more. When the number of functional groups (a) is one, the adhesion to the surface of the zinc-based galvanized steel sheet, the self-crosslinking property of the organosilicon compound (C), and the bonding property to the polyether polyurethane resin (E) described later are reduced, and the film is sufficiently formed. Therefore, all of the effects of the present invention are not obtained. The carbon number of the alkyl group and the 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 most preferably 1 or 2 desirable.

Moreover, as an abundance ratio of the functional group (b) in the said organosilicon compound (C), it should just be one or more in 1 molecule, and it is necessary that the average molecular weight is 1000-10000, and it is preferable that it is 1300-6000. Although the molecular weight here is not specifically limited, Any of the direct measurement by a TOF-MS method and the conversion measurement by a chromatography method may be used, and a molecular weight standard is used using GFC (gel filtration chromatography). Preference is given to using ethylene glycol as the substance. If the average molecular weight calculated | required by the said method is less than 1000, since the water solubility of an organosilicon compound becomes high, the water resistance of the formed film will become remarkably low. On the other hand, when the average molecular weight exceeds 10000, it becomes difficult to dissolve or disperse the organosilicon compound (C) in water stably.

It is necessary for the organosilicon compound (C) to have a cyclic siloxane structure, and the abundance ratio thereof shows an absorbance (C1) of 1090 to 1100 cm ^-1 showing a cyclic siloxane bond by the FT-IR reflection method and a chain siloxane bond. It is most preferable that ratio [C1 / C2] of the absorbance C2 of -1040cm <^-1> is 1.0-2.0. When the ratio [C1 / C1] is 1.0 to 2.0, both the barrier due to the cyclic structure and the flexibility due to the chain structure can be provided in a balanced manner, and all performances such as corrosion resistance, detergent resistance, and film adhesion are improved. In addition, by bonding the resin molecules with the cyclic siloxane linkages, a stronger and more dense coating film is formed.

The method for producing 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 sequentially added to water adjusted to pH 4 for a predetermined time. The method of stirring is mentioned. Here, since the aqueous solution generates heat when the silane coupling agent (A) is added, the cyclic siloxane in the organosilicon compound (C) is cooled by cooling the water in advance, further cooling for a predetermined time, and producing the film in a constant temperature range. The abundance of bonds and chain siloxane bonds can be controlled.

The said polyether polyurethane resin (E) which is an essential component of this invention needs to be a polyether system. The polyester polyurethane resin is not preferable because it generates hydrolysis by an acid or an alkali, and polycarbonate polyurethane is not preferable because it is easy to form a hard and soft coating, and the adhesiveness at the time of processing and the corrosion resistance of the processed portion are inferior.

Moreover, it is preferable that the said polyether polyurethane resin (E) has an aromatic ring and / or alicyclic structure of 4-6 carbon atoms in a molecule | numerator. By having an aromatic ring or an alicyclic structure, the bond with the cyclic structure of the organosilicon compound (C) mentioned above arises, and the barrier property of a film improves. 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 the said amino group is 0.7-1.0 in molar ratio. If the ratio of the quaternary ammonium salt with respect to the total amount of the said amino group is this range, both the dispersion stability of the said polyether polyurethane resin (E), and the water resistance after film-forming can be satisfy | filled.

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. By containing a structural unit (D), since it has a reaction point and a magnetic crosslinking point with the said organosilicon compound (C), a crosslinking degree raises and corrosion resistance and detergent resistance are remarkably improved. In addition, although R9, R10, R11 in the said structural unit (D) is not specifically limited, R9 is a monovalent organic residue chosen from the group which consists of a hydrogen atom, an alkyl group, an aryl group, and an aralkyl group, R10, R11 is independent from each other. It is preferable that it is a functional group selected from the group which consists of an alkoxyl group, an acyloxy group, a hydroxyl group, and a halogen atom, It is most preferable that R9 is an alkyl group, It is most preferable that R10, R11 are hydroxyl groups. In addition, although the number (m) of the ethylene chains of a structural unit (D) is not specifically limited, It is preferable that it is 1-5, and it is most preferable that it is 2 or 3.

In addition, although the polyether polyurethane resin (E) of this invention is not specifically limited, It is a polyurethane resin which is a polycondensation product of polyether polyol and aliphatic, alicyclic, or aromatic polyisocyanate, As a part of polyol to be used, It is a polyurethane obtained by using the polyol which has a (substituted) amino group. Examples of polyether polyols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, hexamethylene glycol, and (addition of aliphatic diols) as initiators. Obtained by addition polymerization of one or more of compounds such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofran, and cyclohexylene using saccharose, methylene glycol, glycerin and the like Tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, dicyclohexyl methane diisocyanate, cyclohexylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate etc. are mentioned as polyisocyanate.

Moreover, about the compounding ratio with respect to solid content of the organosilicon compound (C) and polyether polyurethane resin (E) in the film-forming component (c) of this invention, an organosilicon compound (C) and a polyether polyurethane resin Solid content mass ratio [(E) / (C)] of (E) needs to be 0.33-0.90, It is more preferable that it is 0.33-0.80, It is most preferable that it is 0.35-0.70. If the solid content mass ratio [(E) / (C)] is less than 0.33, the barrier property of the film-forming component (c) is lowered. If the solid content mass ratio [(E) / (C)] is less than 0.33, it is not preferable. It is not preferable because the adhesiveness is markedly lowered and the overall performance is degraded.

Moreover, it is preferable to contain cationic phenol resin (F) which has bisphenol A frame | skeleton in the film forming component (c) of this invention from the point of improving corrosion resistance and solvent resistance. About the compounding ratio with respect to solid content of the said polyether polyurethane resin (E) and said cationic phenol resin (F), the solid content mass ratio of a polyether polyurethane resin (E) and a cationic phenol resin (F) [(F ) / (E)] needs to 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 effect of addition of the cationic phenolic resin (F) is not exhibited and corrosion resistance and solvent resistance are deteriorated, and if it exceeds 0.030, the film is cationic phenolic resin. It is not preferable because it is colored slightly pale yellow, and significant yellowing occurs in a high humidity environment or an ultraviolet exposure environment.

The aqueous metal surface treating agent of the chromium-free surface-treated galvanized steel sheet of the present invention may contain, as an essential component, a fluoro metal complex (H) having at least one selected from titanium and zirconium as an inhibitor component (d). There is a need.

Although it does not specifically limit as a fluoro metal complex compound (H) which has at least 1 sort (s) chosen from the said titanium and zirconium, Titanium hydrofluoric acid, a zirconic hydrofluoric acid, ammonium salt, alkali metal salt, etc. can be illustrated.

Regarding the blending 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, the organosilicon compound (C) Mass ratio [(Si) / (M)] of the metal component (M) of Si (Si) derived from the above) and the fluorometal complex compound (H) having at least one selected from the titanium and zirconium is 0.08 to 0.20. It is preferable, it is more preferable that it is 0.12-0.20, and it is most preferable that it is 0.14-0.18. If the mass ratio [(Si) / (M)] of the said metal component (M) is less than 0.08, since the production amount of the oxide film formed from the said metal component at the time of film formation becomes small, and corrosion resistance becomes low, it is unpreferable and 0.20 When exceeding, since the raw material surface coverage of the oxide film formed from the said metal component becomes high, and the reaction point with the raw material of the said organosilicon compound (C) decreases, the effect of providing adhesion by the organosilicon compound (C) becomes small, It is not preferable because the overall effect of the present invention is lowered.

In addition, it is preferable that the metal component (M) of the fluorometal complex compound (H) contains both titanium (M _T ) and zirconium (M _Z ) in view of achieving 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 most preferably 0.60 to 0.70. If the metal component mass ratio [(M _T ) / (M _Z )] is less than 0.50, the oxide film of titanium decreases, and the existence ratio of the relatively hard zirconium oxide becomes high, so that the film withdraws from deformation due to plastic deformation of the material. It is not preferable because a film defect occurs and corrosion resistance is lowered. On the contrary, if it exceeds 0.80, the abundance ratio of the titanium oxide film having a relatively low alkali resistance is high. Not desirable

In addition, the inhibitor component (d) of the present invention preferably further contains a phosphate compound (J) in order to improve corrosion resistance, and further contains both a phosphate compound (J) and a vanadium (IV) compound (K). It is more preferable to contain. 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, the elution of phosphoric acid can be controlled according to the kind of salt of the phosphoric acid compound (J), and the corrosion resistance holding time can be lengthened. Among them, phosphoric acid or magnesium phosphate is preferable because a larger corrosion resistance improvement effect is obtained, and it is more preferable to use phosphoric acid and magnesium phosphate together.

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 such as alkali resistance and corrosion resistance, which are the effect of adding the phosphate compound (J), are not exhibited. It is not preferable because it is lowered.

The vanadium (IV) compound (K) is not particularly limited but may be vanadium pentoxide [V ₂ O ₅ ], metavanadate [HVO ₃ ], ammonium metavanadate [NH ₄ VO ₃ ], metavanadine Reduction of vanadium (V) of compounds such as sodium acid [NaVO ₃ ] and oxytrivalent vanadium chloride [VOCl ₃ ] to vanadium (IV) using reducing agents such as alcohols and organic acids, vanadium dioxide [VO _2] ], vanadium oxy-acetylacetonate _{[VO (C 5 H 7 O} 2) 2], oxysulfate vanadium [VOSO _4] (ⅳ) vanadium, such as containing compound, vanadium acetylacetonate _{[V (C 5 H 7 O} 2) ₃ ], vanadium (III) of compounds such as vanadium trioxide [V ₂ O ₃ ], vanadium trichloride [VCl ₃ ], and the like, oxidized to vanadium (IV) with an optional 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. If the solid content mass ratio [(K) / (C)] is less than 0.020, the inhibitor effect due to the vanadium (IV) compound (K) is not obtained. If the solid content mass ratio [(K) / (C)] is less than 0.020, it is not preferable. It is not preferable because the coating compound tends to be colored yellow in high humidity due to a complex with an organic substance contained in the coating.

It is preferable to contain polyethylene wax (L) in the water-based metal surface treatment agent of the present invention in terms of improving processability and sliding mobility. Regarding the blending ratio of the polyethylene wax (L), the mass ratio [(L) / (C)] between the organosilicon compound (C) and the solid content of the polyethylene wax (L) needs to be 0.05 to 0.30, and 0.07 to It is preferable that it is 0.30, and it is most preferable that it is 0.10 to 0.25. If the mass ratio [(L) / (C)] is less than 0.05, sufficient lubricity is not expressed, and if it is more than 0.30, the continuity of the film is inhibited by the polyethylene wax and the film is easily broken, and the corrosion resistance is lowered. Not preferred.

It is preferable that the surface treatment metal material of this invention apply | coats the said water-based metal surface treatment agent, performs drying at the reaching temperature of 50-250 degreeC, and it is preferable that the film weight after drying is 0.2-5.0 g / m <2>. About drying temperature, it is preferable that reached temperature is 50 degreeC-250 degreeC, It is more preferable that it is 70 degreeC-150 degreeC, It is most preferable that it is 100 degreeC-140 degreeC. If the achieved temperature is less than 50 ° C, the solvent of the aqueous metal surface treating agent is not completely volatilized, which is not preferable. On the contrary, when it exceeds 250 degreeC, since the part of the organic chain of the film formed with the said water-based metal surface treatment agent decomposes, it is unpreferable. 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, and thus corrosion resistance is remarkably lowered, which is not preferable. On the contrary, when it exceeds 5.0 g / m <2>, since film adhesiveness falls, it is not preferable.

The aqueous metal surface treatment agent used for this invention can use the leveling agent, water-soluble solvent, a metal stabilizer, an etching inhibitor, etc. for improving coating property, in the range which does not impair the effect of this invention. Examples of the leveling agent include nonionic or cationic surfactants, and polyethylene oxide or polypropylene oxide adducts, acetylene glycol compounds, and the like, and water-soluble solvents include alcohols such as ethanol, isopropyl alcohol, t-butyl alcohol, and propylene glycol. And 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 etch inhibitor include amine compounds such as ethylenediamine, triethylenepentamine, guanidine, and pilimidine. In particular, what has two or more amino groups in 1 molecule is effective also as a metal stabilizer, and it is more preferable.

The surface-treated galvanized steel sheet of the present invention is excellent in water resistance such as corrosion resistance, detergent resistance such as alkali resistance and solvent resistance, coating adhesion, paint adhesion and printing adhesion, and water resistance such as moisture discoloration resistance and dew condensation resistance. Processability and sliding mobility are also excellent. This reason is estimated as follows, but the present invention is not bound by such a guess.

The film formed using the water-based metal surface treatment agent used for this invention contains an organosilicon compound (C) and a polyether polyurethane resin (E) as a film forming component. First, corrosion resistance is such that when a part of the organosilicon compound is concentrated by drying or the like, the organosilicon compounds react with each other to form a continuous film, and -OR groups formed by hydrolysis of a part of the organosilicon compound and the metal surface By forming Si-OM bond (M: metal element on the to-be-coated surface), it is estimated that it is because it exhibits a remarkable barrier effect. In addition, various effects are 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. However, if the siloxane bond is annular, the film of the three-dimensional siloxane bond upon drying It forms, and since the resistance to invasion of oxygen, moisture, etc. increases, it exhibits very excellent barrier property. However, the cyclic siloxane bond has no deformation freedom due to skeletal reasons, resulting in a hard but soft coating. On the other hand, the chain siloxane bond does not form a three-dimensional structure such as a cyclic siloxane bond, and thus has a low barrier property as compared with the cyclic siloxane bond, but has a high degree of deformation freedom. By coexisting these siloxane bonds of a different property in a fixed ratio, the film excellent in barrier property or adhesiveness can be formed. In the case of a polyether polyurethane resin having a structural unit (D) having a polyetherurethane resin bonded to the film formation and having a reactivity with the organosilicon compound, the organosilicon compound and the polyether polyurethane resin are bonded to Very high barrier property. In addition, the cationic phenol resin (F) is a compound having a resonance stabilizing structure, and the film containing the cationic phenol resin (F) is close enough to overlap with the outer track of the material metal by reacting and fixing with the metal surface. The surface potential is kept uniform by providing delocalized electrons generated by corrosion by using the? orbit, thereby providing excellent corrosion resistance.

On the other hand, the effect of the inhibitor component (d) has the effect of removing the oxide film by etching the material surface, precipitation and film formation by the pH rise accompanying etching, formation of a poorly soluble salt with metal ions due to the eluted material, Alleviation of the pH rise accompanying the corrosion of the film, uniformity of the surface potential, and the like. The fluorometal complex compound having at least one selected from titanium and zirconium has the effect of removing the oxide film by etching the material surface, and at the same time, dissociates fluorine and precipitates it as an oxide or hydroxide by the pH rise accompanying it. It is presumed to provide corrosion resistance by forming a film. Moreover, it has the effect of forming metal ion and poorly soluble salt which originate in the raw material eluted by corrosion, and slowing progress of corrosion. On the other hand, the phosphoric acid compound has an effect of alleviating pH increase accompanying material corrosion, and particularly has an effect as an elutable inhibitor. The vanadium compound is presumed to have an effect of consuming electrons generated by corrosion by redox reaction of vanadium and suppressing the progress of corrosion. By expressing the adhesiveness and barrier property resulting from the inhibitor component which has such an effect, and the above-mentioned film formation component in a balanced manner, the adhesiveness, moisture resistance, such as corrosion resistance, alkali resistance, and solvent resistance, film adhesiveness, paint adhesiveness, printing adhesiveness, etc. It is inferred that it is possible to form a film which is excellent in water resistance, such as discoloration resistance and dew condensation resistance, and very excellent in workability and sliding mobility.

<Examples>

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

Trial

(1) Test material

Commercially available materials shown below were used.

Electro galvanized steel sheet (EG): plate thickness = 0.8 mm, coating amount = 20/20 (g / ㎡)

Hot dip galvanized steel sheet (GI): plate thickness = 0.8 mm, coating amount = 90/90 (g / ㎡)

Alloyed hot dip galvanized steel sheet (GA): plate thickness = 0.8 mm, coating amount = 90/90 (g / ㎡)

Molten zinc-11% aluminum-3% magnesium-0.2% silicon plated steel sheet (SD): plate thickness = 0.8 mm, coating amount = 60/60 (g / ㎡)

(2) Degreasing treatment

The material was sprayed for 2 minutes under conditions of a concentration of 20 g / L and a temperature of 60 ° C. using a fine cleaner 4336 (registered trademark: Nippon Parka Co., Ltd.) of silicate-based alkali degreasing agent, and washed with pure water for 30 seconds. After drying, the test plates were dried.

The silane coupling agents used in Examples and Comparative Examples are shown in Table 1, urethane resins in Table 2, phosphoric acid compounds in Table 3, vanadium compounds in Table 4, polyethylene wax in Table 5, and the formulation examples, the amount of the coating and The drying temperature is shown in Table 6.

[Adjustment Method of Organic Silicon Compound (C)]

By the combination and compounding ratio shown in Table 6, the silane coupling agent shown in Table 1 was made to react in ethanol, it mixed with the water adjusted to pH4-4.5 with acetic acid, and it adjusted so that solid content might be 20%. The absorbance (C1) and chain siloxane bond of 1090-1100cm <^-1> which show the molecular weight per functional group (a) of the organosilicon compound obtained in this way, the molecular weight per hydrophilic group (b), and cyclic siloxane bond by FT-IR reflection method Table 6 shows the ratio [C1 / C2] of the absorbance (C2) of 1030-1040 cm < ^-1 >.

[Synthesis method of urethane resin (E1)]

Polyether polyol (synthetic component: tetramethylene glycol and ethylene glycol, molecular weight 1500): 150 parts by mass, trimethylolpropane: 6 parts by mass, N-methyl-N, N-diethanol amine: 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 allowed to react for 1 hour while maintaining at 70 ° C to 75 ° C to generate a urethane prepolymer. Then, 10 mass parts of 3 aminopropyl trimethoxysilanes were added, it was made to react for 1 hour, keeping at 80 degreeC-85 degreeC, and structural unit (D1) was formed. Subsequently, 15 mass parts of dimethyl sulfuric acid was put into the said reaction container, and it reacted at 50-60 degreeC for 30 to 60 minutes, and produced the cationic urethane prepolymer. Subsequently, 576 mass parts of water was put into the said reaction container, the mixture was emulsified uniformly, methyl ethyl ketone and the remaining 3 aminopropyl trimethoxysilane were collect | recovered, and water-soluble cationic urethane resin was obtained. Si content with respect to resin solid content was 0.5 mass%.

[Synthesis method of urethane resin (E2)]

Polyether polyol (synthetic component: tetramethylene glycol and ethylene glycol, molecular weight 1500): 150 parts by mass, trimethylolpropane: 6 parts by mass, N-methyl-N, N-diethanol amine: 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 allowed to react for 1 hour while maintaining at 70 ° C to 75 ° C to generate a urethane prepolymer. Subsequently, 15 mass parts of dimethyl sulfuric acid was put into the said reaction container, and it reacted at 50-60 degreeC for 30 to 60 minutes, and produced the cationic urethane prepolymer. Subsequently, 576 mass parts of water were put into the said reaction container, the mixture was emulsified uniformly, methyl ethyl ketone was collect | recovered, and water-soluble cationic urethane resin was obtained.

[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-diethanol amine: 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 allowed to react for 1 hour while maintaining at 70 ° C to 75 ° C to produce a urethane prepolymer. Subsequently, 15 mass parts of dimethyl sulfuric acid was put into the said reaction container, and it reacted at 50-60 degreeC for 30 to 60 minutes, and produced the cationic urethane prepolymer. Subsequently, 576 mass parts of water was put into the said reaction container, the mixture was emulsified uniformly, methyl ethyl ketone and the remaining 3 aminopropyl trimethoxysilane were collect | recovered, and water-soluble cationic urethane resin was obtained.

[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-diethanol amine: 24 parts by mass, isophorone di Isocyanate: 94 mass parts and 135 mass parts of methyl ethyl ketones were put into the reaction container, and it reacted for 1 hour, keeping at 70 degreeC-75 degreeC, and produced the urethane prepolymer. Subsequently, 15 mass parts of dimethyl sulfuric acid was put into the said reaction container, and it reacted at 50-60 degreeC for 30 to 60 minutes, and produced the cationic urethane prepolymer. Subsequently, 576 mass parts of water was put into the said reaction container, the mixture was emulsified uniformly, methyl ethyl ketone and the remaining 3 aminopropyl trimethoxysilane were collect | recovered, and water-soluble cationic urethane resin was obtained.

[Synthesis method of urethane resin (E5)]

Polyether polyol (synthetic component: tetramethylene glycol and 1, 4-cyclohexane-dimethanol, molecular weight 1500): 150 parts by mass, trimethylolpropane: 6 parts by mass, N-methyl-N, N-diethanol amine: 24 Mass part, isophorone diisocyanate: 94 mass part, and 135 mass part of methyl ethyl ketone were put into the reaction container, it was made to react for 1 hour, keeping at 70 degreeC-75 degreeC, and the urethane prepolymer was produced. Then, 10 mass parts of 3 aminopropyl trimethoxysilanes were added, it was made to react for 1 hour, keeping at 80 degreeC-85 degreeC, and structural unit (D1) was formed. Subsequently, 15 mass parts of dimethyl sulfuric acid was put into the said reaction container, and it reacted at 50-60 degreeC for 30 to 60 minutes, and produced the cationic urethane prepolymer. Subsequently, 576 mass parts of water was put into the said reaction container, the mixture was emulsified uniformly, methyl ethyl ketone and the remaining 3 aminopropyl trimethoxysilane were collect | recovered, and water-soluble cationic urethane resin was obtained. Si content with respect to resin solid content was 0.5 mass%.

[Synthesis method of urethane resin (E6)]

Polyether polyol (synthetic component: PO 2 mole adduct of tetramethylene glycol and bisphenol A, molecular weight 1500): 150 parts by mass, trimethylol propane: 6 parts by mass, N-methyl-N, N-diethanol amine: 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 allowed to react for 1 hour while maintaining at 70 ° C to 75 ° C to produce a urethane prepolymer. Then, 10 mass parts of 3 aminopropyl trimethoxysilanes were added, and it was made to react for 1 hour, keeping at 80 degreeC-85 degreeC, and structural unit (D1) was formed. Subsequently, 15 mass parts of dimethyl sulfuric acid was put into the said reaction container, and it reacted at 50-60 degreeC for 30 to 60 minutes, and produced the cationic urethane prepolymer. Subsequently, 576 mass parts of water was put into the said reaction container, the mixture was emulsified uniformly, methyl ethyl ketone and the remaining 3 aminopropyl trimethoxysilane were collect | recovered, and water-soluble cationic urethane resin was obtained. Si content with respect to resin solid content was 0.5 mass%.

[Synthesis method of urethane resin (E7)]

Polyether polyol (synthetic component: tetramethylene glycol and 1, 4-cyclohexane-dimethanol, molecular weight 1500): 150 parts by mass, trimethylol propane: 6 parts by mass, N-methyl-N, N-diethanol amine: 24 Mass part, isophorone diisocyanate: 94 mass part, and 135 mass part of methyl ethyl ketone were put into a reaction container, and it reacted for 1 hour, keeping at 70 degreeC-75 degreeC, and produced the urethane prepolymer. Subsequently, 15 mass parts of dimethyl sulfuric acid was put into the said reaction container, and it reacted at 50-60 degreeC for 30 to 60 minutes, and produced the cationic urethane prepolymer. Subsequently, 576 mass parts of water were put into the said reaction container, the mixture was emulsified uniformly, methyl ethyl ketone was collect | recovered, and water-soluble cationic urethane resin was obtained.

[Synthesis method of urethane resin (E8)]

Polyether polyol (synthetic component: PO2 mole adduct of tetramethylene glycol and bisphenol A, molecular weight 1500): 150 parts by mass, trimethylolpropane: 6 parts by mass, N-methyl-N, N-diethanol amine: 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 allowed to react for 1 hour while maintaining at 70 ° C to 75 ° C to produce a urethane prepolymer. Subsequently, 15 mass parts of dimethyl sulfuric acid was put into the said reaction container, and it reacted at 50-60 degreeC for 30 to 60 minutes, and produced the cationic urethane prepolymer. Subsequently, 576 mass parts of water were put into the said reaction container, the mixture was emulsified uniformly, methyl ethyl ketone was collect | recovered, and water-soluble cationic urethane resin was obtained.

[Synthesis method of urethane resin (E9)]

Polyether polyol (synthetic component: tetramethylene glycol and 1, 4-cyclohexane-dimethanol, molecular weight 1500): 150 parts by mass, trimethylol propane: 6 parts by mass, N-methyl-N, N-diethanol amine: 24 Mass part, isophorone diisocyanate: 94 mass part, and 135 mass part of methyl ethyl ketone were put into a reaction container, and it reacted for 1 hour, keeping at 70 degreeC-75 degreeC, and produced the urethane prepolymer. Subsequently, 13 mass parts of dimethyl sulfuric acid was put into the said reaction container, and it reacted at 50-60 degreeC for 30 to 60 minutes, and produced the cationic urethane prepolymer. Subsequently, 576 mass parts of water were put into the said reaction container, the mixture was emulsified uniformly, methyl ethyl ketone was collect | recovered, and water-soluble cationic urethane resin was obtained.

[Synthesis method of urethane resin (E10)]

Polyether polyol (synthetic component: tetramethylene glycol and 1, 4-cyclohexane-dimethanol, molecular weight 1500): 150 parts by mass, trimethylol propane: 6 parts by mass, N-methyl-N, N-diethanol amine: 24 Mass part, isophorone diisocyanate: 94 mass part, and 135 mass part of methyl ethyl ketone were put into the reaction container, it was made to react for 1 hour, keeping at 70 degreeC-75 degreeC, and the urethane prepolymer was produced. Subsequently, 20 mass parts of dimethyl sulfuric acid was put into the said reaction container, and it reacted at 50-60 degreeC for 30 to 60 minutes, and produced the cationic urethane prepolymer. Subsequently, 576 mass parts of water were put into the said reaction container, the mixture was emulsified uniformly, methyl ethyl ketone was collect | recovered, and water-soluble cationic urethane resin was obtained.

[Synthesis method of urethane resin (E11)]

Polyether polyol (synthetic component: tetramethylene glycol and 1, 4-cyclohexane-dimethanol, molecular weight 1500): 150 parts by mass, trimethylol propane: 6 parts by mass, N-methyl-N, N-diethanol amine: 24 Mass part, isophorone diisocyanate: 94 mass part, and 135 mass part of methyl ethyl ketone were put into the reaction container, it was made to react for 1 hour, keeping at 70 degreeC-75 degreeC, and the urethane prepolymer was produced. Subsequently, 576 mass parts of water and 30 mass parts of acetic acid were put into the said reaction container, the mixture was emulsified uniformly, methyl ethyl ketone was collect | recovered, and water-soluble cationic urethane resin was obtained.

[Synthesis method of urethane resin (E12)]

Polyether polyol (synthetic component: tetramethylene glycol and 1, 4-cyclohexane-dimethanol, molecular weight 1500): 150 parts by mass, trimethylol propane: 6 parts by mass, isophorone diisocyanate: 94 parts by mass and methyl ethyl ketone 135 The mass part was put into the reaction container, and it reacted for 1 hour, keeping at 70 degreeC-75 degreeC, and produced the urethane prepolymer. Subsequently, 576 mass parts of water were put into the said reaction container, the mixture was emulsified uniformly using the nonionic emulsifier, methyl ethyl ketone was collect | recovered, and water-soluble urethane resin was obtained.

[Method of measuring molecular weight]

The molecular weight was measured using gel filtration chromatography at a column temperature of 40 ° C. to dilute the component concentration to 5% by weight to obtain the molecular weight of the organosilicon compound (C). Moreover, it was set as conversion into polyethyleneglycol (molecular weight: 600-12000).

[FT-IR]

The FT-IR device was equipped with an infrared total reflection absorption spectrum device. In addition, the measurement was performed by the temperature range of 650-4000 cm <^-1> , resolution 4cm <^-1> , 16 times of integration times, and 25 degreeC. In this way a base line method from the infrared absorption spectrum thus obtained (900㎝ ^-1, 1200㎝ ^-1), representing the cyclic siloxane bond represents the absorbance (C1) and the chain siloxane bond 1090 to 1100㎝ ^-1 1030 to 1040㎝ by The absorbance (C2) of ^-1 was obtained.

Surface Treatment Stability

The chemical | medical agent after a pharmaceutical was put in the airtight container, and the chemical stability at 40 degreeC was observed.

◎ = No change in liquid phase for 3 months

○ No change in liquid phase for 1 month

Viscosity increase or precipitation occurs within △ = 1 month

Increase viscosity or settle within 1 week

[Evaluation test]

Corrosion resistance

The salt spray test by JIS-Z-2371 was performed for 240 hours, and the white-rust generation condition was observed.

<Evaluation Criteria>

◎ = Rust is less than 3% of the total area

○ = Rust generation is more than 3% and less than 10% of the total area

△ = Rust generation is more than 10% and less than 30% of the total area

× = Rust is more than 30% of the total area

Degreasing resistance

After film formation, using a silicate-based alkali degreasing agent, Percline N364S (registered trademark: Nippon Parkerizing Co., Ltd.), spray treatment was performed at a concentration of 20 g / L and a temperature of 60 ° C. for 2 minutes, and JIS-Z-2371 The salt spray test by was carried out for 240 hours, and the white rust generation condition was observed.

<Evaluation Criteria>

◎ = Rust is less than 3% of the total area

○ = Rust generation is more than 3% and less than 10% of the total area

△ = Rust generation is more than 10% and less than 30% of the total area

× = Rust is more than 30% of the total area

Sweat resistance

After film formation, after 1 drop of artificial perspiration (JIS-L-0848D method) was dripped, it left still at 65 degreeC 93% RH for 48 hours, and evaluated by the following reference | standard.

<Evaluation Criteria>

◎ = No appearance change

○ = No change in appearance

△ = Area of less than 30% of loading drops

× = area of more than 30% of loading drops

Solvent resistance

MEK (methyl ethyl ketone) was immersed in the gauze, and the trace which rubbed five reciprocations with the load of 500 g was evaluated by the L value increase and decrease before and behind a test.

<Evaluation Criteria>

◎ = △ L is less than 0.5

○ = △ L is more than 0.5 and less than 1.0

△ = △ L is 1.0 or more and less than 2.0

× = △ L is 2.0 or more

Film adhesion

The part cut | disconnected by the 1 mm checker eye was extruded by 7 mm with the Eriksen tester, and tape peeled, and evaluation of adhesiveness was performed by the remaining number ratio (number remaining / number of cuts: 100 pieces).

<Evaluation Criteria>

◎ = 100%

○ = less than 20% more than 95%

△ = 90% or more, less than 95%

× = less than 90%

Paint adhesion

The melamine alkyd paint was applied with a bar coat, bonded at 120 ° C. for 20 minutes, and cut with a 1 mm checkerboard eye, and evaluation of adhesion was performed at the remaining number ratio (number of remaining / cut: 100 pieces).

<Evaluation Criteria>

◎ = 100%

○ = 95% or more

△ = 90% or more, less than 95%

× = less than 90%

Print adhesion

The screen printing ink was beta-printed, bonded at 120 ° C. for 20 minutes, cut with a 1 mm checkerboard eye, and the adhesiveness was evaluated at the remaining number ratio (number remaining / number of cuts: 100).

<Evaluation Criteria>

◎ = 100%

○ = 95% or more

△ = 90% or more, less than 95%

× = less than 90%

Moisture resistance discoloration

It left still for 72 hours in the high temperature, high humidity environment of 65 degreeC of temperature, and 95% of humidity, and evaluated by the color tone change (DELTA) E before and behind a test.

◎ = △ 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

Frost resistance

1 cc of pure water was dripped at the test piece which stood still in the environment of the temperature of 25 degreeC, and 60% of humidity, and it evaluated by the color tone change (DELTA) E before and behind the test when it is made to dry naturally.

◎ = △ 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

Using a blank plate of 115 mm diameter, a high speed cylindrical deep drawing test was conducted under the conditions of punch diameter = 50 mm, blank holder pressure 1 Ton, deep drawing speed 30 m / min, and no coating.

<Evaluation Criteria>

◎ = limit limit ratio is more than 2.50

○ = limit throttle ratio more than 2.40 less than 2.50

△ = limit throttle ratio is more than 2.30 and less than 2.40

× = limit throttle ratio less than 2.30

[Result of evaluation examination]

From the evaluation results of the first to fourth examples and the first and second comparative examples, when the silane coupling agents (A) and (B) used for the organosilicon compound (C) deviate from the claims, that is, the silane coupling agent When there is too much (B), a film will become hard on molecular structure, and film adhesiveness will fall and performance will fall in all the evaluation items. On the contrary, when there are too many silane coupling agents (A), it is inferior to dew condensation resistance and moisture discoloration resistance because of the provision of excess hydrophilicity by an amino group, or the coloring structure by an amino group. On the contrary, if it is a suitable range within a claim, it turns out that all the performances are satisfied.

From the second, fifth to seventh examples, and the third to fifth comparative examples, when there is only one functional group (a), the same effect as that of the general silane coupling agent other than the organosilicon compound (C) of the present invention Since only one is obtained, all performance is significantly reduced.

From the evaluation results of the second, eighth to ninth examples and the fifth to sixth comparative examples, when the molecular weight per functional group (B) is 500, the coating component is easily solubilized, so that the degreasing resistance, solvent resistance, dew condensation, and moisture discoloration It is inferior in property, and when it exceeds 15000, film-forming property is inferior and film adhesiveness falls, and overall performance falls.

From the tenth to fifteenth examples and the seventh comparative example, when the cyclic siloxane bonds are not provided, the corrosion resistance and the wettability are inferior. However, when the cyclic siloxane bonds are contained in a suitable range, they are very excellent in all evaluation items. It can be seen that having.

From the evaluation results of the fourth example and the eighth to ninth comparative examples, when the urethane resin (E) does not have an ether structure, it is easy to hydrolyze if the urethane resin (E) is an ester type, and thus degreasing resistance, wetting resistance, and dew condensation resistance are poor. Since carbonate system is too strong rigidity, film adhesiveness and workability are inferior.

From the evaluation results of the thirteenth, sixteenth to nineteenth examples and the tenth to eleventh comparative examples, when the ratio of the organosilicon compound (C) and the urethane resin (E) is outside the claims, that is, when the urethane resin is small It is found that the barrier property of the film forming component (c) is lowered, so that the corrosion resistance and wettability are inferior. On the contrary, when the urethane resin is large, the adhesion to the material is significantly lowered, so that the film adhesion and the paint adhesion are inferior.

From the evaluation results of the twentieth to twenty-first examples and the twelfth to nineteenth comparative examples, when Ti or Zr fluorometal complex compound (H) was not contained as an inhibitor component, corrosion resistance and wettability were very poor. The performance deterioration is equivalent even if a phosphoric acid compound (J) or a vanadium (IV) compound is added, and the effect of the fluoro metal complex of Ti or Zr as an inhibitor component can be seen.

From the evaluation results of the twenty-second to twenty-ninth examples and the twentieth to twenty-first comparative examples, the urethane resin having a suitable structure with respect to the skeleton of the urethane resin is excellent in overall performance, and in particular, the structural unit (D1) If contained, the performance is very good. On the other hand, when the quaternary ammonium salt content in all the amino groups is 0, and also when it does not have an amino group, processing agent stability falls, and especially when it does not have an amino group, it turns out that overall performance falls because of lack of processing agent stability.

From the evaluation results of Examples 30 to 90, the content of the phenol resin, the kind and content of the fluorometal complex compound, the kind and content of the phosphate compound, the kind and content of the vanadium compound (K), and the kind and content of the polyethylene wax By adjusting to an appropriate range, it turns out that it has the performance of the practical use level in the whole evaluation item. Similarly, for W, Co, and Mg, it was found that there is an effect of improving corrosion resistance without breaking the balance held in the overall evaluation items. These performances can be achieved if drying is performed at an attainment temperature of 50 to 250 ° C and the coating weight after drying is 0.2 to 5.0 g / m 2, particularly, the reaching temperature is 100 to 200 ° C. and the coating amount is 1.2 to 1.5 g / m 2. It has become clear that it has very good performance.

From the above evaluation results, by coating and drying the water-based metal surface treatment agent of the present invention to form a composite film containing each component, the detergent resistance such as corrosion resistance, alkali resistance and solvent resistance, sweat resistance, film adhesion, paint adhesion and printing It can be seen that a chromium-free surface-treated galvanized steel sheet is obtained that is excellent in adhesion such as adhesion, water resistance such as moisture discoloration resistance, dew condensation resistance, and also excellent in workability and sliding mobility.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6-1]

[Table 6-2]

[Table 6-3]

[Table 6-4]

[Table 7-1]

[Table 7-2]

[Table 7-3]

Table 7-4

[Table 8-1]

[Table 8-2]

[Table 8-3]

Table 8-4

[Table 9-1]

[Table 9-2]

Table 9-3

Table 9-4

[Table 10-1]

[Table 10-2]

Table 10-3

Table 10-4

Claims (17)

(1) The silane coupling agent (A) containing one amino group in a molecule and the silane coupling agent (B) containing one glycidyl group in a molecule are 0.50 to a solid content mass ratio [(A) / (B)]. At least 1 selected from two or more functional groups (a) represented by the following general formula [1] in a molecule | numerator obtained by mix | blending in the ratio of 0.75 from a hydroxyl group (separate from what can be contained in a functional group (a)), and an amino group. It contains one or more hydrophilic functional groups (b) of a species, the average molecular weight is 1000-10000, and has cyclic siloxane bond in a skeleton,
Absorption (C2) of 1030 to 1040 cm ^-1 indicating an absorbance (C1) of 1090 to 1100 cm ^-1 representing a cyclic siloxane bond by the FT-IR reflection method and a siloxane bond and a chain siloxane bond. Organosilicon compound (C) having a ratio [C1 / C2] of 1.0 to 2.0,
[Chemical Formula 1]

(Wherein R 1, R 2 and R 3 independently of one another represent an alkoxy group or a hydroxyl group, and at least one represents an alkoxy group)
(2) the film-forming component (c) containing the polyether polyurethane resin (E) which has a structural unit derived from a polyether polyol in a molecule | numerator,
(3) an inhibitor component (d) having as an essential component a fluoro metal complex (H) having at least one member selected from titanium and zirconium;
(4) A zinc-based plated steel sheet in which a composite film containing each component is formed by coating and drying an aqueous metal surface treatment agent containing an aqueous medium, and further, in the film forming component (c) of the aqueous treatment agent.
(5) The surface treatment zinc-based galvanized steel sheet, wherein the solid content mass ratio [(E) / (C)] of the organosilicon compound (C) and the polyether polyurethane resin (E) is 0.33 to 0.90. The polyether polyurethane resin (E) has an aromatic ring, an alicyclic structure having 4 to 6 carbon atoms, or an aromatic ring and an alicyclic structure having 4 to 6 carbon atoms, according to claim 1, Surface Treatment Galvanized Steel Sheet. The surface treatment zinc system according to claim 1, wherein the polyether polyurethane resin (E) contains an amino group in a molecule, and the ratio of the quaternary ammonium salt to the total amount of the amino group is 0.7 to 1.0 in molar ratio. Plated steel plate. The surface-treated galvanized steel sheet according to claim 1, wherein the polyether polyurethane resin (E) has a structural unit (D) represented by the following General Formula [2] in a molecule.
(2)

Wherein R 9 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 R 10 and R 11 are each independently selected from the group consisting of an alkoxyl group, an acyloxy group, a hydroxyl group and a halogen atom M represents an integer of 1 to 5) The surface-treated galvanized steel sheet according to claim 3, wherein the polyether polyurethane resin (E) has a structural unit (D) represented by the following General Formula [2] in a molecule.
(2)

Wherein R 9 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 R 10 and R 11 are each independently selected from the group consisting of an alkoxyl group, an acyloxy group, a hydroxyl group and a halogen atom M represents an integer of 1 to 5) 2. The solid content mass ratio of the polyether polyurethane resin (E) and the cationic phenol resin (F) according to claim 1, further comprising a cationic phenol resin (F) having a bisphenol A skeleton in the film forming component (c). [(F) / (E)] is 0.010 to 0.030, The surface-treated galvanized steel sheet. 6. The solid content mass ratio of the polyether polyurethane resin (E) and the cationic phenol resin (F) according to claim 5, further comprising a cationic phenol resin (F) having a bisphenol A skeleton in the film forming component (c). [(F) / (E)] is 0.010 to 0.030, The surface-treated galvanized steel sheet. The method according to claim 1, wherein the inhibitor component (d) is
(6) A surface-treated galvanized steel sheet, further comprising a phosphoric acid compound (J). The method according to claim 8, wherein the inhibitor component (d) is
(7) The surface-treated galvanized steel sheet further comprising vanadium (IV) compound (K). The mass ratio of the metal component (M) of (9) Si (Si) derived from the said organosilicon compound (C), and the fluoro metal complex (H) which has at least 1 sort (s) chosen from the said titanium and zirconium. [(M) / (Si)] is 0.08 to 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 surface-treated galvanized steel sheet according to claim 1, wherein solid mass ratio [(K) / (C)] of the organosilicon compound (C) and the vanadium (IV) compound (K) is 0.02 to 0.06. The metal component (M) of the fluorometal complex (H) contains both titanium (M _T ) and zirconium (M _Z ), and each metal component mass ratio [(M _T ) / ( M _Z )] is 0.50 to 0.80, The surface-treated galvanized steel sheet. The metal component (M) of the fluoro metal complex (H) contains both titanium (M _T ) and zirconium (M _Z ), and each metal component mass ratio [(M _T ) / ( M _Z )] is 0.50 to 0.80, The surface-treated galvanized steel sheet. The surface-treated galvanized steel sheet according to claim 1, wherein the inhibitor component (d) further contains at least one metal component selected from Mg, Co, and W. The water-based metal surface treatment agent further comprises polyethylene wax (L), and the solid content mass ratio [(L) / (C)] of the organosilicon compound (C) and polyethylene wax (L) is 0.05. To 0.30, characterized in that the surface-treated galvanized steel sheet. The water-based metal surface treatment agent according to claim 1 is applied to the surface of the galvanized steel sheet, dried at an reaching temperature of 50 to 250 ° C, and the film weight after drying is 0.2 to 5.0 g / m 2. Galvanized steel plate. The water-based metal surface treatment agent according to claim 14 is applied to the surface of the galvanized steel sheet, dried at an reaching temperature of 50 to 250 ° C, and the coating weight after drying is 0.2 to 5.0 g / m 2. Galvanized steel plate. delete