TW575686B - Aqueous agent for metal surface treatment without including hexa-valent chromium and metal sheet surface-treated therewith - Google Patents

Description

575686 A7 B7 V. Description of the invention ([Detailed description of the invention] [Technical field to which the invention belongs] The invention of this case is a kind of water-based metal surface treatment agent, which does not contain the six-valent way of harmful substances to the human body, and can On the metal surface, a film layer with excellent resistance to scratches and conductivity m and a surface-treated metal plate treated with the water-based metal surface treatment agent in this case are formed. [Known Technology] -Generally known steel plates for household electrical appliances and Steel plate for construction materials, white is treated with chromate on the sub-gold plated steel plate to improve its purity resistance. However, this type of acid salt treatment contains precious materials for the environment and the human body. Synthetic treatments that do not include hexavalent network, and even more to be processed ^ 10% of the treatment is more intense, and after these synthetics, their surname resistance, conductivity, fingerprint resistance # must still be related to The conventional synthetic processing has the same effect. The traditional technique of synthetic processing of the robe of the robe of the robes of the robes by the Eighth Zhen, is described in 1572_—054157 Jie Mo Bao and ㈣2_-Gang No. 519. Physiological agents, such as Hexavalent The surface of the synthesis of chromium and fluoride reached temporary day two: ", used in conventional synthetic treatments' in the case of chromate treatment for hours, rust :: degree (with a chromium adhesion amount of 10mg / m2, brine spray 72 The effect of the film is not fully touched, and the amount of the film is maintained at 1. What is important? However, the fingerprint resistance of the obtained film is still not enough for this paper—using 575686 5. Description of the invention ([Detailed description of the invention] [Invention The technical field that it belongs to ^ is not for humans. ^ Is an aqueous metal surface treatment agent. The treatment agent is conductive and conductive. »T is hexavalent chromium of high quality and can form corrosion resistance on metal surfaces. All are based on the Asian material plating ^ products off the plate and stainless steel plate 'Chromium, because it contains hexavalent harmful to the environment and the human body. It is not included in the price of 20% of households: Dong does not include hexavalent chromium synthetic treatment. What's more, after processing, the expectation is more intense, and the properties of these composites are still Λ, ^ electrical properties, fingerprint resistance, coating adhesion and other properties must be the same as the conventional synthetic processing. The effect of the eight-four 4 known techniques for this type of synthetic processing, in JP 2QG The method is described in -054157 and Japanese Patent Application Publication No. 2_- Ganggang No. 519. In 4 inch publication No. 2000-054157, a method containing phosphorus and molybdenum: genus genus and divalent chromium ions is disclosed, but hexavalent is not included. At the synthetic surface of chromium and fluoride, the α-scraper treatment agent is used in the conventional synthetic treatment. When chromate treatment is performed, it can achieve the degree of rust prevention. (When the chromium adhesion amount is 1 Omg / m2, the brine is sprayed. The fog 72 is small =, the area ratio of white rust occurrence is less than 10%), it is necessary to maintain the film amount above ig / m, but the fingerprint resistance of the obtained film still cannot make people ----.-- -· ------ • Prayer Pack—— (Please read the notes on the back before filling out this page) Order .. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) V. Description of the invention (): The weight of the genus is characterized by the metal and component ⑻ in the component (A), and the ratio of the weight to weight (A) / ⑻ of the genus is in the range of 5/95 ~ 95/5. In the water-based metal surface treatment agent, the component ⑻ nitrate metal salt belongs to the test soil. This is a gold ^ ^ metal formed from heterogenous nickel, iron, and anatase. It is ideal, and relatively The total amount of the component (A), the component ⑻, and the solid content of the component 计量 is preferably between 10 and 90% by weight. Among the above-mentioned water-based metal surface treatment agents, it is preferable to include a water-based resin which is regarded as an additional component. Water-based resin is transported from a group of acrylic resin, urinary resin, and epoxy resin to the species. Hydroponic resin is ideal. It is also desirable to include a phosphate compound (E) 2 (E) as an additional component. In addition, it is preferable to include a lubricant (F) which is regarded as the additive component (F). Furthermore, the invention of the present invention is a surface metal-treated plate having a film with a dry film weight of 0.1 to 5 g / m2, which is partially coated with the above-mentioned water-based metal surface treatment agent on the metal surface and then dried. [Implementation Mode of the Invention] The invention of this case will be described in detail below. The water-based metal surface treatment agent of the present invention contains a compound of component (A) trivalent chromium, but does not contain a compound of hexavalent chromium. The compound of trivalent chromium is not particularly limited. Examples include chromium sulfate (III) and chromium nitrate (III) ), Chromium (III) phosphate, chromium (III) fluoride, chromium halide (ΙΠ), etc., and even trivalent chromium completely reduced by using hexavalent chromium is fine, and the aqueous metal surface of the present invention The 5th paper sees the / f drop for ΦΙ1 national standard (C) VS 44 specifications (21〇 > < 297mm) 575686 A7 _____ Β7 5. Description of the invention () The combination of the relevant component (A) in the physical agent The amount is not particularly limited. Although the metal in the component (B) metal nitrate used in the present invention is not particularly limited, it is formed by alkaline earth metals such as magnesium, calcium, and barium, and cobalt, nickel, " iron, zirconium, and titanium. At least one metal selected from the group is more suitable; there is no particular x limitation on the amount of the component (B) in the water-based metal surface treatment agent of the present invention. As mentioned above, although there are no particular restrictions on the amount of the component (A) and component (B) in the aqueous metal surface treatment agent of the present invention, the weight ratio of the metal in the component ^) to the metal in the component (B) (A ) / (B) must be maintained in the range of 5/95 ~ ^ / 5, and when (A) / (B) is in the range of 15/85 ~ 85 and 85, it is more than 10 / 9〇 ~ 90/10 The range is ideal, but when the ratio of (A) / (B) is less than 5/95 or exceeds 95/5, the degree of corrosion resistance is not good, which is not ideal. The water-dispersible silica of the component (C) used in the present invention includes colloidal silica and fumed silica, and the colloidal silica is not particularly limited, and examples thereof include SNOWTAX C, SNOWTAX 0, SNOWTAX N, SNOWTAX S, SNOWTAX UP, SNOWTAX PS-M, SNOWTAX PS-L, SNOWTAX 20, SNOWTAX30, SNOWTAX40, etc. (brand names, all manufactured by Nissan Chemical Industry Co., Ltd.), the fumed silica is not particularly limited, either Examples include AEROJIL 50, AEROJIL 130, AEROJIL 200, AEROJIL 300, AEROJIL 380, AEROJIL TT600, AEROJIL MOX80, AEROJIL MOX170 (brand names, all of which are manufactured by Yosan Chemical Industry Co., Ltd.). In the water-based metal surface treatment agent of the present invention, relative to component (A), — — — IIIIIII · I I (Please read the precautions on the back before filling this page) Order · · 575686 A7

I I I I I

I 575686 Λ7 B7 V. Description of the invention (limited to Moses) ’Adecabontiter-HUX-232, Adecabontiter- HUX-'Adecabontiter-HUX- (brand names, all manufactured by Asahi Chemical Industry Co., Ltd.). 77 The water-based epoxy resin in the invention of the present invention is not particularly limited to aminated modified products such as double-check type epoxy resin, stupid line-type secret varnish-type epoxy resin, phenol novolac-type novolak-type epoxy resin, etc. : AdecareginEPE-0436B can be listed (the ideal parent is 7 votes, for example, t Co., Ltd. Π 'are all manufactured by Asahi Chemical Industry Co., Ltd.) Relative to components (A) ~ (D), the full solid part solid form The percentage ratio is 10% to 90% by weight as Lipon and heavy star%, and the component (D) is considered. However, when the ratio is less than 10%, money resistance cannot be improved. The components (A) to (c) that have the effect of corrosion resistance are not ideal. The reduction in the amount of more than 90% is also the economical property if (E) phosphate compound is added as an additional component. The scale acid compound is not particularly limited, and it is possible to increase ammonium dihydrogen phosphate 'hydrogen phosphate. Examples of the diammonium and trihydrogen phosphate include: disodium hydrogen, trisodium phosphate, potassium dihydrogen phosphate, hydrogen phosphate-diacetate sodium, magnesium hydrogen phosphate, acid filling town, hydrogen phosphatidyl phosphate, and disulfonic acid , Bis = ^ potassium trilinate, sodium shiyi, potassium trimerate, magnesium trimerate, trimeric continuum κ%, sodium diphosphate, potassium pyrophosphate, magnesium pyrophosphate, far calcium pyrophosphate, Ammonium pyrophosphate, with respect to the total solids content of the ingredients (A) ~ (E) 10 () heavy denier 1 The solid content ratio is preferably 0; 1 ~ 10% by weight, ideally, the ingredients (magic " ϋ · 2 to 5% by weight is more -------------- loading --- (Please read the precautions on the back before filling in this page) J ^ T ·-turn-taxi From Tan P; Fentian Shi closed the order Yanhuai Λ 1 闼 Kan (9 Chuan 575686

V. Description of the invention (Ideal J for the full solid shape of f (A) ~ ⑻ * 1GG% by weight, when the content is ⑻1% by weight, the performance cannot be improved, and the super i blending effect is saturated, but it is not economical. It is resistant to lungs, and can also be expected to use ^. It is possible to improve the lubricants. There are no special appointments. Examples include thread worms, polypropylene 1 worms, micro worms, carbopa sign, polytetrafluoride. Water dispersions such as ethylene are also not limited in this way. The method of dispersing water in lubricating continents is not particularly limited, but it is ideal to disperse water with surfactants, acidified insects 1, such as: Chemipeariw900, ChemipearlWP25 (K brand name , All manufactured by Mitsui Chemicals Co., Ltd.) / Opposite side, 100% by weight of the solids of the knife (A) to (F), and the proportion of the solid seven knives of the component (F) is preferably 20% by weight. 2 to 15% by weight is more desirable, = 100% by weight of the solid content of the components (A) to (F), and the component ⑺ is less than 1% of the solid knife, the corrosion resistance cannot be When the increase is more than 10%, the effect of sexual orientation is saturated, but it is not economical. The surface-treated metal plate of the present invention is explained. The surface-treated metal of this case is reversed. The water-based metal surface 1 of the invention of the present invention is coated on at least one side of the surface of the metal material, and then dried to form A film with a dry film weight of 〇 · 丨 ~ 5 ^, if the dry film weight is not less than f ^ lg / m2, its insufficient corrosion resistance is not ideal, and when the dry film weight exceeds 5 g / m2, its corrosion resistance is Enhance the effect to reach saturation, but not economical. ------ r ---- I --- (Please read the precautions on the back before filling this page) Order:

/ \ 5. Description of the invention () / The metal plate of the surface-treated metal plate of the invention of the present case can be a plated Ⅰσ series steel plate (for example, a mine electrical steel plate, a ore-melted metal plate, or an alloyed molten lead plate) Steel plates, etc.), aluminized leaded steel plates (aluminum-containing fused leaded steel plates, 55% aluminized molten leaded steel plates, etc.), aluminized steel plates, lead-nickel plated gold plates, etc. After the step of degreasing and pickling the surface with an alkali, the surface is coated with the water-based metal surface treatment agent of the present invention, and then dried. The coating method of the water-based metal surface treatment agent is not particularly limited. The roller method, the dipping method, the electrostatic coating method, and the like can be used. After coating, it is preferably dried to reach a plate temperature of 60 to 200 ° C. The surface-treated metal plate treated with the water-based metal surface treatment agent of the present invention is also used for coating to form a resin film for the purpose of strengthening the corrosion resistance. The resin film is not particularly limited, but acrylic resin and urethane are used. Resins, epoxy resins, polystyrene resins, etc. are the main components of the surface treatment agent, which are ideally formed by coating, and the dry weight of the resin film weight is preferably in the range of 0.5 to 10 g / m2. [Examples] 〃 The following is a description of this case with examples and comparative examples-a detailed description. It should be noted that these examples are only described in the system of the invention of this application, and the use of this application is secretly determined. x [Production of experimental materials] (1) Check materials A7 Five

Description (

Use the following commercially available materials as equipment. • Electroplated leaded steel sheet (EG) plate thickness 0.8mm plating adhesion 20/20 (g / m2) • Plating molten leaded steel sheet (Gi) plate thickness 0.8mm plating adhesion 60/60 (g / m2) • Plated with 5% Asian oblique steel (gf) plate thickness 0.8mm Electroplating adhesion amount 90/90 (g / m2) • Plated with aluminum 55% molten lead-free steel plate (gl) Plate thickness 0.8mm Electroplating adhesion amount 90/90 ( g / m2) (2) Degreasing treatment Each of the above mentioned materials was degreased with Finecleaner 4336 (g recorded trademark · made by Japan Bakalai Kinshi Co., Ltd.) for degreasing (concentration 20g / L) 'Temperature 60 ° C, spray treatment for 20 seconds), then rinse with tap water. [Preparation of water-based metal surface treatment agent] The trivalent chromium compounds used in the adjustment of the water-based metal surface treatment agent in the examples and comparative examples are shown in Table 1, the nitrate metal salt is shown in Table 2, and the water-dispersible second silicon is shown in the table. 3. Water-based resins are shown in Table 4, phosphate compounds are shown in Table 5, and emulsion b is shown in Table 6. Another’slip 11 9Q7 Public Bi 1 Order 575686

7 7 AB V. Description of the invention () Solid content concentration of chromium compound A1 10% aqueous solution of chromium A2 10% reducing solution of chromic acid 10% A3 30% reducing solution of hexavalent chromium 10% Salt solid content concentration B1 Nitric acid drill aqueous solution 10% B2 Calcium nitrate aqueous solution 10% B3 Subnitrate nitrate aqueous solution 10% [Table 3] Solid dispersion concentration of water-dispersible silicon dioxide manufacturing company C1 SNOWTAX 0 Chemical industry 20% C2 AEROJIL 200 Water dispersion Japan AEROJIL 10% [Table 4] Solid content concentration of water-based resin manufacturing company D1 Adecabontiter HUX-670 Asahi Denki Chemical Industry 30% D2 Primal K-3 Loam & Hearth 46% D3 Adecaregin EPE-0436B Asahi Denki Chemical Industry 25%- I --- (Please read the precautions on the back before filling this page) Ordering · Side · 12 575686, Description of the invention ([Table 5] ----- Phosphate compound solid content concentration E1 Dihydrogen ammonium dihydronate solution 10% E2 L ~ --- · ..___ Filled with hydrogen acid # 5 aqueous solution 10% Table 6] ----- F1 Lubricant Manufacturing Company Solid content concentration ChemipearlW900 Mitsui Chemicals 40% F2 ChemipearlWP250 Mitsui Chemicals 50% equipment --- (Please read Note on the back, please fill in this page again.) At room temperature, set the trivalent chromium compound in Table 1, the nitrate metal salt in Table 2, the water-dispersible stone dioxide in Table 3, the water-based resin in Table 4, and The acid salt compound and the lubricant of Table 6 are thrown into distilled water according to the composition ratios shown in Table 7 and Table 8 in order, and mixed with a spiral mixer to prepare an aqueous metal surface treatment agent. The composition of the water-based metal surface treatment agent is shown in Table 7, and the composition of the water-based metal surface treatment agent of the comparative example is shown in Table 7 and Table 8. The solid content concentration of the water-based metal surface treatment agent is 10% by weight. .

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A7 Γ- Β7 V. Description of the invention () [Table 7] Example Solid composition of water-based metal surface treatment agent 1 ~ (A) / ⑻ * 2 66/34 Trivalent chromium compound stone oxalic acid metal salt dispersibility II Oxide stone evening water resin pursuit ^^ 氺 3 1 AK60) Bl (30) Cl (10) None None 2 A2 (40) BK20) Cl (40) None 76/24 3 AK50) B2 (25) Cl (25) No No 72/28 4 AK60) B3 (30) Cl (20) No # ,,, / 36 66/34 59/41 5 AK40) BK20) C2 (40) No benefit 6 Al (30) Bl (20) Cl ( 20) D1C30) Μ 7 AK30) Bl (20) Cl (20) D2C30) None 59/41 8 AK30) Bl (20) Cl (20) D3 (30) None 59/41 9 AK30) BK20) Cl (20) DK28) EK2) 59/41 10 AK30) BK20) Cl (20) DK28) E2⑵ 59/4 plant 10 11 AK72) Bl (8) C1 (2G) No No 12 AK6) Bl (54) Cl (40) No No 10/90 13 AK50) Bl (25) Cl (25) None None 66/34 14 Al (lO) Bl (lO) Cl (80) None None 49/51 15 Al (60) BK30) Cl (10) None None 66/34 16 Al (40) BK18) Cl (40) without EK2) 68/32 17 Al (40) BK18) Cl (40) without E2 (2) 18 Al (40) Bl (18) Cl (30) without Fl (12) 68/32 19 Al (40) Bl (18) Cl (30) without F2 (12) / 39 * 1 100% by weight of the solid content in the metal surface treatment agent〉 * 2 · The weight ratio of the metal component in the component (A) to the metal in the component (B) * 3: the component (E) and the component (F ) 14 575686 A7 _B7 V. Description of the invention () [Table 8] Solid composition of the water-based metal surface treatment agent of the comparative example 作为 1 Reason for the comparative example Trivalent chromium compound nitrate metal salt water-dispersible silica water-based resin additional component氺 3 20 A3C40) BK20) C1C40) Yes No No 6 Chromium Chromium 21 AK60) C1C40) Yes No No Nitrate Metal Salt 22 No BK60) C1C40) No No No Trivalent Chromium 23 AK70) No No No Silica 24 AK79) BK1) CC20) None None (A) / (B) * 4 = 99/1 * 1: The values in () indicate the solid content weight% of the water-based metal surface treatment agent with respect to 100% by weight of the total solid content * 3: Component (E) and component (F) * 4: The weight ratio of the metal component in the component (A) to the metal in the component (B) [Surface treatment using a water-based metal surface treatment agent: production of a surface-treated metal plate] Each water-based metal surface treatment agent prepared is applied with a bar paint machine to Each of the aforementioned experimental boards that have been degreased is dried at a temperature of 240 ° C to produce a surface metal-treated board. In addition, the amount of coating (g / m2) is adjusted based on the solid content concentration of the water-based metal surface treatment agent. After a moderate adjustment, each of the obtained surface-treated metal plates was used as a test plate for performance testing. [Performance test of surface-treated metal plate] 15 Shi ri 卩 Right: Tuo Tuo Qi Liang Ming F Chuan, 1 2 3!; Owing,. Loading ·-(Please read the precautions on the back before filling this page) Order ： # W5686 A7 、 Explanation of the invention ((1) Corrosion resistance of the flat part is according to the salt water spray test of JIS-Z-2371. It is divided into EG material and GI material for 72 hours of salt water spray, and GF material and concrete material for hour. Spray the salt water, and then observe the occurrence of white rust, and make an evaluation based on the following. # ≪ Evaluation Criteria > ◎ • The white rust occurrence area is less than 3% of the total area. More than 10%, under white rust occurrence area accounts for more than 10% of the total area, under 30% white rust occurrence area accounts for more than 30% of the total area. (2) Electrical conductivity is measured by the electrical conductivity of Erai Chemical Co., Ltd. MCP- T350 to measure its resistance value and make an evaluation based on the following < evaluation criteria >

ΔX

◎ △ ΔX resistance value is less than 10-3Ω, resistance value is less than 10-1ω, resistance value is more than 10-iQ, not full ---- install --- (Please read the precautions on the back before filling (This page) with a Loresta resistance value of 101 ^ or more (3) The hue α value, a value, and 仏 of the fingerprint resistance test board, measured with a color difference meter (ZE__, manufactured by NEC Corporation). Next, on this test board Shihlin was coated with «Swipe», and then the color was changed to f. The hue is the best choice. Panda nb idle net smoke: 16 575686 A7 _B7 V. Description of the invention () The difference of the amount (ΔΕ) is less than The benchmark is evaluated. ΔΕ = ((L2-L!) 2+ (a2-ai) 2+ (b2-b2) 2) ° * 5 In the formula, 'L :, h., ^ Are Vaseline before coating' L2, a2, and bg are Vaseline Measured value after coating. < Evaluation criteria >: △ E less than 2 〇 ·· △ E 2 or more, less than 3 △: △ E 3 or more, less than 5 X: △ E 5 or more [Result of performance test] Example of the invention The test results of the surface-treated metal plate are shown in Table 9, and the test results of the comparative example surface-treated metal plate are shown in Table 10. ------------- Packing.— (Please read the precautions on the back before filling this page) Order · 17 575686 A7 B7 V. Description of the invention () [Table 9] Example material Water-based metal Surface treatment agent reaches board temperature X: Film performance type * ι Film amount * 2g / m2 Money-resistant conductive fingerprint property 1 EG 1 0.5 80 ○ ◎ 2 GI 2 0.5 80 ○ ◎ 3 GF 3 0.5 80 〇 ◎ ◎ 4 EL 4 0.5 80 〇 ◎ 5 EG 5 0.5 80 〇 ◎ 6 GI 6 0.5 80 ◎ ◎ ◎ 7 1 GF 7 0.5 80 ◎ ◎ 8 GL 8 0.5 80 ◎ ◎ 9 EG 9 0.5 80 ◎ ◎ ◎ 10 GI 10 0.5 80 ◎ 〇 ◎ 11 GF 11 0.5 80 〇 ◎ ◎ 12 GL 12 0.5 80 〇 ◎ ◎ 13 EG 13 0.5 80 ○ ◎ 14 GI 14 0.5 80 ○ ◎ 15 GF 15 0.5 80 ○ ◎ 16 GL 16 0.5 80 ◎ ◎ ◎ 17 EG 17 0.5 80 ◎ ◎ ◎ 18 GI 18 0.5 80 ◎ ◎ ◎ 19 GF 19 0.5 80 ◎ ◎ ◎ 20 GL 20 0.5 80 〇 ◎ 21 21 EG 21 0.5 80 ◎ ◎ ◎ 22 GI 22 0.5 60 〇 ◎ ◎ 23 GF 23 0.5 150 ◎ ◎ ◎ * 1: The serial number of the water-based metal surface treatment agent example * 2: Dry film weight 18 ------------- Installation --- (Please read the precautions on the back before filling out this page) 士 厶 ft 孑 根 口 I #: 吞 ® rb ㈤ 印 令 * 4 ， 4 士 3 i 夂 γ〇ιη v, ',, 575686 V. Description of the invention (Table 10) Materials Water surface metal surface treatment agent

EG

GI

GF

EL 20 21 22 23 24 Film amount ^ 2g / m2 0.5 0.5 0.5 Reach plate temperature t: ~ 80 Wave film performance Money resistance ◎ 80

X

X Fingerprint resistance ◎ ◎ ◎ 80

X

X ------------ [| \ J I Water-based metal dry film weight ~ ◎ ◎ ◎

X ◎ Order α Use the water-based metal surface treatment of Example 19 of the invention of the present invention, and the surface-treated metal plate of Example 23, the surname resistance and fingerprint resistance are all good in the flat part. In addition, the water-based metal surface treatment is used. Although the surface treatment metal plate of Comparative Example ^ obtained by Shui Le metal surface treatment agent of Example 20 shows good results, it contains hexavalent chromium, which is harmful to the human body and% i. It is based on the subject matter of the invention of the present invention, and uses the water-based metal surface treatments of Comparative Examples 21 to 24 outside the scope of the invention of the present invention. The obtained surface-treated metal plates of Comparative Examples 2 to 5 have a conductivity and resistance. The texture is good, but the corrosion resistance of the flat part, which is the most important property, is poor. 19 575686 A7 B7 i. Description of the invention ([Effect of the invention] As explained above, the water-based metal surface treatment agent of the present invention is applied to the surface of the metal material, and the film formed after it is dried is not only in corrosion resistance and conductivity It is superior in fingerprint resistance, and does not contain hexavalent chromium, which is harmful to humans and the environment. It has a great value in the industry. 20 \ The scale is applicable to Chinese national standards (CNSM4 regulations (210 X 297 public caution). Installation ·-(Please read the precautions on the back before filling out this page)

Claims (1)

575686 Λ 8 Β8 C8 D8 7T, Shen Qing patented dry encapsulation 11 1. —Species containing (A) trivalent chromium compounds, (β) nitric acid metals, Ministry of Chemical Industry, now η 今, Ά 今 / 今 η Social printing% sexual dioxygen The water system of cutting and water is all surface = wide salt, water-dispersing I, all belong to Xinba, ... / agent, in which the weight ratio of metal in component (A) to metal in component (B) (A ) / (B), Hexavalent chromium-free water-based metal surface treatment agent in the range of 95/5. , = 1__ At the surface of the water-based metal described in item i! The metal in the acid salt of the second (B) is at least one selected from the group of self-examination earth metals, inscriptions, records, iron into LI, and titanium group. Of the metal. 3. As in the water system described in item 丨 or item 2 of the scope of the patent application, the ratio of the solid content of the component (C) to 10 in the solid content of the component (A), the component ⑻ and the component 10 is 10 ~ 90% by weight of the water-based gold ^ surface treatment d described in item 1 to item 2 of the patent scope of application 1 of the door 2, which contains additional components ③) water-based resin. 5. As described in item 4 of the scope of patent application Water-based metal surface treatment agent, in which the water-based resin is at least one type of water-based resin selected from the group consisting of acrylic resin, urinary fat and epoxy resin. The water-based metal surface treatment agent according to the description, which contains (E) phosphoric acid compound as an additional component. 7. The water-based metal surface treatment agent as described in the first to the second item of the patent application scope, which contains (F) an additional component. Lubricants.-8 · Water-based metal surface treatments described in claims i to 2 of the scope of patent application ^ Apply to at least one side of the metal surface and allow it to dry to form a dry film with a weight of 0.1 to 5 g / m2 Surface-treated metal 21 Fan Ά spent (210X 297 ^ «use in ® (CNS) AUm