KR20020083580A - Nonchromate metallic surface-treating agent, method for surface treatment, and treated steel material - Google Patents

Abstract

PURPOSE: A non-chromate metal surface treating agent suitable for metal base frame, particularly for metal coated steel product capable of giving high formability and corrosion resistance during manufacturing of coated material or other processes, a metal surface treating method using the same, and a surface treated steel product are provided. CONSTITUTION: The non-chromate metal surface treating agent comprises the following materials for 1 liter of non-chromate metal surface treating agent: (a) 0.01 to 100 g/L of silane coupling agent and/or dehydrated condensation products thereof, (b) 0.05 to 100 g/L of water dispersed silica, (c) 0.01 to 50 g/L of zirconium compound for Zr ions and/or 0.01 to 50 g/L of titanium compound for Ti ions, (d) 0.01 to 100 g/L of thiocarbonyl contained compound, and/or (e) 0.1 to 100 g/L of water soluble acrylic resin, wherein the non-chromate metal surface treating agent further comprises 0.01 to 100 g/L of phosphate ions. The metal surface treating method comprises the process of treating the surface of a steel product with the above metal surface treating agent, wherein the steel product is metal coated steel product.

Description

Non-chromate metal surface treatments, surface treatment methods, and treated steels {NONCHROMATE METALLIC SURFACE-TREATING AGENT, METHOD FOR SURFACE TREATMENT, AND TREATED STEEL MATERIAL}

Cold rolled steel, hot rolled steel, stainless steel, electroplated zinc coated steel, hot-dip zinc coated steel, zinc-aluminum alloy coated steel, zinc-iron alloy coated steel, zinc-magnesium alloy coated steel Surface treatment agents for steel substrates, such as zinc-aluminum-magnesium alloy coated steel, aluminum-coated steel, aluminum-silicon alloy coated steel, tin coated steel, lead-tin alloy coated steel, and chromium coated steel A method of treatment, a method of making a coated steel material having a top coating on a treated surface, and a coated steel product produced by the method.

As metal surface treatment agents, chromium-containing surface treatment agents such as chromate-based or phosphate-chromate-based have been widely used until now and are still used today. However, in view of recent trends in stringent regulations on environmental protection, the use of such coating systems is likely to be limited due to the fear of chromium's toxicity, especially carcinogenicity. Therefore, there is a waiting for the development of a metal surface treatment which does not contain chromium and is still effective as a chromium oxidant in providing adhesion and corrosion resistance.

As disclosed in Japanese Patent Application Laid-Open Hei-11-29724, the inventors have described resins based on water and non-chromate rust inhibitors as included above, and thiocarbonyl group-containing compounds, phosphate ions, And non-chromate rust inhibitors containing water dispersible silica. Unfortunately, however, the system is known to be unsuitable for such applications, which require strict processability and adhesion, even if they provide good corrosion resistance. On the other hand, with respect to the silane coupling agent, an acidic surface treatment agent containing two different silane coupling agents is disclosed in Japanese Patent Laid-Open No. Hei-8-73775. However, the system is very poor in corrosion resistance for use in applications requiring good corrosion resistance and processability after metal surface treatment as in the present invention.

Moreover, Japanese Laid-Open Publication Hei-10-60315 discloses a steel surface treatment agent containing a silane coupling agent having an optional functional group reactive with water based emulsions, but the corrosion resistance required for this is only relatively mild test conditions. For example, as far as satisfying the conditions of the wet test, and when it comes to corrosion resistance, the system differs significantly from rust inhibitors that meet the very critical corrosion resistance conditions as provided by the present invention. Despite references to the prior art as background, there has been a need for the development of metal surface treatment agents that exhibit sufficient corrosion resistance and process adhesion at thin coating thicknesses.

The present invention aims to provide a non-chromate metal surface treatment agent suitable for metal substrates, in particular metal coated steels, and despite the presence of chromium, it has high processability and resistance in the manufacture of coatings or other procedures. Corrosiveness can be imparted.

The non-chromate metal surface treatment agent according to the invention contains for one liter thereof:

(a) 0.01 to 100 g / l of a silane coupling agent and / or its dehydration condensation product,

(b) 0.05 to 100 g / l of water dispersible silica (as a solid), and

(c) 0.01 to 50 g / l zirconium compound for Zr ions, and / or 0.01 to 50 g / l titanium compound for Ti ions, and / or

(d) 0.01 to 100 g / l of thiocarbonyl-containing compound, and / or

(e) 0.1-100 g / l of water-soluble acrylic resin.

The non-chromate metal surface treatment agent according to the present invention may contain from 0.01 to 100 g / l of phosphate ions.

The metal surface treatment method according to the present invention consists in treating a surface of a steel material or a metal coated steel material with the metal surface treatment agent, and the method is most suitable for the surface treatment of a zinc coated steel material.

The surface-treated steel material and the surface-treated metal coated steel material according to the present invention can be obtained by the above method with the metal surface treatment agent.

The manufacturing method of the coated steel material which concerns on this invention consists of treating the surface of a metal coated steel material with the said metal surface treatment agent, and then applying a top coating.

The coated steel material of this invention can be obtained by the said method using the said metal surface treating agent.

As a silane compound which is one of the essential components, the metal surface treatment agent of the present invention contains a silane coupling agent and / or a dehydration condensation product thereof. Dehydration condensation product of a silane coupling agent means an oligomer obtainable by dehydration condensation of a silane coupling agent.

The silane coupling agent that can be used in the present invention is not particularly limited but examples thereof are as follows: vinylmethoxysilane, vinyltrimethoxysilane, vinylethoxysilane, vinyltriethoxysilane, 3-aminopropyltri Ethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3 -(Triethoxysilyl) -l-propanamine, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine, N- (β-aminoethyl) -γ-aminopropylmethylmethoxysilane , N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Glycidoxy-propyltriethoxysilane, γ-glycidoxypropylmethyl-dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl-trimethoxy Column, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyl-triethoxysilane and N- (2- (Vinylbenzylamino) ethyll-3-aminopropyltrimethoxysilane.

Particularly preferred silane coupling agents include: vinylmethoxysilane, vinylethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyl-trimethoxysilane, 3-methacryloxypropyltrimeth Methoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -propanamide and N, N'-bis [3- ( Trimethoxysilyl) propyl] ethyleneamine. These silane coupling agents may be used alone or in combination as appropriate.

In the present invention, the silane compound may be formulated at a concentration of 0.01 to 100 g / l, preferably 0.05 to 25 g / l with respect to 1 L of the metal surface treatment agent. If the concentration of the silane compound is less than 0.01 g / l, not only the effect of improving adhesion to the non-chromate primer but also the effect of improving the corrosion resistance will be insufficient, but if the silane compound is used in excess of 100 g / l, The impact of the is excessively uneconomical.

The metal treating agent of the present invention contains water dispersible silica. The water dispersible silica that can be used is not particularly limited but is preferably spherical silica, chain silica or aluminum modified silica, which is free of sodium and other impurities and weak bases. Spherical silicas include colloidal silicas such as "Snowtex N", "" Snowtex UP "(manufactured by Nissan Chemical) and fumed silicas such as" Aerosil "(Japan Aerosil), and the chained silica includes silica gels such as" Snowtex PS " (Manufactured by Nissan Chemical), and aluminum modified silica includes "Adelite AT-20A" (Asahi Denka), all of which are commercially available.

The water dispersible silica is formulated at 0.05 to 100 g / l, preferably 0.5 to 60 g / l with respect to 1 L of the metal surface treatment agent on a solid basis. If the concentration of the water-dispersible silica is less than 0.05 g / l, the effect of improving corrosion resistance will be insufficient. However, if silica is used in excess of 100 g / l, it is not supplemented by further improvement of corrosion resistance, but rather a bath of a metal surface treatment agent. Decreases stability.

The metal surface treatment agent of the present invention contains a zirconium compound and / or a titanium compound. Zirconium compounds include: zirconyl ammonium carbonate, zirconium hydrofluoride, ammonium zirconium fluoride, potassium zirconium fluoride, sodium zirconium fluoride, zirconium acetylacetonate, zirconium butoxide-1-butanol solution, Zirconium n-propoxy and the like. Titanium compounds include: titanium hydrofluoride, ammonium titanium fluoride, potassium titanium oxalate, titanium isopropoxide, isopropyl titanate, titanium ethoxide, titanium 2-ethyl-l-hexanolate, Tetraisopropyl titanate, tetra-n-butyl titanate, potassium titanium fluoride, sodium titanium fluoride and the like. These compounds may be used alone or in combination as appropriate.

The zirconium compound and / or titanium compound is formulated at a concentration of 0.01 to 50 g / l, preferably 0.05 to 5 g / l, in terms of zirconium ions or titanium ions with respect to 1 l of the metal surface treatment agent. If the concentration of the compound is less than 0.01 g / l, the corrosion resistance will be insufficient. If it exceeds 50 g / l, processing adhesion will not be improved and bath stability will be rather inferior.

The metal surface treatment agent according to the present invention contains a thiocarbonyl group-containing compound and / or a water-soluble acrylic resin. A thiocarbonyl group containing compound is a compound having one or more thiocarbonyl groups, including: thiourea, dimethylthiourea, 1,3-dimethylthiourea, dipropylthiourea, dibutylthiourea, 1,3-diphenyl 2-thiourea, 2,2-ditolylthiourea, thioacetamide, sodium dimethyldithiocarbamate, tetramethylthiuram monosulfide, tetrabutylthiuram disulfide, N-ethyl-N-phenyldithi Zinc Ocarbamate, Zinc Dimethyldithiocarbamate, Piperidine Salt of Pentamethylenedithiocarbamate, Zinc Diethyldithiocarbamate, Sodium Diethyldithiocarbamate, Isopropyl Acid Zinc carbonate, ethylenethiourea, dimethylxanthogen disulfide, dithiooxamide, polydithiocarbamic acid or salts thereof and the like. These compounds may be used independently or two or more of the compounds may be used in combination as appropriate.

Said thiocarbonyl-containing compound is formulated at a concentration of 0.01 to 100 g / l, preferably 0.1 to 10 g / l. If the concentration of the compound is less than 0.01 g / l, the corrosion resistance is insufficient. If the concentration exceeds 100 g / l, the effect of improving the corrosion resistance is excessive and not economical.

Water soluble acrylic resins are copolymers based on acrylic acid and / or methacrylic acid and include such copolymers with methyl acrylate, methyl methacrylate, ethyl methacrylate and the like (including derivatives thereof) and other acrylic monomers. Acrylic acid and / or methacrylic acid are particularly preferably 70% or more of the total monomers constituting the copolymer. The acrylic resin is formulated at a concentration of 0.1 to 100 g / l per 1 l of the metal surface treatment agent of the present invention. When the concentration of the acrylic resin is less than 0.1 g / l, the bend adhesion property and the compaction property cannot be sufficiently improved. On the other hand, the concentration of more than 100 g / L is not economical because the improvement effect on bending adhesion and compaction formation is excessive.

The molecular weight of the acrylic resin is preferably 10,000 or more on average. More preferably 300,000 to 2,000,000. If it exceeds 2,000,000, the viscosity which adversely affects workability becomes too large.

The metal surface treatment agent of the present invention can be supplemented with phosphate ions to improve the corrosion resistance.

The addition of the above phosphate ions is accomplished by adding a compound capable of forming phosphate ions in water. As such compounds, mention may be made of: phosphoric acid, salts of phosphoric acid represented by Na ₃ PO ₄ , Na ₂ HPO ₄ and NaH ₂ PO ₄ ; And concentrated phosphoric acid compounds such as concentrated phosphoric acid, polyphosphoric acid, metaphosphoric acid, pyrophosphoric acid, ultraphosphoric acid and the like and salts thereof. These compounds may be used alone or in combination as appropriate.

The phosphate ions may be formulated at a concentration of 0.01 to 100 g / l, preferably 0.1 to 10 g / l with respect to 1 L of the metal surface treatment agent. If the concentration is less than 0.01 g / l, the effect of improving the corrosion resistance will be insufficient. On the other hand, an excess of 100 g / l is not preferable because zinc-coated steel will be over-etched to cause deterioration of performance or gelation when water-based resin is contained as an additional component. .

The metal surface treatment agent of this invention contains another component further. As such other components, mention may be made of tannic acid and salts thereof, phytic acid and salts thereof, and water based resins. Water based resins that may be used include urethane resins, epoxy resins, ethylene-acrylic copolymers, phenolic resins, polyester resins, polyolefin resins, alkyd resins and polycarbonate resins. These water-based resins can be used independently or in combination. When using a resin based on water, an organic solvent is used incidentally to improve film formability to provide a more uniform and smooth film. In addition, leveling agents, wetting agents and antifoaming agents can also be used.

The metal surface treatment agent of the present invention can be used as a surface treatment agent for steel substrates with particularly beneficial effects in the case of metal precoated steels: cold rolled steel, hot rolled steel, stainless steel, electroplated zinc coating Steel, hot-dip zinc coated steel, zinc-aluminum alloy coated steel, zinc-iron alloy coated steel, zinc-magnesium alloy coated steel, zinc-aluminum-magnesium alloy coated steel, aluminum-coated steel, aluminum-silicon Alloy coated steel, tin coated steel, lead-tin alloy coated steel, chrome-coated steel; Ni coating steel etc. The method of using the surface treatment agent, that is, the steel surface treatment method consists of applying the metal surface treatment agent to the base metal surface and drying the coating, or previously heating the base material, It consists of applying a metal surface treatment agent and drying the coating using the residual heat of the base.

In all of the above, the drying procedure can be performed at room temperature to 250 ° C. for 2 seconds to 5 minutes. Above 250 ° C., the adhesion and corrosion resistance will be inferior. Preferable conditions are 40-180 degreeC and 5 second-2 minutes.

In the metal surface treatment method according to the invention, the amount of deposition of the metal surface treatment agent is preferably at least 0.1 mg / m ² based on the dry film. If the range is less than 0.1 mg / m ² , the antirust effect will be insufficient. On the other hand, if it exceeds the range, it will be uneconomical as a pretreatment for coating. Thus, the most preferred range is 0.5 to 500 mg / m ² , in particular 1 to 250 mg / m ² .

In carrying out the metal surface treatment method according to the present invention, the form of use of the metal surface treatment agent is not particularly limited. Thus, general techniques such as roller coating, shower coating, spray coating, dip coating and brush coating can optionally be used. Optimal steel substrates include metal coated steels, in particular various plated steels.

The method for producing coated steel according to the present invention consists in treating a metal surface with the metal surface treatment agent, drying the coating and applying a top coating. The top coating may be a top coating formed after application and drying of the non-chromate primer, or a functional coating formed to impart a role such as anti-fingerprint or smoothness.

The above manufacturing techniques can be applied to precoated steels as well as postcoated steels, and the term "coated steels" herein includes steels of all of the above types. The term "steels" also includes any and all steels (steels). Sheets and plates).

Non-chromate primers that may be used may be any primer that does not contain a chromate type antirust pigment in the formulation. The primer preferably contains an antirust pigment of the vanadate type or an antirust pigment of the phosphate type (V / P pigment primer), or preferably an antirust pigment of the calcium silicate type.

The coating amount of the primer is preferably 1 to 20㎛ in dry thickness. If the dry thickness is less than 1 μm, the corrosion resistance will be insufficient. If the thickness exceeds 20 mu m, the processing adhesion will not be satisfactory.

The baking conditions for the non-chromate primers are metal surface temperatures of 150 to 250 ° C. and baking times of 10 seconds to 5 minutes.

The top coating is not particularly limited, but may be any of the conventional top coatings.

Functional coatings include, but are not particularly limited to, all types of coatings used on chromate pretreated surfaces.

Coating techniques for the non-chromate primers, top coatings and functional coatings include, but are not limited to, roller coatings, shower coatings, air spray coatings, airless spray coatings and dip coatings.

Non-chromate metal surface treatment agents according to the present invention may be selected from silane coupling agents and / or their dehydration condensation products, water dispersible silica, zirconium compounds and / or titanium compounds and thiocarbonyl-containing compounds and / or water-soluble acrylic resins. It contains. The metal surface treatment agent is suitable for the treatment of metals, especially plated steel materials, and can impart excellent processability and corrosion resistance to the coating base without the aid of chromium.

Furthermore, by applying the metal surface treatment agent of the present invention to a method for producing a non-chromate coated steel material, the steel material is provided with workability, compaction resistance and corrosion resistance or obtained by using a chromate-containing rust inhibitor. It is superior to conventional steel materials that can be.

This advantage is that since the metal surface treatment agent of the present invention contains a silane coupling agent, the reactive portion of the silane coupling agent is firmly bonded to the base metal surface through metasiloxane bonds, and the organic portion of the hydrophobic group is incorporated into the organic film. It appears to stem from the fact that it is firmly bonded to improve adhesion and contribute to increased corrosion resistance. Moreover, particles of water dispersible silica are absorbed and oriented on the gas surface to inhibit corrosion, acting as a barrier to corrosive ions and moisture, but silanol groups present on the silica surface are formed between the formed organic film and the metal surface. Improves the adhesion. For zirconium ions, the formation of a zirconium oxide film on the metal surface improves the corrosion resistance, while at the same time zirconium acts as a crosslinker for the deposited film to increase the crosslink density of the organic film, resulting in corrosion resistance, adhesion and coin Contributes more to scratch resistance. In addition, thiocarbonyl-containing compounds and phosphate ions are easily absorbed on the metal surface to protect the coating on the metal surface, and when present together, they have a synergistic effect of significantly improving corrosion resistance.

Since an acrylic resin acts as a binder for inorganic components, such as dispersible silica, zirconium, etc., it seems to contribute to the improvement of the adhesiveness of a process part, and formation of compaction property.

The coated steels obtained according to the present invention have excellent workability and corrosion resistance and are applied to various applications such as household electrical appliances, computer-related devices, building materials and automobiles, and other industrial materials.

Example

The following examples illustrate the invention in detail but do not limit the scope thereof.

Example 1

2.5 g of "Sila-Ace S-330"(γ-aminopropyltriethoxysilane; Chisso Corporation) was added to 1 L of pure water, and the mixture was stirred at room temperature for 5 minutes. Next, 1.0 g of "Snowtex N" (water dispersible silica; Nissan Chemical) was further added, and the honba was stirred for 5 minutes. Further, 2.5 g of "Zirocosol AC-7)" (zirconyl ammonium carbonate; Daiichi Rare Elements Co.) was added in terms of Zr ions. Next, 5.0 g of thiourea and 1.25 g of ammonium phosphate (in terms of phosphate ions) were further added and the mixture was stirred for 5 minutes to obtain a non-chromate metal surface treatment agent. The metal surface treatment agent was degreased with an alkaline cleaner (Surf Cleaner 155; Nippon Paint), and a commercially available dry hot-dip galvanized steel sheet (Nippon Test) using a # 3 bar coater. Panel Co .; 70 x 150 x 0.4 mm) was applied with a dry film thickness of 20 mg / m ² . After drying at a metal surface temperature of 60 ° C., the V / P pigment-containing bichromate primer was applied to a dry film thickness of 5 μm using a # 16 bar coater and dried at a metal surface temperature of 215 ° C. In addition, using a # 36 bar coater, Flexicoat 1060 (Polyester Top Coating; Nippon Paint) was applied as a top coating to a dry film thickness of 15 μm and dried at a metal surface temperature of 230 ° C. to prepare a test piece. Flexural adhesion, corrosion resistance and scratch resistance of the test pieces were evaluated by the method described below, and the results are shown in Table 1.

Examples 2 to 22, and Comparative Examples 1 and 2

The type and concentration of the silane coupling agent, the water dispersible silica, the zirconium compound, the thiocarbonyl-containing compound and the water-soluble acrylic resin were changed, and the concentration of the phosphate ions was changed as shown in Table 1, but according to the procedure of Example 1 A metal surface treatment agent was prepared. Using the metal surface treatment agent, a test piece was produced in the same manner as in Example 1. These test pieces and the metal surface treatment agent were evaluated by the same method as the above. The results are shown in Table 1.

Comparative Example 3

Instead of the metal surface treatment agent of the present invention, a commercially available coating chromate agent (resin containing type) is applied at a chromium deposition rate of 20 mg / m ² and dried and a chromate containing primer (a strontium chromium pigment containing primer) is used. , The test piece was manufactured by the same procedure as Example 1. The evaluation results are shown in Table 1.

Metal Surface Treatment Formulations Coupling agent Silica Zr compound Thiocarbonyl Compound Acrylic resin PO ₄ Kinds g / ℓ Kinds g / ℓ Kinds g / ℓ Kinds g / ℓ Kinds g / ℓ g / ℓ Example Number 12345678910111213141516171819202122232425 1213242121211211121212222 2.5510.029052.52.55051.52.515100.50.052.511.552.51555 1111121111212111111111111 110.079030.52550.110.51.52.5120.512.52.5512.5111 1112232121451 + 5111111111111 2.50.54010.1100.550.10.250.50.5 + 0.55552.5402.5402.5400.50.50.5 123456789101112131415161112--222 52.5800.021010.0550152.51.55301.50.52.512.51--2.52.52.5 ---------------- PAA * 1PAAPMA * 2PMAPAAPAAPAAPMAPAA ---------------- 150 150 150 252 525 1.250.50.0210590200.5102521.50.51.50.50.50.5110.510.50.50.5 Comparative example number 12 12 2000.005 11 2000.03 22 1000.005 56 1200.005 - - 1200.005 3 Coating Type Chromate * 1: polyacrylic acid, Mw: 100 x 10 ⁴ * 2: polymethacrylic acid, Mw: 100 x 10 ⁴ Footnotes) Examples Nos. 23 and 24 show that acsin formation was performed on high-performance formulation 2 This is the case by the addition.

Bend Adhesive Apsin formation Corrosion resistance Coin scratch resistance Primary Secondary Cutting cotton Distal face Example Number 12345678910111213141516171819202122232425 5555555555555555555555555 5555555555555555555555555 2222222222222222555544553 5554444444444444444444554 5544444444444444444444554 4555555555555555555555555 Comparative example number 12 12 11 22 42 32 21 3 5 4 3 4 3 4 * 1: polyacrylic acid, Mw: 100 x 10 ⁴ * 2: polymethacrylic acid, Mw: 100 x 10 ⁴ Footnotes) Examples Nos. 23 and 24 show that acryl formation was obtained by high performance formulation 2. This is the case by the addition.

Examples 23-26

The treated sheet was prepared in the same manner as above, and instead of the primer coating and the top coating, an anti-fingerprint coating as a kind of functional coating was applied to a dry film thickness of 1 μm using a bar coater # 3 and the metal surface It dried at the temperature of 120 degreeC, and manufactured the test piece. The evaluation results of these test pieces are shown in Table 2 below.

Examples 27-30

The treated sheet was prepared in the same manner as above, and instead of the primer coating and the top coating, a smooth coating as a kind of functional coating was applied with a bar coater # 3 to a dry film thickness of 1 μm and the metal surface temperature It dried at 120 degreeC, and prepared the test piece. The evaluation results of these test pieces are shown in Table 2 below.

Comparative Example 30

Instead of a metal surface treatment agent, commercially available coating type chromateating agents (resin containing grades) were applied at a chromium deposition rate of 20 mg / m ² and dried to prepare specimens in the same manner as in Example 27 and evaluated similarly. The evaluation results are shown in Table 2 below.

Metal Surface Treatment Formulations Coupling agent Silica Zr compound Thiocarbonyl Compound PO ₄ Acrylic resin Kinds g / ℓ Kinds g / ℓ Kinds g / ℓ Kinds g / ℓ g / ℓ PAA PMA Example Number 2324252627282930 12131213 2.5510.052.5510.05 11111111 112.52.5112.52.5 11121112 2.50.5512.50.551 12341234 52.510.0552.510.05 1.250.50.02101.250.50.0210 -2.5 --- 2.5-- --- 2.5 --- 2.5 Comparative example 4 Coating Type Chromate

Bend Adhesive Corrosion Resistance (2) Anti-fingerprint Smoothness Primary Secondary Machined surface Flat surface Example 2324252627282930 55555555 55555555 55555555 55555555 5555 Not rated Not rated Not rated Not rated not rated not rated5555 Comparative example 4 5 5 5 5 2 2

For the silane coupling agents, water-dispersible silica, zirconium compounds, titanium compounds, thiocarbonyl-containing compounds and acrylic resins mentioned in Tables 1 and 2 above, the following commercially available products are used.

Silane coupling agent

1: Sila-Ace S-330 (γ-aminopropyltriethoxysilane; Chisso Corp.)

2: Sila-Ace S0-510 (γ-glycidoxypropyltrimethoxysilane; Chisso Corp.)

3: Sila-Ace S-810 (γ-mercaptopropyltrimethoxysilane; Chisso Corp.)

4: Sila-Ace S-340 (N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamide; Chisso Corp.)

Water Dispersible Silica

1: Snowtex N (Nissan Chemical Ind.)

2: Snowtex O (Nissan Chemical Ind.)

Zirconium Compound

1: Zircosol AC-7 (zirconyl ammonium carbonate; Daiichi Rare ElementsCo.)

2: ammonium zirconium fluoride (reagent)

3: zirconium hydrofluoride (reagent)

4: titanium fluoride (reagent)

5: ammonium titanium fluoride (reagent)

Thiocarbonyl-containing compounds

1: thiourea (reagent)

2: ethylenethiourea (reagent)

3: sodium diethylcarbamate (reagent)

4: 1,3-diethyl-2-thiourea (reagent)

5: zinc dimethyldithiocarbamate (reagent)

6: Zinc isopropyl carbonate (reagent)

7: Dimethylxanthogen sulfide (reagent)

8: tetramethylthiuram sulfide (reagent)

9: sodium dimethyldithiocarbamate (reagent)

10: sodium dibutyldikiocarbamate (reagent)

11: tetrabutylthiuram disulfite (reagent)

12: dipentamethylenethiuram tetrasulfide (reagent)

13: N-ethyl-N-phenyldithiocarbamate (reagent)

14: piperidine pentamethylenedithiocarbamate (reagent)

15: dimethyldithiocarbamate acid (reagent)

16: dibutylthiourea (reagent)

Water soluble acrylic resin

1: polyacrylic acid (reagent), Mw = 1,000,000

2: polymethacrylic acid (reagent), Mw = 1,000,000

Assessment Methods

Evaluation of Bend Adhesiveness, Compression Moldability, Corrosion Resistance (1) and Coin Scratch Resistance of Examples 1 to 22 and Comparative Examples 1 to 3, and Coating Adhesion of Examples 23 to 30 and Comparative Example 4 In the evaluation of the resistance and corrosion resistance (2), the following methods and criteria were used.

Bend Adhesive

(Primary adhesion)

The test piece was bent to 180 ° without interference of the spacer in a controlled environment at 20 ° C, and the bent portion was peeled three times using an adhesive tape. Peeling degree was measured under 20 times glass and graded as follows.

score

5 points: no crack

4 points: cracks throughout the bend

3 points | pieces: peeling area is less than 20% of a bend part

2 points | pieces: Peeling area is 20% or more and less than 80% of a bending part.

1 point: More than 80% of peeling area bends.

Secondary adhesion

The specimens were placed in water for 2 hours and then left indoors for 24 hours. The treated specimens were bent in the same manner as above and graded in the same manner as the primary adhesion test.

Apsin formation

The conical cup test was performed at 20 ° C. under the following conditions: draw ratio: 2.3, wrinkle limit pressure: 2t, punch R: 5 mm, die shoulder R: 5 mm and no holding. Then, after cutting the side surface of the test piece horizontally and immersing in breaking water for 1 hour, the peeling distance of the film of the cut part was measured. It was graded as follows.

score

5 points: bubble width <1 mm

4 points: Bubble width ≥1mm, <2mm

3 points: Bubble width ≥2mm, <3mm

2 points: Bubble width ≥3mm, <5mm

1 point: Bubble width ≥ 5 mm.

Corrosion Resistance (1)

(Cutting area)

The test piece was cut horizontally and the same salt spray test was performed according to JIS Z 2317 for 500 hours. The width of the bubbles formed on one side of the cutting line was measured and graded as follows.

score

5 points: bubble width = 0 mm

4 points: bubble width <1 mm

3 points: Bubble width ≥1mm, <3mm

2 points: Bubble width ≥3mm, <5mm

1 point: Bubble width ≥ 5 mm.

(edge)

The specimens were subjected to the same salt spray test according to JIS Z 2317 for 500 hours and the width of the bubbles formed along the rough edges of the top was graded as used in the cutting zone.

Coin scratch resistance

5 points: exposed primer area <10%; Base metal not exposed

4 points: exposed primer area ≧ 10% but <70%; Base metal not exposed

3 points: exposed primer area ≧ 70%; Exposed substrate metal area <30%

2 points: exposed primer area> 70%; Exposed substrate metal area ≥30%, <70%

1 point: exposed primer area ≧ 70%; Exposed substrate metal area ≥70%

Coating adhesion

(Primary adhesion)

Using a bar coater, the precoated steel sheet obtained in Examples 23 to 30 was coated with a melamine alkyd resin coating (Kansai Paint, Amilac # 1000) to a dry film thickness of 30 μm and baked for 20 minutes at an oven temperature of 30 ° C. Dried. The sheet was left overnight and then processed to an Erichsen value of 7 mm. Adhesive tape (Nichiban (trade name Cellotapa)) was applied to the machined area and quickly peeled off at a slope of 45 °. Coating adhesion was evaluated in the following grades according to the fractional (%) peel area.

5 points | pieces: No peeling

4 points: fractional peeling area <5%

3 points: fractional peeling area ≥ 5%, <30%

2 points: fractional peeling area ≥30%, <50%

1 point: fragmental peeling area ≧ 50%.

(Secondary adhesion)

As a primary adhesion test, the precoated sheet was coated with a melamine alkyd resin coating and left overnight. Each sheet was then immersed in breaking water for 30 minutes and then processed to an Erichsen value of 7 mm. Adhesive tape (Nichiban (trade name Cellotapa)) was applied to the machined area and quickly peeled off at a slope of 45 °. Based on the fractional peel area, coating adhesion was evaluated in the following grades.

5 points | pieces: No peeling

4 points: fractional peeling area <5%

3 points: fractional peeling area ≥ 5%, <30%

2 points: fractional peeling area ≥30%, <50%

1 point: fragmental peeling area ≧ 50%.

Corrosion Resistance (2)

(Flat area)

Each of the precoated steel sheets obtained in Examples 23 to 30 was sprayed with 5% NaCl aqueous solution at a caution temperature of 35 ° C. according to the salt spray test of JIS Z2371, and corrosion resistance was generated in accordance with the following grade after the occurrence of white rust after 240 hours. Evaluated.

5 points: no white rust

4 points: White rust <10%

3 points: white rust ≥10%, <20%

2 points: White rust ≥20%, <30%

1 point: white rust 30%.

(Machined part)

The precoated steel sheet obtained in Examples 23 to 30 was machined to an Erichsen value of 7 mm. Then, according to the salt spray test method of JIS Z2371, each sample was sprayed with 5% NaCl aqueous solution at an attention temperature of 35 ° C. After 72 hours, the occurrence of white rust in the processed area was evaluated in the following grade.

5 points: no white rust

4 points: White rust <10%

3 points: white rust ≥10%, <20%

2 points: White rust ≥20%, <30%

1 point: white rust 30%.

Fingerprint resistance

Using the precoated steel sheets obtained in Examples 23 to 26, the degree of remarkableness of the obtained fingerprint was evaluated in the following grade, leaving traces of fingerprint on the coated surface.

5 points: No identifiable fingerprint display

4 points: some fingerprints are seen

3 points: fingerprint is visible

2 points: clear fingerprints

1 point: Remarkable fingerprint display

Smoothness

Using a hydraulic molding tester with a conical punch, the precoated steel sheets obtained in Examples 27 to 30 were subjected to molding tests under the following conditions, and smoothness was evaluated using wear and tear as an indicator.

Punch Diameter: 70 mmφ

Blank Diameter: 150 mm

Vias load: 5 kgf / cm ²

Molding speed: 3.3 × 10 ^-2 m / s

Jig: FCD-500

Molding was always performed up to 80% of the maximum molding height. The degree of wear and tear was evaluated macroscopically, and the results are shown in the following grades.

5 points: flawless on steel surface

4 points: no defect on steel surface, slight defect on sliding surface

3 points: slight wear and tear on the steel surface

2 points: Many linear wear marks on steel surface

1 point: not molded

The present invention provides a non-chromate metal surface treatment agent suitable for metal substrates, in particular metal coated steels, to provide high processability and corrosion resistance in the manufacture of coatings or other procedures despite the presence of chromium. Can be.

Claims (8)

Non-chromate metal surface treating agent containing 1 liter of non-chromate metal surface treating agent: (a) 0.01 to 100 g / l of a silane coupling agent and / or its dehydration condensation product, (b) 0.05 to 100 g / l of water dispersible silica (as a solid), and (c) 0.01 to 50 g / l zirconium compound for Zr ions, and / or 0.01 to 50 g / l titanium compound for Ti ions, and / or (d) 0.01 to 100 g / l of thiocarbonyl-containing compound, and / or (e) 0.1-100 g / l of water-soluble acrylic resin. The non-chromate metal surface treatment agent according to claim 1, which contains 0.01 to 100 g / l of phosphate ions. A method of treating a metal surface, comprising treating the surface of a steel material with the metal surface treatment agent according to claim 1. 4. A method according to claim 3, wherein the steel is a metal coated steel. Surface treated steel obtainable by the method according to claim 3. Surface treated metal coated steel obtainable by the process according to claim 4. A method for producing a coated steel material comprising treating the metal coated steel material with the metal surface treatment agent according to claim 1 and then applying a top coating. Coated steels obtainable by the process according to claim 7.