JP5592579B2 - How to paint metal materials - Google Patents

Description

  The present invention relates to a method for coating a metal material.

  Conventionally, chromate treatment and phosphate treatment are generally performed to improve the corrosion resistance of metal surfaces. However, the toxicity of chromium has become a social problem in recent years, and the surface treatment method using chromate is a problem of scattering of chromate fume in the treatment process, and requires a large amount of cost for wastewater treatment equipment, Furthermore, there is a problem due to elution of chromic acid from the chemical conversion coating.

  Also, in phosphate treatment, zinc phosphate and iron phosphate surface treatments are usually performed, but in order to provide corrosion resistance, chrome treatment is usually performed after phosphating for rinsing with chromic acid. In addition to these problems, there are problems such as waste water treatment of reaction accelerators and metal ions in the phosphate treatment agent, and sludge treatment by elution of metal ions from the metal to be treated.

  On the other hand, zirconium-based and titanium-based surface treatment agents are known as treatment methods other than chromate treatment and zinc phosphate treatment. For example, Patent Document 1 proposes a chemical conversion treatment agent for iron and / or zinc-based substrates that contains substantially no phosphate ions but contains zirconium ions and / or titanium ions and fluorine ions. Yes. Patent Document 2 discloses (I) a compound containing at least one metal element selected from Ti, Zr, Hf and Si, and (II) a surface treatment of a metal containing a fluorine-containing compound as a source of fluorine ions. By using the composition, a surface treatment film having excellent corrosion resistance can be deposited on the surface of a metal containing at least one of iron and zinc, and the surface adjustment (surface tone) step is not required, so that the treatment step is shortened. It is disclosed to save space.

  Patent Document 3 discloses an iron-based material containing zirconium ions and / or titanium ions, fluorine ions, and a soluble epoxy resin and having substantially no phosphate ions and a pH of 2.5 to 4.5. A metal surface treatment composition for a substrate is disclosed.

  In addition, Patent Document 4 discloses a step (1) of forming a chemical conversion film on the surface of an aluminum-based substrate by a chemical conversion treatment with a chemical conversion treatment agent comprising a fluorine- and zirconium-containing compound, and a hydrophilic film using a hydrophilic treatment agent. A surface treatment method for an aluminum-based substrate comprising the step (2) of forming, wherein the chemical conversion treatment is performed by electrolytic treatment. ing.

  In Patent Document 5, an amorphous surface treatment layer containing an oxide and / or hydroxide of zirconium and / or titanium is provided on the surface of a metal material as a ground treatment for powder coating or solid lubricant coating. A coating method is disclosed.

  However, even when the surface treatment composition described in any of the above is used, corrosion resistance comparable to chromate treatment or zinc phosphate treatment is not obtained, and adhesion with the coating film formed by the coating process after treatment In some cases, the properties were insufficient.

JP 2003-155578 A International Publication No. 02/103080 Pamphlet JP 2003-253461 A JP 2005-2370 A JP 2006-255540 A

  The object of the present invention is to form a treatment film that provides corrosion resistance comparable to chromate treatment and zinc phosphate treatment, and also has excellent adhesion to the coating film formed by the coating process after treatment. The object is to provide a method of painting a metal material.

The present invention includes a metal surface treatment composition (I) containing (A) a titanium compound and / or a zirconium compound, and (B) a condensation reaction product of an aminosilane (b1) and a polysilyl functional silane (b2). A treatment liquid contact process in which a surface treatment liquid is brought into contact with a metal material, a water washing process in which the metal material that has undergone the treatment liquid contact process is washed with water, and a painting process in which a baking paint (II) is applied onto the obtained surface treatment film layer A method of painting a metal material including
The aminosilane (b1) in the condensation reaction product (B) is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane. N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyltriethoxysilane, and polysilyl functional silane (b2) Is represented by the following general formula (I):

(In Formula (I), R 1, R 2, R 3 and R 4 independently represent a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms. Y represents a divalent organic group or amine. X 1 And X2 independently represent a hydrolyzable group, a and b are independently 0, 1, or 2 and 0 ≦ a + b ≦ 2, c and d are independently 0, 1 or 2 and 0 ≦ c + d ≦ 2), and the use ratio of aminosilane (b1) and polysilyl functional silane (b2) is 50/50 to 99/1 in molar ratio,
A metal characterized in that the baked paint (II) is a powder paint containing a carboxyl group-containing polyester resin and a hydroxyalkylamide compound, or a powder paint containing a hydroxyl group-containing polyester resin and a blocked polyisocyanate compound. The present invention relates to a method of painting a material.

  According to the method of the present invention, by adding a specific silane condensation reaction product to a zirconium-based or titanium-based surface treatment agent, the obtained surface-treated film has corrosion resistance comparable to chromate treatment or zinc phosphate treatment. Furthermore, it is very excellent in adhesion with a coating film formed by a coating process after treatment. In particular, even when a baking coating that generates a large shrinkage stress in the coating film during baking is used, the coating film does not cause poor adhesion.

  Therefore, the method of the present invention is very useful for industrial coating applications such as home appliances and steel furniture.

  The metal surface treatment composition (I) used in the method of the present invention contains a titanium compound and / or a zirconium compound (A), and a condensation reaction product (B) of an aminosilane (b1) and a polysilyl functional silane (b2). .

  The titanium compound and / or zirconium compound (A) is blended to form a chemical conversion film containing titanium and / or zirconium on the surface of the metal material, and a metal surface treatment liquid containing the composition (I) is used. When contacted with a metal material, it is possible to deposit a chemical conversion coating layer containing an oxide and / or hydroxide of titanium and / or zirconium on the surface of the metal material.

  The titanium compound and / or zirconium compound (A) is usually at least one compound selected from titanium halides and salts thereof, zirconium halides and salts thereof, zirconium carbonate and salts thereof, and zirconyl nitrate. Preferably, it contains at least one compound selected from zirconium fluoride, titanium fluoride, zirconium carbonate and salts thereof, and zirconyl nitrate.

  Specific examples thereof include, for example, zirconium hydrofluoric acid, sodium zirconium fluoride, potassium zirconium fluoride, lithium zirconium fluoride, ammonium zirconium fluoride, zirconium carbonate, zirconyl nitrate, titanium hydrofluoric acid, sodium titanium fluoride, Examples include potassium titanium fluoride, lithium titanium fluoride, and ammonium ammonium fluoride. Of these, zirconyl nitrate, zirconium ammonium fluoride, and titanium ammonium fluoride are particularly suitable.

  The content of the titanium and / or zirconium compound (A) in the metal surface treatment composition (I) is 5 to 10,000 ppm, preferably 20 to 2,000 ppm, more preferably 50 to 500 ppm in terms of metal element. It is suitable from the point of ensuring the amount of the film deposited on the surface of the metal material and economical.

  The condensation reaction product (B) of the aminosilane (b1) and the polysilyl functional silane (b2) is blended for improving the corrosion resistance of the film and improving the adhesion with the coating film formed by the coating process after the treatment. Yes, usually obtained by hydrolyzing aminosilane (b1) and polysilyl functional silane (b2) in water, alcohol, acidic aqueous solution or the like. When an acid is used for hydrolysis, for example, hydrochloric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid and the like can be used.

  As aminosilane (b1), for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, and the like.

  The polysilyl functional silane (b2) is preferably one represented by the following general formula (I).

(In the formula (I), R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms. Y represents a divalent organic group or an amine. X ¹ and X ² independently represent a hydrolyzable group, a and b are independently 0, 1, or 2 and 0 ≦ a + b ≦ 2, and c and d are , Independently, 0, 1, or 2 and 0 ≦ c + d ≦ 2.)
In the above, R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms. Examples of monovalent organic groups include hydrocarbon groups such as alkyl groups, alkenyl groups, cycloalkyl groups, and aryl groups; hydrocarbon groups having functional groups such as hydroxyl groups, epoxy groups, and amino groups, and particularly methyl groups. And a lower alkyl group such as an ethyl group is preferred.

  In the above, Y represents a divalent organic group or amine. Examples of the divalent organic group include an alkylene group, an alkyleneoxy group, and an alkylenethio group, or a group containing these groups as a partial structure, and an alkylene group is particularly preferable. These carbon numbers are preferably 2 to 30, particularly 2 to 12.

^{X 1} and ^{X 2} in the above shows a hydrolyzable group. As a hydrolysable group, a C1-C4 alkoxyl group is mentioned, A methoxyl group and an ethoxyl group are especially preferable. Moreover, both a + b and c + d are preferably 0 or 1.

  Specific examples of the polysilyl functional silane (b2) include, for example, bis (trimethoxysilyl) methane, bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1,2-bis (tri Methoxysilyl) ethane, bis (triethoxysilyl) hexane, bis (trimethoxysilyl) hexane, 1,9-bis (triethoxysilyl) nonane, 1,9-bis (trimethoxysilyl) nonane, 1,8-bis (Triethoxysilyl) octane, bis (trimethoxysilyl) amine, bis (triethoxysilyl) amine, bis (triethoxysilylmethyl) amine, bis (triethoxysilylpropyl) amine, etc. , 2-Bis (triethoxysilyl) ethane is safe for handling, improved corrosion resistance of the coating, and coating It is preferred in view of adhesion improvement.

  The aminosilane (b1) and polysilyl functional silane (b2) are used in a molar ratio of 50/50 to 99/1, preferably 70/30 to 99/1, and more preferably 80/20 to 95/5. The range is preferable from the viewpoints of preventing gelation during production, improving the corrosion resistance of the film, and economical.

  In the present invention, when the condensation reaction product (B) is produced, in addition to the aminosilane (b1) and the polysilyl functional silane (b2), an organosilane (b3) other than these may be added as necessary.

  Examples of such organosilane (b3) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, and vinyltrimethoxy. Silane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane 3-acryloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. It is. The organosilane (b3) is used from the viewpoint of precipitation control as long as the solubility in a solvent is not hindered, and is usually 100 mol% with respect to the total molar amount of the aminosilane (b1) and the polysilyl functional silane (b2). Hereinafter, it is desirable to use it at 50 mol% or less.

  The content of the component (B) in the metal surface treatment composition (I) is in the range of 1 to 5,000 ppm, preferably 20 to 500 ppm in terms of solid content concentration, ensuring the coating amount and economical points. To preferred.

  The metal surface treatment composition (I) further includes magnesium, zinc, calcium, aluminum, gallium, indium, copper, iron, manganese, nickel, cobalt, cerium, strontium, rare earth elements, tin, bismuth, yttrium, vanadium, It is preferable to further contain at least one metal element selected from the group consisting of barium, chromium, molybdenum, tungsten, and silver from the viewpoints of improving the corrosion resistance of the coating and improving the adhesion to the coating. The supply source of these metal elements is not particularly limited, and can be blended in the chemical conversion treatment agent as, for example, nitrate, sulfate, or fluoride. In addition, these metal elements may be metal ions eluted when an object to be processed such as an iron-based substrate, an aluminum-based substrate, or a zinc-based substrate is processed.

  When the metal element is contained in the metal surface treatment composition (I), the content is suitably in the range of 0.1 to 5,000 ppm in terms of metal element.

  Among the above metal elements, magnesium, aluminum, and the like are suitable particularly from the viewpoint of improving adhesion to the coating film, and the content thereof is in the range of 1 to 5,000 ppm, preferably 20 to 2,000 ppm. Is appropriate. Also, from the viewpoint of improving the corrosion resistance of the film, copper, vanadium, and the like are suitable, and the content is suitably in the range of 0.5 to 100 ppm, preferably 2 to 50 ppm.

  The metal surface treatment composition (I) is at least selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, phosphonic acid, hypophosphorous acid and salts thereof from the viewpoints of promoting film formation and improving the corrosion resistance of the film. One kind can be further contained. The content thereof is suitably in the range of 1 to 50,000 ppm, preferably 5 to 30,000 ppm in terms of solid content.

  The metal surface treatment composition (I) can further contain a water-soluble or water-dispersible organic resin from the viewpoints of improving the corrosion resistance of the film and improving the adhesion to the coating film. Examples of the water-soluble or water-dispersible organic resin include epoxy resin, acrylic resin, polyester resin, polyallylamine resin, polyvinylamine resin, polybutadiene resin, polyurethane resin, polyvinyl alcohol, and ethylene-vinyl acetate resin. Moreover, a melamine resin, a benzoguanamine resin, a urea resin, (block) polyisocyanate, a phenol resin, etc. can be mix | blended suitably as needed.

  When the water-soluble or water-dispersible organic resin is used in the metal surface treatment composition (I), the content thereof is 0.1 to 300,000 ppm, preferably 5 to 5,000 ppm in terms of solid content. It is desirable that it is within the range from the viewpoints of film formability, improved corrosion resistance of the film, and improved adhesion to the film.

  The metal surface treatment composition (I) can further contain a surfactant for the purpose of improving the stability and precipitation of the composition. Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. Among these, anionic surfactants, nonionic surfactants, and these Those used in combination are preferred.

  Examples of the anionic surfactant include fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, and alkyl phosphates. Examples of the cationic surfactant include alkylamine salts and quaternary ammonium salts.

  When a nonionic surfactant is used, the HLB is 8 or more, preferably about 10 to about 20. The HLB is an abbreviation for Hydrophile-Lipophile Balance showing the balance between the hydrophilic group and the lipophilic group in the molecule. Examples of such nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene derivatives, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, and polyoxyethylene fatty acid. Examples thereof include esters, polyoxyethylene alkylamines, and alkyl alkanolamides.

  When an anionic surfactant and a nonionic surfactant are used in combination, the anionic surfactant / nonionic surfactant = 99.9 / 0.1 (mass%) based on the total solid content of both components ) To 10/90 (mass%), preferably in the range of 80/20 (mass%) to 50/50 (mass%).

  When the surfactant is used in the metal surface treatment composition (I), the content thereof is in the range of 5 to 300,000 ppm, preferably 25 to 100,000 ppm in terms of solid content. It is preferable from the viewpoints of sufficient degreasing treatment, economy and the like.

  The pH of the metal surface treatment composition (I) is preferably in the range of 1.5 to 6.5, particularly 3.0 to 4.5. For adjusting the pH, the above-mentioned acidic compounds such as nitric acid and sulfuric acid and basic compounds such as sodium hydroxide, potassium hydroxide and ammonia can be used.

  In addition to the above components, the metal surface treatment composition (I) can contain any component as necessary, and examples thereof include silica such as water-dispersible silica.

  The metal surface treatment method of the present invention includes a treatment liquid contact step in which a metal surface treatment liquid containing the metal surface treatment composition (I) obtained as described above is brought into contact with a metal material, and a metal material that has undergone the treatment liquid contact step. A water-washing step of washing the water and a coating step of painting the baked paint (II) on the surface treatment film layer obtained.

  The treatment liquid contact step is not particularly limited, and for example, a method such as a dipping method, a spray method, or a roll coating method can be employed. It is preferable to perform the treatment by adjusting the temperature of the treatment liquid within a range of 20 to 70 ° C, particularly 30 to 55 ° C.

  Examples of the metal material usually include iron-based substrates, aluminum-based substrates, and zinc-based substrates. Iron, aluminum, and zinc-based substrate are iron-based substrates in which the substrate is made of iron and / or an alloy thereof, aluminum substrates in which the substrate is made of aluminum and / or an alloy thereof, and the substrate is made of zinc and / or Or the zinc-type base material consisting of the alloy is meant. The metal surface treatment composition (I) should also be used for chemical conversion treatment of an object to be coated consisting of a plurality of metal substrates among an iron-based substrate, an aluminum-based substrate, and a zinc-based substrate. Can do. The method of the present invention is particularly suitable for an iron-based substrate.

  These metal materials are preferably subjected to a degreasing process and a degreasing water washing process before the treatment liquid contact process, and a water washing process after the treatment liquid contact process.

  The degreasing treatment is performed to remove oil and dirt adhering to the surface of the base material, and usually with a degreasing agent such as a phosphorus-free and nitrogen-free degreasing cleaning solution at 30 to 70 ° C. for several seconds to Immersion treatment is performed for several minutes. If desired, a preliminary degreasing process can be performed before the degreasing process.

  The water washing step after contact with the treatment liquid is performed once or more so as not to adversely affect the adhesion, corrosion resistance and the like after the various coatings. In this case, it is appropriate that the final water washing is performed with pure water. This water washing treatment may be either spray water washing or immersion water washing, and these methods may be combined for water washing.

  A drying process can be employ | adopted as needed after the said water washing process. When performing a drying process, cold air drying, hot air drying, etc. can be performed.

The film obtained from the metal surface treatment composition (I) by the method of the present invention has an adhesion amount to the metal material of 0.1 to 2,000 mg / m ² , especially 5 to 200 mg in terms of the metal element contained in the treatment agent. / M ² is preferable from the standpoints of improving the corrosion resistance of the coating and improving the adhesion to the coating.

  In the coating step according to the method of the present invention, the baking paint (II) is applied onto the film obtained as described above.

  As the baked paint (II), a conventionally known baked paint can be used without particular limitation, and examples thereof include organic solvent diluted paint, water-based paint, and powder paint.

  Examples of the organic solvent dilution type paint include polyester resin, alkyd resin, epoxy resin, acrylic resin, urethane resin, fluororesin, vinyl chloride resin, and modified resins thereof as base resin components. Examples include amino resins that can react with functional groups such as hydroxyl groups and epoxy groups in the resin component (for example, melamine resins), (blocked) polyisocyanate compounds, and polycarboxylic acid containing curing agents, Of these, polyester / melamine resin-based paints, alkyd / melamine resin-based paints, acrylic resin-based paints, and the like can be suitably used.

  The organic solvent dilution type paint further contains an organic solvent, and if necessary, paints such as curing catalysts, pigments, antifoaming agents, coating surface conditioners, antisettling agents, pigment dispersants, formalin supplements, etc. Additives are appropriately blended.

  The organic solvent-diluted paint is a roll coating method, spray coating method, brush coating method, electrostatic coating method, dipping method, curtain coating method, roller coating on a film obtained from the metal surface treatment composition (I). A coating film can be formed by coating and drying by a known method such as a method. Although the film thickness of this coating film is not specifically limited, Usually, 3-100 micrometers, Preferably it is selected in 15-50 micrometers. What is necessary is just to set drying of a coating film suitably according to the kind of resin to be used, etc. However, when the thing painted by the coil coating method etc. is baked continuously, normally a material reach | attainment maximum temperature is 160-250. It is baked for 15 to 60 seconds under the condition of ° C, preferably 180 to 230 ° C. When baking by a batch type, it can carry out by baking for 5 to 60 minutes, for example at atmospheric temperature 80-180 degreeC.

  The above-mentioned powder coating is obtained by melt-kneading a coating composition containing a coating film-forming resin and a color pigment or extender pigment and other additives that are added as necessary, and pulverized into powder. It can be produced by a known method. As the film-forming resin, a thermosetting resin or a thermoplastic resin that has been conventionally used as a film-forming resin for powder coatings can be used, and a thermosetting resin is generally used. As such a thermosetting resin, for example, (i) a combination of a hydroxyl group-containing solid resin and a curing agent having a functional group that undergoes a curing reaction with the hydroxyl group by heat, (ii) a carboxyl group-containing solid resin, A combination of a carboxyl group and a curing agent having a functional group that undergoes a curing reaction by heat, and (iii) a combination of an epoxy group-containing solid resin and a curing agent having a functional group that undergoes a curing reaction by the epoxy group and heat. it can. The “solid” of the resin here means a solid at room temperature, and preferably has a softening point of 80 to 200 ° C. Further, the curing agent may be solid or liquid, but a solid one is preferably used.

  As the hydroxyl group-containing solid resin, for example, a resin used in a known powder coating material such as a hydroxyl group-containing acrylic resin or a hydroxyl group-containing polyester resin can be used. Examples of the “curing agent having a functional group that undergoes a curing reaction with a hydroxyl group and heat” that can be used in combination with the hydroxyl group-containing solid resin are used in known powder coatings such as blocked polyisocyanate compounds and aminoplast resins. A curing agent can be used. As the carboxyl group-containing solid resin, for example, a resin used in a known powder coating such as a carboxyl group-containing acrylic resin and a carboxyl group-containing polyester resin can be used. Examples of the “curing agent having a functional group that undergoes a curing reaction with a carboxyl group by heat” that can be used in combination with this carboxyl group-containing solid resin include, for example, bisphenol A to epichlorohydrin type epoxy resin, alicyclic epoxy resin, and novolac type epoxy resin. Curing agents used in known powder coating materials such as epoxy resins such as epoxy group-containing acrylic resins and hydroxyalkylamide compounds can be used. As the epoxy group-containing solid resin, for example, bisphenol A to epichlorohydrin type epoxy resin, alicyclic epoxy resin, novolac type epoxy resin, epoxy group-containing acrylic resin, and other resins used in known powder coatings can be used. . Examples of the “curing agent having a functional group that undergoes a curing reaction with an epoxy group and heat” that can be used in combination with the epoxy group-containing solid resin include, for example, a carboxyl group-containing polyester resin, an organic acid polyhydrazide compound, an imidazole compound, a dicyandiamide compound, Curing agents used in known powder coating materials such as polycarboxylic acid compounds and acid anhydrides can be used.

  Of these, a combination of a carboxyl group-containing polyester resin and a hydroxyalkylamide compound is particularly preferred from the viewpoint of good corrosion resistance of the formed coating film even at a low baking temperature.

  The powder coating is applied on the film obtained from the metal surface treatment composition (I) by a known method such as electrostatic coating, fluid dipping, spraying, or in-mold method. A cured coating film can be formed by baking in an outer furnace, an induction heating furnace, or the like. The film thickness of the formed coating film is the film thickness after baking, and is usually 30 to 250 μm, and preferably in the range of 40 to 150 μm. Appropriate baking conditions for the powder coating are a surface temperature of the metal material of 130 to 350 ° C., preferably 140 to 250 ° C., and 30 seconds to 60 minutes, preferably 1 to 50 minutes.

  In this invention, even if it is a case where the coating material with high shrinkage stress of a cured coating film is used among the said coating materials (II), it is excellent in the adhesiveness of a coating film.

  Moreover, the coated metal plate obtained as described above may have only a coating film formed of the coating material, or may have a multilayer structure in which a top coating film is appropriately formed.

  Hereinafter, the present invention will be described in more detail with reference to examples. Hereinafter, “parts” and “%” represent “parts by mass” and “% by mass”, respectively.

Production Example 1 of Silane Condensation Reaction Product (B)
200 g of isopropanol and 200 g of deionized water were charged into a 1 L round bottom flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirrer, and stirring was started. Nitrogen was blown into the gas phase, and 90 g of 3-aminopropyltrimethoxysilane and 10 g of bis (triethoxysilyl) ethane were added all at once with stirring. After stirring at room temperature for 1 hour and reacting at 60 ° C. for 6 hours, the fraction was removed, and the temperature was raised until the boiling point reached 120 ° C. while exchanging with propylene glycol monomethyl ether. After cooling to 60 ° C., the solution was concentrated by distillation under reduced pressure to obtain 120 g of a 40% nonvolatile solution of the product (P1). The obtained 40% non-volatile solution of the product (P1) was a colorless transparent viscous liquid.

Production Examples 2-12
In Production Example 1, each product (P1) to (P8) and (R1) to (R4) was obtained in the same manner as in Production Example 1 except that the raw material composition was as shown in Table 1.

Examples 1-26 and Comparative Examples 1-4
Preparation of composition for metal surface treatment Table (2) using (P1) to (P8) and (R1) to (R4) prepared above with zircon hydrofluoric acid and titanium hydrofluoric acid, nitrates of each metal, and the like. A metal surface treatment composition having the composition shown in FIG. In Table 2, the concentration of each metal component is shown in terms of metal element, and the concentration of the other components indicates the solid content concentration. In Table 2, (Note 1) to (Note 3) indicate the following.

(Note 1) Organic resin: “PAA25”, trade name, manufactured by Nittobo Co., Ltd., polyallylamine resin aqueous solution (Note 2) Surfactant: “New Coal 1100”, trade name, manufactured by Nippon Emulsifier Co., Ltd., nonionic interface Activator (Note 3) Silica: “Snowtex O”, trade name, manufactured by Nissan Chemical Industries, Ltd., water dispersible (colloidal) silica

Chemically treated cold-rolled steel sheet (SPCC-SD, manufactured by Nippon Test Panel, 70 mm x 150 mm x 0.8 mm), galvanized steel sheet (GA steel sheet, manufactured by Nippon Test Panel, 70 mm x 150 mm x 0.8 mm) The following processes and Table 2 using 5000 series aluminum (Nihon Test Panel, 70 mm x 150 mm x 0.8 mm) or 6000 series aluminum (Nihon Test Panel, 70 mm x 150 mm x 0.8 mm) as a base material The chemical conversion treatment was performed under the following conditions.

  (1) The substrate was immersed in a commercially available degreasing solution adjusted to 40 ° C. for 2 minutes for degreasing treatment, and then washed with tap water for 30 seconds.

  (2) Next, as shown in Table 3, the metal substrate after washing with water was immersed in the metal surface treatment compositions of Examples and Comparative Examples adjusted to pH and temperature for 10 to 300 seconds. The pH was adjusted to 3.2-4.2 using nitric acid or sodium hydroxide. The temperature was adjusted to 35-50 ° C.

  (3) Each substrate after the above treatment was washed with tap water for 30 seconds, and further washed with ion-exchanged water for 30 seconds. Subsequently, it was made to dry at 80 degreeC for 5 minute (s) using the hot air drying furnace, and it was set as each chemical conversion treatment board.

  The amount of the coating film on each chemical conversion treatment plate was analyzed as the total amount of the deposited metal using “XRF1700” (manufactured by Shimadzu Corporation, fluorescent X-ray analyzer). The results are shown in Table 3.

Preparation of test coating plate (1) On each chemical conversion treatment plate obtained above, “Magiclon # 1000” (manufactured by Kansai Paint Co., Ltd., acrylic / melamine resin-based organic solvent dilution type paint) was adjusted to a dry film thickness of 30 μm. Each test coating plate was prepared by performing air spray coating and heating and baking at 160 ° C. for 30 minutes. Each obtained test coating board was used for the following evaluation test. The results are shown in Table 3.

Preparation of test coating plate (2) On each of the chemical conversion treatment plates obtained above, “Amilak # 1000” (manufactured by Kansai Paint Co., Ltd., alkyd / melamine resin organic solvent dilution type paint) was dried to a thickness of 30 μm. Each test coating plate was prepared by performing air spray coating and heating and baking at 130 ° C. for 30 minutes. Each obtained test coating board was used for the following evaluation test. The results are also shown in Table 3.

Preparation of test coating plate (3) On each chemical conversion treatment plate obtained above, “ASIME” (manufactured by Kansai Paint Co., Ltd., polyester / melamine resin organic solvent dilution paint) is air sprayed so that the dry film thickness becomes 30 μm. Coating was performed, and heating was performed at 140 ° C. for 30 minutes, followed by baking to prepare each test coating plate. Each obtained test coating board was used for the following evaluation test. The results are also shown in Table 3.

Preparation of test coating plate (4) On each chemical conversion treatment plate obtained above, “Evaclad 8900” (manufactured by Kansai Paint Co., Ltd., carboxyl group-containing polyester resin / hydroxyalkylamide compound-containing powder coating material) is 60 μm in dry film thickness. Electrostatic powder coating was performed so that the test coating plates were prepared by heating at 150 ° C. for 30 minutes and baking. Each obtained test coating board was used for the following evaluation test. The results are also shown in Table 3.

Preparation of test coating plate (5) On each chemical conversion treatment plate obtained above, “Evaclad 4900” (manufactured by Kansai Paint Co., Ltd., hydroxyl group-containing polyester resin / blocked polyisocyanate compound-containing powder coating material) was 70 μm in dry film thickness. Electrostatic powder coating was performed as described above, and each test coating plate was prepared by baking at 180 ° C. for 30 minutes. Each obtained test coating board was used for the following evaluation test. The results are also shown in Table 3.

Comparative Example 5
Except for using a commercially available zinc phosphate-based chemical conversion treated steel plate (base material: SPCC-SD, manufactured by Nippon Test Panel Co., Ltd.), each coating was carried out in the same manner as in Examples 1-26 and Comparative Examples 1-4. It was created. Each obtained test coating board was used for the following evaluation test. The results are also shown in Table 3.

Comparative Example 6
Except for using a commercially available zinc phosphate-based chemical conversion treated steel plate (base material: GA steel plate, manufactured by Nippon Test Panel Co., Ltd.), each coating is carried out in the same manner as in Examples 1-26 and Comparative Examples 1-4. Created. Each obtained test coating board was used for the following evaluation test. The results are also shown in Table 3.

Comparative Example 7
Except for using a commercially available chromate-based chemical conversion treatment plate (base material: 5000 series aluminum, manufactured by Nippon Test Panel Co., Ltd.), each coating is made in the same manner as in Examples 1-26 and Comparative Examples 1-4. did. Each obtained test coating board was used for the following evaluation test. The results are also shown in Table 3.

Evaluation test (* 1) Corrosion resistance: The test coating plates (1) to (3) of each example and comparative example were cross-cut with a knife so as to reach the substrate, and this was subjected to a salt spray corrosion test (SST: According to JIS Z-2371, salt water temperature of 35 ° C. was used for 240 hours, and then the knife wound part was attached and peeled with an adhesive tape, and the peel width of the coating film was measured. Moreover, about the test coating board (4)-(5) of each Example and a comparative example, a cross-cut damage | wound is put into a coating film with a knife so that it may reach a base, and this is applied to a salt spray corrosion test (SST: JISZ-2371). (Salt water temperature 35 ° C.) for 480 hours, and then the adhesive film was attached to and peeled from the knife scratches, and the peel width of the coating film was measured. The evaluation criteria are as follows.

◎: No peeling ○: Peeling width within 3 mm △: Peeling width exceeding 3 mm and within 5 mm ×: Peeling width exceeding 5 mm

  (* 2) (After water resistance) Adhesiveness: The test coating plates (1) to (5) of each Example and Comparative Example were immersed in warm water (40 ° C.) for 240 hours, and immediately after pulling up (10 × 10 pieces) (1 mm interval) cuts were made, and sticking / peeling with an adhesive tape was performed, and the number of peeling masses of the coating film was examined. The evaluation criteria are as follows.

◎: No peeling mass ○: Within 5 peeling cells △: 6-10 peeling cells ×: 11 or more peeling cells

Claims (8)

(A) A metal surface treatment liquid comprising a metal surface treatment composition (I) containing a titanium compound and / or a zirconium compound, and (B) a condensation reaction product of an aminosilane (b1) and a polysilyl functional silane (b2). A metal comprising: a treatment liquid contact step for contacting a metal material; a water washing step for washing the metal material that has undergone the treatment liquid contact step; and a painting step for painting a baking paint (II) on the surface treatment film layer obtained. A method of painting a material,
The aminosilane (b1) in the condensation reaction product (B) is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane. N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyltriethoxysilane, and polysilyl functional silane (b2) Is represented by the following general formula (I):

(In Formula (I), R 1, R 2, R 3 and R 4 independently represent a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms. Y represents a divalent organic group or amine. X 1 And X2 independently represent a hydrolyzable group, a and b are independently 0, 1, or 2 and 0 ≦ a + b ≦ 2, c and d are independently 0, 1 or 2 and 0 ≦ c + d ≦ 2), and the use ratio of aminosilane (b1) and polysilyl functional silane (b2) is 70/30 to 99/1 in molar ratio,
A metal characterized in that the baked paint (II) is a powder paint containing a carboxyl group-containing polyester resin and a hydroxyalkylamide compound, or a powder paint containing a hydroxyl group-containing polyester resin and a blocked polyisocyanate compound. How to paint the material.

Content of titanium compound and / or zirconium compound (A) in metal surface treatment composition (I) is 5 to 10,000 ppm in terms of metal element, and condensation of aminosilane (b1) and polysilyl functional silane (b2) The method for coating a metal material according to claim 1, wherein the content of the reactant (B) is 1 to 5,000 ppm in terms of solid content. 2. The titanium compound and / or zirconium compound (A) contains at least one compound selected from titanium halides and salts thereof, zirconium halides and salts thereof, zirconium carbonate and salts thereof, and zirconyl nitrate. Or the coating method of the metal material of 2. The titanium compound and / or zirconium compound (A) contains at least one compound selected from zirconium fluoride, titanium fluoride, zirconium carbonate and salts thereof, and zirconyl nitrate. The coating method of the metal material as described in 2. Metal surface treatment composition (I) is magnesium, zinc, calcium, aluminum, gallium, indium, copper, iron, manganese, nickel, cobalt, cerium, strontium, rare earth element, tin, bismuth, yttrium, vanadium, barium, The method for coating a metal material according to any one of claims 1 to 4, further comprising at least one metal element selected from the group consisting of chromium, molybdenum, tungsten, and silver. The metal surface treatment composition (I) further contains at least one selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, phosphonic acid, hypophosphorous acid, and salts thereof. 2. A method for coating a metal material according to item 1. The method for coating a metal material according to any one of claims 1 to 6, wherein the metal surface treatment composition (I) further contains a water-soluble or water-dispersible organic resin. The method for coating a metal material according to any one of claims 1 to 7, wherein the metal surface treatment composition (I) further contains a surfactant.