TWI500814B - Composition for metal surface treatment, metal surface treatment method and coating method of metal material - Google Patents

Description

Metal surface treatment composition, metal surface treatment method, and metal material coating method

The present invention relates to a metal surface treatment composition, a metal surface treatment method, and a metal material coating method.

Conventionally, in order to improve the corrosion resistance of a metal surface, chromate treatment and phosphate treatment are usually performed. However, in recent years, the toxicity of chromium is becoming a social problem. The surface treatment method using chromate also has the problem of chromate soot scattering in the processing steps, the extremely high cost of the drainage treatment equipment, and the conversion of chromic acid from the chemical. Problems such as dissolution in the treated film.

Further, in the phosphate treatment, surface treatments of zinc phosphates and iron phosphates are usually carried out, and in order to impart corrosion resistance, after the phosphate treatment, chromic acid is usually used for rinsing treatment, so that there is a problem of chromium treatment. At the same time, there are problems such as a reaction catalyst in a phosphate treatment agent, a drainage treatment such as metal ions, and a sludge treatment in which metal ions are eluted from the metal to be treated.

On the other hand, a surface treatment agent of zirconium or titanium is known as a treatment method other than the chromate treatment or the phosphate treatment. For example, Japanese Laid-Open Patent Publication No. 2003-155578 proposes a chemical conversion treatment agent for an iron and/or zinc-based substrate containing substantially no phosphate ions and containing zirconium ions and/or titanium ions and fluorine ions. . In International Publication No. 02/103080, the use of a compound containing (I) containing at least one metal element selected from the group consisting of Ti, Zr, Hf and Si, and (II) as a source of a fluoride ion is disclosed. The metal surface treatment composition of the fluorine compound can precipitate a surface treatment film having excellent corrosion resistance on a metal surface containing at least one of iron or zinc, and can shorten the treatment step since the surface adjustment step is not required. To achieve space savings.

In addition, Japanese Laid-Open Patent Publication No. 2003-253461 discloses an iron containing zirconium ions and/or titanium ions, fluoride ions and soluble epoxy resins, and substantially free of phosphate ions, and having a pH of 2.5 to 4.5. A composition for metal surface treatment of a substrate.

Further, Japanese Laid-Open Patent Publication No. 2005-2370 discloses a surface treatment method for an aluminum-based substrate, which is characterized in that chemical conversion treatment is carried out by using a chemical conversion treatment agent formed of a compound containing fluorine and zirconium, thereby The step (1) of forming a chemical conversion film on the surface of the aluminum-based substrate, and the step (2) of forming a hydrophilic film using a hydrophilic treatment agent, and the chemical conversion treatment reaction described above are subjected to chemical conversion treatment by electrolytic treatment.

In addition, Japanese Laid-Open Patent Publication No. 2006-255540 discloses an amorphous surface treatment layer containing an oxide and/or a hydroxide containing zirconium and/or titanium on the surface of a metal material as a powder coating. A method of coating a substrate or a solid lubricant coated substrate.

However, when any of the surface treatment compositions described above is used, there is a corrosion resistance which is not comparable to chromate treatment or zinc phosphate treatment, and a coating film formed by a coating step after the treatment. The adhesion is not sufficient.

An object of the present invention is to provide a metal surface treatment composition, a metal surface treatment method, and a metal material coating method, which can form a treatment film obtained by treating a chromate or a phosphate The film is treated with considerable corrosion resistance, and a film which is excellent in adhesion to the coating film formed by the coating step after the treatment can be formed.

As means for achieving the above object of the present invention, the following [1], [2], and [3] can be provided.

[1] An invention for providing a composition for metal surface treatment characterized by containing (A) a titanium compound and/or a zirconium compound, and (B) an amino decane (b1) and a polydecyl-functional decane (b2) Condensation reactant.

[2] An invention for a metal surface treatment method comprising the step of contacting a treatment liquid in contact with a metal surface treatment liquid containing the metal surface treatment composition according to [1], and the treatment The water-washing step of the metal material in the liquid contacting step.

[3] An invention of a coating method for a metal material, comprising the step of contacting a treatment liquid for contacting a metal surface treatment liquid containing the metal surface treatment composition according to [1] with a metal material, The water washing step of washing the metal material of the treatment liquid contacting step and the coating step of coating the sintered coating material (II) on the obtained surface treatment coating layer.

Embodiments of the present invention will be described below.

In the present invention, the titanium compound and/or the zirconium compound (A) is a compound for forming a chemical conversion film containing titanium and/or zirconium on the surface of a metal material, and is a metal containing the composition of the present invention. When the surface treatment liquid is brought into contact with the metal material, a chemical conversion film containing oxides and/or hydroxides of titanium and/or zirconium may be chromatographed onto the surface of the metal material.

The titanium compound and/or the zirconium compound (A) usually contains at least one compound selected from the group consisting of a halide of titanium and a salt thereof, a halide of zirconium and a salt thereof, zirconium carbonate and a salt thereof, and zirconium nitrate. It is preferred to contain at least one compound selected from the group consisting of zirconium fluoride, titanium fluoride, zirconium carbonate and salts thereof, and zirconium nitrate.

Specific examples thereof include fluorozirconic acid, sodium zirconium fluoride, potassium zirconium fluoride, lithium zirconium fluoride, ammonium zirconium fluoride, zirconium carbonate, zirconium nitrate, fluorotitanic acid, sodium titanium fluoride, and fluorination. Titanium potassium, lithium titanium fluoride, ammonium fluoride fluoride, and the like. Among them, zirconium nitrate, ammonium zirconium fluoride, and ammonium fluoride fluoride are particularly preferable.

In the composition of the present invention, the content of the titanium and/or zirconium compound (A) is from 5 to 10,000 ppm, preferably from 20 to 2,000 ppm, and more preferably from 50 to 500 ppm, in terms of metal element, which ensures the metal The viewpoint of the amount of the film deposited on the surface of the material, as well as economy and the like, is preferable.

In the present invention, the condensation reaction product (B) of the amino decane (b1) and the polydecylalkyl functional decane (b2) is used for improving the corrosion resistance of the film, and is improved by the coating step after the treatment. The substance to be adhered to the formed coating film is usually obtained by hydrolyzing an amino decane (b1) and a polydecyl-functional decane (b2) in water, an alcohol or an acidic aqueous solution or the like. When hydrolysis is carried out using an acid, for example, hydrochloric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid or the like can be used.

The amino decane (b1) may, for example, be 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-aminopropylmethyldiethoxydecane, or N. -phenyl-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3- Aminopropyltriethoxydecane, and the like.

The polyalkylene functional decane (b2) is preferably represented by the following formula (I).

(X ¹ ) _3-ab (R ¹ ) _a (R ² ) _b Si-Y-Si(R ³ ) _c (R ⁴ ) _d (X ² ) _3-cd ‧‧(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 independently represent 0, 1 or 2, and 0 ≦ a + b ≦ 2. c and d independently represent 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. The monovalent organic group may, for example, be a hydrocarbon group such as an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group; a hydrocarbon group having a functional group such as a hydroxyl group, an epoxy group or an amine group; and particularly preferably a methyl group or an ethyl group. Such as lower alkyl.

In the above, Y represents a divalent organic group or an amine. The divalent organic group may, for example, be an alkyl group, an alkylene ether group or an alkylthioether group, or a group containing these groups as a partial structure, and particularly preferably an alkylene group. These carbon atoms are 2 to 30, and particularly preferably 2 to 12.

In the above, X ¹ and X ² represent a hydrolyzable group. The hydrolyzable group may, for example, be an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group or an ethoxy group. Further, both a+b and c+d are preferably 0 or 1.

Specific examples of the above polyalkylene-functional decane (b2) include bis(trimethoxydecylalkyl)methane, bis(trimethoxydecylalkyl)ethane, and 1,2-di(triethoxy).矽alkyl)ethane, 1,2-bis(trimethoxydecyl)ethane, bis(triethoxydecyl)hexane, bis(trimethoxydecyl)hexane, 1,9-di ( Triethoxynonyl) decane, 1,9-bis(trimethoxydecyl)decane, 1,8-bis(triethoxydecyl)octane, bis(trimethoxydecyl)amine , bis(triethoxydecyl)amine, bis(triethoxydecylmethyl)amine, bis(triethoxydecylpropyl)amine, etc., among which, the safety of the operation and the improvement of the film resistance are improved. From the viewpoint of corrosiveness, adhesion to a coating film, and the like, 1,2-bis(triethoxydecyl)ethane is preferred.

The ratio of the above-mentioned amino decane (b1) and polydecyl-functional decane (b2) is 50/50 to 99/1, preferably 70/30 to 99/1 in terms of a molar ratio, and further preferably In the range of 80/20 to 95/5, it is preferable from the viewpoints of preventing gelation at the time of production, improving corrosion resistance of the film, economy, and the like.

In the present invention, in addition to the above-described amino decane (b1) and polydecyl-functional decane (b2), the organic decane (b3) other than the above may be appropriately added as needed in the production of the condensation reaction product (B).

As such an organic decane (b3), for example, methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, 2-(3,4 ring) Oxycyclohexyl)ethyltrimethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, p-styryltrimethoxydecane, 3-methylpropenyloxypropylmethyldimethyl Oxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyltriethoxylate Alkane, 3-propenyloxypropyltrimethoxydecane, 3-chloropropyltrimethoxydecane, 3-mercaptopropylmethyldimethoxydecane, 3-mercaptopropyltrimethoxydecane, and the like. From the viewpoint of controlling precipitation, the organodecane (b3) is used in a range that does not hinder solubility in a solvent, and generally, relative to the total of the amino decane (b1) and the polydecyl-functional decane (b2) The amount of the ear is desirably used in an amount of 100 mol% or less, preferably 50 mol% or less.

In the composition of the present invention, the content of the component (B) is preferably from 1 to 5,000 ppm, and preferably from 20 to 500 ppm, in terms of solid content. This is preferable from the viewpoint of ensuring the amount of the film and economic efficiency.

The composition of the present invention preferably further contains magnesium, zinc, calcium, aluminum, gallium, indium, copper, iron, manganese, and nickel from the viewpoint of improving the corrosion resistance of the film and improving the adhesion to the coating film. At least one metal element of the group consisting of cobalt, ruthenium, osmium, rare earth elements, tin, antimony, bismuth, vanadium, niobium, chromium, molybdenum, tungsten and silver. The supply source of these metal elements is not particularly limited, and for example, it can be blended as a nitrate, a sulfate, or a fluoride in a chemical conversion treatment agent. Further, these metal elements may be, for example, metal ions which are eluted when the object to be treated such as an iron-based substrate, an aluminum-based substrate, or a zinc-based substrate is treated.

When the metal element is contained in the composition of the present invention, the content thereof is preferably in the range of 0.1 to 5000 ppm in terms of metal element.

Among the above-mentioned metal elements, magnesium, aluminum, and the like are preferable, and the content thereof is preferably in the range of 1 to 5,000 ppm, and preferably 20 to 2,000 ppm, from the viewpoint of improving the adhesion to the coating film. Further, from the viewpoint of improving the corrosion resistance of the film, etc., copper, vanadium or the like is preferable, and the content thereof is preferably in the range of 0.5 to 100 ppm, and preferably in the range of 2 to 50 ppm.

The composition of the present invention may further contain at least one selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, phosphonic acid, hypophosphorous acid, and the like, from the viewpoint of further promoting film formation and improving corrosion resistance of the film. . The content thereof is preferably in the range of 1 to 50,000 ppm, and preferably 5 to 30,000 ppm, based on the solid content.

The composition of the present invention may further contain a water-soluble or water-dispersible organic resin from the viewpoint 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 an epoxy resin, an acrylic resin, a polyester resin, a polyallylamine resin, a polyvinylamine resin, a polybutadiene resin, and a polyurethane. Resin, polyvinyl alcohol, ethylene-vinyl acetate resin, and the like. Further, a melamine resin, a benzoguanamine resin, a urea resin, a (blocked) polyisocyanate, a phenol resin, or the like can be appropriately blended as needed.

When the water-soluble or water-dispersible organic resin is used in the composition of the present invention, the content is based on the solid content concentration from the viewpoints of the formation property of the film, the improvement of the corrosion resistance of the film, and the adhesion to the coating film. It is desirably in the range of 0.1 to 300,000 ppm, and preferably 5 to 5,000 ppm.

In order to further improve the stability and precipitation of the composition, the composition of the present invention may contain a surfactant. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant. Among them, an anionic surfactant, a nonionic surfactant, and preferably And use these together.

The anionic surfactant may, for example, be a fatty acid salt, an alkyl sulfate salt, an alkylbenzenesulfonate or an alkyl phosphate. The cationic surfactant may, for example, be an alkylamine salt or a quaternary ammonium salt.

When a nonionic surfactant is used, the HLB is 8 or more, and preferably in the range of about 10 to about 20. Further, the above HLB represents an equilibrium value of a hydrophilic group and a lipophilic group in the molecule, and is an abbreviation of Hydrophile-Lipophile Balance. Examples of such a nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene derivative, sorbitan fatty acid ester, and polyoxyethylene sorbitan fat. An acid ester, a glycerin fatty acid ester, a polyoxyethylene fatty acid ester, a polyoxyethylene alkylamine, an alkyl alkanolamine or the like.

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

When the surfactant is used in the composition of the present invention, the content thereof is preferably from 5 to 300,000 ppm, and more preferably from 25 to 100,000 ppm, from the viewpoint of performing sufficient degreasing treatment, economy, and the like.

The pH of the composition of the present invention is preferably from 1.5 to 6.5, and particularly preferably from 3.0 to 4.5. As the pH adjustment, an acidic compound such as nitric acid or sulfuric acid, or a basic compound such as sodium hydroxide, potassium hydroxide or ammonia can be used.

In the composition of the present invention, in addition to the above-mentioned components, an optional component may be blended as necessary, and examples thereof include cerium oxide such as water-dispersible cerium oxide.

The metal surface treatment method of the present invention comprises a step of contacting a treatment liquid containing a metal surface treatment liquid containing the metal surface treatment composition obtained as described above and a metal material, and washing the metal material having passed through the treatment liquid contacting step Washing steps.

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 preferred to adjust the temperature of the treatment liquid to a temperature of 20 to 70 ° C, particularly 30 to 55 ° C.

Examples of the metal material include an iron base material, an aluminum base material, and a zinc base material. The iron, aluminum and zinc-based substrate means that the substrate is an iron-based substrate formed of iron and/or an alloy thereof, the substrate is an aluminum-based substrate formed of aluminum and/or an alloy thereof, and the substrate is A zinc-based substrate formed of zinc and/or an alloy thereof. The composition of the present invention can also be used for chemical conversion treatment of a coated object formed of a plurality of metal substrates from an iron-based substrate, an aluminum-based substrate, and a zinc-based substrate. The method of the present invention is particularly preferably used for an iron-based substrate.

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

The above degreasing treatment is for removing oil and dirt adhering to the surface of the substrate, and the treatment is a degreasing agent such as a phosphorus-free or nitrogen-free degreasing washing liquid, and is usually carried out at 30 to 70 ° C for several seconds to several minutes. Left and right immersion treatment. Pre-degreasing treatment may also be carried out before degreasing treatment as needed.

In order not to adversely affect the adhesion, corrosion resistance, and the like after various coatings, the water washing step after the contact of the treatment liquid is performed one or more times. At this time, the final water washing is suitable for pure water. The water washing treatment may be spray water washing or immersion water washing, or these methods may be combined and washed with water.

After the above water washing step, a drying step may be employed as needed. When the drying step is performed, cold air drying, hot air drying, or the like can be performed.

In the film obtained by the method of the present invention, the amount of adhesion to the metal material is preferably from the viewpoint of the metal element contained in the treatment agent, from the viewpoint of improving the corrosion resistance of the film and improving the adhesion to the coating film. 0.1 to 2000 mg/m ² and particularly preferably 5 to 200 mg/m ² .

On the film obtained as described above, a conventionally known coating material may be used for coating to form a coating film layer, and an organic resin coating layer may be provided through the adhesive layer. As the coating material, a conventionally known coating material can be used without particular limitation, and examples thereof include an organic solvent-diluted coating material, an aqueous coating material, and a powder coating material.

Further, the coating method of the present invention comprises contacting a metal surface treatment liquid containing the metal surface treatment composition obtained as described above (sometimes referred to as "metal surface treatment composition (I)") with a metal material. The treatment liquid contacting step, the water washing step of washing the metal material subjected to the treatment liquid contacting step, and the coating step of applying the sintered coating material (II) on the obtained surface treatment coating layer.

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 preferred to adjust the temperature of the treatment liquid to a temperature of 20 to 70 ° C, particularly 30 to 55 ° C.

Examples of the metal material include an iron base material, an aluminum base material, and a zinc base material. The iron, aluminum and zinc-based substrate means that the substrate is an iron-based substrate formed of iron and/or an alloy thereof, the substrate is an aluminum-based substrate formed of aluminum and/or an alloy thereof, and the substrate is A zinc-based substrate formed of zinc and/or an alloy thereof. The metal surface treatment composition (I) can also be used for chemical conversion treatment of a coated object formed of a plurality of metal substrates from an iron base material, an aluminum base material, and a zinc base material. The method of the present invention is particularly preferably used for an iron-based substrate.

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

The above degreasing treatment is for removing oil and dirt adhering to the surface of the substrate, and the treatment is a degreasing agent such as a phosphorus-free or nitrogen-free degreasing washing liquid, and is usually carried out at 30 to 70 ° C for several seconds to several minutes. Left and right immersion treatment. Pre-degreasing treatment may also be carried out before degreasing treatment as needed.

The water washing step after the contact of the treatment liquid is performed one or more times in order not to adversely affect the adhesion, corrosion resistance, and the like after various coatings. At this time, the final water washing is suitable for pure water. The water washing treatment may be spray water washing or immersion water washing, and these methods may be combined for water washing.

After the above water washing step, a drying step may be employed as needed. When the drying step is performed, cold air drying, hot air drying, or the like can be performed.

In the method of the present invention, the film obtained by the metal surface treatment composition (I) has a treatment agent for the adhesion amount of the metal material from the viewpoint of improving the corrosion resistance of the film and improving the adhesion to the coating film. The metal element contained in the conversion is preferably 0.1 to 2000 mg/m ² , and particularly preferably 5 to 200 mg/m ² .

In the coating step of the method of the present invention, the sintered coating (II) is applied on the film obtained as described above.

As the sintered coating material (II), a conventionally known sintered coating material can be used without particular limitation, and examples thereof include an organic solvent-diluted coating material, an aqueous coating material, and a powder coating material.

Examples of the organic solvent-diluted coating material include a polyester resin, an alkyd resin, an epoxy resin, an acrylic resin, a urethane resin, a fluororesin, a vinyl chloride resin, and the like, and the like. The base resin component contains, if necessary, an amine-based resin (for example, a melamine resin), a (blocked) polyisocyanate compound, or a polybasic acid which can react with a functional group such as a hydroxyl group or an epoxy group in the matrix resin component. As the coating material of the curing agent, a polyester/melamine resin coating, an alkyd/melamine resin coating, an acrylic coating, or the like can be preferably used.

In the organic solvent-diluted coating material, an organic solvent is further blended, and if necessary, a coating agent such as a curing catalyst, a pigment, an antifoaming agent, a coating surface adjusting agent, an anti-settling agent, a pigment dispersing agent, or a fumarin additive is appropriately blended. additive.

The organic solvent-diluted coating material can be used for a composition for treating a metal surface by a known method such as a roll coating method, a spray coating method, a brush coating method, an electrostatic coating method, a dipping method, a curtain coating method, or a roll coating method ( I) Coating is performed on the obtained film, and a coating film is formed by drying. The film thickness of the coating film is not particularly limited, but is usually selected in the range of 3 to 100 μm, preferably 15 to 50 μm. The drying of the coating film may be appropriately set depending on the type of the resin to be used, etc., but when the material to be coated by the coil coating method or the like is continuously sintered, the maximum temperature of the material is usually 160 to 250 ° C. It is preferably sintered at 180 to 230 ° C for 15 to 60 seconds. When sintering is carried out in a batch type, for example, it may be carried out by sintering at a gas atmosphere temperature of 80 to 180 ° C for 5 to 60 minutes.

The powder coating material is a coating material which is obtained by melt-kneading a coating composition containing a coating film-forming resin, a coloring pigment or a filler pigment and other additives which are added as needed, and then pulverizing and pulverizing, and a known method can be used. Made for manufacturing. As the coating film-forming resin, a thermosetting resin or a thermoplastic resin which has been conventionally used as a coating film of a powder coating material to form a resin can be used, and the thermosetting resin is generally used. The thermosetting resin may, for example, be a combination of (i) a hydroxyl group-containing solid resin and a curing agent having a functional group which undergoes a curing reaction with the hydroxyl group by heat, (ii) a carboxyl group-containing solid resin, and a combination of a curing agent of a functional group which undergoes a curing reaction with the carboxyl group by heat, (iii) a combination of an epoxy group-containing solid resin, and a curing agent having a functional group which undergoes a curing reaction with the epoxy group by heat . The "solid" of the resin herein means a solid shape at normal temperature, and preferably has a softening point of 80 to 200 °C. Further, the curing agent may be in a solid shape or in a liquid form, and is preferably a substance having a solid shape.

As the hydroxyl group-containing solid resin, for example, a known resin for a powder coating material such as a hydroxyl group-containing acrylic resin or a hydroxyl group-containing polyester resin can be used. As a "curing agent having a functional group which undergoes a curing reaction with the hydroxyl group by heat", which can be used in combination with the hydroxyl group-containing solid resin, for example, a blocked polyisocyanate compound or an amine-based plastic resin can be used. A curing agent for powder coatings. As the carboxyl group-containing solid resin, for example, a carboxyl group-containing acrylic resin or a carboxyl group-containing polyester resin known as a resin for a powder coating material can be used. As a "curing agent having a functional group which undergoes a curing reaction with the carboxyl group by heat", which can be used in combination with the carboxyl group-containing solid resin, for example, a bisphenol A to epichlorohydrin type epoxy resin or an alicyclic ring can be used. A known curing agent for a powder coating material such as an epoxy resin such as an epoxy resin, a novolak type epoxy resin, or an epoxy group-containing acrylic resin, or a hydroxyalkylguanamine compound. Further, as the epoxy group-containing solid resin, for example, a bisphenol A to epichlorohydrin type epoxy resin, an alicyclic epoxy resin, a novolac type epoxy resin, an epoxy group-containing acrylic resin, or the like can be used. A resin for powder coatings. As a "curing agent having a functional group which undergoes a curing reaction with the epoxy group by heat", which can be used in combination with the epoxy group-containing solid resin, for example, a carboxyl group-containing polyester resin or an organic acid polymer can be used. A known curing agent for a powder coating material such as a ruthenium compound, an imidazole compound, a dicyandiamide compound, a polycarboxylic acid compound, or an acid anhydride.

From the viewpoint of good corrosion resistance of the coating film even if the sintering temperature is low, a combination of a carboxyl group-containing polyester resin and a hydroxyalkylguanamine compound is particularly preferable.

The powder coating material can be applied to a film obtained from the metal surface treatment composition (I) by a known method such as an electrostatic coating method, a flow dipping method, a spray coating method or an in-mold decoration method, and a hot air furnace can be used. The infrared furnace, the induction heating furnace, and the like are sintered to form a cured coating film. The film thickness of the coating film is a film thickness after sintering, and is usually in the range of 30 to 250 μm, and preferably 40 to 150 μm. The sintering condition of the powder coating material is suitably carried out at a temperature of from 130 to 350 ° C, preferably from 140 to 250 ° C, for a period of from 30 seconds to 60 minutes, and preferably from 1 to 50 minutes.

In the present invention, even when the coating material having a high shrinkage stress of the cured coating film is used in the coating material (II), the adhesion of the coating film is excellent.

Further, the coated metal sheet obtained as described above may have a structure in which a coating film is formed only from the above-described coating material, and may have a multilayer structure in which a top coat coating film is further appropriately formed.

Effect of the invention

According to the metal surface treatment composition and the metal surface treatment method of the present invention, it is possible to obtain a chromate treatment or a phosphate treatment by including a specific decane condensation reactant in a surface treatment agent of zirconium or titanium. Corrosion resistance, and it is possible to form a film which is excellent in adhesion to the coating film formed by the coating step after the treatment.

Further, according to the coating method of the present invention, by providing a surface treatment agent of zirconium or titanium type with a specific decane condensation reaction product, the obtained surface treated film can be obtained to have resistance equivalent to chromate treatment or phosphate treatment. It is also highly corrosive and has excellent adhesion to the coating film formed by the coating step after the treatment. In particular, when a sintered paint having a large shrinkage stress in the coating film during sintering is used, adhesion to the coating film does not occur.

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

The best form of implementing the invention

Hereinafter, the present invention will be described in more detail by way of examples. In addition, "parts" and "%" mean "parts by mass" and "% by mass" unless otherwise stated.

Manufacture of decane condensation reactant (B)

Manufacturing example 1

In a 1 L round bottom flask equipped with a reflux condenser, a thermometer, a nitrogen gas introduction tube, and a stirrer, 200 g of isopropyl alcohol and 200 g of deionized water were added to start stirring. Nitrogen gas was introduced in the gas phase, and while stirring, 90 g of 3-aminopropyltrimethoxydecane and 10 g of bis(triethoxydecylalkyl)ethane were placed in one portion. After stirring at normal temperature for 1 hour, the reaction was carried out at 60 ° C for 6 hours, and then the fraction was removed, and the temperature was raised to 120 ° C while exchanging with propylene glycol monomethyl ether. After cooling to 60 ° C, it was concentrated by distillation under reduced pressure to obtain a solution of 120 g of a product (P1) having a nonvolatile content of 40%. The non-volatile component of the obtained product (P1) was a 40% solution, and it was a colorless and transparent viscous liquid.

Manufacturing Examples 2 to 12

In the same manner as in Production Example 1, except that the raw material composition was as shown in Table 1, the respective products (P1) to (P8) and (R1) to (R4) were obtained.

Examples 1 to 26 and Comparative Examples 1 to 4 Production of metal surface treatment composition

In the above-mentioned (P1) to (P8) and (R1) to (R4), the composition of the metal surface treatment having the composition shown in Table 2 was adjusted using fluorozirconic acid, fluorotitanic acid, and a nitrate of each metal. Things. In Table 2, the concentration of each metal component is expressed in terms of a metal element, and the other component concentrations indicate the solid content concentration.

Chemical conversion treatment and painting

Commercially available cold-rolled steel sheet (SPCC-SD, manufactured by Japan Test Panel Co., Ltd., 70 mm × 150 mm × 0.8 mm), galvanized steel sheet (GA steel sheet, manufactured by Test Panel, Japan, 70 mm × 150 mm × 0.8 mm), 5000 series Aluminum (manufactured by Test Panel, Japan, 70 mm × 150 mm × 0.8 mm) or 6000 series aluminum (manufactured by Japan Test Panel Co., Ltd., 70 mm × 150 mm × 0.8 mm) as a substrate, the following steps (1) to (4) were carried out. And chemical conversion treatment under the conditions of Table 3.

(1) The base material was immersed in a commercially available degreased liquid adjusted to 40 ° C for 2 minutes, degreased, and then subjected to a water washing treatment for 30 seconds using tap water.

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

(3) Each of the substrates after the above treatment was washed with tap water for 30 seconds, and then washed with ion-exchanged water for 30 seconds. Subsequently, it was dried at 80 ° C for 5 minutes using a hot air drying oven to form each chemical conversion treatment plate.

The amount of the treated film of each chemical conversion treatment plate was analyzed as a total amount of the attached metal using "XRF1700" (a fluorescent X-ray analyzer manufactured by Shimadzu Corporation). The results are shown in Table 4.

(4) Gas spray coating was performed on each of the chemical conversion treatment plates obtained above, and the dry film thickness of "Akabe RIZE" (aqueous polyester polyurethane-based sintered coating material) was 30 μm. The mixture was heated at 150 ° C for 30 minutes to carry out sintering, and each test coated plate was produced. Each of the obtained test coated sheets was supplied to the following evaluation test. The results are shown in Table 4.

Further, (Note 1) to (Note 3) in Table 2 are as follows.

(Note 1) Organic resin: "PAA25", trade name, manufactured by Ridong Textile Co., Ltd., polyallylamine resin aqueous solution

(Note 2) Surfactant: "Newcol 1100", trade name, manufactured by Japan Emulsifier Co., Ltd., nonionic surfactant

(Note 3) cerium oxide: "Snowtex O", trade name, manufactured by Nissan Chemical Industry Co., Ltd., water-dispersible (colloidal) cerium oxide

Comparative Example 5

Gas spray coating on a commercially available zinc phosphate chemical conversion treated steel sheet (substrate: SPCC-SD, manufactured by Test Panel, Japan) to "Akabe RIZE" (aqueous polyester polyurethane) The coating material had a dry film thickness of 30 μm and was sintered by heating at 150 ° C for 30 minutes to prepare a test coated plate. The obtained test coated panels were supplied to the evaluation test described below. The results are shown in Table 4.

Comparative Example 6

A test coated plate was produced in the same manner as in Comparative Example 5 except that a commercially available zinc phosphate-based chemical conversion-treated steel sheet (base material: GA steel sheet, manufactured by Test Panel, Japan) was used. The obtained test coated panels were supplied to the evaluation test described below. The results are shown in Table 4.

Comparative Example 7

A test coated plate was produced in the same manner as in Comparative Example 5 except that a commercially available chromate-based chemical conversion-treated steel sheet (base material: 5000 series aluminum, manufactured by Japan Test Panel Co., Ltd.) was used. The obtained test coated panels were supplied to the evaluation test described below. The results are shown in Table 4.

Evaluation test

(*1) Corrosion resistance: For each test coated board, a cross-cut cut deep to the base was cut on the coating film with a knife to perform a salt spray corrosion test (SST: according to JIS Z-2371. The brine temperature was After 35 hours at 35 ° C, the adhesive portion was adhered and peeled off using an adhesive tape, and the peeling width of the coating film was measured. The evaluation criteria are as follows.

◎: not stripped

○: The peeling width is within 3 mm

△: peeling width exceeds 3mm and is within 5mm

×: The peeling width exceeded 5 mm.

(*2) (after water resistance) Adhesion: Each test coated plate was immersed in warm water (40 ° C) for 240 hours, and immediately after the removal, a checkerboard shape was cut out (10 × 10, with an interval of 1 mm). The cut marks are bonded and peeled using an adhesive tape, and the number of peeling marks of the coating film is checked. The evaluation criteria are as follows.

◎: no stripping grid

○: The stripping grid is less than 5

△: 6 to 10 stripping grids

×: The stripping grid is 11 or more

Examples 27 to 52 and Comparative Examples 8 to 11 Production of metal surface treatment composition

In the above-mentioned (P1) to (P8) and (R1) to (R4), the composition of the metal surface treatment having the composition shown in Table 5 was adjusted using fluorozirconic acid, fluorotitanic acid, and a nitrate of each metal. Things. In Table 5, the concentration of each metal component is expressed in terms of a metal element, and the other component concentrations indicate the solid content concentration. Further, (Note 1) to (Note 3) in Table 5 are as follows.

(Note 1) Organic resin: "PAA25", trade name, manufactured by Ridong Textile Co., Ltd., polyallylamine resin aqueous solution

(Note 2) Surfactant: "Newcol 1100", trade name, manufactured by Japan Emulsifier Co., Ltd., nonionic surfactant

(Note 3) cerium oxide: "Snowtex O", trade name, manufactured by Nissan Chemical Industry Co., Ltd., water-dispersible (colloidal) cerium oxide chemical conversion treatment

Commercially available cold-rolled steel sheet (SPCC-SD, manufactured by Japan Test Panel Co., Ltd., 70 mm × 150 mm × 0.8 mm), galvanized steel sheet (GA steel sheet, manufactured by Test Panel, Japan, 70 mm × 150 mm × 0.8 mm), 5000 series Aluminum (manufactured by Japan Test Panel Co., Ltd., 70 mm × 150 mm × 0.8 mm) or 6000 series aluminum (manufactured by Japan Test Panel Co., Ltd., 70 mm × 150 mm × 0.8 mm) as a substrate, and the following steps and conditions under Table 5 were carried out. Chemical conversion treatment.

(1) The base material was immersed in a commercially available degreased liquid adjusted to 40 ° C for 2 minutes, degreased, and then subjected to a water washing treatment for 30 seconds using tap water.

(2) Next, the metal substrate after washing with water was immersed for 10 to 300 seconds in the metal surface treatment composition of each of the examples and the comparative examples adjusted to the pH and temperature shown in Table 6. The pH was adjusted to 3.2 to 4.2 using nitric acid or sodium hydroxide. Also, the temperature was adjusted to 35 to 50 °C.

(3) Each of the substrates after the above treatment was washed with tap water for 30 seconds, and then washed with ion-exchanged water for 30 seconds. Subsequently, it was dried at 80 ° C for 5 minutes using a hot air drying oven to form each chemical conversion treatment plate.

The "XRF1700" (manufactured by Shimadzu Corporation, a fluorescent X-ray analyzer) was used to analyze the amount of the treated film of each chemical conversion treatment plate as a total amount of the attached metal. The results are shown in Table 6.

Production of test coated board (1)

Gas spray coating was performed on each of the chemical conversion treatment plates obtained above, and the dried film thickness of "Magicron #1000" (manufactured by Kansai Paint Co., Ltd., acrylic acid/melamine resin-based organic solvent-diluted paint) was 30 μm, and was 160. The mixture was heated at ° C for 30 minutes for sintering to prepare each test coated plate. Each of the obtained test coated sheets was supplied to the following evaluation test. The results are shown in Table 6.

Production of test coated board (2)

Gas spray coating was performed on each of the chemical conversion treatment plates obtained above, and the dry film thickness of "Amilac #1000" (manufactured by Kansai Paint Co., Ltd., alkyd/melamine resin-based organic solvent-diluted paint) was 30 μm, and The test was applied to each of the test coated panels by heating at 130 ° C for 30 minutes for sintering. Each of the obtained test coated sheets was supplied to the following evaluation test. The results are shown together in Table 6.

Production of test coated board (3)

Gas spray coating was performed on each of the chemical conversion treatment plates obtained above, and the dry film thickness of "ASIME" (manufactured by Kansai Paint Co., Ltd., polyester/melamine resin type organic solvent diluted type coating) was 30 μm, and was 140 ° C. The mixture was heated for 30 minutes to be sintered, and each test coated plate was produced. Each of the obtained test coated sheets was supplied to the following evaluation test. The results are shown together in Table 6.

Production of test coated board (4)

Electrostatic powder coating was carried out on each of the chemical conversion treatment plates obtained above, and the dried film thickness of "Evaclad 8900" (manufactured by Kansai Paint Co., Ltd., powder coating containing a carboxyl group-containing polyester resin/hydroxyalkylamine compound) Each of the test coated sheets was prepared by sintering at 60 °m and heating at 150 ° C for 30 minutes. Each of the obtained test coated sheets was supplied to the following evaluation test. The results are shown together in Table 6.

Production of test coated board (5)

Electrostatic powder coating was carried out on each of the chemical conversion treatment plates obtained above, and the dry film thickness of "Evaclad 4900" (a powder coating of a hydroxyl group-containing polyester resin/capped polyisocyanate compound manufactured by Kansai Paint Co., Ltd.) was used. Each of the test coated sheets was prepared by sintering at 70 °m and heating at 180 ° C for 30 minutes. Each of the obtained test coated sheets was supplied to the following evaluation test. The results are shown together in Table 6.

Comparative Example 12

Each of the test coatings was prepared in the same manner as in Examples 27 to 52 and Comparative Examples 8 to 11 except that a commercially available zinc phosphate-based chemical conversion-treated steel sheet (base material: SPCC-SD, manufactured by Test Panel, Japan) was used. Install the board. Each of the obtained test coated sheets was supplied to the following evaluation test. The results are shown together in Table 6.

Comparative Example 13

Each of the test coatings was prepared in the same manner as in Examples 27 to 52 and Comparative Examples 8 to 11 except that a commercially available zinc phosphate-based chemical conversion-treated steel sheet (base material: GA steel sheet, manufactured by Test Panel, Japan) was used. board. Each of the obtained test coated sheets was supplied to the following evaluation test. The results are shown together in Table 6.

Comparative Example 14

Each test was carried out in the same manner as in Examples 27 to 52 and Comparative Examples 8 to 11 except that a commercially available chromate-based chemical conversion treatment plate (base material: 5000 types of aluminum, manufactured by Japan Test Panel Co., Ltd.) was used. Coating board. Each of the obtained test coated sheets was supplied to the following evaluation test. The results are shown together in Table 6.

Evaluation test

(*1) Corrosion resistance: For the test coated sheets (1) to (3) of the respective examples and comparative examples, a cross cut deep to the base was cut on the coating film with a knife to cause salt spray corrosion The test (SST: according to JIS Z-2371. The salt water temperature was 35 ° C) was used for 240 hours, and then the adhesive portion was adhered and peeled off using an adhesive tape, and the peeling width of the coating film was measured. Further, with respect to the test coated sheets (4) to (5) of the respective examples and comparative examples, a cross cut deep to the base was cut on the coating film with a knife to carry out a salt spray corrosion test (SST: according to JIS Z-2371. The temperature of the brine was 35 ° C for 480 hours, and then the adhesive portion was used to bond and peel the wound portion, and the peeling width of the coating film was measured. The evaluation criteria are as follows.

◎: not stripped

○: The peeling width is within 3 mm

△: peeling width exceeds 3mm and is within 5mm

×: The peeling width exceeded 5 mm.

(*2) (after water resistance) Adhesion: The test coated sheets (1) to (5) of the respective examples and comparative examples were immersed in warm water (40 ° C) for 240 hours, and immediately cut off after being taken out. A cut mark having a checkerboard shape (10 × 10 intervals, 1 mm apart) was bonded and peeled using an adhesive tape, and the number of peeling cells of the coating film was examined. The evaluation criteria are as follows.

◎: no stripping grid

○: The stripping grid is less than 5

△: 6 to 10 stripping grids

×: The stripping grid is 11 or more

Claims (13)

A metal surface treatment composition comprising a metal surface treatment of (A) a titanium compound and/or a zirconium compound, and (B) a condensation reaction of an amino decane (b1) and a polydecyl-functional decane (b2) A composition characterized in that the amino decane (b1) of the condensation reactant (B) is selected from the group consisting of 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and 3- Aminopropylmethyldiethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, And at least one of N-(2-aminoethyl)-3-aminopropyltriethoxydecane; the polynonylalkyl functional decane (b2) is represented by the following formula (I), (X ¹ _3-ab (R ¹ ) _a (R ² ) _b Si-Y-Si(R ³ ) _c (R ⁴ ) _d (X ² ) _3-cd .. (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, and X ¹ and X ² independently represent a hydrolyzable group. , a and b independently represent 0, 1 or 2, and 0 ≦ a + b ≦ 2, c and d independently represent 0, 1 or 2, and 0 ≦ c + d ≦ 2; and, amino decane (b1 And polydecane Silane functional (b2) is used in a proportion, in terms of molar ratio of 70 / 30-99 / 1. The metal surface treatment composition according to the first aspect of the invention, wherein the content of the titanium compound and/or the zirconium compound (A) is 5 to 10000 ppm in terms of metal elements, and the amino decane (b1) and polydecyl group functions are used. The content of the condensation reaction product (B) of decane (b2) is 1 to 5000 ppm in terms of solid content concentration. The metal surface treatment composition according to claim 1 or 2, wherein the titanium compound and/or the zirconium compound (A) contains a halide selected from titanium and a salt thereof, a halide of zirconium and a salt thereof, and zirconium carbonate and a salt thereof, and at least one compound of zirconium nitrate. The metal surface treatment composition according to claim 1 or 2, wherein the titanium compound and/or the zirconium compound (A) contains a group selected from the group consisting of zirconium fluoride, titanium fluoride, zirconium carbonate and salts thereof, and zirconium nitrate. At least one compound. The metal surface treatment composition according to claim 1 or 2, further comprising magnesium, zinc, calcium, aluminum, gallium, indium, copper, iron, manganese, nickel, cobalt, lanthanum, cerium, rare earth At least one metal element of the group consisting of elements, tin, antimony, bismuth, vanadium, niobium, chromium, molybdenum, tungsten, and silver. The metal surface treatment composition according to claim 1 or 2, further comprising at least one selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, phosphonic acid, hypophosphorous acid, and the like. The composition for metal surface treatment according to claim 1 or 2, which further comprises a water-soluble or water-dispersible organic resin. The composition for metal surface treatment according to claim 1 or 2, further comprising a surfactant. A metal surface treatment method for treating a surface of a metal material, comprising the step of contacting a treatment liquid containing the metal surface treatment liquid of the metal surface treatment composition according to any one of claims 1 to 8 with the metal material And a water washing step of washing the metal material that has passed through the step of contacting the treatment liquid. A coating method of a metal material, comprising the step of contacting a treatment liquid containing a metal surface treatment liquid containing the metal surface treatment composition according to any one of claims 1 to 8 with a metal material, The water washing step of the metal material subjected to the treatment liquid contacting step, and the coating step of coating the sintered surface coating layer with the sintered coating material (II). A coating method of a metal material according to claim 10, wherein the sintered coating (II) is an organic solvent diluted coating. The coating method of the metal material according to claim 11, wherein the organic solvent diluted coating material is at least one selected from the group consisting of a polyester/melamine resin coating, an alkyd/melamine resin coating, and an acrylic coating. . A coating method of a metal material according to claim 10, wherein the sintered coating (II) is a powder coating.