JP2551964B2 - Contamination resistant titanium material and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention is a titanium material having improved stain resistance by forming a fluoropolymer film having excellent adhesion, processability, weather resistance and stain resistance. And a manufacturing method thereof.

[Conventional technology]

Conventionally, galvanized steel sheets, painted steel sheets and the like have been mainly used as metal building materials. However, it is already known that these steel sheets have insufficient corrosion resistance under severe corrosive environments such as coastal zones, industrial zones or subtropical zones.

Therefore, as a metal building material to replace these steel plates,
Conventionally, colored aluminum and colored stainless steel sheets have come to be used, but these materials also do not show sufficient corrosion resistance under the above-mentioned high corrosive environment, and depending on the degree of corrosive environment, it may take several months to several years. It is recognized that white rust and pitting corrosion occur.

Therefore, recently, titanium materials, which have extremely excellent corrosion resistance, have been attracting attention as metal building materials. However, when titanium materials are contaminated with fingerprints, oil, etc., compared with other metal materials. And dirt is very noticeable,
In order to improve such a problem, a method of applying a stain-preventing paint has been adopted.

[Problems to be solved by the invention]

However, when painting a titanium material with anti-contamination paint,
Titanium material is a material with excellent corrosion resistance and weather resistance, and the paint applied to this material must have high corrosion resistance and weather resistance comparable to those of titanium material. Is requested at the same time,
Conventional paints have not been able to be said to sufficiently meet these requirements. That is, the acrylic, polyester, urethane, and silicon-based paints that are commonly used for surface protection of color iron plates and the like have insufficient weather resistance of the coating film, and when exposed to a highly corrosive environment for a long time, There is a problem in that the coating film is yellowed and blisters are generated in the coating film, which not only impairs the aesthetics but also causes the coating film to peel off, and the effect of using the titanium material is not enjoyed.

On the other hand, the applicant of the present application has developed a stain resistant titanium material having improved stain resistance by forming a fluoropolymer film having excellent adhesion, weather resistance and stain resistance on the surface of the titanium material. However, there is room for further improvement in the adhesion of the coating film with this stain resistant titanium material.

In view of this point, the present invention does not provide a stain resistant titanium material and a method for producing the same, which can significantly improve the adhesion of the coating when forming a fluoropolymer coating on the surface of the titanium material. It is what

[Means for solving problems]

Therefore, the stain-resistant titanium material according to the present invention forms a fluoropolymer film containing a coupling agent composed of any of silane-based, aluminate-based, and titanate-based materials or a mixture thereof on the surface of the titanium material. It is characterized by having done. Further, the method for producing a stain-resistant titanium material according to the present invention, the coupling agent is previously added to the fluoropolymer.
Apply a coating mixture of 0.001 to 5.0 wt% to the titanium material or 0.008 the coupling agent in advance on the titanium material surface.
˜5.0 g / m ^{2 is} applied, and thereafter, a fluoropolymer film is applied and formed on the coating film.

Here, the titanium material to which the present invention is applied may be any surface finish such as annealing finish, pickling finish, etc., or may be a mirror finish, a hairline finish, an embossing finish or a panel finish. It is also possible to use a colored titanium material that has been subjected to a coloring treatment such as anodic oxidation, atmospheric heating oxidation, or chemical oxidation, or a film formed by PVD, CVD or the like. It should be noted that these can be used in any shape or size such as plate, rod, tubular, etc., but the most common one is to continuously perform secondary processing including painting, cutting, etc. It is a long coiled product that is convenient above.

Further, as the fluorine-based polymer, any polymer containing a considerable amount of fluorine in the molecule can be used. Considering comprehensively the adhesion to titanium material, weather resistance, and the original purpose of preventing pollution, for example, the reactivity of tetrafluoroethylene resin, trifluoroethylene chloride resin, vinylidene fluoride resin, hydroxyl group, etc. And a fluoroolefin polymer having a group of Particularly, from the viewpoints of workability, solvent resistance of the coating film, strength, etc., a fluoroolefin polymer having a reactive group and soluble in a solvent is preferably adopted.

Examples of such fluoroolefin polymers include tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, monofluoroethylene, hexafluoropropylene or (per) fluoroalkyl trifluorovinyl ether [however,
(Per) fluoroalkyl group has 1 to 4 carbon atoms], fluoroolefins such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether or hydroxyhexyl vinyl ether are particularly preferable, and in addition, Monomers and co-polymers having reactive groups such as hydroxyalkyl esters of (meth) acrylic acid such as β-hydroxyethyl (meth) acrylate, β-hydroxypropyl (meth) acrylate and β-hydroxybutyl (meth) acrylate. A copolymer obtained by copolymerizing a polymerizable monomer is preferable. Such monomers include ethyl vinyl ether, n-propyl vinyl ether, iso-propyl vinyl ether, n-butyl vinyl ether, iso-butyl vinyl ether, t-butyl vinyl ether, lauryl vinyl ether, octadecyl vinyl ether, 2-chloroethyl vinyl ether or cyclopentyl vinyl ether, Alkyl or cycloalkyl vinyl ethers such as cyclohexyl vinyl ether and methyl cyclohexyl vinyl ether;
2,2,3,3-tetrafluoropropyl vinyl ether, 2,2,
3,3,4,4,5,5-octafluoropentyl vinyl ether,
2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl vinyl ether, trifluoromethyl vinyl ether, pentafluoroethyl vinyl ether, heptafluoro (Per) fluoroalkyl vinyl ethers such as propyl vinyl ether, heptadecafluorooctyl vinyl ether, and undecafluorocyclohexyl vinyl ether; vinyl acetate, vinyl propionate, vinyl acetate, vinyl isoacetate, vinyl bivalate, vinyl cyclohexanecarboxylate, vinyl benzoate. , p−tert−
Vinyl butyl benzoate, vinyl ester of aliphatic monocarboxylic acid having C _{2 to} C ₉ branched alkyl group, vinyl caproate, vinyl caprate, vinyl caprylate, vinyl laurate, or vinyl stearate Vinyls; olefins such as ethylene, propylene, vinyl chloride or vinylidene chloride or chloroolefins; (meth) acryl such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate or cyclohexyl (meth) acrylate Examples include acid esters. Among them, it is preferable to use at least one selected from the group consisting of cycloalkyl vinyl ether, alkyl vinyl ether and carboxylic acid vinyl ester in combination. When a carboxylic acid vinyl ester is used in combination, the vinyl ester of an aliphatic monocarboxylic acid having a C _{4 to} C ₁₇ branched alkyl group and cyclohexanecarboxylic acid are used in terms of the balance of hardness and flexibility of the cured coating film. It is particularly preferable to use at least one selected from the group consisting of vinyl acid salt, vinyl benzoate, and pt-butyl vinyl benzoate.

In addition, it is preferable that the fluorine-containing polymer film is used in combination with a crosslinking agent in addition to the above-mentioned fluorine-containing polymer because the mechanical properties of the film are improved.

As such a crosslinking agent, one that reacts with the reactive group of the fluoroolefin polymer is used. Typical examples include aminoplasts, polyisocyanate compounds, blocked polyisocyanate compounds, polybasic acids and polybasic acid anhydrides.

Furthermore, it does not matter whether the fine particle pigment is added to the fluoropolymer.

As the silane coupling agent, for example, a general formula: R ¹
・ Si ・ R ² _3-a・ R ³ _a [In the formula, R ¹ is a chlorine atom, an amino group, an aminoalkyl group,
C1 to C10 alkyl group or vinyl group having at least one functional atom or group selected from ureido group, glycidoxy group, epoxycyclohexyl group, acryloyloxy group, methacryloyloxy group, mercapto group and vinyl group, R ² and R ³ are chlorine atoms,
An atom or a group selected from a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxy-substituted alkoxy group having 2 to 15 carbon atoms, a hydroxyalkyloxy group having 2 to 4 carbon atoms, and an acyloxy group having 2 to 15 carbon atoms; Represents 0, 1 or 2. ] The silane compound shown by these can be mentioned.

R ¹ is an alkyl group having a functional substituent, and preferred examples thereof include β-aminoethyl group, γ-aminopropyl group, N (β-aminoethyl) -γ-aminopropyl group, γ-ureidopropyl group, γ-glycidoxypropyl group, β- (3,4-epoxycyclohexyl) ethyl group, γ-acryloyloxypropyl group, γ-methacryloyloxypropyl group, γ-mercaptopropyl group, β-chloroethyl Group, γ-chloropropyl group, γ-
A vinyl propyl group etc. can be illustrated. R ¹ may be a vinyl group.

Specific examples of the above-mentioned silane system preferably used include, for example, γ-aminopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, and γ-
Ureidopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethylsilane, γ-methacryloxydipropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ- Chloropropyltrimethoxysilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, N-β-aminoethyl-γ-aminopropyl Examples thereof include methyldimethoxysilane and β-aminoethyl-β-aminoethyl-γ-aminopropyltrimethoxysilane.

As the titanate system, a titanium compound will be described as a typical example, but not only titanium but also zirconium, hafnium and thorium compounds contained in Group IVa of the same kind as titanium are included.

Examples of the compound of titanium, zirconium, hafnium and thorium include, for example, the general formula: T (OR) ₄ [wherein T represents titanium, zirconium, hafnium or thorium, and R represents an alkyl group, a cycloalkyl group or an aryl group. ] The ortho acid ester shown by these and this at least 1
There may be mentioned a derivative obtained by reacting one or more kinds of compounds having individual functional groups. Examples of the compound having at least one functional group include polyhydric alcohols such as glycerin, ethylene glycol, 1,3-butanediol, 2,3-butanediol, hexylene glycol, octylene glycol, salicylaldehyde and glucose. Such as oxyaldehydes, diacetone alcohol, oxyketones such as fructose, glycolic acid, lactic acid, dioxymaleic acid, oxycarboxylic acids such as citric acid, diketones such as diacetylacetone,
Ketone acids such as acetoacetic acid, ketone acid esters such as ethyl acetoacetate, oxyamines such as triethanolamine and diethanolamine, and oxyphenol compounds such as catechol and pyrogallol can be used.

For example, when T is titanium, a specific compound is tetraalkyl titanate (for example, tetraethyl titanate,
Tetraisopropyl titanate, tetrabutyl titanate), tetraethylene glycol titanate, triethanolamine titanate, titanium acetylacetonate, isopropyl trioctanoyl titanate, isopropyl trimethacryl titanate, isopropyl triacrylic titanate, isopropyl tri (butyl, methyl pyro) Examples thereof include phosphate) titanate, tetraisopropyldi (dilaurylphosphite) titanate, dimethacryloxyacetate titanate, diacryloxyacetate titanate, and di (dioctylphosphate) ethylene titanate.

As the zirconium compound, the same compound as the above titanium compound can be used. Specific examples thereof include tetraalkyl zirconates such as tetraethyl zirconate and tetrabutyl zirconate, n-propyl zirconate, isopropyl zirconate, n-butyl zirconate, isobutyl zirconate, and zirconium acetylacetonate.

As the hafnium and thorium compounds, the same compounds as titanium and zirconium can be used.

Examples of the aluminate system include aluminum isopropylate, mono sec-butoxy aluminum diisopropylate, aluminum sec-butyrate, ethyl acetoacetate aluminum diisopropylate and aluminum tris (ethyl acetoacetate).

Although the method for forming the coating film will not be described in detail, a coating material containing a fluoropolymer may be applied to the surface of the titanium material by a conventional method, dried, and baked if necessary.

Next, the reason for limiting the addition amount and coating amount of the coupling agent will be described. When a coupling agent is added to a coating containing a fluoropolymer, if the amount added is less than 0.001 wt%, the effect of improving the adhesion by the addition of the coupling agent is not sufficient, and if it exceeds 5.0 wt%, the weather resistance is increased. The adhesion after the test becomes poor. Therefore, the addition amount was made 0.001 to 5.0 wt%, but considering the adhesion and aging characteristics after the boiling test,
A more preferable range is 0.02 to 1.0 wt%.

When a coupling agent is applied to the titanium material surface before coating, if the amount of the coupling agent applied is less than 0.008 g / m ² , the effect of improving the adhesiveness due to the application of the coupling agent is not sufficient, and 5.0 g / m ² If it exceeds m ² , the adhesion after the weather resistance test will be poor. Therefore, the coating amount is set to 0.008 to 5.0 g / m ² , but a more preferable coating amount is 0.08 to 1.0 g / m ² in consideration of each adhesion after the boiling water test and the weather resistance test.

[Action]

In the present invention, the titanium material surface is coated with a coupling agent in advance, or by applying a coating material in which a coupling agent is mixed with a fluoropolymer, a fluorine-based material containing a coupling agent on the titanium material surface. Since a polymer film is formed, the OH groups contained in the coating material react with the curing agent to form a coating film with excellent durability, and at the same time, due to the low surface energy of the fluoropolymer, excellent coating properties are obtained. The water and oil repellency of the film is obtained, which protects the titanium material from surface contamination, and the coupling agent has an affinity for both the organic fluoropolymer and the titanium material. And titanium material adhere well.

〔Example〕

 Hereinafter, the present invention will be described based on examples.

Example 1 36.0 parts by weight of a fluoroolefin-vinyl ether polymer having an OH value of 53 mgKOH / gr was dissolved in a mixed solvent of 44.0 parts by weight of xylene and 10.0 parts by weight of methyl isobutyl ketone. 0.2 parts by weight of blocked isocyanate and 5 × 10 ^-4 parts by weight of dibutyltin dilaurate as a curing agent 0.2
Part by weight was mixed to prepare a transparent coating material having various coupling agent concentrations shown in Table 1. Then, this is applied by air spray to the titanium material surface that has been degreased with a strong alkaline degreasing agent so that the dry film thickness is 10 ± 5 μm, and dried at 180 ° C. for 20 minutes, and then used for the test. did. In addition,
As a comparative example, a sample which does not use a coupling agent was also tested.

In the test, initial adhesion, boiling water resistance, weather resistance and aging characteristics were examined. Here, each test was conducted as follows.

Initial adhesion Using a cutter knife, draw 11 parallel and 11 horizontal and vertical lines at intervals of 1 mm and make cuts in a grid pattern so that 100 squares can be created in 1 cm ² . Stick Cellotape (trade name) on it and peel it off, and specify the number of remaining coating films on the substrate.

Boiling resistance The test piece is immersed in boiling water for 4 hours, then taken out and the appearance is observed. Then, the same operation as the standard adhesion (initial adhesion) is performed.

Durability test 500 hours or 200
After 0 hours, the peeling rate is calculated as an area ratio.

Aging characteristics A predetermined amount of coupling agent is added to the coating material, and the time until it solidifies (pot life) is measured. After adding the coupling agent to the paint, leave it for 72 hours. Then, after coating it, a cross-cut peeling test is performed, and the number of remaining coating films is specified.

Table 1 shows the test results. As Comparative Example A, the case where no coupling agent is used is shown. According to Table 1, the coatings C, D, E, F having a coupling agent concentration within the range of the present invention are shown.
Show better results in initial adhesion, boiling water resistance, weather resistance and aging characteristics than Comparative Example A and Coating B outside the scope of the present invention. It is understood that the adhesion of the coating film is significantly improved by forming the coating film with the addition of the coupling agent.

Example 2 A coupling agent was dissolved in ethyl alcohol, and this was coated on the surface of a titanium material in various amounts shown in Table 2, and at 50 ° C.
It was dried for 30 minutes. The surface of this titanium material was spray-coated with the coating material of Example 1 (Table A) to give a coating film thickness of 10 μm. Further, it was dried at 180 ° C. for 20 minutes and a performance test was conducted.

Table 2 shows the test results. According to Table 2, coating films B to E, G and H in which the coating amount of the coupling agent is within the range of the present invention have initial adhesiveness, boiling water resistance and weather resistance as compared with coating films A and F in which the coating amount is outside the range. Good results It is understood that the results show that good adhesion between the coating film and the titanium material can be obtained by applying a predetermined amount of the coupling agent before applying the fluoropolymer coating material.

〔The invention's effect〕

As described above, according to the stain resistant titanium material and the method for producing the same according to the present invention, since the fluoropolymer film containing the cup rig material is formed on the titanium material surface, the adhesion between the coating film and the titanium material is improved. It is possible to obtain a titanium material which exhibits a good corrosion resistance even in a highly corrosive environment and has an excellent stain resistance for a long period of time.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shoichi Kawakami 2-17-16 Hanazono, Chiba City, Chiba Prefecture (72) Inventor Tetsuo Goto 186 Finkeisaki, Nagareyama City, Chiba Prefecture

Claims (3)

(57) [Claims] 1. A fluorine-containing polymer film containing a coupling agent made of any of silane-based, aluminate-based, and titanate-based materials, or a mixture thereof, on the surface of a titanium material. Contaminating titanium material. 2. A coupling agent, which is a fluorine-based polymer, is selected from silane-based, aluminate-based, titanate-based, or a mixture thereof on the surface of a titanium material in an amount of 0.001 to 0.001.
A method for producing a stain resistant titanium material, which comprises applying a coating material containing 5.0% by weight. 3. A solution of an upling agent, which is one of a silane type, an aluminate type, a titanate type, or a mixture thereof, is applied to the surface of a titanium material in an amount of 0.008 to 5.0 g / m ² , and thereafter, A method for producing a stain resistant titanium material, which comprises applying a fluoropolymer coating on a coating film.