JP2001220687A - Composition of zirconium and titanium series coating agent and producing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a titanium or zirconium series coating agent improved in preservative stability and also good in film deposition properties and chemical resistance. SOLUTION: This coating composition contains (i) Zr(OR)4 or Ti(OR1)4 of mol, (ii)a β-diketone or β-keto-acid ester of 0.5 to 2 mol to the above, (iii) an alcohol of [4-X] mol, (iv) an inorganic acid of 1/125 to 1/10 mol, (v) an organic acid shown by the general formula of R6COOH or water of 1 to 4 mol, and (vi) a hydrophilic organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition of a zirconium- and titanium-based coating agent, which has excellent storage stability and excellent performance on the surface of metals such as stainless steel, aluminum and copper, and inorganic materials such as ceramics and glass. The present invention relates to a zirconium- and titanium-based coating composition for forming a thin film having the same, a method for producing the same, a film-forming method using the same, and a substrate having a zirconium- or titanium-oxide film.

[0002]

2. Description of the Related Art Metals such as copper and iron are easily corroded by acids and alkalis. Even corrosion resistant stainless steel is exposed to hydrochloric acid. Further, glass and ceramics are generally said to have good corrosion resistance, but have insufficient alkali resistance.

In recent years, in order to overcome the disadvantages of the above-mentioned materials, coating agents having excellent water resistance, heat resistance, solvent resistance, acid resistance, corrosion resistance, abrasion resistance, abrasion resistance, moisture resistance, film formability, storage stability, etc. Is required.

As an inorganic oxide film which meets such a demand, a coating agent which reacts a chelating agent or an organic acid with titanium or zirconium and performs hydrolysis and polycondensation with water has been proposed.

[0005] However, in the conventional method, polycondensation is carried out by a hydrolysis reaction, so that there is a problem that the reaction proceeds even during storage, and gelation and a precipitate are generated. In order to avoid this drawback, the hydrolysis rate is controlled or the stability of the solution is determined by adding a chelating agent or the like.

[0006] However, this method cannot improve the stability of the liquid and obtain good film forming conditions.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a titanium or zirconium-based coating agent having improved storage stability and excellent film forming properties and chemical resistance.

It is another object of the present invention to provide a titanium or zirconium-based oxide film having particularly excellent properties such as water resistance, heat resistance, and moisture resistance.

It is known that when a substrate on which a film is formed is easily oxidized like copper, characteristics such as chemical resistance are extremely deteriorated.

Accordingly, it is a further object of the present invention to provide a film exhibiting good characteristics even on these substrates.

[0011]

Means for Solving the Problems The present invention provides the following items 1 to
Regarding item 4. Item 1. (i) a zirconium compound represented by the general formula Zr (OR) ₄ (wherein R represents an alkyl group having 2 to 5 carbon atoms) and a general formula Ti (OR ¹ ) ₄ (where R ¹ is carbon (Ii) relative to 1 mol of at least one compound selected from the group consisting of titanium compounds represented by formulas ( ² ) to (5), wherein R ² COCH ₂ COR ³ (wherein R
² represents an alkyl group having 1 to 5 carbon atoms, and R ³ represents an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms.) Β-diketones or β-keto acid esters 0 .
5 to 2 moles, (iii) a compound represented by the general formula R ⁴ OR ⁵ OH (wherein R ⁴
Is an alkyl group having 1 to 2 carbon atoms, and R ⁵ is an alkylene group having 2 to 3 carbon atoms) [4-X]
Moles (X represents the number of moles of β-diketones or β-keto acid esters), (iv) 1/125 to 1/10 moles of an inorganic acid, (v) a general formula R ⁶ COOH (R ⁶ is hydrogen or Carbon number 1
1 to 4 moles of at least one selected from the group consisting of organic acids and water represented by
(vi) a coating composition containing a hydrophilic organic solvent. Item 2. (i) a zirconium compound represented by the general formula Zr (OR) ₄ (wherein R represents an alkyl group having 2 to 5 carbon atoms) and a general formula Ti (OR ¹ ) ₄ (where R ¹ is carbon (Ii) relative to 1 mol of at least one compound selected from the group consisting of titanium compounds represented by formulas ( ² ) to (5), wherein R ² COCH ₂ COR ³ (wherein R
² represents an alkyl group having 1 to 5 carbon atoms, and R ³ represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms). 0.5 to 2 mol, (iii) a compound represented by the general formula R ⁴ OR ⁵ OH
⁴ represents an alkyl group having 1 to 2 carbon atoms, and R ⁵ represents an alkylene group having 2 to 3 carbon atoms).
X] moles (X is the number of moles of β-diketones or β-keto acid esters), heated under reflux and then (iv)
Inorganic acid 1/125 to 1/10 mol, (v) general formula R ⁶ CO
Mixing an organic acid represented by OH (R ⁶ represents hydrogen or an alkyl group having 1 to 4 carbon atoms) and / or 1 to 4 mol of water, and (vi) a hydrophilic organic solvent and heating under reflux. A method for producing a coating composition, comprising: Item 3. Item 1. The composition for applying a Zr-based and / or Ti-based coating according to item 1 on a substrate.
Alternatively, a method of forming a Ti oxide film. Item 4. Item 4. A substrate having a Zr and / or Ti oxide film obtainable by the method of Item 3.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As a film forming method, when applied to an oxidation-resistant substrate such as stainless steel or glass, it is applied to the substrate by spin coating or dipping, and naturally dried at room temperature and air. Film. After that, heat treatment can be performed in the air (oxidizing atmosphere). In addition, when applied to a substrate that is easily oxidized such as copper, a film is formed by spin coating or dipping, and naturally dried at room temperature and in the air.
After that, heat treatment can be performed with nitrogen or a mixed gas of nitrogen and hydrogen (reducing atmosphere).

The features of the present invention are described below.

[0014] Although the prior art is satisfactory in chemical resistance, it cannot be obtained, but the present invention produces a film with improved chemical resistance for the following reasons. (i) a group consisting of a zirconium compound represented by the general formula Zr (OR) ₄ (R is the same as described above) and a titanium compound represented by the general formula Ti (OR ¹ ) ₄ (R ¹ is the same as described above) At least one selected from the above and (ii) a general formula R ² COCH ₂ CO
Compounds formed by β-diketones or β-keto acid esters represented by R ³ (R ² and R ³ are the same as described above) have the formula (iii) R ⁴ OR ⁵ OH (where R ⁴ and R ⁵ are After the reaction in the presence of the alcohol represented by
(iv) an inorganic acid, and (v) at least one selected from the group consisting of an organic acid represented by the general formula R ⁶ COOH (where R ⁶ is the same as described above) and water is added and reacted to smoothly proceed with polycondensation. Let it.

The composition of the present invention is obtained by strictly controlling the ratio of these additives, and a film having improved chemical resistance can be obtained by selecting the film forming conditions.

Due to the oxidation resistance of the substrate to which the coating agent of the present invention is applied, a dense film can be obtained and the properties such as chemical resistance are improved by selectively using the heat treatment of the film in the air and in a reducing atmosphere. .

First, the composition of the present invention will be described for each constitutional requirement. (1) From the group consisting of a zirconium compound represented by the general formula Zr (OR) ₄ (R is the same as described above) and a titanium compound represented by the general formula Ti (OR ¹ ) ₄ (R ¹ is the same as described above) At least one selected from the above and (2) a general formula R ² COCH ₂ C
A compound formed by a β-diketone or a β-keto acid ester represented by OR ³ (R ² and R ³ are the same as described above) has the general formula R ⁴ OR ⁵ OH (where R ⁴ and R ⁵ are The compounds obtained by reacting the alcohols represented by the same as above) have appropriate stability. Next, the obtained compound is (4)
An organic acid of the general formula R ⁶ COOH (where R ⁶ is the same as above) undergoes an esterification reaction with an alcohol which is a hydrophilic organic solvent, and is hydrolyzed by reaction with generated water or (5) water directly added.

A part of the organic acid to be added causes an acylation reaction with a zirconium compound or a titanium compound, and further acts to stabilize the compound and slow the hydrolysis. This hydrolyzate causes polycondensation to obtain a coating composition.

The coating composition comprises a catalytic amount of an acid,
The reaction can be controlled by the type and amount of the organic acid, the amount of water, and the type and amount of the hydrophilic solvent, and a composition having good storage stability can be obtained. An improved zirconium or titanium oxide film can be obtained.

In the zirconium compound, R is an alkyl group having 2 to 5 carbon atoms, specifically, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group. , N-pentyl group, i-pentyl group and the like, and a linear or branched alkyl group having 2 to 5 carbon atoms.

Specific examples of the zirconium compound represented by the general formula Zr (OR) ₄ include zirconium tetraethoxide,
Zirconium tetra-n-propoxide, zirconium tetra-i-propoxide, zirconium tetra-n-
Butoxide, zirconium tetra-sec-butoxide, zirconium tetra-t-butoxide, zirconium tetra-n-pentoxide, zirconium tetra-i
-Pentoxide and the like.

Of these, zirconium tetraethoxide, zirconium tetra-n-butoxide and zirconium tetra-n-propoxide are preferred, and zirconium tetra-n-butoxide is particularly preferred.

In the titanium compound represented by the general formula Ti (OR ¹ ) ₄ , R ¹ is an alkyl group having 2 to 5 carbon atoms, specifically, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl. A straight-chain or branched alkyl group having 2 to 5 carbon atoms such as a group, a sec-butyl group, a t-butyl group, an n-pentyl group and an i-pentyl group.

Specific examples of the titanium compound represented by the general formula Ti (OR ¹ ) ₄ include titanium tetraethoxide, titanium tetra-n-propoxide, titanium tetra-i-propoxide, titanium tetra-n-butoxide, Examples thereof include titanium tetra-sec-butoxide, titanium tetra-t-butoxide, titanium tetra-n-pentoxide, and titanium tetra-i-pentoxide. Of these compounds, titanium tetraethoxide, titanium tetra-i-propoxide and titanium tetra-n-butoxide are preferable, and titanium tetra-n-butoxide is particularly preferable. (ii) β-diketones or β-keto acid esters β-diketones or β-keto acid esters represented by the general formula R ² COCH ₂ COR ³ (R ² and R ³ are as defined above) (i) It is considered to form a complex with a zirconium compound or a titanium compound, to stably promote hydrolysis and polycondensation of the zirconium compound or the titanium compound, and to prevent precipitation.

R ² is an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group,
C1-C1 having a straight or branched chain such as an n-pentyl group
5 is an alkyl group, and R ³ is the same as described above for 1 to 1 carbon atoms.
In addition to the alkyl group of 5, an alkoxy group having 1 to 5 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an i-
Propoxy group, n-butoxy group, sec-butoxy group,
It is a linear or branched alkoxy group having 1 to 5 carbon atoms such as t-butoxy group and pentyloxy.

Specific examples of the β-diketones or β-keto acid esters include acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, n-acetoacetate. Butyl, sec-butyl acetoacetate, t-butyl acetoacetate, 2,4-hexane-dione, 2,4-heptane-
Dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonanedione, 5-methyl-hexane-dione and the like can be mentioned.

Of these components, ethyl acetoacetate, acetylacetone, n-butyl acetoacetate, 2,4-
Hexane-dione is preferred, and ethyl acetoacetate is particularly preferred. (Ii) The amount of the β-diketone or β-keto acid ester used is in the range of 0.5 to 2 mol. If the amount is less than 0.5 mol, the obtained compound becomes unstable and precipitates. May be. If the total amount of β-diketones and β-keto acid esters is in the range of 0.5 to 2 mol, both may be used in combination.

On the other hand, if it exceeds 2 moles, the compound is too stabilized, so that hydrolysis and polycondensation are not promoted, film formability is reduced, and chemical resistance of the oxide film is deteriorated.

The above-mentioned (i) general formula Zr (OR)_Four(R is before
Zirconium compound or a general formula represented by
Ti (OR¹)_Four(R¹Is the same as above)
Compound and (ii) the general formula R^TwoCOCH_TwoCOR^Three(R^TwoPassing
And R^ThreeIs the same as described above), or
Hydrolysis of compounds formed by β-keto acid esters
(Iii) In order to promote the dissolution and condensation polymerization smoothly,
^FourOR^FiveOH (R^FourAnd R ^FiveIs the same as above)
Use rucols.

(Iii) Alcohols represented by the general formula R ⁴ OR ⁵ OH (wherein R ⁴ represents an alkyl group having 1 to 2 carbon atoms and R ⁵ represents an alkylene group having 2 to 3 carbon atoms) Exchange with the alkoxy group of the zirconium compound or titanium compound to form a new zirconium compound or titanium compound. Thereby, it is considered that hydrolysis and polycondensation of these compounds are stably promoted, and an effect of preventing the formation of precipitates is obtained.

[0031] In the formula, R ⁴ is an alkyl group such as methyl group, ethyl group having 1 to 2 carbon atoms, R ⁵ is 2 carbons
And 3 alkylene groups such as an ethylene group and a propylene group. The structures of these alcohols are alcohols having an ether bond, Zr compound and T
The exchange reaction between the i-compound and the alkoxy group proceeds.

Further, the oxygen in the ether-bonded portion of these alcohols bonded is such that the unpaired electron pair of the alcohol has Zr.
It is presumed that it has an action of controlling the hydrolysis reaction by interacting with Ti and Ti elements.

Specific examples of the alcohols include 2-
Methoxyethanol, 2-ethoxyethanol, 2-methoxypropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol and the like can be mentioned. Of these components, 2-methoxyethanol, 2-ethoxyethanol, and 1-methoxy-2-propanol are preferred, and 2-methoxyethanol and 1-methoxyethanol are particularly preferred.
-Methoxy-2-propanol is preferred. (iv) the purpose of the inorganic acid is to promote the hydrolysis and polycondensation of the zirconium compound or titanium compound, and
It is used for the purpose of (v) reacting an organic acid represented by the general formula R ⁶ COOH with (vi) a hydrophilic organic solvent to promote the esterification reaction.

Examples of such inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, and the like. Hydrochloric acid and nitric acid are preferred, and nitric acid is particularly preferred. (v) The organic acid represented by the general formula R ⁶ COOH (R ⁶ is the same as described above) causes an acylation reaction with (i) a zirconium compound or a titanium compound, thereby contributing to the stabilization of the compound and (vi) hydrophilically Reacts with a volatile organic solvent to cause an esterification reaction, generating water as a by-product. This causes hydrolysis and polycondensation of the zirconium compound or the titanium compound. As such an organic acid, R ⁶ is hydrogen or an alkyl group having 1 to 4 carbon atoms,
Specific examples include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid and the like, and acetic acid and propionic acid are preferred, and acetic acid is particularly preferred. Water causes hydrolysis and polycondensation of the zirconium compound or the titanium compound.

As such water, general tap water, distilled water,
Ion exchange water, industrial water and the like can be used. In particular, when the composition is to be highly purified, distilled water or ion-exchanged water is preferred. These waters can be used in combination with the above-mentioned organic acids. Water is mixed with (vi) a hydrophilic organic solvent to prevent rapid hydrolysis and polycondensation of the zirconium compound or titanium compound.
It is desirable to make a mixed solution as a solution containing 0% by weight or less.

[0036] In general formula R ⁶ COOH (R ⁶ is as defined above) an organic acid and water is represented by may be used as a mixture of either or both of the general formula R ⁶ COO
The total amount of the organic acid and water represented by H (R ⁶ is the same as above) is in the range of 1 to 4 mol, preferably 2 to 3 mol, and 1 mol or less, per 1 mol of the zirconium compound or the titanium compound. In such a case, hydrolysis and polycondensation become insufficient, film formability is poor, and chemical resistance of the oxide film is reduced. On the other hand, if it exceeds 4 mol, the reaction rapidly proceeds, and gelation or precipitation may occur, which is not preferable. (vi) Examples of the hydrophilic organic solvent include alcohols.

These alcohols include, for example, methanol, ethanol, n-propyl alcohol, i-
Propyl alcohol, n-butyl alcohol, i-butyl alcohol, sec-butyl alcohol, n-pentyl alcohol and the like can be mentioned. The frame of the selection of the organic solvent is (v) a lower alcohol which is likely to cause an esterification reaction with the organic acid represented by the general formula R ⁶ COOH (R ⁶ is the same as above). These hydrophilic organic solvents are preferably methanol, ethanol and n-propyl alcohol, and particularly preferably methanol and ethanol. These hydrophilic organic solvents can be used alone or in combination of two or more.

The composition of the present invention containing the above components (i) to (vi) is preferably (1) (i) a compound of the general formula Zr (O
R) ₄ (wherein, R represents an alkyl group having 2 to 5 carbon atoms)
Or a general formula Ti (OR
¹ ) ₄ (wherein R ¹ represents an alkyl group having 1 to 5 carbon atoms) per mole of a titanium compound represented by the formula (ii): R ² COCH ₂ COR ³ (where R ² is An alkyl group having 1 to 5 carbon atoms, and R ³ represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.) Β-diketones or β-keto acid esters 0.5 ~ 2 mol, (i
ii) alcohols represented by the general formula R ⁴ OR ⁵ OH (wherein R ⁴ represents an alkyl group having 1 to 2 carbon atoms, and R ⁵ represents an alkyl group having 2 to 3 carbon atoms) [4-X] Moles (X is the number of moles of β-diketones or β-keto acid esters),
Heat under reflux, then [2] (iv) inorganic acid 1/125
And (v) an organic acid represented by the general formula R ⁶ COOH (R ⁶ represents an alkyl group having 0 to 4 carbon atoms) or / and 1 to 4 mol of water, and (vi) a hydrophilic organic solvent. Mix
It is added dropwise to [1], and then heated under reflux.

Here, in the step (1), the components (i) and (i)
The component (i) and the component (iii) are mixed to prepare a mixed solution.In this case, the component (i), the component (ii) and the component (iii) are mixed, and the mixture is stirred under reflux for 2 hours or more by heating. Things are preferred.

After the components (i), (ii) and (iii) are mixed and the mixture is heated under reflux for less than 2 hours, the following [2]
Precipitation may occur when hydrolyzed in the process, and the chemical resistance of the film-formed substrate may be worse than that of a substrate refluxed for 2 hours or more.

Next, in the step [2], the component (iv), the component (v) and the component (vi) are previously mixed or separately added dropwise to the reaction product in the step [1]. In this case, the zirconium coating agent is preferably stirred and heated for 5 hours or more under reflux, and the electric conductivity is about 14 mS.
/ M or less. Also,
It is desirable to heat the titanium coating agent for 6 hours or more, and it is preferable to control the electric conductivity to be about 20 mS / m or less. In this [2] step,
Hydrolysis of the compound obtained in the step (1) by adding water obtained by reacting the organic acid of the component (v) with the hydrophilic organic solvent of the component (vi) or directly adding the water of the component (v), and Polycondensation occurs.

The proportion of the component (v) used here is in the range of 1 to 4 moles, preferably 1.5 to 3 moles, based on the component (i). And the chemical resistance of the film obtained by coating decreases. On the other hand, when the molar ratio exceeds 4 times, the reaction proceeds rapidly, causing gelation and storage stability to be remarkably deteriorated.

The composition obtained by the present invention may have a solid content of 5 to 15 with the above-mentioned hydrophilic organic solvent if necessary.
It is adjusted to about weight% and used for coating.

The composition thus prepared is applied to a substrate of stainless steel, aluminum, copper, iron, ceramics, glass, or the like by a film forming method such as spin coating, dipping, spraying, etc., and immediately or after natural drying. And heat treatment. -Oxidation-resistant substrates such as stainless steel and glass Heat treatment is performed in the air (oxidizing atmosphere). -Substrates that are easily oxidized such as copper Heat treatment is performed with nitrogen or a mixed gas of nitrogen and hydrogen (reducing atmosphere).

In the case of a mixed gas of nitrogen and hydrogen, if the content of hydrogen exceeds 10%, carbon is generated on the film, and the alkali resistance, abrasion resistance and the like are deteriorated. Therefore, 10%
The following is preferred. Heat treatment conditions, for example, 100 to 50
It is cured by heating at a temperature of about 0 ° C. for about 10 to 60 minutes.

[0046]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Various measuring methods in the examples are as follows.

The storage stability of the coating composition was stored tightly in a polyethylene bottle at room temperature, and gelation was visually judged. For those that have not gelled,
The viscosity was measured by a BL type viscometer (manufactured by Tokyo Keiki Co., Ltd.), and those having a change rate of 200% or less were regarded as no change.

After the grid test according to JIS K5400, the tape peeling test was conducted three times, and the average was taken.

The hardness was based on pencil hardness according to JIS K5400.

The alkali resistance was determined by dropping 1 cc of a 1% aqueous solution of sodium hydroxide onto the coating film, leaving it in a petri dish with a lid for one day, washing with water, and observing the state of the coating film.

The alkali resistance was determined by dropping 1 cc of a 10% aqueous solution of sodium hydroxide onto the coating film, leaving it in a petri dish with a lid for one day, washing with water, and observing the state of the coating film.

The acid resistance is as follows: 1% hydrochloric acid having a concentration of 5%
After dropping cc, let it stand in a Petri dish with lid for 1 day, wash with water,
The state of the coating film was observed.

The acid resistance is as follows.
After dropping cc, let it stand in a Petri dish with lid for 1 day, wash with water,
The state of the coating film was observed.

The weather resistance was measured in accordance with JIS K5400 using an irradiation test for 4000 hours with a weather meter, and the state of the coating film was observed.

For the resistance to organic chemicals, toluene was placed in a petri dish with a lid, and the coated substrate was immersed in the dish at room temperature for 60 days, and the state of the coating film was observed.

The moisture resistance was measured at a temperature of 50 ° C. and a humidity of 95%.
After holding continuously for 1000 hours, it was taken out and the state of the coating film was observed.

For water resistance, the coating film was immersed in tap water at room temperature for 60 days, and the state of the coating film was observed. Examples 1 to 14 Table 1 shows the composition of the zirconium-based coating composition.

Step [1]: Zirconium compounds, β-diketones or β-keto acid esters shown in Table 1,
The alcohols are mixed and heated under reflux for 2 hours, and then step [2]: an inorganic acid, an organic acid or water represented by the general formula R ⁶ COOH, a hydrophilic organic solvent are mixed, and then, under reflux, By heating for 5 hours, each coating composition was prepared.

The synthesized composition was applied to a copper plate having a size of 100 × 100 × 0.3 mm by spin coating (2,000 rpm).
m) and dried by heating at 300 ° C. for 30 minutes (3% hydrogen-97% nitrogen under a reducing atmosphere). Table 3 shows the results of various tests performed using the test pieces thus obtained. Comparative Examples 1 to 8 Table 2 shows the composition of the zirconium-based coating composition.

Step [1]: Zirconium compounds, β-diketones or β-keto acid esters shown in Table 2,
The alcohols are mixed and heated under reflux for 2 hours, and then step [2]: an inorganic acid, an organic acid or water represented by the general formula R ⁶ COOH, a hydrophilic organic solvent are mixed, and then, under reflux, By heating for 5 hours, each coating composition was prepared.

The synthesized composition was applied to a copper plate having a size of 100 × 100 × 0.3 mm by a spin coating method (2000 rpm).
m) and dried by heating at 300 ° C. for 30 minutes (3% hydrogen-97% nitrogen under a reducing atmosphere). Table 3 shows the results of various tests performed using the test pieces thus obtained. Examples 15 to 27 Table 4 shows the compositions of titanium-based coating compositions.

Step [1]: Titanium compounds, β-diketones or β-keto acid esters and alcohols shown in Table 4 are mixed and heated under reflux for 2 hours. An acid, an organic acid represented by the general formula R ⁶ COOH or water, and a hydrophilic organic solvent were mixed, and then heated under reflux for 6 hours to prepare respective coating compositions.

On a copper plate having dimensions of 100 × 100 × 0.3 mm, the synthesized composition was spin-coated (2,000 rpm).
m) and dried by heating at 300 ° C. for 30 minutes (3% hydrogen-97% nitrogen under a reducing atmosphere). Table 6 shows the results of various tests performed using the test pieces thus obtained. Comparative Examples 9 to 16 Table 5 shows the compositions of the titanium-based coating compositions.

Step [1]: Titanium compounds, β-diketones or β-keto acid esters and alcohols shown in Table 5 are mixed and heated under reflux for 2 hours. An acid, an organic acid represented by the general formula R ⁶ COOH or water, and a hydrophilic organic solvent were mixed, and then heated under reflux for 6 hours to prepare respective coating compositions.

The synthesized composition was applied to a copper plate having a size of 100 × 100 × 0.3 mm by spin coating (2,000 rpm).
m) and dried by heating at 300 ° C. for 30 minutes (3% hydrogen-97% nitrogen under a reducing atmosphere). Table 6 shows the results of various tests performed using the test pieces thus obtained.

The compounds described herein other than the compounds specified in Tables 1 to 6 showed similar results. Similar results were obtained with substrates other than the copper plate.

[0068]

The coating composition obtained according to the present invention has good storage stability, adhesion, alkali resistance, acid resistance, film formability, water resistance, chemical resistance, moisture resistance, weather resistance, It is possible to provide a coating composition which can significantly improve abrasion resistance, insulation resistance, and the like, and in particular, can form a coating film having extremely high alkali resistance and high hardness, and a method for producing the same.

[0069]

[Table 1]

[0070]

[Table 2]

[0071]

[Table 3]

[0072]

[Table 4]

[0073]

[Table 5]

[0074]

[Table 6]

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshihiro Mitani F-term in Fuji Chemical Co., Ltd. 3-2-33 Higashinoda-cho, Miyakojima-ku, Osaka-shi, Osaka 4K044 AA03 AA06 AA12 AA13 BA12 BC00 BC01 BC02 CA16 CA53 CA62

Claims (4)

[Claims] (I) a zirconium compound represented by the general formula Zr (OR) ₄ (where R represents an alkyl group having 2 to 5 carbon atoms) and a general formula Ti (OR ¹ ) ₄ (wherein , R ¹ represents an alkyl group having 2 to 5 carbon atoms) and at least one compound selected from the group consisting of titanium compounds represented by the general formula R ² COCH ₂ COR ³ (formula 1) In the formula, R ² is an alkyl group having 1 to 5 carbon atoms, and R ³ is an alkyl group having 1 carbon atom.
Β-diketones or β-keto acid esters represented by 0.5 to 2 moles represented by the following general formula R ⁴ OR ⁵ OH (showing an alkyl group having from 5 to 5 and an alkoxy group having from 1 to 5 carbon atoms): In the formula, R ⁴ is an alkyl group having 1 to 2 carbon atoms, and R ⁵ is 2 alkyl groups.
(X represents the number of moles of β-diketones or β-keto acid esters), and (iv) an inorganic acid 1/125. 1
/ 10 mol, and (v) 1 to 4 mol of at least one selected from the group consisting of an organic acid represented by the general formula R ⁶ COOH (R ⁶ represents hydrogen or an alkyl group having 1 to 4 carbon atoms) and water. And (vi) a coating composition comprising a hydrophilic organic solvent. (I) a zirconium compound represented by the general formula Zr (OR) ₄ (where R represents an alkyl group having 2 to 5 carbon atoms) and a general formula Ti (OR ¹ ) ₄ (wherein , R ¹ represents an alkyl group having 2 to 5 carbon atoms) and at least one compound selected from the group consisting of titanium compounds represented by the general formula R ² COCH ₂ COR ³ (formula 1) In the formula, R ² is an alkyl group having 1 to 5 carbon atoms, and R ³ is an alkyl group having 1 to 5 carbon atoms.
A β-diketone or a β-keto acid ester represented by 0.5 to 2 mol represented by an alkyl group of 5 or an alkoxy group having 1 to 5 carbon atoms, (iii) a general formula R ⁴ OR ⁵ OH (formula Wherein R ⁴ is an alkyl group having 1 to 2 carbon atoms, and R ⁵ is an alkyl group having 2 carbon atoms.
), (X represents the number of moles of β-diketones or β-keto acid esters), heated under reflux, and then ( iv) 1/125 to 1/10 mol of inorganic acid, (v) general formula R
An organic acid represented by ⁶ COOH (R ⁶ represents hydrogen or an alkyl group having 1 to 4 carbon atoms) and / or 1 to 4 mol of water, and (vi) a hydrophilic organic solvent are mixed and heated under reflux. A method for producing a coating composition, comprising: 3. A Zr-based and / or Ti-based coating composition according to claim 1, which is applied on a substrate.
A method for forming an r and / or Ti oxide film. 4. Z obtained by the method of claim 3.
A substrate having an r and / or Ti oxide film.