JPH04202373A - Zirconium based coating composition and producing of zirconium oxide-coated graphite formed article - Google Patents

Abstract

PURPOSE:To obtain the title composition containing a zirconium tetraalkoxide, tetraalkoxysilane, diamine compound, organic solvent and water at a specific ratio and capable of providing a coating film having excellent initial adhesion, resistance to boiling water and resistance to acids. CONSTITUTION:The objective coating composition containing (A) a zirconium tetraalkoxide expressed by formula I (R<1> is 1-5C aliphatic hydrocarbon), (B) a tetraalkoxysilane expressed by formula II (R<2> is 1-5C aliphatic hydrocarbon), (C) a diamine compound such as N,N'-dimethylethylene diamine consisting of ethylene diamine (derivative), (D) an organic solvent such as methyl alcohol or benzene and (E) water, having molar ratios of the above-mentioned components expressed by the following ranges; component B/component A=0.2-9, component C/component A=0.5-6, component D/components (A+B)=0.05-500 and component E/components (A+B)=0.02-2 and capable of storing for a long period.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention can be stored for a long time, can be easily coated,
The present invention relates to a zircon-based coating composition that provides a coating film with excellent stability. The present invention further relates to a method for easily producing a zircon-based oxide-coated graphite molded body having a coating film with excellent stability.

(Conventional technology) Conventionally, coatings have been used to form coatings on materials such as metal, plastic, wood, paper, cement, and graphite in order to improve their corrosion resistance, heat resistance, abrasion resistance, insulation, etc. Among them, zircon-based compositions have excellent corrosion resistance, heat resistance, abrasion resistance, insulation properties, etc.
Due to its low coefficient of thermal expansion, it is useful as a coating composition for the above materials.

Zircon-based compositions are disclosed, for example, in JP-A No. 61-25006.
No. 3 describes a composition formed by mixing a zirconium compound represented by the formula Zr(,0CsL+)4, ethyl silicate, and isopropyl alcohol, and JP-A-63-190175 discloses a composition containing a zirconium oxyacid. Compositions consisting of a salt, a silicon alkoxide or a derivative thereof, water and an organic solvent are described. However, the above-mentioned composition had the disadvantage that it had poor long-term storage stability and that the coating film obtained by coating it on a substrate was prone to cracking and peeling.

On the other hand, among the above materials, graphite in particular is known as a material with a low coefficient of thermal expansion and excellent thermal shock resistance, and is used as a material for jigs for use at high temperatures. but,
Graphite has the disadvantage of poor oxidation resistance at high temperatures. In addition, when using a graphite jig for powder metallurgy, it is necessary to sprinkle alumina powder on the graphite surface, or use alumina-based
It is necessary to apply a binder such as silica to prevent the molten metal from wetting or reacting with the graphite, but the former method
In addition to being a complicated process, the work environment is worsened by the fine alumina powder.The latter method has the disadvantage that the binder is removed from the graphite surface due to the difference in thermal expansion coefficient between the binder and graphite. In addition to being easy to peel off, under a hydrogen atmosphere, the silica in the binder reacts with hydrogen at high temperatures to generate water vapor, which hinders the sintering of the metal.

In order to solve the above-mentioned drawbacks, it has been proposed to form a coating of a zircon-based composition on the surface of a graphite molded body. Methods for forming this coating include vapor deposition, sputtering, and CVD.
method, thermal spraying method, paste sintering method, coating film pyrolysis method, etc., but with these methods, it is difficult to form a thick film of 0.1 μm or more, and the oxidative deterioration of graphite etc. This was insufficient to prevent this.

Furthermore, JP-A-1-122982 discloses that a solution of tetraalkoxysilane, its hydrolyzate and/or partial condensate, and zirconium tetraalkoxide, its hydrolyzate and/or partial condensate, etc., is applied to a graphite molded body. A method of coating or impregnating and drying is described, and the coating film obtained by the above method has a coefficient of thermal expansion approximately equal to that of graphite, and for this coating film, molten metal shows no wettability or reactivity, and the coating film does not react with hydrogen. However, the above method has the disadvantage that the coating solution cannot be stored for a long time because it is easily hydrolyzed. Moreover, the stability of the resulting coating film is poor and cracks and peeling are likely to occur.

(Problems to be Solved by the Invention) The present invention has been made in view of the above-mentioned drawbacks, and its purpose is to provide a zircon-based coating that can be easily coated, provides a coating film with excellent stability, and can be stored for a long time. An object of the present invention is to provide a coating composition and a method for producing zircon-based oxide-coated graphite using the coating composition.

(Means for solving the problem) Zirconium tetraalkoxide used in the present invention (
a) is a compound represented by the general formula Zr(ORS), where R' represents an aliphatic hydrocarbon group, but as the number of carbon atoms increases, the stability of the zircon-based coating composition decreases. Therefore, the number of carbon atoms is limited to 1 to 5.

As the zirconium tetraalkoxide (a),
Examples include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetra-1so-propoxide, zirconium tetra-n-butoxide, zirconium tetra-5ec-butoxide, zirconium tetra-tert-butoxide, and especially zirconium tetra-n -butoxide and zirconium tetra-1so-propoxide are preferred. These may be used alone or in combination of two or more.

The tetraalkoxysilane (b) used in the present invention is
It is a compound represented by the general formula 5i(OR")+, where R2 represents an aliphatic hydrocarbon group, but as the number of carbon atoms increases, the stability of the zircon-based coating composition decreases, making it difficult to store it for a long time. The number of carbon atoms is limited to 1 to 5 because the properties are poor.

Examples of the above tetraalkoxysilane (b) include:
Tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-1so-propoxysilane, tetra-n-butoxysilane, tetra-5ec
-butoxysilane, tetra-tert-butoxysilane, etc., and tetraethoxysilane and tetramethoxysilane are particularly preferred. These may be used alone or in combination of two or more.

If the amount of the above-mentioned tetraalkoxysilane (b) added to the zirconium tetraalkoxide (a) is too small, the stability of the zircon-based coating composition will decrease, resulting in poor long-term storage stability, and if it is too large, cracks will occur in the resulting coating film. Tetraalkoxysilane (b)/
Zirconium tetraalkoxide (a) (molar ratio) is 0
．． It is limited to 2 to 9, preferably 0.25 to 2.5.

The diamine compound (c) used in the present invention is a compound selected from the group consisting of ethylenediamine and ethylenediamine derivatives.

Examples of the diamine compound (c) include ethylenediamine, N,N'-dimethylethylenediamine,
Examples include N, N'-diethylethylenediamine, N-hydroxyethyl-N'-ethylethylenediamine, and the like, and these may be used alone or in combination of two or more.

If the amount of the diamine compound (c) added to the zirconium tetraalkoxide (a) is too small, the stability of the zircon-based coating composition will decrease, resulting in poor long-term storage stability, and if it is too large, the resulting coating film will be prone to cracking. Therefore, the diamine compound (c)/zirconium tetraalkoxide (a) (molar ratio) is limited to 0.5 to 6.

The organic solvent (d) used in the present invention is not particularly limited as long as it is compatible with the zirconium tetraalkoxide (a) and tetraalkoxysilane (b) (hereinafter referred to as total alkoxide). Examples include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and butyl alcohol, ketones such as acetone and methyl ethyl ketone, benzene, and toluene, and isopropyl alcohol is particularly preferred. These may be used alone or in combination of two or more.

If the amount of the organic solvent (d) added to the total alkoxide is small, the stability of the zircon-based coating composition will be reduced and the long-term storage stability will be poor, and if it is too large, pinholes will easily occur in the resulting coating film. Organic solvent (d)
/total alkoxide (molar ratio) is limited to 0.05-500, preferably 0.2-300.

When the amount of water (e) added to the total alkoxide used in the present invention is small, cracks are likely to occur in the resulting coating film, and when it is too large, the stability of the zircon-based coating composition decreases, resulting in poor long-term storage. Therefore, water (e)
/total alkoxide (mole ratio) is limited to 0.02-2.

It is preferable that an acid or a base be added to the water (e) as a catalyst to promote hydrolysis of all alkoxides.

Examples of the above acids include inorganic acids such as hydrochloric acid, hydrofluoric acid, and nitric acid, and organic acids such as acetic acid and formic acid. Examples of the base include:
Examples include ammonia, sodium hydroxide, potassium hydroxide, etc., and hydrochloric acid is particularly preferred.

If the amount of the acid or base added is too small, there will be no effect of promoting hydrolysis, and if it is too large, the stability of the zircon-based coating composition will decrease and the long-term storage property will be poor. 15 mol is preferred.

The zircon-based coating composition of the present invention is obtained by mixing the above-mentioned constituent materials, and the mixing method is not particularly limited. Solvent (d
) is preferably mixed, then the tetraalkoxysilane fb) and water (e) are added.

Zircon powder may be added to the zircon-based coating composition of the present invention in order to further improve the stability (cracking resistance, peeling resistance, etc.) of the resulting coating film.

If the average particle size of the zircon powder is small, it becomes difficult to disperse it into the zircon-based coating composition, and if it becomes large, cracks are likely to occur in the resulting coating film.
The thickness is preferably 0.01 to 100 μm, particularly preferably 0.02 to 2 μm.

If the amount of the above-mentioned zircon powder added to the zircon-based coating composition is small, the degree of improvement in the stability of the resulting coating film will be low, and if it is too large, the stability of the zircon-based coating composition will decrease and the long-term shelf life will be affected. Therefore, it is preferably 1 to 60% by weight of the total zircon-based oxide (total amount of the oxide formed from zirconium tetraalkoxide (a) and tetraalkoxysilane (b) and zircon powder). Incidentally, it is preferable that the zircon powder is added after mixing and stirring the constituent materials of the zircon-based coating composition.

In the method for manufacturing a zircon-based oxide-coated graphite molded body according to the second aspect of the present invention, the above-described zircon-based coating composition is applied or impregnated onto a graphite molded body, and the graphite molded body is dried to be coated with a zircon-based oxide.

Any method may be used to produce the graphite molded body, such as a method of molding natural graphite, artificial graphite, etc. as a starting material by extrusion molding, cast molding, etc., and then firing it, anthracite, coal coke, etc. Examples include a method in which an amorphous carbonaceous material such as petroleum coke, pitch coke, or carbon black is used as a starting material and formed by extrusion molding, cast molding, etc., followed by firing and graphitization. In addition,
The graphite molded body may contain other materials such as clay and metal.

The shape of the graphite molded body is not particularly limited, and examples thereof include a rod shape, a plate shape, a block shape, a roll shape, a crucible shape, and the like.

The above-mentioned coating method is not particularly limited, and examples include coating methods using a brush, spray coating, dip coating, spin cord, roll coating, and the like.

The above-mentioned impregnation method is not particularly limited and includes, for example, a method of impregnation by immersion under normal pressure, a method of impregnation by immersion under reduced pressure, etc. It is preferable to impregnate by immersion under reduced pressure, and the degree of vacuum is: When the temperature decreases, it becomes difficult for the zircon-based coating composition to be impregnated inside the pores of the graphite molded body.
If the pressure is higher, the zircon-based coating composition will volatilize more intensely and the solution viscosity will increase, making it difficult for the zircon-based coating composition to be impregnated into the pores of the graphite molded body.

The above drying method is not particularly limited, and includes, for example, a method of naturally drying at room temperature, a method of naturally drying at room temperature and then heating drying, a method of naturally drying at room temperature and then high temperature heat treatment, Examples include a method of air drying at room temperature, heat drying, and then further high temperature heat treatment.

The conditions at each stage in the above drying method are appropriately determined depending on the type of zircon-based coating composition and graphite molded object, but natural drying at room temperature is preferably carried out for 2 to 48 hours, and heating drying is carried out for 60 hours. ~30 minutes at ~300℃~48
The high temperature heat treatment is preferably carried out at 450 to 1700°C for 30 minutes to 10 hours in a non-oxidizing atmosphere.

(Example) The present invention will be explained in detail below.

The methods for evaluating each physical property regarding the zircon-based coating composition and the zircon-based oxide-coated graphite molded body shown in the results are as follows.

1. Physical properties of zircon-based coating composition (1)
Initial adhesion A slide glass (manufactured by Matsunami Co., Ltd.) that had been ultrasonically cleaned with acetone was immersed in the obtained zircon-based coating composition, pulled up at a speed of 300 mm/min, and dried under the following conditions to form a zircon-based coating composition. An evaluation sample was prepared by forming an oxide coating layer, and a cross-cut tape peeling test was performed in accordance with JIS D 0202. Evaluation was made by measuring the eye ratio (peeling rate).

(Drying conditions) Initial drying: 25°C, 24 hours Final drying = 500°C (temperature raised from 25°C at 50°C/hr)
, 2 hours (2) Boiling water resistance (cracking resistance and adhesion durability) Using the obtained zircon-based coating composition, an evaluation sample prepared in the same manner as in the above initial adhesion evaluation was immersed in boiling water. After being immersed for 8 hours, the surface condition was sensory tested and the crack resistance was evaluated according to the following criteria.

(Judgment criteria) 02 No cracks on the surface ×: Cracks on the surface After performing the above sensory test, a cross-cut tape peeling test was performed in the same manner as the above initial adhesion evaluation, and the adhesion durability was evaluated by the peeling rate. evaluated.

(3) Acid resistance (cracking resistance and adhesion durability) Using the obtained zircon-based coating composition, an evaluation sample was prepared in the same manner as in the above initial adhesion evaluation.
After being immersed in wt% hydrochloric acid for 75 hours, the surface condition was sensory tested and the crack resistance was evaluated according to the following criteria.

(Judgment criteria) 02 No cracks on the surface x 2 Cracks on the surface After performing the above sensory test, a cross-cut tape peeling test was performed in the same manner as the above initial adhesion evaluation, and the adhesion durability was evaluated by the peeling rate. evaluated.

(4) Long-term shelf life After leaving the sealed container containing the obtained zircon-based coating composition in an atmosphere of 50°C and 65% RH for 6 months, cross-linking was performed in the same manner as in the above initial adhesion evaluation. A cut tape peel test was conducted, and long-term storage stability was evaluated according to the following criteria.

(Judgment criteria) ○: Peeling rate is 20% or less △: Peeling rate is 21-50% ×: Peeling rate is more than 50% 2. Items related to zircon-based oxide coated graphite molded bodies [Heat resistance] Obtained After the zircon-based oxide-coated graphite molded body was left to stand at 600° C. for 10 hours in an air atmosphere, the weight loss rate with respect to the initial weight of the zircon-based oxide-coated graphite molded body was measured to evaluate heat resistance.

Examples 1 to 15 Predetermined amounts of zirconium tetraalkoxide, diamine compound, and isopropyl alcohol shown in Table 1 were supplied to a separable flask, and stirred at room temperature for 15 hours at a stirring speed of 800 rpm to obtain stabilized zirconium tetraalkoxide. An alcoholic solution of alkoxide was obtained.

A predetermined amount of tetraalkoxysilane shown in Table 1 was added to the obtained alcohol solution, and the mixture was stirred at room temperature for 1 hour at a stirring speed of 8.
After stirring at 00 rpm, a hydrochloric acid aqueous solution consisting of a predetermined amount of water and hydrochloric acid shown in Table 1 was added, and the mixture was stirred at room temperature for 1 hour at a stirring speed of 80 rpm to obtain a zircon-based coating composition.

Using the obtained zircon-based coating composition, various physical properties were measured based on the measurement method described above, and the results are shown in Table 1.

Next, the obtained zircon-based coating composition was supplied into a vacuum container, and a cylindrical graphite molded body (diameter: 20°C mn, height: 20cm) that had been ultrasonically cleaned with acetone was placed in the zircon-based coating composition. After immersing the graphite molded body in water, the pressure inside the vacuum vessel was reduced to 5 Torr to impregnate the zircon-based coating composition into the graphite molded body. Next, the pressure inside the vacuum container was returned to normal pressure, and the graphite molded body was taken out to obtain a graphite molded body impregnated with a zircon-based coating composition.

The obtained graphite molded body impregnated with the zircon-based coating composition was naturally dried at room temperature for 24 hours, and then heated in a heating container for 1 hour.
Dry at 00℃ for 24 hours, and then dry at 150℃ under nitrogen atmosphere.
After treatment at 0° C. for 1 hour, a zircon-based oxide-coated graphite molded body was obtained.

Using the obtained zircon-based oxide-coated graphite molded body, the weight loss rate was measured based on the measurement method described above, and the results are shown in Table 1.

Example 16 As shown in Table 1, a zircon-based coating composition was obtained in the same manner as in Example 1 except that the amount of isopropyl alcohol added was changed.

Adding a predetermined amount of zircon powder (average particle size 1 μm) shown in Table 1 to the obtained zircon-based coating composition,
The mixture was stirred at room temperature for 1 hour at a stirring speed of 1000 rpm to obtain a zircon-based coating composition containing zircon powder.

Using the obtained zircon powder-containing zircon-based coating composition, each physical property was measured based on the measurement method described above, and the results are shown in Table 1.

A zircon-based oxide-coated graphite molded body was obtained in the same manner as in Example 1 using the above-mentioned zircon-based coating composition containing zircon powder.

Using the obtained zircon-based oxide-coated graphite molded body, the weight loss rate was measured based on the measurement method described above, and the results are shown in Table 1.

Comparative Examples 1 to 8 As shown in Table 2, zircon-based coating compositions were obtained in the same manner as in Example 1, except that the amounts of the constituent materials in the composition were changed.

Using the obtained zircon-based coating composition, various physical properties were measured based on the measurement method described above, and the results are shown in Table 2.

A zircon-based oxide-coated graphite molded body was obtained in the same manner as in Example 1 using the above-mentioned zircon-based coating composition.

Using the obtained zircon-based oxide-coated graphite molded body, the weight loss rate was measured based on the measurement method described above, and the results are shown in Table 2.

Comparative Example 9 As shown in Table 2, a zircon-based coating composition containing zircon powder was obtained in the same manner as in Example 15, except that the amount of zircon powder added was changed.

Using the obtained zircon powder-containing zircon-based coating composition, each physical property was measured based on the measurement method described above, and the results are shown in Table 2.

A zircon-based oxide-coated graphite molded body was obtained in the same manner as in Example 1 using the above-mentioned zircon-based coating composition containing zircon powder.

Using the obtained zircon-based oxide-coated graphite molded body, the weight loss rate was measured based on the measurement method described above, and the results are shown in Table 2.

(The following is a blank space) Using a graphite molded body similar to that used in Example 1, the weight loss rate was measured based on the measurement method described above, and the results were 3.
It was 5wt%.

ILLI-Zircon based coating composition with alumina concentration of 7% by weight
An alumina colloid-impregnated graphite molded body was obtained in the same manner as in Example 1, except that the aqueous dispersion of alumina colloid (manufactured by Catalyst Kasei Co., Ltd., trade name: Cataloid AS-3) was used.

The obtained alumina colloid-impregnated graphite molded body was heated at room temperature for 2
After air drying for 4 hours, it was dried in a heating container at 150° C. for 1 hour to obtain an alumina-coated graphite molded body.

Using the obtained alumina-coated graphite molded body, the weight loss rate was measured based on the measurement method described above, and it was found to be 3.1 wt%.
Met.

Comparative Example 12 Zircon-based coating composition with silica concentration of 30% by weight
Alcohol dispersion of silica colloid (manufactured by Catalyst Kasei Co., Ltd.,
A graphite molded body impregnated with silica colloid was obtained in the same manner as in Example 1 except that the product name was changed to 03CAL).

The obtained silica colloid-impregnated graphite molded body was heated at room temperature for 24 hours.
After air drying for an hour, it was dried in a heating container at 150°C for 1 hour to obtain a silica-coated graphite molded body.

Using the obtained silica-coated graphite molded body, the weight reduction rate was measured based on the measurement method described above and found to be 2.9 wt%.

(Effects of the Invention) The composition of the zircon-based coating composition of the present invention is as described above, and since it is composed of specific amounts of zirconium tetraalkoxide, tetraalkoxysilane, diamine compound, organic solvent, and water, it can be easily coated. The zircon-based coating composition can be stored for a long period of time, and the coating film obtained from the zircon-based coating composition has excellent initial adhesion, boiling water resistance, and acid resistance.

The above-mentioned zircon-based coating composition is suitably used for coating metals, plastics, wood, paper, cement, graphite, and the like.

In the method for producing a zircon-based oxide-coated graphite molded body according to the second invention, since the above-mentioned zircon-based coating composition is used, a graphite molded body coated with a zircon-based oxide can be easily obtained. Zircon-based oxide-coated graphite molded bodies have excellent heat resistance.

The zircon-based oxide-coated graphite molded body is suitably used for metal melting crucibles, firing jigs, and the like.

Claims (1)

[Claims] 1. (a) General formula Zr(OR^1)_4 (wherein R^1
represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms), (b) General formula Si(OR^2)_4 (wherein R^2 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms (d) an organic solvent; and (e) water. and the molar ratio of each component in the composition is (b)/(a)
=0.2~9,(c)/(a)=0.5~6,(d)/
((a)+(b))=0.05~500 and (e)/
A zircon-based coating composition in which ((a)+(b))=0.02-2. 2. A method for producing a zircon-based oxide-coated graphite molded body, which comprises applying or impregnating the zircon-based coating composition according to claim 1 onto a graphite molded body, and drying it.