JPS60262865A - Heat-resistant film-forming composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which can form a film at room temp. and can be converted into a vitreous material at a high temp. to form an insulator, containing an alkyl or aryl silicate, an inorg. lead compd. and an inorg. boron compd. as essential components. CONSTITUTION:A film-forming compsn. contains an alkyl or aryl silicate (e.g. methyl orthosilicate or phenyl orthosilicate), inorg. lead compd. (e.g. PbO or Pb3O4) and an inorg. boron compd. (e.g. B2O3 or H3BO4) as essential components. This compsn. has excellent thick-coatability and can be easily applied by brushing, spray coating or bar coating. The formed film is dried at room temp. and the dried film has excellent adhesion at room temp., is hardly peeled off and can be converted into a vitreous material at a temp. of 600 deg.C or above to form an insulator. When the compsn. is applied to a ceramic board, a vitreous insulating film is formed thereon.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a heat-resistant film-forming composition, and more particularly to a heat-resistant film-forming composition containing an alkyl (or allyl) silicate, an inorganic lead compound, and an inorganic boron compound as major components. The present invention relates to a composition.

In general, the heat resistance of paints that use organic resin as a binder component decreases significantly at temperatures above 400°C, so inorganic paints have traditionally been used for applications that require higher heat resistance. is underused.

However, since the material formed in conventional inorganic paints is porous, when the material is a metal surface, for example, an iron base, the iron surface is easily oxidized and the coating may peel off. It is also believed that this peeling phenomenon is partly due to the fact that the thermal expansion coefficient of the coating is smaller than that of iron.

Therefore, the inventor of the present invention first discovered a heat-resistant coating composition that has excellent adhesion to metal materials and does not peel off even at high temperatures of about 400°C or higher.
No. 0332, JP-A-53-117027, JP-A-53
-121824 etc.). These prior art methods actively vitrify the formed specimens at high temperatures and
It forms a test material that does not deteriorate and maintains its cosmetic effect even at temperatures above .degree.

The above-mentioned coating composition exhibits excellent coating film performance when applied to metal materials, especially iron materials, but the coefficient of thermal expansion is smaller than that of metal materials such as ceramics. When applied to inorganic materials, since the coating composition uses enamel (IJ) as an essential component, the coefficient of thermal expansion of the material to be tested becomes close to that of metals, especially iron materials. It had the disadvantage of warping and peeling. In order to avoid this drawback, it is necessary to prepare a coating composition that forms a film with a coefficient of thermal expansion suitable for the object to be coated, which may limit the use of floating frits or cause problems in the formulation of the coating. There was a problem that required preliminary consideration. Furthermore, the use of the Haurou Fri9to has the problem of being expensive and cumbersome.

Therefore, the present inventors have the ability to form a test material at room temperature, the film can be melted and vitrified at a high temperature of approximately 400°C or higher, and the thermal expansion coefficient of the test material is similar to that of a ceramic material. As a result of extensive research into obtaining a coating composition that can form a similar film by repeatedly using enamel frit, we have found that alkyl (or allyl) silicate is used as a binder component, and inorganic lead compounds and inorganic boron compounds are used as a binder component. Finding that a composition obtained by adding fCO satisfies the above performance, he completed the present invention.Thus, according to the present invention, fCO) is an alkyl (or allyl) silicate, and (to) an inorganic lead compound. and (O) A heat-resistant film-forming composition characterized by containing an inorganic boron compound as a main component is provided.

The heat-resistant film-forming composition of the present invention has excellent thick coating properties and can be easily applied by means such as brush coating, spray coating, and percoater coating, and the formed film dries at room temperature. It has excellent adhesion even at room temperature and does not peel off easily. Further, in a temperature range of 600° C. or higher, the coating changes to a glassy state, forming an insulator, and when coated on a ceramic substrate, for example, it becomes a glassy insulation test.

To explain in more detail the process of vitrifying the film described above, the heat-resistant test-formable composition of the present invention is first
At temperatures below ~450°C, a film consisting of an alkyl silicate, an inorganic lead compound, and an inorganic boron compound is formed, and at temperatures above that, the inorganic lead compound and inorganic boron compound each form PbO.

It begins to change to oxides such as Pb3O4, 8203, etc. 60
S i02 of alkyl silicate compound from around 0℃
It is thought that it melts with other ingredients and transforms into lead siligate phosphate glass.

Alkyl (or allyl) used in the present invention
As the silicate (4), the following general formula (R is 1 carbon number
~8 alkyl groups or allyl (Allyl or A
ryl) group, where n represents an integer of 0 or 11 or less) K is a tetraalkyl (or tetraallyl) orthosilicate or a lower condensate thereof. Specifically, for example, methyl orthosilicate, ethyl orthosilicate, n-propylorthosilicate, n-butyl orthosilicate, n-octylorthosilicate,
Phenyl orthosilicate, benzyl orthosilicate, and phenethyl orthosilicate, Allyl
yl) orthosilicate, methacryl orthosilicate, and low condensates produced by dehydration condensation of these orthosilicates.

Furthermore, as the alkyl (or allyl) silicate (A) that can be suitably used in the present invention, the above-mentioned tetraalkyl (or allyl) orthosilicate and the following general formula (R and n represent the above meanings, R' represents an alkyl group having 1 to 12 carbon atoms or allyl) (e.g., methyl) I
J. methoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane and their low condensates) in the presence of an acid catalyst, and after cooling, the pH was adjusted to 7 using an alkaline substance. Examples include organosilicon high condensates having a fine metal of 20 or more and a molecular weight of about 3,000 or more, which do not have a silanol group at the molecular end, and which are obtained by condensation by condensation. This high condensate may be used alone or in combination with the alkyl silicate of general formula CD. In this high condensate, the blending ratio of both components of the general formula [1] and [1] is 11fl
It is appropriate to mix them in the following proportions based on #.

Compound of general formula [1]: 5 to 95% by weight, preferably 20 to 80% by weight Compound of general formula [I]: 5 to 95% by weight, preferably 20 to 80% by weight In the above formulation, the amount of compound [I] is 5% by weight, preferably 20 to 80% by weight. When the amount is less than 955% by weight, that is, when the [1] compound exceeds 955], the curability of the inorganic coating formed using the condensate with KFi is poor at room temperature.

Further, when the amount of the [I] compound is less than 5% by weight, that is, when the amount of the [1] compound exceeds 95% by weight, the test material tends to peel off when thickly coated using this condensate.

In the present invention, said 41! When a silicon high condensate is used as the active ingredient, the resulting film-forming composition can be applied thickly (up to a dry thickness of about 100 μm), is easily cured by moisture in the air, and the film formed is excellent. It has high heat resistance.

Inorganic lead compounds used in the present invention
Lead oxides such as PbaO4) and litharge (pbo) can be mentioned, among which lead oxides have excellent storage stability when used as a paint #I composition and the aesthetic appearance of the film formed. It is suitable for

Further, the inorganic boron compound used in the present invention may be one that forms a B2O3 component at high temperatures.
For example, boron oxide (B203), horic acid (H3BO3)
, Hokusand (Na2B4O7.10H20), etc. can be used.

The proportions of the alkyl (or allyl) silicate (2), inorganic lead compound (1), and inorganic boron compound (O), which are the main components in the film-forming composition of the present invention, are the final changed oxides, i.e. 5i02.Pb
In terms of weight of O (or PbaO4) and B2O3, 5iOz: 5 to 65% by weight, preferably 1O to 50% by weight, Pb0 (9:30 to 90% by weight, preferably 40 to 85% by weight) B203(0 : 5 to 65% by weight, preferably 5 to 25% by weight.

In the above formulation, if (A) Fft exceeds 65% by weight, cracks may occur in the coating, the transition temperature of the coating to a vitreous film will become high, and continuous vitreous strips will be difficult to form. On the other hand, if it is less than 5% by weight, a film cannot be formed at room temperature. In addition, if the content exceeds 90% by weight, the film will warp at room temperature and the glassy film formation temperature will become high, making it difficult to form a continuous glassy film. Furthermore, if the O component exceeds 65% by weight, the viscosity at the time of melting is low and the H1 coated surface is likely to repel. On the other hand, if it is less than 5% by weight, the test material may have poor heat resistance. It is difficult to form a loose glassy film.

In the present invention, in addition to the fC, (A) to (0) components described above, a relay pigment, a raw material for glass, an inorganic additive, etc. may be blended as necessary.

Examples of Il-free materials include titanium white as a coloring agent,
Red rosewood, alumina, carbon gras, yellow, cyanine blue, zinc white, etc. can be used, and as extender pigments, talc, tantalum, clay, mica, palic, feldspar, etc. can be used.

In addition, raw materials for glass include refractory raw materials (silica stone, silica sand, feldspar, etc.), meltable raw materials (soda ash, chili saltpetre,
Potassium saltpeter, lyticum carbonate, potassium carbonate, calcium carbonate, barium carbonate, magnesium carbonate, calcium hydroxide, zinc oxide, etc.), weak yL white raw materials (fluorite, cryolite,
(sodium fluoride, aluminum fluoride, sodium fluorosilicide, etc.), strong opalescent ingredients (tin oxide, antimony oxide, metal antisone, sodium antimonate, titanium oxide, zirconium oxide, zirconium silicate, arsenite, cerium oxide, etc.) ), coloring raw materials (sulfur oxide, cobalt oxide, chromium oxide, nickel oxide, manganese dioxide, copper oxide, iron oxide, potassium dichromate, cadmium sulfate,
(metallic selenium, lead chromate, etc.) and adhesives (metallic selenium, nickel oxide, manganese dioxide, etc.) can be used.

Further, as the inorganic additive, mica, clay, bentonite, Erosil, etc. may be used in order to suppress sedimentation of the pigment.

Additionally, asbestos, glass fiber, glass powder, and glass flakes can be used in combination to prevent paint cracking.

The addition ratio of the above-mentioned inorganic pigments, raw materials for glass, inorganic additives, etc. can be added in a total amount of 50% by weight based on the solid content in the test type yielding composition, but it is preferable. is 20% by weight or less.

IP target of the present invention! The formable composition is applied to materials such as glass plates, ceramics, and metals by means of bald coating, spray coating, etc., but the objects to which this composition is particularly preferably used are alumina, magnesia, zirconia, These include oxide-based ceramic materials such as titania and baricum titanate, and non-oxide-based ceramic materials such as nitrides, carbides, and chlorides.

The film formed by the test-formable composition of the present invention is
It dries at room temperature, has excellent adhesion, is hard, and can withstand high temperatures of 800°C or higher. Such characteristics are not found in ordinary inorganic paints. The reason why such an excellent film can be obtained is that the components in the composition form a glassy substance at high temperatures, and the coefficient of thermal expansion of the film is close to that of the material to be coated. This is because it has become.

Hereinafter, zero-shot one-force MJK will be explained in more detail using Examples and Comparative Examples.

Note that parts and % indicate parts by weight and % by weight unless otherwise specified.

Example 1 Paint compositions were prepared by dispersing various inorganic paint compositions having the following compositions in a paint conditioner for about 2 hours.

Ethyl silicate 66% hydrolyzate solution *150 parts Red lead 70 parts Honic acid 20 parts
A mixture consisting of 100 parts of Si02 min 40%), 90 parts of isopropyl alcohol, and 10 parts of IN-hydrochloric acid was maintained at room temperature for 24 hours for hydrolysis. The hydrolysis rate of the obtained ethyl silicate was 66%, and the nonvolatile content Vi20
%Met.

Example 2 A coating composition was prepared in the same manner as in Example 1 using the following formulation.

50% hydrolyzate solution of ethyl silicate *2 25 parts: barrel stone 2 parts: silica powder 10 parts: lead Red 70 parts: star sand (anhydrous) 10 parts: 2 Ethyl orthosilicate (manufactured by Nihon Colcoat Chemical Co., Ltd., 5 parts)
i02 min 28%) 248 parts, Inglobil alcohol 2
A mixture of 50s and 18 parts of IN-hydrochloric acid was maintained at room temperature for 24 hours to allow hydrolysis. The hydrolysis rate of the obtained ethyl orthosilicate was 50%, and the nonvolatile content was 16%.

Example 3 A coating composition was prepared in the same manner as in Example 1 using the following formulation.

Organosilicon high condensate solution *3 40s Potassium nitrate 2 parts Red lead 100 parts Stone 10 parts Granules 2085 *3 1 Tetraethoxysilane 622, methyltriethoxysilane 125F and ethyl alcohol were heated to 80℃ in a reaction vessel. Thereafter, 30 f' of 0.2 N-hydrochloric acid was added and the mixture was reacted at 80°C for 10 hours. Next, triethylamine 302 was added to this reaction product to raise the pH to 7 or higher, and the reaction mixture was heated at 80°C for 2 hours. After that, benzene was added to remove the solvent in a trench with a non-volatile content of 36%. I did it.

Example 4 A coating composition was prepared in the same manner as in Example 1 using the following formulation.

Organosilicon high condensate solution *4 40 parts Lead red 1o part Honic acid 10 parts Long stone 1 o part *4 Add tetrabutoxysilane 132F to the reaction vessel.

Add 138v of phenyltriptoxysilane and 2702v of butyl alcohol, and heat the contents with stirring to 1.
After the temperature reached 00℃, add 5% formic acid aqueous solution 66F to 10℃.
The reaction was carried out at 0°C for 1 hour. Then, this reaction product vC
N-Methylmorpholine 302 was added to raise the pH to 7 or higher, and a feeding reaction was carried out at 90° C. for 2 hours. Thereafter, 100 V of toluene was added, and the solvent was removed by sieving until the nonvolatile content was 40%.

Comparative Example 1 A paint composition was prepared in the same manner as in Example 1 using the following formulation.

Ethyl silica used in Example 1) 10 parts titanium white
20 parts alumina 10 parts Comparative Example 2 Heat-resistant paint "Terumo 300" (manufactured by Kansai Paint Co., Ltd.) was subjected to a test.

The paints obtained in the above Examples and Comparative Examples were applied to an oxide-based ceramic plate using a brush, dried at room temperature, and used for testing.1. Ta. The test results are shown in Table 1 below.

〔Test items〕

Hardness: After drying the coating at room temperature for one week, the hardness was measured at 17.

Adhesion: After the paint was allowed to dry at room temperature for 5 days, a cross cut was made with a knife and then peeled off with Sellotape to see if it would adhere to it.

Heat resistance: After being placed in an electric furnace at 400°C and 800°C for 3 hours, it was left at room temperature and observed for cracking or peeling of the paint.

◎: Indicates no cracks or peeling. vinegar ○: Very slight cracks can be seen, but the product is actually Indicates a condition in which there is no problem in use.

Table-1 Procedural amendment written on December 2, 1980, 1, Indication of the case, 1982 Patent Application No. 117844 2, Name of the invention: Heat-resistant film-forming composition 3, Person making the amendment Relationship with the case Application Person Address: 33-1 Kanzaki-cho, Amagasaki City, Hyogo Prefecture Name (140) Kansai Paint Co., Ltd. Showa Year Month
Date (shipment date: Showa year, month, day) 5. [Detailed description of the invention column] of the specification to be amended 6. Contents of the amendment Contents of the amendment 1. "Film-forming composition" on page 1, line 13 of the specification letter is corrected to "film-forming composition."

2. Correct "inferior" to "inferior" on page 7, line 13 of the same book.

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Claims (1)

[Claims] (to) alkyl (or allyl) silicate, (B)
A heat-resistant film-forming composition comprising an inorganic lead compound and an inorganic boron compound as main components.