JPS60262863A - 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 and a lead oxide as essential components. CONSTITUTION:A film-forming compsn. contains a mixture of 3-70wt% alkyl or aryl silicate (e.g. methyl orthosilicate or phenyl orthosilicate) and 97-30wt% PbO and/or Pb3O4 as an essential component. This compsn. has excellent thick- coatability and can be easily applied by brushing, spray coating or bar coating. The formed film can be dried at room temp., and the dried film has excellent adhesion at room temp., is hardly peeled off and 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 film-forming composition, and more particularly to a film-forming composition having excellent heat resistance and containing an alkyl (or allyl) silicate and lead oxide as main components.

In general, the heat resistance of paints that use IN 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. ing. However, since the film formed with conventional inorganic paints is porous, when the material to be coated is a metal surface, for example, an iron base, the base surface is easily oxidized and peeling may occur. It is also believed that this peeling phenomenon is partly due to the fact that the coefficient of thermal expansion of the test material is smaller than that of iron.

Therefore, the present inventor previously proposed a heat-resistant coating composition that has excellent adhesion to metal materials and does not peel off even at high temperatures of approximately 400°C or higher (for example, JP-A-53-140
No. 332, JP-A-53-117027, JP-A-53-
121824 etc.). These prior art methods actively vitrify the formed film at high temperatures, approximately 800°C.
It forms a coating that does not deteriorate even at temperatures above and maintains its cosmetic effect.

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 7rivt as an essential component, the coefficient of thermal expansion of the material to be tested is close to that of metals, especially iron materials, so the coating may warp. , a loaf that has the disadvantage of 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, and the use of the coating material is limited to the use of the coating material. There was a problem in that the formulation required a considerable amount of preliminary consideration. Furthermore, there is a problem in that the use of the 7-lit Haurou is expensive.

Therefore, inventor C- has 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 furthermore, the coefficient of thermal expansion of the test material is ceramic. As a result of repeated research on lead content in order to obtain a coating composition that can form a test material similar to that of the material without using enamel frit, it was found that alkyl (or allyl) silicate was used as the binder component and lead oxide was added to the kneading material. It was discovered that a composition obtained by adding a specific amount of the above-mentioned ingredients achieved the above-mentioned performance, and the present invention was completed.

Thus, according to the present invention: (4) Alkyl (or allyl) silicate 3-7
0% by weight and (B lead oxide (Pbo) and/or red lead (Pb304)
) There is provided a film-forming composition characterized in that it contains as an essential component a mixture of 30 to 97% by weight.

The film-forming composition of the present invention can be easily applied by means such as pressing, brushing, spraying, and Percoke-Is, and the formed film dries at room temperature.

The test material has excellent adhesion even at room temperature and does not peel off easily. Further, in a temperature range of 60 (lt) or higher, the material changes to a glassy state and forms an insulator. For example, when a ceramic substrate is coated, the material becomes a glassy insulating material.

To explain in more detail the process of forming the film into glass, the film-forming composition of the present invention forms a film made of alkylsilicate chilead oxide at temperatures below 300 to 450°C; If the temperature exceeds this temperature, for example, at about 600° C. or higher, the 5lo2 component and lead oxide in the alkyl silicate compound are considered to melt and transform into silicate-lead glass.

Alkyl (or allyl) used in the present invention
Silicate (4) and 1. , the following general formula (R is an alkyl group having 1 to 8 carbon atoms, allyl (AIlyl or
R'1Aryl) group, n represents O or an integer of 11 or less), or a lower condensate thereof. Specifically, for example, methyl orthosilicate,
Ethyl orthosilicate, n-propyl orthosilicate, n-butyl orthosilicate, n-octyl orthosilicate, phenyl orthosilicate, benzyl orthosilicate, phenethyl orthosilicate, allyl (Al1y+) orthosilicate, methacryl orthosilicate, etc. Examples include low condensates produced by dehydration of orthosilicates.

As the alkyl (Moshikke allyl) silicate (4) that can be suitably used in Saratra and Kibatsu Fj4, the above-mentioned tetraalkyl (Moshikuri tetraallyl) orthosilicate and the following general formula (where R and n have the above meanings) are used. and R' represents an alkyl group having 1 to 12 carbon atoms or allyl) (for example, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and their derivatives). Condensation products, etc.) are hydrolyzed in the presence of an acid catalyst and then condensed using an alkaline substance to adjust the pH to 7 or more. Examples include organosilicon high condensates of 3000 or more. This high condensate may be used alone or may be used in combination with the alkyl silicate of the general formula (D). The appropriate blending ratio is as follows based on weight.

Compound of general formula [I]: 5-95% by weight, preferably 20-80% by weight Compound of general formula [1]: 5-95% by weight, preferably 20-80% by weight In the above formulation, the amount of compound [I] is 5% by weight, preferably 20-80% by weight. If the amount is less than 95% by weight, that is, if the amount of compound (1) exceeds 95% by weight, the curability of the inorganic coating formed using this condensate at room temperature will be poor.

In addition, when the amount of the [seal] compound is less than 511%, that is, when the amount of the [1] compound exceeds 95% by weight, the thick coating using this condensate tends to peel off.

In the present invention, when the organosilicon high condensate is used as the component (2), the resulting test-formable composition can be applied thickly (up to a dry film thickness of about 100 seconds) and is easily cured by moisture in the air. However, the film formed has excellent heat resistance.

In the present invention, lead oxide (Pb0) 2 red lead (PbaO4) is used as an ingredient, and red lead is particularly excellent in storage stability when used as a paint composition and in aesthetic appearance when formed into a film. This is preferable in this respect.

Alkyl silicate (4), which is an essential component in the film-forming composition of the present invention, and lead oxide and/or red lead (the blending ratio in the publication is based on solid content weight, (A: 3 ~ It is inappropriate to blend in the range of 70% by weight, preferably 5 to 50% by weight (a: 30 to 97% by weight, preferably 50 to 95% by weight).

In the above step 1, if the component (4) exceeds 70% by weight, that is, if the El component is less than 30% by weight, cracks may occur in the film or the vitrification temperature will become high, resulting in continuous glassy reflection. On the other hand, if it is less than 3%, that is, if the same component exceeds 977, the coating will easily peel off when dried at room temperature, making it difficult to form a test material.

In the zero-shot 1IFl, the above 1. In addition to the components A and (Second 1), inorganic pigments, raw materials for glass, inorganic additives, etc. can be blended as necessary. 1, Inorganic pigments and 17
Teke, Tozu is colored and has titanium white, Hengara, alumina, and carbon glass 1. Yellow, cyanine blue, and zinc oxide can be used, and as extender pigments, amber, tanchar, clay, mica, parita, feldspar, etc. can be used.

゛In addition, as raw materials for glass, refractory raw materials (silica stone,
silica sand, feldspar, etc.), molten raw materials (soda ash, chili saltpeter, potash saltpetre, lithium carbonate, potassium carbonate, calcium carbonate, barium carbonate, magnesium carbonate, calcium hydroxide, zinc oxide, etc.), weak opalescent spores (fluorite, etc.) , cryolite,
(sodium fluoride, aluminum fluoride, sodium chloride, etc.), strong opalescent ingredients (tin oxide, antimony oxide, antimony metal, 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, domicum sulfate, metallic selenium, lead phosphate, etc.) and adhesives (cobalt oxide, 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.

Furthermore, asbestos, glass fiber, glass powder, and glass flakes can also be used in combination to prevent cracking of the paint film.

The above-mentioned inorganic pigments, raw materials for glass, inorganic additives, etc. can be added in a total amount of up to 1% by weight of 50% by weight in the test forming composition, but preferably Vi20% by weight. % or less.

The test forming composition of the present invention is applied to materials such as glass plates, ceramics, metals, etc. by means of bald coating, spray coating, etc., and the present composition is particularly preferably applied to materials to be coated. are oxide-based ceramic materials such as alumina, magnesia, zirconia, titania, and barium titanate, and non-oxide-based ceramic materials such as nitrides, carbides, and holides.

The film-forming set bottom of the present invention 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, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

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

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

Ethyl silicate 66% hydrolyzate solution *150 parts Red lead 70 parts *1 Ethyl silicate (manufactured by Nippon Korfut Chemical Co., Ltd., polymerization degree 4
~6.5i02min 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 non-volatile fraction was 20%.

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 is marble stone 2 parts guinea powder 10 parts lead red 70 parts *2 Ethyl orthosilicate (manufactured by Nippon Full Coat Chemical Co., Ltd., S
A mixture consisting of 248 parts of i02 min 28%), 250 parts of isopropyl alcohol, and 18 parts of IN-hydrochloric acid was maintained at room temperature for 24 hours (hydrolyzed for 7 hours). The hydrolysis rate of the obtained ethyl orthosilicate was 50%, and the nonvolatile content was #t1
It was 6%.

Example 3 A raw meat grade product was prepared in the same manner as in Example 1 using the following composition.1. Ta.

Silicon high condensate solution *3 40 parts Potassium nitrate 2 parts Lead Red 100 parts Stone io part 3 Reaction volume iK, tetraethoxysilane 622, methyltriethoxysilane 1252 and ethyl alcohol 1872
was added, and the contents were heated to 80°C with stirring, and then 0.2 N-salt e30. f/ and 10 at 80°C.
The reaction was allowed to proceed for 0 hours. Next, 30% of triethylamine was added to this reaction product to raise the pH to 7 or above and to 80'.
Carry out an MJN reaction for 2 hours at C, then add benzene and remove the solvent with a sieve until the non-volatile content is 36%.Example 4 Paint #1 was prepared in the same manner as in Example 1 with the following composition.
17th step of preparing the product.

Organosilicon high condensate solution *4 40 parts Stone 10 parts Lead Red 70 parts *4 In a reaction vessel, add 1322 parts of tetrabutoxysilane, 1382 parts of phenyltriptoxysilane, and 270 parts of butyl alcohol.
2 was added, and the contents were heated with stirring until the temperature reached 100°C, and then 66 f of a 5% formic acid aqueous solution was added, and the mixture was heated to 100 t.
Allowed time to react. Next, 30f of N-methylmorpholine was added to this reaction product to raise the pH to 7 or higher and the pH was adjusted to 90.
The sequential reaction was carried out at ℃ for 2 hours, and then toluene 1002
was added to remove the solvent until the nonvolatile content became 40%.

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

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

Test 1: The paints obtained in the above Examples and Comparative Examples were applied to an oxide-based ceramic plate with a brush, and then softened at room temperature.
1. The trial results are shown in Table 1.

〔Test items〕

Hardness: The paint film was allowed to dry at room temperature for one week, and then the hardness was measured.

Adhesion: After the coating was allowed to dry for 5 days at room temperature, a cross cut was made with a knife and marked with cellophane tape to see if it would adhere to it.

Heat resistance: After being placed in an electric furnace at 400°C and 800°C for 1 hour, it was left at room temperature and the coating film was observed for cracking or peeling.

◎: Indicates no cracking or peeling 0: Indicates that there is very little cracking but no practical problem Application No. 117842 2, Name of the invention: Film-forming composition 3, Relationship with the person making the amendment Applicant address: 33-1 Kanzaki-cho, Amagasaki-shi, Hyogo Name (140) Kansai Paint Co., Ltd. Showa Year/Month
Date (Shipping 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. "Inferiority" on page 7, line 13 of the specification Corrected to "inferior."

Claims (1)

[Claims] (4) Alkyl (or allyl) silicates 3 to 7
011f% and (g) Lead oxide (Pb0) and/or red lead (Pba04)
1. A test-formable composition comprising as an essential component a mixture consisting of 30 to 97% by weight.