JP3307471B2 - Composition for ceramic coating and coating method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a silicon-nitrogen-oxygen-metal element or a silicon-nitrogen-oxygen-metal element containing a modified polysilazane as an essential component and capable of forming a coating film having excellent heat resistance, abrasion resistance and corrosion resistance.
The present invention relates to a composition for a nitrogen-oxygen-carbon-metal element ceramic coating and a coating method using the same.

[0002]

2. Description of the Related Art In order to obtain high heat resistance, abrasion resistance and corrosion resistance, organic coatings are not sufficient, and ceramic coatings are used. Conventionally, as a method of forming a ceramic coating, PVD (sputtering method, etc.),
CVD, sol-gel methods, polytitanocarbosilane-based coatings, poly (disil) silazane-based coatings, polysilazane-based coatings, polymetallosilazane-based coatings, and the like are known.

[0003]

The above-mentioned ceramic coating methods are known, but all have problems. That is, the apparatus is expensive in the PVD and CVD methods. In the sol-gel method, the required firing temperature is as high as 500 ° C. or higher. Low-temperature baking (4
(Less than 00 ° C.). Those using a poly (disil) silazane-based polymer have difficulty in construction and cause cracks. Polysilazane and polymetallosilazane coatings can be fired at 200 to 500 ° C, but firing at less than 300 ° C does not necessarily result in good film quality.

Accordingly, the present invention solves the above-mentioned problems in the prior art, and provides heat resistance by firing at a low temperature (50 ° C. to 350 ° C.) or holding at a temperature lower than 50 ° C. without firing. To provide a coating composition that gives a dense coating film with excellent wear resistance and corrosion resistance and has no cracks, and a method for applying the coating composition. It is intended to be able to coat on.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, by adding an acetylacetonato complex containing a metal to polysilazane, the coating film of the adduct was formed. It has been found that the curing reaction when firing in air is promoted, and a good coating is formed at a firing temperature lower than before.

Thus, according to the present invention, mainly the general formula (I):

[0007]

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(However, R ¹ , R ² , and R ³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a group other than these groups in which carbon is directly bonded to silicon.) , An alkylsilyl group, an alkylamino group, or an alkoxy group, provided that R ¹ , R
^At least one of R ² and R ³ is a hydrogen atom. ) And a polysilazane having a number average molecular weight of 100 to 50,000 having a main skeleton composed of units represented by the following general formula (CH ₃ COCH):
COCH ₃ ) _n M, wherein M represents an n-valent metal, wherein the weight ratio of acetylacetonato complex / polysilazane obtained by reacting the acetylacetonato complex is in the range of 0.000001 to 2 and Number average molecular weight is about 2
A silicon-nitrogen-oxygen-metal element system containing at least 100,000 to 500,000 acetylacetonato complex-added polysilazane
Alternatively , a composition for a silicon-nitrogen-oxygen-carbon-metal element ceramic coating is provided.

The number average molecular weight of the acetylacetonato complex-added polysilazane used in the present invention is in the range of 200,000 to 500,000, preferably 500 to 10,000. The method for producing the acetylacetonato complex-added polysilazane used in the present invention comprises reacting polysilazane and an acetylacetonato complex in a solvent-free or solvent-free atmosphere under an inert atmosphere.

The polysilazane to be used may be any polysilazane having at least a Si—H bond or an N—H bond in the molecule. Not only polysilazane alone, but also a copolymer of polysilazane with another polymer or polysilazane with other polysilazane may be used. Can also be used as a mixture with the compound of formula (1). The polysilazane to be used includes a polysilazane having a chain, cyclic or cross-linked structure, and a polysilazane having a plurality of these structures in a molecule at the same time.

The following are typical examples of the polysilazane to be used, but are not limited thereto. In the general formula (I), those having a hydrogen atom at R ¹ , R ² and R ³ are perhydropolysilazanes, and their production methods are described, for example, in JP-A-60-145903, D. Seyf
erth et al. Communication of Am. Cer. Soc., C-13, January
1983. Has been reported to. What is obtained by these methods is a mixture of polymers having various structures, but basically contains a chain portion and a cyclic portion in the molecule,

[0012]

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Can be represented by the following chemical formula: An example of the structure of perhydropolysilazane is as follows.

[0014]

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In the general formula (I), R ¹ and R ^{2 represent} a hydrogen atom,
A method for producing a polysilazane having a methyl group at R ³ is described in D.
Seyferth et al.Polym.Prepr., Am.Chem.Soc., Div.Polym.Che
m ,. 25 , 10 (1984). The polysilazane obtained by this method has a repeating unit of-
It is a chain polymer and a cyclic polymer of (SiH ₂ NCH ₃ ) —, and neither has a crosslinked structure.

In the general formula (I), R ¹ and R ^{3 represent} a hydrogen atom,
A method for producing a polyorgano (hydro) silazane having an organic group at R ² is described in D. Seyferth et al., Polym. Prepr., Am. Chem. Soc.,
Div. Polym. Chem., 25 , 10 (1984);
-89230. The polysilazane obtained by these methods includes-(R ² SiHNH)
-As a repeating unit having a cyclic structure having a degree of polymerization of 3 to 5 or (R ³ SiHNH) _x [(R ² S
iH) _1.5 N] _1-X (0.4 <x <1) Some molecules have both a chain structure and a cyclic structure in a molecule represented by the chemical formula.

In the general formula (I), polysilazane having a hydrogen atom for R ¹ and an organic group for R ² and R ³ , and R ¹ and R ²
Having an organic group and a hydrogen atom at R ³ is-(R ¹ R ²
SiNR ³ ) — is a repeating unit and the degree of polymerization is mainly 3
-5 ring structures. Next, representative examples of the polysilazane used other than the general formula (I) will be given.

Among polyorgano (hydro) silazanes, D. Seyferth et al., Communication of Am. Cer. Soc., C-1.
32, July 1984. Some have a crosslinked structure in the molecule as reported. An example is as follows.

[0019]

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A polysilazane (R) having a crosslinked structure obtained by ammonia decomposition of R ¹ SiX ₃ (X: halogen) as reported in JP-A-49-69717.
¹ Si (NH) _X), or R ¹ SiX ₃ and R ² ₂ S
Polysilazane having the following structure obtained by co-ammonium decomposition of iX ₂ can also be used as a starting material.

[0021]

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The polysilazane used has a main skeleton composed of the unit represented by the general formula (I) as described above, but the unit represented by the general formula (I) may be cyclized as is apparent from the above. In such a case, the cyclic portion becomes a terminal group, and when such cyclization is not carried out, the terminal of the main skeleton can be the same group as R ¹ , R ² , R ³ or hydrogen.

There is no particular limitation on the molecular weight of the polysilazane to be used, and any available polysilazane can be used. However, in view of reactivity with the acetylacetonato complex, R ¹ , R ² and R ³ in the formula (I) are used. Is preferably a group having small steric hindrance. That is, R ¹ , R ² and R ³ represent a hydrogen atom and C
Alkyl group is preferably from ₁ -C _5, a hydrogen atom and C ₁ ~
Alkyl C ₂ is more preferred. The acetylacetonato complex to be used is a complex in which an anion acac ⁻ generated by acid dissociation from acetylacetone (2,4-pentadione) is coordinated to a metal atom, and generally has a formula (CH ₃ C)
OCHCOCH ₃ ) _n M wherein M represents a metal having an ionic value of n. ]. Suitable metals M include, for example, nickel, platinum, palladium, aluminum, rhodium and the like. For example, when nickel is used as the metal M, it has the following structure.

[0024]

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The mixing ratio of the polysilazane and the acetylacetonate complex is such that the weight ratio of the acetylacetonato complex / polysilazane is from 0.000001 to 2, preferably from 0.001 to 1, and more preferably from 0 to 1. Add from 0.01 to 0.5. If the amount of the acetylacetonate complex is increased beyond this range, the molecular weight of the polysilazane becomes too high to cause gelation, and if the amount is small, sufficient effects cannot be obtained.

The reaction can be carried out without solvent,
In general, it is better to use an organic solvent because the reaction control is more difficult than in the case of using an organic solvent and a gel-like substance may be generated. As the solvent, a hydrocarbon solvent of an aromatic hydrocarbon, an aliphatic hydrocarbon, an alicyclic hydrocarbon, a halogenated hydrocarbon, an aliphatic ether, an alicyclic ether, or an aromatic amine can be used. Preferred solvents include, for example, benzene, toluene, xylene, methylene chloride, chloroform, n-hexane, ethyl ether, tetrahydrofuran, pyridine, methylpyridine and the like, and particularly preferred solvents include xylene, pyridine, methylpyridine and the like. Atmosphere inert to the reaction,
For example, the reaction is preferably performed in an atmosphere of nitrogen, argon, or the like, but may be performed in an oxidizing atmosphere such as air.

The reaction temperature can be varied over a wide range. For example, when an organic solvent is used, it may be heated to a temperature lower than the boiling point of the organic solvent, but it is necessary to obtain a solid having a high number average molecular weight. The reaction can also be carried out by subsequently heating the organic solvent to a boiling point or higher to distill off the organic solvent. In general, the reaction temperature is preferably set to 150 ° C. or lower.

Although the reaction time is not particularly important, it is usually 1
It is about 50 hours. In general, the reaction is preferably carried out at around normal pressure. In the present invention, in order to prepare a coating composition using the acetylacetonato complex-added polysilazane, the acetylacetonato complex-added polysilazane may be usually dissolved in a solvent.

Examples of the solvent include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbon hydrocarbon solvents, halogenated hydrocarbons such as halogenated methane, halogenated ethane, and halogenated benzene; aliphatic ethers; Ethers such as cyclic ethers can be used. Preferred solvents are methylene chloride, chloroform, carbon tetrachloride, bromoform, ethylene chloride, ethylidene chloride, trichloroethane, halogenated hydrocarbons such as tetrachloroethane, ethyl ether,
Ethers such as isopropyl ether, ethyl butyl ether, butyl ether, 1,2-dioxyethane, dioxane, dimethyl dioxane, tetrahydrofuran, tetrahydropyran, pentanehexane, isohexane, methylpentane, heptane, isoheptane, octane, isooctane, cyclopentane, methylcyclopentane And hydrocarbons such as cyclohexane, methylcyclohexane, benzene, toluene, xylene, and ethylbenzene.

When these solvents are used, two or more kinds of solvents may be mixed to adjust the solubility of the acetylacetonato complex-added polysilazane and the evaporation rate of the solvent. The amount (proportion) of the solvent used is selected so as to improve the workability depending on the coating method to be used, and it depends on the average molecular weight, molecular weight distribution and structure of the acetylacetonato complex-added polysilazane. It is possible to mix up to about 10% by weight, preferably 10 to 50% by weight.

The concentration of the solvent depends on the average molecular weight, molecular weight distribution and structure of the polysilazane to which the acetylacetonato complex is added, but good results are usually obtained in the range of 0 to 90% by weight. In the present invention, a suitable filler may be added as needed. Examples of the filler include fine powders of oxide-based inorganic substances such as silica, alumina, zirconia, and mica, and non-oxide-based inorganic substances such as silicon carbide and silicon nitride. Depending on the application, metal powder such as aluminum, zinc, and copper can be added. Further examples of fillers include silica silica, quartz, novacurite, diatomaceous earth, and other silica-based materials: synthetic amorphous silica: kaolinite, mica, talc, wollastonite, asbestos, calcium silicate, aluminum silicate Glass bodies such as glass powder, glass spheres, hollow glass spheres, glass flakes, foam glass spheres: boron nitride, boron carbide, aluminum nitride, aluminum carbide, silicon nitride, silicon carbide, titanium boride, nitride Non-oxide inorganic substances such as titanium and titanium carbide: calcium carbonate: metal oxides such as zinc oxide, alumina, magnesia, titanium oxide, beryllium oxide: barium sulfate, molybdenum disulfide,
Tungsten disulfide, carbon fluoride, and other inorganic substances: metal powders such as aluminum, bronze, lead, stainless steel, and zinc; and carbon bodies such as carbon black, coke, graphite, pyrolytic carbon, and hollow carbon spheres.

These fillers may be used alone or in various shapes such as needles (including whiskers), granules, and scales.
A mixture of more than one species can be used. Further, it is desirable that the particle size of these fillers is smaller than the film thickness that can be applied at one time. The addition amount of the filler is in the range of 0.05 part by weight to 10 parts by weight based on 1 part by weight of the acetylacetonato complex-added polysilazane, and the particularly preferable addition amount is in the range of 0.2 part by weight to 3 parts by weight. is there. Further, the surface of the filler may be surface-treated by coupling agent treatment, vapor deposition, plating or the like before use.

The coating composition may contain various pigments, leveling agents, defoamers, antistatic agents, ultraviolet absorbers, pH adjusters, dispersants, surface modifiers, plasticizers, drying accelerators, if necessary. An anti-flow agent may be added. According to the present invention,
Similarly, there is provided a coating method using the coating composition as described above. This coating method is repeatedly applied once or twice or more to the above-mentioned coating composition on a substrate, and then baked to obtain silicon-nitrogen- The present invention is characterized in that a coating film made of an oxygen-metal element-based or silicon-nitrogen-oxygen-carbon-metal-element ceramic is formed.

Further, the present invention provides a coating method characterized in that the coating film fired as described above is held for a long time under a condition of less than 50 ° C. to improve the properties of the coating film. Further, the present invention, after repeatedly applying the coating composition as described above to the substrate once or twice or more, holding the coating film under a condition of less than 50 ° C for a long time, silicon-nitrogen-oxygen-metal element system or A coating method characterized by forming a coating film made of silicon-nitrogen-oxygen-carbon-metal element ceramics.

The substrate on which the coating composition is applied is not particularly limited, and may be any of metals, ceramics, plastics and the like. As a coating means as a coating, a usual coating method, that is, dipping, roll coating, bar coating, brush coating, spray coating, flow coating or the like is used. In addition, if the substrate is sanded, degreased, or surface-treated with various types of blasting before application, the adhesion performance of the coating composition is improved.

After coating by such a method and sufficiently drying, heating and baking are performed. The acetylacetonato complex-added polysilazane is crosslinked, condensed, or oxidized, hydrolyzed and cured depending on the calcination atmosphere by this calcination to form a tough coating. The calcination conditions vary depending on the molecular weight and structure of the polysilazane to which the acetylacetonato complex is added. The heating rate is not particularly limited, but is 0.5 to 10 ° C.
A slow heating rate per minute is preferred. Preferred firing temperatures range from 250 ° C to 350 ° C. The firing atmosphere may be any of oxygen, air, or an inert gas, but air is more preferable. Oxidation of the acetylacetonate complex-added polysilazane or hydrolysis by water vapor coexisting in the air proceeds by firing in air, and the Si—O bond or Si—
A tough coating mainly composed of N bonds can be formed.

Depending on the type of acetylacetonate complex-added polysilazane to be coated, conversion to ceramics may be incomplete under limited firing conditions,
In this case, it is possible to hold the fired coating film under a condition of less than 50 ° C. for a long time to improve the properties of the coating film. In this case, the holding atmosphere is preferably in air, and more preferably in humid air having an increased water vapor pressure. The holding time is not particularly limited, but is 10 minutes or more and 30 minutes or more.
Within days is practically appropriate. Further, the holding temperature is not particularly limited, but a temperature of 0 ° C. or more and less than 50 ° C. is practically appropriate. Although it is naturally effective to maintain the temperature at 50 ° C. or higher, the heating operation at 50 ° C. or higher is defined as “firing” in the text. That is, after baking at a certain temperature for a certain period of time, it is effective to perform baking for a long time by lowering the temperature to, for example, 50 ° C., but this operation is a type of the “heating and baking” operation described above.

Oxidation of the acetylacetonato complex-added polysilazane or hydrolysis by water vapor coexisting in the air is further promoted by the holding in air, and the conversion into ceramics is completed, and the properties are further improved. A tough coating film can be formed. According to the above method, the firing temperature can be lowered, and various problems caused by the high firing temperature can be reduced.

Further, depending on the type of the acetylacetonato complex-added polysilazane to be coated, calcination at 50 ° C. or higher is not performed at all, and the coated film after application is held at a temperature lower than 50 ° C. for a long time. Can be improved. In this case, the holding atmosphere is preferably in air, and more preferably in humid air having an increased water vapor pressure. The holding time is not particularly limited.
It is practically appropriate that the time is from 0 minutes to 30 days. Further, the holding temperature is not particularly limited, but a temperature of 0 ° C. or more and less than 50 ° C. is practically appropriate. Although it is naturally effective to maintain the temperature at 50 ° C. or higher, the heating operation at 50 ° C. or higher is defined as “firing” in the text. Oxidation of acetylacetonato complex-added polysilazane by holding in this air,
Alternatively, hydrolysis by water vapor coexisting in the air proceeds, and conversion to ceramics is completed, and a tough coating film mainly composed of Si—O bonds or Si—N bonds can be formed. According to the above method, various problems caused by a high firing temperature can be significantly reduced, and in some cases, conversion to ceramics at around room temperature becomes possible.

[0040]

[Production of raw material perhydropolysilazane]

A four-necked flask having an inner volume of 11 was equipped with a gas blow-in tube, a mechanical stirrer, and a dewar condenser. After the inside of the reactor was replaced with deoxygenated dry nitrogen, 490 ml of degassed dry pyridine was placed in a four-necked flask and cooled with ice. Next, when 51.6 g of dichlorosilane was added, an adduct (SiH ₂ Cl.2C ₅ H ₅ N) as a white solid was formed. The reaction mixture was ice-cooled, and heated with stirring while blowing 51.0 g of purified ammonia through a sodium hydroxide tube and an activated carbon tube.

After completion of the reaction, the reaction mixture was centrifuged, washed with dry pyridine, and filtered under a nitrogen atmosphere to obtain 850 ml of a filtrate. The solvent was distilled off from 5 ml of the filtrate to obtain 0.1 g of resinous solid perhydropolysilazane. The number average molecular weight of the obtained polymer was measured by freezing point depression method (solvent: dry benzene).
903. IR (infrared absorption) spectrum (solvent:
Concentration of dry o-xylene; perhydropolysilazane: 1
0.2 g / 1) has a wave number (cm ^-1 ) of 3340 (apparent extinction coefficient ε = 0.5571 g ^-1 cm ^-1 ) and an N of 1175
Absorption based on H; Absorption based on SiH at 2160 (ε = 3.14); SiH and SiNSi from 1024 to 820
Based on the absorption. ¹ H NMR (proton nuclear magnetic resonance) spectra (60 MHz, solvent CDCl ₃ / standard substance TMS) all show broad absorption. That is,
δ 4.8 and 4.4 (br., SiH); 1.5 (b
r. , NH) was observed.

Comparative Example 1 (Evaluation of ceramic formation during firing) In general, during firing of polysilazane, breaking of Si—R ₁ , N—R ₂ (R ₁ and R ₂ represent hydrogen atoms or alkyl groups) bonds And S
The formation of i-N, Si-O bonds (the latter is limited to firing in an oxidizing atmosphere) occurs, and polysilazane is silicon nitride,
Converted to ceramics such as silicon oxynitride and silica. This process is called ceramicization. In this Comparative Example or Example, the polysilazane was mainly changed to silica because the calcination was performed in the air atmosphere. However, semi-quantitative evaluation of the progress of the ceramic formation was performed by the IR method.

SiH residual rate = (SiH absorbance after heating /
SiN absorbance before heating) × 100 (%) SiO / SiN ratio = SiO absorbance after heating / S after heating
iN Absorbance Both values are indicators of the progress of ceramic formation. The smaller the residual ratio of SiH and the larger the ratio of SiO / SiN, the more advanced the ceramic formation.

Here, the characteristic absorption of SiN, SiO and SiH was about 840, 1160 and 2160 cm ^-1 , respectively. The absorbance was calculated as follows: Absorbance = log ( _Io / I). (See Figure 1 for definitions of I _o and I)

Example 1 Tonen's Perhydropolysilazane Type-1 (PHPS
−1; 0.05 g of palladium acetylacetonate (manufactured by Strem Chemicals. Inc., purity 99%) was added to 113.6 g of a 4.4% pyridine solution having a number average molecular weight of 600 to 900), and the mixture was heated at 50 ° C. in a nitrogen atmosphere. The reaction was carried out with stirring for 2 hours. This solution was decompressed to remove the solvent, and then diluted with xylene to obtain a 10% xylene solution. The number average molecular weight of this solution was 1,267 as measured by GPC. As a result of the IR spectrum analysis, the wave number (cm) was larger than that before the reaction with palladium acetylacetonate.
^-1 ) Absorption based on CH of 2960 and 2940 was confirmed. In addition, as a result of ¹ HNMR spectrum (CDCl ₃ ) analysis, absorption of δ = 1.4 was confirmed. This solution was used as a coating solution and applied onto a silicon wafer having a diameter of 4 inches and a thickness of 0.5 mm using a spin coater (1000 rp).
m, 20 seconds), and heated at 350 ° C. for 1 hour in an air atmosphere to obtain a coating film having a thickness of 3132 °. The progress of ceramicization of this coating film was evaluated by IR. (The evaluation method was the same as for the glycidol system.) SiH residual ratio 6%, SiO / Si
The N ratio was 6.1 (FIG. 2). In addition, 49%
When treated with a mixed solution of 18 ml of hydrofluoric acid (manufactured by Daikin Industries, Ltd.) and 1763 ml of 61% nitric acid (manufactured by Komune Chemical Co., Ltd.), the etching rate was 1078 ° / min. On the other hand, when a coating solution of polysilazane to which palladium acetylacetonate was not added was applied and evaluated by the same process, the residual ratio of SiH was 21%, and SiO / S
iN ratio = 1.1, etching rate is 2335 ° / min.
That was all. (FIG. 3). (See Table 1)

Example 2 Using platinum acetylacetonate, the reaction, construction and evaluation were carried out in exactly the same manner as in Example 1. The number average molecular weight of this solution was 1086. In addition, as a result of the IR spectrum analysis, absorption based on CH at wave numbers (cm ^-1 ) of 2960 and 2940 was confirmed as compared with before the reaction with platinum acetylacetonate. In addition, ¹ H NMR spectrum (CDCl ₃ )
As a result of the analysis, an absorption at δ = 1.4 was confirmed. Further, the coating film after heating has a thickness of 3435 °, a residual ratio of SiH of 6%, SiO 2
/ SiN ratio = 3.14, etching rate 1290 °
/ Min. (See Table 1)

Example 3 Using rhodium acetylacetonate, the reaction, construction and evaluation were carried out in exactly the same manner as in Example 1. The number average molecular weight of this solution was 901. The coated film after heating has a thickness of 3693.
Å, SiH residual ratio 2%, SiO / SiN ratio = 3.18,
The etching rate was 1086 ° / min. (Table 1
reference)

[0048]

[Table 1]

[0049]

According to the present invention, silicon-nitrogen-oxygen is excellent in heat resistance, abrasion resistance and corrosion resistance and has good adhesion to a substrate.
Metal element or silicon-nitrogen-oxygen-carbon-metal element
Lamic coatings are obtained by unprecedented firing at low temperatures.
The composition of the present invention includes not only metals and ceramics, but also
It is suitable as a surface protective agent for plastic materials and electronic components that are unsuitable for high-temperature treatment. In particular, hard coating agents for plastics, coating agents for suppressing gas permeation of synthetic resin films and containers, protective films and insulating films for semiconductors, such as passivation films, interlayer insulating films, chip coat films, etc., semiconductor sealants, and liquid crystal displays It can also be used as a body undercoat film or alignment film.

[Brief description of the drawings]

FIG. 1 is an IR spectrum diagram for evaluating a ceramic of a comparative example.

FIG. 2 is an IR spectrum showing the ceramics of Example 1 evaluated.

FIG. 3 is an IR spectrum diagram for evaluating the ceramics of Example 1.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C09D 1/00-201/10 C08G 77/62

Claims (3)

(57) [Claims] 1. A compound of the general formula (I): (However, R ¹ , R ² and R ³ are each independently a hydrogen atom,
An alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a group in which, other than these groups, a group directly bonded to silicon is carbon, an alkylsilyl group, an alkylamino group, or an alkoxy group. However, at least one of R ¹ , R ² and R ³ is a hydrogen atom. A polysilazane having a number average molecular weight of 100 to 50,000 having a main skeleton composed of units represented by the following formula: and a general formula (CH ₃ COCHCOCH ₃ ) _n M wherein M represents a metal having an ionic value of n. The acetylacetonate complex / polysilazane weight ratio obtained by reacting the acetylacetonate complex is in the range of 0.000001 to 2 and the number average molecular weight is about 2
A silicon-nitrogen-oxygen-metal element system containing at least 100,000 to 500,000 acetylacetonato complex-added polysilazane
Alternatively , a composition for a silicon-nitrogen-oxygen-carbon-metal element ceramic coating . Wherein silicofluoride of said metal M is nickel acetylacetonate complexes, platinum, palladium, aluminum, according to claim 1, wherein at least one selected from rhodium
Element-nitrogen-oxygen-metal element system or silicon-nitrogen-oxygen-char
An element-metal element-based ceramic coating composition. 3. After repeatedly applying the coating composition according to claim 1 or 2 to a substrate one or more times,
A coating method comprising sintering at a temperature of 50 ° C. or higher to form a coating film made of silicon-nitrogen-oxygen-metal element ceramic or silicon-nitrogen-oxygen-carbon-metal element ceramic.