JPH0948951A - Colored coating composition, and colored glass and its production using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a colored coating compsn. which can be converted by a simple process at a low temp. into a colored silica-base ceramic film capable of being colored deep even when it is thin and to produce a colored glass from the compsn. SOLUTION: This compsn. mainly comprises a (modified) polysilazane, an inorg. or org. colorant, and their solvent or dispersion medium. This colored glass comprises glass and a colored coating film formed thereon by applying the compsn. and converting it into a ceramic. In this production process, the compsn. is applied to glass and converted into a ceramic.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a colored coating composition, a colored glass using the same, and a method for producing the same, and more specifically, a colored coating composition containing polysilazane and a ceramic obtained by applying the composition to glass. TECHNICAL FIELD The present invention relates to a colored glass obtained by liquefying and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, in the field of materials such as glass, ceramics, plastics, and metals, coloring treatment technology is one of the extremely important basic technologies. Information processing, optical components such as color filters and mirrors, and automobile lamps. (Yellowing of headlights and fog lamp bulbs, reding of brake lights, yellowing of flasher lamps or amber), infrared lamps for kotatsu (red, yellow),
It is widely used for decorative glass, automobile glass and building glass (bronze, gray, blue, green, etc.). In particular, for parts exposed to severe environments such as high temperature, wear, and corrosion, a technique of coating a heat-resistant substrate (for example, glass or metal) with an inorganic colorant-containing ceramic is adopted.

For example, when coloring glass,
In the molten state, metal ions are injected into the glass to develop color,
Obtaining bulk colored glass, coating colored low melting glass at a temperature above the melting point on glass, or acrylic resin instead of glassy material for lowering the temperature,
A method has been used in which resins such as epoxy resin are colored and coated on glass to obtain a similar colored glass. Therefore, the methods (1) and (2) have a drawback that the firing temperature is high, and the methods (2) have a drawback that the environmental resistance of the obtained product is poor.

Therefore, a treatment liquid obtained by adding an organic colorant to a hydrosilicofluoric acid aqueous solution in which silicon dioxide is supersaturated,
A method of contacting with a substrate (glass), or a method in which the treatment liquid is brought into contact with powders to obtain silica-coated powders, which are dispersed in a transparent dispersion medium, and then coated on the substrate (Japanese Patent Laid-Open No. 4-91171) has been proposed. However, in this method, as described in the publication, when the treatment liquid is simply brought into contact with a substrate, a thick film thickness is required for a highly colored application such as a color filter, and a long film formation is required. Since it takes time, a complicated process of bringing the treatment liquid into contact with the powder and granules to form a colored silica coating on the powder and granules, and contacting the treatment liquid in which the dispersion is dispersed in a transparent dispersion medium with the substrate. There is a drawback that it requires.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances of the prior art, and it is a colored siliceous ceramic film capable of forming a dark color even in a thin film in a simple process at a low temperature. It is an object of the present invention to provide a colored coating composition that can be converted into a composition, a colored glass using the composition, and a method for producing the same.

[0006]

That is, according to the present invention, firstly, coloring characterized by mainly containing polysilazane or a modified product thereof and an inorganic or organic coloring agent and a solvent or a dispersion medium thereof. A coating composition is provided. Secondly, there is provided a colored glass characterized by comprising a glass and a glass, which is obtained by applying the composition described in the above-mentioned first to glass, and ceramicizing the glass. Thirdly, there is provided a method for producing a colored glass, which comprises applying the composition according to the first aspect to glass and converting the composition into a ceramic.

Since the colored coating composition of the present invention contains polysilazane or a modified product thereof as a siliceous ceramics forming component, it is possible to form a dark color in a simple process at low temperature and in a thin film. Thus, the colored siliceous ceramic film can be formed on the substrate (glass).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The composition for colored coating of the present invention is mainly composed of polysilazane or a modified product thereof and an inorganic or organic coloring agent and a solvent or a dispersant thereof, that is, it contains polysilazane or a modified product thereof as a ceramic forming component. And The polysilazane and its modified product used in the present invention are mainly represented by the following general formula (I).

Embedded image (In the formula, 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 other than these groups which is directly bonded to silicon such as a fluoroalkyl group. Represents a group which is carbon, an alkylsilyl group, an alkylamino group or an alkoxy group, provided that at least one of R ¹ , R ² and R ³ is a hydrogen atom). The polysilazane having a number average molecular weight of about 100 to 50,000 or a polysilazane modified by adding a metal or the like thereto.

That is, the polysilazane used in the present invention contains at least Si-H bond or N-H bond in the molecule.
Any polysilazane having a bond may be used, and it is possible to use not only polysilazane alone but also a copolymer of polysilazane and another polymer or a mixture of polysilazane and another compound. The polysilazanes to be used include those having a chain structure, a cyclic structure, or a crosslinked structure, or those having a plurality of these structures simultaneously in the molecule, and these can be used alone or in a mixture.

Typical examples of the polysilazane to be used are as follows, but the polysilazane is not limited thereto. The compound having a hydrogen atom at R ¹ , R ² and R ³ in the general formula (I) is perhydropolysilazane, and its production method is described in, for example, JP-A-60-145903, D.C. Se
yferth et al Communication of A
m. Cer. Soc. , C-13, January 1
983. Has been reported to. What is obtained by these methods is a mixture of polymers having various structures,
Basically, it contains a chain part and a cyclic part in the molecule,

Embedded image Can be represented by the chemical formula:

An example of the structure of perhydropolysilazane is shown below.

Embedded image

In the general formula (I), R ¹ and R ² are hydrogen atoms, R
^The method for producing a polysilazane having a methyl group at ³ is described in D.
Seeyferth et al., Polym. Prepr. Am. C
hem. Soc. , Div. Polym. Chem,.
25, 10 (1984). The polysilazane obtained by this method has a repeating unit of-(Si
H ₂ NCH ₃₎ - is a chain polymer and a cyclic polymer,
None have a crosslinked structure.

In the general formula (I), R ¹ and R ² are hydrogen atoms, R
^The method for producing a polyorgano (hydro) silazane having an organic group at ³ is described in D.S. Seeyferth et al., Polym. Pre
pr. Am. Chem. Soc. , Div. Poly
m. Chem,. 25, 10 (1984), JP-A-61-61
-89230. The polysilazanes obtained by these methods include-(R ² SiHNH)-
Having a cyclic structure having a degree of polymerization of 3 to 5 as a repeating unit or (R ³ SiHNH) _x [(R ² SiH)
_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), R ¹ is a hydrogen atom, R ² and R ³
A polysilazane having an organic group at R ¹ and R ² , an organic group at R ¹ and R ² , and a hydrogen atom at R ³ are represented by-(R ¹ R ² SiN
R ³⁾ - as a repeating unit, mainly the degree of polymerization has a cyclic structure 3-5.

Next, of the polysilazanes to be used, typical examples other than those of the general formula (I) will be given. Some polyorgano (hydro) silazanes include D.I. Seeferth et al. Co
mmunication of Am. Cer. So
c. C-132, July 1984. Some have a crosslinked structure in the molecule as reported. An example is as follows.

Embedded image

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

Embedded image

The polysilazane to be 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) can be cyclized as is apparent from the above. And in that case, the cyclic portion serves as a terminal group, and when such cyclization is not carried out, the terminal of the main skeleton may be a group similar to R ¹ , R ² or R ³ or a hydrogen atom. .

As the polysilazane modified product, for example, a polymetallosilazane containing a metal atom as shown in the following structure (in the formula, M which is a side chain metal atom may be crosslinked) is also used as a starting material. be able to.

[Chemical 6]

In addition, the repeating unit as reported in JP-A-62-195024 is [(SiH ₂ ) _n
(NH) _m ] and [(SiH ₂ ) _r O] (wherein
n, m, and r are 1, 2 and 3, respectively), and the heat resistance produced by reacting a boron compound with polysilazane as reported in JP-A-2-84437. Excellent polyborosilazanes, polymetallosilazanes produced by reacting polysilazanes with metal alkoxides as reported in JP-A-63-81212, JP-A-63-191832 and JP-A-2-77427. JP-A-1-138108, 1-
No. 138107, No. 1-203429, No. 1-203
No. 430, 4-63833 and 3-320167, the molecular weight was increased (the former four of the above publications) and the hydrolysis resistance was improved (the latter two). And inorganic silazane high polymers and modified polysilazanes described in JP-A-2-175726, JP-A-5-86200, and JP-A-5-86200.
Copolymerized silazanes, which are advantageous for thickening by introducing an organic component into polysilazane, as reported in JP-A Nos. 331293 and 3-31326, JP-A-5-238827, and JP-A-4-272020, No. 5-93275,
No. 5-214268, No. 5-30750, No. 5-3
No. 38524, a low temperature ceramic polysilazane which can be applied to a metal such as plastics or aluminum in which a polysilazane is added or added with a catalytic compound for accelerating the ceramic formation, and ceramicized at a lower temperature. Can be used in the same way.

In the present invention, the following low temperature ceramized polysilazane can be used. For example, a silicon alkoxide-added polysilazane described in Japanese Patent Application No. 4-39595 by the applicant of the present application may be mentioned. This modified polysilazane is different from the polysilazane represented by the general formula (I) in the following general formula (IV): Si (OR ⁴ ) ₄ (IV) (wherein R ⁴ may be the same or different, A hydrogen atom, which represents an alkyl group or an aryl group having 1 to 20 carbon atoms, and at least one R ⁴ is the above-mentioned alkyl group or aryl group), and is obtained by a heat reaction. Alkoxide-derived silicon /
A silicon alkoxide-added polysilazane having a polysilazane-derived silicon atom ratio in the range of 0.001 to 3 and a number average molecular weight of about 200 to 500,000.

Another example of low-temperature ceramic polysilazane is glycidol-added polysilazane described in Japanese Patent Application Laid-Open No. 6-122852 by the present applicant. The modified polysilazane is obtained by reacting the polysilazane represented by the general formula (I) with glycidol, and has a glycidol / polysilazane weight ratio of 0.001.
And glycidol-added polysilazane having a number average molecular weight of about 200,000 to 500,000.

Another example of the low temperature ceramic polysilazane is polysilazane with an acetylacetonato complex described in Japanese Patent Application No. 5-35604 filed by the present applicant. This modified polysilazane is obtained by reacting the polysilazane represented by the general formula (I) with an acetylacetonate complex containing nickel, platinum, palladium or aluminum as a metal, and has a weight ratio of acetylacetonato complex / polysilazane of 0. 0.0000000
An acetylacetonato complex-added polysilazane having a number average molecular weight of about 200 to 500,000 within a range of 1 to 2. The metal-containing acetylacetonate complex is a complex in which an anion acac ⁻ generated by acid dissociation from acetylacetone (2,4-pentadione) is coordinated to a metal atom,
Generally represented by the formula (CH ₃ COCHCOCH ₃ ) _n M, wherein M represents an n-valent metal.

Another example of the low temperature ceramic polysilazane is a metal carboxylate-added polysilazane described in Japanese Patent Application No. 5-93275 filed by the present applicant. The modified polysilazane is a polysilazane represented by the general formula (I) and at least one metal selected from the group consisting of nickel, titanium, platinum, rhodium, cobalt, iron, ruthenium, osmium, palladium, iridium, and aluminum. Is a metal carboxylate-added polysilazane having a metal carboxylate // polysilazane weight ratio in the range of 0.000001 to 2 and a number average molecular weight of about 200 to 500,000 obtained by reacting a metal carboxylate containing . The metal carboxylate has a formula (R
COO) _n M wherein R is an aliphatic or alicyclic group having 1 to 22 carbon atoms, M represents at least one metal selected from the above metal group, and n is a metal Which is the valence of M]. The metal carboxylate may be an anhydride or a hydrate. The metal carboxylate / polysilazane weight ratio is preferably from 0.001 to 1, more preferably from 0.01 to 0.5. For the preparation of the polysilazane to which the metal carboxylate is added, see the above-mentioned Japanese Patent Application No. 5-93275.

Further, in the present invention, a composition obtained by adding amines and / or acids to a polysilazane having a main skeleton composed of the structural unit represented by the general formula (I) or a modified product thereof is used as a starting material. It can also be used.
This amine / acid-added polysilazane has an advantage that it can be converted into silica-based ceramics at low temperature and high speed. The amines to be added include those represented by the general formula R ⁶ R ⁷ R ⁸ N
(Wherein R ^{6 to} R ⁸ represent an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, an alkoxy group or a hydrogen atom). In addition to triamines, pyridines and DB
U, DBN, etc., and the added acids include acetic acid,
There are organic acids such as propionic acid and maleic acid, and inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid. Incidentally, these amines and / or acids may be added after the raw material polysilazane is dissolved in an ester solvent described later.

Such a polysilazane or a modified product thereof, which is in a liquid state, is directly used for the colored coating composition of the present invention. In addition, solid substances are usually suitable solvents such as hydrocarbons such as pentane, hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, acetone and methyl isobutyl ketone (MIBK).
And the like, and esters such as methyl acetate, ethyl acetate, and isobutyl acetate, and others such as methylene chloride, chloroform, tetrahydrofuran (THF), amines, pyridine, etc. to provide a coating composition.

As the colorant in the colored coating composition of the present invention, both inorganic and organic colorants are used, and any one is selected from the viewpoint of required color tone, color resistance and the like. Examples of the inorganic colorant include oxide type, molybdic acid chromate type, selenide sulfide type, ferrocyanide type, aluminum silicate type, metal powder and carbon.

The organic colorants include pigments and dyes, and specific examples thereof include the following. Pigments: azo type, pyrrolopyrrole type, anthraquinone type,
Phthalocyanine, perinone, perylene, quinacridone, dioxazine, thioindigo, isoindolinone, etc. Dyes: azo, anthraquinone, perinone, quinophthalone, nigrosine, etc.

As the solvent or dispersion medium for the colorant, for example, pentane, hexane, heptane, benzene, toluene, xylene, acetone, methyl isobutyl ketone,
Methyl acetate, ethyl acetate, isobutyl acetate, methylene chloride, chloroform, tetrahydrofuran, amines, pyridine, etc. The colored coating composition of the present invention may of course contain, if necessary, various additives and fillers that do not adversely affect the color tone formed.

Further, according to the present invention, there is provided a colored glass comprising a glass and a colored ceramic coating formed by applying the above-mentioned colored coating composition to glass and converting the composition into a ceramic, and a method for producing the same. Application of the above coating composition to a glass substrate to form a ceramic is accomplished by applying the composition once or twice or more to the glass substrate and then firing.

Any glass can be used as the substrate to which the pigmented coating composition is applied, but the present invention is advantageously applied to the joining of tempered glass which is not subjected to high temperature treatment. As a method for applying the colored coating composition, a usual application method, for example, dipping, roll coating, bar coating, brush coating, spray coating, flow coating or the like is used.

The colored coating composition is applied onto glass by such a method, dried sufficiently, and then heated and baked. By this firing, polysilazane is crosslinked, condensed,
Alternatively, depending on the firing atmosphere, it is oxidized and hydrolyzed to be hardened to form a tough film. The firing conditions differ depending on the polysilazane used or the coating composition. The heating rate is not particularly limited, but a slow heating rate of 0.5 to 10 ° C./min is preferable. The preferred firing temperature is room temperature to about 250 ° C. The firing atmosphere may be any of oxygen, air, or an inert gas, but air is more preferable.

By the heat treatment at the above temperature, Si is usually used.
It is possible to form a tough ceramic film mainly composed of -O bond. However, depending on the type of polysilazane (modified product) used or the composition of the coloring coating composition, heat treatment at the above temperature may result in Si-O bond and Si-bond.
In some cases, —N, Si—H, N—H bonds and the like still exist. This indicates that the conversion to ceramics is still incomplete. In such a case, by adopting the following method, it is possible to completely convert into ceramics at a low temperature.

Heat treatment in a pressurized saturated steam atmosphere The pressure is not particularly limited, but 1 to 3 atm is practically suitable. Temperature is effective above room temperature,
Room temperature-250 degreeC is preferable. The relative humidity is not particularly limited, but 10% RH to 100% RH is preferable. The heat treatment time is not particularly limited, but 10 minutes to 30 days is practically appropriate. By heat treatment in a pressurized saturated steam atmosphere, oxidation of polysilazane or a modified product of polysilazane or hydrolysis with steam proceeds, and a tough ceramic coating mainly composed of Si—O bond is formed at a low firing temperature as described above. Can be formed.

Immerse in distilled water containing the catalyst. The catalyst is preferably an acid or a base, and the type thereof is not particularly limited, but examples thereof include triethylamine, diethylamine, monoethanolamine, diethanolamine, triethanolamine, n-hexylamine, and n.
-Butylamine, di-n-butylamine, tri-n-butylamine, guanidine, piguanine, imidazole,
Amines such as 1,8-diazabicyclo- [5,4,0] -7-undecene and 1,4-diazabicyclo- [2,2,2] -octane; sodium hydroxide, potassium hydroxide, lithium hydroxide, Alkalines such as pyridine and ammonia water; Inorganic acids such as phosphoric acid; Lower monocarboxylic acids such as glacial acetic acid, acetic anhydride, propionic acid, and propionic anhydride, or their anhydrides, oxalic acid, fumaric acid, maleic acid, Lower dicarboxylic acids or their anhydrides such as succinic acid, organic acids such as trichloroacetic acid; perchloric acid, hydrochloric acid, nitric acid, sulfuric acid, sulfonic acid, paratoluenesulfonic acid, boron trifluoride and its complexes with electron donors , Etc; SnCl
₄ , ZnCl ₂ , FeCl ₃ , AlCl ₃ , SbCl ₃ , T
Lewis acids such as iCl ₄ and complexes thereof can be used. The content ratio of the catalyst is 0.01 to 50% by weight, preferably 1 to 10% by weight. The holding temperature is effective from room temperature to the boiling point. The holding time is not particularly limited, but 10 minutes to 30 days is practically appropriate.

By immersing in distilled water containing a catalyst, oxidation of polysilazane or a modified polysilazane or hydrolysis with water is further accelerated by the presence of the catalyst,
It becomes possible to form a tough ceramic coating mainly composed of Si—O bonds at the low firing temperature as described above. It should be noted that the combination of the above two methods is naturally effective for making ceramics. (The catalyst is not limited to acid or hydrochloric acid, but hydrochloric acid is particularly preferable)

Immerse in an aqueous solution containing Pd ²⁺ ions. The method of supplying Pd ²⁺ ions is not particularly limited, but for example, palladium compounds (palladium salts) such as palladium acetate, palladium acetylacetonate, palladium chloride, palladium hydroxide, palladium iodide, palladium nitrate, and palladium oxide can be used as water. Pd ²⁺ by dissolving it in water, adding (dissolving) metallic palladium to an aqueous acid solution such as hydrochloric acid or nitric acid, or applying a voltage to the metallic palladium in the aqueous solution.
A method of eluting ions can be adopted. Alternatively, a method such as contacting polysilazane containing a palladium compound with water or contacting polysilazane containing metal palladium with an acid (generally an aqueous solution) may be used.

The supply amount of Pd ²⁺ ions is silica (SiO 2
₂ ) In order to obtain a ceramic having a composition close to that of the composition, it is preferable that the total amount of Si—H groups and Si—N groups of polysilazane is equal to or more than the equimolar amount. However, (a) P such as CuCl _{2 is} contained in the reaction system.
When an oxidation catalyst for d ⁰ (0-valent palladium) is added, or when (b) an operation such as electrochemically oxidizing Pd ⁰ is performed at the same time, the amount of Pd ²⁺ ions may be less than the above. The same effect can be obtained. However, even if the amount of Pd ²⁺ ions is small, a certain effect can be obtained, and therefore the above-mentioned preferable supply amount is not limited. Therefore, in the case where the above operations (a) and (b) are not performed, generally 1/100 mol or more, preferably 1/10 mol, relative to the total number of moles of Si-H groups and Si-N groups of polysilazane. that's all,
And more preferably 1 mol or more, practically 1/10
Supply more than moles of Pd ²⁺ . The amount of Pd added is 1 /
In the case of 10 moles, the addition weight of Pd is expediently multiplied by 0.2 times the mole amount of Si (silicon) of polysilazane.

Water can be supplied by immersing the polysilazane in water, atomizing the water and spraying it on the polysilazane, exposing the polysilazane to water vapor, and the like. At this time, Pd ²⁺ ions can be dissolved in water. The amount of water supplied is preferably equimolar or more to the sum of the Si—H groups and Si—N groups of polysilazane in order to obtain a ceramic having a composition close to silica (SiO ₂ ). Use a normal large excess of water.

The reaction conditions for making the polysilazane into ceramics are not particularly limited, such as the pH of the aqueous solution containing Pd ²⁺ ions, the reaction temperature, the reaction pressure and the reaction atmosphere. However, the reaction temperature may be 100% though it is warmed if necessary.
The reaction proceeds sufficiently at a low temperature of ℃ or less. For example, 80 ° C. or lower, and even 40 ° C. or lower is possible. According to the method of bringing the polysilazane into contact with Pd ²⁺ ions and water, ceramics containing silica as a main component is generally produced at a low temperature, and is particularly suitable as a method for forming a silica coating film at a low temperature.

The colored coating composition of the present invention can be applied to the following functional applications in addition to the standard coloring applications for the above-mentioned optical parts, automobile lamps, automobile or architectural glass and the like. it can. -Infrared absorption: If a naphthalene-based infrared absorbing dye is used, a slightly bluish infrared absorbing glass can be coated. Also, if used for automobiles and building materials,
The heat rays of sunlight are blocked by glass, and an energy saving effect can be expected.・ Electromagnetic wave absorption: By using iron oxide or carbon black as a pigment, electromagnetic wave absorbing glass can be coated. This field is drawing attention from the viewpoint of preventing the leakage of confidential information in intelligent buildings. It can be said that it has an energy-saving effect because it blocks direct sunlight as well as electromagnetic waves.・ Photochromic: If a photochromic dye such as spiro is used, it becomes possible to coat photochromic glass whose color tone changes depending on the intensity of sunlight. It can be applied to automobiles, building materials, as well as coating small items such as glasses.

[0041]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the technical scope of the present invention.

Example 1 Perhydropolysilazane Type-1 (P manufactured by Tonen K.K.)
HPS-1; 4% of 0.5% xylene solution of palladium (II) propionate [manufactured by NE Chem Kit Co.] was added to 10 g of 20% xylene solution having a number average molecular weight of 900), and 6 g of xylene was further added. , 3 at 20 ℃ in air
The reaction was carried out with stirring for a time. Further concentration to a concentration of 20
A weight% solution was prepared (solution A). The number average molecular weight of this solution was 961 as measured by GPC.

Into the meta-xylene which had been sufficiently dehydrated by adding a molecular sieve and then filtered, diazo dye as red, phthalocyanine dye as blue, and pyrazolone dye as yellow were 5, 10, 15, 20, and 25, respectively. ,
A colored xylene dissolved at 30% by weight was prepared (each B
Liquid, liquid C, liquid D).

Liquid A and liquid B, liquid A and liquid C, and liquid A and liquid D were mixed at a weight ratio of 1: 1 to obtain a coating liquid for a colored film. The obtained coating liquid is applied to 4 inch optical glass.
It was spin-coated at a rotation speed of 000 rpm for 30 seconds and then heated at 150 ° C. for 1 hour to obtain a film having a thickness of about 1 μm to 2 μm.

With respect to the obtained colored glass, the appearance, scratch resistance, pencil hardness and discoloration resistance of the coating film were evaluated according to the following measuring methods and criteria. Table 1 shows the results. Scratch resistance Using the AB-101 Taber abrasion tester manufactured by Tester Sangyo Co., Ltd., Taber abrasion test (500 g, 1000
Times) was performed, and the haze value before the test (fog condition) was compared with the haze value after the test to determine scratch resistance. The haze value is a haze meter NDH30 manufactured by Nippon Denshoku Co., Ltd.
It was measured using 0-A. Fading resistance A sunshine weather meter accelerated weather resistance test was carried out for 100 hours. Evaluation criteria are judged from the absorbance at a specific absorption wavelength before and after the test. Regarding the absorbance, the absorbance was compared between the polysilazane colored glass and the colored acrylic resin in which the same dye was mixed in the acrylic resin, where the absorbance of the glass before the test was 100%.

[0046]

[Table 1]

Example 2 Perhydropolysilazane Type-1 (P manufactured by Tonen K.K.)
A 20% xylene solution of HPS-1; number average molecular weight 900) was prepared, and iron oxide fine particles as an inorganic pigment were mixed therein. In the same manner as in Example 1, this was spin-coated on a 4-inch optical glass at a rotation speed of 200 rpm for 30 seconds and then baked at 200 ° C. for 1 hour to have a thickness of about 1 μm to 2 μm.
A film of This became amber colored heat resistant colored glass.

[0048]

The composition for colored coating of the present invention comprises
Since polysilazane or a modified product thereof is contained as the siliceous ceramics forming component, the following excellent effects are exhibited, and a high quality colored glass can be obtained at low cost by a simple operation. (A) The colored siliceous ceramic coating can be formed at a temperature of 250 ° C. or lower, or around 100 ° C. depending on the firing method, and in a simple process. (B) Since the ceramic coating can be formed at a low temperature,
No distortion of the glass used as the substrate. (C) Since the melting limit of the colorant is high, it is possible to produce a clear and dark color even in a thin film. (D) Since a film of any color can be formed on a transparent substrate,
Even if colored glass is not manufactured in bulk, colorless glass can be colored by coating. Therefore, in manufacturing colored glass, there is an advantage that contamination of a melting pot and inventory burden of colored glass are eliminated. (E) A coating that is extremely hard and has excellent weather resistance can be obtained as compared with the resin coating. (F) When an organic dye is used as the coloring agent, the coloring property is good and there is no aggregation of the coloring agent particles. Usually, it is difficult to use an organic dye for coloring a vitreous film because it has poor heat resistance, but since the composition of the present invention can form a ceramic film at a low temperature, an organic dye of an inorganic glass is used. Coloring becomes possible. (G) When an inorganic pigment is used as a colorant, a ceramic coating having excellent heat resistance and shielding properties can be formed, and therefore, it can be suitably applied to coloring of electric bulbs and black matrix of LCD color filters.

Claims (3)

[Claims] 1. A colored coating composition comprising polysilazane or a modified product thereof, an inorganic or organic colorant, and a solvent or dispersion medium thereof as main components. 2. A colored glass comprising the glass according to claim 1 applied to glass, and a colored ceramic coating made into ceramics, and the glass. 3. A method for producing a colored glass, which comprises applying the composition according to claim 1 to glass and converting the composition into a ceramic.