JP7321965B2 - Composition containing polysilazane compound - Google Patents

Description

The present invention relates to a polysilazane compound-containing composition.

Since the polysilazane compound forms a high-quality siliceous glass film by curing, it exhibits excellent gas barrier properties, heat resistance, and insulating properties. For this reason, it is useful as a protective film for preventing moisture and corrosive gases from penetrating into electronic parts that require high reliability when used in high-temperature environments. A further feature of the siliceous film formed from the polysilazane compound is that it has excellent transparency. This feature is advantageous as a coating material that does not impair the design of the appearance of the object to be coated. On the other hand, due to the high transparency, it is extremely difficult to visually determine the presence or absence of the protective film, and it is no exaggeration to say that the determination is completely impossible especially in a dark place such as inside an apparatus. Although it is possible to determine the presence or absence of a protective film by using a chemical surface analysis device, many of the analysis devices used therefor are large and expensive. Furthermore, the measurement often takes a long time and may require the operator to be proficient in analytical techniques. This causes product inspection to take a long time and a high degree of difficulty, which is a great disadvantage in improving the efficiency of the product manufacturing process.

Patent Document 1 reports that a siloxane elastomer becomes fluorescent by introducing a fluorescent dye substituent such as boron dipyrromethene (BODIPY), which is known as a fluorescent compound, or coumarin into the siloxane polymer structure. In such cases, a synthetic operation is required to introduce the fluorescent compound into the polymer, which raises concerns about increased product manufacturing costs and adverse effects on the physical properties of the polymer due to the fluorescent compound occupying some of the polymer bonds. be done.

In Patent Document 2, it is reported that visible light fluorescent glass can be produced by mixing an oxide of a rare earth element such as terbium (Tb) or europium (Eu) with a raw material of glass, and then melting and molding the mixture. . Substances containing rare earth elements have excellent luminescence, so they are useful as a means of imparting luminescence to materials. mentioned. Furthermore, in the case of a coating agent made of an organic substance, it is absolutely impossible to introduce a high-temperature manufacturing process that melts oxides, unlike the above-described glass molding.

Patent Document 3 discloses a wavelength conversion member in which a polysilazane compound is applied to the surface of a wavelength conversion body having a fluorescent compound to provide an oxygen gas barrier property with a siliceous glass film. Further, Patent Document 4 discloses a coating composition and a wavelength conversion sheet obtained by adding a lanthanum compound, a transition metal compound, an organic light emitter, and an inorganic nanophosphor as a wavelength conversion agent to polysilazane. These examples do not discuss the solubility of the fluorescent compound in the dispersion medium resin or the composition containing the polysilazane compound. In addition, in the development of coating agents, if the viscosity of the coating agent is low, there is a concern that organic pigments and inorganic phosphors may settle or aggregate in the coating agent, making it difficult to apply the components in a uniform state. .

In view of the above, there is a demand for the development of a technique that enables the existence of a glass film to be visually recognized while maintaining the characteristics of forming a high-quality silica glass film of a polysilazane compound.

Japanese translation of PCT publication No. 2018-516307 JP-A-10-167755 International publication WO2019/031102 JP 2017-207757 A

The present invention has been made to solve the above problems, and provides a polysilazane compound-containing composition that improves the visibility of a siliceous film that is essentially colorless and transparent and has poor visibility and is formed from a polysilazane compound. Another object of the present invention is to provide a polysilazane compound-containing composition that allows the presence of the siliceous film to be visually recognized even in a dark place, particularly by light irradiation.

The present invention has been made to achieve the above objects, and provides a polysilazane compound-containing composition exhibiting the following characteristics.

That is, a composition containing a polysilazane compound,
(A) a polysilazane compound,
(B) at least one luminescent compound selected from (B1) to (B3) below;
(B1) a tetraphenylethylene-based compound,
(B2) a silole compound,
(B3) A polysilazane compound-containing composition characterized by containing a xanthene dye (C) an organic solvent.

Such a polysilazane compound-containing composition is a composition containing a polysilazane compound that improves the visibility of a siliceous film, which is essentially colorless and transparent and has poor visibility, formed from the polysilazane compound, particularly by light irradiation. The polysilazane compound-containing composition allows the existence of the siliceous film to be visually recognized even in a dark place.

Further, in the present invention, the component (A) is preferably perhydropolysilazane.

With such a polysilazane compound-containing composition, the effect of the present invention can be improved.

In the present invention, the amount of component (B) to be blended is preferably 0.1 to 5 parts by mass per 100 parts by mass of component (A).

With such a polysilazane compound-containing composition, the effects of the present invention can be further improved.

（式中、Ｒ^１は互いに独立して、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数２～６のアルケニル基、炭素数１～６のアルコキシ基、炭素数２～６のアシル基、水酸基、ニトロ基、アミノ基、（メタ）アクリロイルオキシ基、カルボキシ基およびその塩、スルホ基およびその塩、リン酸基およびその塩、またはボロン酸基から選ばれる基である。） Further, in the present invention, the component (B1) is preferably a tetraphenylethylene compound represented by the following formula (1).

(In the formula, each R ¹ is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, A group selected from an acyl group, a hydroxyl group, a nitro group, an amino group, a (meth)acryloyloxy group, a carboxy group and its salts, a sulfo group and its salts, a phosphoric acid group and its salts, or a boronic acid group.)

With such a polysilazane compound-containing composition, component (B) has excellent compatibility with components (A) and (C), and can have an appropriate absorption wavelength and molar extinction coefficient.

（式中、Ｒ^２は炭素数６～１２のアリール基、Ｒ^３は水素原子、炭素数１～６のアルキル基、または炭素数６～１２のアリール基から選ばれる基であり、それぞれ同じであっても異なっていてもよい。） Further, in the present invention, the component (B2) is preferably a silole compound represented by the following formula (2).

(wherein R ² is an aryl group having 6 to 12 carbon atoms, R ³ is a group selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and may or may not be the same.)

With such a polysilazane compound-containing composition, component (B) has excellent compatibility with components (A) and (C), and can have an appropriate absorption wavelength and molar extinction coefficient.

（式中、Ｒ^４は互いに独立して、水素原子、メチル基、またはエチル基であり、Ｒ^５は互いに独立して、水素原子またはメチル基であり、Ｒ^６は水素原子、メチル基、エチル基またはオクタデシル基であり、Ｘは塩化物イオンまたは過塩素酸イオンである。）

（式中、Ｒ^７は互いに独立して、水素原子またはハロゲン原子であり、Ｒ^８は水素原子、アミノ基、ニトロ基、カルボキシル基、イソチオシアネート基、マレイミド基、セミカルバジド基またはチオセミカルバジド基である。） Further, in the present invention, the component (B3) is preferably a xanthene dye represented by the following formula (3-1) or (3-2).

(wherein R ⁴ is each independently a hydrogen atom, a methyl group, or an ethyl group; R ⁵ is each independently a hydrogen atom or a methyl group; and R ⁶ is a hydrogen atom, a methyl group, an ethyl or octadecyl group, and X is chloride or perchlorate.)

(wherein R ⁷ is independently a hydrogen atom or a halogen atom, and R ⁸ is a hydrogen atom, an amino group, a nitro group, a carboxyl group, an isothiocyanate group, a maleimide group, a semicarbazide group, or a thiosemicarbazide group .)

With such a polysilazane compound-containing composition, component (B) has excellent compatibility with components (A) and (C), and can have an appropriate absorption wavelength and molar extinction coefficient.

In the present invention, the polysilazane compound-containing composition may further contain (D) a curing catalyst.

With such a polysilazane compound-containing composition, the curing reaction rate can be improved.

In the present invention, the polysilazane compound-containing composition may further contain (E) an inorganic filler.

With such a polysilazane compound-containing composition, the properties (strength, heat resistance, insulating properties, etc.) of the resulting cured film can be improved.

According to the invention, an appropriately selected luminescent compound has excellent compatibility with the polysilazane compound and the solvent. Furthermore, the composition comprising them gives a cured product whose presence is visible even in the dark when irradiated with a light beam of 365 nm, for example, without affecting the appearance and hardness of the cured film of the polysilazane compound.

As described above, there has been a demand for the development of a polysilazane compound-containing composition that can improve the visibility without affecting the properties of the cured product of the polysilazane compound.

In particular, as described above, coating agents in which an inorganic phosphor is added to polysilazane may cause these additives to settle or aggregate if the viscosity of the coating agent is low. Removed by dissolving in matter. Accordingly, the present inventors have conceived of searching for an additive that is a luminescent compound to be added and that is compatible with the polysilazane compound-containing composition.

As a result of intensive studies on the above problems, the present inventors have found that a specific light-emitting compound has excellent compatibility with a polysilazane compound and a solvent, and can be used without affecting the appearance and hardness of the cured film of the polysilazane compound. The inventors have found that irradiation with light of 365 nm gives a cured product whose presence is visible even in a dark place, thus completing the present invention.

That is, the present invention provides a composition containing a polysilazane compound,
(A) a polysilazane compound,
(B) at least one luminescent compound selected from (B1) to (B3) below;
(B1) a tetraphenylethylene-based compound,
(B2) a silole compound,
(B3) A polysilazane compound-containing composition characterized by containing a xanthene-based dye (C) an organic solvent.

Although the embodiments of the present invention will be described below, they are shown by way of example, and needless to say, various modifications are possible without departing from the technical idea of the present invention.

<(A) Polysilazane compound>
The polysilazane compound-containing composition of the present invention forms a vitreous cured film when cured. Examples of the polysilazane compound include perhydropolysilazane, which is an inorganic polysilazane, modified polysilazanes such as methylpolysilazane, phenylpolysilazane, and vinylpolysilazane, which are organic polysilazanes, and hydroxyl groups that chemically react with polysilazane to form a crosslinked structure. , hydrocarbon compounds having reactive groups such as vinyl groups, amino groups, and silyl groups, cyclic saturated hydrocarbon compounds, cyclic unsaturated hydrocarbon compounds, saturated heterocyclic compounds, unsaturated heterocyclic compounds, and silicone compounds. crosslinked polysilazane, which is crosslinked, and the like. The polysilazane compound can be arbitrarily selected from one type alone, one or more polysilazane mixtures selected from two or more types, or a polysilazane copolymer composed of two or more types of polysilazane structures. It preferably contains at least one hydrogen atom directly bonded to a silicon atom, and more preferably perhydropolysilazane.

The polysilazane compound, which is the component (C), has a weight average molecular weight of 100 to 100,000,000, preferably 1,000 to 1,000,000, from the viewpoint of solubility in an organic solvent and workability during coating. More preferably, it is within the range of 2,000 to 500,000. When the weight average molecular weight is 100 or more, the volatility is low, and the polysilazane compound itself does not volatilize during the volatilization of the organic solvent and the curing process, so that the quality of the coating film does not deteriorate. , is preferred because of its high solubility in organic solvents.

The weight average molecular weight referred to in this specification refers to a value obtained using polystyrene as a standard material by gel permeation chromatography (GPC) measured under the following conditions.
[Measurement condition]
Developing solvent: tetrahydrofuran (THF)
Flow rate: 0.35mL/min
Detector: Differential refractive index detector Column: TSKguardcolumn SuperMP (HZ)-M
TSKgel Super Multipore HZ-M
(4.6 mm I.D.×15 cm, 4 μm×4)
(both manufactured by Tosoh Corporation)
Column temperature: 40°C
Sample injection volume: 20 μL (THF solution with a concentration of 0.5% by mass)

<(B) Luminescent compound>
The luminescent compound of the present invention improves the visibility of the cured film when added to the composition. If the luminescent compound is not compatible with the solution consisting of (A) the polysilazane compound and (C) the organic solvent and remains precipitated, the location of the luminescent compound is unevenly distributed during coating on the substrate, and finally There is concern that the light-emitting sites of the cured film are localized. For this reason, it is necessary to use a compound that is compatible with the polysilazane compound and the organic solvent as the luminescent compound.

Moreover, these light-emitting compounds must be compounds that emit light by absorbing light of a specific wavelength. If the molar extinction coefficient is used as a measure of the magnitude of absorption, the greater the molar extinction coefficient at the wavelength of the irradiated light, the more efficient the absorption, so the molar extinction coefficient can be any large. However, when there is no absorption, the luminescent compound is not electronically excited in the first place, so the molar extinction coefficient must be a numerical value greater than zero. The wavelength of the light to be irradiated is one that electronically excites the light-emitting compound, and is preferably in the range of 200 to 1,000 nm.

The luminescent compound used in the present invention is characterized by being at least one luminescent compound selected from (B1) a tetraphenylethylene-based compound, (B2) a silole-based compound, and (B3) a xanthene-based dye. Such a light-emitting compound is compatible with the polysilazane compound and the organic solvent, and emits light by absorbing light of a specific wavelength (that is, the molar extinction coefficient is greater than 0). Each will be described in detail below.

（式中、Ｒ^１は互いに独立して、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数２～６のアルケニル基、炭素数１～６のアルコキシ基、炭素数２～６のアシル基、水酸基、ニトロ基、アミノ基、（メタ）アクリロイルオキシ基、カルボキシ基およびその塩、スルホ基およびその塩、リン酸基およびその塩、またはボロン酸基から選ばれる基である。） (B1) Tetraphenylethylene Compound The tetraphenylethylene compound (B1) used in the present invention is preferably a tetraphenylethylene compound represented by the following formula (1).

(In the formula, each R ¹ is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, A group selected from an acyl group, a hydroxyl group, a nitro group, an amino group, a (meth)acryloyloxy group, a carboxy group and its salts, a sulfo group and its salts, a phosphoric acid group and its salts, or a boronic acid group.)

Here, a salt of a carboxy group refers to a group (for example, COONa) in which the proton of the carboxy group (COOH) is substituted with another cation. The same applies to sulfo groups and phosphate groups.

Specific examples of the tetraphenylethylene compounds include tetraphenylethylene, tetrakis(chlorophenyl)ethylene, tetrakis(bromophenyl)ethylene, tetrakis(iodophenyl)ethylene, tetrakis(methylphenyl)ethylene, tetrakis(ethylphenyl)ethylene, Tetrakis(propylphenyl)ethylene, Tetrakis(butylphenyl)ethylene, Tetrakis(pentylphenyl)ethylene, Tetrakis(hexylphenyl)ethylene, Tetrakis(vinylphenyl)ethylene, Tetrakis(methoxyphenyl)ethylene, Tetrakis(ethoxyphenyl)ethylene, Tetrakis (propoxyphenyl)ethylene, tetrakis(butoxyphenyl)ethylene, tetrakis(allyloxyphenyl)ethylene, tetrakis(phenoxyphenyl)ethylene, tetrakis(acetylphenyl)ethylene, tetrakis(hydroxyphenyl)ethylene, tetrakis(nitrophenyl)ethylene, tetrakis (aminophenyl)ethylene, tetrakis(acryloyloxyphenyl)ethylene, tetrakis(methacryloyloxyphenyl)ethylene, tetrakis(carboxyphenyl)ethylene, (ethene-1,1,2,2-tetrayl)tetrabenzenesulfonic acid, (ethene- 1,1,2,2-tetrayl)sodium tetrabenzenesulfonate, (ethene-1,1,2,2-tetrayl)tetrabenzenephosphonic acid, (ethene-1,1,2,2-tetrayl)tetrabenzenephosphonate sodium acid, (ethene-1,1,2,2-tetrayl)tetraphenylboronic acid, 1,2-bis(chlorophenyl)-1,2-diphenylethylene, 1,2-bis(bromophenyl)-1,2 -diphenylethylene, 1,2-bis(iodophenyl)-1,2-diphenylethylene, 1,2-bis(methylphenyl)-1,2-diphenylethylene, 1,2-bis(ethylphenyl)-1, 2-diphenylethylene, 1,2-bis(propylphenyl)-1,2-diphenylethylene, 1,2-bis(butylphenyl)-1,2-diphenylethylene, 1,2-bis(pentylphenyl)-1 ,2-diphenylethylene, 1,2-bis(hexylphenyl)-1,2-diphenylethylene, 1,2-bis(vinylphenyl)-1,2-diphenylethylene, 1,2-bis(methoxyphenyl)- 1,2-diphenylethylene, 1,2-bis(ethoxyphenyl)-1,2-diphenylethylene, 1,2-bis(propoxyphenyl)-1,2-diphenylethylene, 1,2-bis(butoxyphenyl) -1,2-diphenylethylene, 1,2-bis(allyloxyphenyl)-1,2-diphenylethylene, 1,2-bis(phenoxyphenyl)-1,2-diphenylethylene, 1,2-bis(acetyl Phenyl)-1,2-diphenylethylene, 1,2-bis(hydroxyphenyl)-1,2-diphenylethylene, 1,2-bis(nitrophenyl)-1,2-diphenylethylene, 1,2-bis( aminophenyl)-1,2-diphenylethylene, 1,2-bis(acryloyloxyphenyl)-1,2-diphenylethylene, 1,2-bis(methacryloyloxyphenyl)-1,2-diphenylethylene, 1,2 -bis(carboxyphenyl)-1,2-diphenylethylene, (1,2-diphenylethene-1,2-diyl)dibenzenesulfonic acid, (1,2-diphenylethene-1,2-diyl)dibenzenesulfone sodium acid, (1,2-diphenylethene-1,2-diyl)dibenzenephosphonic acid, sodium (1,2-diphenylethene-1,2-diyl)dibenzenephosphonate, (1,2-diphenylethene- 1,2-diyl)bisphenylene boronic acid and the like, preferably tetraphenylethylene.

（式中、Ｒ^２は炭素数６～１２のアリール基、Ｒ^３は水素原子、炭素数１～６のアルキル基、または炭素数６～１２のアリール基から選ばれる基であり、それぞれ同じであっても異なっていてもよい。） (B2) Silole Compound The silole compound (B2) used in the present invention is preferably a silole compound represented by the following formula (2).

(wherein R ² is an aryl group having 6 to 12 carbon atoms, R ³ is a group selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and may or may not be the same.)

Specific examples of the silole compounds include 1,1,2,3,4,5-hexaphenyl-1H-silole, 1,1-dimethyl-2,3,4,5-tetraphenyl-1H-silole, 1,1-diethyl-2,3,4,5-tetraphenyl-1H-silole, 1,1-dipropyl-2,3,4,5-tetraphenyl-1H-silole, 1,1-dibutyl-2, 3,4,5-tetraphenyl-1H-silole, 1,1-dipentyl-2,3,4,5-tetraphenyl-1H-silole, 1,1-dihexyl-2,3,4,5-tetraphenyl -1H-silole, 1,1-ditolyl-2,3,4,5-tetraphenyl-1H-silole, 1,1-dixylyl-2,3,4,5-tetraphenyl-1H-silole, 1,1 -dinaphthyl-2,3,4,5-tetraphenyl-1H-silole, 2,3,4,5-tetraphenyl-1H-silole, 1,1,2,3,4,5-hexatolyl-1H-silole , 1,1-dimethyl-2,3,4,5-tetratolyl-1H-silole, 1,1-diethyl-2,3,4,5-tetratolyl-1H-silole, 1,1-dipropyl-2,3 ,4,5-tetratolyl-1H-silole, 1,1-dibutyl-2,3,4,5-tetratolyl-1H-silole, 1,1-dipentyl-2,3,4,5-tetratolyl-1H-silole , 1,1-dihexyl-2,3,4,5-tetratolyl-1H-silole, 1,1-diphenyl-2,3,4,5-tetratolyl-1H-silole, 1,1-dixylyl-2,3 , 4,5-tetratolyl-1H-silole, 1,1-dinaphthyl-2,3,4,5-tetraphenyl-1H-silole, 2,3,4,5-tetratolyl-1H-silole, 1,1, 2,3,4,5-hexaxylyl-1H-silole, 1,1-dimethyl-2,3,4,5-tetraxylyl-1H-silole, 1,1-diethyl-2,3,4,5-tetraxylyl- 1H-silole, 1,1-dipropyl-2,3,4,5-tetraxylyl-1H-silole, 1,1-dibutyl-2,3,4,5-tetraxylyl-1H-silole, 1,1-dipentyl- 2,3,4,5-tetraxylyl-1H-silole, 1,1-dihexyl-2,3,4,5-tetraxylyl-1H-silole, 1,1-diphenyl-2,3,4,5-tetraxylyl- 1H-silole, 1,1-ditolyl-2,3,4,5-tetraxylyl-1H-silole, 1,1-dinaphthyl-2,3,4,5-tetraxylyl-1H-silole, 2,3,4, 5-tetraxylyl-1H-silole and the like, preferably 1,1,2,3,4,5-hexaphenyl-1H-silole.

（式中、Ｒ^４は互いに独立して、水素原子、メチル基、またはエチル基であり、Ｒ^５は互いに独立して、水素原子またはメチル基であり、Ｒ^６は水素原子、メチル基、エチル基またはオクタデシル基であり、Ｘは塩化物イオンまたは過塩素酸イオンである。）

（式中、Ｒ^７は互いに独立して、水素原子またはハロゲン原子であり、Ｒ^８は水素原子、アミノ基、ニトロ基、カルボキシル基、イソチオシアネート基、マレイミド基、セミカルバジド基またはチオセミカルバジド基である。） (B3) Xanthene Colorant The (B3) xanthene colorant used in the present invention is preferably a xanthene colorant represented by the following formula (3-1) or (3-2).

(wherein R ⁴ is each independently a hydrogen atom, a methyl group, or an ethyl group; R ⁵ is each independently a hydrogen atom or a methyl group; and R ⁶ is a hydrogen atom, a methyl group, an ethyl or octadecyl group, and X is chloride or perchlorate.)

(wherein R ⁷ is independently a hydrogen atom or a halogen atom, and R ⁸ is a hydrogen atom, an amino group, a nitro group, a carboxyl group, an isothiocyanate group, a maleimide group, a semicarbazide group, or a thiosemicarbazide group .)

Specific examples of the xanthene dyes include rhodamine B, rhodamine 6G, rhodamine 110, rhodamine 123, rhodamine 590 chloride, rhodamine 6G perchlorate, rhodamine B octadecyl ester chloride, rhodamine B octadecyl ester perchlorate, rhodamine compounds such as rhodamine 19 perchlorate, tetramethylrhodamine methyl ester perchlorate, fluorescein, 2',7'-dichlorofluorescein, 4',5'-dibromofluorescein, tetraiodofluorescein, 5-aminofluorescein, 6-aminofluorescein, 5-nitrofluorescein, 6-nitrofluorescein, 5-carboxyfluorescein, 6-carboxyfluorescein, fluorescein-5-isothiocyanate, fluorescein-6-isothiocyanate fluorescein-5-maleimide, fluorescein-6-maleimide , fluorescein-5-semicarbazide, fluorescein-6-semicarbazide, fluorescein-5-thiosemicarbazide, and fluorescein-6-thiosemicarbazide.

The light-emitting compounds (B1) to (B3) may be used alone, or two or more of them may be used in combination.

The amount of the luminescent compound (B) added is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 1 part by mass, per 100 parts by mass of the polysilazane compound (A).

<(C) Organic solvent>
The polysilazane compound used in the present invention is used after being diluted with an organic solvent for the purpose of improving workability during coating and storage stability. The organic solvent is not particularly limited as long as it dissolves the (A) polysilazane compound and (B) the luminescent compound. For example, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, n-octane, i-octane, n-nonane, i-nonane, n-decane, i-decane, etc. saturated aliphatic hydrocarbons such as 1-octene, 1-nonene, 1-decene, 1-dodecene, β-myrcene, cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, deca saturated alicyclic hydrocarbons such as hydronaphthalene, unsaturated alicyclic hydrocarbons such as cyclohexene, terpene compounds such as p-menthane, d-limonene, l-limonene, dipentene, benzene, toluene, xylene, ethylbenzene, diethylbenzene, Aromatic hydrocarbons such as trimethylbenzene, triethylbenzene and tetrahydronaphthalene; ester compounds such as n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, isoamyl acetate, ethyl acetoacetate and ethyl caproate; alkyl ether compounds such as propyl ether, dibutyl ether, dipentyl ether, dihexyl ether and tert-butyl methyl ether; aryl ether compounds such as anisole and diphenyl ether; bis(2-methoxyethyl) ether, bis(2-ethoxyethyl) ether; Examples include glycol ether compounds such as bis(2-butoxyethyl) ether.

From the viewpoint of workability during application and storage stability of the polysilazane compound, the dilution ratio is preferably in the range of 100 to 100,000 parts by mass of the organic solvent to 100 parts by mass of the polysilazane compound. 000 parts by mass is more preferable.

The amount of water contained in the polysilazane compound-containing composition of the present invention is preferably 500 ppm or less, more preferably 300 ppm or less. If the water content is 500 ppm or less, the polysilazane does not react with the contained water, so there is no risk of heat generation, generation of hydrogen gas or ammonia gas, and thickening or gelation. Therefore, it is preferable.

<(D) Curing catalyst>
A curing catalyst can be added to the polysilazane compound-containing composition of the present invention for the purpose of improving the curing reaction rate.

The curing catalyst is not particularly limited as long as it becomes a catalyst for curing reaction by standing at room temperature, heating, UV irradiation, etc. For example, if it is an inorganic compound, titanium, manganese, cobalt, nickel, zinc, etc. homogeneous or heterogeneous metal catalysts containing metal elements represented by d-block elements belonging to the group of metals such as ruthenium, rhodium, palladium, osmium, iridium and platinum, or compounds containing these metal elements. In the case of organic compounds, aliphatic amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine and tetramethylethylenediamine, aliphatic aminoalcohols such as methylaminoethanol and dimethylaminoethanol, aniline, aromatic amines such as phenylethylamine and toluidine; heterocyclic amines such as pyrrolidine, piperidine, piperazine, pyrrole, pyrazole, imidazole, pyridine, pyridazine, pyrimidine, pyrazine, diazabicyclononene and diazabicycloundecene; mentioned.

<(E) Inorganic filler>
An inorganic filler may be added to the polysilazane compound-containing composition of the present invention. Examples of the inorganic filler include fumed silica, fused silica, alumina, zirconium oxide, calcium carbonate, calcium silicate, titanium dioxide, ferric oxide, and zinc oxide.

By adding such an inorganic filler, the properties (strength, heat resistance, insulation, etc.) of the resulting cured film are improved.

The amount of the inorganic filler to be added is not particularly limited, but is preferably 0.1 to 400 parts by mass, more preferably 1 to 100 parts by mass, per 100 parts by mass of component (A).

The polysilazane compound-containing composition of the present invention can be prepared by adding component (B) and, optionally, component (D) and/or component (E) to a solution obtained by mixing component (A) and component (C), for example, It can be obtained by stirring while applying ultrasonic waves. In addition, additives other than these can be added to the composition of the present invention depending on the purpose.

<Method of forming cured film>
The method for forming a cured film using the polysilazane compound-containing composition of the present invention includes a coating step of coating the polysilazane compound-containing composition on a substrate, and then volatilizing the organic solvent from the coating film coated on the substrate. - A method including a solvent volatilization step for removal and a curing step for curing the light-emitting compound-containing polysilazane compound may be used.

<Coating process>
Examples of methods for applying the polysilazane compound-containing composition of the present invention to a substrate include a direct gravure coater, chamber doctor coater, offset gravure coater, reverse kiss coater, reverse roll coater, slot die, lip coater, air doctor coater, Single roll kiss coater, forward rotation roll coater, blade coater, impregnation coater, MB coater, MB reverse coater, knife coater, bar coater, spin coat method, dispense method, dip method, spray method, transfer method, slit coat method and the like.

The thickness of the coating film varies depending on the intended use of the cured film, but the cured film thickness is preferably 10 to 100,000 nm, more preferably 100 to 10,000 nm.

Before applying the polysilazane compound-containing composition, the substrate may be subjected to a surface modification treatment. Surface modification treatment is mainly performed for the purpose of improving the adhesion between the base material and the polysilazane compound, and is achieved by decomposing and removing organic substances adhering to the base material surface and by forming chemical reaction points on the base material surface. be. Examples of the surface modification treatment method include argon plasma treatment, oxygen plasma treatment, ozone treatment, UV irradiation treatment, xenon excimer light irradiation treatment, etc., which are selected according to the type of substrate.

<Solvent volatilization process>
After the coating step, the solvent volatilization step is performed to volatilize the organic solvent from the coating film formed on the substrate. The solvent volatilization step is preferably carried out at 20 to 300°C, more preferably 25 to 200°C. Within this range, the organic solvent quickly volatilizes and the curing process can be started. If the temperature of the solvent volatilization step is 300° C. or less, it is preferable because there is no risk of decomposition of the light-emitting substance or ignition of the volatilized solvent. Moreover, since the curing reaction of polysilazane does not occur at the same time, the organic solvent does not remain in the cured film and does not cause discoloration.

For the above reason, the boiling point of the (C) organic solvent used in the present invention is preferably 25 to 300° C., more preferably 25 to 150° C. under atmospheric pressure (1013 hPa). Within this range, the organic solvent does not remain in the cured film and the handling property is good.

<Curing process>
After the solvent volatilization step, the process proceeds to the step of curing the polysilazane compound containing the light-emitting compound. The curing treatment of the polysilazane compound is not particularly limited as long as the curing reaction proceeds, but it is necessary to appropriately select a method that does not alter the base material. Examples of curing treatment methods include heat treatment, steam heat treatment, atmospheric pressure plasma treatment, low temperature plasma treatment, UV treatment, and excimer light treatment.

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. The weight average molecular weight is a value measured by GPC under the above conditions.

(A) Polysilazane compound
[Synthesis Example 1] Synthesis of polysilazane compound (A) Dehydrated pyridine (4,500 g) was cooled to -10°C under a nitrogen atmosphere, dichlorosilane (64 L) was blown thereinto, and the mixture was stirred at -10°C for 1 hour. Ammonia (216 L) was blown in, and the mixture was stirred for 12 hours while returning to 25°C. The resulting solid was filtered off, and n-dibutyl ether (1,000 g) was added to the filtrate. Pyridine in the liquid was distilled off under reduced pressure while azeotroping with n-dibutyl ether, and when the distillate reached 4,500 g, n-dibutyl ether (1,000 g) was further added. Subsequently, pyridine was distilled off under reduced pressure while azeotroping with n-dibutyl ether to obtain an n-dibutyl ether solution of perhydropolysilazane. The weight average molecular weight of this perhydropolysilazane was 6,100. After that, n-dibutyl ether was added so that the polysilazane compound was 20 parts by mass when the total solution was 100 parts by mass. In the following examples and comparative examples, this solution was used as having 20 parts by mass of perhydropolysilazane as component (A) and 80 parts by mass of n-dibutyl ether as component (C).

(B) Luminescent compound (B-1) Tetraphenylethylene (manufactured by Tokyo Chemical Industry Co., Ltd.)
(B-2) 1,1,2,3,4,5-hexaphenyl-1H-silole (manufactured by SIGMA-ALDRICH)
(B-3) Rhodamine B (manufactured by Alfa Aesar)
(B-4) Anthracene (manufactured by Tokyo Chemical Industry Co., Ltd.)
(B-5) Benzanthrone (manufactured by Tokyo Chemical Industry Co., Ltd.)
(B-6) Maleimide compound (compound synthesized in [Synthesis Example 2] below)
(B-7) p-terphenyl (manufactured by Tokyo Kasei Kogyo)
(B-8) Europium (III) chloride hexahydrate (manufactured by Tokyo Chemical Industry Co., Ltd.)
(B-9) Cerium-added yttrium aluminum garnet (YAG) phosphor (manufactured by INTEMATIX, NYAG4653-L)

[Synthesis Example 2] Synthesis of maleimide compound (B-6) To dimethyl acetylenedicarboxylate (1.50 g) was added dropwise aniline (1.01 g) at 0°C. After stirring at room temperature (25°C) for 24 hours, methanol (4 g) and n-butylamine (2.37 g) were added, and the mixture was further stirred at room temperature (25°C) for 24 hours. The resulting precipitate was filtered to obtain the desired product (B-6) represented by the following structural formula as a yellow solid.

(C) Organic solvent n-dibutyl ether (manufactured by Kanto Kagaku)

(D) Curing catalyst 3-aminopropyltriethoxysilane (KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.)

(E) Inorganic filler Fused silica (Excelica SE-8 manufactured by Tokuyama)

[Examples 1 to 20, Comparative Examples 1 to 7]
(1) Solubility Evaluation In the ratio shown in Table 1, the solution obtained by mixing the (A) component and the (C) component prepared in Synthesis Example 1 is added to the (B) component, and optionally the (D) component or ( A polysilazane compound-containing composition was prepared by adding component E) and stirring for 5 minutes while applying ultrasonic waves (38 kHz) using an ultrasonic cleaner. The polysilazane compound-containing composition thus obtained was visually checked. If the composition containing the polysilazane compound was transparent without the component (B) remaining undissolved, the result was ◯. X is indicated in Table 1 when the composition became opaque.

(2) Evaluation of molar extinction coefficient of component (B) (B-1) to (B-9) except for (B-3) in n-dibutyl ether at 30 µmol/L, component (B-3) in ethanol was placed in a quartz cell with an optical path length of 1 cm, and the absorption spectrum of the component (B) solution was measured using a spectrophotometer (manufactured by Hitachi High-Tech Science). Absorbance A at 365 nm, cell length b [cm], molar concentration c [mol / L] of component (B), molar extinction coefficient ε [L / (mol cm)] Lambert-Beer's law ε = A The molar extinction coefficient at 365 nm was calculated according to /(b·c), and the values are shown in Table 1.

(3) Evaluation of Luminescence First, a cured film of a polysilazane compound-containing composition was formed through the following steps.

Coating process Each of the polysilazane compound-containing compositions prepared as described above and marked with a good solubility in Table 1 was spin-coated onto a slide glass (rotation speed: 500 rpm, rotation time: 30 seconds).

Solvent volatilization step The polysilazane compound-containing composition applied as described above was allowed to stand at 25°C for 15 minutes to volatilize the solvent.

Curing Step The polysilazane compound-containing composition from which the solvent was volatilized as described above was heated in a drier at 150° C. for 48 hours to form a cured film on the surface of the slide glass.

The cured film formed above was irradiated with a UV-LED (manufactured by Eyegraphics) having a wavelength of 365 nm in a dark place at a peak intensity of 130 mW / cm ² , and Comparative Example 1 containing no component (B) and a fluorescent lamp. The appearance was visually compared below. Table 1 shows the change in appearance from that of Comparative Example 1, that is, ◯ when the appearance of light emission was observed, and x when the appearance was not observed.

(4) Evaluation of pencil hardness The pencil hardness of the cured film formed above was measured with a load of 750 g using a pencil hardness tester (manufactured by Pepareth Seisakusho) and a pencil (6B to 6H of Hi-Uni manufactured by Mitsubishi Pencil), and the results were obtained. Table 1 shows.

From Comparative Examples 6 and 7, it can be said that the inorganic compound has poor compatibility with the polysilazane compound and the organic solvent. Therefore, from the viewpoint of compatibility, it can be said that an inorganic compound is not suitable as a luminescent compound to be added in order to impart luminescent properties to a siliceous film formed from a polysilazane compound-containing composition.

From Comparative Example 5, a compound that does not correspond to the component (B) of the present invention and has no absorption in the wavelength irradiated for visual recognition of the siliceous film cannot impart luminescence to the siliceous film. Even if there is absorption in the irradiated wavelength as in cases 1 to 4, if the structure does not correspond to the structure of the present invention, the siliceous film cannot be given luminescence.

On the other hand, Examples 1 to 20 containing the (B) component in the present invention can impart luminescence to the siliceous film and have the same pencil hardness as Comparative Example 1. It can be said that the density of the siliceous film formed from the polysilazane compound can be maintained even when the luminescent property is imparted to the siliceous film.

As a result, it can be said that, in the present invention, the siliceous film formed from the polysilazane compound has the luminescent property for improving the visibility without impairing the conventional performance.

The polysilazane-containing composition of the present invention can form a siliceous film that emits light when irradiated with a light beam of 365 nm, and is therefore useful for easily determining whether a substrate is properly coated with a siliceous film. .

In addition, this invention is not limited to the said embodiment. The above-described embodiment is an example, and any device having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effect is the present invention. included in the technical scope of

Claims (7)

A composition containing a polysilazane compound,
(A) a polysilazane compound,
(B) at least one luminescent compound selected from the following (B1) to (B 2 );
(B1) a tetraphenylethylene-based compound,
(B2) a silole compound ,
( C) A composition containing a polysilazane compound, characterized by containing an organic solvent. 2. The polysilazane compound-containing composition according to claim 1, wherein the component (A) is perhydropolysilazane. 3. The polysilazane compound-containing composition according to claim 1, wherein the amount of component (B) is 0.1 to 5 parts by mass per 100 parts by mass of component (A). thing. 4. The polysilazane compound-containing composition according to any one of claims 1 to 3, wherein the component (B1) is a tetraphenylethylene compound represented by the following formula (1).

(In the formula, each R ¹ is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, A group selected from an acyl group, a hydroxyl group, a nitro group, an amino group, a (meth)acryloyloxy group, a carboxy group and its salts, a sulfo group and its salts, a phosphoric acid group and its salts, or a boronic acid group.) 5. The polysilazane compound-containing composition according to any one of claims 1 to 4, wherein the component (B2) is a silole compound represented by the following formula (2).

(wherein R ² is an aryl group having 6 to 12 carbon atoms, R ³ is a group selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and may or may not be the same.) 6. The polysilazane compound-containing composition according to any one of claims 1 to 5 , further comprising (D) a curing catalyst. 7. The polysilazane compound-containing composition according to any one of claims 1 to 6 , further comprising (E) an inorganic filler.