JP2000198160A - METHOD FOR FORMING SiO2 CERMICS FILM - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart solvent resistance to a base material of every kind and to enhance the adhesion of a polysilazane film to the base material of every kind without providing an intermediate layer. SOLUTION: In a method for forming a coating film containing polysilazane on a base material and subjecting the same to ceramics forming treatment to form a ceramics film substantially comprising SiO2, a process providing a primer layer containing a silane coupling agent between the base material and the coating film is provided. A coating compsn. containing polysilazane and the silane coupling agent is prepared and a coating film is formed on the base material from the coating compsn. and subjected to ceramics forming treatment to form the ceramics film substantially comprising SiO2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for forming an SiO ₂ ceramic film derived from polysilazane on a substrate, and more particularly to a method for forming a ceramic film having high adhesion to a substrate.

[0002]

2. Description of the Related Art In order to impart gas barrier properties, scratch resistance, heat resistance, corrosion resistance, flattening properties, ion barrier properties, etc. to materials having low heat resistance, such as plastic films, polysilazane is applied substantially. A technique has been developed which can form a ceramic film composed of SiO ₂ at low temperature and quickly. For example, Japanese Unexamined Patent Publication No.
Japanese Patent Publication No. 112879 describes a method for producing a SiO ₂ -coated plastic film, which comprises a step of forming a polysilazane film on at least one surface of a plastic film and converting the film into a ceramic. The polysilazane used here is called a low-temperature ceramicized polysilazane, and various modified polysilazanes are disclosed. Among them, particularly preferred low-temperature ceramicized polysilazane is polysilazane with a metal carboxylate described in JP-A-6-299118, and a modified polysilazane in which the metal is palladium (Pd) is more preferable. Is described.

Further, Japanese Patent Application No. 7-3416 filed by the present applicant has been disclosed.
In the specification of JP-A No. 01, before or after the application of a specific polysilazane or a modified product thereof, an amine compound and / or
Alternatively, there is described a method of coating a plastic film with SiO ₂ -based ceramics by contacting with an acid compound. Further, as a method of contacting the amine compound and / or the acid compound, a first embodiment in which the amine compound and / or the acid compound is added to the polysilazane or a modified product thereof before coating, and a method in which the polysilazane coating film is coated with the amine compound and A second embodiment is described in which the polysilazane coating is immersed in an aqueous solution containing an amine compound and / or an acid compound after application.

In order to form such a polysilazane coating film, a coating composition obtained by dissolving polysilazane in an organic solvent is generally used. Therefore, a polysilazane solution cannot be applied to a substrate that is affected by the organic solvent used. Further, depending on the substrate, the adhesion of the obtained polysilazane coating film, and thus the ceramic film, to the substrate may be insufficient, and may not be practically used.

Japanese Patent Application Laid-Open No. 9-39161 discloses that in order to impart solvent resistance to a plastic film and to improve the adhesion of a polysilazane film to the film,
Between a plastic film and a polysilazane film, a resin containing 50% by weight or more of at least one selected from the group consisting of an epoxy cured resin, a phenoxy resin, a urethane resin, a silicone resin, and a (meth) acrylate resin. A method for producing a laminated film characterized by providing an intermediate layer is described. However, JP-A-9-39161 does not disclose or suggest that a primer layer containing a silane coupling agent is provided as the intermediate layer.

Further, Japanese Patent Application Laid-Open No. 9-174782 discloses that
In order to impart solvent resistance to a polycarbonate-based film without providing an intermediate layer, a ceramic layer is directly formed on the film by using a coating composition containing polysilazane and a mixed solvent containing an aliphatic hydrocarbon-based solvent. A method for producing a transparent laminated film characterized by lamination is described. However, Japanese Patent Laid-Open No. 9-1
No. 74782 does not disclose or suggest adding a silane coupling agent to the coating composition, nor does it intend to improve the adhesion of the polysilazane coating film to the film.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for imparting solvent resistance to various substrates and increasing the adhesion of a polysilazane film to various substrates. A second object of the present invention is to provide a method for improving the adhesion of a polysilazane film to various substrates without providing an intermediate layer.

[0008]

According to the present invention, the first object is to form (A) a coating film containing polysilazane on a base material and subject the coating film to a ceramic treatment to substantially form S
This is achieved by a method of forming a ceramic film made of iO ₂ , comprising a step of providing a primer layer containing a silane coupling agent between the base material and the coating film. Further, according to the present invention, the second object is to prepare a coating composition containing (B) a polysilazane and a silane coupling agent, and then form a coating film of the coating composition on a substrate, This is achieved by a method characterized by forming a ceramic film consisting essentially of SiO ₂ by subjecting the coating film to a ceramic treatment.

By adopting the constitution of the above (A), solvent resistance is imparted to various substrates regardless of the kind of solvent contained in the coating composition for a polysilazane coating film, and the polysilazane film and substantially SiO _The adhesion of the ceramic film made of ₂ to various substrates can be improved. Further, by adopting the configuration of the above (B), the polysilazane film and eventually the S
The adhesion of the ceramic film made of iO ₂ to various substrates can be improved. Hereinafter, the present invention will be described in detail.

In the method (A) of the present invention, a method of forming a coating film containing polysilazane on a substrate and subjecting the coating film to a ceramic treatment to form a ceramic film substantially composed of SiO ₂ , A step of providing a primer layer containing a silane coupling agent between the substrate and the coating film is included. The step of providing a primer layer containing a silane coupling agent includes a step of preparing a composition for a primer layer containing a silane coupling agent, a step of applying the composition for a primer layer, and a step of curing the primer layer.

The silane coupling agent used for preparing the composition for a primer layer according to the present invention is generally X-Si
It is a compound represented by R ₃ . Here, X represents a functional group capable of reacting with an organic group, for example, an amino group, an epoxy group, a vinyl group, a thiol group, a halogen (eg, chlorine or bromine), and R represents a hydrolyzable group. For example, an alkoxy group (eg, methoxy group, ethoxy group), a halogen (eg,
Chlorine, bromine). Specific examples of such a silane coupling agent are shown by chemical structural formulas.

[0012]

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The preferred silane coupling agent depends on the type of the substrate on which the silane coupling agent is applied. For example, when the substrate to be applied is a polycarbonate or polyimide resin, CH ₂ ＣCCH ₃ COOC ₃ H ₆ Si (OCH
₃ ) ₃ [Nihon Unicar Co., Ltd. A-174] or NH ₂ C ₃
It is preferable to use H ₆ Si (OC ₂ H ₅ ) ₃ [same as A-1100]. A person skilled in the art can appropriately select a silane coupling agent preferable for a specific substrate.

The composition for a primer layer according to the present invention includes:
Alcohol and water are added to polymerize the silane coupling agent via hydrolysis and formation of silanol groups.
When the silane coupling agent has an alkoxy group, the alcohol added preferably has the same alkyl moiety as the alkyl moiety of the alkoxy group. For example, methanol in the case of the silane coupling agent having a methoxy group (-OCH _3), in the case of the silane coupling agent having an ethoxy group (-OC ₂ H ₅₎ It is preferable to use ethanol.

The amount of the alcohol to be added is from 40% by weight to 99% by weight, preferably 50% by weight, based on the silane coupling agent.
% By weight to 60% by weight. In particular, when the addition amount of the alcohol is less than 40% by weight, the polymerization of the silane coupling agent becomes insufficient, which is not preferable. The amount of water added is 0.01 to 5 molar equivalents, preferably 0.1 to 3 molar equivalents, based on the silane coupling agent. If the amount of water is less than 0.01 molar equivalent, the polymerization of the silane coupling agent will be insufficient, which is not preferable. Also,
If the amount of water exceeds 5 molar equivalents, polymerization occurs rapidly,
It is not preferable because the primer layer becomes cloudy. As the water, it is preferable to use distilled water.

The order of adding the alcohol and water to the silane coupling agent may be either first or both at the same time. However, in order to prevent rapid polymerization, the alcohol is added first and then the water is added. Is preferably added. In addition, it is preferable that the addition of alcohol and water is gradually added (eg, dropped) while stirring the silane coupling agent. Note that an acid catalyst can be added to the silane coupling agent if desired. Examples of the acid catalyst include acetic acid, hydrochloric acid, sulfuric acid, nitric acid, and the like. The amount of the acid catalyst to be added is preferably such that the pH of the final primer layer composition is in the range of 4 to 6. The addition of the acid catalyst is preferably performed before the addition of the alcohol in order to increase the wettability to the substrate. When adding an acid catalyst, gradually add the silane coupling agent while stirring,
Preferably, it is preferable to drop.

The composition for a primer layer according to the present invention includes:
In order to prevent the turbidity of the primer layer by controlling the polymerization rate of the silane coupling agent, it is preferable to include a high-boiling organic solvent. Here, “high boiling point” generally means that the boiling point is higher than 150 ° C. In addition, since the organic solvent comes into contact with the substrate when the composition is applied, it is necessary to select a solvent that does not corrode the substrate. From these viewpoints, preferable high-boiling organic solvents include ethylene glycol monobutyl ether, toluene, and butanol known under the trade name of butyl cellosolve. A particularly preferred high boiling organic solvent is butyl cellosolve. The high boiling organic solvent is used in an amount of 50% by weight to 99% by weight, preferably 80% by weight based on the composition for the primer layer.
It is used in an amount of 99% by weight.

A primer layer is formed by applying the prepared primer layer composition to a substrate. The coating method is a commonly used coating method, for example, dip coating, roll coating, bar coating, web coating (gravure, kiss, kissmeyer bar, die, flexo, etc.), brush coating, spray coating, spin coating, flow coating. Are used. When the substrate is a plastic film (especially in the case of a long film), a preferable application method is a gravure (reverse) coating method. After the application, a silane coupling agent is polymerized by performing a curing treatment to complete the primer layer. The curing treatment is performed at room temperature to 200 ° C., preferably 8
The heat treatment is performed at 0 ° C. to 120 ° C. for 10 minutes to 120 minutes, preferably for 10 minutes to 30 minutes.

The thickness of the primer layer is 0.01 to 10 μm
And more preferably 0.1 to 5 μm
And If the thickness of the primer layer is less than 0.01 μm, there is a possibility that a solvent for polysilazane described later permeates and reaches the base material. On the other hand, if the thickness of the primer layer is 1
If the thickness is larger than 0 μm, problems such as cracks may occur.

In the method (A) of the present invention, after providing a primer layer on a substrate, a coating film containing polysilazane is formed,
The coating film is converted into a ceramic to form a ceramic film substantially made of SiO ₂ . The polysilazane used in the present invention has at least a Si—H bond or N—
Any polysilazane having an H bond may be used, and not only polysilazane alone, but also a copolymer of polysilazane and another polymer or a mixture of polysilazane and another compound can be used. Some polysilazanes have a chain, cyclic or cross-linked structure, or those having a plurality of these structures simultaneously in the molecule. These can be used alone or in a mixture. Polysilazane is represented by the following general formula (I).

[0021]

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The following are typical examples of the polysilazane to be used, but are not limited thereto. Perhydropolysilazane is preferable in terms of hardness and denseness of the obtained film, and organopolysilazane is preferable in terms of flexibility. Those skilled in the art can appropriately select these polysilazanes according to the application. In the above formula (I), those having a hydrogen atom at R ¹ , R ² and R ³ are perhydropolysilazane, and the production method thereof is described in, for example, JP-B-63-16325, D. Seyfert.
h et al. Communication of Am. Cer. Soc., C-13, January
1983. 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,

[0023]

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Can be represented by the following chemical formula. An example of the structure of perhydropolysilazane is shown below.

[0025]

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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. Po.
lym. Chem., 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. A method for producing a polyorgano (hydro) silazane having a hydrogen atom for R ¹ and R ³ and an organic group for R ² in the general formula (I) is described in D. Seyferth et al.
Polym. Prepr., Am. Chem. Soc., Div. Polym. Chem.,
25 , 10 (1984), JP-A-61-89230, 6
It is reported in JP 2-156135. The polysilazane obtained by these methods includes-(R ² SiHN).
H)-is a repeating unit, and the degree of polymerization is mainly 3-5.
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), 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 at R ³ and a hydrogen atom at R ³ are represented by-(R ¹ R
^It has a cyclic structure mainly having a degree of polymerization of 3 to 5 using ² SiNR ³ )-as a repeating unit. The polysilazane used has a main skeleton consisting of the unit represented by the above general formula (I). However, the unit represented by the general formula (I) may be cyclized as is apparent from the above description. In the case where is not a cyclic group, the terminal of the main skeleton can be a group similar to R ¹ , R ² or R ³ or hydrogen.

Among polyorgano (hydro) silazanes, D. Seyferth et al., Communication of Am. Cer. Soc., C.
-132, July 1984. Some have a crosslinked structure in the molecule. An example is shown below.

[0029]

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

[0031]

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

[0033]

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In addition, a repeating unit as reported in JP-A-62-195024 is represented by [(SiH ₂ )
_n (NH) _m] and [(SiH _{2) r} O] (in these formulas, n, m, r are each 1, 2 or 3) polysiloxazanes, JP-A 2-84437 discloses represented by Polyborosilazane produced by reacting a boron compound with polysilazane as reported in JP-A-63-81212, JP-A-63-191832, and JP-A-2-77427. Polymetallosilazane produced by reacting polysilazane with metal alkoxide as described in JP-A-1-138108,
-138107, 1-203429, 1-20
No. 3430, No. 4-63833, No. 3-320167
JP-A No. 2 (1995), which has been reported to increase the molecular weight as reported in Japanese Unexamined Patent Publication (the former four of the above-mentioned publications) or to improve the hydrolysis resistance (the latter two). 175726, 5-86200, 5-
Copolymerized polysilazane, which is advantageous in increasing the film thickness, obtained by introducing an organic component into polysilazane as reported in JP-A-331293 and JP-A-3-31326 can be used in the same manner.

Further, in the present invention, polysilazane which has been subjected to a low-temperature treatment by adding a catalyst to polysilazane or a modified product thereof (hereinafter referred to as low-temperature ceramicized polysilazane) may be used. Examples of such low-temperature ceramicized polysilazane include a silicon alkoxide-added polysilazane described in JP-A-5-238827 by the present applicant. This modified polysilazane is represented by the following general formula (II): Si (OR ⁴ ) ₄ (II) (wherein R ⁴ may be the same or different, A hydrogen atom, an alkyl group or an aryl group having 1 to 20 carbon atoms, wherein at least one R ⁴ is the above-described alkyl group or aryl group), which is obtained by a heat reaction. A silicon alkoxide-added polysilazane having an alkoxide-derived silicon / polysilazane-derived silicon atom ratio in the range of 0.001 to 3 and a number average molecular weight of about 200,000 to 500,000. R ⁴ is more preferably an alkyl group having 1 to 10 carbon atoms,
Alkyl groups having 1 to 4 carbon atoms are most preferred. Further, it is preferable that the silicon atom ratio derived from alkoxide / silicon derived from polysilazane is in the range of 0.05 to 2.5. For the preparation of the silicon alkoxide-added polysilazane, see the above-mentioned JP-A-5-238827.

Another example of the low temperature ceramicized polysilazane is glycidol-added polysilazane described in JP-A-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 a glycidol-added polysilazane having a number average molecular weight of about 200,000 to 500,000. The weight ratio of glycidol / polysilazane is preferably from 0.01 to 1, and more preferably from 0.05 to 0.5. For the preparation of glycidol-added polysilazane,
See JP-A-6-122852.

Another example of the low temperature ceramicized polysilazane is an alcohol-added polysilazane described in JP-A-6-240208 by the present applicant. The modified polysilazane is obtained by reacting the polysilazane represented by the general formula (I) with an alcohol, and has a weight ratio of alcohol / polysilazane of 0.001 to 2;
And an alcohol-added polysilazane having a number average molecular weight of about 100,000 to 500,000. The alcohol is preferably an alcohol having a boiling point of 110 ° C. or higher, for example, butanol, hexanol, octanol, nonanol, methoxyethanol, ethoxyethanol, and furfuryl alcohol. The alcohol / polysilazane weight ratio is preferably from 0.01 to 1, and more preferably from 0.1 to 1.
It is more preferably from 0.5 to 0.5. The preparation of the alcohol-added polysilazane is described in JP-A-6-24.
See No. 0208.

As another particularly preferred example of the low temperature ceramicized polysilazane, Japanese Patent Application Laid-Open No. 6-2 / 1994 by the present applicant is disclosed.
And the metal carboxylate-added polysilazane described in JP-A-99118. 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 is represented by the formula (RCOO) _n M wherein R represents 1 to 2 carbon atoms.
Two aliphatic groups or alicyclic groups, M represents at least one metal selected from the above metal group, and n is a valence of the metal M]. It is particularly preferred that M is palladium (Pd). 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 1.
０．５0.5. For the preparation of the polysilazane to which the metal carboxylate is added, see the above-mentioned JP-A-6-299118.

As still another example of low-temperature ceramicized polysilazane, Japanese Patent Application Laid-Open No. 6-30632 by the present applicant.
An acetylacetonate complex-added polysilazane described in JP-A No. 9-No. 9 is exemplified. This modified polysilazane is
The weight ratio of the acetylacetonato complex / polysilazane obtained by reacting the polysilazane represented by the general formula (I) with an acetylacetonato complex containing nickel, platinum, palladium or aluminum as a metal is 0.0000.
An acetylacetonato complex-added polysilazane having a number average molecular weight of about 200 to 500,000 in the range of 01 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,
In general, the formula (CH ₃ COCHCOCH ₃ ) _n M
Represents an n-valent metal]. The weight ratio of acetylacetonato complex / polysilazane is preferably 0.001 to
1, more preferably 0.01 to 0.5. For the preparation of acetylacetonato complex-added polysilazane, see the above-mentioned JP-A-6-306329.

As another example of the low temperature ceramicized polysilazane, there is polysilazane added with metal fine particles described in Japanese Patent Application Laid-Open No. 7-196886 by the present applicant. This modified polysilazane is a modified polysilazane obtained by adding fine particles of a metal such as Au, Ag, Pd, and Ni to a coating solution containing polysilazane represented by the general formula (I) as a main component. The preferred metal is Ag. The particle diameter of the metal fine particles is preferably smaller than 0.5 μm, more preferably 0.1 μm or less, and further preferably smaller than 0.05 μm.
In particular, those obtained by dispersing independently dispersed ultrafine particles having a particle size of 0.005 to 0.01 μm in a high-boiling alcohol are preferred. The addition amount of the metal fine particles is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the polysilazane. For the preparation of polysilazane to which metal fine particles are added, refer to the above-mentioned Japanese Patent Application Laid-Open No. 7-199698.

As another example of low temperature ceramicized polysilazane, Japanese Patent Application No. 7-200584 filed by the applicant of the present invention.
And / or polysilazanes added with amines and / or acids. This modified polysilazane is
The polysilazane represented by the general formula (I) or a modified product thereof may be added to an amine compound represented by the general formula R ⁴ R ⁵ R ⁶ N, pyridines, DBU, DBN, etc., and / or an organic acid or an inorganic acid. An acid compound such as an acid is added.

As a typical example of the amine compound, the following general formula
And those represented by (III). R ⁴ R ⁵ R ⁶ N (III) In the formula, R ^{4 to} R ⁶ each represent a hydrogen atom, an alkyl group,
Represents an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group. Specific examples of the amine compound include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, tributylamine, pentylamine, dipentylamine, tripentylamine, Hexylamine,
Dihexylamine, trihexylamine, heptylamine, diheptylamine, triheptylamine, octylamine, dioctylamine, trioctylamine, phenylamine, diphenylamine, triphenylamine,
And the like. In addition, the hydrocarbon chain contained in these amine compounds may be linear or branched.
Particularly preferred amine compounds are triethylamine, tripentylamine, tributylamine, trihexylamine, triheptylamine and trioctylamine.

Specific examples of pyridines include pyridine, α
-Picoline, β-picoline, γ-picoline, piperidine, lutidine, pyrimidine, pyridazine and the like. Furthermore, DBU (1,8-diazabicyclo [5.
4.0] -7-undecene), DBN (1,5-diazabicyclo [4.3.0] -5-nonene), and the like can also be used. On the other hand, specific examples of the acid compound include organic acids such as acetic acid, propionic acid, butyric acid, valeric acid, maleic acid, and stearic acid, hydrochloric acid, nitric acid, sulfuric acid, hydrogen peroxide,
And the like. Particularly preferred acid compounds are propionic acid, hydrochloric acid and hydrogen peroxide.

The amount of the amine compound to be added to the polysilazane may be 1 ppm or more based on the weight of the polysilazane, and is preferably 100 ppm to 10%. An amine compound having a higher basicity (pKb value in an aqueous solution) and a higher boiling point tends to promote ceramic formation. The amount of the acid compound to be added to the polysilazane may be 0.1 ppm or more, preferably 10 ppm to 10%, based on the weight of the polysilazane. A particularly preferred amine compound is tripentylamine, and the acid compound is propionic acid.

According to the present invention, a coating composition containing the above-mentioned polysilazane or a modified product thereof or low-temperature ceramicized polysilazane is prepared. In this preparation, a solvent for polysilazane is generally used. Examples of the solvent include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, halogenated hydrocarbons such as halogenated methane, halogenated ethane, and halogenated benzene, aliphatic ethers, and alicyclic ethers. And the like. Preferred solvents are methylene chloride, chloroform, carbon tetrachloride, bromoform, ethylene chloride,
Ethylidene chloride, trichloroethane, halogenated hydrocarbons such as tetrachloroethane, ethyl ether, isopropyl ether, ethyl butyl ether, butyl ether, 1,2-dioxyethane, dioxane, dimethyl dioxane, tetrahydrofuran, ethers such as tetrahydropyran, pentanehexane, isohexane, Methylpentane, heptane, isoheptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylcyclohexane, cyclohexene, p-menthane, limonene, decalin, tetralin, phenylcyclohexane, cyclohexane , Nonane, decane, n-hexane, pentane, dimethyldiethoxysila , Methyl triethoxysilane, hydrocarbons such like. When these solvents are used, two or more solvents may be mixed in order to adjust the solubility of polysilazane and the evaporation rate of the solvent.

According to the method (A) of the present invention, since such a solvent does not come into contact with the substrate, it is not necessary to consider the influence on the substrate when selecting the solvent. The amount (proportion) of the solvent used is selected so as to improve the workability by the coating method to be employed, and the average molecular weight, the molecular weight distribution, and the structure of the polysilazane used are different.
Can be mixed freely. Preferably, they can be mixed in a solid content range of 1 to 50% by weight.

In the coating composition of the present invention, a suitable filler and / or extender can 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. These fillers may be of various shapes such as needles (including whiskers), granules, and scales, or may be used alone or in combination of two or more.
Further, it is desirable that the size of the particles 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 polysilazane, and the particularly preferable addition amount is in the range of 0.2 part by weight to 3 parts by weight. In the coating composition, if necessary, an ultraviolet absorber, various pigments, a leveling agent, an antifoaming agent,
Antistatic agent, pH adjuster, dispersant, surface modifier, plasticizer,
A drying accelerator and a flow stopper may be added.

In the method of the present invention, plastic, metal,
An SiO ₂ ceramic film can be formed on the surface of a wide variety of base materials including ceramics, glass, and the like. The method of the present invention imparts solvent resistance to various substrates regardless of the type of polysilazane solvent, and can increase the adhesion of the polysilazane film to various substrates. It is particularly advantageous to apply it to plastic materials with poor adhesion.

As a substrate to which the method of the present invention can be particularly effectively used, polycarbonate (PC), polyarylate (PAr), polyethylene (PE), polypropylene (PP), amorphous polyolefin (α-PO:
Example: Resin film, resin sheet and resin molded product (bulk) of "Arton" (trade name) manufactured by Nippon Synthetic Rubber Co., Ltd. and polyimide (PI: "Upilex" (trade name) manufactured by Ube Industries, Ltd.) ).

According to the present invention, a polysilazane film is formed by applying the above-mentioned coating composition to the above-mentioned various substrates. The coating method is a commonly used coating method, for example, dip coating, roll coating, bar coating, web coating (gravure, kiss, kissmeyer bar, die, flexo, etc.), brush coating, spray coating, spin coating, flow coating. And the like can be used and can be appropriately selected depending on the shape of the object to be coated and the like. A preferred application method for the plastic film is a gravure (reverse) coating method. After the application, if desired, a step of drying the polysilazane coating film may be separately provided. However, the polysilazane solvent generally has a high volatility and can proceed to the next step without providing a special drying step, and can be simultaneously dried in other steps.

In the method (B) of the present invention, a coating composition containing a polysilazane and a silane coupling agent is prepared, and then a coating film of the coating composition is formed on a substrate. The treatment is performed to form a ceramic film substantially made of SiO ₂ . That is, in the method (B), the silane coupling agent is directly mixed into the coating composition containing polysilazane. According to the method (B), the adhesion of the polysilazane film, and thus the ceramic film substantially composed of SiO _2, to various substrates can be increased without providing a primer layer of the silane coupling agent independently.

The silane coupling agent used for preparing the coating composition according to the method (B) of the present invention is a compound generally represented by X-SiR ₃ as in the method (A). Here, X is a functional group capable of reacting with an organic group, for example, an amino group, an epoxy group, a vinyl group, a thiol group,
R represents a hydrolyzable group, for example, an alkoxy group (eg, methoxy group, ethoxy group), halogen (eg, chlorine, bromine) or the like.

The silane coupling agent used in the method (B) preferably does not react with the polysilazane to be mixed. Further, the silane coupling agent varies depending on the type of the substrate on which the silane coupling agent is applied. For example, when the substrate to be applied is a polycarbonate or polyimide resin, CH ₂ ＣCCH ₃ COOC ₃ H ₆
Si (OCH ₃ ) ₃ [Nihon Unicar Co., Ltd. A-174]
Or NH ₂ C ₃ H ₆ Si (OC ₂ H ₅ ) ₃ [A-110
0] is preferably used.

In the preparation of the coating composition according to the method (B) of the present invention, a silane coupling agent is gradually added to the above-mentioned coating composition containing polysilazane or a modified product thereof or low-temperature ceramicized polysilazane while stirring the mixture. , Preferably by dropwise addition. As a solvent used in the coating composition, any of the solvents mentioned above as a solvent for polysilazane may be used as long as the solvent does not corrode the base material and dissolves the silane coupling agent.

The amount of the silane coupling agent in the coating composition is from 0.1% by weight to 50% by weight, preferably 0.1% by weight, based on the polysilazane contained in the composition.
It is 1% by weight to 10% by weight. When the amount of the silane coupling agent is less than 0.1% by weight, the adhesion of the polysilazane coating film to the substrate becomes insufficient. On the other hand, if the silane coupling agent is more than 50% by weight, the properties desired for the final ceramic film are impaired.

According to the method (B), the coating composition thus prepared is applied to the substrate as described in the method (A) by the above-mentioned coating method, whereby the coating composition is obtained. Is formed on a substrate. After the application, if desired, a step of drying the coating film may be separately provided. However, the polysilazane solvent generally has a high volatility and can proceed to the next step without providing a special drying step, and can be simultaneously dried in other steps.

After forming a coating film containing polysilazane by the method (A) or the method (B), the coating film is subjected to a ceramic treatment to form a SiO ₂ ceramic film. At the time of this ceramicization treatment, the following temperature reduction step can be performed on the polysilazane coating film in order to lower the ceramicization temperature.

As a first embodiment of the temperature lowering step, a vapor generated from an aqueous solution containing an amine compound and / or an acid compound can be brought into contact with the coating film. Examples of the amine compound and the acid compound include those described above. The amine compound is preferably soluble in water, and its concentration in the aqueous solution can be arbitrarily selected within a range of 100 ppm or more. The concentration of the acid compound in the aqueous solution is
0.1 ppm or more, preferably 10 ppm
〜１０10%. A particularly preferred amine compound in this first embodiment is triethylamine. Room temperature is sufficient for generating steam, but it can be arbitrarily selected in the range of 0 ° C. to the boiling point of the aqueous solution.

As an alternative to the first embodiment, an amine compound and / or an acid compound and / or water are vaporized independently instead of an aqueous solution containing an amine compound and / or an acid compound. May be brought into contact with the polysilazane coating film. In carrying out the first embodiment, the vapor of the amine compound generated by another vapor generator can be carried by a carrier gas (eg, nitrogen gas) and introduced into the drying zone. Of course, it is possible to introduce the acid compound into the drying zone in the same manner, but it is generally necessary to perform an acid corrosion treatment on the incidental equipment. As a method for generating the amine compound vapor, a method in which an inert carrier gas such as nitrogen gas is blown into an aqueous solution of the amine compound as described above for bubbling is advantageous. The steam generator may be maintained at room temperature, or may be heated to about 40 ° C. if desired.

The vapor thus generated can be carried by a carrier gas to a solvent drying zone, and can be sprayed onto the polysilazane coating via preferably a plurality of spray nozzles. The pressure for spraying depends on the outlet diameter of the spray nozzle, etc., but generally the pressure in the steam generator is about 9.8 × 10 ⁴ to about 2.0 × 10 ⁵ Pa (about 1 to about 2 kPa).
gf / cm ² ) may be adjusted by adjusting the blowing pressure of the carrier gas into the apparatus. As described above, by employing a method in which the amine compound vapor is generated by another steam generator and sprayed in the drying zone, the amine compound vapor and the steam can be stably supplied. Furthermore, the use of an inert gas such as nitrogen gas does not adversely affect the curing of the polysilazane coating film, and under such an inert gas atmosphere, the risk of explosion due to amine compounds is reduced. Is also advantageous.

In a second embodiment of the step of lowering the temperature, a coating film of the above-mentioned polysilazane or a modified product thereof is formed on the surface of a base material, and then the aqueous solution containing the above-mentioned amine compound and / or acid compound is added thereto. By dipping the coating film, the polysilazane can be brought into contact with the amine compound and / or the acid compound. The amine compound is preferably soluble in water, and its concentration in the aqueous solution can be arbitrarily selected from the range of 100 ppm to the solubility limit. The concentration of the acid compound in the aqueous solution may be 0.1 ppm or more, preferably 10 ppm to 10%. In this embodiment, a particularly preferred amine compound is butylamine, and the acid compound is hydrogen peroxide.

In the first and second embodiments, the treated polysilazane-coated sample (eg, film, silicon wafer) may be exposed to a water vapor atmosphere, if necessary.
It is preferable to perform any of immersion in water, immersion in an aqueous solution of an acid compound, immersion in an aqueous solution of an alkali compound, or standing in the air, or a combination thereof.

For the exposure to the water vapor atmosphere, a humidifying furnace or steam is generally used. Specifically, steam is introduced into the solvent drying zone, and steam is introduced therein (at a temperature of 50 to 100 ° C.,
Residence time 10-6 in relative humidity (50-100% RH)
The method of passing in 0 minutes or the solvent drying zone in which the steam that has passed during the drying of the solvent after coating was introduced, and the residence time was 10 to 10 minutes.
A method of passing the gas again in 60 minutes is conceivable. Alternatively, the immersion in the aqueous acid compound or alkali compound solution may employ the method described in the second embodiment. However, in addition to the above acid compounds, the acid compounds include inorganic acids such as phosphoric acid;
Glacial acetic acid, acetic acid, propionic acid, lower monocarboxylic acids such as caproic acid or anhydrides thereof, oxalic acid, fumaric acid,
Maleic acid, lower dicarboxylic acids such as succinic acid or anhydrides thereof, and organic acids such as trichloroacetic acid; perchloric acid;
Hydrochloric acid, nitric acid, sulfuric acid, sulfonic acid, paratoluenesulfonic acid, boron trifluoride and its complex with an electron donor, etc .;
SnCl ₄ , ZnCl ₂ , FeCl ₃ , AlCl ₃ , S
Lewis acids such as bCl ₃ and TiCl ₄ and complexes thereof are included. The alkali compound includes sodium hydroxide, ammonium chloride, potassium hydroxide, lithium hydroxide, pyridine, ammonia, and the like, in addition to the amine compound.

When the substrate is a long plastic film, it is preferable to wind the film after the treatment of the first or second embodiment together with the separator sheet into a roll. This separator sheet is a sheet-shaped material for preventing the wound films from contacting each other,
A nonwoven fabric applied to the entire surface or a part of the polysilazane-coated film (for example, one at each end of the coated film);
Includes side tapes, embossed films, etc. As side tape, thickness 12 ~ 100μm, width 10 ~ 30m
m, and commercially available products of various materials can be used. As a specific example of a commercially available product, a PET film (Lumirror X-42 to 45 manufactured by Toray, Lumimat manufactured by Panac), a matted PET film on one surface or both surfaces, a foamed PET film [Crisper manufactured by Toyobo Co., Ltd.] PET film (Panac alpet film), and the like. The embossed film is a film in which both sides of the film are embossed, and it is preferable to use a film having a thickness of 75 to 150 μm and an emboss (projection) height of 1 to 10 mm. Further, it is preferable to use an embossed film having a film width wider than the application width. As a commercially available product of such an embossed film, a polyimide film (706410H12 or 706420H12 manufactured by Dainichi Kasei Kogyo Co., Ltd.) having both surfaces embossed can be mentioned.

The conditions of the standing treatment are as follows:
° C) ~ 60 ° C, preferably about 25 ° C, relative humidity 10-9.
3 to 2 at 0% RH, preferably 50 to 70% RH
Preferably, it is 4 hours. If desired, the coating film containing polysilazane can be irradiated with ultraviolet light after the application by the above method, before the above-mentioned low-temperature step, after the low-temperature step, or simultaneously with the low-temperature step. The substrate is heated by this ultraviolet irradiation, and O ₂ and H ₂ O contributing to ceramic conversion (silica conversion), an ultraviolet absorber, and polysilazane itself are excited and activated. The formation of ceramics is promoted, and the resulting ceramic film becomes more dense.

Irradiation with ultraviolet rays is effective no matter if it is performed after the formation of the coating film. That is, before the coating film is dried immediately after the formation of the coating film containing the polysilazane, during the coating film drying, after the coating film drying, before another lowering step described later, during the lowering step and after the lowering step. It is valid. However, performing ultraviolet irradiation after performing at least one temperature lowering step as described above is particularly effective in terms of further lowering and speeding up ceramic formation. Although optional, it is more effective to bring ozone or hydrogen peroxide gas into contact with the polysilazane-containing coating film at the same time as irradiation with ultraviolet light.

In addition to the above-described ultraviolet irradiation, if necessary, the coating film containing polysilazane may be irradiated with infrared rays to further promote the ceramic formation of the coating film. In addition, as in the case of the above-described ultraviolet irradiation, the infrared irradiation is effective at any time after the formation of the polysilazane-containing coating film. Further, when used in combination with the ultraviolet irradiation, the infrared irradiation can be performed before or after the ultraviolet irradiation, or simultaneously with the ultraviolet irradiation.

For infrared irradiation, any commonly used infrared generator can be used.
As used herein, "infrared" refers to radiation having a generally understood wavelength, specifically, a wavelength of about 0.8-1000 [mu] m. This infrared ray has a wavelength of about 0.8 to 2.
It is divided into three regions: a near-infrared ray of 0 μm, a mid-infrared ray having a wavelength of about 2.0 to 4.0 μm, and a far-infrared ray having a wavelength of about 4.0 to 1000 μm. In general, when these infrared rays are irradiated from the coating film side, near infrared rays penetrate to and heat a coated substrate (eg, a plastic substrate), depending on the film thickness. In the case of mid-infrared rays, the light is transmitted from the interface between the substrate and the coating film to the inside of the coating film and heated. Further, in the case of far infrared rays, the light is transmitted from the inside of the coating film to the coating film surface and heated. In the method of the present invention, it is preferable to use a mid-infrared ray rather than a near-infrared ray, and further use a far-infrared ray rather than a mid-infrared ray from the viewpoint that the substrate is not easily damaged. That is, in the method of the present invention, it is generally 0.8 to 1000 μm, preferably 2.0 to 1000 μm, and more preferably 4.0.
Infrared light of １０００1000 μm is used.

By the above-mentioned lowering temperature step and / or ultraviolet irradiation and / or infrared irradiation, Si—O,
A film in which Si-N, Si-H, and NH exist is formed. At this point, a part of the polysilazane coating film may be converted to ceramics, but this coating film may still be incompletely converted to ceramics. This coating can be completely converted to ceramics by the following heat treatment and / or post-treatment. Of course, it is possible to directly perform the following processing by omitting the temperature lowering step and the like.

When a heat treatment is employed, the heat treatment temperature is a temperature at which the polysilazane is completely turned into ceramics, usually 3 times.
It is preferably at least 00 ° C. When the polysilazane is subjected to the above-mentioned low-temperature step, a low temperature that does not impair the base material (particularly, plastic or tempered glass), preferably 150 ° C.
The heat treatment can be performed below. Generally, in the case of a plastic substrate, if the heat treatment is performed at 150 ° C. or higher, the plastic substrate is damaged such as deformation and strength deterioration.

The heating rate of the heat treatment is not particularly limited.
A gradual heating rate of 〜20 ° C./min is preferred. The heat treatment atmosphere may be any of oxygen, air, or an inert gas, but air is more preferable. Oxidation of polysilazane or hydrolysis by water vapor coexisting in the air proceeds by heat treatment in air, and a dense ceramic coating mainly composed of Si-O bond or Si-N bond at a low heat treatment temperature as described above. Formation is possible. This coating contains 0.005 to 5% of atomic percent of nitrogen due to polysilazane.

In the above-described heat treatment at a low temperature, Si-
A film in which O, Si—N, Si—H, and N—H bonds exist may be formed. This film is still incompletely converted to ceramics. This film can be converted into ceramics by one or both of the following two methods (post-treatment). In addition, even if the post-treatment is directly performed by omitting the above-mentioned heat treatment at a low temperature, it is possible to promote the conversion of polysilazane into a ceramic.

Processing in a steam atmosphere. The pressure is not particularly limited, but 1 to 3 atm is practically appropriate. The relative humidity is not particularly limited, but is preferably 10 to 100% RH. The temperature is effective at room temperature or higher, but is preferably room temperature to 150 ° C. The steaming time is not particularly limited, but is 10 minutes to 30 minutes.
The day is realistically appropriate.

By the treatment in a steam atmosphere, the oxidation of polysilazane or the hydrolysis with steam proceeds.
At such a low heating temperature, a dense film substantially made of SiO ₂ can be formed. However, since this SiO ₂ film is derived from polysilazane, nitrogen is added in an atomic percentage of 0.1%.
It contains 0.5-5%. If the nitrogen content is more than 5%, the film becomes insufficiently ceramic, and the desired effect (for example, scratch resistance) cannot be obtained. On the other hand, when the nitrogen content is 0.0
It is difficult to make it less than 5%. The preferred nitrogen content is 0.1 to 3% in atomic percent.

Immerse in distilled water containing the catalyst. The catalyst is preferably an acid or a base, and the type thereof is not particularly limited. For example, triethylamine, diethylamine, monoethanolamine, diethanolamine, triethanolamine, n-exylamine, 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, Alkalis such as pyridine and aqueous ammonia; inorganic acids such as phosphoric acid; lower monocarboxylic acids such as peracetic acid, acetic anhydride, propionic acid and propionic anhydride, or anhydrides thereof, oxalic acid, fumaric acid, maleic acid, Lower dicarboxylic acids such as succinic acid or anhydrides thereof, and organic acids such as trichloroacetic acid; perchloric acid, hydrochloric acid, nitric acid, sulfuric acid, sulfonic acid, paratoluenesulfonic acid, boron trifluoride, and complexes thereof with an electric donor , Etc .; SnCl
₄ , ZnCl ₂ , FeCl ₃ , AlCl ₃ , SbC
Lewis acids such as l ₃ and TiCl ₄ and their complexes can be used. The preferred catalyst is hydrochloric acid. The content of the catalyst is 0.01 to 50% by weight, preferably 0.1 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.

[0076] By immersing in distilled water containing the catalyst, hydrolysis of the oxidation or water polysilazane, is further accelerated by the presence of a catalyst, at a low heating temperature as described above, the dense consisting essentially SiO ₂ It is possible to form a thin film. However, as described above, since this SiO ₂ film is derived from polysilazane, it also contains nitrogen in an atomic percentage of 0.05 to 5%.

As another post-treatment method, after forming a polysilazane-containing coating film and subjecting the coating film to a low-temperature step, a reactive mixed solution containing alkoxysilane and water is brought into contact with the coating film. There are also methods. The alkoxysilane used can be arbitrarily selected from alkoxysilanes generally used for forming a SiO ₂ ceramic coating by a sol-gel method.

A preferred alkoxysilane is Si (OR)
₄ [wherein R independently represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylamino group or an alkylsilyl group]. Preferred R is a methyl group, an ethyl group, a propyl group, a butyl group and an isopropenyl group. Among them, particularly preferred alkoxysilanes are tetramethoxysilane and tetraethoxysilane.

In the method of the present invention, R ′ _n Si (OR)
_{4-n wherein} R represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylamino group or an alkylsilyl group, and R ′ each independently represents, in addition to the above R, Represents a vinyl group, an epoxy group, an amino group, a methacryl group or a mercapto group, and n is 1 to
Organoalkoxysilane represented by 2 is an integer], or _{R 'n (RO) 3-} n Si-R "-Si (OR)
'In _m [wherein, R each independently represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylamino group or an alkylsilyl group, R' _3-m R are each independently the R Represents a vinyl group, an epoxy group, an amino group, a methacryl group or a mercapto group, and R ″ represents
Represents a divalent organic bonding group or -O-, wherein n is 0 to 3, m
Represents an integer of 0 to 3, provided that n + m is 4 or less.] May be used.
Such organic groups R ′ and R ″ may be used in such a manner that the final ceramic coating obtained has a desired film quality (for example, heat resistance and scratch resistance).
As shown in the figure, those skilled in the art can appropriately select.

The water (H) used in the reactive mixed solution
₂ O) includes ordinary ion-exchanged water, industrial water, filtered water,
Etc. can be used. However, it is preferable to use pure water in consideration of the film quality and the like of the obtained final ceramic coating. It is also possible to use hydrogen peroxide water instead of water. The content ratio of alkoxysilane and water in the mixed solution is, based on volume, alkoxysilane / water = 0.
The range is preferably from 01 to 100, more preferably from 0.1 to 10. When this ratio is smaller than 0.01, the reaction by water is mainly performed, and the film quality of the obtained ceramic is deteriorated. On the other hand, when it is larger than 100, the hydrolysis rate of the alkoxysilane becomes slow. The reactivity of the mixed solution can be controlled by changing the ratio.

This mixed solution may be mixed with R ″ OH
Can be contained. Here, R ″ represents the same group as R described above for alkoxysilane, that is, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylamino group, or an alkylsilyl group. "And R of the alkoxysilane are preferably the same, but may be different. When the alcohol is contained, hydrolysis of the alkoxysilane is promoted, and the reactivity of the solution is increased.

The content ratio of the alkoxysilane to the alcohol in the mixed solution is preferably alkoxysilane / alcohol = 100-0.01, more preferably 10-10, on a volume basis.
A range of 0.1 is preferred. When this ratio is larger than 100, the decomposition of the alkoxysilane is small, and the reactivity of the solution is low. On the other hand, when it is smaller than 0.01, the reaction between the alcohol and the silazane is mainly performed, and the film quality is deteriorated. Further, similarly to the case of water described above, the reactivity of the mixed solution can be controlled by changing the ratio.

A reactive mixed solution containing an alkoxysilane and water can contain a catalyst to promote the hydrolysis of the alkoxide and the reaction with polysilazane. The catalyst is preferably an acid or a base, and the type thereof is not particularly limited. Examples thereof include hydrochloric acid, sulfuric acid, hydrofluoric acid, nitric acid and salts thereof, ammonia, ammonium hydroxide, ammonium chloride, triethylamine, diethylamine, and monoethanolamine. , Diethanolamine, triethanolamine and the like, and sodium hydroxide, potassium hydroxide and the like. The addition amount of these acid and base catalysts is 0.0001 to 10 mol%, more preferably 0.1 to 10 mol%, per mol of alkoxysilane.
001-1.0 mol% is preferable. Similarly, the reactivity of the mixed solution can be controlled by the amount of the catalyst added.

The reactive mixed solution containing the alkoxysilane and water thus prepared is brought into contact with the above-mentioned polysilazane coating film after irradiation with an ultraviolet ray by an appropriate method. Examples of the contacting method include a dipping method and a spraying method. This contact causes a reaction between the polysilazane and the alkoxysilane, which is converted into a ceramic of SiO _x composition. Although the temperature at the time of this contact (for example, the temperature of the immersion liquid) is sufficient at room temperature, it may be heated to a range from room temperature to the boiling point of the mixed solution or lower, if desired. The contact time is not limited, but generally does not exceed one hour, and preferably ranges from 1 to 10 minutes.

By performing these ceramic treatments, the Si-silicon contained in the polysilazane or a modified product thereof is
N, Si-H, NH bonds and the like disappear, and a tough ceramic film mainly composed of Si-O bonds is formed on the substrate surface. Since the SiO ₂ film is derived from polysilazane, it contains 0.005 to 5% of nitrogen in atomic percentage. If the nitrogen content is more than 5%, the film is not sufficiently ceramicized, and the desired effect (for example, abrasion resistance) cannot be obtained. On the other hand, it is difficult to make the nitrogen content less than 0.005%.

The thickness of the SiO ₂ film obtained by one application is preferably 50 ° to 5 μm, more preferably 100 μm.
Å-2 μm. If the film thickness is more than 5 μm, cracks often occur during the heat treatment, and the flexibility is further deteriorated, and cracking or peeling due to bending or the like is likely to occur. Conversely, if the film thickness is less than 50 °, desired effects, for example, desired gas barrier properties and scratch resistance cannot be obtained. This film thickness changes the concentration of the coating composition and / or
Alternatively, it can be controlled by coating conditions.
That is, when it is desired to increase the film thickness, the solid content concentration of the coating composition can be increased (solvent concentration is reduced), the mesh of the roll is made finer, and the coating composition is applied multiple times. By doing so, the film thickness can be further increased.

[0087]

The present invention will be further described with reference to the following examples, but it should be understood that these examples do not limit the present invention.

[0088]Reference example[Synthesis of perhydropolysilazane] A gas blowing tube and a mechanical
I attached a cal stirrer and a dewar condenser. Anti
After replacing the inside of the reactor with deoxygenated dry nitrogen,
Add 490 ml of degassed dry pyridine to Lasco, and add
Was cooled on ice. Then, 51.9 g of dichlorosilane was added.
Then, a white solid adduct (SiCl _Two・ 2C₆H_Five
N). The reaction mixture is cooled on ice and stirred with water.
Ammo purified through sodium oxide tube and activated carbon tube
After blowing in 51.0 g of near, the mixture was heated at 100 ° C.
After completion of the reaction, the reaction mixture was centrifuged, and dried pyridine was removed.
And then filtered under a dry nitrogen atmosphere.
850 ml of filtrate were obtained. Remove solvent under reduced pressure from 5 ml of filtrate
Then, the resinous solid perhydropolysilazane 0.102
g was obtained.

The number average molecular weight of the obtained polymer was measured by a freezing point depression method (solvent: dry benzene).
20. Infrared absorption (IR) spectrum (solvent: dry o-xylene; perhydropolysilazane concentration 10.2)
g / l) are the N of the wave numbers (cm ^-1 ) 3390 and 1180.
-H based absorption, 2170 Si-H based absorption,
It showed absorption of 1040 to 800 based on Si-N-Si.

Method (A): Purification of silane coupling agent
Method for Providing Immer Layer Example 1 Silane Coupling Agent CH ₂ ＣC in Butyl Cell Solve
While stirring CH ₃ COOC ₃ H ₆ Si (OCH ₃ ) ₃ [Nippon Unicar Co., Ltd. A-174], methanol (50% by weight with respect to the silane coupling agent) and distilled water (to the silane coupling agent) were added. (1 molar equivalent) was added dropwise to prepare a primer layer composition having a solid content of 2% by weight. The obtained primer layer composition was
0cm square, 0.3mm thick polycarbonate (PC)
It was applied to a sheet plate by a flow coating method. The PC sheet plate after application was treated at 120 ° C. for 10 minutes to cure the primer layer. The thickness of the obtained primer layer was 0.1 μm.

The perhydropolysilazane synthesized in Reference Example was dissolved in m-xylene to prepare a polysilazane solution having a concentration of 10% by weight. To this solution, 0.01 part by weight of palladium propionate per 1 part by weight of polysilazane was added, and the reaction was carried out while stirring at 20 ° C. for 3 hours in the air. Thereafter, the mixture was filtered through a PTFE filter having a pore size of 0.1 μm. This solution was applied onto the previously prepared primer layer by a spin coating method (500 rpm × 2 seconds → 2000 rpm).
pm × 20 seconds) to form a polysilazane coating film. Thereafter, the polysilazane coating film was treated in a clean oven at 120 ° C. for 1 hour, and then treated in a thermo-hygrostat at 95 ° C. and 80% RH for 3 hours to convert the polysilazane coating film into a ceramic.

Example 2 Except that the substrate was changed to a polyethylene terephthalate (PET) sheet plate having a size of 10 cm square and 1 mm in thickness, and the conditions for ceramic treatment of the polysilazane coating film were changed to 350 ° C. for 1 hour, It was the same as in Example 1. Example 3 A substrate (10 cm square, 75 μm thick polyimide (PI))
Same as Example 1 except that the film was changed.

Example 4 The procedure of Example 1 was repeated except that the substrate was changed to a 10 cm square, 100 μm thick polycarbonate (PC) film. Example 5 A substrate having a size of 10 cm square and 75 μm thick polyarylate (P
Ar) The procedure was the same as in Example 1 except that the film was changed. Example 6 The silane coupling agent was NH ₂ C ₃ H ₆ Si (OC ₂ H
₅ ) _{3 In the same} manner as in Example 1 except that [Nihon Unicar Co., Ltd. A-1100] was used and ethanol was used instead of methanol. Example 7 A substrate (10 cm square, 75 μm thick polyimide (PI))
Example 6 was carried out in the same manner as in Example 6, except that the film was changed to a film, and the conditions for ceramic treatment of the polysilazane coating film were changed to 350 ° C for 1 hour.

Comparative Examples 1 to 7 Comparative Examples 1 to 7 were obtained by directly applying a polysilazane solution on a substrate without providing a primer layer in Examples 1 to 7 described above.

Evaluation of Film Properties The adhesion and abrasion resistance of the ceramic films obtained in Examples 1 to 7 and Comparative Examples 1 to 7 to a substrate were evaluated. -Adhesion: cross cut tape peeling test (JIS-K5400
Compliance).・ Scratch resistance: Steel wool # 000, load 500
g, (2 cm square area) The test was performed under 100 reciprocating conditions, the number of scratches was visually observed, and A to E were rated. Evaluation A: No scratch, Evaluation B: 2 scratches or less, Evaluation C: 3 to 5 scratches, Evaluation D: 6 to 10 scratches, Evaluation E: 11 or more scratches. The evaluation of the film properties is shown below.

[0096] adhesion abrasion whitening example scratches substrate 1 100/100 A Appearance No change Example 2 100/100 A Appearance No change Example 3 100/100 A-B Appearance No change Example 4 100/100 AB No change in appearance Example 5 100/100 AB No change in appearance Example 6 100/100 A No change in appearance Example 7 100/100 AB No change in appearance Comparative Example 10 0/100 E Whitening Comparative Example 2 0/100 E No change in appearance Comparative Example 3 0/100 E No change in appearance Comparative Example 4 0/100 E Whitening Comparative Example 5 0/100 E Whitening Comparative Example 6 0/100 E Whitening Comparative Example 7 0/100 E External View No change

The above data shows that the provision of the primer layer according to the present invention not only imparts solvent resistance to various substrates, but also enhances the adhesion of the ceramic film substantially composed of SiO ₂ to various substrates. Shows that

Method (B): Coat containing polysilazane
Example 8 Method of Adding a Silane Coupling Agent to a Coating Composition Example 8 Perhydropolysilazane synthesized in Reference Example was dissolved in dibutyl ether (DBE). To this solution, 0.01 part by weight of palladium propionate per 1 part by weight of polysilazane was added, and the reaction was carried out while stirring at 20 ° C. for 3 hours in the air. Next, 1% by weight of silane coupling agent NH ₂ C ₃ H ₆ Si based on polysilazane was added to the reaction solution.
(OC ₂ H ₅ ) ₃ [Nihon Unicar Co., Ltd. A-1100]
Was added, the mixture was stirred in the atmosphere at 23 ° C. for 10 minutes, and filtered through a PTFE filter having a pore size of 0.1 μm to prepare a coating solution containing a silane coupling agent. The polysilazane concentration in this solution was 20% by weight. The obtained coating solution is spin-coated on a 10 cm square, 0.3 mm thick PC sheet plate (500 r
pm × 2 seconds → 2000 rpm × 20 seconds) to form a polysilazane coating film containing a silane coupling agent. Thereafter, the polysilazane coating film was treated in a clean oven at 120 ° C. for 1 hour, and then treated in a thermo-hygrostat at 95 ° C. and 80% RH for 3 hours to convert the polysilazane coating film into a ceramic.

Example 9 The procedure of Example 8 was repeated except that the amount of the silane coupling agent was changed from 1% by weight to 10% by weight. Example 10 From 1% by weight to 5% by weight of silane coupling agent
The solvent was changed from DBE to m-xylene, and the substrate was made of a 1 mm thick PET from a PC sheet plate.
Example 8 was carried out in the same manner as in Example 8 except that the sheet plate was changed and the condition of the ceramics treatment was changed to 350 ° C for 1 hour. Example 11 From 1% by weight to 5% by weight of silane coupling agent
, The solvent was changed from DBE to m-xylene, and the substrate was changed from a PC sheet plate to a 75 μm-thick PI film.

Example 12 A coating solution obtained in the same manner as in Example 8 except that the amount of the silane coupling agent added was changed to 5% by weight and the polysilazane concentration was changed to 12% by weight was changed to a film having a thickness of 100 μm. Gravure (reverse) while conveying a PC film with a width of 600 mm and a total length of 300 m at 2 m / min
By coating by a coating method (roll # 80), a polysilazane coating film containing a silane coupling agent was formed.
Next, this film was subjected to a drying treatment for 3 minutes through a drying furnace (120 ° C., 3 m). After drying the film,
A separator sheet was applied to both ends of the film, and the film was wound around a roll while being sandwiched together. Thereafter, the roll body was treated in a clean oven at 120 ° C. for 1 hour, and then in a thermo-hygrostat at 95 ° C. and 80% RH for 3 hours to convert the polysilazane coating into ceramics. Example 13 The procedure of Example 12 was repeated, except that the solvent was changed from DBE to m-xylene, and the substrate was changed from a PC film to a PAm film having a thickness of 75 μm.

Example 14 The silane coupling agent was changed to CH ₂を CCH ₃ COOC ₃ H
₆ Si (OCH ₃ ) ₃ [Nihon Unicar Co., Ltd. A-17
4], except that it was changed to 4). Example 15 Same as Example 14 except that the addition amount of the silane coupling agent was changed from 1% by weight to 10% by weight.

Comparative Examples 8 to 15 In the above Examples 8 to 15, Comparative Examples 8 to 15 were prepared by adding no silane coupling agent to the coating solution containing polysilazane.

Evaluation of Film Properties The ceramic films obtained in Examples 8 to 15 and Comparative Examples 8 to 15 were evaluated for their denseness, adhesion to a substrate, and scratch resistance. Denseness: Evaluated by the corrosion depth (etching rate) of the film per unit time with a 0.5% by weight buffered hydrofluoric acid aqueous solution. -Adhesion: cross cut tape peeling test (JIS-K5400
Compliance).・ Scratch resistance: Steel wool # 000, load 500
g, (2 cm square area) The test was performed under 100 reciprocating conditions, the number of scratches was visually observed, and A to E were rated. Evaluation A: No scratch, Evaluation B: 2 scratches or less, Evaluation C: 3 to 5 scratches, Evaluation D: 6 to 10 scratches, Evaluation E: 11 or more scratches. The evaluation of the film properties is shown below.

Etching Rate Adhesion Scratch Resistance (μm / min) Example 8 0.15 100/100 A Example 9 0.15 100/100 A Example 10 0.15 100/100 A Example 110 15 100/100 AB Example 12 0.15 100/100 AB Example 13 0.15 100/100 AB Example 14 0.15 100/100 A Example 15 0.15 100/100 A Comparative Example 8 0.15 0/100 E Comparative Example 9 0.15 0/100 E Comparative Example 10 0.15 0/100 E Comparative Example 11 0.15 0/100 E Comparative Example 12 0.15 0/100 E Comparative Example 13 0.15 0/100 E Comparative Example 14 0.15 0/100 E Comparative Example 15 0.15 0/100 E

The above data shows that the addition of a silane coupling agent to a coating composition containing polysilazane according to the present invention allows various types of ceramic films to be formed without deteriorating the film density without providing an intermediate layer. This indicates that the adhesion to the material could be improved.

[0106]

According to the present invention, by providing a primer layer containing a silane coupling agent between a base material and a polysilazane coating film, various base materials are imparted with solvent resistance and substantially made of SiO _2. The adhesion of the resulting ceramic film to various substrates can be improved. Further, according to the present invention, by adding a silane coupling agent to the coating composition containing polysilazane, it is possible to enhance the adhesion of the ceramic film substantially composed of SiO ₂ to various substrates without providing an intermediate layer. it can.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AA20B AD00B AH06C AK45 AK52B AK80B AS00C AT00A BA02 BA03 BA10A BA10B EH462 EJ082 EJ422 EJ65C JB07 JK06 4G014 AH00

Claims (2)

[Claims] A coating film containing polysilazane is formed on a substrate, and the coating film is subjected to ceramic treatment to substantially form SiO 2.
_2. A method for forming a ceramic film comprising the step of providing a primer layer containing a silane coupling agent between the substrate and the coating film. 2. A coating composition comprising a polysilazane and a silane coupling agent is prepared, and then a coating film of the coating composition is formed on a substrate, and then the coating film is subjected to a ceramic treatment to substantially form SiO 2. A method characterized by forming a ceramic film comprising ( ₂₎ .