JPH10279362A - Method for forming SiO2 ceramic film - Google Patents

Abstract

(57) [Problem] To improve a manufacturing process of a ceramic film derived from polysilazane. SOLUTION: A coating film containing polysilazane is formed on a substrate surface, and the coating film is subjected to a ceramic treatment to substantially form Si.
In a method of forming a ceramic film made of O ₂ ,
A method comprising the steps of lowering the temperature required for ceramicization and irradiating the coating with ultraviolet light.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for forming a polysilazane-derived SiO ₂ ceramic at a low temperature.

[0002]

2. Description of the Related Art Polysilazane is applied to a material having low heat resistance such as a plastic film in order to impart gas barrier property, scratch resistance, heat resistance, corrosion resistance, flattening property, ion barrier property and the like. 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 herein is called 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 bringing the amine compound and / or the acid compound into contact, a first embodiment in which the amine compound and / or the acid compound is added to 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.

[0004] Japanese Patent Application Laid-Open No. 5-105486 describes that by applying ultraviolet irradiation to a polysilazane coating film, the heating temperature and the heating time during the formation of the silica coating film can be reduced. However, it does not disclose that a catalyst is used to lower the temperature of ceramic formation, and that a film having good gas barrier properties can be obtained when applied to a plastic film.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to increase the efficiency of the above-described method for forming an SiO ₂ ceramic film quickly and at a low temperature. Further, another object of the present invention is to improve film properties such as gas barrier properties, light transmittance, hardness, and adhesion of a finally obtained ceramic film.

[0006]

According to the SUMMARY for the present invention, the above object is achieved, (1) a coating film containing polysilazane is formed on the substrate surface, said coating substantially of SiO ₂ is treated ceramization This is achieved by a method for forming a ceramic film comprising a step of lowering the temperature required for the ceramic formation and a step of irradiating the coating with ultraviolet light.

Hereinafter, preferred embodiments of the present invention will be listed. (2) The step of lowering the temperature required for ceramic formation is a step of subjecting the coating film to a catalytic treatment. (1)
The method described in the section. (3) The method according to (2), wherein the catalyst treatment is performed on the coating film before the ultraviolet irradiation. (4) The method according to (2), wherein the catalyst treatment is performed on the coating film being irradiated with the ultraviolet light. (5) The method according to (2) or (3), wherein the catalyst treatment is a treatment of bringing the coating film into contact with an aqueous solution of an amine and / or an acid. (6) The method according to any one of (2) to (4), wherein the catalyst treatment is a method in which the coating film is brought into contact with a catalyst vapor containing an amine and / or an acid. (7) The polysilazane has the following general formula (I):

[0008]

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(In the above formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a group other than these groups directly bonded to silicon. Represents an alkylsilyl group, an alkylamino group, or an alkoxy group, provided that
Wherein at least one of R ¹ , R ² and R ³ is a hydrogen atom), and is a polysilazane having a number average molecular weight of 100 to 50,000 having a main skeleton consisting of a structural unit represented by (1) to (1). (6) The method according to any one of the above items. (8) The method according to (7), wherein the step of lowering the temperature required for ceramic formation is a step of adding a catalyst to the polysilazane. (9) The polysilazane-modified product obtained by adding the catalyst,
A metal carboxylic acid containing 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 Item (8), which is a metal carboxylate-added polysilazane having a metal carboxylate / polysilazane weight ratio of 0.000001 to 2 and a number average molecular weight of about 200 to 500,000 obtained by reacting the salt. The described method. (10) The method according to (9), wherein the metal is palladium.

(11) The method according to (8), wherein the modified polysilazane obtained by adding the catalyst is an amine compound adduct. (12) The method according to (8), wherein the modified polysilazane obtained by adding the catalyst is an acid compound adduct. (13) Following the step of lowering the temperature required for the ceramic formation and the step of irradiating the coating with ultraviolet light,
The method according to any one of (1) to (12), further comprising performing a heat treatment and / or a post-treatment on the coating film. (14) The method according to (13), wherein the post-treatment is a steam treatment.

(15) A plastic film having an SiO ₂ film containing 0.05 to 5% of atomic percentage of nitrogen formed by the method described in (1) to (14). (16) SiO formed by the method described in (1) to (14) and containing 0.05 to 5% of nitrogen by atomic percentage.
Gas barrier film including _two films. (17) SiO formed by the method described in (1) to (14) and containing 0.05 to 5% of nitrogen by atomic percentage.
Undercoat for touch panels including _two films. (18) A liquid crystal device comprising the plastic film according to the item (15). (19) The plastic film described in (15)
CRT used as RT protection film. (20) A polarizing plate comprising the plastic film according to (15).

According to the present invention, the time required for ceramicizing the coating film is reduced by combining the step of lowering the temperature required for ceramicizing the coating film containing polysilazane and the step of irradiating the coating film with ultraviolet rays. In addition to improving the efficiency of forming the ceramic film, the characteristics of the finally obtained ceramic film are improved, such as the film becoming denser, the abrasion resistance (surface hardness) is increased, and the gas barrier property is improved.

The method for forming a SiO ₂ -based ceramic film according to the present invention comprises a step of lowering the temperature required for ceramicizing a polysilazane-containing coating (lowering step) and a step of irradiating the coating with ultraviolet rays (ultraviolet irradiation step). ). Either of these two steps may be performed first or, where possible, simultaneously. Further, the lowering step may be performed by dividing a plurality of different steps. However, as described below, when the step of lowering the temperature is performed before forming the polysilazane-containing coating, for example, when the step of lowering the temperature is performed before preparing the polysilazane coating composition, the ultraviolet irradiation step is inevitable. This is performed at least after the first temperature lowering step. In general, when an ultraviolet irradiation step is performed after at least one temperature lowering step, the effect of the present invention becomes higher. When the step of lowering the temperature and the step of irradiating ultraviolet rays can be carried out simultaneously, the catalyst lowering step may be brought into contact with the polysilazane-containing coating film as described below. In this case, the polysilazane-containing coating film can be simultaneously subjected to the step of lowering the temperature and the irradiation of ultraviolet rays.

Therefore, the following embodiments can be considered as the basic process sequence of the present invention. (1) Step of lowering temperature → Step of preparing polysilazane coating composition at lower temperature → Step of forming coating film containing polysilazane at lower temperature → Ultraviolet irradiation step (2) First step of lowering temperature → Step of preparing polysilazane coating composition at lower temperature → Lower temperature Of forming polysilazane-containing coating film →
Second low temperature step → ultraviolet irradiation step (3) First low temperature step → Preparation step of low temperature polysilazane coating composition → Formation step of low temperature polysilazane-containing coating film →
UV irradiation step → Second low temperature step (4) First low temperature step → Preparation step of low temperature polysilazane coating composition → Formation step of low temperature polysilazane-containing coating →
Second temperature lowering step and ultraviolet irradiation step (5) Preparation step of polysilazane coating composition → formation of polysilazane-containing coating → low temperature step → ultraviolet irradiation step (6) Preparation step of polysilazane coating composition → preparation of polysilazane-containing coating Formation → Low Temperature Step and UV Irradiation Step Hereinafter, the present invention will be described in detail.

Polysilazane and its modified product The polysilazane used in the present invention has at least S in its molecule.
Any polysilazane having an iH bond or an N--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. The polysilazane to be used includes a polysilazane having a chain, cyclic or crosslinked structure, or a polysilazane having a plurality of these structures in a molecule at the same time, and these can be used alone or in a mixture.

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 general formula (I), those having a hydrogen atom at R ¹ , R ² and R ³ are perhydropolysilazane, and their production methods are described, for example, in 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,

[0017]

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

[0019]

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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 composed of the unit represented by the above general formula (I), but the unit represented by the general formula (I) may be cyclized as is apparent from the above. In the case where is not a cyclic group, the terminal of the main skeleton can be the same group as 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.

[0023]

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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.

[0025]

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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.

[0027]

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In addition, a repeating unit as reported in JP-A-62-195024 may be represented by [(SiH ₂ )
_n (NH) _m ] and [(SiH ₂ ) _r O] (wherein n, m and r are 1, 2 or 3 respectively), JP-A-2-84437. 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) and to improve the hydrolysis resistance (the latter two). 175726, 5-86200, 5-
Copolymerized polysilazane, which is advantageous for thickening the film 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.

First Temperature- Lowering Step According to the present invention, when the low-temperature step is carried out before the formation of the polysilazane-containing coating film, polysilazane or polysilazane which has been subjected to a low-temperature treatment in advance by adding a catalyst to polysilazane or a modified product thereof is used. Hereinafter, low temperature ceramicized polysilazane) can be used. As such a low temperature ceramicized polysilazane, Japanese Patent Application Laid-Open No.
And silicon alkoxide-added polysilazane described in JP-A-238827. This modified polysilazane includes a polysilazane represented by the general formula (I),
The following general formula (II): Si (OR ⁴ ) ₄ (II) (wherein R ⁴ may be the same or different and represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group) Wherein at least one R ⁴ is the above-mentioned alkyl group or aryl group), and the alkoxide-derived silicon / polysilazane-derived silicon atom ratio obtained by heating and reacting the silicon alkoxide is in the range of 0.001 to 3; And it is a silicon alkoxide-added polysilazane having 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, JP-A-6-2 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 has been disclosed.
An acetylacetonate complex-added polysilazane described in JP-A No. 9-No. 9 is exemplified. This modified polysilazane is
The acetylacetonate complex / polysilazane weight ratio obtained by reacting the polysilazane represented by the general formula (I) with an acetylacetonate complex containing nickel, platinum, palladium or aluminum as a metal is 0.00000.
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 acetylacetonato 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.

Another example of the low temperature ceramicized polysilazane is polysilazane added with metal fine particles described in Japanese Patent Application Laid-Open No. 7-19698 filed 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 present applicant
And / or polysilazanes added with amines and / or acids. This modified polysilazane is
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. Representative examples of the amine compound include those represented by the following general formula (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, preferably 100 ppm to 10%, based on the weight of the polysilazane. 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.

The effect of the method according to the present invention, that is, the improvement of the film quality, is particularly remarkable when a low-temperature ceramicized polysilazane as described above in which polysilazane has been subjected to a low-temperature treatment in advance is used. In particular, in the present invention, it is preferable to use a metal silicic acid salt-added polysilazane or an amine compound and / or an acid compound-added polysilazane.

Preparation of Coating Composition According to the present invention, a coating composition containing the above 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,
Halogenated hydrocarbons such as carbon tetrachloride, bromoform, ethylene chloride, ethylidene chloride, trichloroethane, tetrachloroethane, ethyl ether, isopropyl ether, ethyl butyl ether, butyl ether, 1,2-
Ethers such as dioxyethane, dioxane, dimethyldioxane, tetrahydrofuran, 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,
Hydrocarbons such as nonane, decane, n-hexane, pentane, dimethyldiethoxysilane, and methyltriethoxysilane. 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.

The amount (proportion) of the solvent used is selected so as to improve the workability by the coating method to be used, and it varies depending on the average molecular weight, molecular weight distribution and structure of the polysilazane used. . 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.

As an ultraviolet absorber, a substance that absorbs ultraviolet light can be added or added. In particular, addition or addition of a substance having a phenyl group or a C ＝ C bond can be considered. Specifically, diphenylbis (t-
A phenyl group-containing compound such as butylperoxy) silane can be added. Further, the addition of a cinnamyl group by a reaction of cinnamyl alcohol or the like, the addition of an acryl group by a reaction of acryloxypropyldichlorosilane or the like, or the reaction of an acrylate siloxane with the main skeleton of polysilazane to form an acryl group It is possible to give.

The substances (metal carboxylate, amine, etc.) applied in the low temperature step also play a role as an ultraviolet absorber. It is more preferable to use a substance that absorbs ultraviolet rays, particularly a substance having a phenyl group or a C ＝ C bond, as the solvent of the coating composition. As other ultraviolet absorbers, zinc oxide, titanium oxide, and the like are preferable.

[0044] According to the method of the coating material present invention, metal, ceramics, glass,
It is possible to form a SiO ₂ ceramic film on the surface of various kinds of base materials such as the above. According to the method of the present invention, ceramics can be rapidly formed at a low temperature, and therefore, it is particularly advantageous to apply the method to a substrate having low heat resistance, such as a plastic film or an electronic component (eg, a Si wafer). In addition to the advantages derived from being applicable at low temperatures such as not damaging the substrate, the surface smoothness derived from using a solution containing polysilazane and the final film obtained in the present invention are dense siliceous ceramics From these, adhesion, hardness, gas barrier properties, transparency, chemical resistance, flattening properties, ion barrier properties, etc. can be imparted to the base material, so that one or more of these properties are required. It is suitably used in the field.

For example, at a low temperature, a plastic film is used as a base material, and a silica film requiring surface smoothness, gas barrier properties and transparency can be applied to the base material. It is. Examples of products using these include an electrode film for a liquid crystal display element using a plastic film such as polyethersulfone as a substrate, an electroluminescence device, and the like. In addition, since it can be applied at a low temperature and a flat and dense silica film can be obtained, it is understood that an electronic device such as a semiconductor device provided with wiring can be suitably used as a substrate. Furthermore, since it can be applied at a low temperature, a silica film can be applied to a substrate that has already been subjected to a treatment such as an ITO treatment without damaging the pretreatment.

In addition, since one or more of the above properties are also required without damaging the base material, a hard coat of a CRT protective film, a polarizing plate used in an optical field such as a liquid crystal field, a gas or water vapor, etc. Can be suitably used suitably for a barrier coat, an undercoat of a touch panel, and the like. When the SiO ₂ -based ceramic film of the present invention is applied to a semiconductor device, it can be used as various insulating films, so that it can be applied to portions conventionally provided for the purpose of insulation. For example, it can be provided between a semiconductor substrate and a metal wiring layer, between metal wiring layers, or on various elements provided on a semiconductor substrate. In the liquid crystal field, the present invention can be applied to a portion conventionally provided to impart ion barrier properties, gas barrier properties, and hardness. For example, a gas barrier property and hardness may be provided between a transparent conductive film such as ITO as an alkali passivation film and a glass or film substrate, or on a liquid crystal element in which ITO is applied to a glass or film substrate as an alignment film to provide a liquid barrier. It is provided to increase the life of the element. In addition, in order to eliminate steps on the electrode surface of the color liquid crystal display device and eliminate color unevenness of a displayed image, and to flatten the steps, the SiO ₂ ceramic film of the present invention is applied on an electrode or a color filter. It can also be applied. It is possible to apply the method of the present invention to SiO ₂ portions that have been conventionally manufactured by another method. It is easy to apply the above characteristics if the field requires one kind or particularly two or more kinds.

Examples of plastic materials include polyethylene terephthalate (PET), polyimide (PI; for example, a polycondensation product of pyromellitic anhydride and diaminodiphenyl ether marketed under the trade name Kapton), polycarbonate (PC), Axial oriented polypropylene (OPP), polyphenylene sulfide (PP
S), polyvinyl alcohol (PVA), polyethylene naphthalate (PEN), polyether sulfone (PE)
S), polyetherimide (PEI), polyetheretherketone (PEEK), polyarylate (PA
R), polystyrene, polyamide (nylon (trade mark)), polyamide imide, polyvinyl chloride, polyester resin (eg, LISA, ISARYL (registered trademark)), acrylic resin (eg, polymethyl methacrylate (PMMA)) , Polynorbornene-based resin (ARTON (registered trademark), manufactured by Nippon Synthetic Rubber Co., Ltd.), ZEONEX (registered trademark, manufactured by Nippon Zeon Co., Ltd.), and artificial resin films such as cellulose acetate and triacetyl cellulose (TAC). Or a sheet-like material, a composite film thereof or a composite sheet thereof, a biaxially stretched para-aramid film, a norbornene-based polyolefin film, an ultrathin film with a support, and the like. There is no particular limitation on the area and thickness of the plastic film, and a film having an arbitrary area and thickness depending on the use such as a long film can be used. Furthermore, a multilayer film in which two or more of these films or sheets are laminated may be used. In addition, the film may be subjected to a pretreatment such as a corona discharge treatment, an application of a silane coupling agent, etc. to improve adhesion,
Well-known processing can be performed according to the application.

[0048] According to the coating method of the present invention, to form a film of polysilazane by applying a coating composition as described above to various substrates as described above. The coating method is a commonly used coating method, for example, dip coating, roll coating, bar coating,
Web application (gravure, kiss, kissmeyer bar, die,
Flexo, etc.), brush coating, spray coating, spin coating,
Flow coating or the like is used. 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.

Second Temperature- Lowering Step According to the present invention, when the low-temperature step is carried out on a polysilazane-containing coating film, as a first embodiment,
Vapor generated from an aqueous solution containing an amine compound and / or an acid compound can be brought into contact. Examples of the amine compound and the acid compound include those described above. According to the mode in which a vapor generated from an aqueous solution containing an amine compound and / or an acid compound is brought into contact with the polysilazane-containing coating film, the above-mentioned coating film of polysilazane or a modified product thereof is formed on the substrate surface, Before, during, or after irradiating the coating film with ultraviolet light, the polysilazane and the amine compound are exposed to a vapor generated from an aqueous solution containing an amine compound and / or an acid compound as described above. And / or an acid compound. 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 may be 0.1 ppm or more, preferably 10 ppm to 10%. A particularly preferred amine compound in this first embodiment is triethylamine. Room temperature is sufficient for generating steam, but 0 ° C.
To the aqueous solution boiling point.

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 transported to the solvent drying zone by a carrier gas, and can be sprayed on 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 supplied stably. Furthermore, the use of an inert gas such as nitrogen gas does not adversely affect the curing of the polysilazane coating film. Under such an inert gas atmosphere, the danger of explosion due to amine compounds is reduced. Is also advantageous.

According to the second embodiment, after the coating film of the polysilazane or a modified product thereof is formed on the surface of the base material, the coating film is irradiated with the ultraviolet light as described above before, while irradiating, or After the irradiation, the polysilazane can be brought into contact with the amine compound and / or the acid compound by immersing the polysilazane in the aqueous solution containing the amine compound and / or the acid compound as described above. 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, if necessary, the treated polysilazane-coated sample (eg, film, silicon wafer) is exposed to a steam atmosphere.
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. Is generally used in a humidifier or steam. Specifically, a method in which steam is introduced into a solvent drying zone and passed through the inside thereof (at a temperature of 50 to 100 ° C. and a relative humidity of 50 to 100% RH) for a residence time of 10 to 60 minutes, A method is conceivable in which steam is passed again through the solvent drying zone in which steam that has passed during drying is introduced with a residence time of 10 to 60 minutes. 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,
Organic acids such as lower monocarboxylic acids such as acetic acid, propionic acid and caproic acid or anhydrides thereof, lower dicarboxylic acids such as oxalic acid, fumaric acid, maleic acid and succinic acid or anhydride thereof, and trichloroacetic acid; Chloric acid, hydrochloric acid,
Nitric acid, sulfuric acid, sulfonic acid, paratoluenesulfonic acid, boron trifluoride and its complex with electron donor, etc .; SnC
l ₄ , ZnCl ₂ , FeCl ₃ , AlCl ₃ , SbCl
₃ , Lewis acids such as TiCl ₄ and complexes thereof, and the like. In addition to the above-mentioned amine compound,
Sodium hydroxide, ammonium chloride, potassium hydroxide, lithium hydroxide, pyridine, ammonia, and the like.

In the leaving treatment in the air, when the long plastic film is converted into ceramics, it is preferable to wind the film after the treatment of the first or second mode together with the separator sheet into a roll. The separator sheet is a sheet-like material for preventing the wound films from coming into contact with each other, and is applied to the entire surface or a part of the polysilazane-coated film (for example, one at each end of the coated film). Nonwoven fabric, side tape, embossed film, etc. The side tape preferably has a thickness of about 12 to 100 μm and a width of about 10 to 30 mm, and commercially available products of various materials can be used. As a specific example of a commercially available product, PET film [Lumirror X-42 manufactured by Toray Co., Ltd.
45, Lumimat manufactured by Panac), foamed PET film (Crisper manufactured by Toyobo Co., Ltd.), PET film laminated or vapor-deposited with Al (Alpet film manufactured by Panac), 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 embossed on both sides of the film [706410 manufactured by Dainichi Kasei Kogyo Co., Ltd.]
H12 or 706420H12].

For the method of winding a polysilazane-coated film using the separator sheet, see Japanese Patent Application No. 7-59259 by the present applicant. It is preferable that the condition for the standing treatment is 3 to 24 hours at around room temperature (about 10 ° C.) to 60 ° C., preferably about 25 ° C., and a relative humidity of 10 to 90% RH, preferably 50 to 70% RH.

[0056] According to the ultraviolet radiation present invention, after coating the above method, prior to the low temperature step, after the cold reduction step, or the low-temperature step at the same time, irradiated with ultraviolet rays to the coating film containing polysilazane. The substrate is heated by this ultraviolet irradiation, and O ₂ and H ₂ O, which contribute to ceramic conversion (silica conversion), an ultraviolet absorber, and polysilazane itself are excited and activated. Ceramics are promoted,
Further, the obtained ceramic film becomes more dense. Irradiation with ultraviolet light is effective even if it is performed at any time after the formation of the coating film. That is, before the coating film is dried immediately after the formation of the coating film containing 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 the method of the present invention, any commonly used ultraviolet ray generator can be used. As used herein, the term “ultraviolet light” refers to radiation that includes a generally understood wavelength, specifically, UV light having a wavelength of 400 nm or less, X-rays, and electron beams. In a preferred embodiment of the method of the present invention, ultraviolet light of 150 to 400 nm, more preferably 200 to 350 nm is used.

The irradiation of the ultraviolet rays is performed under the irradiation intensity and / or range within a range where the substrate supporting the coating film to be irradiated is not damaged.
Alternatively, the irradiation time should be set. Taking a case where a plastic film is used as a base material as an example, 2 kW (80
(W / cm × 25 cm) using a lamp having a substrate surface strength of 20 to 300 mW / cm ² , preferably 50 to 200 mW / cm ² .
mW / cm ² so that the distance between the substrate and the lamp (eg, 1
5 cm), and irradiation can be performed for 0.05 to 3 minutes.

Generally, when the substrate temperature during the ultraviolet irradiation treatment is 1
When the temperature is 50 ° C. or higher, the base material is damaged such as deformation of the base material or deterioration of the strength in the case of a plastic film or the like. However, in the case of a film having high heat resistance such as polyimide, or a substrate such as a silicon wafer, glass, metal, etc., processing at a higher temperature is possible. The conversion method can complete the ceramic formation only by the ultraviolet irradiation step, and is actually effective in improving the film characteristics. Therefore, there is no general upper limit for the substrate temperature during the irradiation of ultraviolet rays, and a person skilled in the art can appropriately set the temperature according to the type of the substrate. There is no particular limitation on the atmosphere in which the ultraviolet light is irradiated, and the irradiation may be performed in air.

As a method for generating such an ultraviolet ray, for example, a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a xenon arc lamp, a carbon arc lamp, and an excimer lamp (1172 nm, 222 nm, 30 nm)
8 nm single wavelength, for example, Ushio Inc.), U
V-light lasers, etc., are not particularly limited. Also, when irradiating the generated ultraviolet rays to the polysilazane coating film, in order to achieve uniform irradiation to improve efficiency, the ultraviolet rays from the source should be reflected by a reflector before being applied to the coating film. Is desirable.

The UV irradiation is applicable to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be coated. For example, in the case of batch processing, a base material (eg, a silicon wafer) having a polysilazane coating film on its surface can be processed in an ultraviolet firing furnace equipped with the above-described ultraviolet light source. The ultraviolet firing furnace itself is generally known, and for example, a product manufactured by Eye Graphics Co., Ltd. can be used. When the substrate having a polysilazane coating film on the surface is in the form of a long film, the ceramic is continuously irradiated with ultraviolet rays in a drying zone equipped with the above-mentioned ultraviolet ray generating source while being conveyed. Can be The time required for UV irradiation
Although it depends on the composition and concentration of the substrate to be applied and the coating composition, it is generally 0.02 to 10 minutes, preferably 0.05 to 10 minutes.
~ 3 minutes.

Irradiation of Infrared (Optional) According to the present invention, it is possible to further promote the formation of ceramics of the coating film by irradiating infrared rays to the coating film containing polysilazane, if necessary, in addition to the above-mentioned ultraviolet irradiation. 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.

When irradiating infrared rays, any commonly used infrared ray 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.

Irradiation with infrared rays is carried out at a temperature lower than the heat-resistant temperature of the substrate supporting the coating film to be irradiated, depending on the type of the substrate.
Hereinafter, the irradiation intensity is adjusted so that the temperature is preferably maintained at 100 ° C. or lower. There is no particular limitation on the atmosphere for infrared irradiation, and the irradiation may be performed in air. Examples of a method for generating such infrared rays include a method using an infrared radiator and an infrared ceramic heater, but are not particularly limited. When an infrared radiator is used, a near-infrared radiator having an intensity peak at a wavelength of 1.3 μm, a mid-infrared radiator having an intensity peak at a wavelength of 2.5 μm, and a wavelength of 4.5 μm are used, depending on the wavelength of infrared light used. Far infrared radiators with intensity peaks can be used.

In order to improve the irradiation efficiency,
Only illuminated at wavelengths that are effective in turning lysilazane into ceramics
The infrared laser that has a single spectrum.
It is preferred to use. As a specific example of infrared laser
, HF, DF, HCl, DCl, HBr, DBr, etc.
Gas chemical laser (irradiation wavelength 2.5-6 μm), CO
_TwoGas laser, N_TwoO gas laser (irradiation wavelength about 10
μm), CO_TwoGas laser pumped far infrared laser (NH
_Three, CF_Four, Etc.) (irradiation wavelength 12-16 μm), Pb
(Cd) S, PbS (Se), Pb (Sn) Te, Pb
(Sn) Se, compound semiconductor laser (irradiation wavelength
2.5 to 20 μm). Also generated
When irradiating infrared rays to the polysilazane coating film,
In order to achieve uniform irradiation because of the above,
It is desirable to reflect the infrared rays on the
Good.

As in the case of the above-described ultraviolet irradiation, the infrared irradiation can be applied to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be coated. For example, in the case of batch processing, a substrate (eg, a silicon wafer) having a polysilazane coating film on the surface can be processed in an infrared firing furnace equipped with an infrared source as described above. The infrared firing furnace itself is generally known, and for example, a product made by ULVAC can be used. When the substrate having a polysilazane coating film on the surface thereof is in the form of a long film, the ceramics are continuously irradiated with infrared rays in a drying zone equipped with an infrared source as described above while being conveyed. Can be promoted.
This infrared irradiation may be performed alone or in combination with conventional hot air drying. However, in order to promote the removal of the evaporated solvent, it is preferable to combine infrared irradiation and hot air drying. An example of a commercially available continuous drying apparatus combining infrared irradiation and hot air drying in this manner is an IR float dryer (trade name) manufactured by Inoue Metal Industry Co., Ltd. When performing infrared irradiation, the required time is generally 0.1 to 10 minutes, preferably 1 to 10, depending on the composition and concentration of the substrate or coating composition to be applied.
3 minutes.

Additional ceramic treatment (heat treatment and / or
According to the present invention, the target SiO ₂ ceramic film can be obtained by subjecting the polysilazane-containing coating film to a low-temperature step and ultraviolet irradiation. However, by further adding another ceramic treatment to the low-temperature step and the ultraviolet irradiation, the ceramic formation can be further promoted. Hereinafter, this additional ceramicization treatment will be described.

In the above-mentioned lowering temperature step and ultraviolet irradiation, Si—O, Si—N, Si—H, N
A film in which -H exists is formed. At this point, a part of the polysilazane coating may be ceramicized,
The coating may still be incompletely converted to ceramics. This coating can be converted to ceramics by the heat treatment and / or post-treatment described below.

When a heat treatment is employed, the heat treatment temperature is a temperature at which the polysilazane is completely turned into ceramics, usually 4 ° C.
Although the temperature is preferably at least 00 ° C., for example, when coating is applied to the outside of a device containing a liquid crystal, the temperature is lower than the heat resistance temperature of the liquid crystal to be used, generally 240 ° C. or less, preferably 2 ° C. or less.
It is preferable to adopt a temperature of 00 ° C. or lower. However,
Since the polysilazane according to the present invention has been subjected to the step of lowering the temperature, it can be subjected to a heat treatment at a low temperature that does not impair the liquid crystal and / or the base material (particularly, plastic or tempered glass), preferably at 150 ° C. or lower. 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 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-mentioned 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 when the post-treatment is directly performed without the heat treatment at a low temperature as described above, 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 effects (for example, gas barrier properties and abrasion resistance) cannot be obtained. On the other hand, it is difficult to make the nitrogen content less than 0.05%. 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.

[0075] 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, a polysilazane-containing coating film is formed, the coating film is subjected to a step of lowering the temperature and ultraviolet irradiation, and then a reactive mixed solution containing alkoxysilane and water is applied to the coating film. May be contacted. 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 In the} formula, each R is independently an alkoxysilane represented by 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)
_3-m R ′ _m [wherein, R independently represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylamino group or an alkylsilyl group, and R ′ is each independently the above 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 way that the final ceramic coating obtained has the desired film quality (eg, heat resistance, abrasion resistance,
(Flexibility) can be appropriately selected by those skilled in the art.

The water (H
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 used, if necessary, with R ″ OH
Can be contained. Here, R ″ represents the same group as R described above for the 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 ratio of the alkoxysilane to the alcohol in the mixed solution is preferably in the range of 100 to 0.01, more preferably 10 to 0.1, on a volume basis. This ratio is 10
When it is larger than 0, the decomposition of the alkoxysilane is small,
The reactivity of the solution is reduced. 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 ultraviolet rays 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.

After the step of contacting with the mixed solution, the post-heating step can be carried out at a temperature lower than the heat-resistant temperature of the substrate for the purpose of drying the obtained film and improving the film quality. The formation reaction of the ceramic film between polysilazane and alkoxysilane is considered to be based on the following three elementary reactions. That is, in the mixed solution, the alkoxysilane is hydrolyzed as in the following formula: ≡Si—OR + H ₂ O—> ≡Si—OH + ROH, and the silanol group generated at this time is converted into the following formula: ≡Si— OH + ≡Si-H-> ≡Si-O-Si≡ + H ₂ ≡Si-OH + ≡Si-NH-Si≡-> ≡Si-O-Si≡ + ≡Si-NH ₂ The film is converted to SiO _x by reacting with the Si—H and / or N—H bonds of the polysilazane. According to this method, a dense S-substrate substantially containing Si—O bonds
An iO ₂ ceramic coating can be obtained at room temperature and in a short time.

By combining the above-mentioned low-temperature step and the ultraviolet irradiation step, and further performing an additional ceramic treatment as necessary, the Si—N, Si—H, and N—H bonds contained in polysilazane or a modified product thereof are obtained. Etc. disappear,
A tough ceramic film mainly composed of Si—O bonds is formed on the surface of the base material. The SiO ₂ film is derived from polysilazane and 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 effects (eg, gas barrier properties and abrasion resistance) cannot be obtained. On the other hand, it is difficult to make the nitrogen content less than 0.005%. When an amine compound is used, the amine compound may be contained in the SiO ₂ film. This can be controlled by the type of the amine compound and the conditions for ceramic formation, and it is easy to produce a SiO ₂ film containing no amine at all.

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 abrasion 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 of the coating composition can be increased (solvent concentration can be reduced), the mesh of the roll can be made finer, and the coating composition can be applied multiple times. By doing so, the film thickness can be further increased.

In order to impart other functions, it is possible to add a conventional functional filler or to laminate various layers. For example, it is possible to add conductive fine particles to impart conductivity, or to laminate a flexible intermediate layer to impart flexibility.
In the SiO ₂ film thus formed, since the ceramicization of the coating film is promoted by the low-temperature step and the ultraviolet irradiation, the characteristics of the finally obtained ceramic film are improved as compared with the case where the ultraviolet irradiation is not performed.

[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.

Example 1 Perhydropolysilazane synthesized in Reference Example was dissolved in m-xylene to prepare a 12% by weight polysilazane solution. 0.01 part by weight of polysilazane is added to this solution.
Add parts by weight of palladium propionate and add
The reaction was carried out with stirring at 0 ° C. for 3 hours. Thereafter, the mixture was filtered through a PTFE filter having a pore size of 0.1 μm. This solution was mixed with a polyethylene terephthalate (PET) film substrate having a thickness of 75 μm, a width of 60 cm, and a total length of 300 m.
It was applied on one side by a gravure (reverse) coating method (roll # 80) while conveying at m / min. After application, metal halide lamp (irradiation conditions: output 2 kW, distance 25 cm)
For 1 minute. Next, the polysilazane coating film was dried by passing through a solvent drying zone (120 ° C., 2 minutes). After passing through the drying zone, the polysilazane-coated film was wound around a roll while applying a side tape to both ends of the film and sandwiching the same together. Thereafter, the roll was treated at 95 ° C. and 80% RH for 2 hours.

Comparative Example 1 Perhydropolysilazane synthesized in Reference Example was dissolved in m-xylene to prepare a polysilazane solution having a concentration of 12% by weight. 0.01 part by weight of polysilazane is added to this solution.
Add parts by weight of palladium propionate and add
The reaction was carried out with stirring at 0 ° C. for 3 hours. Thereafter, the mixture was filtered through a PTFE filter having a pore size of 0.1 μm. This solution was mixed with a polyethylene terephthalate (PET) film substrate having a thickness of 75 μm, a width of 60 cm, and a total length of 300 m.
It was applied on one side by a gravure (reverse) coating method (roll # 80) while conveying at m / min. After coating, the polysilazane coating film was dried by passing through a solvent drying zone (120 ° C., 3 minutes). After passing through the drying zone, the polysilazane-coated film was wound around a roll while applying a side tape to both ends of the film and sandwiching the same together. Thereafter, the roll was treated at 120 ° C. for 1 hour, and further treated at 95 ° C. and 80% RH for 3 hours.

Example 2 Perhydropolysilazane synthesized in Reference Example was dissolved in m-xylene to prepare a polysilazane solution having a concentration of 12% by weight. 0.01 part by weight of polysilazane is added to this solution.
Add parts by weight of palladium propionate and add
The reaction was carried out with stirring at 0 ° C. for 3 hours. Thereafter, the mixture was filtered through a PTFE filter having a pore size of 0.1 μm. This solution was mixed with a polyethylene terephthalate (PET) film substrate having a thickness of 75 μm, a width of 60 cm, and a total length of 300 m.
It was applied on one side by a gravure (reverse) coating method (roll # 80) while conveying at m / min. After the application, ultraviolet rays were irradiated for 1 minute by a high-pressure mercury lamp (irradiation conditions: output 2 kW, distance 25 cm). Next, the solvent drying zone (1)
(20 ° C., 2 minutes) to dry the polysilazane coating film. After passing through the drying zone, the polysilazane-coated film was wound around a roll while applying a side tape to both ends of the film and sandwiching the same together. Thereafter, the roll was treated at 95 ° C. and 80% RH for 2 hours.

Example 3 Perhydropolysilazane synthesized in Reference Example was dissolved in m-xylene to prepare a 12% by weight polysilazane solution. 0.01 part by weight of polysilazane is added to this solution.
Add parts by weight of palladium propionate and add
The reaction was carried out with stirring at 0 ° C. for 3 hours. Thereafter, the mixture was filtered through a PTFE filter having a pore size of 0.1 μm. This solution was mixed with a polyethylene terephthalate (PET) film substrate having a thickness of 75 μm, a width of 60 cm, and a total length of 300 m.
It was applied on one side by a gravure (reverse) coating method (roll # 80) while conveying at m / min. After application, 222n
m excimer lamp (irradiation conditions: output 1 kW, distance 5 c
m) for 1 minute. Next, the polysilazane coating film was dried by passing through a solvent drying zone (120 ° C., 2 minutes). After passing through the drying zone, the polysilazane-coated film was wound around a roll while applying a side tape to both ends of the film and sandwiching the same together. Thereafter, the roll was treated at 95 ° C. and 80% RH for 2 hours.

Example 4 Perhydropolysilazane synthesized in Reference Example was dissolved in m-xylene to prepare a 12% by weight polysilazane solution. 0.01 part by weight of polysilazane is added to this solution.
Add parts by weight of palladium propionate and add
The reaction was carried out with stirring at 0 ° C. for 3 hours. Thereafter, the mixture was filtered through a PTFE filter having a pore size of 0.1 μm. The gravure (reverse) coating method (roll # 8) is applied to this solution while transporting a triacetate (TAC) film substrate having a thickness of 80 μm, a width of 60 cm and a total length of 300 m at 2 m / min.
0) was applied on one side. After coating, the solvent drying zone (12
(0 ° C., 2 minutes) to dry the polysilazane coating film. Next, ultraviolet rays were irradiated for 1 minute using a metal halide lamp (irradiation conditions: output 2 kW, distance 30 cm). After passing through the drying zone, the polysilazane-coated film was wound around a roll while applying a side tape to both ends of the film and sandwiching the same together. afterwards,
The roll is treated at 120 ° C. for 1 hour,
The mixture was treated at 80 ° C. and 80% RH for 1 hour.

Example 5 Perhydropolysilazane synthesized in Reference Example was dissolved in m-xylene to prepare a 12% by weight polysilazane solution. 0.01 part by weight of polysilazane is added to this solution.
Add parts by weight of palladium propionate and add
The reaction was carried out with stirring at 0 ° C. for 3 hours. Thereafter, the mixture was filtered through a PTFE filter having a pore size of 0.1 μm. This solution was mixed with a polyethersulfone (PES) film substrate having a thickness of 75 μm, a width of 60 cm, and a total length of 300 m at 2 m /
Gravure (reverse) coating method (roll # 80) on one side while conveying in minutes. After the application, ultraviolet rays were irradiated for 1 minute by a metal halide lamp (irradiation conditions: output 2 kW, distance 25 cm). Next, the solvent drying zone (1)
(50 ° C., 2 minutes) to dry the polysilazane coating film. After passing through the drying zone, the polysilazane-coated film was wound around a roll while applying a side tape to both ends of the film and sandwiching the same together. Thereafter, the roll was treated at 150 ° C. for 0.5 hour, and further treated at 95 ° C. and 80% RH for 1 hour.

Example 6 Perhydropolysilazane synthesized in Reference Example was dissolved in m-xylene to prepare a 12% by weight polysilazane solution. 0.01 part by weight of polysilazane is added to this solution.
Add parts by weight of palladium propionate and add
The reaction was carried out with stirring at 0 ° C. for 3 hours. Thereafter, the mixture was filtered through a PTFE filter having a pore size of 0.1 μm. This solution was applied to a 10 cm square, 1 mm thick glass plate using a dip coating method. After the application, ultraviolet rays were irradiated by a metal halide lamp (irradiation conditions: output 2 kW, distance 15 cm).
Irradiated for minutes. After the ultraviolet irradiation, a heat treatment was performed at 250 ° C. for 40 minutes.

Comparative Example 2 Perhydropolysilazane synthesized in Reference Example was dissolved in m-xylene to prepare a polysilazane solution having a concentration of 12% by weight. 0.01 part by weight of polysilazane is added to this solution.
Add parts by weight of palladium propionate and add
The reaction was carried out with stirring at 0 ° C. for 3 hours. Thereafter, the mixture was filtered through a PTFE filter having a pore size of 0.1 μm. This solution was applied to a 10 cm square, 1 mm thick glass plate using a dip coating method. After the application, heat treatment was performed at 250 ° C. for 60 minutes.

Example 7 Perhydropolysilazane synthesized in Reference Example was dissolved in m-xylene to prepare a polysilazane solution having a concentration of 12% by weight. To this solution was added propionic acid to a concentration of 5% by weight. This solution was used to prepare polyethylene terephthalate (PET) having a thickness of 75 μm, a width of 60 cm and a total length of 300 m
The film substrate was applied on one side by a gravure (reverse) coating method (roll # 80) while being conveyed at 2 m / min. After coating, a high-pressure mercury lamp (irradiation conditions: output 2 kW, distance 2
5 cm) for 1 minute. Next, by passing through a solvent drying zone (80 ° C., 2 minutes)
The polysilazane coating was dried. Once the polysilazane-coated film that has passed through the drying zone is once wound up and then unwound, the film is passed through a humidifying furnace in a steam atmosphere (95 ° C., 60% RH), so that the polysilazane coating film is formed.
Exposure to a water vapor atmosphere for minutes.

Example 8 Perhydropolysilazane synthesized in Reference Example was dissolved in dibutyl ether to prepare a polysilazane solution having a concentration of 12% by weight. To this solution was added triethylamine to a concentration of 25% by weight. This solution is 75 μm thick and 6 μm wide.
A polyarylate (PAr) film substrate having a total length of 0 cm and a total length of 300 m was applied to one surface by a gravure (reverse) coating method (roll # 80) while being conveyed at 2 m / min. After the application, ultraviolet rays were irradiated for 1 minute by a metal halide lamp (irradiation conditions: output 2 kW, distance 25 cm). Then
The polysilazane coating film was dried by passing through a solvent drying zone (80 ° C., 2 minutes). The polysilazane-coated film that had passed through the drying zone was once wound up, and then unwound while passing through a humidifying furnace in a steam atmosphere (95 ° C., 60% RH), thereby exposing the polysilazane coating film to a steam atmosphere for 7 minutes.

Example 9 Perhydropolysilazane synthesized in Reference Example was dissolved in m-xylene to prepare a 12% by weight polysilazane solution. To this solution was added tripentylamine to a concentration of 25% by weight. This solution is 100 μm thick and 6 μm wide.
0cm, total length 300m polyethersulfone (P
ES) The film substrate was coated on one side by a gravure (reverse) coating method (roll # 80) while being conveyed at 2 m / min. After application, metal halide lamp (irradiation condition: output 2
(kW, distance 25 cm) for 1 minute.
Next, the polysilazane coating film was dried by passing through a solvent drying zone (80 ° C., 2 minutes). The polysilazane-coated film that has passed through the drying zone is once wound up,
Then, unwind and steam atmosphere (95 ° C, 60% R
The polysilazane coating film was exposed to a steam atmosphere for 7 minutes by passing through the humidifying furnace of H).

Comparative Example 3 Perhydropolysilazane synthesized in Reference Example was dissolved in m-xylene to prepare a polysilazane solution having a concentration of 12% by weight. To this solution was added tripentylamine to a concentration of 25% by weight. This solution is 100 μm thick and 6 μm wide.
0cm, total length 300m polyethersulfone (P
ES) The film substrate was coated on one side by a gravure (reverse) coating method (roll # 80) while being conveyed at 2 m / min. After coating, the polysilazane coating film was dried by passing through a solvent drying zone (80 ° C., 3 minutes). The polysilazane-coated film that has passed through the drying zone is once wound up, and then unwound, and then steamed (at 95 ° C., 60 ° C.).
% RH), the polysilazane coating was exposed to a water vapor atmosphere for 10 minutes.

Example 10 Perhydropolysilazane synthesized in Reference Example was dissolved in m-xylene to prepare a polysilazane solution having a concentration of 12% by weight. Octylamine was added to this solution to a concentration of 25% by weight. This solution is 80 μm thick and 60 c wide.
gravure (reverse) while transporting a triacetate (TAC) film substrate with a total length of 300 m at 2 m / min
It was applied to one side by a coating method (roll # 80). After application,
The polysilazane coating film was dried by passing through a solvent drying zone (80 ° C., 2 minutes). Next, ultraviolet rays were irradiated for 1 minute using a high-pressure mercury lamp (irradiation conditions: output 2 kW, distance 30 cm). The polysilazane-coated film after the ultraviolet irradiation was once wound up, and then passed through a humidifier in a steam atmosphere (95 ° C., 60% RH) while unwinding, thereby exposing the polysilazane coating film to the steam atmosphere for 7 minutes.

Example 11 Perhydropolysilazane synthesized in Reference Example was dissolved in m-xylene to prepare a 12% by weight polysilazane solution. To this solution, propionic acid and tripentylamine were added so as to be 5% by weight and 5% by weight, respectively. This solution was applied to a 10 cm square, 1 mm thick polymethyl methacrylate (PMMA) sheet using a dip coating method. After the application, ultraviolet rays were irradiated for 1 minute by a metal halide lamp (irradiation conditions: output 2 kW, distance 30 cm). After the UV irradiation, the polysilazane coating
The treatment was performed for 7 minutes in a thermo-hygrostat at 60 ° C. and 60% RH.

Example 12 Perhydropolysilazane synthesized in Reference Example was dissolved in dibutyl ether to prepare a 12% by weight polysilazane solution. This solution was applied to one surface by a gravure (reverse) coating method (roll # 80) while conveying a polyarylate (PAr) film substrate having a thickness of 75 μm, a width of 60 cm, and a total length of 300 m at 2 m / min. After the application, 36% hydrochloric acid was bubbled with nitrogen at room temperature and transported inside a zone (30 ° C., 40% RH) in which hydrogen chloride gas was generated, and the coating film was exposed to hydrogen chloride gas for 2 minutes. . Next, a metal halide lamp (irradiation condition: output 2 kW,
(A distance of 25 cm). The ultraviolet-irradiated polysilazane-coated film is once wound up and then unwound while in a steam atmosphere (95 ° C., 60% R).
The polysilazane coating film was exposed to a steam atmosphere for 3 minutes by passing through the humidifying furnace of H).

Example 13 Perhydropolysilazane synthesized in Reference Example was dissolved in dibutyl ether to prepare a 12% by weight polysilazane solution. This solution is gravure (reverse) while conveying a polyvinyl alcohol (PVA) film base material having a thickness of 60 μm, a width of 60 cm and a total length of 300 m at 2 m / min.
It was applied to one side by a coating method (roll # 80). After application,
The film is transported in a zone (30 ° C., 40% RH) into which methylamine vapor generated by mixing a water-containing nitrogen flow through water and methylamine from a liquefied cylinder is introduced, and the coating film is converted into methylamine gas. Exposure was for 2 minutes. Next, ultraviolet rays were irradiated for 1 minute using a high-pressure mercury lamp (irradiation conditions: output 2 kW, distance 30 cm). The polysilazane-coated film after the ultraviolet irradiation was once wound up, and then passed through a humidifier in a steam atmosphere (95 ° C., 60% RH) while being unwound, thereby exposing the polysilazane coating film to the steam atmosphere for 3 minutes.

Example 14 Perhydropolysilazane synthesized in Reference Example was dissolved in dibutyl ether to prepare a polysilazane solution having a concentration of 12% by weight. This solution is 100 μm thick, 60 cm wide,
A polycarbonate (PC) film substrate having a total length of 300 m was applied to one surface by a gravure (reverse) coating method (roll # 80) while being conveyed at 2 m / min. After the application, triethylamine and distilled water were bubbled with nitrogen at room temperature and transported in a zone (30 ° C., 40% RH) in which triethylamine gas was generated, and the coating film was exposed to triethylamine gas for 2 minutes. Next, ultraviolet rays were irradiated for 1 minute using a metal halide lamp (irradiation conditions: output 2 kW, distance 30 cm). The polysilazane-coated film after the ultraviolet irradiation was once wound up, and then passed through a humidifier in a steam atmosphere (95 ° C., 60% RH) while being unwound, thereby exposing the polysilazane coating film to the steam atmosphere for 3 minutes.

Comparative Example 4 Perhydropolysilazane synthesized in Reference Example was dissolved in dibutyl ether to prepare a 12% by weight polysilazane solution. This solution is 100 μm thick, 60 cm wide,
A polycarbonate (PC) film substrate having a total length of 300 m was applied to one surface by a gravure (reverse) coating method (roll # 80) while being conveyed at 2 m / min. After the application, triethylamine and distilled water were bubbled with nitrogen at room temperature and transported in a zone (30 ° C., 40% RH) in which triethylamine gas was generated, and the coating film was exposed to triethylamine gas for 3 minutes. The polysilazane-coated film after the exposure treatment was once wound up, and then passed through a humidifier in a steam atmosphere (95 ° C., 60% RH) while unwinding, thereby exposing the polysilazane coating film to the steam atmosphere for 5 minutes.

Example 15 Perhydropolysilazane synthesized in Reference Example was dissolved in dibutyl ether to prepare a 12% by weight polysilazane solution. This solution is 100 μm thick, 60 cm wide,
A polyethersulfone (PES) film substrate having a total length of 300 m was applied to one surface by a gravure (reverse) coating method (roll # 80) while being conveyed at 2 m / min. After coating, a butylamine aqueous solution was bubbled with nitrogen at room temperature to generate butylamine gas inside the zone (3).
(0 ° C., 40% RH), and the coating film was exposed to triethylamine gas for 3 minutes, and irradiated with ultraviolet rays for 3 minutes by a metal halide lamp (irradiation conditions: output 2 kW, distance 25 cm). The polysilazane-coated film after the ultraviolet irradiation was once wound up, and then passed through a humidifier in a steam atmosphere (95 ° C., 60% RH) while being unwound, thereby exposing the polysilazane coating film to the steam atmosphere for 3 minutes.

Evaluation of Film Properties The ceramic coatings obtained in Examples 1 to 15 and Comparative Examples 1 to 4 were subjected to Si-H vibration (N-H
Vibration) By the disappearance of the peak and the appearance of the Si-O vibration peak, it was confirmed that all of them were substantially converted to silica.
Further, the thickness of each of these ceramic coatings was calculated by spectroscopy using a peak that caused interference in the spectrum in the visible region, and found to be 0.4 μm in all cases.

The properties of these ceramic coatings were evaluated for the following items. For reference, the properties of the used plastic film substrate itself were also measured except for (5) adhesion. (1) Oxygen permeability (unit: cc / m ^2/24 hours / at
m) It was measured at 25 ° C. and 65% RH using a Mocon measuring instrument. (2) water vapor permeability (unit: g / m ^2/24 hours) 40 ° C. using a Mocon made meter was measured at 90% RH. (3) Light transmittance The visible light average transmittance was measured using a haze meter. (4) Scratch resistance Steel wool # 000, load 500g, (area 2c
The test was carried out under 100 reciprocating conditions (m square), the number of scratches was visually observed, and A to E were graded. Evaluation A: No scratch, Evaluation B: 2 or less scratches, Evaluation C: 3 to 5 scratches, Evaluation D: 6 to scratches
10 pieces, evaluation E: 11 or more scratches. (5) Adhesion It evaluated by the crosscut tape peeling test.

The pencil hardness of Examples 6 and 11 and Comparative Example 2 was measured. The results of the various measurements are summarized in Table 1 below.

[0112]

[Table 1]

[0113]

According to the present invention, the step of lowering the temperature required for ceramicizing a coating film containing polysilazane and the step of irradiating the coating film with ultraviolet light promote the ceramicization of the coating film, The characteristics of the ceramic film finally obtained are improved as compared with the case where no irradiation is performed.

Claims (1)

[Claims] 1. A coating film containing polysilazane is formed on the surface of a substrate, and the coating film is subjected to ceramic treatment to substantially form Si
In a method of forming a ceramic film made of O ₂ ,
A method comprising the steps of lowering the temperature required for ceramicization and irradiating the coating with ultraviolet light.