JP3537197B2 - Electrode substrate for liquid crystal display device and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to gas barrier properties, hardness,
The present invention relates to an electrode substrate for a liquid crystal display device comprising a plastic film coated with a polysilazane-derived SiO ₂ film having excellent adhesion to a transparent conductive film such as ITO and a method for producing the same.

[0002]

2. Description of the Related Art Development of thin and lightweight liquid crystal display devices has been progressing. Particularly, improvement of portability and improvement of impact resistance against drop and external pressure stress are important issues in designing a small liquid crystal display device. One of the barriers to solving such a problem is glass conventionally used as a transparent electrode substrate of a liquid crystal display device. That is, glass has essential problems such as being heavy, cannot be made thin, has poor impact resistance, is easily broken, cannot be bent, and is difficult to be mass-produced. Therefore, recently, the above-mentioned problem has been solved by using a plastic film substrate, which is characterized by being unbreakable, thin, and light, as an electrode substrate.

An electrode substrate for a liquid crystal display device has optical characteristics,
Heat resistance, dimensional stability, solvent resistance, electrical insulation, workability,
Characteristics such as gas barrier properties, low hygroscopicity, and smoothness are required. A plastic film satisfying all these required properties is not available. Therefore, currently used plastic film substrates generally include a gas barrier layer for preventing gas permeation of oxygen and the like, a hard coat layer for protecting the surface and imparting moisture resistance, and an ITO transparent conductive film for the film. Various layers are provided, including an undercoat layer for imparting adhesion and solvent resistance of the conductive film.

The following patent publication discloses a surface coating method which imparts gas barrier properties, hardness and heat resistance to a plastic film and does not impair transparency. Japanese Patent Application Laid-Open No. Hei 4-80030 discloses a method for forming an inorganic / organic composite film on the surface by applying an alkoxysilane solution using a sol-gel method. JP-A-6-93120 discloses that a base film having a high gas barrier property is vacuum-deposited,
A method for forming a SiO ₂ film by a dry plating method such as ion plating and sputtering is disclosed.

[0005]

However, the method disclosed in Japanese Patent Application Laid-Open No. Hei 4-80030 has a limitation on the types of plastic film substrates that can be used because high temperatures are required for film formation. There are problems such as not being dense and the mechanical strength of the film being insufficient. Further, the method disclosed in Japanese Patent Application Laid-Open No. Hei 6-93120 has problems that the film formation cost is extremely high, gas barrier properties are poor, and cracks occur when the film is made thick.

Accordingly, a film having all of the characteristics of a gas barrier layer, a hard coat layer and an undercoat layer required for an electrode substrate for a liquid crystal display device can be easily formed at a low temperature at a low cost without damaging a plastic film. A method that can be formed into a film is desired.

An object of the present invention is to solve the above-mentioned problems in the prior art and to provide an electrode substrate for a liquid crystal display device made of a plastic film coated with a SiO ₂ film and a method of manufacturing the same.

[0008]

SUMMARY OF THE INVENTION These and other objects, forming a metal carboxylate added polysilazane film on at least one surface on the (1) plus plastic film,
Subjecting the film to a heat treatment and then subjecting the film to an immersion treatment with an aqueous solution containing a catalyst.
This is achieved by a method of manufacturing an electrode substrate for a liquid crystal display device comprising an O ₂ -coated plastic film.

Preferred embodiments of the present invention are listed below. ( 2) The method according to ( 1 ), wherein the catalyst is hydrochloric acid. ( 3 ) The method according to ( 1 ) or ( 2 ), wherein the immersion treatment is performed at room temperature.

According to the present invention, an SiO ₂ film is formed at a low temperature without damaging the plastic film substrate by using polysilazane as a starting material, and particularly preferably by employing a low-temperature ceramic treatment method. You. The SiO ₂ film of the present invention has all of the properties of a gas barrier layer, a hard coat layer, and an undercoat layer required for an electrode substrate for a liquid crystal display device, and has a much lower film formation cost than the dry plating method described above. It can be formed by a low and simple coating method.

In the present invention, any polysilazane can be used if it can be ceramicized at a low temperature.
An iO ₂ film can be formed. Such a polysilazane is hereinafter referred to as "low temperature ceramicized polysilazane".

The low-temperature ceramicized polysilazane usable in the present invention is obtained by modifying polysilazane having a main skeleton consisting of a unit represented by the following general formula (I) and having a number average molecular weight of 100 to 50,000.

[0013]

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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 a group, an alkylsilyl group, an alkylamino group, or an alkoxy group. Where R ¹ ,
At least one of R ² and R ³ is a hydrogen atom. In the present invention, polysilazane in which all of R ¹ , R ² and R ³ are hydrogen atoms is particularly preferred.

An example of such a low-temperature ceramicized polysilazane is disclosed in Japanese Patent Application No. 4-39595 by the present applicant.
Alkoxide-added polysilazane described in the above specification. This modified polysilazane is different from the polysilazane represented by the above general formula (I) and the following general formula (II): Si (OR ⁴ ) ₄ (II) (where R ⁴ may be the same or different, A hydrogen atom, an alkyl group or an aryl group having 1 to 20 carbon atoms, wherein at least one R ⁴ is the above-mentioned alkyl group or aryl group). It is a silicon alkoxide-added polysilazane having an alkoxide-derived silicon / polysilazane-derived silicon atom ratio in the range of 0.001 to 3 and a number average molecular weight of about 200,000 to 500,000. R ⁴ is more preferably an alkyl group having 1 to 10 carbon atoms,
Alkyl groups having 1 to 4 carbon atoms are most preferred. Further, it is preferable that the silicon atom ratio derived from alkoxide / silicon derived from polysilazane is in the range of 0.05 to 2.5. For the preparation of the silicon alkoxide-added polysilazane, see the above-mentioned Japanese Patent Application No. 4-39595.

Another example of the low temperature ceramicized polysilazane is glycidol-added polysilazane described in JP-A-6-122852 by the present applicant. This modified polysilazane is obtained by reacting the polysilazane represented by the general formula (I) with glycidol, and has a glycidol / polysilazane weight ratio of 0.001.
And glycidol-added polysilazane having a number average molecular weight of about 200,000 to 500,000. 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 Japanese Patent Application No. 5-30750 filed 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. Further, the weight ratio of alcohol / polysilazane 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. For the preparation of the alcohol-added polysilazane, see Japanese Patent Application No. Hei.
See 750.

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

As still another example of low-temperature ceramicized polysilazane, Japanese Patent Application No. 5-35604 filed by the present applicant is disclosed.
Acetylacetonate complex-added polysilazane described in the specification. 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 acetylacetonate complex is a complex in which an anion acac ⁻ generated by acid dissociation from acetylacetone (2,4-pentadione) is coordinated to a metal atom, and generally has the formula (CH ₃ COCHCOCH ₃ ) _n M [Wherein, M represents an n-valent metal]. The weight ratio of acetylacetonato complex / polysilazane is preferably 0.0
It is from 01 to 1, more preferably from 0.01 to 0.5. For the preparation of acetylacetonato complex-added polysilazane, refer to the above-mentioned Japanese Patent Application No. 5-35604.

As another example of low temperature ceramicized polysilazane, Japanese Patent Application No. 5-338524 filed by the present applicant has been proposed.
Polysilazane to which metal fine particles are added as described in the specification can be used. 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 size 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 ultra-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 100
0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, per part by weight.
It is 0.5 to 5 parts by weight. For the preparation of polysilazane containing metal fine particles, see the above-mentioned Japanese Patent Application No. 5-338524.

In the present invention, any low temperature ceramicized polysilazane can be suitably used. A particularly preferred low temperature ceramicized polysilazane is a metal carboxylate-added polysilazane, but more preferably the metal is palladium (Pd).

The SiO ₂ -coated plastic film according to the present invention is produced by forming a low-temperature ceramicized polysilazane film as described above on at least one surface of a plastic film and then converting this film to low-temperature ceramic. Low-temperature ceramicized polysilazane film formation
Usually, it is carried out by dissolving low-temperature ceramicized polysilazane in a solvent to prepare a coating composition.

Examples of the solvent include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbon solvents, halogenated hydrocarbons such as halogenated methane, halogenated ethane, and halogenated benzene, aliphatic ethers, and aliphatic hydrocarbons. Ethers such as cyclic ethers can be used. Preferred solvents are
Halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, bromoform, ethylene chloride, ethylidene chloride, trichloroethane, tetrachloroethane, ethyl ether, isopropyl ether, ethyl butyl ether, butyl ether, 1,2-dioxyethane, dioxane, dimethyl dioxane, Ethers such as tetrahydrofuran and tetrahydropyran, pentanehexane,
Hydrocarbons such as isohexane, methylpentane, heptane, isoheptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, and ethylbenzene. When these solvents are used, two or more kinds of solvents may be mixed in order to adjust the solubility of the low-temperature ceramicized polysilazane and the evaporation rate of the solvent.

The amount (proportion) of the solvent used is selected so that the workability is improved by the coating method employed, and the average molecular weight of the low-temperature ceramicized polysilazane used,
Since it differs depending on the molecular weight distribution and its structure, it can be freely mixed as appropriate. Preferably the solid content concentration is 1 to
It can be mixed in the range of 50% by weight.

In the coating composition of the present invention, a suitable filler and / or extender can be added as required. Examples of the filler include oxide-based inorganic substances such as silica, alumina, zirconia, and mica, and fine powders of non-oxide-based inorganic substances such as silicon carbide and silicon nitride. Depending on the application, it is also possible to add a metal powder such as aluminum, zinc and copper. Further elaborating examples of the filler, silica sol, zirconia sol,
Sols such as alumina sol and titania sol: silica sand, quartz,
Silica such as novacurite and diatomaceous earth: synthetic amorphous silica: kaolinite, mica, talc, wollastonite,
Silicates such as asbestos, calcium silicate, and aluminum silicate: glass powder, glass spheres, hollow glass spheres, glass flakes, foam glass spheres, etc .: boron nitride,
Non-oxide inorganic substances such as boron carbide, aluminum nitride, aluminum carbide, silicon nitride, silicon carbide, titanium boride, titanium nitride and titanium carbide: calcium carbonate: metals such as zinc oxide, alumina, magnesia, titanium oxide and beryllium oxide Oxides: barium sulfate, molybdenum disulfide, tungsten disulfide, carbon fluoride, and other inorganic substances: metal powders such as aluminum, bronze, lead, stainless steel, and zinc: carbon black, coke, graphite, pyrolytic carbon, hollow carbon spheres, etc. Carbon bodies and the like. Preferred fillers are ultrafine particles of an oxide-based inorganic substance such as silicon oxide, zinc oxide, titanium oxide, aluminum oxide, and zirconium oxide, and silica sol.

These fillers may be used alone or in various shapes such as needles (including whiskers), granules, and scales.
A mixture of more than one species can be used. The size of the particles of these fillers is desirably smaller than the film thickness applicable at one time. The addition amount of the filler is in the range of 0.05 to 10 parts by weight, particularly preferably 0.2 to 3 parts by weight, per 1 part by weight of the low temperature ceramicized polysilazane.

The coating composition may contain various pigments, leveling agents, defoamers, antistatic agents, ultraviolet absorbers, pH adjusters, dispersants, surface modifiers, plasticizers, drying accelerators, if necessary. , A flow stopper and the like.

The plastic film used for the electrode substrate for a liquid crystal display of the present invention includes various plastic materials. Preferred materials from the viewpoint of heat resistance and solvent resistance 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), biaxially oriented polypropylene (OPP), polyphenylene sulfide (PPS), polyethylene naphthalate (PE)
N), polyethersulfone (PES), polyetherimide (PEI), polyetheretherketone (PE
EK), polyarylate (PAR), biaxially stretched para-aramid film, norbornene-based polyolefin film, ultrathin film with a support, and the like. The area and thickness of the plastic film are not particularly limited, and a film having an arbitrary area and thickness depending on the application can be used.

These plastic films can be subjected to a pretreatment such as a corona discharge treatment or a silane coupling agent application for improving the adhesion.

According to the present invention, a low temperature ceramicized polysilazane film is formed by applying a coating composition as described above to at least one side of a plastic film as described above. As a method of application, an ordinary method of applying to a plastic film, that is, dipping, roll coating, bar coating, brush coating, spray coating, flow coating, or the like is used. A particularly preferred application method is the gravure coating method.

After coating by such a method, a temperature that does not damage the plastic film, preferably 15 ° C.
Heat treatment is performed at 0 ° C. or less. Generally, a heat treatment of 150
If performed above ℃, plastic film may be deformed,
The plastic film is damaged, for example, its strength is deteriorated. However, in the case of a plastic film having high heat resistance such as polyimide, treatment at a higher temperature is possible, and this heat treatment temperature can be appropriately set by those skilled in the art depending on the type of the film. The heating atmosphere may be either oxygen or air.

In the heat treatment at the above temperature, Si-
A film in which O, Si-N, Si-H, and NH exist is formed. This film is still incompletely converted to ceramics. This film can be converted to ceramics by one or both of the following two methods.

Heat treatment 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.
0-100% RH is preferred. The temperature is effective at room temperature or higher, but is preferably room temperature to 150 ° C. Although the heat treatment time is not particularly limited, 10 minutes to 30 days is practically appropriate.

The heat treatment in a steam atmosphere promotes the oxidation of low-temperature ceramicized polysilazane or hydrolysis with steam, so that a dense film substantially made of SiO _{2 can} be formed at the low heating temperature as described above. It becomes possible.
However, this SiO ₂ film is derived from polysilazane and contains nitrogen in an atomic percentage of 0.005 to 5%. If the nitrogen content is more than 5%, the film becomes insufficiently ceramic, 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%. 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, n-butylamine, di-n-butylamine, tri-n-butylamine, guanidine, piguanine, imidazole, 1,8
-Diazabicyclo- [5,4,0] -7-undecene,
Amines such as 1,4-diazabicyclo- [2,2,2] -octane; alkalis such as sodium hydroxide, potassium hydroxide, lithium hydroxide, 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 Organic anhydrides such as anhydrides and trichloroacetic acid; perchloric acid, hydrochloric acid, nitric acid, sulfuric acid,
Sulfonic acid, p-toluenesulfonic acid, boron trifluoride and its complex with an electric donor, etc .; SnCl ₄ , ZnC
l ₂ , FeCl ₃ , AlCl ₃ , SbCl ₃ , TiCl
Lewis acids such as _4, their complexes, and the like can be used. The preferred catalyst is hydrochloric acid. The content of the catalyst is 0.01 to 50% by weight, preferably 1 to 10% by weight. The holding temperature is effective from room temperature to the boiling point. The holding time is not particularly limited, but 10 minutes to 30 days is practically appropriate.

[0036] By immersing in distilled water containing a catalyst, the hydrolysis of the oxidized or water low temperature ceramics of polysilazane, is further accelerated by the presence of a catalyst, at a low heating temperature as described above, substantially SiO ₂ It is possible to form a dense film composed of However, as described above, since this SiO ₂ film is derived from polysilazane, it also contains nitrogen in an atomic percentage of 0.005 to 5%.

The thickness of the SiO ₂ film obtained by one application is preferably 500 ° to 5 μm, more preferably 10 μm to 5 μm.
It is in the range of 00 ° to 2 μm. If the film thickness is more than 5 μm, cracks often occur during heat treatment, and the flexibility is deteriorated, so that cracks or peeling due to bending or the like are likely to occur.
Conversely, if the film thickness is less than 500 °, desired effects, for example, desired gas barrier properties and hardness cannot be obtained. This film thickness can be controlled by changing the concentration of the coating composition. That is, when it is desired to increase the film thickness, the solid content concentration of the coating composition can be increased (the solvent concentration can be decreased). Further, the film thickness can be further increased by applying the coating composition a plurality of times.

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 fine particles such as TiO ₂ having an ultraviolet absorbing function to impart an ultraviolet absorbing function, or to laminate a flexible intermediate layer to impart flexibility.

The SiO ₂ film according to the present invention is made of ceramics and can be formed at a low temperature by an ordinary simple method of coating and curing. The SiO ₂ film shows a SiO ₂ film and the same or higher gas barrier properties by the conventional deposition method, is excellent in hardness (wear resistance), it can moreover be transparent. Further, the SiO ₂ film according to the present invention shows good adhesion to a transparent conductive film such as ITO on an electrode substrate for a liquid crystal display device. The electrode substrate for a liquid crystal display device according to the present invention can replace a conventional electrode substrate, and can construct an electrode substrate utilizing characteristics of a plastic film.

[0040]

The present invention will be further described by way of examples. Example 1 Tonen Perhydropolysilazane Type-1 (PHPS
-1; 20% xylene solution 10 having a number average molecular weight of 900)
To 0 g, 40 g of a 0.5% xylene solution of palladium (II) acetate (manufactured by NE Chemcat Corporation) was added,
Further, 60 g of xylene was added, and the reaction was carried out with stirring at 20 ° C. for 3 hours in the air.

The number average molecular weight of this solution was 932 as measured by GPC. This solution was used as a coating solution, filtered through a PTFE filter having a pore size of 0.1 μm, applied to both sides of a 75 μm-thick PET film by dip coating, and heat-treated at 150 ° C. for 1 hour in an air atmosphere.

A solution was prepared by adding 1% by weight of hydrochloric acid to distilled water, and the heat-treated coating film was immersed in this solution at room temperature for 3 hours and dried at room temperature. The thickness of this coating was about 1 μm. The degree of progress of ceramicization of this coating film was evaluated by infrared spectroscopy (IR).
No absorption due to H was observed. Also, 940cm
^{At -1} , absorption due to O-H was observed at 3,400 cm ^-1 . Further, the density of the film was measured by a gravimetric method and found to be 2.1 g / cm ³ . The refractive index of the film measured by an ellipsometer was 1.45.
Met. These values are those of fused silica glass (density 2.
20 g / cm ³ and a refractive index of about 1.46), and it was confirmed that the composition of the obtained coating film was substantially SiO ₂ . In addition, when the nitrogen content in the coating film was evaluated by secondary ion mass spectrometry (SIMS), it was 0.54% in atomic percentage.

The gas permeability of oxygen and water vapor of the coated PET film thus produced was measured. For these measurements, a differential pressure type gas permeability measurement system GTR-30XD manufactured by Yanagimoto Seisakusho Co., Ltd. was used. The measurement conditions for oxygen permeability are
Measurement temperature: 25 ± 1 ° C, test gas: dry oxygen (ZERO-U grade, manufactured by Sumitomo Seika Co., Ltd.), test gas pressure: 6.0k
gf / cm ² , gas permeation area: 15.2 cm ² (diameter 4
4 mm) and permeated gas storage time: 33, 37 and 47 hours. The measurement conditions of the water vapor transmission rate were as follows: measurement temperature: 40 ± 1 ° C., test gas: a mixed gas of water vapor and dry oxygen, steam generation: saturated steam at 23 ° C., test gas pressure: about 1 kgf / cm ² [water vapor Partial pressure =
2809.6 Pa ≒ 0.0286 kgf / cm ² ．0.
028 atm (saturated steam pressure at 23 ° C.)], relative humidity: about 38% RH (determined by the ratio between the measured temperature and the saturated steam pressure at the steam generation temperature), gas permeation area: 15.2c
m ² (diameter 44 mm), permeated gas storage time: 33, 45
And 60 hours. The measurement was performed after a sufficient time had passed since the test gas was applied to the sample at a predetermined pressure. The gas permeability of the coated PET film obtained by the above measurement is such that the oxygen permeability is 0.1 cc / m ² · 2.
4 h · atm and water vapor transmission rate of 0.6 g / m ² ·
24h.

The pencil hardness of the coated PET film was 2H. Further, 100 watts at 60 rpm while applying a load of 250 g with steel wool of model number # 0000.
No scratches could be visually confirmed on the coated PET film after the rotation.

Example 2 The same solution as used in Example 1 was used. The solution was filtered through a PTFE filter having a pore diameter of 0.1 μm, and then a PET film having a thickness of 75 μm was used.
The film was applied on both sides by dip coating, and heat-treated at 150 ° C. for 1 hour in an air atmosphere.

The heat-treated coating film was heated at 95 ° C. for 3 hours at 80% RH (relative humidity) under atmospheric pressure. The thickness of this coating film was about 1 μm. When the degree of progress of the formation of ceramics of this coating film was evaluated by IR, no absorption due to Si-H was observed. In addition, the 940cm ^-1 Si-
OH at 3400 cm ^-1 showed absorption due to OH. Further, the density of the film was measured by a gravimetric method and found to be 2.1 g / cm ³ . The refractive index of the film measured by an ellipsometer was 1.45.
These values are those of fused silica glass (density 2.20 g / c
m ³ and a refractive index of about 1.46), and it was confirmed that the composition of the obtained coating film was substantially SiO ₂ . Further, when the nitrogen content in the coating film was evaluated by SIMS, it was 1.6% in atomic percentage.

The gas permeability of the coated PET film thus manufactured was measured in the same manner as in Example 1.
Oxygen permeability at 0.1cc / m ² · 24h · at
m, and the water vapor permeability at 40 ° C. is 0.9 g / m
It was ² · 24h.

The pencil hardness of the coated PET film was 2H. Further, 100 watts at 60 rpm while applying a load of 250 g with steel wool of model number # 0000.
No scratches could be visually confirmed on the coated PET film after the rotation.

Table 1 below summarizes data on gas barrier properties, and Table 2 summarizes data on hardness.

Table 1: Gas barrier water vapor permeability Oxygen permeability g / m ² · 24 h cc / m ² · 24 h · atm Base PET film 8.0 25.0 Example 1 0.6 0.1 Implementation Example 2 0.9 0.1

Table 2: Hardness Pencil hardness # 0000 Steel wool base PET film 3B Scratched Example 1 2H No scratch Example 2 2H No scratch

An ITO film was formed on one side of the double-sided coated films obtained in Examples 1 and 2 by a sputtering method to produce an electrode substrate for a liquid crystal display device. When the adhesion between the ITO and the film on the electrode substrate was evaluated by a cross-cut test method, good adhesion (100/100) was exhibited with any of the samples of Example 1 and Example 2.

The electrode substrate for a liquid crystal display device of the present invention having the above-mentioned characteristics shows performance equal to or higher than that of a conventional substrate, and it has been found that a high-performance electrode substrate can be constructed.

[0054]

According to the present invention, by applying polysilazane, which turns into a ceramic at a low temperature, to a plastic film, S
An electrode substrate for a liquid crystal display device having an iO ₂ film is obtained.
This SiO ₂ film has all of the properties of a gas barrier layer, a hard coat layer, and an undercoat layer required for an electrode substrate for a liquid crystal display device, and has a much lower film formation cost than a dry plating method such as an evaporation method. It can be formed by a simple coating method.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-105486 (JP, A) JP-A-5-119307 (JP, A) JP-A-5-238827 (JP, A) 323303 (JP, A) JP-A-5-333326 (JP, A) JP-A-6-122852 (JP, A) JP-A-6-148645 (JP, A) JP-A-6-222348 (JP, A) JP-A-6-240208 (JP, A) JP-A-6-299118 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G02F 1/13-1/141

Claims (3)

(57) [Claims] At least one side of a plastic film
Form a film of polysilazane with metal carboxylate on it
And water containing a catalyst after the film is subjected to a heat treatment.
Performing a immersion treatment with a solution.
Liquid crystal table composed of SiO ₂ coated plastic film
A method for manufacturing an electrode substrate for a display device. 2. The method according to claim 1, wherein said catalyst is hydrochloric acid.
Method. 3. The method according to claim 1, wherein the immersion treatment is performed at room temperature.
Or the method of 2.