JP5160880B2 - Method for producing ion diffusion prevention film, substrate with ion diffusion prevention film and liquid crystal display cell - Google Patents

Description

  The present invention provides a method for producing an ion diffusion prevention film having excellent adhesion to a glass substrate, heat resistance of the film, degassing characteristics of the film, film strength and the like, and excellent ion diffusion prevention performance. The present invention relates to a substrate with an ion diffusion prevention film having an ion diffusion prevention film produced by a method for producing an ion diffusion prevention film, and a liquid crystal display cell having the substrate with an ion diffusion prevention film.

  Conventionally, a pair of transparent electrode-equipped substrates in which a transparent electrode film such as ITO, an insulating film (transparent ion getter film), and an alignment film made of a polymer such as polyimide are sequentially laminated on the surface of a glass substrate, There is known a liquid crystal display cell in which liquid crystal is sealed in a gap opened at a predetermined interval by a spacer so that the transparent electrode films face each other through a spacer.

  However, in the case of a glass substrate containing an alkali such as a soda lime glass substrate, alkali ions diffuse and display defects and reliability decrease. In particular, in a TFT type liquid crystal display cell device, alkali ions diffuse and TFT There was a problem that the voltage characteristics of the semiconductor layer changed and caused malfunction.

For this reason, for example, in a TFT liquid crystal display cell device, in order to have a high voltage holding ratio characteristic, a measure is taken to reduce ions caused by the material constituting the cell.
It is also known to provide an alkali passivation film between a glass substrate and a transparent electrode film (Japanese Patent Laid-Open No. 2000-169766, Patent Document 1).

Conventional alkali passivation films are mainly composed of films made of organic resins such as acrylic resins and polyester resins, inorganic coatings such as SiO ₂ and Si ₃ N ₄ , and organic / inorganic composite alkyltrihydroxysilane polymers. Is used.

  JP-A-9-235514 (Patent Document 2) discloses a coating liquid for forming a silica-based film containing a hydrolysis product of a specific alkoxysilane compound, an ether derivative of a polyhydric alcohol, and ketol. Yes.

JP 2000-169766 A JP-A-9-235514

  Conventional alkali passivation films tend to adsorb moisture gradually when used over a long period of time, and the alkali passivation effect may decrease correspondingly, and display unevenness occurs when used in a liquid crystal display device. There was a thing. Further, among them, it is disclosed that an alkoxysilane compound and carboxylic acid or water are hydrolyzed in an organic solvent in the presence of a catalyst such as phosphoric acid. Occasionally, an alkali component of soda lime glass is extracted, and the alkali moves to the surface of the ion diffusion preventing film, which may cause malfunction in the TFT type liquid crystal display cell device.

As a result of intensive studies in view of the above problems, a film formed using a coating solution containing a silicon compound obtained by hydrolyzing a specific hydrolyzable organosilicon compound in the presence of tetraalkylammonium hydroxide (TAAOH) It was found that when hydrothermal treatment was performed, the diffusion of alkali ions in the soda lime glass substrate was suppressed, and the present invention was completed.

[1] A method for producing an ion diffusion preventing film comprising the following steps (a) to (d):
(A) Ion diffusion prevention containing a silicon compound obtained by hydrolyzing an organosilicon compound represented by the following general formula (I) and / or the following general formula (II) in the presence of tetraalkylammonium hydroxide (TAAOH) Step X _n Si (OR) _4-n (I) for preparing a coating solution for film formation
(In the formula, X represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 8 carbon atoms, a fluorine-substituted alkyl group, an aryl group or a vinyl group, and R represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, Represents an aryl group or a vinyl group, and n is an integer of 0 to 3.)

（式中、Ｒ¹はメチレン基、エチレン基またはプロピレン基を表し、Ｒ²〜Ｒ⁷は同一でも
異なっていてもよく、水素原子、または炭素数１〜８のアルキル基、フッ素置換アルキル基、アリール基もしくはビニル基を表す。）
（ｂ）イオン拡散防止膜形成用塗布液をガラス基材上に塗布する工程
（ｃ）塗布膜を２５〜３５０℃の温度で乾燥処理する工程（乾燥工程）
（ｄ）水蒸気の存在下、塗布膜を１０５〜４５０℃の温度条件下で加熱処理する工程（水熱処理工程）

(In the formula, R ¹ represents a methylene group, an ethylene group or a propylene group, and R ^{2 to} R ⁷ may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a fluorine-substituted alkyl group, Represents an aryl group or a vinyl group.)
(B) The process of apply | coating the coating liquid for ion diffusion prevention film formation on a glass base material (c) The process of drying a coating film at the temperature of 25-350 degreeC (drying process)
(D) A step of heat-treating the coating film in the presence of water vapor at a temperature of 105 to 450 ° C. (hydrothermal treatment step)

[2] The organic silicon compound is one or more selected from n = 0 organic silicon compounds (tetraalkylorthosilicate (TAOS)) of the general formula (I), and n = 1 of the general formula (I). A method for producing a coating liquid for forming an ion diffusion preventing film according to [1], which is a mixture with one or more selected from organic silicon compounds (alkoxysilane (AS)) of ~ 3.

[3] After the step (d),
(E) The manufacturing method of the coating liquid for ion diffusion prevention film formation of [1] which performs the process (baking process) which bakes a coating film on 350-450 degreeC temperature conditions in presence of inert gas.

[4] Number of moles of tetraalkylorthosilicate (TAOS) used in step (a) (
M _TAOS) and the alkoxysilane moles of silane _(AS) (M AS) and the molar ratio of _{(M TAOS) / (M AS} ) is ion diffusion preventing film [2] in the range of 0.25 to 1.5 Manufacturing method.

[5] In the step (a), tetraalkylammonium hydroxide (TA
AOH) number of moles of (M _T) and the total number of moles of the organic silicon compound (M _S) and the molar ratio of (M _T) /
(M _S) is a manufacturing method of the ion diffusion preventing film [2] to [4] in the range of 0.1 to 0.7.

[6] A method for producing an ion diffusion prevention film obtained by the method of [1] to [5] and having a film thickness in the range of 100 to 2,500 nm.

[7] The ion diffusion prevention film according to [6], further having an average pore diameter in the range of 1.0 to 3.0 nm and an alkali content of 50 ppb or less.

[8] A substrate with an ion diffusion prevention film comprising a glass substrate and an ion diffusion prevention film formed on the glass substrate, wherein the ion diffusion prevention film is obtained by the method of [1] to [5] A substrate with an ion diffusion prevention film, which is characterized in that

  [9] The substrate with an ion diffusion prevention film according to [8], wherein the film thickness of the ion diffusion prevention film is in a range of 100 to 2,500 nm.

  [10] The substrate with an ion diffusion prevention film according to [8], wherein the ion diffusion prevention film has an average pore diameter in the range of 1.0 to 3.0 nm and an alkali content of 50 ppb or less.

  [11] A pair of substrates with a transparent electrode in which an ion diffusion preventing film, a transparent electrode film, a transparent insulating film (ion getter film) and an alignment film are sequentially laminated on the surface of at least one glass substrate, In a liquid crystal display cell that is arranged with a predetermined interval so that the transparent electrodes face each other, and liquid crystal is sealed in a gap formed between the pair of substrates with transparent electrodes, an ion diffusion prevention film is A liquid crystal display cell formed by the method for producing an ion diffusion prevention film according to any one of [1] to [5].

  [12] A pair of substrates with a transparent electrode in which an ion diffusion preventing film, a color filter, a transparent insulating film (ion getter film), a transparent electrode film, and an alignment film are sequentially laminated on the surface of at least one glass substrate. In a liquid crystal display cell in which liquid crystal is sealed in a gap between the pair of transparent electrode-equipped substrates, the transparent electrodes are arranged so as to face each other, and prevent diffusion of ions. A liquid crystal display cell, characterized in that the film is an ion diffusion preventing film formed by the method for producing an ion diffusion preventing film of [1] to [5].

  [13] A pair in which an ion diffusion preventing film, a TFT array (TFT element, data electrode), a transparent insulating film (ion getter film), a transparent electrode film and an alignment film are sequentially laminated on the surface of at least one glass substrate. The transparent electrode-equipped base material is disposed at a predetermined interval so that the respective transparent electrodes are opposed to each other, and liquid crystal is sealed in a gap formed between the pair of transparent electrode-equipped base materials. A liquid crystal display cell, wherein the ion diffusion preventing film is formed by the method for producing an ion diffusion preventing film of [1] to [5] in the display cell.

  According to the present invention, the ion diffusion preventing film is applied with a predetermined coating solution for forming an ion diffusion preventing film on a glass substrate, and has undergone a predetermined drying step and hydrothermal treatment step. Diffusion can be prevented, and when used in a liquid crystal display cell, the voltage characteristics of the semiconductor layer of the TFT can be changed to prevent malfunction, and the amount of movable ions in the liquid crystal is not increased. Therefore, it is possible to provide a liquid crystal display cell with low power consumption, no display unevenness, and excellent display quality.

Hereinafter, first, a method for producing an ion diffusion preventing film according to the present invention will be described.
Method for Manufacturing Ion Diffusion Prevention Film The method for manufacturing an ion diffusion prevention film according to the present invention is characterized by comprising the following steps (a) to (d).
(B) The process of apply | coating the coating liquid for ion diffusion prevention film formation on a glass base material (c) The process of drying a coating film at the temperature of 25-350 degreeC (drying process)
(D) A step of heat-treating the coating film in the presence of water vapor at a temperature of 105 to 450 ° C. (hydrothermal treatment step)

Step of preparing a coating solution for forming an ion diffusion prevention film (step (a))
First, an ion diffusion prevention film containing a silicon compound obtained by hydrolyzing an organosilicon compound represented by the following general formula (I) and / or the following general formula (II) in the presence of tetraalkylammonium hydroxide (TAAOH) A forming coating solution is prepared.
X _n Si (OR) _4-n (I)
(In the formula, X represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 8 carbon atoms, a fluorine-substituted alkyl group, an aryl group or a vinyl group, and R represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, Represents an aryl group or a vinyl group, and n is an integer of 0 to 3.)

（式中、Ｒ¹はメチレン基、エチレン基またはプロピレン基を表し、Ｒ²〜Ｒ⁷は同一でも
異なっていてもよく、水素原子、または炭素数１〜８のアルキル基、フッ素置換アルキル基、アリール基もしくはビニル基を表す。）

(In the formula, R ¹ represents a methylene group, an ethylene group or a propylene group, and R ^{2 to} R ⁷ may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a fluorine-substituted alkyl group, Represents an aryl group or a vinyl group.)

As the organosilicon compound represented by the formula (I),
Tetraalkylorthosilicates (TAOS) such as tetramethylorthosilicate, tetraethylorthosilicate, tetrapropylorthosilicate, tetraisopropylorthosilicate, tetrabutylorthosilicate,
Methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, octyltrimethoxysilane, octyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxy Silane, phenyltrimethoxysilane, phenyltriethoxysilane, trimethoxysilane, triethoxysilane, triisopropoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldi Ethoxysilane, dimethoxysilane, diethoxysilane, difluorodimethoxysilane, difluorodiethoxysilane, trifluoromethyl Trimethoxysilane, alkoxysilanes such as trifluoromethyl triethoxysilane (AS) and the like.

  Among these, an ion diffusion prevention film obtained by using methyltrimethoxysilane (MTMS), methyltriethoxysilane (MTES) or a mixture thereof is preferable because it is excellent in thermal stability.

In addition, bis (trialkoxysilyl) alkane (BTASA) represented by the above general formula (II)
As such bis (trialkoxysilyl) alkane (BTASA) as bis (
Trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (tripropoxysilyl) methane, bis (trimethoxysilyl) ethane, bis (triethoxysilyl) ethane, bis (tripropoxysilyl) ethane, bis (trimethoxy Silyl) propane, bis (triethoxysilyl) propane, bis (tripropoxysilyl) propane and the like. Among them, bis (trialkoxysilyl) alkane (BTASA) is bis (trimethoxysilyl) methane (BTMSM), bis (triethoxysilyl) methane (BTESM), bis (trimethoxysilyl) ethane (BTMSE), bis ( Preference is given to using triethoxysilyl) ethane (BTESE) or mixtures thereof.

In the present invention, the organosilicon compound is one or more selected from the organosilicon compounds of n = 0 of the general formula (I) (tetraalkyl orthosilicate (TAOS)), and n = of the general formula (I). It is preferable that it is a mixture with 1 or more types chosen from 1-3 organosilicon compounds (alkoxysilane (AS)).

Step tetraalkyl orthosilicate used in (a) the number of moles of _(TAOS) (M TAOS) and the alkoxysilane moles of silane _(AS) (M AS) and the molar ratio of _{(M TAOS) / (M AS} ) is It is preferably in the range of 0.25 to 1.5, more preferably 0.4 to 1.
If the molar ratio (M _TAOS ) / (M _AS ) is too small, the pore size becomes large, and the ion diffusion preventing performance of the membrane may be insufficient. If the molar ratio (M _TAOS ) / (M _AS ) is too large, the membrane may have insufficient ion diffusion preventing performance, possibly due to an increase in the hydrophilicity of the membrane or moisture adsorption.

  The amount of the organosilicon compound used is such that the hydrolyzate concentration of the organosilicon compound in the finally obtained coating solution for forming an ion diffusion preventing film is 2 to 20% by weight, preferably 3 to 15% by weight as a solid content. It is preferable to adjust to be in the range.

  If the hydrolyzate concentration is too low, the film thickness may become too thin or pinholes may be formed, and the ion diffusion preventing performance of the film may be insufficient. If the hydrolyzate concentration exceeds 20% by weight as the solid content, the film thickness may become too thick or cracks may occur, and the ion diffusion preventing performance of the film may be insufficient.

  Tetraalkylammonium hydroxide (TAAOH) includes tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetra-n-octylammonium hydroxide, and n-hexadecyltrimethylammonium. Examples thereof include hydroxide and n-octadecyltrimethylammonium hydroxide. Among these, it is preferable to use tetrapropylammonium hydroxide (TPAOH), tetrabutylammonium hydroxide (TBAOH) or a mixture thereof.

  TAAOH functions as a hydrolysis catalyst for organosilicon compounds. Conventionally, an alkali metal hydroxide compound or an acid catalyst has been used. However, these have a problem of becoming a zeolite having micropores.

  Usually, tetraalkylammonium hydroxide (TAAOH) marketed for general use includes alkali metal element compounds such as sodium (Na) and potassium (K) as impurities, and bromine (Br), It is known that halogen group compounds such as chlorine (Cl) are contained at a level of several hundred weight ppm to several weight percent on an element basis. However, if impurities containing an alkali metal element compound such as sodium (Na) or potassium (K) are contained in an amount larger than 50 ppb on an element basis, alkali ions diffuse in the TFT type liquid crystal display cell device. The voltage characteristics of the semiconductor layer of the TFT may change and cause malfunction.

  Further, when impurities containing halogen compounds such as bromine (Br) and chlorine (Cl) are contained in an amount of more than 1 ppm by weight on an element basis, an alkali component of soda lime glass is extracted at the time of coating, and an ion diffusion preventing film In particular, in TFT type liquid crystal display cell devices, alkali ions may diffuse and cause TFT malfunction.

Furthermore, when the impurities of these alkali metal element compounds are contained in an amount of more than 50 wt. Ppb, the present inventors have introduced tetraalkyl orthosilicate (TAOS) and the above general formula (I
When the alkoxysilane (AS) represented by) is hydrolyzed in the presence of tetraalkylammonium hydroxide (TAAOH), this impurity acts as a catalyst, and the resulting silicon compound is converted into zeolitic crystalline silica. I found out that As a result, it has been found that the ion diffusion preventing film formed on the glass substrate becomes a zeolite crystalline having micropores, so that sufficient ion diffusion preventing performance cannot be obtained.

  Therefore, when using a commercially available tetraalkylammonium hydroxide (TAAOH) having the above properties, it is necessary to remove the impurities contained therein to the above level in advance. That is, the tetraalkylammonium hydroxide (TAAOH) used in the method of the present invention is included in a commercially available tetraalkylammonium hydroxide subjected to a cation exchange resin treatment step and an anion exchange resin treatment step. It is preferable to improve the purity by substantially removing impurities composed of compounds of alkali metal elements such as sodium (Na) and potassium (K) and halogen group elements such as bromine (Br) and chlorine (Cl). .

The molar ratio (M _T ) / (M _S ) between the number of moles (M _T ) of the tetraalkylammonium hydroxide (TAAOH) used in the step (a) and the total number of moles (M _S ) of the organosilicon compound is It is preferably in the range of 0.1 to 0.7, more preferably 0.1 to 0.6.

If the molar ratio (M _T ) / (M _S ) is small, hydrolysis may be insufficient, or if an ion diffusion prevention film is formed using a coating solution containing such a hydrolyzate, cracks occur and ions The anti-diffusion performance may be insufficient. If the molar ratio (M _T ) / (M _S ) is too large, the ion diffusion preventing film becomes porous, resulting in insufficient film strength and insufficient ion diffusion preventing performance.

Next, the coating solution for forming an ion diffusion preventing film used in the present invention can be prepared as follows.
(I) An organosilicon compound, preferably a tetraalkylorthosilicate (TAOS) and an alkoxysilane (AS) represented by the above general formula (I) are mixed with an organic solvent, and then at a temperature of about 10 to 30 ° C. Stir at a speed of 100-200 rpm until the ingredients are well mixed.

(Ii) Next, the mixed solution prepared in (i) and an aqueous solution of tetraalkylammonium hydroxide (TAAOH) are mixed for 5 to 20 minutes, and the temperature is approximately 10 to 30 ° C. for 30 to 90 minutes. Stir at a speed of ~ 200 rpm.

Instead of the above (i) and (ii), tetraalkyl orthosilicate (TAOS)
Can be hydrolyzed or partially hydrolyzed in the presence of tetraalkylammonium hydroxide (TAAOH) and then mixed with alkoxysilane (AS) or a hydrolyzate or partial hydrolyzate thereof.

(Iii) Next, after heating to a temperature of 30 to 80 ° C., the ion containing a partial hydrolyzate of the organosilicon compound produced by stirring at a speed of 100 to 200 rpm for 1 to 72 hours while maintaining this temperature. A coating solution for forming a diffusion barrier film can be prepared.

The organosilicon compound and tetraalkylammonium hydroxide (TAAOH) are used by mixing or adding each so as to have the molar ratio described above.
Examples of the organic solvent used include alcohols, ketones, ethers, esters, hydrocarbons, and the like. More specifically, for example, alcohols such as methanol, ethanol, propanol, and butanol, methyl ethyl ketone, methyl Ketones such as isobutyl ketone, glycol ethers such as methyl cellosolve, ethyl cellosolve, propylene glycol monopropyl ether, glycols such as ethylene glycol, propylene glycol, hexylene glycol, methyl acetate, ethyl acetate, methyl lactate, ethyl lactate, etc. Esters, hydrocarbons such as hexane, cyclohexane, and octane, and aromatic hydrocarbons such as toluene, xylene, and mesitylene. Among these, it is preferable to use alcohols such as ethanol.

The organic solvent is preferably used so that the concentration (solid content concentration) of the above components in the resulting coating solution for forming an ion diffusion preventing film is in the range of 2 to 20% by weight, more preferably 3 to 15% by weight.
If the concentration of the solid content of the coating solution for forming the ion diffusion preventing film is small, the film thickness may be too thin or a pinhole may be formed, and the ion diffusion preventing performance may be insufficient. If the solid content concentration is too high, the film thickness may become too thick or cracks may occur, and the ion diffusion preventing performance may be insufficient.

  The tetraalkylammonium hydroxide (TAAOH) aqueous solution to be mixed with the mixed organic solvent is 5 to 40% by weight, preferably 10 to 30% by weight of tetraalkylammonium hydroxide (TAAOH) in distilled water or ultrapure water. It is desirable to include it in proportion. The water used at this time is used to cause a hydrolysis reaction of an organosilicon compound such as tetraalkyl orthosilicate (TAOS) and alkoxysilane (AS), and therefore includes an amount necessary for the hydrolysis reaction. Must be a thing. Therefore, it is desirable that the amount of water is at least equivalent to Si—OR or Si—X in the organosilicon compound. As a catalyst for promoting this hydrolysis reaction, tetraalkylammonium hydroxide (TAAOH) has its function, so it is necessary to add another catalyst (for example, ammonia) from the outside. There is no.

  The hydrolysis is performed at a temperature of 30 to 80 ° C., preferably 35 to 60 ° C. for 1 to 72 hours, preferably 10 to 48 hours with stirring. The number average molecular weight of the silicon compound (TAOS and AS hydrolyzate) contained in the obtained coating solution for forming an ion diffusion prevention film is 500 to 1,000,000, preferably 1,000 to 100,000 in terms of polystyrene. It is desirable to be in the range. If this number average molecular weight is in the above range, a coating solution for forming an ion diffusion preventing film can be prepared which exhibits excellent stability over time and good coating properties.

In the coating solution for forming an ion diffusion preventing film of the present invention, if necessary, silica-based fine particles having an average particle diameter of 5 to 50 nm, or alkoxysilanes represented by the following general formula (V) and the following general formulas: Poly which is a reaction product of one or more silicon compounds selected from the group consisting of halogenated silanes represented by (VI) and / or their hydrolysates and silica-based fine particles having an average particle diameter of 5 to 50 nm. Siloxane (PS) particulates can be included.
X _n Si (OR) _4-n (V)
_{X n Si (X ') 4} -n (VI)
(In the formula, X represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 8 carbon atoms, a fluorine-substituted alkyl group, an aryl group or a vinyl group, and R represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, Represents an aryl group or a vinyl group, X ′ represents a halogen atom, and n is an integer of 0 to 3.)

Silica-based fine particles can be obtained by mixing one or more of the alkoxysilanes of the general formula (V) with an organic solvent and subjecting them to hydrolysis / condensation polymerization in the presence of water and ammonia. Polysiloxane (PS) Fine particles can be obtained by reacting the above-mentioned alkoxysilane and / or halogenated silane hydrolyzate on the surface of silica fine particles. (For details, see JP-A-9-315812, etc.)
The amount of such silica-based fine particles or polysiloxane (PS) fine particles used is desirably in the range of 10 to 80% by weight, more preferably 20 to 60% by weight, as a solid content in the obtained ion diffusion preventing film. When silica-based fine particles or polysiloxane (PS) fine particles are contained in the above range, an ion diffusion preventing film excellent in adhesion to a soda lime glass substrate, strength, cracking suppression, and the like can be obtained.

Application process (b)
Next, as a process (b), the coating liquid for ion diffusion prevention film formation is apply | coated on a glass base material.
As the glass substrate, a glass substrate such as alkali-free glass or soda lime glass is used. Alkali-free glass that does not substantially contain alkali is used for the liquid crystal display cell, but since it is expensive, it is desirable to be able to use an inexpensive soda-lime glass with a high alkali content without problems. ing.

A coating solution for forming an ion diffusion preventing film is applied on a glass substrate. Examples of the coating method include dipping method, spinner method, spray method, roll coater method, flexographic printing, and slit coater method. In the present invention, the spinner method and the slit coater method are recommended because of the uniformity of the coating film thickness.
The thickness of the coating film is not particularly limited, and is appropriately selected according to the thickness of the ion diffusion prevention film finally formed.

Drying step (c)
The formed coating film is dried by drying at 25 to 350 ° C, more preferably 40 to 250 ° C.

The drying method is not particularly limited as long as the organic solvent and water can be substantially removed, and a conventionally known method can be employed. In addition, it can also carry out in a dry gas stream at the time of drying.
If the drying temperature is low, drying may be insufficient, and the thickness of the formed film may be nonuniform. If the drying temperature is too high, decomposition of the tetraalkylammonium hydroxide (TAAOH) will occur and will be released together with the organic solvent and water, resulting in the formation of relatively large pores and voids in the membrane. There is. Further, when heat treatment described later is performed, densification due to shrinkage of the film is less likely to occur, so that the film strength may be insufficient or the ion diffusion preventing performance may be insufficient. In addition, it is preferable to supply gas, such as carrier gas used in the hydrothermal processing apparatus mentioned later, also in a drying process for drying.

Hydrothermal process (d)
The dried coating film is hydrothermally treated in the presence of water vapor under a temperature condition of 105 to 450 ° C., preferably 150 to 350 ° C.

As the hydrothermal treatment apparatus, it is preferable to use a closed system capable of supplying water vapor under heating and exhausting water vapor and other exhaust gases.
When the hydrothermal treatment temperature is low, the decomposition or desorption of tetraalkylammonium hydroxide (TAAOH) does not progress so much, so this remains in the film, and when used in a liquid crystal display device, power consumption increases as ionic impurities. It may adversely affect display unevenness.

  When the hydrothermal treatment temperature exceeds 450 ° C., the remaining alkyl groups and alkoxy groups derived from the organosilicon compound decrease, and accordingly, moisture adsorption occurs on the film and the ion diffusion prevention performance tends to be insufficient. There is.

The hydrothermal treatment time varies depending on the temperature, but it is desirable to carry out for 1 to 70 minutes, preferably 10 to 60 minutes.
As the water vapor, water vapor obtained from a commercially available water vapor generator can be used. More specifically, water vapor generated using a boiler or the like (temperature: about 100 ° C.) is used as it is, or HORIBA STEC Co., Ltd. Liquid material vaporizer (TL series) and Lintec (
There is a method in which water vapor generated using a water vaporizer (VU-450) manufactured by Co., Ltd. is mixed with a carrier gas such as nitrogen gas.

By supplying water vapor, desorption or decomposition of tetraalkylammonium hydroxide (TAAOH) can be promoted, and further, crosslinking of a film containing silica as a main component can be promoted to obtain an ion diffusion prevention film having excellent strength. Can do.
In this invention, it is preferable to perform the following baking process (e) following the said process (d).

Firing step (e)
In the firing step (e), the coating is fired under a temperature condition of 350 to 450 ° C. in the presence of an inert (N ₂ ) gas. In this step (e), the gas containing water vapor in the step (d) is switched to an inert gas and supplied.

  If the firing temperature is low, firing will be insufficient and polymerization of the silica-based film forming component (formation of the network) or densification will not proceed easily, so that the film strength is insufficient, or ion diffusion prevention performance is insufficient. May be. If the firing temperature is too high, moisture adsorption occurs on the film in response to the decrease in the remaining alkyl groups and alkoxy groups derived from the organosilicon compound, and the ion diffusion prevention performance tends to be insufficient in response to this. is there.

In addition, although baking time changes with temperature, it is desirable to carry out for 5 to 90 minutes, Preferably it takes 10 to 60 minutes.
As the inert gas, a gas such as helium, neon, argon, xenon, or nitrogen is used. In the present invention, inexpensive nitrogen gas is preferable from the viewpoint of economy.

Note that a small amount of air or oxygen gas can be added to the inert gas, and specifically, an inert gas containing about 500 to 10,000 ppm by volume of oxygen may be used.
When a small amount of air or oxygen gas is contained in the inert gas, the crosslinking of the film proceeds and the film strength is improved. Furthermore, moisture adsorption of the film is difficult to occur, and the ion diffusion preventing property can be improved.

Thus, it is preferable that the film thickness of the ion diffusion prevention film formed on the substrate is in the range of 100 to 2,500 nm, more preferably 200 to 1,500 nm.
If the ion diffusion preventing film is thin, the ion diffusion preventing performance may be insufficient. If the ion diffusion preventing film is too thick, cracks may occur and the ion diffusion preventing performance may be insufficient.

Further, the alkali content in the ion diffusion preventing film is preferably 50 ppb or less, more preferably 10 ppb or less.
When the alkali content in the ion diffusion preventing film exceeds 50 ppb, especially in the TFT type liquid crystal display cell device, alkali ions may diffuse and cause malfunction of the TFT.

In addition, the content of anions such as Cl and Br in the ion diffusion preventing film is preferably 10 ppm or less, more preferably 1 ppm or less.
When the content of anions in the ion diffusion preventing film exceeds 10 ppm, the diffusion of alkali ions from the base glass may be promoted, and the alkali ion diffusion preventing performance may be insufficient.

The alkali content is preferably adjusted by a method using a cation or anion exchange resin. This analysis is measured by atomic absorption.
Further, the ion diffusion preventing film has a Young's modulus of 3.0 to 15 GPa, more preferably 5.0.
It preferably has a film strength of ˜15 GPa. If the strength is low, it may be damaged when a transparent electrode film, a transparent insulating film (ion getter film), an alignment film or the like is provided on the ion diffusion preventing film. Those having a high strength of 15 GPa are difficult to obtain by the method of the present invention. In addition, the film | membrane intensity | strength measured the Young's elastic modulus by the nano indentation method using MTS SystemsCorp: Nanoindenter XP.
Below, the base material with an ion diffusion prevention film concerning the present invention is explained.

A substrate with an ion diffusion preventing film A substrate with an ion diffusion preventing film according to the present invention comprises a glass substrate and an ion diffusion preventing film formed on the glass substrate by the above-described method for producing an ion diffusion preventing film. It is characterized by that.

As the substrate, the same glass substrate as described above is used.
The film thickness of the ion diffusion preventing film is preferably in the range of 100 to 2,500 nm, more preferably 200 to 1,500 nm. If the ion diffusion prevention film is thin, the ion diffusion prevention performance may be insufficient. If the ion diffusion prevention film is thick, cracks may occur, and the ion diffusion prevention performance is insufficient. May be.

  Further, the alkali content in the ion diffusion preventing film is preferably 50 ppb or less, more preferably 10 ppb or less as Na or the like. In addition, the content of anions such as Cl and Br in the ion diffusion preventing film is preferably 10 ppm or less, more preferably 1 ppm or less.

Further, the ion diffusion preventing film has a Young's modulus of 3.0 to 15 GPa, more preferably 5.0.
It preferably has a film strength of ˜15 GPa.
Next, the liquid crystal display cell according to the present invention will be described.

Liquid crystal display cell In the first liquid crystal display cell according to the present invention, an ion diffusion prevention film, a transparent electrode film, a transparent insulating film (ion getter film) and an alignment film are sequentially laminated on the surface of at least one soda lime glass substrate. A pair of transparent electrode-equipped substrates are arranged at a predetermined interval so that the transparent electrodes face each other, and liquid crystal is enclosed in a gap formed between the pair of transparent electrode-equipped substrates. In the liquid crystal display cell, the ion diffusion preventing film is an ion diffusion preventing film formed by the method for producing an ion diffusion preventing film.

  FIG. 1 is a cross-sectional view schematically showing an embodiment of the first liquid crystal display cell according to the present invention. This liquid crystal display cell 1 includes a pair of substrates 2 with a transparent electrode in which an ion diffusion prevention film 17, a transparent electrode film 18, a transparent ion getter film 13 and an alignment film 14 are sequentially laminated on the surface of a soda lime glass substrate 11. 2 are arranged at a predetermined interval d by a plurality of spacer particles 3 so that the transparent electrode films 18 face each other, and in the gap between the transparent electrode-equipped substrates 2 opened at the predetermined interval d. The liquid crystal 6 is enclosed and formed.

The ion diffusion preventing film 17 is formed by applying the ion diffusion preventing film forming coating solution on the surface of the soda lime glass substrate 21. Therefore, this film is excellent in transparency and scratch resistance, has high insulation resistance, and can effectively prevent diffusion of alkali ions from the substrate.

  A liquid crystal display cell according to another aspect of the present invention includes a pair of substrates with a transparent electrode in which a color filter, a transparent ion getter film, a transparent electrode film, and an alignment film are sequentially laminated on the surface of at least one substrate, respectively. This is a liquid crystal display cell in which liquid crystal is sealed in a gap formed between the pair of substrates with a transparent electrode, which is disposed with a predetermined interval so that the transparent electrodes face each other.

FIG. 2 is a schematic view schematically showing an example of an embodiment of the second liquid crystal display cell according to the present invention. The color liquid crystal display device 1 ′, whose characteristic parts are shown in FIG. 2, has an ion diffusion prevention film 21b, a plurality of pixel electrodes 21c, a transparent ion getter film 21d and an alignment film 21e on a soda lime glass substrate 21a. And a counter electrode plate 22 in which an ion diffusion prevention film 22b, a color filter 22c, a transparent ion getter film 22d, a transparent electrode 22e, and an alignment film 22f are sequentially stacked on a glass substrate 22a. A liquid crystal display cell 2 ′ and a pair of polarizing plates 3 ′ and 4 ′ are provided on both sides of the liquid crystal display cell. Among these, the transparent ion getter films 21d and 22d are films formed by applying the coating liquid for forming the transparent ion getter film.

  The electrode plate 21 and the counter electrode plate 22 of the liquid crystal display cell 2 are arranged such that each of the plurality of pixel electrodes 21c and each of the plurality of color filters R, G, and B has the glass base materials 21a and 22a outside. It arrange | positions so that it may oppose. A liquid crystal 23 is sealed in a gap between the electrode plate 21 and the counter electrode plate 22.

Further, a circuit (not shown) is formed between each of the plurality of pixel electrodes 21c and the transparent electrode 22e, and this circuit is connected to the main body of the color liquid crystal display device 1. The color filter 22c formed on the passivation film 22b of the counter electrode plate 22 is composed of a plurality of color elements R (red filter), G (green filter), and B (blue filter). A circuit formed between the specific pixel electrode 21c and the transparent electrode 22e is actuated by a display signal sent from the liquid crystal display device 1 ′ main body so as to be regularly arranged so as to correspond to the display signal. A color image can be observed through the polarizing plate 4 disposed outside the counter electrode plate 22.

  A third liquid crystal display cell according to the present invention has a pair of substrates with a transparent electrode in which a TFT array, a transparent ion getter film, a transparent electrode film, and an alignment film are sequentially laminated on the surface of at least one substrate. In this liquid crystal display cell, liquid crystal is sealed in a gap formed between the pair of transparent electrode-equipped substrates, with the transparent electrodes disposed so as to face each other.

  FIG. 3 is a schematic cross-sectional view schematically showing an example of an aspect of the third liquid crystal display cell according to the present invention. In the liquid crystal display cell 1 ″, an ion diffusion prevention film 38 is formed on the surface of a soda lime glass substrate 31, and an insulating film 36 and a TFT array 32 are further formed on the surface. A transparent insulating substrate 31 having a transparent ion getter film 33, a pixel electrode 34, and an alignment film 35 sequentially stacked on the surface, an ion diffusion preventing film 38, a black matrix (shielding film) 42, a color filter 43, The transparent ion getter film 44, the counter electrode 45, and the counter substrate 41 on which the alignment film 46 is sequentially stacked are configured so that the alignment films 35 and 46 face each other with the liquid crystal layer 51 interposed therebetween.

Since the liquid crystal display cell according to the present invention as described above is formed with an ion diffusion prevention film obtained through a specific process, the diffusion of alkali ions from the substrate can be prevented, and the liquid crystal display cell When used in a TFT, the voltage characteristics of the semiconductor layer of the TFT are changed to prevent malfunction, and the amount of movable ions in the liquid crystal is not increased, so that there is no display unevenness with low power consumption. Excellent display quality.

[Example]
EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[Example 1]
Preparation of coating solution (1) for forming an ion diffusion prevention film 1 kg of an aqueous solution containing 40% by weight of tetrapropylammonium hydroxide (TPAOH, manufactured by Lion Corporation) and 300 g of cation exchange resin powder (WK-40, Mitsubishi Chemical) (Made by Co., Ltd.) was added and stirred at room temperature for 1 hour at a speed of 100 rpm, and the added cation exchange resin powder was removed by filtration. Next, 2100 g of anion exchange resin powder (SAT-10, manufactured by Mitsubishi Chemical Corporation) was added and stirred at room temperature for 1 hour at a speed of 100 rpm, and then the added anion exchange resin powder was filtered. Removed.

Ultrapure water is added to the resulting aqueous solution of tetrapropylammonium hydroxide (TPAOH) to adjust the concentration to 10% by weight, and sodium (Na) and potassium (K) alkali metals contained as impurities in the aqueous solution Amounts of elemental compounds and halogen group compounds of bromine (Br) and chlorine (Cl) were determined by atomic absorption spectrometry (AAS method, polarized Zeeman atomic absorption photometer Z-5710, manufactured by Hitachi, Ltd.) and ion chromatography, respectively. Measured by the method (2020i made by DIONEX).

  Further, after adding ultrapure water to the aqueous solution (commercial product) of the tetrapropylammonium hydroxide before the ion exchange treatment described above to adjust the concentration to 10% by weight, the impurities contained therein are similarly treated. The content was measured.

  As a result, the amount of impurities contained in the aqueous solution before the ion exchange treatment was 50 ppm by weight of sodium, 2500 ppm by weight of potassium, 2250 ppm by weight of bromine, and 13 ppm by weight of chlorine on the element basis. The content of impurities contained in the subsequent aqueous solution was 10 wt ppb or less of sodium (detection limit), 10 wt ppb (detection limit) of potassium, 1 wt ppm or less of bromine and 1 wt ppm or less of chlorine on an element basis. That is, the purity of the tetrapropylammonium hydroxide aqueous solution (commercial product) could be increased to the allowable impurity level required in the present invention.

  Next, 89.3 g of tetraethylorthosilicate (TEOS, manufactured by Tama Chemical Industry Co., Ltd.), 56.8 g of methyltrimethoxysilane (MTMS, manufactured by Shin-Etsu Chemical Co., Ltd.), and 260.000 ethanol at a concentration of 99.5% by weight. 7 g (ETOH, manufactured by Wako Pure Chemical Industries, Ltd.) was mixed, and this mixed solution was kept at a temperature of 20 ° C. and stirred at a speed of 150 rpm for 30 minutes.

To this mixed solution, 593.2 g of a purified tetrapropylammonium hydroxide aqueous solution (containing 10 wt% TPAOH) was added dropwise over 10 minutes, and further 20 ° C.
For 1 hour at a speed of 200 rpm. Then, it heated to the temperature of 50 degreeC, and hydrolyzed TEOS and MTMS for 20 hours, stirring at the speed of 200 rpm under this temperature condition.

Next, ethanol (organic solvent) in the mixed solution containing the hydrolyzate is mixed with propylene glycol monopropyl ether (PGP, Nippon Emulsifier Co., Ltd.) using a rotary evaporator (R-114 manufactured by Shibata Kagaku Co., Ltd.). In the solvent substitution step, the concentration of the silicon compound consisting of a hydrolyzate of tetraethylorthosilicate (TEOS) and methyltrimethoxysilane (MTMS) and water is adjusted, and the silicon compound is 12% by weight on the basis of SiO ₂ conversion. In this way, 416.73 g of a coating solution (1) for forming an ion diffusion preventing film containing 1% by weight of water was obtained.

When the number average molecular weight of the silicon compound contained in the obtained coating solution for forming an ion diffusion preventing film was measured (liquid chromatographic method), it was about 15.0 based on polyethylene oxide conversion standard.
00.

Preparation of Ion Diffusion-Preventing Base Material (1) The above-mentioned coating solution for forming an ion diffusion-preventing film (1) is spin-coated on a soda lime glass base material (Asahi Glass Co., Ltd .: Na content: 13% by weight). And dried at 60 ° C. for 3 minutes. Thereafter, a hydrothermal treatment was performed in heated steam at 250 ° C. for 30 minutes, and then the substrate was baked at 400 ° C. for 30 minutes in a nitrogen gas atmosphere to prepare a substrate (1) with an ion diffusion prevention film.

With respect to the obtained substrate (1) with an ion diffusion preventing film, the film thickness, the alkali content in the film, the alkali ion diffusion preventing performance, the average pore diameter and the film strength were measured, and the results are shown in Table 1. The film strength and alkali ion diffusion prevention performance were measured by the following methods.

Evaluation of Alkali Ion Diffusion Prevention Performance 10 ml of distilled water was dropped on a substrate (1) with an ion diffusion prevention film and allowed to stand at 30 ° C. for 2 hours, and then all of the distilled water was recovered. The alkali ions (sodium ions) in the collected liquid were quantified by ICP-MS, and the results are shown in Table 1.

Preparation of coating liquid (1) for forming transparent insulating film 14.6 g of ethyl silicate 28 (manufactured by Tama Chemical Industry Co., Ltd .: SiO ₂ concentration 28.8 wt%) as a matrix forming component, 5 g of pure water and 62.3 g of ethyl alcohol Then, 0.1 g of nitric acid having a concentration of 61% was added thereto to prepare a partial hydrolyzate (oligomer) solution (dispersion) of ethyl silicate.

Into this solution, inorganic ion adsorbent fine particles having an average particle diameter of 200 mm (Sb ₂ O ₅ .0.1H ₂ O) as inorganic ion adsorbent fine particles are uniformly dispersed in hexylene glycol and having a solid content of 10% by weight. 1.0 g of the fine particle sol was added and stirred for 24 hours, and then 70 g of hexylene glycol was added, followed by distillation under reduced pressure to prepare a coating liquid (1) for forming a transparent insulating film having a solid content concentration of 6.0% by weight. .

Formation of transparent insulating film (1) Obtained by applying coating solution (A) by flexographic printing on a patterned soda lime glass substrate with ITO display electrode (Asahi Glass Co., Ltd .: 30Ω / □ or less) The coated film was dried at 90 ° C. for 5 minutes, then irradiated with ultraviolet light under a condition of an integrated light intensity of 6,000 mJ / cm ² (measured with a 365 nm sensor) with a high-pressure mercury lamp, and then baked at 300 ° C. for 30 minutes. A transparent insulating film (1) was formed. The film thickness of the obtained transparent insulating film (1) was measured with a stylus type surface roughness meter to be 80 nm.

Preparation of liquid crystal display cell (1) Next, a coating for forming a polyimide film on the transparent insulating film (1) (Nissan Chemical Co., Ltd .: Sunever)
Was applied by flexographic printing, dried at 100 ° C. for 5 minutes, heat-treated at 240 ° C. for 30 minutes to form a polyimide film, and then rubbed.

In this way, a pair of substrates with a transparent electrode was obtained in which an ion diffusion preventing film (1), a transparent electrode, a transparent insulating film (1), and a rubbing-treated alignment film were sequentially laminated on a soda lime glass substrate.

  Spacers of (particle diameter corresponding to the distance between two substrates) are dispersed on one of the obtained substrates with a transparent electrode, and (epoxy resin resin and on the other substrate) Sealing material for sealing (consisting of silica fine particles) is printed, these substrates are bonded so that the transparent electrodes face each other, STN liquid crystal is sealed, and the sealing port is sealed with a sealing material A liquid crystal display cell (1) was prepared.

Observation of display unevenness of the liquid crystal panel In addition, 10 liquid crystal display cells (1) were prepared, and the environment was high temperature and high humidity (relative humidity 95%, temperature 8).
After 500 hours exposure to 0 ° C., a lighting display test of each liquid crystal panel was performed, and the presence or absence of display unevenness and display performance at this time were visually observed. Table 1 shows the number of panels in which display unevenness did not occur. Shown in

[Example 2]
Preparation of substrate with ion diffusion preventing film (2) Preparation of substrate (2) with ion diffusion preventing film in the same manner as in Example 1 except that hydrothermal treatment was performed in heated steam at 150C for 30 minutes. did.

With respect to the obtained substrate (2) with an ion diffusion prevention film, the film thickness, the alkali content in the film, the alkali ion diffusion prevention performance, the average pore diameter and the film strength were measured, and the results are shown in Table 1.

In the creation Example 1 of the liquid crystal display cell (2), except for using an ion diffusion preventing film substrate with (2) to create a liquid crystal display cell (2) in the same manner. The obtained liquid crystal display cell (2) was visually observed for the presence of display unevenness and display performance, and the results are shown in Table 1.

[Example 3]
Preparation of substrate with ion diffusion preventing film (3) A substrate with ion diffusion preventing film (3) was prepared in the same manner as in Example 1 except that hydrothermal treatment was performed in heated steam at 350 ° C for 30 minutes. With respect to the obtained substrate (3) with an ion diffusion prevention film, the film thickness, the alkali content in the film, the alkali ion diffusion prevention performance, the average pore diameter and the film strength were measured, and the results are shown in Table 1.

In preparing a first embodiment of the liquid crystal display cell (3), except for using an ion diffusion preventing film-substrate (3) to create a liquid crystal display cell (3) in the same manner.
The obtained liquid crystal display cell (3) was visually observed for the presence of display unevenness and display performance, and the results are shown in Table 1.

[Example 4]
Preparation of Coating Solution (4) for Forming Ion Diffusion Prevention Film Same as in Example 1 except that 89.3 g of tetraethylorthosilicate, 190.7 g of methyltrimethoxysilane and 260.7 g of ethanol of 99.5 wt% concentration were mixed. Thus, 90.0 g of a coating solution for forming an ion diffusion prevention film containing 12% by weight of a silicon compound on a SiO ₂ conversion basis and 1% by weight of water was obtained.

When the number average molecular weight of the silicon compound contained in the obtained coating solution (4) for forming an ion diffusion preventing film was measured (liquid chromatographic method), it was about 10,000 in terms of polyethylene oxide.

Preparation of base material (4) with an ion diffusion prevention film A base material (4) with an ion diffusion prevention film was prepared in the same manner as in Example 1 except that the coating liquid (4) for forming an ion diffusion prevention film was used. With respect to the obtained substrate (4) with an ion diffusion prevention film, the film thickness, the alkali content in the film, the alkali ion diffusion prevention performance, the average pore diameter and the film strength were measured, and the results are shown in Table 1.

In preparing a first embodiment of the liquid crystal display cell (4), except for using an ion diffusion preventing film-substrate (4) was prepared a liquid crystal display cell (4) in a similar manner. The obtained liquid crystal display cell (4) was visually observed for the presence of display unevenness and display performance, and the results are shown in Table 1.

[Example 5]
Preparation of coating solution (5) for forming an ion diffusion preventing film The same as in Example 1, except that 122.9 g of tetraethylorthosilicate, 56.8 g of methyltrimethoxysilane and 260.7 g of ethanol having a concentration of 99.5% by weight were mixed. Thus, 500 g of a coating solution for forming an ion diffusion preventing film containing 12% by weight of a silicon compound in terms of SiO ₂ and 1% by weight of water was obtained.

When the number average molecular weight of the silicon compound contained in the obtained coating solution for forming an ion diffusion preventing film was measured (liquid chromatographic method), it was about 30,000 in terms of polyethylene oxide.
00.

Preparation of base material (5) with an ion diffusion prevention film A base material (5) with an ion diffusion prevention film was prepared in the same manner as in Example 1 except that the coating liquid (5) for forming an ion diffusion prevention film was used.
With respect to the obtained substrate (5) with an ion diffusion prevention film, the film thickness, the alkali content in the film, the alkali ion diffusion prevention performance, the average pore diameter and the film strength were measured, and the results are shown in Table 1.

In preparing a first embodiment of the liquid crystal display cell (5), except for using an ion diffusion preventing film substrate with (5) to create a liquid crystal display cell (5) in the same manner. The obtained liquid crystal display cell (5) was visually observed for the presence of display unevenness and display performance, and the results are shown in Table 1.

[Example 6]
Preparation of coating solution (6) for forming an ion diffusion preventing film In Example 1, except that 261.7 g of a highly purified tetrapropylammonium hydroxide aqueous solution (containing 10 wt% TPAOH) was added dropwise over 10 minutes. Similarly, 416.7 g of a coating solution for forming an ion diffusion preventing film containing 12% by weight of a silicon compound on a SiO ₂ conversion basis and 1% by weight of water was obtained.

When the number average molecular weight of the silicon compound contained in the obtained coating solution (6) for forming an ion diffusion preventing film was measured (liquid chromatographic method), it was about 12,000 in terms of polyethylene oxide conversion.

Preparation of base material (6) with an ion diffusion prevention film A base material (6) with an ion diffusion prevention film was prepared in the same manner as in Example 1 except that the coating liquid (6) for forming an ion diffusion prevention film was used.
With respect to the obtained substrate (6) with an ion diffusion prevention film, the film thickness, the alkali content in the film, the alkali ion diffusion prevention performance, the average pore diameter, and the film strength were measured, and the results are shown in Table 1.

In preparing a first embodiment of the liquid crystal display cell (6), except for using an ion diffusion preventing film-substrate (6) has created a liquid crystal display cell (6) in a similar manner.
The obtained liquid crystal display cell (6) was visually observed for the presence of display unevenness and display performance, and the results are shown in Table 1.

[Example 7]
Preparation of Coating Solution for Forming Ion Diffusion Prevention Film (7) In Example 1, except that 1046.8 g of highly purified tetrapropylammonium hydroxide aqueous solution (containing 10 wt% TPAOH) was added dropwise over 20 minutes. Similarly, 416.7 g of a coating solution for forming an ion diffusion preventing film containing 12% by weight of a silicon compound on a SiO ₂ conversion basis and 1% by weight of water was obtained.

When the number average molecular weight of the silicon compound contained in the obtained coating solution (7) for forming an ion diffusion preventing film was measured (liquid chromatographic method), it was about 50,000 in terms of polyethylene oxide.

Preparation of substrate (7) with ion diffusion preventing film A substrate (7) with ion diffusion preventing film was prepared in the same manner as in Example 1 except that the coating solution (7) for forming an ion diffusion preventing film was used.
The film thickness, the alkali content in the film, the alkali ion diffusion preventing performance, the average pore diameter and the film strength of the obtained substrate (7) with an ion diffusion preventive film were measured, and the results are shown in Table 1.

In preparing a first embodiment of the liquid crystal display cell (7), except for using an ion diffusion preventing film-substrate (7) to create a liquid crystal display cell (7) in the same manner. The obtained liquid crystal display cell (7) was visually observed for the presence of display unevenness and display performance, and the results are shown in Table 1.

[Example 8]
Preparation of Coating Solution for Forming Ion Diffusion Preventing Film (8) In Example 1, tetramethylorthosilicate 65.4 g (TMOS, manufactured by Tama Chemical Co., Ltd.), methyltriethoxysilane 74.9 g (MTES, Shin-Etsu Chemical Co., Ltd.) And 129.5% by weight of silicon compound in terms of SiO ₂ , except that 260.7 g of ethanol having a concentration of 99.5% by weight (ETOH, manufactured by Wako Pure Chemical Industries, Ltd.) was mixed, and 425.0 g of a coating solution for forming an ion diffusion preventing film containing 1% by weight of water was obtained.

When the number average molecular weight of the silicon compound contained in the obtained coating solution (8) for forming an ion diffusion barrier film was measured (liquid chromatographic method), it was about 20,000 in terms of polyethylene oxide.

Preparation of base material (8) with an ion diffusion prevention film A base material (8) with an ion diffusion prevention film was prepared in the same manner as in Example 1 except that the coating liquid (8) for forming an ion diffusion prevention film was used.
The film thickness, the alkali content in the film, the alkali ion diffusion preventing performance, the average pore diameter and the film strength of the obtained substrate (8) with an ion diffusion preventive film were measured, and the results are shown in Table 1.

In preparing a first embodiment of the liquid crystal display cell (8), except for using an ion diffusion preventing film-substrate (8) to create a liquid crystal display cell (8) in a similar manner. The obtained liquid crystal display cell (8) was visually observed for the presence of display unevenness and display performance, and the results are shown in Table 1.

[Example 9]
Preparation of Coating Solution (9) for Formation of Ion Diffusion Prevention Film 22.5 g of bis (triethoxysilyl) ethane (BTESE, manufactured by GELEST), 52.5 g of methyltrimethoxysilane (MTMS, manufactured by Shin-Etsu Chemical Co., Ltd.) and 99 147 g of ethanol having a concentration of 5% by weight (ETOH, manufactured by Wako Pure Chemical Industries, Ltd.) was mixed, and this mixed solution was kept at a temperature of 20 ° C. and stirred at a speed of 150 rpm for 30 minutes.

To this mixed solution, 417 g (containing 10 wt% TPAOH) of the high purity tetrapropylammonium hydroxide aqueous solution prepared in Preparation Example 1 was added dropwise over 10 minutes, and further 1 at a speed of 200 rpm at a temperature of 20 ° C. Stir for hours. Then, it heated to the temperature of 75 degreeC, and hydrolyzed the said silica type film formation component (BTESM and MTMS) for 20 hours, stirring at the speed | rate of 200 rpm under this temperature condition.

Next, ethanol (organic solvent) in the mixed solution containing the hydrolyzate of the silica-based film-forming component was mixed with propylene glycol monopropyl ether (PGP, Nippon Emulsifier) using a rotary evaporator (R-114 manufactured by Shibata Kagaku Co., Ltd.). And the concentration of water and the silicon compound consisting of a hydrolyzate of bis (triethoxysilyl) methane (BTESM) and methyltrimethoxysilane (MTMS) 554 g of an ion diffusion prevention film forming coating solution (9) containing 6% by weight of the compound on a SiO ₂ conversion basis and 0.5% by weight of water was prepared.

When the number average molecular weight of the silicon compound in the coating solution (9) for forming an ion diffusion preventing film was measured (liquid chromatographic method), it was about 21,000 in terms of polyethylene oxide.

Preparation of base material (9) with an ion diffusion prevention film A base material (9) with an ion diffusion prevention film was prepared in the same manner as in Example 1 except that the coating liquid (9) for forming an ion diffusion prevention film was used.
With respect to the obtained substrate (9) with an ion diffusion prevention film, the film thickness, the alkali content in the film, the alkali ion diffusion prevention performance, the average pore diameter, and the film strength were measured, and the results are shown in Table 1.

A liquid crystal display cell (9) was prepared in the same manner as in preparation 1 of the liquid crystal display cell (9) except that the base material (9) with an ion diffusion preventing film was used.
The obtained liquid crystal display cell (9) was visually observed for the presence of display unevenness and display performance, and the results are shown in Table 1.

[Example 10]
Preparation of coating solution (10) for ion diffusion prevention film formation 14 g of bis (triethoxysilyl) ethane (BTESE, manufactured by GELEST), 21 g of methyltrimethoxysilane (MTMS, manufactured by Shin-Etsu Chemical Co., Ltd.), 24 g of tetraethylorthosilicate ( TEOS (manufactured by Tama Chemical Co., Ltd.) and 98 g of ethanol of 99.5% by weight (ETOH, manufactured by Wako Pure Chemical Industries, Ltd.) were mixed, and this mixed solution was kept at a temperature of 20 ° C. Stir at speed for 30 minutes.

To this mixed solution, 308 g of the high-purity tetrapropylammonium hydroxide aqueous solution prepared in Preparation Example 1 (containing 10 wt% TPAOH) was added dropwise over 10 minutes, and further 1 at a temperature of 20 ° C. and a speed of 200 rpm. Stir for hours. Then, it heated to the temperature of 75 degreeC, and hydrolyzed the said silica type film formation component (BTESE, MTMS, and TEOS) for 20 hours, stirring at the speed of 200 rpm on this temperature condition.

Next, 500 g of propylene glycol monopropyl ether (PGP, Japan) was added to the ethanol (organic solvent) in the mixed solution containing the hydrolyzate of the silica-based film forming component using a rotary evaporator (R-114 manufactured by Shibata Kagaku Co., Ltd.). Emulsifier (manufactured by Co., Ltd.) and a solvent substitution process, silicon compound consisting of hydrolyzate of bis (triethoxysilyl) ethane (BTESE), methyltrimethoxysilane (MTMS) and tetraethylorthosilicate (TEOS) and moisture In this way, 371 g of an ion diffusion prevention film-forming coating solution (10) containing 6% by weight of the silicon compound on a SiO ₂ conversion basis and 4% by weight of water was prepared.

When the number average molecular weight of the silicon compound in the coating solution (10) for forming an ion diffusion preventing film was measured (liquid chromatographic method), it was about 17,000 in terms of polyethylene oxide.

Preparation of Substrate (10) with Ion Diffusion Prevention Film A substrate (10) with an ion diffusion prevention film was prepared in the same manner as in Example 1 except that the coating liquid (10) for forming an ion diffusion prevention film was used.
With respect to the obtained substrate (10) with an ion diffusion prevention film, the film thickness, the alkali content in the film, the alkali ion diffusion prevention performance, the average pore diameter and the film strength were measured, and the results are shown in Table 1.

In preparing a first embodiment of liquid crystal display cell (10), except for using an ion diffusion preventing film-substrate (10) to create a liquid crystal display cell (10) in a similar manner. The obtained liquid crystal display cell (10) was visually observed for the presence of display unevenness and display performance, and the results are shown in Table 1.

[Comparative Example 1]
Preparation of coating solution (R1) for forming an ion diffusion preventing film Tetraethyl orthosilicate 89.3 g (TEOS, manufactured by Tama Chemical Co., Ltd.), methyltrimethoxysilane 56.8 g (MTMS, manufactured by Shin-Etsu Chemical Co., Ltd.) and 260.7 g of ethanol having a concentration of 99.5% by weight (ETOH, manufactured by Wako Pure Chemical Industries, Ltd.) was mixed, and this mixed solution was kept at a temperature of 20 ° C. and stirred at a speed of 150 rpm for 30 minutes.

To this mixed solution, 49.3 g of a 10 wt% NH ₃ aqueous solution was added dropwise over 10 minutes, and the mixture was further stirred at a temperature of 20 ° C. and a speed of 200 rpm for 1 hour. Then, it heated to the temperature of 50 degreeC, and hydrolyzed TEOS and MTMS for 20 hours, stirring at the speed of 200 rpm under this temperature condition.

Next, ethanol (organic solvent) in the mixed solution containing the hydrolyzate is mixed with propylene glycol monopropyl ether (PGP, Nippon Emulsifier Co., Ltd.) using a rotary evaporator (R-114 manufactured by Shibata Kagaku Co., Ltd.). In the solvent substitution step, the concentration of the silicon compound consisting of a hydrolyzate of tetraethylorthosilicate (TEOS) and methyltrimethoxysilane (MTMS) and water is adjusted, and the silicon compound is 12% by weight on the basis of SiO ₂ conversion. 416.7 g of a coating solution for forming an ion diffusion preventing film containing 1% by weight of water was obtained.

  When the number average molecular weight of the silicon compound contained in the thus obtained coating solution for forming an ion diffusion preventing film was measured (liquid chromatographic method), it was about 12,000 in terms of polyethylene oxide.

Preparation of Ion Diffusion-Preventing Substrate (R1) In Example 1, the same procedure was used except that the ion-diffusion-preventing film-forming coating solution (R1) was used and hydrothermal treatment was not performed in heated steam at 250 ° C. for 30 minutes. Thus, a base material (R1) with an ion diffusion preventing film was prepared.
The film thickness, alkali content in the film, alkali ion diffusion preventing performance, average pore diameter and film strength of the obtained substrate (R1) with ion diffusion preventing film were measured, and the results are shown in Table 1.

In preparing a first embodiment of the liquid crystal display cell (R1), except for using an ion diffusion preventing film substrate with (R1) was prepared a liquid crystal display cell (R1) in a similar manner.
The obtained liquid crystal display cell (R1) was visually observed for display unevenness and display performance, and the results are shown in Table 1.

[Comparative Example 2]
Preparation of substrate with ion diffusion preventing film (R2) In Example 1, with the use of ion diffusion preventing film, except that the coating liquid for forming ion diffusion preventing film (R1) prepared in the same manner as Comparative Example 1 was used. A substrate (R2) was prepared.
With respect to the obtained substrate (R2) with an ion diffusion prevention film, the film thickness, the alkali content in the film, the alkali ion diffusion prevention performance, the average pore diameter and the film strength were measured, and the results are shown in Table 1.

In preparing a first embodiment of the liquid crystal display cell (R2), except for using an ion diffusion preventing film substrate with (R2) was prepared a liquid crystal display cell (R2) in a similar manner. The obtained liquid crystal display cell (R2) was visually observed for the presence of display unevenness and display performance, and the results are shown in Table 1.

[Comparative Example 3]
Preparation of substrate with ion diffusion preventing film (R3) A substrate with ion diffusion preventing film (R3) was prepared in the same manner as in Example 1 except that hydrothermal treatment was performed in heated steam at 100 ° C for 30 minutes.
With respect to the obtained substrate (R3) with an ion diffusion prevention film, the film thickness, alkali content in the film, alkali ion diffusion prevention performance, average pore diameter, and film strength were measured, and the results are shown in Table 1.

In preparing a first embodiment of the liquid crystal display cell (R3), except for using an ion diffusion preventing film substrate with (R3) has created a liquid crystal display cell (R3) in the same manner.
The obtained liquid crystal display cell (R3) was visually observed for the presence of display unevenness and display performance, and the results are shown in Table 1.

[Comparative Example 4]
Preparation of substrate with ion diffusion preventing film (R4) A substrate with ion diffusion preventing film (R4) was prepared in the same manner as in Example 1 except that hydrothermal treatment was performed in heated steam at 500 ° C for 30 minutes.
The obtained substrate (R4) with an ion diffusion prevention film was measured for film thickness, alkali content in the film, alkali ion diffusion prevention performance, average pore diameter and film strength, and the results are shown in Table 1.

In preparing a first embodiment of the liquid crystal display cell (R4), except for using an ion diffusion preventing film-substrate (R4) has created a liquid crystal display cell (R4) in the same manner.

  The obtained liquid crystal display cell (R4) was visually observed for the presence of display unevenness and display performance, and the results are shown in Table 1.

The schematic sectional drawing of the example of 1 aspect of the 1st liquid crystal display cell which concerns on this invention is shown. The schematic sectional drawing of the example of 1 aspect of the 2nd liquid crystal display cell which concerns on this invention is shown. The schematic sectional drawing of the example of 1 aspect of the 3rd liquid crystal display cell which concerns on this invention is shown.

Explanation of symbols

1, 1 ', 1 "... liquid crystal display cell 2, 2' ... liquid crystal display cell 3, 4, ... polarizing plate 5 ... spacer particles 6 ... ······························································································· Orientation Film 17... Ion diffusion prevention film 18... Transparent electrode film 21... Electrode plate 21 a. Diffusion prevention film 21c... Multiple pixel electrodes 21d... Transparent ion getter film 21e... Orientation film 22. ··· Glass substrate 22b ··· Ion diffusion preventing film 22c ··· Color filter 22d ··· Transparent ion getter film 22e ···・ Transparent electrode 22f ・ ・ ・ ・ ・ ・ Alignment film 23 ・ ・ ・ ・ ・ ・ Liquid crystal 31 ・ ・ ・ ・ ・ ・ Transparent insulating substrate 32 ・ ・ ・ ・ ・ ・ TFT array 33 ・ ・ ・.. Transparent ion getter film 34... Pixel electrode 35... Alignment film 36. ···································· Black matrix (shielding film)
43 ... Color filter 44 ... Transparent ion getter film 45 ... Counter electrode 46 ... Orientation film 51 ... Liquid crystal layer

Claims (13)

The manufacturing method of the ion diffusion prevention film | membrane characterized by including the following process (a)-(d).
(A) Ion diffusion prevention containing a silicon compound obtained by hydrolyzing an organosilicon compound represented by the following general formula (I) and / or the following general formula (II) in the presence of tetraalkylammonium hydroxide (TAAOH) Step X _n Si (OR) _4-n (I) for preparing a coating solution for film formation
(In the formula, X represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 8 carbon atoms, a fluorine-substituted alkyl group, an aryl group or a vinyl group, and R represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, Represents an aryl group or a vinyl group, and n is an integer of 0 to 3.)

(In the formula, R ¹ represents a methylene group, an ethylene group or a propylene group, and R ^{2 to} R ⁷ may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a fluorine-substituted alkyl group, Represents an aryl group or a vinyl group.)
(B) The process of apply | coating the coating liquid for ion diffusion prevention film formation on a glass base material (c) The process of drying a coating film at the temperature of 25-350 degreeC (drying process)
(D) A step of heat-treating the coating film in the presence of water vapor at a temperature of 105 to 450 ° C. (hydrothermal treatment step)   The organosilicon compound is one or more selected from n = 0 organic silicon compounds (tetraalkylorthosilicate (TAOS)) of the general formula (I), and n = 1 to 3 of the general formula (I). 2. The method for producing a coating liquid for forming an ion diffusion preventing film according to claim 1, wherein the coating liquid is a mixture with one or more selected from an organosilicon compound (alkoxysilane (AS)). 3. The method according to claim 1, wherein after the step (d), (e) a step (baking step) of baking the coating film under a temperature condition of 350 to 450 ° C. in the presence of an inert gas is performed. The manufacturing method of the coating liquid for ion diffusion prevention film description of description . Step tetraalkyl orthosilicate used in (a) the number of moles of _(TAOS) (M TAOS) and the alkoxysilane moles of silane _(AS) (M AS) and the molar ratio of _{(M TAOS) / (M AS} ) is The method for producing an ion diffusion preventing film according to any one of claims 1 to 3, wherein the method is in a range of 0.25 to 1.5. In the step (a), the number of moles of the tetraalkyl ammonium hydroxide (TAAOH) (M _T) and the total number of moles of the organic silicon compound (M _S) and the molar ratio of _{(M T) / (M S} ) is 0. It exists in the range of 1-0.7, The manufacturing method of the ion diffusion prevention film in any one of Claims 1-4 characterized by the above-mentioned.   A method for producing an ion diffusion preventing film obtained by the method according to claim 1 and having a film thickness in the range of 100 to 2,500 nm. Furthermore, the average pore diameter is in the range of 1.0 to 3.0 nm, and the alkali content is 50 ppb or less.   A substrate with an ion diffusion prevention film comprising a glass substrate and an ion diffusion prevention film formed on the glass substrate, wherein the ion diffusion prevention film is obtained by the method according to claim 1. A substrate with an ion diffusion prevention film, which is characterized in that   The base material with an ion diffusion preventing film according to claim 8, wherein the film thickness of the ion diffusion preventing film is in a range of 100 to 2,500 nm.   9. The substrate with an ion diffusion preventing film according to claim 8, wherein the ion diffusion preventing film has an average pore diameter in a range of 1.0 to 3.0 nm and an alkali content of 50 ppb or less.   A pair of substrates with a transparent electrode, in which an ion diffusion preventing film, a transparent electrode film, a transparent insulating film (ion getter film) and an alignment film are sequentially laminated on the surface of at least one glass substrate, In a liquid crystal display cell in which liquid crystal is sealed in a gap formed between the pair of substrates with a transparent electrode and arranged at a predetermined interval so as to face each other, the ion diffusion preventing film is formed from claim 1. A liquid crystal display cell formed by the method for producing an ion diffusion preventing film according to any one of.   On the surface of at least one glass substrate, a pair of substrates with a transparent electrode, in which an ion diffusion preventing film, a color filter, a transparent insulating film (ion getter film), a transparent electrode film and an alignment film are sequentially laminated, In a liquid crystal display cell that is arranged with a predetermined interval so that the transparent electrodes face each other, and liquid crystal is sealed in a gap formed between the pair of substrates with transparent electrodes, an ion diffusion prevention film is A liquid crystal display cell comprising an ion diffusion prevention film formed by the method for producing an ion diffusion prevention film according to claim 1.   A pair of transparent electrodes in which an ion diffusion preventing film, a TFT array (TFT element, data electrode), a transparent insulating film (ion getter film), a transparent electrode film and an alignment film are sequentially laminated on the surface of at least one glass substrate In the liquid crystal display cell in which the base material is disposed at a predetermined interval so that the transparent electrodes face each other, and liquid crystal is sealed in the gap formed between the pair of base materials with the transparent electrode A liquid crystal display cell, wherein the ion diffusion preventing film is formed by the method for producing an ion diffusion preventing film according to claim 1.

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