JP2000169766A - Coating solution for formation of transparent ion getter film, film-attached substrate, and liquid crystal display cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating solution for transparent film formation, which is capable of forming a film that is excellent in scratch resistance, acid resistance, alkali resistance, water resistance and insulating property, is excellent in adhesion to an electrode film or an aligned film made of a highly hydrophobic resins such as a polyimide resin, and is able to reduce an impurity ion component in a liquid crystal, and a film-attached substrate and a liquid crystal display cell, both having such a film as mentioned above. SOLUTION: The coating solution for the formation of a transparent ion getter film comprises (A) a matrix-forming component, and (B) ion-adsorbing inorganic fine particles, each dispersed in a mixed solvent of water and an organic solvent, wherein the ion-adsorbing inorganic fine particles (B) have an average particle size ranging from 1 nm to 10 μm, and the ion-adsorbing inorganic fine particles have an ion adsorption capacity ranging from 0.1 to 3.0 mmols/g.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a coating solution for forming a transparent ion getter film, a substrate having a transparent ion getter film, and a liquid crystal display cell. More specifically, the present invention is excellent in abrasion resistance, acid resistance, alkali resistance, water resistance, adhesion to an alignment film and the like, and can flatten a substrate having fine irregularities of about several μm, A coating liquid for forming a transparent coating capable of forming a coating capable of reducing the amount of ions in a liquid crystal display panel, a coated substrate having a coating formed from the coating liquid for forming a coating, and the coated substrate The present invention relates to a liquid crystal display cell having the same.

[0002]

BACKGROUND OF THE INVENTION Conventionally, I
A pair of substrates with transparent electrodes, on which a transparent electrode film such as TO and an alignment film made of a polymer such as polyimide are sequentially laminated, face each other via a spacer such that the respective transparent electrode films face each other. There is known a liquid crystal display cell in which liquid crystal is sealed in gaps formed at predetermined intervals.

In this type of liquid crystal display cell, the alignment film is damaged by foreign substances and spacers mixed in the liquid crystal cell during the manufacturing process, and as a result, conduction occurs between the upper and lower electrodes.
In some cases, display defects caused by this conduction occur.

For this reason, in the above-mentioned liquid crystal display cell, an insulating film is formed between the transparent electrode film and the alignment film of the substrate with a transparent electrode (Japanese Patent Laid-Open No. 60-260021, Japanese Patent Laid-Open No. -150116, JP-A-2-221
923).

By the way, a resin having a strong hydrophobicity such as a polyimide resin is often used as the alignment film. When an alignment film made of such a highly hydrophobic resin is formed on an insulating film, the adhesion between the insulating film and the alignment film becomes insufficient, and display unevenness such as rubbing scratches may occur on the liquid crystal display cell. . For this reason, the applicant of the present application has disclosed in
No. 247427 proposes a coating liquid containing an inorganic compound having a specific particle diameter as a coating liquid capable of forming an insulating film having excellent adhesion to an alignment film.

In addition, when such an insulating film is formed between the transparent electrode and the alignment film, the alignment film may be damaged or defective in alignment due to static electricity generated when the alignment film is rubbed. For this reason, the applicant of the present application has disclosed in
No. 2459 proposes forming a protective film on the transparent electrode surface, which is made of conductive fine particles and a matrix and has a surface resistance of 10 ⁹ to 10 ¹³ Ω / □.

As a liquid crystal display using such a liquid crystal display cell, a TFT type liquid crystal display and an STN type liquid crystal display are known. In a TFT type liquid crystal display device, a TFT array such as a TFT (thin film transistor) element and a data electrode is provided on a transparent substrate. After the unevenness due to the TFT array is flattened by the flattening film, a display electrode such as ITO is mounted thereon, so that the aperture ratio is improved and the alignment disorder of the liquid crystal due to the unevenness of the TFT array is eliminated. I have. Further, also in a liquid crystal display device having a color filter, an insulating protective film is provided for flattening the color filter pixels or improving the reliability.

As a material for forming a flattening film and an insulating protective film in the field of electronic materials, organic resins such as acrylic resins and polyester resins, SiO ₂ and Si ₃ N are used.
Inorganic substances such as _4, and a polymer of an organic / inorganic hybrid alkyltrihydroxysilane are used. However, these film-forming materials have problems in heat resistance, crack generation, film strength, formation of a resist film on the film, and the like. For this reason, the present applicant has filed WO 97/49
No. 775 proposes a coating liquid for forming a transparent film containing a hydrolyzate of inorganic compound particles and a specific organosilicon compound.

[0009] Among the various liquid crystal display devices described above, in order to provide a high voltage holding ratio characteristic in a TFT type liquid crystal display device, ions originating in the material constituting the cell and ions entering in the cell manufacturing process are used. Although measures have been taken to reduce the amount of impurities, it has been required to further reduce impurities in the liquid crystal in order to increase reliability.

[0010] In the STN type liquid crystal display device,
Liquid crystal materials are being improved to reduce power consumption. In order to reduce the power consumption, a liquid crystal having a strong polar functional group exhibiting a low threshold voltage has been used as a liquid crystal material, but a panel using such a liquid crystal is a conventional liquid crystal. Display defects may be caused by movable ions in the liquid crystal as compared with the display panel. For this reason, mobile ions (ionic impurities) in the liquid crystal have been reduced, but it is difficult to remove the ions highly and effectively, and the problem of display failure has not been solved. Further, such ionic impurities may be eluted from the cell constituent material with time, and lack long-term reliability. Therefore, it is required to keep the ionic impurity concentration low for a long time.

Under these circumstances, the present inventors have conducted intensive studies on a method for reducing the impurity ion component in the liquid crystal, and found that ion adsorption between the transparent electrode of the liquid crystal display cell and the alignment film was performed. It has been found that by providing a transparent ion getter film containing inorganic ultrafine particles having a function, ions in the liquid crystal can be reduced and the display quality of the liquid crystal display device can be improved, and the present invention has been completed.

[0012]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems in the prior art, that is, it has excellent scratch resistance, acid resistance, alkali resistance, water resistance, and insulating properties, and has an electrode film or It has excellent adhesion to alignment films made of highly hydrophobic resin such as polyimide resin, and is capable of forming a coating that reduces impurity ion components in liquid crystal. It is an object of the present invention to provide a coated substrate and a liquid crystal display cell having the same.

[0013]

The coating solution for forming a transparent ion getter film according to the present invention comprises (A) a matrix-forming component and (B)
The ion-adsorbing inorganic fine particles are dispersed in a mixed solvent of water and an organic solvent, and the average particle diameter of the (B) ion-adsorbing inorganic fine particles is in a range of 1 nm to 10 μm,
And the ion adsorption capacity of the ion-adsorbing inorganic fine particles is 0.1
Mmol3.0 mmol / g.

It is preferable that the (A) matrix-forming component comprises one or a mixture of two or more selected from an acetylacetonato chelate compound, an organosilicon compound, a metal alkoxide and polysilazane.

The substrate with a transparent ion getter film according to the present invention is characterized in that a transparent ion getter film is formed by applying the coating solution for forming a transparent ion getter film on the surface of the substrate.

In the first liquid crystal display cell according to the present invention, a pair of substrates with a transparent electrode in which a transparent electrode film, a transparent ion getter film and an alignment film are sequentially laminated on the surface of the substrate are provided. In a liquid crystal display cell, which is disposed at a predetermined interval so as to face each other, and in which liquid crystal is sealed in a gap provided between the pair of transparent electrode-attached substrates,
The transparent ion getter film is a film formed by applying the coating solution for forming a transparent ion getter film.

In the second liquid crystal display cell according to the present invention, a pair of transparent electrode substrates each having a color filter, a transparent ion getter film, a transparent electrode film, and an alignment film sequentially laminated on the surface of the substrate are provided. In a liquid crystal display cell in which electrodes are arranged at predetermined intervals so as to face each other and liquid crystal is sealed in a gap provided between the pair of transparent electrode-attached substrates, the transparent ion getter film is formed of the transparent ion getter film. The film is characterized by being a film formed by applying a coating liquid for forming an ion getter film.

In the third liquid crystal display cell according to the present invention, a pair of transparent electrode substrates each having a TFT array, a transparent ion getter film, a transparent electrode film, and an alignment film sequentially laminated on the surface of the substrate are provided. In a liquid crystal display cell in which the transparent electrodes are arranged at predetermined intervals so as to face each other and the liquid crystal is sealed in a gap provided between the pair of transparent electrode-attached substrates, the transparent ion getter film is It is a film formed by applying a coating solution for forming a transparent ion getter film.

[0019]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the coating liquid for forming a transparent ion getter film, the substrate with the film and the liquid crystal display cell according to the present invention will be described in detail.

[Transparent Ion Getter Film Forming Coating Solution] First, the transparent ion getter film forming coating solution according to the present invention will be described. The coating solution for forming a transparent ion getter film according to the present invention comprises (A) a matrix-forming component and (B)
( A) Matrix-forming component The ( A) matrix-forming component used in the coating solution for forming a transparent ion getter film of the present invention is ( A) a matrix-forming component in which the ion-adsorbing inorganic fine particles are dispersed in a mixed solvent composed of water and an organic solvent. It is preferably composed of one or a mixture of two or more selected from a) an acetylacetonato chelate compound, (b) an organosilicon compound, (c) a polysilazane, and (d) a metal alkoxide. In addition,
Such a matrix forming component is a precursor of the matrix.

(A) Acetylacetonate chelate compound The acetylacetonate chelate compound used in the present invention is a chelate compound having acetylacetone as a ligand,
It is a compound represented by the following chemical formula (1) or a condensate thereof.

[0022]

Embedded image

(Where a + b is 2 to 4;
a is 0 to 3, b is 1 to 4, R is -C _n H
_2n + 1 is (n = 3 or 4), X is -CH _3, -OC
H _3, a -C ₂ H ₅ or -OC ₂ H _5. M ₁ is a periodic table of groups IB, IIA, B, IIIA, B, IVA,
An element selected from Group B, VA, Group B, Group VIA, Group VIIA and Group VIII, or vanadyl (VO). Of these, preferred combinations of these elements and a and b are as shown in the following table. ]

[0024]

[Table 1]

Specific examples of such a compound include, for example, dibutoxy-bisacetylacetonatozirconium, tributoxy-monoacetylacetonatozirconium, lead bisacetylacetonato, iron trisacetylacetonato, dibutoxy-bisacetylacetonatohafnium, Monoacetylacetonato-tributoxyhafnium and the like.

(B) Silicon Compound The organosilicon compound used in the present invention includes a compound represented by the general formula: R _a —Si (OR ′) _4-a (2) (where R is —C _n H _{2n + 1)} or a C ₆ H _5, R 'is -C _n H _{2n + 1} or _{-C 2 H 4 OC n H 2n} + 1
Wherein a is an integer of 0 to 3, and n is 1 to 4
Is an integer. The organic silicon compound represented by the formula (1) is used.

Specific examples of such an organosilicon compound include, for example, tetramethoxysilane, tetraethoxysilane, monomethyltrimethoxysilane, monoethyltriethoxysilane, monoethyltrimethoxysilane, and monomethyltriethoxysilane. Used.

These organosilicon compounds may be used as they are or after partial hydrolysis. Such partial hydrolysis can be obtained according to a conventional method, for example, a method in which an organosilicon compound is mixed with an alcohol such as methanol or ethanol, and water and an acid are added to perform partial hydrolysis. .

The coating liquid for forming a transparent film according to the present invention, to which the above-mentioned organosilicon compound is added, is applied on a substrate, and the obtained film is dried and fired to obtain scratch resistance, acid resistance, alkali resistance, water resistance. A film having excellent properties and insulating properties is formed.

(C) M ₂ (OR) _n (where M ₂ is a metal atom, and R is an alkyl group or —C _m H _2m O _{2) 2} (m = 3 ~
10), and n is the same integer as the valence of M ₂ . )
Or a condensate thereof is preferred, and one or more of these compounds or condensates thereof can be used in combination. M ₂ in the above formula is not particularly limited as long as it is a metal,
Preferred M ₂ is Be, Al, Sc, Ti, V, Cr,
Fe, Ni, Zn, Ga, Ge, As, Se, Y, Z
r, Nb, In, Sn, Sb, Te, Hf, Ta, W,
Pb, Bi, Ce or Cu.

As such a metal alkoxide, specifically, tetrabutoxyzirconium, diisopropoxy-dioctyloxytitanium, diethoxylead and the like are preferably used.

When the coating liquid for forming a transparent film according to the present invention to which the above-mentioned metal alkoxide is added is applied, dried and fired,
By the polymerization and curing of the metal alkoxide, a film having excellent scratch resistance, acid resistance, alkali resistance, water resistance and insulation properties is formed.

(D) Polysilazane or polysilazane used as a matrix-forming component has a repeating unit represented by the following formula (3).

[0034]

Embedded image

Wherein R ₁ , R ₂ and R ₃ are
Each is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. When a polysilazane represented by the formula (3) is used as a matrix-forming component, a polysilazane in which the alkyl group is a methyl group, an ethyl group, or a propyl group is preferable. In this case, there is no alkyl group that decomposes when heated, and the film shrinks less during heating, and therefore, cracks are less likely to occur during shrinkage stress, and a transparent ion getter film with almost no cracks is obtained.

The polysilazane having a repeating unit represented by the above formula (3) may be linear or cyclic, and is obtained by mixing linear polysilazane and cyclic polysilazane. May be included.

Further, the number average molecular weight of such a polysilazane is 500 to 10,000, preferably 1,000.
It is desirable to be in the range of 0 to 4,000. When the number average molecular weight is less than 500, the low molecular weight polysilazane volatilizes during heating and curing, and the obtained transparent ion getter film tends to be porous. When the molecular weight exceeds 10,000, the fluidity of the coating solution becomes poor. Tends to decrease.

In the present invention, such a (A) matrix
Components may be used alone or in combination of two or more.
They may be used in combination. (A) When two or more types are used in combination as matrix forming components
(A) acetylacetonato chelate compound, (b) organic ketone
Iodine compound, (c) polysilazane, (d) metal alkoxide
When converted to oxides and nitrides, respectively,
(a) An acetylacetonato chelate compound (M₁O_x)so
And (b) an organosilicon compound represented by (SiO 2)_Two) And (c)
Lysilazane is represented by (SiN), and (d) metal alkoxide is
(M_TwoO _x), The weight ratio of each component is
It is desirable to satisfy such a relationship.

0 ≦ M ₁ O _x / (SiO ₂ + SiN + M ₂ O _x ) ≦ 10 When an acetylacetonato chelate compound is used, if this value is 0.001 or more, alkali resistance, acid resistance, salt water resistance, A film having excellent water resistance and solvent resistance can be obtained.

The mixing ratio of the organosilicon compound and the polysilazane to the metal alkoxide is 0 ≦ M ₂ O _x /
It is preferable that (SiO ₂ + SiN + M ₂ O _x ) ≦ 1.0. (B) Ion-adsorbing inorganic fine particles The (B) ion-adsorbing inorganic fine particles used in the coating solution for forming a transparent ion getter film of the present invention are fine particles capable of adsorbing inorganic ions, particularly inorganic ions present in the liquid crystal. The average particle diameter is preferably in the range of 1 nm to 10 μm, and more preferably 10 nm to 5 μm. The ion adsorption capacity is 0.1 to 3.0 mmol /
g, preferably in the range of 0.2 to 3.0 mmol / g. In addition, (B) ions that can be adsorbed by the ion-adsorbing inorganic fine particles include, for example, Na ⁺ ,
K ⁺ , Rb ⁺ , Cs ⁺ , Li ⁺ , Ag ⁺ , Mg ⁺ , Ca ⁺ , S
r ⁺ , Ba ⁺ , NH ₄ ^{+ and the} like.

The ion-adsorbing inorganic fine particles tend to have a higher ion-adsorbing capacity and a higher ion-adsorbing speed when the average particle diameter is smaller, but have a higher ion-adsorbing capacity when the average particle diameter is smaller than 1 nm. In addition, the ion adsorption speed does not increase, and another film made of a highly hydrophobic resin such as a polyimide resin cannot be formed on the surface of the transparent ion getter film with good adhesion. On the other hand, if the average particle size exceeds 10 μm, the ion adsorption capacity and the ion adsorption rate may be reduced, and the transparency of the ion getter film may be reduced.

In particular, using a coating solution containing ion-adsorbing inorganic fine particles having an average particle diameter of 50 nm or less, preferably 10 to 40 nm, the ions formed between the electrode film and the alignment film with a thickness of 30 nm to 100 μm. The getter film has 1
Since it has a uniform surface roughness of 10 to 10 nm, it has excellent adhesion to a hydrophobic alignment film.

The ion adsorption capacity is 0.1 mmol /
If the amount is less than 0.1 g, ions cannot be sufficiently adsorbed, so that display defects due to mobile ions may occur or long-term reliability may be lacking. Fine particles are difficult to obtain.

The average particle diameter of such ion-adsorbing inorganic fine particles can be determined by a laser Doppler method or TEM observation. The ion adsorption capacity of the ion-adsorbing inorganic fine particles is measured by the following method.

100 g of a 1% by weight aqueous NaCl solution
Was added at room temperature (25 ° C.) for 15 hours, and then filtered to collect the filtrate. The Na ion concentration in the filtrate was measured by atomic absorption. The amount of ion adsorption (mmol / g) of the inorganic ion adsorbent is determined from the concentration difference from the original Na ion concentration of the aqueous NaCl solution.

[0046] The ion-adsorbing inorganic fine particles used in the transparent ion getter film-forming coating solution of the present invention is not particularly limited if the ion adsorption capacity and average particle diameter of above range, with MO _X · nH ₂ O In the formula, any one of crystal water, structural hydroxyl group, and surface hydroxyl group other than the adhered water is converted into water (H ₂ O) per mole of metal oxide (MO _X ) by mole number n of 0.0.
Metal oxides having from 2 to 5 are preferred. A more preferred range is from 0.1 to 3.

Constituting such ion-adsorbing inorganic fine particles
The metal oxide to be used is SiO._Two, Al_TwoO_Three, ZrO_Two,
TiO_Two, SnO_Two, In_TwoO_Three, Sb_TwoO_FiveMetal oxides, such as
SiO _Two・ Al_TwoO_Three, SiO_Two・ TiO_Two, In_TwoO_Three・ SnO_Two,
Sb_TwoO_Five・ SnO_Two, SnO_Two・ In_TwoO_Three・ Sb_TwoO_FiveAnd so on
Mixed metal oxide or solid solution, zeolite (crystalline
Minosilicate) and the like. In addition, these
Mixtures of two or more are also preferably used.

If the value of the number of moles n of water in the above-mentioned ion-adsorbing inorganic fine particles is less than 0.02 mol, the ion adsorption capacity is too small to effectively adsorb the ions in the liquid crystal. If it is too high, when forming an ITO film on the ion getter film by sputtering,
It is not preferable because the desorption as water molecules tends to increase the time to reach vacuum in the sputtering apparatus.

The value of the number of moles n of water contained in such ion-adsorbing inorganic fine particles was determined by differential thermal analysis of the ion-adsorbing inorganic fine particles dried at 120.degree.
It can be determined by calculating the amount of water reduced to ° C. as moles of water per mole of metal oxide.

Further, if necessary, insulating or conductive inorganic compound fine particles other than the above-mentioned ion-adsorbing inorganic fine particles may be used. Such ion-adsorbing inorganic fine particles are preferably used in the form of a sol dispersed in water or an organic solvent, but the ion-adsorbing inorganic fine particles are monodispersed or nearly monodispersed in a coating solution for forming a transparent ion getter film. As long as the particles can be dispersed in the state, the ion-adsorbing inorganic fine particles in a state other than the sol may be used.

Composition of the Coating Solution for Forming a Transparent Film The coating solution for forming a transparent film according to the present invention is prepared by uniformly dissolving (A) the matrix-forming component and (B) the ion-adsorbing inorganic fine particles in a mixed solvent comprising water and an organic solvent. Dissolved or dispersed in

As the organic solvent used in such a coating liquid for forming a transparent film, a known organic solvent selected from alcohols, ethers, glycols, ketones and the like is used. Such organic solvents may be used alone or in combination of two or more.

The solid content concentration in the coating solution according to the present invention is:
The total value of (A) the matrix-forming component and (B) the ion-adsorbing inorganic fine particles as oxides and nitrides is 15
It is preferable that the content be not more than weight%. This value is 15% by weight
If the solids concentration is extremely low, on the other hand, if the solid content concentration is extremely low, it will be necessary to repeat the coating operation many times to obtain the desired film thickness. The solid content concentration is practically 0.1% by weight or more.

The matrix-forming component (A) is an oxide,
In terms of nitride, 30 to
It is desirable that it be contained in the coating liquid in an amount of 95% by weight.

Further, (B) the ion-adsorbing inorganic fine particles may be present in the coating solution in such an amount as to be in the range of 5 to 70% by weight in the formed ion getter film in terms of oxide. preferable. In such a range, when the ion-adsorbing inorganic fine particles are present in the ion getter film, the surface of the ion getter film obtained from this coating solution is further coated with another highly hydrophobic resin such as a polyimide resin. Can be formed with good adhesion and a transparent ion getter film capable of effectively reducing ions in the liquid crystal panel can be formed. If the concentration exceeds 70% by weight, the adhesion between the ion getter film formed from this coating solution and the lower substrate, the TFT array, the color filter, etc. may be reduced.

Further, if necessary, even when insulating or conductive inorganic compound fine particles other than these ion-adsorbing inorganic fine particles are contained, the coating solution contains the ion-adsorbing inorganic fine particles and the ion-adsorbing inorganic fine particles. Fine particles other than fine particles
It is preferable that the total amount of oxides and nitrides is present in the formed ion getter film in the range of 5 to 70% by weight.

The coating solution for forming a transparent film according to the present invention preferably has a water concentration in the range of 0.1 to 50% by weight. When the water concentration is less than 0.1% by weight, an acetylacetonato chelate compound, an organosilicon compound,
Hydrolysis, polycondensation, and complexation of polysilazane and metal alkoxide are not sufficiently performed, and the resulting coating tends to have reduced scratch resistance and durability. The coating liquid may be easily repelled from the base material, making it difficult to form a film.

In the coating liquid for forming a transparent film according to the present invention,
The mixing ratio of (A) the matrix-forming component and (B) the ion-adsorbing inorganic fine particles contained in the coating liquid, (A) the metal species contained in the matrix-forming component, (B) the type of the ion-adsorbing inorganic fine particles, etc. The refractive index and the dielectric constant of the obtained film can be freely controlled.

By forming an ion getter film having a controlled refractive index on the transparent electrode of the substrate with a transparent electrode in this manner, for example, the electrode or the like is made higher than the refractive index of the alignment film formed thereon. It can prevent seeing through.

The transparent ion getter film formed using the coating solution for forming a transparent ion getter film of the present invention has a pore volume in the range of 0.01 to 0.3 ml / g and an average pore diameter of 1 to 0.3 ml / g. It preferably has pores in the range of 20 nm.

If the pore volume is less than 0.01 ml / g, the pores are so small that the ion-adsorbing inorganic fine particles cannot sufficiently exhibit the ion-adsorbing ability. May be insufficient.

When the average pore diameter is less than 1 nm, the diffusion rate of ions when a voltage is applied is low, and the ion-adsorbing inorganic fine particles may not be able to sufficiently exhibit the ion-adsorbing ability. If the average pore diameter exceeds 20 nm, the strength of the membrane may be insufficient.

The pore volume and the average pore diameter of such a transparent ion getter film are measured by peeling the transparent ion getter film formed on the substrate, and using the peeled transparent ion getter film by the N ₂ adsorption method.

[Coated Substrate] Next, the coated substrate according to the present invention will be specifically described. The substrate with a film according to the present invention is characterized in that a transparent ion getter film formed by applying the above-mentioned coating solution for forming a transparent ion getter film is formed on the surface of the substrate.

[0065] The pore volume of the transparent ion getter membrane is 0.1 mm.
It is preferably in the range of from 01 to 0.3 ml / g, preferably from 0.05 to 0.2 ml / g. Further, the average pore diameter of the transparent ion getter membrane is preferably in the range of 1 to 20 nm, preferably 2 to 8 nm.

The substrate with a transparent ion getter film according to the present invention may be prepared by dipping the above-mentioned coating solution for forming a transparent film on a surface of a substrate such as glass or plastic by a dipping method, a spinner method, or the like.
Spray method, roll coater method, applied by a method such as flexographic printing, and then the coating thus formed on the substrate surface is dried at room temperature to 90 ° C., and further dried at 200 ° C. or more.
In some cases, it is formed by a method such as heating to 300 ° C. or more to cure.

Further, the coating formed on the substrate is
The curing acceleration treatment may be performed by the following method.
Specifically, as the curing acceleration treatment, after the coating step or the drying step, or during the drying step, the coating at the uncured stage is irradiated with electromagnetic waves having a wavelength shorter than visible light, or the coating at the uncured stage is cured. For example, a treatment of exposing in a gas atmosphere that promotes the reaction may be mentioned.

The electromagnetic wave applied to the uncured coating before heating is, for example, an ultraviolet ray, an electron beam, or an X-ray.
Rays, γ rays and the like are exemplified, and ultraviolet rays are particularly preferable. When performing the ultraviolet irradiation treatment, for example, the emission intensity is about 2
A high-pressure mercury lamp having a maximum at 50 nm and 360 nm and a light intensity of 10 mW / cm ² or more is used as an ultraviolet light source, and has a light intensity of 100 mJ / cm ² or more, preferably 1 mW / cm ² or more.
It is desirable to irradiate an ultraviolet ray having an energy amount of 000 mJ / cm ² or more.

Examples of the gas for promoting the curing reaction of the uncured film before heating include ammonia and ozone. When such a gas treatment is performed, the uncured film is treated with a gas concentration of 100 to 100,
000 ppm, preferably 1000 to 10,000 pp
Exposure to the above active gas atmosphere of 1 to 60 minutes is desirable.

The same effect can be obtained even if this gas treatment is performed after heat curing. When the above-mentioned curing acceleration treatment is performed, polycondensation and complexation of the (A) matrix-forming component such as an acetylacetonate chelate compound, an organosilicon compound, polysilazane, and a metal alkoxide contained in the transparent ion getter film are promoted. At the same time, evaporation of water and solvent remaining in the film is promoted. For this reason, the heat curing conditions such as the heating temperature and the heating time required in the next heating step are relaxed, and the production of the substrate with an ion getter film according to the present invention can be efficiently advanced.

The substrate with the transparent ion getter film according to the present invention is obtained by the above steps. The transparent ion getter film formed on this substrate has high surface hardness, excellent adhesiveness and transparency, and also has excellent durability such as scratch resistance, water resistance, alkali resistance, and the like. Can be effectively reduced, the insulation resistance is high, and it is also suitable as an insulating film.

[Liquid Crystal Display Cell] Next, the liquid crystal display cell according to the present invention will be specifically described. Each of the liquid crystal display cells according to the present invention uses a substrate with a transparent electrode having a transparent ion getter film formed using the above-mentioned coating solution for forming a transparent ion getter film.

In the first liquid crystal display cell according to the present invention, a pair of transparent electrode-containing substrates, each having a transparent electrode film, a transparent ion getter film and an alignment film sequentially laminated on at least one of the surfaces of the substrate, is provided with a transparent electrode film. This is a liquid crystal display cell in which electrodes are arranged at predetermined intervals so as to face each other, and liquid crystal is sealed in a gap provided between the pair of transparent electrode-attached substrates.

FIG. 1 is a sectional view schematically showing one embodiment of the first liquid crystal display cell according to the present invention. In this liquid crystal display cell 1, a pair of substrates 2 with a transparent electrode, in which a transparent electrode film 12, a transparent ion getter film 13 and an alignment film 14 are sequentially laminated on a surface of a glass substrate 11, are formed of transparent electrode films 12, 12 respectively. A plurality of spacer particles 5 are arranged so as to face each other at a predetermined interval d, and the liquid crystal 4 is sealed in the gap between the transparent electrode films 12 and 12 at the predetermined interval d. .

The transparent ion getter film 13 is a film formed by applying the above-mentioned coating solution for forming a transparent ion getter film on the transparent electrode film 12. This film has a high surface hardness, transparency and scratch resistance. In addition to having excellent properties, high insulation resistance, good adhesion between the transparent ion getter film 13 and the alignment film 14, (movable) ions in the liquid crystal panel can be effectively reduced.

In the first liquid crystal display cell according to the present invention, an additional S is provided between the glass substrate 11 and the transparent electrode film 12.
Various modifications are possible, such as using a substrate with a transparent electrode on which an alkali passivation film such as an iO ₂ film is formed.

The second liquid crystal display cell according to the present invention comprises a pair of transparent electrode substrates each having a color filter, a transparent ion getter film, a transparent electrode film, and an alignment film sequentially laminated on at least one substrate surface. This is a liquid crystal display cell in which transparent electrodes are arranged at predetermined intervals so as to face each other, and liquid crystal is sealed in a gap provided between the pair of transparent electrode-attached substrates.

FIG. 2 is a schematic diagram schematically showing one embodiment of the second liquid crystal display cell according to the present invention. A color liquid crystal display device 1 'whose characteristic part is shown in FIG.
Is an electrode plate 21 in which an alkali passivation film 21b, a plurality of pixel electrodes 21c, a transparent ion getter film 21d, and an alignment film 21e are sequentially laminated on a glass substrate 21a.
A liquid crystal display cell 2 ′ having a counter electrode plate 22 in which an alkali passivation 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 pair of polarizing plates 3 ', 4' is 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 a transparent ion getter film.

The electrode plate 21 and the counter electrode plate 22 of the liquid crystal display cell 2 are
With a being outside, each of the plurality of pixel electrodes 21c and each of the plurality of color filters R, G, B are arranged so as to face each other. 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 includes a plurality of R (red filter), G (green filter), and B (blue filter) color elements. The circuits are regularly arranged so as to be adjacent to each other, whereby a circuit formed between a specific pixel electrode 21c and a transparent electrode 22e is operated by a display signal sent from the main body of the liquid crystal display device 1 ', and the circuit responds to the display signal. A color image can be observed through the polarizing plate 4 disposed outside the counter electrode plate 22.

In the third liquid crystal display cell according to the present invention, 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 at least one substrate surface. This is a liquid crystal display cell in which the transparent electrodes are arranged at predetermined intervals so as to face each other, and a liquid crystal is sealed in a gap provided between the pair of substrates with transparent electrodes.

FIG. 3 is a schematic sectional view schematically showing one embodiment of the third liquid crystal display cell according to the present invention. This liquid crystal display cell 1 "has a TFT array 32 formed on the surface thereof,
A transparent ion getter film 3 is formed on the surface of the TFT array 32.
3, a transparent insulating substrate 31 on which a pixel electrode 34 and an alignment film 35 are sequentially laminated, and a black matrix (shielding film) 42, a color filter 43, a transparent ion getter film 44, a counter electrode 45, and an alignment film 46 on the surface in this order. The laminated counter substrate 41 and the alignment film 35 sandwich the liquid crystal layer 51 therebetween.
And 46 are configured to face each other.

Note that, as shown in FIG.
Spacer particles may be interposed between them. The TFT array 32 includes TFT elements, data electrodes, and the like.

In the first to third liquid crystal display cells, the pore volume of the transparent ion getter film is in the range of 0.01 to 0.3 ml / g, and the average pore diameter is in the range of 1 to 20 nm. Is preferred.

In the liquid crystal display cell according to the present invention as described above, mobile ions (ionic impurities) in the liquid crystal are reduced by the transparent ion getter film. Therefore, the liquid crystal display cell according to the present invention is excellent in high voltage holding ratio characteristics, does not cause display failure, is excellent in long-term reliability, and requires less power consumption, so that power efficiency can be improved.

[0086]

As described above, the coating solution for forming a transparent ion getter film according to the present invention is selected from (A) a matrix-forming component selected from acetylacetonatochelate compounds, organosilicon compounds, polysilazanes and metal alkoxides. Or a mixture or a composite of two or more kinds thereof, and (B) ion-adsorbing inorganic fine particles having a specific ion-adsorbing capacity and particle diameter.

For this reason, using a coating liquid containing ion-adsorbing inorganic fine particles having an average particle diameter of 50 nm or less, the surface of the substrate has, for example, an average surface roughness of 1 to 10 nm, and the height of the unevenness is almost constant. The distribution can also form a uniform film, the resulting film is excellent in scratch resistance, acid resistance, alkali resistance, water resistance and insulation, and further, a film formed thereon, for example, It also has excellent adhesion to films made of highly hydrophobic resins such as polyimide resins.
Further, a substrate having irregularities using the coating liquid according to the present invention,
For example, the surface of an ion getter film formed on a substrate with a TFT array or a substrate with a color filter is flattened, and the surface of the alignment film in contact with the liquid crystal layer is also flattened. This is effective for suppressing display disturbance of liquid crystal, preventing generation of display domains, reducing light leakage during panel display, improving contrast, and the like.

In particular, the ion getter film according to the present invention
Since it contains inorganic ion-adsorbing fine particles having ion-adsorbing ability, (movable) ions in the liquid crystal panel can be effectively reduced.

For this reason, the coating film formed from the coating solution for forming a transparent ion getter film according to the present invention includes an insulating film formed between the transparent electrode film of the transparent electrode used for the liquid crystal display cell and the alignment film, Alternatively, it is suitable as a low-dielectric-constant flattening film formed on a substrate with a TFT array or a substrate with a color filter, and the resulting liquid crystal display device is excellent in display quality and long-term reliability.

[0090]

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

[0091]

Example 1 Preparation of Coating Solution 14.6 g of ethyl silicate 28 (manufactured by Tama Chemical Industry Co., Ltd., SiO ₂ concentration: 28.8% by weight) as a matrix forming component
Was added to a mixed solvent of 5 g of pure water and 62.3 g of ethyl alcohol, and 0.1 g of nitric acid having a concentration of 61% was added thereto, and a partial hydrolyzate (oligomer) of ethyl silicate was added.
A solution (dispersion) was prepared.

In this solution, antimony pentoxide fine particles (Sb ₂ O ₅ .2.7H ₂ O) having an average particle diameter of 20 nm and an ion adsorption capacity of 2.4 mmol / g as ion-adsorbing inorganic fine particles were uniformly dispersed in hexylene glycol. 18 g of an ion-adsorbing inorganic fine particle sol having a solid content
After stirring for an hour and then adding 70 g of hexylene glycol, vacuum distillation was performed to prepare a coating solution (A) having a solid content of 6.0% by weight.

Formation of Transparent Ion Getter Film The coating solution (A) was applied by flexographic printing on a patterned glass substrate with an ITO display electrode (product of Asahi Glass Co., Ltd .: 30 Ω / □ or less), and the resulting coating was obtained. After the film was dried at 90 ° C. for 5 minutes, the accumulated light amount was 6,000 with a high-pressure mercury lamp.
Ultraviolet rays were irradiated under the conditions of mJ / cm ² (measured with a sensor for 365 nm), followed by baking at 300 ° C. for 30 minutes to form an ion getter film (A). Table 2 shows the properties of the obtained ion getter film (A). When the film thickness of the obtained ion getter film (A) was measured by a stylus type surface roughness meter, it was 80 nm.

Preparation of Liquid Crystal Display Cell Next, a paint for forming a polyimide film (Sun Ever, manufactured by Nissan Chemical Industries, Ltd.) was applied on the ion getter film (A) by flexographic printing and dried at 100 ° C. for 5 minutes. 3 at 240 ° C
Heat treatment was performed for 0 minutes to form a polyimide film, and then rubbing treatment was performed.

Thus, the transparent electrode and the glass substrate
A substrate with a transparent electrode was prepared in which the ion getter film (A) and the rubbed alignment film were sequentially laminated. Two substrates obtained with the transparent electrodes were used, and (2
A spacer having a particle diameter corresponding to the distance between two substrates is sprayed, and a sealing material made of epoxy resin and silica fine particles is printed on the other substrate, and the transparent electrodes of these substrates face each other. Stuck together, S
TN liquid crystal is sealed, then the sealing opening is sealed with a sealing material,
A liquid crystal display cell (A) was prepared.

Measurement of the amount of mobile ions The obtained amount of mobile ions in the liquid crystal display cell (A) was measured using an ion density measuring device (MTR-1 manufactured by Toyo Technica) at an applied voltage of 10 V and a triangular wave frequency of 0.1 Hz. It measured on condition of. No peak due to mobile ions in the liquid crystal was detected.

Observation of Display Unevenness of Liquid Crystal Display Cell Further, ten liquid crystal display cells (A) were prepared by the above-mentioned method, a lighting display test was performed, and the presence or absence of display unevenness was observed by visual observation. At this time, the number of panels in which display unevenness did not occur was examined.

Table 2 shows the results. Evaluation of long-term reliability Ten liquid crystal display cells (A) produced by the above method were
50 in high temperature and high humidity environment (relative humidity 95%, temperature 80 ° C)
After the exposure for 0 hour, a lighting display test of the liquid crystal display cell was performed, and visual observation was made for the presence or absence of display unevenness. At this time, the number of panels in which display unevenness did not occur was examined.

Table 2 shows the results.

[0100]

Example 2 Preparation of Coating Solution The average particle size obtained by drying silica sol as the ion-adsorbing inorganic fine particles was 25 nm, and the ion adsorption capacity was 0.2 mmol / g.
A coating solution (B) having a solid content of 6.0% by weight was prepared in the same manner as in Example 1 except that the silica fine particles (SiO ₂ · 0.1H ₂ O) were used.

Formation of Transparent Ion Getter Film and Liquid Crystal Display
In the same manner as created in Example 1 shows the cell, to form an ion getter film (B), and the creation of a liquid crystal cell (B). Table 2 shows the properties of the obtained ion getter film (B).

Measurement of the amount of mobile ions When the amount of mobile ions in the obtained liquid crystal display cell (B) was measured, a peak due to mobile ions was detected near an applied voltage of 1 V, and the amount of mobile ions was 6.0 nC / It was cm ^2.

Observation of display unevenness of the liquid crystal display cell Further, the liquid crystal display cell (B) was visually observed for display unevenness in the same manner as in Example 1. Table 2 shows the results.

Evaluation of Long-Term Reliability The long-term reliability of the liquid crystal display cell (B) was evaluated in the same manner as in Example 1. Table 2 shows the results.

[0105]

Example 3 Preparation of Coating Solution Silica-alumina fine particles having an average particle size of 25 nm and an adsorption capacity obtained by drying silica-alumina sol (USB sol, manufactured by Catalysis Chemical Industry Co., Ltd.) as ion-adsorbing inorganic fine particles.
25SiO ₂ · 0.75Al the ₂ O ₃ · 0.3H ₂ O) except for using to prepare Example 1 in the same manner as in solids concentration 6.0% by weight of the coating solution (C).

Formation of Transparent Ion Getter Film and Liquid Crystal Display
Preparation of a Cell In the same manner as in Example 1, an ion getter film (C) was formed and a liquid crystal cell (C) was prepared. Table 2 shows the properties of the obtained ion getter film (C).

Measurement of the amount of mobile ions When the amount of mobile ions in the obtained liquid crystal display cell (C) was measured, a peak due to mobile ions was detected near an applied voltage of 1 V, and the amount of mobile ions was 2.5 nC / It was cm ^2.

Observation of Display Unevenness of Liquid Crystal Display Cell Further, the liquid crystal display cell (C) was visually observed for display unevenness in the same manner as in Example 1. Table 2 shows the results.

Evaluation of Long-Term Reliability The liquid crystal display cell (C) was evaluated for long-term reliability in the same manner as in Example 1. Table 2 shows the results.

[0110]

Example 4 Preparation of Coating Solution Methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: SiO ₂ concentration: 44.1% by weight) as a matrix-forming component
100 g and 17 g of tributoxyzirconium acetylacetonate (manufactured by Matsumoto Pharmaceutical Co., Ltd .: ZrO ₂ concentration 13.5% by weight) were added to a mixed solvent of 200 g of isopropyl alcohol and 60 g of butanol, and the mixture was stirred.
Add 114 g of pure water and 1.0 g of nitric acid having a concentration of 61%, and add
A dispersion of the hydrolysis and polycondensate of methyltrimethoxysilane and tributoxyzirconium acetylacetonate was prepared at 0 ° C. for 15 hours. This dispersion is added to 30
The solution was cooled to a temperature of not more than ℃, an anion exchange resin was added to remove anions, and then the anion exchange resin was separated to obtain a pH of 5.
5 was obtained.

Next, after adding 211 g of the same antimony pentoxide fine particle dispersion sol used in Example 1, 100 g of ethyl cellosolve and 90 g of diethylene glycol to this dispersion, vacuum distillation was carried out to obtain a coating solution having a solids concentration of 20% by weight. D) was prepared.

Formation of Ion Getter Film A coating solution (D) was applied on a glass substrate on which a color filter was formed by spin coating at a rotational speed of 800 rpm.
After drying at 50 ° C. for 120 minutes.
Heat treatment was performed at 60 ° C. for 60 minutes to form a 1.6 μm-thick ion getter film (D), thereby overcoating the color filter pixels. Table 2 shows the properties of the obtained ion getter film (D).

Further, an ITO film was formed on the ion getter film (D) by a sputtering method. Preparation of Liquid Crystal Display Cell The ITO film was patterned by a conventional method to form a display electrode, and a polyimide alignment film was formed thereon in the same manner as in Example 1, followed by rubbing. In this manner, a pair of substrates with a transparent electrode, in which a color filter, an ion getter film (D), a transparent electrode, and a rubbed alignment film were sequentially laminated on a glass substrate, was obtained.

Next, the substrate with the common electrode is bonded to the opposing substrate with a sealing material via a spacer, STN liquid crystal is injected into the gap between the substrates, the injection port is sealed with a sealing material, and the liquid crystal cell (D) is formed. Created.

Measurement of the amount of mobile ions The amount of mobile ions in the obtained liquid crystal display cell (D) was measured, but no peak due to mobile ions was detected.

Observation of Display Unevenness of Liquid Crystal Display Cell Further, the liquid crystal display cell (D) was visually observed for display unevenness in the same manner as in Example 1. Table 2 shows the results.

Evaluation of Long-Term Reliability The liquid crystal display cell (D) was evaluated for long-term reliability in the same manner as in Example 1. Table 2 shows the results.

[0118]

Comparative Example 1 Preparation of Coating Solution A coating solution (E) having a solid content of 6.0% by weight was prepared in the same manner as in Example 1 except that the sol in which antimony pentoxide fine particles were dispersed was not used.

Formation of ion getter film and liquid crystal display cell
In the same manner as in Example 1, an ion getter film (E) was formed and a liquid crystal cell (E) was formed. Table 2 shows the properties of the obtained ion getter film (E).

[0120]Measuring the amount of mobile ions The amount of mobile ions in the obtained liquid crystal display cell (E) was measured.
When the applied voltage was around 1 V,
Is detected, and the amount of mobile ions is 19.6 nC / cm. ^TwoSo
Was.

Observation of display unevenness of the liquid crystal display cell Further, the liquid crystal display cell (E) was visually observed for display unevenness in the same manner as in Example 1. Table 2 shows the results.

Evaluation of long-term reliability The long-term reliability of the liquid crystal display cell (E) was evaluated in the same manner as in Example 1. Table 2 shows the results.

[0123]

Comparative Example 2 Preparation of Coating Solution A coating solution (F) having a solid content of 20% by weight was prepared in the same manner as in Example 4, except that the sol in which antimony pentoxide fine particles were dispersed was not used.

The formation of the ion getter film and the liquid crystal display cell
In the same manner as in Example 2, an ion getter film (F) was formed and a liquid crystal cell (F) was formed. Table 2 shows the characteristics of the obtained ion getter film (F).

Measurement of the amount of mobile ions When the amount of mobile ions in the obtained liquid crystal display cell (F) was measured, a peak due to mobile ions was detected near an applied voltage of 1 V, and the amount of mobile ions was 25 nC / cm ^2. Met.

Observation of Display Unevenness of Liquid Crystal Display Cell Further , the liquid crystal cell (F) was visually observed for display unevenness in the same manner as in Example 1. Table 2 shows the results.

[0127]

[Table 2]

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of one embodiment of a first liquid crystal display cell according to the present invention.

FIG. 2 is a schematic cross-sectional view of one embodiment of a second liquid crystal display cell according to the present invention.

FIG. 3 is a schematic cross-sectional view of one embodiment of a third liquid crystal display cell according to the present invention.

[Explanation of symbols]

 1, 1 ', 1 "liquid crystal display cell 2, 2' ... liquid crystal display cell 3, 4, ... polarizing plate 5, ..., spacer particles 6, ...・ ・ ・ ・ ・ ・ Liquid crystal 11 ・ ・ ・ ・ ・ ・ Glass substrate 12 ・ ・ ・ ・ ・ ・ ・ Transparent electrode film 13 ・ ・ ・ ・ ・ ・ ・ Transparent ion getter film 14 ・ ・ ・ ・ ・ ・ ・ ・ ・ Alignment film 21 ... Electrode plate 21a ... Glass substrate 21b ... Alkali passivation film 21c ... Plural pixel electrodes 21d ... Transparent ion getter Film 21e: Alignment film 22: Counter electrode plate 22a: Glass substrate 22b: Alkali passivation 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... Insulating film 41... Opposite substrate 42. Film) 43 Color filter 44 Transparent ion getter film 45 Counter electrode 46 Alignment film 51 ..Liquid crystal layers

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G09F 9/37 310 G09F 9/37 310B (72) Inventor Toshiro Komatsu Kitaminato-cho, Wakamatsu-ku, Kitakyushu-shi, Fukuoka Prefecture No. 13-2 F-term (in reference) at Wakamatsu Plant of Catalysts & Chemicals Co., Ltd. NA10 NA42 NA46 NA54 NA62 NA64 PB20 PC01 PC80 4J038 HA156 HA216 HA436 HA446 JA17 JA20 JA23 JA24 JA32 JC32 JC35 JC38 KA12 KA20 MA06 MA10 MA14 NA04 NA11 NA12 NA21 PB09 5C094 AA02 AA22 AA31 AA42 EB01 BA03 BA01 BA03 BA03 BA03 GB10 JA01 JA08 JA20

Claims (8)

[Claims] (A) a matrix-forming component and (B)
The ion-adsorbing inorganic fine particles are dispersed in a mixed solvent comprising water and an organic solvent, and the (B) ion-adsorbing inorganic fine particles have an average particle diameter of 1 nm.
A coating liquid for forming a transparent ion getter film, wherein the coating liquid has a particle diameter of 0.1 to 3.0 μm and an ion adsorption capacity of the ion-adsorbing inorganic fine particles of 0.1 to 3.0 mmol / g. 2. The transparent ion according to claim 1, wherein the matrix-forming component comprises one or a mixture of two or more selected from an acetylacetonato chelate compound, an organosilicon compound, a metal alkoxide and polysilazane. Coating solution for getter film formation. 3. A substrate with a transparent ion getter film, wherein a transparent ion getter film formed by applying the coating solution for forming a transparent ion getter film according to claim 1 or 2 is formed on the surface of a substrate. Wood. 4. The transparent ion getter membrane having a pore volume of 0.0
It is in the range of 1 to 0.3 ml / g, and the average pore diameter is 1 to 20 nm
4. The substrate with a transparent ion getter film according to claim 3, wherein: 5. A pair of substrates with transparent electrodes, each having a transparent electrode film, a transparent ion getter film, and an alignment film sequentially laminated on the surface of at least one of the substrates, at a predetermined interval so that the transparent electrodes face each other. 3. A transparent ion getter film according to claim 1 or 2, wherein the liquid crystal display cell is arranged such that liquid crystal is sealed in a gap provided between the pair of substrates with transparent electrodes. A liquid crystal display cell, which is a film formed by applying a forming coating solution. 6. A pair of substrates provided 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 at least one substrate surface, so that the transparent electrodes face each other. 3. The liquid crystal display cell, wherein the transparent ion getter film is disposed at a predetermined interval and a liquid crystal is sealed in a gap provided between the pair of transparent electrode-attached substrates, the transparent ion getter film according to claim 1 or 2. A liquid crystal display cell, which is a film formed by applying a coating solution for forming an ion getter film. 7. 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 at least one of the surfaces of the substrate so that the transparent electrodes face each other. 3. A liquid crystal display cell, wherein a liquid crystal is sealed in a gap provided between the pair of transparent electrode-attached substrates and a transparent ion getter film according to claim 1 or 2. A liquid crystal display cell, which is a film formed by applying a coating solution for forming a transparent ion getter film. 8. The transparent ion getter membrane having a pore volume of 0.0
It is in the range of 1 to 0.3 ml / g, and the average pore diameter is 1 to 20 nm
The liquid crystal display cell according to claim 5, wherein: