JPWO2004108845A1 - Coating liquid for forming transparent film, base material with film and liquid crystal display cell - Google Patents

Abstract

The present invention is excellent in scratch resistance, acid resistance, alkali resistance, water resistance, insulation, excellent adhesion to an electrode film or a film (alignment film) made of a highly hydrophobic resin such as polyimide resin, Furthermore, a coating liquid for forming a transparent film capable of forming a transparent film having excellent toughness and flexibility is provided. The coating liquid for forming a transparent film according to the present invention is a coating liquid for forming a transparent film in which a matrix-forming component is dispersed in a mixed solvent composed of water and an organic solvent, and the matrix-forming component has 2 hydrolyzable groups. It contains an organosilicon compound having at least one or a hydrolyzate thereof.

Description

  The present invention relates to a novel transparent film-forming coating solution, a coated substrate having a coating formed from such a coating-forming coating solution, and a liquid crystal display cell having the coated substrate. More specifically, the coating for forming a transparent film, which is difficult to obtain with the conventional coating liquid for forming a transparent film, has excellent flexibility and toughness, and further can form a transparent film with excellent scratch resistance. Regarding liquids.

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

  In this type of liquid crystal display cell, the alignment film is damaged by foreign substances or spacers mixed in the liquid crystal cell during the manufacturing process, which causes conduction between the upper and lower electrodes, and display defects due to this conduction occur. was there.

  For this reason, in the liquid crystal display cell as described above, a transparent insulating film is formed between the transparent electrode film of the substrate with a transparent electrode and the alignment film (JP-A-60-260021, JP-A-1- 150116, JP-A-2-221923, etc.).

  By the way, as the alignment film, a highly hydrophobic resin such as a polyimide resin is often used. When such an alignment film made of 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 due to rubbing scratches or the like may occur in the liquid crystal display cell. . For this reason, the applicant of the present application includes an inorganic compound having a specific particle size as a coating liquid capable of forming an insulating film excellent in adhesion to the alignment film in Patent Document 1 (Japanese Patent Laid-Open No. 4-247427). Has proposed.

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 due to static electricity generated when the alignment film is rubbed. For this reason, the present applicant, in Patent Document 2 (Japanese Patent Application Laid-Open No. H5-232459), has a protective film composed of conductive fine particles and a matrix and having a surface resistance of 10 ⁹ to 10 ¹³ Ω / □ on the surface of the transparent electrode. Propose to form.

  However, due to the recent demands for thinning, high-definition, and large screens of liquid crystal display devices, those having higher adhesion to the alignment film and higher scratch resistance have been desired. Further, in a substrate such as plastic, excellent flexibility and toughness are desired for the insulating film itself.

In recent years, TFT type liquid crystal display devices have been widely used.
The TFT type liquid crystal display device uses a liquid crystal display cell in which TFT arrays such as TFT (thin film transistor) elements and data electrodes are provided on a transparent substrate. The unevenness due to the TFT array is flattened by providing a flattening film, and a display electrode such as ITO is provided thereon, thereby improving the aperture ratio of the TFT type liquid crystal display device, and the liquid crystal due to the unevenness of the TFT array. The alignment disorder is eliminated.

  Further, in a liquid crystal display device having a color filter, an insulating protective film is provided in order to flatten the color filter and improve the reliability of the liquid crystal display device.

Examples of the flattening film / insulating protective film used in such a liquid crystal display device include organic resin films made of acrylic resin, polyester resin, etc., inorganic films such as SiO ₂ and Si ₃ N ₄ , alkyls, etc. An organic-inorganic composite coating made of a polymer of trihydroxysilane has been used.

  However, the organic resin film has insufficient heat resistance, which may cause cracks. Further, when exposed to high temperatures, the gas component may be released or the film strength may be reduced. Further, with this organic resin coating, there are many problems such as difficulty in forming a resist film on the coating.

In addition, the inorganic coating film has many problems such as a hygroscopic problem in the coating film itself, a difficulty in forming a resist film on the coating film, and an increase in the thickness of the coating film itself.
Furthermore, the organic / inorganic composite coating has problems such as a fragile coating and easy scratching on the surface, and a problem in the formability of a resist film on the coating.
JP-A-4-247427 JP-A-5-232459

  Under these circumstances, the present inventors have intensively studied to solve the above problems, and as a result, by using an organosilicon compound having a specific structural formula or a hydrolyzate thereof, the water resistance and water repellency are improved. The inventors have found that a transparent film excellent in toughness and flexibility can be obtained, and have completed the present invention.

  The present invention has been made to solve the above-mentioned problems in the prior art, and is excellent in scratch resistance, acid resistance, alkali resistance, water resistance, insulation, and hydrophobicity such as an electrode film or a polyimide resin. A coating solution for forming a transparent film capable of forming a transparent film having excellent adhesion to a film (alignment film) made of a strong resin, and having excellent toughness and flexibility, and a film having such a film It aims at providing a base material and a liquid crystal display cell.

The gist of the present invention includes the following matters.
[1] A coating solution for forming a transparent film in which a matrix-forming component is dispersed in a mixed solvent comprising water and an organic solvent, wherein the matrix-forming component is a) an organosilicon compound represented by the following formula (I) Or a hydrolyzate thereof, b) an organic silicon compound represented by the following formula (II), or a hydrolyzate thereof, or c) one or more selected from a mixture thereof. .

R ¹ —SiR ² _m R ³ _(3-m) (I)
Wherein, ^{R 1} - is _{^{R 8 (CR 9 2) n}} - or represented by ^R 10 X-.
R ⁸ represents a hydrolyzable group, a hydroxyl group, a hydrogen atom or a halogen atom.

R ⁹ each independently represents a hydrogen atom or a halogen atom.
R ¹⁰ represents a methyl group, a hydrogen atom or a hydrolyzable group.
n is an integer of 3 to 30.

X is — (CH ₂ ) q—, — (Ph) — [wherein Ph represents a benzene ring],
_{- (CH 2) q- (Ph} ) -, - (CH 2) q- (Ph) - (CH 2) y-,
_{- [(CH 2) q (} CF 2) y (CH 2) r] - and _{- (CH 2) q- (S} ) - (CH 2) r- from divalent group [where selected, q, r and y represent an integer of 1 to 30].

R ² represents a hydrolyzable group.
R ³ represents an organic group having 1 to 30 carbon atoms which may contain a halogen atom.
m shows the number of 1-3.

However, Formula (I) has 2 to 3 hydrolyzable groups in one molecule. ]
^{_{R 4 n R 5 3-n}} Si- (X) -SiR 6 p R 7 (3-p) (II)
[Wherein R ⁴ and R ⁶ independently represent a hydrolyzable group.

R ⁵ and R ^{7 each} independently represents a monovalent organic group having 1 to 30 carbon atoms which may contain a halogen atom.
X _{is, - (CH 2) q -} , - (Ph) - ( wherein, Ph represents a benzene ring),
_{- (CH 2) q- (Ph} ) -, - (CH 2) q- (Ph) - (CH 2) y-,
_{- [(CH 2) q (} CF 2) y (CH 2) r] -
_{- (CH 2) q- (S} ) - (CH 2) r- and - (S) divalent group selected from q- [wherein, q, r and y is an integer of 1 to 30].

n represents a number from 0 to 3.
p represents a number from 0 to 3.
However, Formula (II) has two or more hydrolyzable groups in one molecule. ]
[2] The organosilicon compound of formula (I) has more than two hydrolyzable groups in one molecule, and the organosilicon compound of formula (II) has more than two hydrolysates in one molecule. The coating liquid for forming a transparent film according to [1], which has a decomposable group.
[3] The matrix-forming component is further a) an organosilicon compound represented by the following formula (III) R _t Si (OR ′) _4-t (III)
[Wherein R is selected from a methyl group, an ethyl group, a vinyl group or an epoxy group. R ′ is an alkyl group having 1 to 6 carbon atoms. t is a number from 0 to 4. ] The coating liquid for forming a transparent film according to [1] or [2], comprising at least one selected from b) acetylacetonato chelate compound, c) metal alkoxide and d) polysilazane.
[4] The coating liquid for forming a transparent film according to any one of [1] to [3], wherein the matrix-forming component further contains inorganic compound particles.
[5] A substrate with a transparent coating, wherein a transparent coating is formed by applying the coating liquid for forming a transparent coating according to any one of [1] to [4] to the surface of the substrate.
[6] A pair of substrates with a transparent electrode, in which a transparent electrode film, a transparent film, and an alignment film are sequentially laminated on the surface of at least one substrate, are arranged at predetermined intervals so that the transparent electrodes face each other. In a liquid crystal display cell in which liquid crystal is sealed in a gap opened between the pair of substrates with transparent electrodes,
A liquid crystal display cell, wherein the transparent film is a film formed by applying the transparent film forming coating solution according to any one of [1] to [4].
[7] A pair of substrates with a transparent electrode, in which a color filter, a transparent coating, a transparent electrode film, and an alignment film are sequentially laminated on the surface of at least one substrate, have a predetermined interval so that the transparent electrodes face each other. In a liquid crystal display cell that is arranged in a gap and liquid crystal is sealed in a gap opened between the pair of substrates with transparent electrodes,
A liquid crystal display cell, wherein the transparent film is a film formed by applying the transparent film forming coating solution according to any one of [1] to [4].
[8] A pair of substrates with a transparent electrode in which a TFT array, a transparent coating, a transparent electrode film, and an alignment film are sequentially laminated on the surface of at least one substrate are spaced apart from each other so that the transparent electrodes face each other. In a liquid crystal display cell that is arranged in a gap and liquid crystal is sealed in a gap opened between the pair of substrates with transparent electrodes,
A liquid crystal display cell, wherein the transparent film is a film formed by applying the transparent film forming coating solution according to any one of [1] to [4].

As described above, the coating liquid for forming a transparent film according to the present invention contains a matrix forming component made of a specific organosilicon compound.
For this reason, the obtained transparent film is excellent in water repellency, toughness, flexibility and the like.

  Furthermore, if such a transparent film is formed on a substrate having irregularities, for example, a substrate with a TFT array or a substrate with a color filter, the surface can be extremely flattened. In addition, since it is possible to form a flat alignment film on the surface of this transparent film, it suppresses liquid crystal display disturbance due to the surface shape, prevents the generation of display domains, reduces light leakage during panel display, and improves contrast. This is effective.

Hereinafter, the coating liquid for forming a transparent film, the substrate with a film, and the liquid crystal display cell according to the present invention will be specifically described.
[Transparent coating solution]
First, the coating liquid for forming a transparent film according to the present invention will be described.

In the coating liquid for forming a transparent film according to the present invention, the matrix forming component is dispersed in a mixed solvent composed of water and an organic solvent.
Matrix-forming component The matrix-forming component is a) an organosilicon compound represented by the following formula (I) or a hydrolyzate thereof, b) an organosilicon compound represented by the following formula (II) or a hydrolyzate thereof, or c) 1 type or more chosen from those mixtures is included.

^{_{R 1 -SiR 2 m -R 3 (}} 3-m) (I)
[Wherein R ¹ -represents R ⁸ (CR ⁹ ₂ ) _n -or R ¹⁰ X-.
R ⁸ represents a hydrolyzable group, a hydroxyl group, a hydrogen atom or a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

  Here, the hydrolyzable group means an atom or an atomic group substituted with a hydroxyl group by a chemical reaction with water. Examples of the hydrolyzable group include an alkoxy group having 1 to 6 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, an arylalkoxy group having 1 to 9 carbon atoms, and an alkyl aryloxy group having 1 to 9 carbon atoms, A methoxy group or an ethoxy group is preferably selected.

R ⁹ each independently represents a hydrogen atom or a halogen atom. R ⁹ may be all hydrogen atoms, a part thereof may be a halogen atom, or all may be a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

n is an integer of 3 to 30, preferably 3 to 20, and more preferably 3 to 12.
Therefore, typical examples of R ⁸ (CR ⁹ ₂ ) _n — include an alkyl group, a halogenated alkyl group, particularly a perfluoroalkyl group.

R ¹⁰ is selected from a methyl group, a hydrogen atom, or a hydrolyzable group. Examples of the hydrolyzable group are the same as those described above, and preferably selected from alkoxy groups having 1 to 6 carbon atoms. As the alkoxy group, a methoxy group and an ethoxy group are particularly preferable.

X is — (CH ₂ ) q—, — (Ph) — [wherein Ph represents a benzene ring],
_{- (CH 2) q- (Ph} ) -, - (CH 2) q- (Ph) - (CH 2) y-,
_{- [(CH 2) q (} CF 2) y (CH 2) r] - and _{- (CH 2) q- (S} ) - (CH 2) a bivalent group selected from r-.

Here, q, r, and y are each independently an integer of 1-30, preferably 1-20, and more preferably 2-12.
X is particularly preferably — (CH ₂ ) q— or — (Ph) — among the divalent groups.

Accordingly, as typical examples of R ¹⁰ X—, CH ₃ O— (CH ₂ ) q—, C ₂ H ₅ O— (CH ₂ ) q—, CH ₃ O— (Ph) —, C ₂ H ₅ O- (Ph)-.
R ² represents a hydrolyzable group. Examples of the hydrolyzable group are the same as those described above, and preferably selected from alkoxy groups having 1 to 6 carbon atoms. As the alkoxy group, a methoxy group and an ethoxy group are particularly preferable.

R ³ represents an organic group having 1 to 30, preferably 1 to 20, and more preferably 1 to 12 carbon atoms which may contain a halogen atom. Examples of the organic group include an alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon having 6 to 20 carbon atoms, an alkylaryl group having 7 to 27 carbon atoms, an arylalkyl group having 7 to 27 carbon atoms, and 2 to 20 carbon atoms. And an alkyl halide group having 1 to 20 carbon atoms. Examples of the halogen atom of the halogenated alkyl group include fluorine, chlorine, bromine and iodine. In the halogenated alkyl group, all hydrogen atoms may be substituted with halogen atoms, or some hydrogen atoms may be substituted with halogen atoms.

m represents a number of 1 to 3, preferably 3.
In addition, the organosilicon compound of the formula (I) has 2 to 3 hydrolyzable groups in one molecule.
As the organosilicon compound represented by the formula (I), those having at least one halogenated alkyl group in one molecule are preferable.

Examples of the organosilicon compound represented by the formula (I) include 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, and heptadecatrifluorodecylmethyl. Examples include dimethoxysilane, n-perfluorooctylethyltriethoxysilane, and heptadecatrifluorodecyltrimethoxysilane. ]
^{_{R 4 n R 5 3-n}} Si- (X) -SiR 6 p R 7 (3-p) (II)
[Wherein R ⁴ and R ⁶ independently represent a hydrolyzable group.

R ⁵ and R ^{7 each} independently represents a monovalent organic group having 1 to 30 carbon atoms which may contain a halogen atom.
Specific examples and preferred examples of the hydrolyzable group and the organic group are the same as those described for the formula (I).

  X is the same as that described in relation to the formula (I), and may be-(S) q-. Here, q is an integer of 1 to 30, preferably 1 to 20, and more preferably 2 to 12 as described above.

n represents a number from 0 to 3, preferably 2 or 3.
p represents a number from 0 to 3, preferably 2 or 3.
However, the organosilicon compound of the formula (II) has 2 or more, preferably 3 to 6, hydrolyzable groups in one molecule. ]
Examples of the organosilicon compound represented by the formula (II) include bis (trifluoropropyldimethoxysilyl) hexane, bis (trimethoxysilyl) ethane, bis (trimethoxysilyl) propane, bis (trimethoxysilyl) butane, (tri Methoxysilyl) pentane, bis (trimethoxysilyl) hexane, bis (trimethoxysilyl) heptane, bis (trimethoxysilyl) octane, bis (trimethoxysilyl) nonane, bis (trimethoxysilyl) decane, bis (trimethoxysilyl) ) Dodecane, bis (trimethoxysilyl) heptadecane, bis (trimethoxysilyl) octadecane, bis (triethoxysilyl) hexane, bis (tripropoxysilyl) hexane, bis (tri-n-butoxysilyl) hexane, bis (tri-i-) Butoxy L) hexane, bis (allyldimethoxysilyl) hexane, bis (vinyldimethoxysilyl) hexane, bis (acryldimethoxysilyl) hexane, bis (3-triethoxysilylpropyl) tetrasulfide, 1,4bis (trimethoxysilylethyl) Examples include benzene.

  An organosilicon compound having such a specific structural formula or a hydrolyzate thereof has high hydrophobicity, so that a transparent film excellent in water resistance and water repellency, as well as in toughness and flexibility can be obtained. In addition, it has excellent scratch resistance, acid resistance, alkali resistance, water resistance, insulation, and forms a film with excellent adhesion to electrode films or films made of highly hydrophobic resins such as polyimide resins (alignment films). it can.

In the present invention, an organosilicon compound represented by the formula (II) or a hydrolyzate thereof is preferably used.
The organosilicon compound represented by the formula (II) has-(X)-, X is hydrophobic, and can be bent when the chain length of X is increased. And toughness can be improved. Further, the organosilicon compound represented by the formula (II) has high reactivity since both ends are hydrolyzable groups.

  In the present invention, the organosilicon compound can be used as it is (that is, without being hydrolyzed), but it can also be used as a hydrolyzate. When the hydrolyzate is used, it is possible to obtain a coating solution that does not react during storage and has excellent long-term stability, and it is also possible to form a uniform film.

  The hydrolyzate can be obtained, for example, by hydrolysis in the presence of an acid catalyst in a water-alcohol mixed solvent of an organosilicon compound. Such a hydrolyzate may be a partial hydrolyzate or a condensation polymer of the hydrolyzate.

  The hydrolyzate preferably has a polystyrene-equivalent number average molecular weight of 500 to 20,000, particularly preferably 700 to 10,000. Within such a range, both film strength and substrate adhesion are high, stable in the coating solution, and a uniform film can be formed.

  When the number average molecular weight in terms of polystyrene of the hydrolyzate is small, there is no substantial change from that which has not been hydrolyzed. If the number average molecular weight in terms of polystyrene of the hydrolyzate is too large, the stability of the coating solution is shortened, and a transparent film having a uniform film thickness may not be obtained.

The matrix-forming component is one selected from an organosilicon compound represented by the above formula (I) or a hydrolyzate thereof, an organosilicon compound represented by the above formula (II), a hydrolyzate thereof, or a mixture thereof. In addition to the above, it is more preferable to further include one or more selected from the following components.
a) an organosilicon compound [except for those corresponding to the organosilicon compounds of formula (I) and formula (II)],
b) an acetylacetonato chelate compound,
c) metal alkoxides and d) polysilazanes.

Hereinafter, these components will be specifically described.
(A) In addition to the organosilicon compounds (I) and (II) above, the organosilicon compound matrix-forming component may be described as other organosilicon compounds (hereinafter referred to as organosilicon compounds (a)). May be included). As such another organosilicon compound, for example, an organosilicon compound represented by the following formula (III) can be used.

(R _t Si (OR ′) _4-t (III)
[Wherein R is selected from a methyl group, an ethyl group, a vinyl group or an epoxy group.
R ′ is an alkyl group having 1 to 6 carbon atoms. t is an integer from 0 to 4. ]
Specific examples of such an organosilicon compound (a) include tetramethoxysilane, tetraethoxysilane, monomethyltrimethoxysilane, monoethyltriethoxysilane, monoethyltrimethoxysilane, monomethyltriethoxysilane, vinyltrimethyl. Ethoxysilane, epoxytriethoxysilane and the like are preferably used.

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

  When the coating liquid for forming a transparent film according to the present invention to which the organosilicon compound (a) is added is applied onto a substrate, and the resulting film is dried and fired, scratch resistance, acid resistance, alkali resistance, water resistance A film having excellent properties and insulating properties is formed.

(B) Acetylacetonate chelate compound The acetylacetonate chelate compound (b) is a chelate compound having acetylacetone as a ligand, and is a compound represented by the following formula (IV) or a condensate thereof.

[Wherein, a + b is 2 to 4, a is 0 to 3, b is 1 to 4, R is —C _n H _{2n + 1} (n = 3 or 4), and X is − CH _3, -OCH, is _-C 2 _{H 5} or _-OC 2 _{H 5.} M is an element selected from Groups 2 to 15 of the periodic table or vanadyl (VO). Among these, preferred combinations of these elements and a and b are as shown in the following table. ]

  Specific examples of such compounds include, for example, dibutoxy-bisacetylacetonatozirconium, tributoxy-monoacetylacetonatozirconium, bisacetylacetonatolead, trisacetylacetonatoiron, dibutoxy-bisacetylacetonatohafnium, monoacetylacetate. And nato-tributoxy hafnium.

A coating solution for forming a transparent film to which such an acetylacetonato chelate compound is added can obtain a film excellent in alkali resistance, acid resistance, salt water resistance, water resistance and solvent resistance.
(C) Metal alkoxide As metal alkoxide (c),
M ₂ (OR) _n (V)
(Wherein M ₂ is a metal atom, R is an alkyl group or —C _m H _2m O ₂ (m = 3 to 10), and n is the same integer as the valence of M ₂ ). Or a condensate thereof, and one or two or more selected from these compounds or the condensates thereof can be used in combination. M ₂ in the above formula is not particularly limited as long as it is a metal, but preferred M ₂ is Be, Al, Sc, Ti, V, Cr, Fe, Ni, Zn, Ga, Ge, As, Se, Y, Zr, 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 solution for forming a transparent film according to the present invention to which the above metal alkoxide is added is applied, dried, and fired, the metal alkoxide is polymerized and cured, so that it has excellent scratch resistance, acid resistance, alkali resistance, water resistance and insulation. A film is formed.

(D) Polysilazane Polysilazane having a repeating unit represented by the following formula (VI) is used as polysilazane (d).

[Wherein, R ₁ , R ₂ and R ₃ are each a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]
When the polysilazane represented by the formula (VI) is used as the matrix forming component, polysilazane whose alkyl group is a methyl group, an ethyl group, or a propyl group is desirable. In this case, there is no alkyl group that decomposes during heating, and there is little shrinkage of the film during heating. Therefore, cracks are less likely to occur during shrinkage stress, and a transparent film with almost no cracks can be obtained.

  The polysilazane having a repeating unit represented by the above formula (VI) may be linear or cyclic, and contains a mixture of linear polysilazane and cyclic polysilazane. Also good.

  Furthermore, the polystyrene-reduced number average molecular weight of such polysilazane is desirably in the range of 500 to 10,000, preferably 1,000 to 4,000. When the number average molecular weight is less than 500, the low molecular weight polysilazane volatilizes at the time of heat curing, and the resulting transparent film tends to be porous. When the number average molecular weight exceeds 10,000, the fluidity of the coating solution is low. There is a tendency to decrease.

Mixed solvent The matrix-forming component is dispersed in a mixed solvent composed of water and an organic solvent.
As the organic solvent, a known organic solvent selected from alcohols, ethers, glycols, ketones and the like is used. Such organic solvents may be used alone or in admixture of two or more.

The ratio of water in the mixed solvent is not particularly limited, but is preferably in the range of 0.1 to 10% by weight, more preferably 0.1 to 5% by weight in the mixed solvent.
Inorganic Compound Particles The coating liquid for forming a transparent film according to the present invention may further contain inorganic compound particles (ion adsorbing particles).

Examples of inorganic compound particles include metal oxides such as SiO ₂ , Al ₂ O ₃ , ZrO ₂ , TiO ₂ , SnO ₂ , In ₂ O ₃ , and Sb ₂ O ₅ , SiO ₂ · Al ₂ O ₃ , SiO ₂ · TiO _2. , In ₂ O ₃ .SnO ₂ , Sb ₂ O ₅ .SnO ₂ , SnO ₂ .In ₂ O ₃ .Sb ₂ O _5, or other mixed metal oxides or solid solutions, zeolite (crystalline aluminosilicate), and the like. Furthermore, a mixture of two or more of these is also preferably used.

  When these inorganic compound particles are included, for example, mobile ions belonging to any one of inorganic cations, inorganic anions, organic cations, organic anions, etc. present in the liquid crystal can be adsorbed. For this reason, since the concentration of mobile ions in the liquid crystal can be reduced, the obtained liquid crystal display device is excellent in high voltage holding ratio characteristics, consumes less power, has high power efficiency, and does not cause display defects. Excellent long-term reliability.

  The average particle diameter of the inorganic compound particles used in the present invention is preferably in the range of 1 nm to 10 μm, more preferably in the range of 10 nm to 2 μm, and particularly preferably in the range of 10 nm to 0.5 μm. If the average particle size of the inorganic compound particles is less than 1 nm, another film made of a highly hydrophobic resin such as a polyimide resin may not be formed with good adhesion on the surface of the transparent coating.

On the other hand, when the average particle diameter exceeds 10 μm, the ion adsorption capacity and the ion adsorption speed may be lowered and the transparency of the transparent film may be lowered.
When the average particle size of the inorganic compound particles is in the above range, the surface of the transparent film formed on the substrate having unevenness, for example, the substrate with TFT array or the substrate with color filter is flattened. Since the surface of the contacted alignment film is also flattened, it is effective in suppressing liquid crystal display disturbance due to the surface shape, preventing the occurrence of display domains, reducing light leakage during panel display, and improving contrast.

  Note that conventionally known ion exchange resin particles can be used for the purpose of reducing mobile ions only. Specific examples of the cation exchange resin include Diaion SK series (manufactured by Mitsubishi Chemical Corporation), carboxymethyl cellulose, SE cellulose, P cellulose, Sephadex (manufactured by Pharmacia) and the like. Examples of the anion exchange resin include Diaion SA series (manufactured by Mitsubishi Chemical Corporation), DEAE cellulose, triethylammonium ethylcellulose, ECTEOLA cellulose, Sephadex (manufactured by Pharmacia) and the like. Further, amphoteric ion exchange resins such as Diaion (manufactured by Mitsubishi Chemical Corporation) can be mentioned.

  When such a transparent coating containing inorganic compound particles or ion exchange resin particles is used in a liquid crystal display cell or the like, it can remove ions in the liquid crystal and functions as a transparent ion getter film.

The ion adsorption capacity of such inorganic compound particles or ion exchange resin particles is preferably in the range of 0.1 to 6.0 mmol / g.
If the ion adsorption capacity is less than 0.1 mmol / g, ions cannot be adsorbed sufficiently, which may cause poor display due to mobile ions and lack long-term reliability. Ion adsorption exceeding 6.0 mmol / g The body is difficult to obtain.

The ion adsorption capacity in the present invention is measured by the following method.
(1) Measurement of inorganic cation adsorption capacity To 100 g of NaCl aqueous solution having a concentration of 1% by weight, 1.5 g of inorganic ion adsorbent dried and constant at 120 ° C. was added and stirred at room temperature (25 ° C.) for 15 hours. The filtrate was collected by filtration, and the Na ion concentration in the filtrate was analyzed by atomic absorption spectrometry. From the concentration difference with the Na ion concentration of the original NaCl aqueous solution, the amount of Na ion adsorption of the inorganic ion adsorbent (mmol / g) )
(2) Measurement of inorganic anion adsorption capacity To 100 g of 1% by weight NaCl aqueous solution, 1.5 g of ion-adsorbing fine particles dried at 120 ° C. and made constant are added and stirred at room temperature (25 ° C.) for 15 hours. The filtrate was collected by filtration, and the Cl ion concentration in the filtrate was analyzed by atomic absorption spectrometry. From the concentration difference from the Cl ion concentration of the original NaCl aqueous solution, the amount of Cl ion adsorption of the ion-adsorbing fine particles (mmol / g )
(3) Measurement of organic cation adsorption capacity To 100 g of an aqueous tetramethylammonium hydroxide solution having a concentration of 1% by weight, 1.5 g of ion-adsorbing fine particles dried and constant at 120 ° C. are added, and 15 at room temperature (25 ° C.). After stirring for a period of time, the filtrate was vortexed to collect the filtrate, and the tetramethylammonium ion concentration in the filtrate was analyzed by ion chromatography. From the difference in concentration from the original aqueous solution, the amount of organic cation adsorbed on the ion-adsorbing fine particles ( mmol / g).
(4) Measurement of organic anion adsorption capacity To 100 g of acetic acid aqueous solution with a concentration of 1% by weight, 1.5 g of ion-adsorbing fine particles dried at 120 ° C. and made constant are added and stirred at room temperature (25 ° C.) for 15 hours. The filtrate is collected by filtration, the acetate ion concentration in the filtrate is analyzed by ion chromatography, and the organic anion adsorption amount (mmol / g) of the ion-adsorbing fine particles is determined from the concentration difference from the original aqueous solution.

The inorganic compound particles as the ion-adsorptive fine particles can be used in various mixtures depending on the kind of ions in the liquid crystal, the kind of ions eluted in the liquid crystal, and the ratio of these.
Further, if necessary, insulating or conductive inorganic compound fine particles or resin fine particles other than these inorganic compound particles may be used.

Such inorganic compound particles are preferably used in the form of a sol dispersed in water or an organic solvent, but if the inorganic compound particles can be dispersed in a monodisperse or nearly monodisperse state in a coating solution for forming a transparent film, other than the sol You may use the inorganic compound particle | grains in this state.
Matrix-forming component of the coating liquid transparent film-forming coating solution is preferably 15 wt% or less as solids concentration. If this value exceeds 15% by weight, the storage stability of the coating solution tends to decrease. On the other hand, if this solid content concentration is extremely low, a large number of coating operations are repeated to obtain the desired film thickness. Therefore, the solid content concentration is practically 0.1% by weight or more.

  Organosilicon compound (including hydrolyzate) represented by formula (I) or (II) with respect to the total solid content (total amount of matrix components, inorganic compound particles / ion exchange particles, etc.) in the coating liquid for forming a transparent film The amount of is preferably 18% by weight or more, and more preferably 40% by weight or more. If it is such a range, the transparent film excellent in the effect of this invention, ie, water repellency, toughness, and flexibility, can be formed.

  The content of the organosilicon compound (a), acetylacetonato chelate compound (b), metal alkoxide (c) and polysilazane (d) is 75% by weight or less, further 1 to 40% by weight in the total solid content. It is preferable that it exists in the range. The amount of the inorganic compound particles is preferably 70% by weight or less, more preferably 4.5 to 50% by weight in the total solid content.

  When the amount of the organosilicon compound (a), the acetylacetonato chelate compound (b), the metal alkoxide (c) and the polysilazane (d) and the amount of the inorganic compound particles are increased, the formula (I) or (II) In some cases, the effect of using the organosilicon compound, that is, the toughness, flexibility, scratch resistance, water repellency and the like of the obtained transparent film may be insufficient.

[Substrate with coating]
Next, the coated substrate according to the present invention will be specifically described.
The substrate with a coating according to the present invention is characterized in that a transparent coating formed by applying the coating liquid for forming a transparent coating on the surface of the substrate is formed.

  The substrate with a transparent coating according to the present invention is a method such as a dipping method, a spinner method, a spray method, a roll coater method, a flexographic printing, etc., on the surface of a substrate such as glass or plastic. Then, the coating formed on the surface of the substrate in this manner is dried at room temperature to 80 ° C., and further, if necessary, further heated to 120 ° C. or higher, and in some cases, heated to 300 ° C. or higher to be cured. It is formed.

Furthermore, the coating film formed on the base material may be subjected to curing acceleration treatment 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 an electromagnetic wave having a wavelength shorter than visible light, or the coating at the uncured stage, For example, it may be exposed to a gas atmosphere that promotes the curing reaction.

Specific examples of the electromagnetic wave applied to the uncured coating film before heating include ultraviolet rays, electron beams, X-rays, and γ rays, and ultraviolet rays are particularly preferable.
When performing the ultraviolet irradiation treatment, for example, a high-pressure mercury lamp having a maximum light emission intensity of about 250 nm and 360 nm and a light intensity of 10 mW / cm ² or more is used as an ultraviolet light source, preferably 100 mJ / cm ² or more. Is preferably irradiated with ultraviolet rays having an energy amount of 1000 mJ / cm ² or more.

  Examples of the gas that accelerates the curing reaction include ammonia and ozone. When such gas treatment is performed, the uncured coating film may be exposed to the above active gas atmosphere having a gas concentration of 100 to 100,000 ppm, preferably 1000 to 10,000 ppm for 1 to 60 minutes. desirable.

The same effect can be obtained even if this gas treatment is performed after heat curing.
When the curing acceleration treatment as described above is performed, condensation polymerization and complexation of the matrix forming component contained in the transparent film are promoted, and at the same time, evaporation of water and solvent remaining in the film is promoted. For this reason, the heating and 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 a transparent coating according to the present invention can be advanced efficiently.

  The substrate with a transparent coating according to the present invention can be obtained by the steps as described above. The coating formed on the substrate has toughness and flexibility, excellent adhesion and transparency, and scratch resistance. In addition, it has excellent durability such as water resistance and alkali resistance, and when it contains ion-adsorbing inorganic compound particles, it can effectively reduce the mobile ions in the liquid crystal panel, has high insulation resistance, and has an insulating film It is also suitable.

[Liquid crystal display cell]
Next, the liquid crystal display cell according to the present invention will be specifically described.
All the liquid crystal display cells according to the present invention use a substrate with a transparent electrode having a transparent coating formed using the coating liquid for forming a transparent coating.

  In the first liquid crystal display cell according to the present invention, a transparent electrode film, a transparent film, and an alignment film are sequentially laminated on a surface of at least one substrate, and a pair of substrates with a transparent electrode are opposed to each other. Thus, the liquid crystal display cell is arranged with a predetermined interval therebetween, and liquid crystal is sealed in a gap provided between the pair of substrates with transparent electrodes.

A substrate, a transparent electrode film, an alignment film, a liquid crystal, etc. can use a well-known thing without a restriction | limiting especially except a transparent film using the said coating liquid.
FIG. 1 is a cross-sectional view schematically showing one embodiment of the first liquid crystal display cell according to the present invention.

  In the liquid crystal display cell 1, a pair of substrates 2 with a transparent electrode in which a transparent electrode film 12, a transparent film 13, and an alignment film 14 are sequentially laminated on the surface of a substrate 11 are opposed to each other. Thus, the liquid crystal 6 is formed in a gap between the transparent electrode films 12 and 12 arranged at a predetermined interval d by a plurality of spacer particles 5 and having a predetermined interval d.

  The substrate may be a glass substrate or a plastic substrate. The plastic substrate is not particularly limited as long as it is made of a transparent resin. Furthermore, a resin film such as polyethylene terephthalate, polyethylene, or polycarbonate can be used as the substrate. In particular, if the resin is a flexible resin, the film can be bent into an arbitrary shape.

  The transparent film 13 is a film formed by applying the above-described coating liquid for forming a transparent film on the transparent electrode film 12, and this film is excellent in toughness, flexibility, water repellency, etc., and has transparency and scratch resistance. In addition, the insulation resistance is high, and the adhesion between the transparent coating 13 and the alignment film 14 is good.

In the first liquid crystal display cell according to the present invention, a substrate with a transparent electrode in which an alkali passivation film such as a SiO ₂ film is further formed between the substrate 11 and the transparent electrode film 12 may be used. Deformation is possible.

  In the second liquid crystal display cell according to the present invention, a pair of substrates with a transparent electrode, in which a color filter, a transparent coating, a transparent electrode film, and an alignment film are sequentially laminated on the surface of at least one substrate, Is a liquid crystal display cell in which liquid crystal is sealed in a gap provided between the pair of substrates with a transparent electrode.

FIG. 2 is a cross-sectional 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 part is shown in FIG. 2, is an electrode in which an alkali passivation film 21b, a plurality of pixel electrodes 21c, a transparent film 21d, and an alignment film 21e are sequentially laminated on a glass substrate 21a. A liquid crystal display cell 2 ′ having a plate 21, a counter electrode plate 22 in which an alkali passivation film 22b, a color filter 22c, a transparent coating 22d, a transparent electrode 22e, and an alignment film 22f are sequentially laminated on the glass substrate 22a; A pair of polarizing plates 3 and 4 are provided on both sides of the cell. Among these, the transparent films 21d and 22d are films formed by applying the coating liquid for forming a transparent 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 substrates 21a and 22a outside. It arrange | positions so that it may oppose. A liquid crystal 23 is sealed in a gap between the electrode 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 alkali passivation film 22b of the counter electrode plate 22 includes a plurality of color elements of 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 activated by the display signal sent from the liquid crystal display device 1 ′ main body so as to be regularly arranged so as to be adjacent to each other. The color image thus obtained 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 coating, a transparent electrode film, and an alignment film are sequentially laminated on the surface of at least one substrate, Is a liquid crystal display cell in which liquid crystal is sealed in a gap provided between the pair of substrates with a transparent electrode.
Known alkali passivation films, pixel electrodes, alignment films, glass substrates, color filters, transparent electrodes, polarizing plates, and liquid crystals can be used without particular limitation.

FIG. 3 is a cross-sectional view schematically showing an example of an aspect of the third liquid crystal display cell according to the present invention.
The liquid crystal display cell 1 ″ has a TFT array 32 formed on the surface thereof, and a transparent insulating substrate 31 in which a transparent coating 33, a pixel electrode 34, and an alignment film 35 are sequentially stacked on the surface of the TFT array 32;
The alignment films 35 and 46 are opposed to the liquid crystal layer 51 with the counter substrate 41 having a black matrix (shielding film) 42, a color filter 43, a transparent film 44, a counter electrode 45 and an alignment film 46 sequentially laminated on the surface. Is configured to do.

As shown in FIG. 1, spacer particles may be interposed between the alignment films 35 and 46.
The TFT array 32 includes TFT (thin film transistor) elements, data electrodes, auxiliary capacitors, and the like.

As the pixel electrode, the alignment film, the black matrix, the color filter, the counter electrode, and the substrate, known ones can be used without particular limitation.
In the liquid crystal display cell according to the present invention as described above, the transparent film includes a matrix-forming component made of a specific organosilicon compound, and is excellent in water resistance, water repellency, toughness, flexibility and the like.

  Furthermore, when the transparent coating contains ion-adsorbing inorganic compound particles, mobile ions (ionic impurities) in the liquid crystal are reduced. For this reason, the liquid crystal display cell according to the present invention has excellent high voltage retention characteristics, does not cause display defects, has excellent long-term reliability, and requires less power consumption, thereby improving power efficiency.

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

Preparation of Transparent Film Forming Coating Liquid (A) As a matrix forming component, 25.6 g of bis (trimethoxysilyl) hexane (manufactured by Toray Dow Corning Silicone Co., Ltd.), 47.0 g of pure water and 526. 4 g of nitric acid having a concentration of 61% by weight was added thereto, and the mixture was kept at 60 ° C. for 24 hours with stirring, and a partially hydrolyzed solution of bis (trimethoxysilyl) hexane (A -1). After cooling to room temperature, 18 g of both ion exchange resins (Diaion) was added to the partially hydrolyzed solution (A-1), and the ions were removed by stirring at room temperature for 16 hours, and then the ion exchange resin was filtered off. Further, 85 g of hexylene glycol was added to this solution and distilled under reduced pressure to obtain a hydrolyzate solution (A-2) having a solid content concentration of 16% by weight using hexylene glycol as a main solvent component.

94.2 g of the hydrolyzate solution (A-2) was charged with hexylene glycol as Sb ₂ O ₅ · 2.7H ₂ O fine particles having an average particle diameter of 20 nm and an Na ion adsorption capacity of 2.4 mmol / g as ion-adsorbing fine particles. 42.2 g of ion-adsorptive fine particle sol having a solid content concentration of 10% by weight uniformly dispersed therein was added and stirred for 1 hour, and then 7.3 g of tetraethoxysilane (28.8% by weight as SiO ₂ ) and hexylene glycol. 206.1 g and 2.0 g of water were added, and the mixture was stirred at 40 ° C. for 24 hours to prepare a coating solution (A) for forming a transparent film having a solid content concentration of 6% by weight.

Formation of transparent coating (A) A transparent coating-forming coating solution (A) is applied by flexographic printing onto a patterned glass substrate with an 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 amount of 6,000 mJ / cm ² (measured with a 365 nm sensor) with a high-pressure mercury lamp, and then baked at 200 ° C. for 30 minutes. A transparent coating (A) was formed. It was 80 nm when the film thickness of the obtained transparent film (A) was measured with the stylus type surface roughness meter.

Further, the vertical load test and the scratch strength measurement were performed as follows, and the results are shown in Tables 2 and 3.
Vertical load test A needle with a 1 mm radius of curvature with a DC voltage of 12V applied between the ITO electrode surface and the transparent film upper surface is pressed against the transparent film surface, and the load value when the voltage reaches 3V is The load resistance in the vertical direction of the film was evaluated as a mechanical short circuit. Load resistance was measured at 10 locations on the transparent coating. The average values are shown in Tables 2 and 3.

Scratch strength measurement The scratch strength of the transparent coating (A) was measured using a scratch tester (Reska Co., Ltd .: CSR-02). The average values are shown in Tables 2 and 3.

Preparation of liquid crystal display cell (A) Next, a polyimide film-forming paint (Nissan Chemical Co., Ltd .: Sunever) was applied on the transparent film (A) by flexographic printing, dried at 100 ° C. for 5 minutes, A polyimide film (alignment film) was formed by heat treatment at 30 ° C. for 30 minutes, and then a rubbing treatment was performed.

  In this way, a pair of substrates with a transparent electrode was obtained in which a transparent electrode, a transparent coating (A), and a rubbing-treated alignment film were sequentially laminated on a glass substrate. Spacers (particle diameter corresponding to the distance between the two substrates) are sprayed on one of the obtained substrates with transparent electrodes, and a sealing material is printed on the other substrate. Were bonded so that the transparent electrodes were opposed to each other, STN liquid crystal was sealed, and then the sealing port was sealed with a sealing material to prepare a liquid crystal display cell (A).

Measurement of mobile ion amount The amount of mobile ions in the obtained liquid crystal display cell (A) was measured using an ion density measuring machine (manufactured by Toyo Technica Co., Ltd .: MTR-1) with an applied voltage of 10 V and a triangular wave frequency of 0.1 Hz. Measured under conditions. A peak due to mobile ions was detected in the vicinity of an applied voltage of 0.8 V, and the amount of mobile ions was 0.8 nC / cm ² .

Observation of display unevenness of liquid crystal display cell In addition, 30 liquid crystal display cells were prepared by the above method, a lighting display test was performed, and visual observation was performed for the presence or absence of display unevenness. At this time, the number of panels in which display unevenness occurred was examined. The average values are shown in Tables 2 and 3.

Evaluation of long-term reliability Using the liquid crystal display cell (A) in which display unevenness did not occur by the above method, 10 sheets were in a high temperature environment (relative humidity 20%, temperature 80 ° C.), and the other 10 sheets were high temperature. After exposure for 500 hours in a high humidity environment (relative humidity 95%, temperature 80 ° C.), a liquid crystal display cell lighting display test was performed, and visual observation was performed for the presence or absence of display unevenness. At this time, the number of panels in which display unevenness did not occur was examined. The average values are shown in Tables 2 and 3.

Preparation of coating liquid for forming transparent film (B) As a matrix forming component, 94.2 g of hydrolyzate solution (A-2) prepared in the same manner as in Example 1 was used as ion-adsorbing fine particles, with an average particle diameter of 25 nm, Na 42.2 g of an ion-adsorbing fine particle sol having a solid content concentration of 10% by weight, in which SiO ₂ .Al ₂ O ₃ fine particles having an ion adsorption capacity of 0.5 mmol / g were uniformly dispersed in hexylene glycol, was added and stirred for 1 hour. Next, 7.5 g of tetraisopropoxytitanium (28 wt% as TiO ₂ ), 205.9 g of hexylene glycol and 2.0 g of water were added, and the mixture was stirred at 40 ° C. for 24 hours to obtain a transparent film having a solid content concentration of 6 wt%. A forming coating solution (B) was prepared.

Formation of Transparent Film (B) A transparent film (B) was formed in the same manner as in Example 1 except that the coating liquid (B) for forming a transparent film was used. It was 70 nm when the film thickness of the obtained transparent film (B) was measured with the stylus type surface roughness meter. In addition, a vertical load test and a scratch strength measurement were performed. The results are shown in Tables 2 and 3.

Preparation of liquid crystal display cell (B) Next, a liquid crystal display cell (B) was prepared in the same manner as in Example 1 except that a polyimide film was formed on the transparent film (B). The obtained liquid crystal display cell (B) was measured for the amount of mobile ions, observed for display unevenness, and evaluated for long-term reliability. The results are shown in Tables 2 and 3.

Preparation of coating liquid for forming transparent film (C) As matrix forming component, 94.2 g of hydrolyzate solution (A-2) prepared in the same manner as in Example 1 as ion-adsorbing fine particles, average particle size 45 nm, Cl 42.2 g of an ion-adsorbing fine particle sol having a solid concentration of 10% by weight in which MgO fine particles having an ion adsorption capacity of 0.3 mmol / g are uniformly dispersed in hexylene glycol are added and stirred for 1 hour, and then dibutoxy-bisacetylacetate. 15.1 g of natozirconium (14% by weight as ZrO ₂ ), 198.3 g of hexylene glycol and 2.0 g of water are added, and the mixture is stirred at 40 ° C. for 24 hours to form a transparent film having a solid content of 6% by weight. Liquid (C) was prepared.

Formation of Transparent Film (C) A transparent film (C) was formed in the same manner as in Example 1 except that the coating liquid (C) for forming a transparent film was used. It was 90 nm when the film thickness of the obtained transparent film (C) was measured with the stylus type surface roughness meter. In addition, a vertical load test and a scratch strength measurement were performed. The results are shown in Tables 2 and 3.

Preparation of liquid crystal display cell (C) Next, a liquid crystal display cell (C) was prepared in the same manner as in Example 1 except that a polyimide film was formed on the transparent film (C). The obtained liquid crystal display cell (C) was measured for the amount of mobile ions, observed for display unevenness, and evaluated for long-term reliability. The results are shown in Tables 2 and 3.

Preparation matrix-forming component of the transparent film-forming coating liquid (D), 39.5 weight hydrolyzate solution (A-2) 53.8g, prepared in the same manner as in Example 1, as tetramethoxysilane (SiO ₂ %) 32.1 g, hexylene glycol 264.3 g, and water 2.0 g were added, and the mixture was stirred at 40 ° C. for 24 hours to prepare a coating solution (D) for forming a transparent film having a solid content concentration of 6% by weight.

Formation of Transparent Film (D) A transparent film (D) was formed in the same manner as in Example 1 except that the coating liquid (D) for forming a transparent film was used. It was 80 nm when the film thickness of the obtained transparent film (D) was measured with the stylus type surface roughness meter. In addition, a vertical load test and a scratch strength measurement were performed. The results are shown in Tables 2 and 3.

Preparation of liquid crystal display cell (D) Next, a liquid crystal display cell (D) was prepared in the same manner as in Example 1 except that a polyimide film was formed on the transparent film (D). The obtained liquid crystal display cell (D) was measured for the amount of mobile ions, observed for display unevenness, and evaluated for long-term reliability. The results are shown in Tables 2 and 3.

Preparation of coating liquid for forming transparent film (E) As a matrix forming component, 121.1 g of the hydrolyzate solution (A-2) prepared in the same manner as in Example 1 was used as ion-adsorbing fine particles with an average particle diameter of 20 nm, Na Add 5.3 g of ion-adsorbing fine particle sol having a solid content concentration of 20 wt% in which Sb ₂ O ₅ · 2.7H ₂ O fine particles having an ion adsorption capacity of 2.4 mmol / g are uniformly dispersed in propylene glycol, and stir for 1 hour. Then, 10.6 g of a butanol solution of tributoxy-monoacetylacetonatozirconium (10 wt% as ZrO ₂ ) and 0.5 g of water were added, and the mixture was stirred at 40 ° C. for 24 hours to obtain a solid content concentration of 15.6 wt%. A coating solution (E) for forming a transparent film was prepared.

Formation of transparent film (E) On a glass substrate on which a color filter is formed, a coating liquid (E) for forming a transparent film is applied by spin coating at 1500 rpm for 10 seconds, and then dried at 50 ° C. for 120 minutes. Thereafter, a heat treatment was performed at 120 ° C. for 60 minutes to form a transparent film (E), thereby overcoating the color filter pixels. It was 2 micrometers when the film thickness of the obtained transparent film (E) was measured with the stylus type surface roughness meter. In addition, a vertical load test and a scratch strength measurement were performed. The results are shown in Tables 2 and 3.

Furthermore, an ITO electrode film was formed on the transparent coating (E) by a sputtering method.
Preparation of liquid crystal display cell (E) This ITO electrode 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 treatment. In this manner, a pair of substrates with a transparent electrode was obtained in which a color filter, a transparent coating (E), a transparent electrode, and a rubbing-treated alignment film were sequentially laminated on a glass substrate.

  Next, the opposing substrate with common electrode is bonded with a sealing material through a spacer, STN liquid crystal is injected into the gap between the substrates, and the injection port is sealed with the sealing material to form the liquid crystal display cell (E). Created. The obtained liquid crystal display cell (E) was measured for the amount of mobile ions, observed for display unevenness, and evaluated for long-term reliability. The results are shown in Tables 2 and 3.

Preparation of coating liquid for transparent film formation (F) As a matrix-forming component, 17 g of CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ (manufactured by Shin-Etsu Chemical Co., Ltd., KBM7803) 0.06 g of ethyl alcohol and 526.4 g of ethyl alcohol, 1.0 g of nitric acid having a concentration of 61% by weight was added thereto, and the mixture was kept at 60 ° C. for 24 hours while stirring, and a portion of heptadecatrifluorotrimethoxysilane was added. It was set as the hydrolysis solution (F-1).

  After cooling this to room temperature, 18 g of both ion exchange resins (Diaion) was added to the partially hydrolyzed solution (F-1) and stirred for 16 hours at room temperature, and then the ion exchange resin was filtered off to remove ions. Further, 85 g of hexylene glycol was added to this solution, followed by distillation under reduced pressure to obtain a hydrolysis solution (F-2) having a solid content concentration of 16% by weight using hexylene glycol as a main solvent component.

Sb ₂ O ₅ · 2.7H ₂ O fine particles having an average particle diameter of 20 nm and Na ion adsorption capacity of 2.4 mmol / g as ion-adsorbing fine particles were added to 94.2 g of this hydrolyzed solution (F-2) in hexylene glycol. 21.1 g of ion-adsorptive fine particle sol having a solid concentration of 10% by weight dispersed uniformly was added and stirred for 1 hour, and then 14.6 g of tetraethoxysilane (28.8% by weight as SiO ₂ ) and hexylene glycol 221. 6 g and 4.0 g of water were added, and the mixture was stirred at 40 ° C. for 24 hours to prepare a coating solution (F) for forming a transparent film having a solid content concentration of 6% by weight.

Formation of Transparent Film (F) A transparent film (F) was formed in the same manner as in Example 1 except that the coating liquid (F) for forming a transparent film was used. It was 75 nm when the film thickness of the obtained transparent film (F) was measured with the stylus type surface roughness meter. In addition, a vertical load test and a scratch strength measurement were performed. The results are shown in Tables 2 and 3.

Preparation of liquid crystal display cell (F) Next, a liquid crystal display cell (F) was prepared in the same manner as in Example 1 except that a polyimide film was formed on the transparent film (F). The obtained liquid crystal display cell (F) was measured for the amount of mobile ions, observed for display unevenness, and evaluated for long-term reliability. The results are shown in Tables 2 and 3.
(Comparative Example 1)
Preparation of coating liquid for forming transparent film (G) As a matrix forming component, 51.3 g of tetraethoxysilane (28.8 wt% as SiO ₂ ) was mixed in a mixed solvent of 9.0 g of pure water and 432.2 g of ethyl alcohol. Then, 0.2 g of nitric acid having a concentration of 61% by weight was added thereto, and the mixture was kept at 60 ° C. for 24 hours while stirring to obtain a partially hydrolyzed solution of tetraethoxysilane (G-1).

  After cooling to room temperature, 18 g of both ion exchange trees (Diaion) was added to the partially hydrolyzed solution (G-1) and stirred for 16 hours at room temperature, and then the ion exchange resin was filtered off to remove ions. Furthermore, 85 g of hexylene glycol was added to this solution, and a tetraethoxysilane hydrolysis solution (G-2) having a solid content concentration of 16% by weight using hexylene glycol as a main solvent component was obtained by distillation under reduced pressure.

In 94.2 g of this hydrolyzed solution (G-2), Sb ₂ O ₅ · 2.7H ₂ O fine particles having an average particle diameter of 20 nm and an Na ion adsorption capacity of 2.4 mmol / g as ion-adsorbing particles were added in hexylene glycol. 16.4 g of ion-adsorptive fine particle sol having a solid content concentration of 10% by weight, 161.1 g of hexylene glycol and 2.0 g of water were added and stirred at 40 ° C. for 24 hours to obtain a solid content concentration of 6 wt. % Transparent film-forming coating solution (G) was prepared.

Formation of Transparent Film (G) A transparent film (G) was formed in the same manner as in Example 1 except that the coating liquid (G) for forming a transparent film was used. It was 80 nm when the film thickness of the obtained transparent film (G) was measured with the stylus type surface roughness meter. In addition, a vertical load test and a scratch strength measurement were performed. The results are shown in Tables 2 and 3.

Preparation of liquid crystal display cell (G) Next, a liquid crystal display cell (G) was prepared in the same manner as in Example 1 except that a polyimide film was formed on the transparent film (G). The obtained liquid crystal display cell (G) was measured for the amount of mobile ions, observed for display unevenness, and evaluated for long-term reliability. The results are shown in Tables 2 and 3.

Preparation of coating liquid for forming transparent film (H) As a matrix-forming component, 26.9 g of the hydrolysis solution (F-2) prepared in the same manner as in Example 6, an average particle size of 25 nm, Na ions as ion-adsorbing fine particles 21.1 g of an ion-adsorbing fine particle sol having a solid content concentration of 10% by weight, in which SiO ₂ —Al ₂ O ₃ fine particles having an adsorption capacity of 0.5 mmol / g were uniformly dispersed in hexylene glycol, was added and stirred for 1 hour. Add 52.8 g of tetraisopropoxytitanium (28 wt% as TiO ₂ ), 251.0 g of hexylene glycol and 3.0 g of water, and stir at 40 ° C. for 24 hours to form a transparent film with a solid content concentration of 6 wt% Coating solution (H) was prepared.

Formation of Transparent Film (H) A transparent film (H) was formed in the same manner as in Example 1 except that the coating liquid (H) for forming a transparent film was used. It was 75 nm when the film thickness of the obtained transparent film (H) was measured with the stylus type surface roughness meter. In addition, a vertical load test and a scratch strength measurement were performed. The results are shown in Tables 2 and 3.

Preparation of liquid crystal display cell (H) Next, a liquid crystal display cell (H) was prepared in the same manner as in Example 1 except that a polyimide film was formed on the transparent film (H). The obtained liquid crystal display cell (H) was measured for the amount of mobile ions, observed for display unevenness, and evaluated for long-term reliability. The results are shown in Tables 2 and 3.

Preparation of coating liquid (I) for forming transparent film As a matrix-forming component, 95.0 g of hydrolyzate solution (A-2) prepared in the same manner as in Example 1, 155.0 g of hexylene glycol and 2.0 g of water And stirred at 40 ° C. for 24 hours to prepare a coating solution (I) for forming a transparent film having a solid content concentration of 6% by weight.

Formation of Transparent Film (I) A transparent film (I) was formed in the same manner as in Example 1 except that the coating liquid (I) for forming a transparent film was used. It was 80 nm when the film thickness of the obtained transparent film (I) was measured with the stylus type surface roughness meter. In addition, a vertical load test and a scratch strength measurement were performed. The results are shown in Tables 2 and 3.

Preparation of liquid crystal display cell (I) Next, a liquid crystal display cell (I) was prepared in the same manner as in Example 1 except that a polyimide film was formed on the transparent film (I). The obtained liquid crystal display cell (I) was measured for the amount of mobile ions, observed for display unevenness, and evaluated for long-term reliability. The results are shown in Tables 2 and 3.

Preparation of coating liquid for forming transparent film (J) Hydrolyzate prepared in the same manner as in Example 6 in 47.1 g of hydrolyzate solution (A-2) prepared in the same manner as in Example 1 as a matrix forming component 47.1 g of the solution (F-2) was added and stirred for 1 hour, and then 155.0 g of hexylene glycol and 2.0 g of water were added, and the mixture was stirred at 40 ° C. for 24 hours. A coating solution (J) for film formation was prepared.

Formation of Transparent Film (J) A transparent film (J) was formed in the same manner as in Example 1 except that the coating liquid for forming a transparent film (J) was used. It was 80 nm when the film thickness of the obtained transparent film (J) was measured with the stylus type surface roughness meter. In addition, a vertical load test and a scratch strength measurement were performed. The results are shown in Tables 2 and 3.

Preparation of liquid crystal display cell (J) Next, a liquid crystal display cell (J) was prepared in the same manner as in Example 1 except that a polyimide film was formed on the transparent coating (J). The obtained liquid crystal display cell (J) was measured for the amount of mobile ions, observed for display unevenness, and evaluated for long-term reliability. The results are shown in Tables 2 and 3.

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] FIG. 2 shows a schematic cross-sectional view of an embodiment of a second liquid crystal display cell according to the present invention.
[FIG. 3] FIG. 3 shows a schematic cross-sectional view of one embodiment of a third liquid crystal display cell according to the present invention.

The reference numbers in the figure are as follows.
1, 1 ', 1 "... liquid crystal display cell, 2, 2' ... liquid crystal display cell, 3, 4 ... polarizing plate, 5 ... spacer particle, 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 ... multiple pixel electrodes, 21d ... transparent coating, 21e ... alignment film, 22 ... counter electrode plate, 22a ... glass substrate, 22b ... alkali passivation film, 22c ... color filter, 22d ... transparent coating, 22e ... transparent electrode, 22f ... alignment film, 23 ... liquid crystal, 31 ... transparent insulating substrate, 32 ... TFT array, 33 ... transparent coating 34 ... Pixel electrode, 35 ... Alignment film, 36 ... Insulating film, 41 ... Counter substrate, 42 ... Black matrix (shielding film), 43 ... Color filter, 44 ... Transparent coating, 45 ... Counter electrode, 46 ... orientation film 51 ... liquid crystal layer

Claims (8)

A coating liquid for forming a transparent film in which a matrix-forming component is dispersed in a mixed solvent comprising water and an organic solvent, wherein the matrix-forming component is a) an organosilicon compound represented by the following formula (I) or a hydrate thereof A coating solution for forming a transparent film, comprising one or more selected from a decomposed product, b) an organosilicon compound represented by the following formula (II) or a hydrolyzate thereof, or c) a mixture thereof.
R ¹ —SiR ² _m R ³ _(3-m) (I)
Wherein, ^{R 1} - is _{^{R 8 (CR 9 2) n}} - or represented by ^R 10 X-.
R ⁸ represents a hydrolyzable group, a hydroxyl group, a hydrogen atom or a halogen atom.
R ⁹ each independently represents a hydrogen atom or a halogen atom.
R ¹⁰ represents a methyl group, a hydrogen atom or a hydrolyzable group.
n is an integer of 3 to 30.
X is — (CH ₂ ) q—, — (Ph) — [wherein Ph represents a benzene ring],
_{- (CH 2) q- (Ph} ) -, - (CH 2) q- (Ph) - (CH 2) y-,
_{- [(CH 2) q (} CF 2) y (CH 2) r] - and _{- (CH 2) q- (S} ) - (CH 2) r- from divalent group [where selected, q, r and y represent an integer of 1 to 30].
R ² represents a hydrolyzable group.
R ³ represents an organic group having 1 to 30 carbon atoms which may contain a halogen atom.
m shows the number of 1-3.
However, Formula (I) has 2 to 3 hydrolyzable groups in one molecule. ]
_{^{R 4 n R 5 3-n}} Si- (X) -SiR 6 p R 7 (3-p) (II)
[Wherein, R ⁴ and R ⁶ independently represent a hydrolyzable group.
R ⁵ and R ^{7 each} independently represents a monovalent organic group having 1 to 30 carbon atoms which may contain a halogen atom.
X _{is, - (CH 2) q -} , - (Ph) - ( wherein, Ph represents a benzene ring),
_{- (CH 2) q- (Ph} ) -, - (CH 2) q- (Ph) - (CH 2) y-,
_{- [(CH 2) q (} CF 2) y (CH 2) r] -
_{- (CH 2) q- (S} ) - (CH 2) r- and - (S) divalent group selected from q- [wherein, q, r and y is an integer of 1 to 30].
n represents a number from 0 to 3.
p represents a number from 0 to 3.
However, Formula (II) has two or more hydrolyzable groups in one molecule. ] The organosilicon compound of the formula (I) has more than two hydrolyzable groups in one molecule, and the organosilicon compound of the formula (II) has more than two hydrolyzable groups in one molecule. The coating liquid for forming a transparent film according to claim 1, wherein The matrix-forming component is further a) an organosilicon compound represented by the following formula (III) R _t Si (OR ′) _4t (III)
[Wherein R is selected from a methyl group, an ethyl group, a vinyl group or an epoxy group. R ′ is an alkyl group having 1 to 6 carbon atoms. t is a number from 0 to 4. And b) an acetylacetonate chelate compound, c) a metal alkoxide, and d) a polysilazane. The coating liquid for forming a transparent film according to claim 1, wherein the matrix forming component further contains inorganic compound particles. A substrate with a transparent coating, wherein a transparent coating formed by applying the coating solution for forming a transparent coating according to any one of claims 1 to 4 onto the surface of the substrate is formed. A pair of substrates with a transparent electrode, in which a transparent electrode film, a transparent film, and an alignment film are sequentially laminated on the surface of at least one substrate, are arranged at predetermined intervals so that the transparent electrodes face each other. In a liquid crystal display cell in which liquid crystal is sealed in a gap opened between a pair of substrates with transparent electrodes,
A liquid crystal display cell, wherein the transparent film is a film formed by applying the coating liquid for forming a transparent film according to claim 1. A pair of substrates with a transparent electrode, in which a color filter, a transparent coating, a transparent electrode film, and an alignment film are sequentially laminated on the surface of at least one substrate, are arranged at predetermined intervals so that the transparent electrodes face each other. In a liquid crystal display cell in which liquid crystal is sealed in a gap opened between the pair of substrates with transparent electrodes,
A liquid crystal display cell, wherein the transparent film is a film formed by applying the coating liquid for forming a transparent film according to claim 1. A pair of substrates with a transparent electrode, in which a TFT array, a transparent coating, a transparent electrode film, and an alignment film are sequentially laminated on the surface of at least one substrate, are arranged at predetermined intervals so that the transparent electrodes face each other. In a liquid crystal display cell in which liquid crystal is sealed in a gap opened between the pair of substrates with transparent electrodes,
A liquid crystal display cell, wherein the transparent film is a film formed by applying the coating liquid for forming a transparent film according to claim 1.

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