KR20060002011A - Coating liquid for forming transparent coating film, base with such coating film, and liquid crystal display cell - Google Patents

Abstract

A coating liquid for forming transparent coating films is disclosed which enables to form a transparent coating film that is excellent in abrasion resistance, acid resistance, alkali resistance, water resistance, insulating property, adhesiveness to an electrode film or a film (an alignment film) made of a resin with high hydrophobicity such as polyimide resin, toughness, and flexibility. The coating liquid for forming transparent coating films wherein a matrix-forming component is dispersed in a mixed solvent composed of water and an organic solvent is characterized in that the matrix-forming component contains an organic silicon compound having two or more hydrolyzable groups or a hydrolysate thereof.

Description

Coating liquid for forming a transparent film, such a coating base material and a liquid crystal display cell {Coating liquid for forming transparent coating film, base with such coating film, and liquid crystal display cell}

The present invention relates to a coating part substrate having a novel coating liquid for forming a coating film and a coating film formed from such a coating liquid for forming a coating film, and a liquid crystal display cell having such a coating part substrate. More specifically, it is related with the coating liquid for transparent film formation which can form the transparent film which was excellent in the urinary property, toughness, and abrasion resistance which were difficult to obtain with the conventional coating liquid for transparent film formation.

Conventionally, a transparent electrode portion substrate in which a transparent electrode film such as ITO or an alignment film made of a polymer such as polyimide is sequentially stacked on the surface of a glass substrate is opposed to each other via a spacer so as to face each transparent electrode film. The liquid crystal display cell which enclosed liquid crystal in the clearance gap opened by predetermined | prescribed space by this is known.

In this type of liquid crystal display cell, the alignment film is damaged by foreign substances or spacers mixed inside the liquid crystal cell in the manufacturing process, which results in leakage of current between the upper and lower electrodes, which may cause display defects due to the leakage of this current. .

For this reason, in the liquid crystal display cell as described above, a transparent insulating film is formed in a gap between the transparent electrode film and the alignment film of the transparent electrode part substrate (see Japanese Patent Application Laid-Open No. 60-2600021, Japanese Patent Laid-Open No. 1-150166, Japanese Patent Laid-Open No. 2). 221923, etc.).

By the way, many resins with strong hydrophobicity, such as a polyimide resin, are used as said orientation film. When an alignment film made of such a hydrophobic resin is formed on the insulating film, adhesion between the insulating film and the alignment film is insufficient, and display unevenness may occur in the liquid crystal display cell due to rubbing scratches or the like. For this reason, the present applicant proposes in Patent Document 1 (Patent No. 4-247427) to contain an inorganic compound having a specific particle size as a coating liquid capable of forming an insulating film excellent in adhesion with an alignment film.

In addition, when such an insulating film is formed in the gap between the transparent electrode and the alignment film, damage or poor orientation may occur in the alignment film due to static electricity or the like generated during rubbing of the alignment film. For this reason, the present applicant proposes to form the protective film which consists of electroconductive particle and a matrix, and surface resistance of 10 <^9> -10 <^13> Pa / square on the transparent electrode surface in patent document 2 (Unexamined-Japanese-Patent No. 5-232459).

However, in recent years, the demand for thinning, high-definition, large screen, and the like of liquid crystal displays has been required to have higher adhesion to the alignment film and higher scratch resistance. On the other hand, in substrates such as plastic, excellent urination and toughness are required for the insulating film itself.

In recent years, TFT type liquid crystal displays 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. By flattening the unevenness by the TFT array by providing a flattening film and providing a display electrode such as ITO thereon, the aperture ratio of the TFT type liquid crystal display device is improved, and the alignment disorder of the liquid crystal due to the unevenness of the TFT array is attempted. .

In addition, in the liquid crystal display device having a color filter, an insulating protective film is provided to flatten the color filter or to improve the reliability of the liquid crystal display device.

Examples of the flattening film and insulating protective film used in such liquid crystal display devices include organic resin films made of acrylic resins, polyester resins, and the like, inorganic films such as SiO ₂ and Si ₃ N _4, and alkyltrihydroxysilanes. Organic inorganic composite films and the like made of a polymerized product thereof are used.

However, in the organic resin film, heat resistance is insufficient, which may cause cracks, and when a high temperature is exposed, gas components may be released or the film strength may decrease. Moreover, in this organic resin substrate, even if it is going to form a resist film on a film, there existed a problem that formation was difficult.

On the other hand, in the inorganic coating, there are many problems such as hygroscopicity in the coating itself, difficulty in forming a resist film on the coating, and thickening of the coating itself.

In addition, in the organic-inorganic composite film, there is a problem that the film is weak and easy to be scratched on the surface, and there is a problem such as the formation of a resist film on the film (Patent Document 1: Japanese Patent Laid-Open No. 4-247427, Patent Document 2: Japanese Patent Application Laid-Open). See publication 5-232459)

Disclosure of the Invention

Problems to be Solved by the Invention

The present inventors have diligently studied to solve the above problems under such circumstances, and have found that by using an organosilicon compound having a specific structural formula or a hydrolyzate thereof, a transparent film excellent in water resistance, water repellency, toughness, urination, etc. has been found. The invention was completed.

The present invention is to solve the problems in the prior art as described above, and is excellent in scratch resistance, acid resistance, alkali resistance, water resistance, insulation, and adhesion to a film (orientation film) made of a resin having high hydrophobicity such as an electrode film or a polyimide resin. An object of the present invention is to provide a coating film for forming a transparent film that can form a transparent film that is excellent in toughness and excellent in toughness, urinability, and the like.

Means for Solving the Invention

The gist of the present invention includes the following.

[1] A transparent film-forming coating liquid in which a matrix forming component is dispersed in a mixed solution of 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) A coating liquid for forming a transparent film, comprising at least one selected from an organosilicon compound represented by the following formula (II) or a hydrolyzate thereof or c) a mixture thereof.

R ¹ -SiR ² R ³ (Ⅰ)

[Wherein R ¹ -is represented by 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.

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 3-30.

X is-(CH ₂ ) q-,-(Ph)-[where 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

A _divalent group selected from-(CH ₂ ) q- (S)-(CH ₂ ) r-, wherein q, r and y are represented by integers of 1 to 30;

R ² represents a hydrolyzable group.

R <^3> represents the C1-C30 organic group which may contain the halogen atom.

m represents the number of 1-3.

However, Formula (I) has 2-3 hydrolyzable groups in 1 molecule.]

R ⁴ _n R ⁵ _3-n Si- (X) -SiR ⁶ _p R ⁷ _(3-p) (II)

[Wherein, R ⁴ and R ⁴ independently represent a hydrolyzable group.

R <^5> and R <^7> represents the C1-C30 monovalent organic group which may independently contain the halogen atom.

X is-(CH ₂ ) q-,-(Ph)-[where 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]-,

A _{divalent group selected} from-(CH ₂ ) q- (S)-(CH ₂ ) r- and-(S) q, wherein q, r and y are represented by integers of 1 to 30;

n represents the number of 0-3.

p represents the number of 0-3.

Provided that Formula (II) has two or more hydrolyzable groups in one molecule.]

[2] The organosilicon compound of formula (I) having more than two hydrolyzable groups in one molecule, and the organosilicon compound of formula (II) having more than two hydrolyzable groups in one molecule [1] Coating liquid for transparent film formation of description.

[3] The organosilicon compound, wherein the matrix forming component is also represented by a)

R _t Si (OR ') _4-t (III)

[Wherein R is selected from methyl group, ethyl group, vinyl group or epoxy group. R 'is a C1-C6 alkyl group. t is a number from 0 to 4], b) an acetylacetate chelating compound, c) a metal alkoxy and d) a polysilazane, wherein said transparent film comprises [1] or [2]. Coating liquid for formation.

[4] The coating liquid for forming a transparent film according to any one of [1] to [3], wherein the matrix forming component further contains an inorganic compound particle.

[5] A transparent coating part base material, wherein a transparent coating is formed by applying the coating liquid for forming a transparent film according to any one of [1] to [4] to a substrate surface.

[6] One transparent electrode unit substrate on which at least one substrate has a transparent electrode film, a transparent film, and an alignment film sequentially stacked is arranged at a predetermined interval so that the transparent electrodes face each other, and the single transparent electrode unit substrate A transparent film is a film formed by applying the coating liquid for transparent film formation as described in any one of [1] to [4] with respect to the liquid crystal display cell in which liquid crystal is enclosed in the space | interval opened at the space | interval.

[7] One transparent electrode unit substrate on which at least one substrate has a color filter, a transparent film, a transparent electrode film, and an alignment film are sequentially stacked so as to face each transparent electrode at a predetermined interval, and the transparent film A transparent film is a film formed by applying the coating liquid for forming a transparent film according to any one of [1] to [4] to a liquid crystal display cell in which liquid crystal is enclosed at a gap opened in a gap of an electrode part substrate. Display cell.

[8] A single transparent electrode unit substrate on which at least one substrate has a TFT array, a transparent film transparent electrode film, and an alignment film are sequentially stacked is disposed at a predetermined interval so that the transparent electrodes face each other. The transparent film is a film formed by coating the coating liquid for forming a transparent film according to any one of [1] to [4] with respect to a liquid crystal display cell in which liquid crystal is enclosed at a gap opened in a gap between the sub-substrates. Cell.

Effects of the Invention

According to the above description, the coating liquid for transparent film formation concerning this invention contains the matrix formation component which consists of specific organosilicon compounds.

For this reason, the obtained transparent film is excellent in water repellency, toughness, urination, and the like.

In addition, when such a transparent film is formed on a substrate having irregularities, for example, a TFT array substrate or a color filter substrate, it is possible to extremely flatten the surface. In addition, it is also possible to form a flat alignment film on the surface of the transparent coating, which is effective in suppressing the display unevenness of the liquid crystal due to the surface shape, preventing the occurrence of display domains, reducing the light emission during panel display, and improving the contrast. have.

Best Mode for Carrying Out the Invention

Hereinafter, the coating liquid for transparent film formation concerning this invention, such a film part base material, and a liquid crystal display cell are demonstrated concretely.

[Coating Liquid for Transparent Film Formation]

First, the coating liquid for transparent film formation which concerns on this invention is demonstrated.

The coating liquid for transparent film formation which concerns on this invention makes a matrix formation component disperse | distribute in the mixed solvent which consists of water and an organic solvent.

Matrix Forming Ingredient

The matrix forming component may be selected from 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) a mixture thereof. Include.

R ¹ -SiR ² _m R ³ _(3-m) (I)

[Wherein, R ¹ -is 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.

The hydrolyzable group herein 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 alkylaryloxy group having 1 to 9 carbon atoms, and preferably a methoxy group and an epoxy group are selected. do.

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

n is 3-30, Preferably it is 3-20, More preferably, it is an integer of 3-12. Thus, typical examples of R ^8- (CR ⁹ ₂ ) _n -include alkyl groups, halogenated alkyl groups, in particular perfluoroalkyl groups.

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

X is-(CH ₂ ) q-,-(Ph)-[where 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-.

Q, r, and y are each independently an integer of 1 to 30, preferably 1 to 20, and more preferably 2 to 12.

Among the divalent X rosseoneun especially _{- (CH 2) q-, -} (Ph) - is preferred.

Thus, 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) q- is mentioned.

R ² represents a hydrolyzable group. Examples of the hydrolyzable group include the same ones as described above, and are preferably selected from alkoxy groups having 1 to 6 carbon atoms. As an alkoxy group, a methoxy group and an ethoxy group are especially preferable.

R ³ represents an organic group having 1 to 30 carbon atoms, preferably 1 to 20, and more preferably 1 to 12 carbon atoms, which may contain a halogen atom. As such an organic group, a C1-C20 alkyl group, a C6-C20 aromatic hydrocarbon, a C7-C27 alkylaryl group, a C7-C27 arylalkyl group, a C2-C20 alkenyl group, and a C1-C20 halogenation An alkyl group is illustrated. Moreover, as a halogen atom of such a halogenated alkyl group, fluorine, chlorine, bromine, and iodine are illustrated. In the halogenated alkyl group, all hydrogen atoms may be substituted with halogen atoms, and some hydrogen atoms may be substituted with halogen atoms.

m represents the number of 1-3, Preferably it is three.

Moreover, the organosilicon compound of Formula (I) has 2-3 hydrolysable groups in 1 molecule. As the organosilicon compound represented by formula (I), one having at least one halogenated alkyl group in one molecule is preferable.

Examples of the organosilicon compound represented by formula (I) include 3,3,3, -trifluoropropyltrimethoxysilane, methyl-3,3,3, -trifluoropropyldimethoxysilane and heptadecatrifluoro Decylmethyldimethoxysilane, n-perfluorooctylethyltriethoxysilane, heptadecatrifluorodecyltrimethoxysilane, etc. are mentioned.]

R ⁴ _n R ⁵ _3-n Si- (X) -SiR ⁶ _p R ⁷ _(3-p) (II)

[Wherein, R ⁴ and R ⁴ independently represent a hydrolyzable group.

R <^5> and R <^7> represents the C1-C30 monovalent organic group which may independently contain the halogen atom.

Specific examples of the hydrolyzable group and the organic group are the same as those described in connection with the above formula (I).

X is also the same as described with reference to formula (I) above, and may be-(S) q-. Q is an integer of 1 to 30, preferably 1 to 20, and more preferably 2 to 12 in the same manner as described above.

n represents the number of 0-3, Preferably 2 or 3.

p represents the number of 0-3, Preferably 2 or 3.

Provided that the organosilicon compound of formula (II) has two or more, preferably 3 to 6, hydrolysable groups in one molecule]

Examples of the organosilicon compounds represented by formula (II) include bis (trifluoropropyldimethoxysilyl) hexane, bis (trimethoxysilyl) ethane, bis (trimethoxysilyl) propyl, bis (trimethoxysilyl) butane, ( Trimethoxysilyl) 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 (trin-butoxysilyl) hexane, bis (trii-butoxysilyl) hexane, bis (aryldimethoxysilyl) hexane, bis (vinyldimethoxysilyl) hexane, bis (acryldimethoxysilyl) hexane, bis (3-triethoxysilylpropyl) tetrasulfide, 1, 4-bis (trimethoxysilylethyl) benzene, etc. are mentioned.

The organosilicon compound having a specific structural formula or hydrolyzate thereof has a high hydrophobic property, and thus, a transparent coating having excellent water resistance and water repellency and excellent toughness and urination properties can be obtained. In addition, it is possible to form a film having excellent scratch resistance, acid resistance, alkali resistance, water resistance and insulation, and excellent adhesion to a film (orientation film) made of an electrode film or a hydrophobic resin such as polyimide resin.

In the present invention, the organosilicon compound represented by formula (II) or a hydrolyzate thereof is suitably used.

The organosilicon compound represented by formula (II) has-(X)-, X is hydrophobic, and it may be bent when the chain length of X is increased, so it is possible to improve the water repellency, urinability, and toughness of the film. . Moreover, in the organosilicon compound shown by Formula (II), since both terminal is a hydrolysable group, it is highly reactive.

In the present invention, the organosilicon compound can be used as it is (ie without being hydrolyzed), but can also be used as a hydrolyzate. By using a hydrolyzate, it is possible to obtain a coating liquid excellent in long-term stability without reacting during storage and to form a uniform coating.

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

As for the said hydrolyzate, the number average molecular weight of polystyrene conversion is 500-20,000, Especially preferably, the range of 700-10,000 is preferable. When it exists in such a range, both the film strength and the adhesiveness of a base material are high, and it becomes possible to form a stable and uniform film in a coating liquid.

If the number average molecular weight in terms of polystyrene in the hydrolyzate is small, there is no substantial change from the one without hydrolysis. If the number average molecular weight in terms of polystyrene of the hydrolyzate is too large, the stability of the coating liquid may be shortened, and a transparent film having a uniform film thickness may not be obtained.

The matrix forming component is at least one selected from organosilicon compounds represented by formula (I) or hydrolyzates thereof, organosilicon compounds represented by formula (II) or hydrolyzates thereof or mixtures thereof or at least one selected from the following components: It is more preferable to include.

a) organosilicon compounds (except those equivalent to the organosilicon compounds of formulas (I) and (II) above),

b) an acetylacetonate chelate compound,

c) metal alkoxides and

d) polysilazane.

Hereinafter, these components will be described in detail.

(a) organosilicon compounds

As the matrix forming component, in addition to the organosilicon compounds of (I) and (II), other organosilicon compounds (hereinafter, referred to as organosilicon compounds (a)) may be included. As such other organosilicon compounds, for example, organosilicon compounds represented by the following formula (III) can be used.

R _t Si (OR ') _4-t (III)

[Herein, R is selected from methyl group, ethyl group, vinyl group or epoxy group.

R 'is an alkyl group having 1 to 6 carbon atoms, t is an integer of 0 to 4]

Specific examples of such organosilicon compounds (a) include tetramethoxysilane, tetraethoxysilane, monomethyltrimethoxysilane, monoethyltriethoxysilane, monoethyltrimethoxysilane and monomethyltri. Ethoxysilane, vinyl triethoxysilane, epoxy triethoxysilane, etc. are used preferably.

These organosilicon compounds (a) may be used in the state or hydrolyzed. Such a hydrolyzate can be obtained by a conventional method which is conventionally performed, for example, by mixing an organosilicon compound (a) with an alcohol such as methanol or ethanol and adding water and an acid to hydrolyze it.

When the coating liquid for transparent film formation which concerns on this invention which the said organosilicon compound (a) was added is apply | coated on a base material, and the obtained film is dried and baked, the film excellent in abrasion resistance, acid resistance, alkali resistance, water resistance, and insulation will be formed.

(b) acetylacetonate chelate compounds

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 polymer thereof.

[Equation 1]

(Ⅳ)

(Ⅳ)

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

a 0 to 1 0 to 2 0 to 3 b 1 to 2 1 to 3 1 to 4 a + b 2 3 4 M Co, Cu, Mg, Mn, Pb, Ni, Zn, Sn, Ba, Be, VO Al, Cr, Fe, V, Co, In, Ta, Y, B Ti, Zr, Hf, Sb

Specific examples of such compounds include, for example, dibutoxybisacetylacetonate zirconium, tributoxy monoacetylacetonate zirconium, bisacetylacetonate lead, trisacetylacetonate iron, dibutoxybisacetylacetonate hafnium, and monoacetylaceto. Natritributoxy hafnium etc. are mentioned.

The coating liquid for transparent film formation to which such an acetylacetonate chelate compound was added can obtain the film excellent in alkali resistance, acid resistance, saline resistance, water resistance, and solvent resistance.

(c) metal alkoxides

Moreover, as a metal alkoxide (c)

M ₂ (OR) _n (Ⅴ)

Preferred are the compounds represented by (wherein M ₂ is a metal atom and R is an alkyl group or -C _m H _2m O ₂ (m = 3 to 10) and n is an integer equal to the valence of M ₂ ); It is possible to use 1 type, or 2 or more types of combinations chosen from the compound or its condensate. In the formula, M ₂ 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.

Specifically as such metal alkoxide, tetrabutoxy zirconium, diisopropoxy dioctyloxy titanium, diethoxy lead, etc. are used preferably.

When the coating liquid for forming a transparent film according to the present invention to which the metal alkoxide was added was applied, dried, and fired, a film excellent in scratch resistance, flame resistance, alkali resistance, water resistance, and insulation was formed by polymerization curing of the metal alkoxide.

(c) polysilazane

As polysilazane (d), polysilazane having a repeating unit represented by the following formula (VI) is used.

[Equation 2]

(Ⅵ)

(Ⅵ)

[Wherein R ₁ , R ₂ and R ₃ are each a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.]

When using the polysilazane shown by said Formula (VI) as a matrix formation component, polysilazane whose alkyl group is a methyl group, an ethyl group, or a propyl group is preferable. In this case, there is no alkyl group decomposed at the time of heating, and the shrinkage of the film at the time of heating is small, which results in less cracking at the time of shrinkage stress and a transparent film with almost no cracks is obtained.

In addition, the polysilazane having a repeating unit represented by the above formula (VI) may be linear or cyclic, or may contain a mixture of linear polysilazane and cyclic polysilazane.

Moreover, the number average molecular weight of polystyrene conversion of such polysilazane is 500-10,000, Preferably the unit of 1,000-4,000 is preferable. When the number average molecular weight is less than 500, the transparent coating obtained by volatilization of low molecular weight polysilazane at the time of heat curing tends to be porous, and when the number average molecular weight exceeds 10,000, the fluidity of the coating liquid tends to decrease.

Mixed solvent

The matrix forming component is dispersed in a mixed solvent of water and an organic solvent.

As the organic solvent, a known organic solvent selected from alcohols, ethyl, glycols, ketones and the like is used. You may use such an organic solvent individually or in mixture of 2 or more types.

The proportion 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 transparent film formation which concerns on this invention may also contain inorganic compound particle (ion adsorbent particle).

Examples of the 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 , SiO _{2 · SnO 2, Sb 2 O} 5 · SnO 2, SnO 2 · in 2 O 3 · Sb 2 O 5 , such as a complex metal oxide or a solid solution, a zeolite (crystalline alumina silicate) of the like can be given. In addition, a mixture of two or more thereof is also preferably used.

If these inorganic mixture particles are included, it is possible to adsorb movable ions belonging to any one of inorganic cations, inorganic anions, organic cations, organic anions and the like present in the liquid crystal, for example. For this reason, the liquid crystal display device obtained by reducing the concentration of movable ions in the liquid crystal is excellent in high voltage storage characteristics, has low power consumption, satisfies high power efficiency, does not cause display defects, and has excellent long-term reliability.

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

If the average particle size exceeds 10 µm, the ion adsorption capacity and ion adsorption rate may decrease, and the transparency of the transparent coating may decrease.

When the average particle size of the inorganic compound particles is in the above range, the surface of the transparent film formed on the uneven substrate, for example, the TFT array substrate or the color filter substrate, is flattened, so that the surface of the alignment film in contact with the liquid crystal layer is also flattened. Averaging is effective in suppressing the display stain of the liquid crystal due to the surface shape, preventing the occurrence of the display domain, reducing the light emission during panel display, and improving the contrast.

In addition, when only the purpose of reducing movable ions is aimed at, conventionally well-known ion exchange resin particles can be used. Specific examples of cation exchange resins include diamond ion SK series (manufactured by Samneung Chemical Co., Ltd.), carboxymethyl cellulose, SE cellulose, P cellulose, and sephaxex (manufactured by Bowmasia Co., Ltd.). Examples of the anion exchange resin include diamond ion SA series (manufactured by Samneung Chemical Co., Ltd.), DEAE cellulose, triethylammonium ethyl cellulose, ECTEOLA cellulose, and cephaxe (manufactured by Bowimasia Co., Ltd.). Moreover, cation exchange resins, such as diamond ion (made by Samneung Chemical Co., Ltd.), are mentioned.

The transparent coating containing such inorganic compound particles or ion exchange resin particles can remove ions in the liquid crystal when used in a liquid crystal display cell 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, it is not possible to adsorb ions sufficiently, resulting in poor display by mobile ions or lack of long-term reliability and difficulty in obtaining an ion adsorbent exceeding 6.0 mmol / g. .

In the present invention, the ion adsorption capacity is measured by the following method.

(1) Measurement of inorganic cation adsorption capacity

1.5 g of an inorganic ion adsorbent dried at 120 ° C. was added to 100 g of an aqueous NaCl solution having a concentration of 1% by weight, and stirred at room temperature (25 ° C.) for 15 hours, followed by filtration to collect a filtrate. Is analyzed by atomic absorption method to determine the Na ion adsorption amount (mmol / g) of the inorganic ion adsorbent from the concentration difference with the Na ion concentration of the original NaCl aqueous solution.

(2) Measurement of inorganic anion adsorption capacity

1.5 g of ion-adsorbable fine particles dried at 120 ° C. to 100 g of a 1% by weight aqueous NaCl solution were added and stirred at room temperature (25 ° C.) for 15 hours, followed by filtration to obtain a filtrate. Analysis by atomic absorption method finds Cl ion adsorption amount (mmol / g) of ion-adsorbing microparticles | fine-particles from the concentration difference with Cl ion concentration of the original NaCl aqueous solution.

(3) Measurement of organic cation adsorption capacity

To 100 g of aqueous tetramethylammonium hydrooxide solution at a concentration of 1% by weight, 1.5 g of ion-adsorbing fine particles dried at 120 ° C. were added, stirred at room temperature (25 ° C.) for 15 hours, filtered, and the filtrate was collected. The tetramethylammonium ion concentration is analyzed by ion chromatography, and the organic cation adsorption amount (mmol / g) of the ion-adsorbing fine particles is obtained from the concentration difference with the original aqueous solution.

(4) Measurement of organic anion adsorption capacity

1.5 g of ion-adsorbable fine particles dried at 120 ° C. and dried at 100 ° C. in a 1% by weight acetic acid aqueous solution were added, stirred at room temperature (25 ° C.) for 15 hours, filtered and the filtrate was collected. The organic anion adsorption amount (mmol / g) of the ion-adsorbing fine particles is determined from the concentration difference with the original aqueous solution by analysis by ion chromatography.

The inorganic compound particles as the ion-adsorbing fine particles can be mixed and used depending on the kind of ions in the liquid crystal and the kind of ions eluted in the liquid crystal. It is also preferable to use insulating or electroconductive inorganic compound fine particles or resin fine particles other than these inorganic compound particles as needed.

It is preferable to use such inorganic compound particles in a sol state dispersed in water or an organic solvent, but inorganic particles in a state other than sol can be dispersed in a monodisperse or near monodisperse state in the coating liquid for forming a transparent film. It is also preferable to use compound particles.

Coating liquid

As for the matrix formation component in the coating liquid for transparent film formation, 15 weight% or less is preferable as solid content concentration. If this value exceeds 15% by weight, the storage stability of the coating liquid tends to be lowered. If the solid concentration becomes extremely low, it is necessary to repeat the coating liquid operation several times to obtain the desired film thickness. Solid content concentration is practically 0.1 weight% or less.

The amount of the organosilicon compound (including the hydrolyzate) represented by the formula (I) or (II) was 18% by weight for all the solids (the total amount of the matrix component, the inorganic compound particles and the ion exchange particles, etc.) in the coating liquid for forming the transparent film. As mentioned above, 40% or more is suitable suitably. If it is such a range, it is possible to form the transparent film excellent in the effect of this invention, ie, water repellency, toughness, and urination.

The content of the organosilicon compound (a), the acetylacetonate chelate compound (b), the metal alkoxide (c) and the polysilazane (d) is 75% by weight or less, more preferably 1 to 40% by weight in all solids. Range. The amount of the inorganic compound particles is in the range of 70% by weight or less, more preferably 4.5 to 50% by weight in all solids.

When the amount of the organosilicon compound (a), the acetylacetonate chelate compound (b), the metal alkoxide (c) and the polysilazane (d) and the amount of the inorganic compound particles increase, the above formula (I) or (II) The amount of organosilicon compounds shown in the figure becomes less, and the effect of using such organosilicon compounds, that is, the toughness, urinary resistance, scratch resistance, water repellency, etc. of the obtained transparent film is insufficient.

[Film part mention]

Next, the coating part base material concerning this invention is demonstrated concretely.

The coating part base material which concerns on this invention is characterized by the formation of the transparent film which apply | coats the said coating film for transparent film formation on the surface of a base material.

The transparent coating part base material which concerns on this invention apply | coats the above-mentioned coating film for transparent film formation to the surface of base materials, such as glass and plastics, by the dipping method, the spinner method, the spray method, the roller coat method, the freckled printing method, and the like. Next, the film formed on the surface of the base material is dried at room temperature to 80 ° C, and further formed by a method such as heating and curing at 120 ° C or higher and in some cases, 30 ° C or lower as necessary.

In addition, the film formed on this base material may be subjected to a curing promoting treatment in the following manner.

Specifically as a curing accelerator treatment, the uncured film is irradiated with an electromagnetic wave having a wavelength shorter than visible light after the coating liquid process or the drying process or during the drying process, or the uncured film is irradiated in a gas atmosphere that promotes the curing reaction. The processing to mention is mentioned.

As an electromagnetic wave irradiated to the film of the uncured step before heating like this, specifically, an ultraviolet-ray, an electromagnetic wave, X wave, (gamma) ray, etc. are illustrated, and an ultraviolet-ray is especially preferable.

During the ultraviolet irradiation treatment, for example, a high-pressure mercury lamp having a luminous intensity of about 250 nm and 360 nm and having a light intensity of 10 mW / cm 2 or more is used as an ultraviolet light source, and an amount of energy of 100 mJ / cm 2 or more, preferably 1000 mJ / cm 2 or more. It is preferable to irradiate ultraviolet rays.

Moreover, as gas which accelerates | stimulates hardening reaction, ammonia, ozone, etc. are illustrated, for example. In the case of performing such a gas treatment, it is preferable to expose the uncured film in the active gas atmosphere having a gas concentration of 100 to 100,000 ppm, preferably 1000 to 10,000 ppm for 1 to 60 minutes.

Moreover, even if this gas process is performed after heat hardening, the same effect can be acquired.

As described above, the curing promotion treatment promotes condensation polymerization and complexation of the matrix component contained in the transparent coating, and at the same time, evaporation of the water and the solvent remaining in the coating is also promoted. For this reason, if necessary for the following heating step, heat curing conditions such as heating temperature and heating time are alleviated, and the production of the transparent coating part base material according to the present invention can be efficiently carried out.

Although the transparent coating part base material which concerns on this invention can be obtained by the above process, the film formed on this base material is toughness and urination property, and it is excellent in adhesiveness and transparency, and also durability of scratch resistance, water resistance, alkali resistance, etc. It is excellent in the case of containing the ion-adsorbable inorganic compound particles, it is possible to effectively reduce the movable ions in the liquid crystal panel, high insulation resistance and very suitable as an insulating film.

[LCD display cell]

Next, the liquid crystal display cell which concerns on this invention is concretely demonstrated.

All the liquid crystal display cells which concern on this invention use the transparent electrode part board | substrate which has a transparent film formed using the said coating film for transparent film formation.

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 stacked on the surface of at least one of the substrates, and a single transparent electrode part substrate is disposed so as to face each transparent electrode. It is a liquid crystal display cell which is arrange | positioned at intervals and the liquid crystal is enclosed in the clearance gap located between this one transparent electrode part board | substrate.

A substrate, a transparent electrode film, an alignment film, a liquid crystal, etc. can use a well-known thing, without restrict | limiting especially a transparent film except using the said coating liquid.

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

The liquid crystal display cell 1 includes a plurality of spacers such that one transparent electrode part substrate 2 in which the transparent electrode film 12, the transparent film 13, and the alignment film 14 are sequentially stacked on the surface of the substrate 11 face each other. Liquid crystal 6 is enclosed and formed by the particle | grains 5 in the space | interval between the transparent electrode films 12 and 12 which were arrange | positioned with predetermined space | interval d, and this space | interval opened.

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. Moreover, resin films, such as polyethylene terephthalate, polyethyl, and polycarbonate, can also be used as a board | substrate, In particular, it is also possible to bend and use a film in arbitrary forms, if it is a urinary resin.

The transparent film 13 is a film formed by applying the coating film for forming a transparent film on the transparent electrode film 12. The film is excellent in toughness, urinability, water repellency, etc., and has excellent transparency and scratch resistance, high insulation resistance, and a transparent film 13 and an alignment film. Adhesion with 14 is favorable.

Also it may be used for the first liquid crystal display cell in the substrate 11 and the transparent electrode film in the gap 12 between the alkali passivation transparent electrode substrate portion form a film, such as SiO ₂ film relating to the present invention can take various forms.

In the second liquid crystal display cell according to the present invention, one transparent electrode unit substrate, in which a color filter, a transparent film, a transparent electrode film, and an alignment film are sequentially stacked on at least one surface of the substrate, is defined such that each transparent electrode unit faces each other. It is a liquid crystal display cell arrange | positioned with the space | interval of this liquid crystal, and the liquid crystal is enclosed in the clearance gap located between this one transparent electrode part board | substrate.

2 is a diagram schematically showing an embodiment of a second liquid crystal display cell according to the present invention.

The color liquid crystal display device 1 ', the characteristic part of which is shown in FIG. 2, includes an electrode plate 21 and a glass substrate in which an alkali passivation film 21b, a plurality of pixel electrodes 21c, a transparent film 21d, and an alignment film 21e are sequentially stacked on a glass substrate 21a. A liquid crystal display cell 2 'having an electrode plate 22 facing each other in which an alkali passivation film 22b, a color filter 22c, a transparent film 22d, a transparent electrode 22e and an alignment film 22f are sequentially stacked on 22a, and one on both sides of the liquid crystal display cell. Equipped with polarizers 3 and 4. 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 the respective glass substrates 21a and 22a face each other and the plurality of pixel electrodes 21 and the plurality of color filters R, G, and B face each other. The liquid crystal 23 is sealed in the gap between the electrode 21 and the counter electrode plate 22.

Although not shown in the figure, a circuit is formed in the gap between each of the plurality of pixel electrodes 21c and the transparent electrode 22e, and the circuit is connected to the color liquid crystal display 1 'main body. In addition, the color filter 22c formed on the alkali passivation film 22b of the counter electrode plate 22 becomes a plurality of color elements of R (red filter), G (green filter), and B (blue filter), so that each color element is alternately adjacent to each other. The circuit formed in the gap 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 by the rule, and the color image corresponding to the display signal is displayed on the outside of the counter electrode plate 22. It can be observed through the polarizing plate 4 arrange | positioned at.

In the third liquid crystal display cell according to the present invention, a transparent electrode unit substrate in which a TFT array, a transparent film, a transparent electrode film, and an alignment film are sequentially stacked on at least one substrate surface is predetermined such that each transparent electrode unit faces each other. It is a liquid crystal display cell arrange | positioned with the space | interval of this liquid crystal, and the liquid crystal is enclosed in the clearance gap located between this one transparent electrode part board | substrate.

As an alkali passivation film, a pixel electrode, an oriented film, a glass substrate, a color filter, a transparent electrode, a polarizing plate, and a liquid crystal, a well-known thing can be used without a restriction | limiting in particular.

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

The liquid crystal display cell 1 "includes a transparent insulating substrate 31 in which a TFT array 32 is formed on the surface, and a transparent film 33, a pixel electrode 34, and an alignment layer 35 are sequentially stacked on the surface of the TFT array 32, and a black matrix 42 on the surface. It is comprised so that the alignment films 35 and 46 may be replaced by sandwiching the counter substrate 41 and the liquid crystal layer 51 which the color filter 43, the transparent film 44, the counter electrode 45, and the alignment film 46 were sequentially laminated.

In addition, space particles may be interposed between the alignment films 35 and 46 as shown in FIG. 1.

The TFT array 32 is composed of TFT (thin film transistor) elements, data electrodes, storage 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.

The liquid crystal display cell according to the present invention as described above comprises a matrix forming component in which the transparent film is formed of a specific organosilicon compound, and is excellent in water resistance, water repellency, toughness, urination, and the like.

In addition, when the transparent film contains the particles of the ion-adsorbable inorganic compound, the movable 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 storage characteristics, no display defects, excellent reliability for a long time, and low power consumption and satisfactory power efficiency.

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these examples.

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

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

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

* Explanation of Reference Numbers

1, 1 ', 1 ": liquid crystal display cell 2, 2': liquid crystal display cell

3,4: polarizing plate 5: space 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: a plurality of pixel substrates

21d: transparent film 21e: alignment film

22: counter electrode plate 22a: glass substrate

22b: alkali passivation film 22c: color filter

22d: transparent film 22e: transparent electrode

22f: alignment layer 23: liquid crystal

31 transparent insulating substrate 32 TFT array

33: transparent film 34: pixel electrode

35: alignment film 36: insulating film

41: opposing substrate 42: black matrix (shielding film)

43: color filter 44: transparent film

45: counter electrode 46: alignment film

51: liquid crystal layer

(Example 1)

Preparation of the coating liquid (A) for transparent film formation

As a matrix forming component, 25.6 g of bis (trimethoxysilane) hexane (manufactured by Toray Dow Corning Silicon Co., Ltd.) was added to a mixed solvent of 47.0 g of pure water and 526.4 g of ethyl alcohol. 1.0 g was added, it was hold | maintained at 60 degreeC for 24 hours, stirring, and it was set as the partial hydrolyzate solution (A-1) of bis (trimethoxysilane) hexane. After cooling at room temperature, 18 g of a cation exchange resin (dia ion) was added to the partial hydrolyzate solution (A-1), and stirred at room temperature for 16 hours to remove ions, and the ion exchange resin was filtered out. Furthermore, 85 g of hexylene glycol was added to this solution, and the hydrolyzate solution (A-2) of 16 weight% of solid content concentration which used hexylene glycol as the main solvent component by distillation under reduced pressure was obtained.

In 94.2 g of this hydrolyzate solution (A-2), Sb ₂ O ₅ · 2.7H ₂ O particles having an average particle size of 20 nm and a Na ion adsorption capacity of 2.4 mmol / g were uniformly dispersed in hexylene glycol as solid ions. 42.2 g of an ion-adsorbing particulate sol having a concentration of 10% by weight was added thereto, and stirred for 1 hour, followed by 7.3 g of tetraethoxysilane (28.8% by weight of SiO ₂ ), 206.1 g of hexylene glycol, and 2.0 g of water were added thereto at 40 ° C. Stirring was performed for 24 hours to prepare a coating liquid (A) for forming a transparent film having a solid content concentration of 6% by weight.

Formation of Transparent Film (A)

The coating film obtained by applying a transparent film-forming coating liquid (A) on a freckled print on a glass substrate with a patterned ITO display electrode (manufactured by Ukcho Co., Ltd .: 30 Ω / □ or less) was dried at 90 ° C. for 5 minutes. After irradiating with ultraviolet light under a condition of accumulated light amount of 6,000 mJ / cm 2 (measured by a sensor for 365 nm) in a high-pressure mercury lamp, it was then baked at 200 ° C. for 30 minutes to form a transparent film (A). It was 80 nm that the film thickness of the obtained transparent film (A) was measured with the stylus type surface analyzer.

In addition, the following vertical load test and scratch strength measurement were performed and the results are shown in Tables 2 and 3.

Vertical load test

A needle having a tip of curvature radius of 1 mm flowing a DC voltage of 12 V between the ITO electrode surface and the upper surface of the transparent film was pressed against the transparent film surface, and the load value at the time when the voltage reached 3 V was regarded as an electrical short. Load tolerance was evaluated. Load tolerance was measured about 10 places on a transparent film. The average values are shown in Tables 2 and 3.

Scratch strength measurement

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

Preparation of liquid crystal display cell A

Next, the polyimide film-forming coating material (manufactured by Ilsan Chemical Co., Ltd .: San Ever) on the transparent film (A) was applied by freckling printing, dried at 100 ° C. for 5 minutes, and heated at 200 ° C. for 30 minutes. The mid film (alignment film) was formed, and the rubbing process was then performed.

Thus, one transparent electrode part base material in which a transparent electrode, a transparent film (A), and a rubbing treatment alignment film were sequentially stacked on a glass substrate was obtained. One substrate (particle size corresponding to the distance between two substrates) is scattered on one of the substrates with one transparent electrode obtained, and the other substrate is printed with a sealing material and these substrates are printed. The liquid crystal display cell (A) was created by sealing a STN liquid crystal so that transparent electrodes may mutually face each other, and then closing the sealing opening with the finishing material.

Measurement of the amount of movable ions

The amount of movable ions in the obtained liquid crystal display cell (A) was measured on condition of an applied voltage of 10 V and a triangular wave frequency of 0.1 Hz using an ion density measuring instrument (manufactured by Dongyang Technica Co., Ltd .: MTR-1). The peak by movable ion was detected in the vicinity of 0.8V of applied voltage, and the movable ion amount was 0.8nC / cm <2>.

Observation of Display Unevenness in Liquid Crystal Display Cells

In addition, 30 liquid crystal display cells were created by the above method, and a point display test was performed to visually observe the presence or absence of display unevenness. At this time, the number of panels in which the display stain occurred was counted. The average values are shown in Tables 2 and 3.

Long-term Reliability Assessment

Under the high temperature environment (relative humidity 20%, temperature 80 ° C) with respect to 10 sheets using the liquid crystal display cell A in which the display unevenness did not generate | occur | produced in the said method, the environment of high temperature, high humidity (95% relative humidity, Temperature treatment at 80 ° C.) for 500 hours, and then subjected to a viscosity display test of the liquid crystal display cell to visually observe the presence or absence of display unevenness. At this time, the number of panels in which the display stain did not occur was counted. The average values are shown in Tables 2 and 3.

(Example 2)

Preparation of the coating liquid (B) for transparent film formation

94.2 g of the hydrolyzate solution (A-2) prepared in the same manner as in Example 1 as a matrix-forming component was used as SiO ₂ · Al ₂ O ₃ fine particles having an average particle size of 25 nm and a Na ion adsorption capacity of 0.5 mmol / g. Disperse homogeneously in hexylene glycol, add 42.2 g of solid content concentration 10 wt% ionic adsorbent fine particle sol, and stir for 1 hour, followed by 7.5 g of tetraisopropoxytitanium (28 wt% as TiO ₂ ), 205.9 g of hexylene glycol, and water 2.0 g was added and stirring was carried out at 40 ° C. for 24 hours to prepare a coating liquid (B) for forming a solid content concentration of 6% by weight transparent film.

Formation of Transparent Film (B)

The transparent film B was formed like Example 1 except having used the coating liquid for transparent film formation. It was 70 nm that the film thickness of the obtained transparent film (B) was measured with the stylus type surface analyzer. Moreover, the vertical load test and the scratch strength measurement were performed. The results are shown in Tables 2 and 3.

Preparation of liquid crystal display cell (B)

Subsequently, the liquid crystal display cell B was created by the method similar to Example 1 except having formed a polyimide film on the transparent film B, and the like. About the obtained liquid crystal display cell (B), the measurement of the amount of movable ions, observation of display unevenness, and evaluation of long-term reliability were performed. The results are shown in Tables 2 and 3.

(Example 3)

Preparation of the coating liquid (C) for transparent film formation

94.5 g of the hydrolyzate solution (A-2) prepared in the same manner as in Example 1 as the matrix-forming component was uniformly dispersed in hexylene glycol with MgO particles having an average particle size of 45 nm and a Cl ion adsorption capacity of 0.3 mmol / g. 42.2 g of ion-adsorbing particulate sol having a concentration of 10% by weight of solids was dispersed, and stirred for 1 hour, followed by 15.1 g of dibutoxy-bisacetylacetonatzirconium (14% by weight as ZrO ₂ ), 198.3 g of hexylene glycol, and 2.0 g of water. Then, stirring was performed at 40 ° C. for 24 hours to prepare a coating liquid (C) for forming a transparent film having a solid content concentration of 6% by weight.

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 that the film thickness of the obtained transparent film (C) was measured with the stylus type surface analyzer. The vertical load test and the scratch strength measurement were performed. The results are shown in Tables 2 and 3.

Preparation of liquid crystal display cell (C)

Subsequently, the liquid crystal display cell C was created by the method similar to Example 1 except having formed a polyimide film on the transparent film C, and the like. About the obtained liquid crystal display cell (C), the measurement of the amount of movable ions, observation of display unevenness, and evaluation of long-term reliability were performed. The results are shown in Tables 2 and 3.

(Example 4)

Preparation of the coating liquid (D) for transparent film formation

To 53.8 g of the hydrolyzate solution (A-2) prepared in the same manner as in Example 1 as the matrix-forming component, 32.1 g of tetramethoxysilane (39.5 wt% as SiO ₂ ), 264.3 g of hexylene glycol, and 2.0 g of water were added thereto. It stirred at 24 degreeC for 24 hours, and prepared the coating liquid (D) for transparent film formation of 6 weight% of solid content concentration.

Formation of Transparent Film (D)

The transparent film D was formed like Example 1 except having used the coating liquid D for transparent film formation. It was 80 nm that the film thickness of the obtained transparent film (D) was measured with the stylus type surface analyzer. Moreover, the vertical load test and the scratch strength measurement were performed. The results are shown in Tables 2 and 3.

Preparation of liquid crystal display cell (D)

Subsequently, the liquid crystal display cell D was created by the method similar to Example 1 except forming a polyimide film on the transparent film D, and the like. About the obtained liquid crystal display cell (D), the measurement of the amount of movable ions, observation of the display unevenness, and evaluation of long-term reliability were performed. The results are shown in Tables 2 and 3.

(Example 5)

Preparation of the coating liquid (E) for transparent film formation

Average for ion adsorption particles in the same manner as in Example 1 a hydrolyzate solution (A-2) 121.1g prepared by a matrix-forming component particle size 20nm, Na ion adsorption capacity of 2.4mmol / g of Sb ₂ O ₅ · 2.7H ₂ O 5.3 g of an ion-adsorbing particulate sol having a solid concentration of 20% by weight in which the fine particles were uniformly dispersed in propylene glycol was added and stirred for 1 hour, followed by a butanol solution of tributoxy-monoacetylacetonate zirconium (10% by weight as ZrO ₂ ). 10.6 g and 0.5 g of water were added thereto, followed by stirring at 40 ° C. for 24 hours to prepare a coating solution (E) for forming a transparent film having a solid content concentration of 15.6 wt%.

Formation of Transparent Film (E)

The coating liquid (E) for forming a transparent film was coated on the glass substrate on which the color filter was formed by the spin coating method under conditions of 1500 rpm and 10 seconds, followed by drying at 50 ° C. for 120 minutes and then heating at 120 ° C. for 60 minutes. The overcoat of the color filter surface was performed by forming a transparent film (E). It was 2 micrometers which measured the film thickness of the obtained transparent film (E) with the stylus type surface analyzer. Moreover, the vertical load test and the scratch strength measurement were performed. The results are shown in Tables 2 and 3.

Furthermore, the ITO electrode film was formed on the transparent film E by the sputtering method.

Preparation of liquid crystal display cell E

The 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. Thus, one transparent electrode part base material in which the color filter on the glass substrate, the transparent film (E), the transparent electrode, and the rubbing process oriented film were laminated | stacked sequentially was obtained.

Subsequently, the common electrode substrate facing each other was attached to the sealing material through a spacer to face each other, STN liquid crystal was injected into the gap between the substrates, and the injection hole was finished with a finishing material to prepare a liquid crystal display cell (E). About the obtained liquid crystal display cell (E), the measurement of the amount of movable ions, observation of the display unevenness, and evaluation of long-term reliability were performed. The results are shown in Tables 2 and 3.

(Example 6)

17 g of CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ (manufactured by Shinwol Chemical Co., Ltd., KBM7803) was added to a mixed solvent of 47.0 g of pure water and 526.4 g of ethyl alcohol. 1.0 g of acetic 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 partial hydrolysis solution (F-1) of heptadecatrifluorotrimethoxysilane.

After cooling at room temperature, 18 g of cation exchange resin (tire ion) was added to the partial hydrolysis solution (F-1), and the mixture was stirred at room temperature for 16 hours, and the ion exchange resin was filtered 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 wt%, using hexylene glycol as the main solvent component.

In 94.2 g of this hydrolysis solution (F-2), the average particle size was 20 nm and the Na ion adsorption capacity was 2.4 mmol / g Sb ₂ O ₅ · 2.7H ₂ O fine particles as homogeneous dispersion in hexylene glycol. 21.1 g of 10% by weight of the ion-adsorbable particulate sol was added thereto, and stirred for 1 hour, followed by 14.6 g of tetraethoxysilane (28.8% by weight of SiO ₂ ), 221.6 g of hexylene glycol, and 4.0 g of water, for 24 hours at 40 ° C. Stirring was performed, and the coating liquid (F) for transparent film formation of 6 weight% of solid content concentration was prepared.

Formation of Transparent Film F

The transparent film F was formed like Example 1 except having used the coating liquid F for transparent film formation. It was 75 nm that the film thickness of the obtained transparent film (F) was measured with the stylus type surface type analyzer. Moreover, the vertical load test and the scratch strength measurement were performed. The results are shown in Tables 2 and 3.

Preparation of liquid crystal display cell F

Subsequently, the liquid crystal display cell F was created like Example 1 except having formed the polyimide film on the transparent film F, and the like. About the obtained liquid crystal display cell F, the measurement of the amount of movable ions, observation of the display unevenness, and evaluation of long-term reliability were performed. The results are shown in Tables 2 and 3.

(Comparative Example 1)

Preparation of the coating liquid (G) for transparent film formation

51.3 g of tetraethoxysilane (28.8% by weight as SiO ₂₎ as a matrix-forming component was added to a mixed solvent of 9.0 g of pure water and 432.2 g of ethyl alcohol, and 0.2 g of acetic acid having a concentration of 61% by weight was added thereto, followed by stirring. While maintaining at 60 ℃ for 24 hours to give a partial hydrolysis solution (G-1) of tetraethoxysilane.

After cooling at room temperature, 18 g of a cation exchange resin (die ions) was added to the partial hydrolysis solution (G-1), stirred at room temperature for 16 hours, and the ion exchange resin was filtered to remove ions. Furthermore, 85 g of hexylene glycol was added to this solution, and the tetraethoxysilane hydrolysis solution (G-2) of 16 weight% of solid content concentration which uses hexylene glycol as a main solvent component by distillation under reduced pressure was obtained.

In 94.2 g of this hydrolysis solution (G-2), Sb ₂ O ₅ · 2.7H ₂ O fine particles having an average particle size of 20 nm and a Na ion adsorption capacity of 2.4 mmol / g were uniformly dispersed in hexylene glycol as solid ions. 16.4 g of ion-adsorbable particulate sol, 10.1 g of hexylene glycol, and 2.0 g of water were added thereto at a concentration of 10% by weight, and stirred at 40 ° C for 24 hours to prepare a coating solution (G) for forming a transparent film having a solid content of 6% by weight. .

Formation of Transparent Film G

The transparent film G was formed like Example 1 except having used the coating liquid G for transparent film formation. It was 80 nm that the film thickness of the obtained transparent film G was measured with the stylus type surface analyzer. Moreover, the vertical load test and the scratch strength measurement were performed. The results are shown in Tables 2 and 3.

Preparation of liquid crystal display cell G

Subsequently, the liquid crystal display cell G was created like Example 1 except having formed the polyimide film on the transparent film G, and the like. About the obtained liquid crystal display cell (G), the measurement of the amount of movable ions, observation of display unevenness, and evaluation of long-term reliability were performed. The results are shown in Tables 2 and 3.

(Example 7)

Preparation of coating liquid (H) for transparent film formation

As the matrix forming component, 26.9 g of the hydrolyzate solution (F-2) prepared in the same manner as in Example 6 was used as SiO ₂ · Al ₂ O ₃ fine particles having an average particle size of 25 nm and a Na ion adsorption capacity of 0.5 mmol / g. Disperse uniformly in hexylene glycol, add 21.1 g of ion-adsorbable particulate sol having a solid content of 10% by weight, and stir for 1 hour, followed by 52.8 g of tetraisopropoxytitanium (28% by weight of TiO ₂ ), 251.0 g of hexylene glycol, and water 3.0 g was added and stirring was performed at 40 degreeC for 24 hours, and the coating liquid (H) for solid content concentration 6 weight% transparent film formation was prepared.

Formation of Transparent Film (H)

The transparent film H was formed like Example 1 except having used the coating liquid H for transparent film formation. It was 75 nm that the film thickness of the obtained transparent film (H) was measured with the stylus type surface analyzer. Moreover, the vertical load test and the scratch strength measurement were performed. The results are shown in Tables 2 and 3.

Preparation of liquid crystal display cell H

Subsequently, the liquid crystal display cell H was created by the method similar to Example 1 except having formed a polyimide film on the transparent film H, and the like. About the obtained liquid crystal display cell (H), the measurement of the amount of movable ions, observation of the display unevenness, and evaluation of long-term reliability were performed. The results are shown in Tables 2 and 3.

(Example 8)

Preparation of the coating liquid (I) for transparent film formation

155.0 g of hexylene glycol and 2.0 g of water were added to 94.2 g of the hydrolyzate solution (A-2) prepared in the same manner as in Example 1 as the matrix-forming component, and the mixture was stirred at 40 ° C. for 24 hours to give a solid having a solid content of 6% by weight. Coating liquid (I) for film formation was manufactured.

Formation of Transparent Film (I)

The transparent film I was formed like Example 1 except having used the coating liquid I for transparent film formation. It was 80 nm that the film thickness of the obtained transparent film (I) was measured with the stylus type surface analyzer. Moreover, the vertical load test and the scratch strength measurement were performed. The results are shown in Tables 2 and 3.

Preparation of liquid crystal display cell (I)

Subsequently, the liquid crystal display cell I was created by the method similar to Example 1 except having formed a polyimide film etc. on the transparent film I. About the obtained liquid crystal display cell (I), the measurement of the amount of movable ions, observation of display unevenness, and evaluation of long-term reliability were performed. The results are shown in Tables 2 and 3.

(Example 9)

Preparation of the coating liquid (J) for transparent film formation

47.1 g of the hydrolyzate solution (F-2) prepared in the same manner as in Example 6 was added to 47.1 g of the hydrolyzate solution (A-2) prepared in the same manner as in Example 1, followed by stirring for 1 hour. 155.0 g of silylene glycol and 2.0 g of water were added thereto, and the mixture was stirred at 40 ° C. for 24 hours to prepare a coating film (J) for forming a transparent film having a solid content of 6% by weight.

Formation of Transparent Film J

The transparent film J was formed similarly to Example 1 except having used the coating liquid J for transparent film formation. It was 80 nm that the film thickness of the obtained transparent film (J) was measured with the stylus type surface analyzer. Moreover, the vertical load test and the scratch strength measurement were performed. The results are shown in Tables 2 and 3.

Preparation of liquid crystal display cell J

Subsequently, the liquid crystal display cell J was created by the method similar to Example 1 except forming a polyimide film on the transparent film J, and the like. About the obtained liquid crystal display cell J, the measurement of the amount of movable ions, observation of the display unevenness, and evaluation of long-term reliability were performed. The results are shown in Tables 2 and 3.

Transparent film Liquid crystal display cell Long-term reliability Thickness Vertical load immunity Scratch strength Operation ion Stain Splat stain Relative Humidity 20% Temperature 80 ℃ Relative Humidity 95% Temperature 80 ℃ nm Kg mN nC / ㎠ 10 sheets 10 sheets 10 sheets Comparative Example 1 80 5 0.8 3.6 4 3 8 Example 1 80 18 or more 3.5 0.8 0 0 0 Example 2 70 18 or more 3 2.4 0 One One Example 3 90 14 2.5 1.6 0 One One Example 4 80 12 3.6 8.2 4 3 2 Example 5 2000 18 or more 3.3 2.2 3 One 0 Example 6 75 14 2.8 2.2 2 2 One Example 7 75 7 1.2 3.6 3 2 2 Example 8 80 18 or more 3.8 7.8 3 2 2 Example 9 80 18 or more 4.0 7.7 3 2 One

Claims (8)

A coating film for forming a transparent film in which a matrix forming component is dispersed in a mixed solution of 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) The coating liquid for transparent film formation containing at least 1 sort (s) chosen from the organosilicon compound represented by Formula (II), its hydrolyzate, or c) its mixture. R ¹ -SiR ² R ³ (Ⅰ) [Wherein R ¹ -is represented by 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. 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 3-30. X is-(CH ₂ ) q-,-(Ph)-[where 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 A _divalent group selected from-(CH ₂ ) q- (S)-(CH ₂ ) r-, wherein q, r and y are represented by integers of 1 to 30; R ² represents a hydrolyzable group. R <^3> represents the C1-C30 organic group which may contain the halogen atom. m represents the number of 1-3. However, Formula (I) has 2-3 hydrolyzable groups in 1 molecule.] R ⁴ _n R ⁵ _3-n Si- (X) -SiR ⁶ _p R ⁷ _(3-p) (II) [Wherein, R ⁴ and R ⁴ independently represent a hydrolyzable group. R <^5> and R <^7> represents the C1-C30 monovalent organic group which may independently contain the halogen atom. X is-(CH ₂ ) q-,-(Ph)-[where 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]-, A _{divalent group selected} from-(CH ₂ ) q- (S)-(CH ₂ ) r- and-(S) q, wherein q, r and y are represented by integers of 1 to 30; n represents the number of 0-3. p represents the number of 0-3. Provided that Formula (II) has two or more hydrolyzable groups in one molecule.] 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 hydrolyzable groups in one molecule. Coating liquid for forming a transparent film, characterized in that The organosilicon compound according to claim 1 or 2, wherein the matrix forming component is further represented by a) an organosilicon compound represented by the following formula (III): R _t Si (OR ') _4-t (III) [Wherein R is selected from methyl group, ethyl group, vinyl group or epoxy group. R 'is a C1-C6 alkyl group. t is a number from 0 to 4], b) an acetylacetate chelating compound, c) metal alkoxy, and d) polysilazane. The coating liquid for forming a transparent film according to any one of claims 1 to 3, wherein the matrix forming component further contains inorganic compound particles. The transparent coating part base material which forms a transparent film by apply | coating the coating liquid for transparent film formation in any one of Claims 1-4 to a base material surface. One transparent electrode unit substrate, in which a transparent electrode film, a transparent film, and an alignment film are sequentially stacked on at least one substrate surface, is disposed at a predetermined interval so that the transparent electrodes face each other. A liquid crystal display cell in which liquid crystal is enclosed at open intervals, wherein the transparent film is a film formed by applying the coating liquid for forming a transparent film according to any one of claims 1 to 4. One transparent electrode unit substrate, in which a color filter, a transparent film, a transparent electrode film, and an alignment film are sequentially stacked on at least one substrate surface, is disposed at predetermined intervals to face each transparent electrode, and the single transparent electrode unit substrate A liquid crystal display cell in which a liquid crystal is enclosed in an open interval between the liquid crystal display cells, wherein the transparent film is a film formed by applying the coating liquid for forming a transparent film according to any one of claims 1 to 4. One transparent electrode unit substrate in which a TFT array, a transparent film, a transparent electrode film, and an alignment film are sequentially stacked on at least one substrate surface is disposed at a predetermined interval so that the transparent electrodes face each other. A liquid crystal display cell in which a liquid crystal is enclosed in an open gap between the liquid crystal display cells, wherein the transparent film is a film formed by applying the coating liquid for forming a transparent film according to any one of claims 1 to 4.

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