JP2003011262A - Base plate for display unit - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a base plate for a display unit which has easy lightening and thinning, a strength against an impact, excellent flatness, adhesive properties to an ITO electrode, an easy manufacture, further excellent gas barrier properties at a high humidity, and a high performance in a wide range. SOLUTION: The base plate for the display unit comprises a plastic film having a mean light transmittance at a wavelength of 400 to 700 nm of 70% or more and a glass transition point of 100 deg.C or higher, and a gas barrier layer of a single or multi-component metal oxide glass by a sol-gel process. Or, the base plate for the display unit comprises a plastic film having a mean light transmittance at a wavelength of 400 to 700 nm of 70% or more and a glass transition point of 100 deg.C or higher, and a gas barrier layer containing an inorganic layer-like compound and a single or multi-component metal oxide glass.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a display device in various fields such as a personal computer, an AV device, a mobile phone, an information communication device, a game and a simulation device, and an in-vehicle navigation system, and more particularly, STN (Super Twisted). The present invention relates to a display device substrate used for a liquid crystal display device suitable for a nematic liquid crystal display device, a two-terminal element type liquid crystal display device, a three-terminal element type liquid crystal display device, and the like.

[0002]

2. Description of the Related Art Conventionally, information devices, communication devices, etc.
N-type liquid crystal display devices, MIN liquid crystal display devices, TFT liquid crystal display devices and the like are used. As a substrate for these liquid crystal display devices, a borosilicate glass plate having a thickness of 1 mm or less,
Soda lime glass plate, non-alkali glass plate, etc. are used, but the glass substrate has low impact resistance and there is a problem such as breaking when dropped, so there is a need to replace it with a plastic substrate with excellent impact resistance. high.

However, the plastic substrate has a lower gas barrier property against water vapor, oxygen, etc. than the glass substrate. Therefore, in order to maintain the performance of the liquid crystal preferably,
High gas barrier properties are required, and various techniques for imparting gas barrier properties to plastic substrates have been studied.

For example, Japanese Patent No. 3054235 discloses a gas barrier layer made of a resin such as polyvinyl chloride, polyester, polyacrylonitrile, vinyl alcohol and a copolymer thereof, and an inorganic compound such as silicon dioxide. A vapor deposition layer and the like are disclosed. Also, the patent No. 3
No. 059866 discloses a thickness of 0.0015 to 0.25.
A method of attaching mm thin glass to plastic is disclosed.

However, polyvinyl alcohol (P
In order to form a layer having a desired gas barrier property with an organic substance such as VA), it is necessary to form a thick layer.
Also, the humidity greatly affects the gas barrier properties. In this case, if an inorganic compound is used, the thickness of the layer can be reduced, but if stress is applied, there is a problem that the layer will crack or the cost will increase. Furthermore, when ultra-thin glass is used, there is a problem that the ultra-thin glass is easily broken, it is technically difficult to bond the ultra-thin glass with good yield, and high cost is caused.

On the other hand, the inorganic layered compound-containing film has a high barrier property against gas and low molecular weight compounds. Among such inorganic layered compound-containing films, a mica / gelatin film and a mica / PVA film using a water-soluble polymer as a binder are used. It is known that the membrane has a remarkable effect in suppressing the permeation of gas, low molecular weight compounds, etc. (Japanese Patent Laid-Open No. 10-90828).

However, such a hybrid film using a water-soluble polymer as a binder has high humidity (80% R
Under H) or more), there is a problem that the gas barrier effect is significantly reduced.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the various problems in the prior art and achieve the following objects. That is, the present invention is easy to reduce the weight and thickness,
An object is to provide a substrate for a display device that is resistant to impact, has excellent flatness and adhesion to an ITO electrode, is easy to manufacture, has an excellent gas barrier property under high humidity, and exhibits high performance in a wide band. To do.

[0009]

Means for solving the above-mentioned problems are as follows. The invention of claim 1 has an average light transmittance of 7 at a wavelength of 400 to 700 nm.
A display device substrate comprising a plastic film having a glass transition point of 0% or more and a glass transition point of 100 ° C. or more and a gas barrier layer of a single or multi-component metal oxide glass by a sol-gel method.

The invention of claim 2 has a wavelength of 400 to 700 n.
m has an average light transmittance of 70% or more and a glass transition point of 100 ° C. or more, and a gas barrier layer containing an inorganic layered compound and a single or multi-component metal oxide glass. It is a substrate for a display device.

A third aspect of the present invention is the display device substrate according to the first or second aspect, wherein the retardation (Re) value at a wavelength of 632.8 nm is 15 nm or less.

A fourth aspect of the present invention is the display device substrate according to any one of the first to third aspects, in which the inorganic layered compound is a swelling synthetic mica.

A fifth aspect of the present invention is the display device substrate according to any one of the first to fourth aspects, wherein the aspect ratio of the inorganic layered compound is 20 or more.

The invention according to claim 6 is the substrate for a display device according to any one of claims 1 to 5, wherein the aspect ratio of the inorganic layered compound is 100 or more.

The invention according to claim 7 is the display device according to any one of claims 1 to 6, wherein the inorganic layered compound is hydrophobized with a tertiary or quaternary salt compound having a hydrophobic group. The substrate.

According to the eighth aspect of the invention, the gas barrier layer has an oxygen permeability (temperature of 40 ° C., humidity of 90%) of 0.5 ml / m ^2.
The display device substrate according to any one of claims 1 to 7, which has a value of atm / day or less.

According to the invention of claim 9, on the gas barrier layer,
9. The display device substrate according to claim 1, comprising at least one of a hard coat layer and an adhesion layer.

The invention of claim 10 is the substrate for a display device according to claim 9, which has a transparent conductive layer on at least one of the hard coat layer and the adhesion layer.

An eleventh aspect of the present invention is the display device substrate according to the tenth aspect, which has a color filter between at least one of the hard coat layer and the adhesion layer and the transparent conductive layer.

The display device substrate of the present invention comprises the plastic film and the gas barrier layer. The first aspect of the gas barrier layer is formed from a single or multi-component metal oxide glass by the sol-gel method, and this metal oxide glass is excellent in gas barrier property, and a high performance display device substrate can be obtained. To be

The second aspect of the gas barrier layer includes a single or multi-component metal oxide glass excellent in gas barrier property and an inorganic layered compound. The inorganic layered compound is cleaved into a large number of thin pieces, and the thin pieces are layered and dispersed in a state of being offset from each other in a direction substantially orthogonal to the thickness direction of the gas barrier layer. Therefore, in order for the gas to permeate the gas barrier layer, the gas enters the layer from one surface of the gas barrier layer, and once travels through the layer along the layer wall of the piece of the inorganic layered compound dispersed in a layered manner. It is necessary to repeat the process of advancing through the layer in the thickness direction at the end of the layer wall and reach the other surface of the gas barrier layer for permeation. Therefore, in order for the gas to pass through the gas barrier layer, it is necessary to travel a considerably long distance in the gas barrier layer as compared with the distance in the thickness direction of the gas barrier layer. As a result, the gas is
The substrate for a display device according to the present invention is excellent in gas barrier properties and hardly exhibits gas barrier properties, and particularly has a large gas barrier effect under high humidity (80% RH or more).

In the gas barrier layer, the metal oxide glass and the inorganic layered compound prepared by the sol-gel method are
It can be formed by a general coating method. Therefore, the manufacturing is easy, the productivity is high, and the manufacturing cost is low.

As a result, by including the metal oxide glass and the inorganic layered compound having excellent gas barrier properties in the gas barrier layer, it is easy to reduce the weight and thickness, and is resistant to the impact such as cracks, flatness, and the ITO electrode. It is possible to provide a substrate for a display device, which has high adhesiveness, is easy to manufacture, has an excellent gas barrier property, and exhibits high performance in a wide band.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The substrate for a display device of the present invention will be described in detail below. The display device substrate of the present invention includes a plastic film and a gas barrier layer, and optionally other members.

[Plastic Film] The plastic film is not particularly limited as long as it has an average light transmittance of 70% or more at a wavelength of 400 to 700 nm and a glass transition point of 100 ° C. or more. For example, polyether sulfone (PES) , Polycarbonate (PC), Polyarylate (PAr), Polyethylene terephthalate (PE
Examples of the film include known materials such as T), norbornene-based polymers, polyesters, and epoxy-butadiene copolymers. These may be used alone or in combination of two or more. Further, two or more kinds of these may be used to form a film having a laminated structure, or may be used as a copolymer composed of these monomers. Among these, polyethylene terephthalate (PET), norbornene-based polymer and the like are preferable in terms of transparency and low expression of birefringence.

The thickness of the plastic film is preferably 80 to 500 μm, and 100 to
More preferably, it is 300 μm. The thickness is 5
If it exceeds 00 μm, it may not be sufficient in terms of thinning and weight reduction.

[Gas Barrier Layer of First Embodiment] The gas barrier layer is formed of a single or multi-component metal oxide glass by the sol-gel method in the first embodiment.

The metal oxide glass film has a pH of 4.5 to 4.5 in which a hydrolyzable organometallic compound is used as a catalyst in the reaction liquid consisting of water and an organic solvent in the presence of boron ions in the presence of boron ions. After being hydrolyzed and dehydrated and condensed while adjusting to 5.0, the reaction purified product is applied to the surface of a substrate such as a plastic film and vitrified at a temperature of 200 ° C. or lower.

The organometallic compound is hydrolyzable
It is not particularly limited as long as it is
Expression: MR^Two _m(OR¹)_nmIs represented by
It is In the formula, M is a metal with an oxidation number of n, R¹And R^TwoA
A rualkyl group, m represents an integer of 0 to (n-1). R¹as well as
R^TwoMay be the same or different groups. Especially preferred
Shii is R¹And R^TwoIs an alkyl of 4 or less carbon atoms
Group, ie methyl group CH _Three(Hereinafter referred to as Me), ethyl
Group C_TwoH₅(Hereinafter referred to as Et), propyl group C_ThreeH₇
(Hereinafter referred to as Pr), isopyropyr group i-C_ThreeH
₇(Hereinafter, represented by i-Pr), butyl group C_FourH₉(Below
Below, represented by Bu) Isobutyl group i-C_FourH₉(Hereafter, i
A lower alkyl group such as -Bu) is preferably used.
It

Examples of the metal alkoxide include:
Lithium ethoxide LiOEt, niobium ethoxide Nb
(OEt)₅, Magnesium isopropoxide Mg (O
Pr-i)_Two, Aluminum isopropoxide Al (O
Pr-i)_Three, Zinc propoxide Zn (OPr)_Two, Te
Traethoxysilane Si (OEt)_Four, Titanium isopro
Poxide Ti (OPr-i)_Four, Barium ethoxide B
a (OEt)_Two, Barium isopropoxide Ba (OP
r-i)_Two, Triethoxyborane B (OEt) _Three, Jill
Conium propoxide Zr (OPr)_Four, Lantern pro
Poxide La (OPr)_Three, Yttrium propoxide
Y (OPr)_Three, Lead isopropoxide Pb (OPr-
i)_TwoEtc. What are these metal alkoxides
These are also commercially available products and can be easily obtained. Well
In addition, metal alkoxides are obtained by partial hydrolysis.
Low condensates are also commercially available and can be used as raw materials.
It is also possible.

The hydrolyzable organometallic compound may be used in the reaction as it is, but it is preferable to use it after diluting it with a solvent in order to facilitate the control of the reaction. Any solvent can be used as the diluent as long as it can dissolve the organometallic compound and can be uniformly mixed with water. Generally, lower aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, ethylene glycol, propylene glycol and mixtures thereof are preferably used. It is also possible to use a mixed solvent such as butanol + cellosolve + butyl cellosolve, or xylol + cellosolve acetate + methyl isobutyl ketone + cyclohexane.

Among the organometallic compounds, the metals are Ca and M.
When it is g, Al, etc., it reacts with water in the reaction solution to form a hydroxide, or when carbonate ion CO ₃ ²⁻ is present, a carbonate is formed to cause precipitation, so that it is used as a masking agent. It is desirable to add an alcohol solution of triethanolamine. The concentration of the organometallic compound when mixed and dissolved in a solvent is usually 70% by mass or less, and preferably diluted to a range of 5 to 70% by mass before use.

The reaction liquid generally comprises water and an organic solvent. The organic solvent used in the reaction solution may be any solvent that can form a homogeneous solution with water, an acid and an alkali, and aliphatic lower alcohols that are usually used for diluting the organometallic compound are preferable. Among the lower alcohols, propanol, isopropanol, butanol and isobutanol, which have more carbon atoms than methanol and ethanol, are preferable. This is because the growth of the produced metal oxide glass film is stable. The ratio of water to the organic solvent constituting the reaction liquid may be in the range of 0.2 to 50 mol / liter as the concentration of water.

The presence of boron ions in the reaction solution
In the presence of organometallic compounds using halogen ions as catalysts
It is characterized by being hydrolyzed. Boron ion B³⁺To
As the compound to give, trialkoxyborane [B (O
R)_Three] Is used. Among them, triethoxyborane
[B (OEt)_Three] Is preferred. B in the reaction solution³⁺I
The on concentration is in the range of 1.0 to 10.0 mol / liter.
Preferably. Or halogen ion is F⁻And Cl
⁻Alternatively, a mixture of these is used. Compound used
In the above reaction solution,⁻Ion and Cl⁻ion
As long as it causes⁻For the ion source,
Ammonium hydrogen fluoride (NH_FourF ・ HF), Nato fluoride
Li (NaF), etc., Cl⁻Ammonium chloride is used as the ion source
Umm (NH _FourCl) and the like are preferable.

The concentration of the halogen ions in the reaction solution varies depending on the film thickness of the metal oxide glass to be produced and other conditions, so that it is difficult to limit the range.
Generally, it is 0 .. to the total mass of the reaction liquid containing the catalyst.
001 to 2 mol / kg, especially 0.002 to 0.3 mol / kg
The range of kg is preferred. When the concentration of the halogen ions is lower than 0.001 mol / kg, hydrolysis of the organometallic compound is difficult to proceed sufficiently, and it may be difficult to form a film. On the other hand, the concentration of halogen ions is 2 mol / k
If it exceeds g, the metal oxide glass to be produced tends to be non-uniform, which is not preferable.

Regarding the boron used in the reaction, when it is contained as a B ₂ O ₃ component in the design composition of the metal oxide to be obtained, the calculated amount of the organic boron compound according to the content is added as it is. The product may be used, and when it is desired to remove boron, after film formation, boron can be evaporated and removed as boron methyl ester by heating in the presence of methanol as a solvent or by immersing in methanol and heating. it can.

The hydrolysis reaction of an organometallic compound is usually carried out by dissolving a predetermined amount of an organometallic compound in a mixed solvent of a prescribed amount of water and an organic solvent and dissolving it, and a prescribed amount of a halogen ion containing a prescribed amount of halogen ion. The reaction solution and the reaction solution are mixed at a predetermined ratio and sufficiently stirred to form a uniform reaction solution, and then the pH of the reaction solution is adjusted to a desired value with an acid or an alkali and aged for several hours. A predetermined amount of the boron compound is mixed and dissolved in the main agent solution or the reaction solution in advance. When using alkoxy borane,
It is advantageous to dissolve in the base solution with other organometallic compounds.

The pH of the reaction solution must be selected according to the purpose. That is, when a metal oxide glass film is intended, for example, an acid such as hydrochloric acid is used to adjust the pH to 4.5.
Adjust to a range of ~ 5 and ripen. In this case, it is convenient to use, for example, methyl red + bromocresol green as an indicator. The film is formed by coating the reaction solution after aging as it is or by adding an appropriate thickener if necessary onto the surface of the base material such as the plastic film.
It is heated to a temperature of 00 ° C. or lower, dried, and vitrified.
In heating, the temperature is gradually raised particularly in the temperature range of 50 to 70 ° C., and the temperature is further raised after the preliminary drying (solvent volatilization) step. This drying is particularly important for forming a non-porous film.

As the method for forming the metal oxide glass film, the main ingredient solution and the reaction solution (containing B ³⁺ and halogen ions) of the same component and the same concentration are sequentially adjusted to the same pH while adjusting the film to a predetermined pH. It can also be simply and continuously produced by additionally adding in proportion. In addition, the concentration of the above-mentioned reaction solution is within a range of ± 50% by mass, the concentration of water (including acid or alkali) is within a range of ± 30% by mass, and the concentration of halogen ions is within a range of ± 30% by mass. Can be changed.

The metal oxide glass film thus obtained constitutes the gas barrier layer according to the first aspect of the present invention. The characteristics of the gas barrier layer will be described later.

[Gas Barrier Layer of Second Embodiment] The gas barrier layer of the second embodiment contains an inorganic layered compound and a single or multi-component metal oxide glass. In this case, as the single or multi-component metal oxide glass, the same as the single or multi-component metal oxide glass by the sol-gel method according to the first aspect can be used.

-Inorganic Layered Compound- The inorganic layered compound has a laminated structure including a unit crystal lattice layer having a thickness of about 10 to 15 angstroms (Å),
Intralattice metal atom substitution is significantly greater than other clay minerals.
For this reason, the lattice layer is deficient in positive charges, and cations are adsorbed and interposed between the layers to compensate for it. The cations (exchangeable cations) interposed between these layers are exchanged with various cations. In particular, when the ionic radius of the cation is small, the bond between the layered crystal lattices is weak, so that the cation swells greatly with water or the like. When the inorganic layered compound is swollen in the swollen state, it is easily cleaved to form a stable sol in water.

In the inorganic layered compound, the cations (exchangeable cations) interposed between the layers are Na ⁺ and Ca.
²⁺ , Mg ^2+, etc., and the cations are Li ⁺ , Na
^In the case of ⁺ , since the ionic radius is small, the bond between the layered crystal lattices is weak, and it swells greatly in water, and is preferably used in the present invention.

Preferred examples of the inorganic layered compound include smectites such as natural smectite and synthetic smectite, and swellable inorganic layered compounds such as swelling synthetic mica and vermiculite.

The smectite is a tetrahedral sheet in which a Si-O tetrahedron containing Si at the center spreads in a plane, and
Octahedral sheet containing metal atoms such as l and Mg in the center,
Has a structure composed of 2: 1.

In the smectite, the tetrahedral type has a structure in which Si is replaced by Al, and the octahedral type has Al replaced by Mg.
Since the structure is replaced with, the smectite crystal layer lacks positive charge and has negative surface charge. In the former case, tetrahedral substitution type (charged tetrahedron)
And examples thereof include beidellite, nontronite, volkonskite, saponite, and the like. In the latter case, it is an octahedral substitution type (octahedral charged type), for example,
Examples include montmorillonite, hectorite, and stevensite.

Among the above-mentioned smectites, montmorillonite, saponite, hectorite, etc. have been commercialized as natural smectites. As synthetic smectites, saponite, hectorite, stevensite, etc. have been commercialized.

The swellable inorganic layered compound has the general formula:
_{A (B, C) 2-3 Si} 4 O 10 (OH, F, O)
₂ [However, A is either Na or Li, and B and C are
Either Mg or Li] or the like.

Examples of the swelling synthetic mica include N
a Tetrasic mica NaMg _{2. 5} (Si ₄ O ₁₀ )
F ₂ , Na or Li Teniolite (NaLi) Mg ₂ L
i (Si ₄ O ₁₀ ) F ₂ , Na or Li hectorite (NaLi) _1/3 Mg _2/3 Li _1/3 (Si ₄ O
₁₀ ) F ₂ and the like.

Among the above-mentioned inorganic layered compounds, bentonite, swellable synthetic mica and the like are preferable in that the degree of swelling with water is large and the sol is easily cleaved in water to easily form a stable sol. It is suitable.

Since these inorganic layered compounds have hydrophilic surfaces, they easily swell in water and are easily dispersed by applying shear. At this time, water-miscible organic solvents, for example, alcohols such as methanol, ethanol, propanol, ethylene glycol, diethylene glycol; dimethyl sulfoxide, dimethylformamide, acetone and the like can be mentioned.

The size of the inorganic layered compound is preferably 1 to 50 nm, more preferably 2 to 10 nm in terms of thickness. The surface size is preferably 20 to 200,000 nm, more preferably 40 to 20,000 nm. The aspect ratio is preferably 10 to 5,000, and 2
0 to 5,000 is more preferable, 40 to 3,000 is further preferable, and 100 to 3,000 is particularly preferable. If the aspect ratio is less than 10, the gas barrier property may be poor.

-Hydrophobic Inorganic Layered Compound- The inorganic layered compound is preferably hydrophobized with a tertiary or quaternary salt compound having a hydrophobic group. By adding the inorganic layered compound that has been made hydrophobic in this way, it can be dispersed in various organic solvents and / or polysiloxanes.

As the organic solvent, various organic solvents having high polarity, low polarity or non-polarity, specifically, aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as tetrahydrofuran, acetone and methyl ethyl ketone are used. , Ketones such as methyl isobutyl ketone; lower alcohols such as methanol, ethanol, propanol, isopropanol; higher alcohols such as decanol, hexanol, decanol; carbon tetrachloride, chloroform, dichloromethane, dichloroethane, perchloroethylene, chlorobenzene, etc. Halogenated hydrocarbons; amides such as dimethylformamide; esters such as ethyl acetate and phthalic acid dioctide, dimethyl sulfoxide, methyl cellosolve, N-methyl-2-
Disperse in a solvent such as pyrrolidone. The polysiloxanes can be dispersed in various silicone oils, for example.

The tertiary or quaternary salt compound having a hydrophobic group is not particularly limited, but examples of the tertiary salt compound include dimethylhexylamine hydrochloride, dimethyloctylamine hydrochloride and dimethyldecylamine hydrochloride. Salt, dimethyldodecylamine hydrochloride, dimethyllaurylamine hydrochloride, dimethylstearylamine hydrochloride, dimethylcocoamineamine hydrochloride, dimethyltetradecylamine hydrochloride, dimethyloleylamine acetate, dimethylstearylamine acetate, dimethylstearylaminopropylamine acid Acid salts, amine salt types such as dimethyloctadecylamine acetate, and pyridinium salt types such as laurylpyridinium chloride, myristylpyridinium chloride, and cetylpyridinium chloride can be used.

The quaternary salt compound is preferably a quaternary ammonium salt represented by the following general formula (1).

[0057]

[Chemical 1] [In the formula, R⁶Is an alkyl group having 8 to 22 carbon atoms or an alkene
Nyl group, R⁷, R⁸, R ⁹Are all carbon numbers 1 to 5
Rukiru group or (AO)_sH group (however, AO has 2 to 2 carbon atoms)
4 is an oxyalkylene group, and s is a real number from 1 to 10.
Yes, and R⁷, R⁸, R⁹At least of
One is (AO)_sH group. X⁻Indicates a counter anion
You ]

In the formula (1), R ⁶ is an alkyl group or alkenyl group having 8 to 22 carbon atoms, preferably 12 to 20 carbon atoms. In addition, R ⁶ may be a mixed alkyl group or a mixed alkenyl group which is a natural fatty acid residue of plant or animal origin.

AO represents an oxyalkylene group having 2 to 4 carbon atoms, preferably an oxyethylene group, and s is 1 to
10, preferably 1-5.

X ⁻ represents an inorganic or organic anion, for example, Cl ⁻ , Br ⁻ , NO ₃ ⁻ , OH ⁻ , CH ₃ COO.
^{And the} like, anion such as ⁻ , acetate anion residue, methosulfate anion and the like.

Examples of such a quaternary salt compound having a hydrophobic group include lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride,
Stearyltrimethylammonium chloride, dilauryldimethylammonium chloride, distearyldimethylammonium chloride, lauryldihydroxyethylmethylammonium chloride, oleylbispolyoxyethylenemethylammonium chloride, stearylhydroxyethyldimethylammonium chloride, lauryldimethylbenzylammonium chloride, lauroylaminopropyldimethyl Ethyl ammonium ethosulfate, lauroyl aminopropyl dimethyl hydroxyethyl ammonium perchlorate, dodecyl trimethyl ammonium chloride, palm alkyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, tallow alkyl trimethyl ammonium chloride Ride, hardened tallow alkyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, coconut alkyl dimethyl benzyl ammonium chloride, tetradecyl dimethyl benzyl ammonium chloride, octadecyl dimethyl benzyl ammonium chloride, N- tallow-alkyl N, N,
N ', N', N'-pentamethylpropylenediammonium dichloride, l-hydroxyethyl 2-alkyl (hardened beef tallow) imidazoline quaternary salt, cocoalkylisoquinolinium bromide, di-hardened beef tallow alkyldimethylammonium chloride, geo Rail dimethyl ammonium chloride, didecyl dimethyl ammonium chloride, N, N-dipolyoxyethylene N-stearyl N-methylammonium chloride, triethylmethylammonium chloride, N-polyoxyethylene N, N-dioleyl N-methylammonium chloride, etc. Can be mentioned.

The method for hydrophobizing the inorganic layered compound is carried out by exchanging the cations existing between the layers of the inorganic layered compound with the hydrophobic groups of the tertiary or quaternary salt compound having the hydrophobic group. You can For example, the inorganic layered compound is dispersed in water to prepare a suspension of the inorganic layered compound. In this case, the dispersion concentration is not particularly limited, but is usually 1 to 15% by mass. Next, the tertiary or quaternary salt compound solution having the above-mentioned hydrophobic group is added to the suspension of the inorganic layered compound, or conversely, to the tertiary or quaternary salt compound solution having the above-mentioned hydrophobic group. A composite of an inorganic layered compound and a tertiary or quaternary salt compound can be produced by adding a suspension of the inorganic layered compound.

In this case, the addition amount of the tertiary or quaternary salt compound solution is preferably the same as the cation exchange capacity of the inorganic layered compound, but it is possible to produce even a smaller amount. There is no problem even if an excessive amount is added to the cation exchange capacity, and specifically, 0.5 to 1.5 times the cation exchange capacity of the inorganic layered compound (milliequivalent conversion), particularly 0.8 to The amount is preferably 1.2 times.

The reaction proceeds sufficiently even at room temperature, but may be heated. The maximum heating temperature can be arbitrarily set as long as it is equal to or lower than the decomposition point of the tertiary or quaternary salt compound used. Then, the solid-liquid is separated, and the resulting composite of the inorganic layered compound and the tertiary or quaternary salt compound is washed with water to sufficiently remove the by-product electrolyte. This is dried and, if necessary, pulverized to obtain a hydrophobized inorganic layered compound.

In the gas barrier layer according to the second aspect,
The content of the inorganic layered compound is 1 to 50% by mass, more preferably 5 to 30% by mass, based on the entire composition. If the content of the inorganic layered compound is less than 1% by mass, the gas barrier property may not be sufficient. on the other hand,
If it exceeds 50% by mass, transparency and haze may increase.

The gas barrier layer is prepared by adding the swelling inorganic layered compound while sufficiently stirring the solvent such as water, so that the inorganic layered compound is sufficiently swelled, and then dispersed by a disperser. It is formed by coating, etc. This, after adding and stirring in the coating agent of the metal oxide glass before vitrification, a method of applying on the plastic film, a metal oxide glass film and a plastic film separately prepared in advance with an adhesive It can be formed by a method such as laminating.

In this case, since the surface of the inorganic layered compound is hydrophilic, it is easily swelled in water and easily dispersed by shearing. At this time, a water-miscible organic solvent, for example, alcohols such as methanol, ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol, etc., as well as dimethyl sulfoxide, dimethylformamide, acetone, etc. can be added if desired.

When a swellable inorganic layered compound whose surface is hydrophobized with a quaternary salt surfactant or the like is used, the gas barrier layer contains the hydrophobized inorganic layered compound,
Toluene, xylene, methyl ethyl ketone, acetone,
Methyl isobutyl ketone, propanol, isopropanol, quaternary salt carbon, perchlorethylene, methyl cellosolve, dimethylformamide, etc. After sufficiently swelling and swelling, dispersed with a disperser, formed by coating etc. It

Examples of the disperser include dispersers such as various mills for mechanically applying a direct force to disperse, a high-speed stirring disperser having a large shearing force, and a disperser giving high-strength ultrasonic energy. . Specifically, a ball mill, a sand grinder mill, a visco mill, a colloid mill, a homogenizer dissolver, a polytron, a homomixer, a homo blender kedy mill, a jet agitator, a capillary emulsifier, a liquid siren, an electromagnetic distortion type ultrasonic generator, a pole. There is an emulsifier with a man whistle. The dispersion obtained by being dispersed by the disperser has a high viscosity or a gel state,
Storage stability is very good. When it is added to the coating liquid, it is diluted with water or a solvent and sufficiently stirred, and then added.

<Characteristics of Gas Barrier Layer> The first and second
The thickness of the gas barrier layer of the embodiment is 0.1 to 10 μm.
It is preferably m, and more preferably 1 to 2 μm. If the thickness is less than 0.1 μm, the gas barrier property may not be sufficient, while if it exceeds 10 μm, the thinning and weight reduction may not be sufficient.

The oxygen permeability (temperature 40 ° C., humidity 90%) of the gas barrier layers of the first and second aspects of the present invention is as follows.
0.5 ml / m ² · atm · day or less is preferable,
0.2 ml / m ² · atm · day or less is more preferable. When the oxygen permeability is within the above numerical range, the gas barrier layer has sufficient gas barrier properties. The oxygen permeability is a value obtained by a gas permeability measuring device (manufactured by Mocon).

[Other Members] Examples of the other members include a hard coat layer, a protective layer, an adhesion layer, a transparent conductive layer, and a color filter.

Materials for the hard coat layer, the protective layer, and the adhesion layer are epoxy resin, epoxy acrylate, and S.
iO ₂ , Si _x O, Al ₂ O ₃ , Si ₃ O ₄ , Ti
O ₂ , AlN, ZnO, ZnS, ZrO ₂ , SiC, S
i: O: N, Si: O: H, Si: N: H, Si: O:
Known materials such as N: H can be preferably used. The hard coat layer and the adhesion layer are preferably disposed on the gas barrier layer.

The material of the transparent conductive layer is ITO.
Known materials can be used as the material of the transparent conductive layer such as (indium tin oxide). The transparent conductive layer is preferably provided on the hard coat layer and the adhesion layer.

The material of the color filter includes dyes (dyeing: photolithography, dye dispersion: etching), pigments (photolithography, etching, printing, electrodeposition, vapor deposition),
Known materials can be used as the material of the color filter such as metal oxide type and cholesteric liquid crystal type. The color filter is preferably arranged between the hard coat layer, the adhesion layer and the like and the transparent conductive layer.

<Physical Properties of Display Device Substrate> The retardation (Re) value of the display device substrate of the present invention at a wavelength of 632.8 nm is 15 nm or less in terms of excellent optical isotropy. Is preferable and 10 nm or less is more preferable.

<Structure of Display Device Substrate> The structure of the display device substrate of the present invention is such that the gas barrier layer is formed on both surfaces of the plastic film in terms of gas barrier properties, strength, curl prevention and the like. It is preferable to have. When the display device substrate of the present invention is used in a liquid crystal display device, it is particularly preferable to dispose the gas barrier layer on at least the surface in contact with the liquid crystal cell.

<Uses of Display Device Substrate> The display device substrate of the present invention is easy to reduce in weight and thickness, strong against impact,
Flatness, adhesion to ITO electrode, easy manufacturing, and
Since it has an excellent gas barrier property under high humidity and exhibits high performance in a wide band, it can be particularly suitably used for a liquid crystal display device that can be used as a display device in various fields.

[0079]

The present invention will be described in more detail below by showing Examples and Comparative Examples, but the present invention is not limited to these Examples.

Example 1 Main agent: Tetraethoxysilane Si (OEt) ₄ in a mass ratio of 5: 1 (solvent) of water + methanol + ethanol + isopropanol (hereinafter, H ₂ O + MeOH + EtOH +).
i-PrOH) = 1: 1: 1: 4, and mixed with triethoxyborane B (OEt) ₃ at a rate of 0.2 mol / kg. The main ingredient was prepared by adding and stirring and dissolving for 10 minutes. Catalyst; acidic ammonium fluoride N as a halogen ion source
It was prepared by using H ₄ F.HF so that the F ⁻ concentration was 0.1 mol / kg with respect to the total mass of the main solvent and the same mixed solvent.

After mixing the main agent and the catalyst prepared as described above in a mass ratio of 3: 1 and stirring for 10 minutes, the pH of the mixed solution was adjusted to 5.0 (indicator with hydrochloric acid and aqueous ammonia). As an ethanol solution of methyl red + bromocresol green), and aged for 3 hours for hydrolysis and dehydration condensation to obtain a coating agent.

A 100 μm thick cycloolefin compound film (trade name: ZEONOR 16) was applied to this coating agent.
00) with a film thickness of 10 μm,
For the display device of Example 1, the temperature was gradually raised in a temperature range of up to 70 ° C., the temperature was gradually raised to perform preliminary drying (solvent volatilization step), and then the temperature was held at 120 ° C. for 30 minutes to be baked and vitrified. A substrate was produced.

Example 2 A coating agent prepared by adding 5% by mass of swelling synthetic mica [ME-100 (manufactured by Cope Chemical Co.)] to the coating agent of Example 1 was used.
A cycloolefin compound film (trade name: Zeonoa 1600) having a thickness of 10 μm is applied to a m-thick cycloolefin compound film, and the applied film is preliminarily dried by gradually raising the temperature in a temperature range of 50 to 70 ° C. (solvent volatilization step). ) And then at 120 ° C for 3
The display device substrate of Example 2 was manufactured by holding it for 0 minutes, firing and vitrifying.

Example 3 A coating agent prepared by adding 10% by mass of swelling synthetic mica [ME-100 (manufactured by Corp Chemical)] to the coating agent of Example 1 was prepared.
μm-thick cycloolefin compound film (trade name:
ZEONOR 1600) was applied to a film thickness of 10 μm, and the obtained coated film was preliminarily dried (solvent volatilization step) by gradually raising the temperature in the temperature range of 50 to 70 ° C., and then 1
The substrate for a display device of Example 3 was manufactured by holding at 20 ° C. for 30 minutes, firing and vitrifying.

Example 4 A coating agent obtained by adding 20% by mass of swelling synthetic mica [ME-100 (manufactured by Corp Chemical) to the coating agent of Example 1 was used.
μm-thick cycloolefin compound film (trade name:
ZEONOR 1600) was applied to a film thickness of 10 μm, and the obtained coated film was preliminarily dried (solvent volatilization step) by gradually raising the temperature in the temperature range of 50 to 70 ° C., and then 1
The substrate for a display device of Example 4 was manufactured by holding at 20 ° C. for 30 minutes, firing and vitrifying.

Example 5 The surface of swelling synthetic mica [ME-100 (manufactured by Coop Chemical Co.)] of the coating agent of Example 1 was hydrophobized with a quaternary ammonium salt represented by the following general formula. A coating agent containing 5% by mass of synthetic mica was applied to a cycloolefin compound film (trade name: Zeonor 1600) having a thickness of 100 μm in a thickness of 10 μm, and the obtained coating film was applied at a temperature range of 50 to 70 ° C. After carefully raising the temperature gradually and performing preliminary drying (solvent volatilization step), the substrate for a display device of Example 5 was manufactured by holding at 120 ° C. for 30 minutes and baking to vitrify.

[0087]

[Chemical 2] (However, n = 25 and X = Cl are represented.)

[Example 6] The surface of swelling synthetic mica [ME-100 (manufactured by Cope Chemical Co.)] of the coating agent of Example 1 was hydrophobized with the same quaternary ammonium salt as in Example 5. A coating agent containing 10% by mass of synthetic mica is applied to a cycloolefin compound film (trade name: Zeonoa 1600) having a thickness of 100 μm in a thickness of 10 μm, and the obtained coating film is heated at a temperature range of 50 to 70 ° C. After carefully raising the temperature gradually and performing preliminary drying (solvent volatilization step), the substrate for display device of Example 6 was manufactured by holding at 120 ° C. for 30 minutes and baking to vitrify.

[Example 7] The surface of swelling synthetic mica [ME-100 (manufactured by Corp Chemical)] of the coating agent of Example 1 was hydrophobized with a quaternary ammonium salt as in Example 5. A coating agent containing 20% by mass of synthetic mica is applied to a cycloolefin compound film (trade name: Zeonor 1600) having a thickness of 100 μm in a thickness of 10 μm, and the obtained coating film is subjected to a temperature range of 50 to 70 ° C. Carefully, the temperature was gradually raised to perform preliminary drying (solvent volatilization step), and then the mixture was held at 120 ° C. for 30 minutes to be baked and vitrified, whereby a display device substrate of Example 7 was produced.

Comparative Example 1 A cycloolefin compound film (trade name: ZEONOR 1600) having a thickness of 100 μm was coated with a gas barrier layer having a thickness of 10 μm using polyvinyl alcohol to prepare a substrate for a display device of Comparative Example 1.

With respect to the obtained substrates for display devices of Examples 1 to 7 and Comparative Example 1, the oxygen permeability and moisture permeability were measured by the following methods. The results are shown in Table 1.

<Measurement of Oxygen Permeability> With respect to the obtained substrate for a display device, the oxygen permeability at a temperature of 40 ° C. and a humidity of 90% was determined by a gas permeability measuring device (manufactured by Mocon).

<Measurement of Moisture Permeability> The moisture permeability of the obtained display device substrate was measured by L80 manufactured by LYSSY.

[0094]

[Table 1]

[0095]

EFFECTS OF THE INVENTION According to the present invention, it is easy to reduce the weight and thickness, is resistant to impacts, has excellent flatness and adhesion to ITO electrodes, is easy to manufacture, and has a gas barrier property under high humidity. It is possible to provide a substrate for a display device which is excellent and has high performance in a wide band.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI Theme Coat (reference) G02F 1/1333 505 G02B 1/10 Z (72) Inventor Kohei Arakawa 200 Nakamura, Fujinomiya-shi, Shizuoka Fuji Photo film Co., Ltd. in the F-term (reference) 2H048 AA05 AA12 AA18 2H090 HD02 HD06 HD08 JA07 JB03 JC07 JC18 JD05 JD11 LA04 LA15 2K009 AA15 BB02 CC03 CC42 CC45 EE00 4F100 AA00B AA17B AC05B AG00B AK01A AK02A BA02 BA03 BA04 BA05 BA07 BA10A BA10C BA10D CC00C DE02B GB41 GB56E JA05A JB06B JD02 JD02B JD03B JG01D JK10 JK12C JK15 JL03 JN01A JN01D YY00A

Claims (11)

[Claims] 1. A plastic film having an average light transmittance of 70% or more at a wavelength of 400 to 700 nm and a glass transition point of 100 ° C. or more, and a gas barrier layer of a single or multi-component metal oxide glass by a sol-gel method. A substrate for a display device having. 2. A plastic film having an average light transmittance of 70% or more at a wavelength of 400 to 700 nm and a glass transition point of 100 ° C. or more, and a gas barrier layer containing an inorganic layered compound and a single or multi-component metal oxide glass. A substrate for a display device, comprising: 3. The substrate for a display device according to claim 1, which has a retardation (Re) value of 15 nm or less at a wavelength of 632.8 nm. 4. The substrate for a display device according to claim 1, wherein the inorganic layered compound is synthetic mica. 5. The aspect ratio of the inorganic layered compound is 20.
The display device substrate according to any one of claims 1 to 4, which is as described above. 6. The aspect ratio of the inorganic layered compound is 10.
The display device substrate according to any one of claims 1 to 5, which is 0 or more. 7. The display device substrate according to claim 1, wherein the inorganic layered compound is hydrophobized with a tertiary or quaternary salt compound having a hydrophobic group. 8. The oxygen permeability of the gas barrier layer (temperature 40
℃, humidity 90%), 0.5 ml / m ² · atm · da
The display device substrate according to any one of claims 1 to 7, which is y or less. 9. The gas barrier layer having at least one of a hard coat layer and an adhesion layer on the gas barrier layer.
A substrate for a display device according to any one of 1. 10. The display device substrate according to claim 9, further comprising a transparent conductive layer on at least one of the hard coat layer and the adhesion layer. 11. The display device substrate according to claim 10, further comprising a color filter between at least one of the hard coat layer and the adhesion layer and the transparent conductive layer.