JP2003015113A - Substrate for display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a substrate for a display device easily lightened in weight and thinned, strong against impact, excellent in flatness and adhesion to an ITO electrode, easily manufactured, excellent in gas barrier properties under high humidity and exhibiting high performance over a wide range. SOLUTION: The substrate for the display device has phase difference plate having >=70% average light transmittance in the 400-700 nm wavelength region and >=100 deg.C glass transition temperature and satisfying the formula Re (450) < Re (550) < Re (650), when the retardation values at wavelengths of 450 nm, 550 nm and 650 nm are defined as Re (450), Re (550) and Re (650), respectively, and a gas barrier layer of mono-or multicomponent metal oxide glass formed by a sol-gel method.

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.
0% or more, glass transition point 100 ° C or more, and wavelength 4
Retardation values at 50 nm, 550 nm and 650 nm are Re (450) and Re (550), respectively.
And Re (650), Re (450) <Re
A substrate for a display device, comprising: a retardation film satisfying (550) <Re (650); 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.
The average light transmittance at m is 70% or more, the glass transition point is 100 ° C. or more, and the retardation values at wavelengths of 450 nm, 550 nm and 650 nm are Re, respectively.
When (450), Re (550) and Re (650) are set, Re (450) <Re (550) <Re (65
A substrate for a display device, comprising: a retardation film satisfying 0) and a gas barrier layer containing an inorganic layered compound and a single or multi-component metal oxide glass.

In the invention of claim 3, the retardation plate contains a material having a positive intrinsic birefringence value and a material having a negative intrinsic birefringence value.
It is the substrate for a display device described.

A fourth aspect of the present invention is the display device substrate according to the third aspect, wherein the material having a positive intrinsic birefringence value and the material having a negative intrinsic birefringence value are polymers.

According to a fifth aspect of the invention, the wavelength of the retardation plate is 45 nm.
5. The display device substrate according to claim 1, wherein the value of retardation (Re) / wavelength (λ) at 0 nm, 550 nm and 650 nm is 0.2 to 0.3.

The invention according to claim 6 is the substrate for a display device according to any one of claims 1 to 5, wherein the inorganic layered compound is synthetic mica.

The invention according to claim 7 is the substrate for a display device according to any one of claims 1 to 6, wherein the aspect ratio of the inorganic layered compound is 20 or more.

The invention of claim 8 is the substrate for a display device according to any one of claims 1 to 7, wherein the aspect ratio of the inorganic layered compound is 100 or more.

The invention of claim 9 is a display device according to any one of claims 1 to 8, wherein the inorganic layered compound is hydrophobized with a tertiary or quaternary salt compound having a hydrophobic group. The substrate.

According to a tenth aspect of the present invention, the oxygen permeability of the gas barrier layer (temperature: 40 ° C., humidity: 90%) is 0.5 ml / m.
The display device substrate according to any one of claims 1 to 9, which has a density of ² · atm · day or less.

An eleventh aspect of the present invention is the display device substrate according to any one of the first to tenth aspects, which has at least one of a hard coat layer and an adhesion layer on the gas barrier layer.

A twelfth aspect of the present invention is the display device substrate according to the eleventh aspect, which has a transparent conductive layer on at least one of the hard coat layer and the adhesion layer.

The invention according to claim 13 is the substrate for a display device according to claim 12, 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 has the retardation plate 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 properties 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 cost is low.

As a result, by including the metal oxide glass and the inorganic layered compound having an excellent gas barrier property 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.

[0026]

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 has a retardation plate and a gas barrier layer, and optionally other members.

[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 dehydration-condensed while adjusting to 5.0, the reaction purified product is applied to the surface of the substrate 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).

[Phase retarder] The retarder has a wavelength of 450
Re (450) <Re (5), where Re (450), Re (550) and Re (650) are the retardation values at nm, 550 nm and 650 nm, respectively.
50) <Re (650) is satisfied. In other words, it is necessary that the retardation value and the wavelength have a positive correlation. By having this correlation, it has a constant phase difference characteristic with respect to the incident light in the visible light region, and it becomes easy to make black and white and color. Further, the retardation plate has a wavelength of 4
The average light transmittance at 70 to 70 nm is 70% or more,
The glass transition point needs to be 100 ° C. or higher.

The wavelength of the retardation plate is 450 nm, 550
(Re) at nm and 650 nm
The value of / wavelength (λ) may vary to some extent depending on the properties of the liquid crystal used, but is preferably 0.2 to 0.3, and more preferably 0.23 to 0.27. When the value of the retardation (Re) / wavelength (λ) is within the above numerical range, a wideband 1/4 phase difference plate having more uniform phase difference characteristics with respect to incident light in the entire visible light range is obtained. .

<Aspect of Retardation Plate> As an aspect of the retardation plate, a first embodiment containing a material having a positive intrinsic birefringence value and a material having a negative intrinsic birefringence value, a layer made of a material having a positive intrinsic birefringence value And a second aspect including a laminate of layers made of a negative material, a third aspect including a material having a positive intrinsic birefringence value and a negative intrinsic birefringence value, and the material described in WO00 / 26705 is used. The fourth aspect, such as the fifth aspect utilizing cellulose acetate, it is possible to effectively use a material having a quarter-wave plate characteristic in a wide band in one sheet, but in the present invention,
It is particularly preferable that the intrinsic birefringence value has a combination of positive and negative values because the photoelasticity is small.

<< First Mode >> In the first mode, the retardation plate contains a material having a positive intrinsic birefringence value and a material having a negative intrinsic birefringence value (meaning “containing in the same layer”). However, it is an embodiment in which other components are contained as necessary. --- Material having a positive intrinsic birefringence value --- The material having a positive intrinsic birefringence value is a material having a property of exhibiting optically positive uniaxiality when a uniaxial orientation rule is given to a molecule. Examples thereof include polymers, rod-shaped liquid crystals and rod-shaped liquid crystal polymers. These may be used alone or in combination of two or more. In the present invention, among these, polymers having a positive intrinsic birefringence value are preferable.

In the material having a positive intrinsic birefringence value, examples of the polymer having a positive intrinsic birefringence value include a polyolefin-based polymer (eg, polyethylene, polypropylene, norbornene-based polymer, etc.) and a polyester-based polymer (eg, polyethylene terephthalate). , Polybutylene terephthalate, etc.), polyarylene sulfide-based polymers (eg, polyphenylene sulfide, etc.), polyvinyl alcohol-based polymers, polycarbonate-based polymers, polyarylate-based polymers, cellulose ester-based polymers (the ones in which the intrinsic birefringence value is negative are also available. A), polyether sulfone polymer, polysulfone polymer, polyallyl sulfone polymer,
Examples thereof include polyvinyl chloride-based polymers, and multi-component (binary, ternary, etc.) copolymers thereof. These may be used alone or in combination of two or more. In the present invention, among these, polycarbonate-based polymers such as modified polycarbonate, norbornene-based polymers, polyether sulfone-based polymers, etc.
It is preferable in terms of transparency.

Suitable examples of the rod-shaped liquid crystal include a liquid crystal exhibiting a rod-shaped nematic orientation, and may be a low-molecular liquid crystal or a high-molecular liquid crystal. Specific examples of the low-molecular liquid crystal include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyridines, and phenyldioxane. Preferable examples thereof include tolanes, tolans, alkenylcyclohexylbenzonitriles, and the like.

--- Material with Negative Intrinsic Birefringence Value --- The material with a negative intrinsic birefringence value has a characteristic of exhibiting optically negative uniaxiality when a uniaxial orientation rule is given to a molecule. Examples of the material include polymers such as polymers, discotic liquid crystals, and discotic liquid crystal polymers. These may be used alone or in combination of two or more. In the present invention, among these, polymers having a negative intrinsic birefringence value are preferable.

In the material having a negative intrinsic birefringence value, examples of the polymer having a negative intrinsic birefringence value include polystyrene-based polymers, polyacrylonitrile-based polymers, polymethylmethacrylate-based polymers, and cellulose ester-based polymers such as cellulose acetate-based polymers. (Some of the above-mentioned intrinsic birefringence values are positive), or multi-component (binary, ternary, etc.) copolymers thereof. These are 1
They may be used alone or in combination of two or more. In the present invention, among these, a styrene-based polymer or the like is preferable in terms of birefringence manifestation, and a copolymer of styrene and maleic anhydride is more preferable in terms of heat resistance.

It is preferable that the material having a positive intrinsic birefringence value and the material having a negative intrinsic birefringence value have greatly different wavelength dispersions from each other, and it is preferable that both the retardation (Re) are highly developable.

As a material having a negative intrinsic birefringence value and a large expression of retardation (Re), a styrene-based material is particularly preferable. Since the styrene-based material has a large wavelength dispersion, a material having a small wavelength dispersion is preferably used as a material having a positive intrinsic birefringence value to be combined. Examples of the material having a small wavelength dispersion include olefin-based and polyvinyl alcohol-based polymers, and cycloolefin-based polymers such as norbornene-based polymers are particularly preferable in terms of heat resistance and dimensional stability. .

--Other Components-- The other components contained in the retardation plate are not particularly limited as long as they do not impair the effects of the present invention, and can be appropriately selected according to the purpose. Suitable examples include solubilizers. The compatibilizer can be preferably used when phase separation occurs when a material having a positive intrinsic birefringence value and a material having a negative birefringence value are mixed, and the compatibilizer is used. This makes it possible to improve the mixed state of the material having a positive intrinsic birefringence value and the material having a negative intrinsic birefringence value.

--Production of Retardation Plate in First Embodiment--
-As the method for producing the retardation plate in the first aspect,
There is no particular limitation and it can be appropriately selected according to the purpose. For example, a material having a positive intrinsic birefringence value and a material having a negative intrinsic birefringence value are appropriately selected, the compounding ratio is determined, the compatibilizer and the like are added as necessary, and these are compounded. After that, the composition is formed into a film or sheet according to a solution film forming method in which the composition is applied and dried and then formed, or an extrusion forming method in which the mixture is pelletized, melt-extruded and formed, and the like and stretched to form a letter. The retardation plate is manufactured by controlling the value of the retardation (Re) within the above numerical range. The stretching, longitudinal uniaxial stretching to stretch in the mechanical flow direction,
Suitable examples include lateral uniaxial stretching (for example, tenter stretching) in which stretching is performed in a direction orthogonal to the mechanical flow direction, but biaxial stretching may be used as long as it is slight.

<< Second Mode >> In the second mode, the retardation plate includes a laminate of a layer made of a material having a positive intrinsic birefringence value and a layer made of a material having a negative intrinsic birefringence value. And other layers.

As the material having a positive intrinsic birefringence value and the material having a negative birefringence value in the laminate, the same materials as those already described in the above-mentioned "first aspect" are preferably mentioned, and particularly preferable materials. Is the same for all. Examples of the other layer include an adhesive layer capable of favorably adhering the layer made of a material having a positive intrinsic birefringence value and the layer made of a negative material.

--Production of Retardation Plate in Second Mode--
-The method for producing the retardation plate in the second aspect is not particularly limited, but in that the laminate is easily produced, the intrinsic birefringence value is coextruded with a positive material and a negative material. It is preferably formed. In the co-extrusion, for example, the intrinsic birefringence value positive polymer, negative polymer,
And, if desired, the polymer for the adhesive layer may be introduced into the extrusion die, and the polymers may be brought into contact with each other inside the die or in the opening of the die to integrate them to form a laminate.

The die is not particularly limited, but T
A die can be preferably used, and the internal shape of the T die is not particularly limited and various shapes can be mentioned. If desired, the extruded molten laminate may be stretched over a plurality of rolls and moved by following the rotation of the rolls to adjust the thickness of the laminate to a desired thickness.

FIG. 1 is a schematic block diagram of a coextrusion apparatus preferably used for the coextrusion. The co-extrusion device 20 includes an extrusion die 22, extruders 24 and 26, and a tension roll 2.
It has 8, 30, 32. In the co-extrusion device 20, the polymer having a positive intrinsic birefringence value and the polymer having a negative intrinsic birefringence value, which are stored in the extruder 24 and the extruder 26, are introduced into the extrusion die 22 and meet at the opening of the extrusion die 22. , The respective polymers are brought into contact with each other and integrated to form a laminated body 34. When the adhesion between the polymer having a positive intrinsic birefringence value and the polymer having a negative intrinsic birefringence value is poor, an extruder for forming an adhesive layer may be further provided. The formed laminated body 34 is a stretched roll 2 that rotates.
Stretched by 8, 30, 32 and stretched rolls 28, 3
If the retardation (Re) value on the front surface is 110 to 165 nm, it is within the above numerical range as it is. If it does not exist, the retardation (Re) value is controlled within the above numerical range by further stretching to produce a retardation plate. Preferable examples of the stretching include the same stretching as the “stretching” described in the above “Production of retardation plate in first embodiment”.

<< Third Aspect >> In the third aspect, the retardation plate contains a material having a positive intrinsic part and a negative intrinsic birefringence value, and if necessary, other components. It is an aspect to contain.

--- Material having positive and negative portions of intrinsic birefringence value --- As the material having positive and negative portions of intrinsic birefringence value, when uniaxial orientation rule is given In addition, a copolymer composition having a chain exhibiting positive uniaxiality and a chain exhibiting negative uniaxiality is preferable, and a monomer constituting the polymer having a positive intrinsic birefringence value (monomer) and a negative polymer are A copolymer composition with the constituent monomers is particularly preferable. The copolymer composition is not particularly limited, but a graft copolymer having a main chain and a graft chain graft-bonded to the main chain is preferred, and the main chain has a positive intrinsic birefringence value. It is particularly preferable that the graft chain is a chain composed of a monomer constituting the polymer of 1. and the graft chain is a chain composed of a monomer constituting the polymer having a negative intrinsic birefringence value. As the polymer having a positive intrinsic birefringence value and the polymer having a negative birefringence value, the “first aspect” is used.
The same polymers as those already mentioned above are preferably mentioned, and particularly preferable polymers and the like are also the same.

The method for producing the graft copolymer is not particularly limited, and bulk polymerization, precipitation polymerization, emulsion polymerization,
Well-known polymerization methods such as solution polymerization and suspension polymerization are preferred. Among these, suspension polymerization or solution polymerization is preferable.

The suspension polymerization method is referred to, for example, the method described in “Experimental Method for Polymer Synthesis” (Takayuki Otsu, Masayoshi Kinoshita, Kagaku Dojinsha), pages 130 and 146 to 147. can do.

According to the suspension polymerization, the graft copolymer is obtained by an addition polymerization reaction initiated by an oil-soluble initiator using an aqueous dispersion medium in the presence of inorganic salts and / or a water-soluble polymer dispersant. , 50 μm or more.

The above-mentioned inorganic salts are used for the purpose of stabilizing dispersion and preventing water-solubilization of monomers and the like.
For example, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, ammonium chloride, potassium sulfate, calcium sulfate, magnesium sulfate, ammonium sulfate, potassium aluminum sulfate, sodium carbonate, potassium carbonate, calcium hydrogen phosphate and the like can be mentioned.

Examples of the water-soluble polymer dispersant include polyvinyl alcohol, sodium polyacrylate, an alkaline hydrolyzate of a styrene-maleic anhydride copolymer (for example, "isoban" manufactured by Kuraray Co., Ltd.), sodium alginate and water-soluble agents. Examples of the functional cellulose derivative (“Mayprogut”, “Kelco SCS”, “Quar gum” manufactured by Sansho Co., Ltd., “MH-K” manufactured by Hoechst Japan KK) and the like.

The polymerization initiator used in the suspension polymerization is preferably a water-insoluble and oil-soluble polymerization initiator, and examples thereof include azobis (cyclohexane-1-carbonitrile), azobisisobutyronitrile, and 2,2. '-Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, benzoyl peroxide, lauroyl peroxide, Peroxide-t-butyl,
Peroxide-t-amyl, cumyl peroxide, t-butyl peroxide benzoate, t-butyl peroxide phenylacetate,
Etc. Among these, peroxide-based polymerization initiators are preferable.

The polymerization temperature at the time of the graft polymerization varies depending on the kind of the monomer to be graft-polymerized, the boiling point, the ceiling temperature (the temperature at which the polymerization and the depolymerization reach equilibrium), etc., but cannot be specified unconditionally. , Usually 0 to 100 ° C, preferably 40 to 90 ° C.

--Other Components-- As the other components contained in the retardation plate, other components similar to those described in the above-mentioned "first embodiment" are preferably cited.

--Production of Retardation Plate in Third Mode--
-As the method for manufacturing the retardation plate in the third aspect,
There is no particular limitation and it can be appropriately selected according to the purpose. For example, a material having a positive portion and a negative portion having the intrinsic birefringence value is appropriately selected, and a compatibilizer or the like is added if desired, and these are blended. Then, thereafter, this composition is formed into a film or sheet according to a solution film-forming method of forming a solution by applying and drying, or an extrusion forming method of forming by pelletizing, melt-extruding, and the like, The value of the retardation (Re) in front of it is
If it is 110 nm to 165 nm, the retardation (Re) value is controlled within the above numerical range by further stretching if it is not within the above numerical range, and the retardation plate is manufactured.

Suitable examples of the stretching include the same stretching as the “stretching” described in the above “Production of retardation plate in the first embodiment”.

<Physical Properties of Retardation Plate> The photoelasticity of the retardation plate is preferably 20 Brewster or less, more preferably 5 Brewster or less. If the photoelasticity exceeds 20 Brewster, birefringence may occur due to strain when stress is applied to the retardation plate, which may be undesirable due to light leakage or the like.

The thickness of the retardation plate is not particularly limited, but is preferably 30 to 300 μm, and 50 to 200 μm.
m is more preferred.

[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.

<Structure of Display Device Substrate> The display device substrate of the present invention has a gas barrier layer on both surfaces of the retardation plate in terms of gas barrier properties, strength, curl prevention and the like. Preferably. 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> In the display device substrate of the present invention described above, the conventional broadband quarter-wave plate or the like and the glass substrate are replaced with a substantially single plastic substrate having a gas barrier layer. Therefore, it is easy to reduce the weight and thickness, is resistant to impact, is flat, has good adhesion to ITO electrodes, is easy to manufacture, and 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.

[0109]

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-Preparation of Retardation Plate- 16 parts by mass of norbornene resin (manufactured by JSR; Arton "F") (material having a positive intrinsic birefringence value) and styrene and maleic anhydride are co-weighted. Combined (manufactured by Sekisui Chemical Co., Ltd .; “Dailark 232”) (material having a negative intrinsic birefringence value) 11 parts by mass,
Was dissolved in toluene to prepare a coating liquid (27% by mass). The coating solution was cast on a glass plate using a doctor blade and dried to obtain a transparent film (thickness: 120 μm).
m) was obtained. The transparent film was uniaxially stretched at 125 ° C. by 35% to produce a retardation plate.

<Measurement of Wavelength Dispersion> Regarding the obtained retardation plate, a retardation measuring device (manufactured by Oji Scientific Co., Ltd .; “K”) was used.
OBRA-21ADH ") was used to measure the wavelength dispersion of the retardation (Re). The results are shown in Figure 2.

As shown in FIG. 2, in the retardation plate of Example 1, the retardation (Re) values at wavelengths of 450 nm, 550 nm and 650 nm were Re (45), respectively.
0), Re (550) and Re (650),
It was found that Re (450) <Re (550) <Re (650) was satisfied, and that it had excellent 1/4 retardation plate characteristics in a wide band. The average light transmittance of the retardation plate was 90%, and the glass transition point was 155 ° C.

-Preparation of substrate for display device-Main ingredient: 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, hydrochloric acid and aqueous ammonia were used to adjust the pH of the mixed solution to 5.0 (indicator As an ethanol solution of methyl red + bromocresol green), and aged for 3 hours for hydrolysis and dehydration condensation to obtain a coating agent.

This coating agent is applied to the retardation plate 10 times.
After coating with a film thickness of μm, the coating film is preliminarily dried (solvent volatilization step) by gradually raising the temperature in the temperature range of 50 to 70 ° C., and then baked at 120 ° C. for 30 minutes. It was vitrified to prepare a display device substrate of Example 1.

[Example 2] The retardation plate of Example 1 was prepared by adding 5% by mass of swelling synthetic mica [ME-100 (manufactured by Coop Chemical Co.)] to the coating agent of Example 1. After coating with a film thickness of 10 μm, the coating film is preliminarily dried by gradually raising the temperature in the temperature range of 50 to 70 ° C. (solvent volatilization step), and then at 120 ° C. for 30 minutes.
The substrate for display device of Example 2 was manufactured by holding for a minute and firing to vitrify.

[Example 3] A coating agent prepared by adding 10% by mass of swelling synthetic mica [ME-100 (manufactured by Corp Chemical Co.)] to the coating agent of Example 1 was applied to the retardation plate of Example 1 described above. After coating with a film thickness of 10 μm, the coating film thus obtained is gradually heated in a temperature range of 50 to 70 ° C. to be preliminarily dried (solvent volatilization step), and then 12
The substrate for a display device of Example 3 was manufactured by holding at 0 ° C. for 30 minutes, firing and vitrifying.

Example 4 A coating agent prepared by adding 20% by mass of swelling synthetic mica [ME-100 (manufactured by Cope Chemical Co.)] to the coating agent of Example 1 was applied to the retardation plate of Example 1 described above. After coating with a film thickness of 10 μm, the coating film thus obtained is gradually heated in a temperature range of 50 to 70 ° C. to be preliminarily dried (solvent volatilization step), and then 12
The substrate for display device of Example 4 was produced by holding at 0 ° C. for 30 minutes, firing and vitrifying.

Example 5 With respect to the coating agent of Example 1, the surface of swelling synthetic mica [ME-100 (manufactured by Corp Chemical)] 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 the retardation plate of Example 1 to have a film thickness of 10 μm, and the obtained coated film was gradually heated while paying attention to a temperature range of 50 to 70 ° C. After preliminary drying (solvent volatilization step), the substrate for display device of Example 5 was manufactured by holding at 120 ° C. for 30 minutes and baking to vitrify.

[0120]

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

[Example 6] The surface of swelling synthetic mica [ME-100 (manufactured by Coop Chemical Co.)] with respect to 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 was applied to the retardation film of Example 1 to a film thickness of 10 μm, and the obtained coating film was gradually heated while paying attention to the temperature range of 50 to 70 ° C. Then, preliminary drying (solvent volatilization step) was performed, and then the glass substrate was held at 120 ° C. for 30 minutes to be baked and vitrified, whereby a display device substrate of Example 6 was manufactured.

[Example 7] The surface of swelling synthetic mica [ME-100 (manufactured by Coop Chemical Co.)] with respect to the coating agent of Example 1 was hydrophobized with the same quaternary ammonium salt as in Example 5. A coating agent containing 20% by mass of synthetic mica was applied to the retardation plate of Example 1 to have a film thickness of 10 μm, and the obtained coated film was gradually heated while paying attention to a temperature range of 50 to 70 ° C. Then, preliminary drying (solvent volatilization step) was performed, and then the glass substrate was held at 120 ° C. for 30 minutes to be baked and vitrified, whereby a display device substrate of Example 7 was manufactured.

[Comparative Example 1] In the retardation plate of Example 1,
A gas barrier layer having a thickness of 10 μm was formed from polyvinyl alcohol to prepare a display device substrate of Comparative Example 1.

With respect to the obtained display device substrates 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 display device substrate, 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 determined by L80 manufactured by LYSSY.

[0127]

[Table 1]

[0128]

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.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of a co-extrusion device suitably used for co-extrusion.

FIG. 2 is a diagram showing the results of measuring the wavelength dispersion of retardation (Re) with respect to the display device substrate obtained in Example 1, using a retardation measuring device.

[Explanation of symbols]

20 Coextrusion equipment 22 Extrusion die 24 extruder 26 Extruder 28 tension roll 30 tension roll 32 tension roll

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02B 1/10 G02B 5/30 5C094 5/30 G09F 9/30 310 G09F 9/30 310 G02B 1/10 Z (72) Inventor Kohei Arakawa 200 Onakazato, Fujinomiya-shi, Shizuoka Fuji Photo Film Co., Ltd. F-term (reference) 2H049 BA06 BA42 BB62 BC09 2H090 JA06 JB03 JB13 JC07 JD01 JD11 LA06 2K009 AA15 CC02 CC03 CC06 CC42 CC45 EE00 4F006A02 AA12 AA15 AA17 AA19 AA22 AA35 AA36 AA40 AB64.

Claims (13)

[Claims] 1. An average light transmittance at a wavelength of 400 to 700 nm is 70% or more, a glass transition point is 100 ° C. or more, and retardation values at wavelengths of 450 nm, 550 nm and 650 nm are Re (450) and Re, respectively.
(550) and Re (650), Re (45
0) <Re (550) <Re (650), and a gas barrier layer of a single or multi-component metal oxide glass by a sol-gel method. 2. The average light transmittance at a wavelength of 400 to 700 nm is 70% or more, the glass transition point is 100 ° C. or more, and the retardation values at wavelengths of 450 nm, 550 nm and 650 nm are Re (450) and Re, respectively.
(550) and Re (650), Re (45
0) <Re (550) <Re (650), and a gas barrier layer containing an inorganic layered compound and a single or multi-component metal oxide glass. . 3. The display device substrate according to claim 1, wherein the retardation plate contains a material having a positive intrinsic birefringence value and a material having a negative intrinsic birefringence value. 4. The display device substrate according to claim 3, wherein the material having a positive intrinsic birefringence value and the material having a negative intrinsic birefringence value are polymers. 5. The wavelength of the retardation plate is 450 nm and 550 n.
Retardation (Re) at m and 650 nm
The display device substrate according to claim 1, wherein the value of the wavelength (λ) is 0.2 to 0.3. 6. The substrate for a display device according to claim 1, wherein the inorganic layered compound is synthetic mica. 7. The aspect ratio of the inorganic layered compound is 20.
The substrate for a display device according to claim 1, which is the above. 8. The aspect ratio of the inorganic layered compound is 10.
The display device substrate according to any one of claims 1 to 7, which is 0 or more. 9. The substrate for a display device according to claim 1, wherein the inorganic layered compound is hydrophobized with a tertiary or quaternary salt compound having a hydrophobic group. 10. 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 9, which is y or less. 11. The display device substrate according to claim 1, further comprising at least one of a hard coat layer and an adhesion layer on the gas barrier layer. 12. The display device substrate according to claim 11, further comprising a transparent conductive layer on at least one of the hard coat layer and the adhesion layer. 13. The display device substrate according to claim 12, further comprising a color filter between at least one of the hard coat layer and the adhesion layer and the transparent conductive layer.