JPH0644116B2 - Electrode substrate for liquid crystal display panel - Google Patents

Description

TECHNICAL FIELD The present invention relates to an electrode substrate for a liquid crystal display panel, which has good smoothness and flatness and excellent gas resistance to oxygen, nitrogen and the like. In addition to the display device, it can also be used as an electrode for a photoconductive photoconductor, a surface heating element, or as a filter or a decorative plate for various displays from window sticking of buildings.

[Conventional technology]

In recent years, liquid crystal panels are (1) thinner, (2) lighter, (3) larger,
There are demands for (4) arbitrary shape, (5) curved surface, and (6) cost reduction, and liquid crystal panels using plastic substrates have been studied and put into practical use in order to meet these demands. The following characteristics are required for the plastic substrate for liquid crystal panel.

(1) Optically transparent in the visible light range.

(2) It is optically isotropic and does not cause coloring interference.

(3) The surface is smooth and hard.

(4) Chemical resistance and heat resistance (100 ° C or higher) that can withstand manufacturing processes such as liquid crystal assembly.

(5) Adhesion with the sealing material is good and it is airtight for a long period of time.

(6) Must be moisture permeable.

(7) Must have air resistance.

(8) It has liquid crystal resistance and is stable over a long period of time.

It is difficult to satisfy all of these characteristics, but the present inventors have already proposed a plastic substrate with a transparent electrode for liquid crystal display having these characteristics (Japanese Patent Laid-Open No. 56-1300).
(See Publication No. 10).

However, further long-term reliability and, when used under severe conditions such as automobiles, further excellent moisture resistance, especially air resistance is required. For example, it has been found that when the moisture resistance is insufficient, the power consumption increases and the liquid crystal and lung tunica membrane deteriorate. On the other hand, it has been found that when the air resistance is insufficient, air bubbles are mixed and a fixed point such as a black dot is generated on the display portion.

Among the above-mentioned drawbacks, a plastic substrate for a display device is known in which a plastic layer having a moisture permeability lower than that of the substrate is formed on at least one surface of a plastic plate for the purpose of improving the moisture resistance. -135817), fluororesin, non-polar resin, and polar resin are exemplified as the material of the plastic layer, but these have poor adhesion to the plastic substrate and discoloration due to post-process such as heat treatment. It was not practical because it had drawbacks such as

[Problems to be solved by the invention]

The present inventors have drawbacks in the above-mentioned conventional techniques, that is, in the liquid crystal display panel electrode substrate, defects such as black spots in the display portion due to air bubbles mixed due to insufficient air resistance,
Various defects that occur to further improve air resistance,
For example, as a result of earnest research and efforts to solve problems such as adhesion between the air-permeable layer and the plastic substrate and coloring of the air-permeable layer, the present invention has finally been completed.

[Means for solving problems]

That is, the present invention provides a transparent electrode on at least one surface of a composite substrate having a visible light transmittance of 60% or more prepared by coating or laminating a polymer resin layer on one or both surfaces of a non-optical rotation film or sheet having a retardation value of 100 mμ or less. An electrode substrate for a liquid crystal display panel, wherein the polymer resin layer contains a vinyl alcohol component-containing linear polymer, a vinyl alcohol component-containing graft copolymer, and a vinylidene halide component of 60 to 90 mol%. One or more selected from coalesce and oxygen permeability of 30cc
/ 24 hr · m ² · atm or less and peel strength from a non-optically rotating film or sheet is 50 g or more.

The non-optical rotatory film or sheet used in the present invention has a retardation value (R value) of 100 mμ or less, preferably 30 m.
It is less than or equal to μ. The R value is the absolute value | n1 of the difference between the film thickness d and the two diffraction rates in the direction perpendicular to the film.
It is expressed as the product of −n2 |

R = d | n1-n2 | (where n1 is the refractive index in an arbitrary direction and n2 is the refractive index in the direction orthogonal to the n1 direction) When this R value exceeds 100 mμ, the proper viewing angle as a panel becomes narrow and interference fringes occur. Occurs, the readability of the liquid crystal display device deteriorates.

A synthetic resin that should be used as a material for a film that satisfies these conditions is amorphous, and if it has crystallinity, it partially crystallizes, resulting in poor transparency and optical anisotropy. Encounters the problem of high R value. All resins satisfying such conditions can be used in the present invention, but considering the use of the present invention, it is desired that they have excellent chemical stability such as organic chemical resistance and liquid crystal resistance. Then, as the synthetic resin which can be used in the present invention, poly-4-methylpentene-1, polyacrylonitrile resin, phenoxy ether type polymer, phenoxy ether type crosslinked polymer, polyphenylene oxide type resin, epoxy type resin Resin, cellulose resin, vinyl resin, styrene copolymer resin, polycarbonate resin, polysulfone resin, polyethersulfone resin, polyarylene ester resin, polyamide, polyolefin, polyester, polymethylmethacrylate, polychlorination Vinyl, epoxy butadiene copolymer, aromatic polyether amide (see JP-A-58-208729), polychloroethylene, polyfunctional acrylate resin and the like are exemplified, but in the present invention,
A preferred synthetic resin is a phenoxyether type polymer represented by the following general formula or a phenoxyether type processed polymer obtained by crosslinking a hydrogen moiety of a hydroxyl group with a polyfunctional compound.

(Wherein R ^{1 to} R ⁶ are each hydrogen or a lower alkyl group having 1 to 3 carbon atoms, R ⁷ is a lower alkyl group having 2 to 4 carbon atoms, and m is 0
Is an integer of 3 to 3, and n is an integer of 20 to 300 respectively.) In the above general formula, examples of the lower alkyl group having 1 to 3 carbon atoms represented by R ^{1 to} R ⁶ include methyl, ethyl, propyl,
Saturated lower alkyl such as isopropyl is exemplified, and the lower alkylene group having 2 to 4 carbon atoms represented by R ⁷ includes ethylene, propylene, trimethylene and butylene.

Further, as the polyfunctional compound to be reacted to obtain a crosslinked polymer, a group having high reaction activity with a hydroxyl group, for example, an isocyanato group, a carboxy group, a reactive induction group in a carboxy group (for example, halide, active amide, active ester) ,
Acid anhydride group, etc.), mercapto group, etc.
A compound having the above, for example, tolylene diisocyanate,
Polyisocyanates such as m-phenylene diisocyanate, p-phenylene diisocyanate and 4,4'-diphenylmethane diisocyanate and their polyhydric alcohol adducts; blocked polyisocyanates such as phenol blocked tolylene diisocyanate; Adipic acid, tartaric acid, sepacic acid, phthalic acid and other polycarboxylic acids and reactive derivatives at the carboxy group; mercapto-substituted organic carboxylic acids such as thioglycolic acid; and others, epichlorohydrin, sodium thiosulfate, melamine-formaldehyde, phenol Resins, urea-formaldehyde resins and the like can also be used.

These synthetic resins are produced by the usual wet film forming method, dry film forming method,
The film is formed into a film or a sheet by the melt film forming method, but the dry film forming method is optimal in consideration of the optical isotropy of the film. The thickness of the film or sheet is usually 5 to 1
It is 000μ, preferably 20 to 200μ.

In the present invention, the polymer resin layer (hereinafter referred to as an air permeation resistant layer) constituting the composite substrate with the non-optical rotatory film or sheet has an oxygen permeability (measured according to ASTM D-1434-75) of 30 cc. / 24 hr · m ² · atm or less, preferably 20 cc / 24 hr · m ² · atm or less, and a peel strength (measured according to ASTM D1876) from a non-optically-rotating film or sheet of 50 g or more, preferably 150 g or more. If the oxygen transmission rate exceeds 30 cc / 24 hr · m ² · atm, no matter how thick the thickness may be, black spots may appear on the display due to severe conditions with severe temperature changes and long-term use, which is not preferable. When the peel strength is less than 50 g, the transparent electrode treatment in the next step or the patterning acid / alkali aqueous solution treatment for liquid crystal panel production,
It is not preferable because it peels off during the organic chemical treatment, the assembly process and the like.

The visible light transmittance of the composite substrate of the non-optical rotatory film or sheet and the air permeation resistant layer must be 60% or more. 6
If it is less than 0%, the contrast of the display portion is deteriorated, which is not preferable.

Examples of the gas-permeable polymer resin that forms the gas-permeable layer satisfying the above conditions include vinyl alcohol (hereinafter referred to as VA) component-containing linear polymer, VA component-containing graft copolymer, and vinylidene halide components 60 to 90. The copolymer etc. which contained mol% are mentioned.

The VA component-containing polymer has a VA content of 50 to 95 mol%.
If necessary, a crosslinking agent is added to the VA-containing linear and graft copolymers. The linear VA-containing copolymer includes an olefin-vinyl alcohol (hereinafter referred to as OVA) copolymer and a vinyl acetate-vinyl alcohol (hereinafter referred to as Va · VA) copolymer, and the OVA copolymer is Substituted or non-substituted fats such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl stearate, trimethyl vinyl acetate, vinyl chloroacetate, vinyl benzoate, vinyl p-methylbenzoate, etc. Vinyl ester of aromatic or aromatic carboxylic acid is copolymerized with a predetermined amount of olefin (for example, ethylene, propylene or a mixture thereof, ethylene-propylene copolymer, etc.) to give a vinyl ester.
It is obtained by obtaining an olefin-vinyl ester copolymer containing 0 to 95 mol% and saponifying this. The saponification may be complete saponification, but part of the saponified ester bond may remain. The Va / VA copolymer can be obtained by partially saponifying a vinyl acetate polymer.

As a method for saponifying an olefin-vinyl ester copolymer and a vinyl acetate polymer, the polymer is dissolved in a solvent such as methanol, ethanol or butanol, and transesterified in the presence of a small amount of acid or alkali, Alternatively, a method in which the hydrolysis reaction is carried out in the presence of an excessive amount of alkali is adopted. Here, if the VA content in the OVA copolymer or the Va · VA copolymer is less than 50 mol%, the gas permeability becomes high and sufficient air resistance cannot be obtained. On the other hand, if it exceeds 95 mol%, the moisture resistance is lowered and the gas permeability is increased due to moisture absorption.

The VA component-containing graft copolymer is a polyvinyl alcohol of 50 to 100% saponification of polyvinyl acetate (hereinafter referred to as P
This is referred to as VA) and an addition-polymerizable monomer is graft-copolymerized. If the degree of saponification is less than 50%, a stable emulsion latex cannot be obtained even if the grafted product described below is obtained. Therefore, even if it is applied, sufficient adhesion cannot be obtained and sufficient air resistance cannot be obtained.

As the addition-polymerizable monomer, a water-insoluble compound having an addition-polymerizable double bond is used. Water-insolubility is a required property for insolubilizing PVA, and it is generally recommended that the solubility in water at 20 ° C. is 10% by weight or less. With more than 10% monomer,
When the obtained graft copolymer is used, a stable emulsion dope cannot be obtained, the moisture resistance is lowered, and the gas barrier is not sufficient. Any of those that meet the above conditions can be used as the preferred monomer in the present invention. To explain with more specific examples, olefin-based monomers (such as ethylene and propylene), diene-based monomers (such as butadiene), and styrene-based monomers. Monomers (eg vinylbenzene, divinylbenzene, etc.),
Vinyl halides (eg vinyl chloride, vinyl bromide, chloroprene, etc.), vinyl acetate monomers (eg vinyl acetate etc.), acrylonitrile monomers (eg acrylonitrile etc.), vinylidene cyanide, vinyl ethers (eg methyl vinyl ether, ethyl vinyl ether) , N-butyl vinyl ether, etc.), acrylic acid ester-based monomer [eg, methyl acrylate, ethyl acrylate, n-amyl acrylate, n-propyl acrylate, tetrahydrofurfuryl acrylate, mono (2-acryloyloxyethyl) acid phosphate, etc.] , Methacrylic acid ester-based monomers [eg methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, iso-
Propyl methacrylate, sec-butyl methacrylate, n-amyl methacrylate, methoxyethyl methacrylate, n-butoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, glycyl methacrylate, 1,3-butanediol methacrylate, mono (2-methacryloyloxyethyl) acid And the like, and other substituents such as lower alkyl groups (methyl, ethyl, propyl, butyl, etc.), lower alkoxy groups (methoxy, ethoxy, propoxy, butoxy, etc.), halogens, etc. Etc. may be included.

The reaction conditions for producing a graft polymer from PVA and a polymerizable monomer are not particularly limited, but are usually cerium ammonium nitrate, cerium ammonium sulfate, potassium persulfate, ammonium persulfate, sodium persulfate. And a water-soluble polymerization initiator such as hydrogen peroxide are allowed to coexist, and the reaction is carried out in an aqueous medium. Generally, the concentration of PVA in the reaction system is preferably 2 to 50%. This is because the mixture after the reaction is used as it is as a dope for film formation, and if it is less than 2%, a film having a uniform thickness cannot be obtained. When it exceeds 50%, gelation of the dope occurs in the film formation, and it becomes impossible to obtain a uniform coating film. On the other hand, the concentration of the polymerizable monomer is preferably 1 to 70 parts by weight based on 100 parts by weight of PVA. If it is less than 1 part by weight, it has no moisture resistance, while if it exceeds 70 parts by weight, it is PVA.
And the air resistance is insufficient.

The water-soluble polymerization initiator is preferably added in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of PVA. If it is less than 0.05 parts by weight, it is difficult to start the polymerization reaction, while if it exceeds 10 parts by weight, the PVA may deteriorate due to the initiator.
This is because the graft polymerization rate rather decreases. However, the more preferable addition amount is 0.5 to 5 parts by weight based on the above-mentioned standard. The graft polymerization reaction is usually carried out under cooling or heating, and is generally 0 to 100 ° C, preferably 5 to 80 ° C.
℃ is recommended. Below 0 ℃, the polymerization rate is slow,
This is because if it exceeds the above range, the polymerization initiator is decomposed, the stability of the polymerization system is lowered, and gelation occurs.

In the reaction product thus obtained, in addition to the graft copolymer product, PVA and homopolymers of polymerizable monomers are mixed, but these can be directly used as the film substrate without separation.

Examples of the crosslinking agent added to improve the moisture resistance and chemical resistance of the VA component-containing polymer include formalin-based crosslinking agents, formalin, glyoxal, paraform, aldehydes, and N-methylol resin-based crosslinking agents. , Dimethylol ethylene urea, trimethylol melamine. Examples of the water-soluble urethane cross-linking agent include block isocyanate and water-soluble epoxy resin.
The addition amount of these cross-linking agents is 0.05 to 0.5 parts by weight, particularly 0.1 to 0.1 parts by weight based on 1 part by weight of the VA-containing polymer.
It is preferable to add 3 parts by weight. If it is less than 0.05 parts by weight with respect to 1 part by weight of the VA-containing polymer, the effect of addition will not be obtained, and if it exceeds 0.5 parts by weight, the solution tends to gel and a uniform coating film cannot be obtained.

In addition to the above, a copolymer containing a vinylidene halide component in an amount of 60 to 90 mol% is exemplified, and for example, vinylidene halide such as vinylidene chloride, vinylidene bromide, vinylidene fluoride and vinyl acetate, acrylonitrile, ethylene vinyl chloride, Examples thereof include copolymers with vinyl bromide, vinyl fluoride, styrene, vinyl acrylate and the like.
If the vinylidene halide component is less than 60 mol%, the gas permeation resistance will not be improved, while if it exceeds 90 mol%, it will be colored when heated to a high temperature, which is not preferable.

In the present invention, the air permeation resistant layer formed of the polymer resin has a thickness of 1 to 50 µ, preferably 2 to 20 µ. If it is less than 1μ, the improvement of air resistance is insufficient, and 50μ
If it exceeds, curling may occur when the composite substrate is formed, which is not preferable.

Next, in the present invention, as a method for forming a composite substrate with a non-optical rotatory film or sheet and an air permeation resistant layer,
The air-permeable polymer resin is dissolved in one or more of its solvents, coated on the non-optical rotation film or sheet surface, dried, and heat-treated to form a gas-proof layer to form a composite substrate. can get.

Among the air-permeable polymer resins, in the case of a linear copolymer containing a VA component, a mixed liquid of water and alcohol, particularly water and isopropanol (mixing ratio 1: 1), water and n-butanol (mixing ratio 1 1) and the like. In the case of the graft copolymer containing the VA component, it is applied as it is. On the other hand, when the vinylidene halide component-containing polymer is used, examples of the solvent include dimethylformamide, tetrahydrofuran, cyclohexanone, dimethylacetamide, dioxane, trichloroethane, ethylene chloride, monochlorobenzene, and methyl ethyl ketone.

As a method for applying the solution in which the air-permeable polymer resin is dissolved in the solvent, a usual method such as a roll coater, a gravure roll coater, a rod coater, an air knife coater, and a spray coater is adopted. In this way, the air-permeable polymer resin is applied and dried by a usual method to remove the solvent, and then the peel strength (ASTM D1876) 50
It is necessary to perform heat treatment in order to obtain adhesion of g or more. The heat treatment conditions may be appropriately selected depending on the film or sheet to be coated or the air-permeable polymer resin to be coated, but usually 100 ° C to 250 ° C, preferably 120 ° C to 200
It is carried out at a temperature of several minutes to several tens of minutes, but if necessary, the film to be coated is subjected to a corona treatment, and then heat is applied after coating and drying, whereby the adhesion is improved and the heat treatment effect becomes remarkable. Particularly in the case of a hardening type film or sheet, the adhesion effect by corona treatment is good. The normal heat treatment conditions for the air-permeable polymer resin used are 150 to 2 for the linear copolymer containing the VA component.
20 ° C., several minutes to several tens of minutes, 120 in the case of a resin containing a VA component-containing graft copolymer and a vinylidene halide component.
C. to 160.degree. C., preferably several minutes to several tens of minutes. In either case, if the heat treatment conditions are insufficient, sufficient adhesion cannot be obtained, and if the heat treatment is performed severely, coloring occurs and the resulting composite film has a visible light transmittance of less than 60%, which is preferable. Absent.

The method for producing the composite substrate of the present invention is not limited to the above-mentioned method, and a gas permeable polymer resin film is formed, and a non-optical rotatory film or sheet is closely formed on at least one surface of the film. A composite substrate can be obtained. For example, a polyester film is coated with a mixed solution of ethylene / vinyl alcohol copolymer (molar ratio 30/70) in water and isopropyl alcohol and dried to form an air-permeable film, and then a phenoxy resin / tolylene diisocyanate is formed on the film. A composite substrate is obtained by applying the solution of (1), drying it, and then heat-treating it to remove the polyester film.

Next, to prepare an electrode substrate for a liquid crystal display panel of the present invention,
A transparent conductive layer is formed on one side or both sides of the composite substrate obtained by the above method to impart transparent conductivity. The forming method may be a known method or a new method to be developed in the future, but as a typical method, a vacuum deposition method, a sputtering method, an ion plating method, a metal spraying method, a metal plating method or the like is adopted. To be done. Among these, the vacuum deposition method and the sputtering method are recommended for satisfying the two points of forming a thin layer and forming a uniform layer. As the material for forming the conductive layer, Sn, In,
Metals such as Ti and Pb or oxides thereof are generally used, and when a simple substance of metal is formed on the substrate by the above method, it may be oxidized thereafter if desired. There is also a method of depositing and forming as an oxide layer from the beginning, but first, a film is formed in the form of a simple metal or a lower oxide, and then subjected to an oxidation treatment such as heating oxidation, anodic oxidation or liquid phase oxidation. It is also possible to employ a transparent means. In addition to the above, noble metals such as Au, Pt and Ag may be used. Also, the conductive layer made of these metals or their oxides should have a layer thickness according to the required characteristics such as transparency and conductivity, but usually 100 Å or more, 300 Å or more to give stable conductivity. Is desired.

The above-mentioned conductive layer may be usually a single layer, but it may be formed as a plurality of two or more layers in consideration of mechanical strength and chemical resistance. Further, the uniformity and adhesion of the coating, and further abrasion resistance and the like. An undercoat or overcoat may be applied for the purpose of improving Silicon-based and epoxy-based resins are used as the former example, and gelatin is used as the latter example.
Silicon, corrosion, etc. are used. If necessary, a layer of a photoconductive substance or a layer of an electroluminescence material may be further formed on these.

Next, the present invention will be described with reference to the drawings.

FIG. 1 is a sectional view of a liquid crystal display panel manufactured using the electrode substrate of the present invention. Reference numeral 1 is a liquid crystal, 2 is a transparent conductive film, 3 is a non-optical rotatory film, 4 is an air permeation resistant layer, 5 is a polarizing plate, and even if there is an adhesive layer between the polarizing plate 5 and the air permeation resistant layer 4. Good. 2 to 5 are cross-sectional views of various embodiments of the liquid crystal display panel electrode substrate of the present invention. Figure 2 shows the air-permeable layer 4
Is formed on the transparent conductive film 2 side, and in FIG. 3, it is formed on both sides of the non-optical rotatory film 3. FIG. 4 shows that an anchor agent layer such as a silane coupling agent is provided between the transparent conductive film 2 and the composite substrate (non-optically rotatory film 3 + permeation resistant layer 4) to strengthen the adhesiveness. FIG. 5 shows an example in which a reinforcing layer such as polyether sulfone, polyester, or polyarylate is formed as a composite substrate to further improve heat resistance, moisture resistance or brittleness, and the position of the reinforcing layer is arbitrary. Is.

(Examples) The present invention will be specifically described below with reference to examples. In addition,
The retardation value was measured using a Senarmont convensor equipped with a polarizing microscope (manufactured by Japan Chika Co., Ltd.) and a sodium lamp as a light source.

Peel strength according to ASTM D1876, Tensilon UTM
-3L (manufactured by Toyo Baldwin), 20 ° C, 6
The T-type peel strength was measured at 5% RH and a sample width of 25 mm.

Oxygen permeability is measured according to ASTM D1434 / 75, using industrial and industrial trial type gas permeability measuring device (manufactured by Rika Seiki Engineering Co., Ltd.).
It was measured in% RH. In addition, "parts in the examples" means "parts by weight".

Example 1 40 parts of phenoxy resin (manufactured by Union Carbide Co.) was mixed with methyl ethyl ketone / cellosolve acetate (65/3).
(5 wt.%), Dissolved in 60 parts by heating, cooled to room temperature, added with 40 parts of Coronate L (polyfunctional isocyanate, made by Nippon Polyurethane), and the stirred homogeneous solution was cast on a polyester film of 50 μm at 80 ° C. for 10 minutes. After drying for a minute, peel it from the polyester film and fix it in a metal frame 160
After heat-setting at 30 ° C. for 30 minutes, the thickness is 105 μ, the retardation value is 8 nm, and the visible light transmittance is good (400 mμ: 87).
%, 500 mμ: 91%) of a non-optical rotatory film was obtained.
One side of the obtained non-optical rotatory film was subjected to corona treatment with an applied voltage of 160 V, an applicator was used on this corona surface, and a gas-permeable polymer resin solution described below was formed into a gap of 150 μ using a doctor knife. After applying 70 ℃,
Dry for 10 minutes, then fix to a metal frame at 200 ° C for 10
Heat treated for minutes. The thickness of the obtained composite substrate is 120μ.
(Gas barrier layer thickness: about 15μ), good visible light transmittance (400mμ: 86%, 500mμ: 90%),
The heat resistance, liquid crystal resistance, and chemical resistance were good, and the retardation value was 9 nm. When the peel strength between the non-optical rotatory film and the air permeation resistant layer of this composite substrate was measured, it was not peeled at all, and cohesive failure occurred. And the gas permeability is 2c
It was extremely good at c / 24 h · m ² · atm. Air-permeable polymer resin solution (liquid A) A 0.08% solution of tetraoctyl titanate in n-hexane was applied to the surface of the obtained composite substrate opposite to the air-permeable layer,
It was heated at 100 ° C. for 10 minutes to perform a primer treatment, and a transparent conductive film treatment was performed with a low temperature sputtering device under the following conditions.
The thickness of the conductive film layer is 280Å and the resistance value is 610 Ω / cm ^2.
Met.

[Transparent conductive film processing conditions]

The obtained electrode substrate had a visible light transmittance of 400 mμ and was 78
%, Good at 84% at 500 mμ, good liquid crystal resistance, chemical resistance, and air resistance of 2 cc / 24 before transparent electrode treatment.
It was h · m ² and atm. When a liquid crystal display panel was produced using the electrode substrate and a reliability test was carried out, the same good display performance as that before the test was obtained.

Example 2 The same air-permeable polymer resin solution (solution A) as in Example 1 was applied onto a biaxially stretched polyester film and dried to obtain a film having a thickness of 16 μm. Then, the curing solution of the phenoxy resin used in Example 1 was applied onto this film, dried, and then peeled from the polyester film and fixed on a metal frame and heat-treated at 210 ° C. for 10 minutes. The obtained composite substrate had a thickness of 106 μ and a retardation value of 3 nm. When a peeling test was performed on the composite surface of the composite substrate, peeling was impossible, cohesive failure occurred, and adhesion was good. On the other hand, the air permeation resistance is 1.5cc / 24h ・ m ²・ atm (25
C, 0% RH).

Then, on the side opposite to the air-permeable layer, under the same conditions as in Example 1,
A transparent conductive film treatment was performed to obtain an electrode substrate.

Example 3 A non-optical rotatory (retardation value: 8 nm) phenoxy resin cured film having a thickness of 105 μm obtained in Example 1 was coated with an applicator on one side of the following air-permeable resin solution (solution B), C., and dried for 15 minutes. This composite film was fixed on a metal frame and heat-treated at 130 ° C. for 2 hours. The obtained composite substrate had a thickness of 120 μ (permeation-resistant layer thickness: about 15 μ), retardation value of 8 nm, and good visible light transmittance (400 mμ: 86%, 500 mμ: 90%).
Met. The air-permeable layer of this composite substrate has an adhesion of 350 g.
/ 25mm, oxygen gas permeability is 2cc / 24hr · m ²
・ It was atm. Then, a transparent conductive film treatment was performed on the surface opposite to the air permeation resistant layer under the same conditions as in Example 1 to obtain an electrode substrate. Air-permeable polymer resin solution (B liquid) Example 4 The non-optical rotatory film having a thickness of 105 μm used in Example 1 was corona-treated on one side with an applied voltage of 160V. On the other hand, polyvinyl alcohol (Nippon Gosei Kagaku: Gosenol NH-2
0) 100 parts of an aqueous solution of a copolymer obtained by grafting 10 parts of glycidyl methacrylate and 10 parts of butyl acrylate in the presence of cerium nitrate (11 wt%) Sumitex Range M3 (methylol melamine condensate: Sumitomo Chemical Co., Ltd.) 2 0.5 parts and 1 part of Sumitex Accelerator MX (manufactured by Sumitomo Chemical Co., Ltd.) were added and stirred to prepare a uniform mixed solution. The mixed solution was cast on the corona-treated surface of the non-optical rotation film and dried at 80 ° C. for 5 minutes.
After heat treatment at 0 ° C. for 10 minutes, the thickness is 117 μ (thickness of gas and barrier layer: about 12 μ), retardation value is 7 nm,
Good visible light transmittance (400mμ: 82%, 500m
A composite substrate of μ: 86%) was obtained. The peel strength between the air-permeable layer and the non-optical rotatory film of the composite substrate was 342 gr / 25 m.
Oxygen gas permeability of 2.5 cc / 24 hr · m ² · at
It was m. Then, a transparent conductive film treatment was performed on the surface opposite to the air permeation resistant layer under the same conditions as in Example 1 to obtain an electrode substrate.

Comparative Example The solution for a cured phenoxy resin film used in Example 1 was cast on a polyester film under the same conditions as in Example 1 and dried at 80 ° C. for 10 minutes, and then at 100 ° C. for 5 minutes to remove the polyester film from the polyester film. Peeled off. This film was fixed to a metal frame in the same manner as in Example 1 and heat-treated at 160 ° C. for 30 minutes to have a thickness of 125 μ and a retardation value of 9 nm visible light transmittance (400 mμ: 86%, 500 mμ: 90).
%) A good non-optical rotatory film was obtained. The oxygen gas permeability of this film was 45 cc / 24 h · m ² · atm. Then, a transparent conductive film was formed on one surface of the non-optical rotatory film under the same processing conditions as in Example 1. Conductive layer thickness 36
0Å resistance value 500Ω / cm ² , visible light transmittance 400mμ
79%, 85% at 500 mμ, liquid crystal resistance, chemical resistance,
Although an electrode substrate having good heat resistance was obtained, the oxygen gas permeability of the substrate was still 45 cc / 24 h · m ² · atm.

Next, a liquid crystal display panel was produced using the electrode substrate in the same manner as in Example 1, and the panel was subjected to a cycle test at −20 to 100 ° C., whereupon black spots due to air permeation occurred in the display part and before the test. It was found that the display ability was lower than that of the conventional one, and the air permeation resistance of the electrode substrate was insufficient.

(Effects of the Invention) As described above, the electrode substrate for a liquid crystal display panel of the present invention having such a configuration is (1) optically transparent in the visible light region.

(2) It is optically isotropic and does not cause coloring interference.

(3) The surface is smooth and hard.

(4) Chemical resistance and heat resistance (100 ° C or higher) that can withstand manufacturing processes such as liquid crystal assembly.

(5) Adhesion with the sealing material is good and it is airtight for a long period of time.

(6) Must be moisture permeable.

(7) Must have air resistance.

(8) It has liquid crystal resistance and is stable over a long period of time. Since the liquid crystal display panel using the substrate of the present invention can withstand harsh indoor and outdoor conditions and long-term use because it has features such as There are no black spots due to mixing, so for the first time,
It could be put on the market as a liquid crystal display panel using a plastic substrate.

[Brief description of drawings]

FIG. 1 is a sectional view of a liquid crystal display panel manufactured by using the electrode substrate of the present invention, and FIGS. 2 to 5 are sectional views of various embodiments of the electrode substrate of the present invention. 1: Liquid crystal 2: Transparent conductive film 3: Non-optical rotatory film 4: Air permeation resistant layer 5: Polarizing plate 6: Anchor layer 7: Strengthening layer

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Claims (2)

[Claims] 1. A transparent electrode is provided on at least one surface of a composite substrate having a visible light transmittance of 60% or more obtained by coating or laminating a polymer resin layer on one or both surfaces of a non-optically rotating film or sheet having a retardation value of 100 mμ or less. An electrode substrate for a liquid crystal display panel, wherein the polymer resin layer contains a vinyl alcohol component-containing linear polymer, a vinyl alcohol component-containing graft copolymer, and a vinylidene halide component of 60 to 90 mol%. One or more selected from coalesce and oxygen permeability of 30cc
/ 24 h · m ² · atm or less and peel strength from a non-optically rotating film or sheet is 50 g / 25 mm or more, an electrode substrate for a liquid crystal display panel. 2. The electrode substrate for a liquid crystal display panel according to claim 1, wherein an anchor agent is present between the non-optical rotatory film or sheet or the polymer resin layer and the transparent electrode.