JPH0268519A - Reactive air permeation resistant polymer for production of electrode substrate for liquid crystal display panel and electrode substrate for liquid crystal display panel using the same - Google Patents

Abstract

PURPOSE:To maintain stable performance over a long period of time even under severe use conditions by using the reactive air permeation resistant polymer formed by polymerizing a monomer mixture consisting of a specific ethylenic unsatd. amide monomer and a vinyl polymerizable monomer in the copresence of a vinyl alcohol polymer as a substrate material. CONSTITUTION:The monomer mixture (M) consisting of the ethylenic unsatd. amide monomer (Ma) expressed by formula I and the vinyl polymerizable monomer (Mb) having a carboxyl group in the molecule is polymerized in the copresence of the vinyl alcohol polymer (V) to obtain the reactive air permeation resistant polymer. In formula I, R<1>, R<2> are H or lower alkyl group; R<3> is 1 to 4C alkylene group. The molar ratio of (Ma)/(Mb) or this reactive air permeation resistant polymer (Ma)/(Mb) is 0.05 to 5.0 and the weight ratio of (M)/(V) is 0.02 to 0.5. The layer 2 consisting of such reactive air permeation resistant polymer is provided on one or both surfaces of a base material layer consisting of a non-optically active transparent film or sheet having <=80nm retardation value, by which the electrode substrate is formed.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a reactive air permeation-resistant polymer suitable for manufacturing an electrode substrate for a liquid crystal display panel and an electrode substrate for a liquid crystal display panel using the same.

Conventional technology In recent years, liquid crystal display panels have become thinner, lighter, and lighter.
There are demands for ■larger size, ■arbitrary shapes, ■curved surfaces, and ■lower costs.As a response to these demands, liquid crystal display panels using plastic substrates have been studied and put into practical use.

One of the present inventors has also made inventions related to plastic 6x substrates for this purpose, which are listed in the following patent applications.

In other words, a transparent conductive film in which a transparent conductive layer is provided on a non-optically active film formed from a phenoxy ether crosslinked polymer (Japanese Patent Publication No. 61-27841), a copolymer containing a styrene derivative component, or a derivative containing an acrylonitrile component. A transparent conductive film in which a transparent conductive layer is provided on a non-optically active film formed from
A conductive film for liquid crystal displays in which a transparent conductive layer is formed on a composite film obtained by coating an amorphous synthetic resin film with a retardation value of 30 nm or less with a curable resin or a monomer and then curing the film (Japanese Patent Laid-Open No. 1983-1999) 11319), a colored conductive film in which a transparent conductive layer is formed on a colored non-optically active film using a phenoxy ether type polymer (JP-A-60-35409)
(Japanese Patent Application Laid-Open No. 60-158420), a non-optically active film formed from a curable resin composition containing an epoxy compound and a carboxyl group-containing photopolymerizable compound (Japanese Patent Application Laid-open No. 158420/1983), a transparent conductive layer on a plasma-treated polymer film. A curable polymer film is formed on a non-optically active film formed from a phenoxy ether type crosslinked polymer (Japanese Patent Application Laid-Open No. 60-230307), and a transparent conductive layer is further provided on the non-optically active film. transparent conductive film (Japanese Unexamined Patent Publication No. 60-232612), an electrode substrate for a liquid crystal display panel in which a non-optically active film with a retardation value of 1100 n or less is provided with a polymer resin layer having air permeability, and a transparent electrode is further provided. (Unexamined Japanese Patent Publication No. 61-41122), retardation value 30n
A liquid crystal display in which a transparent electrode is provided on a composite substrate on which an aqueous anchor coating layer of a non-optically active film with a diameter of less than m is formed, and then a protective layer made of an air-permeable resin or/and a cured cross-linked resin is provided thereon. Electrode substrate for panels (Unexamined Japanese Patent Publication No. 6
3-71829), especially the last two cases,
In other words, JP-A-61-41122 and JP-A-63-7
The invention described in Publication No. 1829 is important.

Problems to be Solved by the Invention Plastic substrates for liquid crystal display panels are generally required to have the following characteristics.

(1) Be optically transparent in the visible light range.

(2) It should be optically isotropic and should not produce colored interference fringes.

(3) The surface is smooth and hard.

(4) It must have chemical resistance that can withstand manufacturing processes such as liquid crystal assembly, and heat resistance of 100°C or higher.

(5) Good adhesion with the sealing material and long-term airtightness.

(6) Must be moisture permeable.

(7) Must be air permeable.

(8) It should have liquid crystal resistance and be stable over a long period of time.

Especially when long-term reliability is required or when used under harsh conditions such as in automobiles, it is important to not only have excellent air permeability but also to have low humidity dependence (even under high humidity). It is required that there is no decrease in air permeability), and further excellent adhesion to living rooms, liquid crystal resistance, and heat resistance is required. If all of these requirements are not met, problems will occur, such as air bubbles being mixed in and causing black spots on the marking section, and stable performance not being achieved over a long period of time.

However, conventional plastic substrates for liquid crystal display panels do not necessarily meet such strict requirements.

In an attempt to further improve the invention described in JP-A-61-41122 and JP-A-63-71829, the present inventors discovered a specific reactive air-permeable polymer as an air-permeable layer. By using this layer, we have found an electrode substrate that can fully meet the above requirements.

Means for Solving the Problems The reactive air permeability resistant polymer for producing an electrode substrate for a liquid crystal display panel of the present invention has the following formula (where Hl, R7- is A monomer mixture consisting of an ethylenically unsaturated amide monomer (Ha) represented by H or a lower alkyl group, R3 is a fullkylene group having 1 to 4 carbon atoms) and a vinyl polymerizable monomer (Mb) having a carboxyl group in the molecule. It is obtained by polymerizing M).

Further, the electrode substrate for a liquid crystal display panel of the present invention is as follows.

It has a laminated structure in which an air permeation resistant layer (2) is provided on one or both sides of a base layer (1) made of a non-optically active transparent film or sheet with a retardation value of 80 nm or less, and the air permeation resistance of the laminate is In an electrode substrate for forming a substrate for a liquid crystal display panel by providing a transparent electrode on the layer (2) side surface, the air permeation resistant layer (2) is made of the above reactive air permeation resistant polymer (P). It is characterized by being composed of layers.

Furthermore, the electrode substrate for a liquid crystal display panel of the present invention is provided with an air permeable layer (2) on one or both sides of the base layer (1) made of a non-optically active transparent film or sheet with a retardation value of 80 nm or less, Furthermore, a crosslinkable resin cured product (C) is applied on at least one of the air permeable layers (2).
It has a laminated structure in which a protective layer (3) is provided, and a transparent electrode is provided on the surface of the laminate on the protective layer (3) side or on the surface of the air-permeable layer (2) side. In the electrode substrate for use as a substrate, the air permeability layer (2)
is characterized by comprising a layer of the above-mentioned reactive air-permeable polymer (P).

The present invention will be explained in detail below.

The base layer (1) is composed of a non-optically active transparent film or sheet having a retardation value of 80 nm or less, particularly 30 nm or less.

Here, the retardation value (R) is as shown in the following formula,
The thickness d of the film and 2 in the direction perpendicular to the film
This is the value expressed as the product of the absolute value of the difference between the two refractive indices.

R=d*ln'-n" 1 (where nl is the refractive index in any direction, R2- is the refractive index perpendicular to the n1 direction), and if the turbulence value exceeds 80 nm, the appropriate viewing angle for the panel is As the width becomes narrower, interference fringes occur, and when applied to a liquid crystal display device, the readability deteriorates.

The resin that should be used as the material for the film or sheet that satisfies these conditions is of inferior quality, and if it has crystallinity, it will partially crystallize, resulting in poor transparency and optical anisotropy. The problem is that the retardation value becomes high.

Specific examples of the base layer (1) include layers formed from resins such as polycarbonate resin, polyethersulfone resin, polysulfone resin, polyarylene ester resin, polyparabanic acid resin, and polyimide resin. It will be done.

The air permeable layer (2) is made of vinyl alcohol polymer (V).
in the coexistence of 1 formula (wherein R and R are H or a lower alkyl group.

A monomer mixture CM) consisting of an ethylenically unsaturated amide monomer (Ma) represented by R is a fullkylene group having 1 to 4 carbon atoms and a vinyl polymerizable monomer (Mb) having a carboxyl group in the molecule is polymerized. It consists of a layer of reactive air permeability polymer (P) obtained by

Here, as the vinyl alcohol polymer (V), ■ polyvinyl alcohol with various degrees of polymerization and saponification, ■ α-olefin, ethylenically unsaturated carboxylic acid or its ester, acrylonitrile, methacrylonitrile, acrylamide, methacryl Copolymerized modified polyvinyl alcohols modified with any comonomer that can be copolymerized with vinyl acetate, including amides, ■ Post-modified products of these polyvinyl alcohols or copolymerized modified polyvinyl alcohols (e.g., acetalized or urethanized products), etc. .

Among these, ethylene-vinyl alcohol copolymers obtained by saponifying the vinyl acetate units of ethylene-vinyl acetate copolymers with an ethylene content of 20 to 60 mol% are 70 mol% or more, and even 90 mol% or more. It is particularly useful because it has excellent properties in terms of both water resistance and air permeability, and polyvinyl alcohol is also practically useful.

As the ethylenically unsaturated amide monomer (Ma) represented by formula (i), N-hydroxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-hydroxypropyl (meth)acrylamide, N-methoxy Methyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-propoxyethyl (meth)acrylamide, N-butoxymethyl (
meth)acrylamide, N-methoxyethyl (meth)acrylamide, N-ethoxyethyl (meth)acrylamide, N-propoxyethyl (meth)acrylamide,
Examples include N-butoxyethyl (meth)acrylamide, N-methoxypropyl (meth)acrylamide, N-ethoxypropyl (meth)acrylamide, N-propoxypropyl (meth)acrylamide, and N-butoxypropyl (meth)acrylamide.

Examples of the vinyl polymerizable monomer (Mb) having a carboxyl group in the molecule include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; ethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid. Acids, monoalkyl esters thereof, g-hydrates thereof (fumaric acid is excluded because it does not form anhydrides); unsaturated tricarboxylic acids represented by the formula 0; and the like.

The reactive air-permeable polymer (P) is typically prepared by combining the vinyl alcohol-based polymer (V) with water or/and a solvent such as a lower alcohol (e.g., water, water/n-propanol, water/isopropanol). In the solution, an ethylenically unsaturated amide monomer (Ma) and a carboxy Jjkz group-containing vinyl polymerizable 7 It can be obtained by polymerizing a monomer mixture (M) consisting of Mb and Mb. It is believed that graft polymerization occurs at least partially through such polymerization.

In this case, the molar ratio of (Ma)/(Mb) is 0.05
It is preferable to set it within the range of ~5.0; if it deviates from this range, the reactive air permeability resistant polymer (P) obtained by polymerization will lack crosslinking points, so when the humidity increases, the air permeability may decrease. , which may adversely affect adhesion.

In addition, the (M)/(V)(7) weight ratio is 0.02 to 0.
5 (7) It is preferable that the ratio be within the range; if the ratio is too small, the reactive air permeability resistant polymer (P) obtained by polymerization will lack crosslinking points, while if it is too large, its air permeability will be impaired. become.

The oxygen permeability (AS) of the air permeable layer (2) made of the reactive air permeable polymer (P) thus obtained is
Measured according to TM D-1434-75) is 30cc/
The type of polymerization raw material or the charging ratio is set so that it is less than 24hr * rn" * atm, preferably less than 20cc/24hr@go・atm. If the oxygen permeability exceeds 30cc/24hr * m"eat11, the temperature There is a risk that black spots may appear on the display due to harsh conditions that are subject to severe changes or long-term use.

Ho 1 Suiyu” Tsu- The protective layer (3) is composed of a cured crosslinkable resin (C).

This protective layer (3) is an optional layer provided as necessary.

Examples of the crosslinkable resin cured product (C) include cured products of phenoxy ether type crosslinkable resins, epoxy resins, acrylic resins, melamine resins, phenol resins, urethane resins, and the like.

A particularly preferred resin among the crosslinkable resins is a phenoxy ether type polymer. A phenoxy ether type crosslinked polymer is obtained by subjecting the hydrogen moieties of the hydroxyl groups of this polymer to a crosslinking reaction with a polyfunctional compound as a crosslinking agent. The cross-linking agent (polyfunctional compound) to be reacted to obtain a cross-linked polymer is a group having a high reaction activity with a hydroxyl group, such as an incyanate group, a carboxyl group, or a reactive derivative group in a carboxyl group (such as a halide). , active amide, active ester, acid anhydride group, etc.), mercapto groups, etc., and compounds having two or more of the same or different mercapto groups.

Other preferred crosslinkable resins are acrylic resins. The resin is mainly composed of a polyfunctional unsaturated monomer containing a compound containing at least three or more acryloyloxy groups or/and methacryloyloxy groups in the molecule or/and its initial radical reactant. Examples include compositions that have the following properties.

Anchor coating 4 Anchor coating layer ( 4) can be interposed.

The anchor coating layer (4) is urethane-based,
Ordinary organic solvent types such as epoxy, polyester, and acrylic can also be used, but in particular, an anchor coating layer (4) is interposed between the base layer (1) and the air permeability layer (2). In this case, it is desirable to form the core layer (4) using an anchoring agent dissolved or dispersed in water or an aqueous medium consisting of water and alcohol.

Among such aqueous-based anchoring agents, polymers are polymerized with at least one type of bonding group selected from the group consisting of ester bonds, amide bonds, urethane bonds, and ether bonds, and are polymers that are polymerized by at least one type of bonding group selected from the group consisting of ester bonds, amide bonds, urethane bonds, and ether bonds. It is best to use a polymer based on a polymer having a sufficient amount of parent groups in the molecule to dissolve or disperse it in the medium. Examples of such parent groups include sulfonic acid metal bases, carboxyl groups, 1
Examples include a secondary amine group, a secondary amine group, a tertiary amine group, and a quaternary ammonium base. Anchor agents include
In addition to the main ingredient, water or a water-soluble organic solvent, a surfactant, a basic neutralizing agent, etc. can be included.

Typical examples of polymers containing parent wood groups in the molecule include polyester resins containing the above parent wood groups, polyamide resins containing the above parent wood groups, polyurethane resins containing the above parent wood groups, and polyurethane resins containing the above parent wood groups. Examples include polyester urethane resin containing parent wood groups, and ionic polymer complexes consisting of a mixture of polyethyleneimine, polyacrylic acid, and modified starch.

Good: The electrode substrate for a liquid crystal display panel of the present invention has the following laminated structure.

■ Base material layer (1)/Air permeability layer (2) ■ Air permeability layer (2)/Base material layer (1)/Air permeability layer (2)
) ■ Base layer (1) / Air permeable layer (2) / Protective layer ■ Air permeable layer (2) / Base layer (1) / Air permeable layer (2) / Protective layer (3) ■ Protection Layer (3)/Air permeability layer (2)/Base layer (1)/
ITFt air permeable layer (2)/protective layer (3) between the base layer (1) and the air permeable layer (2), the air permeable layer (2) and the protective layer (
3), an anchor coating layer (
As mentioned above, 4) can be intervened.

1 to 5 are cross-sectional views showing examples of the electrode substrate of the present invention.
, FIG. 4 corresponds to the above (2), and FIG. 5 corresponds to the above (2). In addition, in each figure, the case where the anchor coating layer (4) was interposed between the base material layer (1) and the air-permeable layer (2) was shown as a typical example. In each figure, the virtual line (5
) is a transparent electrode.

The base material layer (1) is formed by a wet film forming method (casting), a dry film forming method, a melt film forming method, or the like. Base material layer (1
) is suitably about 20 to 1000 m thick.

When providing the anchor coating layer (4) on the base layer (1), an anchor agent is applied onto the base layer (1), dried, and heat-treated if necessary. The thickness of the anchor coating layer (4) is often about 0.5 to 5 ILm.

Directly or anchor coating layer (
4) To form the air-permeable layer (2) through the layer, the reactive air-permeable polymer (P) is dissolved or dispersed in the solvent (usually the polymer solution is used as it is or after adjusting the concentration). ), it can be applied directly to the base layer (1) and dried, or it can be applied to the anchor coating layer (4), dried, and then heat-treated.However, when providing the protective layer (3), this heat treatment is sufficient. This can also serve as a heat treatment for curing the protective layer (3).

The thickness of the air permeable layer (2) (thickness of one layer) is 1 to 50 JL
11, preferably in the range of 2 to 20 lm. If it is less than 1 layer, the air permeability will be insufficient, and if it exceeds 50 layers, it will tend to curl when forming a substrate and will be disadvantageous in terms of cost.

Peel strength (A
STM D-1878 standard measurement) is 50g or more,
It is preferably 150 g or more, more preferably 200 g or more. If the peel strength is less than 50g, it may be necessary to use transparent electrode treatment in the next process, pattern formation for liquid crystal panel manufacturing, acid,
In processes such as alkaline aqueous solution treatment, organic chemical treatment, and assembly process, the air permeable layer (2) (or the air permeable layer (2) and the J layer (3)) may peel off from the base layer (1). There is a risk that the product may become damaged. Therefore, the base material layer (1) and the air permeability layer (
When the peel strength between 2) and 2) is insufficient, it is preferable to provide an anchor coating layer (4) as described above.

In addition, if the anchor coating layer (4) is formed using an anchor agent dissolved or dispersed in water or a water-alcohol mixed solvent, the solvent in the subsequent process will be used to form the base material layer (4).
1) It is possible to reliably prevent the surface from being corroded.

When providing the protective layer (3), its formation also depends on the air permeability layer (
2) It can be carried out in the same manner as in the case of formation.

When forming the protective layer (3) on the air permeability M (2), use a crosslinking agent that can crosslink the crosslinkable resin and also react with the air permeability layer (2). Strong living room adhesion can be obtained without intervening the anchor coating layer (4). For example, if a phenoxy ether type crosslinkable resin containing a phenoxy ether type polymer and a polyisocyanate is used as the protective layer (3),
Even without intervening the anchor coating layer (4), strong adhesion with the air-permeable layer (2) can be obtained to the extent that it cannot be peeled off (to the extent that it causes destruction of the base material).

The thickness of the protective layer (3) (thickness of one layer) is set in the range of 1 to 100 mm, preferably 5 to 500 mm.

Within this range, liquid crystal resistance and light weight can be suitably ensured.

Although the overall thickness of the electrode substrate of the present invention having the laminated structure of (1) to (4) above may vary widely, it is suitably about 50 to 500 gm. The visible light transmittance of the entire electrode substrate needs to be 60% or more, preferably 70% or more, and if it is less than 60%, the contrast of the display portion will deteriorate.

A transparent conductive layer is formed on one or both sides of the electrode substrate obtained above to form a transparent electrode (5). ■ and ■ above
In case 2, a transparent electrode (5) is provided on the surface facing the air-permeable layer (2), and in cases 1 and 2, a transparent electrode (5) is provided on the surface facing the protective layer (3). In the case of ■ above, protective layer (3)
A transparent electrode (
5) may be provided.

Although any method may be used to form the transparent conductive layer, typical methods include vacuum evaporation, sputtering, ion blasting, metal spraying, and metal plating. Among these, the vacuum evaporation method and the sputtering method are particularly recommended as they satisfy the two requirements of being able to form a thin layer and being able to form a uniform layer.

Examples of materials for forming the transparent conductive layer include Sn and In.
, Ti, Pb, or their oxides are commonly used, and when a single metal is formed on a substrate by the above method, it may be oxidized afterwards as desired. There is also a method of depositing it as an oxide layer from the beginning, but first a film is formed in the form of a single metal or a lower oxide, and then it is made transparent by performing oxidation treatment such as thermal oxidation, anodic oxidation, or liquid phase oxidation. It is also possible to adopt means to do so.

In addition to the above, noble metals such as Au, Pt, and Ag may also be used.

The thickness of the conductive layer made of these metals or their oxides is set according to the required characteristics such as transparency and conductivity.1 Usually, the thickness is 100A or more, and in order to provide stable conductivity, the thickness is 3ooA or more. It is desirable to do so.

The above-mentioned conductive layer may normally be a single layer, but may also be formed as a plurality of layers of two or more layers in consideration of mechanical strength and chemical resistance. In addition, in order to improve the uniformity and adhesion of the film, as well as its abrasion resistance, undercoat and O/(
- May be coated. Examples of the former include silicone-based and epoxy-based resins, and examples of the latter include gelatin, silicone, collodion, and the like. Furthermore, if necessary, a layer of photovoltaic groove material or a layer of electroluminescent material may be further formed on these.

The electrode substrate of the present invention can be used not only for liquid crystal display devices, but also as filters and decorative plates for various displays such as electrodes for photoconductive photoreceptors, surface heating elements, and building window panels.

Function In the present invention, the air permeation resistant layer (2) is a layer of a specific reactive air permeation resistant polymer (P), that is, a layer represented by formula (i) in the coexistence of a vinyl alcohol polymer (V). A layer of a reactive air permeable polymer (P) obtained by polymerizing a monomer mixture (M) consisting of an ethylenically unsaturated amide monomer (Ma) and a vinyl polymerizable monomer (Mb) having a carboxyl group in the molecule. is used.

Since the reactive air-permeable polymer (P) becomes three-dimensional by heating, its humidity dependence is reduced while maintaining its air-permeability.

Therefore, the air permeable layer (2) has good adhesion to the base layer (1) even under high humidity, has a small decrease in air resistance even under high humidity, and has good heat resistance and Liquid crystallinity is also further improved. Therefore, the transparent electrode (
5), and when a liquid crystal display panel is manufactured, reliability is maintained over a long period of time.

Example Next, the present invention will be further explained with reference to Examples.

Example 1 A polycarbonate film (manufactured by Mitsubishi Gas Chemical Co., Ltd.) having a film thickness of 80 gm and a retardation value of 20 nm was prepared.

Anchor Coaching 4 An aqueous dispersion with a solid content of 40% based on anchor polyester urethane (NeoRezR-9314, manufactured by Kusumoto Kasei Co., Ltd.) was diluted with water to make 100 parts of an aqueous dispersion with a solid content of 20%. An anchor agent was prepared by blending 2.5 parts of a water-soluble epoxy curing agent (World Lock X-2030, manufactured by Kyoritsu Kagaku Sangyo Co., Ltd.).

A fourth flask equipped with a polymer stirrer, thermometer, reflux condenser, and nitrogen inlet tube was charged with 137.5 g of n-propanol and 112.5 g of purified water, and while stirring, ethylene-vinyl alcohol (mol. ratio 32/68) copolymer (
EVAL EP-F IOIA) 5 manufactured by Kuraray Co., Ltd.
Added 0g. The system was stirred for about 4 hours while heating at 70 to 80°C to completely dissolve the ethylene-vinyl alcohol copolymer.

The system was cooled to 40 to 50°C, 2.5 g of N-methoxymethylacrylamide and 1.0 g of methacrylic acid were added, and oxygen in the system was sufficiently expelled by passing nitrogen through the system. 2.0 g of a 4% aqueous ammonium persulfate solution was added and stirred well, and 5 minutes later, 2.0 g of a 2% aqueous sodium bisulfite solution was added to initiate polymerization. The initiator was added every 2 hours in the same manner as above, and polymerization was carried out for about 8 hours. During this time, the internal temperature was 40-50'
It was held at 0.

This resulted in a viscous, translucent, reactive, air-resistant polymer liquid of approximately 16% solids.

3's A crosslinkable resin liquid having the following composition was prepared.

On one side of the above polycarbonate film (1), 0
．． The above anchor agent was applied using a 1 mmφ wire round doctor and dried at 120° C. for 2 minutes to form an anchor coating layer (4) with a thickness of 1.5 pm.

On this anchor coating layer (4), the above-mentioned reactive air permeability resistant polymer liquid was applied using an applicator with a gap of 85 p-ra, and dried at 70 to 90°C for 10 minutes, resulting in an air permeability of about 104 m. Layer (2) was formed.

Similarly, the same anchor coating layer (4) was formed on the other side of the polycarbonate film (1).

Further, on the anchor coating layer (4), an air permeability layer (2) of approximately 10 p, rs was formed in the same manner.

As a result, (2)/ (4)/ (1)/ (4)/
An electrode substrate having the layer structure (2) and whose cross-sectional view is shown in FIG. 2 was obtained. The characteristic values and appearance of this electrode substrate were as follows.

Peel strength between base layer (1) and air permeable layer (2)
580 g/25m+a other side
575 g/25+sm Oxygen gas permeability 20℃, 98%RH 1,2cc/24hr * m'
* atm30°C198%RH2, Elcc/24h
r * rn' e atm Total light transmittance 89% Retardation value 17 partsm Appearance is excellent One side of the electrode substrate obtained above is coated with a thickness of 500A made of a mixture of indium oxide and tin oxide in a weight ratio of 95:5. A transparent conductive layer was formed by a sputtering method to form a transparent electrode (5).

A liquid crystal display panel was prepared by a conventional method using the substrate obtained above, and it was found to be extremely preferable in terms of air resistance, adhesion to living rooms, and heat resistance. No cracks or peeling of the transparent electrode (5) was observed, and the liquid crystal resistance was excellent.

Example 2 (2)/(4)/(1)/(4) obtained in Example 1
)/(2) Using an applicator, apply the above crosslinking resin liquid directly to one side of the laminate with a gap of 354 m, and heat at 80°C for 10 minutes, and then heat for 120 m.
℃ for 30 minutes to form a protective layer (3) with a thickness of 10 gm. Similarly, a protective layer (3) with a thickness of 10 gta was formed on the other side.

As a result, (3)/ (2)/ (4)/ (1)/
An electrode substrate having a layer structure of (4)/(2)/(3) and whose cross-sectional view is shown in FIG. 5 was obtained. The characteristic values and appearance of this electrode substrate were as follows.

Peel strength between base layer (1) and air permeable layer (2)
625 g/25+gn other
600 g/25mm Peel strength between air permeable layer 2) and protective layer (3) One side Base material failure Other side Base material failure Oxygen gas permeability 20℃, 98XRH0.8cc/24hr @ rn”
a atm30℃, 98%R81,5cc/24hr
a rn"e atmTotal light transmittance 87% Retardation value 7 nmExcellent appearance and appearanceA transparent electrode (5) was formed on one side of the electrode substrate obtained above in the same manner as in Example 1, and this substrate was A liquid crystal display panel was prepared by a conventional method using the same, and it was found to be extremely favorable in terms of air resistance, interlayer adhesion, and heat resistance, and no cracks or peeling of the transparent electrode (5) were observed. The liquid crystal quality was also excellent.

Comparative Example 1 The air permeability layer (2) was formed (each approximately 1O2 thick) using 20 parts of ethylene-vinyl alcohol (molar ratio 32768) copolymer, 48 parts of water, 32 parts of n-propanol, and methylol. An electrode substrate was produced by repeating Example 2, except that a solution consisting of 4 parts of melamine (Sumitic M-3, manufactured by Sumitomo Chemical Industries, Ltd.) was used. The characteristic values and appearance of this electrode substrate were as follows, and compared to Example 2, the adhesiveness and air resistance were insufficient.

Peel strength between base layer (1) and air-permeable layer (2), one side air-permeable layer (2)-protective layer, one side oxygen gas permeability 20°C, 98XRH 30°C, 98XRH Total light transmittance 87" % Retardation value 17n+s 2.8cc/24hr *rn” e atm?
, 5cc/24hr @rn” * atm3 2 5
g/25 layer Layer 3 10 g/25 m Peel strength between layers (3) Base material fracture Base material fracture Appearance Excellent Examples 3 to 5 50 g of ethylene-vinyl alcohol (molar ratio 32/68) copolymer, N-butoxymethylacrylamide 3.
A reactive air-permeable polymer liquid was obtained in the same manner as in Example 1, except that 5 g of acrylic acid and 2.0 g of acrylic acid were polymerized (Example 3).
).

Also, ethylene-vinyl alcohol (molar ratio 32/6
8) Add 4.0 g of N-methoxymethylacrylamide to 50 g of copolymer. A reactive air-permeable polymer liquid was obtained in the same manner as in Example 1, except that Og and 5.0 g of acrylic acid were polymerized (
Example 4).

Furthermore, ethylene-vinyl alcohol (molar ratio 32
/68) A reactive air-permeable polymer liquid was obtained in the same manner as in Example 1, except that 2.5 g of N-methylolacrylamide and 2.5 g of methacrylic acid were polymerized to 50 g of the copolymer (Example 5).

When Example 1 was repeated except that the above-obtained reactive air-permeable polymer liquid was used as the reactive air-permeable polymer liquid in Example 1, almost the same results as in Example 1 were obtained.

Example 6 After charging 350 g of a 13% aqueous solution of polyvinyl alcohol (degree of polymerization 1500, degree of saponification 88 mol%) into a flask, the system was heated to 40 to 50°C, and 4.5 g of N-methylolacrylamide and 2 methacrylic acid were charged. .0 g was added, and oxygen in the system was sufficiently expelled by passing nitrogen through the system. 3.0 g of a 4% aqueous ammonium persulfate solution was added and stirred well, and 5 minutes later, 3.0 g of a 2% aqueous sodium bisulfite solution was added to initiate polymerization. The initiator was added every 2 hours in the same manner as above, and polymerization was carried out for about 8 hours. During this time, the internal temperature is 40-50℃
was held at

This resulted in a viscous, translucent, reactive, air-resistant polymer liquid of approximately 14% solids.

3's A crosslinkable resin liquid having the formulation of Example 1 was used.

11L Shinji 11 According to Example 2 except that the above reactive air-permeable polymer liquid and crosslinkable resin liquid were used, (3)/(2)/(4)
/ (1) / (4) / The fourth layer having the layer structure of (2)
An electrode substrate whose cross-sectional view is shown in the figure was manufactured. However, the thickness of the air permeable layer (2) was set to 8 mm, and the thickness of the protective layer (3) was set to 12 mm.

The characteristic values and appearance of this electrode substrate were as follows.

Peel strength between base layer (1) and air permeable layer (2)
540 g/25mm other side
5 7 0 g/25 Peel strength between carbon dioxide layer air permeable layer (2) and protective layer (3) (one side)
Base material destruction Other Base material destruction oxygen gas permeability 20°C, 98$RH1,2cc/24hr * m'
* atm30℃, 98$RH2, 1cc/24hr
* rn'' * atm Total light transmittance 89% Retardation value 1 nm Excellent appearance Example 7 According to Example 1, an anchor coating layer (4) was placed on one side of the base material layer (1), and an air permeation resistant layer was added on top of it. A layer (2) was formed, and a protective layer (3) was further formed thereon.

As a result, an electrode substrate having a layer structure of (1)/(4)/(2)/(3) and whose cross-sectional view is shown in FIG. 3 was obtained. A transparent electrode (5) was formed in the same manner as in Example 1.

Example 8 According to Example 1, an anchor coating layer (4) was formed on one side of the base layer (1), and an air-permeable layer (2) was formed thereon.

As a result, an electrode substrate having a layer structure of (2)/(4)/(1) and whose cross-sectional view is shown in FIG. 1 was obtained.
A transparent electrode (5) was formed on the air-permeable layer (2) in the same manner as in Example 1.

Example 9 As the base layer (1), a polyether sulfone film (IC
A film was formed using a solution of Victnex 300PI (manufactured by I Japan Co., Ltd.) dissolved in dimethylformamide, and the same anchor agent used in Example 1 was used, and the thickness of the anchor coating layer (4) was approximately 3 pm in each case.
An electrode substrate was produced in accordance with Example 1, except that the following settings were made.

Example 10 An aqueous polyamide anchoring agent (containing a sulfonic acid group, a carboxyl group, an alkyl group-substituted tertiary nitrogen group, and an alkylene group-substituted quaternary nitrogen group) with a resin concentration of 30% was used as the anchor agent, and an anchor coating layer ( Electrode substrates were produced according to Example 1, except that the thickness of 4) was set to about 3 mm.

Example 11 A polyarylene ester film (manufactured by Unitika Co., Ltd.) with a thickness of 100 JL and a retardation value of 17 nm was used as the base layer (1), and as an anchoring agent, an aqueous polyurethane anchoring agent (sulfonate) with a resin concentration of 20% was used. The anchor coating layer (4) was set to about 1.51 parts m in thickness. An electrode substrate was produced according to Example 1.

Example 12 As the base layer (1), a polysulfone film with a thickness of 100 μm and a retardation value of 15 nm (made by Union Carbide Co., Ltd.) was formed using a solution in which needle was dissolved in 1.1,2° 2-tetrachloroethane. ), and a protective layer (3
) as pentaerythritol tetraacrylate 4
An electrode substrate was prepared in the same manner as in Example 2, except that a calendar coated with a composition consisting of: did.

The characteristic values of the electrode substrates obtained in Examples 6 to 12 were similar to those in Example 1 or 2.

Effects of the Invention Since the electrode substrate of the present invention uses a specific air-permeable layer,
A liquid crystal display panel manufactured using this electrode substrate exhibits stable performance over a long period of time, similar to that immediately after manufacture, even when used under harsh conditions such as a high humidity atmosphere or a high temperature atmosphere.

[Brief explanation of the drawing]

1 to 5 are cross-sectional views showing examples of the electrode substrate of the present invention. (1) Base material layer, (2) Air permeability layer, (3)
...protective layer, (4) ...anchor coating layer,
(5)...Transparent electrode Figure 1

Claims (1)

[Claims] 1. In the coexistence of the vinyl alcohol polymer (V), there is a formula ▲ mathematical formula, chemical formula, table, etc. ▼ (i) (In the formula, R^1 and R^2 are H or lower Alkyl group, R
^3 is an alkylene group having 1 to 4 carbon atoms) A monomer mixture (M) consisting of an ethylenically unsaturated amide monomer (Ma) represented by an alkylene group having 1 to 4 carbon atoms and a vinyl polymerizable monomer (Mb) having a carboxyl group in the molecule is polymerized. A reactive air permeation-resistant polymer for manufacturing electrode substrates for liquid crystal display panels. 2. The liquid crystal display panel according to claim 1, which is obtained by adding and polymerizing the monomer mixture (M) represented by formula (i) to a water or/and lower alcohol solution of the vinyl alcohol polymer (V). Reactive air permeation resistant polymer for manufacturing electrode substrates. 3. (Ma)/ in reactive air-permeable polymer (P)
The molar ratio of (Mb) is 0.05 to 5.0, and (M
)/(V) weight ratio is 0.02 to 0.5.
The electrode substrate described. 4. The electrode substrate according to claim 1, wherein the vinyl alcohol polymer (V) is an ethylene-vinyl alcohol copolymer or polyvinyl alcohol. 5. It has a laminated structure in which an air permeation resistant layer (2) is provided on one or both sides of a base layer (1) made of a non-optically active transparent film or sheet with a retardation value of 80 nm or less, and the laminate has an air permeation resistance layer (2) on one or both sides. In an electrode substrate for forming a substrate for a liquid crystal display panel by providing a transparent electrode on the surface on the gaseous layer (2) side, the gas permeable layer (2) is made of the reactive gas permeable polymer (2) according to claim 1. An electrode substrate for a liquid crystal display panel, comprising a layer P). 6. An air-permeable layer (2) is provided on one or both sides of the base layer (1) made of a non-optically active transparent film or sheet with a retardation value of 80 nm or less, and the air-permeable layer (
It has a laminated structure in which a protective layer (3) made of a crosslinkable resin cured product (C) is provided on at least one layer of 2),
The protective layer (3) side of the laminate or the air permeable layer (2)
In an electrode substrate for forming a substrate for a liquid crystal display panel by providing a transparent electrode on a side surface, the air permeation resistant layer (2) is made of a layer of the reactive air permeation resistant polymer (P) according to claim 1. An electrode substrate for a liquid crystal display panel, characterized in that: 7. Oxygen permeability of air permeability layer (2) consisting of a layer of reactive air permeability polymer (P) (ASTMD-1434-75
) is 30cc/24hr・m^2・at
The electrode substrate according to claim 5 or 6, wherein the electrode substrate has a thickness of m or less. 8. Claim 5, wherein the base layer (1) is a layer formed from a polycarbonate resin, a polyethersulfone resin, a polysulfone resin, a polyarylene ester resin, a polyparabanic acid resin, or a polyimide resin.
Or the electrode substrate according to 6. 9. The cured crosslinkable resin (C) constituting the protective layer (3) is a cured crosslinkable resin selected from phenoxy ether type crosslinkable resins, epoxy resins, acrylic resins, melamine resins, phenolic resins, or urethane resins. The electrode substrate according to claim 5 or 6, which is a material.