JP2002287661A - Polymer resin substrate, liquid crystal element and electroluminescence element which uses the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer resin substrate excellent in optical characteristics, heat resistance and mechanical strength and having high barrier property and to provide a liquid crystal element and an EL element which use the substrate. SOLUTION: A DLC film 1 is formed on one surface of a substrate 2 made of a polymer resin which uses polyethylene terephthalate. The DLC film 1 is formed by plasma polymerization of hydrocarbon gas or a mixture gas of hydrocarbons and argon or by sputtering of carbon and graphite. A transparent electrode film 3 is formed by a spray method, metal thermal spray method or the like on the other surface of the substrate 2 different from the above surface where the DLC film 1 is formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polymer resin substrate, a liquid crystal device using the same, and an electroluminescence (hereinafter, referred to as "EL") device.

[0002]

2. Description of the Related Art Glass has conventionally been used as a substrate for liquid crystal elements and EL elements (inorganic dispersion type EL and organic EL). However, in recent years, weight reduction, thinning, breakage resistance, etc. In view of this, it has been proposed to use a polymer resin substrate. However, it has been found that when a polymer resin substrate is used, water vapor or oxygen passing through the polymer resin substrate causes performance degradation of the element. In order to solve such a problem, it is necessary to impart a gas barrier property to the polymer resin substrate.

For example, Japanese Patent Application Laid-Open No. Sho 59-204545 discloses a transparent conductive film in which an oxide layer is provided on a polymer film and a coating containing indium oxide as a main component is formed on at least one surface of the polymer layer. Have been. Also,
JP-A-60-190342 proposes a polymer film in which polyvinyl alcohol, ethylene / vinyl alcohol copolymer, monochloroethylene trifluoride or transparent metal oxide is laminated.

[0004]

However, the polymer resin substrate provided with the oxide layer has a problem that a thin film of the oxide film is apt to crack and the barrier property tends to be incomplete. In addition, when a metal such as aluminum is deposited, the barrier property is exhibited but the transparency is impaired, which is not suitable for a substrate for a transparent conductive film.

Further, a polymer resin substrate using an organic substance for a barrier layer is susceptible to the influence of temperature and humidity, and has a problem that the barrier property is deteriorated particularly at high temperature and high humidity.

An object of the present invention is to provide a high-barrier polymer resin substrate having excellent optical properties, heat resistance and mechanical strength, and a liquid crystal element and an EL element using the same.

[0007]

In order to achieve the above object, the present invention provides a base made of a polymer resin and a DLC (Diamond) formed on at least one surface of the base.
on Like Carbon) film.

By providing the DLC film on the surface of the substrate, a high barrier property is provided.

The present invention is a polymer resin substrate, wherein the substrate is a laminate in which a plurality of substrates are laminated.

[0010] The present invention provides the method, wherein the DL is provided between at least one of the substrate and a substrate different from the substrate.
This is a polymer resin substrate on which a C film is formed.

The present invention is a polymer resin substrate, wherein at least one of the substrates is a substrate that blocks ultraviolet rays.

The present invention is a liquid crystal element using any one of the polymer resin substrates described above.

The present invention is an electroluminescent device using any one of the polymer resin substrates described above.

[0014]

Embodiments of the present invention will be described below. (Embodiment 1) FIG. 1 is a schematic longitudinal sectional view of a polymer resin substrate 41 according to a first embodiment of the present invention. Figure 1
In the figures, 1 is a DLC film, 2 is a substrate, and 3 is a transparent conductive film. In the present embodiment, a base 2 made of a polymer resin is used. As the polymer resin used for the substrate 2 of the present invention, polyethylene terephthalate is often used. In addition, polypropylene, polyolefins such as ethylene-propylene copolymer, polycycloolefin, polyester,
Polyamide, ionomer, ethylene-vinyl acetate copolymer,
Acrylic resin such as acrylic acid ester and methacrylic acid ester, polyvinyl acetal, phenol, modified epoxy resin, vinyl acetate resin, silicone RTV,
It may be a polymer alloy type polyimide.

A DLC film 1 is formed on the upper surface of the substrate 2. The DLC film 1 is formed by plasma polymerization of hydrocarbon gas or a mixed gas of hydrocarbon and argon, or carbon,
It can be formed by graphite sputtering. When formed by plasma polymerization of a hydrocarbon gas, a hydrocarbon gas or a mixed gas of a hydrocarbon gas and an inert gas is introduced into a vacuum vessel, and a pressure of 0.001 to 1 is introduced.
While maintaining the pressure of Torr, the inside of the vacuum vessel is discharged to generate a plasma of hydrocarbon gas, and
A DLC film 1 is formed on the surface of. The discharge type may be either an external electrode type or an internal electrode type, and the discharge frequency can be experimentally determined. Further, by applying a voltage of 0 to −3 KV to the electrode on the base 2 side, the hardness of the DLC film 1 can be increased and the adhesion can be improved.

As the hydrocarbon gas, methane, ethane,
Propane, butane, pentane, hexane, heptane, octane, benzene and the like can be used.

In order to form a hard DLC film, it is desirable to increase discharge energy as much as possible.
It is also desirable that the temperature of the base 2 be as high as possible. Alternatively, the sputtering method includes DC sputtering, AC sputtering, high-frequency sputtering, magnetron sputtering, ion beam sputtering, and the like, and any method may be used. To form a hard DLC film, the pressure is 0.01
Torr or less is desirable, and the energy density is preferably high. For example, in the case of high-frequency magnetron sputtering, the target is preferably 1 W / cm ² or more per target area. Also, by applying a voltage of 0 to −3 KV to the electrode holding the base 2 and performing sputtering, the same as in the case of plasma polymerization. In addition, the hardness of the DLC film 1 and the adhesion can be improved. The thickness of the DLC film 1 is desirably 0.01 to 5 μm in order to achieve both an effect of improving gas barrier properties and adhesion, durability, and transparency.

Then, a transparent electrode film 3 is formed on the upper surface of the base 2. The method for forming the transparent conductive film 3 includes spraying, metal spraying, metal plating, vacuum evaporation, ion plating, sputtering, molecular beam epitaxy (MBE), CVD, and plasma CVD. No. Among them, an ion plating method and a sputtering method are suitable for forming a film on the surface of a polymer resin substrate in view of a film forming temperature and a film forming speed. The thickness of the transparent conductive film 3 is usually 8 nm to 700 nm, preferably 10 nm to 300 nm, and more preferably 50 nm.
m to 150 nm. Also, the transparent conductive film 3 or DL
When the C film 1 is formed on the base 2, a plasma treatment, a chemical treatment, or the like may be performed as a pretreatment of the base 2.

The polymer resin substrate 41 composed of the substrate 2 covered with the DLC film 1 formed in this way not only can significantly reduce the permeability of oxygen and water vapor, but also has the transparency of the substrate 2. There is no loss. The substrate 2 may be transparent or have a color. (Embodiment 2) FIG. 2 is a schematic longitudinal sectional view of a polymer resin substrate 42 according to a second embodiment of the present invention. In FIG. 2, reference numeral 1 denotes a DLC film, reference numeral 3 denotes a transparent conductive film, and reference numeral 30 denotes a laminate in which a plurality of substrates 21, 22, and 23 are bonded. The laminated body 30 of the bases 21, 22, and 23 is manufactured by attaching the base gaps 4, 5 with a transparent adhesive. Alternatively, it can be manufactured by heating and fusing the base gaps 4 and 5 while pressing the stacked bases 21, 22, and 23.

The polymer resin substrate 42 has a DLC film 1 on the upper surface of the substrate 21 and a transparent conductive film 3 on the lower surface of the substrate 23.
Is formed, the upper surface of the substrate 22 and the lower surface of the substrate 21 are attached to each other, and the lower surface of the substrate 22 and the upper surface of the substrate 23 are attached to each other, thereby enabling lamination. Alternatively, the substrate 2
After laminating the base 1, the base 22, and the base 23 to form the laminate 30, the DLC film 1 may be formed on the upper surface of the base 21, and the transparent conductive film 3 may be formed on the lower surface of the base 23. DLC film 1
The transparent electrode film 3 can be formed by the method described in Embodiment Mode 1. In this embodiment, 3
Although the stacked body 30 including the bases 21, 22, and 23 has been described as an example, the number of bases to be stacked is not limited to this. Even if the number of substrates is two or four or more, it can be similarly manufactured.

The polymer resin substrate 42 thus constructed
By using the laminate 30 for the bases 21, 22, and 23, gas barrier properties can be improved as compared with a single-layer polymer resin substrate. (Embodiment 3) FIG. 3 is a schematic vertical sectional view of a polymer resin substrate according to a third embodiment of the present invention. In FIG. 3, 11 and 12 are DLC films, 24 and 25 are substrates, and 3 is a transparent electrode film.

The base laminate 31 has a DLC film 1 on both surfaces.
After the substrates 24 and 25 on which the substrates 1 and 12 have been formed are bonded together, the transparent conductive film 3 is formed on the lower surface of the substrate 25 to manufacture. Alternatively, one in which the DLC film 11 is formed on the upper surface of the base 24 and one in which the DLC film 12 is formed on the upper surface of the base 25 are prepared. DLC film 1 of lower surface of substrate 24 and substrate 25
2 and the upper surface thereof. After this bonding, the transparent conductive film 3 may be formed on the lower surface of the base 25 to manufacture the base. Alternatively, after the DLC film 12 is formed on the lower surface of the base 25 and the transparent conductive film 3 is formed on the lower surface of the base 25, the base 25 and the base 24 are bonded to each other. After that, the DLC film 11 may be formed on the upper surface of the base 24. The DLC film 12 is formed on the upper surface of the substrate 25, and the transparent conductive film 3 is formed on the lower surface of the substrate 25.
Are respectively formed. The DLC film 11 is formed on the upper surface of the base 24. Then, the base 25 and the base 24 may be bonded together.

The formation of the substrate is not limited to the above procedure. As for these manufacturing methods, it is preferable to appropriately select a method that meets the purpose according to cost manufacturing equipment, ease of manufacturing, and the like. For example, considering low-cost manufacturing, D
A plurality of substrates 24 (or 25) each having the LC film 11 (or 12) formed only on one surface are prepared, and these are laminated to form a laminate. Then, the transparent conductive film 3 is formed on the lower surface of the laminate. The method is suitable. The DLC film 1 and the transparent electrode film 3 can be formed by the above-described method. In the present embodiment, the laminated body 31 composed of two substrates is described as an example, but the number of substrates to be laminated is not limited to this.

The polymer resin substrate 43 thus constructed
In this case, the gas barrier property becomes stronger due to the multilayer structure of the DLC film. (Embodiment 4) FIG. 4 is a schematic vertical sectional view of a polymer resin substrate according to a fourth embodiment of the present invention. In FIG. 4, 1 is a DLC film, 2 is a substrate, 8 is a substrate that blocks ultraviolet rays, and 3 is a transparent electrode film. In the embodiment,
A base 8 that blocks ultraviolet light is bonded to the upper surface of the base 2. The DLC film 1 is formed on a substrate 8 that blocks ultraviolet rays. on the other hand,
On the lower surface of the base 2, a transparent electrode film 3 is formed. When a plurality of substrates are laminated, the substrate 8 that blocks ultraviolet rays is not limited to being disposed on the uppermost surface of the laminated substrates, and may be disposed at any position on the laminated substrates.

Next, a manufacturing method for manufacturing this embodiment will be described. The substrate 2 and the substrate 8 having the transparent conductive film 3 formed on the lower surface are bonded and laminated. The DLC film 1 is formed on the upper surface of the laminated base 31. Alternatively, the substrate 8 having the DLC film 1 formed on the upper surface and the substrate 2 are bonded and laminated. The transparent conductive film 3 is formed on the lower surface of the laminated base 31.

Alternatively, the base 2 and the base 8 are bonded to form a laminate 32. DLC film 1 on the upper surface of the laminate 32
May be formed on the lower surface of the transparent conductive film 3. In the present embodiment, the laminated body 32 composed of two substrates has been described as an example, but the number of substrates to be laminated is not limited to this.

In the polymer resin substrate thus configured, weather resistance can be improved by blocking ultraviolet rays that cause deterioration of organic substances and the like. (Embodiment 5) FIG. 5 is a schematic longitudinal sectional view of an embodiment of a liquid crystal element using a polymer resin substrate according to the present invention. In this embodiment, the polymer resin substrate 41 described in Embodiment 1 is used. Two polymer resin substrates 41 are arranged with a gap so that the respective transparent conductive films 3 face each other. A liquid crystal material 50 is injected into the gap, and the liquid crystal material 50 is held to form a liquid crystal element. Note that an alignment film (not shown) may be appropriately provided on the surface of the opposed transparent conductive film 3 depending on the operation mode of the liquid crystal element. (Embodiment 6) FIG. 6 is a schematic vertical sectional view of an embodiment of an EL element using a polymer resin substrate according to the present invention. In this embodiment mode, the polymer resin substrate 41 described in Embodiment Mode 1 is used. At least one or more EL layers 51 are formed on the transparent conductive film 3 by a printing method or a spin coating method. Further, a cathode 9 is formed on the upper surface to form an EL element. The cathode 9 and the upper surface of the polymer resin substrate 45 are bonded. At this time, the DLC film 1 is formed on the lower surface of the polymer resin substrate 45.
Polymer resin substrate 45 provided with DLC film 1 on the lower surface of base 2
Is a sealing substrate for protecting the EL layer 51 from water vapor, oxygen and the like. Note that the EL layer 51 may be an organic EL or an inorganic dispersion type EL.

By using the polymer resin substrate of the DLC film formed as described above for a liquid crystal element or an EL element, it is possible to reduce the performance of the element due to water vapor and oxygen, and to reduce the weight, thickness and damage resistance of the element. Excellent in properties.

[0029]

The present invention is embodied in the form described above and has the effects described below.

By forming a DLC film on the surface of a base made of a polymer resin, cracks are prevented from occurring, and the base can be protected against gases such as water vapor and oxygen. Also, by using a DLC film,
Transparency in the visible region can be ensured. Therefore, it has transparency in the visible region, has excellent barrier properties against gases such as water vapor and oxygen, and has weather resistance, chemical resistance, and abrasion resistance.

Further, by using a polymer resin substrate having a DLC film for the liquid crystal element and the EL element, the barrier property against gas such as water vapor and oxygen is excellent, and the weather resistance, chemical resistance and abrasion resistance are improved. Can have. Further, transparency can be ensured.

[Brief description of the drawings]

FIG. 1 is a schematic vertical sectional view of a polymer resin substrate according to Embodiment 1 of the present invention.

FIG. 2 is a schematic vertical sectional view of a polymer resin substrate according to a second embodiment of the present invention.

FIG. 3 is a schematic vertical sectional view of a polymer resin substrate according to a third embodiment of the present invention.

FIG. 4 is a schematic vertical sectional view of a polymer resin substrate according to a fourth embodiment of the present invention.

FIG. 5 is a schematic vertical sectional view of a liquid crystal element according to a fifth embodiment of the present invention.

FIG. 6 is a schematic longitudinal sectional view of an EL element according to a sixth embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 DLC film 2 Substrate 3 Transparent conductive film 4 Gap 5, 6, 7 Gap 8 Substrate which blocks ultraviolet rays 9 Cathode 11, 12 DLC film 21, 22, 23, 24, 25 Substrate 31, 32, 33 Lamination 41, 42 , 43, 44 Polymer resin substrate 50 Liquid crystal material 51 EL layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H05B 33/02 H05B 33/02 33/14 33/14 A // C08L 67:02 C08L 67:02 F term (Ref.) BA10C EH56 EH61 EH66 GB41 JD03 JD04 JD09A JD09C JG01 JM02B JN01 5C094 AA36 AA37 AA38 AA43 AA55 BA27 BA43 DA12 DA13 EA05 EB02 ED02 FA02 FB02 FB12 GB10

Claims (6)

[Claims] 1. A polymer resin substrate comprising: a base made of a polymer resin; and a DLC film formed on at least one surface of the base. 2. The polymer resin substrate according to claim 1, wherein said substrate is a laminate in which a plurality of substrates are laminated. 3. The polymer resin substrate according to claim 2, wherein the DLC film is formed between at least one of the substrate and a substrate different from the substrate. 4. The polymer resin substrate according to claim 1, wherein at least one of the substrates is a substrate that blocks ultraviolet rays. 5. A liquid crystal device using the polymer resin substrate according to claim 1. 6. An electroluminescent device using the polymer resin substrate according to claim 1.