JPS6025104A - Substrate with transparent conductive film and method of producing same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a substrate having a transparent conductive film and a method for manufacturing the same, and particularly to a substrate having excellent adhesion and durability between the transparent conductive film and the base made of plastic. A substrate having a transparent conductive film that is excellent in chemicals and has low moisture permeability and is suitable for a liquid crystal element substrate material, and a transparent conductive film suitable for manufacturing such a substrate regardless of its heat resistance. 7 concerning a substrate and its manufacturing method.

[Background of the invention]

Methods for forming transparent conductive films include vacuum evaporation, chemical vapor deposition, sputtering, spraying, and dipping, but all of them are processed at relatively high temperatures, so transparent conductive films can be formed on plastic materials with poor heat resistance. Methods for directly forming films are limited. In particular, 5n02, which has excellent transparency. In
In the case of metal oxide films such as 20a, heat treatment is essential. Methods that can form films at relatively low temperatures include sputtering and vacuum evaporation, and these methods are exclusively used for plastic films and sheets. However, even if this method is used, unless a heat treatment of 1,000 or more times is performed, the film will not have a dense structure and will have poor chemical resistance, making it impractical. Therefore, the plastic members that can be used are limited to materials with relatively high heat resistance, such as polyethylene terephthalate. However, since the polyethylene tele-7 tallate film is biaxially stretched, it has a large optical anisotropy, and a liquid crystal display element using a polarizing element has the drawback that the field of view is extremely narrow.

Further, even if a transparent conductive film is directly formed on a plastic member, there is a problem that the adhesiveness between the member and the film is poor and the film easily peels off. Furthermore, in liquid crystal panels and the like, since the transparent conductive film is patterned, it is impossible to prevent moisture from permeating through the plastic member, resulting in the effect of accelerating the deterioration of the liquid crystal element.

[Purpose of the invention]

An object of the present invention is to provide a substrate having a transparent conductive film that has excellent adhesion between the transparent conductive film and a base made of plastic, has excellent chemical resistance, and has low moisture content. be.

Still another object of the present invention is to have excellent adhesion between a transparent conductive film and a base made of plastic, and to have excellent chemical resistance.
Moreover, it is an object of the present invention to provide a method by which a substrate having a transparent conductive film with low moisture permeability can be easily manufactured without regard to the heat resistance of the substrate.

[Summary of the invention]

In the present invention, a transparent conductive film containing a metal oxide as a main component is not directly formed on a substrate made of plastic with poor heat resistance, but is provided via an organic adhesive layer. Furthermore, the feature is that an inorganic insulating film is provided as a moisture permeable barrier layer between the transparent conductive film and the substrate so that moisture does not permeate into the liquid crystal even if the transparent conductive film is patterned. .

In addition, in order to manufacture a substrate with such a transparent conductive film, an organic adhesive layer is formed on a transparent substrate made of plastic with relatively poor heat resistance, and a separate non-adhesive surface is formed on the transparent substrate. A transparent conductive film containing a metal oxide as a main component is formed on the substrate surface, and an insulating inorganic film is further laminated thereon, and then this laminated film is transferred and fixed to the organic adhesive layer. This is what I did.

In other words, when forming a transparent conductive film whose main component is a metal oxide, it is processed at a relatively high temperature. The film is transferred and fixed onto a substrate made of a plastic material that has the characteristics required as a substrate on which a transparent conductive film will ultimately be provided, regardless of its heat resistance.

The present invention will be explained in more detail below.

In the present invention, the substrate on which the transparent conductive film containing metal oxide as the main component is formed has relatively high heat resistance and is transferred to another substrate in a subsequent process, so It is necessary that the adhesive has poor adhesion. Examples of such a substrate include a film or sheet of plastic such as polyolefin, polyester, or fluororesin, a glass plate coated with these resins, or a highly heat-resistant plastic film such as polyimide.

Also useful are metal mirror plates, such as 7Erochrome plates.

The transparent conductive film is 8n02. InaOa fr, which metal oxide is the main component, and any known method such as vacuum evaporation, chemical vapor deposition, sputtering, spraying, or dipping can be used for its formation. can.

As the insulating inorganic film, a transparent and highly electrically insulating film is used. Generally, it is better to use a silicon oxide film. Silicon oxide films can be formed in a variety of ways. For example, C
These methods include the VD method, sputtering method, dipping method, and spin code method. Either method can be applied as long as the processing temperature does not exceed the heat resistance of the non-adhesive substrate used for primary formation.

On the other hand, an organic adhesive layer is formed on the surface of a transparent substrate made of plastic that is prepared separately from the above-mentioned substrate. Here, since the transparent substrate is the substrate on which the transparent conductive film is finally formed, a substrate made of any material can be selected depending on the characteristics required of the substrate.

As the organic adhesive layer, thermosetting resins and photocuring resins are effective, but depending on the application, an adhesive layer may be used. As such an adhesive, epoxy resin, urethane resin, silicone resin, polyester resin, acrylic resin, etc. can be used.

A laminated film consisting of the above-described transparent conductive film and inorganic insulating film is transferred and fixed onto the adhesive layer surface of the substrate having such an organic adhesive layer. Before transfer, the adhesive layer on the surface of the transparent substrate is in an uncured or semi-cured state. Immediately after transferring the laminated film, in the case of a thermosetting resin, it is cured by heating, and in the case of a photocurable resin, it is cured by ultraviolet rays, etc. It is cured by irradiation.

The transparent conductive film may be patterned into a desired shape by etching or the like on a non-adhesive substrate. In this case, a patterned transparent conductive film is formed on the plastic substrate.

The substrate having the transparent conductive film thus obtained can be used as an electrode substrate for displays using liquid crystals, optical shutters, optical devices using electroluminescent materials, etc., and as a sheet heating element for aircraft, trains, and automobiles. It can be used in window defroster devices, such as window defrosters, and window films for solar energy collectors as a selective light transmission film.

In the case of electrode plates for liquid crystal displays, there is the advantage of greatly simplifying the process if the polarizing plate is used as an electrode plate, but considering the material composition of the polarizing plate, 100C
Since the above-described heat treatment cannot be performed, the method of the present invention is extremely effective for attaching a high-quality transparent conductive film.

In addition, since an inorganic insulating film is formed on the entire surface, liquid crystal resistance is not necessarily an essential condition for the substrate, so other requirements such as optical isotropy, transparency, material cost, etc. Material selection becomes possible. For example, materials such as polycarbonate, polysulfone, polyethersulfone, and polyarylene ester will become available.

[Embodiments of the invention]

(9) Figure 1 shows the configuration of an apparatus for forming a transparent conductive film on one surface of a film of synthetic resin such as polyolefin, polyester, or fluororesin.
This is a vacuum chamber to obtain a high degree of vacuum.
n203'f - A crucible 2 containing a metal oxide as a main component, a tungsten coil 3 for heating the metal oxide in this crucible, and a vacuum level in the tank and a heating temperature for the metal oxide in the crucible are installed. can be controlled individually from the outside.

The formation of the vapor deposited film is carried out in the same manner as in conventional vacuum vapor deposition, by using a vacuum device that connects an oil diffusion pump and a rotary pump (not shown) to increase the degree of vacuum in the vacuum chamber 1 to about 10-6 TOrr, and to maintain this state. When the metal oxide placed in the crucible 2 is heated by the coil 3, evaporation starts and a deposited film is formed on the film 4. After this, film 4 becomes 1
50t:' to 250C to form a dense transparent conductive film.

FIG. 2 shows the process from a film 4 provided with an insulating film 5' and a transparent conductive film 5 formed in this way to (10) transferring these films 5' and 5 to a substrate 6 to be finally attached. This shows an apparatus in which a substrate 6 is preliminarily provided with an uncured or semi-cured adhesive layer 7 made of epoxy resin, urethane resin, polyester resin, or the like. 8a, 8b
, 9a and 9b are heating and pressure rollers, respectively. The film 4 and the substrate 6 are passed all the way between the rollers 8a and 8b and between the rollers 9a and 9b, with the film 5 and the resin layer 7 facing each other. These rollers function to melt the resin layer and advance the curing reaction, so that the film 4 and the substrate 6 become integrated.

Next, when the transparent conductive film 5 is separated from the film 4,
As shown in FIG. 3, an insulating film 5' and a transparent conductive film 5 are transferred onto a substrate 6 via a resin layer 7. In this state, if necessary, heat treatment is performed until the resin layer 7 is completely cured.

Although both the film 4 and the substrate 6 are shown as single pieces, it goes without saying that these may be long films wound into rolls.

Further, the resin layer may be of an ultraviolet curing type, and in that case (11), an ultraviolet irradiation device is provided between the pressure rollers 8a, 8b and 9a, 9b.

Figure 4 (A) shows an example of a method for manufacturing a liquid talk device using a substrate having an insulating film and a transparent conductive film as shown in Figure 3.
This will be explained based on FIG. 4(F).

Insulating inorganic film 5', transparent groove If, transparent film (transparent electrode)
A resist film 10 is formed on a substrate (polarizing film) 6 having a polarizing film 5 (B). An electrode pattern corresponding to the pattern of this resist film 10 is formed (C). Next, an alignment film 11 is formed on the electrode pattern side (D). Further, a sealant 12 is printed on the transparent conductive film 5 provided on the outer periphery of the base 6 (E). Next, a liquid crystal element is produced by bonding the sealant sides of the pair of members shown in FIG. 4(E) (F).

Example 1 A Teflon sheet with a thickness of 2 mm and a thickness of 100 mm x 100+ mm was washed and dried and set in the apparatus shown in FIG. at the same time,
In the crucible, In20a 95ffit part, 5nu25
Add a mixture consisting of parts by weight. After that, vacuum (12
) After the inside of the tank 1 is evacuated to about -10 Torr, the coil 3 is energized from an external power source and heated.

After heating and degassing for a certain period of time, 4X10-I'To
The deposition was carried out at a constant vacuum of rr and a deposition rate of about 20 A/m. The deposited film thickness I″ was 1500A.Subsequently, vacuum chamber 1
Remove the Teflon sheet from the
, heat treatment for 2 hours.

Next, use a spinner to apply SO onto the surface of this transparent conductive film.
G liquid was applied and dried at 250C for 1 hour to form a silicon oxide insulating film of 12,000 layers.

Separately, prepared triacetate film (thickness 100
pm, 100m1X 100wn), after washing and drying,
On one side, a layer of polyester resin (Vylon ■300 manufactured by Toyobo Co., Ltd.) is formed from a methyl cellosolve acetate solution using a roll coater.

Next, the silicon oxide film forming side of the Teflon sheet and the polyester resin M (ill) of the triacetate film are placed facing each other, introduced into an apparatus as shown in Fig. 3, and heated and pressurized.The temperature of the heating roller is 100C= 5C, and the actual heating time is about 15 seconds (13).After cooling, the end part was smoked, and it was easily heated.
A triacetate film with a transparent conductive film having a structure as shown in FIG. 3 was obtained. The obtained film has a resistance value of 1
0Ω/sq, transmittance 89%.

Example 2 Conductivity was applied to the Teflon sheet in the same manner as in Example 1.

A film and a silicon oxide insulating film are formed and heat treated at 200 tT for 2 hours.

Separately, an epoxy resin layer having the following composition was applied to the same triacetate film as in Example 1 using an applicator,
Temporarily dry at 70C for 5 minutes.

[Epoxy resin composition 1] Main agent: Epicor) 828 (Shell oil (t[)) 100 Heavy Industries Rozilna 380 (Nippon Aerosil Group) 2 parts by weight Curing agent: Sanmydna 1036 (Sansho Kasei Co., Ltd.) 50 parts by weight Blending ratio Main agent 102 /Curing agent 50 (Multilayering) (14) Next, the conductive film surface of the Teflon sheet and the epoxy resin coated surface of the triacetate film are placed facing each other and heated and pressurized using the apparatus shown in FIG. 2.The heating conditions are as shown in the example. Same as 1. After that, in the bonded state, from both sides, a thickness of 3 m
The entire surface of the sheet was held down with an aluminum plate and cured at 100 U for 2 hours while applying pressure at 0.2 kg/l. after that,
The temperature is returned to room temperature, the Teflon sheet is peeled off, and a triacetate film with a transparent conductive film having the structure shown in FIG. 3 is completed.

Example 3 A layer of [epoxy resin composition 1] was formed in the same manner as in Example 2 on a PVA to iodine polarizing film (250 μm thick, 100×100) with acrylic resin as a protective thickness, and 70C
Dry for 5 minutes. A Teflon sheet with a transparent conductive film and a silicon oxide insulating film formed in the same manner as in Example 1 was then placed directly facing the epoxy resin layer and the insulating film layer, and bonded under heat and pressure using the apparatus shown in Fig. 2. do. Further, in the same manner as in Example 2, a 100C, 2h curing treatment is performed. After returning to room temperature, the Teflon sheet was peeled off (15). As a result, the acrylic resin layer 1 as shown in FIG.
3a, a PVA to iodine polarizing film 14, an acrylic resin layer 13b1, an adhesive layer 7, and an insulating film 5', a transparent conductive film 5 were formed in this order on a substrate.

Comparative Example 1 Triacetate film of the same quality as Example 1 (100 μm
The film (thickness: 100M x 100B) was washed and dried, set in the apparatus shown in FIG. 1, and vapor deposition was performed under exactly the same conditions as in Example 1. After that, remove the film from the vacuum chamber 7
The substrate was heat-treated in air at 100 C for 2 hours to obtain a substrate in which a transparent conductive film 5 was formed on 6 surfaces of the triacetate film. (Figure 6) Comparative Example 2 A polarizing film of the same quality as that used in Example 3 was washed and dried,
Using the apparatus shown in FIG. 1, vapor deposition was carried out under exactly the same conditions as in Example 1. Thereafter, the film was taken out from the vacuum chamber and heat treated in air at 100C for 1 hour.

As a result, as shown in FIG. 7, the acrylic resin layer 13B,
A substrate was obtained in which a PVA to iodine film (6) lume 14, an acrylic resin layer 13b, and a transparent conductive film 5 were sequentially formed.

For the films with transparent conductive films of Examples 1 to 3 and Comparative Examples 1 and 2, a peel adhesion test was conducted as a method for evaluating alkali resistance and adhesion, which serves as a marker for chemical resistance.

[Test method: Alkali resistance: A film is immersed in a 1 volume % NaOH aqueous solution at 60C, and evaluated by the time until the surface resistance becomes twice the initial value.

Adhesion: Film'e 10rMnX 60rtan
Cut out the same size as used in Example 2, with the transparent conductive film surfaces facing each other [1 epoxy resin composition, 2 sheets pasted together (approximately 30 tas from the end of the pasting length)]
After curing at 100C for 2 hours, the adhesive strength is measured at room temperature. Calculate the average value of the 5 samples.

The peeling speed is 20 mm/square. The state of the peeling at that time was observed and classified as follows.

Interfacial destruction: When destruction occurs at the interface between the film and the transparent conductive film. Check (17) by measuring the surface resistance on the film surface.

Cohesive failure: Failure in the adhesive layer.

Film breakage: Failure in which the film itself breaks.

The test results are shown in the table below.

As is clear from the table, all examples have excellent alkali resistance and adhesion.

In addition, as can be seen from the configuration in Figure 4 (F), since the insulating inorganic film covers the entire liquid crystal layer, when the substrate of the present invention is used as a liquid crystal element, moisture infiltration into the liquid crystal layer is greatly reduced. to 1
it1. +)-, which significantly improves reliability.

〔Effect of the invention〕

As described above, according to the present invention, since the transparent conductive film is attached to the plastic member through the organic adhesive layer on the transfer surface (18), the material of the plastic member is independent of the processing conditions during the formation of the transparent conductive film. In addition, since the plastic member having the transparent conductive film has an organic adhesive layer interposed therebetween, the adhesiveness and chemical resistance are improved.

[Brief explanation of drawings]

Fig. 1 is a schematic diagram of an apparatus for forming a transparent conductive film on a substrate surface having a non-adhesive surface, and Fig. 2 is a schematic diagram of an apparatus for transferring a transparent conductive film obtained by the apparatus of Fig. 1. Diagram,
FIG. 3 is a cross-sectional view showing one embodiment of a substrate having a transparent conductive film of the present invention, and FIGS. 4(A) to 4(F') show a liquid crystal element using a substrate having a transparent conductive film. 5 is a sectional view showing another example of a substrate having a transparent conductive film of the present invention, and FIGS. 6 and 7 are comparative examples of transparent conductive films, respectively. FIG. 1... X empty L 2... Crucible, 3... Tungsten coil, 4... Film, 5... Transparent conductive film,
5'... Insulating inorganic film, 6... Substrate, 7... Adhesive layer (resin layer), (19) sa, sb... Pressure roller, 9a, 9b... Heating roller, 10... Resist film, 11... Alignment film, 12
...Sealing agent, 13a, 13b...Acrylic resin layer, 14...PVA to iodine polarizing film. Agent Patent Attorney Akio Takahashi (20) Condolences 1 Zu Inn 2 Zu Yu 3 Zu Ke ll-coma

Claims (1)

[Claims] 1. An insulating transparent inorganic film layer and a transparent conductive film mainly composed of a metal oxide are laminated on the surface of a transparent substrate made of glass via a transparent organic adhesive layer. A substrate having a transparent conductive film. 2. In claim 1, the adhesive layer comprises:
A substrate having a transparent conductive film characterized by being made of a thermosetting resin or a photocurable resin. 3. A substrate having a transparent conductive film according to claim 1, wherein the substrate having the transparent conductive film is a liquid crystal display element substrate. 4. The transparent conductive material according to claim 1, wherein the plastic is one of polycarbonate, polysulfone, polyether sulfone, polyarylene ester, and polyether ether ketone;
Substrate with a sexual membrane. 5. A process of forming an organic adhesive layer on the surface of a transparent substrate made of plastic, a process of forming a transparent conductive film mainly composed of a metal oxide on a substrate surface having a non-adhesive surface, a transparent insulation 1. A method for producing a substrate having a transparent conductive film, the method comprising: forming a transparent conductive film; and transferring and fixing the transparent conductive film and the transparent insulating film onto the organic adhesive layer. 6. The method of manufacturing a substrate having a transparent conductive film according to claim 5, wherein the organic adhesive layer is a thermosetting resin or a photocuring resin. 7. A method of manufacturing a substrate having a transparent conductive film according to claim 5, wherein the substrate having the transparent conductive film is a liquid crystal element substrate. 8. Production of a substrate having a transparent conductive film according to claim 5, wherein the plastic is one of polycarbonate, polysulfone, polyethersulfone, polyarylene ester, and polynietheneetherketone. Method.