JPH0483635A - Transparent conductive laminate - Google Patents

Abstract

PURPOSE:To obtain an ELD having a high luminous efficiency when the title laminate is used as a transparent electrode for the ELD and also obtain the transparent conductive laminate excellent in shelf stability by forming a transparent conductive layer consisting of a metallic oxide, and a cyanoethyl resin layer containing fine particles of a metallic compound on polymeric organic moldings. CONSTITUTION:This transparent conductive laminate consists of a transparent conductive layer comprising an oxide, and a cyanoethyl resin layer containing fine particles of a metallic compound, both layers being formed on polymeric organic moldings, which are not particularly limited if they are made of a transparent polymeric organic compound having heat resistance. The transparent conductive layer comprises metallic oxides of tin and/or a fluorine-containing indium oxide and the like. The cyanoethyl resin is resin in which 50% or more of a hydroxyl group is cyano-ethylated and which is a cyanoethyl polyvinyl alcohol and the like. Examples of the fine particles of the metallic compound, which are contained in the cyanoethyl resin layer, include antimony-containing tin oxide and the like. When this laminate is used as a transparent electrode for an ELD, there is no deterioration in the transparent conductive layer and, further, the laminate has excellent properties of adhesion to a luminous layer and also has excellent transparency.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a transparent conductive laminate, and particularly to a transparent conductive laminate suitable for electroluminescent display applications.

[Prior art] A transparent conductive layer consisting of a vs film of gold WA oxide is formed on the surface of a transparent organic polymer molded article to provide transparency and 1.
! Electrically conductive laminates are used in various fields. Among these fields of application, attempts have been made to use it as a transparent electrode opposite to the aluminum electrode of electroluminescent display (ELD).

ELDs are used as backlights for liquid crystal displays installed in portable personal combination coaters, word processors, and the like. Portable personal computers and word processors are powered by batteries. In order to extend battery life, ELDs are required to operate with low power consumption. That is, it is necessary to improve the luminous efficiency of the ELD.

Conventionally, transparent conductive laminates are known in which a cyanoethyl resin layer is formed on a transparent conductive layer either directly or via a Pd 1111 layer. If this is used for ELD creation, E
Although an effect was seen in improving the yield of the LD manufacturing process, there was no change in the luminous efficiency of the ELD compared to the case where a transparent conductive laminate without a cyanethyl resin layer was used.

Conventionally, the luminous efficiency of an ELD is thought to be determined by the luminescent layer, and almost no approach has been taken to improve the luminous efficiency of an ELD from the side of a transparent conductive laminate.

Furthermore, when a transparent conductive laminate with a cyanoethyl resin layer formed thereon is rolled up in layers or rolled up and left under the skin at high humidity, a part of the cyanoethyl resin layer may be transferred to the back surface of another transparent conductive laminate. There was a problem with poor appearance.

[Problems to be Solved by the Invention] An object of the present invention is to provide a transparent 81 conductive laminate that can provide an ELD with high luminous efficiency when used as a transparent electrode of an ELD and has excellent storage stability. .

[Means for Solving Problem VI] The present invention provides a transparent conductive layer (B) made of an oxide on an organic polymer molded product (A), and further a cyanoethyl resin layer containing fine particles of a metal compound thereon. (C) is a transparent conductive laminate formed by forming.

Hereinafter, the present invention will be explained in detail along with the progress that has been made.

The present inventors focused on the overcoat layer on the transparent conductive layer interposed between the transparent conductive layer and the light-emitting layer, and found that the key to improving luminous efficiency was the result of intensive research on the overcoat layer. It has been surprisingly found that the luminous efficiency of ELD is improved by using a cyanethyl resin layer containing fine particles of a metal compound as the overcoat layer.

Furthermore, when a cyanoethyl resin layer containing fine particles of a metal compound is used, even if the transparent conductive laminate is stacked or rolled up and left under high humidity, other transparent conductive conductors in the cyanoethyl resin layer will be removed. The present invention was achieved based on the discovery that transfer to the back surface of the laminate and occurrence of poor appearance can be prevented.

The organic polymer compound constituting the organic polymer molded article (Δ) in the present invention is not particularly limited as long as it is a transparent organic polymer compound having heat resistance.

Usually, the heat resistance is preferably 100''C or more.

If the heat resistance is less than 100° C., deformation becomes significant when bonding with a light-emitting layer or a water-trapping film, and the resistance value of the transparent conductive layer increases and the appearance becomes poor, which is not preferable.

These organic polymer compounds include, for example, polyimide; polyethersulfone; polysulfone: borivalabanic acid; polyhydantoin: polyarylate, polyethylene terephthalate, polyethylene-2,
Polyester resins such as 6-naphthalene dicarboxylate, polydiallyl phthalate, and polycarbonate;
Examples include aromatic polyamide and cellulose triazetate. Of course, they can be used as homopolymers, copolymers, alone or in blends.

The shape of the molded product of the organic polymer compound is not particularly limited, but sheet-like or film-like products are usually preferred, and film-like products can be rolled up and can be continuously produced. Therefore, it is particularly preferable.

In general, when a film-like material is used, the thickness of the film is preferably 6 to 500 μm, and 12 to 500 μm.
~200 μm.

is particularly preferred.

Pigments may be added to these films or sheets to the extent that transparency is not impaired, or surface treatments such as sand matting may be applied.

Further, these films or sheets may be used alone or in a laminated manner.

The transparent conductive layer <8) of the present invention is composed of a metal oxide. For example, tin and/or fluorine-containing indium oxide, CTO (Cadgaiui TinQxide)
, antimony-containing tin oxide, titanium oxide, and the like. Among them, ITO (2ndium Tin
Oxide>11 is particularly preferable because it has particularly excellent transparency and S-electroconductivity, and also has characteristics such as easy electrode patterning (excellent etching properties).

The thickness of the transparent conductive N layer (B) is preferably 50A or more in order to obtain sufficient conductivity.

Furthermore, in order to obtain a film with sufficiently high transparency, the thickness of the transparent conductive layer (B) is preferably 500 Å or less, more preferably 400 Å or less.

Methods for forming the transparent S conductive layer (8) include physical G1 methods such as vacuum evaporation, sputtering, and ion blating; coating methods using a coating liquid containing conductive fine particles; chemical plating methods, etc. However, a physical film forming method is preferable in terms of uniformity and transparency of the transparent 81 electrolyte layer.

Furthermore, in order to improve the adhesion between the transparent S conductive layer (B) and the organic polymer molded product (A), an intermediate layer may be formed on the organic polymer molded product before forming the transparent 101 layer.

As the intermediate layer, a layer produced by hydrolysis of an organometallic compound such as an organosilicon compound, a titanium alkyl ester, or a zirconium alkyl ester is preferably used. This intermediate layer may have a multilayer structure.

After coating the surface of the organic polymer molded article with a coating solution containing an organometallic compound, the intermediate layer is formed by heating; ion bombardment or ultraviolet rays; It is obtained by hydrolyzing and curing an organometallic compound under the action of radiation such as , TFll, etc.

In addition, for coating the intermediate layer, known coating machines such as a doctor knife, bar coater, gravure roll coater, curtain coater, knife coater, etc. are used depending on the shape and properties of the transparent organic polymer molding and coating liquid. A coating method, a spray method, a dipping method, etc. can be used.

The thickness of the intermediate layer is preferably 100 to 1,000 people, particularly preferably 200 to 900 people.

If the thickness of the intermediate layer is less than 100, it will not form a continuous layer and will not have the effect of improving adhesion.
If the number exceeds 0, cracks or peeling may occur, which is undesirable.The transparent conductive laminate of the present invention has a structure in which transparent conductive layers are laminated on both sides of an organic polymer molded material via an intermediate layer if necessary. You can also do this.

The cyanoethyl resin used to form the cyanethyl resin layer (C) of the present invention refers to
% or more of the resin is cyanoethylated, and examples include cyanoethyl polyvinyl alcohol, cyanoethyl pullulan, cyanoethyl hydroxyethyl cellulose, cyanoethyl saccharose, cyanethyl xylitol, cyanoethyl amylose, and cyanoethyl phenoxy resin. These cyanoethyl resins alone have 2
A mixture of more than one species may be used. Further, cyanethyl resin and other resins may be mixed and used within a range that does not impede the effects of the present invention.

The cyan ethyl resin of the present invention may optionally contain an adhesion promoter,
It can also be used in combination with various additives such as wettability improvers, plasticizers, various stabilizers, No. 11 fuel agents, and antioxidants.

Next, it is preferable that the metal compound fine particles contained in the cyanoethyl resin layer (C) of the present invention have a primary particle size of 100 to 1000 particles.

The metal compound fine particles used in the present invention include antimony-containing tin oxide, tin Il oxide, tin-containing indium oxide, indium oxide, silicon oxide, zinc II oxide, aluminum oxide, yttrium-containing zirconium oxide, tl
Examples include metal oxides such as zirconium oxide, cerium oxide, and titanium oxide, metal fluorides such as magnesium fluoride, barium titanate, lead titanate, lead zirconate titanate, lead lanthanum zirconate titanate, and aluminum titanate. .

Among these, silicon oxide fine particles whose surfaces are hydrophobicized or modified and which can be transparently dispersed in a colloidal dimension as primary particles even in a hydrophobic solvent such as toluene are particularly preferred. In particular, the primary particle size is 100 to 10
00 people is preferable in terms of stability of dispersion.

If the dispersion state of the metal compound fine particles in the cyanoethyl resin layer is poor, the adhesion between the transparent conductive laminate and the light emitting layer will decrease. In this respect, silicon oxide fine particles are preferred because they have good compatibility with the cyanoethyl resin and are uniformly dispersed in the cyanoethyl resin.

The cyanoethyl resin@(C) of the present invention is produced by forming a transparent sN layer (B) made of a metal oxide on an organic polymer molded product (A), and then layering the cyanethyl resin and the metal compound fine particles on top of the transparent sN layer (B) made of a metal oxide. It is formed by coating with a coating liquid containing.

The coating liquid can be obtained from a solution containing the cyanoethyl resin and a solution in which fine particles of the metal compound are colloidally dispersed.

For coating with the coating liquid, the shape of the organic polymer molding and the coating liquid,
Depending on the properties, a coating method using a known coating machine such as a doctor knife, a bar coater, a gravure coater, a curtain coater, a knife coater, a spray method, a dipping method, etc. can be used.

The average in-plane thickness of the cyanoethyl resin layer (C) is 100
-1000 people are preferable, and 100-500 people are particularly preferable. If the average film thickness of the cyanoethyl resin layer (C) is less than 100, it becomes difficult to form a continuous layer, resulting in poor adhesion with the light emitting layer, while if it exceeds 1,000, poor appearance may occur. Undesirable.

There are various methods for measuring the thickness of the cyan ethyl resin layer (C), and a preferred example is shown below.

After covering and reinforcing the cyanoethyl resin layer with a plasma polymerized film, it is hardened with an epoxy resin so as to cover the entire transparent conductive laminate. Thereafter, a section is cut out that shows the cross section of the transparent conductive laminate, and the cyanoethyl resin layer is observed using a transmission electron microscope. If the cyanoethyl resin layer has almost no irregularities, measure the film thickness at several normal parts and average these to determine the average film thickness. If the cyanoethyl resin layer has irregularities, calculate the average film thickness of the recesses and projections, then calculate the average film thickness =
The average film thickness is calculated as 1/2 (the average film thickness of the concave portions and the average film thickness of the convex portions).

By the way, when an ELD is continuously lit under conditions of high temperature and high humidity, the brightness of the ELD may suddenly decrease due to deterioration of the transparent conductive layer.

As a means to prevent deterioration of the transparent conductive layer, the transparent conductive layer (B
) Palladium, platinum, ruthenium directly or via a cyanoethyl resin layer (C).

A thin film 11 (D) of at least one metal and/or metal oxide selected from the group consisting of osmium, iridium, and rhodium can be formed.

These metals and/or gold a oxides may be used alone or as a mixture. Further, a structure in which thin film layers of these metals and/or gold WA oxides are laminated may be used.

The thickness of the metal and/or metal oxide layer (D) is preferably 0.5 Å or more and less than 20 Å. If it is less than 0.5 people, there is no effect of preventing deterioration of the transparent conductive layer.

On the other hand, if the thickness is 20 Å or more, the transparency decreases, which is not preferable.

As a method for forming the metal and/or metal oxide thin film layer (D), a physical film forming method such as a vacuum evaporation method, a sputtering method, or an ion blasting method is preferably used.

[Example] Hereinafter, the present invention will be described in more detail with reference to Examples. Example 1 and Comparative Example 1 Cyanoethyl pullulan was mixed with a mixed solution (1) of medyl cellosolve, methyl edyl ketone, and cyclohexanone and its surface was made hydrophobic. From a solution (2) in which silicon oxide fine particles (particle size: 120 particles) are colloidally dispersed in toluene,
Cyanoethyl pullulan.

The solid content concentration of silicon oxide fine particles is 1.0 weight a
%, 0.5% by weight coating liquid was prepared. For comparison, cyanoethyl pullulan and methyl cellosolve. A coating liquid having a solid concentration of cyanoethyl pullulan of 1.0% by weight was prepared from methyl ethyl ketone and cyclohexanone.

On the other hand, a polyethylene terephthalate film having a thickness of 75 μm was fixed to a substrate holder in a DC magnetron sputtering device, and the vacuum level was evacuated to a vacuum level of 2×10′lIT orr.

After that, Ar102 mixed gas (Oz = 25%) was introduced into the tank and the degree of vacuum was maintained at 4 x 1O-3T orr, and then a target made of In/Sn alloy (Sn = 5% by weight) was used. Transparent S made of indium tin oxide film with a film thickness of about 250 mm by reactive sputtering method
A film with an electric layer was created.

The transmittance of the film with transparent conductive layer (550nl) is 83
%, and the resistance was 260Ω/mouth.

Next, the coating liquid is applied to the surface on which the transparent conductive layer is formed using a bar coater, and then dried at 140° C. for 1 minute to form a cyanoethyl resin layer containing cyanoethyl pullulan and silicon oxide fine particles or a cyanogen layer containing only cyanoethyl pullulan. Forming an ethyl resin layer, Example 1 and Comparative Example 1
A transparent conductive laminate was obtained. The average thickness of the cyanoethyl resin layer was about 350 and about 300, respectively.

Separately, a coating solution in which barium titanate powder was dispersed in cyanoethyl pullulan was applied onto an aluminum sheet with a thickness of 100 μm and dried to form an insulating layer with a thickness of several μm. Furthermore, a coating liquid containing zinc sulfide-based phosphor powder dispersed in cyanoethyl pullulan was applied on top of the test sheet and dried to form a light-emitting layer several tens of micrometers thick. It was created.

After facing the surface of the transparent conductive laminate on which the transparent conductive layer was formed and the light emitting layer of the test sheet, the roller temperature was set to 11.
They were bonded and integrated using a laminator adjusted to 0° C. and a linear pressure of 15 Nf/cm.

At this time, silver paste electrodes were printed in advance on the surface of the transparent conductive laminate on which the transparent conductive layer was formed.
A 15 μm thick stainless steel foil was further connected to the silver paste electrode as a terminal for applying external power and was sandwiched between the transparent conductive laminate and the test sheet.

After that, after connecting the external power application terminal to the aluminum surface, a water-absorbing film [Z E-135, manufactured by Daicel ■] was applied to both sides of the integrally fixed Zamble at a roller temperature of 120°C and a linear pressure of 8 Ny/cm. They were glued and integrated using an adjusted laminator.

Furthermore, a moisture-proof film [manufactured by Nitto Electric Industries ■, 4820] is adhered to the outside of the water-catching film using a laminator adjusted to a roller temperature of 120°C and a linear pressure of /ly/cm. 150Cd) was created.

The moisture-proof film used is larger than the transparent conductive laminate, the test sheet, and the water-trapping film, and the moisture-proof films are pasted together around the ELD. The entire water-trapping sheet and water-catching film are covered.

The brightness and luminous efficiency of the ELD produced in this way were investigated when it was driven at 100V and 400Hz.

The measured results are shown in Table 1.

It can be seen that by using the transparent conductive laminate of the present invention, the luminous efficiency of ELD is improved by about 10%.

Table 1 Example 2 and Comparative Example 2 A mixed solution (1) of cyanoethyl pullulan and cyanoethylpolyvinyl alcohol, methyl ceronelube, methyl ethyl ketone, and cyclohexanone and silicon oxide fine particles (particle size: about 120 particles) whose surface has been made hydrophobic are mixed in toluene. From the colloidally dispersed solution (2), the solid content concentrations of cyanoethyl pullulan, cyanoethyl polyvinyl alcohol, and silicon oxide fine particles were 0.2% by weight and 0.0% by weight, respectively.
．． A coating solution containing 8% F and 0.5% by weight was prepared.

On the other hand, in the same manner as in Example 1, a film with a transparent ring M layer made of indium tin oxide was prepared using a polyethylene terephthalate film having a thickness of 15 μm.

Transmittance (550rv) of film with transparent conductive layer is 83
%, and the resistance was 210Ω/mouth.

Next, Ar gas was introduced into the tank and the vacuum level was increased to 4×10-3.
After maintaining the film thickness at 7 orr, a sputtering method using a PD gold metal target was used to obtain a film with a film thickness of about 2 mm.
An Il1 layer was formed on the transparent conductive layer.

Then a transparent conductive layer, followed by a thin layer of Pd metal! l
The coating liquid was applied to the surface on which layer A was formed using a bar coater, and then dried at 140°C for 1 minute to form a cyanethyl resin layer containing cyanoethyl pullulan, cyanoethyl polyvinyl alcohol, and silicon oxide fine particles with an average thickness of about 350 people. A transparent conductive vA layer of Example 2 was obtained. As Comparative Example 2, a transparent conductive laminate without a cyanoethyl resin layer was used.

Using the transparent conductive laminates of Example 2 and Comparative Example 2, ELD (light emitting area: 150 ci) was performed in the same manner as in Example 1.
It was created.

Similar to Example 1, Table 2 does not show the measurement results of luminance, power consumption, and luminous efficiency when driven at 100 V and 400 Hz.

It can be seen that by using the transparent conductive laminate of the present invention, the luminous efficiency of ELD is improved by about 10%.

Table 2 Example 3 and Comparative Example 3 Solid content concentration of cyanoethyl pullulan, cyanoethyl polyvinyl alcohol, methyl cellosolve, methyl ethyl ketone, and cyclohexanone was 0.2% by weight, respectively.
A coating liquid containing 0.8% by weight of cyanoethyl pullulan and cyanoethyl polyvinyl alcohol was prepared.

A transparent conductive laminate of Comparative Example 3 was obtained in exactly the same manner as in Example 2 except that the above coating liquid was used.

The average thickness of the cyanoethyl resin layer was about 300.

The transparent conductive laminate of Example 3 and the transparent conductive laminate of Comparative Example 3 prepared in exactly the same manner as Example 2 were heated to 40W.
nx 40g After cutting into pieces of 1m in size, stack 5 sheets so that the side on which the cyanoethyl resin layer was formed is in contact with the opposite side,
Roughly cover the top and bottom with glass plates (65g+lx 6511X 2
．． A test sample was prepared by sandwiching the sample with St.

The sample was placed in an atmosphere of 60°C and 90% RH for 20hrtll.
After storage, the transparent conductive laminate was taken out and changes in appearance of the transparent conductive laminate were examined.

The measurement results are shown in Table 3.

It can be seen that the transparent conductive laminate of the present invention does not change in appearance and has excellent storage stability.

Table 3 [Effects of the Invention] According to the present invention, when used as a transparent electrode for ELD, there is no deterioration of the transparent conductive layer, and it has excellent adhesion with the light emitting layer and good transparency, and can be fully used for ELD. A transparent conductive v4Wa body can be provided.

The transparent conductive laminate obtained by the present invention is not only suitable for ELD, but also for example, transparent touch panels, electrophotography, and antistatic material one-sided heating elements.

Solid-state displays, optical memories, photoelectric conversion elements.

It is useful for a wide range of applications such as optical communications, optical information processing, and solar energy utilization materials.

Procedural Amendment Patent Applicant: Teijin Co., Ltd. 1,
Indication of Case Patent Application No. 197999 No. 2, Title of Invention: Transparent Conductive Laminate (1) Specification, page 15, line 19 1 Approximately 350 people and approximately 30
0AJ is corrected to "approximately 600 people and approximately 350 people."

(2) On page 19, line 15, “approximately 350 people” was replaced with “approximately 60 people.”
0 people,” he corrected.

(3) “About 300 people” on page 21, line 6 of the same page was changed to “about 350 people.”
"People," he corrected.

(4) In the third line of page 12, “100 to 500 people” was changed to “1
00-800 people,” he corrected.

(5) Lines 20 on page 15 to line 7 on page 16 are corrected as follows.

[Separately, a coating solution prepared by dispersing barium titanate powder in cyanoethyl pullulan and cyanoethyl polyvinyl alcohol (solid content weight ratio, cyanoethyl pullulan/cyanoethyl polyvinyl alcohol/barium titanate) was prepared on an aluminum sheet with a thickness of 100 μm. powder = 3
5/15, /'50) was applied and dried to a thickness of 40 μm.
An insulating layer was formed. Furthermore, a coating solution containing phosphor powder containing zinc sulfide as a main component dispersed in cyanoethyl pullulan and cyanoethyl polyvinyl alcohol (solid content weight ratio, cyanoethyl pullulan 7/cyanoethyl polyvinyl alcohol/phosphor powder - 10/10) /80) was applied and dried to form a light-emitting layer with a thickness of 40 μm to prepare a test sheet. "that's all

Claims (3)

[Claims] (1) A transparent conductive layer in which a transparent conductive layer (B) made of a metal oxide is formed on an organic polymer molded product (A), and a cyanoethyl resin layer (C) containing fine particles of a metal compound is further formed thereon. Sex laminate. (2) Directly or via the cyanoethyl resin layer (C) on the transparent conductive layer (B), at least one metal selected from the group consisting of palladium, platinum, ruthenium, osmium, iridium, and rhodium; The transparent conductive laminate according to claim 1, further comprising a thin film layer (D) of a metal oxide. (3) The fine particles of the metal compound contained in the cyanoethyl resin layer (C) have a primary particle diameter of 100 to 1000 Å.
The transparent conductive laminate according to claim 1 or 2, which is fine particles of silicon oxide.