JPS61114843A - Conductive laminate - 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 A. Field of Industrial Application The present invention relates to a conductive laminate, and more specifically, to a conductive laminate suitable for use in a display device such as a liquid crystal display device.

Conventional transparent conductive films or transparent conductive laminates are used, for example, as electrodes for liquid crystal displays, electrodes for electroluminescent display devices, electrodes for photoconductive photoreceptors, cathode ray tubes, and window portions of various measuring instruments. It is widely used in electrical and electronic fields such as electrostatic shielding layers, antistatic layers, and heating elements. Among these, transparent conductive films having selective light transmittance are used as window materials for collectors for utilizing solar energy or as window materials for buildings due to their infrared light reflecting ability.

In addition, with the development of information processing, various solid-state displays using electroluminescence, liquid crystal, plasma, and ferroelectric materials have been developed as display devices to replace cathode ray tubes, and these displays always require transparent electrodes. used.

In addition, new electro-optical elements and recording materials based on the interaction or mutual conversion of electrical signals and optical signals are being considered useful for future information processing technology, but these also have transparency and conductivity. A membrane is required. On the other hand, such transparent conductive films are used as window glasses for preventing condensation in automobiles, airplanes, etc., or as antistatic films for polymers, glass, etc.
It can also be used as a transparent insulating window to prevent the dissipation of solar energy.

In particular, in recent years, there has been an increasing demand for high-pixel displays in liquid crystal displays, electroluminescent displays, plasma displays I, electrochromic displays, fluorescent displays, etc. It has been proposed to form a signal application line using a low resistance electrode made of a metal layer at the same time as forming the pixel display speed, and to improve the image quality.

By the way, in display devices such as liquid crystal display devices, the transparent conductive layer of the conductive laminate is generally patterned by photoetching, and in order to remove the photoresist remaining on the conductive laminate, it is immersed in an alkaline solution. After the process and patterning, there is a process of washing the surface of the conductive laminate with acid. In these steps, cracks or localized peeling may occur in the transparent conductive layer, which will cause serious defects in the conductive laminate as described below.

Although the cause of the above phenomenon is not clearly understood, it is thought that internal stress generated within the transparent conductive layer due to the difference in coefficient of thermal expansion between the substrate and the transparent conductive layer acts.

That is, when depositing a transparent conductive layer on a substrate by vapor deposition, the substrate is heated to a temperature of, for example, 300° C. or lower in order to increase the degree of oxidation of the vapor-deposited layer and thereby improve transparency and conductivity. In addition, the thermal expansion coefficient of the substrate is wide (5.5 x IQ-S for the polyether sulfone (PES) used).
c+m/cs/'C, 1.5 X 10-'am/c for polyethylene terephthalate (PET)
trr / "C, whereas indium oxide (Inz), which is widely used as a transparent conductive layer material,
Ox, X≦3) and indium-tin oxide (ITO)
It is on the order of 10-"ca/am/'l:, and there is a large difference in the coefficient of thermal expansion between the substrate and the transparent conductive layer.

Therefore, it is thought that internal stress is generated in the transparent conductive layer at room temperature due to contraction of the substrate, and that this internal stress causes corrosion to progress in the acid or alkaline solution, causing cracks and local peeling.

On the other hand, a two-layer transparent conductive film has been proposed in which an indium oxide film is formed on a transparent substrate and a tin oxide film is then formed (Japanese Patent Laid-Open No. 52-22789). For example, when used as a transparent electrode plate for a liquid crystal display element, the panel is firmly sealed using a glass sealant at a temperature of 500°C or higher, but the transparency and conductivity after this heat treatment are The purpose is to maintain good sexual health.

In this transparent conductive film, if there are pinholes or cracks in the tin oxide layer, the resistance to the aforementioned acids and alkalis will decrease; side etching will be large due to the difference in solubility between the indium oxide layer and the tin oxide layer. , patterning is difficult; when an indium oxide layer is provided on the substrate side, both acid resistance and alkali resistance are unsatisfactory, and as a result, the transparent conductive film is susceptible to cracking and peeling.

C1 Purpose of the Invention The purpose of the present invention is to solve the problems of the conventional conductive laminate as described above and to provide a conductive laminate that exhibits sufficient resistance to acids and alkalis. There is.

21 Structure of the Invention That is, the present invention provides a conductive laminate in which a transparent conductive layer is formed on a substrate, and in which the transparent conductive layer has at least chemical resistance between the substrate and the transparent conductive layer. The present invention relates to a conductive laminate characterized in that it is provided with an intermediate layer that imparts.

In the present invention, as the material of the substrate, inorganic glasses such as quartz glass, soda glass, potash glass, etc. can be used. Regarding polymeric organic materials,
For example, polyethylene terephthalate (PET), polyethylene naphthalate, polyhexamethylene diamide,
Polyetherimide, polymeta-xylene diamine terephthalamide, aromatic polyester or aromatic polyester carbonate whose main components are bisphenol A and its halides and acid dichloride, copolymers of meta-phenylene diamine and isophthalic acid and terephthalic acid, etc. polyamide, polycarbonate, polypropylene, polyimide, polyamide, imidoborighenzimidazole,
Polyethersulfone (PES), polyetheretherketone, polysulfone, polyetherimide, triacetylcellulose can be used. It may have a polarizing filter function, and if stretching is required during manufacturing, both uniaxial and biaxial properties can be used.

A plurality of polymer resins may be laminated or mixed on the surface of the substrate opposite to the surface on which the intermediate layer or transparent conductive layer is formed. For example, it is possible to laminate a vinylidene chloride resin saran coat as a barrier layer to prevent water permeation, and layers with other functions, such as anti-reflection, anti-scratch effects, and gas barrier resins, to Iff/, f-// 〆L520, L51
When a polyvinylidene chloride material consisting of 1 is coated with a wire bar on a polymer film substrate, the effect of preventing water permeation becomes extremely large.

The coating conditions are, for example, diluted to twice that of the substrate, wire bar wet film thickness 3 to 20 μm, conveyance speed 1
00 to 200 m/min, drying hot air at 90 to 140°C, coating layer dry thickness 1 to 70 μm,
The thickness of the base is 0.2 to 20 mm for glass ones;
For those manufactured by Polymer Organicsho, approximately 100n+n+ is suitable.

Materials for the transparent conductive layer include A u SP d , Cr,
Metal thin film such as Ni, Sn Oz, 1nz03, Zn
O5TiOz, Cd01CdO-3nO, and the above-mentioned ITO are suitable. Also, its thickness is 200
-10,000 people, especially 200 to 1,000 people are preferred.

However, in the case of ITO, the tin content is preferably less than 10 atomic %, and in addition to the above components, one containing Cd, Zn, A1, etc. can also be used.

As the material for the intermediate layer, tin oxide or ITO can be used, and the tin content is preferably 7 atomic % or more, particularly preferably 10 atomic % or more. Also, like the transparent conductive layer, Cd, Zn, Aj! Those containing the like can also be used.

FIG. 1 shows a cross section of a conductive laminate 1 according to the invention, in which an intermediate layer 3 and a transparent conductive layer 4 are successively deposited on a substrate 2. FIG. Between the intermediate layer 3 and the transparent conductive layer 4, Al z O is used to improve the light transmittance due to the optical interference effect, for example.
Other intermediate layers such as the s-layer, a layer made of another inorganic substance, or a layer made of a polymeric substance may be provided.

E. Examples In the following, examples in which indium oxide or ITO is used as the transparent conductive layer material will be described.

First, the progress that led to the completion of the present invention will be explained.

In all of the following tests, the substrate was made of PE with a thickness of 100 μm.
S was used, and the intermediate layer and transparent conductive layer were formed by reactive vapor deposition or reactive sputtering.

Test 1 Regarding a conventional conductive laminate without an intermediate layer, the relationship between the tin content of the transparent conductive layer and the sheet resistance was determined. however,
The film forming temperature (substrate temperature during vapor deposition) was 10 to 300°C, and the film thickness was 600°C.

The test results are shown in Figure 2.

Up to a tin content of 7 atomic%, the sheet resistance R0 shows a nearly constant value of 100 Ω/mouth, and when this exceeds 7 atomic%, the sheet resistance gradually increases, and at 10 atomic %, the sheet resistance rises rapidly to 170 Ω/roto resistance. As a result, it becomes difficult to control the sheet resistance to a constant value, and it becomes impossible to maintain a low resistance value. Therefore, the tin content of the transparent conductive layer should be 10 at % or less In particular, it is desirable that the content be 7 atomic % or less.

Wiki 1 (i) For a conventional conductive laminate without an intermediate layer, the relationship between the substrate temperature during film formation (film formation temperature) and the change in sheet resistance before and after immersion in acid was determined. However, the transparent conductive layer contains 10 atom% of tin, in this example In2O2, and the film thickness is 60%.
The acid was 0.05N hydrochloric acid, the temperature was 20°C, and the immersion time was 30 minutes.

The test results are shown in Figure 3. The figure also shows the film forming temperature (Table 1) with respect to the tin content of ITO, which will be described later.

Ro is the sheet resistance before immersion in acid, and R is the sheet resistance after immersion in acid. Ro is 100-300Ω/mouth, light transmittance before acid immersion is 82% at a wavelength of 5,500 people (the same applies hereinafter)
It is.

When the film forming temperature T is lower than 90° C., R/R increases rapidly as T3 decreases. When T exceeds 90°C, R/R decreases to about 2.0, and when T exceeds 150°C, R/R increases slightly. T.

This is because when T is lower than 90° C., the solubility of the transparent conductive layer in acid is high, and as T becomes higher, the above-mentioned solubility decreases. Furthermore, when T exceeds 150° C., although the above-mentioned solubility decreases, R/Ro increases because cracks occur in the transparent conductive layer.

(ii) The closer R/R0 is to 1, the more desirable it is; 2.
It is desired that it be 0 or less. Regarding the conductive laminate using indium oxide or ITO as the transparent conductive layer material (
Find R/R in the same manner as i), and then calculate R/R.

When we investigated the film forming temperature that satisfies ≦2.0, we found that the following
The results shown in the table were obtained. The tin content in ITO was set to 10 atomic % based on the results of Test 1 above.

From Table 1, it can be seen that the higher the tin content of the transparent conductive layer, the more it is necessary to raise the film-forming temperature. In addition, the higher the film formation temperature, the lower the solubility in acids and the lower R/R.
Similar to the case (i) above, as the film forming temperature becomes higher, cracks are more likely to occur.

The reason why cracks occur in the transparent conductive layer as the film forming temperature increases is due to the difference in thermal expansion coefficient between the substrate and the transparent conductive layer (internal stress generated in the transparent conductive layer increases, and this causes acid This is thought to be caused by inducing cracking during immersion.

As can be seen from the results (i) and (ii), when the film forming temperature is increased, R/R decreases, but there is a tendency for cracks to occur. In some cases, even minute cracks that occur in the transparent conductive layer (especially when fine wiring is installed) can cause wire breakage, causing problems with LCD displays using this conductive laminate. This causes some parts of the device and other display devices to not work.

In such cases, even minute cracks are serious defects for the conductive laminate.

In view of the above circumstances, it would be extremely advantageous if cracking could be prevented even if the film formation temperature was raised.

Regarding the conductive laminate 1 having the structure shown in FIG. 1, the material of the intermediate layer 3 was ITO, and the tin content of the intermediate layer was investigated so that cracks and peeling would not occur in the transparent conductive layer 4 due to acid immersion. . However, the transparent conductive layer 3 is indium oxide or ITO1 containing 0 to 8 at% of tin at a film forming temperature of 90 to 300°C, particularly 10
0 to 200°C (100°C for SnO atomic%, 200°C for Sn6 atomic%), and the thickness is 400.

The film forming temperature of the intermediate layer 3 is 20 to 200°C (preferably 50°C
~100°C), and the thickness is 200 people.

R/R by performing acid immersion in the same manner as in Test 2 above.

The tin content in the intermediate layer that maintains ≦2.0 and does not cause cracking or peeling in the transparent conductive layer was determined.

The results are shown in Table 2 below. The same table also includes the film forming temperature T.

Table 2 The following can be understood from Table 2. In order to satisfy the above conditions, the tin content of the transparent conductive layer must be high (indeed, the tin content of the intermediate layer must be high, and the tin content of the intermediate layer must always be higher than that of the transparent conductive layer). need to be higher.

This fact is due to the fact that the higher the tin content of the transparent conductive layer, the higher the film formation temperature needs to be (see Test 2 above), and the internal stress generated in the transparent conductive layer due to the difference in thermal expansion coefficient with the substrate. This is thought to be due to the fact that the internal stress is alleviated by providing an intermediate layer with a higher tin content between the substrate and the transparent conductive layer, thereby preventing cracking and peeling when immersed in acid. It will be done.

With respect to the conductive laminate 1 having the structure shown in FIG. 1, the material of the intermediate layer 3 was tin oxide, and the relationship between its thickness and the change in sheet resistance R/R before and after immersion in acid was determined. The transparent conductive layer 4 was the same as in Test 3 above. Ro is 40
0~600Ω/mouth, light transmittance before acid immersion is 82~75%
It is. Film thicknesses of 300 Å or more were measured using a crystal tube, and thicknesses smaller than 300 Å were determined by calculation from the smoke rate and film formation time (the same applies to subsequent tests).

The test results are shown in Figure 4.

When the thickness of the middle layer becomes less than 80 people, R/R.

There is also. ) is the result.

When the thickness of the intermediate layer is 80 people, R/Ro is 1.4, and as this thickness increases, R/R becomes smaller, and at 500 Å or more, R/R becomes l. No cracks were observed in the transparent conductive layer when the thickness of the intermediate layer was 80 Å or more.

Substantially the same results as above were obtained when the intermediate layer material was ITO containing 10 atomic % of tin.

From the above results, it can be understood that the thickness of the intermediate layer is preferably 80 Å or more.

Test 5 Regarding the conductive laminate 1 having the structure shown in FIG.
For example, ITO containing 6 atomic percent was used, and the thickness was 400. The film forming temperature is 100-140℃ for the former and 2 for the latter.
It is 00℃.

The material of the intermediate layer 3 is 7 at% or more, in this example, tin oxide, and the thickness and the 5 wt% KOH aqueous solution (20°C) are
The relationship between the change in sheet resistance (R/R) before and after immersion for 0 minutes was determined, and the surface condition was observed.

The film forming temperature of the intermediate layer is 20 to 200°C, in this example 50 to 200°C.
The temperature is 100°C.

The sheet resistance R0 before immersion in the KOH aqueous solution is 400 to 300 Ω/hole when the transparent conductive layer 1 is made of ITO containing 6 atom % of tin, and the light transmittance is 80% or more.

The test results are shown in Table 3 below. In the same table, ○,
Δ and × indicate the following conditions (the same applies to subsequent tests).

○: R/R, ≦2.0, no cracks or peeling observed △:
R/Ro≦2.0, no cracking or peeling x:
R/Ro>2.0, both cracking and peeling occur Table 3: When the thickness of the intermediate layer is 70 Å or more, R/R is less than 2.0, and no cracking or peeling is observed.

Test 6 Regarding the conductive laminate 1 having the structure shown in FIG.
ITO or tin oxide changed to
00°C (70°C in this example), the thickness was set to 200 people, and a test similar to that in Test 5 above was conducted to determine the relationship between the tin content of the intermediate N2 and the alkali resistance. The sheet resistance R before KOH immersion is 400 to 300 Ω/hole, and the light transmittance is 80% or more.

The test results are shown in Table 4 below.

Table 4: R/Ro is 2.0 when the tin content of the intermediate layer is 7 at% or more.
Below, no cracks or peeling are observed.

The results of Tests 1 to 6 above are summarized as follows.

(a) In order to improve acid resistance, (11) the tin content of the intermediate layer is higher than that of the transparent conductive layer, and is 7 atomic % or more, preferably 10 atomic % or more.

(2) The thickness of the intermediate layer may be at least 80 Å, and the film forming temperature may be at most a temperature that the substrate can withstand. For example, in PES, the temperature may be 200°C or less.

(3) The tin content of the transparent conductive layer is 10 atomic % or less, preferably 7 atomic % or less.

(4) The higher the tin content, the higher the film formation temperature of the transparent conductive layer (it is better to set it to the temperature shown in Table 1 according to the tin content. However, the temperature that the substrate can withstand, for example PES In this case, the temperature shall be 200℃ or less.

(b) In order to improve alkali resistance, (5) the above (
Same as 1), (6) The thickness of the intermediate layer shall be 70 Å or more, and (2)
).

The present invention has been made based on the above findings.

Next, specific examples of the present invention will be described.

100μ thick coated with water permeation prevention layer made of Den resin.
An intermediate layer and a transparent conductive layer were sequentially deposited on the surface of the PES sheet substrate opposite to the water permeation prevention layer to obtain a transparent conductive laminate.

The vapor deposition apparatus is partitioned into chambers 30.31b, 31a, and 32, and a take-up roll 36 and a supply roll 33 for the sheet substrate 2 are arranged in the chambers 32.30 on both sides, and the substrate 2 is sequentially transferred between the two rolls. The following processing is performed while the data is being sent.

First, the sheet substrate 2 is conveyed in a meandering manner by five conveyance rollers 26 in the chamber 30, and is preheated by a halogen heater lamp 27 disposed between the sheet substrates 2 to remove adsorbed moisture on the sheet substrate 2. , is subjected to discharge treatment in the discharge device 25 and cleaned.

The operating conditions within the chamber 30 are as follows.

Heating temperature -80~150℃, degree of vacuum: 10-'~10
-'Torr, electric current (0 to 100 OW (OW is not subjected to discharge treatment)) Next, the sheet substrate 2 is conveyed into the chamber 31b, and is brought into close contact with a constant temperature roller 29 (controllable between -10°C and 250°C) to a predetermined position. While maintaining the temperature, the intermediate layer is evaporated by the 1 atmosphere generated from the evaporation source 42b to form an intermediate layer. The thickness of the intermediate layer is detected and controlled by a crystal vibrating film thickness monitor 28.

The operating conditions in chamber 3Ib are as follows.

Evaporation source 42b: binary evaporation of 5nSSn and In, SnO
□ or ITO containing 7 at% or more of Sn Heating method: Electron gun heating (S n O2 or ITO)
Resistance heating (Sn or binary combination of Sn and In) Gas discharge device 37; High frequency discharge (details will be described later) Evaporation rate: 100 x 1000 people/min Oxygen pressure: 5 Xl0-'~3. OXl0-'Torr
High frequency power: 200~800W (13,56M
Hz) Substrate holding temperature: 20 to 200°C, in this example 50
~100°C Next, the sheet substrate 2 is conveyed into a chamber 31a having a similar structure to the chamber 3ib, and a transparent conductive layer is formed on the intermediate layer.

The operating conditions within the chamber 31a are as follows.

Evaporation source 42a: In or ITO below 5nlO atomic % Heating method: Electron gun heating or resistance heating discharge device 37: Same evaporation rate as above: 100 to 2000 people/min Oxygen pressure
: 3 Xl0-'~'3 Xl0-'Torr high frequency power; Same as above Substrate holding temperature: 90°C if the evaporation source does not contain Sn
For example, the temperature is 130° C., and if the evaporation source contains 5 atomic % of Sn, the temperature is 180° C. or higher, for example 190° C. Other conditions are the same as in the chamber 31b.

Finally, the sheet substrate 2 is conveyed into the chamber 32, the sheet resistance is measured between the two conveyance rollers 26 by the sheet resistance monitor 24, and the sheet substrate 2 is wound onto a take-up roll 36.

The details of the high frequency discharge device 37 arranged in the chambers 31b and 31a are as follows.

As shown in FIG. 6, the discharge electrode includes a plurality of rings 45 arranged so as to enclose the circumferential surface of the gas (oxygen) introduction tube 43.
It consists of a and 45b. A water-cooled tube is wrapped around the entire discharge device 37 to cool it, but this water-cooled tube is not shown.

One ring-shaped electrode 45a is connected to the high frequency introduction terminal 48 by a lead wire 67, and the other ring-shaped electrode 45b
is connected to the metal adhesion prevention member 44 by a lead wire 58, and the metal attachment is grounded via a plate 39. The electrodes 45a and 45b have, for example, an inner diameter of 2 to 10 cmφ and a width of 0.
．． It consists of a 5 to 10 cm band ring made of copper, stainless steel, or platinum, and generates a C-coupling type (capacitive coupling type) discharge within the introduction tube 43. By wrapping a water-cooled tube around the band ring and cooling it, high-power and high-frequency waves can be introduced for a long period of time.

The reactive vapor deposition method using the gas discharge device 37 as described above has the following features (1) to (6) compared to conventional methods.

(1) Since the reaction gas is activated or ionized by applying a high-frequency voltage to the discharge device, it is possible to increase the reactivity of the reaction gas and promote the reaction with the vapor deposition material, and in the discharge section, the discharge electrode 45 can be provided at a position not in contact with the discharge area. Therefore, the electrode 45 is not bombarded during discharge, and the electrode material does not mix into the gas and contaminate the deposited film.On the other hand, it is also possible to discharge by applying a DC voltage to the discharge device. However, in this case, the electrode needs to be placed in contact with the discharge region, which is inappropriate.

(2) By arranging the discharge electrode 45 around the outer circumference of the introduction tube 43, the gas inside the introduction tube 43 can be efficiently ionized or activated by maintaining the gas pressure at a high level without increasing the gas pressure in the vapor deposition space. can be converted into

Therefore, the amount and rate of gas introduction can be increased. In addition, the gas pressure in the evaporation space can be lowered, eliminating the need for electric field acceleration of the evaporation material, allowing the use of both metals and oxides as the evaporation material, widening the selection range and broadening the range of substrates to be evaporated. , heating and cooling can be easily performed.

(3), the gas discharge area is limited to the inside of the introduction tube 43, and the electrode 45
Since the electrode 45 is isolated from the electrode 45, it is possible to prevent the electrode 45 from being bombarded by gas ions generated during discharge.

In other words, it is possible to prevent the electrode material from being heated or evaporated by bombardment, thereby preventing contamination of the deposition space.

(4) Since the adhesion prevention members 44 and 46 were provided so as to enclose the introduction tube 43 and the electrode 45, the introduction tube 43, the electrode 45,
It is possible to prevent evaporated substances from adhering to the high-frequency introduction terminal 48, and also to effectively prevent leakage of high-frequency waves through the plate 39, the electrode 45, and the introduction tube 43, so that discharge can be performed stably.

(5) Since the gas discharge device 37 can be installed in the Pelger with a simple structure via an installation stand, a plurality of gas discharge devices can be installed at a time.

(6) Since the direction of the gas discharge port can be easily changed, it can be set so that the discharge is not disturbed even when the evaporation rate changes. In particular, if the gas discharge device is installed so that the gas discharge port is not directed between the evaporation source and the substrate, the discharge will continue stably and the quality of the deposited film can be made uniform.

(7) By cooling the mount, the discharge electrode 45, and the adhesion prevention member 44 with water, heating during discharge can be prevented, high-power radio frequency waves can be introduced, and reactive vapor deposition can be promoted.

Thus, as shown in FIG. 7, a transparent conductive laminate was obtained in which the intermediate layer 3 and the transparent conductive layer 4 were sequentially formed on one surface of the substrate 2, and the water permeation prevention layer 5 was formed on the other surface. .

The aforementioned chambers 31b, 31. The sheet resistance, light transmittance, and acid resistance and alkali resistance of the obtained transparent conductive laminate were evaluated in the same manner as in Test 5.6 above under each operating condition.

Examples of the results are shown in Table 5 below. In the same table, T is the substrate holding temperature and RF is the high frequency power.

(The following is a blank space) Comparative Example 1.2 does not contain Sn in the intermediate layer, and as a result, acid resistance and alkali resistance are not good. On the other hand, all of the examples that satisfy the above-mentioned conditions have excellent acid resistance and alkali resistance, and also show sufficiently satisfactory sheet resistance and light transmission rate.

The above example is an example in which two layers, an intermediate layer and a transparent conductive layer, are laminated with side heat, but it is also possible to continuously change the tin content and film formation temperature from the intermediate layer to the transparent conductive layer. good. The relationship between the distance from the substrate surface and the tin content of the conductive laminate thus formed is shown in FIG. 8, for example.
In the figure, curve A shows the tin content of the layer formed as in the above example, and curves B, C, D and E show the tin content of the layer in which the tin content was changed continuously. Tin content fi7~1
The range of 0 atomic % is the boundary region between the intermediate layer and the transparent conductive layer.

Curves B, C, D, or E can be obtained by continuously changing the deposition operating conditions.

In the film forming chamber 31b shown in FIG. 5, a tin or tin oxide evaporation source 42b-1 is provided on the introduction side of the substrate transport as shown in FIG. 9, and an indium or indium oxide evaporation source 42b- 2 on the substrate delivery side, the tin concentration distributions shown in curves B, C1D, and E can be obtained.

FIG. 10 shows an example of a liquid crystal display device based on the present invention in which a transparent conductive layer and an intermediate layer of a conductive laminate are pattern-etched into a predetermined pattern.

A transparent conductive laminate 1 is formed by sequentially laminating a patterned intermediate layer 3 and a transparent conductive layer 4 on a transparent substrate 2, with the transparent conductive layers 4 facing each other, and liquid crystal A liquid crystal display device 9 is formed by sandwiching the liquid crystal display device 6 in a square shape. On both sides of the transparent substrate 2, a water permeation prevention layer 5,
Deflection films 8 are sequentially deposited.

The conductive laminate disclosed in the present invention is suitable for use not only in liquid crystal display devices but also in various display devices such as electroluminescent display devices, electrochromic display devices, and fluorescent display devices.

As described in detail in Section 1 of the Invention, the conductive laminate according to the present invention has a structure in which an intermediate layer is provided between the substrate and the transparent conductive layer to impart at least chemical resistance to the transparent conductive layer. Therefore, it has high resistance to acids and alkalis, and can be used with full reliability when used in liquid crystal display devices, for example, without causing cracks or peeling on the surface during post-patterning processing. .

[Brief explanation of drawings]

The drawings all show examples of the present invention: Figure 1 is a cross-sectional view of a conductive laminate, Figure 2 is a graph showing the relationship between the tin content and sheet resistance of the transparent conductive layer, and Figure 2 is a graph showing the relationship between the tin content and sheet resistance of the transparent conductive layer. Figure 3 is a graph showing the relationship between the film formation temperature of the transparent electrosensitive layer and the change in sheet resistance due to acid immersion, and Figure 4 is a graph showing the relationship between the film thickness of the tin oxide intermediate layer and the change in sheet resistance due to acid immersion. , FIG. 5 is a schematic cross-sectional view of the vapor deposition apparatus used for film formation, FIG. 6 is a perspective view of the gas discharge device in the thin deposition apparatus, FIG. 7 is a cross-sectional view of another conductive laminate, and FIG. 8 is a cross-sectional view of another conductive laminate. A graph showing an example of the relationship between the distance from the substrate surface and the tin content in the layer. Figure 9 is a schematic diagram of another vapor deposition apparatus used for film formation □
Sectional view: FIG. 10 is a cross-sectional view of a liquid crystal display device. In addition, in the symbols shown in the drawings, 1...
... Conductive laminate 2 ... Base 3 ... Intermediate layer 4 ... Transparent conductive layer 5 ... ...Water permeation prevention layer 6...Liquid crystal 7...Alignment film 8...Deflection film 9... ...Liquid crystal display device 29... Constant temperature roller 37 ... Gas discharge devices 42a, 42b ... Evaporation source. Agent Patent Attorney Hiroshi Aisaka (Figure 1, Figure 2, Sn C8+0n) Figure 3, Figure 4, Figure 5, Figure 6! Fig. 7 Fig. 8 Illustration (A book front page 6 7 Giant Bird 1 (Included) Fig. 9 Fig. 10 (Spontaneous) Proceedings of the 10th February 10, 1988 1, Indication of the incident 1988 Patent Teruon No. 236442 No. 2, Name of the invention Conductive laminate 3, Relationship to the case of the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name Name
(127) Konishiroku Photo Industry Co., Ltd. 4, Agent address: 2-4-11 Shibasaki-cho, Tachikawa-shi, Tokyo 'FINE
Bill 6, Number of inventions increased by amendment 7, Detailed description of the invention column (1) of the specification subject to amendment, page 7, lines 4-5 of the specification, “opposite side” is changed to “
"Between the opposite surface or substrate and the intermediate layer." (2), ``r 300℃'' on the 5th line from the bottom of page 9 is changed to ``2''.
00℃" I corrected it. (3) 8, page 18, lines 4-5, "200 people" is corrected to "200 people, transparent conductive layer 4 and". -That's all-

Claims (1)

[Claims] 1. In a conductive laminate in which a transparent conductive layer is formed on a substrate, an intermediate layer that imparts at least chemical resistance to the transparent conductive layer is provided between the substrate and the transparent conductive layer. A conductive laminate characterized by: