JPH0449724B2 - - Google Patents

Description

[Detailed description of the invention]

a. Field of Application The present invention relates to a transparent conductive laminate, more specifically, it is mainly composed of a transparent organic polymer molded product (A), an intermediate layer (B), and a transparent conductive layer (C) made of a metal oxide. The present invention relates to the laminate. b. Prior Art With the advent of a highly information-oriented society, there has been remarkable progress in parts and equipment that utilize the features of both optics and electronics. Furthermore, with the rapid spread of microcomputers, innovations in computer peripherals have been remarkable. Transparent tablets are being developed as input devices for these computers. A transparent electrode using a polymer substrate is used as one form of this component, but for this purpose, higher abrasion resistance and transparency are required than in the case of use as a keyboard. Furthermore, a liquid crystal display as an output device,
The transparent electrode is also used for electroluminescent displays and the like, but the abrasion resistance and transparency of the transparent electrode are similarly required for this purpose. However, a transparent conductive laminate in which a transparent conductive layer of metal oxide is provided on the surface of an organic polymer molded product,
Polymer molded products (mostly films) have many characteristics due to their excellent transparency, flexibility, and processability, but when compared with transparent conductive glass, the abrasion resistance of the transparent conductive layer and the The transparency of the transparent conductive laminate was poor. This is probably due to the difficulty in forming chemical bonds between the transparent organic polymer molding and the metal oxide layer, or the heat resistance of the organic molding is limited, making it difficult to perform sufficient heat treatment during or after the formation of the metal oxide film. This is thought to be due to the fact that crystallization of the metal oxide does not proceed, and optically, the reflection of molded organic polymers such as polyester films used as substrates is greater than that of glass. Previously, JP-A-52-67647, JP-A-52-
As shown in Publication No. 116896, it has been proposed to provide an intermediate layer of Si, SiO, TiO ₂ , Si ₂ N ₄ , etc. as a means to improve the adhesion strength and conductivity between the substrate and the transparent conductive film or optical thin film. There is. However, although this method slightly improves the conductivity and adhesion strength, it is still insufficient and has the disadvantage that optical properties deteriorate. c. Purpose of the Invention The present invention was made in view of the current situation, and its object is to provide a transparent conductive laminate having excellent durability and optical properties. d. Structure of the Invention The present inventors focused on an intermediate layer provided between a transparent organic polymer molded product and a transparent conductive layer as a means to achieve the above-mentioned object. As a result of extensive research into the intermediate layer, we discovered that the intermediate layer with a new composition made of a specific organosilicon compound has sufficient durability to withstand use as an electrode for transparent tablets, and is effective in improving optical properties. We have discovered that there is, and have arrived at the present invention. That is, the present invention provides a transparent organic polymer molded product.
In a transparent conductive laminate in which a transparent conductive layer (C) made of a metal oxide is laminated on (A) via an intermediate layer (B),
The intermediate layer (B) is a layer produced by hydrolysis of one or more organosilicon compounds selected from the group consisting mainly of compounds represented by the following formula and oligomers produced by hydrolysis thereof ), and the layer (B1) is in contact with a transparent conductive layer (C). (However, R ₁ is a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, or

A group represented by [Formula]; R ₂ is a hydrogen atom or a carbon atom number of 1 to
2 alkyl groups; R ₃ and R ₄ each independently represent an alkyl group having 1 to 2 carbon atoms; x and y each independently represent an integer of 1 to 3; w is 0 or 1 to 2
z represents an integer from 1 to 3,
w+z=3. In the formula, R ₅ and R ₆ are each independently a hydrogen atom or a group selected from the group consisting of an alkyl group having 1 to 2 carbon atoms. ) The organic polymer compound constituting the transparent organic polymer molded product (A) in the present invention is not particularly limited as long as it is a transparent organic polymer compound with excellent heat resistance, but usually has a heat resistance of 80°C or higher, preferably 100
℃ or higher, particularly preferably 120℃ or higher, such as polyimide, polyethersulfone, polysulfone, polyparabanic acid, polyhydantoin, polyethylene terephthalate, polyethylene-2,6-naphthalene dicarboxylate, polydiallyl. Examples include polyester resins such as phthalate and polycarbonate, aromatic polyamides, polyamides, polypropylene, and cellulose triacetate. Of course, these can be used as homopolymers, copolymers, alone or as 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 among them, film-like products can be rolled up and can be continuously produced. Therefore, it is particularly preferable. Furthermore, when a film-like material is used, the thickness of the film is 6 to 6.
The thickness is preferably 500μ, more preferably 12 to 125μ. In addition, these films may contain pigments to an extent that does not impair the transparency, which is a feature of the present invention.
Further, surface processing such as sand mat processing may be applied. The transparent conductive layer (C) made of metal oxide used in the present invention includes indium, tin, cadmium,
Examples include oxides of one or more metals selected from the group consisting of zirconium and titanium. These metal oxides are originally transparent electrical insulators, but
It becomes a semiconductor when it contains a trace amount of impurities, when it has a slight oxygen deficiency, when it is an oxide of two or more metals, etc. The metal oxide constituting the transparent conductive film of the present invention must be a semiconductor. Preferred semiconductor metal oxides include, for example, tin-doped indium oxide [(In)
_{2 - x ( Sn ) _ _} can. In order to obtain sufficient conductivity, the thickness of these metal oxide films is preferably 10 Å or more, more preferably 30 Å or more. In addition, in order to obtain a film with sufficiently high transparency, the thickness is preferably 500 Å or less,
More preferably, the thickness is 300 Å or less. Methods for providing these semiconductor metal oxide films on a layer made of at least one type of organometallic compound include methods such as sputtering, vacuum evaporation, and ion plating. Various conventional methods can be used for sputtering, but a low-temperature sputtering method in which plasma is confined around a target using a magnetron and the molded substrate is placed outside the plasma is preferably used. Various conventional methods are used for vacuum deposition.
For example, there are resistance heating methods, high frequency induction heating methods, and electron beam heating methods. There is also a reactive deposition method in which metal is deposited in an oxygen gas atmosphere. Various conventional methods can be used for ion plating, but a high frequency ion plating method in which discharge is performed using a 13.56 MHz high frequency electric field and ions are accelerated using a DC electric field is preferably used. In order to improve the mechanical properties or chemical durability of the metal oxide coating obtained by these methods, heat treatment (annealing) can be performed during or after the coating is formed. In particular, in the vacuum evaporation method, the surface of the molded substrate is hardly heated during film formation, so heat treatment is required after the metal oxide film is formed. In particular, when heat treatment is performed in an oxygen atmosphere such as air, oxidation and crystallization of the metal oxide film progresses, resulting in improved transparency, mechanical properties, and
Chemical durability is significantly improved. The organosilicon compound forming the layer (B1) of the intermediate layer (B) in the present invention is one selected from the group consisting of compounds represented by the following formula (1) and/or oligomers produced by hydrolysis thereof. Or two types of compounds. However, in the above formula, R ₁ is a hydrogen atom, or an alkyl group having 1 to 2 carbon atoms, or the following formula (2) It is a group represented by In addition, R ₂ is a hydrogen atom,
or an alkyl group having 1 to 2 carbon atoms, R ₃ and
R ₄ each independently represents an alkyl group having 1 to 2 carbon atoms, x and y each independently represents an integer of 1 to 3, w represents 0 or an integer of 1 to 2, and z represents an integer of 1 to 3. and w+z=3. Also(2)
In the formula, R ₅ and R ₆ are each independently a hydrogen atom or a group selected from the group consisting of an alkyl group having 1 to 2 carbon atoms. Among these, those containing an amino group (-NH 2 ) as a functional group are preferred as exhibiting excellent durability when used as a laminate of the present invention, such as those containing an amino group (-NH ₂ ) as a functional group.
_NH2- ( _CH2 ) ₃ -Si-( _OCH3 ) ₃ , and/or _NH2
−(CH ₂ ) ₃ −Si−(OC ₂ H ₅ ) ₃ , and or NH ₂ −(CH ₂ ) ₂ −NH−(CH ₂ ) ₃ −Si
-( _OCH3 ) ₃ , and or _NH2- ( _CH2 )-NH-( _CH2 ) ₃ -Si
−(OC ₂ H ₅ ) ₃ and or NH ₂ −(CH ₂ ) ₂ −NH
−(CH ₂ ) ₃ −Si(CH ₃ )−(OCH ₃ ) ₂ , and or NH ₂ −(CH ₂ ) ₂ −NH−(CH ₂ ) ₃ −Si
It is one or more compounds selected from the group consisting of monomers of (CH ₃ )-(OC ₂ H ₅ ) ₂ and/or oligomers with a degree of polymerization of 10 or less produced by hydrolysis thereof. Particularly preferred. The laminate of the present invention exhibits excellent properties even when the intermediate layer (B) is composed only of the above-mentioned intermediate layer (B1), but the following intermediate layer (B2)
By laminating between the intermediate layer (B1) and the transparent organic polymer molding (A), a laminate with surprisingly high transparency can be obtained. The intermediate layer (B2) in the present invention is a layer mainly containing an oxide having a high refractive index, and preferred oxides include titanium oxide or zirconium oxide, which can be formed by sputtering, vacuum evaporation,
Transparent organic It is preferable in terms of adhesion to the polymer molded product (A) and ease of film formation. Alkyl ester containing Ti and/or Zr has the general formula TiO _n (R ₇ ) _o (where R ₇ is an alkyl group,
m, n are positive integers) and/or an alkyl zirconate represented by ZrXp(OR ₈ ) _4- p. Among the alkyl titanates represented by the above general formula, especially m=4+(-1)×3, n=4
+(-1)×2, = 1 to 30 is preferably used from the viewpoint of ease of film formation (for example, coating) and properties of the obtained intermediate layer. The value of may not be uniform but may have a distribution, but especially if the distribution of the value of is
Alkyl titanates with maximum values below 15 are preferred in terms of coating solution viscosity and hydrolysis. In the above general formula, an alkyl substituent R ₇ having 1 to 20 carbon atoms is preferably used. In particular, those with alkyl substituents having 2 to 11 carbon atoms are suitable for film formation operations, such as ease of coating, as well as hydrolysis rate.
It is preferably used in terms of the mechanical properties and transparency of the resulting film. Note that a mixture of two or more of the above alkyl titanates may be used. The alkyl titanate is dissolved in an organic solvent to form a solution, and when applied to the surface of a molded product, it is hydrolyzed, and then converted into dealkyl hydroxyside through a condensation reaction to form a network structure. Depending on the coating conditions, alkyl titanates can approach titanium oxide. The titanium oxide thin film layer containing an organic substance constituting the laminate of the present invention preferably contains 50% by weight or more of titanium oxide in order to exhibit the desired effects of the present invention. In order to exhibit the desired effect of the presence of organic components as described above,
Organic component: 0.1% by weight or more, preferably 0.5% by weight
The above items are required to be included. Examples of the alkyl titanate used in the laminate of the present invention include tetratebutyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrastearyl titanate, and tetra-2-
Examples include ethylhexyl titanate, diisopropoxy titanium bisacetylacetonate, and particularly tetrabutyl titanate and tetrapropyl titanate are preferably used. These alkyl titanates may be used as is,
Precondensed products such as dimers, tetramers, and decamers can also be preferably used. Furthermore, these alkyl titanates may be stabilized with something like acetylacetone before use. In addition, in the alkyl zirconate represented by the above general formula, X is an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group, a phenyl group, a vinyl group, or a β-diketone compound or β- It is a residue of a ketoester compound. Further, R ₈ is an alkyl group having 1 to 6 carbon atoms, and p is an integer of 0 to 4. Examples of zirconium compounds include acetylacetone zirconium salts (tributoxyzirconium acetylacetonate, dibutoxyzirconium diacetylacetonate, monobutoxyzirconium triacetylacetonate, etc.), zirconium tetraalkoxides (tetrabutylzirconate, tetrapropylzirconate, etc.) ,
Zirconium-trialkoxy-monoalkyl acetoacetate (zirconium-tributoxy-
zirconium-dialkoxy-dialkyl acetoacetate (such as zirconium-dibutoxy-diethylacetoacetate), zirconium-monoalkoxy-trialkylacetoacetate (such as zirconium-monobutoxy-triethylacetoacetate), and the like. These Ti and/or Zr alkyl titanates may be composed of one or a mixture of two or more organosilicon compounds. These organosilicon compounds include, for example,
Butyl silicate, ethyl silicate, butyl trimethoxysilane, vinyl trimethoxysilane,
Vinyltriethoxysilane, vinyltris β-methoxyethoxysilane, γ-methacryloxypropyltrimethoxysilane, phenyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, N-βaminoethyl γ-aminopropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, vinyltrichlorosilane, β-(3,4 epoxycyclohexyl)ethyltrimethoxysilane, N-β(aminoethyl)-
γ-aminopropylmethyldimethoxysilane, γ
Examples include -chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-ureidopropyltriethoxysilane. In addition, the layer (B3) produced by hydrolysis of one or more organosilicon compounds selected from the group consisting of these monomers and/or oligomers produced by hydrolysis thereof may not impede the effects of the present invention. It may be provided between the intermediate layer (B1) and (B2) within the range. Further, when forming the intermediate layer (B1), one or more monomers selected from the group consisting of one or more monomers of the above-mentioned organosilicon compounds and/or oligomers produced by hydrolysis thereof are added to the organosilicon compound of formula (1). Two or more types of organosilicon compounds can be mixed and used within a range that does not impede the effects of the present invention. Such organometallic compounds may optionally contain curing catalysts, adhesion promoters, wettability improvers, plasticizers, various stabilizers, flame retardants, antioxidants, lubricants, antifoaming agents, and/or
Alternatively, it can be used in combination with a thickener or the like. The organometallic compound may be used as it is or after being dissolved in a solvent. Examples of such organic solvents include hexane, cyclohexane, heptane, octane, methylcyclohexane, toluene, benzene, xylene, octene, nonene, solvent naphtha, methanol, ethanol, isopropanol, butanol, pentanol, cyclohexanol, methylcyclohexanol, and phenol. , cresol,
Ethyl ether, propyl ether, tetrahydrofuran, dioxane, acetone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, methyl benzoate, glacial acetic acid, chlorophoform, carbon tetrachloride, trichlene , trichloroethane, chlorobenzene, dibromoethane,
Examples include organic solvents such as hydrocarbon-based solvents such as methyl cellosolve, cellosolve, and cellosolve acetate, alcohol-based solvents, ether-based solvents, ester-based solvents, carboxylic acid-based solvents, and halogen-substituted hydrocarbon-based solvents. Among others, isopropanol, butanol, normal
Hexane, toluene, etc. are preferably used. These organic solvents can be used alone or in combination of two or more, if necessary. Furthermore, depending on the case, a water-containing solvent may be used. The intermediate layer is coated on the transparent organic polymer molding, dried, heated, ion bombarded, or exposed to ultraviolet light.
It is cured by radiation such as β rays and γ rays. In addition, for coating the intermediate layer, a known coating machine such as a doctor knife, bar coater, gravure roll coater, curtain coater, knife coater, etc. is used depending on the shape and properties of the transparent organic polymer molding and coating solution. Coating methods, spray methods, dipping methods, etc. are used. The thickness of the intermediate layer (B1) formed from the organosilicon compound is preferably 100 to 1000 Å,
In particular, 200 to 900 Å is preferable. If the thickness is less than 100 Å, a continuous layer will not be formed and the effects of the present invention will not be exhibited. On the other hand, if it exceeds 1000 Å, the optical properties will deteriorate, which is not preferable. When the intermediate layer is composed of the (B1) layer and the (B2) layer, the preferred film thickness ranges are: 200 to 1000 Å for the intermediate layer (B1) and 200 to 1000 Å for the intermediate layer (B2), particularly preferably, The intermediate layer (B1) is 200-900Å and the intermediate layer (B2) is
It is 300-900 Å. In addition, the laminate according to the present invention has a protective layer (D) on the transparent isoelectric layer (C) made of a metal oxide for the purpose of so-called surface protection to improve scratch resistance.
may be laminated. Such a protective layer (D) includes TiO ₂ , SnO ₂ ,
Transparent oxides such as SiO ₂ , ZrO ₂ , ZnO, etc. or transparent organic compound polymers such as acrylonitrile resin, styrene resin, acrylate resin, polyester resin, etc. can be used. The thickness of the protective film (D) can be set arbitrarily within a range that does not deteriorate the characteristics of the transparent conductive layer. Further, the transparent conductive laminate according to the present invention may have a structure in which transparent conductive layers (C) are laminated on both sides of an organic polymer molded product (A) with an intermediate layer (B) interposed therebetween, or a polymer molded product In a structure in which a transparent conductive layer (C) is laminated on one side of (A) via an intermediate layer (B), the purpose is to improve adhesion, surface hardness, optical properties, etc. without impairing transparency on the other side. For example, a layer similar to the above-mentioned intermediate layer (B1), an oxide layer, a nitrogen layer, a sulfide layer, a carbide layer, or an organic layer may be provided. e. Effect The laminate of the present invention has excellent properties not previously available. That is, the intermediate layer (B1) according to the invention
Due to the interaction between the amino groups inside and the metal oxide forming the transparent conductive layer (C), it has extremely excellent abrasion resistance and can be used in transparent tablet applications. Furthermore, in the prior art, the optical properties were degraded due to the presence of the intermediate layer, but in the intermediate layer (B1) according to the present invention, the optical properties were improved, and the optical properties of the intermediate layer (B1) and (B2) were improved. By forming the intermediate layer in a two-layer structure, a transparent conductive laminate having extremely excellent optical properties can be obtained. The transparent conductive laminate of the present invention is not only suitable as an electrode for transparent keyboards, but also the resulting products include, for example, electrophotography, antistatic materials, surface heating elements, solid displays, optical memories, photoelectric conversion elements, It has a wide range of uses including optical communications, optical information processing, and solar energy utilization materials. EXAMPLES Hereinafter, the effects of the present invention will be explained in more detail with reference to Examples. Note that parts in the examples are parts by weight. Example 1 and Comparative Example 1 On one side of a 100 μm thick polyethylene tethyphthalate film, A mixed alcoholic solution of butanol and isopropanol (concentration 0.6% by weight) of a trimer association product produced by hydrolysis of a compound represented by NH ₂ was applied using a bar coater and dried at 120° C. for 1 minute.
The thickness of the thin film after drying was 500 Å. The sample was fixed on a substrate holder in a DC magnetron sputtering device, and the vacuum chamber was evacuated to a vacuum level of 2×10 ⁻⁵ Torr. After that, Ar/O ₂ mixed gas (O ₂ 25%) was introduced into the tank and the degree of vacuum was increased to 5×.
In/Sn alloy (Sn5 wt%) after keeping at 10 ^-3 Torr
An In ₂ O ₃ /SnO ₂ (ITO) film was formed by reactive sputtering using a target consisting of: The film formation rate was about 15 Å/sec, and the film thickness was 200 Å.
The characteristics of the sample are transmittance at a wavelength of 550 nm.
87%, resistance was 490Ω/□. Further, as Comparative Example 1 in contrast to Example 1 described above, an ITO film was directly formed to a thickness of 200 Å on a polyethylene terephthalate film of the same thickness without forming a coating film. The sample characteristics were the transmittance of 83% and resistance of 570Ω/□. For each sample, a transparent switch was fabricated with the ITO film surfaces facing each other with a spacer at a distance of 100 μm. Silicone rubber rod with 7R tip (weight 200
g) was continuously freely dropped onto a transparent switch using a solenoid (stroke 0.5 mm). A switch is pressed each time the rod falls, and the constant current power supply
1mA flows to the switch. The life of the switch was investigated while observing the pulse waveform when the transparent switch was pressed using a synchroscope. In Example 1, in which a coating liquid was applied that defined the life of the switch as the time when the waveform was no longer observed, there was no significant change in the waveform even after 1 million presses (the life was 100
(more than 10,000 times). However, in Comparative Example 1 without a coating film, 5
The waveform became distorted after 10,000 cycles, and the waveform could no longer be observed after 200,000 cycles (lifespan: 200,000 cycles). Example 2 and Comparative Examples 2, 3, and 4 Association degree 5 produced by hydrolysis of a compound represented by the molecular formula (C ₂ H ₅ O) ₃ -Si-C ₃ H ₆ NH ₂ on a 75 μm thick polyethylene terephthalate film.
A mixed alcoholic solution of methanol, ethanol, and isopropanol containing 0.3% by weight of the oligomer was coated on both sides with a gravure roll coater, and 150%
Dry at ℃ for 1 minute. The film thickness after drying was about 200 Å. The sample was placed in a vacuum evaporation device, and after ion bombardment treatment using Ar gas glow discharge,
A mixture consisting of 95 parts of In ₂ O ₃ and 5 parts of SnO ₂ was mixed 5×
It was deposited under 10 ^-5 Torr with a deposition rate of 120 Å/sec.
The metal oxide film thickness was 220 Å. The film has a light transmittance of 38% at a wavelength of 550nm and a resistance
The resistance was 20KΩ/□, and when heat treated at 150°C, the light transmittance was 85% and the resistance was 480KΩ/□. In contrast to the above Example 2, samples of Comparative Examples 2, 3, and 4 were prepared and evaluated as follows. As Comparative Example 2, an ethanol/isopropanol solution containing 0.2% by weight of monomethylpolysiloxane was applied onto the same 75 μm thick polyethylene terephthalate film using a gravure roll coater.
It was dried at 150°C for 1 minute. The film thickness after drying is 150 Å. As Comparative Example 3, an isopropanol solution containing 1% by weight of tetrabutyl titanate (manufactured by Nippon Soda Co., Ltd.), which is one of the layers (B2), was applied onto the same 75 μm thick polyethylene terephthalate film using a gravure roll coater. Dry at ℃ for 1 minute. The film thickness after drying is approximately 200 Å. ITO films were formed under the same conditions as in Example 2 on the samples of Comparative Examples 2 and 3 and on the polyethylene terephthalate film without coating the coating liquid as Comparative Example 4. Comparative Example 2, which was coated with a monomethylpolysiloxane coating liquid, had a transmittance of 84% at a wavelength of 550 nm and a resistance of 480Ω/□, and Comparative Example 3, which had a tetrabutyl titanate coating liquid, had a transmittance of 82% and a resistance of 480.
Ω/□, and comparative example 4 without coating liquid has a transmittance of 83
%, resistance was 550Ω/□. Table 1 shows the resistance change when these samples were rubbed under a load of 100 dl/cm ² using a clock meter (manufactured by TOYOSEIKI). In addition, the evaluation is the resistance after 10 frictions against the resistance R ₀ before friction.
Ratio of R ₁₀ and resistance R ₁₀₀ after 100 frictions R ₁₀ /R ₀ ,
It was done at R ₁₀₀ /R ₀ .

[Table] It can be seen from Example 2 that by providing layer (B1), a transparent conductive laminate having extremely excellent abrasion resistance can be obtained. Examples 3 to 13, Comparative Examples 5 to 12 Intermediate layers each having a two-layer configuration of (B1) layer only, (B2) layer only, (B1) layer and (B2) layer were formed on a 75 μm thick polyethylene terephthalate film. It was formed by the following method. (B1) layer is (C ₂ H ₅ O) ₃ −Si−
A mixed alcoholic solution of butanol and isopropanol of a trimer association produced by hydrolysis of a compound represented by C ₃ H ₆ NHCH ₂ CH ₂ NH ₂ was applied with a gravure roll coater and dried at 150°C for 1 minute. Formed. Layer (B2) was formed in the same manner as in Comparative Example 3 except that the concentration of the coating solution was changed. The film thicknesses of the (B1) layer and (B2) layer were varied by changing the concentration of the coating solution. Table 2 shows the film thickness conditions of the (B1) layer and (B2) layer of each sample and the measurement results of the light transmittance at a wavelength of 550 nm. By providing the layer (B1) according to the present invention,

【table】

[Table] The transmittance reaches a maximum of 87%, and the two-layer structure of (B1) layer and (B2) layer further increases the transmittance to the highest level.
A transparent conductive laminate with improved conductivity of up to 90% was obtained.
The durability of the product with (B1) layer and (B2) layer is as follows:
(B1) Compared to the durability of the one with only a layer,
There was almost no difference. Invention As explained above, the transparent conductive laminate of the present invention can be produced by using the compound constituting the intermediate layer (B1), for example, the prior art disclosed in JP-A-54
It has excellent abrasion resistance that cannot be achieved by the compounds specifically described in Publication No. 8670. Incidentally, according to the specification of the present application, Example 2 using the compound of the present invention, Comparative Example 2 using monomethylpolysiloxane, which is a compound similar to ethyl silicate described in Example 1 of the above publication,
_Resistance R 10 of the laminate of Comparative Example 3 using tetrabutyl titanate described in Example 2 after 10 times of friction under a load of 100 Kg/cm ² versus resistance R ₀ before friction
and the ratio of resistance R ₁₀₀ after 100 frictions R ₁₀ /R ₀ ,
R ₁₀₀ /R ₀ is as shown in Table 3.

[Table] From Table 3, 10 laminates of Example 2 of the present invention
Even after being subjected to friction 100 times, there is little change in the resistance value, indicating that the laminate of the present invention has significantly superior wear resistance compared to that specifically described in the above-mentioned publication. Furthermore, the present invention is based on the following general formulas (1A) and (2A) among silicon-containing organometallic compounds listed as examples of the transparent thermosetting polymer of the invention described in the above publication. "However, 1a, 2a, 3a, 4a, wa, xa, ya and za
1, 2, 3, 4, w, x, y and z of the publication
corresponds to '' It produces a remarkable effect that cannot be obtained even if the compound represented by the following is used as an intermediate layer. That is, a laminate using the same compound as used in Example 2 of the present specification as an intermediate layer (Example
14), the same as above for a laminate (Comparative Example 13) using an oligomer produced by hydrolysis of a compound represented by the formula (CH ₃ O) ₃ -C ₃ H ₆ -SH corresponding to the above formula (1A) The wear resistance is shown in Table 4.

[Table] Also, the same laminate as Example 14 (Example 15),
Formula corresponding to the above formula (2A) Example 1 of a laminate (Comparative Example 14) using an oligomer produced by hydrolysis of a compound represented by
The switch life measured in the same manner as in the comparative example
14 is 500,000 times, while in Example 15
2 million times. It is understood from the wear resistance shown in Table 4 and the above-mentioned switch life that the laminate of the present invention has a remarkable effect compared to the case where the compound described in the above-mentioned publication is used.

Claims (1)

[Scope of Claims] 1. A transparent conductive laminate in which a transparent conductive layer (C) made of a metal oxide is laminated on a transparent organic polymer molded product (A) via an intermediate layer (B), wherein the intermediate layer The layer (B) is a layer (B1) produced by hydrolysis of one or more organosilicon compounds selected from the group consisting mainly of compounds represented by the following formula and oligomers produced by hydrolysis thereof. A transparent conductive laminate characterized in that the layer (B1) is in contact with a transparent conductive layer (C). (However, R1 is a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, or a group represented by the formula; _R2 is a hydrogen atom or a group having 1 to 2 carbon atoms.
2 alkyl groups; R ₃ and R ₄ each independently represent an alkyl group having 1 to 2 carbon atoms; x and y each independently represent an integer of 1 to 3; w is 0 or 1 to 2
z represents an integer from 1 to 3,
w+z=3. In the formula, R ₅ and R ₆ are each independently a hydrogen atom or a group selected from the group consisting of an alkyl group having 1 to 2 carbon atoms. 2. The transparent conductive laminate according to claim 1, wherein the intermediate layer (B) comprises two layers: the layer (B1) and the layer (B2) mainly containing titanium oxide and/or zirconium oxide. 3. The layer (B1) is composed of organosilicon compound monomers containing an amino group (-NH ₂ ) as a functional group and/or a degree of polymerization produced by hydrolysis thereof.
The transparent conductive laminate according to claim 1 or 2, which is produced by hydrolysis of one or more organosilicon compounds selected from the group consisting of 10 or less oligomers. 4. The transparent conductive laminate according to claim 2 or 3, wherein the layer (B2) is produced by hydrolysis of an alkyl ester mainly containing Ti and/or Zr.