JPH05156426A - Method for forming polymer formed body coated with transparent conductive film - Google Patents

Abstract

PURPOSE:To form a transparent conductive plastic film with the adhesiveness of the substrate to a thin transparent conductive film improved in wear resistance and surface hardness by forming a specified primer layer on the surface of the polymer substrate and then forming thin transparent conductive film of metal thereon. CONSTITUTION:A primer layer obtained by three-dimensionally cross-linking a binder polymer (1,000 to 500,000 number average mol.wt. expressed in terms of GPC-polystylene) having a silicon group shown by the formula by metal- oxygen bond is formed on the surface of a polymer substrate. A transparent conductive film of metal or metal oxide is then formed thereon. In the formula, R<1> and R<2> are hydrogen or a hydrocarbon group selected from 1-10C alkyl, aryl, and aralkyl, X is a group selected from halogen, alkoxyl, acyloxy group, aminoxy group, phenoxy group, thioalkoxy group and amino group, and (a) is an integer of 0 to 2. Consequently, a film useful for electrophotographic recording, antistatic effect, electromagnetic wave shielding, etc., is provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polymer molding covered with a transparent conductive thin film. More specifically, it relates to a method for forming a transparent conductive thin film on a polymer molded body, which improves abrasion resistance, surface hardness, and adhesion to the surface of a substrate.

[0002]

2. Description of the Related Art Transparent conductive films are used in many fields such as image pickup tubes, electroluminescence (EL) display boards, anti-fogging and anti-icing products for window glass of aircrafts, liquid crystal display boards and the like.

A typical transparent conductive material used in the past has been a metal oxide such as tin oxide deposited on a glass substrate, but recently, a transparent conductive material such as this has been formed on a plastic substrate. Transparent conductive films with various metal oxides are now on the market (plastic age, 2
Volume 8, Issue 2, p. 75 (1982)).

However, these plastic transparent conductive films have a higher adhesiveness to the substrate than those made of glass.
It was inferior in wear resistance and surface hardness.

[0005]

DISCLOSURE OF THE INVENTION The present invention improves the drawbacks of these transparent conductive plastic materials, and provides a transparent conductive polymer molding excellent in adhesion to a substrate, abrasion resistance and surface hardness. It provides a manufacturing method.

[0006]

Means for Solving the Problems As a result of repeated studies to solve the above-mentioned problems of the prior art, the present inventors have used a primer using a thermosetting acrylic resin as a precoat layer, It has been found that a transparent conductive polymer molding having excellent adhesion to a polymer base material, abrasion resistance, and surface hardness can be produced by a method of forming a metal or a metal oxide thereon.

That is, according to the present invention, a primer layer formed by three-dimensionally cross-linking a binder polymer having a silicon group as a side chain by a metal-oxygen bond is formed on the surface of a polymer base material, and then formed thereon. The present invention relates to a method for producing a polymer molded body coated with a transparent conductive thin film, which forms a transparent conductive thin film made of a metal or a metal oxide.

Here, the binder polymer having a silicic group in its side chain means the following general formula (1)

[0009]

[Chemical 2] (In the formula, R ¹ and R ² are hydrogen or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group, X is a halogen, an alkoxy, an acyloxy, an aminoxy, a phenoxy, a thioalkoxy and an amino group. A group selected from the group, a is an integer of 0 to 2) means a polymer having at least two groups in the molecule. Such polymers include acrylic acid ester, methacrylic acid ester, acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene, maleic acid, maleic anhydride. The number average molecular weight based on the selected homopolymer or copolymer is 1,000 to 50.
Vinyl resins and the like up to 30,000 (GPC-polystyrene conversion) are included. A more desirable value for this molecular weight is 5,000 to 300,000.

As an example of the binder polymer, the following general formula (4) is used.

[0011]

[Chemical 3] (In the formula, R ⁶ is hydrogen or an alkyl group having 1 to 5 carbon atoms,
R ⁷ represents an alkyl group having 1 to 5 carbon atoms, l is 1 to 3,
Alkoxysilyl represented by a radical copolymer having a side chain of an alkoxysilyl group represented by m / n in a molar ratio of 99/1 to 80/20 (number average molecular weight 1,000 to 500,000: polystyrene conversion). Examples include polymers having a group in the side chain.

Further, as a method for forming a transparent conductive thin film made of a metal or a metal oxide on the primer layer, a vacuum vapor deposition method or a sputtering method is preferably adopted (see "Handbook of preparation and evaluation of thin film and its application technique"). Fuji Techno System, 1984).

As the metal or metal oxide material for forming the transparent conductive layer by the vacuum vapor deposition method, SnO ₂ , In
₂ O ₃ , In ₂ O ₃ —SnO ₂ , Cd ₂ SnO ₄ , Zn
_{O-Al 2 O 3, SnO} 2 -Sb 2 O 3, Au and P
The compound containing a compound selected from d as a main component is 10
^{When a} polymer molded body is run in a metal vapor generated by heating these metals or metal oxides to a melting point or higher under a vacuum of about ⁻⁴ to 10 ⁻⁵ Torr, the metal vapor forms a polymer. It condenses on the body surface and becomes fine particles to form a thin film.

In the sputtering method, a thin film is formed on the surface of the polymer molded body by utilizing the sputtering phenomenon that occurs when the inert gas ions generated by glow discharge in vacuum are accelerated and collided with the target surface. The material for forming the transparent conductive layer used at this time is the same metal or metal oxide as in the above-mentioned vacuum deposition method. Since the sputtering method can form a thin film at a lower temperature than the vacuum deposition method, it is convenient for forming a transparent conductive film on the surface of the polymer molded body.

In the present invention, the primer layer is formed on the polymer substrate by 1 to 90% by weight of a binder polymer represented by the general formula (1) having a silicon group as a side chain, and the following general formula (2) R ³ _b M (OR ⁴ ) _4-b (2) (In the formula, R ³ represents hydrogen, an alkoxy group having 1 to 5 carbon atoms or a phenoxy group, an alkyl group having 1 to 5 carbon atoms or a phenyl group, and R ⁴ Represents an alkyl group having 1 to 5 carbon atoms or a phenyl group, M represents Si, Ti, Sn or Zr, and b represents an integer of 0 to 2) and / or the following general formula (3 ) (R ⁵ O) _c M ′ (Acac) (3) (M ′ represents Ti, Sn or Zr, and R ⁵ has 1 carbon atom.
An alkyl group of 5 to 5, Acac is an acetylacetonate, and c is an integer of 2 to 4) and a Lewis acid is added to 99 to 10% by weight of a metal chelate compound in an organic solvent solution. It can be carried out by coating the surface of the polymer substrate with the polymer and then thermally crosslinking it.

Specific examples of the binder polymer having an alkoxysilyl group in the side chain used in the present invention include acrylic acid, methyl acrylate, ethyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, and anhydrous. At least one compound selected from maleic acid and preferably 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltributoxysilane, 3-methacryloxypropylpropoxysilane, 3 -Methacryloxypropylisopropoxysilane, 2-methacryloxyethyltrimethoxysilane, 2
-Methacryloxyethyltriethoxysilane, 2-methacryloxyethyltributoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltributoxysilane, 3-acryloxypropyltrimethoxysilane,
3-acryloxypropyltriethoxysilane, 3-acryloxypropyltributoxysilane, 2-acryloxyethyltrimethoxysilane, 2-acryloxyethyltriethoxysilane, 2-acryloxyethyltripropoxysilane, 2-acryloxyethyl It is a radical copolymer with a compound selected from tributoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane and acryloxymethyltributoxysilane, the composition of which is a molar ratio of 99: 1.
The range of 80:20 is preferable. When maleic anhydride is used, its polymerization amount is preferably 20% by weight or less based on the whole polymer.

These copolymers can be prepared by a known synthesis method using a known polymerization initiator. In this case, the solution radical polymerization method is preferable.

In the above-mentioned polymerization, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane and cyclohexane, ester-based solvents such as ethyl acetate and ethylene glycol monoethyl ether acetate, and acetone. , Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones,
An alcohol-based or ether-based solvent such as methanol, ethanol, isopropanol, n-butanol, isobutanol, diglyme, or ethylene glycol monoethyl ether can be used.

The number average molecular weight of the obtained copolymer is preferably 1,000 to 500,000 in terms of polystyrene. More preferably, 5,000 to 300,00
It is 0. The monomer concentration is preferably 0.5 to 5 mmol / ml, more preferably 0.8 to 1.5 mmol / ml.
ml. The polymerization temperature is preferably 60 to 80 ° C, more preferably 65 to 75 ° C. The polymerization time is preferably about 4 to 8 hours, more preferably about 6 to 7 hours.

In an organic solution of a binder polymer having an alkoxysilyl group in the side chain thus obtained, a compound represented by the general formula (2) and / or (3) (hereinafter referred to as a cross-linking agent) is added with a Lewis acid or the like. When the primer composition to which the crosslinking accelerator is added is applied onto a substrate and heated, the primer layer is formed by at least one or more kinds of metal-oxygen bonds (as metals, Si, Ti, Zr, Sn).
A dimensional stitch is formed and the resulting primer layer crosslinks while maintaining transparency.

The binder polymer used in the crosslinking reaction is
The polymerization solution obtained by the polymerization may be used as it is or may be isolated once. However, it is preferable to use the polymerization solution obtained in the operation as it is.

As the cross-linking agent (2) used, tetramethoxysilane, tetraethoxysilane, tetraphenoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane, ethyltriphenoxysilane, phenyltrimethoxysilane, Alkoxysilanes such as phenyltriethoxysilane and phenyltriphenoxysilane, tetrabutyl titanate,
Examples thereof include titanic acid esters such as tetraisopropyl titanate, tin alkoxides such as tin methoxide and tin ethoxide, zirconium alkoxides such as zirconium ethoxide, zirconium isopropoxide and zirconium butoxide.

On the other hand, as the cross-linking agent (3), a chelate compound such as titanium alkoxybis acetylacetonate, tin acetylacetonate dibromide, zirconium acetylacetonate or the like is used.

These cross-linking agents (2) and / or (3) used during cross-linking may be used alone or in combination of two or more. The crosslinking agent used for the binder polymer having an alkoxysilyl group in the side chain is preferably 10 to 99% by weight.

When the amount of the cross-linking agent added is less than 10% by weight, the heat curing may be insufficient, and when it is more than 99% by weight, the crosslinking proceeds excessively and the adhesion of the primer layer is deteriorated. There is. The amount of crosslinking agent used is 1
When it is 0 to 99% by weight, the composition of the two components can be selected as desired, the shrinkage phenomenon of the primer layer at the time of curing is not observed, and its transparency is maintained. When high hardness (5H or more) is required, the amount of the cross-linking agent may be 40% by weight or more.

The process leading to the formation of the primer layer on the substrate is easily achieved, for example, by using the known sol-gel method.

That is, a Lewis acid is added to an organic mixed solution composed of a binder polymer having an alkoxysilyl group in the side chain and a cross-linking agent and stirred at room temperature to obtain a stable sol solution in 20 to 30 minutes. This sol solution is applied onto various base materials by spin coating (or dip coating) and heated in the atmosphere to form a transparent and highly adhesive primer layer through a sol-gel transition.

The temperature at the time of crosslinking and curing is set in the range of 50 ° C. to 300 ° C. depending on the heat resistance of the polymer base material used.
More preferably, it is 80 ° C to 200 ° C. The time required for curing may be about 5 minutes to 2 hours, and the higher the curing temperature, the shorter the required time. As the Lewis acid used at the time of curing, a protic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid or acetic acid is preferable. At this time, the crosslink density of the cured product can be 70% or more.

The type of polymer base material used is polypropylene, polystyrene, methacrylic resin, polyvinyl chloride, polyamide, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, cellulose acetate, maleimide copolymer, diallyl phthalate, melamine resin, Polysulfone, polyethersulfone, polyarylate, polyimide, polyetheretherketone, methacryl-styrene copolymer resin,
There are polyphenylene oxide, polyphenylene sulfide, polymethylpentene-1, polyacetal, acryl-vinyl chloride copolymer resin, etc., and they are not particularly limited.

The primer coating having the above composition formed on the substrate in this manner is excellent in transparency and adhesiveness at a different interface (inorganic-organic interface).

On the primer layer formed on a plastic substrate, for example, an organic solution obtained by adding a Lewis acid to a compound represented by the general formula (2) and / or (3) is applied and heat-cured. The synergistic effect of the primer coating and the polymetalloxane formed from the compounds (2) and / or (3) provides the advantage of excellent transparency, surface hardness and abrasion resistance. Solvent used in the formation of the polymetalloxane layer on the primer layer,
Regarding the Lewis acid used, the crosslinking temperature, and the crosslinking time, the same conditions as those for forming the primer layer can be used. At this time, (2) and / or (3) used can be used in an arbitrary amount ratio.

In this way, the thermal crosslinking reaction is carried out in a uniform state, and 3
The film obtained by dimensional stitching is in a completely compatible state and shows high transparency. Furthermore, it shows the properties superior to those predicted from the properties and composition ratio of each polymer.

[0033]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

The formation of the primer layer was performed by spin coating on a polymer substrate. The surface hardness of the coating is J
It was conducted according to the pencil hardness test described in IS-K5401.
The peeling test of the coating was performed according to the method described in JIS-K5400. The coating thickness was measured from the fracture surface using a scanning electron microscope. The transparency of the coating is 300-900.
It was judged from the UV-VIS absorption at nm.

Although the synthesized binder polymer can be used for forming the primer layer with or without isolation, the example in which the binder polymer is not isolated is shown in this embodiment for simplification of the operation. The molecular weight of the binder polymer used in the examples is about 100,000 to 120,000 in terms of number average molecular weight (GPC-polystyrene conversion).

The conditions for forming the transparent conductive film on the surface of the polymer substrate by sputtering are as follows.

Equipment: ULVAC SV-450-T10 Method: DC magnetron side sputter Power: 1 W / cm ² O ₂ partial pressure: 1.5% Vacuum degree: 0.005 Torr T / S distance: 53 mm, thickness: 2000 Å _{target: In 2 O 3 -SnO 2 (} SnO 2 is 10 wt%) example 1 methyl methacrylate (8.56g, 85.5mmo
1), 3-methacryloxypropyltrimethoxysilane (1.12 g, 4.5 mmol), azoisobutyronitrile (AIBN) (15 mg, 90 μmol), and diglyme (80 ml) are put in a sealed tube and deaerated. While shaking the sealed tube, the reaction was carried out at 70 ° C. for 6 hours in a constant temperature bath.
After completion of the reaction, open the sealed tube and add 10 ml of the reaction solution to 50 ml.
Iglyme (10 ml) and tetraethoxysilane (0.24 m
Ol, 50.34 g) was added, and then 0.1 N hydrochloric acid (5 m
l) was added dropwise. After 30 minutes, 0.1 ml of the reaction solution was spin-coated on a polymethylmethacrylate (length 50 mm × width 50 mm × thickness 2 mm) substrate. The coated substrate was then transferred to an oven and heated at 130 ° C. for 1 hour, forming a transparent thin film on the substrate.

The UV-VIS absorption before and after coating has a maximum of 0.3% in the wavelength range of 300 to 900 nm.
However, the transparency of the substrate by the coating is hardly impaired.

When the fracture surface of the coating film was observed with a scanning electron microscope, it was about 2 μm, and the surface hardness was 3H. When the coating was baked and the ash was subjected to atomic absorption spectrometry, the amount of the crosslinking agent added at the time of preparation was almost consumed in the crosslinking reaction. Silicon contained in the total weight of the coating is 26.4% by weight.
Met. Solid state ²⁹ Si-NMR (97.3 MH) of the coating
z; polydimethylsiloxane standard) from spectrum 4
The absorption peak of the book is δ-48.7 ppm, δ-57.2p
pm, δ-66.2 ppm, δ-75.2 ppm, and the respective absorption peak intensity ratios were 0.01: 9.
It was 99:72:18. Table 1 shows the attribution of these absorptions.
Shown in.

[0040]

[Table 1] From the attribution of these peaks and the absorption intensity, the degree of crosslinking of this film is 0.01 × 1/4 + 9.99 × 2/4 + 72 × 3/4 + 18 × 4/4 = 77%.

A transparent conductive film was formed on the surface of the substrate by sputtering under the above conditions using the polymethylmethacrylate substrate on which the obtained primer layer was formed. The resistivity of this surface was 8.5 × 10 ⁻⁴ Ωcm, the light transmittance was 70%, and the surface hardness was 7H. Further, a peeling test of the coating was conducted, but no peeling was observed.

Example 2 A transparent conductive film was formed in the same manner as in Example 1 except that the polymethylmethacrylate substrate was the polycarbonate substrate and the diglyme of the polymerization solvent was 2-ethoxyethanol. The resistivity of the obtained material surface is 8.2.
× 10 ⁻⁴ Ωcm, light transmittance 70%, surface hardness 3H
Met. Further, a peeling test of the coating was conducted, but no peeling was observed.

Example 3 A transparent conductive film was formed in the same manner as in Example 1 except that the cyclohexylmaleimide-isobutene alternating copolymer substrate was used as the polymethylmethacrylate substrate. The resistivity of the obtained material surface is 8.2 × 10 ⁻⁴ Ωc
m, the light transmittance was 73%, and the surface hardness was 7H. Further, a peeling test of the coating was conducted, but no peeling was observed.

Comparative Example 1 A transparent conductive film was formed on the polycarbonate substrate used in Example 2 by direct sputtering. The resistivity of this surface was 8.0 × 10 ⁻⁴ Ωcm and the light transmittance was 72%, but the surface hardness was B. As a result of the peeling test of the coating, about 30% peeling was observed. confirmed.

Comparative Example 2 A transparent conductive film was formed by direct sputtering on the cyclohexylmaleimide-isobutene alternating copolymer substrate used in Example 3. The resistivity of this surface is 7.9 x 1
Although it was 0 ⁻⁴ Ωcm and the light transmittance was 75%, the surface hardness was 4H, and as a result of the peeling test of the coating, about 40% peeling was confirmed.

Example 4 Methyl methacrylate (8.56 g, 85.5 mmo)
l), 3-methacryloxypropyltrimethoxysilane (1.12 g, 4.5 mmol), AIBN (15 m
g, 90 μmol), 2-ethoxyethanol (80 m
Place l) in a sealed tube and degas. The sealed tube was shaken and reacted at 70 ° C. for 6 hours in a constant temperature bath. After the reaction,
Open the sealed tube, transfer 10 ml of the reaction solution to a 50 ml flask, and stir in the air while stirring to obtain diglyme (10 m
1), tetraethoxysilane (0.16 mol, 32.
76 g) and tetrapropoxy titanium (2.3 mmo
1, 0.67 g), and then 0.1 N hydrochloric acid (5 ml)
Was dripped. After 30 minutes, 0.1 ml of the reaction solution was spin-coated on a polycarbonate (length 50 mm x width 50 mm x thickness 2 mm) substrate. Next, the substrate was transferred to an oven and heated at 130 ° C. for 1 hour to form a transparent thin film on the polycarbonate substrate.

The UV-VIS absorption before and after coating has a maximum of 0.3% in the wavelength range of 300 to 900 nm.
However, the transparency of the substrate by the coating is hardly impaired.

When the fracture surface of the coating film was observed with a scanning electron microscope, it was about 2 μm, and the surface hardness was 3H. When the coating was baked and the ash was subjected to atomic absorption spectrometry, the amount of the crosslinking agent added at the time of preparation was almost consumed in the crosslinking reaction. The content of metal species contained in the total weight of the coating was 23% by weight. Solid state ²⁹ Si-NMR (97.3) of the coating
MHz; polydimethylsiloxane standard) From the spectrum, four absorption peaks were δ-48.7 ppm, δ-5
7.2 ppm, δ-66.2 ppm, δ-75.2 pp
It can be read as m, and the absorption peak intensity ratio is 8:
It was 0:65:27. The amount of tetrapropoxytitanium used is about 1/100 of the amount of tetraalkoxysilane and can be ignored. Therefore, the crosslinking degree is 8 × 1/4 + 65 × 3/4 + 27 × 4/4 = 77.75% from the ²⁹ Si-NMR absorption as in the case of Example 1.

Using the polycarbonate substrate on which the obtained primer layer was formed, a transparent conductive film was formed on the surface of the substrate by sputtering under the above conditions. The resistivity of this surface is 8.4 × 10 ⁻⁴ Ωcm, and the light transmittance is 7
The surface hardness was 0% and the hardness was 4H. Further, a peeling test of the coating was conducted, but no peeling was observed.

Example 5 Methyl methacrylate (7.71 g, 77.0 mmo)
l), maleic acid (0.99 g, 8.55 mmol),
3-methacryloxypropyltrimethoxysilane (1.
12 g, 4.5 mmol), AIBN (15 mg, 90
μmol) and diglyme (80 ml) are put in a sealed tube and deaerated. The sealed tube was shaken and reacted at 70 ° C. for 6 hours in a constant temperature bath. After completion of the reaction, open the sealed tube and let reaction solution 1
0 ml was transferred to a 50 ml flask and stirred under air with diglyme (10 ml), tetraethoxysilane (0.15 mol, 32.55 g), tetrapropoxytitanium (2.3 mmol, 0.67 g) and zirconium acetylacetate. Nart (0.81 mmol, 0.3
After adding 9 g), 0.1 N hydrochloric acid (5 ml) was added dropwise. After 30 minutes, 0.1 ml of the reaction solution was added to a cyclohexylmaleimide-isobutene copolymer (50 mm in length × 50 in width).
mm × thickness 2 mm) Spin-coated on a substrate. Next, the substrate was transferred to an oven and heated at 130 ° C. for 1 hour to form a transparent thin film on the substrate.

The UV-VIS absorption before and after coating has a maximum of 0.3% in the wavelength range of 300 to 900 nm.
However, the transparency of the substrate by the coating is hardly impaired.

When the fracture surface of the coating was observed with a scanning electron microscope, it was about 2 μm, and the surface hardness was 7H. When the coating was baked and the ash was subjected to atomic absorption spectrometry, the amount of the crosslinking agent added at the time of preparation was almost consumed in the crosslinking reaction. The content of metal species contained in the total weight of the coating is 22.
It was 5% by weight (calculated as the metal oxide contained in the coating). Solid state ²⁹ Si-NMR (97.3 MH) of the coating
z; polydimethylsiloxane standard) from spectrum 4
The absorption peak of the book is δ-48.7 ppm, δ-57.2p
pm, δ-66.2 ppm, δ-75.2 ppm, and the respective absorption peak intensity ratios are 5: 0: 70:
It was 25. The amounts of tetrapropoxytitanium and zirconium acetylacetonate used are about 1/100 of the amount of tetraalkoxysilane and can be ignored. Therefore, the degree of crosslinking was determined by ²⁹ Si-NMR as in the case of Example 1.
Can be determined from the absorption of 5 × 1/4 + 70 × 3/4 + 25 × 4/4 = 78.75%.

Using the cyclohexylmaleimide-isobutene copolymer substrate on which the obtained primer layer was formed, a transparent conductive film was formed on the substrate surface by sputtering under the above conditions. The resistivity of this surface is 8.2.
× 10 ⁻⁴ Ωcm, light transmittance 72%, surface hardness 8H
Met. Further, a peeling test of the coating was conducted, but no peeling was observed.

Example 6 Methyl methacrylate (8.56 g, 85.5 mmo)
l), 3-methacryloxypropyltrimethoxysilane (1.12 g, 4.5 mmol), AIBN (15 m
g, 90 μmol), 2-ethoxyethanol (80 m
Place l) in a sealed tube and degas. The sealed tube was shaken and reacted at 70 ° C. for 6 hours in a constant temperature bath. After the reaction,
Open the sealed tube, transfer 10 ml of the reaction solution to a 50 ml flask, and stir in the air while stirring to obtain diglyme (10 m
1), tetraethoxysilane (0.16 mol, 32.
76 g) and tetrapropoxy titanium (2.3 mmo
1, 0.67 g), and then 0.1 N hydrochloric acid (5 ml)
Was dripped. After 30 minutes, 0.1 ml of the reaction solution was spin-coated on a polycarbonate (length 50 mm x width 50 mm x thickness 2 mm) substrate. Next, the substrate was transferred to an oven and heated at 130 ° C. for 1 hour to form a transparent thin film on the polycarbonate substrate.

The UV-VIS absorption before and after coating is up to 0.3% in the wavelength range of 300 to 900 nm.
However, the transparency of the substrate by the coating is hardly impaired.

When the fracture surface of the coating film was observed with a scanning electron microscope, it was about 2 μm and the surface hardness was 3H.

[0057]

Industrial Applicability The method for producing a polymer molded body coated with a transparent conductive thin film of the present invention is a transparent conductive plastic film having improved adhesion, abrasion resistance and surface hardness between a substrate and the transparent conductive thin film. It is useful for making The obtained film is extremely useful for electrophotographic recording, antistatic, electromagnetic wave shielding, fixed display and the like.

Claims (8)

[Claims] 1. A polymer represented by the following general formula (1): (In the formula, R ¹ and R ² are hydrogen or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group, X is a halogen, an alkoxy, an acyloxy, an aminoxy, a phenoxy, a thioalkoxy and an amino group. Binder polymer (number average molecular weight of 1,0) having a silicon group represented by a group selected from
After forming a primer layer formed by three-dimensionally cross-linking (00-500,000, GPC-polystyrene equivalent) by a metal-oxygen bond, a transparent conductive thin film made of a metal or a metal oxide is formed thereon. A method for producing a polymer molded body coated with a transparent conductive thin film. 2. The polymer molded body coated with the transparent conductive thin film according to claim 1, wherein the primer layer contains one or more kinds of metals selected from Si, Ti, Zr and Sn. Manufacturing method. 3. The transparent conductive thin film according to claim 1, wherein the method for forming the transparent conductive thin film made of a metal or a metal oxide on the primer layer is a vacuum deposition method. Method for producing a polymer molded body. 4. The transparent conductive thin film according to claim 1, wherein the method for forming the transparent conductive thin film made of a metal or a metal oxide on the primer layer is a sputtering method. Method for producing polymer molded body. 5. The binder polymer is selected from the group consisting of acrylic acid ester, methacrylic acid ester, acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene, maleic acid and maleic anhydride. The molecular weight based on the selected homo- or copolymer is 1,0
The method for producing a polymer molded body coated with the transparent conductive thin film according to any one of claims 1 to 4, which is a vinyl resin of 00 to 500,000. 6. The metal or metal oxide forming the transparent conductive thin film is SnO ₂ , In ₂ O ₃ , In ₂ O ₃ —Sn.
_{O 2, Cd 2 SnO 4,} ZnO-Al 2 O 3, SnO 2
Preparation of -Sb 2 O _{3, Au} and polymer-extruded article is coated with a transparent conductive thin film according to any one of claims 1 to 5, the selected compound of Pd, characterized in that the main component Method. 7. The formation of a primer layer on a polymer substrate,
1 to 90% by weight of a binder polymer having a silicon group in a side chain represented by the general formula (1), the following general formula (2) R ³ _b M (OR ⁴ ) _4-b (2) (wherein R ³ is Hydrogen, an alkoxy group having 1 to 5 carbon atoms or a phenoxy group, an alkyl group having 1 to 5 carbon atoms or a phenyl group, R ⁴ represents an alkyl group having 1 to 5 carbon atoms or a phenyl group, and M represents Si or Ti. , Sn or Zr, and b represents an integer of 0 to 2) and / or the following general formula (3) (R ⁵ O) _c M ′ (Acac) (3) (M ′ is Ti. , Sn or Zr, and R ⁵ has 1 carbon atom
An alkyl group of 5 to 5, Acac is an acetylacetonate, and c is an integer of 2 to 4), and an organic solvent solution obtained by adding a Lewis acid to 99 to 10% by weight of a metal chelate compound as a polymer group The method for producing a polymer molded body coated with the transparent conductive thin film according to claim 1, wherein the method is applied to the surface of the material and then thermally crosslinked. 8. A primer layer is coated with an organic solution obtained by adding a Lewis acid to a compound represented by the formula (2) and / or (3) to form a thermally crosslinked cured coating, and the cured coating is formed on the cured coating. A method for producing a polymer molded body coated with the transparent conductive thin film according to claim 1, wherein a transparent conductive thin film is formed.