JP3223527B2 - Transparent conductive composite material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive composite material suitably used for a transparent conductor or a high-frequency circuit board.

[0002]

2. Description of the Related Art Conventionally, a transparent conductive material used for a transparent electrode, a resistance heating element, or the like has been formed by forming a transparent conductive film made of a metal oxide on glass. Because of its excellent light weight, productivity, and the possibility of increasing the area, the use of a polymer material instead of glass is being studied.

[0003]

At present, polyester, fluororesin, epoxy resin, polyimide, polypropylene, alicyclic polyolefin and the like have been proposed as polymer materials which can substitute for glass. However, although these polymer materials are excellent in workability, lightness, etc.,
It did not satisfy all of the acid resistance, alkali resistance, heat resistance, and adhesion to the transparent conductive film required for the transparent conductive material.

The present invention has been made in view of the above-mentioned problems of the prior art, and is a transparent conductive composite material having good absorption resistance, alkali resistance, heat resistance and adhesion between a polymer material and a transparent conductive film. The purpose is to provide.

[0005]

According to the present invention, there is provided the following formula (I):
Hydrogenation obtained by further hydrogenating a monomer comprising at least one norbornene derivative represented by or a polymer obtained by ring-opening polymerization of this monomer and a copolymerizable monomer copolymerizable therewith. A transparent conductive film is formed on the surface of a polymer molded body, and the hydrogenated
An object of the present invention is to provide a transparent conductive composite material, wherein the content of the gel contained in the union is 5% by weight or less .

Embedded image (Wherein, A and B is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X and Y is a hydrogen atom or a monovalent organic group, at least one of X and Y, -
Carboxylic ester group represented by (CH ₂ ) _n COOR ¹
Wherein R ¹ is a hydrocarbon group having 1 to 20 carbon atoms,
n is an integer of 0 or 1. ) Examples of the hydrogenated polymer used in the present invention include, for example, JP-A-1-24051.
No. 7, JP-B-57-8815, and the like.

In the tetracyclododecene derivative represented by the above formula (I), it is necessary that X and Y contain a polar group from the viewpoint of adhesion to the transparent conductive film. This
Here, this polar group is represented by — (CH ₂ ) _n COOR ^1.
Carboxylic acid ester group, and the water
The addition polymer has a high glass transition temperature. In particular, the polar substituent consisting of this carboxylic acid ester group,
It is preferable that one tetracyclododecene derivative of the formula (I) be contained per molecule, since the resulting hydrogenated polymer can have low hygroscopicity while maintaining high heat resistance.

Further, among the carboxylic acid ester groups represented by — (CH ₂ ) _n COOR ¹ , the smaller the value of n, the higher the glass transition temperature of the obtained hydrogenated polymer, which is preferable. In the above formula (I), R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, and it is preferable that the number of carbon atoms increases as the hygroscopicity of the obtained hydrogenated polymer decreases. From the viewpoint of the balance with the glass transition temperature of the union, a chain alkyl group having 1 to 4 carbon atoms or a (poly) cyclic alkyl group having 5 or more carbon atoms is preferable, and a methyl group, an ethyl group, and a cyclohexyl group are particularly preferable. Preferably, there is.

Further, the tetracyclododecene derivative of the formula (I) wherein a hydrocarbon group having 1 to 10 carbon atoms is simultaneously bonded as a substituent to the carbon atom to which the carboxylate group is bonded, is obtained by hydrogenation. It is preferable because the hygroscopicity is reduced without lowering the glass transition temperature of the polymer. In particular,
The tetracyclododecene derivative of the general formula (I) in which the substituent is a methyl group or an ethyl group is preferable in that the synthesis is easy. These tetracyclododecene derivatives or a mixture of an unsaturated cyclic compound copolymerizable therewith are disclosed , for example, in JP-A-4-77520, page 4, upper right.
The hydrogenation polymer used in the present invention can be obtained by metathesis polymerization and hydrogenation by the method described in column 12, line 12 to page 6, lower right column, line 6 .

In the present invention, the hydrogenated polymer preferably has an intrinsic viscosity ([η] _{_i_n_h_} ) measured at 30 ° C. in chloroform in the range of 0.3 to 1.5 dl / g. In the present invention, the weight average molecular weight of the hydrogenated polymer is usually 5,000 to 1,000,000, preferably 8,000 to 200,000 in order to obtain sufficient strength. The hydrogenation rate of the hydrogenated polymer is 60 MH.
The value measured by z, ¹ H-NMR is 50% or more, preferably 90% or more, and more preferably 98% or more. The higher the hydrogenation rate, the better the stability to heat and light. The hydrogenated polymer used in the present invention is
And a gel containing organic content in the hydrogenated during coalescence 5 wt%, preferably not more than 1 wt%. The hydrogenated polymer used in the present invention may optionally contain other thermoplastic resins.

The above-mentioned hydrogenated polymer includes additives such as a stabilizer, an antioxidant, a lubricant, an antistatic agent, an ultraviolet absorber, a fluorescent brightener, a plasticizer, a mold release agent, a quartz fiber and a glass fiber. A reinforcing material such as an aromatic polyamide fiber or a high-strength high-elasticity polyethylene fiber can also be blended . The transparent conductive composite material of the present invention is obtained by forming a transparent conductive film on a molded product (hereinafter simply referred to as a molded product) obtained by molding the above-mentioned specific hydrogenated polymer by a known method such as extrusion, injection, compression, or wet casting. It is formed. In the present invention, the shape of the molded body may be selected depending on the application. However, when the molded body is used for a transparent electrode or a resistance heating element, the molded body usually has a thickness of about 0.1 mm.
It is formed into a sheet or film of 01 to 10 mm.

In the present invention, the molded article is not particularly required since it has excellent adhesion to the transparent conductive film, but an adhesive layer may be formed between the molded article and the transparent conductive film. Examples of the adhesive layer include heat-resistant resins such as epoxy resin, polyimide, polybutadiene, phenol resin, and polyetheretherketone. In the present invention, as the transparent conductive film, polyacetylene, polypyrrole,
Organic compounds such as polypyridine, polyaniline, polyparaphenylene, polyphenylenevinylene, polythiophene, polyperinaphthalene, polyacrylonitrile, polyvinylbenzyltrimethylammonium chloride, oligo (poly) styrenesulfonic acid, and copper, aluminum, nickel, gold, silver, etc. metal or metal compound, b
Semiconductors such as n-tin oxide, tin-antimony oxide, tin-iron oxide, cadmium oxide, cadmium-tin oxide, titanium oxide, zirconium oxide, and copper iodide, and organic or inorganic complex compounds and the like. be able to. After forming these transparent conductive films into sheets, films, etc., they are adhered to the formed bodies, plasma polymerization, sputtering, vacuum deposition, plating, ion plating, spraying, electrolytic deposition, etc. Formed on the molded body. The thickness of these transparent copper conductive films is usually 10 to 10000 angstroms, preferably 50 to 5000 angstroms, and the specific resistance of the transparent conductive films is preferably 100 ohm cm or less. The light transmittance of the transparent conductive composite material of the present invention is 40
When light of 0 to 800 nm is used, it is usually 80% or more.

The transparent conductive composite material of the present invention can be used for various display devices such as a liquid crystal display device, an electroluminescence display device, and an electrophoretic display, a resistance heating element used for an anti-fog window glass of an automobile or an aircraft, a thermoplastic recording, Optical memory such as ferroelectric memory, terminal equipment such as transparent tablet, photoelectric conversion element, heat ray reflection application,
It can be suitably used for windows and floors of TV cathode ray tubes, meters, clean rooms, and the like.

[0013]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples. In the examples, parts and% are based on weight unless otherwise specified. Various measurements in the examples are as follows.

[0014] Reference Example 1 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^{2, 5.} 1 ^{7, 10} ] dodeca-3-ene 1
00 g, 60 g of 1,2-dimethoxyethane, 240 g of cyclohexane, 25 g of 1-hexene, and 3.4 ml of a toluene solution of 0.96 mol / l of diethylaluminum chloride were added to a 1-liter autoclave. On the other hand, in another flask, a 0.05 mol / l solution of tungsten hexachloride in 1,2-dimethoxyethane 20 was added.
ml and 10 ml of a 0.1 mol / l 1,2-dimethoxyethane solution of paraaldehyde were mixed. 4.9 ml of this mixed solution was added to the mixture in the autoclave. After sealing, the mixture was heated to 80 ° C. and stirred for 3 hours. To the obtained polymer solution, a mixed solvent of 2/8 (weight ratio) of 1,2-dimethoxyethane and cyclohexane was added to make the polymer / solvent 1/10 (weight ratio), and then 20 g of triethanolamine was added. Was added and stirred for 10 minutes.

To this polymerization solution, 500 g of methanol was added, stirred for 30 minutes and allowed to stand. The upper layer separated into two layers was removed, methanol was added again, and the mixture was stirred and allowed to stand, and then the upper layer was removed. The same operation was further performed twice, and the obtained lower layer was appropriately diluted with cyclohexane and 1,2-dimethoxyethane to obtain a cyclohexane-1,2-dimethoxyethane solution having a polymer concentration of 10%. 20 g of palladium / silica magnesia (manufactured by Nikki Chemical Co., Ltd., palladium amount = 5%) was added to this solution, and hydrogen pressure was set to 40 in an autoclave.
After the reaction at 165 ° C. for 4 hours at kg / cm ² , the hydrogenation catalyst was removed by filtration to obtain a hydrogenated polymer solution.
Further, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] as an antioxidant was added to this hydrogenated polymer solution.
After 0.1% was added to the hydrogenated polymer, the solvent was removed at 380 ° C under reduced pressure. Next, the molten resin was pelletized by an extruder under a nitrogen atmosphere, and an intrinsic viscosity of 0.5 dl / g (30 ° C. in chloroform) and a hydrogenation rate of 9 were obtained.
A hydrogenated polymer having 9.5% and a glass transition temperature of 168 ° C. was obtained.

Reference Example 2 6-ethylidene-2-tetracyclododecene was subjected to metathesis ring-opening polymerization in the same manner as in Reference Example 1, then hydrogenated, pelletized, and had an intrinsic viscosity of 0.56 dl / g (30 ° C., A thermoplastic resin having a degree of hydrogenation of 99% and a glass transition temperature of 140 ° C. was obtained.

Reference Example 3 55 mol% of ethylene and 45 mol% of 2-methyl-1,4,5,8-dihydronaphthalene were subjected to addition polymerization and pelletized, and the intrinsic viscosity was 0.64 dl / g (decalin at 35 ° C.). Medium), a thermoplastic resin having a glass transition temperature of 140 ° C. was obtained.

Example 1 A sheet having a length of 200 mm, a width of 200 mm and a thickness of 0.1 mm was formed from the hydrogenated polymer pellets obtained in Reference Example 1 as a raw material. An indium-tin oxide (ITO) film was formed on the obtained sheet under the following conditions using a sputter machine (Chugai Furnace Industry). Power supply High frequency power supply of MHz Substrate temperature 70 ° C Target In ₂ O ₃ / SnO ₂ = 90/10 (weight ratio) Alloy Atmosphere Under argon gas flow Sputter speed 270 Å / min Sputter pressure 10 ^-2 Torr The thickness is 2500 angstroms,
The specific resistance is 1.5 × 10 ⁻³ ohm cm, and the light transmittance of the transparent conductive composite material at 400 to 800 nm is 84.
%Met. Regarding the adhesion between the hydrogenated polymer of the obtained transparent conductive composite material and the ITO film, JIS K-5400
As a result of the test according to (8.5.2 panel test), no peeling was observed. Furthermore, after the obtained transparent conductive composite material was kept at a temperature of 90 ° C. and a humidity of 95% for one week, no change was observed in the conductive characteristics and appearance.

[0019] Comparative Example 1 hydrogenated polymer, except for using a thermoplastic resin obtained in Reference Example 2, in the same manner as in Example 1, the thickness of 2800 Å ITO film, resistivity 2 × 10 ^{- 3} ohm c
m, a transparent conductive composite material having a light transmittance of 79% at 400 to 800 nm of the transparent conductive composite material was manufactured. When the adhesion between the hydrogenated polymer and the ITO film of the obtained transparent conductive composite material was tested in the same manner as in Example 1, 30% was peeled off.

Comparative Example 2 An ITO film having a thickness of 25 was obtained in the same manner as in Example 1 except that the polymer obtained in Reference Example 3 was used instead of the hydrogenated polymer.
00 Å, specific resistance 1 × 10 ^-2 ohm cm,
A transparent composite material having a light transmittance of 76% at 400 to 800 nm of the transparent conductive composite material was manufactured. When the adhesion between the polymer of the obtained transparent conductive composite material and the ITO film was tested in the same manner as in Example 1, 28% was peeled off.

[0021]

The transparent conductive composite material of the present invention has excellent heat resistance and excellent adhesion between the hydrogenated polymer as the substrate and the transparent conductive film. The transparent conductive composite material of the present invention includes a transparent touch panel for a display, a transparent key for a calculator, a heat ray shielding film for a car window, a terraroster for an anti-fog mirror, a terraroster for a frozen showcase, an antistatic packaging bag, a surface emitting panel, and the like. It can be suitably used for various applications.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI B32B 27/06 B32B 27/06 C08F 8/04 C08F 8/04 32/08 32/08 C08G 61/06 C08G 61/06

Claims (1)

(57) [Claims] 1. A polymer obtained by ring-opening polymerization of a monomer comprising at least one kind of norbornene derivative represented by the following formula (I) or a copolymerizable monomer thereof. Is formed by forming a transparent conductive film on the surface of a molded article of a hydrogenated polymer obtained by further hydrogenating, and the gel content contained in the hydrogenated polymer.
Is 5% by weight or less . Embedded image (Wherein, A and B is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X and Y is a hydrogen atom or a monovalent organic group, at least one of X and Y, -
Carboxylic ester group represented by (CH ₂ ) _n COOR ¹
Wherein R ¹ is a hydrocarbon group having 1 to 20 carbon atoms,
n is an integer of 0 or 1. )