JPH07105724A - High polymer conductive resistor and its manufacture - Google Patents

Abstract

PURPOSE:To provide the high polymer conductive resistor which has conductive particles uniformly distributed while being stable in electrical characteristics and high in heat resistance. CONSTITUTION:The high polymer conductive resistor includes at least one kind of metallic oxide to be selected out of irdium oxide, luthenium oxide, and rhrodium oxide in its heat resistant high polymer. The high polymer conductive resistor furthermore may include at least one kind of an element selected out of silicone, bismuth, lead, aluminum, zilconium, calcium, tin, boron, titanium and barium to adjust its resistance value. The high polymer conductive resistor can be used for an electromgnetic shielding member, a switch, a connector contact, a keyboard for an electronic calculator and the like, a resistor, antistatic agent, exothermic body and the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to polymer conductive / resistors used as conductors and resistors for electronic devices, that is, electromagnetic wave shielding materials, switches, connector contacts, keyboards for calculators, resistors, charging. The present invention relates to a polymer conductive / resistor used as a preventive material, a heating element, and the like, and a manufacturing method thereof.

[0002]

2. Description of the Related Art Conductive polymers are known such that the polymer itself has conductivity, and that in which conductive powder is dispersed in a resin ("Technology for imparting new conductivity to polymers. Practical Development and Practical Use "p. 193, Chubu Business Development Center Publishing Department (1983)," Structure / Processing Evaluation Latest Composite Materials / Technology Guide "p. 426, Industrial Technology Service Center Co., Ltd. (1990) And JP-A-2-
187423). As the polymer itself having conductivity, there are polyacetylene, polypyrrole, polythiophene, and the like, but there is a problem in processability and only some of them have been put into practical use. The conductive powder-dispersed resin is mainly a molding thermoplastic resin in which metal powder (stainless steel, aluminum, copper, etc.), metal fibers, carbon black, carbon fibers, etc. are dispersed as a conductive material, and carbon black is mainly used. Has been. As the resin, polyethylene, vinyl chloride, polypropylene, ABS resin, polyamide, epoxy resin, phenol resin or the like is used. These conductive powder-dispersed resins generally include a method of melt-kneading a resin and a conductive powder of millimeter to micron size, a method of dispersing the conductive powder in a solution of the resin in a solvent, and molding by coating or the like ( "Technology for imparting new conductivity to macromolecules, its practical application development and practical application", page 193, Chubu Business Development Center Publishing Department (1983), "Structure / Processing Evaluation Latest Composite Materials / Technology Overview", No. 426 page,
Industrial Technology Service Center Co., Ltd. (1990), JP-A-49-91594, JP-A-51-10619, JP-A-54-143462 and JP-A-3-31.
347 publication). However, in this case, it is difficult to uniformly disperse the conductive powder, and the characteristics are likely to vary greatly depending on the processing conditions. Further, since a large amount of dispersed particles having a large particle size are mixed, there is a defect that transparency is poor and mechanical properties are deteriorated.

On the other hand, in the polyamic acid solution,
Salts of group metals (sodium, lithium, potassium, silver) (US Pat. No. 3,073,784) or metal salts of copper and the like (US Pat. No. 3,073,785)
It is known that a solution of a polyamic acid metal salt is dissolved, and then applied and heat-treated to prepare a metal particle-dispersed polyimide.However, in the case of a free metal, there is a problem that the characteristics are changed by oxidation or the like. Further, in the case of a metal that is easily oxidized, there is a problem in that the manufacturing conditions are troublesome, for example, it is necessary to manufacture in a vacuum or in a nitrogen atmosphere.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polymer conductive / resistor in which conductive particles are uniformly dispersed and which has stable electric characteristics and high heat resistance. , And to provide a technique for producing such a polymer conductive / resistor by a simple method.

[0005]

In order to solve the above-mentioned problems, the inventors of the present invention have dissolved an organometallic compound in a heat-resistant polymer or thermosetting heat-resistant polymer compound precursor solution, and after coating and drying. A method for precipitating fine particles of a metal oxide while heating the organic metal compound to be thermally decomposed and causing a curing reaction when the thermosetting heat-resistant polymer compound precursor was used was examined. Then, as a result of investigating various polymers and organometallic compounds with respect to this method, the above-mentioned problems were solved in a heat-resistant polymer containing at least one kind of iridium oxide, ruthenium oxide and rhodium oxide. They have found what they can do and have completed the present invention.

The first polymer conductive / resistor of the present invention contains at least one metal oxide selected from iridium oxide, ruthenium oxide and rhodium oxide in a heat resistant polymer compound. It is characterized by Further, the second polymer conductive / resistor of the present invention comprises a heat-resistant polymer compound, and at least one metal oxide selected from iridium oxide, ruthenium oxide and rhodium oxide, and silicon or bismuth. And at least one element selected from lead, aluminum, zirconium, calcium, tin, boron, titanium, and barium. In the present invention, it is preferable to use, as the heat-resistant polymer compound, a polymer compound having a repeating structural unit represented by the following structural formula (1).

[Chemical 5] (In the formula, X represents a tetravalent organic group having 2 or more carbon atoms, and Y represents a divalent organic group having 2 or more carbon atoms.)

The first polymer conductive / resistor of the present invention comprises:
Produced by applying a solution containing a heat-resistant polymer or its heat-resistant polymer precursor and at least one of an organic iridium compound, an organic ruthenium compound, and an organic rhodium compound to a substrate to be coated and then heat-treating it. be able to. The second polymer conductive / resistor of the present invention is a heat-resistant polymer or a heat-resistant polymer precursor thereof, and at least one of an organic iridium compound, an organic ruthenium compound and an organic rhodium compound, and silicon and bismuth. , Lead, aluminum, zirconium, calcium,
It can be produced by applying a solution containing a compound containing at least one element selected from tin, boron, titanium and barium to a substrate to be coated and then heat-treating it. In this case, as the heat resistant polymer precursor,
It is preferable to use a polyamic acid having a repeating structural unit represented by the following structural formula (2).

[Chemical 6]

According to the above method of the present invention, the heat-resistant polymer or the heat-resistant polymer precursor in which the organometallic compound, which is the raw material of the conductive particles, is dissolved is heat-treated, so that
It is possible to obtain a polymer / metal oxide composite in which conductive particles of several hundreds nm are uniformly dispersed, and the iridium oxide, ruthenium oxide, and rhodium oxide that are formed are stable and have characteristics due to oxidation and the like. It has an excellent effect that no deterioration / change is observed.

The detailed production conditions, compound examples, etc. of the present invention will be described below. The manufacturing process of this method can be roughly divided into the following four processes. That is, the coating solution preparation step,
These are a coating process, a drying process, and a heat treatment process. In the coating solution preparation step, the following heat-resistant polymer was dissolved in a solvent or a solution of a thermosetting heat-resistant polymer precursor was prepared, and an organometallic compound was directly added to this solution or prepared separately. Add the organometallic compound solution and stir it sufficiently to make it uniform. At this time, additives such as a viscosity modifier and a leveling agent may be added. Also, the final solution may be filtered using a filter. The concentration of this solution is appropriately adjusted depending on the coating method used in the coating step in the next step and the finally required film thickness of the composite film. The solvent used may be one that dissolves the raw materials used such as heat resistant polymers and thermosetting heat resistant polymer precursors. For example, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, dimethyl. Sulfamide, m
-Cresol, p-chlorophenol, dimethylimidazolidone, tetramethylurea, diglyme, triglyme, tetraglyme, methylene chloride, chloroform, toluene, xylene, acetone, methyl ethyl ketone, ethyl acetate, terpineol, sulfolane and the like are used.

The heat-resistant polymer compound used herein is not particularly limited as long as it is solvent-soluble and does not decompose at the thermal decomposition temperature of the organometallic compound, and examples thereof include polycarbonate and poly. Examples thereof include ether sulfone, polyarylate, polyamide and polyamideimide. Further, as the thermosetting heat resistant polymer,
A heat-crosslinking resin such as an epoxy resin or polyimide is used, but in this step, it is used in the form of its precursor. It is preferable that these polymers have good compatibility with the organometallic compound so that the organometallic compound is not precipitated as much as possible after the drying step of the next step. In this respect, and from the viewpoint of heat resistance, polyimide is particularly preferable among these polymers. As the polyimide, one having a repeating structural unit represented by the above-mentioned general formula (1) is used, which is formed from a polyamic acid which is a precursor thereof and having the repeating structural unit represented by the general formula (2).

In the formula, X represents a tetravalent organic group having 2 or more carbon atoms, and Y represents a divalent organic group having 2 or more carbon atoms. Specifically, X is alkyl or benzene ring may tetravalent be substituted by fluoroalkyl or a direct bond,, -O -, - CO - , - SO 2 -,
_{-C (CH 3) 2 -,} - C (CF 3) 2 - or - (C
An example is a tetravalent group consisting of two benzene rings bound by F ₂ ) _n- (k = 1 to 6). Further, Y is alkyl, fluoroalkyl, alkoxy, or a phenylene group optionally substituted by a halogen atom,
A direct bond, -O -, - S -, - SO 2 -, - CH 2 -,
A divalent group consisting of 2 to 4 benzene rings linked by one or more selected from —C (CH ₃ ) ₂ — and —C (CF ₃ ) ₂ — or linked by an organopolysiloxane An example of the divalent group is an aliphatic group.

In the present invention, specific examples of the groups X and Y in the general formulas (1) and (2) are shown below. As the group X, organic groups represented by the structural formulas shown below are exemplified. be able to.

[Chemical 7] (In the formula, k represents an integer of 1 to 6.)

Examples of Y include organic groups represented by the structural formulas shown below.

[Chemical 8]

[0014]

[Chemical 9] (In the formula, m represents an integer of 1 to 1000.)

The polyamic acid compounds exemplified here are:
J. Appl. Polym. Sci. , 30, 2
883 (1985) and the like, a tetracarboxylic dianhydride having a group X represented by the general formula (6) as a central structure and a group Y represented by the general formula (7) as a central structure. Can be synthesized from the diamine. When these polyamic acid compounds are further heated, the following reactions occur to form polyimide. The reaction formula is shown below.

[0016]

[Chemical 10]

In the present invention, in the preparation of the coating solution, the compound represented by the general formula (6) is reacted with the compound represented by the general formula (7) in a solvent to obtain a polyamic acid solution. The degree of polymerization of the polyamic acid is preferably such that the intrinsic viscosity [η] at 30 ° C. in dimethylacetamide or the like is in the range of 0.1 to 6 dl / g in view of the strength of the polymer composite. The intrinsic viscosity referred to here is a value obtained by extrapolating the logarithmic viscosity or reduced specific viscosity at each concentration to zero, which is calculated from the measured value of the relative viscosity at various polymer concentrations. When the intrinsic viscosity is less than the above value, the obtained film becomes brittle.

In the present invention, the metal component used for forming the metal oxide is required to have a stable oxide and high conductivity, and ruthenium, Iridium and rhodium are used. That is, ruthenium oxide, iridium oxide,
Rhodium oxide is not easily affected by the external environment, is stable, and has high conductivity. Further, the respective conductivity is different by about one digit, and a polymer composite having a desired conductivity can be obtained by properly using them. In the present invention, the conductivity may be adjusted by mixing these metal components. The organic ruthenium compound, the organic iridium compound, and the organic rhodium compound, which are the raw materials for the respective metal oxides used in the coating solution preparation step, are used in the form of carboxylates, acetylacetonates, alkoxides, commercially available metal resinates, etc. However, it is not particularly limited as long as it is soluble in the solvent used or is soluble by interaction with the polymer or polymer precursor. However, the compounds represented by the following general formulas (3) to (5) are particularly preferable. M (R ¹ COO) ₃ (3) M (R ² COCR ⁴ COR ³ ) ₃ (4)

[Chemical 11] (In the formula, M represents iridium, ruthenium or rhodium, R ¹ , R ² and R ³ each represent an alkyl group or an aryl group, R ⁴ represents a hydrogen atom or an alkyl group, R ⁵ represents a hydrogen atom, Represents an alkyl group or an alkoxy group.)

Specific examples include the following compounds, but the compounds are not particularly limited to these (the metal M in the specific examples below represents ruthenium, iridium or rhodium). Specific examples of the compound represented by the general formula (3) include the following compounds. Metal _{propionate: M (C 2 H 5 COO} ) 3 Metal n- _{butyrate: M (C 3 H 7 COO} ) 3 metal _{2-methylpropionate: M [(CH 3) 2} CH
COO)] ₃ metal n-pentanate: M (C ₄ H ₉ COO) ₃ metal 2-methylbutyrate: M [C ₂ H ₅ (CH ₃ ) C
HCOO)] ₃ metal 3-methyl _{butyrate: M [(CH 3) 2} CHCH
₂ COO)] ₃ metal pivalate: M [(CH ₃ ) ₃ CCOO)] ₃ metal n-hexanate: M (C ₅ H ₁₁ COO) ₃ metal n-octanoate: M (C ₇ H ₁₅ COO) ₃ metal 2- Ethyl hexanate: M [C ₄ H ₉ CH (C ₂
H ₅ ) COO)] ₃ metal n-decanoate: M (C ₉ H ₁₉ COO) ₃ metal n-dodecanoate: M (C ₁₁ H ₂₃ COO) ₃ metal n-tetradecanoate: M (C ₁₃ H ₂₇ COO) ₃ metal n- hexadecanol _{sulfonate: M (C 15 H 31 COO} ) 3 metal n- octadecanol _{sulfonate: M (C 17 H 35 COO} ) 3 metal _{oleate: M (C 8 H 17 CH} = CHC 7 H 14 CO
O) ₃

Specific examples of the compound represented by the general formula (4) include the following compounds. Metal 2,4-pentanedionate: M (CH ₃ COCH
COCH ₃ ) ₃ metal 3,5-heptanedionate: M (C ₂ H ₅ COC
HCOC ₂ H _{5) 3} Metal 4,6 Nonanjioneto: M (C ₃ H ₇ COCH
COC ₃ H _{7) 3} metal 2,6-dimethyl-3,5-heptanedionate:
M [(CH ₃ ) ₂ CHCOCHCOCH (CH ₃ ) ₂ ]
₃ Metal 5,7-undecandionate: M (C ₄ H ₉ CO
CHCOC ₄ H ₉ ) ₃ metal 3,7-dimethyl-4,6-nonanedionate: M
_{[C 2 H 5 CH (CH} 3) COCHCOCH (CH 3)
C ₂ H _{5] 3} metal 2,8-dimethyl-4,6-Nonanjioneto: M
[(CH ₃ ) ₂ CHCH ₂ COCHCOCH ₂ CH (C
H _{3) 2] 3} metal _{2,2,6,6-tetramethyl-3,5-heptanedionate: M [(CH 3) 3} CCOCHCOC (CH
₃ ) ₃ ] ₃ Metal 3-methyl-2,4-pentanedionate: M
_{(CH 3 COCCH 3 COCH 3)} 3 metal 4-methyl-3,5-heptanedionate: M (C
₂ H ₅ COCCH ₃ COC ₂ H ₅ ) ₃ metal 5-methyl 4,6-nonanedionate: M (C ₃ H
₇ COCCH ₃ COC ₃ H ₇ ) ₃ Metal 2,4,6-trimethyl-3,5-heptanedionate: M [(CH ₃ ) ₂ CHCOCCH ₃ COCH (C
H _{3) 2] 3} metal 6-methyl 5,7-undecane dionate: M (C
₄ H ₉ COCCH ₃ COC ₄ H ₉ ) ₃ Metal 3,5,7-trimethyl-4,6-nonanedionate: M [C ₂ H ₅ CH (CH ₃ ) COCCH ₃ COCH
_{(CH 3) C 2 H 5} ] 3 metal _{2,5,8-trimethyl-4,6-Nonanjioneto: M [(CH 3) 2} CHCH 2 COCCH 3 COCH
_{2 CH (CH 3) 2]} 3 metal _{2,2,4,6,6-pentamethyl-3,5-heptanedionate: M [(CH 3) 3} CCOCCH 3 CO
C (CH ₃ ) ₃ ] ₃

Specific examples of the compound represented by the general formula (5) include the following compounds. The metal tris (N-benzylidene anthranilate) represented by the formula (8) and the metal tris [N- represented by the formula (9).
(P-Methylbenzylidene) anthranilate], the metal tris [N- (p-ethylbenzylidene) anthranilate] represented by the formula (10), and the metal tris [N- (p-propyl) represented by the formula (11). Benzylidene) anthranilate], a metal tris [N-
(P-Methoxybenzylidene) anthranilate], the metal tris [N- (p-ethoxybenzylidene) anthranilate] represented by the formula (13), and the metal tris [N- (m-methyl) represented by the formula (14). Benzylidene) anthranilate], a metal tris represented by the formula (15) [N-
(O-Methylbenzylidene) anthranilate].

[0022]

[Chemical 12]

In the present invention, at least one element selected from silicon, bismuth, lead, aluminum, zirconium, calcium, tin, boron, titanium and barium is contained as an additive element in order to adjust the resistance value. You may let me. In that case, a compound containing these additive elements is used as a mixture with the organometallic compound, but the compound containing additive elements is soluble in the solvent used, or interacts with the polymer or polymer precursor. As long as it is soluble, it is not particularly limited. In particular,
For example, the following compounds, commercially available metal resinates, etc. may be mentioned. Si poly (ditolyl siloxane), tetraethoxysilane Bi 2-Bismuth 2-ethylhexanoate Pb 2-Lead 2-ethylhexanoate Al Aluminum laurate Zr 2-Ethylhexanoate oxide Zirconium oxide Ca 2-Ethylhexanoate Sn 2-Ethylhexanoic acid Tin B Boron 2-ethylhexanoate Ti Tetraisopropoxy titanium Ba 2-Barium 2-ethylhexanoate

By adding these additional elements, the resistance value can be changed without reducing the amount of metal oxide in the polymer. The amount ratio of the metal of the metal oxide to the additive element is determined by the desired resistance value, but the atomic ratio of (additive element) / (metal) is 2/1 or less, preferably 1
It is used so as to be about /1/0.01/1. The amount ratio of the polymer compound and the organometallic compound for forming the metal oxide is determined by the desired electrical characteristics, but the metal atom per repeating structural unit of the polymer compound of the final polymer composite is Is 1 to 300%, and preferably 5 to 200%. When it is 1% or less, the polymer composite becomes insulating, and when it is 300% or more, the polymer composite tends to be brittle.

Next, the coating process will be described. The application is
It is applied onto a substrate to be coated having a desired shape, for example, a device by a commonly used coating method such as spin coating, dip coating, bar coating, and spray coating. A film can be easily formed by applying it to a glass plate or the like and peeling it off after the subsequent step. Further, it can be processed into a fiber shape. The drying step after coating is performed by any of natural drying, heat drying, vacuum drying, and the like, or a combination thereof. The temperature for heating and drying is 50 to 200 ° C, and the conditions vary depending on the solvent used, but generally, it is 50 to 150 ° C.
It is preferable to carry out. This drying step may be performed under a flow in an inert atmosphere such as nitrogen.

The heat treatment step is carried out in an atmosphere or flow of air, oxygen, an air / oxygen mixed system, an inert gas such as nitrogen, an inert gas / air mixed system, or the like. The temperature depends on the decomposition temperature of the raw materials (polymer, polymer precursor, organometallic compound, etc.) used, the thermosetting temperature, etc., and the decomposition temperature of the organometallic compound or the thermosetting temperature of the thermosetting polymer compound or higher, It is below the decomposition temperature of the polymer compound. About 150-50
Perform at 0 ° C. The heat treatment time is determined by the decomposition rate of the organometallic compound, the thermosetting rate of the thermosetting polymer compound, and the like, but it is preferable to be as short as possible so that the polymer compound does not deteriorate. It is about 1 minute to 24 hours.

[0027]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples, and various modifications and applications are possible without departing from the concept of the present invention. Is. Example 1 J. Appl. Polym. Sci. , 42, 2
267 (1991), N of polyamideimide (intrinsic viscosity 1.42d1 / g at 30 ° C. in N-methyl-2-pyrrolidone) consisting of repeating structural units represented by the following structural formula (16). -Methyl-2-pyrrolidone solution (solid content ratio 10%) (5.0 g) was mixed with 0.25 g of iridium 2-ethylhexanoate N-methyl-2-pyrrolidone solution (iridium content 30%). This mixed solution was applied on a glass plate with an Erichsen applicator and dried at 130 ° C. for 1 hour. Then, heat treatment was performed at 300 ° C. for 1 hour in a nitrogen atmosphere. As a result of measuring the surface resistance of the obtained film by the four-terminal method, 3
It was × 10 ⁸ Ω / □.

[Chemical 13]

Example 2 0.958 g of diaminodiphenyl ether represented by the following structural formula (17) was dissolved in 20 ml of dimethylacetamide under a stream of dry nitrogen, and when completely dissolved, 10 to 10 was obtained.
1.04 g of pyromellitic dianhydride represented by the following structural formula (18) is gradually added at 15 ° C. Then, under a dry nitrogen stream, the mixture was slowly stirred for 1 hour while maintaining the temperature at 10 to 15 ° C., and further continuously stirred for 3 hours while maintaining the temperature at 20 to 25 ° C. for the repeating structural unit represented by the following structural formula (19). A solution of polyamic acid was obtained (intrinsic viscosity in dimethylacetamide at 30 ° C. of 1.55 dl / g). Iridium resinate (A-1123, iridium content of NE Chemcat) was added to 5 g of this polyamic acid solution.
20%) 0.25 g was added and mixed. This mixed solution was coated on a glass plate with an Erichsen applicator, left to stand for 1 hour, and then dried at 130 ° C. for 1 hour. Then, heat treatment was performed at 350 ° C. for 1 hour in a nitrogen atmosphere. As a result, a polyimide film containing an iridium oxide and having a repeating structural unit represented by the following structural formula (20) was formed. When the cross section of the film was observed with a TEM (transmission electron microscope), particles of several nm to several tens nm were observed. As a result of measuring the surface resistance by the four-terminal method, 1 × 10 ⁸ Ω
It was / □.

[Chemical 14]

Example 3 A solution of polyamic acid was prepared in the same manner as in Example 2
20% of iridium ethylhexanoate, iridium acetylacetonate, or iridium tris [N- (ethylbenzylidene) anthranilate], or a solution thereof is added to the repeating structural unit of polyamic acid.
It was adjusted to be mol%. This was applied on a polyimide film (Kapton manufactured by Toray DuPont) using an Erichsen applicator. After drying at 130 ° C. for 1 hour, heat treatment was performed at 300 ° C. for 1 hour. The surface resistance is about 10 ⁷ when any of the above iridium compounds is used.
A film of Ω / □ was obtained. Example 4 Ruthenium 2-ethylhexanoate or ruthenium acetylacetonate was used as the organometallic compound, and 10 mol% relative to the repeating structural unit of the polyamic acid.
The same procedure as in Example 3 was carried out except that the adjustment was made so that
When any of the above ruthenium compounds was used, a film having a surface resistance of about 10 ⁷ Ω / □ was obtained. Example 5 Rhodium 2-ethylhexanoate as an organometallic compound,
Alternatively, it was carried out in the same manner as in Example 3 except that rhodium acetylacetonate was used and adjusted to be 15 mol% with respect to the repeating structural unit of the polyamic acid. The surface resistance was about 10 ⁹ Ω / □.

Example 6 7.5 ml of dimethylacetamide under a stream of dry nitrogen
2,2-bis [4 represented by the following structural formula (21)
1.028 g of (4-aminophenoxy) phenyl] hexafluoropropane was dissolved, and when completely dissolved, 0.888 g of 4,4 '-(hexafluoroisopropylidene) 2 phthalic anhydride represented by the following structural formula (22) was dissolved. Gradually added. Subsequently, under a dry nitrogen stream, the mixture was slowly stirred for 1 hour while maintaining the temperature at 10 to 15 ° C., and further stirred for 2 hours while maintaining at 20 to 25 ° C. to prepare a polymer compound represented by the following structural formula (23). A solution was obtained. Using this solution, a polymer composite was prepared in the same manner as in Example 3. As a result, a polyimide film containing iridium oxide and represented by the following structural formula (24) was formed. Its surface resistance is about 10
It was ⁷ Ω / □.

[Chemical 15] (In the formula, n'is about 500.)

Example 7 A polymer composite was prepared by further adding ruthenium 2-ethylhexanoate in an amount corresponding to 10% with respect to iridium in Example 3. As a result, the surface resistance was reduced.

Example 8 Structural formula (16) similar to that described in Example 1
Polyamideimide (3 in N-methyl-2-pyrrolidone
N-methyl-2 having an intrinsic viscosity of 1.42 dl / g at 0 ° C
-Pyrrolidone solution (solid content ratio 10%) 5.0 g, 2-
0.40 g of N-methyl-2-pyrrolidone solution of iridium ethylhexanoate (iridium content 30%), 0.01 g of poly (ditolylsiloxane) and 0.01 g of bismuth 2-ethylhexanoate were added and mixed. Apply this mixed solution on a glass plate with an Erichsen applicator,
It was dried at 130 ° C. for 1 hour. Then, in a nitrogen atmosphere, 30
Heat treatment was performed at 0 ° C. for 1 hour. The surface resistance of the obtained film was measured by the four-terminal method, and was 5 × 10 ⁸ Ω.
It was / □.

Example 9 0.958 g of diaminodiphenyl ether represented by the above structural formula (17) was dissolved in 20 ml of dimethylacetamide under a stream of dry nitrogen, and when completely dissolved, 10 to 10 was obtained.
1.04 g of pyromellitic dianhydride represented by the structural formula (18) is gradually added at 15 ° C. Then, under a dry nitrogen stream, the mixture was slowly stirred for 1 hour while maintaining the temperature at 10 to 15 ° C., and further stirred for 3 hours while maintaining the temperature at 20 to 25 ° C. for the repeating structural unit represented by the structural formula (19). A solution of the following polyamic acid was obtained (intrinsic viscosity at 30 ° C. in dimethylacetamide 1.45 dl / g). Iridium resinate (A-1123, iridium content of NE Chemcat) was added to 5 g of this polyamic acid solution.
20%) 0.50 g, lead 2-ethylhexanoate 0.01
g and 0.01 g barium 2-ethylhexanoate were added and mixed. This mixed solution was applied on a glass plate with an Erichsen applicator, left to stand for 1 hour, and then dried at 130 ° C. for 1 hour. Then, heat treatment was performed at 350 ° C. for 1 hour in a nitrogen atmosphere. As a result, a polyimide film containing the repeating structural unit represented by the structural formula (20) containing iridium oxide, lead and barium was formed. When the cross section of the film was observed with a TEM (transmission electron microscope), particles of several nm to several tens nm were observed. The surface resistance was measured by the four-terminal method and found to be 3 × 10 ⁸ Ω / □.

Example 10 A solution of polyamic acid was prepared in the same manner as in Example 9,
20% of iridium ethylhexanoate, iridium acetylacetonate, or iridium tris [N- (ethylbenzylidene) anthranilate], or a solution thereof is added to the repeating structural unit of polyamic acid.
It was adjusted to be mol%. Aluminum laurate was added to and mixed with the iridium in an amount of 10%. This was applied onto a glass plate using an Erichsen applicator. After drying for 1 hour at 130 ℃, 300 ℃
Was heat-treated for 1 hour. When any of the above iridium compounds was used, a film having a surface resistance of about 10 ⁸ Ω / □ was obtained.

Example 11 In Example 10, the iridium compound was adjusted to 15 mol% with respect to the repeating structural unit of polyamic acid, and 15% of zirconium 2-ethylhexanoate was added.
Example 10 was prepared in the same manner as in Example 10 except that the addition was made so that the amount of each component was 0.1%. A film having a surface resistance of about 10 ⁹ Ω / □ was obtained. Example 12 Ruthenium 2-ethylhexanoate or ruthenium acetylacetonate was used as the organometallic compound and adjusted to be 10 mol% with respect to the repeating structural unit of the polyamic acid.
The same procedure as in Example 10 was performed except that tin ethylhexanoate was added at a ratio of 1: 1 so that the total amount was 10% with respect to ruthenium. A film having a surface resistance of about 10 ⁸ Ω / □ was obtained when any of the above ruthenium compounds was used. Example 13 Rhodium 2-ethylhexanoate or rhodium acetylacetonate was used as the organometallic compound and adjusted to be 15 mol% with respect to the repeating structural unit of the polymer. The same procedure as in Example 10 was carried out except that propoxy titanium was added at a ratio of 1: 1 so that the total amount was 15% with respect to rhodium. When any of the above rhodium compounds was used, a film having a surface resistance of about 10 ¹⁰ Ω / □ was obtained.

Example 14 7.5 ml of dimethylacetamide under a stream of dry nitrogen
2,2-bis [4 represented by the structural formula (21) above
1.028 g of (4-aminophenoxy) phenyl] hexafluoropropane was dissolved, and when completely dissolved, 0.888 g of 4,4 ′-(hexafluoroisopropylidene) 2 phthalic anhydride represented by the structural formula (22) was dissolved. Gradually added. Then, under a dry nitrogen stream, the mixture is slowly stirred for 1 hour while maintaining the temperature at 10 to 15 ° C., and further stirred for 2 hours while maintaining at 20 to 25 ° C. for the solution of the polyamic acid represented by the structural formula (23). Got Using this solution, a polymer composite was prepared in the same manner as in Example 10. As a result, a polyimide film containing the repeating structural unit represented by the structural formula (24) containing iridium oxide and aluminum was formed. Its surface resistance is about 10 ⁸ Ω
It was / □. Example 15 In Example 10, a ruthenium 2-ethylhexanoate was further added so that the amount was 10% with respect to iridium, to prepare a polymer composite. as a result,
The surface resistance was reduced.

[0037]

According to the present invention, a polymer conductor / resistor having stable electric characteristics can be obtained by a simple process. Also. When the additive element is added, the resistance value can be easily adjusted. Furthermore, it can be easily processed into thin films and fibers. According to the present invention having such a configuration, it can be applied to an electronic device or the like as shown in the technical field of the present invention, and can be easily and directly deposited on an electronic device or the like of any shape at a low temperature, Enables high-quality, inexpensive devices.

Claims (6)

[Claims] 1. A polymer conductive / resistor comprising a heat resistant polymer compound containing at least one metal oxide selected from iridium oxide, ruthenium oxide and rhodium oxide. 2. A heat-resistant polymer compound containing at least one metal oxide selected from iridium oxide, ruthenium oxide and rhodium oxide, and silicon, bismuth, lead, aluminum, zirconium, calcium,
A polymer conductive / resistive material containing at least one element selected from tin, boron, titanium and barium. 3. The polymer conductive / resistor according to claim 1, wherein the heat-resistant polymer compound is a polymer compound comprising a repeating structural unit represented by the following structural formula (1). . [Chemical 1] (In the formula, X represents a tetravalent organic group having 2 or more carbon atoms, and Y represents a divalent organic group having 2 or more carbon atoms.) 4. A solution containing a polyamic acid comprising a repeating structural unit represented by the following structural formula (2) and at least one of an organic iridium compound, an organic ruthenium compound and an organic rhodium compound is applied, and then heated. The method for producing a polymer conductive / resistor according to claim 1, wherein the method is performed. [Chemical 2] (In the formula, X represents a tetravalent organic group having 2 or more carbon atoms, and Y represents a divalent organic group having 2 or more carbon atoms.) 5. A polyamic acid comprising a repeating structural unit represented by the following structural formula (2), at least one of an organic iridium compound, an organic ruthenium compound and an organic rhodium compound, and silicon, bismuth, lead, aluminum, 3. The polymer conductive material according to claim 2, wherein a solution containing a compound containing at least one element selected from zirconium, calcium, tin, boron, titanium and barium is applied and then heat-treated. Resistor manufacturing method. [Chemical 3] 6. An organic iridium compound, an organic ruthenium compound or an organic rhodium compound is represented by the following general formula (3) to
The method for producing a polymer conductive / resistor according to claim 4 or 5, which is at least one selected from the compounds represented by (5). M (R ¹ COO) ₃ (3) M (R ² COCR ⁴ COR ³ ) ₃ (4) (In the formula, M represents iridium, ruthenium or rhodium, R ¹ , R ² and R ³ each represent an alkyl group or an aryl group, R ⁴ represents a hydrogen atom, an alkyl group or an aryl group, and R ⁵ represents Represents a hydrogen atom, an alkyl group or an alkoxy group.)