JP2003082105A - Process for synthesis of conductive polymer by vapor- phase polymerization and product therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide such a process for the synthesis of a conductive polymer by a vapor-phase polymerization as is capable of shortening the manufacturing steps less than those of the conventional processes and reducing the manufacturing cost and, on the other hand, of giving the polymer an excellent thin film characteristics and freely controlling the electroconductivity thereof. SOLUTION: The process for the synthesis of the conductive polymer comprises a step of coating an oxidant on a substrate surface in a thickness of several μm and drying in an oven, a step of carrying out a polymerization reaction on the substrate surface by contacting the oxidant coated substrate with a vapor phase monomer, and a step, after completion of the polymerization, of washing to remove an unreacted monomer and the oxidant.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for synthesizing a conductive polymer by a gas phase polymerization method and a product thereof, and more specifically, coating an oxidizer on the surface of a base material in a unit of several μm and drying it with a drier. And the step of performing a polymerization reaction on the surface of the substrate by bringing the gaseous monomer into contact with the substrate coated with the oxidant, and after the completion of the polymerization, unreacted monomer and oxidation The present invention relates to a method for synthesizing a conductive polymer, including a washing step for removing an agent, a conductive polymer produced by the method, and a method for using the conductive polymer.

[0002] For the past several years, conductive polymers in the form of heterocyclics have been applied to electronic parts and various sensors in a film form. Among the heterocyclic compounds, polypyrrole and polythiophene
Since ne) is easy to synthesize and the synthesized polymer has both high electrical conductivity and excellent atmospheric stability, much research has been conducted on its synthesis and its application.

Conventionally, as a method for synthesizing the above-mentioned compound, an electrochemical polymerization method, a chemical oxidative polymerization method and the like are known, but these are different from other conjugated conductive polymers. Similarly, since it cannot be melted or dissolved, there is a problem that it is difficult to process it into a film. In addition, the polymer synthesized by the chemical oxidation method is in the form of particles, and the polymer synthesized by the electrochemical method is formed in the shape of a thin film and has low mechanical strength.
There are many limitations in practical application.

Many studies have been carried out to complement the above-mentioned problems. As a general method, a conductive polymer in the form of particles is mixed with a general polymer to enhance the processability and physical properties. Methods have been proposed for making composite materials. In particular,
Although an electrochemical polymerization method is widely known as a method for manufacturing a thin conductive composite film, this method has a problem in processability or manufacturing in a continuous process. Recently, a part of the gas-phase polymerization method has been introduced. In this method, a general polymer film in which an oxidant is dispersed is used as a main material, and a method of bringing a vapor of a monomer into contact therewith is used. However, in this case, additional problems such as a long reaction time are raised.

Recently, conductive films have been used for shipping semiconductor IC chips or precision electronic equipment (shipping trays or cars).
It is reported that it can be used not only as a carrier tape) but also as a display material, and its applications can be expanded. Particularly, recently, its function as an electron wave shielding material has been highlighted. However, the conductive film has been manufactured by a method in which a conductive polymer itself is polymerized and then formed into a film in a separate coating step. In addition, a metal thin film formed by vacuum evaporation is used as a transparent conductive material,
Although these have excellent performance as electrode materials, they are difficult to use as materials that require secondary processing such as vacuum forming, and there is a problem that the manufacturing cost is high.

[0006]

Therefore, the object of the present invention is to shorten the manufacturing process and to reduce the manufacturing cost as compared with the conventional method, while the thin film characteristics are excellent.
An object of the present invention is to provide a method for synthesizing a conductive polymer by a gas phase polymerization method, which can freely control the electric conductivity.

Another object of the present invention is to provide a conductive polymer produced according to the above synthetic method.

Another object of the present invention is to provide a method of using the produced conductive polymer in electronic component materials and displays.

[0009]

In order to achieve the above object, the present invention applies an oxidizing agent to the surface of a base material in a unit of several μm,
Drying in a drier, a step of carrying out a polymerization reaction on the surface of the base material by bringing a gaseous monomer into contact with the base material coated with an oxidant, and an unreacted unit after the completion of the polymerization. And a washing step for removing the monomer and the oxidant.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The substrate is a plastic material or a metal material, and the plastic material is polyester (po
lyester), polycarbonate (polycarbonate), polyethersulfone (polyethersulfone) and amorphous polyester (A-PET or P
ET-G).

The oxidizing agent is CuCl ₃ , iron (III) toluenesulfonate (Iron (III) -toluenesulfonate), iron (III) perchlorate (Iron (III) -perchlorate), FeCl ₃ and Cu (ClO ₄ ). _{2 · 6H 2 O (copper (} II) -perchlora
tehexahydrate), and the oxidizing agent is methyl alcohol, 2-butyl alcohol, ethyl cellosolve, ethyl alcohol.
hol), cyclohexane, acetone (ac
etone), ethyl acetate, toluene and methyl ethyl k
It is produced by dissolving in a single solvent or a mixture of organic solvents selected from the group consisting of etone). The solvent may be used alone or in a mixture of 2 to 4 and, for example, an organic solvent composed of methyl alcohol, 2-butyl alcohol and ethyl cellosolve may be used in a ratio of 7: 2: 1.
The mixture is used in the ratio of 6: 2: 2, 6: 3: 1, 5: 3: 2. The oxidizing agent is manufactured in a ratio of 0.5% to 10% by weight based on the total weight.

The substrate coated with the oxidizing agent is dried in a dryer at 50 ° C. to 80 ° C. for 0.1 minutes to 8 minutes.

In addition to the oxidizing agent, a host polymer may be added, and the host polymer may be polybutyl acrylate or polycarbonate.
onate), polyester (polyester), polyurethane (p
olyurethane), polyvinyl chlorid
e), polyvinyl alcohol, copolymer resin containing methyl methacrylate (MMA), methyl cellulose and chitos
It is an ultraviolet (UV) or thermosetting acrylic resin selected from the group consisting of an). The host polymer is manufactured in a ratio of 0.5 to 5% by weight based on the total weight.

The monomers are pyrrole, thiophene, furan, selenophene, 2,3-dihydrothi.
o) selected from the group consisting of -3,4-dioxin and derivatives thereof.

The monomer is vaporized in a vaporizing chamber and brought into contact with a base material coated with an oxidizing agent to carry out a polymerization reaction, and the reaction temperature is 0 ° C. to 1 ° C.
It is 00 ° C. and the reaction time is 10 seconds to 40 minutes.

After the polymerization reaction, the unreacted monomer and the oxidizing agent are washed with methanol or water.

The above-mentioned series of steps is carried out stepwise or continuously.

The conductive polymer produced according to the synthetic method of the present invention has the following chemical structure.

[0019]

[Chemical 2]

Here, X is sulfur (S: sulfur), oxygen (O: oxygen), selenium (Se: selenium) and N.
R ₁ and R ₂ are hydrogen, an alkyl group containing 3 to 15 carbons, an ether containing 3 to 15 carbons, and a ring structure containing an oxygen atom. , A halogen element and a benzene group.

The conductive polymer is preferably polypyrrole or polythiophene.
e), polyfuran, polyselenophene (po)
lyselenophene) and their derivatives, having a diameter of 0.
It is manufactured in the form of a film having a thickness of 05 μm to 5 μm.

The conductive polymer produced according to the present invention is used for preventing static electricity, for preventing static electricity and for shielding electron waves, and for producing an antireflection film having a structure of two or more layers including the above polymer, It can also be used as a functional film or a transparent electrode layer of an electronic display.

According to the present invention, an oxidizer is thinly applied on the surface of a base material such as a polymer or metal in units of several tens of Å to several hundred Å,
While generating a conductive polymer monomer as a vapor in a gaseous state, by contacting the surface of the base material coated with an oxidant, a direct polymerization reaction can be carried out. It is possible to obtain a thin thin conductive coating film.

The conventional method is a method of synthesizing a conductive polymer, mixing it with a host polymer, and then coating it on the surface of a substrate such as plastic or metal. From synthesis to final film production, 5 steps to 6 steps are performed. It should go through a staged process. In particular, considering the cost involved in synthesizing the conductive polymer material, the conductive polymer manufacturing method according to the present invention requires only 2 to 3 steps, so that the manufacturing cost is 2/3 or more. It turns out that there is an advantage of being able to save money.

The conductive polymer produced according to the present invention is mainly a conjugated polymer having a heterocyclic structure, that is, polypyrrole and its derivatives, polythiophene and its derivatives, and polyfuran ( Examples thereof include polyfuran) and its derivatives, and polyselenophene and its derivatives, which can be represented by the above chemical formula 1.

The present invention uses Cu (ClO ₄ ) ₂
6H ₂ O, a strongly acidic Lewis acid such as a transition metal compound FeCl ₃ or the like is used, and these improve adhesion by using various mixed solvents depending on the material of the base material. In some cases, a host polymer having a solid content of about 5% or less may be used in addition to the oxidizing agent. In this case, the host polymer is polyurethane (polyurethan
e), polyvinyl chloride, polyvinyl alcohol, and in some cases, methyl cellulose or chitosan may be used. Since the polymer material generally has excellent moldability and mechanical strength as a film and has a high affinity for monomers such as pyrrole, it is used as a host polymer during gas phase polymerization. Can be mentioned. In some cases, additives may be used to improve the adhesive strength.

The electrical conductivity of the conjugated polymer produced according to the present invention is about 10 ² Ω / □ to 10 ⁸ Ω / □,
The electrical conductivity and mechanical strength differ depending on the concentration of the oxidant, the synthesis time and the temperature. In particular, when pyrrole is used as a monomer, variables such as reaction time, reaction temperature, reaction solvent and oxidant greatly affect the fine structure and electrical conductivity of the synthetic conductive polymer. Further, since pyrrole has a relatively low oxidation potential and a high vapor pressure, it is possible to easily carry out a chemical reaction in a gas phase state.

The synthesis of the conductive polymer by the gas phase polymerization according to the present invention is carried out under the temperature condition of 0 ° C. to 100 ° C., and it is carried out in three steps from synthesis to film formation.

In the first step, 0.5 wt% to 10 wt% of an oxidizing agent is applied to the surface of a substrate such as plastic or metal in a unit of several μm. The solvent conditions at this time differ depending on the type of the substrate used, and usually 2 to 4 types of organic solvents are mixed and used. The base material coated with the oxidizing agent is dried in a hot air dryer at 80 ° C. or lower in consideration of the deformation of the oxidizing agent.

In the second step, the above-mentioned polymerized monomer is vaporized and brought into contact with the base material coated with the oxidizing agent to carry out the polymerization reaction on the surface of the base material. At this time, as a method of vaporizing the monomer, a method of distilling the monomer at 0 ° C. to 100 ° C. in a closed chamber and a CVD (chemical vapor) method are used.
deposition) method and the like. At this time, it is necessary to adjust the temperature condition and the reaction time, and it takes about 10 seconds to 40 minutes, but generally it depends on the physical properties and the kind of the monomer.

In the third step, after the polymerization is completed, a washing step for removing unreacted monomers and oxidizing agents is performed. Alcohols are usually used as a solvent in this case, and in some cases, it is possible to wash with water. The series of steps as described above can be performed stepwise or continuously,
It has the feature that it can be processed in a series of work steps from polymerization to film formation. The conductive polymer film manufactured according to the present invention maintains a pencil strength of about 1H to 3H and has excellent adhesiveness. It should be noted that it usually shows stable characteristics in alcoholic solvents.

Example 1 FeCl ₃ as an oxidant was dissolved in a solvent in which methyl alcohol, 2-butyl alcohol and ethyl cellosolve were mixed at a ratio of 7: 2: 1, respectively, and then dissolved in a weight ratio of 2%. After spin coating on the polyester film as the base material, the temperature condition was about 6
It was dried at 0 to 70 ° C. for 2 to 3 minutes. The polyester film coated with the oxidant was light yellow. Approximately 2 oxidizer coated substrates in a CVD chamber designed to produce saturated pyrrole monomer.
After reacting for 0 to 30 seconds, it was washed with a methanol solvent to remove unreacted materials. The temperature of the reaction chamber at this time was 20 ° C. As a result, a transparent brown conductive polymer polypyrrole film was produced. Each of the films has a transmittance of about 75%, a diameter of about 1 μm to 2 μm, a sheet resistance of about 10 ⁴ Ω / □, is stable against an organic solvent such as isopropyl alcohol, and is 200 ° C. The electric conductivity did not change even with the above high temperature treatment.

Example 2 FeCl ₃ as an oxidant was dissolved in a solvent in which methyl alcohol, 2-butyl alcohol and ethyl cellosolve were mixed at a ratio of 6: 2: 2, respectively, and then dissolved in a weight ratio of 2%. After adding 1% by weight of polyvinyl alcohol having a molecular weight of 80,000 to 120,000 as a host polymer to the polyester film as a base material, spin coating was performed at a temperature of about 60 to 70 ° C. for 2 minutes. Allow to dry for ~ 3 minutes. The polyester film coated with the oxidant was light yellow. After reacting the oxidizer-coated substrate for about 20 to 30 seconds in a CVD chamber designed to generate a saturated pyrrole monomer, a methanol solvent is used to remove unreacted materials. Washed. As a result, a transparent conductive polymer film was produced. Each of the films has a transmittance of about 75%, a diameter of about 1 μm to 2 μm, and a sheet resistance of about 10 ⁴ Ω / □, and is stable to an organic solvent such as isopropyl alcohol.
The electrical conductivity did not change even when subjected to high temperature treatment of 00 ° C or higher. In this case, the formed film was highly uniform and the surface degree of the conductive polymer thin film was improved.

(Example 3) Cu (ClO) as an oxidizing agent
₄₎ 2 _· 6H 2 _O and methyl alcohol, 2-butyl alcohol and ethyl cellosolve, respectively 6: 2: After 3% dissolved at 2 weight ratio mixed solvent at a ratio of, was spin-coated on a polyester film The temperature condition was about 60 ° C. to 70 ° C. and dried for 2 to 3 minutes.
After reacting the oxidizer-coated substrate for about 20 to 30 seconds in a CVD chamber designed to generate a saturated pyrrole monomer, a methanol solvent is used to remove unreacted materials. Washed. As a result, a transparent conductive polymer film was produced. The film has a transmittance of about 75%, a diameter of about 1 μm to 2 μm, and a sheet resistance of about 10 ³ Ω / □, is stable against an organic solvent such as isopropyl alcohol, and is resistant to high temperature treatment of 200 ° C. or higher. The electrical conductivity did not change even with this.

Example 4 FeCl ₃ as an oxidant was dissolved in a solvent in which methyl alcohol, 2-butyl alcohol and ethyl cellosolve were mixed at a ratio of 6: 3: 1, respectively, and then dissolved in a weight ratio of 3%. The amorphous polyester film was spin-coated and then dried at a temperature of about 60 ° C. to 70 ° C. for 2 minutes to 3 minutes. The polyester film coated with the oxidant was yellow. After reacting the oxidant-coated substrate in a CVD chamber designed to produce saturated 2,3-dihydrothio-3,4-dioxin monomer for about 30 to 40 minutes, It was washed with a methanol solvent to remove the reaction product. The reaction temperature at this time was 45 ° C. As a result, a transparent brown conductive polymer film was produced. The film has a transparency of about 75% and a diameter of about 1 μm to 2 μ.
m, the surface resistance was about 550 Ω / □, it was stable to an organic solvent such as isopropyl alcohol, and the electric conductivity did not change even at a high temperature treatment of 200 ° C. or higher.

Example 5 In Example 1, 5% by weight of FeCl ₃ as an oxidizing agent was prepared and used.

Example 6 In Example 1, FeCl ₃ as an oxidizing agent was dissolved in a weight ratio of 3%, and then a polycarbonate film was subjected to dip coating, followed by a temperature condition of about 60 ° C. to 70 ° C. for 2 minutes to 3 minutes. It was dried for a minute.

Example 7 FeCl ₃ as an oxidant in Example 1 was prepared in a weight ratio of 3%, and the solvent conditions were methyl alcohol, 2-butyl alcohol and ethyl cellosolve at a ratio of 5: 5. It was set to 3: 2.

Example 8 In Example 2, methyl cellulose was used as the host polymer.

Example 9 In Example 2, Cu (ClO ₄ ) ₂ .6H ₂ O was used as the oxidizing agent instead of FeCl _3.
Was used in an amount of 3% by weight, the reaction temperature was 45 ° C., and the reaction time was 20 to 30 seconds.

Example 10 FeCl ₃ as an oxidant in Example 3 was prepared at 10% by weight and used.
2,3-dihydrothio-3,4-dioxin monomer was used. The reaction time at this time was adjusted to 40 minutes.

Example 11 In Example 1, 6% by weight of FeCl ₃ as an oxidizing agent was prepared and used, and a furan monomer was used. The reaction time at this time was 30 minutes.

In the present invention, the sheet resistance is measured by the single stick method, the transmittance is measured by using a spectrophotometer (UV / VIS spectrophotometer), and the reliability experiment is measured under a high temperature and high humidity condition of 85 ° C./85% RH. And the hardness was measured by pencil strength. The thermal stability was evaluated by using a TGA2050 spectrometer manufactured by Dupont at a measurement range of 30 ° C to 500 ° C and a thermal rate of 10 ° C /
Made in minutes.

The transparent conductive film produced according to the present invention has its electric conductivity freely adjusted within the range of 200 Ω / □ to 10 ⁸ Ω / □ according to the thickness of the oxidizing agent, the reaction time and the reaction temperature. It can be manufactured by the following methods and can be used not only for static electricity and antistatic coating, but also as an electrode material having a medium resistance or lower. Further, it can be used as a functional film for producing a non-reflective film having a structure of two or more layers including the conductive polymer and as a functional film of a display. Since the conductivity can be maintained up to the stretching of 3 to 5 times, it has characteristics as a molding material.

[0045]

As described above, according to the present invention, by using the gas phase polymerization method, the manufacturing process is shortened to 2 to 3 steps, and thus, compared with the conventional method in which 5 to 6 steps are performed. In addition, the manufacturing cost can be reduced by more than 2/3, the thin film characteristics are excellent, and the electric conductivity can be freely adjusted. Therefore, it can be used for various products such as electrode materials and molding materials. It can be used for manufacturing.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01B 13/00 H01B 13/00 503Z (72) Inventor Jin Yeol Kim Korea, Kyonguid, Anyang- Si, Dong Gang, Samho Apartment Bysang-3 Dong No. 17-803 (72) Inventor En Ryul Kim South Korea, Gyeongguid, Seongnamsi, Bandung, Imwan Apartment Hyojacheon 192, Seohyun-Donnan 305-501 F term (reference) 4J031 AA24 AA26 AA27 AA28 AC01 AE11 AF25 CA02 CA21 CA50 CB03 CE01 4J032 BA01 BA02 BA03 BA04 BA08 BA09 BA13 BA14 BB01 BC02 BC06 BC01 BC10 CE01 FA01 FB03 FC03 GA05 GB01 GC01 5G323 AA01 BA05 BB06

Claims (22)

[Claims] 1. A base material comprising the steps of applying an oxidizer on the surface of a base material in a unit of several μm and drying it in a drier, and bringing a gaseous monomer into contact with the base material coated with the oxidizer. A method for synthesizing a conductive polymer by a gas phase polymerization method, which comprises a step of performing a polymerization reaction on the surface of the polymer, and a washing step of removing unreacted monomers and an oxidizing agent after the polymerization is completed. 2. The method according to claim 1, wherein the substrate is a plastic material or a metal material. 3. The method of claim 2, wherein the plastic material is selected from the group consisting of polyester, polycarbonate, polyamide, polyether sulfone and amorphous polyester. 4. The oxidizing agent is CuCl ₃ , iron (III) -toluenesulfonate (Iron (III) -toluenesulfonate), iron (III) perchlorate (Iron (III) -perchlorate), FeCl ₃ and Cu (ClO). the method of claim 1, _wherein the ₄₎ 2 _· 6H 2 _O is selected from the group consisting. 5. The oxidizer is a single or mixture of organic solvents selected from the group consisting of methyl alcohol, 2-butyl alcohol, ethyl cellosolve, ethyl alcohol, cyclohexane, acetone, ethyl acetate, toluene and methyl ethyl ketone. The method according to claim 1, wherein the method is produced by dissolving. 6. The method according to claim 5, wherein the oxidizing agent is prepared in a proportion of 0.5% by weight to 10% by weight with respect to the total weight. 7. The method according to claim 1, wherein a host polymer is added to the oxidizing agent. 8. The host polymer is polybutyl acrylate, polycarbonate, polyester, polyurethane,
8. An ultraviolet (UV) or thermosetting acrylic resin selected from the group consisting of polyvinyl chloride, polyvinyl alcohol, a copolymer resin containing methyl methacrylate (MMA), methyl cellulose and chitosan. Method. 9. The oxidizing agent and host polymer are methyl alcohol, 2-butyl alcohol, ethyl cellosolve,
The method according to claim 7, wherein the method is prepared by dissolving it in a single or a mixture of organic solvents selected from the group consisting of ethyl alcohol, cyclohexane, acetone, ethyl acetate, toluene and methyl ethyl ketone. 10. The method according to claim 9, wherein the host polymer is manufactured in a ratio of 0.5 wt% to 5 wt% based on the total weight of the host polymer. 11. The monomer is pyrrole, thiophene,
Furan, selenophene, 2,3-dihydrothio-3,4
Method according to claim 1, characterized in that it is selected from the group consisting of dioxins and their derivatives. 12. The monomer is used in a vaporizing chamber.
The method according to claim 1, wherein the polymerization reaction is carried out by contacting with a substrate coated with the oxidant, which is vaporized in mber). 13. The method according to claim 12, wherein the reaction temperature is 0 ° C. to 100 ° C. 14. The method according to claim 12, wherein the reaction time is 10 seconds to 40 minutes. 15. The method according to claim 1, wherein the unreacted monomer and the oxidizing agent are washed with methanol or water. 16. The method according to claim 1, wherein the series of steps are performed stepwise or continuously. 17. A conductive polymer produced by the method according to claim 1 and having the following chemical formula. [Chemical 1] (Where X is selected from the group consisting of sulfur (S), oxygen (O), selenium (Se) and NH, R ₁
And R ₂ is selected from the group consisting of hydrogen, an alkyl group containing 3 to 15 carbons, an ether containing 3 to 15 carbons, a ring structure containing an oxygen atom, a halogen element and a benzene group. . ) 18. The conductive polymer according to claim 17, which is selected from the group consisting of polypyrrole, polythiophene, polyfuran, polyselenophene, and derivatives thereof. 19. The conductive polymer according to claim 17, which is in the form of a film having a diameter of 0.05 μm to 5 μm. 20. The conductive polymer according to claim 17, which is used for antistatic, antistatic and electron wave shielding. 21. The conductive polymer according to claim 17, which is used for producing an antireflection film having a structure of two or more layers including a polymer. 22. The conductive polymer according to claim 17, which is used as a functional film or a transparent electrode layer of an electronic display.