KR20170035676A - Organic Electrode Resin Composition with High Resistance - Google Patents
Organic Electrode Resin Composition with High Resistance Download PDFInfo
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- KR20170035676A KR20170035676A KR1020150134874A KR20150134874A KR20170035676A KR 20170035676 A KR20170035676 A KR 20170035676A KR 1020150134874 A KR1020150134874 A KR 1020150134874A KR 20150134874 A KR20150134874 A KR 20150134874A KR 20170035676 A KR20170035676 A KR 20170035676A
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- H—ELECTRICITY
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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Abstract
Description
More particularly, the present invention relates to a conductive polymer, an initiator, a durability improver, and a dispersion medium, thereby improving the water resistance of the conductive polymer for an organic electrode, thereby lowering the conductivity and deteriorating the performance of the electronic device. And an organic electrode resin composition having a water resistance that can be prevented.
Conventionally, an electronic device using an organic semiconductor compared to an inorganic semiconductor-based electronic device has advantages that it can be worn on a human body or attached to clothing since it is light and folded or kneaded. Recently, studies on flexible displays, sensors, radio frequency identification (RFID), and solar cells based on organic semiconductors have been actively carried out, and attention has been paid to some commercialization possibilities. Of the various organic semiconductor materials for implementing such a flexible electronic device, the organic electrode material must have a low resistance and a high transparency and a high strength so as to be mechanically stable even when the device is bent or folded. Should have similar thermal expansion coefficients to the plastic used. In addition, there is a demand for chemical resistance and heat resistance for various chemicals to be contacted in the process of manufacturing an electronic device.
Organic electrode materials that are currently being investigated are poly (3,4-ethylenedioxythiophene), polyaniline (PANI), polypyrrole (PPy), polypyrrole PEDOT: PSS doped with a conjugated polymer such as polythiophene (PT), poly (4-styrenesulfonate (PSS), camphor sulfonic acid (TSA) PTA: PTSA: PSS: PTA: PPA: CSA, PPy: TSA, PPy: DBSA, PT: PSS: CSA, PT: TSA, PT: DBSA and the like are used.
Such a conductive polymer can be dissolved in water or an alcohol solvent by reacting with an acid group of a dopant and an unshared electron pair present in a conjugated polymer such as PEDOT: PSS and PEN: PSS, Or an organic transparent electrode may be formed on the substrate by coating and drying the substrate on the substrate. Also, the non-covalent electron pair present in the nitrogen of PPy or the non-covalent electron pair present in the sulfur of PT reacts with the acid dopant to form ions, and thus dissolves or disperses in water or alcohol solvents, Whereby an organic transparent electrode can be formed on the substrate.
[Structural formula 1]
[Structural formula 2]
As described above, the conductive polymer for an organic electrode contains ions generated by a reaction between a conjugated polymer and an acidic dopant, and these ions absorb moisture in the air to lower the conductivity of the finally formed organic transparent electrode film there is a problem.
In addition, when implementing and operating an electronic device using an organic transparent electrode, moisture present inside the organic transparent electrode may deteriorate the electronic device, thereby deteriorating the conductivity of the conductive polymer for the organic electrode and deteriorating the performance of the electronic device. And efforts have been made to improve the water resistance in order to prevent it.
SUMMARY OF THE INVENTION The present invention has been made to overcome the problems of the prior art as described above, and it is an object of the present invention to improve the water resistance of the conductive polymer for an organic electrode to prevent the conductivity of the organic electrode from decreasing with time, More specifically, an organic electrode resin composition comprising a conductive polymer, an initiator, a durability improving agent, and a dispersion medium is provided to improve water resistance.
In order to solve the above problems, the present invention provides an organic electrode resin composition comprising a conductive polymer, an initiator, a durability enhancer, and a dispersion medium. More specifically, the durability improver includes a carbon-carbon double bond and an acid group ) At the same time.
Each component and role of the organic electrode resin composition of the present invention will be described in detail as follows.
≪ Conductive polymer &
As described above, the conductive polymer in the organic electrode composition according to the present invention is an acidic substance such as PEDOT [poly (3,4-ethylenedioxythiophene)], PANI (polyaniline), PPy (polypyrrol), PT (polythiophene) PEDOT: PSS, PEDOT: CSA, PEDOT: TSA, PEDOT: DBSA, PANI doped with [PSS: poly (4-styrenesulfonate), CSA: camphor sulfonic acid, TSA: toluene sulfonic acid, DBSA; dodecyl benzene sulfonic acid] Examples are PANSS, PANI: CSA, PANI: TSA, PANI: DBSA, PPy: PSS, PPy: CSA, PPy: TSA, PPy: DBSA, PT: PSS, PT: CSA, .
In such a conductive polymer, the content of the acidic dopant relative to the conjugated polymer such as PEDOT, PANI, PPy, and PT is suitably from 0.1 to 60 wt%. When the content of the acidic dopant is less than 0.1% by weight, the content of the ion is small and the solubility in a solvent which can be mixed with water or water is significantly lowered. When the content of the acidic dopant is more than 60% by weight, Not only the water content becomes excessive, but also the unreacted acidic dopant that does not react with the conjugated polymer acts as an impurity, thereby greatly deteriorating the conductivity.
As can be seen from the structural formula 1, the PEDOT has two non-bonding electrons in the sulfur atom (S) and the sulfonic acid group (-SO 3 H) of PSS (or CSA, TSA, DBSA) To form an ionic conductive polymer. As can be seen from the above structural formula 2, in the case of PANI, one non-covalent electron pair present in the nitrogen atom (N) reacts with the sulfonic acid group of PSS (or CSA, TSA, DBSA) to form an ionic conductive polymer . In the case of PPy, it is possible to react between the non-covalent electron pair present in the nitrogen atom and the acidic dopant. In the case of PT, since the reaction between the non-covalent electron pair present in the sulfur atom and the acid dopant is possible, And polar substances such as alcohols.
The content of the conductive polymer may be 0.05 to 30 wt%, preferably 0.1 to 20 wt%, based on the total amount of the organic electrode resin composition of the present invention. If the content of the conductive polymer is less than 0.05 wt%, the thickness of the formed organic electrode film is too low to increase the resistance of the organic electrode. If the content of the conductive polymer is more than 30 wt%, the visible light transmittance And the function as the transparent electrode is deteriorated.
<Initiator>
In the organic electrode resin composition according to the present invention, the initiator can be used as long as it is a substance capable of generating radicals by thermal decomposition, photolysis or oxidation-reduction reaction, and is commercially available to those having ordinary skill in the art And may be used singly or in combination of two or more.
Examples of pyrolysis initiators include hydrogen peroxide, dibenzoyl peroxide, dilauryl peroxide, cumyl peroxide, di-t-butyl peroxide, tetramethylbutyl peroxyneodecanoate, bis (4-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxycarbonate, butyl peroxyneodecanoate, dipropyl peroxydicarbonate, , diethoxyethyl peroxydicarbonate, diethoxyhexyl peroxydicarbonate, hexyl peroxydicarbonate, dimethoxybutyl peroxydicarbonate, bis (3-methoxy-3-methoxybutyl) peroxydicarbonate, dibutyl peroxydicarbonate, dicetyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxypivalate, hexyl peroxypivalate, , trimethylhexanoyl peroxide, dimethyl hydroxybutyl peroxyneodecanoate, amyl peroxyneodecanoate, butyl peroxyneodecanoate, t-butyl peroxyneoheptanoate, amyl peroxypivalate, t-butyl peroxypivalate, t-amyl peroxy-2-ethylhexanoate, lauroyl peroxide, dilauroyl peroxide, 2-bis (tert-butylperoxy) butane, 1,1- bis (tert-butylperoxy) cyclohexane, 2,5-bis (butylperoxy) -2,5-dimethylhexane, 2,5- Peroxy peroxides such as tertiary butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy isopropyl carbonate, cumene hydroxyperoxide, dicumyl peroxide, lauroyl peroxide and 2,4- compound thermoinitiator, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 4,4-azobis (4-cyanovaleric acid Azo compound-based thermal initiators such as 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), potassium persulfate, sodium persulfate, sodium bisulfate, Sulfuric acid derivatives such as ammonium persulfate, sodium hydrosulfite, Rongalite C, and Rongalite Z may be used.
Examples of the photopolymerization initiator include benzophenone compounds, acetophenone compounds, benzoin ether compounds, thioxanthone compounds, triazine compounds, nonimidazole compounds and oxime compounds, and specific examples thereof include 1- hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-1- 4- , oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] phenylacetophenone, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2- ) -1-propanone, diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide, phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide, bis (eta 5-2,4-cyclopentadien- , bis [2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl] titanium, iodonium, (4-methylphenyl) [4- (2-methylpropyl) phenyl] hexafluorophosph ate (1-), but are not limited thereto.
As the oxidation-reduction reaction initiator, the peroxide-based initiator, FeSO 4 , H 2 S, Na 4 P 2 O 7 and the like may be mixed and used.
The initiator content may be 0.005 to 5 wt%, preferably 0.01 to 1 wt%, based on the total amount of the organic electrode resin composition of the present invention. When the content of the initiator is less than 0.005% by weight, the amount of radicals generated is small and the durability improver can not be effectively reacted. When the content of the initiator exceeds 5% by weight, initiator fragments are present in the final organic electrode film excessively, It can act as a factor for lowering the conductivity of the electrode.
<Durability improver>
In the organic electrode resin composition according to the present invention, the durability enhancer is a compound having both a carbon-carbon double bond and an acid group, which crosslinks the conductive polymer and prevents the ions present in the conductive polymer from being exposed to moisture May be introduced to improve the durability of the finally formed organic electrode by acting as a protective film, and may be selected from one or more compounds represented by the following general formulas (1) to (4).
[Formula 1]
Here, X 1 , X 2 , X 3 , and X 4 may be the same or different, and are selected from the group consisting of oxygen; sulfur; A substituted or unsubstituted C1-C30 alkylene group; A substituted or unsubstituted C1-C30 heteroalkylene group; A substituted or unsubstituted C1-C30 oxyalkylene group; A substituted or unsubstituted C1-C30 thioalkylene group; A substituted or unsubstituted C1-C30 oxyheteroalkylene group; A substituted or unsubstituted C1-C30 thio heteroalkylene group; A substituted or unsubstituted C6-C30 arylene group; A substituted or unsubstituted C6-C30 oxyarylene group; A substituted or unsubstituted C6-C30 thioarylene group; A substituted or unsubstituted C6-C30 arylene alkylene group; A substituted or unsubstituted C2-C30 heteroarylene group; A substituted or unsubstituted C2-C30 oxyheteroarylene group; A substituted or unsubstituted C2-C30 thioheteroarylene group; A substituted or unsubstituted C2-C30 heteroarylene alkylene group; A substituted or unsubstituted C5-C20 cycloalkylene group; A substituted or unsubstituted C5-C20 oxy cycloalkylene group; A substituted or unsubstituted C5-C20 thio cycloalkylene group; A substituted or unsubstituted C5-C20 cycloalkylene alkylene group; A substituted or unsubstituted C2-C30 heterocycloalkylene group; A substituted or unsubstituted C2-C30 oxyheterocycloalkylene group; A substituted or unsubstituted C2-C30 thio heterocycloalkylene group; A substituted or unsubstituted C2-C30 thioheterocycloalkylene alkylene group; A substituted or unsubstituted C1-C30 alkylene ester group; A substituted or unsubstituted C1-C30 heteroalkylene ester group; A substituted or unsubstituted C6-C30 arylene ester group; And a substituted or unsubstituted C2-C30 heteroarylene ester group; A substituted or unsubstituted amide group, and the like. Y 1 , Y 2 , Y 3 and Y 4 may be the same or different and are COOH (carboxylic acid); Alkali metal salts of COOH; SO 3 H; Alkali metal salts of SO 3 H; OSO 3 H; Alkali metal salts of OSO 3 H; SO 2 H; Alkali metal salts of SO 2 H; OSO 2 H; Alkali metal salts of OSO 2 H; PO 3 H 2 ; Alkali metal salts of PO 3 H 2 ; OPO 3 H 2 ; Alkali metal salts of OPO 3 H 2 ; OPO 2 H 2 ; Alkali metal salts of OPO 2 H 2 ; PO 2 H 2 ; Alkali metal salts of PO 2 H 2 ; OPOH 2 ; And an alkali metal salt of OPOH 2 . A, b, c, and d may be the same or different and may be selected from 0 or 1.
[Formula 2]
Wherein R < 1 > is hydrogen; A halogen atom; A hydroxy group; A substituted or unsubstituted C1-C30 alkoxy group; A substituted or unsubstituted C1-C30 alkyl group; A substituted or unsubstituted C1-C30 heteroalkyl group; A substituted or unsubstituted C1-C30 heteroalkoxy group; A substituted or unsubstituted C6-C30 aryl group; A substituted or unsubstituted C6-C30 arylalkyl group; A substituted or unsubstituted C6-C30 aryloxy group; A substituted or unsubstituted C2-C30 heteroaryl group; A substituted or unsubstituted C2-C30 heteroarylalkyl group; A substituted or unsubstituted C2-C30 heteroaryloxy group; A substituted or unsubstituted C5-C20 cycloalkyl group; A substituted or unsubstituted C2-C30 heterocycloalkyl group; A substituted or unsubstituted C1-C30 alkyl ester group; A substituted or unsubstituted C1-C30 heteroalkyl ester group; A substituted or unsubstituted C2-C30 aryl ester group; And a substituted or unsubstituted C2-C30 heteroaryl ester group. X 2 , X 3 and X 4 may be the same or different and are the same as defined in the general formula (1). Y 2 , Y 3 and Y 4 may be the same or different and are the same as defined in formula 1. B, c, and d may be the same or different and are the same as those defined in the general formula (1).
[Formula 3]
Here, R 1 and R 2 may be the same or different and are hydrogen; A halogen atom; A hydroxy group; A substituted or unsubstituted C1-C30 alkoxy group; A substituted or unsubstituted C1-C30 alkyl group; A substituted or unsubstituted C1-C30 heteroalkyl group; A substituted or unsubstituted C1-C30 heteroalkoxy group; A substituted or unsubstituted C6-C30 aryl group; A substituted or unsubstituted C6-C30 arylalkyl group; A substituted or unsubstituted C6-C30 aryloxy group; A substituted or unsubstituted C2-C30 heteroaryl group; A substituted or unsubstituted C2-C30 heteroarylalkyl group; A substituted or unsubstituted C2-C30 heteroaryloxy group; A substituted or unsubstituted C5-C20 cycloalkyl group; A substituted or unsubstituted C2-C30 heterocycloalkyl group; A substituted or unsubstituted C1-C30 alkyl ester group; A substituted or unsubstituted C1-C30 heteroalkyl ester group; A substituted or unsubstituted C2-C30 aryl ester group; And a substituted or unsubstituted C2-C30 heteroaryl ester group. X 3 and X 4 may be the same or different and are the same as defined in the general formula (1). Y 3 and Y 4 may be the same or different and are the same as defined in the general formula (1). C and d may be the same or different and are the same as those defined in the general formula (1).
[Formula 4]
Here, R 1 , R 2 , and R 3 may be the same or different, and are hydrogen; A halogen atom; A hydroxy group; A substituted or unsubstituted C1-C30 alkoxy group; A substituted or unsubstituted C1-C30 alkyl group; A substituted or unsubstituted C1-C30 heteroalkyl group; A substituted or unsubstituted C1-C30 heteroalkoxy group; A substituted or unsubstituted C6-C30 aryl group; A substituted or unsubstituted C6-C30 arylalkyl group; A substituted or unsubstituted C6-C30 aryloxy group; A substituted or unsubstituted C2-C30 heteroaryl group; A substituted or unsubstituted C2-C30 heteroarylalkyl group; A substituted or unsubstituted C2-C30 heteroaryloxy group; A substituted or unsubstituted C5-C20 cycloalkyl group; A substituted or unsubstituted C2-C30 heterocycloalkyl group; A substituted or unsubstituted C1-C30 alkyl ester group; A substituted or unsubstituted C1-C30 heteroalkyl ester group; A substituted or unsubstituted C2-C30 aryl ester group; And a substituted or unsubstituted C2-C30 heteroaryl ester group. X 4 and Y 4 are the same as those defined in general formula (1). Also, d is the same as defined in general formula (1).
As can be seen from the above general formulas 1 to 4, the durability enhancer of the present invention is a compound having a carbon-carbon double bond and an acid group (corresponding to Y 1 , Y 2 , Y 3 and Y 4 in the general formulas 1 to 4 ) ) At the same time. The acidic group (carboxylic acid group, alkali metal salt of carboxylic acid, sulfate group, alkali metal salt of sulfate group, phosphate group, alkali metal salt of phosphoric acid group) constituting the durability improver of the present invention reacts with a pair of non- Thereby linking the durability improver to the conjugated polymer through a chemical bond.
That is, as can be seen from the above-described structural formulas 1 and 2, there exist sulfur atoms (in the case of PEDOT) and nitrogen atoms (in the case of PANI) in the PEDOT and PANI that have not interacted with PSS, The non-covalent electron pairs included in the compounds are capable of further interaction (chemical bonding) with various kinds of acidic substances. Accordingly, when a durability-improving agent having an acidic group is added to the conductive polymer, the durability-improving agent is chemically bonded to the conjugated polymer by reacting with a pair of non-covalent electrons present in the conjugated polymer to form ions. PPy and polythiophene (PT) also react with acidic groups included in the durability enhancer and non-covalent electron pairs contained in the nitrogen and sulfur atoms present in these molecules to form ions, thereby connecting the durability improver to the conjugated polymer through chemical bonding .
The role of the durability enhancer of the present invention is that the carbon-carbon double bond contained in the durability improver proceeds as the reaction proceeds by radicals generated from the initiator, and the crosslinked polymer in which the conductive polymer is chemically bonded And the polymerized durability improver acts as a protective film of ions existing in the conductive polymer, thereby preventing moisture penetration. The durability of the finally produced organic electrode is greatly improved by the crosslinking of the conductive polymer and formation of the ion protective film. That is, physical and chemical properties such as heat resistance, chemical resistance, flexural strength, and water resistance can be improved by crosslinking of the conductive polymer, and physical properties of the organic electrode can be changed by changing the kind of the durability improving agent. That is, when the oleophilic durability improver is used, the water resistance can be further improved due to the lipophilic property of the durability improving agent as well as the effect of crosslinking.
[Reaction Scheme 1]
The content of the durability enhancer may be 0.1 to 30 wt%, preferably 1 to 10 wt%, based on the total amount of the organic electrode resin composition of the present invention. When the content of the durability improver is less than 0.1% by weight, the crosslinking density is low, so that sufficient durability can not be ensured. When the content is more than 30% by weight, the content of the conductive polymer (conjugated polymer + acid dopant) There is a problem that the polymer (the polymer formed by polymerization of the durability-improving agent) is increased, and the conductivity of the organic electrode is lowered.
<Dispersion medium>
In the organic electrode resin composition of the present invention, the dispersion medium serves to dissolve or disperse the conductive polymer, the initiator and the durability improver, and may be a compound that can be mixed with water or water. . Examples of the solvent which can be mixed with the water include ethanol, methanol, acetone, isopropyl alcohol, propanol, methyl ethyl ketone, acetonitrile, butyl alcohol, tetrahydrofuran and the like. It is not.
The content of the dispersion medium may be 20 to 99 wt%, preferably 40 to 95 wt%, based on the total amount of the organic electrode resin composition of the present invention. When the content of the dispersing medium is less than 20% by weight, each component constituting the organic electrode resin composition can not be sufficiently dissolved. When the content is more than 99% by weight, the thickness of the organic electrode film formed is too low, There is a problem that the resistance increases greatly.
The organic electrode resin composition of the present invention may further include at least one additive selected from the group consisting of a conductive polymer, an initiator, a durability enhancer and a dispersing medium, a conductivity enhancer, a surfactant, an antifoaming agent, an aging agent and a silane coupling agent have.
<Conductivity Enhancer>
In the organic electrode resin composition of the present invention, a conductivity improving agent may be further added to improve the conductivity of the final organic electrode film. Such conductivity enhancers include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide (N N-dimethylacetamide, N-methylpropionamide, 2-pyrrolidone, N-methyl pyrrolidone (N-methylpyrrolidone) Amide-based conductivity improvers such as caprolactam and 1,1,3,3-tetramethylurea, methyl sulfoxide, dimethyl sulfoxide, sulfolane, Sulfone type conductivity enhancers such as diphenyl sulfone and the like; and sulfone type conductivity enhancers such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, diethylene glycol, triethylene glycol, methylpentanediol, hexanediol, trimethylolpropane, glycerin, Ethyl hexanediol, Polyhydric alcohol conductivity enhancers such as hexanetriol, polyethylene glycol, polypropylene glycol, polyoxypropylene triol, polytetramethylene glycol, sorbitol and derivatives thereof, and the like can be used alone or in combination.
In general, the acidic dopant constituting the conductive polymer forms a nanoparticle gel in the dispersion medium. When the nanoparticle gel contacts the conductivity enhancer, swelling easily occurs. At this time, the conjugated polymer easily diffuses into the swollen acidic dopant gel to form a conjugated polymer band in the acidic dopant, so that the conductivity of the finally formed film is increased. Particularly, the polyhydric alcohol conductivity enhancer enhances the conductivity of the conjugated polymer by improving the adhesion between the conductive nanoparticles by interaction with the conjugated polymer, and the vacancy space between the adjacent conductive nanoparticles due to the fine phase separation Thereby improving the transmittance of the film.
<Surfactant>
The organic electrode resin composition of the present invention is coated on a substrate of metal, glass, plastic or the like and dried to form an organic electrode film. In order to form a uniform film, wettability to the substrate should be excellent. In addition, it should not be precipitated by aggregation of the conductive polymer constituting the composition. As described above, the organic electrode resin composition of the present invention may further include a surfactant to improve wettability with the substrate and prevent agglomeration of the conductive polymer. Such surfactants include polyoxyalkylene alkyl ethers including polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and the like, polyoxyalkylene alkyl ethers including polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether and the like Sorbitan fatty acid esters including alkylphenyl ethers, sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, and the like; polyoxyalkylene sorbitan esters including polyoxyethylene sorbitan monolaurate; Polyoxyalkylene fatty acid esters including fatty acid esters, polyoxyethylene monolaurate, and polyoxyethylene monostearate, glycerin fatty acid esters including oleic acid monosulfuricide and stearic acid monoglyceride, polyoxyethylene Ethylene-polypropylene block copolymer, etc. Fatty acid salts including sodium stearate, sodium oleate, sodium laurate and the like, alkylaryl sulfonic acid salts including sodium dodecylbenzenesulfonate and the like, alkyl sulfates including sodium lauryl sulfate and the like Alkyl sulfosuccinic acid ester salts including ester salts, sodium monooctylsulfosuccinate, sodium dioctylsulfosuccinate, sodium polyoxyethylene laurylsulfosuccinate and the like, sodium polyoxyethylene lauryl ether sulfate, and the like Anionic surfactants such as polyoxyalkylene alkyl ether sulfuric acid ester salts including polyoxyalkylene alkyl ether sulfuric acid ester salts and sodium polyoxyethylene nonylphenyl ether sulfate, alkylamine salts including laurylamine acetate and the like , Lauryltrimethylammonium chloride, alkylbenzyl Quaternary ammonium salts including dimethyl ammonium chloride and the like, cationic surfactants such as polyoxyethyl alkyl-amines and the like, and amphoteric surfactants, which can be used singly or in combination. Further, when a surfactant in which a part of hydrogen is substituted with fluorine is used in the above-mentioned substance, a more excellent characteristic can be obtained.
<Defoamer>
In order to remove the bubbles contained in the organic electrode resin composition of the present invention, an antifoaming agent may be included. As the antifoaming agent, a mineral oil type antifoaming agent, a silicone type antifoaming agent, a polymer type antifoaming agent and the like may be applied.
<Increasing agent>
In order to control the viscosity of the organic electrode resin composition of the present invention, an increasing agent may be included, and potassium carbomer, potassium chloride, modified cellulose, polyethylene glycol, and the like may be used. However, Do not.
<Silane coupling agent>
A silane coupling agent may be added to improve the adhesion between the final cured film obtained from the organic electrode resin composition of the present invention and various substrates, and a functional group capable of reacting with a hydroxyl group (-OH) A halogen atom, an alkoxy group, a hydroxy group, etc.) and having a carbon-carbon double bond at the same time can be used. The silane coupling agent added to the organic electrode resin composition reacts with the hydroxyl group present on the substrate and the alkoxy group (or halogen atom, hydroxyl group) of the silane coupling agent to introduce the silane coupling agent into the substrate surface. When the durability improver is reacted by the radical, the carbon-carbon double bond forming the silane coupling agent participates in the polymerization reaction and is chemically (covalently) bonded to the substrate and the final organic electrode, so that the substrate / . Typical examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyl methyldimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl trimethoxysilane and 3-mercaptopropylmethyldimethoxysilane. It does not.
When the organic electrode resin composition according to the present invention is coated on a substrate such as glass, plastic, metal or the like and dried to form a film, and the formed film is exposed to light, the initiator is decomposed to generate radicals, The cross-linking reaction of the conductive polymer occurs due to the reaction between the carbon double bonds. If a thermal decomposition initiator is used, the organic electrode resin composition is coated on the substrate, and when heated, the initiator decomposes to generate radicals upon drying, and the reaction between the carbon-carbon double bonds of the durability improver proceeds to crosslink the conductive polymer. Thus, a crosslinked conductive polymer film can be formed to produce an organic electrode having improved water resistance.
The organic electrode resin composition having water resistance according to the present invention comprises a conductive polymer, an initiator, a durability improver and a dispersion medium in a composition, wherein the carbon-carbon double bond contained in the durability improver is polymerized by a radical generated from the initiator And the conductive polymer is chemically bonded to form a crosslinked polymer. The polymerized durability enhancer acts as a protective film for ions present in the conductive polymer, thereby preventing moisture penetration and providing an organic electrode having excellent water resistance. .
1 is a photograph showing a contact angle between a film and water prepared by using the organic electrode resin composition 1-1 (a), 1-2 (b), 1-3 (c) and 1-4 (d) ego,
2 is a graph showing the transmittance of an organic electrode prepared from the organic electrode resin composition of Example 2,
3 is a graph showing the thermal decomposition characteristics of the organic electrode prepared from the organic electrode resin composition of Example 3. Fig.
Hereinafter, the organic electrode resin composition of the present invention will be described in detail with reference to Examples. However, the present invention is not limited to the following Examples.
Example 1
First, 0.8 g of the conjugated polymer PEDOT and 1.1 g of the acidic dopant PSS were dispersed in a mixed dispersion medium of water (83 g) and ethanol (19 g). 2.1 g of dimethyl sulfoxide as a conductivity enhancer and 0.1 g of nonionic polyoxyethylene octyl phenyl ether as a surfactant were added to this mixture to prepare an organic electrode resin composition 1-1. 0.05 g of dimethoxybutyl peroxydicarbonate as an initiator and 0.3 g of 2-acrylamido-2-methyl-1-propanesulfonic acid of the following structural formula 3 as a durability enhancer were added to prepare Resin Composition 1-2. Also, Compositions 1-3, in which the content of the durability improver was increased to 0.6 g, and Compositions 1-4, which were increased to 0.9 g, were also prepared in the organic electrode resin composition. The organic electrode resin compositions 1-1, 1-2, 1-3 and 1-4 prepared by the above process were coated on a PET (poly (ethylene terephthalate)] substrate using a bar coater and dried at 110 ° C. for 10 minutes Thereby forming an organic electrode film. At this time, in the drying process, the initiator pyrolyzes to form a radical and reacts with the durability enhancer to form a crosslinked conductive polymer (organic electrode) film. The contact angle was measured after dropping water on the organic electrode film in order to determine whether the organic electrode film was improved in water resistance. The measured contact angle and the surface energy calculated from the contact angle were shown in Table 1, As shown in Fig.
[Structural Formula 3]
As can be seen from Table 1 and FIG. 1, the contact angle increased as the content of the durability enhancer was increased. As described above, it was found that the radicals were formed by pyrolysis of the initiator in the drying process, and the radicals reacted with the durability enhancer to form crosslinks of the conductive polymers and to form a protective film of ions, thereby weakening the hydrophilicity.
Example 2
A mixture in which 0.9 g of PANI as a conjugated polymer and 1.0 g of CSA as an acidic dopant were dispersed was prepared in a mixed dispersion medium of water (75 g) and isopropyl alcohol (24 g). 1.8 g of N-methylpyrrolidone as a conductivity improver and 0.11 g of nonionic ionic sorbitan monolaurate as a surfactant were added to this mixture to prepare an organic electrode resin composition 2-1. 0.04 g of 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-1-propanone as an initiator and 0.33 g of acrylic acid as a durability enhancer were added to the resin composition 2-2, . The organic electrode resin compositions 2-1 and 2-2 prepared above were coated on top of the glass substrate by a spin coating method (3000 rpm, 30 seconds) and dried at 100 ° C for 10 minutes to form an organic electrode film. The formed film was exposed to ultraviolet rays generated from a mercury lamp for 30 seconds to generate a radical by initiator decomposition and a radical reaction of the durability improver to produce a final organic electrode film. After the formed organic electrode film was separated from the glass substrate, the light transmittance of the visible light region was measured. The results are shown in FIG.
[Structural Formula 4]
It was found that there was no change in the transmittance before and after the durability improving agent of the present invention was included, and it was confirmed that there was no problem in application as a transparent electrode.
Example 3
1.2 g of PPy as a conjugated polymer and 0.9 g of TSA as an acid dopant were added to a mixture of water (95 g) and acetonitrile (10 g) as a dispersion medium. 1.1 g of ethylene glycol as a conductivity improver and 0.14 g of sodium lauryl sulfate as a surfactant were added to this mixture to prepare an organic electrode resin composition 3-1. 0.06 g of?,? -Dimethoxy-? -Phenylacetophenone as an initiator and 0.72 g of 4-styrenesulfonic acid sodium salt of the following structural formula 5 as a durability enhancer were added thereto, and a small amount of a mineral oil defoaming agent and a small amount of a polyethylene glycol- Composition 3-2 was prepared. The organic electrode resin compositions 3-1 and 3-2 prepared above were coated on a glass substrate by a spin coating method (2500 rpm, 20 seconds) and dried at 110 ° C for 10 minutes to form an organic electrode film. The formed film was exposed to ultraviolet rays generated from a mercury lamp for 60 seconds to produce a radical by decomposition of an initiator and a radical reaction of 4-styrenesulfonic acid sodium salt to produce a final organic electrode film. The formed organic electrode film was peeled off from the glass substrate and the thermal decomposition temperature was measured using a thermogravimetric analyzer (TGA). The thermal decomposition temperature of the cured film prepared from the resin composition 3-2 containing the durability improving agent Of the total population. From the result of the improvement in heat resistance, it was found that the durability improving agent reacts with radicals and plays a role of crosslinking. In addition, weight reduction was observed at a low temperature, indicating that a part of ethylene glycol as a conductivity enhancer remained in the finally formed organic electrode film.
[Structural Formula 5]
Example 4
To the mixture of water (102 g) and propanol (11 g) as a dispersion medium, 1.4 g of PT as a conjugated polymer and 0.5 g of DBSA as an acid dopant were added. 0.6 g of ethylene glycol and 0.3 g of N, N-dimethylacetamide were added as a conductivity enhancer to the mixture, and 0.09 g of lauryltrimethylammonium chloride was added as a surfactant to prepare an organic electrode resin composition 4-1. To this was added 0.07 g of bis [2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl] titanium, iodonium as an initiator and 1.01 g of vinylsulfonic acid sodium salt of the following structural formula 6 as a durability- And 0.12 g of 3-methacryloxypropyl trimethoxysilane as a ring agent was added to prepare Resin Composition 4-2. The organic electrode resin compositions 4-1 and 4-2 thus prepared were coated on the glass substrate by a spin coating method (3000 rpm, 20 seconds) and dried at 110 ° C for 15 minutes to form an organic electrode film. The formed film was exposed to ultraviolet rays generated from a mercury lamp for 60 seconds to produce a radical by decomposition of an initiator and a radical reaction of a vinylsulfonic acid sodium salt to produce a final organic electrode film. As a result of observing the shape change of the organic electrode film with time after dropping the water droplet on the organic film, the shape of the organic electrode film made from the resin composition 4-1 was greatly deformed by water , And in the case of the organic electrode film (including the durability improver) prepared from the resin composition 4-2, only fine deformation was observed by water.
[Structural Formula 6]
Example 5
First, a mixture in which 0.9 g of conjugated polymer PEDOT and 1.2 g of PSS as an acidic dopant were dispersed was prepared in a mixed dispersion medium of water (56 g) and isopropyl alcohol (18 g). 0.3 g of N-methylpyrrolidone as a conductivity improver and 0.1 g of glycerin were added to the mixture, and further, a fluorine-substituted surfactant was added to prepare an organic electrode resin composition 5-1. Resin composition 5-2 was prepared by adding 0.02 g of potassium persulfate as an initiator and 0.1 g of vinyl phosphate as shown below. The organic electrode resin compositions 5-1 and 5-2 thus prepared were coated on a polycarbonate substrate using a doctor blade coater and dried at 110 ° C for 10 minutes to form an organic electrode film. During the drying process, the initiator potassium persulfate pyrolyzes to form radicals and reacts with the durability improver to form a crosslinked conductive polymer (organic electrode) film. As a result of observing the shape change of the organic electrode film with time after dropping the water droplet on the organic film, the shape of the film was largely deformed by water in the case of the organic electrode film produced from the resin composition 5-1 , And in the case of the organic electrode film (including the durability improving agent) prepared from the resin composition 5-2, only minute deformation was observed by water.
[Structural Formula 7]
Example 6
Except that the initiator was changed to bis [2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl] titanium and iodonium in Example 5 and the durability improver was changed to maleic acid The organic electrode resin composition 6-2 was prepared. The organic electrode resin composition 6-2 prepared above was coated on the glass substrate by a spin coating method (3000 rpm, 30 seconds) and dried at 100 ° C for 10 minutes to form an organic electrode film. The formed film was exposed to ultraviolet rays generated from a mercury lamp for 30 seconds to generate a radical by initiator decomposition and a radical reaction of the durability improver to produce a final organic electrode film. As a result of observing the shape change of the organic electrode film over time after dropping a water droplet on the organic film, the organic electrode film prepared from the resin composition 5-1 shown in Example 5 showed that the film Although the shape was greatly changed, in the case of the organic electrode film (including the durability improver) produced from the resin composition 6-2, it was confirmed that only minute deformation was caused by water.
[Structural formula 8]
Example 7
An organic electrode resin composition 7-2 was prepared in the same manner as in Example 6 except that the durability improver was changed to (3-methylbut-3-en-1-yl) phosphonic acid of the following structural formula 9. The organic electrode resin composition 7-2 prepared above was coated on top of the glass substrate by a spin coating method (3000 rpm, 30 seconds) and dried at 100 ° C for 10 minutes to form an organic electrode film. The formed film was exposed to ultraviolet rays generated from a mercury lamp for 30 seconds to generate a radical by initiator decomposition and a radical reaction of the durability improver to produce a final organic electrode film. As a result of observing the shape change of the organic electrode film over time after dropping a water droplet on the organic film, the organic electrode film prepared from the resin composition 5-1 shown in Example 5 showed that the film It was confirmed that the organic electrode film (including the durability improving agent) produced from the resin composition 7-2 showed only slight deformation by water.
[Structural Formula 9]
Example 8
Except that the durability improving agent in Example 6 was changed to cesium 2 - ((2,33-trifluoro acrylo) oxy) ethylhydrophosphate represented by the following structural formula 10 to prepare the organic electrode resin composition 8-2 Respectively. The organic electrode resin composition 8-2 prepared above was coated on the glass substrate by a spin coating method (3000 rpm, 30 seconds) and dried at 100 ° C for 10 minutes to form an organic electrode film. The formed film was exposed to ultraviolet rays generated from a mercury lamp for 30 seconds to generate a radical by initiator decomposition and a radical reaction of the durability improver to produce a final organic electrode film. As a result of observing the shape change of the organic electrode film over time after dropping a water droplet on the organic film, the organic electrode film prepared from the resin composition 5-1 shown in Example 5 showed that the film Although the shape was greatly changed, in the case of the organic electrode film (including the durability improver) produced from the resin composition 8-2, it was confirmed that only slight deformation was caused by water.
[Structural Formula 10]
Claims (6)
[Formula 1]
Here, X 1 , X 2 , X 3 , and X 4 may be the same or different, and are selected from the group consisting of oxygen; sulfur; A substituted or unsubstituted C1-C30 alkylene group; A substituted or unsubstituted C1-C30 heteroalkylene group; A substituted or unsubstituted C1-C30 oxyalkylene group; A substituted or unsubstituted C1-C30 thioalkylene group; A substituted or unsubstituted C1-C30 oxyheteroalkylene group; A substituted or unsubstituted C1-C30 thio heteroalkylene group; A substituted or unsubstituted C6-C30 arylene group; A substituted or unsubstituted C6-C30 oxyarylene group; A substituted or unsubstituted C6-C30 thioarylene group; A substituted or unsubstituted C6-C30 arylene alkylene group; A substituted or unsubstituted C2-C30 heteroarylene group; A substituted or unsubstituted C2-C30 oxyheteroarylene group; A substituted or unsubstituted C2-C30 thioheteroarylene group; A substituted or unsubstituted C2-C30 heteroarylene alkylene group; A substituted or unsubstituted C5-C20 cycloalkylene group; A substituted or unsubstituted C5-C20 oxy cycloalkylene group; A substituted or unsubstituted C5-C20 thio cycloalkylene group; A substituted or unsubstituted C5-C20 cycloalkylene alkylene group; A substituted or unsubstituted C2-C30 heterocycloalkylene group; A substituted or unsubstituted C2-C30 oxyheterocycloalkylene group; A substituted or unsubstituted C2-C30 thio heterocycloalkylene group; A substituted or unsubstituted C2-C30 thioheterocycloalkylene alkylene group; A substituted or unsubstituted C1-C30 alkylene ester group; A substituted or unsubstituted C1-C30 heteroalkylene ester group; A substituted or unsubstituted C6-C30 arylene ester group; And a substituted or unsubstituted C2-C30 heteroarylene ester group; A substituted or unsubstituted amide group, and the like. Y 1 , Y 2 , Y 3 and Y 4 may be the same or different and are COOH (carboxylic acid); Alkali metal salts of COOH; SO 3 H; Alkali metal salts of SO 3 H; OSO 3 H; Alkali metal salts of OSO 3 H; SO 2 H; Alkali metal salts of SO 2 H; OSO 2 H; Alkali metal salts of OSO 2 H; PO 3 H 2 ; Alkali metal salts of PO 3 H 2 ; OPO 3 H 2 ; Alkali metal salts of OPO 3 H 2 ; OPO 2 H 2 ; Alkali metal salts of OPO 2 H 2 ; PO 2 H 2 ; Alkali metal salts of PO 2 H 2 ; OPOH 2 ; And an alkali metal salt of OPOH 2 . A, b, c, and d may be the same or different and may be selected from 0 or 1.
[Formula 2]
Wherein R < 1 > is hydrogen; A halogen atom; A hydroxy group; A substituted or unsubstituted C1-C30 alkoxy group; A substituted or unsubstituted C1-C30 alkyl group; A substituted or unsubstituted C1-C30 heteroalkyl group; A substituted or unsubstituted C1-C30 heteroalkoxy group; A substituted or unsubstituted C6-C30 aryl group; A substituted or unsubstituted C6-C30 arylalkyl group; A substituted or unsubstituted C6-C30 aryloxy group; A substituted or unsubstituted C2-C30 heteroaryl group; A substituted or unsubstituted C2-C30 heteroarylalkyl group; A substituted or unsubstituted C2-C30 heteroaryloxy group; A substituted or unsubstituted C5-C20 cycloalkyl group; A substituted or unsubstituted C2-C30 heterocycloalkyl group; A substituted or unsubstituted C1-C30 alkyl ester group; A substituted or unsubstituted C1-C30 heteroalkyl ester group; A substituted or unsubstituted C2-C30 aryl ester group; And a substituted or unsubstituted C2-C30 heteroaryl ester group. X 2 , X 3 and X 4 may be the same or different and are the same as defined in the general formula (1). Y 2 , Y 3 and Y 4 may be the same or different and are the same as defined in formula 1. B, c, and d may be the same or different and are the same as those defined in the general formula (1).
[Formula 3]
Here, R 1 and R 2 may be the same or different and are hydrogen; A halogen atom; A hydroxy group; A substituted or unsubstituted C1-C30 alkoxy group; A substituted or unsubstituted C1-C30 alkyl group; A substituted or unsubstituted C1-C30 heteroalkyl group; A substituted or unsubstituted C1-C30 heteroalkoxy group; A substituted or unsubstituted C6-C30 aryl group; A substituted or unsubstituted C6-C30 arylalkyl group; A substituted or unsubstituted C6-C30 aryloxy group; A substituted or unsubstituted C2-C30 heteroaryl group; A substituted or unsubstituted C2-C30 heteroarylalkyl group; A substituted or unsubstituted C2-C30 heteroaryloxy group; A substituted or unsubstituted C5-C20 cycloalkyl group; A substituted or unsubstituted C2-C30 heterocycloalkyl group; A substituted or unsubstituted C1-C30 alkyl ester group; A substituted or unsubstituted C1-C30 heteroalkyl ester group; A substituted or unsubstituted C2-C30 aryl ester group; And a substituted or unsubstituted C2-C30 heteroaryl ester group. X 3 and X 4 may be the same or different and are the same as defined in the general formula (1). Y 3 and Y 4 may be the same or different and are the same as defined in the general formula (1). C and d may be the same or different and are the same as those defined in the general formula (1).
[Formula 4]
Here, R 1 , R 2 , and R 3 may be the same or different, and are hydrogen; A halogen atom; A hydroxy group; A substituted or unsubstituted C1-C30 alkoxy group; A substituted or unsubstituted C1-C30 alkyl group; A substituted or unsubstituted C1-C30 heteroalkyl group; A substituted or unsubstituted C1-C30 heteroalkoxy group; A substituted or unsubstituted C6-C30 aryl group; A substituted or unsubstituted C6-C30 arylalkyl group; A substituted or unsubstituted C6-C30 aryloxy group; A substituted or unsubstituted C2-C30 heteroaryl group; A substituted or unsubstituted C2-C30 heteroarylalkyl group; A substituted or unsubstituted C2-C30 heteroaryloxy group; A substituted or unsubstituted C5-C20 cycloalkyl group; A substituted or unsubstituted C2-C30 heterocycloalkyl group; A substituted or unsubstituted C1-C30 alkyl ester group; A substituted or unsubstituted C1-C30 heteroalkyl ester group; A substituted or unsubstituted C2-C30 aryl ester group; And a substituted or unsubstituted C2-C30 heteroaryl ester group. X 4 and Y 4 are the same as those defined in general formula (1). Also, d is the same as defined in general formula (1).
The conductive polymer may be an acidic material (PSS), a poly (4-styrenesulfonate), or a CSA (camphor), for example, a conjugated polymer such as PEDOT, polyaniline, PPy or polythiophene. PEDOT: CSA, PEDOT: TSA, PEDOT: DBSA, PANI: PSS, PANI: CSA, PANI: TSA, PANI: DBSA doped with sulfonic acid, TSA: toluene sulfonic acid, DBSA; dodecyl benzene sulfonic acid] At least one member selected from the group consisting of PPy: PSS, PPy: CSA, PPy: TSA, PPy: DBSA, PT: PSS, PT: CSA, PT: TSA and PT: DBSA.
Wherein the initiator is selected from at least one substance capable of generating radicals by thermal decomposition, photolysis or oxidation-reduction reaction.
Wherein the dispersion medium is selected from the group consisting of water or a compound that can be mixed with water.
Wherein the additive is at least one selected from the group consisting of a conductivity enhancer, a surfactant, a defoamer, an additive, and a silane coupling agent.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114496400A (en) * | 2022-01-21 | 2022-05-13 | 芯体素(杭州)科技发展有限公司 | Preparation method of PEDOT (polymer of PEDOT and PSS), 3D (three-dimensional) printing method and application thereof |
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|---|---|---|---|---|
| KR100586660B1 (en) | 2004-04-01 | 2006-06-07 | 주식회사 디피아이 솔루션스 | Composition for coating organic electrode and method of manufacturing organic electrode having excellent transparency using the composition |
| KR101296350B1 (en) | 2012-06-04 | 2013-08-14 | 한국생산기술연구원 | Conductive polymer coated pet film and its manufacturing method and electrode using the film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100586660B1 (en) | 2004-04-01 | 2006-06-07 | 주식회사 디피아이 솔루션스 | Composition for coating organic electrode and method of manufacturing organic electrode having excellent transparency using the composition |
| KR101296350B1 (en) | 2012-06-04 | 2013-08-14 | 한국생산기술연구원 | Conductive polymer coated pet film and its manufacturing method and electrode using the film |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114496400A (en) * | 2022-01-21 | 2022-05-13 | 芯体素(杭州)科技发展有限公司 | Preparation method of PEDOT (polymer of PEDOT and PSS), 3D (three-dimensional) printing method and application thereof |
| CN114496400B (en) * | 2022-01-21 | 2024-03-08 | 芯体素(杭州)科技发展有限公司 | Preparation method of PEDOT (polyether-ether-ketone) -PSS (poly-styrene-ethylene-styrene) conductive polymer gel, 3D (three-dimensional) printing method and application thereof |
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