WO2010090422A1 - Film polyester antisalissure et antistatique - Google Patents
Film polyester antisalissure et antistatique Download PDFInfo
- Publication number
- WO2010090422A1 WO2010090422A1 PCT/KR2010/000612 KR2010000612W WO2010090422A1 WO 2010090422 A1 WO2010090422 A1 WO 2010090422A1 KR 2010000612 W KR2010000612 W KR 2010000612W WO 2010090422 A1 WO2010090422 A1 WO 2010090422A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyester film
- antifouling
- composition
- polyester
- conductive polymer
- Prior art date
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- 229920006267 polyester film Polymers 0.000 title claims abstract description 56
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 42
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 229920000123 polythiophene Polymers 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 23
- 239000011737 fluorine Substances 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000011230 binding agent Substances 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 230000002123 temporal effect Effects 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 17
- 229920000728 polyester Polymers 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 229920005749 polyurethane resin Polymers 0.000 claims description 9
- 229920001225 polyester resin Polymers 0.000 claims description 8
- 239000004645 polyester resin Substances 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 229940093476 ethylene glycol Drugs 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical group CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- 102100029469 WD repeat and HMG-box DNA-binding protein 1 Human genes 0.000 claims 1
- 101710097421 WD repeat and HMG-box DNA-binding protein 1 Proteins 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 5
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 23
- 238000000034 method Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- 239000008199 coating composition Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 229920006026 co-polymeric resin Polymers 0.000 description 5
- 229920000767 polyaniline Polymers 0.000 description 5
- 229920000144 PEDOT:PSS Polymers 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229960002796 polystyrene sulfonate Drugs 0.000 description 4
- 239000011970 polystyrene sulfonate Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000002519 antifouling agent Substances 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- -1 polypyrrol (PPy) Polymers 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- HCIIZCUFTFJFAB-UHFFFAOYSA-N 1,1,2,2,3,3,3-heptafluoropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(F)(F)C(F)(F)C(F)(F)F HCIIZCUFTFJFAB-UHFFFAOYSA-N 0.000 description 1
- RTEKUJFDNWKQGL-UHFFFAOYSA-N 1,1,2,2,3,3,3-heptafluoropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(F)(F)C(F)(F)C(F)(F)F RTEKUJFDNWKQGL-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- ZLGWXNBXAXOQBG-UHFFFAOYSA-N triethoxy(3,3,3-trifluoropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)F ZLGWXNBXAXOQBG-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/5406—Silicon-containing compounds containing elements other than oxygen or nitrogen
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
Definitions
- the present invention relates to a polythiophene-based conductive polymer composition prepared by mixing an aqueous polythiophene-based conductive polymer solution, a binder, a fluorine-based antifouling compound, water and an aprotic highly-dipolar solvent at a predetermined component ratio, and an antifouling and antistatic polyester film formed using the same.
- PAN polyaniline
- PPy polypyrrol
- PT polythiophene
- electrodes for secondary batteries materials for blocking electromagnetic waves, flexible electrodes, antistatic materials, coating materials for anticorrosion, etc.
- materials for blocking electromagnetic waves can be prepared using the electrical characteristics of such conductive polymer compounds.
- they are not commercially available yet due to problems and difficulties in workability, thermal and atmospheric stability, moisture resistance, price, etc.
- these conductive polymer compounds have lately attracted considerable attention as coating materials for the prevention of dust-sticking and static charge. Moreover, they have lately attracted considerable attention as coating materials for blocking electromagnetic waves in various electronic appliances by strictly controlling the standards for blocking electromagnetic waves.
- conductive polymers began to attract considerable attention as conductive coating materials for glass of cathode ray tubes (CRTs) from the time that polyethylene dioxythiophene (PEDT), which is a polythiophene-based conductive polymer, became highlighted.
- PET polyethylene dioxythiophene
- These conductive polymers have excellent transparency compared to other conductive polymers, such as polyaniline-based conductive polymers, polypyrrol-based conductive polymers, polythiophene-based conductive polymers, etc.
- polyethylene dioxythiophene PEDT
- PEDT polyethylene dioxythiophene
- a polymer acid salt such as polystyrene sulfonate
- This water-dispersible polyethylene dioxythiophene coating solution has been variously used as coating materials for glass of cathode ray tubes (CRTs), plastic film and the like because it is easily mixed with alcohol solvents and has excellent workability.
- Baytron P As a typical example of this water-dispersible polyethylene dioxythiophene, there is Baytron P which is manufactured by Bayer Corp. However, since this Baytron P is water dispersion and contains a SO 3 - group, it is weak to water even after it is formed into a polymer film. Therefore, its commercialization was not easy due to the great change in electrical characteristics of the polymer film when it was left alone for a long period of time or was exposed to high-humidity environmental conditions.
- Korean Patent Application Publication No. 2000-10221 discloses a conductive polymer composition containing polyethylene dioxythiophene, an alcohol solvent, an amide solvent, a polyester resin binder, etc.
- Korean Patent Application Publication No. 2005-66209 discloses a coating composition for a conductive light-diffusing film, containing polyethylene dioxythiophene, an alcohol solvent, an amide solvent, a silane coupling agent, etc.
- the conductive polymer composition and the coating composition have a low surface resistance of 1 k ⁇ /m2 or less and high transparency, adhesivity and durability, they cannot also be easily commercially used due to the great change in electrical characteristics of the conductive polymer film with the passage of time and the great change in electrical characteristics thereof under the condition of hot and humid environment.
- polyester film has been used as various base materials for displays or protective films because it has excellent durability and transparency.
- the polyester film has problems that it is easily contaminated by dust, foreign matters, etc. Therefore, in order to impart antistatic and antifouling properties to the polyester film, the following methods have been used.
- Japanese Patent Application Publication No. H11-25615 discloses a method of forming an antistatic layer on a polyester film and then forming an antifouling layer on the antistatic layer
- Korean Patent Application Publication No. 2007-0071992 discloses a method of integrally forming an antistatic layer and an antifouling layer on a polyester film. In these methods, an antistatic agent dispersed in an organic solvent by an off-line coating process using a biaxially-stretched polyester film is used.
- Japanese Patent Application Publication No. 2000-026817 discloses a method of forming an antistatic layer using an antistatic agent used in a process of stretching a polyester film and then an antifouling layer by an off-line coating process
- Korean Patent Application Publication No. 2008-0055266 discloses a method of forming only an antistatic layer using polyaniline as a conductive polymer in a process of stretching a polyester film.
- the methods of forming an antistatic layer and an antifouling layer on a biaxially-stretched polyester film by an off-line coating process has disadvantages that it is not environment-friendly due to the use of an organic solvent, it is not easily processed because both antistatic coating and antifouling coating must be performed, antistatic performance rapidly decreases with time when an antistatic layer and an antifouling layer are integrally formed, and an antistatic property changes depending on humidity and migrates to the surface of the polyester film when polymer salts are used.
- Korean Patent No. 813179 by the present inventors discloses an antifouling and antistatic polyester film formed using a coating composition including a polyester-based urethane resin, conductive polymer, an antifouling agent and a slipping agent.
- this antifouling and antistatic polyester film has a problem that its antistatic property deteriorates at room temperature and its appearance cannot be optically used.
- the present inventors have made efforts to solve the above-mentioned problems of the changes in material properties of an antistatic layer formed on a polyester film depending on environment, an off-line coating process which is not environment-friendly, a process that is inconvenient and requiring high costs.
- a polythiophene-based conductive polymer composition prepared by mixing an aqueous polythiophene-based conductive polymer solution, a binder, a fluorine-based antifouling compound, water and an aprotic highly-dipolar solvent at a predetermined component ratio
- the aprotic highly-dipolar solvent partially re-melts the polymer groups of the aqueous polythiophene-based conductive polymer solution to improve the connectivity and dispersity between polythiophene-based conductive polymers
- the binder increases the binding force between the composition and a polyurethane resin, so that an antistatic layer and an antifouling layer can be integrally formed in a process of biaxially stretching a polyester film, thereby realizing a polyester film having excellent durability.
- an object of the present invention is to provide a water-dispersible coating composition containing a conductive polymer, which can be used in a process of stretching a polyester film, and an antistatic film formed using the coating composition, which can exhibits excellent antistatic and antifouling properties regardless of the change in humidity and post-treatment.
- the present invention provides a water-dispersible polythiophene-based conductive polymer composition having antifouling and antistatic properties, including: 1 - 30 wt% of an aqueous polythiophene-based conductive polymer solution; 1 - 30 wt% of two or more binders selected from the group consisting of a polyester resin, a polyurethane resin, isocyanate and alkxoysilane; 10 - 60 wt% of a fluorine-based antifouling compound; 30 - 65 wt% of water; and 1 - 20 wt% of an aprotic highly-dipolar solvent, and a polyester film formed using the same.
- the present invention provides a polythiophene-based conductive polymer composition prepared by mixing an aqueous polythiophene-based conductive polymer solution, a binder, a fluorine-based antifouling compound, water and an aprotic highly-dipolar solvent at a predetermined component ratio, a antifouling and antistatic polyester film formed using the composition through a biaxial stretching process, and a method of manufacturing the polyester film.
- the present invention provides a polythiophene-based conductive polymer composition, which does not require the use of a sulfonic acid group stabilizer for connecting polythiophene-based conductive polymers, whose surface resistance can be constantly maintained regardless of changes in external environment, which has an excellent antifouling property, high moisture resistance, strong adhesivity, excellent durability, high film uniformity and excellent stability to liquid, which has good physical appearance even after coating, and which can ensure material properties, because the composition is prepared by selectively mixing an aqueous polythiophene-based conductive polymer solution, a binder, a fluorine-based copolymer resin, water and an aprotic highly-dipolar solvent at a predetermined component ratio, wherein the aprotic highly-dipolar solvent partially re-melts the polymer groups of the aqueous polythiophene-based conductive polymer solution to improve the connectivity and dispersity between polythiophene-based conductive polymers, the fluorine-based antif
- the antifouling and antistatic polyester film manufactured by applying the polythiophene-based conductive polymer composition onto one side or both sides of a polyester-based substrate and then laterally-stretching the polyester-based substrate coated with the composition and then thermally fixing the stretched polyester-based substrate coated with the composition has a surface resistance of 1 X 10 6 - 1 X 10 9 ⁇ /sq, an optical transmittance of 89% or more and a water contact angle of 90o or more, and the temporal change in the surface resistance thereof at room temperature and the change in the surface resistance thereof at constant temperature and humidity is maintained within a 10 fold difference.
- the total thickness of the polyester film may be 25 - 250 ⁇ m, and the coating thickness thereof may be 20 - 200 nm.
- the aqueous polythiophene-based conductive polymer solution is not particularly limited as long as it is commonly used in a related field, but, in the present invention, polyethylenedioxythiophene (PEDT) (Baytron P, manufactured by Bayer Corp.) is used. Since the PEDT, which is a stabilizer (dopant), is doped with polystyrene sulfonate (PSS), it can be easily dissolved in water and has excellent thermal stability and atmospheric stability. Further, in order to optimally disperse the PEDT in water, the solid content of PEDT and PSS is adjusted in a range of 1.0 - 1.5 wt%.
- PEDT polyethylenedioxythiophene
- PSS polystyrene sulfonate
- the composition is easily mixed with water, alcohol or a solvent having a high dielectric constant, so that the composition can be easily applied on a substrate by diluting it with such a solvent, and the coating film formed using this composition exhibits excellent transparency compared to other conductive polymers, such as polyaniline, polypyrrol and the like.
- the aqueous polythiophene-based conductive polymer solution is used in an amount of 1 - 30 wt%, preferably, 2 - 20 wt% based on the total amount of the conductive polymer composition.
- a resin be used in the state of an aqueous solution as a binder for imparting moisture resistance, substrate adhesivity and durability because the PEDT conductive polymer solution itself is a water dispersion.
- the binder for improving adhesivity and durability may be two or more selected from the group consisting of a polyester resin, a polyurethane resin, isocyanate and alkoxysilane.
- a polyester film is formed by coating a polyester substrate with a coating composition and laterally-stretching the polyester substrate coated with the coating composition 3 - 6 folds, it is preferred that a polyester resin and a polyurethane resin having a stretching ratio of 200 - 700%, more preferably, 350 - 550%.
- the polyester film is cut during a stretching process, thus resulting in poor appearance.
- the stretching ratio of the binder is more than 700%, the difference in stretching ratio between the binder and the polyester substrate is increased, thus being unable to improve the adhesivity and durability of the polyester film.
- alkoxysilane be methyltrimethoxysilane or tetraethoxysilane.
- the binder is used in an amount of 1 - 30 wt%, preferably, 5 - 20 wt%.
- amount of the binder is less than 1 wt%, the adhesive force between the composition and the polyester substrate and the durability of a conductive film is deteriorated.
- amount thereof is more than 30 wt%, the conductivity of the polyester film is deteriorated.
- the fluorine-based antifouling compound used in the present invention is used to prevent the adhering of pollutants and to easily remove the pollutants.
- the fluorine-based compound is not particularly limited but it includes those antifouling compounds commonly used in the related field. More specifically, the fluorine-based compound may be one or more selected from the group consisting of fluorine-based hydrocarbon compounds and fluorosilane coupling agents.
- the fluorine-based hydrocarbon compounds may include fluorine-containing acrylate resin copolymers.
- the fluorosilane coupling agents may be selected from the group consisting of trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, heptafluoropropyltrimethoxysilane, heptafluoropropylmethyldimethoxysilane.
- a water-dispersible fluorine-based compound be used.
- the fluorine-based copolymer resin is used in an amount of 10 - 60 wt% based on the total conductive polymer composition, preferably, 15 - 50 wt%. When the amount of the fluorine-based copolymer resin is less than 10 wt%, the contact angle is decreased. When the amount thereof is more than 60 wt%, stability to liquid is decreased, and surface resistance is increased.
- the water used in the present invention may be used in an amount of 30 - 65 wt% based on the total conductive polymer composition.
- an aprotic highly-dipolar solvent is used together with water, thus improving the connectivity between conductive polymers and the dispersibility of PEDOT. That is, the aprotic highly-dipolar solvent, which is a polar solvent having hydrogen ions at end groups thereof, is directly bonded with SO 3 - of the PEDOT water dispersion without forming H 3 O + when it is dissolved in water, so that the dispersibility of PEDOT is improved, thereby increasing conductivity.
- the aprotic highly-dipolar (AHD) solvent may be selected from the group consisting of dimethylsulfoxide (DMSO), propylene carbonate (PC), ethylenglycol (EG) and the like.
- the aprotic highly-dipolar (AHD) solvent may be used in an amount of 1 - 20 wt%, preferably 4 - 18 wt%. When the amount of the aprotic highly-dipolar (AHD) solvent is less than 4 wt%, conductivity cannot be obtained. When the amount thereof is more than 18 wt%, boiling point is increased, and thus high-temperature calcination must be performed.
- an additive for improving slipping and leveling may be added in an amount of 0.05 - 5 parts by weight based on 100 parts by weight of the conductive polymer composition.
- a biaxially-stretched polyester film is manufactured by applying the conductive polymer composition onto one side or both sides of a polyester-based substrate which was not primer-treated, laterally-stretching the polyester-based substrate coated with the conductive polymer composition 3 - 6 folds at 100 - 140°C and then thermally-fixing the laterally-stretched polyester-based substrate coated with the conductive polymer composition at 220 - 240°C.
- the polyester film formed by coating a substrate with a polythiophene-based conductive polymer composition and then laterally-stretching the substrate coated with composition exhibits excellent antistatic and antifouling properties.
- this polyester film has surface resistance which slightly changes with time at room temperature, is transparent, and has electrical characteristics which do not change at high temperature and high humidity. Therefore, this polyester film, which is used in the display industry, suppresses static electricity to prevent dust from adhering thereto, and has a high antifouling property to easily remove pollutants therefrom, so that the productivity and processibility of display materials can be improved, and can be practically used in various fields requiring transparency and antistatic and antifouling properties.
- the prepared coating composition was applied on a polyester sheet formed by melt extrusion, and then the polyester sheet coated with the composition was laterally stretched four folds, dried, cured and then thermally fixed at a temperature of 230 °C to manufacture an antistatic and antifouling polyester film having a total thickness of 188 ⁇ m.
- An antistatic and antifouling polyester film was manufactured in the same manner as in Example 1, except that 13 wt% of alkoxysilane was used as a binder.
- An antistatic and antifouling polyester film was manufactured in the same manner as in Example 1, except that 3 wt% of a polyester resin having a stretching ratio of 450 - 550% was used instead of the polyurethane resin having a stretching ratio of 400%.
- Polyester films were manufactured in the same manner as in Example 1 according to the components and contents given in Table 1 below.
- a polyester film was manufactured in the same manner as in Korean Patent No. 813179.
- the haze (%) and optical transmittance of the polyester film were measured using an XL 211 hazemeter manufactured by Gardener Corp.
- the surface resistance ( ⁇ /sq) of the polyester film was measured using a surface resistance meter (model name: 19782) manufactured by DESCO Corp. in U.S. under the conditions of a temperature of 23 °C, a relative humidity of 30% and an applied voltage of 500 V.
- the antistatic and antifouling polyester films manufactured in Examples and Comparative Examples were left alone at room temperature, and then the changes in the surface resistance thereof were measured using the surface resistance meter (model name: 19782) manufactured by DESCO Corp. in U. S. according to the passage of time.
- the antistatic and antifouling polyester films manufactured in Examples and Comparative Examples were left alone at a temperature of 60°C and a relative humidity of 90%, and then the changes in the surface resistance thereof were measured.
- Classifi-cation Optical transmittance (%) Haze (%) Contact angle (o) Temporal change in surface resistance at room temperature ( ⁇ /sq) Change in surface resistance at constant temperature and humidity (RH 90%, 60°C) initial 440 hr initial 440 hr Ex. 1 89.93 2.66 100.6 6 X 10 7 1.5 X 10 8 3 X 10 7 5 X 10 7 Ex. 2 89.87 1.57 102.8 4 X 10 7 8 X 10 7 3.6 X 10 7 4 X 10 7 Ex. 3 89.78 1.50 94.6 1.5 X 10 7 6 X 10 7 2 X 10 7 5 X 10 7 Comp. Ex.
- the antistatic and antifouling polyester films manufactured in Examples and Comparative Examples has a surface resistance of about 10 7 and a water contact angle of 90° or more, and, particularly, that their surface resistances hardly change at room temperature or at constant temperature and relative humidity according to the passage of time.
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
La présente invention a pour objet une composition de polymère conducteur à base de polythiophène préparée par le mélange d'une solution aqueuse de polymère conducteur à base de polythiophène, d'un liant, d'un composé antisalissure à base de fluor, d'eau et d'un solvant aprotique hautement dipolaire avec un rapport des composants prédéterminé, et un film polyester antisalissure et antistatique formé au moyen de la composition. Le film possède une résistance de surface de 1 X 106 - 1 X 109 Ω/sq et un angle de contact avec l'eau de 90º ou plus, la modification temporelle de sa résistance de surface à température ambiante est faible, et il possède une résistance à l'humidité élevée. L'invention concerne également un procédé de fabrication du film polyester.
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KR1020090008568A KR101048893B1 (ko) | 2009-02-03 | 2009-02-03 | 방오성 대전방지 폴리에스테르 필름 |
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CN102476490A (zh) * | 2010-11-23 | 2012-05-30 | 远东新世纪股份有限公司 | 延长透明抗静电膜的抗静电能力的方法及透明抗静电膜 |
CN115298027A (zh) * | 2020-03-09 | 2022-11-04 | 东洋纺株式会社 | 白色易粘接性聚酯膜 |
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KR101285853B1 (ko) * | 2010-12-23 | 2013-07-12 | 도레이첨단소재 주식회사 | 편광판 보호용 폴리에스테르 필름 |
KR102130704B1 (ko) * | 2014-04-30 | 2020-07-06 | 코오롱인더스트리 주식회사 | 폴리에스테르 필름 및 이의 제조방법 |
JP6751198B2 (ja) * | 2017-03-28 | 2020-09-02 | 日東電工株式会社 | 粘着剤層付き偏光フィルム、インセル型液晶パネル用粘着剤層付き偏光フィルム、インセル型液晶パネルおよび液晶表示装置 |
CN115185121B (zh) * | 2017-03-28 | 2024-04-26 | 日东电工株式会社 | 带粘合剂层的偏振膜、内嵌型液晶面板及液晶显示装置 |
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CN102476490A (zh) * | 2010-11-23 | 2012-05-30 | 远东新世纪股份有限公司 | 延长透明抗静电膜的抗静电能力的方法及透明抗静电膜 |
CN102476490B (zh) * | 2010-11-23 | 2015-04-08 | 远东新世纪股份有限公司 | 延长透明抗静电膜的抗静电能力的方法及透明抗静电膜 |
CN115298027A (zh) * | 2020-03-09 | 2022-11-04 | 东洋纺株式会社 | 白色易粘接性聚酯膜 |
CN115298027B (zh) * | 2020-03-09 | 2024-01-12 | 东洋纺株式会社 | 白色易粘接性聚酯膜 |
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