WO2015111765A1 - Ultraviolet-curing perfluoropolyether-modified compound, dirt-resistant coating-agent composition comprising same, and film and dirt-resistant substrate using same - Google Patents
Ultraviolet-curing perfluoropolyether-modified compound, dirt-resistant coating-agent composition comprising same, and film and dirt-resistant substrate using same Download PDFInfo
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- WO2015111765A1 WO2015111765A1 PCT/KR2014/000631 KR2014000631W WO2015111765A1 WO 2015111765 A1 WO2015111765 A1 WO 2015111765A1 KR 2014000631 W KR2014000631 W KR 2014000631W WO 2015111765 A1 WO2015111765 A1 WO 2015111765A1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
- C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/3332—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing carboxamide group
- C08G65/33327—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing carboxamide group cyclic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
- C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers
Definitions
- UV curable perfluorinated polyether modified compound, antifouling coating composition comprising same, membrane and antifouling substrate to which the same is applied
- the present invention does not require an additional radical initiator during UV curing, UV-curable perfluorinated polyether modified compound that can be chemically bonded to the hydrocarbon-based substrate to produce a durable antifouling film, antifouling coating composition comprising the same
- the antifouling coating composition is formed by curing the scratch resistance and durability improved film, the antifouling substrate to which the film is attached.
- Fluorine-based functional materials are attracting worldwide attention as core materials of next-generation technologies in the fields of optical communications, optoelectronics, semiconductors, automobiles, and computers, which are high-tech industries.
- the outermost layer or the beautiful display of rapidly increasing various displays such as liquid crystal displays
- Industrial demand is increasing rapidly for coating layers for preventing contamination caused by fingerprints such as frames.
- various material technologies for manufacturing an optical film including an antifouling layer are very important industrially because they influence the visibility of the screen regardless of the display type.
- the anti-pollution properties of various resin paints are very important in many industrial fields. For example, by providing the anti-pollution properties to the display frame or various home appliances, it is possible to maintain a clean appearance and to apply the anti-pollution paints to the construction or civil engineering fields.
- the use of antifouling is essential for almost all modern industrial life, such as its ability to maintain pollution resistance.
- Patent Document 1 discloses fluorine-silicon.
- C 8 F 17 C 2 H 4 Si (NH) 3/2 , C 4 F 9 C 2 H 4 Si (NH) 3/2 or polysiloxane (polys i loxazane), etc. are disclosed as a series of surface coating agents. It is.
- the compounds are used alone, the inorganic oxide and the semi-crosslinking properties of the base material are poor, and the durability against friction is poor.
- Patent Document 2 uses a silane having a perfluorine group as a glass surface modifier, such a coating agent also has a disadvantage in that it does not simultaneously exhibit sufficient water repellency, antifouling property and decontamination property.
- Patent Documents 2 to 5 propose a so-called silane coupling method in which inorganic materials such as glass and organic materials are combined.
- This method has a chemical structure and a reactive alkoxy silane group having good affinity with an organic functional group or organic material in one molecular increment, and the alkoxy silane groups undergo self-condensation reaction with moisture in the air to form siloxane. At the same time, they form chemical bonds with surfaces such as glass and metal surfaces, resulting in strong adhesion. Therefore, the silane coupling agent is used as a coating component or primer on the surface of various substrates.
- the compound in which the silane coupling agent and the perfluorine group are chemically bonded in the above document has good film formability, can be used as a coating component having good adhesion and durability to the substrate, and a substrate having the fluorine coupling structure.
- the antifouling property water repellency, oil repellency
- the length (molecular weight) of the perfluorine group is limited, and even if the oil repellency is poor, and the length (molecular weight) of the stratified gubleso group is alkoxy to the molecular weight of the whole molecule including the guble group.
- Patent Document 6 discloses a perfluoroether-modified salane compound o represented by the following chemical formula.
- Patent Document 7 discloses a composition containing a carbon-carbon double bond comprising a triisocyanate trimerized (A) diisocyanate, a perfluorinated polyether having active hydrogen, and a silane compound having active hydrogen.
- the oligomeric perfluorinated ether modified silane compound is suitable for imparting fouling resistance to the surface of inorganic materials such as glass and ceramics, but is firstly applied to imparting surface fouling resistance of organic and polymer materials having a much larger range than inorganic materials.
- As the degree of network structure by self-crosslinking it is fixed by van der Waals bonds and thus lacks surface bonding strength and durability.
- Antifouling coating composition comprising a compound of the present invention comprising a compound is applicable to organic materials, such as polymers, excellent compatibility with other organic pharmaceuticals, and by coating and UV curing (rol l to rol) l) It is possible to apply the process, and it was confirmed that it is possible to manufacture a membrane having excellent durability and antifouling property because it can be chemically bonded to a hydrocarbon-based substrate without the need for a radical initiator during UV curing, and completed the present invention. .
- An object of the present invention is applicable to organic materials, such as polymers, excellent compatibility with other organic pharmaceuticals, and can be applied to the roll to roll process by coating and UV curing, as well as UV curing
- the present invention provides an ultraviolet curable perfluorinated polyether-modified compound that does not require an additional radical initiator and can be chemically bonded to a hydrocarbon-based substrate to produce a durable antifouling membrane. It is also an object of the present invention to provide a method for producing the perfluorinated polar ether modified compound. Furthermore, an object of the present invention is to provide an antifouling coating composition comprising the perfluorinated polyether modified compound.
- n is an integer from 1 to 16
- A is any one of the following Chemical Formulas 2 to 4,
- 3 ⁇ 4 is any one of the formulas .5-7,
- 3 ⁇ 4 is any one of the following Chemical Formulas 8 to 12,
- 3 ⁇ 4 is any one of the following Chemical Formulas 5 to 7 or i in the following Chemical Formulas 8 to 12.
- X is d-C 5 linear or branched perfluoroalkylene
- Y is d-C 5 linear or branched perfluoroalkyl
- a, b, c, d, e and f are each independently integers of 0-100.
- a mixture of a compound of Formula 13 and a compound of Formulas 14-16 is reacted under a mixed solvent of a fluorocarbon solvent and a hydrocarbon solvent to prepare a compound of Formula 1 of the perfluorinated polyether modified compound of Formula 1 It provides a manufacturing method.
- G is a halogen element. Furthermore, in order to achieve the above object, the present invention
- Step 2 Preparation of the perfluorinated polyether modified compound of Formula 1 comprising the step (Step 2) of preparing a compound of Formula 1 by reacting the compound of Formula 17 and the compound of Formula 15 in a mixed solvent of a fluorocarbon solvent and a hydrocarbon solvent Provide a method.
- n, 3 ⁇ 4 and 3 ⁇ 4 are as defined in Formula 1,
- a compound of Formula 1 comprising the step of preparing a compound of Formula 1 by reacting a mixture of a compound of Formula 18 with a compound of Formula 15 and a compound of Formula 16 under a mixed solvent of a fluorocarbon solvent and a hydrocarbon solvent (step 2)
- step 2 Provided is a method for producing a perfluorinated polyether modified compound.
- n, 3 ⁇ 4 and 3 ⁇ 4 are as defined in Formula 1,
- 3 ⁇ 4 is any one of Formulas 8 to 12, as defined in Formula 1,
- the antifouling coating composition according to the present invention provides a film formed by curing. Furthermore, the present invention to achieve the above object
- the surface of a base material is coat
- the perfluorinated polyether modified compound according to the present invention does not include a silane group, it can be applied to an organic material such as a polymer, has excellent compatibility with other organic pharmaceuticals, and applies a roll to roll process.
- the perfluorinated polyether group includes antifouling properties and wiping properties such as antifouling properties and wiping properties, and includes a benzophenone-based compound so that ultraviolet curing is possible without the need for an additional radical initiator.
- the film formed by curing the coating composition is capable of chemically bonding to all base materials composed of hydrocarbon-based compounds, thereby improving the antifouling property, endogenous swelling resistance, and durability. It can be usefully used for the substrate.
- Figure 1 shows a -NMR graph of the photocurable perfluorinated polyether modified compound (Example 1) of the present invention by nuclear magnetic resonance (NMR) analysis.
- Figure 2 shows a graph of the permeability of the membrane (Example 11) and the untreated slide glass (Comparative Example 3) formed by curing the antifouling coating composition comprising a photocurable perfluorinated polyether modified compound of the present invention.
- the present invention provides a perfluorinated polyether-modified compound represented by the following Chemical Formula 1;
- n is an integer from 1 to 16
- A is any one of the following Formulas 2 to 4,
- 3 ⁇ 4 is any one of the following Chemical Formulas 5 to 7,
- 3 ⁇ 4 is any one of the following Chemical Formulas 8 to 12,
- 3 ⁇ 4 is any one of the following Chemical Formulas 5 to 7 or the following Chemical Formulas 8 to 12.
- X is d-C 5 straight or branched gublesoalkylene
- Y is d - is perfluoroalkyl of linear or branched C 5
- a, b, c , d, e and f are each independently 0 to an integer of 100.
- a in Chemical Formula 1 is Chemical Formula 2
- one N—c—o one is Chemical Formula 2
- 3 ⁇ 4 is Chemical Formula 2
- 3 ⁇ 4 may be any one of Chemical Formula 5 above.
- n of Chemical Formula 1 may be 1 ⁇ 16, and as another example, n may be 1-12 or 3-6. Since the perfluorinated polyether-modified compound of Formula 1 according to the present invention does not include a silane group, it is applicable to organic materials such as polymers, and other organic pharmaceuticals. It has excellent compatibility and can be applied to the roll to roll process. In addition, the perfluorinated polyether-modified compound of Formula 1 according to the present invention is UV-curable without the need for additional radical initiators, compared to conventional UV-curable compounds having a hydrocarbon-based double bond, and can react with all hydrocarbon compounds and reactions.
- a method of preparing a perfluorinated polyether-modified compound comprising the step of preparing a compound of Formula 1 by reacting a mixture of the compound of Formula 13 and a compound of Formula 14-16 in a mixed solvent of a fluorocarbon solvent and a hydrocarbon solvent to provide.
- E is " OH when D is ⁇ ⁇ C, and J ) is —G, — either OH and —NH 2 , and G is a halogen element.
- the above-described gubled polyether-modified compound according to the present invention More manufacturing methods explain in detail.
- the compound of formula 13 is a hydrocarbon compound having three reactors.
- a nutrimethylene diisocyanate cyclic trimer (trade name: DESMODUR N3300) trimerized can be used.
- the compound of the formula (14) is a perfluorinated polyether compound having a semi-ungung at the end.
- the fluoride polyether compound having a semi-cyclic group at the terminal is generally used in the art, but is not particularly limited, and a perfluorinated polyether compound having ⁇ 0 H or — banung group at the terminal may be used.
- Perfluoropolyether alcohols PFPE-al cohol
- the perfluorinated polyether compound can be synthesized according to a known method as follows [JAMES T. HILL, J. Macromol. Sc i. Chem. , A8, (3), p499 (1974)].
- the solvent is generally used in the art, but is not particularly limited, and for example, a solvent selected from triglyme, tetraglyme, butyl diglyme and ethyl diglyme may be used.
- the degree of polymerization (molecular weight) of the perfluorinated polyether compound synthesized by the above method can be controlled by the introduction rate and reaction temperature of HFP0, and the perfluorinated polyether compound by the gel permeat i on chromatogram method.
- PFPE-al cohol perfluorinated polyether alcohol
- the degree of polymerization is an important parameter in determining the antifouling property, adhesion to the substrate and durability in the compound of Formula 1.
- PFPE-al cohol perfluorinated polyether alcohol
- It can be prepared by the step of methyl esterification and alcoholation. Specifically, the reaction of methyl esterifying the perfluorinated polyether compound may be carried out by stirring the perfluorinated polyether compound at a temperature in the range of 20-30 ° C. in combination with methanol.
- the semi-fluorine can be purified by sequentially purifying, vacuum and drying to obtain a perfluoropolyether-methyl ester compound.
- alcoholization conversion reaction of the -methyl ester compound of perfluorinated polyether can be carried out using a known organic synthesis method.
- alcoholic reaction is possible using NaBH 4 (Sodium borohydride) which is a relatively stable compound.
- the reaction can be terminated by dropwise addition of a perfluoropolyether-methylester compound to a mixture of NaBH 4, C 2 H 5 0 Na (Sodium ethoxide). The progress of the reaction was determined by confirming the conversion rate by gas chromatography or H- ⁇ R analysis. Next, the reaction is purified and dried sequentially to obtain a perfluoropolyether-alcohol compound.
- the compound of Formula 15 is a benzophenone-based light-bonding compound having a reactor at the end.
- the coating composition comprising the compound of Formula 1 according to the present invention may have adhesion to the substrate and the film when the membrane is formed. It is an important variable that determines the durability of the machine.
- the benzophenone-based compound of Formula 15 having a reactive group at the terminal is not particularly limited as commonly used in the art, but is not limited to benzophenone-based
- a phosphorus compound can be used, for example, 4-hydroxybenzophenone can be used.
- the compound of formula 16 is a perfluorinated polyether compound having a semi-cyclic group at the terminal or a benzophenone-based compound having a semi-ungung group at the terminal.
- the type and number of the perfluorinated polyether compound and the benzophenone-based compound included in the compound of Formula 1 may vary.
- the type of the compound of Formula 1 may vary according to the composition ratio of the reactants.
- the molar ratio of the gubleso polyether compound (Chemical Formula 14 or a mixture of Chemical Formula 14 and Chemical Formula 16) having a reactor at the terminal with respect to the hydrocarbon compound having three reaction groups (Formula 13) is 1: 1 to 1: It is preferable that it is two.
- the molar ratio is less than 1: 1, all three reaction products of three hydrocarbon reactors having three reactors generate a large amount of by-products to which benzophenone compounds are attached, and thus, additional difficult separation processes are required. If it is more than 2, all three reaction products generate a large amount of by-products to which the perfluoropolyether compound is attached, and liquid impurities which are not adhered to the surface remain during coating and curing on the substrate.
- a benzophenone-based compound having a reaction group at the terminal (Chemical Formula 15 or a mixture of Chemical Formula 15 and Chemical Formula 16)
- the molar ratio of is preferably a ratio capable of substituting all the reactive groups remaining in the compound of Formula 13, for example, 1: (3 minus the molar ratio of the perfluorinated polyether compound having a reactor at the terminal used above).
- the reaction product of the chemical formulas 13-16 form a uniform phase for the reaction to remain smooth, especially the selection of the reaction solvent is very important.
- the reaction is preferably performed under a mixed solvent of a fluorocarbon solvent and a hydrocarbon solvent.
- the fluorocarbon solvent is trifluoro benzene, 1,3 bistri pullulor benzene, 1.4-bistripuluor benzene, trifluoroluene, perfluorinated heptane, guble fluoride nucleic acid, m-xylene core ⁇ Fluoride, methyl perfluorine butyl ether, ethyl perfluorine butyl ether, perfluorine (2-butyl tetrahydrofuran), 1, 3-dichloro-1, 1,2,2,3—pentafluuropropane Toxy—nonafluorobutane or ethoxy-nonafluorobutane may be used alone or in combination, and the hydrocarbon solvent may be used alone or in combination with acetone, toluene, MIBK or tetrahydrofuran.
- the mixing ratio of the fluorocarbon solvent and the hydrocarbon solvent may be changed depending on the molecular weight of the fluoride polyether used and the type of hydrocarbon compound having three semi-anionic groups, for example, fluorocarbon solvent 100 2-100 parts by weight of a hydrocarbon solvent may be used based on the parts by weight.
- the reaction of the mixture of the compound of Formula 13 and the compound of Formulas 14 to 16 is partially a perfluorinated polyether compound having a reaction group at the end and a hydrocarbon-based compound having three reactors Reacting to form a perfluoropolyether-hydrocarbon-based reactive oligomer, and reacting the oligomer with a benzophenone-based photocoupling compound capable of binding to another hydrocarbon compound and a photocuring reaction to form a compound of Formula 1
- the reaction can proceed simultaneously.
- the reaction of the mixture of the compound of Formula 13 and Chemical Formulas 14 to 16 may be a urethane reaction, an ester reaction, an amide reaction, or the like.
- a perfluorinated polyether modified compound of Formula 1 having a urethane linkage can be prepared.
- the reaction silver of the mixture of the compound of Formula 13 and Chemical Formulas 14 to 16 is preferably maintained at room temperature-50 ° C.
- reaction temperature is 50 or more, the polymerization reaction of the hydrocarbon compound having three reaction groups occurs and it is difficult to obtain a compound having a desired structure. It is a problem that a polymer that does not harm is produced, and the reaction temperature is lower than the phase silver, so the reaction progress is too slow and the reaction may not be terminated.
- the present invention as shown in Scheme 2,
- Preparation of the perfluorinated polyether-modified compound of Formula 1 comprising the step of preparing a compound of Formula 1 by reacting the compound of Formula 17 and the compound of Formula 15 in a mixed solvent of a fluorocarbon solvent and a hydrocarbon solvent Provide a method.
- n, 3 ⁇ 4 and 3 ⁇ 4 are as defined in Formula 1,
- 3 ⁇ 4 is any one of Formulas 5 to 7 defined in Formula 1,
- a reaction mixture of a compound of Formula 18, a compound of Formula 15, and a compound of Formula 16 in a mixed solvent of a carbon-carbon solvent and a hydrocarbon solvent to prepare a compound of Formula 1 (Step 2).
- a method for preparing a bovine polyether modified compound is provided.
- n, 3 ⁇ 4 and B 2 are the same as defined in Formula 1,
- 3 ⁇ 4 is one of Formulas 8 to 12 as defined in Formula 1.
- the compound of Chemical Formula 1 may also be prepared by successive reactions in which a benzophenone-based compound is added to react.
- the specific method for preparing the compound of Formula 1 represented by Banung Formula 2 or 3 is the same as described in the method for preparing the compound of Formula 1 represented by Scheme 1.
- the present invention provides an antifouling coating composition comprising a perfluorinated polyether modified compound of the formula (1).
- the antifouling coating composition according to the present invention may be prepared including 0.05 to 50% by weight of the perfluorinated polyether modified compound of Formula 1 and 50 to 99.95% by weight of the solvent.
- the content of the perfluorinated polyether modified compound is not particularly limited, and it is preferable to select a concentration that is easy to apply on the coating.
- an antifouling coating composition having a concentration of the modified compound is 0.05-50% by weight, but an antifouling coating composition having a concentration of 0.05-20% by weight may be used.
- the solvent is not particularly limited as it is generally used in the art in consideration of the coating method, stability of the composition, wettability to the substrate, volatilization rate, etc.
- a fluorine-modified hydrocarbon-based or hydrocarbon-based solvent may be used, and specifically, trifluoro benzene, 1,3-bis trifluoro benzene, 1.4-bistri pullobenzene, trifluoroluene, perfluoro Bovine heptane, perfluoronucleic acid, m_xylene nucleated fluorofluoride, methyl perfluorine butyl ether, ethyl perfluorine butyl ether, perfluorine (2 ⁇ butyl tetrahydrofuran), 1, 3—dichloro-1,1,2 , 2, 3- pentafluoropropane, meecoxy-nonafluorobutane, eth
- the antifouling coating composition comprising the compound of Formula 1 according to the present invention
- the inherent transparency on the surface of the transparent glass or plastic product is not degraded, and there is an effect capable of forming a film having excellent antifouling resistance, biodegradability and durability.
- the present invention provides a film formed by curing the antifouling coating composition comprising a perfluorinated polyether modified compound of the formula (1).
- the method for coating the antifouling coating composition in the film according to the present invention is not particularly limited to methods generally used in the art, for example, spin coating method, dip coating method, curtain coating method Known methods such as spray coating can be used.
- the thickness of the membrane preferably has a thickness in the range of 0.005-1,000 um. If the thickness of the coating film is less than 0.005 ym, there may be a problem that the antifouling property against water or oil can not be expressed reliably, and if the thickness of the coating film is more than 1,000 um, the light transmittance may be reduced, and the thickness is nonuniform, resulting in deterioration of reflection characteristics. It is good to maintain the thickness in the above range because problems may occur that interference patterns occur.
- Membranes according to the invention can be coated with antifouling coatings on hydrocarbon-based films such as polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), triacetyl terephthalate (TAC), polycarbonate (PC), etc. have.
- the film according to the present invention is antifouling and antireflection of a flat panel display including a frame, a lens, a glass window, a liquid crystal, a flat panel display device (PDP), an organic light emitting device (EL), etc., which is recently increasing industrial demand. It can be used as an optical film such as a transparent film, an optical filter, etc.
- the flat panel display is an LEDC Light Emitting Diode (LCD), a Liquid Crystal Display (LCD), a Plasma Display Panel (PDP), a Field Emission Display (FED) 0 LED (0rganic Light Emitting Diodes) ) Or AMOLEEK Active Matrix Organic Light Emitting Diodes.
- the present invention provides an antifouling substrate with a membrane, wherein the substrate and the surface are covered with the membrane according to the present invention.
- the substrate may be selected and used without limitation as long as the substrate requires antifouling properties.
- the antifouling coating composition comprising the perfluorinated polyether modified compound of Formula 1 is cured to attach a film formed.
- PFPE-COF Small Polyether-COF
- PFPE-C0F prepared in step 1 was placed in a three-necked flask equipped with a bubble trap, and methanol was slowly injected. At this time, methane was used in excess of the molar ratio of PFPE-C0F (more than two times), and stirred using a magnetic bar while slowly injecting methanol. At this time, the generation of HF gas generated by reaction between methanol and PFPE-C0F can be confirmed through bubble trap. PFPE-C0F showed a transparent yellowish color, but it was confirmed that the methane is transparent as it is added, and the reaction was completed after sufficiently stirring for 3 hours.
- the flask was stirred with 9.0 g of ethanol and sodium borohydride (NaBH 4 ) and stirred, and then 200 g of PFPE-methyl ester (molecular weight 1700) was slowly added using a dropping funnel.
- the reaction was continued for about 2 hours, and gas generation continued after the completion of the reaction.
- the reaction proceeded with stirring overnight at room temperature.
- the reaction was confirmed that there was no gas generation in the reaction solution, and the translucent but uniform phase was maintained.
- the conversion was checked by gas chromatography or -NMR analysis.After confirming the conversion, a 10% solution of HC1 was added, and the PFPE-alcohol was separated into two layers.
- HFP0 nucleated fluoropropylene
- HFP0 nucleated fluoropropylene oxide
- PFPE-C0F perfluoropolyether
- HFP0 oligomer and perfluoropolyether were prepared in the same manner as in step 1 of Preparation Example 1, except that 87.75 g of nucleated propylene (HFP) and 420 g of nucleated fluoropropylene oxide (HFP0) were used. Got it.
- This HFP0 oligomer 87.75 g of nucleated propylene (HFP) and 420 g of nucleated fluoropropylene oxide (HFP0) were used. Got it.
- HFP0 oligomer and perfluoropolyether were prepared in the same manner as in step 1 of Preparation Example 1, except that 180 g of nucleated sapfur propylene (HFP) and 860 g of nucleated fluoropropylene oxide (HFP0) were used. Got it.
- This HFP0 oligomer was prepared in the same manner as in step 1 of Preparation Example 1, except that 180 g of nucleated sapfur propylene (HFP) and 860 g of nucleated fluoropropylene oxide (HFP0) were used. Got it.
- a mixture 3 g of nusamethylene diisocyanate cyclic trimer (DESUMIDUR N3300) and 0.2 g of dibutyltin dilaurate (DBTDL) in a solution of 3.14 g of 1,3-bistrifluorobenzene and 0.79 g of acetone were mixed. Mixture produced the mixture A of Example 2.
- DESUMIDUR N3300 nusamethylene diisocyanate cyclic trimer
- DBTDL dibutyltin dilaurate
- a photocurable perfluorinated polyether modified compound of Example 2 was obtained in the same manner as in Example 1, except that Mixture A and Mixture B were used.
- a mixture A mixture of 4.36 g of 1,3-bistrifluorobenzene and 1.09 g of acetone was mixed with 3 g of nucleated methylene diisocyanate cyclic trimer (DESMODUR N3300) and 0.2 g of dibutyl tin dilaurate (DBTDL).
- DESMODUR N3300 nucleated methylene diisocyanate cyclic trimer
- DBTDL dibutyl tin dilaurate
- Mixture B of Example 3 was prepared by mixing 7.05 g of PFPE-al cohol of Preparation Example 3 with a solution of 4.36 g of 1 ⁇ 3-bistrifluorobenzene and 1.09 g of acetone.
- a photocurable perfluorinated polyether modified compound of Example 3 was obtained in the same manner as in Example 1, except that Mixture A and Mixture B were used.
- a complex A solution of 7.30 g of 1,3-bistrifluorobenzene and 1.83 g of acetone was mixed with 3 g of nusamethylene diisocyanate cyclic trimer (DESMODUR N3300) and 0.2 g of dibutyl tin dilaurate (DBTDL). Compound A of Example 4 was prepared.
- DESMODUR N3300 nusamethylene diisocyanate cyclic trimer
- DBTDL dibutyl tin dilaurate
- a mixture B of Example 4 was prepared by mixing 14.4 g of PFPE-alcohol 1 of Preparation Example 4 with a solution of 7.30 g of 1,3-bistrifluorobenzene and 1.83 g of acetone.
- the photocurable perfluorinated polyether modified compound of Example 4 was obtained by the same method as Example 1, except that Compound A and Compound B were used.
- a mixture A solution of 7.05 g of 1,3 ⁇ bistrifluorobenzene and 1.76 g of acetone was mixed with 3 g of nusamethylene diisocyanate cyclic trimer (DESMODUR N3300) and 0.2 g of dibutyl butyric dilaurate (DBTDL). Combined, the mixture A of Example 5 was prepared.
- B mixture Mixture B of Example 5 was prepared by mixing 14.1 g of PFPE-al cohol of Preparation Example 3 in a solution of 05 g of 1,3-bistrifluorobenzene and 1.76 g of acetone.
- Example 1 Compound A, Compound B, and 4-hydroxybenzophenone (4-HBP) (C) were prepared in the same manner as in Example 1, except that 0.32 g instead of 0.65 g was used.
- the photocurable perfluorinated polyether modified compound of Example 5 was obtained.
- the reagent input amount of Examples 1-5 is shown in Table 1 below.
- Comparative Example 1 The silver that is banung banung was performed in Comparative Example 1 in the same way as in Example 1 except that the 60 ° C instead of 40 ° C. However, in Comparative Example 1, due to the high reaction temperature during the synthesis process, the composite was changed into a gel state to form a soluble polymer.
- Comparative Example 2 The reaction of Comparative Example 2 was carried out in the same manner as in Example 1, except that the reaction solvent was a single solvent of only acetone, not a common solvent of two solvents of 1,3 ⁇ bistrifluorobenzene and acetone. . However, in the case of Comparative Example 2, the reaction did not proceed because a sufficient amount during the synthesis process.
- Example u-15 Preparation of Membrane Formed by Curing Antifouling Coating Composition 0.5 mL of the antifouling coating composition prepared above was subjected to spin coating at 2000 rpm for 20 seconds for slide glass (Matsunarai S-llll, 7.6cm X 2.6cm). It was applied to. The applied coating was annealed in a 120 ° C vacuum oven for 10 minutes and then cured for 30-60 seconds at 500 W using ARC Xe LAMP POWER SUPPLY without additional radical initiator, Example 11-15 Formed a film.
- the slide glass coated with the films of Examples 11 to 15 according to the present invention was about 88 ° and 48 ° for water and DIM, respectively, compared to the untreated slide glass of Comparative Example 3. It has been shown to have a high contact angle, compared with the commercial membrane DSX (contact angle for water: 114.3, contact angle for DIM: 88.3) and EGO 1720 (contact angle for water: 110.9, contact angle for DIM: 85.5). It can also be seen that the contact angle is higher.
- the coating composition comprising the compound of the present invention has an effect of producing a film having excellent water and oil repellency.
- the flow angle is a critical angle when a droplet having a specific weight starts to flow on the inclined surface, and the flow angle of the liquid by the surface is defined as shown in Equation 2 below by adding to Wol fram. [Equation 2]
- the flow angle was about 12-14 ° and the commercial membrane was DSX (flow angle for nucleodecane: 15.3 ⁇ ) and EGC-1720 (flow angle for nucleodecane: 19. 1 ° ) showed a significantly lower flow angle. From this, when the film formed by curing the composition in which the perfluorinated ether modified compound dispersed through the embodiment of the present invention is cured is coated, the flow angle of the liquid is lower than that of the uncoated film and the common membrane. It can be seen that the coating composition containing the compound of has the effect of producing a film having excellent water and oil repellency.
- Example 4 Decontamination evaluation of the film formed by curing the antifouling coating composition composition
- the slide glass coated with the film of Examples 11-15 the slide glass coated with the film of Examples 11-15
- the results are shown in Table 5 below. Wipe off the dirt on the treated surface by reciprocating 5 times with the force of 1 k gf using the Kim wipe wipe the fingerprint and name pen attached in Experimental Example 3. According to the following criteria, the dirt attached by visual inspection was determined.
- the transmittance was 91 to 92, and the slide glass of Comparative Example 3 in which the coating film was not formed (permeability 90) Compared with, it is seen that the transmittance is not lowered, but rather higher. From this, the film formed by curing the composition in which the perfluorinated ether modified compound dispersed through the embodiment of the present invention is cured has excellent transmittance, and thus the coating composition including the compound of the present invention is used as a coating agent for displays, optical products, and the like. It can be seen that it can be used effectively.
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Abstract
The present invention relates to an ultraviolet-curing perfluoropolyether-modified compound, to a dirt-resistant coating-agent composition comprising same, and to a film and a dirt-resistant substrate using same, and, more specifically, the compound according to the present invention does not contain a silane group and so can be used in organic materials such as polymers and is outstandingly compatible with other organic drugs and can be used in roll-to-roll processing, and, in addition, the compound contains a perfluoropolyether group and thus has superior transparency and dirt resistance including adhesion prevention and wiping poperties, and the compound contains a benzophenone-based compound and thus can be subjected to ultraviolet curing without the need for any additional radical initiator and so a film formed by curing a coating-agent composition comprising the compound can be chemically bonded with all substrate materials constituted from hydrocarbon-based compounds such that the invention gives the advantage of improved dirt resistance, scratch resistance and durability and so can be used to advantage in substrates in all industrial fields where dirt resistance needs to be imparted.
Description
[명세서】 [Specification】
【발명의 명칭] [Name of invention]
자외선 경화 과불소 폴리에테르 변성 화합물， 이를 포함하는 방오성 코팅제 조성물, 이를 적용한 막 및 방오성 기재 UV curable perfluorinated polyether modified compound, antifouling coating composition comprising same, membrane and antifouling substrate to which the same is applied
[기술분야] [Technical Field]
본 발명은 자외선 경화시 추가적인 라디칼 개시제가 필요하지 않고, 탄화수 소계 기재에 화학적으로 결합이 가능하여 내구성이 우수한 방오성 막을 제조할 수 있는 자외선 경화 가능한 과불소 폴리에테르 변성 화합물， 이를 포함하는 방오성 코팅제 조성물, 상기 방오성 코팅제 조성물이 경화되어 형성된 내스크래치성 및 내 구성이 향상된 막， 상기 막이 부착된 방오성 기재에 관한 것이다. The present invention does not require an additional radical initiator during UV curing, UV-curable perfluorinated polyether modified compound that can be chemically bonded to the hydrocarbon-based substrate to produce a durable antifouling film, antifouling coating composition comprising the same In addition, the antifouling coating composition is formed by curing the scratch resistance and durability improved film, the antifouling substrate to which the film is attached.
【배경기술】 Background Art
불소계 기능성 소재는 첨단산업인 광통신， 광전자， 반도체， 자동차， 컴퓨터 분야 등에서 차세대 기술의 핵심소재로서 전 세계적인 관심이 집중되고 있으며, 특 히 액정 디스플레이 등과 같은 급증하는 각종 디스플레이의 전면 최외각층 또는 미 려한 디스플레이의 프레임 등의 지문 등에 회한 오염을 방지하기 위한 코팅층은 산 업적인 수요가 급증하고 있다. 디스풀레이의 전면에 사용되는 광학필름의 구조를 살펴보면 액정 또는 편광기능층， 액정을 보호하고 평판화하기 위한 하드코팅층 외 부의 광간섭을 방지하여 선명한 화질을 쎄공하기 위한 반사방지층， 그리고 표면의 오염을 방지하는 방오층으로 구성되어 있다. 특히， 방오층을 포함하는 광학필름을 제조하기 위한 각종 소재기술은 디스플레이 종류에 관계없이 화면의 시인성을 좌우 하기 때문에 산업적으로 매우 중요하다. 또한， 각종 수지 도료 등의 오염방지성은 많은 산업 분야에서 매우 중요한데， 예로써 디스플레이의 프레임 또는 각종 가전기 기에 오염방지성을 부여함으로써 깨끗한 외관을 유지할 수 있고， 건축 또는 토목 분야에 오염방지성 도료를 사용함으로써 내오염성을 유지할 수 있는 등 거의 모든 현대 산업생활에 오염방지성 부여는 필수적이다. 종래， 최외곽층에 발수성， 발유성， 오염방지성 등을 부여하기 위한 불소계 재료로는 블소-실리콘 또는 불화탄소 고분자를 포함하는 코팅제가 있다ᅳ 상기 목적 을 달성하기 위하여 특허문헌 1에는 불소-실리콘 계열의 표면코팅제로서 C8F17C2H4Si (NH)3/2 , C4F9C2H4Si (NH)3/2 또는 폴리실록사잔 (polys i loxazane) 등을 개시하
고 있다. 그러나， 상기 화합물들을 단독으로 사용하는 경우 기재인 무기산화물과 반웅가교성이 나빠 마찰에 대한 내구성이 불량하고， 불소화합물만 단독으로 사용하 는 경우에는 불소화합물의 고유 표면 특성인 오염제거성이 불량하며， 폴리실록사잔 화합물의 경우에는 상대적으로 불소화합물보다 표면에너지가 높기 때문에 초기 오 염방지 성능이 불량하다. 또한, 3 차원 구조를 형성하기 위한 기능기의 수에 따라 충분한 가교결합이 이루어지지 않아 유리전이 온도가 낮아져서 오염물이 누적되거 나 붙어있게 되고 손에 의한 지문이 잔존하게 된다. 또한, 특허문헌 2에도 과불소기를 갖는 실란을 유리 표면개질제로 사용하고 있지만 이러한 코팅제 역시 충분한 발수성, 오염 방지성 및 오염제거성을 동시에 나타내지 못하는 단점이 있다. 상기 문제점을 해결하기 위한 수단으로서 특허문헌 2 - 5에는 유리 등의 무 기 재료와 유기 재료를 결합시키는， 이른바 실란 커플링 방법이 제시되고 있다. 이 방법은 한 분자 증에 유기 관능기 또는 유기 재료와 친화성이 좋은 화학 구조와 반 응성 알콕시 실란기를 가지고 있어 이 알콕시 실란기가 공기 중의 수분 등에 의해 자기 축합 반응을 일으켜 실록산이 되어 피막훌 형성한다. 이와 동시에 유리나 금 속 표면 등의 표면과 화학적 결합을 형성해 강고한 밀착성을 발현한다. 따라서， 실 란 커플링제는 각종 기재 표면의 코팅제 성분 혹은 프라이머로써 이용되고 있다. 상기 문헌에 제시된 실란 커플링제와 과불소기를 화학적으로 결합시킨 화합물은 성 막성이 양호하고， 기재와의 밀착성 및 내구성이 양호한 코팅제 성분으로 사용할 수 있으며， 상기 과불소 알킬기를 실란 커플링 구조를 갖는 기재 표면에 고정하게 되 면 방오성 (발수성, 발유성)이 향상한다고 기술하고 있다. 그러나 상기 화합물에서 는 과불소기의 길이 (분자량)에 제한이 있어 발유성능아 불층분하고， 층분한 과블소 기의 길이 (분자량)를 가진다할지라도, 과블소기를 포함한 분자 전체의 분자량에 대 한 알콕시 실란기가 차지하는 비율이 저하되어 접착성 또는 접착 내구성이 부족하 다는 결점이 있었다. 이러한 문제점들은 최근에 분자구조 특성에 의해 매우 우수한 표면 마찰성과 오염제거성을 갖는 올리고머형 과불소에테르 변성 실란 화합물의 사용에 의해 상당 부분 개선이 되어 각종 디스플레이에 적용되고 있다.
특허문헌 6에는 하기 화학식으로 표시되는 과불소에테르 변성 살란 화합물 o 개시되어 있다. Fluorine-based functional materials are attracting worldwide attention as core materials of next-generation technologies in the fields of optical communications, optoelectronics, semiconductors, automobiles, and computers, which are high-tech industries.In particular, the outermost layer or the beautiful display of rapidly increasing various displays such as liquid crystal displays Industrial demand is increasing rapidly for coating layers for preventing contamination caused by fingerprints such as frames. Looking at the structure of the optical film used on the front of the display, the liquid crystal or polarizing layer, the anti-reflection layer for forming clear image quality by preventing light interference outside the hard coating layer to protect and flatten the liquid crystal, and the surface contamination Consists of antifouling layer to prevent. In particular, various material technologies for manufacturing an optical film including an antifouling layer are very important industrially because they influence the visibility of the screen regardless of the display type. In addition, the anti-pollution properties of various resin paints are very important in many industrial fields. For example, by providing the anti-pollution properties to the display frame or various home appliances, it is possible to maintain a clean appearance and to apply the anti-pollution paints to the construction or civil engineering fields. The use of antifouling is essential for almost all modern industrial life, such as its ability to maintain pollution resistance. Conventionally, as a fluorine-based material for imparting water repellency, oil repellency, and antifouling property to the outermost layer, there is a coating agent containing bloso-silicon or a fluorocarbon polymer. In order to achieve the above object, Patent Document 1 discloses fluorine-silicon. C 8 F 17 C 2 H 4 Si (NH) 3/2 , C 4 F 9 C 2 H 4 Si (NH) 3/2 or polysiloxane (polys i loxazane), etc. are disclosed as a series of surface coating agents. It is. However, when the compounds are used alone, the inorganic oxide and the semi-crosslinking properties of the base material are poor, and the durability against friction is poor. When the fluorine compound is used alone, the decontamination property, which is an inherent surface property of the fluorine compound, is poor. In the case of the polysiloxane residue, the initial pollution prevention performance is poor because the surface energy is higher than that of the fluorine compound. In addition, according to the number of functional groups to form a three-dimensional structure, sufficient crosslinking is not achieved, the glass transition temperature is lowered, contaminants accumulate or stick, and fingerprints by hand remain. In addition, although Patent Document 2 uses a silane having a perfluorine group as a glass surface modifier, such a coating agent also has a disadvantage in that it does not simultaneously exhibit sufficient water repellency, antifouling property and decontamination property. As a means for solving the above problem, Patent Documents 2 to 5 propose a so-called silane coupling method in which inorganic materials such as glass and organic materials are combined. This method has a chemical structure and a reactive alkoxy silane group having good affinity with an organic functional group or organic material in one molecular increment, and the alkoxy silane groups undergo self-condensation reaction with moisture in the air to form siloxane. At the same time, they form chemical bonds with surfaces such as glass and metal surfaces, resulting in strong adhesion. Therefore, the silane coupling agent is used as a coating component or primer on the surface of various substrates. The compound in which the silane coupling agent and the perfluorine group are chemically bonded in the above document has good film formability, can be used as a coating component having good adhesion and durability to the substrate, and a substrate having the fluorine coupling structure. When fixed to the surface, the antifouling property (water repellency, oil repellency) improves. However, in the above compounds, the length (molecular weight) of the perfluorine group is limited, and even if the oil repellency is poor, and the length (molecular weight) of the stratified gubleso group is alkoxy to the molecular weight of the whole molecule including the guble group. There was a drawback that the proportion of the silane groups was lowered, resulting in insufficient adhesion or durability. These problems have recently been significantly improved by the use of oligomeric perfluoroether-modified silane compounds having very good surface friction and decontamination properties due to their molecular structure, and have been applied to various displays. Patent Document 6 discloses a perfluoroether-modified salane compound o represented by the following chemical formula.
【발명의 상세한 설명】
【기술적 과제】 [Detailed Description of the Invention] [Technical problem]
본 발명의 목적은 고분자와 같이 유기 재료에 적용이 가능하고， 타 유기약제 와 병용성이 뛰어나며, 코팅 및 자외선 경화에 의해 롤투롤 (rol l to rol l ) 공정의 적용이 가능할 뿐만 아니라， 자외선 경화시 추가적인 라디칼 개시제가 필요하지 않 고, 탄화수소계 기재에 화학적으로 결합이 가능하여 내구성이 우수한 방오성 막을 제조할 수 있는 자외선 경화 가능한 과불소 폴리에테르 변성 화합물을 제공하는 데 있다. 또한， 본 발명의 목적은 상기 과불소 폴라에테르 변성 화합물의 제조방법을 제공하는 데 있다. 나아가， 본 발명의 목적은 상기 과불소 폴리에테르 변성 화합물을 포함하는 방오성 코팅제 조성물을 제공하는 데 있다. ' 또한， 본 발명의 목적은 상기 과불소 폴리에테르 변성 화합물을 포함하는 방 오성 코팅제 조성물이 경화되어 형성된 막을 제공하는 데 있다. 나아가, 본 발명의 목적은 본 발명에 따른 상기 막이 부착된 방오성 기재를 제공하는 데 있다. An object of the present invention is applicable to organic materials, such as polymers, excellent compatibility with other organic pharmaceuticals, and can be applied to the roll to roll process by coating and UV curing, as well as UV curing The present invention provides an ultraviolet curable perfluorinated polyether-modified compound that does not require an additional radical initiator and can be chemically bonded to a hydrocarbon-based substrate to produce a durable antifouling membrane. It is also an object of the present invention to provide a method for producing the perfluorinated polar ether modified compound. Furthermore, an object of the present invention is to provide an antifouling coating composition comprising the perfluorinated polyether modified compound. It is also an object of the present invention to provide a film formed by curing the antifouling coating composition comprising the perfluorinated polyether modified compound. Furthermore, it is an object of the present invention to provide an antifouling substrate with a film according to the present invention.
【기술적 해결방법】 Technical Solution
상기 목적을달성하기 위하여， 본 발명은 In order to achieve the above object, the present invention
하기 화학식 1로 표시되는 과불소 폴리에테르 변성 화합물을 제공한다. [화학식 1]
It provides a perfluorinated polyether modified compound represented by the following formula (1). [Formula 1]
상기 화학식 1에서. In Formula 1 above.
n은 1 - 16의 정수이고， n is an integer from 1 to 16,
A는 하기 화학식 2 내지 4 중 어느 하나이고, A is any one of the following Chemical Formulas 2 to 4,
[화학식 2]
(단， 화학식 2에 있어서 N은 (C¾)n에 연결됨) [Formula 2] (Wherein N is connected to (C¾) n in formula 2)
[화학식 3] [Formula 3]
o o
— C-0— — C-0—
(단， 화학식 3에 있어서 C는 (CH2)n에 연결됨) [화학식 4] (However, in the formula (3) C is connected to (CH 2 ) n) [Formula 4]
H H
— C-N— — C-N—
(단， 화학식 4에 있어서 C는 (C¾)n에 연결됨) (However, in the formula (4) C is connected to (C¾) n)
상기 화학식 2 내지 4에 있어서， In Chemical Formulas 2 to 4,
¾은 하기 화학식 .5 내지 7 중 어느 하나이고， ¾ is any one of the formulas .5-7,
¾는 하기 화학식 8 내지 12 중 어느 하나이고, ¾ is any one of the following Chemical Formulas 8 to 12,
¾는 하기 화학식 5 내지 7 중 어느 하나이거나 하기 화학식 8 내지 12 중 나이다. ¾ is any one of the following Chemical Formulas 5 to 7 or i in the following Chemical Formulas 8 to 12.
[화학식 5] [Formula 5]
-(CF3)CFO-[CF2(CF3)CFO]a-CF2CF2CF3 -(CF 3 ) CFO- [CF 2 (CF 3 ) CFO] a -CF 2 CF 2 CF 3
[화학식 6] [Formula 6]
-X- [0CF2CF2]b- [0CF(CF3) ] c-[0CF(CF3)CF2]d-[0CF2]e-Y -X- [0CF 2 CF 2 ] b- [0CF (CF 3 )] c- [0CF (CF 3 ) CF 2 ] d- [0CF 2 ] e -Y
[화학식 7] [Formula 7]
-CF2CF2-[OCF2CF2CF2] OCF2CF2CF3 상기 화학식 5 내지 7에 있어서, -CF 2 CF 2- [OCF 2 CF 2 CF 2 ] OCF 2 CF 2 CF 3 In Chemical Formulas 5 to 7,
X는 d- C5의 직쇄 또는 측쇄의 과불소알킬렌이고， X is d-C 5 linear or branched perfluoroalkylene,
Y는 d- C5의 직쇄 또는 측쇄의 과불소알킬이고, Y is d-C 5 linear or branched perfluoroalkyl,
a,b,c,d,e 및 f는 각각독립적으로 0 - 100의 정수이다. a, b, c, d, e and f are each independently integers of 0-100.
[화학식 8]
[Formula 8]
[화학식 9]
10]
[Formula 9] 10]
[화학식 11]
또 또한， 상기 목적을 달성하기 위하여， 본 발명은 [Formula 11] In addition, in order to achieve the above object, the present invention
하기 반응식 1에 나타낸 바와 같이， As shown in Scheme 1 below,
화학식 13의 화합물과 화학식 14 - 16의 화합물의 혼합물을 불화탄소계 용매 및 탄화수소계 용매의 흔합 용매하에서 반응시켜 화학식 1의 화합물을 제조하는 단 계를 포함하는 화학식 1의 과불소 폴리에테르 변성 화합물의 제조방법을 제공한다. A mixture of a compound of Formula 13 and a compound of Formulas 14-16 is reacted under a mixed solvent of a fluorocarbon solvent and a hydrocarbon solvent to prepare a compound of Formula 1 of the perfluorinated polyether modified compound of Formula 1 It provides a manufacturing method.
[반응식 1]
Scheme 1
13
상기 반웅식 1에서, 13 In the reaction form 1,
n , B1 ( ¾ 및 B3는 상기 화학식 1에서 정의한 바와 같고 n, B 1 (¾ and B 3 are as defined in formula (I)
D는 ᅳ N=c=o 및 —c— G 중에서 어느 하나이고， D is any one of ᅳ N = c = o and —c— G,
o o
E는 D가 ᅳ N=C=0인 경우 ""OH이고， J)가 ᅳ E is an "" if the D is eu N = C = 0 OH, J ) is eu
하나이고， G는 할로겐 원소이다.
나아가 , 상기 목적을 달성하기 위하여， 본 발명은 One is, and G is a halogen element. Furthermore, in order to achieve the above object, the present invention
하기 반웅식 2에 나타낸 바와같이 , As shown in Reaction 2 below,
화학식 13의 화합물과 화학식 14의 화합물 및 화학식 16의 화합물의 '흔합물 을 불화탄소계 용매 및 탄화수소계 용매의 혼합 용매하에서 반응시켜 화학싶 17의 화합물을 제조하는 단계 (단계 1) ; 및 Reacting a ' mixture of the compound of Formula 13 with the compound of Formula 14 with the compound of Formula 16 in a mixed solvent of a fluorocarbon solvent and a hydrocarbon solvent to prepare a compound of Chemical Formula 17 (step 1); And
화학식 17의 화합물과 화학식 15의 화합물을 불화탄소계 용매 및 탄화수소계 용매의 흔합 용매하에서 반웅시켜 화학식 1의 화합물을 제조하는 단계 (단계 2)를 포함하는 화학식 1의 과불소 폴리에테르 변성 화합물의 제조방법을 제공한다. Preparation of the perfluorinated polyether modified compound of Formula 1 comprising the step (Step 2) of preparing a compound of Formula 1 by reacting the compound of Formula 17 and the compound of Formula 15 in a mixed solvent of a fluorocarbon solvent and a hydrocarbon solvent Provide a method.
[반응식 2] 단계 1 Scheme 2 Step 1
13 단계 2 13 steps 2
17
17
1 One
상기 반응식 2에서， In Scheme 2 ,
n, ¾ 및 ¾는 상기 화학식 1에서 정의한 바와 같고， n, ¾ and ¾ are as defined in Formula 1,
¾는 상기 화학식 1에서 정의한 화학식 5 내지 7 증 어 ¾ is evidence of the formula 5 to 7 defined in the formula (1)
D 및 E는 상기 반웅식 1에서 정의한 바와 갈다. 또한, 상기 목적을 달성하기 위하여， 본 발명은 D and E are the same as defined in Reaction Formula 1 above. In addition, in order to achieve the above object, the present invention
하기 반웅식 3에 나타낸 바와 같이 , As shown in Reaction 3 below,
화학식 13의 화합물과 화학식 14의 화합물을 불화탄소계 용매 및 탄화수소계 용매의 흔합 용매하에서 반웅시켜 화학식 18의 화합물을 제조하는 단계 (단계 1) ;
화학식 18의 화합물과 화학식 15의 화합물 및 화학식 16의 화합물의 흔합물 을 불화탄소계 용매 및 탄화수소계 용매의 흔합 용매하에서 반응시켜 화학식 1의 화합물을 제조하는 단계 (단계 2)를 포함하는 화학식 1의 과불소 폴리에테르 변성 화합물의 제조방법을 제공한다. Reacting a compound of Formula 13 and a compound of Formula 14 in a mixed solvent of a fluorocarbon solvent and a hydrocarbon solvent to prepare a compound of Formula 18 (step 1); A compound of Formula 1 comprising the step of preparing a compound of Formula 1 by reacting a mixture of a compound of Formula 18 with a compound of Formula 15 and a compound of Formula 16 under a mixed solvent of a fluorocarbon solvent and a hydrocarbon solvent (step 2) Provided is a method for producing a perfluorinated polyether modified compound.
[ 3]
상기 반응식 3에서， [3] In Scheme 3,
n , ¾ 및 ¾는 상기 화학식 1에서 정의한 바와 같고， n, ¾ and ¾ are as defined in Formula 1,
¾는상기 화학식 1에서 정의한 화학식 8 내지 12 증 어느 하나이고, ¾ is any one of Formulas 8 to 12, as defined in Formula 1,
D및 E는 상기 반응식 1에서 정의한 바와 같다. 나아가, 상기 목적을 달성하기 위하여 본 발명은 D and E are as defined in Scheme 1 above. Furthermore, the present invention to achieve the above object
본 발명에 따른 상기 과불소 폴리에테르 변성 화합물을 포함하는 방오성 코 팅제 조성물을 제공한다ᅳ 또한， 상기 목적을달성하기 위하여 본 발명은 To provide an antifouling coating agent composition comprising the perfluorinated polyether modified compound according to the present invention. In addition, the present invention to achieve the object
본 발명에 따른 상기 방오성 코팅제 조성물이 경화되어 형성된 막을 제공한 다.
나아가， 상기 목적을 달성하기 위하여 본 발명은 The antifouling coating composition according to the present invention provides a film formed by curing. Furthermore, the present invention to achieve the above object
기재의 표면이， 본 발명에 따른 상기 막으로 피복되어 있는 것을 특징으로 하는 막부착 방오성 기재를 제공한다. The surface of a base material is coat | covered with the said film | membrane which concerns on this invention, The film-proof antifouling base material is provided.
[유리한 효과】 Advantageous Effects
본 발명에 따른 과불소 폴리에테르 변성 화합물은 실란기를 포함하지 않으므 로 고분자와 같이 유기 재료에 적용이 가능하고， 타 유기약제와 병용성이 뛰어나 며， 롤투롤 (rol l to rol l ) 공정의 적용이 가능할 뿐만 아니라， 과불소폴리에테르기 를 포함함으로써 부착방지성, 닦아내는 성질 등 방오성 및 투명성이 우수하고， 벤 조페논계 화합물을 포함함으로써 추가적인 라디칼 개시제 필요없이 자외선 경화가 가능하므로， 상기 화합물을 포함하는 코팅제 조성물이 경화되어 형성된 막은 탄화 수소계 화합물로 구성되는 모든 기저 물질과 화학적 결합이 가능하여 방오성, 내생 채기성 및 내구성이 개선되는 효과가 있으므로, 오염방지성 부여를 필요로하는 모 든 산업분야의 기재에 유용하게 사용할수 있다. Since the perfluorinated polyether modified compound according to the present invention does not include a silane group, it can be applied to an organic material such as a polymer, has excellent compatibility with other organic pharmaceuticals, and applies a roll to roll process. In addition to the above, the perfluorinated polyether group includes antifouling properties and wiping properties such as antifouling properties and wiping properties, and includes a benzophenone-based compound so that ultraviolet curing is possible without the need for an additional radical initiator. The film formed by curing the coating composition is capable of chemically bonding to all base materials composed of hydrocarbon-based compounds, thereby improving the antifouling property, endogenous swelling resistance, and durability. It can be usefully used for the substrate.
【도면의 간단한 설명】 [Brief Description of Drawings]
도 1은 본 발명의 광경화형 과불소폴리에테르 변성 화합물 (실시예 1)을 핵 자기공명법 (NMR)에 의해 분석한 -NMR그래프를 나타낸 것이다. Figure 1 shows a -NMR graph of the photocurable perfluorinated polyether modified compound (Example 1) of the present invention by nuclear magnetic resonance (NMR) analysis.
도 2는 본 발명의 광경화형 과불소폴리에테르 변성 화합물을 포함하는 방오 성 코팅제 조성물이 경화되어 형성된 막 (실시예 11) 및 무처리 슬라이드 글래스 (비 교예 3)의 투과도 그래프를 나타낸 것이다. Figure 2 shows a graph of the permeability of the membrane (Example 11) and the untreated slide glass (Comparative Example 3) formed by curing the antifouling coating composition comprising a photocurable perfluorinated polyether modified compound of the present invention.
【발명의 실시를 위한 최선의 형태】 [Best form for implementation of the invention]
이하， 본 발명올 더욱 구체적으로 설명한다. 본 발명은 하기 화학식 1로 표시되는 과불소 폴리에테르 변성 화합물을 제- Hereinafter, the present invention will be described in more detail. The present invention provides a perfluorinated polyether-modified compound represented by the following Chemical Formula 1;
[화학식 1]
[Formula 1]
상기 화학식 1에서,
n은 1 - 16의 정수이고, In Chemical Formula 1, n is an integer from 1 to 16,
A는 하기 화학식 2 내지 4중 어느 하나이고, A is any one of the following Formulas 2 to 4,
[화학식 2]
[Formula 2]
(단， 화학식 2에 있어서 N은 (C¾)n에 연결됨) (Wherein N is connected to (C¾) n in formula 2)
[화학식 3] [Formula 3]
o o
— C-0— — C-0—
(단， 화학식 3에 있어서 C는 (CH2)n에 연결됨) (However, in the formula (3) C is connected to (CH 2 ) n)
[화학식 4] [Formula 4]
H H
— C-N— — C-N—
(단, 화학식 4에 있어서 C는 (CH2)n에 연결됨) (Wherein C is linked to (CH 2 ) n)
상기 화학식 2 내지 4에 있어서， In Chemical Formulas 2 to 4,
¾은 하기 화학식 5 내지 7중 어느 하나이고, ¾ is any one of the following Chemical Formulas 5 to 7,
¾는 하기 화학식 8 내지 12 중 어느 하나이고， ¾ is any one of the following Chemical Formulas 8 to 12,
¾는 하기 화학식 5 내지 7 중 어느 하나이거나 하기 화학식 8 내지 12 증나이다. ¾ is any one of the following Chemical Formulas 5 to 7 or the following Chemical Formulas 8 to 12.
[화학식 5] [Formula 5]
-(CF3)CF0-[CF2(CF3)CF0]a-CF2CF2CF3 [화학식 6] -(CF 3 ) CF0- [CF 2 (CF 3 ) CF0] a -CF 2 CF 2 CF 3
-X- [0CF2CF2]b- [0CF(CF3) ] c-[0CF(CF3)CF2]d- [0CF2]e-Y [화학식 7] -X- [0CF 2 CF 2 ] b- [0CF (CF 3 )] c- [0CF (CF 3 ) CF 2 ] d- [0CF 2 ] e -Y [Formula 7]
-CF2CF2-[OCF2CF2CF2] 0CF2CF2CF3 -CF 2 CF 2- [OCF 2 CF 2 CF 2 ] 0CF 2 CF 2 CF 3
상기 화학식 5 내지 7에 있어서， In Chemical Formulas 5 to 7,
X는 d - C5의 직쇄 또는측쇄의 과블소알킬렌이고， X is d-C 5 straight or branched gublesoalkylene,
Y는 d - C5의 직쇄 또는 측쇄의 과불소알킬이고, a , b , c , d , e 및 f는 각각 독립적으로 0 - 100의 정수이다.
Y is d - is perfluoroalkyl of linear or branched C 5, a, b, c , d, e and f are each independently 0 to an integer of 100.
[화학식 10]
[Formula 10]
[화학식 11] [Formula 11]
Η:
Η:
12] 12]
5，
이고,5 ， ego,
¾는 상기 화학식 5짖 상기 화학식 8 중 어느 하나일 수 있다. ¾ may be any one of Chemical Formula 5 above.
또한， 본 발명에 따른 상기 화학식 1의 과불소 폴리에테르 변성 화합물에 있 어서, 상기 화학식 1의 n은 1 ᅳ 16일 수 있고, 다른 일례로써 n은 1 - 12 또는 3 - 6일 수 있다. 본 발명에 따른 상기 화학식 1의 과불소 폴리에테르 변성 화합물은 실란기를 포함하지 않으므로， 고분자와 같이 유기 재료에 적용이 가능하고， 타 유기약제와
병용성이 뛰어나며， 를투롤 (rol l to rol l ) 공정의 적용이 가능한 효과가 있다. 또한， 본 발명에 따른 상기 화학식 1의 과불소 폴리에테르 변성 화합물은 종 래의 탄화수소계 이증결합을 보유한 자외선 경화형 화합물과 비교하여， 추가적인 라디칼 개시제 필요없이 자외선 경화 가능하며， 모든 탄화수소 화합물과 반응에 의 해 화학적 결합을 이를 수 있고, 반웅율이 높아 미반응물이 없으며， 그에 따른 기 재와의 밀착성 및 피막 형성성이 우수하다. 따라서 방오성을 발휘하는 과불소 폴리 에테르기가 층분한 중합량 (분자량)으로 중합된 경우, 방오성을 포함한 기재와의 밀 착성 및 피막의 내구성을 확보할 수 있으며, 단독 또는 내첨형으로 다양하게 활용 이 가능하다. 한편， 본 발명은 하기 반웅식 1에 나타낸 바와 같이， In addition, in the perfluorinated polyether modified compound of Chemical Formula 1 according to the present invention, n of Chemical Formula 1 may be 1 × 16, and as another example, n may be 1-12 or 3-6. Since the perfluorinated polyether-modified compound of Formula 1 according to the present invention does not include a silane group, it is applicable to organic materials such as polymers, and other organic pharmaceuticals. It has excellent compatibility and can be applied to the roll to roll process. In addition, the perfluorinated polyether-modified compound of Formula 1 according to the present invention is UV-curable without the need for additional radical initiators, compared to conventional UV-curable compounds having a hydrocarbon-based double bond, and can react with all hydrocarbon compounds and reactions. The chemical bonds can be reached, and the reaction rate is high, there is no unreacted substance, and thus the adhesion to the substrate and the film formability are excellent. Therefore, when the perfluorinated polyether group exhibiting antifouling properties is polymerized in a polymerized amount (molecular weight), adhesion to the substrate including antifouling property and durability of the coating can be ensured, and various applications can be made alone or internally. Do. On the other hand, the present invention, as shown in the following reaction formula 1,
화학식 13의 화합물과 화학식 14 - 16의 화합물의 혼합물을 불화탄소계 용매 및 탄화수소계 용매의 흔합 용매하에서 반응시켜 화학식 1의 화합물을 제조하는 단 계를 포함하는 과불소 폴리에테르 변성 화합물의 제조방법을 제공한다. A method of preparing a perfluorinated polyether-modified compound comprising the step of preparing a compound of Formula 1 by reacting a mixture of the compound of Formula 13 and a compound of Formula 14-16 in a mixed solvent of a fluorocarbon solvent and a hydrocarbon solvent to provide.
[반응식 1]
CH2)n Scheme 1 CH 2 ) n
p- p-
(CH2)n-N C-O (CH 2) nN CO
O (CH2)n 상기 반웅식 1에서， O (CH 2 ) n in the reaction formula 1,
n, Bl t B2 및 ¾는 상기 화학식 1에서 정의한 바와 같고， n, B lt B 2 and ¾ are as defined in Formula 1,
N=c=° 및 ᅳ G 중에서 어느 하나이고 N = c = ° and ᅳ G
E는 D가 ᅳ^ C 인 경우 "OH이고， J)가 — G인 경우 — OH 및 —NH2 중 어 하나이고, G는 할로겐 원소이다. 이하， 본 발명에 따른 상기 과블소 폴리에테르 변성 화합물의 제조방법을 더
욱 구체적으로 설명한다. 구체적으로， 본 발명에 따른 상기 제조방법에 있어서, 화학식 13의 화합물은 3개의 반응기를 갖는 탄화수소계 화합물이다. 상기 3개의 반응기를 갖는 화합물은 당 분야에서 일반적으로 사용되는 것으로서 특별히 한정되지 않으나， 말단에 ᅳ N=c=0 또는 一 ^G 의 반응기를 갖는 탄화수소계 화합물을 사용할 수 있으며 예를 들어 , 디이소시아네이트를 3량체화한 핵사메틸렌 디이소시아네이트 사이클릭트라이 머 (상표명: DESMODUR N3300)를사용할 수 있다. 나아가， 본 발명에 따른 상기 제조방법에 있어서, 화학식 14의 화합물은 말 단에 반웅기를 갖는 과불소 폴리에테르 화합물이다. 상기 말단에 반옹기를 갖는 과 블소 폴리에테르 화합물은 당 분야에서 일반적으로 사용되는 것으로서 특별히 한정 되지 않으나， 말단에 ᅳ0 H 또는 — 반웅기를 갖는 과불소 폴리에테르 화합물을 사용할 수 있으며， 예를 들어， 과불소 폴리에테르 알콜 (PFPE-al cohol )을 사용할 수 있다. 한편， 상기 과불소 폴리에테르 화합물은 다음과 같이 공지된 방법에 따라 합 성할 수 있다 [JAMES T. HILL , J . Macromol . Sc i . Chem . , A8 , (3)， p499 ( 1974) ] . 즉， 핵사 플루오르 플로필렌 (HFP) , 핵사 플루오르 프로필렌 옥사이드 (HFP0)와 세슘 폴루오라이드를 용매에 넣어 반웅시켜 합성할 수 있다. 이때， 상기 용매는 당분야 에서 일반적으로 사용되는 것으로 특별히 한정하지 않으나, 예를 들어 , 트리글리 메， 테트라글리메， 부틸디글리메 및 에틸디글리메 중에서 선택된 용매를 사용할 수 있다. 상기 방법으로 합성된 과불소 폴리에테르 화합물의 중합도 (분자량)는 HFP0의 도입 속도 및 반웅 온도쎄 의해서 제어될 수 있으며， 겔 투과 크로마토그래피 (ge l permeat i on chromatogram) 방법에 의하여 과불소 폴리에테르 화합물의 분자량을 측 정함으로써, 중합도를 확인할 수 있다. 상기 중합도는 상기 화학식 1의 화합물에서 방오성， 기재와의 밀착성 및 내구성을 결정하는 중요한 변수이다. 한편, 상기 화학식 14의 화합물의 일례로 말단에 ᅳ0 H 반응기를 갖는 과블소 폴리에테르 화합물， 즉 과불소 폴리에테르 알콜 (PFPE-al cohol )은 상기 제조된 과불 소 폴리에테르 화합물을 예를 들어， 메틸 에스테르화 및 알콜화하는 단계에 의하여 제조될 수 있다.
구체적으로， 과불소폴리에테르 화합물을 메틸에스테르화하는 반응은 상기 과 블소폴리에테르 화합물은 메탄올과 흔합하여 20 - 30 °C 범위의 온도에서 교반함으 로써 수행될 수 있다. 다음으로, 반웅물을 정제, 진공 및 건조를 순차적으로 수행 하면 과불소폴리에테르-메틸에스테르 화합물을 얻을 수 있다. 다음으로 과불소폴리에테르의-메틸에스테르 화합물의 알콜화 변환반웅은 공 지된 유기합성 방법을 사용하여 수행할 수 있다. 일예로 비교적 안정한 화합물인 NaBH4(Sodium borohydr ide)를 사용하여 알콜화 반응이 가능하다. 즉, 에탄올과E is " OH when D is ᅳ ^ C, and J ) is —G, — either OH and —NH 2 , and G is a halogen element. Hereinafter, the above-described gubled polyether-modified compound according to the present invention. More manufacturing methods Explain in detail. Specifically, in the above production method according to the present invention, the compound of formula 13 is a hydrocarbon compound having three reactors. Compounds having the three reactors is not specified as being commonly used in the art, to use the hydrocarbon-based compound having a reactor eu at the terminal N = c = 0 or一^ G and, for example, diisocyanates A nutrimethylene diisocyanate cyclic trimer (trade name: DESMODUR N3300) trimerized can be used. Furthermore, in the above production method according to the present invention, the compound of the formula (14) is a perfluorinated polyether compound having a semi-ungung at the end. The fluoride polyether compound having a semi-cyclic group at the terminal is generally used in the art, but is not particularly limited, and a perfluorinated polyether compound having ᅳ 0 H or — banung group at the terminal may be used. Perfluoropolyether alcohols (PFPE-al cohol) can be used. On the other hand, the perfluorinated polyether compound can be synthesized according to a known method as follows [JAMES T. HILL, J. Macromol. Sc i. Chem. , A8, (3), p499 (1974)]. In other words, it can be synthesized by adding nucleated fluoro fluorene (HFP), nucleated fluoro propylene oxide (HFP0) and cesium fluoride in a solvent. In this case, the solvent is generally used in the art, but is not particularly limited, and for example, a solvent selected from triglyme, tetraglyme, butyl diglyme and ethyl diglyme may be used. The degree of polymerization (molecular weight) of the perfluorinated polyether compound synthesized by the above method can be controlled by the introduction rate and reaction temperature of HFP0, and the perfluorinated polyether compound by the gel permeat i on chromatogram method. By measuring the molecular weight of the polymerization degree can be confirmed. The degree of polymerization is an important parameter in determining the antifouling property, adhesion to the substrate and durability in the compound of Formula 1. On the other hand, as an example of the compound of Formula 14, a fluoride polyether compound having a ᅳ 0 H reactor at its end, that is, perfluorinated polyether alcohol (PFPE-al cohol), may be used as the perfluorinated polyether compound. It can be prepared by the step of methyl esterification and alcoholation. Specifically, the reaction of methyl esterifying the perfluorinated polyether compound may be carried out by stirring the perfluorinated polyether compound at a temperature in the range of 20-30 ° C. in combination with methanol. Next, the semi-fluorine can be purified by sequentially purifying, vacuum and drying to obtain a perfluoropolyether-methyl ester compound. Next, alcoholization conversion reaction of the -methyl ester compound of perfluorinated polyether can be carried out using a known organic synthesis method. For example, alcoholic reaction is possible using NaBH 4 (Sodium borohydride) which is a relatively stable compound. Ethanol and
NaBH4 , C2H50Na( Sod ium ethoxide) 혼합물에 과불소폴리에테르-메틸에스테르 화합물 을 적가함으로써 반응을 종결할 수 있다. 반응의 진행정도는 기체 크로마토그라피 또는 H-匪 R 분석하여 전환율을 확인함으로써 판단하였다. 다음으로, 반응물을 정제 및 건조과정을 순차적으로 수행하여 과불소폴리에테르 -알콜 화합물을 얻올 수 있 다. 한편， 본 발명에 따른 상기 제조방법에 있어서, 화학식 15의 화합물은 말단 에 반응기를 갖는 벤조페논계 광결합형 화합물이다. 상기 벤조페논계 화합물은 탄 화수소계 기재와 추가적인 라디칼 개시제 필요없이 광경화 반웅에 의해 화학적 결 합할 수 있으므로 본 발명에 따른 화학식 1의 화합물을 포함하는 코팅제 조성물로 막올 형성시에 기재와의 밀착성 및 피막의 내구성을 결정하는 증요한 변수이다. 구체작으로， 말단에 반응기를 갖는 상기 화학식 15의 벤조페논계 화합물은 분야에서 일반적으로 사용되는 것으로서 특별히 한정되지 않으나， 벤조페논계 The reaction can be terminated by dropwise addition of a perfluoropolyether-methylester compound to a mixture of NaBH 4, C 2 H 5 0 Na (Sodium ethoxide). The progress of the reaction was determined by confirming the conversion rate by gas chromatography or H- 匪 R analysis. Next, the reaction is purified and dried sequentially to obtain a perfluoropolyether-alcohol compound. On the other hand, in the production method according to the present invention, the compound of Formula 15 is a benzophenone-based light-bonding compound having a reactor at the end. Since the benzophenone-based compound can be chemically bonded by a photocurable reaction without the need for an additional radical initiator with a hydrocarbon-based substrate, the coating composition comprising the compound of Formula 1 according to the present invention may have adhesion to the substrate and the film when the membrane is formed. It is an important variable that determines the durability of the machine. In detail, the benzophenone-based compound of Formula 15 having a reactive group at the terminal is not particularly limited as commonly used in the art, but is not limited to benzophenone-based
인 화합물을 사용할 수 있으며， 예를 들어， 4-하이드록시벤조페논을 사용할 수 있 다.
한편， 본 발명에 따른 상기 제조방법에 있어서， 화학식 16의 화합물은 말단 에 반옹기를 갖는 과불소 폴리에테르 화합물 또는 말단에 반웅기를 갖는 벤조페논 계 화합물이다. 화학식 16의 화합물의 종류에 따라 화학식 1의 화합물이 포함하는 과불소 폴리에테르 화합물 및 벤조페논계 화합물의 종류 및 수가 달라질 수 있다. 또한, 본 발명의 상기 제조방법에 있어서， 반응물의 조성비에 따라 제조되는 화학식 1의 화합물의 종류가 달라질 수 있다. 구체적으로， 상기 반웅기를 3개 갖는 탄화수소계 화합물 (화학식 13)에 대하여 말단에 반응기를 갖는 과블소 폴리에테르 화합물 (화학식 14 또는, 화학식 14 및 화학식 16의 혼합물)의 몰비는 1 : 1 내지 1 : 2 인 것이 바람직하다. 상기 몰비가 1 : 1 미만인 경우 반응기를 3개 갖는 탄화수소계 화합물의 3개의 반웅기에 모두 벤조페논계 화합물이 부착된 부생성물이 다량 발생 하여 추가적인 어려운 분리 공정이 필요하게 되는 문제점이 있으며， 1 :2 초과인 경 우 3개의 반웅기에 모두 과불소폴리에테르 화합물이 부착된 부생성물이 다량 발생 하여 기재에 코팅 및 경화시에 표면에 고착되지 않은 액상의 불순물이 잔존하게 되 어 코팅표면의 물성을 하락시킨다는 문제점이 있어 바람직하지 못하다. 나아가， 본 발명에 따른 상기 제조방법에 있어서， 상기 반응기를 3개 갖는 탄화수소계 화합물 (화학식 13)에 대하여， 말단에 반웅기를 갖는 벤조페논계 화합물 (화학식 15 또는, 화학식 15 및 화학식 16의 혼합물)의 몰비는 화학식 13의 화합물 에 잔존하는 모든 반응성기를 치환할 수 있는 비율이 적합하며, 예를 들어， 1 : (3에 서 상기 사용된 말단에 반응기를 갖는 과불소폴리에테르 화합물의 몰비를 뺀 값의 1 배 내지 1.2 배)의 몰비로 사용할 수 있고， 바람직하게는 1 : (3에서 상기 사용된 말단에 반웅기를 갖는 과불소폴리에테르 화합물의 몰비를 뺀 값의 1. 1배)의 몰비로 사용할 수 있다. 한편， 본 발명에 따른 상기 제조방법에 있어서， 원활한 반응을 위해서는 화 학식 13 - 16의 반응물이 균일상을 형성하여 반웅이 잔행되는 것이 매우 중요하며， 특히 반응 용매의 선정이 매우 중요하다. 구체적으로 불화탄소계 용매 및 탄화수 소계 용매의 혼합 용매하에서 반웅시키는 것이 바람직하다. 불화탄소계 용매만 사 용하는 경우 탄화수계 화합물인 화학식 13의 화합물 및 벤조페논계 화합물에 대한 용해성이 불량하여 원활한 반웅 진행이 어려우며, 탄화수소계 용매만 사용하는 경
우 과불소플리에테르 화합물에 대한 용해도가 나빠서 원활한 반응 진행이 어렵기 때문에 바람직하지 못하다. 상기 불화탄소계 용매는 트리 플투오르 벤젠， 1，3_비스 트리 풀루오르 벤 젠， 1.4-비스 트리 풀루오르 벤젠, 트리 플루오르 를루엔， 과불소 헵탄, 과블소 핵산， m-키시렌핵^^ 플로오라이드， 메틸 과불소 부틸 에테르， 에틸 과불소 부틸 에 테르, 과불소 (2-부틸 테트라 하이드로 퓨란)， 1 , 3-디클로로 -1，1，2，2，3— 펜타플루 오로프로판， 메톡시—노나플루오로부탄 또는 에톡시-노나플루오로부탄를 단독 또는- 흔합하여 사용할 수 있으며, 상기 탄화수소계 용매는 아세톤， 를투엔， MIBK 또는 테트라하이드로퓨란를 단독 또는 흔합하여 사용할수 있다. 또한, 상기 불화탄소계 용매와 탄화수소계 용매의 혼합비는 사용하는 과블소 폴리에테르의 분자량 및 3개의 반옹기를 갖는 탄화수소계 화합물의 종류에 따라 변 화될 수 있으며， 예를 들어， 불화탄소계 용매 100 중량부에 대하여 탄화수소계 용 매 2 - 100중량부를 사용할수 있다. 한편， 본 발명에 따른 상기 제조방법에 있어서, 화학식 13의 화합물과 화학 식 14 내지 16 화합물의 흔합물의 반웅은 말단에 반웅기를 갖는 과불소 폴리에테르 화합물과 3개의 반응기를 갖는 탄화수소계 화합물이 부분적으로 반응하여 과불소폴 리에테르—탄화수소계 반응성 올리고머가 형성되는 반응 및 상기 올리고머에 타 탄 화수소 화합물과 광경화 반응에 의해 결합할 수 있는 벤조페논계 광결합형 화합물 을 반응하여 화학식 1의 화합물이 형성되는 반응이 동시에 진행될 수 있다. 또한， 본 발명에 따른 상기 제조방법에 있어서， 화학식 13의 화합물과 화학 식 14 내지 16 화합물의 흔합물의 반응은 우레탄 반응， 에스테르 반응， 아마이드 반응 등일 수 있다. 예를 들면， 핵사메틸렌 디이소시아네이트 사이클릭 트라이머 화합물에 과불소폴리에테르 -알콜 및 4-하이드록시벤조페논을 반웅시키는 경우， 우 레탄 연결기를 갖는 화학식 1의 과불소 폴리에테르 변성 화합물을 제조할수 있다. 나아가， 본 발명에 따른 상기 제조방법에 있어서， 화학식 13의 화합물과 화 학식 14 내지 16 화합물의 흔합물의 반응 은도는 상온 - 50 °C를 유지하는 것이 바 람직하다. 반응온도가 50 이상인 경우 3개의 반웅기를 갖는 탄화수소계 화합물 자체의 중합반응이 발생하여 원하는 구조를 갖는 화합물을 얻기 어렵고 용제에 용
해되지 않는 고분자가 생성되는 문제점이 었으며， 반응온도가 상은보다 낮은 경우 반웅 진척도가 너무 느리고 반응이 종결 안 될 가능성이 있어 바람직하지 못하다. 한편， 본 발명은 하기 반응식 2에 나타낸 바와 같이 , A phosphorus compound can be used, for example, 4-hydroxybenzophenone can be used. On the other hand, in the above production method according to the present invention, the compound of formula 16 is a perfluorinated polyether compound having a semi-cyclic group at the terminal or a benzophenone-based compound having a semi-ungung group at the terminal. Depending on the type of the compound of Formula 16, the type and number of the perfluorinated polyether compound and the benzophenone-based compound included in the compound of Formula 1 may vary. In addition, in the preparation method of the present invention, the type of the compound of Formula 1 may vary according to the composition ratio of the reactants. Specifically, the molar ratio of the gubleso polyether compound (Chemical Formula 14 or a mixture of Chemical Formula 14 and Chemical Formula 16) having a reactor at the terminal with respect to the hydrocarbon compound having three reaction groups (Formula 13) is 1: 1 to 1: It is preferable that it is two. When the molar ratio is less than 1: 1, all three reaction products of three hydrocarbon reactors having three reactors generate a large amount of by-products to which benzophenone compounds are attached, and thus, additional difficult separation processes are required. If it is more than 2, all three reaction products generate a large amount of by-products to which the perfluoropolyether compound is attached, and liquid impurities which are not adhered to the surface remain during coating and curing on the substrate. It is not desirable to have the problem of falling. Furthermore, in the above production method according to the present invention, with respect to the hydrocarbon-based compound having three reactors (Chemical Formula 13), a benzophenone-based compound having a reaction group at the terminal (Chemical Formula 15 or a mixture of Chemical Formula 15 and Chemical Formula 16) The molar ratio of is preferably a ratio capable of substituting all the reactive groups remaining in the compound of Formula 13, for example, 1: (3 minus the molar ratio of the perfluorinated polyether compound having a reactor at the terminal used above). 1 to 1.2 times the mole ratio of 1 to 1.2 times), and preferably used as molar ratio of 1: 1 (1 to 1 times the molar ratio of the perfluorinated polyether compound having a semi-cyclic group at the end used in the above). Can be. On the other hand, in the above production method according to the present invention, it is very important that the reaction product of the chemical formulas 13-16 form a uniform phase for the reaction to remain smooth, especially the selection of the reaction solvent is very important. Specifically, the reaction is preferably performed under a mixed solvent of a fluorocarbon solvent and a hydrocarbon solvent. In case of using only fluorocarbon solvent, smooth reaction is difficult due to poor solubility in the compound of Formula 13 and benzophenone compound, which are hydrocarbon-based compounds, and when only hydrocarbon solvent is used. It is not preferable because the solubility in the perfluorinated fluorine compound is bad and the smooth progress of the reaction is difficult. The fluorocarbon solvent is trifluoro benzene, 1,3 bistri pullulor benzene, 1.4-bistripuluor benzene, trifluoroluene, perfluorinated heptane, guble fluoride nucleic acid, m-xylene core ^^ Fluoride, methyl perfluorine butyl ether, ethyl perfluorine butyl ether, perfluorine (2-butyl tetrahydrofuran), 1, 3-dichloro-1, 1,2,2,3—pentafluuropropane Toxy—nonafluorobutane or ethoxy-nonafluorobutane may be used alone or in combination, and the hydrocarbon solvent may be used alone or in combination with acetone, toluene, MIBK or tetrahydrofuran. In addition, the mixing ratio of the fluorocarbon solvent and the hydrocarbon solvent may be changed depending on the molecular weight of the fluoride polyether used and the type of hydrocarbon compound having three semi-anionic groups, for example, fluorocarbon solvent 100 2-100 parts by weight of a hydrocarbon solvent may be used based on the parts by weight. On the other hand, in the preparation method according to the present invention, the reaction of the mixture of the compound of Formula 13 and the compound of Formulas 14 to 16 is partially a perfluorinated polyether compound having a reaction group at the end and a hydrocarbon-based compound having three reactors Reacting to form a perfluoropolyether-hydrocarbon-based reactive oligomer, and reacting the oligomer with a benzophenone-based photocoupling compound capable of binding to another hydrocarbon compound and a photocuring reaction to form a compound of Formula 1 The reaction can proceed simultaneously. In addition, in the preparation method according to the present invention, the reaction of the mixture of the compound of Formula 13 and Chemical Formulas 14 to 16 may be a urethane reaction, an ester reaction, an amide reaction, or the like. For example, when the perfluoropolyether-alcohol and 4-hydroxybenzophenone are reacted with the nucleated methylene diisocyanate cyclic trimer compound, a perfluorinated polyether modified compound of Formula 1 having a urethane linkage can be prepared. . Furthermore, in the preparation method according to the present invention, the reaction silver of the mixture of the compound of Formula 13 and Chemical Formulas 14 to 16 is preferably maintained at room temperature-50 ° C. When the reaction temperature is 50 or more, the polymerization reaction of the hydrocarbon compound having three reaction groups occurs and it is difficult to obtain a compound having a desired structure. It is a problem that a polymer that does not harm is produced, and the reaction temperature is lower than the phase silver, so the reaction progress is too slow and the reaction may not be terminated. On the other hand, the present invention, as shown in Scheme 2,
화학식 13의 화합물과 화학식 14의 화합물 및 화학식 16의 화합물의 혼합물 을 불화탄소계 용매 및 탄화수소계 용매의 혼합 용매하에서 반웅시켜 화학식 17의 화합물을 제조하는 단계 (단계 1) ; 및 Reacting a mixture of a compound of Formula 13, a compound of Formula 14, and a compound of Formula 16 in a mixed solvent of a fluorocarbon solvent and a hydrocarbon solvent to prepare a compound of Formula 17 (step 1); And
화학식 17의 화합물과 화학식 15의 화합물을 블화탄소계 용매 및 탄화수소계 용매의 흔합 용매하에서 반웅시켜 화학식 1의 화합물을 제조하는 단계 (단계 2)를 포함하는 화학식 1의 과불소 폴리에테르 변성 화합물의 제조방법을 제공한다. Preparation of the perfluorinated polyether-modified compound of Formula 1 comprising the step of preparing a compound of Formula 1 by reacting the compound of Formula 17 and the compound of Formula 15 in a mixed solvent of a fluorocarbon solvent and a hydrocarbon solvent Provide a method.
[반응삭 2] 단계
Step 2
13 B2-E 단계 2
13 B 2 -E Step 2
1 7 ᄋ、 ,(CH2)n—— A B2 -1 7 ᄋ 、, (CH 2 ) n—— AB 2-
B,—— A—— (CH2)n-N C=0 B, —— A—— (CH 2 ) nN C = 0
O (CH2)n—— A—— B3 O (CH 2 ) n—— A—— B 3
1 One
상기 반웅식 2에서， In Reaction 2 above,
n , ¾ 및 ¾는 상기 화학식 1에서 정의한 바와 같고， n, ¾ and ¾ are as defined in Formula 1,
¾는 상기 화학식 1에서 정의한 화학식 5 내지 7중 어느 하나이고, ¾ is any one of Formulas 5 to 7 defined in Formula 1,
D 및 E는 상기 반응식 1에서 정의한 바와 같다. 또한， 본 발명은 하기 반웅식 3에 나타낸 바와 같이, D and E are as defined in Scheme 1 above. In addition, the present invention, as shown in the following reaction formula 3,
화학식 13의 화합물과 화학식 14의 화합물을 불화탄소계 용매 및 탄화수소계 혼합 용매하에서 반웅시켜 화학식 18의 화합물을 제조하는 단계 (단계 1) ;
및 Reacting the compound of Formula 13 and the compound of Formula 14 in a fluorocarbon solvent and a hydrocarbon-based mixed solvent to prepare a compound of Formula 18 (step 1); And
화학식 18의 화합물과 화학식 15의 화합물 및 화학식 16의 화합물의 혼합물 을 블화탄소계 용매 및 탄화수소계 용쩨의 혼합 용매하에서 반웅시켜 화학식 1의 화합물을 제조하는 단계 (단계 2)를 포함하는 화학식 1의 과불소 폴리에테르 변성 화합물의 제조방법을 제공한다. A reaction mixture of a compound of Formula 18, a compound of Formula 15, and a compound of Formula 16 in a mixed solvent of a carbon-carbon solvent and a hydrocarbon solvent to prepare a compound of Formula 1 (Step 2). Provided is a method for preparing a bovine polyether modified compound.
[반웅식 3] [Banungsik 3]
+ 단계 Ί + Step Ί
14 14
13 단계 2
13 steps 2
1 8 1 8
n , ¾ 및 B2는 상기 화학식 1에서 정의한 바와 같고， n, ¾ and B 2 are the same as defined in Formula 1,
¾는 상기 화학식 1에서 정의한 화학식 8 내지 12 중 어. 하나이고 ¾ is one of Formulas 8 to 12 as defined in Formula 1. One
D 및 E는 상기 반응식 1에서 정의한 바와 같다. 즉， 본 발명에 따른 상기 화학식 1의 화합물의 제조방법에 있어서， 반응식 1 에 나타낸 바와 같이， 말단에 반응기를 갖는 과불소폴리에테르 화합물과 말단에 반 응기를 갖는 벤조페논계 화합물의 흔합물을 동시에 반웅시켜 화학식 1의 화합물을 제조할 수 있으며， 상기 반웅식 2 또는 3에 나타낸 '바와 같이， 먼저 말단기에 반응 기를 갖는 과불소폴리에테르 화합물을 반응기를 3개 갖는 화학식 13의 화합물에 부 분적으로 반응시켜 과불소 폴리에테르 -탄화수소계 반웅성 올리고머를 제조한 후， 다음으로 벤조페논계 화합물을 추가하여 반웅시키는 연속적인 반웅에 의해서도 화 학식 1의 화합물을 제조할 수 있다.
상기 반웅식 2 또는 3으로 표시되는 화학식 1의 화합물의 구체적인 제조방법 은 상기 반응식 1로 표시되는 화학식 1의 화합물의 제조방법에서 설명한 바와 같 다. 한편， 본 발명은 상기 화학식 1의 과불소 폴리에테르 변성 화합물을 포함하 는 방오성 코팅제 조성물을 제공한다. 구체적으로， 본 발명에 따른 상기 방오성 코팅제 조성물은 상기 화학식 1의 과불소 폴리에테르 변성 화합물 0.05 - 50 중량 % 및 용제 50 - 99.95 중량 %를 포함 하여 제조될 수 있다. 본 발명에 따른 방오성 코팅제 조성물에 있어서， 상기 과불소 폴리에테르 변 성 화합물의 함량이 특별히 제한되는 것은 아니며， 피막 위에 도포하기 쉬운 농도 를 선정하는 것이 좋다. 일반적으로 변성 화합물의 농도가 0.05 - 50 중량 %인 방오 성 코팅제 조성물을 사용하지만, 특별히 0.05 - 20 중량 %인 방오성 코팅제 조성물 을사용할 할수도 있다. 또한， 본 발명에 따른 방오성 코팅제 조성물에 있어서， 상기 용제는 도포 방 법， 조성물의 안정성, 기재에 대한 젖는 성질, 휘발 속도 등을 고려하여， 당 분야 에서 일반적으로 사용되는 것으로서 특별히 한정되지 않으나， 예를 들어, 불소 변 성 탄화수소계 또는 탄화수소계 용제를 사용할 수 있고， 구체적으로， 트리 플루오 르 벤젠, 1 , 3 -비스 트리 플루오르 벤젠， 1.4-비스 트리 풀루오르 벤젠, 트리 플 루오르 를루엔， 과불소 헵탄, 과불소 핵산, m_키시렌핵사플로오라이드, 메틸 과불 소 부틸 에테르， 에틸 과불소 부틸 에테르, 과불소 (2ᅳ부틸 테트라 하이드로 퓨란 )， 1 , 3—디클로로 -1，1，2，2 , 3- 펜타플루오로프로판， 메특시-노나플루오로부탄， 에톡 시노나플루오로부탄, 석유 벤젠， 미네랄 스피리츠, 이소 파라핀， 틀루엔， 크실렌， 아세톤, 메틸 에틸 케톤， 메틸 이소 부틸 케톤, 시클로핵사논， 메틸글리메， 메틸트 리글리메, 메틸테트라글리메 또는 테트라 하이드로 퓨란을 단독 또는 흔합하여 사 용할 수 있다. 본 발명에 따른 상기 화학식 1의 화합물을 포함하는 방오성 코팅제 조성물은
투명한 유리 제품 또는 플라스틱 제품의 표면에 그 고유의 투명성은 저하하지 않으 면서， 방오성， 내생채기성 및 내구성이 우수한 막을 형성할 수 있는 효과가 있다. 한편, 본 발명은 상기 화학식 1의 과불소 폴리에테르 변성 화합물을 포함하 는 방오성 코팅제 조성물이 경화되어 형성된 막을 제공한다. 구체적으로， 본 발명에 따른 막에 있어세 상기 방오성 코팅제 조성물을 도 포하는 방법은 당분야에서 일반적으로 사용되는 방법으로 특별히 한정하지 않으나， 예를 들어， 스핀 코팅법, 침적 코팅법, 커텐 코팅법， 스프레이 코팅법 등의 공지된 방밥을 이용할 수 있다. 또한, 본 발명에 따른 막에 있어서, 막의 두께는 0.005 - 1,000 um범위의 두께를 갖는 것이 바람직하다. 코팅막의 두께가 0.005 ym 미만인 경우 물이나 기 름에 대한 방오성이 확실히 발현할 수 없는 문제점이 발생할 수 있으며， 1,000 um 초과인 경우 광투과성이 감소될 수 있고， 두께가 불균일하여 이로 인한 반사 특성 의 열화 ·간섭무늬가 발생하는 문제점이 발생할 수 있으므로 상기 범위의 두께를 유지하는 것이 좋다. 본 발명에 따른 막은 폴리에틸렌 (PE), 폴리프로필렌 (PP), 폴리에틸렌 텔레프 탈레이트 (PET), 트리아세틸텔레프탈레이트 (TAC), 폴리카보네이트 (PC) 등 탄화수 소계 필름에 오염방지막으로 코팅될 수 있다. 또한， 본 발명에 따른 막은 최근 산업적인 수요가 급증하고 있는 프레임， 렌 즈, 유리창， 액정， 평판표시소자 (PDP), 유기발광소자 (EL) 등을 포함하는 평판 디스 플레이의 오염방지 및 반사방지 투명막， 광학 필터 등과 같은 광학 필름으로 사용 될 수 있으며, 상기 평판 디스플레이는 LEDCLight Emitting Diode), LCD(Liquid Crystal Display) , PDP(Plasma Display Panel), FED(Field Emission Display) 0LED(0rganic Light Emitting Diodes) 또는 AMOLEEK Active Matrix Organic Light Emitting Diodes) 등이 있다. 한편, 본 발명은 기재와표면이， 본 발명에 따른 상기 막으로 피복되어 있는 것을 특징으로 하는 막부착 방오성 기재를 제공한다.
구체적으로， 본 발명의 막 부착 방오성 기재에 있어서, 상기 기재는 방오성 을 필요로 하는 기재라면 제한없이 선택하여 사용할 수 있으며. 예를 들어， 모든 산업 분야의 유리물 또는 플라스틱제의 물품의 기재에 오염방지성을 부여하기 위하 여, 상기 화학식 1의 과불소 폴리에테르 변성 화합물을 포함하는 방오성 코팅제 조 성물이 경화되어 형성된 막을 부착하여 사용할 수 있다. 구체적으로 안경， 카메라 등의 렌즈류， 디스플레이의 프레임， 각종 제품의 액정 표면, 일반 가정용， 산업용, 차량 선박 등의 창문 유리류， 부엌, 욕실 등의 물 주위 용품， 건축 외장재， 미술 용품, 건축 또는 토목 분야에서 오염방지성 부여가 필요한 대상 등을 기재로 사용 할 수 있다. D and E are as defined in Scheme 1 above. That is, in the method for preparing the compound of Chemical Formula 1 according to the present invention, as shown in Scheme 1, a mixture of a perfluoropolyether compound having a reactor at the end and a benzophenone compound having a reactive group at the same time is simultaneously used. banung to as partially to a compound of formula 13 with three of the perfluoropolyether compound to the reactor having a reaction, the first terminal group, as' shown in number, and the banung formula 2 or 3 to prepare a compound of formula (I) After reacting to prepare a perfluorinated polyether-hydrocarbon semi-aromatic oligomer, the compound of Chemical Formula 1 may also be prepared by successive reactions in which a benzophenone-based compound is added to react. The specific method for preparing the compound of Formula 1 represented by Banung Formula 2 or 3 is the same as described in the method for preparing the compound of Formula 1 represented by Scheme 1. On the other hand, the present invention provides an antifouling coating composition comprising a perfluorinated polyether modified compound of the formula (1). Specifically, the antifouling coating composition according to the present invention may be prepared including 0.05 to 50% by weight of the perfluorinated polyether modified compound of Formula 1 and 50 to 99.95% by weight of the solvent. In the antifouling coating composition according to the present invention, the content of the perfluorinated polyether modified compound is not particularly limited, and it is preferable to select a concentration that is easy to apply on the coating. In general, an antifouling coating composition having a concentration of the modified compound is 0.05-50% by weight, but an antifouling coating composition having a concentration of 0.05-20% by weight may be used. In addition, in the antifouling coating composition according to the present invention, the solvent is not particularly limited as it is generally used in the art in consideration of the coating method, stability of the composition, wettability to the substrate, volatilization rate, etc., examples For example, a fluorine-modified hydrocarbon-based or hydrocarbon-based solvent may be used, and specifically, trifluoro benzene, 1,3-bis trifluoro benzene, 1.4-bistri pullobenzene, trifluoroluene, perfluoro Bovine heptane, perfluoronucleic acid, m_xylene nucleated fluorofluoride, methyl perfluorine butyl ether, ethyl perfluorine butyl ether, perfluorine (2 ᅳ butyl tetrahydrofuran), 1, 3—dichloro-1,1,2 ， 2, 3- pentafluoropropane, meecoxy-nonafluorobutane, ethoxysinonafluorobutane, petroleum benzene, mineral spirits, isoparaffin, toluene, xyl To, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclo hex rice, methyl glycidyl methoxy, methyl bit Wrigley methoxy, methyl tetraglyme methoxy or tetrahydrofuran may be used alone or combined common. The antifouling coating composition comprising the compound of Formula 1 according to the present invention The inherent transparency on the surface of the transparent glass or plastic product is not degraded, and there is an effect capable of forming a film having excellent antifouling resistance, biodegradability and durability. On the other hand, the present invention provides a film formed by curing the antifouling coating composition comprising a perfluorinated polyether modified compound of the formula (1). Specifically, the method for coating the antifouling coating composition in the film according to the present invention is not particularly limited to methods generally used in the art, for example, spin coating method, dip coating method, curtain coating method Known methods such as spray coating can be used. In addition, in the membrane according to the present invention, the thickness of the membrane preferably has a thickness in the range of 0.005-1,000 um. If the thickness of the coating film is less than 0.005 ym, there may be a problem that the antifouling property against water or oil can not be expressed reliably, and if the thickness of the coating film is more than 1,000 um, the light transmittance may be reduced, and the thickness is nonuniform, resulting in deterioration of reflection characteristics. It is good to maintain the thickness in the above range because problems may occur that interference patterns occur. Membranes according to the invention can be coated with antifouling coatings on hydrocarbon-based films such as polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), triacetyl terephthalate (TAC), polycarbonate (PC), etc. have. In addition, the film according to the present invention is antifouling and antireflection of a flat panel display including a frame, a lens, a glass window, a liquid crystal, a flat panel display device (PDP), an organic light emitting device (EL), etc., which is recently increasing industrial demand. It can be used as an optical film such as a transparent film, an optical filter, etc. The flat panel display is an LEDC Light Emitting Diode (LCD), a Liquid Crystal Display (LCD), a Plasma Display Panel (PDP), a Field Emission Display (FED) 0 LED (0rganic Light Emitting Diodes) ) Or AMOLEEK Active Matrix Organic Light Emitting Diodes. On the other hand, the present invention provides an antifouling substrate with a membrane, wherein the substrate and the surface are covered with the membrane according to the present invention. Specifically, in the antifouling substrate with a film of the present invention, the substrate may be selected and used without limitation as long as the substrate requires antifouling properties. For example, in order to provide antifouling properties to the substrates of glass or plastic articles of all industrial fields, the antifouling coating composition comprising the perfluorinated polyether modified compound of Formula 1 is cured to attach a film formed. Can be used. Specifically, lenses such as glasses, cameras, frames of displays, liquid crystal surfaces of various products, window glasses for general household, industrial, and vehicle vessels, water accessories such as kitchens and bathrooms, architectural exterior materials, art supplies, construction or It can be used as a base for objects that need to be given pollution prevention in civil engineering.
【발명의 실시를 위한 형태】 [Form for implementation of invention]
이하, 본 발명을 실시예 및 실험예에 의해 더욱 구체적으로 설명한다. 그러 나， 하기의 실시예 및 실험예는 본 발명을 예시하기 위한 것일 뿐， 본 발명의 권리 범위가실시예 및 실험예에 한정되는 것은 아니다. Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following Examples and Experimental Examples are only for illustrating the present invention, and the scope of the present invention is not limited to the Examples and Experimental Examples.
<제조예 1>과불소폴리에테르 알콜의 합성 - 1 Preparation Example 1 Synthesis of Perfluoropolyether Alcohol-1
단계 1 ： 과불소폴리에테르 (PFPE-C0F)의 합성 Step 1: Synthesis of Perfluoropolyether (PFPE-C0F)
교반기， 냉각 자켓， 온도계, 압력계가 달린 스테인레스제 고압반응기에 테트 라글리메 2.49 g , 불화세슘 1.69 g , 핵사풀루오르 프로필렌 (HFP) 35 g 및 핵사 풀 루오르 프로필렌 옥사이드 (HFP0) 165 g을 투입하고， -35 °C에서 반응하여 하기 화 학식 19로 표시되는 HFP0 올리고머, 과불소폴리에테르 (PFPE-C0F)를 얻었다. 이때, 총 반응 시간은 36시간이었다. 2.49 g of tetraglyme, 1.69 g of cesium fluoride, 35 g of nucleated fluoro propylene (HFP) and 165 g of nucleated fluoro propylene oxide (HFP0) were fed into a stainless high pressure reactor with a stirrer, cooling jacket, thermometer and pressure gauge. And, reacted at -35 ° C. to obtain an HFP0 oligomer, perfluoropolyether (PFPE-C0F) represented by the following formula (19). At this time, the total reaction time was 36 hours.
[화학식 19] [Formula 19]
소 폴리에테르 -COF(PFPE-COF)
상기 제조한 HFP0 을리고머를 F-匪 R 측정하여 이하의 스펙트럼 데이터를 얻었으며, 겔 투과 크로마토그래피 (GPC ; Gel permeat i on chromatogram) 분석 결과 평균분자량은 1700이었다. Small Polyether-COF (PFPE-COF) The spectral data was obtained by F-XR measurement of the prepared HFP0 oligomer, and the average molecular weight was 1700 as a result of gel permeation chromatography (GPC) analysis.
19 19
F - NMR (CDC13 , 300 MHz ) : δ ― 83.8 (3F , s , CF3CF2CF2) , - 131 .3 (2F , m ,
CF3CE2CF2) , - 83.2 [ (2F, ra, CF3CF2CF2) , (3F , s , CF(CF3)C0F) ] , - 146.2 ( IF, t , 0CF1CF3)CF2) , - 81.6 [ (3F, m , 0CF(CF3)CF2) , (m , 2F, 0CF(CF3)CE2) ]， - 132.0 ( IF, t , C'F(CF3)C0F, + 25 [IF, s , -CF(CF3)C0F] - 단계 2 ： PFPE-methvl ester의 합성 F-NMR (CDC13, 300 MHz): δ-83.8 (3F, s, CF 3 CF 2 CF 2 ),-131 .3 (2F, m, CF 3 CE2CF 2 ),-83.2 [(2F, ra, CF 3 CF 2 CF 2 ), (3F, s, CF (CF 3 ) C0F)],-146.2 (IF, t, 0CF1CF 3 ) CF 2 ), - 81.6 [(3F, m, 0CF (CF 3) CF 2), (m, 2F, 0CF (CF 3) CE 2)], - 132.0 (IF, t, C 'F (CF 3) C0F, + 25 [IF, s, -CF (CF 3 ) C0F]-Step 2: Synthesis of PFPE-methvl ester
버블트랩이 장착된 3구 플라스크에 단계 1에서 제조한 PFPE-C0F를 넣고, 메 탄올을 천천히 주입하였다. 이때， 메탄을은 PFPE-C0F의 몰비를 초과하여 (2배 이 상) 사용하였으며， 메탄올을 천천히 주입하면서 마그네틱바를 이용하여 교반시켰 다. 이때 메탄올과 PFPE-C0F가 반웅하면서 생기는 HF 기체의 발생여부는 버블 트랩 을 통해 확인할 수 있다. PFPE-C0F는 투명한 노란빛을 보였으나, 메탄을이 투입되 면서 블투명해지는 것을 확인할 수 있었으며， 반웅은 3시간 이상 충분히 교반시킨 후 종료하였다. 반응에 사용된 메탄올을 제거하기 위하여 증류수를 투입하고 교반하여 층분 히 섞은,후 분별 깔대기에서 넣어 층분리 후， 하부층의 PFPE-methyl ester 부분을 분리해냈다. 메탄올이 제거된 것은 가스 크로마토그래피 분석 또는 -NMR분석을 이 용하여 확인할 수 있다. 다음으로， 메탄올 제거를 위해 사용된 증류수를 제거하기 위해서 황산 마그네슘 (MgS04)을 다량 첨가하고， 충분히 교반시킨 후 여과하였다. 반 응물에 잔존하는 휘발성 물질을 제거하기 위하여 진공건조시킨 후 얻어진 최종 합 성물， PFPE-methyl ester은 열은 노란빛의 투명한 액상이다. 단계 3 ： PFPE-al coh 의 합성 PFPE-C0F prepared in step 1 was placed in a three-necked flask equipped with a bubble trap, and methanol was slowly injected. At this time, methane was used in excess of the molar ratio of PFPE-C0F (more than two times), and stirred using a magnetic bar while slowly injecting methanol. At this time, the generation of HF gas generated by reaction between methanol and PFPE-C0F can be confirmed through bubble trap. PFPE-C0F showed a transparent yellowish color, but it was confirmed that the methane is transparent as it is added, and the reaction was completed after sufficiently stirring for 3 hours. In order to remove the methanol used in the reaction, distilled water was added, stirred, and mixed in layers, and then placed in a separatory funnel, followed by layer separation, to separate the PFPE-methyl ester portion of the lower layer. The removal of methanol can be confirmed by gas chromatography analysis or -NMR analysis. Next, in order to remove distilled water used for methanol removal, a large amount of magnesium sulfate (MgS0 4 ) was added, sufficiently stirred, and filtered. The final compound, PFPE-methyl ester, obtained after vacuum drying to remove volatiles remaining in the reactants is a yellowish transparent liquid. Step 3: Synthesis of PFPE-al coh
플라스크에 에탄올과 소듐보로하이드라이드 (NaBH4) 9.0g와 함께 넣고 교반시 킨 후, PFPE-methyl ester (분자량 1700) 200 g을 적하 깔대기 (dropping funnel을 이용하여 천천히 투입하였다. PFPE-methyl ester는 약 2시간에 걸쳐 투입하였고, 투입완료 후에도 가스발생이 계속되었다. 반응은 상온에서 하룻밤 동안 교반시키며 진행하였다. 반웅 용액에서 가스 발생이 없고, 반투명하나 균일상을 유지하고 있음 을 확인하고， 샘플링하여 가스 크로마토그래피 또는 -NMR분석을 통하여 전환율을 확인하였다. 전환율 확인 후 HC1 10% 용액을 투입하면， 2개의 층으로 층분리되어 PFPE-alcohol이 아래층으로 가라앉는 것을 확인할 수 있다. 다음으로， 탄산수소나
트륨 (NaHC03) 포화 용액을 반웅용액의 pH가 7 - 8이 될 때까지 투입한 후， 에탄올 둥 불순물을 제거하기 위하여 증류수를 투입 및 교반 후 층분리하는 과정을 반복하 였다. 다음으로， 사용된 증류수를 제거하기 위해 황산 마그네슘 (MgS04)을 다량 투입 한 후 충분히 교반시켜 여과하고， 진공건조시킨 후 최종 합성물 PFPE-a l coh 을 얻 었으며, 전환율은 98%이상이었다. The flask was stirred with 9.0 g of ethanol and sodium borohydride (NaBH 4 ) and stirred, and then 200 g of PFPE-methyl ester (molecular weight 1700) was slowly added using a dropping funnel. The reaction was continued for about 2 hours, and gas generation continued after the completion of the reaction.The reaction proceeded with stirring overnight at room temperature.The reaction was confirmed that there was no gas generation in the reaction solution, and the translucent but uniform phase was maintained. After conversion, the conversion was checked by gas chromatography or -NMR analysis.After confirming the conversion, a 10% solution of HC1 was added, and the PFPE-alcohol was separated into two layers. sonar The saturated solution of thrium (NaHC0 3 ) was added until the pH of the semi-aqueous solution became 7-8, and then distilled water was added and stirred in order to remove the ethanol floating impurities, and the layers were separated. Next, in order to remove the distilled water used, a large amount of magnesium sulfate (MgS0 4 ) was added, followed by filtration with sufficient stirring, vacuum drying, and the final composite PFPE-a coh was obtained. The conversion rate was more than 98%.
<제조예 2>과불소 폴리에스테르 알콜의 합성 - 2 Preparation Example 2 Synthesis of Perfluorinated Polyester Alcohol-2
단계 1 ： 과불소폴리에테르 (PFPE-C0F)의 합성 Step 1: Synthesis of Perfluoropolyether (PFPE-C0F)
핵사플루오르 프로필렌 (HFP) 50 g 및 핵사 플루오르 프로필렌 옥사이드 (HFP0) 240 g을 사용한 것을 제외하고는 제조예 1의 단계 1과 동일한 방법을 수행 하여 HFP0 을리고머, 과불소폴리에테르 (PFPE-C0F)를 얻었다. 이 HFP0 을리고머를 Except for using 50 g of nucleated fluoropropylene (HFP) and 240 g of nucleated fluoropropylene oxide (HFP0), the same method as in step 1 of Preparation Example 1 was carried out to obtain HFP0 oligomer, perfluoropolyether (PFPE-C0F). Got. This HFP0 oligomer
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F-薩 R 측정한 결과， 제조예 1의 HFP0 올리고머와 스펙트럼 데이터가 동일함을 확 인하였으며， 겔 투과 크로마토그래피 (GPC ; Gel permeat ion chromatogram) 분석 결 과 평균분자량은 2500이었다. 다음으로, 단계 1에서 과블소플리에테르 (PFPE-C0F)에 대하여 제조예 1의 단 계 2 및 단계 3과 동일한 방법을 수행하여 쎄조예 2의 과불소폴리에테르 알콜 (PFPE-al cohol )을 얻었다. As a result of F- 薩 R measurement, it was confirmed that the spectral data of the HFP0 oligomer of Preparation Example 1 were the same, and the average molecular weight of the gel permeat ion (GPC) analysis was 2500. Next, the perfluoropolyether alcohol (PFPE-al cohol) of Sezo Example 2 was obtained by performing the same method as Step 2 and Step 3 of Preparation Example 1 with respect to Gublesopolyether (PFPE-C0F) in Step 1. .
<제조예 3>과불소 폴리에스테르 알콜의 합성 - 3 Preparation Example 3 Synthesis of Perfluorinated Polyester Alcohol-3
단계 1 ： 과불소폴리에테르 (PFPE-C0F)의 합성 Step 1: Synthesis of Perfluoropolyether (PFPE-C0F)
핵사풀루오르 프로필렌 (HFP) 87.75 g 및 핵사 플루오르 프로필렌 옥사이드 (HFP0) 420 g을 사용한 것을 제외하고는 제조예 1의 단계 1과 동일한 방법을 수행 하여 HFP0 올리고머， 과불소폴리에테르 (PFPE-C0F)를 얻었다. 이 HFP0 을리고머를 The HFP0 oligomer and perfluoropolyether (PFPE-C0F) were prepared in the same manner as in step 1 of Preparation Example 1, except that 87.75 g of nucleated propylene (HFP) and 420 g of nucleated fluoropropylene oxide (HFP0) were used. Got it. This HFP0 oligomer
F- N R 측정한 결과， 제조예 1의 HFP0 올리고머와 스펙트럼 데이터가 동일함을 확 인하였으며, 겔 투과 크로마토그래피 (GPC ; Gel permeat ion chromatogram) 분석 결 과 평균분자량은 4400이었다. 다음으로， 단계 1에서 과불소폴리에테르 (PFPE-C0F)에 대하여 제조예 1의 단 계 2 및 단계 3과 동일한 방법을 수행하여 제조예 2의 과불소폴리에테르 알콜 (PFPE-al cohol )을 얻었다.
<제조예 4>과불소 폴리에스테르 알콜의 합성 - 4 As a result of F-NR measurement, it was confirmed that the spectral data of the HFP0 oligomer of Preparation Example 1 were identical, and the average molecular weight of the gel permeat ion (GPC) analysis was 4400. Next, perfluoropolyether (PFPE-C0F) in Step 1 was carried out in the same manner as Steps 2 and 3 of Preparation Example 1 to obtain a perfluoropolyether alcohol (PFPE-al cohol) of Preparation Example 2 . Preparation Example 4 Synthesis of Perfluorinated Polyester Alcohol-4
단계 1 ： 과불소폴리에테르 (PFPE-C0F)의 합성 Step 1: Synthesis of Perfluoropolyether (PFPE-C0F)
핵사플투오르 프로필렌 (HFP) 180 g 및 핵사 플루오르 프로필렌 옥사이드 (HFP0) 860 g을 사용한 것을 제외하고는 제조예 1의 단계 1과 동일한 방법을 수행 하여 HFP0 올리고머， 과불소폴리에테르 (PFPE-C0F)를 얻었다. 이 HFP0 을리고머를 The HFP0 oligomer and perfluoropolyether (PFPE-C0F) were prepared in the same manner as in step 1 of Preparation Example 1, except that 180 g of nucleated sapfur propylene (HFP) and 860 g of nucleated fluoropropylene oxide (HFP0) were used. Got it. This HFP0 oligomer
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F-画 R 측정한 결과， 제조예 1의 HFP0 올리고머와 스펙트럼 데이터가 동일함을 확 인하였으며， 겔 투과 크로마토그래피 (GPC ; Ge l permeat i on chromatogram) 분석 결 과 평균분자량은 9000이었다. 다음으로， 단계 1에서 과불소폴리에테르 (PFPE-C0F)에 대하여 제조예 1의 단 계 2 및 단계 3과 동일한 방법을 수행하여 제조예 2의 과불소폴리에테르 알콜 (PFPE-al cohol )을 얻었다. As a result of the F- 画 R measurement, it was confirmed that the spectral data of the HFP0 oligomer of Preparation Example 1 were the same, and the average molecular weight of the gel permeation chromatography (GPC) was 9000. Next, perfluoropolyether (PFPE-C0F) in Step 1 was carried out in the same manner as Steps 2 and 3 of Preparation Example 1 to obtain a perfluoropolyether alcohol (PFPE-al cohol) of Preparation Example 2 .
<실시예 1>광경화형 과불소폴리에테르 변성 화합물의 합성 - 1 Example 1 Synthesis of Photocurable Perfluorinated Polyether Modified Compound-1
1 , 3 -비스 트리 플루오르 벤젠 2.54 g과 아세톤 0.64 g이 흔합된 용액에 핵 사메틸렌 디이소시아네이트 사이클릭트라이머 (DESM0DUR N3300) 3g , 디부틸틴 디라 울레이트 (DBTDL) 0.2g을 흔합 (A)하고， 1 , 3 -비스 트리 플루오르 벤젠 2.54 g과 아 세톤 0 .64 g이 혼합된 용액에 제조예 1의 PFPE-al coho l 2.5g을 혼합 (B)하여 각각 준비했다. 핵사메틸렌 디이소시아네이트 사이클릭트라이머 (DESM0DUR N3300)이 포 함된 혼합물 (A)을 교반하면서 PFPE-al coh 이 포함된 흔합물 (B)을 일정량씩 투입하 고 상온에서 반응시켰다. 흔합 후 4-하이드록시벤조페논 (4-HBP) 0.65 g을 투입 (C) 하고 40 °C의 반응온도로 승온하여 교반했다. 미반응물은 사이클로핵산과 아세톤 혼합액에 침전 및 교반하여 제거하였다. 3 회 정도 미반웅물 제거과정을 거친 후 진공건조하여 실시예 1의 광경화형 과불소 폴리에테르 변성 화합물을 얻었고， 최종 합성물은 모두 흰색의 가루 형태였다. To a solution of 2.54 g of 1,3-bistrifluorobenzene and 0.64 g of acetone, 3 g of nuclear samethylene diisocyanate cyclic trimer (DESM0DUR N3300) and 0.2 g of dibutyltin dilaurate (DBTDL) were mixed (A) Then, 2.5 g of 1,3-bistrifluorobenzene and 0.64 g of acetone were mixed and (B) 2.5 g of PFPE-al cohol of Preparation Example 1 was prepared, respectively. While stirring the mixture (A) containing the nucleated methylene diisocyanate cyclic trimer (DESM0DUR N3300), a mixture (B) containing PFPE-al coh was added at a constant amount and reacted at room temperature. After mixing, 0.65 g of 4-hydroxybenzophenone (4-HBP) was added (C), and the reaction mixture was heated to 40 ° C. and stirred. Unreacted material was removed by precipitation and stirring in cyclohexane and acetone mixture. Vacuum drying after three times of removal of the semi-aerated water to obtain the photocurable perfluorinated polyether modified compound of Example 1, the final composite was all in the form of a white powder.
<실시예 2>광경화형 과불소 폴리에테르 변성 화합물의 합성 - 2 Example 2 Synthesis of Photocurable Perfluorinated Polyether-Modified Compound-2
A 혼합물: 1，3 -비스 트리 플루오르 벤젠 3. 14 g과 아세톤 0.79 g이 흔합된 용액에 핵사메틸렌 디이소시아네이트 사이클릭트라이머 (DESUMIDUR N3300) 3g , 디 부틸틴 디라울레이트 (DBTDL) 0.2g을 흔합하여 실시예 2의 혼합물 A를 제조하였다. A mixture: 3 g of nusamethylene diisocyanate cyclic trimer (DESUMIDUR N3300) and 0.2 g of dibutyltin dilaurate (DBTDL) in a solution of 3.14 g of 1,3-bistrifluorobenzene and 0.79 g of acetone were mixed. Mixture produced the mixture A of Example 2.
B 흔합물: 1，3ᅳ비스 트리 풀루오르 벤젠 3. 14 g과 아세톤 0.79 g이 흔합된
용액에 제조예 2의 PFPE-al cohol 4 g을 혼합하여 실시예 3의 혼합물 B를 제조하였 다. B complex: 1,3 ᅳ bistripuloorbenzene 3.14 g and acetone 0.79 g Mixture B of Example 3 was prepared by mixing 4 g of PFPE-al cohol of Preparation Example 2 to the solution.
상기 혼합물 A및 혼합물 B를 사용한 것을 제외하고는 실시예 1과 동일한 방 법을 수행하여 흰색 가루 형태의 실시예 2의 광경화형 과불소 폴리에테르 변성 화 합물을 얻었다. A photocurable perfluorinated polyether modified compound of Example 2 was obtained in the same manner as in Example 1, except that Mixture A and Mixture B were used.
<실시예 3>광경화형 과불소폴리에테르 변성 화합물의 합성 - 3 Example 3 Synthesis of Photocurable Perfluorinated Polyether-Modified Compound-3
A 혼합물: 1 , 3 -비스 트리 플루오르 벤젠 4.36 g과 아세톤 1.09 g이 혼합된 용액에 핵사메틸렌 디이소시아네이트 사이클릭트라이머 (DESMODUR N3300) 3g, 디부 틸틴 디라울레이트 (DBTDL) 0.2g을 혼합하여 실시예 3의 흔합물 A를 제조하였다. A mixture: A mixture of 4.36 g of 1,3-bistrifluorobenzene and 1.09 g of acetone was mixed with 3 g of nucleated methylene diisocyanate cyclic trimer (DESMODUR N3300) and 0.2 g of dibutyl tin dilaurate (DBTDL). Compound A of Example 3 was prepared.
B 혼합물: 1ᅳ3 -비스 트리 플루오르 벤젠 4.36 g과 아세톤 1.09 g이 흔합된 용액에 제조예 3의 PFPE-al cohol 7.05 g을 혼합하여 실시예 3의 흔합물 B를 제조하 였다. B mixture: Mixture B of Example 3 was prepared by mixing 7.05 g of PFPE-al cohol of Preparation Example 3 with a solution of 4.36 g of 1 ᅳ 3-bistrifluorobenzene and 1.09 g of acetone.
상기 흔합물 A 및 혼합물 B를사용한 것을 제외하고는 실시예 1과 동일한 방 법을 수행하여 흰색 가루 형태의 실시예 3의 광경화형 과불소 폴리에테르 변성 화 합물을 얻었다. A photocurable perfluorinated polyether modified compound of Example 3 was obtained in the same manner as in Example 1, except that Mixture A and Mixture B were used.
<실시예 4>광경화형 과블소폴리에테르 변성 화합물의 합성 - 4 Example 4 Synthesis of Photocurable Gublesopolyether-Modified Compound-4
A 흔합물: 1，3-비스 트리 플루오르 벤젠 7.30 g과 아세톤 1.83 g이 혼합된 용액에 핵사메틸렌 디이소시아네이트 사이클릭트라이머 (DESMODUR N3300) 3g , 디부 틸틴 디라울레이트 (DBTDL) 0.2g을 흔합하여 실시예 4의 합물 A를 제조하였다. A complex: A solution of 7.30 g of 1,3-bistrifluorobenzene and 1.83 g of acetone was mixed with 3 g of nusamethylene diisocyanate cyclic trimer (DESMODUR N3300) and 0.2 g of dibutyl tin dilaurate (DBTDL). Compound A of Example 4 was prepared.
B 혼합물: 1，3 -비스 트리 플루오르 벤젠 7.30 g과 아세톤 1.83 g이 혼합된 용액에 제조예 4의 PFPE-alcoho l 14.4 g을 혼합하여 실시예 4의 혼합물 B를 제조하 였다. B mixture: A mixture B of Example 4 was prepared by mixing 14.4 g of PFPE-alcohol 1 of Preparation Example 4 with a solution of 7.30 g of 1,3-bistrifluorobenzene and 1.83 g of acetone.
상기 흔합물 A 및 흔합물 B를 사용한 것을 제외하고는 실시예 1과 동일한 방 법을 수행하여 흰색 가루 형태의 실시예 4의 광경화형 과불소 폴리에테르 변성 화 합물을 얻었다ᅳ The photocurable perfluorinated polyether modified compound of Example 4 was obtained by the same method as Example 1, except that Compound A and Compound B were used.
<실시예 5>광경화형 과불소 폴리에테르 변성 화합물의 합성 - 5 Example 5 Synthesis of Photocurable Perfluorinated Polyether-Modified Compound
A 혼합물: 1 , 3ᅳ비스 트리 플루오르 벤젠 7.05 g과 아세톤 1 .76 g이 혼합된 용액에 핵사메틸렌 디이소시아네이트 사이클릭트라이머 (DESMODUR N3300) 3g , 디부 틸틴 디라울레이트 (DBTDL) 0.2g을 흔합하여 실시예 5의 흔합물 A를 제조하였다.
B 혼합물: 1 ,3-비스 트리 플루오르 벤젠 그 05 g과 아세톤 1.76 g이 혼합된 용액에 제조예 3의 PFPE-al cohol 14.1 g을 혼합하여 실시예 5의 혼합물 B를 제조하 였다. A mixture: A solution of 7.05 g of 1,3 ᅳ bistrifluorobenzene and 1.76 g of acetone was mixed with 3 g of nusamethylene diisocyanate cyclic trimer (DESMODUR N3300) and 0.2 g of dibutyl butyric dilaurate (DBTDL). Combined, the mixture A of Example 5 was prepared. B mixture: Mixture B of Example 5 was prepared by mixing 14.1 g of PFPE-al cohol of Preparation Example 3 in a solution of 05 g of 1,3-bistrifluorobenzene and 1.76 g of acetone.
상기 흔합물 A, 흔합물 B 및 4-하이드록시벤조페논 (4-HBP) (C)은 0.65 g 대 신 0.32 g사용한 한 것을 제외하고는 실시예 1과 동일한 방법을 수행하여 흰색 가 투 형태의 실시예 5의 광경화형 과불소 폴리에테르 변성 화합물을 얻었다. 이하, 실시예 1 - 5의 시약 투입량을 하기 표 1에 나타내었다. Compound A, Compound B, and 4-hydroxybenzophenone (4-HBP) (C) were prepared in the same manner as in Example 1, except that 0.32 g instead of 0.65 g was used. The photocurable perfluorinated polyether modified compound of Example 5 was obtained. Hereinafter, the reagent input amount of Examples 1-5 is shown in Table 1 below.
【표 1] [Table 1]
<비교예 1> Comparative Example 1
반웅 은도가 40 °C 대신에 60 °C 인 것을 제외하고는 실시예 1과 동일한 방 법으로 비교예 1의 반웅을 수행하였다. 그러나， 비교예 1의 경우， 합성 과정 중 반 옹온도가 높아서 합성물이 gel 상태로 변화하여 블용성 고분자 형성되었다. The silver that is banung banung was performed in Comparative Example 1 in the same way as in Example 1 except that the 60 ° C instead of 40 ° C. However, in Comparative Example 1, due to the high reaction temperature during the synthesis process, the composite was changed into a gel state to form a soluble polymer.
<비교예 2> Comparative Example 2
반웅 용매가 1 , 3ᅳ비스 트리 플루오르 벤젠과 아세톤의 2 가지의 용매의 흔 합용매가 아닌 아세톤만의 단일 용매인 것을 제외하고는 실시예 1과 동일한 방법으 로 비교예 2의 반웅을 수행하였다. 그러나, 비교예 2의 경우， 합성 과정 중 충분리 가 일어나 반응이 진행되지 않았다. The reaction of Comparative Example 2 was carried out in the same manner as in Example 1, except that the reaction solvent was a single solvent of only acetone, not a common solvent of two solvents of 1,3 ᅳ bistrifluorobenzene and acetone. . However, in the case of Comparative Example 2, the reaction did not proceed because a sufficient amount during the synthesis process.
<실시예 6 - 10>방오성 코팅제 조성물의 제조 <Example 6-10> Preparation of an antifouling coating composition
실시예 1 - 5 에서 합성한 광경화형 과불소 폴리에테르 화합물을 1 , 1 , 2 , 2-테 트라플루오로 -1-프로판올에 lwt%로 교반기를 이용하여 분산시켜 실시예 6 - 10의 방오성 코팅제 조성물을 제조하였다. 분산후 용액은 투명한상태이다.
<실시예 u - 15>방오성 코팅제 조성물이 경화되어 형성된 막의 제조 상기 제조한 방오성 코팅제 조성물 0.5mL을 2000rpm 조건에서 20 초 동안 스핀코팅을 수행하여 슬라이드 글라스 (Matsunarai S-llll , 7.6cm X 2.6cm)에 도포하 였다. 상기 도포된 코팅물은 120°C 진공오븐에서 10분 동안 어닐링 과정을 거친 후 에 추가적인 라디칼 개시제없이， ARC Xe LAMP POWER SUPPLY를 이용하여 500 W 조건 에서 30 - 60초 동안 경화시켜 실시예 11 - 15의 피막을 형성했다. The antifouling coating agent of Examples 6-10 by dispersing the photocurable perfluorinated polyether compound synthesized in Examples 1-5 in lwt% with 1, 1, 2, 2-tetrafluoro-1-propanol using a stirrer The composition was prepared. After dispersion, the solution is clear. Example u-15 Preparation of Membrane Formed by Curing Antifouling Coating Composition 0.5 mL of the antifouling coating composition prepared above was subjected to spin coating at 2000 rpm for 20 seconds for slide glass (Matsunarai S-llll, 7.6cm X 2.6cm). It was applied to. The applied coating was annealed in a 120 ° C vacuum oven for 10 minutes and then cured for 30-60 seconds at 500 W using ARC Xe LAMP POWER SUPPLY without additional radical initiator, Example 11-15 Formed a film.
<비교예 3>무처리 슬라이드 글라스 Comparative Example 3 Untreated Slide Glass
본 발명에 따른 화합물을 포함하는 방오성 코팅제 조성물이 경화되어 형성 된 막의 접촉각， 흐름각 등의 물성， 내오염성， 투과도를 비교 실험하기 위하여， 슬 라이드 글라스에 아무것도 처리를 가하지 않은 것을 비교예 3으로 하여 하기 실험 예 1 - 6을 수행하였다. ' In order to compare and compare the physical properties, fouling resistance and permeability of the contact angle, flow angle, etc. of the film formed by curing the antifouling coating composition comprising the compound according to the present invention, nothing was applied to the slide glass as Comparative Example 3 Experimental Examples 1 to 6 were performed below. '
<실험예 1>방오성 코팅제 조성물이 경화되어 형성된 막의 접촉각측정 본 발명의 화합물을 포함하는 방오성 코팅제 조성물이 경화되어 형성된 막의 표면을 액체가 적시는 정도를 확인하기 위하여， 실시예 11 - 15의 막이 코팅된 글 라스 및 비교예 3의 무처리 슬라이드 글라스에 대하여 접촉각 및 표면에너지를 측 정하여 하기 표 2에 나타내었다. KRUSS사의 DSA100을 이용하여 물 (Water) , 핵사데 칸 (HD^ 다이오도메탄 (DIM)의 접촉각을 측정하였으며， 상온에서 솔벤트양은 7 u L 로 하였다. 이러한 접촉각은 표면 자유에너지에 의해 결정되며， 접촉각이 높을수록 낮은 표면 에너지를 갖는 것을 의미하며， 표면에너지는 하기 수학식 1을 이용한 기 하평균법에 의하여 계산하였다. Experimental Example 1 Measurement of Contact Angle of Membrane Formed by Curing Antifouling Coating Composition In order to confirm the degree of liquid soaking on the surface of the membrane formed by curing the antifouling coating composition comprising the compound of the present invention, the membranes of Examples 11-15 were coated. The contact angle and surface energy of the glass and the untreated slide glass of Comparative Example 3 are shown in Table 2 below. The contact angles of water and nucleodecane (HD ^ diodomethane (DIM) were measured using KRUSS DSA100, and the solvent amount was 7 u L at room temperature. The contact angle is determined by the surface free energy. The higher the contact angle, the lower the surface energy, and the surface energy was calculated by the geometric mean method using Equation 1 below.
[수학식 1] [Equation 1]
【표 21
Table 21
그 결과， 상기 표 2에 나타낸 바와같이， 본 발명에 따른 실시예 11 내지 15 의 막이 코팅된 슬라이드 글라스는 비교예 3의 무처리 슬라이드 글라스와 비교하여 물 및 DIM에 대해서 각각 약 88° , 48° 높은 접촉각을 가지는 것으로 나타났으며 , 또한 상용막인 DSX (물에 대한 접촉각: 114.3， DIM에 대한 접촉각 : 88.3) 및 EGO 1720(물에 대한 접촉각: 110.9， DIM에 대한 접촉각 : 85.5)와 비교하여도 접촉각이 더 높다는 것을 알수 있다. 이로부터 , 본 발명에 따른 실시예를 통해 합성된 과불소 에테르 변성 화합물 이 분산된 조성물이 경화되어 형성된 막이 코팅될 경우， 코팅되지 않은 경우 및 상 용막보다 낮은 표면 에너지를 가지고， 상기 용액의 막의 표면 위에 놓여진다고 해 도 막 표면을 적시지 못하므로， 본 발명의 화합물을 포함하는 코팅제 조성물이 발 수성 및 발유성이 우수한 막을 제조할 수 있는 효과가 있음을 알 수 있다. As a result, as shown in Table 2, the slide glass coated with the films of Examples 11 to 15 according to the present invention was about 88 ° and 48 ° for water and DIM, respectively, compared to the untreated slide glass of Comparative Example 3. It has been shown to have a high contact angle, compared with the commercial membrane DSX (contact angle for water: 114.3, contact angle for DIM: 88.3) and EGO 1720 (contact angle for water: 110.9, contact angle for DIM: 85.5). It can also be seen that the contact angle is higher. From this, when the film formed by curing the composition in which the perfluorinated ether modified compound dispersed through the embodiment according to the present invention is cured is coated, has a lower surface energy than the uncoated film and the surface of the film of the solution Since it does not wet the surface of the film even when placed on it, it can be seen that the coating composition comprising the compound of the present invention has an effect of producing a film having excellent water and oil repellency.
<실험예 2>방오성 코팅제 조성물이 경화되어 형성된 막의 흐름각측정 본 발명의 화합물을 포함하는 방오제 코팅제 조성물이 경화되어 형성된 막의 방오성을 측정하기 위해， 실시예 11 - 15의 막이 코팅된 슬라이드 글라스 및 비교 예 3의 무처리 슬라이드 글라스에 대하여 흐름각을 측정하여 하기 표 3에 나타내었 다ᅳ 일반적으로 접촉각이 표면의 소수성 정도를 평가하는 기준으로 사용되어져 왔 으나, 높은 접촉각을 갖는 표면에 대한 흐름각은 항상 낮은 값만을 갖지 않으므로， 접촉각만으로 표면에 물방울의 흐름 성질을 측정하는 것은 충분하지 않다. 따라서， 소수성과 관련하여 물방울에 대한 흐름각의 측정은 접촉각과는 개별적으로 시행되 어야 한다. 흐름각은 기울어진 표면에 특정 무게를 갖는 물방울이 흐르기 시작할 때의 임계각으로써， 표면에 의한 액체의 흐름각은 Wol fram에 와하여 하기 수학식 2와 같 이 정의되어진다.
[수학식 2] Experimental Example 2 Measurement of Flow Angle of Membrane Formed by Curing Antifouling Coating Composition In order to measure the antifouling property of the membrane formed by curing the antifouling agent composition comprising the compound of the present invention, the slide glass coated with the membrane of Examples 11-15 and The flow angle of the untreated slide glass of Comparative Example 3 was measured and shown in Table 3 below. In general, although the contact angle has been used as a criterion for evaluating the degree of hydrophobicity of the surface, the flow angle with respect to the surface having a high contact angle Does not always have a low value, it is not enough to measure the flow of water droplets on the surface by contact angle alone. Therefore, the measurement of the flow angle for water droplets in relation to hydrophobicity should be carried out separately from the contact angle. The flow angle is a critical angle when a droplet having a specific weight starts to flow on the inclined surface, and the flow angle of the liquid by the surface is defined as shown in Equation 2 below by adding to Wol fram. [Equation 2]
， 2r% ， 2r%
sma=A: 상온에서 30 L의 핵사데칸 솔벤트를 실시예 11 내지 15 및 비교예 3의 슬 라이드 글라스 표면에 떨어뜨려 K USS사의 DSA100을 이용하여 각각의 흐름각을 측 정하였다, sma = A: 30 L of nucleodecane solvent at room temperature was dropped on the surface of the slide glass of Examples 11 to 15 and Comparative Example 3, and the respective flow angles were measured using DSA100 manufactured by K USS.
【표 3】 Table 3
그 결과 상기 표 3에 나타낸 바와 같이 , 본 발명에―따른 실시예 11 내지 15 의 막이 코팅된 슬라이드 글라스의 경우， 흐름각이 약 12 - 14° 로 상용막인 DSX( 핵사데칸에 대한 흐름각: 15.3 。 ) 및 EGC-1720(핵사데칸에 대한 흐름각 : 19. 1 ° ) 와 비교하여 현저히 낮은 흐름각을 가지는 것을 알수 있다. 이로부터， 본 발명에 따른 실시예를 통해 합성된 과불소 에테르 변성 화합물 이 분산된 조성물이 경화되어 형성된 막이 코팅될 경우， 코팅되지 않은 경우 및 상 용막에 비해 액체에 대한 흐름각이 낮아， 본 발명의 화합물을 포함하는 코팅제 조 성물이 발수성 및 발유성이 우수한 막을 제조할 수 있는 효과가 있음을 알 수 있 다 · As a result, as shown in Table 3 above, in the case of the slide-coated slide glass of Examples 11 to 15 according to the present invention, the flow angle was about 12-14 ° and the commercial membrane was DSX (flow angle for nucleodecane: 15.3。) and EGC-1720 (flow angle for nucleodecane: 19. 1 ° ) showed a significantly lower flow angle. From this, when the film formed by curing the composition in which the perfluorinated ether modified compound dispersed through the embodiment of the present invention is cured is coated, the flow angle of the liquid is lower than that of the uncoated film and the common membrane. It can be seen that the coating composition containing the compound of has the effect of producing a film having excellent water and oil repellency.
<실험예 3> 방오성 코팅제 조성물이 경화되어 형성된 막의 오염부착방지성 평가 <Experiment 3> Evaluation of antifouling adhesion of the film formed by curing the antifouling coating composition
본 발명의 화합물을 포함하는 방오제 코팅제 조성물이 경화되어 형성된 막의 방오성을 측정하기 위해， 실시예 11 - 15의 막이 코팅된 슬라이드 글라스 및 비교 예 3의 무처리 슬라이드 글라스에 대하여 오염부착방지성 실험을 한 후， 그 결과를 하기 표 4에 나타내었다. 모니터 화면에 지문， 유성 물질 둥의 오염물이 묻으면 기 재표면에 굴절률이 다른 새로운 광학박막이 형성되어 깨끗하지 못한 화상을 제공할 뿐만 아니라 눈에 피로감을 증가시키는 결과를 초래하여 현재 거의 모든 LCD 패널 의 제품에 오염 방지 기능을 부여하고 있다. 하지만 오염 방지 정도를 평가할 수 있는 확립된 기준이 없고 이를 수치적으로 나타내는 것이 불가능하므로 욕안으로
그 효과를 평가할수 밖에 없다. 본 실험에서는 스쿠알렌에 파란색의 유성 염료 「상품명: Oi l Blue 403」 을 5 중량 % 용해시킨 것을 손가락에 적당량 부착시켜 1 kgf의 힘으로 실시예 11 내 지 15의 막이 코팅된 슬라이드 글라스 경화 피막면 및 비교예 3의 무처리 슬라이드 글라스의 표면에 5초 강압하여 더러운 성분을 부착시켰다. 또한, 시판의 네임펜 (모 나미)의 빨간색과 검은색을 이용해 실시예 11 내지 15의 슬라이드 글라스 경화 피 막면 및 비교예 3의 무처리 슬라이드 글라스의 표면에 선을 그었다. 하기 기준에 따라， 육안 검사로 부착한 더러움을 판정하였다. ' In order to measure the antifouling properties of the film formed by curing the antifouling agent coating composition comprising the compound of the present invention, an antifouling test was conducted on the slide glass coated with the membrane of Examples 11-15 and the untreated slide glass of Comparative Example 3. After that, the results are shown in Table 4 below. Fingerprints and oily contaminants on the monitor screen form a new optical film with different refractive indices on the substrate surface, which not only provides a dirty image, but also increases eye fatigue, which is why almost all LCD panels currently To prevent contamination of products. However, because there is no established standard for evaluating the degree of pollution prevention and it is impossible to represent it numerically, The effect can only be evaluated. In this experiment, 5 wt% of a blue oil dye `` trade name: Oi l Blue 403 '' dissolved in squalene was attached to an appropriate amount on a finger, and the surface of the slide glass cured film coated with the film of Examples 11 to 15 with a force of 1 kg f . And 5 seconds of pressure on the surface of the untreated slide glass of Comparative Example 3 to adhere dirty components. Lines were drawn on the surface of the slide glass cured coating films of Examples 11 to 15 and the untreated slide glass of Comparative Example 3 using red and black colors of commercially available name pens (monami). According to the following criteria, the dirt attached by visual inspection was determined. '
오염물 부착 방자성 판정 기준 Criteria for adhering to pollutants
O: 더러움이 거의 붙지 않는다. O: It's hardly dirty.
ᅀ: 약간 더러움이 붙는다. T: I get a little dirty.
： 꽤 더러움이 붙는다. : There is a pretty dirt.
【표 4】
Table 4
그 결과 상기 표 4에 나타낸 바와 같이 , 본 발명에 따른 실시예 11 내지 15 의 막이 코팅된 경우 유사지문 및 네임펜에 대하여 더러움이 거의 붙지 않음을 육 안으로 확인할 수 있으며， 반면 비교예 3의 코팅막이 형성되지 않은 경우에는 더러 움이 슬라이드 글라스에 남아있는 것을 육안으로 확인할 수 있었다. 또한， 실시예 15의 막이 코팅된 슬라이드 글라스의 경우 네임펜에 대한 부착 방지성이 다른 실시예보다 다소 떨어자는 것을 확인할 수 있었는데 , 이는 벨조페논 계 화합물의 양보다 과불소폴리에테르 화합물의 양이 과다하게 많이 사용되어， 세 개의 이소시아네이트 기에 모두 과불소 폴리에테르 화합물이 부착된 부생성물이 발 생하여 슬라이드 글라스에 코팅 및 경화시에 표면에 고착되지 않은 액상의 불순물 이 잔존하게 되어 코팅막 표면의 물성이 하락되었기 때문으로 판단된다. 이로부터 , 본 발명에 따른 실시예를 통해 합성된 과불소 에테르 변성 화합물 이 분산된 조성물이 경화되어 형성된 막이 코팅될 경우， 코팅되지 않은 경우보다 오염부착방지성이 우수함을 알 수 있으며， 본 발명의 화합물을 포함하는 코팅제 조
성물이 방오성이 우수한 막을 제조할 수 있는 효과가 있음을 알수 있다. As a result, as shown in Table 4, when the film of Examples 11 to 15 according to the present invention is coated, it can be visually confirmed that the dirt is hardly adhered to the similar fingerprint and name pen, whereas the coating film of Comparative Example 3 is formed. If not, it could be visually confirmed that the dirt remained on the slide glass. In addition, in the case of the slide glass coated with the membrane of Example 15, it was confirmed that the anti-adhesion property to the name pen was slightly lower than that of the other examples, which was higher than the amount of the perfluoropolyether compound than the amount of the belzophenone-based compound. It is widely used, and byproducts with perfluorinated polyether compounds attached to all three isocyanate groups generate liquid impurities that are not adhered to the surface during coating and curing on slide glass, resulting in deterioration of the physical properties of the coating film surface. It is judged because From this, it can be seen that when the composition formed by curing the composition of the perfluorinated ether modified compound synthesized through the embodiment according to the present invention is coated with a coating, the antifouling property is better than that without the coating. Coating bath containing compound It can be seen that the material has an effect of producing a film having excellent antifouling properties.
<실험예 4> 방오성 코팅제 조성물이 경화되어 형성된 막의 오염제거성 평가 본 발명의 화합물을 포함하는 방오제 코팅제 조성물이 경화되어 형성된 막의 방오성을 측정하기 위해， 실시예 11 - 15의 막이 코팅된 슬라이드 글라스 및 비교 예 3의 무처리 슬라이드 글라스에 대하여 오염제거성 실험을 한 후， 그 결과를 하 기 표 5에 나타내었다. 상기 실험예 3에서 부착된 지문 및 네임펜을 킴 와이프를 이용해 1 kgf의 힘 으로 5 희 왕복하여 처리된 표면의 더러움을 닦아내고. 하기 기준에 따라, 육안 검 사로 부착한 더러움을 판정하였다. <Experimental Example 4> Decontamination evaluation of the film formed by curing the antifouling coating composition composition In order to measure the antifouling property of the film formed by curing the antifouling coating composition comprising the compound of the present invention, the slide glass coated with the film of Examples 11-15 And after performing the decontamination test for the untreated slide glass of Comparative Example 3, the results are shown in Table 5 below. Wipe off the dirt on the treated surface by reciprocating 5 times with the force of 1 k gf using the Kim wipe wipe the fingerprint and name pen attached in Experimental Example 3. According to the following criteria, the dirt attached by visual inspection was determined.
오염물을 닦아내는 성질 판정 기준 Property judgment standard to wipe off pollutant
O : 더러움올 모두 닦아낼 수 있다. O: All dirts can be wiped off.
Δ : 더러움을 거의 닦아낼 수 있지만 약간자취가 남는다. Δ: The dirt can be almost wiped off, but some trace remains.
： 더러움이 남아 분명하게 자취가남는다. : A dirt remains and traces remain clearly.
【표 5】
Table 5
그 결과 상기 표 5에 나타낸 바와 같이, 본 발명에 따른 실시예 11 내지 15 의 막이 코팅된 경우 유사지문 및 네임펜에 대하여 더러움올 모두 닦아낼 수 있음 을 육안으로 확인할 수 있으며， 반면 비교예 3의 코팅막이 형성되지 않은 경우에는 더러움이 제거되지 않아 슬라이드 글라스에 더러움이 남아 분명하게 자취가 남아 있는 것을 육안으로 확인할 수 있었다. 이로부터， 본 발명에 따른 실시예를 통해 합성된 과불소 에테르 변성 화합물 이 분산된 조성물이 경화되어 형성된 막이 코팅될 경우， 코팅되지 않은 경우보다 오염이 되더라 하더라도， 오염제거성이 우수함올 알 수 있으며, 본 발명의 화합물 을 포함하는 코팅제 조성물이 방오성이 우수한 막을 제조할 수 있는 효과가 있음을 알 수 있다. As a result, as shown in Table 5, when the film of Examples 11 to 15 according to the present invention is coated, it can be visually confirmed that all dirts can be wiped off for the similar fingerprint and name pen, whereas the coating film of Comparative Example 3 If this was not formed, the dirt was not removed, and the dirt remained on the slide glass. From this, when the composition formed by curing the composition in which the perfluorinated ether modified compound dispersed through the embodiment according to the present invention is cured is coated, even if it is contaminated than uncoated, it can be seen that it is excellent in decontamination property. In addition, it can be seen that the coating composition comprising the compound of the present invention has the effect of producing a film having excellent antifouling properties.
<실험예 5>방오성 코팅제 조성물이 경화되어 형성된 막의 투과도 평가
본 발명의 화합물을 포함하는 방오제 코팅제 조성물이 경화되어 형성된 막의 투과도를 측정하기 위해， 실시예 11 - 15의 막이 코팅된 슬라이드 글라스 및 비교 예 3의 무처리 슬라이드 글라스에 대하여 투과도 평가 실험을 한 후， 그 결과를 하 기 표 6에 나타내었다. 상기 투과도 측정은 UV/Vi s spectroscopy (JASCO, V-650)을 이용하여， 공기 분위기 하에서 350 - 800nm 범위의 조건에서 측정하여 550 nm에서의 투과도 값을 값을 표 6에 나타내었다. Experimental Example 5 Evaluation of Permeability of a Membrane Formed by Curing an Antifouling Coating Composition In order to measure the permeability of the membrane formed by curing the antifouling agent composition comprising the compound of the present invention, after performing the permeability evaluation experiment for the slide glass coated with the membrane of Examples 11-15 and untreated slide glass of Comparative Example 3 ， The results are shown in Table 6 below. The transmittance measurement was measured under UV-Vis spectroscopy (JASCO, V-650) under conditions of 350-800 nm under an air atmosphere, and the transmittance values at 550 nm are shown in Table 6.
【표 6】
Table 6
그 결과 상기 표 6에 나타낸 바와 같이， 본 발명에 따른 실시예 11 내지 15 의 막이 코팅된 슬라이드 글라스의 경우 투과도가 91 - 92로, 코팅막이 형성되지 않은 비교예 3의 슬라이드 글라스 (투과도가 90)와 비교하여도, 투과도가 저하되지 않고， 오히려 더 높아졌음을 알 수 있다. 이로부터， 본 발명에 따른 실시예를 통해 합성된 과불소 에테르 변성 화합물 이 분산된 조성물이 경화되어 형성된 막은 투과도가 우수하므로， 본 발명의 화합물 을 포함하는 코팅제 조성물이 디스플레이, 광학제품 등의 코팅제로 효과적으로 사 용될 수 있음을 알 수 있다.
As a result, as shown in Table 6, in the case of the slide glass coated with the films of Examples 11 to 15 according to the present invention, the transmittance was 91 to 92, and the slide glass of Comparative Example 3 in which the coating film was not formed (permeability 90) Compared with, it is seen that the transmittance is not lowered, but rather higher. From this, the film formed by curing the composition in which the perfluorinated ether modified compound dispersed through the embodiment of the present invention is cured has excellent transmittance, and thus the coating composition including the compound of the present invention is used as a coating agent for displays, optical products, and the like. It can be seen that it can be used effectively.
Claims
[화학식 1]
[Formula 1]
(상기 화학식 1에서， „ (In Formula 1 above, „
π은 1 - 16의 정수이고, π is an integer from 1 to 16,
Α는 하기 화학식 2 내지 4중 어느 하나이고， Α is any one of the following formulas 2 to 4,
[화학식 2] . [Formula 2] .
H ί? H??
— N-C-O— —N-C-O—
(단， 화학식 2에 있어서 Ν은 (C¾)n에 연결됨) . (However, in Formula 2, Ν is connected to (C¾)n).
[화학식 3] [Formula 3]
o o
— C-0— —C-0—
(단， 화학식 3에 있어서 C는 (CH2)n에 연결됨) (However, in Formula 3, C is connected to (CH 2 )n)
[화학식 4] [Formula 4]
H H
— C-N— —C-N—
(단， 화학식 4에 있어서 C는 (C¾)n에 연결됨) (However, in Formula 4, C is connected to (C¾)n)
상기 화학식 2 내지 4에 있어서， In Formulas 2 to 4,
¾은 하기 화학식 5 내지 7중 어느 하나이고, ¾ is any one of the following formulas 5 to 7,
¾는 하기 화학식 8 내지 12 중 어느 하나이고， ¾ is any one of the following formulas 8 to 12,
¾는 하기 화학식 5 내지 7 중 어느 하나이거나 하기 화학식 8 내지 12 중 느 하나이다. ¾ is one of the following formulas 5 to 7 or one of the following formulas 8 to 12.
[화학식 5] [Formula 5]
-(CF3)CF0-[CF2(CF3)CF0]a-CF2CF2CF3 -(CF 3 )CF0-[CF 2 (CF 3 )CF0] a -CF 2 CF 2 CF3
[화학식 6] [Formula 6]
-X- [0CF2CF2 ] b-[0CF(CF3) ] c- [0CF(CF3)CF2]d- [0CF2]e-Y [화학식 7]
-CF2CF2- [0CF2CF2CF2] f-0CF2CF2CF3 -X- [0CF 2 CF 2 ] b -[0CF(CF 3 )] c - [0CF(CF 3 )CF 2 ] d - [0CF 2 ] e -Y [Formula 7] -CF 2 CF 2 - [0CF 2 CF 2 CF 2 ] f -0CF 2 CF 2 CF 3
상기 화학식 5 내지 7에 있어서， In Formulas 5 to 7,
X는 d- C5의 직쇄 또는 측쇄의 과불소알킬렌이고， X is d-C 5 linear or branched perfluoroalkylene,
Y는 d- C5의 직쇄 또는 측쇄의 과불소알킬이고， Y is d-C 5 linear or branched perfluoroalkyl,
a.b.cd.e 및 f는 각각 독립적으로 0 - 100의 정수이다. a.b.cd.e and f are each independently integers from 0 to 100.
[화학식 8] [Formula 8]
[청구항 2】 [Claim 2]
제 1항에 있어서， In clause 1,
상기 화학식 1의 A는 하기 화학식 2이고， ¾은 하기 화학식 5이고, ¾는 하 기 화학식 8이고， ¾는 하기 화학식 5 및 하기 화학식 8중 어느 하나인 것을 특징으 로 하는 고 jᅳ불소 폴리에테르 변성 화합물: A of the formula 1 is the formula 2, ¾ is the formula 5, ¾ is the formula 8, and ¾ is any one of the formula 5 and the formula 8. Denatured Compounds:
[화학식 2] [Formula 2]
H H
— -C-0—
[화학식 5] — -C-0— [Formula 5]
-(CF3)CF0-[CF2(CF3)CF0]a-CF2CF2CF3 -(CF 3 )CF0-[CF 2 (CF 3 )CF0] a -CF 2 CF 2 CF3
[화학식 8]
[Formula 8]
(상기 화학식 2에 있어서， n은 1 - 16의 정수이고， (In Formula 2, n is an integer from 1 to 16,
상기 화학식 5에 있어서， a는 0 - 100의 정수이다) . In Formula 5, a is an integer from 0 to 100).
【청구항 3】 【Claim 3】
저 U항에 있어서， In that U port,
상기 화학식 1와 A의 n은 3 - 9인 것올 특징으로 하는 과블소 폴리에테르 변 성 화합물 . A gwableso polyether-modified compound characterized in that n in Formula 1 and A is 3 to 9.
[청구항 4】 [Claim 4]
하기 반응식 1에 나타낸 바와 같이 , As shown in Scheme 1 below,
화학식 13의 화합물과 화학식 14 - 16의 화합물의 흔합물을 불화탄소계 용매 및 탄화수소계 용매의 흔합 용매하에서 반응시켜 화학식 1의 화합물을 제조하는 단 계를 포함하는 제 1항의 과불소 풀리.에테르 변성 화합물의 제조방법: Perfluorinated full-ether modification of claim 1, comprising the step of preparing a compound of Formula 1 by reacting a mixture of the compound of Formula 13 and the compound of Formulas 14 to 16 in a mixed solvent of a fluorocarbon-based solvent and a hydrocarbon-based solvent. Method for preparing the compound:
[반웅식 1]
[Banwoongsik 1]
13 13
O ,(CH2)rv—A—— B2 O ,(CH 2 )rv—A—— B 2
p- p-
B,—— A—— (CH2)n-N C=0 B,—— A—— (CH 2 )nN C=0
O (CH2)n—— A—— B3 O (CH 2 )n—— A—— B 3
1 One
(상기 반웅식 1에서， (In reaction 1 above,
n, ， B2 및 ¾는 청구항 제 1항에서 정의한 바와 같고, n, ， B 2 and ¾ are as defined in claim 1,
o o
D는 -N=C=0 및 一 G 중에서 어느 하나이고，
o D is any one of -N=C=0 and 一 G, o
E는 D가 ᅳ N=C=0인 경우 —OH이고, D가 —S— G인 경우 ᅳ OH 및 ᅳ NH2 중 어느 하나이고, G는 할로겐 원소이다. E is —OH when D is ᅳ N=C=0, and is either ᅳ OH or ᅳ NH 2 when D is —S— G, and G is a halogen element.
【청구항 5】 【Claim 5】
하기 반웅식 2에 나타낸 바와 같이ᅳ As shown in reaction equation 2 below:
화학식 13의 화합물과 화학식 14의 화합물 및 화학식 16의 화합물의 혼합물 을 불화탄소계 용매 및 탄화수소계 용매의 흔합 용매하에서 반응시켜 화학식 17의 화합물올 제조하는 단계 (단계 1) ; 및 Preparing a compound of Formula 17 by reacting a mixture of the compound of Formula 13, the compound of Formula 14, and the compound of Formula 16 in a mixed solvent of a fluorocarbon-based solvent and a hydrocarbon-based solvent (Step 1); and
화학식 17의 화합물과 화학식 15의 화합물을 불화탄소계 용매 및 탄화수소계 용매의 흔합 용매하에서 반응시켜 화학식 1의 화합물을 제조하는 단계 (단계 2) 를 포함하는 제 1항의 과불소 폴리에테르 변성 화합물의 제조방법: Preparation of the perfluorinated polyether-modified compound of claim 1, comprising the step (step 2) of preparing the compound of Formula 1 by reacting the compound of Formula 17 and the compound of Formula 15 in a mixed solvent of a fluorocarbon-based solvent and a hydrocarbon-based solvent. method:
[반응식 2] [Scheme 2]
&계 1
&Total 1
13 단계 2
13 Step 2
17 17
(상기 반응식 2에서， (In Scheme 2 above,
n , ¾ 및 B3는 청구항 제 1항에서 정의한 바와 같고， n, ¾ and B 3 are as defined in claim 1,
¾는 청구항 제 1항에서 정의한 화학식 5 내지 7중 어느 하나이고， ¾ is any one of formulas 5 to 7 defined in claim 1,
D 및 E는 청구항 제 4항에서 정의한 바와 같다) . D and E are as defined in claim 4).
【청구항 6]
하기 반웅식 3에 나타낸 바와 같이， [Claim 6] As shown in reaction equation 3 below,
화학식 13와화합물과 화학식 14의 화합물을 불화탄소계 용매 및 탄화수소계 용매의 흔합 용매하에서 반웅시켜 화학식 18의 화합물을 제조하는 단계 (단계 1) ; 화학식 18의 화합물과 화학식 15의 화합물 및 화학식 16의 화합물의 혼합물 을 불화탄소계 용매 및 탄화수소계 용매의 혼합 용매하에서 반응시켜 화학식 1의 화합물을 제조하는 단계 (단계 2) Preparing a compound of Formula 18 by reacting the compound of Formula 13 and the compound of Formula 14 in a mixed solvent of a fluorocarbon-based solvent and a hydrocarbon-based solvent (Step 1); Preparing a compound of Formula 1 by reacting a mixture of the compound of Formula 18, the compound of Formula 15, and the compound of Formula 16 in a mixed solvent of a fluorocarbon-based solvent and a hydrocarbon-based solvent (Step 2)
를 포함하는 제 1항의 과불소 폴리에테르 변성 화합물의 제조방법 : Method for producing the perfluorinated polyether modified compound of claim 1 comprising:
[반웅식 3] E 단계 1
[Reaction 3] E Stage 1
13 단계 2
13 Step 2
18 18
1 One
(상기 반응식 3에서， (In Scheme 3 above,
n , ¾ 및 ¾는 청구항 제 1항에서 정의한 바와 같고， n, ¾ and ¾ are as defined in claim 1,
¾는 청구항 제 1항에서 정의한 화학식 8 내지 12 중 어느 하나이고， ¾ is any one of formulas 8 to 12 defined in claim 1,
D 및 E는 청구항 제 4항에서 정의한 바와 같다) . D and E are as defined in claim 4).
【청구항 7】 【Claim 7】
제 1항의 과불소 폴리에테르 변성 화합물을 포함하는 것을 특징으로 하는 방 오성 코팅제 조성물. An antifouling coating composition comprising the perfluorinated polyether modified compound of claim 1.
【청구항 8】
제 7항의 방오성 코팅용 조성물이 경화되어 형성된 막. 【Claim 8】 A film formed by curing the antifouling coating composition of claim 7.
【청구항 9】 【Claim 9】
제 8항에 있어서, According to clause 8,
상기 막은 두께가 0.005 ᅳ 1 , 000 인 것을 특징으로 하는 막. 【청구항 10】 A membrane characterized in that the membrane has a thickness of 0.005 ᅳ 1,000. 【Claim 10】
기재의 표면이， 제 8항의 막으로 피복되어 있는 것을 특징으로 하는 막 부착 방오성 기재.
An antifouling substrate with a film, characterized in that the surface of the substrate is covered with the film of claim 8.
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| PCT/KR2014/000631 WO2015111765A1 (en) | 2014-01-22 | 2014-01-22 | Ultraviolet-curing perfluoropolyether-modified compound, dirt-resistant coating-agent composition comprising same, and film and dirt-resistant substrate using same |
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| EP4149758A4 (en) * | 2020-05-14 | 2024-09-11 | 3M Innovative Properties Company | Multilayer optical films comprising at least one fluorinated (co)polymer layer made using a fluorinated photoinitiator, and methods of making and using the same |
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