[go: up one dir, main page]

WO2015111765A1 - Composé modifié par perfluoropolyéther durcissant aux ultraviolets, composition d'agent de revêtement résistant à la salissure comprenant celui-ci, et film et substrat résistant à la salissure utilisant celui-ci - Google Patents

Composé modifié par perfluoropolyéther durcissant aux ultraviolets, composition d'agent de revêtement résistant à la salissure comprenant celui-ci, et film et substrat résistant à la salissure utilisant celui-ci Download PDF

Info

Publication number
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
Authority
WO
WIPO (PCT)
Prior art keywords
formula
compound
film
dirt
curing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2014/000631
Other languages
English (en)
Korean (ko)
Inventor
이수복
박인준
하종욱
이광원
장봉준
이명숙
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Korea Research Institute of Chemical Technology KRICT
Original Assignee
Korea Research Institute of Chemical Technology KRICT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Korea Research Institute of Chemical Technology KRICT filed Critical Korea Research Institute of Chemical Technology KRICT
Priority to PCT/KR2014/000631 priority Critical patent/WO2015111765A1/fr
Publication of WO2015111765A1 publication Critical patent/WO2015111765A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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
    • 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
    • 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
    • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyethers (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un composé modifié par perfluoropolyéther durcissant aux ultraviolets, une composition d'agent de revêtement résistant à la salissure comprenant celui-ci, et un film et un substrat résistant à la salissure utilisant celui-ci, et, plus spécifiquement, le composé selon la présente invention ne contient pas un groupe silane et donc, peut être utilisé dans des matériaux organiques tels que des polymères et est remarquablement compatible avec d'autres médicaments organiques et peut être utilisé dans un traitement rouleau contre rouleau, et, de plus, le composé contient un groupe perfluoropolyéther et a donc une transparence et une résistance à la salissure supérieures comprenant des propriétés antiadhésives et d'essuyage, et le composé contient un composé à base de benzophénone et peut donc être soumis à un durcissement par ultraviolet sans nécessiter un initiateur de radical quelconque et donc, un film formé par durcissement d'une composition d'agent de revêtement comprenant le composé peut être chimiquement lié à tous les matériaux de substrat constitué de composés à base d'hydrocarbures de sorte que l'invention présente l'avantage d'une résistance à la salissure, une résistance à la rayure et une durabilité améliorées et peut donc être utilisée avantageusement dans des substrats dans tous les domaines industriels dans lesquels une résistance à la salissure doit être conférée.
PCT/KR2014/000631 2014-01-22 2014-01-22 Composé modifié par perfluoropolyéther durcissant aux ultraviolets, composition d'agent de revêtement résistant à la salissure comprenant celui-ci, et film et substrat résistant à la salissure utilisant celui-ci Ceased WO2015111765A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/KR2014/000631 WO2015111765A1 (fr) 2014-01-22 2014-01-22 Composé modifié par perfluoropolyéther durcissant aux ultraviolets, composition d'agent de revêtement résistant à la salissure comprenant celui-ci, et film et substrat résistant à la salissure utilisant celui-ci

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/KR2014/000631 WO2015111765A1 (fr) 2014-01-22 2014-01-22 Composé modifié par perfluoropolyéther durcissant aux ultraviolets, composition d'agent de revêtement résistant à la salissure comprenant celui-ci, et film et substrat résistant à la salissure utilisant celui-ci

Publications (1)

Publication Number Publication Date
WO2015111765A1 true WO2015111765A1 (fr) 2015-07-30

Family

ID=53681558

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2014/000631 Ceased WO2015111765A1 (fr) 2014-01-22 2014-01-22 Composé modifié par perfluoropolyéther durcissant aux ultraviolets, composition d'agent de revêtement résistant à la salissure comprenant celui-ci, et film et substrat résistant à la salissure utilisant celui-ci

Country Status (1)

Country Link
WO (1) WO2015111765A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10858478B2 (en) * 2015-08-31 2020-12-08 Daikin Industries, Ltd. Perfluoro(poly)ether group containing silane compound
US20230129152A1 (en) * 2020-05-14 2023-04-27 3M Innovative Properties Company Compounds Comprising Perfluorinated Group, Photoinitiator Group, and Amide Linking Group
EP4149758A4 (fr) * 2020-05-14 2024-09-11 3M Innovative Properties Company Films optiques multicouches comprenant au moins une couche de (co)polymère fluoré préparer à l'aide d'un photo-initiateur fluoré, et leurs procédés de préparation et d'utilisation

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100947710B1 (ko) * 2002-02-04 2010-03-16 이 아이 듀폰 디 네모아 앤드 캄파니 할로겐화된 광학적 중합체 조성물
KR20110072931A (ko) * 2009-12-23 2011-06-29 한국화학연구원 자외선 경화형 과불소 폴리에테르 변성 화합물과 이를 함유한 방오성 코팅제 조성물 및 이를 적용한 막
KR101161643B1 (ko) * 2010-06-14 2012-07-03 한국화학연구원 방오성 과불소 폴리에테르 변성 화합물과 이를 포함한 코팅제 조성물 및 이를 적용한 막
KR20120118208A (ko) * 2011-04-18 2012-10-26 한국화학연구원 접착성이 향상된 자외선 경화 불소계 공중합체와 이를 포함하는 코팅조성물 및 이를 포함하는 막
KR20140002704A (ko) * 2010-12-22 2014-01-08 미쯔비시 레이온 가부시끼가이샤 전사 필름 및 그의 제조방법 및 적층체 및 그의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100947710B1 (ko) * 2002-02-04 2010-03-16 이 아이 듀폰 디 네모아 앤드 캄파니 할로겐화된 광학적 중합체 조성물
KR20110072931A (ko) * 2009-12-23 2011-06-29 한국화학연구원 자외선 경화형 과불소 폴리에테르 변성 화합물과 이를 함유한 방오성 코팅제 조성물 및 이를 적용한 막
KR101161643B1 (ko) * 2010-06-14 2012-07-03 한국화학연구원 방오성 과불소 폴리에테르 변성 화합물과 이를 포함한 코팅제 조성물 및 이를 적용한 막
KR20140002704A (ko) * 2010-12-22 2014-01-08 미쯔비시 레이온 가부시끼가이샤 전사 필름 및 그의 제조방법 및 적층체 및 그의 제조방법
KR20120118208A (ko) * 2011-04-18 2012-10-26 한국화학연구원 접착성이 향상된 자외선 경화 불소계 공중합체와 이를 포함하는 코팅조성물 및 이를 포함하는 막

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10858478B2 (en) * 2015-08-31 2020-12-08 Daikin Industries, Ltd. Perfluoro(poly)ether group containing silane compound
US20230129152A1 (en) * 2020-05-14 2023-04-27 3M Innovative Properties Company Compounds Comprising Perfluorinated Group, Photoinitiator Group, and Amide Linking Group
JP2023525329A (ja) * 2020-05-14 2023-06-15 スリーエム イノベイティブ プロパティズ カンパニー 全フッ素化基、光開始剤基、及びアミド連結基を含む化合物
EP4149758A4 (fr) * 2020-05-14 2024-09-11 3M Innovative Properties Company Films optiques multicouches comprenant au moins une couche de (co)polymère fluoré préparer à l'aide d'un photo-initiateur fluoré, et leurs procédés de préparation et d'utilisation
US12247001B2 (en) * 2020-05-14 2025-03-11 3M Innovative Properties Company Compounds comprising perfluorinated group, photoinitiator group, and amide linking group
JP7792918B2 (ja) 2020-05-14 2025-12-26 スリーエム イノベイティブ プロパティズ カンパニー 全フッ素化基、光開始剤基、及びアミド連結基を含む化合物
US12517285B2 (en) 2020-05-14 2026-01-06 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

Similar Documents

Publication Publication Date Title
KR100940086B1 (ko) 과불소 폴리에테르 변성 실란 화합물과 이를 함유한 방오성 코팅제 조성물 및 이를 적용한 막
CN111051052B (zh) 具有多层结构的硬涂膜和包括该硬涂膜的聚酰亚胺膜
JP5938280B2 (ja) パーフルオロポリエーテル変性シラン化合物、防汚性被膜形成用組成物、防汚性被膜、およびこの被膜を有する物品
CN103998546B (zh) 具有润滑添加剂的氟化涂料
KR101436018B1 (ko) 과불소 폴리에테르 변성 화합물을 포함하는 방오성 광경화 수지 조성물 및 이를 이용한 하드코트용 방오성 투명 박막
TW201706331A (zh) 含氟聚醚之聚合物改質矽烷、表面處理劑及經處理物件
CN113912834B (zh) 一种全氟聚醚硅氧烷产品的制备方法及其在防指纹涂料和防指纹涂层中的应用
CN103773202A (zh) 涂覆剂组合物、包含该组合物的表面处理剂和利用该表面处理剂表面处理后的物品
CN110945072A (zh) 含氟共聚物组合物
KR101335524B1 (ko) 접착성이 향상된 자외선 경화 불소계 공중합체와 이를 포함하는 코팅조성물 및 이를 포함하는 막
KR101161643B1 (ko) 방오성 과불소 폴리에테르 변성 화합물과 이를 포함한 코팅제 조성물 및 이를 적용한 막
TWI874549B (zh) 具有烷氧矽烷基之全氟聚醚化合物，及含其之組成物
WO2015111765A1 (fr) Composé modifié par perfluoropolyéther durcissant aux ultraviolets, composition d'agent de revêtement résistant à la salissure comprenant celui-ci, et film et substrat résistant à la salissure utilisant celui-ci
JP6319905B2 (ja) 被膜形成用組成物及びその製造方法、並びに被膜
KR101422728B1 (ko) 자외선 경화 과불소 폴리에테르 변성 화합물, 이를 포함하는 방오성 코팅제 조성물, 이를 적용한 막 및 방오성 기재
KR101085050B1 (ko) 자외선 경화형 과불소 폴리에테르 변성 화합물과 이를 함유한 방오성 코팅제 조성물 및 이를 적용한 막
KR20140003120A (ko) 자외선 경화 불소계 공중합체, 이를 포함하는 코팅조성물 및 이를 포함하는 막
JP6694718B2 (ja) 親水撥油性回復剤及び親水撥油性被膜の親水撥油性の回復方法、並びに親水撥油性被膜
TW202111038A (zh) 樹脂基材的硬塗覆形成用組成物及使用該組成物的積層體
KR102561788B1 (ko) 과불소폴리에테르-벤조페논 화합물, 이를 포함하는 반사방지 코팅 첨가제 및 코팅 조성물
KR20170119331A (ko) 불소 함유 알콕시 실란 화합물 합성방법, 이에 따라 합성된 불소 함유 알콕시 실란 화합물 및 이를 포함하는 표면 코팅제
KR102776228B1 (ko) 코팅용 수지 조성물 및 코팅필름
KR101219517B1 (ko) 저굴절률 및 방오성 투명 코팅을 위한 혼합물 및 이를 포함하는 조성물
EP4650412A1 (fr) Modificateur de surface
KR20220010452A (ko) 플루오로폴리에테르 변성 아미드실란 화합물, 표면처리제 조성물, 및 물품

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14879800

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14879800

Country of ref document: EP

Kind code of ref document: A1