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WO2013058335A1 - Composition contenant du fluor et ses applications - Google Patents

Composition contenant du fluor et ses applications Download PDF

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Publication number
WO2013058335A1
WO2013058335A1 PCT/JP2012/076993 JP2012076993W WO2013058335A1 WO 2013058335 A1 WO2013058335 A1 WO 2013058335A1 JP 2012076993 W JP2012076993 W JP 2012076993W WO 2013058335 A1 WO2013058335 A1 WO 2013058335A1
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Prior art keywords
fluorine
group
atom
carbon atoms
hydrogen atom
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PCT/JP2012/076993
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English (en)
Japanese (ja)
Inventor
浩治 久保田
三木　淳
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ダイキン工業株式会社
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Publication of WO2013058335A1 publication Critical patent/WO2013058335A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/62—Halogen-containing esters
    • C07C69/65—Halogen-containing esters of unsaturated acids
    • C07C69/653—Acrylic acid esters; Methacrylic acid esters; Haloacrylic acid esters; Halomethacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/22—Esters containing halogen
    • C08F120/24—Esters containing halogen containing perhaloalkyl radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • D06M15/295—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids

Definitions

  • the present invention relates to a fluorine-containing composition and its use.
  • the fluorine-containing composition can be favorably used as a surface treatment agent, for example, a water / oil repellent, an antifouling agent and a release agent.
  • the fluorine-containing compound has an advantage of excellent properties such as heat resistance, oxidation resistance, and weather resistance.
  • the fluorine-containing compound is used as, for example, a water / oil repellent and an antifouling agent by utilizing the characteristic that the free energy of the fluorine-containing compound is low, that is, it is difficult to adhere.
  • US Pat. No. 5,247,008 discloses an aqueous copolymer of a perfluoroalkyl ester of (meth) acrylic acid, an alkyl ester of (meth) acrylic acid, and an aminoalkyl ester of (meth) acrylic acid. Finishing agents for textiles, leather, paper and mineral substrates, which are dispersions, are described.
  • the surface function as a water / oil repellent and antifouling agent is composed of a fluorine-containing monomer having a perfluoroalkyl group having 8 or more carbon atoms in which the perfluoroalkyl group is stably oriented on the surface.
  • Polymers or copolymers have been considered effective.
  • the decomposition product of a fluorine-containing monomer having a perfluoroalkyl group having 8 or more carbon atoms is a compound having a high environmental load.
  • One object of the present invention is to use it as a fluorine-containing monomer that gives sufficient performance required as a water / oil repellent, antifouling agent or mold release agent even for a perfluoroalkyl group having 6 or less carbon atoms.
  • An object of the present invention is to provide a fluorine-containing compound.
  • Other objects of the present invention include performance required as a surface treatment agent, such as water / oil repellency, antifouling properties, mold release properties, adhesion to substrates, corrosion resistance, texture, water resistance, oil resistance, and the like.
  • a fluorine-containing composition having durability in performance is provided.
  • the present invention provides a fluorine-containing polymer having a repeating unit derived from the fluorine-containing compound (fluorine-containing monomer).
  • the present invention provides a fluorine-containing composition comprising the fluorine-containing polymer.
  • the fluorine-containing composition has performance required as a surface treatment agent, for example, good water and oil repellency, antifouling properties, release properties, adhesion to substrates, corrosion resistance, texture, water resistance, oil resistance, these Durable performance.
  • the fluorine-containing composition can be used as a surface treatment agent (for example, a water / oil repellent, an antifouling agent and a release agent).
  • the fluorine-containing composition contains a fluorine-containing polymer.
  • the fluorine-containing polymer has a repeating unit derived from a fluorine-containing monomer.
  • the fluorine-containing monomer (a) is used as a monomer constituting the fluorine-containing polymer. If necessary, a non-fluorine non-crosslinkable monomer (b) and / or a non-fluorine crosslinkable monomer (c) may be used.
  • the fluorine-containing polymer is a polymer composed of only the fluorine-containing monomer (a) (that is, a homopolymer or a copolymer composed of two or more kinds of fluorine-containing monomers (a)), or a fluorine-containing monomer. It may be a copolymer comprising a non-fluorine non-crosslinkable monomer (b) and / or a non-fluorine crosslinkable monomer (c) in addition to the monomer (a).
  • the ⁇ position (of acrylate or methacrylate) may be substituted with a halogen atom or the like.
  • X is a linear or branched alkyl group having 2 to 21 carbon atoms, fluorine atom, chlorine atom, bromine atom, iodine atom, CFX 1 X 2 group (provided that , X 1 and X 2 are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or non-substituted It may be a substituted benzyl group or a substituted or unsubstituted phenyl group.
  • Specific examples of X include H, Me (methyl group), Cl, Br, I, F, CN
  • the aliphatic group is preferably an alkylene group (particularly having 1 to 4, for example, 1 or 2 carbon atoms).
  • the aromatic group, araliphatic group or cycloaliphatic group may be substituted or unsubstituted.
  • Z are direct bonds, A linear alkylene group having 1 to 20 carbon atoms or a branched alkylene group, for example, a group represented by the formula — (CH 2 ) x — (wherein x is 1 to 10, particularly 2 to 8); Or A group represented by the formula —Ar—CH 2 — (wherein Ar is an arylene group optionally having a substituent), or -CH 2 CH 2 N (R 1 ) SO 2 -group (where R 1 is an alkyl group having 1 to 4 carbon atoms), or A group represented by the formula —CH 2 CH (OR 3 ) CH 2 — (wherein R 3 represents a hydrogen atom or an acyl group having 1 to 10 carbon atoms (eg, formyl or acetyl)); For example, a —CH 2 CH (OZ 1 ) CH 2 — group (wherein Z 1 is a hydrogen atom or an acetyl group), or a formula —Ar—CH 2 — (wherein
  • the Rf group is preferably a perfluoroalkyl group.
  • the number of carbon atoms in the Rf group is preferably 1 to 12, for example 1 to 6, particularly 4 to 6.
  • Rf groups are -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF (CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF (CF 3 ).
  • the — (CL (CF 3 ) —CH 2 ) a — group is preferably derived from CL (CF 3 ) ⁇ CH 2 (L is as defined above).
  • a may be an integer of 1 to 20, for example, an integer of 2 to 10.
  • fluorine-containing monomer (a) include, for example, the following, but are not limited thereto.
  • the fluorine-containing monomer includes an iodine transfer reaction product of I—Rf and CL (CF 3 ) ⁇ CH 2 (L is as defined above), CH 2 ⁇ C (—X) —C ( ⁇ O) — It can be synthesized by a reaction with YZ 1 (X and Y are as defined above.
  • Z 1 is a monovalent organic group or a hydrogen atom).
  • Non-fluorine non-crosslinkable monomer The non-fluorine non-crosslinkable monomer (b) is a monomer containing no fluorine atom. The non-fluorine non-crosslinkable monomer (b) does not have a crosslinkable functional group. The non-fluorine non-crosslinkable monomer (b) is non-crosslinkable unlike the crosslinkable monomer (c). The non-fluorine non-crosslinkable monomer (b) is preferably a non-fluorine monomer having a carbon-carbon double bond. The non-fluorine non-crosslinkable monomer (b) is preferably a vinyl monomer containing no fluorine. The non-fluorine non-crosslinkable monomer (b) is generally a compound having one carbon-carbon double bond.
  • linear or cyclic hydrocarbon group having 1 to 22 carbon atoms examples include a linear or branched aliphatic hydrocarbon group having 1 to 22 carbon atoms, a cyclic aliphatic group having 4 to 22 carbon atoms, and 6 to 6 carbon atoms. 22 aromatic hydrocarbon groups and aromatic aliphatic hydrocarbon groups having 7 to 22 carbon atoms.
  • non-fluorine non-crosslinkable monomer (b) examples include, for example, vinyl halides such as ethylene and vinyl chloride, vinylidene halides such as vinylidene chloride, vinyl acetate, acrylonitrile, styrene, and polyethylene glycol (meth) acrylate. , Polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, carboxylic acid vinyl ester, and vinyl alkyl ether.
  • the carboxylic acid vinyl ester is CH 2 ⁇ CHO—C ( ⁇ O) R 0 , wherein R 0 is an aliphatic, aromatic, alicyclic or araliphatic hydrocarbon group having 1 to 22 carbon atoms.
  • R 0 is an aliphatic, aromatic, alicyclic or araliphatic hydrocarbon group having 1 to 22 carbon atoms.
  • specific examples of the carboxylic acid vinyl ester include vinyl cyclohexanecarboxylate, vinyl benzoate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl hexanoate, and vinyl 2-ethylhexanoate.
  • the non-fluorine non-crosslinkable monomer (b) is not limited to these examples.
  • the non-fluorine non-crosslinkable monomer (b) may be a (meth) acrylate ester having an alkyl group.
  • the number of carbon atoms in the alkyl group may be 1-30, for example, 6-30 (eg 10-30).
  • the non-fluorine non-crosslinkable monomer (b) may be a (meth) acrylate monomer having a cyclic hydrocarbon group.
  • the (meth) acrylate monomer having a cyclic hydrocarbon group is a compound having a (preferably monovalent) cyclic hydrocarbon group and a monovalent (meth) acrylate group.
  • the monovalent cyclic hydrocarbon group and the monovalent (meth) acrylate group are directly bonded.
  • Examples of the cyclic hydrocarbon group include saturated or unsaturated monocyclic groups, polycyclic groups, and bridged cyclic groups.
  • the cyclic hydrocarbon group is preferably saturated.
  • the carbon number of the cyclic hydrocarbon group is preferably 4-20.
  • Examples of the cyclic hydrocarbon group include a cyclic aliphatic group having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an araliphatic group having 7 to 20 carbon atoms.
  • the number of carbon atoms of the cyclic hydrocarbon group is particularly preferably 15 or less, for example 10 or less. It is preferred that the carbon atom in the ring of the cyclic hydrocarbon group is directly bonded to the ester group in the (meth) acrylate group.
  • the cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group.
  • cyclic hydrocarbon group examples include a cyclohexyl group, a t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, and a dicyclopentenyl group.
  • the (meth) acrylate group is an acrylate group or a methacrylate group, but is preferably a methacrylate group.
  • the monomer having a cyclic hydrocarbon group examples include cyclohexyl methacrylate, t-butylcyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate, isobornyl acrylate, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, And cyclopentenyl acrylate.
  • the fluorine-containing polymer of the present invention may have a repeating unit derived from the non-fluorine crosslinkable monomer (c).
  • the non-fluorine crosslinkable monomer (c) is a monomer containing no fluorine atom.
  • the non-fluorine crosslinkable monomer (c) may be a compound having at least two reactive groups and / or carbon-carbon double bonds and not containing fluorine.
  • the non-fluorine crosslinkable monomer (c) may be a compound having at least two carbon-carbon double bonds, or a compound having at least one carbon-carbon double bond and at least one reactive group.
  • the non-fluorine crosslinkable monomer (c) may be mono (meth) acrylate, (meth) diacrylate or mono (meth) acrylamide having a reactive group.
  • the non-fluorine crosslinkable monomer (c) may be di (meth) acrylate.
  • One example of the non-fluorine crosslinkable monomer (c) is a vinyl monomer having a hydroxyl group.
  • non-fluorine crosslinkable monomer (c) examples include diacetone (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and 3-chloro-2-hydroxy.
  • “(meth) acrylate” means acrylate or methacrylate
  • “(meth) acrylamide” means acrylamide or methacrylamide.
  • the amount of the non-fluorine non-crosslinkable monomer (b) is 1000 parts by weight or less, for example, 0.1 to 300 parts by weight, particularly 1 to 200 parts by weight,
  • the amount of the non-fluorine crosslinkable monomer (c) may be 50 parts by weight or less, for example, 30 parts by weight or less, particularly 0.1 to 20 parts by weight.
  • the number average molecular weight (Mn) of the fluoropolymer may generally be from 1,000 to 1,000,000, for example from 5,000 to 500,000, especially from 3,000 to 200,000.
  • the number average molecular weight (Mn) of the fluoropolymer is generally measured by GPC (gel permeation chromatography).
  • the fluoropolymer in the present invention can be produced by any ordinary polymerization method, and the conditions for the polymerization reaction can be arbitrarily selected.
  • Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization.
  • a method is adopted in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and is purged with nitrogen as necessary, followed by heating and stirring in the range of 30 to 120 ° C. for 1 to 10 hours.
  • the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. Can be mentioned.
  • the polymerization initiator is used in the range of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.
  • organic solvent examples include those which are inert to the monomer and dissolve them, such as acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, Tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichloro And trifluoroethane.
  • the organic solvent is used in the range of 50 to 2000 parts by weight, for example, 50 to 1000 parts by weight with respect to 100 parts by weight of the total mono
  • emulsion polymerization a method is adopted in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and is purged with nitrogen if necessary, and stirred and copolymerized in the range of 50 to 80 ° C. for 1 to 10 hours. Is done.
  • Polymerization initiators include benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azo Water-soluble materials such as bisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide Oil-soluble ones such as t-butyl peroxypivalate and diisopropyl peroxydicarbonate are used.
  • the polymerization initiator is used in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.
  • the monomer is finely divided into water using an emulsifier that can impart strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer. It is desirable to polymerize using a soluble polymerization initiator.
  • an emulsifier various anionic, cationic or nonionic emulsifiers can be used, and the emulsifier is used in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the monomer. Preference is given to using anionic and / or nonionic and / or cationic emulsifiers.
  • a compatibilizing agent such as a water-soluble organic solvent or a low molecular weight monomer that is sufficiently compatible with these monomers.
  • water-soluble organic solvent examples include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol and the like, and 1 to 50 parts by weight with respect to 100 parts by weight of water.
  • the low molecular weight monomer examples include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., and 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of monomers.
  • it may be used in the range of 10 to 40 parts by weight.
  • the fluoropolymer can be used for surface treatment of various substrates such as fibers.
  • the fluoropolymer can be applied to a fibrous substrate (eg, a fiber product, etc.) by any of the known methods for treating a fiber product with a liquid.
  • the concentration of the fluorosilicone reaction product in the solution applied to the textile product may be, for example, 0.5 wt% to 20 wt%, alternatively 1 wt% to 5 wt%.
  • the textile product is a fabric
  • the fabric may be immersed in the solution, or the solution may be attached or sprayed onto the fabric.
  • the treated fiber product is dried and preferably heated at, for example, 100 ° C. to 200 ° C. in order to develop oil repellency.
  • the fluoropolymer may be applied to the fiber product by a cleaning method, and may be applied to the fiber product in, for example, a laundry application or a dry cleaning method.
  • the textile products to be treated are typically fabrics, which include woven, knitted and non-woven fabrics, fabrics and carpets in clothing form, but fibers or yarns or intermediate fiber products (eg sliver or It may be a roving yarn).
  • the textile product material may be natural fibers (such as cotton or wool), chemical fibers (such as viscose rayon or rheocell), or synthetic fibers (such as polyester, polyamide or acrylic fibers), or May be a mixture of fibers, such as a mixture of natural and synthetic fibers.
  • the production polymer of the present invention is particularly effective in making cellulosic fibers (such as cotton or rayon) oleophobic and oleophobic.
  • the method of the present invention also generally makes the textile product hydrophobic and water repellent.
  • the fibrous base material may be leather.
  • aqueous solutions or aqueous emulsifications at various stages of leather processing, for example during the wet processing of leather or during the finishing of leather You may apply it to leather from things.
  • the fibrous substrate may be paper.
  • the production polymer may be applied to preformed paper or may be applied at various stages of papermaking, for example during the drying period of the paper.
  • the fluorine-containing composition of the present invention is preferably in the form of a solution, an emulsion (particularly an aqueous emulsion) or an aerosol.
  • the fluorine-containing composition comprises a fluorine-containing polymer (active component of the surface treatment agent) and a medium (in particular, a liquid medium such as an organic solvent and / or water).
  • the amount of the medium may be, for example, 5 to 99.9% by weight, particularly 10 to 80% by weight, based on the fluorine-containing composition.
  • the concentration of the fluorine-containing polymer may be 0.01 to 95% by weight, for example, 5 to 50% by weight.
  • the fluorine-containing composition of the present invention can be applied to an object to be processed by a conventionally known method.
  • the fluorine-containing composition is dispersed in an organic solvent or water, diluted, and attached to the surface of an object to be treated by a known method such as dip coating, spray coating, foam coating, etc., and then dried. Taken. Further, if necessary, it may be applied together with an appropriate crosslinking agent and cured.
  • insecticides, softeners, antibacterial agents, flame retardants, antistatic agents, paint fixing agents, anti-wrinkle agents, and the like can be added to the fluorine-containing composition of the present invention.
  • the concentration of the fluoropolymer in the treatment liquid brought into contact with the substrate may be 0.01 to 10% by weight (particularly in the case of dip coating), for example 0.05 to 10% by weight.
  • Examples of objects to be treated with the fluorine-containing composition (for example, water and oil repellent) of the present invention include textile products, stone materials, filters (for example, electrostatic filters), dust masks, and fuel cell components (for example, gas). Diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, plasters and the like.
  • Various examples can be given as textile products.
  • natural animal and vegetable fibers such as cotton, hemp, wool, and silk
  • synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene
  • semi-synthetic fibers such as rayon and acetate, glass fibers, and carbon fibers
  • Inorganic fibers such as asbestos fibers, or mixed fibers thereof.
  • the fiber product may be in the form of a fiber, cloth or the like.
  • the carpet When the carpet is treated with the fluorine-containing composition of the present invention, the carpet may be formed after the fibers or yarns are treated with the fluorine-containing composition, or the formed carpet is treated with the fluorine-containing composition. Also good.
  • the fluorine-containing composition of the present invention can also be used as an internal release agent or an external release agent.
  • “Processing” means applying a treatment agent to an object to be treated by dipping, spraying, coating, or the like. By the treatment, the fluoropolymer which is an active ingredient of the treatment agent penetrates into the treatment object and / or adheres to the surface of the treatment object.
  • Water and oil repellency As a water / oil repellency evaluation of a fluoropolymer, the dynamic contact angle of water droplets (surface tension 72 mN / m) and n-hexadecane droplets (surface tension 27 mN / m, hereinafter abbreviated as HD) was measured as follows. did. As an index of the dynamic contact angle, the falling angle (deg) and the hysteresis (deg) representing the difference between the advancing contact angle and the receding contact angle were measured and evaluated. That is, the fluoropolymer was made into a 1% solution in an organic solvent, applied to a glass substrate by a spin coating method (2000 rpm), and then dried to form a film.
  • a spin coating method 2000 rpm
  • the dynamic contact angle of 20 ⁇ l of water droplet or 5 ⁇ l of HD droplet was measured.
  • the measurement is performed at a temperature of 15 to 20 ° C. and a relative humidity of 50 to 70%. The smaller the falling angle and the smaller the hysteresis, the better the water / oil repellency.
  • Shower water repellency was measured according to JIS-L-1092 water repellency No. (See Table 1 below).
  • Water repellency test Store the treated test cloth in a constant temperature and humidity machine at a temperature of 21 ° C. and a humidity of 65% for 4 hours or more.
  • a test solution isopropyl alcohol (hereinafter abbreviated as IPA), water, and a mixture thereof, as shown in Table 2) also stored at a temperature of 21 ° C. is used.
  • the test is performed in a constant temperature and humidity chamber at a temperature of 21 ° C. and a humidity of 65%.
  • IPA isopropyl alcohol
  • Oil repellency test Store the treated test cloth in a constant temperature and humidity machine at a temperature of 21 ° C. and a humidity of 65% for 4 hours or more. A test solution (shown in Table 3) also stored at a temperature of 21 ° C. is used. The test is performed in a constant temperature and humidity chamber at a temperature of 21 ° C. and a humidity of 65%. When 0.05 ml is gently dropped on the test cloth and left to stand for 30 seconds, if the liquid remains on the test cloth, the test liquid is passed. The oil repellency is the highest score of the passed test solution, and evaluated from 9 grades of Fail, 1, 2, 3, 4, 5, 6, 7, and 8 from a poor oil repellency to a good level.
  • the iodine transfer reaction product I- (CF (CF 3 ) —CH 2 ) 2 — (CF 2 ) 6 F 30 g (0.045 mol) obtained above was placed in a 300 ml autoclave, and the system was replaced with nitrogen. The oxygen was removed.
  • 1.9 g (0.068 mol) of ethylene and 0.7 g of t-butyl peroxypivalate were added, the temperature was gradually raised, and an iodine transfer reaction was carried out at 60 ° C. for 10 hours.
  • the obtained iodine transfer reaction product was identified by gas chromatography, 1 H-NMR, 19 F-NMR, and 13 C-NMR analysis.
  • Example 7 The fluoropolymer obtained in Example 1 was made into a 1% solution in HCFC225 solvent, applied to a glass substrate by spin coating (2000 rpm), and then vacuum-dried at room temperature for 48 hours to form a film.
  • Table 4 shows the results of measuring the falling angle and hysteresis of water drops
  • Table 5 shows the results of measuring the falling angle and hysteresis of HD drops.
  • Example 8 A film was formed by repeating the same procedure as in Example 7 except that the fluoropolymer obtained in Example 2 was used.
  • Table 4 shows the results of measuring the falling angle and hysteresis of water drops
  • Table 5 shows the results of measuring the falling angle and hysteresis of HD drops.
  • Example 9 A film was formed by repeating the same procedure as in Example 7 except that the fluoropolymer obtained in Example 3 was used.
  • Table 4 shows the results of measuring the falling angle and hysteresis of water drops
  • Table 5 shows the results of measuring the falling angle and hysteresis of HD drops.
  • Example 10 A film was formed by repeating the same procedure as in Example 7 except that the fluoropolymer obtained in Example 4 was used. Table 4 shows the results of measuring the falling angle and hysteresis of water drops, and Table 5 shows the results of measuring the falling angle and hysteresis of HD drops.
  • Example 11 A film was formed by repeating the same procedure as in Example 7 except that the fluoropolymer obtained in Example 5 was used.
  • Table 4 shows the results of measuring the falling angle and hysteresis of water drops
  • Table 5 shows the results of measuring the falling angle and hysteresis of HD drops.
  • Example 12 A film was formed by repeating the same procedure as in Example 7 except that the fluoropolymer obtained in Example 6 was used.
  • Table 4 shows the results of measuring the falling angle and hysteresis of water drops
  • Table 5 shows the results of measuring the falling angle and hysteresis of HD drops.
  • Comparative Example 3 A film was formed by repeating the same procedure as in Example 7 except that the fluoropolymer obtained in Comparative Example 1 was used.
  • Table 4 shows the results of measuring the falling angle and hysteresis of water drops
  • Table 5 shows the results of measuring the falling angle and hysteresis of HD drops.
  • Comparative Example 4 A film was formed by repeating the same procedure as in Example 7 except that the fluoropolymer obtained in Comparative Example 2 was used. Table 4 shows the results of measuring the falling angle and hysteresis of water drops, and Table 5 shows the results of measuring the falling angle and hysteresis of HD drops.
  • fluorine-containing monomer CH 2 CH—COO—CH 2 CH 2 — (CF (CF 3 ) —CH 2 ) 2 — (CF 2 ) 6 F 150 g (0.232 mol), stearyl acrylate 75. 0 g (0.231 mol), 3-chloro-2-hydroxypropyl methacrylate 3.0 g (0.017 mol), pure water 300 g, tripropylene glycol 80 g, acetic acid 0.45 g, octadecyltrimethylammonium chloride 6 g, polyethylene glycol lauryl ether 9 g And emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring.
  • stearyl acrylate was changed to 87.9 g (0.231 mol) of behenyl acrylate to obtain a 20% aqueous dispersion of the fluorine-containing copolymer of the present invention.
  • Comparative Example 6 The same procedure as in Example 13 was repeated except that the fluorine-containing monomer was changed to 150 g (0.347 mol) of CH 2 ⁇ C (CH 3 ) —COO—CH 2 —CH 2 — (CF 2 ) 6 F. A 20% aqueous dispersion of the fluorinated copolymer was obtained.
  • Example 15 1.0 g of the aqueous dispersion of the fluorine-containing copolymer obtained in Example 13 and 0.3 g of NICCA Assist V2 (MDI-based blocked isocyanate, Nikka Chemical Co., Ltd.) were diluted with 98.7 g of water, A treatment solution was obtained.
  • a Polyester cloth taffeta, 25 cm ⁇ 25 cm
  • a T / C blended cloth Polyyester 65 / Cotton 35, Broad, 25 cm ⁇ 25 cm
  • the fabric was completely dried by drying at 120 ° C. for 3 minutes and further heat treating at 160 ° C.
  • Table 6 shows the results of the shower water repellency test, the water repellency test, and the oil repellency test on the obtained fabric.
  • the treated fabric is washed according to the AATCC method at a bath temperature of 40 ° C. in a normal condition with a washing time of 12 minutes (not including the time for rinsing), and tumbler-dried. This was set as one cycle, and the treated water repellency test, water repellency test, and oil repellency test were also performed on the treated cloths that were subjected to this cycle repeatedly. The results are shown in Table 6.
  • Example 16 The cloth was treated by repeating the same procedure as in Example 15 except that the aqueous dispersion of the fluorine-containing copolymer obtained in Example 14 was used. Table 6 shows the results of the shower water repellency test, the water repellency test, and the oil repellency test including the washing durability of the obtained fabric.
  • Comparative Example 7 The fabric was treated by repeating the same procedure as in Example 15 except that the aqueous dispersion of the fluorinated copolymer obtained in Comparative Example 5 was used. Table 6 shows the results of the shower water repellency test, the water repellency test, and the oil repellency test including the washing durability of the obtained fabric.
  • Comparative Example 8 The cloth was treated by repeating the same procedure as in Example 15 except that the aqueous dispersion of the fluorine-containing copolymer obtained in Comparative Example 6 was used. Table 6 shows the results of the shower water repellency test, the water repellency test, and the oil repellency test including the washing durability of the obtained fabric.
  • the fluoropolymer of the present invention has low measured values for the falling angle and hysteresis.
  • the small falling angle and hysteresis indicate that the environmental responsiveness to water droplets and HD droplets is small, indicating that the fluoropolymer of the present invention is excellent in water and oil repellency.
  • Table 6 also shows that the water- and oil-repellency of the fluorine-containing copolymer of the present invention is excellent even in the use of water- and oil-repellent agents for fibers.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Textile Engineering (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition contenant du fluor comprenant un polymère contenant du fluor comportant un motif répété issu d'un monomère contenant du fluor représenté par la formule (a) : CH2=C(-X)-C(=O)-Y-Z-(CL(CF3)-CH2)a-Rf (dans cette formule, X représente un atome d'hydrogène, un groupe organique monovalent ou un atome d'halogène ; Y représente -O- ou -NH- ; Z représente une liaison directe ou un groupe organique divalent ; Rf représente un groupe fluoroalkyle comportant de 1 à 20 atomes de carbone ; L représente un atome de fluor, un atome de chlore ou un atome d'hydrogène ; et a représente un nombre entier de 1 à 50.) Ladite composition contenant du fluor présente les propriétés requises d'un agent de traitement de surface, par exemple des propriétés hydrofuges, oléofuges et antisalissures, elle facilite également le démoulage, adhère bien à un support, résiste à la corrosion, est facile à manipuler, résiste bien à l'eau et à l'huile et conserve durablement lesdites propriétés.
PCT/JP2012/076993 2011-10-19 2012-10-18 Composition contenant du fluor et ses applications WO2013058335A1 (fr)

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Cited By (2)

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JP2016018008A (ja) * 2014-07-04 2016-02-01 旭化成イーマテリアルズ株式会社 ペリクル、ペリクル付フォトマスク、及び半導体素子の製造方法
WO2021251302A1 (fr) * 2020-06-10 2021-12-16 ダイキン工業株式会社 Composé contenant du fluor

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* Cited by examiner, † Cited by third party
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WO2016104602A1 (fr) * 2014-12-26 2016-06-30 ダイキン工業株式会社 Matériau antisalissures marin, revêtement antisalissures marin, panneau antisalissures marin, structure sous-marine et procédé pour empêcher l'adhérence de micro-organismes marins à une structure sous-marine
CN111848926B (zh) * 2020-07-02 2023-01-06 深圳飞扬骏研新材料股份有限公司 一种氟改性固化剂及其制备方法

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WO2009034773A1 (fr) * 2007-09-10 2009-03-19 Unimatec Co., Ltd. Polymère contenant du fluor et modificateur de surface le contenant en tant qu'ingrédient actif
JP2009545653A (ja) * 2006-08-03 2009-12-24 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー テロマー組成物および製造方法
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JPS5883011A (ja) * 1981-11-12 1983-05-18 Daikin Ind Ltd フツ素含有アクリレ−トまたはメタクリレ−トの重合体およびその用途
JPS58164672A (ja) * 1982-03-24 1983-09-29 Nippon Mektron Ltd 撥水撥油剤
JP2009545653A (ja) * 2006-08-03 2009-12-24 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー テロマー組成物および製造方法
CN1927894A (zh) * 2006-09-28 2007-03-14 东华大学 一种含氟碳链丙烯酸酯及其共聚物的制备方法和应用
JP2010521541A (ja) * 2007-02-28 2010-06-24 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー フルオロポリマー組成物および使用方法
WO2009034773A1 (fr) * 2007-09-10 2009-03-19 Unimatec Co., Ltd. Polymère contenant du fluor et modificateur de surface le contenant en tant qu'ingrédient actif

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Publication number Priority date Publication date Assignee Title
JP2016018008A (ja) * 2014-07-04 2016-02-01 旭化成イーマテリアルズ株式会社 ペリクル、ペリクル付フォトマスク、及び半導体素子の製造方法
WO2021251302A1 (fr) * 2020-06-10 2021-12-16 ダイキン工業株式会社 Composé contenant du fluor
JPWO2021251302A1 (fr) * 2020-06-10 2021-12-16
JP7560762B2 (ja) 2020-06-10 2024-10-03 ダイキン工業株式会社 含フッ素化合物

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