US20070197717A1 - Polymer for masonry treatment and treating agent - Google Patents

Polymer for masonry treatment and treating agent Download PDF

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Publication number
US20070197717A1
US20070197717A1 US11/547,969 US54796905A US2007197717A1 US 20070197717 A1 US20070197717 A1 US 20070197717A1 US 54796905 A US54796905 A US 54796905A US 2007197717 A1 US2007197717 A1 US 2007197717A1
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group
fluorine
atom
monomer
acid group
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Akihiko Ueda
Teruyuki Fukuda
Koji Nagashima
Masahiko Maeda
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Daikin Industries Ltd
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Assigned to DAIKIN INDUSTRIES, LTD. reassignment DAIKIN INDUSTRIES, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MAEDA, MASAHIKO, NAGASHIMA, KOJI, FUKUDA, TERUYUKI, UEDA, AKIHIKO
Publication of US20070197717A1 publication Critical patent/US20070197717A1/en
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/48—Macromolecular compounds
    • C04B41/4838—Halogenated polymers
    • C04B41/4842—Fluorine-containing 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
    • C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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

Definitions

  • the present invention relates to a polymer, treatment agent and treatment method for treating a masonry, and a treated article.
  • JP-A-57-23662 describes that an acrylate having a Rf group is coated on a concrete and a stone to form a protective film.
  • JP-A-07-109317 discloses a treatment agent comprising a fluorine-containing copolymer comprising a monomer having a Rf group, and a silicone-based vinyl monomer.
  • JP-A-11-507687 discloses a masonry-treatment agent comprising a water-soluble polymer having a Rf group, a carboxyl group, an oxyalkylene group and a silyl group.
  • EP1225187 discloses the treatment of ceramics with a polymer having a silyl group which comprises a Rf group-containing monomer, a fluorine-free monomer and a silyl group-containing monomer.
  • JP-A-11-077677 proposes that a stone is treated with a phosphate ester having a Rf group.
  • treatment agents do not have both of sufficient water repellency and sufficient oil repellency, are weak to aqueous soil in the case of an aqueous treatment agent, and cannot impart sufficient soil resistance for a masonry-treatment agent.
  • JP-A-2001-504874 describes that an amphipathic polymer comprising a fluorinated monomer is used for leather, but the treatment of masonry is not considered.
  • PFOA perfluorooctanoic acid
  • telomers have a possibility to produce PFOA when decomposed or metabolized (herein, the telomer means a long chain fluoroalkyl group), and also that telomers have been widely used in foam fire extinguishers, care products, washing materials, carpets, textiles, paper, leather, etc., in order to impart water and oil repellency and soil resistance to them.
  • An object of the present invention is to provide a treatment agent which imparts both of excellent water- and oil-repellency and excellent soil resistance to masonry.
  • the present invention provides a fluorine-containing polymer for a masonry treatment, comprising:
  • the present invention provides a fluorine-containing polymer comprising:
  • the present invention provides a fluorine-containing polymer comprising:
  • the present invention can give masonry excellent in water- and oil-repellency and an antifouling property.
  • the fluorine-containing polymer of the present invention comprises repeating units derived from each of the monomers (A), (B) and (C).
  • examples of the fluorine-containing monomer (A) include a monomer having: at least one fluorine-containing group selected from the group consisting of a fluoroalkyl group, a fluoroalkenyl group and a fluoroether group (hereinafter referred to as “fluorine-containing group”), and an unsaturated group of the formula: —O—CO—CX ⁇ CH 2 wherein X is a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (in which X 1 and X 2 are each 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, a substituted or unsubsti
  • fluorine-containing group selected
  • X is preferably a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (in which X 1 and X 2 are each 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, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, because higher water- and oil-repellency can be obtained.
  • the fluorine-containing monomer includes, for example, an acrylate monomer, maleate monomer, fumarate monomer, and urethane monomer having the fluorine-containing group.
  • the acrylate monomer having the fluorine-containing group is, for example, represented by the formula: wherein X is a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (in which X 1 and X 2 are each 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, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group,
  • the Rf group in the formula (I) is a fluoroalkyl group
  • the Rf group is preferably a perfluoroalkyl group.
  • the Rf group has 1 to 21 carbon atoms, particularly 1 to 15 carbon atoms, especially 2 to 15 carbon atoms, for example, 2 to 12 carbon atoms.
  • the upper limit of the carbon atom number in the Rf group may be 6 or 4.
  • Rf group examples include —CF 3 , —CF 2 CF 3 , —CF 2 CF 2 CF 3 , —CF(CF 3 3 ) 2 , —CF 2 CF 2 CF 2 CF 3 , —CF 2 CF(CF 3 ) 2 , —C(CF 3 ) 3 , —(CF 2 ) 4 CF 3 , —(CF 2 ) 2 CF(CF 3 ) 2 , —CF 2 C(CF 3 ) 3 , —CF(CF 3 )CF 2 CF 2 CF 3 , —(CF 2 ) 5 CF 3 , —(CF 2 ) 3 CF(CF 3 ) 2 , —(CF 2 ) 4 CF(CF 3 ) 2 , —(CF 2 ) 7 CF 3 , —(CF 2 ) 5 CF(CF 3 ) 2 , —(CF 2 ) 6 CF(CF 3 ) 2 , —(CF 2 ) 9 ,
  • examples of the Rf group include —C(CF(CF 3 ) 2 ) ⁇ C(CF 3 )(CF 2 CF 2 CF 3 ), —C(CF(CF 3 ) 2 ) ⁇ C(CF 3 )(CF(CF 3 ) 2 ) and —C(CF 3 ) ⁇ C(CF(CF 3 ) 2 ) 2 .
  • examples of the Rf group include F(CF 2 CF 2 CF 2 O) a CF 2 CF 2 — and F(CF(CF 3 )CF 2 O) a CF(CF 3 )— wherein “a”, on average, is from 2 to 100, particularly 5 to 50, for example, 25.
  • Y is a direct bond, an aliphatic group having 1 to 10 carbon atoms which optionally has an oxygen atom, an aromatic, cycloaliphatic or araliphatic group having 6 to 10 carbon atoms which optionally has an oxygen atom, a —CH 2 CH 2 N(R 1 )SO 2 — group (in which R 1 is an alkyl group having 1 to 4 carbon atoms) or a —CH 2 CH(OY 1 )CH 2 — group (in which Y 1 is a hydrogen atom or an acetyl group).
  • the aliphatic group is an alkylene group (particularly having 1 to 4 carbon atoms, for example, 1 or 2 carbon atoms).
  • the aromatic group and the cycloaliphatic group may be substituted or may not be substituted.
  • fluorine-containing monomer examples include the followings: Rf-(CH 2 ) 10 OCOCH ⁇ CH 2 Rf-(CH 2 ) 10 OCOC(CH 3 ) ⁇ CH 2 Rf-CH 2 OCOCH ⁇ CH 2 Rf-CH 2 OCOC(CH 3 ) ⁇ CH 2 Rf-(CH 2 ) 2 OCOCH ⁇ CH 2 Rf-(CH 2 ) 2 OCOC(CH 3 ) ⁇ CH 2 Rf-SO 2 N(CH 3 )(CH 2 ) 2 OCOCH ⁇ CH 2 Rf-SO 2 N(C 2 H 5 )(CH 2 ) 2 OCOCH ⁇ CH 2 Rf-CH 2 CH(OCOCH 3 )CH 2 OCOC(CH 3 ) ⁇ CH 2 Rf-CH 2 CH(OH)CH 2 OCOCH ⁇ CH 2 wherein Rf is a linear or branched fluoroalkyl or fluoroalkenyl group having 1 to 21 carbon atoms, or a fluoroether group having totally
  • the maleate or fumarate monomer having the fluorine-containing group, which derives the fluorine-containing polymer is, for example, represented by the formula: wherein Rf and Y are the same as in the formula (I).
  • the fluoroalkyl group-containing urethane monomer deriving the fluorine-containing polymer can be prepared by reacting:
  • Examples of the compound (a) include the followings:
  • the compound (a) is preferably a diisocyanate.
  • a triisocyanate and a polyisocyanate can be also used for the reaction.
  • trimer of diisocyanate polymeric MDI (diphenylmethane diisocyanate) and an adduct of diisocyanate with a polyhydric alcohol such as trimethylol propane, trimethylol ethane and glycerol can be also used for the reaction.
  • a polyhydric alcohol such as trimethylol propane, trimethylol ethane and glycerol
  • the compound (b) may be, for example, of the formula:
  • X is the same as in the formula (I).
  • p is from 0 to 10 (for example, 1 to 5).
  • Z include the followings: wherein m and n are the number of 1 to 300.
  • the compound (c) may be a compound of the formula: Rf-Y—OH or Rf-Y—NH 2 wherein Rf and Y are the same as in the formula (I).
  • Examples of the compound (c) include the followings:
  • the compounds (a), (b) and (c) may be reacted such that when the compound (a) is a diisocyanate, both the compounds (b) and (c) are in amounts of 1 mol based on 1 mol of the compound (a); when the compound (a) is a triisocyanate, the compound (b) is in an amount of 1 mol and the compound (c) is in an amount of 2 mol based on 1 mol of the compound (a).
  • the acid group is selected from the group consisting of a carboxylic acid group (—C( ⁇ O)OH), a phosphoric acid group (—O—P( ⁇ O)(OH) 2 ), a phosphonic acid group (—P( ⁇ O)(OH) 2 ), a phosphinic acid group (—P( ⁇ O)H(OH)), a sulfuric acid group (—O—S( ⁇ O) 2 OH), a sulfonic acid group (—S( ⁇ O) 2 OH) and a sulfinic acid group (—S( ⁇ O)OH).
  • the acid group can be a site capable of forming a salt.
  • the formation of the salt improves the solubility or dispersibility in water.
  • the acid group contributes a bonding property when masonry contains a metal.
  • carboxylic acid group-containing monomer examples include methacrylic acid, acrylic acid, 2-methacryloyloxyethyl succinate, 2-acryloyloxyethyl succinate, 2-methacryloyloxyethyl phthalate, 2-acryloyloxyethyl phthalate, 2-methacryloyloxyethyl hexahydrophthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxypropyl phthalate, 2-acryloyloxypropyl hexahydrophthalate, 2-acryloyloxypropyl tetrahydrophthalate, itaconic acid, carboxyethyl acrylate, methacryloxyethyl trimellitate, crotonic acid, N-acryloyl alanine, maleic anhydride, citraconic anhydride, and 4-vinylbenzoic acid.
  • the phosphoric acid group-containing monomer examples include 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, acid phosphoxypropyl methacrylate, 3-chloro-2-acid phosphoxypropyl methacrylate, and a 2-methacryloyloxyethyl acid phosphate monoethanolamine half salt.
  • phosphonic acid group-containing monomer examples include vinyl phosphonate.
  • sulfonic acid group-containing monomer examples include acrylamide-tert.-butyl sulfonate, 2-acrylamide-2-methylpropane sulfonate, 2-sulfoethyl acrylate, 2-sulfoethyl methacrylate, 2-sulfopropyl acrylate, 4-sulfophenyl acrylate, 2-hydroxy-3-sulfopropyl acrylate, 2-acrylamidepropane sulfonate, 4-methacrylamide benzene sulfonate, p-styrene sulfonate, and vinyl sulfonate.
  • sulfinic acid group-containing monomer examples include p-vinylbenzene sulfinate.
  • hydrophobic group in the hydrophobic group-containing fluorine-free monomer (C) examples include a hydrocarbon group and a silicon-containing group.
  • hydrocarbon group examples include an aliphatic hydrocarbon group (for example, an alkyl group and an alkenyl group), a cycloaliphatic hydrocarbon group and an aromatic hydrocarbon group.
  • the carbon number of the hydrocarbon group may be 1 to 30, for example, 4 to 30.
  • silicon-containing group include a polysiloxane group.
  • the fluorine-free monomer (C) may be a (meth)acrylate ester having an alkyl group.
  • the number of carbon atoms of the alkyl group may be from 1 to 30.
  • the fluorine-free monomer (C) may be also a (meth)acrylate ester having a polysiloxane group.
  • a (meth)acrylate ester having an alkyl group having 4 to 30 carbon atoms and a (meth)acrylate ester having a polysiloxane group of the following formula: wherein R 1 is a hydrogen atom or an organic group, x is the number such that the number-average molecular weight of this compound is from 300 to 20000, particularly 1000.
  • the fluorine-containing polymer may contain an other monomer (D) in addition to the monomers (A), (B) and (C).
  • the other monomer (D) include, for example, ethylene, vinyl acetate, vinyl halide (for example, vinyl chloride) vinylidene halide (for example, vinylidene chloride), acrylonitrile, styrene, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycerol (meth)acrylate, polyethyleneglycol (meth)acrylate, polypropyleneglycol(meth)acrylate, methoxypolyethyleneglycol(meth)acrylate, methoxypolypropyleneglycol(meth)acrylate, tetrahydro-furfuryl (meth)acrylate, 3-chloro-2-hydroxypropyl(meth)acrylate, vinyl alkyl ketone, vinyl alkyl
  • the weight-average molecular weight of the fluorine-containing polymer may be, for example, from 2,000 to 5,000,000, particularly from 3,000 to 5,000,000, especially from 10,000 to 1,000,000.
  • the weight-average molecular weight of the fluorine-containing polymer can be measured by GPC (gel permeation chromatography) (in terms of polystyrene).
  • the amounts of the monomers may be as follows, based on 100 parts by weight the monomer (A): 5 to 100 parts by weight, for example, 10 to 90 parts by weight, particularly, 15 to 80 parts by weight, especially 15 to 60 parts by weight of the monomer (B), 1 to 100 parts by weight, for example, 1 to 90 parts by weight, particularly, 2 to 60 parts by weight, especially 3 to 40 parts by weight of the monomer (C), and 0 to 100 parts by weight, for example, 0 to 70 parts by weight, particularly, 0.1 to 50 parts by weight, especially 1 to 30 parts by weight of the monomer (D).
  • X in the formula (I) is a hydrogen atom or a methyl group, it is preferable that:
  • the fluorine-containing polymer in the present invention can be prepared by any of conventional polymerization methods. Conditions for polymerization reaction can be arbitrarily selected. Such polymerization methods include a solution polymerization and an emulsion polymerization.
  • a method of dissolving the monomer(s) into an organic solvent in the presence of a polymerization initiator replacing the atmosphere by nitrogen, and stirring the mixture with heating at the temperature within the range from 50° C. to 120° C. for 1 hour to 10 hours.
  • the polymerization initiator include azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate and diisopropyl peroxydicarbonate.
  • the polymerization initiator may be used in the amount within the range from 0.01 to 5 parts by weight, based on 100 parts by weight of total of the monomers.
  • the organic solvent is inert to the monomer(s) and dissolves the monomer(s), and examples thereof include pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, isopropyl alcohol, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane and trichlorotrifluoroethane.
  • the organic solvent may be used in the amount within the range from 50 to 1,000 parts by weight, based on 100 parts by weight of total of the monomers.
  • an emulsion polymerization there can be used a method of emulsifying monomers in water in the presence of a polymerization initiator and an emulsifying agent, replacing the atmosphere by nitrogen, and polymerizing with stirring, for example, at the temperature within the range from 50° C. to 80° C. for 1 hour to 10 hours.
  • polymerization initiator for example, water-soluble initiators (e.g., azobisisobutylamidine dihydrochloride, sodium peroxide, potassium persulfate and ammonium persulfate) and oil-soluble initiators (e.g., azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate and diisopropyl peroxydicarbonate) are used.
  • the polymerization initiator may be used in the amount within the range from 0.01 to 5 parts by weight based on 100 parts by weight of the monomers.
  • the monomers are atomized in water by using an emulsifying device capable of applying a strong shattering energy (e.g., a high-pressure homogenizer and an ultrasonic homogenizer) and then polymerized with using the oil-soluble polymerization initiator.
  • an emulsifying device capable of applying a strong shattering energy (e.g., a high-pressure homogenizer and an ultrasonic homogenizer) and then polymerized with using the oil-soluble polymerization initiator.
  • Various emulsifying agents such as an anionic emulsifying agent, a cationic emulsifying agent and a nonionic emulsifying agent can be used as the emulsifying agent.
  • the emulsifying agent examples include a hydrocarbon emulsifying agent, a fluorine-containing emulsifying agent and a silicone emulsifying agent.
  • the amount of the emulsifying agent may be within the range from 0.5 to 50 parts by weight, for example, from 0.5 to 10 parts by weight, based on 100 parts by weight of the monomers.
  • a compatibilizing agent e.g., a water-soluble organic solvent and a low-molecular weight monomer
  • the emulsifiability and polymerizability can be improved.
  • water-soluble organic solvent examples include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol and N-methyl-2-pyrrolidone.
  • the water-soluble organic solvent may be used in the amount within the range from 1 to 50 parts by weight, e.g., from 10 to 40 parts by weight, based on 100 parts by weight of water.
  • the treatment agent comprises (1) the fluorine-containing polymer and (2) a liquid medium, for example, water and/or an organic solvent.
  • the treatment agent generally contains a neutralizing agent.
  • the treatment agent may be in the form of a solution of the fluorine-containing polymer (a solution in water or an oragnic solvent), or a dispersion of the fluorine-containing polymer (in water or an organic solvent). Since the fluorine-containing polymer of the present invention contains the acid group, a salt can be formed together with a base (that is, a neutralizing agent).
  • the fluorine-containing polymer, which has formed the salt can dissolve in water to form an aqueous solution of the fluorine-containing polymer.
  • the neutralizing agent and water may be added to form the treatment agent.
  • the organic solvent may be removed before or after the addition of the neutralizing agent and water.
  • Examples of the base added to the fluorine-containing polymer include ammonia, an amine (for example, triethylamine, diethylamine, triethanolamine, diethanol amine), and a basic metal salt (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate and sodium acetate).
  • the amount of the added base may be from 0.1 to 3 equivalents, for example, 0.5 to 1.5 equivalents, based on 1 equivalent of the acid group in the fluorine-containing polymer.
  • the amount of fluorine-containing polymer is not particularly limited and may be selected from the range which can homogeneously dissolve or disperse the fluorine-containing polymer.
  • the amount of the fluorine-containing polymer may be from 0.1 to 80% by weight, for example, 0.2 to 20% by weight, based on the treatment agent.
  • the treatment liquid of the present invention may contain (3) a silicon-containing compound, in addition to the fluorine-containing polymer (1) and the liquid medium (2).
  • the silicon-containing compound (3) is preferably a compound having at least one siloxane linkage.
  • the silicon-containing compound (3) may be a compound represented by the following general formula (I): wherein R 1n is an alkyl group containing 1 to 18 carbon atoms and, when nn is at least 2 or more, the R 1n groups may be the same or different; R 2n is a hydrogen atom or an alkyl group containing 1 to 5 carbon atoms and, when nn is 2 or more, the R 2n groups may be the same or different; and nn is an integer of 1 to 20.
  • R 1n is an alkyl group containing 1 to 18 carbon atoms and, when nn is at least 2 or more, the R 1n groups may be the same or different
  • R 2n is a hydrogen atom or an alkyl group containing 1 to 5 carbon atoms and, when nn is 2 or more, the R 2n groups may be the same or different
  • nn is an integer of 1 to 20.
  • the alkyl group containing 1 to 18 carbon atoms as represented by R 1n is not particularly restricted but includes, among others, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group. These may be straight-chained or branched.
  • the alkyl group containing 1 to 5 carbon atoms as represented by R 2n is not particularly restricted but includes, among others, methyl, ethyl, propyl, butyl and pentyl. These may be straight-chained or branched.
  • nn represents an integer of 1 to 20, for example an integer of 1 to 10.
  • silicon-containing compound (3) there may more specifically be mentioned, among others, methyltrimethoxysilane, ethyltrimethoxysilane, propyl-trimethoxysilane, butyltrimethoxysilane, pentyltrimethoxy-silane, hexyltrimethoxysilane, heptyltrimethoxysilane, octyltrimethoxysilane, nonyltrimethoxysilane, decyl-trimethoxysilane, undecyltrimethoxysilane, dodecyl-trimethoxysilane, tridecyltrimethoxysilane, tetradecyl-trimethoxysilane, pentadecyltrimethoxysilane, hexadecyl-trimethoxysilane, heptadecyltrimethoxysilane, octadecyl-tri
  • silicon-containing compounds may be used also in their dimer form as the silicon-containing compound (3) in the present invention.
  • nn is 2 or 3, for instance.
  • nn is up to 20 may be used as well.
  • the silicon-containing compound (3) is preferably used in an emulsified form.
  • emulsification can be conducted in the conventional manner, for example by using an emulsifying agent.
  • Said emulsifying agent is not particularly restricted but may be a nonionic emulsifier, an anionic emulsifier, or the like.
  • Said nonionic emulsifier is not particularly restricted but includes, among others, common nonionic emulsifiers such as glycerol monostearate, glycerol monooleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylenesorbitan monolaurate, polyoxyethylenesorbitan monopalmitate, polyoxyethylenesorbitan monostearate, polyoxyethylenesorbitan monooleate, polyoxyethylenesorbitan trioleate, polyoxyethylenesorbitan sesquioleate, polyoxyethylenesorbitol tetraoleate, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ethers, polyoxyethylene octylphenyl ether, polyoxyethylene nony
  • nonionic emulsifier there may be mentioned fluorinated emulsifiers, silicone type emulsifiers and the like.
  • the fluorinated emulsifiers may comprises a fluorinated resin, or a combination of fluorinated resin with another resin.
  • the other resin include an acrylic resin, an acryl-silicone resin, an epoxy resin, a urethane resin and an ester resin.
  • silicone type emulsifiers there may be mentioned polyalkylene oxide-modified polydimethylsiloxane compounds represented by the following general formulas:
  • R represents a hydrogen atom or an alkyl group
  • m2, n2, a2, b2, c2, d2 and e2 each represents an integer indicative of the number of repetitions(for example, 0 to 200, particularly 1 to 100).
  • anionic emulsifier is not particularly restricted but includes, among others, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalene sulfonates, sodium dialkyl sulfosuccinates, sodium alkyldiphenyl ether disulfonates, alkyl phosphate diethanolamine salts, alkyl phosphate potassium salts, sodium polyoxyethylene lauryl ether sulfate, polyoxyethylene alkyl ether sulfuric acid triethanolamines, sodium polyoxyethylene alkylphenyl ether sulfates, sodium alkane sulfonates, mixed fatty acid soda soaps, semihardened beef tallow fatty acid soda soaps, semihardened beef tallow fatty acid potash soaps, stearic acid potash soap, oleic acid potash soap, castor oil potash soap, sodium higher alcohol
  • the proportion of the anionic emulsifier in the sum of emulsifiers is not particularly restricted but is preferably from 0 to 20% by weight, for example, from 0.01 to 20% by weight.
  • the nonionic emulsifiers mentioned above and the anionic emulsifiers mentioned above may respectively be used either singly or in combination, or one or more of the nonionic emulsifiers and one or more of the anionic emulsifiers may be used in combination. It is preferable, however, to use any of the nonionic emulsifiers and any of the anionic emulsifiers in combination.
  • the nonionic emulsifiers polyalkylene oxide-modified polydimethylsiloxanes and fluorinated alkyl group-containing polyalkylene oxides are preferred.
  • Emulsification can be conducted, for example, by stirring a mixture of the silicon-containing compound (3) and the emulsifier(s) at a high speed using a homomixer or the like and adding water dropwise thereto gradually.
  • a stable emulsion-like aqueous dispersion can be obtained by the addition of water.
  • concentration and viscosity may be higher or an insoluble matter may appear or a transparent solution may be formed at an initial point in some instances. In such cases, a uniform aqueous dispersion can be obtained as the amount of water is gradually increased.
  • the amount of the silicon-containing compound (3) may be from 0 to 200 parts by weight, for example, from 0 to 50 parts by weight, e.g., from 0.1 to 50 parts by weight, based on 100 parts by weight of the fluorine-containing polymer (1).
  • the treatment agent is coated on the substrate so that the water- and oil-repellency and soil-antifouling property are imparted to the substrate.
  • the substrate is masonry such as stone.
  • the masonry include stone, brick, concrete and tile.
  • stone include natural stone (for example, marble and granite), and artificial stone.
  • the masonry is treated by applying the treatment agent to the substrate.
  • the treatment agent may be coated in the amount of 20 to 1000 g/m 2 , preferably 50 to 500 g/m 2 .
  • the coating may be conducted once or a plurality of times.
  • the coating method may be any of brushing, spraying, rolling, dipping, using rags containing the treatment agent, or the like. Excess treatment agent may be wiped off according to the necessity. Then the treatment agent is dried to remove the liquid medium. The drying may be conducted at room temperature, and/or the baking may be conducted at 80° C. to 250° C.
  • the “treatment” means that a treatment agent is applied to a substrate by immersion, spraying, coating or the like.
  • the treatment gives the result that a fluorine-containing polymer which is an active component of the treatment agent is adhered to surfaces of the substrate and/or penetrated into the internal parts of the substrate.
  • a soil was put on a treated substrate, and droplets were left for 24 hours and wiped off with a paper towel.
  • the visual evaluation was conducted according to the following criteria.
  • Example 2 Into the same apparatus as in Example 1, 12.0 g of CF 3 CF 2 (CF 2 CF 2 ) 3 CH 2 CH 2 OCOCCH ⁇ CH 2 , 4.0 g of stearyl acrylate, 4.0 g of acrylic acid and 30.0 g of isopropyl alcohol were charged and heated to 60° C. 0.2 g of azobisvaleronitrile was added and the polymerization reaction was conducted with stirring at 60° C. for at least 12 hours. A gas chromatography revealed that a polymerization reaction conversion was at least 97%.
  • Example 2 Into the same apparatus as in Example 1, 10.0 g of CF 3 CF 2 (CF 2 CF 2 ) 3 CH 2 CH 2 OCOCCH ⁇ CH 2 , 2.0 g of CF 3 CF 2 (CF 2 CF 4 CH 2 CH 2 —OCOCCH ⁇ CH 2 , 3.0 g of stearyl acrylate, 5.0 g of acrylic acid and 30.0 g of acetone were charged and heated to 60° C. 0.2 g of azobisvaleronitrile was added and the polymerization reaction was conducted with stirring at 60° C. for at least 12 hours. A gas chromatography revealed that a polymerization reaction conversion was at least 97%.
  • Example 2 Into the same apparatus as in Example 1, 12.0 g of CF 3 CF 2 (CF 2 CF 2 ) 3 CH 2 CH 2 OCOCCH ⁇ CH 2 , 2.0 g of CF 3 CF 2 (CF 2 CF 2 ) 4 CH 2 CH 2 —OCOCCH ⁇ CH 2 , 1.0 g of lauryl acrylate, 5.0 g of acrylic acid and 30.0 g of acetone were charged and heated to 60° C. 0.2 g of azobisvaleronitrile was added and the polymerization reaction was conducted with stirring at 60° C. for at least 12 hours. A gas chromatography revealed that a polymerization reaction conversion was at least 97%.
  • Example 2 Into the same apparatus as in Example 1, 14.0 g of CF 3 CF 2 CF 2 CF 2 CH 2 CH 2 OCOCCl ⁇ CH 2 , 1. 0 g of stearyl acrylate, 5.0 g of acrylic acid and 30.0 g of tetrahydrofuran were charged and heated to 60° C. 0.2 g of azobisvaleronitrile was added and the polymerization reaction was conducted with stirring at 60° C. for at least 12 hours. A gas chromatography revealed that a polymerization reaction conversion was at least 97%.
  • Example 2 Into the same apparatus as in Example 1, 12.0 g of CF 3 CF 2 (CF 2 CF 2 ) 3 CH 2 CH 2 OCOCCH ⁇ CH 2 , 2.0 g of stearyl acrylate, 1.0 g of styrene, 5.0 g of citraconic anhydride and 30.0 g of tetrahydrofuran were charged and heated to 60° C. 0.2 g of azobisvaleronitrile was added and the polymerization reaction was conducted with stirring at 60° C. for at least 12 hours. An aqueous solution containing 1.5 g of ammonia was added to the resultant polymer solution. Tetrahydrofuran was distilled off under reduced pressure. The mixture was diluted with water to give a treatment liquid having a solid content of 3%. The treatment and the soil resistance test were conducted in the same manner as in Example 1. The evaluation results are shown in Table 1 and Table 2.
  • Example 2 Into the same apparatus as in Example 1, 14.0 g of CF 3 CF 2 CF 2 CF 2 CH 2 CH 2 OCOCF ⁇ CH 2 , 1.5 g of stearyl acrylate, 0.5 g of a polysiloxane group-containing methacrylate ester: wherein R 1 is a hydrogen atom or an organic group, x is the number such that the number-average molecular weight of this compound is 1000 (SILAPLANE FM0711 manufactured by Chisso Corp.), 4.0 g of acrylic acid and 30.0 g of tetrahydrofuran were charged and heated to 60° C. 0.2 g of azobisvaleronitrile was added and the polymerization reaction was conducted with stirring at 60° C. for at least 12 hours. A gas chromatography revealed that a polymerization reaction conversion was at least 97%.
  • Example 2 7 Grams of the treatment liquid prepared in Example 2 having solid content of 3% and 3 g of an aqueous emulsion of hexyltriethoxysilane having a solid content 3% which is prepared by using polyoxyethylene lauryl ether as an emulsifying agent were mixed to give a mixture treatment liquid.
  • the treatment and the soil resistance test were conducted in the same manner as in Example 1. The evaluation results are shown in Table 1 and Table 2.
  • Example 2 Isopropyl alcohol was added to the polymer solution prepared in Example 2 for dilution to give a treatment liquid having a solid content 3%.
  • the treatment and the soil resistance test were conducted in the same manner as in Example 1. The evaluation results are shown in Table 1 and Table 2.
  • the soil resistance test was conducted in the same manner as in Example 1, except that the treatment liquid was not coated on granite and limestone.
  • Example 2 The polymerization was conducted in the same procedure as in Example 2 except that acrylic acid was replaced by methoxypolyethyleneglycol methacrylate. Water was added to the resultant polymer solution and isopropyl alcohol was distilled off under reduced pressure. The mixture was diluted with water to give a treatment liquid having a solid content of 3%. The treatment and the soil resistance test were conducted in the same manner as in Example 1. The evaluation results are shown in Table 1 and Table 2.
  • Example 2 Into the same apparatus as in Example 1, 14.0 g of CF 3 CF 2 (CF 2 CF 2 ) 3 CH 2 CH 2 OCOCCH ⁇ CH 2 , 8.0 g of acrylic acid and 30.0 g of tetrahydrofuran were charged and heated to 60° C. 0.2 g of azobisvaleronitrile was added and the polymerization reaction was conducted with stirring at 60° C. for at least 12 hours. A gas chromatography revealed that a polymerization reaction conversion was at least 97%.
  • Example 2 Into the same apparatus as in Example 1, 12.0 g of CF 3 CF 2 (CF 2 CF 2 ) 3 CH 2 CH 2 OCOCCH ⁇ CH 2 , 8.0 g of stearyl acrylate and 30.0 g of tetrahydrofuran were charged and heated to 60° C. 0.2 g of azobisvaleronitrile was added and the polymerization reaction was conducted with stirring at 60° C. for at least 12 hours. A gas chromatography revealed that a polymerization reaction conversion was at least 97%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Aftertreatments Of Artificial And Natural Stones (AREA)
  • Paints Or Removers (AREA)
US11/547,969 2004-04-09 2005-04-06 Polymer for masonry treatment and treating agent Abandoned US20070197717A1 (en)

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JP2004-115457 2004-04-09
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US20090149616A1 (en) * 2005-12-01 2009-06-11 Audenaert Frans A Fluorinated surfactants
US20100168319A1 (en) * 2007-11-01 2010-07-01 Asahi Glass Company, Limited Fluorocopolymer and water and oil proofing composition, and processes for their production
US20100183889A1 (en) * 2007-06-06 2010-07-22 Dams Rudolf J Fluorinated compositions and surface treatments made therefrom
US20100227173A1 (en) * 2007-05-15 2010-09-09 Daikin Industries, Ltd. Water-repellent oil-repellent antifouling agent having good solubility in solvent
US20120016070A1 (en) * 2009-03-25 2012-01-19 Daikin Industries Ltd. Surfactant comprising fluorine-containing polymer
WO2012083292A1 (fr) 2010-12-17 2012-06-21 E. I. Du Pont De Nemours And Company Copolymères fluorés
WO2012083293A1 (fr) 2010-12-17 2012-06-21 E. I. Du Pont De Nemours And Company Copolymère de revêtement de copolymère fluoré
WO2012083295A1 (fr) 2010-12-17 2012-06-21 E. I. Du Pont De Nemours And Company Procédé de production de copolymères fluorés de complexes de (méth)acrylates et d'amine d'acide (méth)acrylique
US8476385B2 (en) 2007-06-06 2013-07-02 3M Innovative Properties Company Fluorinated ether compositions and methods of using the same
WO2013142304A1 (fr) 2012-03-20 2013-09-26 E. I. Du Pont De Nemours And Company Résistance de gravure acide pour des substrats calcaires
US8629089B2 (en) 2008-12-18 2014-01-14 3M Innovative Properties Company Method of contacting hydrocarbon-bearing formations with fluorinated ether compositions
US8674031B2 (en) 2008-11-11 2014-03-18 Daikin Industries, Ltd. Method of preparing water- and oil-repellent soil-resistant composition
WO2014097309A1 (fr) 2012-12-17 2014-06-26 Asian Paints Ltd. Revêtement autonettoyant répondant à des stimuli
US20140303305A1 (en) * 2008-12-19 2014-10-09 3M Innovative Properties Company Composition and method for providing stain release or stain repellency to substrates
US8975348B2 (en) 2010-02-12 2015-03-10 E I Du Pont De Nemours And Company Non-aqueous composition comprising partially fluorinated methacrylic polymers
EP2752435A4 (fr) * 2011-08-29 2015-04-29 Agc Seimi Chemical Co Ltd Copolymère pour cosmétiques, agent de traitement superficiel pour poudre cosmétique, poudre pour cosmétiques et préparation cosmétique
US9057012B2 (en) 2008-12-18 2015-06-16 3M Innovative Properties Company Method of contacting hydrocarbon-bearing formations with fluorinated phosphate and phosphonate compositions
US10167356B2 (en) 2014-12-18 2019-01-01 3M Innovative Properties Company Fluorinated polymers comprising phosphonic moieties

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CN100374474C (zh) * 2003-06-09 2008-03-12 大金工业株式会社 砖石处理剂
WO2007127267A2 (fr) * 2006-04-27 2007-11-08 Dow Corning Corporation Composition pour le traitement d'une maçonnerie
GB2466281A (en) 2008-12-19 2010-06-23 3M Innovative Properties Co Composition comprising a fluorinated compound and a phosphate ester for treating surfaces
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CN108276521B (zh) * 2017-12-22 2020-08-18 英德科迪颜料技术有限公司 一种聚丙烯酸酯磷酸钠分散剂及其制备方法

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US20090149616A1 (en) * 2005-12-01 2009-06-11 Audenaert Frans A Fluorinated surfactants
US20100227173A1 (en) * 2007-05-15 2010-09-09 Daikin Industries, Ltd. Water-repellent oil-repellent antifouling agent having good solubility in solvent
US9688785B2 (en) 2007-06-06 2017-06-27 3M Innovative Properties Company Fluorinated compositions and surface treatments made therefrom
US20100183889A1 (en) * 2007-06-06 2010-07-22 Dams Rudolf J Fluorinated compositions and surface treatments made therefrom
US8476385B2 (en) 2007-06-06 2013-07-02 3M Innovative Properties Company Fluorinated ether compositions and methods of using the same
US8945712B2 (en) 2007-06-06 2015-02-03 3M Innovative Properties Company Fluorinated compositions and surface treatments made therefrom
US8193276B2 (en) * 2007-11-01 2012-06-05 Asahi Glass Company, Limited Fluorocopolymer and water and oil proofing composition, and processes for their production
US20100168319A1 (en) * 2007-11-01 2010-07-01 Asahi Glass Company, Limited Fluorocopolymer and water and oil proofing composition, and processes for their production
TWI457352B (zh) * 2007-11-01 2014-10-21 Asahi Glass Co Ltd The fluorine-containing copolymer and water and oil proofing composition, and manufacturing method
US8674031B2 (en) 2008-11-11 2014-03-18 Daikin Industries, Ltd. Method of preparing water- and oil-repellent soil-resistant composition
US9057012B2 (en) 2008-12-18 2015-06-16 3M Innovative Properties Company Method of contacting hydrocarbon-bearing formations with fluorinated phosphate and phosphonate compositions
US8629089B2 (en) 2008-12-18 2014-01-14 3M Innovative Properties Company Method of contacting hydrocarbon-bearing formations with fluorinated ether compositions
US20140303305A1 (en) * 2008-12-19 2014-10-09 3M Innovative Properties Company Composition and method for providing stain release or stain repellency to substrates
US9410054B2 (en) * 2008-12-19 2016-08-09 3M Innovative Properties Company Composition and method for providing stain release or stain repellency to substrates
US20120016070A1 (en) * 2009-03-25 2012-01-19 Daikin Industries Ltd. Surfactant comprising fluorine-containing polymer
US8975348B2 (en) 2010-02-12 2015-03-10 E I Du Pont De Nemours And Company Non-aqueous composition comprising partially fluorinated methacrylic polymers
US8808868B2 (en) 2010-12-17 2014-08-19 E I Du Pont De Nemours And Company Fluorinated copolymers of (meth)acrylates and (meth)acrylic acid amine complexes
US8809209B2 (en) 2010-12-17 2014-08-19 E I Du Pont De Nemours And Company Fluorinated copolymers
US8563672B2 (en) 2010-12-17 2013-10-22 E I Du Pont De Nemours And Company Process for producing fluorinated copolymers of (meth)acrylates and (meth)acrylic acid amine complexes
WO2012083295A1 (fr) 2010-12-17 2012-06-21 E. I. Du Pont De Nemours And Company Procédé de production de copolymères fluorés de complexes de (méth)acrylates et d'amine d'acide (méth)acrylique
AU2011343453B2 (en) * 2010-12-17 2015-07-16 The Chemours Company Fc, Llc. Fluorinated copolymer coating copolymer
WO2012083293A1 (fr) 2010-12-17 2012-06-21 E. I. Du Pont De Nemours And Company Copolymère de revêtement de copolymère fluoré
WO2012083292A1 (fr) 2010-12-17 2012-06-21 E. I. Du Pont De Nemours And Company Copolymères fluorés
EP2752435A4 (fr) * 2011-08-29 2015-04-29 Agc Seimi Chemical Co Ltd Copolymère pour cosmétiques, agent de traitement superficiel pour poudre cosmétique, poudre pour cosmétiques et préparation cosmétique
US8642177B2 (en) 2012-03-20 2014-02-04 E I Du Pont De Nemours And Company Acid etch resistance for calcareous substrates
WO2013142304A1 (fr) 2012-03-20 2013-09-26 E. I. Du Pont De Nemours And Company Résistance de gravure acide pour des substrats calcaires
WO2014097309A1 (fr) 2012-12-17 2014-06-26 Asian Paints Ltd. Revêtement autonettoyant répondant à des stimuli
US10167356B2 (en) 2014-12-18 2019-01-01 3M Innovative Properties Company Fluorinated polymers comprising phosphonic moieties

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CN1938346A (zh) 2007-03-28
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WO2005097850A1 (fr) 2005-10-20
EP1743910A4 (fr) 2007-05-09

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