[go: up one dir, main page]

WO2011122442A1 - Agents hydrofuges et oléofuges utilisant un α-chloroacrylate - Google Patents

Agents hydrofuges et oléofuges utilisant un α-chloroacrylate Download PDF

Info

Publication number
WO2011122442A1
WO2011122442A1 PCT/JP2011/057194 JP2011057194W WO2011122442A1 WO 2011122442 A1 WO2011122442 A1 WO 2011122442A1 JP 2011057194 W JP2011057194 W JP 2011057194W WO 2011122442 A1 WO2011122442 A1 WO 2011122442A1
Authority
WO
WIPO (PCT)
Prior art keywords
monomer
group
water
meth
oil repellent
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/JP2011/057194
Other languages
English (en)
Japanese (ja)
Inventor
正樹 福森
育男 山本
憲正 上杉
浩治 久保田
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.)
Daikin Industries Ltd
Original Assignee
Daikin Industries Ltd
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 Daikin Industries Ltd filed Critical Daikin Industries Ltd
Priority to CN201180015093.XA priority Critical patent/CN102822309B/zh
Priority to JP2012508246A priority patent/JP5626337B2/ja
Publication of WO2011122442A1 publication Critical patent/WO2011122442A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • 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
    • 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
    • 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
    • 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
    • D06M2200/11—Oleophobic properties
    • 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
    • D06M2200/12—Hydrophobic properties

Definitions

  • the present invention relates to a water- and oil-repellent agent having water and oil repellency, processing stability, and soft texture on an article, and more specifically, a fluorine-containing copolymer comprising ⁇ -chloroacrylate having a C 6 perfluoroalkyl group as a constituent monomer.
  • the present invention relates to a water / oil repellent containing a polymer.
  • a polymer of a polymerizable compound having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic acid group or a methacrylic acid group is useful as a water / oil repellent agent for a textile fabric or the like.
  • Aqueous dispersions dispersed in an aqueous medium with a surfactant are widely used industrially.
  • excellent durability can be imparted by copolymerizing the above-mentioned fluorine-containing polymerizable compound with a chlorine-containing polymerizable compound such as vinyl chloride or vinylidene chloride.
  • a water / oil repellent comprising a compound that traps hydrochloric acid generated from the copolymer.
  • the fluoroalkyl group in the side chain of these fluorine-containing (meth) acrylate polymers that are practically used usually has 8 or more carbon atoms, and is usually called “telomer”.
  • telomer may generate PFOA (perfluorooctanoic acid), a fluorine-containing carboxylic acid having 8 carbon atoms, by decomposition or metabolism, and "telomer” is a foam extinguishing agent; care products and cleaning products It has also been announced that it is used in many products including water and oil repellent coatings and antifouling coatings on carpets, textiles, paper and leather (EPA OPPT FACT SHEET April 14, 2003) (Http://www.epa.gov/opptintr/pfoa/pfoafacts.pdf).
  • a polymer containing a polymerization unit of a polymerizable monomer containing a polyfluoroalkyl group (hereinafter referred to as Rf group) in the molecule is used.
  • An article is processed using a combination or a copolymer of this and another monomer, or a low molecular compound having an Rf group as an organic solvent solution or an aqueous dispersion.
  • This expression of water and oil repellency is attributed to the formation of a “low surface energy surface” having a low critical surface tension on the surface due to the surface orientation of the R f group in the coating film.
  • R f group-containing monomer achieves its purpose in terms of expression of water and oil repellency, other practical functions have been improved.
  • a monomer having a high hardness or a monomer having a crosslinking reactive group is used together with an Rf group-containing monomer, or the obtained copolymer is coated with a film. Improvements such as blending with high strength polymers and blending with blocked isocyanates have been made.
  • Japanese Patent No. 3624615 Rf group (meth) acrylate and stearyl (meth) acrylate and a quaternary copolymer having two other monomers as essential components
  • Japanese Patent No. 3433024 a blend of a fluorine-based water / oil repellent and a specific chain length of an R f group-containing alcohol or a perfluoropolyether group-containing alcohol
  • JP-A-8-109580 reaction product of amino group-containing silicone and R f group-containing ester compound
  • WO2009-122919 Rf group (meth) acrylate monomer, copolymer containing hydrocarbon (meth) acrylate monomer and mercapto group-containing silicone
  • WO2009-113589 including a (meth) acrylate having no polyfluoroalkyl group and having an alkyl group having 20 to 30 carbon atoms, a halogenated olefin, and a monomer having a fluoroalkyl group having
  • An object of the present invention is to provide a polymerizable compound having a C6 perfluoroalkyl group and an ⁇ -halogenated acrylic acid group, a chlorine-containing polymerizable compound, and other polymerizable compounds copolymerizable therewith. And a water- and oil-repellent agent that has processing stability and washing durability and can impart excellent water- and oil-repellency to a substrate.
  • the inventors of the present invention have studied a completely novel mechanism of water / oil repellency.
  • a hydrocarbon-based monomer that does not exhibit water and oil repellency with a homopolymer, that is, due to a synergistic effect that enhances surface orientation. It was found that water and oil repellency was developed.
  • This water- and oil-repellent agent does not have the conventional problems of water repellency reduction, texture hardening, film embrittlement, etc., quality deterioration, instability during processing (gum-up), and washing durability. It is possible to impart water and oil repellency to the article.
  • the present invention provides a fluorine-containing copolymer comprising polymerized units of the following monomer (a) and polymerized units of the following monomer (b).
  • Monomer (a) ⁇ -chloroacrylate having a C 6 perfluoroalkyl group.
  • the present invention also provides a water / oil repellent containing the above-mentioned fluorine-containing copolymer.
  • a polymerized unit of the monomer (a) it is important to include a polymerized unit of the monomer (a).
  • having a copolymerizable with the monomer (a) and it is also important that contain polymerized units of a monomer (b) having an organic group other than the R f group, substantial R f A monomer (ie, monomer (a)) and monomer (b) copolymer is essential.
  • a blocked polyisocyanate can also be included.
  • substantially comprising polymerized units of monomer (b) comprising polymerized units, and R f organic group other than groups of polymerizable ⁇ - chloro acrylate monomer containing the R f group of homopolymers (a) A water / oil repellent (that is, a water / oil repellent composition) containing a copolymer as an active ingredient can impart water / oil / oil repellency to an article, even though it does not have fine crystals peculiar to the R f group. In addition, since the composition forms a flexible film, it can impart water and oil repellency to the article without losing quality such as texture.
  • superior water repellency can be expressed as compared with conventional perfluoro (meth) acrylate products having 6 carbon atoms.
  • the initial performance can be maintained as compared with the conventional one.
  • the surface of the film can be further coated with a functional film.
  • the monomer (a) used in the present invention is a monomer having a C6 perfluoroalkyl group and an ⁇ -chloroacrylate group.
  • Y represents a direct bond, an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms or a cyclic aliphatic group, a —CH 2 CH 2 N (R 1 ) SO 2 — group (where R 1 Is an alkyl group having 1 to 4 carbon atoms) or —CH 2 CH (OZ 1 ) CH 2 — group (where Z 1 is a hydrogen atom or an acetyl group) or — (CH 2 ) m —SO A 2- (CH 2 ) n — group or a — (CH 2 ) m —S— (CH 2 ) n — group (where m is 1 to 10 and n is 0 to 10) is preferable.
  • the monomer (a) a mixture of two or more kinds may be used.
  • the monomer (b) in the present invention is a monomer having an organic group other than a polyfluoroalkyl group, and is linear or cyclic (generally saturated) having 12 to 20 carbon atoms (that is, 12 to 19 carbon atoms).
  • Monomer (b) is preferably (meth) acrylates, vinyl ethers or vinyl esters. Particularly preferred is a C 12-19 alkyl ester of (meth) acrylate.
  • Particularly preferred specific examples of the monomer (b) are lauryl (meth) acrylate, isobornyl (meth) acrylate, cetyl (meth) acrylate and stearyl (meth) acrylate.
  • the monomer (b) may contain a small number (for example, 1 to 10, especially 1 to 5) of fluorine atoms that are not normally regarded as R f groups, or a monomer that does not contain a fluorine atom. It may be.
  • the molar ratio of the monomer (a) polymer unit / monomer (b) polymer unit is 0.01 / 1 to 10/1, for example 0.1 / 1 to 9/1, in particular 0.2 / 1 to 5/1 is preferable, and 0.2 / 1 to 1.5 / 1 is particularly preferable.
  • the copolymer is a monomer other than the monomer (a) and the monomer (b) for the purpose of improving physical properties other than water and oil repellency, such as adhesion to a substrate, adhesiveness, durability against friction, etc. , Monomer (c)).
  • ethylene vinylidene chloride, vinyl chloride, vinylidene fluoride, vinyl acetate, styrene, ⁇ -methylstyrene, p-methylstyrene, glycidyl (meth) acrylate, (meth) acrylamide, N, N-dimethyl (Meth) acrylamide, N, N-dimethylpropyl (meth) acrylamide, diacetone (meth) acrylamide, methylolated diacetone (meth) acrylamide, N-methylol (meth) acrylamide, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone , Butadiene, isoprene, chloroprene, aziridinylethyl (meth) acrylate, benzyl (meth) acrylate, aziridinyl (meth) acrylate, polyoxyalkylene (meth) acrylate ,
  • vinyl chloride or a monomer containing a reactive group such as a hydroxyl group in the molecule is preferable from the viewpoint of improving the adhesion of the composition containing the copolymer to the substrate.
  • the monomer (c) is preferably a compound having one or more hydroxyl groups in addition to the carbon-carbon double bond.
  • the monomer (c) is particularly preferably an ester of a divalent or higher divalent to pentavalent linear or cyclic saturated aliphatic (particularly alkyl) alcohol and (meth) acrylic acid.
  • Specific examples of the linear or cyclic saturated aliphatic alcohol having 2 or more valences are alkylene glycol (the alkylene has 2 to 6, preferably 2 or 3, particularly 2 or a combination of 2 and 3), glycerin And pentaerythritol.
  • the alcohol may be a polyalkylene glycol obtained by polymerizing alkylene glycol.
  • the alcohol is obtained by adding alkylene oxide (2 to 6, preferably 2 or 3, particularly 2 or a combination of 2 and 3) with glycerol or pentaerythritol as an initiator (for example, Polyoxyalkylene glycerin or polyoxyalkylene pentaerythritol).
  • alkylene oxide 2 to 6, preferably 2 or 3, particularly 2 or a combination of 2 and 3
  • glycerol or pentaerythritol for example, Polyoxyalkylene glycerin or polyoxyalkylene pentaerythritol.
  • the molecular weight of the polyalkylene glycol, polyoxyalkylene glycerin and polyoxyalkylene pentaerythritol may be 200-20000.
  • the monomer (c) include alkylene glycol mono (meth) acrylate (for example, hydroxyethyl (meth) acrylate), polyalkylene glycol mono (meth) acrylate, glycerin mono (meth) acrylate, and glycerin di (meth) acrylate. , Polyoxyalkylene glycerol mono (meth) acrylate, polyoxyalkylene glycerol di (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate.
  • alkylene glycol mono (meth) acrylate for example, hydroxyethyl (meth) acrylate
  • polyalkylene glycol mono (meth) acrylate for example, hydroxyethyl (meth) acrylate
  • polyalkylene glycol mono (meth) acrylate for example, hydroxyethyl (meth) acrylate
  • the mercapto functional organopolysiloxane can be incorporated into the polymer by polymerizing the fluorinated monomer in the presence of the mercapto functional organopolysiloxane.
  • the amount of mercaptofunctional organopolysiloxane may be 0.1 to 50 parts by weight, for example 1 to 30 parts by weight, based on 100 parts by weight of the polymer.
  • R N (monovalent amino functional organic group), the -R 1 NHR 2 , -R 1 NR 2 2 , or -R 1 NHR 1 NHR 2
  • each R 1 is independently a divalent hydrocarbon group (particularly an alkylene group) having 2 or more carbon atoms (eg, 2 to 20 carbon atoms)
  • R 2 is a hydrogen atom or 1 or more carbon atoms (eg, 1 to 10 carbon atoms).
  • Alkyl group Alkyl group.
  • R S (monovalent mercapto functional organic group) are: -R 1 SH, -R 1 SR 2 , or -R 1 SR 1 SH [Wherein, each R 1 is independently a divalent hydrocarbon group (particularly an alkylene group) having 2 or more carbon atoms (eg, 2 to 20 carbon atoms), and R 2 is a hydrogen atom or 1 or more carbon atoms (eg, 1 to 10 carbon atoms). ) Alkyl group. ] It is.
  • a monomer having a linear or cyclic (saturated or unsaturated) hydrocarbon group having 20 or more carbon atoms, for example, 20 to 30 carbon atoms can also be used.
  • Particularly preferred are (meth) acrylates containing saturated hydrocarbon groups (eg behenyl acrylate).
  • a (meth) acrylate having a cyclic hydrocarbon group is also preferred.
  • Vinyl esters containing saturated hydrocarbon groups are also preferred.
  • the amount of the monomer (c) may be 50% by weight or less, for example, 0.1 to 30% by weight with respect to the fluorine-containing copolymer.
  • a particularly preferable monomer that is, vinyl chloride, a monomer containing a reactive group such as a hydroxyl group in the molecule, a monomer containing a mercapto-functional organopolysiloxane, and a straight chain having 20 to 30 carbon atoms.
  • the amount of the monomer having a chain or cyclic hydrocarbon group may be 30% by weight or less, for example, 0.02 to 20% by weight with respect to the fluorine-containing copolymer.
  • the amount of the monomer (c) other than these particularly preferable monomers may be 30% by weight or less, for example, 0.02 to 20% by weight with respect to the fluorine-containing copolymer.
  • the weight average molecular weight of the fluorinated copolymer of the present invention may be 1,000 to 1,000,000, preferably 5,000 to 500,000.
  • the weight average molecular weight is a value obtained by gel permeation chromatography in terms of polystyrene.
  • the method for preparing a copolymer as an active ingredient is not particularly limited.
  • a usual polymerization method such as a solution polymerization method using an organic solvent, a dispersion polymerization method using water as a dispersion medium and a nonionic surfactant and / or a cationic surfactant, and an emulsion polymerization method can be employed.
  • the obtained copolymer solution, dispersion, and emulsion may be used as they are, or may be used after dilution.
  • the copolymer after separating the copolymer, it may be dissolved, dispersed, or emulsified in a solvent, a dispersion medium, or an emulsification medium.
  • the form of the water / oil repellent composition is preferably an aqueous dispersion containing a small amount of a surfactant and / or an organic solvent in view of ease of handling.
  • the surfactant may be used in an amount of 0.5 to 10 parts by weight with respect to 100 parts by weight of the copolymer.
  • the obtained copolymer can be prepared in any form such as emulsion, organic solvent solution, aerosol, etc. after being diluted or dispersed in water or organic solvent, if necessary, to make a water and oil repellent composition.
  • the copolymer functions as an active ingredient of the water / oil repellent composition.
  • the water / oil repellent composition comprises a fluorine-containing copolymer and a medium (particularly a liquid medium) (for example, an organic solvent and / or water).
  • aqueous medium refers to a medium composed only of water and an organic solvent in addition to water (the amount of the organic solvent is 80 parts by weight or less, for example, 0.1 to 50 parts by weight, in particular 5 to 30 parts by weight).
  • the concentration of the fluorine-containing copolymer may be, for example, 0.01 to 50% by weight in the water / oil repellent composition.
  • the water / oil repellent composition of the present invention preferably comprises a fluorine-containing copolymer and an aqueous medium.
  • water / oil repellent composition organic acid, crosslinking agent, other polymer, other water repellent, oil repellent, insect repellent, flame retardant, antistatic agent, dye stabilizer, anti-wrinkle agent, etc.
  • the additive may be included.
  • cross-linking agents essential polymerization of blocked polyisocyanate compounds, melamine resin compounds, glyoxal resin compounds, urea resin compounds, crosslinkable monomers (blocked products of N-methylolacrylamide, 2-isocyanatoethyl methacrylate, etc.) Examples thereof include a polymer as a unit, and a blocked isocyanate compound or a melamine resin compound is preferable.
  • the blocked polyisocyanate compound is a compound having no polymerizable unsaturated group, and a compound having a structure in which the isocyanate group of the polyisocyanate is blocked with a blocking agent is preferable.
  • the block polyisocyanate composition can be improved in washing durability by blending, etc., and the deterioration in performance due to friction and washing is small, and the performance in the initial stage of processing can be stably maintained.
  • excellent size, water repellency and oil resistance can be imparted to the paper even under low temperature and short drying conditions.
  • the melamine resin compound include trimethylol melamine and hexamethylol melamine.
  • the water / oil repellent composition of the present invention can be used for water / oil repellent treatment of work clothes or uniforms. Moreover, it can also be used for the use as a coating agent for a filtering material, a surface protective agent, a coating agent for electronics, and an antifouling coating agent used in the presence of an organic solvent liquid or its vapor.
  • the article is treated with the water / oil repellent composition of the present invention, since the film is flexible, the texture of the fiber product becomes flexible and high quality water / oil repellency can be imparted to the article.
  • the article to be treated with the water / oil repellent composition of the present invention is not particularly limited, and examples thereof include fiber products made of natural fibers, synthetic fibers or blended fibers thereof, metal, glass, resin, paper, leather, and the like. .
  • Synthesis example 1 Synthesis of Siloxane A: A three-necked round bottom flask equipped with a condenser, a top stirrer, and a thermocouple was added to a silanol-terminated polydimethylsiloxane (743 g, Mn about 300), mercaptopropylmethyldiethoxysilane (230 g), aminopropylmethyldiethoxysilane ( 27 g), trimethylethoxysilane (39 g), barium hydroxide (0.62 g) and sodium orthophosphate (0.25 g). The reaction mixture was heated to 75 ° C. and kept at this temperature for 3 hours, after which the removal of volatiles was carried out at 75 ° C. and 200 mbar vacuum for 4 hours. The physical and structural properties of aminomercaptosiloxane are described below:
  • siloxane A amino-mercapto functional organopolysiloxane
  • test cloths were prepared by the following methods, and water repellency, oil repellency, gum-up rate, and texture were evaluated. The results are shown in Table 3.
  • a treatment liquid is prepared by diluting the aqueous dispersion with water so that the solid content concentration is 0.5% by weight.
  • a polyester cloth was dipped in the treatment liquid and squeezed with a mangle to obtain a wet pickup of 65%, dried at 100 ° C. for 2 minutes, and dried at 160 ° C. for 1 minute to prepare a test cloth. The water and oil repellency, gum-up rate, and texture of this treated fabric were evaluated.
  • a further small amount of diacetone acrylamide is used as the monomer of Example 2, 3-methoxy-3-methyl-1-butanol (hereinafter referred to as “Solfit”) is used in place of tripropylene glycol as a solvent, and a blocked isocyanate.
  • Solfit 3-methoxy-3-methyl-1-butanol
  • a dispersion was produced in the same manner (Example 6) except that BI 7982 (Baxenden) was added.
  • siloxane A amino-mercapto functional organopolysilox
  • the following formulations were performed for Examples 1 to 6 and Comparative Examples 1 to 7.
  • the treatment tank was mixed with 15 g of water repellent, 282 g of water and 3 g of BN69 (MDI block isocyanate; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) for fiber treatment, and the following washing durability and Bundesmann water repellency were evaluated.
  • BN69 MDI block isocyanate
  • test cloth to be treated was washed in water containing 0.83 g / L of detergent (trade name: Attack, Kao Corporation) at a temperature of 40 ° C. and a bath ratio of 1:40 (cloth: treatment liquid (g: g)). Wash using a washing machine for 25 minutes, then rinse for 12 minutes, dehydrate for 3 minutes, and air dry. This was repeated 2 times and 6 times as 5 cycles, and the water repellency was measured as a result of washing 10 times and 30 times to obtain a washing durability value. These are written as HL10 and HL30. Further, after the above operation, tumbler drying instead of air drying is expressed as HL10 + tumbler and HL30 + tumbler.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Cette invention concerne des agents hydrofuges et oléofuges qui sont capables de conférer ces deux propriétés à des articles, et qui présentent une excellente stabilité lors du traitement et une sensation douce au toucher. L'invention concerne spécifiquement un agent hydrofuge et oléofuge contenant, comme composant essentiel, un polymère fluoré comprenant des unités polymérisées dérivées d'un monomère (a) et des unités polymérisées dérivées d'un monomère (b), et qui présente une excellente stabilité lors du traitement ; l'invention concerne également l'agent hydrofuge et oléofuge tel que décrit ci-dessus, le polymère fluoré contenant par ailleurs des unités polymérisées dérivées d'un monomère (c) conférant des propriétés physiques améliorées (adhésion étroite, adhésivité et durabilité par exemple) à certains articles. Le monomère (a) est un monomère a-chloroacrylate comportant un groupe perfluoroalkyle en C6 ; le monomère (b) est un monomère tel qu'un (méth)acrylate contenant un groupe hydrocarboné linéaire renfermant de 12 20 atomes de carbone au plus et/ou un (méth)acrylate contenant un groupe hydrocarboné cyclique ; et le monomère (c) est un monomère copolymérisable, à l'exception des monomères (a) et (b), ou une oléfine halogénée.
PCT/JP2011/057194 2010-03-30 2011-03-24 Agents hydrofuges et oléofuges utilisant un α-chloroacrylate Ceased WO2011122442A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201180015093.XA CN102822309B (zh) 2010-03-30 2011-03-24 使用α-氯丙烯酸酯的拨水拨油剂
JP2012508246A JP5626337B2 (ja) 2010-03-30 2011-03-24 α−クロロアクリレートを使用した撥水撥油剤

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010078578 2010-03-30
JP2010-078578 2010-03-30

Publications (1)

Publication Number Publication Date
WO2011122442A1 true WO2011122442A1 (fr) 2011-10-06

Family

ID=44712151

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/057194 Ceased WO2011122442A1 (fr) 2010-03-30 2011-03-24 Agents hydrofuges et oléofuges utilisant un α-chloroacrylate

Country Status (3)

Country Link
JP (1) JP5626337B2 (fr)
CN (1) CN102822309B (fr)
WO (1) WO2011122442A1 (fr)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102899897A (zh) * 2011-07-26 2013-01-30 台氟科技股份有限公司 氟素拨水拨油剂
CN103183775A (zh) * 2011-12-28 2013-07-03 大金工业株式会社 含氟组合物和含氟聚合物
WO2013099611A1 (fr) 2011-12-28 2013-07-04 ダイキン工業株式会社 Composition et polymère contenant du fluor
JP2013136666A (ja) * 2011-12-28 2013-07-11 Daikin Industries Ltd 含フッ素重合体の製造方法および含フッ素組成物
JP2013136686A (ja) * 2011-12-28 2013-07-11 Daikin Industries Ltd 表面処理剤
JP2013136687A (ja) * 2011-12-28 2013-07-11 Daikin Industries Ltd 表面処理剤およびその製造方法
JP2015025234A (ja) * 2012-07-06 2015-02-05 ダイキン工業株式会社 透湿防水布帛およびその製法
WO2016000831A1 (fr) * 2014-07-04 2016-01-07 Archroma Ip Gmbh Composition hydrofuge contenant du fluor
JP2016067875A (ja) * 2014-09-29 2016-05-09 ダイキン工業株式会社 防護衣服材料及びそれを用いた防護衣服
JP2016183347A (ja) * 2016-06-07 2016-10-20 ダイキン工業株式会社 表面処理剤およびその製造方法
JP2016196651A (ja) * 2016-06-17 2016-11-24 ダイキン工業株式会社 含フッ素組成物および含フッ素重合体
JP2017160433A (ja) * 2016-03-11 2017-09-14 ダイキン工業株式会社 表面処理剤組成物
KR101816464B1 (ko) 2013-10-23 2018-01-08 다이킨 고교 가부시키가이샤 불소 함유 중합체 및 처리제
WO2019124341A1 (fr) * 2017-12-22 2019-06-27 第一工業製薬株式会社 Copolymère, produit hydrofuge et oléofuge, et agent de revêtement
WO2021246475A1 (fr) * 2020-06-03 2021-12-09 明成化学工業株式会社 Composition hydrofuge, kit, produit fibreux hydrofuge et procédé de fabrication associé
KR20240072254A (ko) 2022-01-28 2024-05-23 다이킨 고교 가부시키가이샤 처리 섬유 제품의 제조 방법

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107675504A (zh) * 2016-08-02 2018-02-09 大金工业株式会社 无纺布
TWI688647B (zh) * 2016-12-15 2020-03-21 日商大金工業股份有限公司 撥水劑
CN113279257B (zh) * 2021-06-08 2022-04-19 广东德美精细化工集团股份有限公司 一种无氟防水剂及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6399285A (ja) * 1986-05-28 1988-04-30 Daikin Ind Ltd 撥水撥油剤
WO2004108779A1 (fr) * 2003-06-09 2004-12-16 Daikin Industries, Ltd. Agent de traitement utilise en maçonnerie
JP2004352976A (ja) * 2003-05-02 2004-12-16 Daikin Ind Ltd 含フッ素重合体を含んでなる表面処理剤
WO2008143299A1 (fr) * 2007-05-22 2008-11-27 Asahi Glass Company, Limited Composition d'agent anti-tâches, son procédé de fabrication et article traité par celle-ci
WO2009113589A1 (fr) * 2008-03-12 2009-09-17 旭硝子株式会社 Copolymère et procédé de production associé

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06192325A (ja) * 1992-12-24 1994-07-12 Mitsui Toatsu Chem Inc 密着性に優れた熱可塑性アクリル樹脂組成物
JP3832459B2 (ja) * 2003-09-16 2006-10-11 オンキヨー株式会社 コンテンツ選択装置及びそのプログラム
CN101175780B (zh) * 2005-05-09 2011-02-02 陶氏康宁公司 氨基-巯基官能的有机基聚硅氧烷
JP5625352B2 (ja) * 2007-05-15 2014-11-19 ダイキン工業株式会社 溶剤溶解性の良好な撥水撥油防汚剤
JP5398723B2 (ja) * 2008-02-06 2014-01-29 ダイキン工業株式会社 フルオロシリコーンおよび含フッ素含ケイ素表面処理剤
EP2265758B1 (fr) * 2008-03-31 2013-05-29 Daikin Industries, Ltd. Dispersion de fuorosilicones et agent de traitement de surface comprenant du fluor et du silicium
JP5171452B2 (ja) * 2008-07-22 2013-03-27 Ａｇｃセイミケミカル株式会社 電子部品用樹脂付着防止組成物
CN103788288B (zh) * 2008-09-15 2016-08-17 大金工业株式会社 拒水和拒油组合物
WO2010030041A1 (fr) * 2008-09-15 2010-03-18 Daikin Industries, Ltd. Fluorosilicones et agent de traitement de surface
JP5529121B2 (ja) * 2008-09-15 2014-06-25 ダイキン工業株式会社 水性重合体分散組成物および表面処理剤
JP5576364B2 (ja) * 2008-09-15 2014-08-20 ダイキン工業株式会社 フルオロシリコーン重合体および表面処理剤

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6399285A (ja) * 1986-05-28 1988-04-30 Daikin Ind Ltd 撥水撥油剤
JP2004352976A (ja) * 2003-05-02 2004-12-16 Daikin Ind Ltd 含フッ素重合体を含んでなる表面処理剤
WO2004108779A1 (fr) * 2003-06-09 2004-12-16 Daikin Industries, Ltd. Agent de traitement utilise en maçonnerie
WO2008143299A1 (fr) * 2007-05-22 2008-11-27 Asahi Glass Company, Limited Composition d'agent anti-tâches, son procédé de fabrication et article traité par celle-ci
WO2009113589A1 (fr) * 2008-03-12 2009-09-17 旭硝子株式会社 Copolymère et procédé de production associé

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102899897A (zh) * 2011-07-26 2013-01-30 台氟科技股份有限公司 氟素拨水拨油剂
TWI609895B (zh) * 2011-12-28 2018-01-01 大金工業股份有限公司 含氟組成物及含氟聚合物
CN103183775A (zh) * 2011-12-28 2013-07-03 大金工业株式会社 含氟组合物和含氟聚合物
JP2013136666A (ja) * 2011-12-28 2013-07-11 Daikin Industries Ltd 含フッ素重合体の製造方法および含フッ素組成物
KR20190069363A (ko) * 2011-12-28 2019-06-19 다이킨 고교 가부시키가이샤 불소 함유 조성물 및 불소 함유 중합체
JP2013136687A (ja) * 2011-12-28 2013-07-11 Daikin Industries Ltd 表面処理剤およびその製造方法
JP2013136668A (ja) * 2011-12-28 2013-07-11 Daikin Industries Ltd 含フッ素組成物および含フッ素重合体
JP2013151651A (ja) * 2011-12-28 2013-08-08 Daikin Industries Ltd 含フッ素組成物および含フッ素重合体
TWI625339B (zh) * 2011-12-28 2018-06-01 Daikin Ind Ltd 表面處理劑及其製造方法
WO2013099611A1 (fr) 2011-12-28 2013-07-04 ダイキン工業株式会社 Composition et polymère contenant du fluor
TWI610948B (zh) * 2011-12-28 2018-01-11 大金工業股份有限公司 含氟組成物及含氟聚合物
JP2013136686A (ja) * 2011-12-28 2013-07-11 Daikin Industries Ltd 表面処理剤
US10640594B2 (en) 2011-12-28 2020-05-05 Daikin Industries, Ltd. Fluorine-containing composition and fluorine-containing polymer
KR102041857B1 (ko) * 2011-12-28 2019-11-08 다이킨 고교 가부시키가이샤 불소 함유 조성물 및 불소 함유 중합체
KR101507698B1 (ko) * 2011-12-28 2015-03-31 다이킨 고교 가부시키가이샤 불소 함유 조성물 및 불소 함유 중합체
JP2015025234A (ja) * 2012-07-06 2015-02-05 ダイキン工業株式会社 透湿防水布帛およびその製法
KR101816464B1 (ko) 2013-10-23 2018-01-08 다이킨 고교 가부시키가이샤 불소 함유 중합체 및 처리제
US10597816B2 (en) 2014-07-04 2020-03-24 Archroma Ip Gmbh Fluorine-containing water-repellent composition
WO2016000831A1 (fr) * 2014-07-04 2016-01-07 Archroma Ip Gmbh Composition hydrofuge contenant du fluor
JP2016067875A (ja) * 2014-09-29 2016-05-09 ダイキン工業株式会社 防護衣服材料及びそれを用いた防護衣服
JP2017160433A (ja) * 2016-03-11 2017-09-14 ダイキン工業株式会社 表面処理剤組成物
JP2016183347A (ja) * 2016-06-07 2016-10-20 ダイキン工業株式会社 表面処理剤およびその製造方法
JP2016196651A (ja) * 2016-06-17 2016-11-24 ダイキン工業株式会社 含フッ素組成物および含フッ素重合体
JP2019112531A (ja) * 2017-12-22 2019-07-11 第一工業製薬株式会社 共重合体、撥水撥油剤およびコーティング剤
WO2019124341A1 (fr) * 2017-12-22 2019-06-27 第一工業製薬株式会社 Copolymère, produit hydrofuge et oléofuge, et agent de revêtement
WO2021246475A1 (fr) * 2020-06-03 2021-12-09 明成化学工業株式会社 Composition hydrofuge, kit, produit fibreux hydrofuge et procédé de fabrication associé
JP7009675B1 (ja) * 2020-06-03 2022-01-25 明成化学工業株式会社 撥水剤組成物、キット、撥水性繊維製品及びその製造方法
CN115698221A (zh) * 2020-06-03 2023-02-03 明成化学工业株式会社 防水剂组合物、试剂盒、防水性纤维制品及其制造方法
KR20240072254A (ko) 2022-01-28 2024-05-23 다이킨 고교 가부시키가이샤 처리 섬유 제품의 제조 방법

Also Published As

Publication number Publication date
CN102822309B (zh) 2015-12-09
CN102822309A (zh) 2012-12-12
JP5626337B2 (ja) 2014-11-19
JPWO2011122442A1 (ja) 2013-07-08

Similar Documents

Publication Publication Date Title
JP5626337B2 (ja) α−クロロアクリレートを使用した撥水撥油剤
KR102041857B1 (ko) 불소 함유 조성물 및 불소 함유 중합체
JP6107921B2 (ja) 表面処理剤
JP5459219B2 (ja) 含フッ素重合体および撥水撥油剤
JP5915641B2 (ja) 撥水撥油剤組成物
JP5577704B2 (ja) 水性重合体分散組成物および撥水撥油剤
EP1652901B1 (fr) Agent de traitement de surface fluorochimique contenant silicium
CN107001917B (zh) 憎水憎油剂组合物、其制造方法及物品
EP2799458B1 (fr) Composition et polymère contenant du fluor
CN108884379B (zh) 表面处理剂
JP5862745B2 (ja) 含フッ素重合体および処理剤
JP2017165872A (ja) 共重合体および表面処理剤
KR100689941B1 (ko) 발수 발유제 수성 분산액 조성물
WO2004069924A1 (fr) Emulsion aqueuse
JP6191736B2 (ja) 含フッ素組成物および含フッ素重合体

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201180015093.X

Country of ref document: CN

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

Ref document number: 11762673

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2012508246

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11762673

Country of ref document: EP

Kind code of ref document: A1