[go: up one dir, main page]

WO2000037583A1 - Dispersion aqueuse hydrophobe et oleophobe - Google Patents

Dispersion aqueuse hydrophobe et oleophobe Download PDF

Info

Publication number
WO2000037583A1
WO2000037583A1 PCT/JP1999/007006 JP9907006W WO0037583A1 WO 2000037583 A1 WO2000037583 A1 WO 2000037583A1 JP 9907006 W JP9907006 W JP 9907006W WO 0037583 A1 WO0037583 A1 WO 0037583A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
oil
aqueous dispersion
group
weight
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/JP1999/007006
Other languages
English (en)
French (fr)
Inventor
Masayuki Yamana
Tsukasa Aga
Masahiro Miyahara
Masaki Fukumori
Ryosuke Hara
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 EP99961294A priority Critical patent/EP1172428B1/en
Priority to JP2000589643A priority patent/JP4457497B2/ja
Priority to US09/868,767 priority patent/US6753376B1/en
Publication of WO2000037583A1 publication Critical patent/WO2000037583A1/ja
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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/144—Alcohols; Metal alcoholates
    • D06M13/148—Polyalcohols, e.g. glycerol or glucose
    • 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
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • 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
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
    • 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
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • 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
    • 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
    • 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
    • D06M15/29—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing a N-methylol group or an etherified N-methylol group; containing a N-aminomethylene group; containing a N-sulfidomethylene group
    • 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
    • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols 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
    • D06M15/347—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated ethers, acetals, hemiacetals, ketones or aldehydes
    • 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
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
    • Y10T428/31544—Addition polymer is perhalogenated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2164—Coating or impregnation specified as water repellent
    • Y10T442/2172—Also specified as oil repellent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2164—Coating or impregnation specified as water repellent
    • Y10T442/2189—Fluorocarbon containing

Definitions

  • the present invention relates to various kinds of polymers comprising a polymer of a polymerizable compound having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic acid group or a methacrylic acid group as components.
  • the present invention relates to a water- and oil-repellent aqueous dispersion.
  • 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 for ii fabric
  • an aqueous dispersion obtained by dispersing the polymer in an aqueous medium with an emulsifier is widely used industrially.
  • the water- and oil-repellency of a fiber fabric treated with a conventional general aqueous dispersion is unsatisfactory in resistance to physical actions such as friction, that is, durability.
  • the conventional aqueous dispersion does not have excellent storage stability even though it has a durable water and oil repellency.
  • the present invention is a.
  • a water- and oil-repellent aqueous dispersion comprising:
  • the polymer (A) copolymerized with a polymerizable compound having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic acid group or a methacrylic acid group.
  • the former is at least 25% by weight in the copolymer, preferably at least 40% by weight.
  • Examples of the polymerizable compound having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic acid group or a methacrylic acid group include a compound represented by the formula:
  • Rf is a perfluoroalkyl group or a perfluoroalkenyl group having 3 to 21 carbon atoms
  • Ri is hydrogen or an alkyl group having 1 to 10 carbon atoms
  • R 2 is an alkylene group having 1 to 10 carbon atoms
  • R 3 Represents a hydrogen or methyl group
  • Ar represents an aryl group which may have a substituent
  • n represents an integer of 1 to 10.
  • the organic solvent ( ⁇ ) in the present invention is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-acetate
  • the amount of organic solvent (B) can be from 5 to 200 parts by weight, for example from 10 to 100 parts by weight, in particular from 20 to 60 parts by weight, per 100 parts by weight of polymer (A).
  • the surfactant (C) used to disperse the polymer and the organic solvent is a cationic, anionic or nonionic emulsifier. It is preferable that the emulsifier is a cationic emulsifier or a non-ionic emulsifier, or a mixture of both (a preferable weight ratio of the cationic emulsifier to the non-ionic emulsifier is 1: 9 to 9: 1).
  • Cationic emulsifiers include dodecyltrimethylammonium acetate, trimethyltetradecammonium chloride, hexadecinoletritrimethammonium bromide, trimethyloctadecylammonium bromide, (dodecylmethyl chloride) Benzyl) trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi (hydropolyoxyethylene) ammonium chloride, benzyldodecyldi (hydropolyoxyethylene) ammonium chloride Ride, ⁇ -
  • [2- (Jethylamino) ethyl] oleamide hydrochloride is included.
  • Nonionic surfactants Kishirufueno to a Echirenokishido Ichiru, isobutyl O Kutachi Ruch Hainaut Le to, Kisadekanonore, Orein acid, Anorekan (C 1 2 - C 1 6 ) Chionore, Sonorebita Nmono fatty (C ⁇ C 19 ) or alkyl (C 2 -C i 8 ) amines.
  • the weight of the surfactant (C) may be from 0.01 to 30 parts by weight, for example, from 1 to 20 parts by weight, per 100 parts by weight of the polymer (A).
  • the polymerizable compound is emulsion-polymerized in water to which an organic solvent (B) has been added in the presence of a surfactant (C) to obtain an emulsion of the polymer (A). Get. If necessary, add water and Z or a surfactant to the emulsion.
  • Suitable substrates to which the dispersions of the present invention are applied include films, fibers, yarns, woven fabrics, carbets, and filaments obtained from natural or modified natural or synthetic polymer materials, Products made of fiber or yarn.
  • the substrate is a textile product in the form of fibers, yarns or fabrics.
  • the dispersion of the present invention is preferably applied to a substrate by coating, dipping, spraying, padding, roll coating, or a combination of these methods.
  • a bath content of 0.1 to 10 weight ⁇ 1 ⁇ 2 is used as a pad bath.
  • the substrate is padded with this bath and then the dry absorption (weight of the dry polymer on the substrate) is usually about 0.01 to 1 weight of the substrate by removing excess liquid with a squeeze roll. / 0 .
  • the substrate is preferably heated to 100 to 200 ° C.
  • the treatment liquid is prepared by diluting the polymer dispersion with water so that the solid content concentration becomes 0.08% by weight. Immerse the polyester cloth in the treatment liquid, squeeze it with a mandal to obtain a wet pick-up of 65%, dry it at 100 ° C for 2 minutes, heat treat it at 160 ° C for 1 minute, and evaluate the water and oil repellency of the treated cloth I do.
  • the water repellency is represented by the water repellency No. (see Table 1 below) by the spray method of JIS-L-1092.
  • the oil repellency was measured using AATCC-TMl18. Apply several drops of the test solution shown in Table 2 below on the test cloth and observe the state of penetration after 30 seconds. The test solution without immersion gave the highest oil repellency. Make the points oil-repellent. Water repellency No.
  • Example 1 The procedure of Example 1 was repeated except that 40 g of propylene glycol was used instead of 40 g of tripropylene glycol.
  • Example 1 The procedure of Example 1 was repeated except that 40 g of dipropylene glycol was used instead of 40 g of tripropylene glycol.
  • Example 2 The procedure of Example 2 was repeated except that 30 g of propylene glycol was used instead of 30 g of tripropylene glycol.
  • Example 2 The procedure of Example 2 was repeated except that 30 g of dipropylene glycol was used instead of 30 g of tripropylene glycol.
  • Example 4 The procedure of Example 4 was repeated except that 50 g of propylene glycol was used instead of 50 g of tripropylene glycol. Table 3
  • Tripropylene glycol used in the present invention is excellent in harmlessness.
  • the aqueous dispersion of the present invention is effective in reducing environmental pollution, and has durable water and oil repellency and excellent storage stability.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Emergency Medicine (AREA)
  • Health & Medical Sciences (AREA)
  • Dispersion Chemistry (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)
  • Compositions Of Macromolecular Compounds (AREA)

Description

明 細 書
撥水撥油剤水性分散液
技術分野
本発明は、 パ一フルォロアルキル基もしくはパーフルォロアルケニル基および ァクリル酸基もしくはメタクリル酸基を有する重合性化合物の重合体を成分とす る、 各種の； Kilに撥水撥油性を付与する撥水撥油剤水性分散液に関する。
関連技術
パーフルォロアルキル基もしくはパーフルォロアルケニル基およびァクリル酸 基もしくはメタクリル酸基を有する重合性化合物の重合体が ii維織物の撥水撥油 剤として有用であることは知られており、 特に該重合体を乳化剤により水性媒体 中に分散せしめた水性分散液が工業的に広く使用されている。 しカゝし、 従来の一 般的な水性分散液によって処理された繊維織物の撥水撥油性は、 摩擦などの物理 的な作用に対する抵抗性、 すなわち、 耐久性において不満足である。 さらに、 従 来の水性分散液は、 耐久性のある撥水撥油性を有するものであっても、 優れた貯 蔵安定性を有していない。
発明の要旨
本発明の目的は、 耐久性のある撥水撥油性および優れた貯蔵安定性を有する撥 水撥油剤水性分散液を提供することにある。
本発明は、
(A) パーフルォロアルキル基もしくはパーフルォロアルケニル基およびァクリ ル酸基もしくはメタクリル酸基を有する重合性化合物の少なくとも 1種のホモ重 合体もしくは共重合体またはそれらと共重合可能な重合性化合物との共重合体、
( B ) トリプロピレングリコールである有機溶剤、 および
( C ) 界面活性剤
を含有してなる撥水撥油剤水性分散液を提供する。
発明の詳細な説明
重合体（A)において、 パーフルォロアルキル基もしくはパ一フルォロアルケ二 ル基およびァクリル酸基もしくはメタクリル酸基を有する重合性化合物と共重合 可能な他の重合性化合物との共重合体の場合では、 前者が少なくとも共重合体中 25重量％であり、 好ましくは少なくとも 40重量％である。
パーフルォロアルキル基もしくはパーフルォロアルケニル基およびァクリル酸 基もしくはメタクリル酸基を有する重合性化合物の例として、 式：
Figure imgf000004_0001
Rf-(CH.)nOCOCR=CH2 (2)
Figure imgf000004_0002
OH
Rf-CH2CHCH2OCOCR3=CH9 (4)
OCORJ
Rf-CH7CHC¾OCOCR3=CH, (5)
Rf-0-Ar-C¾OCOCR -CH2 (6)
[式中、 Rfは炭素数 3〜21のパーフルォロアルキル基またはパーフルォロア ルケニル基、 Ri は水素または炭素数 1〜 10のアルキル基、 R2 は炭素数 1 〜10のアルキレン基、 R3 は水素またはメチル基、 Ar は置換基を有するこ ともあるァリール基、 n は 1〜10の整数を表わす。 ]
で示される （メタ） アタリレートエステルを挙げることができる。
さらに具体的には、
CF3(CF2)7(CH2)OCOCH=CH2
CF3(CF2)6 (CH2)OCOC(CH3) = CH2、
(CF3)2CF(CF2)6(CH2)2OCOCH=CH2、
CF3(CF2)7(CH2)2OCOC(CH3) = CH , CF3(CF2)7(CH2)2OCOCH = CH2、
CF3(CF2)7S02N(CH3) (CH2)2OCOCH = CH2
CF 3(CF2) 7 S 02N(C2H5) (CH2) 2OCOC (CH3) = CH2、
(CF3)2CF(CF2)6CH2CH(OCOCH3)CH2OCOC(CH3) = CH2, (CF3)2CF(CF2)6CH2CH(OH)CH2OCOCH = CH2,
Figure imgf000005_0001
を例示することができる。
他の共重合可能な重合性化合物には種々のものがあるが、 例示すると、
(1)アクリル酸およぴメタクリル酸ならびにこれらのメチル、 ェチル、 ブチル、 イソブチル、 t—プチル、 プロピル、 2—ェチルへキシル、 へキシル、 デシル、 ラウリノレ、 ステアリノレ、 ィソボノレ二ノレ、 β—ヒ ドロキシェチノレ、 グリシジノレエス テル、 フエニル、 ベンジル、 4—シァノフエニルエステル類、 （2)酢酸、 プロピ オン酸、 力プリル酸、 ラウリル酸、 ステアリン酸等の脂肪酸のビニルエステル類、 (3)スチレン、 α—メチルスチレン、 ρ—メチルスチレン等のスチレン系化合物、 (4)フツイヒビニル、 塩化ビニル、 臭化ビニル、 フッ化ビニリデン、 塩化ビニリデ ン等のハロゲン化ビニルまたはビニリデン化合物類、 （5)ヘプタン酸ァリル、 力 プリル酸ァリル、 力プロン酸ァリル等の脂肪族のァリルエステル類、 （6)ビエル メチルケトン、 ビニルェチルケトン等のビニルアルキルケトン類、 （7)Ν—メチ ルアクリルアミ ド、 Ν—メチ口一ルメタクリルアミ ド等のアクリルアミ ド類およ び（8) 2, 3—ジクロ口 一 1, 3—ブタジエン、 イソプレン等のジェン類などを例 示できる。
本発明における有機溶剤（Β)は、 トリプロピレンダリコール
H [OCH2CH (CH3) ] 3OHである。
有機溶剤（B)の量は重合体（A) 100重量部当たり 5〜200重量部、 例えば 10〜： I 00重量部、 特に 20〜60重量部であってよい。 重合体および有機溶剤を分散するために使用される界面活性剤 (C) は、 陽ィ オン性、 陰イオン性または非イオン性乳化剤である。 陽イオン性乳化剤または非 ィォン性乳化剤あるいは両者の混合物 （陽ィォン性乳化剤と非ィオン性乳化剤と の好ましい重量比は 1 ： 9〜9 ： 1である） であるのが望ましい。 陽イオン性乳 化剤には、 ドデシルトリメチルアンモニゥムァセテート、 トリメチルテトラデシ アンモニゥムクロライド、 へキサデシノレトリメチ アンモニゥムブロマイド、 トリメチルォクタデシルァンモ -ゥムクロライ ド、 （ドデシルメチルべンジル） ト リメチルァンモニゥムクロライド、 ベンジルドデシルジメチルァンモニゥムクロ ライド、 メチルドデシルジ（ヒ ドロポリオキシエチレン）アンモニゥムクロライド、 ベンジルドデシルジ（ヒ ドロポリオキシエチレン）アンモユウムクロライ ド、 Ν -
[ 2 - (ジェチルァミノ）ェチル]ォレアミ ド塩酸塩が包含される。 非イオン性界面 活性剤には、 エチレンォキシドとへキシルフエノ一ル、 イソォクタチルフエノー ル、 へキサデカノーノレ、 ォレイン酸、 ァノレカン（C 1 2- C 1 6)チォーノレ、 ソノレビタ ンモノ脂肪酸（C厂 C 1 9)またはアルキル（C 2 - C i 8)アミンなどとの縮合生成 物が包含される。
界面活性剤（C)の重量は重合体（A) 1 0 0重量部当たり 0 . 0 1〜3 0重量部、 例えば 1〜 2 0重量部であつてよい。
本発明の分散液を製造するには、 界面活性剤 （C) の存在下で重合性化合物を、 有機溶剤 ( B ) を加えた水中で乳化重合して、 重合体 （A) の乳濁液を得る。 必 要に応じて、 乳濁液に、 水および Zまたは界面活性剤を加える。
本発明の分散液を適用する適当な基体は、 フィルム、 繊維、 糸、 織布、 カーべ ットならびに天然重合体物質や変性された天然重合体物質や合成重合体物質から 得られたフィラメント、 繊維あるいは糸で作られた製品である。 基体は、 繊維、 糸または布の形態である繊維製品であることが好ましい。
本発明の分散液を基体に適用するには、 塗布、 浸漬、 吹きつけ、 パッデイング、 ロール被覆あるいはこれらの方法の組み合せによるのが望ましい。 例えば、 浴の 固形分量を 0 . 1〜 1 0重量 <½にすることによってをパッド浴として使用する。 基体をこの浴でパッドし、 次に普通絞りロールで過剰の液を除いて乾燥吸収（基 体上の乾燥重合体の重量）が基体の約 0 . 0 1〜 1重量。 /0となるようにする。 次い で処理基体を 1 00〜200°Cに加熱するのがよレ、。
発明の好ましい態様
以下に実施例および比較例を示し、 本発明を更に詳しく説明する。
特性は、 次のようにして測定した。
撥水撥油性
重合体分散液を固形分濃度が 0.08重量％になるよう水で希釈して処理液を 調製する。 ポリエステル布を処理液に浸漬し、 マンダルで絞って、 ウエットピッ クアップ 65 %とし、 100 °Cで 2分間乾燥し、 1 60 °Cで 1分間熱処理した後 に、 処理布の撥水撥油性を評価する。
撥水性は J I S-L- 1092のスプレー法による撥水性 No. (下記表 1参 照）をもって表す。
撥油性は AATCC— TMl 18によって下記表 2に示す試験溶液を試験布上、 2箇所に数滴たらし、 30秒後の浸透状態を観察し、 浸漬を示さない試験溶液が 与える撥油性の最高点を撥油性とする。 撥水性 No. 状 態—
5 表面に付着湿潤のないもの
4 表面にわずかに付着湿潤を示すもの
3 表面に部分的湿潤を示すもの
2 表面に湿潤を示すもの
1 表面全体に湿潤を示すもの―
表 2
撥油性 試験溶液 表面張力 （dYne,cm、 25°C)
8 n—ヘプタン 20.0
7 n—オクタン 21.8
6 n—デカン 23. 5
5 n—ドデカン 25.0
4 n—テトラデカン 26. 7
3 n—へキサデカン 27.3
2 n—へキサデカン 35 29.6
ヌジヨール 65混合溶液
1 ヌジョール 31. 2
0 1に及ばないもの 貯蔵安定性
水性分散液 （固形分 30重量％) を、 40°Cで 1ヶ月保存し、 沈降の発生を観 察する。
〇 全く沈降なし
Δ わずかに沈降あり
X 多く沈降あり 実施例 1
500 c cフラスコに CnF2: CH2CH2OCOCH=CH.
(n = 6, 8， 10， 12， 14 (nの平均 8) の化合物の混合物） 100 g、 ステアリルァクリレート 50 g、 N—メチロールァクリルアミ ド 2 g、 純水 20 0 g、 トリプロピレングリコール 40 g、 酢酸 0. 3 g、 アルキルトリメチルァ ンモニゥムク口ライ ド 4 g、 ポリオキシエチレンアルキルフエニルエーテル 10 gを入れ、 撹拌下に 60°Cで 1 5分間、 超音波で乳化分散させた。 ァゾビスイソ プチルァミジン一 2塩酸塩 0. 75 gを添加し、 5時間反応させ、 重合体の水性 分散液を得た。 撥水撥油性および貯蔵安定性を評価した。 結果を表 3に示す。
実施例 2
5000 じフラスコに〇。？211十1〇^12じ^1„0じ0〇？1==〇^12
(n = 6, 8， 10， 1 2， 14 (nの平均 8) の化合物の混合物） 100 g、 ステアリルァクリレート 50 g、 3 _クロロー 2—ヒ ドロキシプロピルメタクリ レート 2 g、 純水 200 g、 トリプロピレングリコ一ル 30 g、 酢酸 0. 3 g、 アルキルトリメチルアンモニゥムクロライ ド 4 g、 ポリオキシエチレンアルキル フエニルエーテル 10 gを入れ、 撹拌下に 60°Cで 1 5分間、 超音波で乳化分散 させた。 ァゾビスイソブチルァミジン _ 2塩酸塩 0. 75 gを添加し、 5時間反 応させ、 重合体の水性分散液を得た。
撥水撥油性および貯蔵安定性を評価した。 結果を表 3に示す。
実施例 3
500 c cフラスコにCnF2n+1CH2CH2OCOCH = CH2
(n = 6， 8， 10， 1 2， 14 (nの平均 8) の化合物の混合物） 100 g、 ステアリルァクリレート 25 g、 2 _ェチルへキシルメタクリレート 25 g、 純 水 200 g、 トリプロピレングリコール 80 g、 酢酸 0. 3 g、 ァノレキルトリメ チルアンモニゥムク口ライ ド 4 g、 ポリオキシエチレンアルキルエーテル 10 g を入れ、 撹拌下に 60°Cで 1 5分間、 超音波で乳化分散させた。 ァゾビスイソブ チルァミジン一 2塩酸塩 0. 75 gを添加し、 5時間反応させ、 重合体の水性分 散液を得た。
撥水撥油性および貯蔵安定性を評価した。 結果を表 3に示す。
実施例 4
500じ （；フラスコに〇[1?211+1。？12〇^120じ0〇^^ =。^^
(n = 6， 8， 10， 1 2， 14 (nの平均 8) の化合物の混合物） 100 g、 ステアリルァクリレート 50 g、 ダイァセントンァクリルアミ ド 2 g、 純水 20
0 g、 トリプロピレングリコ一ル 50 g、 酢酸 0· 3 g、 アルキルトリメチルァ ンモニゥムクロライ ド 4 g、 ポリオキシエチレンアルキルフエニルエーテル 10 gを入れ、 撹拌下に 60°Cで 1 5分間、 超音波で乳化分散させた。 ァゾビスイソ プチルァミジン一 2塩酸塩 0. 75 gを添カ卩し、 5時間反応させ、 重合体の水性 分散液を得た。
撥水撥油性および貯蔵安定性を評価した。 結果を表 3に示す。
実施例 5
500 c cフラスコにCnF2n十1CH2CH2OCOCH=CH2
(n = 6, 8, 10, 1 2, 14 (nの平均 8) の化合物の混合物） 100 g、 ステアリルァクリレート 25 g、 2—ェチルへキシルメタクリレート 25 g、 N —メチロールァクリルアミ ド 2 g、 純水 200 g、 トリプロピレンダリコール 6 0 g、 酢酸 0. 3 g、 アルキルトリメチルアンモニゥムクロライ ド 4 g、 ポリオ キシエチレンアルキルエーテル 10 gを入れ、 撹拌下に 60°Cで 1 5分間、 超音 波で乳化分散させた。 ァゾビスィソプチルァミジン一 2塩酸塩 0. 75 gを添加 し、 5時間反応させ、 重合体の水性分散液を得た。
撥水撥油性および貯蔵安定性を評価した。 結果を表 3に示す。
比較例 1
トリプロピレングリコール 40 gに代えてプロピレングリコール 40 gを使用 する以外は、 実施例 1の手順を繰り返した。
比較例 2
トリプロピレングリコール 40 gに代えてジプロピレングリコール 40 gを使 用する以外は、 実施例 1の手順を繰り返した。
比較例 3
トリプロピレングリコール 30 gに代えてプロピレングリコール 30 gを使用 する以外は、 実施例 2の手順を繰り返した。
比較例 4
トリプロピレングリコール 30 gに代えてジプロピレングリコール 30 gを使 用する以外は、 実施例 2の手順を繰り返した。
比較例 5
トリプロピレングリコール 50 gに代えてプロピレングリコール 50 gを使用 する以外は、 実施例 4の手順を繰り返した。 表 3
Figure imgf000011_0001
注）
HL-3 ： J I S L— 02 1 7— 1 03法による洗濯 3回後
DC— 3 ： J I S L— 1 0 9 2— 3 22法によるドライクリーニング 3回後 発明の効果
本発明において使用するトリプロピレングリコールは、 無害性の点で優れてい る。 本発明の水性分散液は、 環境汚染の低減に有効であり、 耐久性のある撥水撥 油性および優れた貯蔵安定性を有している。

Claims

請 求 の 範 囲
1. (A) パ一フルォロアルキル基もしくはパ一フルォロアルケ-ル基および ァクリル酸基もしくはメタクリル酸基を有する重合性化合物の少なくとも 1種の ホモ重合体もしくは共重合体またはそれらと共重合可能な重合性化合物との共重 合体、
(B) トリプロピレングリコールである有機溶剤、 および
(C) 界面活性剤
を含有してなる撥水撥油剤水性分散液。
2. 有機溶剤（B)の量が重合体（A) 100重量部当たり 5〜 200重量部であ る特許請求の範囲第 1項記載の分散液。
3. 有機溶剤（B)の量が重合体（A) 100重量部当たり 1 0〜100重量部で ある特許請求の範囲第 1項記載の分散液。
4. 請求項 1に記載の分散液を適用した繊維製品。
PCT/JP1999/007006 1998-12-22 1999-12-14 Dispersion aqueuse hydrophobe et oleophobe Ceased WO2000037583A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP99961294A EP1172428B1 (en) 1998-12-22 1999-12-14 Aqueous dispersion of repellant for water and oil
JP2000589643A JP4457497B2 (ja) 1998-12-22 1999-12-14 撥水撥油剤水性分散液
US09/868,767 US6753376B1 (en) 1998-12-22 1999-12-14 Aqueous water-and oil-repellent dispersion

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP36429898 1998-12-22
JP10/364298 1998-12-22

Publications (1)

Publication Number Publication Date
WO2000037583A1 true WO2000037583A1 (fr) 2000-06-29

Family

ID=62620473

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1999/007006 Ceased WO2000037583A1 (fr) 1998-12-22 1999-12-14 Dispersion aqueuse hydrophobe et oleophobe

Country Status (4)

Country Link
US (1) US6753376B1 (ja)
EP (1) EP1172428B1 (ja)
JP (2) JP4457497B2 (ja)
WO (1) WO2000037583A1 (ja)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1236783A1 (de) * 2001-02-27 2002-09-04 Ciba Spezialitätenchemie Pfersee GmbH Wässrige Dispersionen von Fluorpolymer und Stabilisator
US6979711B2 (en) 2003-11-18 2005-12-27 E. I. Du Pont De Nemours And Company Fluorine efficient finishes for textiles
WO2006022122A1 (ja) * 2004-08-25 2006-03-02 Daikin Industries, Ltd. 撥水撥油剤組成物
US9534343B2 (en) 2012-10-18 2017-01-03 The Chemours Company Fc, Llc Partially fluorinated copolymer emulsions containing fatty acids and esters

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000061696A1 (en) * 1999-04-07 2000-10-19 Daikin Industries, Ltd. Aqueous water-and-oil repellant dispersion
WO2003062347A1 (en) * 2002-01-21 2003-07-31 Daikin Industries, Ltd. Aqueous water-and-oil repellant dispersion
US8236946B2 (en) * 2004-08-24 2012-08-07 Btg International Limited Process for the preparation of 17-0-vinyl-triflates as intermediates
JP4998260B2 (ja) * 2005-04-27 2012-08-15 ダイキン工業株式会社 Ｓ−Ｓｕｌｆａｔｅ基を持つ含フッ素重合体およびこの重合体を含む撥水撥油剤組成物
US20090030114A1 (en) * 2007-07-25 2009-01-29 Ying Wang Fluoropolymer emulsions
US8178004B2 (en) * 2008-06-27 2012-05-15 Aculon, Inc. Compositions for providing hydrophobic layers to metallic substrates
US8507601B2 (en) * 2009-11-09 2013-08-13 E. I. Du Pont De Nemours And Company Method using fluoropolymer emulsions
US8329822B2 (en) * 2009-11-09 2012-12-11 E.I. Du Pont De Nemours And Company Fluoropolymer emulsions
EP2518125A4 (en) * 2009-12-25 2015-07-22 Asahi Glass Co Ltd WATER- AND OIL-REPELLING COMPOSITION, METHOD FOR THE PRODUCTION THEREOF AND METHOD FOR THE TREATMENT OF AN ARTICLE
KR102449752B1 (ko) * 2022-08-18 2022-09-30 선유규 내구성이 우수한 수성 발수제 제조방법 및 이를 이용한 시공 방법

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0925478A (ja) * 1995-07-07 1997-01-28 Sunstar Inc 水分散型撥水撥油剤組成物
WO1997048780A1 (en) * 1996-06-21 1997-12-24 Daikin Industries, Ltd. Aqueous dispersion type fluorinated water- and oil-repellent

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5876481A (ja) * 1981-10-31 1983-05-09 Lion Corp 撥水撥油剤組成物
JPS6040182A (ja) 1983-08-16 1985-03-02 Asahi Glass Co Ltd 高引火点を有する撥水撥油剤
JPH05263070A (ja) 1992-03-17 1993-10-12 Daikin Ind Ltd 高引火点撥水撥油剤およびその製法
JPH0617034A (ja) 1992-07-03 1994-01-25 Asahi Glass Co Ltd 撥水撥油剤組成物およびその製造方法
JPH0814362B2 (ja) 1992-07-06 1996-02-14 株式会社三浦研究所 燃焼ガス再循環機構を備えたボイラシステム
JP3399107B2 (ja) * 1994-09-05 2003-04-21 ダイキン工業株式会社 撥水撥油性を有する防汚加工剤組成物
JPH09291481A (ja) * 1996-04-22 1997-11-11 Dai Ichi Kogyo Seiyaku Co Ltd 繊維用撥水撥油加工剤
JP3864610B2 (ja) * 1998-05-21 2007-01-10 旭硝子株式会社 水分散型撥水撥油剤組成物およびその製造方法
JP2000087014A (ja) * 1998-09-11 2000-03-28 Asahi Glass Co Ltd 撥水撥油剤組成物
JP2000136495A (ja) * 1998-10-30 2000-05-16 Asahi Glass Co Ltd 紙処理用組成物および処理紙

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0925478A (ja) * 1995-07-07 1997-01-28 Sunstar Inc 水分散型撥水撥油剤組成物
WO1997048780A1 (en) * 1996-06-21 1997-12-24 Daikin Industries, Ltd. Aqueous dispersion type fluorinated water- and oil-repellent

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1172428A4 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1236783A1 (de) * 2001-02-27 2002-09-04 Ciba Spezialitätenchemie Pfersee GmbH Wässrige Dispersionen von Fluorpolymer und Stabilisator
US6979711B2 (en) 2003-11-18 2005-12-27 E. I. Du Pont De Nemours And Company Fluorine efficient finishes for textiles
WO2006022122A1 (ja) * 2004-08-25 2006-03-02 Daikin Industries, Ltd. 撥水撥油剤組成物
JPWO2006022122A1 (ja) * 2004-08-25 2008-05-08 ダイキン工業株式会社 撥水撥油剤組成物
US7820745B2 (en) 2004-08-25 2010-10-26 Daikin Industries, Ltd. Water-repellent/oil-repellent composition
JP4816455B2 (ja) * 2004-08-25 2011-11-16 ダイキン工業株式会社 撥水撥油剤組成物
US9534343B2 (en) 2012-10-18 2017-01-03 The Chemours Company Fc, Llc Partially fluorinated copolymer emulsions containing fatty acids and esters

Also Published As

Publication number Publication date
JP2010043277A (ja) 2010-02-25
US6753376B1 (en) 2004-06-22
EP1172428A1 (en) 2002-01-16
EP1172428A4 (en) 2006-05-31
EP1172428B1 (en) 2011-06-01
JP4457497B2 (ja) 2010-04-28

Similar Documents

Publication Publication Date Title
JP5915641B2 (ja) 撥水撥油剤組成物
JP2010043277A (ja) 撥水撥油剤水性分散液
JP2022111181A (ja) 表面処理剤
WO2006022122A1 (ja) 撥水撥油剤組成物
JPS62577A (ja) 撥水撥油剤
WO2002024828A1 (en) Aqueous dispersion of water- and oil-repellent and process for the production thereof
JP6866699B2 (ja) 表面処理剤組成物
TWI260343B (en) A water and oil repellent aqueous dispersion
JP4760707B2 (ja) 撥水撥油剤組成物およびその製造法
JP2006188546A (ja) 仕上げ加工用水性分散液
JPWO2000037583A1 (ja) 撥水撥油剤水性分散液
TW201947003A (zh) 撥水撥油劑及纖維製品
JP4251075B2 (ja) 撥水撥油剤水性分散液
WO2013141249A1 (ja) 水性エマルション組成物
KR100689941B1 (ko) 발수 발유제 수성 분산액 조성물
WO2004069924A1 (ja) 水性エマルション組成物
TWI656207B (zh) 表面處理劑組成物
JPH0344593B2 (ja)
JPH0674409B2 (ja) 撥水撥油剤水性分散液
JP2001158877A (ja) 撥水撥油剤水性分散液の製造方法
JPWO2000061696A1 (ja) 撥水撥油剤水性分散液

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
ENP Entry into the national phase

Ref country code: JP

Ref document number: 2000 589643

Kind code of ref document: A

Format of ref document f/p: F

WWE Wipo information: entry into national phase

Ref document number: 1999961294

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 09868767

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: 1999961294

Country of ref document: EP