CN118087269A - Nonwoven fabric - Google Patents

Nonwoven fabric Download PDF

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Publication number
CN118087269A
CN118087269A CN202410220458.1A CN202410220458A CN118087269A CN 118087269 A CN118087269 A CN 118087269A CN 202410220458 A CN202410220458 A CN 202410220458A CN 118087269 A CN118087269 A CN 118087269A
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CN
China
Prior art keywords
group
nonwoven fabric
carbon atoms
monomer
fluoropolymer
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Pending
Application number
CN202410220458.1A
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Chinese (zh)
Inventor
南晋一
福森正树
榎本孝司
山本育男
朱敏
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Daikin Industries Ltd
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Daikin Industries Ltd
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Priority to CN202410220458.1A priority Critical patent/CN118087269A/en
Publication of CN118087269A publication Critical patent/CN118087269A/en
Pending legal-status Critical Current

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    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/16—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated carboxylic acids or unsaturated organic esters, e.g. polyacrylic esters, polyvinyl acetate
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/32—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising halogenated hydrocarbons as the major constituent
    • 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
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/248—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing chlorine
    • 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
    • D06M15/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having amino or quaternary ammonium groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • D06M15/295—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/22—Polymers or copolymers of halogenated mono-olefins
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
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    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/01—Stain or soil resistance
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
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    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

A nonwoven fabric having a fluoropolymer attached to a substrate, wherein the fluoropolymer comprises: (a) Repeating units derived from a fluoromonomer which is an alpha-chloroacrylate or alpha-chloroacrylamide having a fluoroalkyl group; and (b) repeating units derived from a haloalkene monomer, the fluoropolymer having no repeating units derived from a (meth) acrylate having a linear or branched hydrocarbon group having 18 or more carbon atoms (for example, 16 or more, particularly 14 or more). The nonwoven fabric has excellent water-repellency and oil-repellency, for example, excellent strong water repellency and high water pressure resistance.

Description

Nonwoven fabric
(The present application is a divisional application of the application name "nonwoven fabric" filed 8/2/2016.)
Technical Field
The present invention relates to a nonwoven fabric, and more particularly, to a nonwoven fabric to which a fluoropolymer is attached.
Background
In the prior art, treatment of fibrous articles with fluorine-containing treatment agents has been proposed.
International publication No. 2010/030044 discloses a treating agent composition containing a fluoropolymer having repeating units derived from a fluorine-containing monomer and a (meth) acrylate monomer having a cyclic hydrocarbon group. International publication No. 2011/122442 discloses a treatment agent composition containing a fluoropolymer having repeating units derived from an α -chloroacrylate and a (meth) acrylate monomer having a hydrocarbon group. In these publications, no study has been made on the application of nonwoven fabrics.
International publication No. 2013/99611 describes a method of treating a nonwoven fabric with a fluorine-containing treating agent. However, the nonwoven fabric cannot achieve satisfactory water and oil repellency.
Patent document 1: international publication No. 2010/030044
Patent document 2: international publication No. 2011/122442
Patent document 3: international publication No. 2013/99611
Disclosure of Invention
The invention aims at providing a non-woven fabric with high water and oil repellency and mechanical strength.
The present invention relates to a nonwoven fabric to which a fluoropolymer is attached.
The present invention provides a nonwoven fabric, which is formed by attaching a fluorine-containing polymer to a base material, wherein the fluorine-containing polymer comprises:
(a) Repeating units derived from a fluoromonomer which is an alpha-chloroacrylate or alpha-chloroacrylamide having a fluoroalkyl group; and
(B) Repeating units derived from a haloalkene monomer,
The fluoropolymer does not have a repeating unit derived from a (meth) acrylate having a linear or branched hydrocarbon group having 18 or more carbon atoms (for example, 16 or more, particularly 14 or more).
The fluoropolymer imparts water repellency, oil repellency, and/or stain resistance to the substrate.
Effects of the invention
The nonwoven fabric of the present invention has excellent water repellency, oil repellency, such as excellent strong water repellency and high water pressure resistance, and also has excellent mechanical strength, such as high tensile strength.
Detailed Description
In the present invention, a fluoropolymer is attached to a nonwoven fabric. The nonwoven fabric having the fluoropolymer attached thereto can be produced, for example, by applying a fluorine-containing treating agent to a nonwoven fabric (untreated nonwoven fabric substrate).
The fluorine-containing treating agent contains a fluorine-containing polymer and a liquid medium.
[ Fluoropolymer ]
The fluoropolymer has:
(a) Repeating units derived from a fluoromonomer which is an alpha-chloroacrylate or alpha-chloroacrylamide having a fluoroalkyl group; and
(B) Repeating units derived from a haloalkene monomer,
The fluoropolymer does not have a repeating unit derived from a (meth) acrylate having a linear or branched hydrocarbon group having 18 or more carbon atoms.
(A) Fluorine-containing monomer
The fluoromonomer (a) may be of the formula: CH 2 =c (-Cl) -C (=o) -Y-Z-Rf.
[ Wherein Y is-O-or-NH-, Z is a directly bonded or divalent organic group, and Rf is a fluoroalkyl group having 1 to 20 carbon atoms. ]
The fluoromonomer is preferably a compound represented by the following general formula:
CH2＝C(-Cl)-C(＝O)-Y-Z-Rf (I)
[ wherein Y is-O-or-NH-;
Z is a direct bond,
A linear or branched aliphatic group having 1 to 20 carbon atoms (particularly an alkylene group) such as a group represented by the formula- (CH 2)x - (wherein x is 1 to 10),
An aromatic group or a cyclic aliphatic group having 6 to 30 carbon atoms, a group represented by the formula-R 2(R1)N-SO2 -or the formula-R 2(R1) N-CO-, wherein R 1 is an alkyl group having 1 to 10 carbon atoms, and R 2 is a linear alkylene group or a branched alkylene group having 1 to 10 carbon atoms,
Wherein R 3 is a hydrogen atom or an acyl group having 1 to 10 carbon atoms (e.g., formyl, acetyl or the like), ar represents an optionally substituted arylene group, and p represents 0 or 1),
In the formula-CH 2-Ar-(O)q - (wherein Ar is an arylene group having a substituent as required), q is 0 or 1), or
- (CH 2)m-SO2-(CH2)n -or- (CH 2)m-S-(CH2)n -group) (wherein m is 1 to 10, n is 0 to 10);
Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms.
In the fluoromonomer, the Rf group is preferably a perfluoroalkyl group. The Rf group preferably has 1 to 12 carbon atoms, for example, 1 to 6, particularly 4 to 6, and more preferably 6. Examples of Rf groups include -CF3、-CF2CF3、-CF2CF2CF3、-CF(CF3)2、-CF2CF2CF2CF3、-CF2CF(CF3)2、-C(CF3)3、-(CF2)4CF3、-(CF2)2CF(CF3)2、-CF2C(CF3)3、-CF(CF3)CF2CF2CF3、-(CF2)5CF3、-(CF2)3CF(CF3)2、-(CF2)4CF(CF3)2、-C8F17.
The fluoromonomer is preferably an acrylate in which the Y group is-O-.
The Z group may specifically be a linear or branched aliphatic group (e.g., alkylene) having 1 to 20 carbon atoms (e.g., 1 to 10 carbon atoms, particularly 1 to 4 carbon atoms, particularly 1 or 2 carbon atoms), a group represented by the formula- (CH 2)x - (wherein x is 1 to 10)), a radical,
An aromatic group or a cyclic aliphatic group having 6 to 18 carbon atoms, a group represented by the formula-R 2(R1)N-SO2 -or the formula-R 2(R1) N-CO- (wherein R 1 is an alkyl group having 1 to 10 carbon atoms, R 2 is a linear or branched alkylene group having 1 to 10 carbon atoms), for example-CH 2CH2N(R1)SO2 -group (wherein R 1 is an alkyl group having 1 to 4 carbon atoms),
Formula-CH 2CH(OR3)CH2-[Ar-(O)q]p - (wherein R 3 is a hydrogen atom or an acyl group having 1 to 10 carbon atoms (for example, formyl group or acetyl group, etc.), ar is an arylene group having a substituent as required (for example, phenylene group), p is 0 or 1, q is 0 or 1), formula- (CH 2)n-Ar-(O)q - (wherein Ar is an arylene group having a substituent as required (for example, phenylene group), n is 0 to 10, q is 0 or 1), or
- (CH 2)m-SO2-(CH2)n -group or- (CH 2)m-S-(CH2)n -group) (wherein m is 1 to 10 and n is 0 to 10).
The aromatic or cycloaliphatic group may be substituted or unsubstituted. The S group or SO 2 group may be directly bonded to the Rf group.
Specific examples of the fluorine-containing monomer (a) include, but are not limited to, the following compounds.
CH2＝C(-Cl)-C(＝O)-O-(CH2)2-Rf
CH2＝C(-Cl)-C(＝O)-O-(CH2)4-Rf
CH2＝C(-Cl)-C(＝O)-O-(CH2)2-S-Rf
CH2＝C(-Cl)-C(＝O)-O-(CH2)2-S-(CH2)2-Rf
CH2＝C(-Cl)-C(＝O)-O-(CH2)2-SO2-Rf
CH2＝C(-Cl)-C(＝O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2＝C(-Cl)-C(＝O)-NH-(CH2)2-Rf
CH2＝C(-Cl)-C(＝O)-O-(CH2)3-S-Rf
CH2＝C(-Cl)-C(＝O)-O-(CH2)3-S-(CH2)2-Rf
CH2＝C(-Cl)-C(＝O)-O-(CH2)3-SO2-Rf
CH2＝C(-Cl)-C(＝O)-O-(CH2)3-SO2-(CH2)2-Rf
CH2＝C(-Cl)-C(＝O)-O-CH2CH2N(CH3)SO2-Rf
CH2＝C(-Cl)-C(＝O)-O-CH2CH(OCOCH3)CH2-Rf
CH 2＝C(-Cl)-C(＝O)-O-CH2 -Ph-O-Rf (here, ph is 1, 4-phenylene)
CH2＝C(-Cl)-C(＝O)-O-CH2CH(OH)CH2-Ph-O-Rf
CH2＝C(-Cl)-C(＝O)-O-CH2-Ph-Rf
CH2＝C(-Cl)-C(＝O)-O-CH2CH(OCOCH3)CH2-Ph-Rf
[ In the above formula, rf is a fluoroalkyl group having 1 to 20 carbon atoms. ]
(B) Halogenated alkene monomer
The haloalkene monomer (haloalkene) preferably has no fluorine atom.
The haloalkene is preferably an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms. The haloalkene is preferably a chloroene having 2 to 20 carbon atoms, particularly a C2 to 5 olefin having 1 to 5 chlorine atoms. Preferred specific examples of haloalkenes are: vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide; vinylidene halides such as vinylidene chloride, vinylidene bromide, and vinylidene iodide. Vinyl chloride and vinylidene chloride are preferred, and vinyl chloride is particularly preferred.
(C) Other monomers
The other monomers (c) than the monomers (a) and (b) are preferably free of fluorine. Examples of the other monomer (c) include a non-fluorine non-crosslinkable monomer (c 1) and a non-fluorine crosslinkable monomer (c 2).
The other monomer (c) is a (meth) acrylate containing no linear or branched hydrocarbon group having 18 or more carbon atoms (for example, 16 or more, particularly 14 or more). That is, in the present invention, a (meth) acrylate having a linear or branched hydrocarbon group having 18 or more carbon atoms (for example, 16 or more, particularly 14 or more), for example, stearyl (meth) acrylate or behenyl (meth) acrylate is not used.
(C1) Non-fluorine non-crosslinking monomer
The non-fluorine non-crosslinkable monomer (c 1) is a monomer containing no fluorine atom. The non-fluorine non-crosslinkable monomer (c 1) does not have a crosslinkable functional group. The non-fluorine non-crosslinkable monomer (c 1) is non-crosslinkable, unlike the crosslinkable monomer (c 2). The non-fluorine non-crosslinkable monomer (c 1) is preferably a non-fluorine monomer having a carbon-carbon double bond. The non-fluorine non-crosslinkable monomer (c 1) is preferably a vinyl monomer containing no fluorine. The non-fluorine non-crosslinkable monomer (c 1) is usually a compound having 1 carbon-carbon double bond.
Preferred non-fluorine non-crosslinkable monomers (c 1) are of the formula: CH 2 =a compound shown as CA-T.
[ Wherein A is a hydrogen atom, a methyl group or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom),
T is a hydrogen atom, a chain (straight or branched) hydrocarbon group having 1 to 17 carbon atoms (for example, 2 to 15, particularly 3 to 14, particularly 4 to 13), a cyclic hydrocarbon group having 4 to 30 carbon atoms, or a chain or cyclic organic group having 1 to 31 carbon atoms and having an ester bond. ]
Examples of the cyclic hydrocarbon group having 4 to 30 carbon atoms include a cyclic aliphatic group having 4 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic aliphatic hydrocarbon group having 7 to 30 carbon atoms.
Examples of the chain or cyclic organic group having 1 to 31 carbon atoms with an ester bond are-C (=o) -O-Q and-O-C (=o) -Q (here, Q is a chain (straight or branched) aliphatic hydrocarbon group having 1 to 17 carbon atoms (e.g., 2 to 15, particularly 3 to 14, particularly 4 to 13), a cyclic aliphatic group having 4 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or an aromatic aliphatic hydrocarbon group having 7 to 30 carbon atoms.
Preferred examples of the non-fluorine non-crosslinkable monomer (c 1) include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and vinyl alkyl ether. The non-fluorine non-crosslinkable monomer (c 1) is not limited to these examples.
The non-fluorine non-crosslinkable monomer (c 1) may be a (meth) acrylate having an alkyl group. The number of carbon atoms of the alkyl group may be 1 to 17, for example, 2 to 15 (particularly 3 to 14, particularly 4 to 13). For example, the non-fluorine non-crosslinkable monomer (c 1) may be of the general formula: an acrylate represented by CH 2＝CA1 COOA2.
[ Wherein A 1 is a hydrogen atom, a methyl group or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom),
A 2 is an alkyl group represented by C nH2n+1 (n=1 to 17). ]
A preferred specific example of A 2 is butyl or lauryl.
The non-fluorine non-crosslinkable monomer (c 1) may be a (meth) acrylate monomer having a cyclic hydrocarbon group.
The cyclic hydrocarbyl containing acrylate monomer is preferably of the formula: a compound shown in CH 2＝CA21-C(＝O)-O-A22.
[ Wherein A 21 is a hydrogen atom or a methyl group, and A 22 is a cyclic hydrocarbon-containing group having 4 to 30 carbon atoms. ]
The cyclic hydrocarbon group-containing acrylate monomer is a monomer whose homopolymer has a high glass transition temperature (for example, 50℃or higher, particularly 80℃or higher).
The cyclic hydrocarbon group-containing acrylate monomer does not have a fluoroalkyl group. The cyclic hydrocarbon group-containing acrylate monomer may contain a fluorine atom, but preferably does not contain a fluorine atom.
A 21 may be a hydrogen atom.
A 22 is a cyclic hydrocarbon group which may have a chain group (for example, a linear or branched hydrocarbon group). Examples of the cyclic hydrocarbon group include saturated or unsaturated, monocyclic group, polycyclic group, bridged group, and the like. The cyclic hydrocarbon group is preferably a saturated cyclic hydrocarbon group. The cyclic hydrocarbon group has 4 to 30 carbon atoms, preferably 6 to 20 carbon atoms. Examples of the cyclic hydrocarbon group include: a cyclic aliphatic group having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an aromatic aliphatic group having 7 to 20 carbon atoms. The cyclic hydrocarbon group has particularly preferably 15 or less, for example 12 or less, carbon atoms. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group. Specific examples of the cyclic hydrocarbon group include cyclohexyl, t-butylcyclohexyl, isobornyl, dicyclopentanyl, and adamantyl.
Specific examples of the cyclic hydrocarbon group-containing acrylate monomer include: cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclopentyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, and the like.
The water repellency and oil repellency imparted by the copolymer is enhanced by the presence of the cyclic hydrocarbon group-containing acrylate monomer.
(C2) Non-fluorine crosslinking monomer
The fluoropolymer may have repeating units derived from a non-fluorine crosslinkable monomer (c 2). The non-fluorine-crosslinking monomer (c 2) is a monomer containing no fluorine atom. The non-fluorine crosslinkable monomer (c 2) may be a compound having at least 2 reactive groups and/or carbon-carbon double bonds and containing no fluorine. The non-fluorine crosslinkable monomer (c 2) may be a compound having at least 2 carbon-carbon double bonds, or a compound having at least 1 carbon-carbon double bond and at least 1 reactive group. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups, and the like. The non-fluorine crosslinkable monomer (c 2) may be a mono (meth) acrylate, a di (meth) acrylate or a mono (meth) acrylamide having a reactive group. Alternatively, the non-fluorine crosslinkable monomer (c 2) may be a di (meth) acrylate.
Examples of the non-fluorine-crosslinkable monomer (c 2) include diacetone (meth) acrylamide, N-methylol (meth) acrylamide, methylol (meth) acrylate, hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, butadiene, isoprene, chloroprene, glycidyl (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like.
By copolymerizing the non-fluorine non-crosslinkable monomer (c 1) and/or the non-fluorine crosslinkable monomer (c 2), it is possible to improve various properties such as water repellency, oil repellency, stain resistance, and cleaning resistance, washing resistance, solvent solubility, hardness, feel, and the like of these properties as needed.
In this specification, in the case of simply referred to as "acrylate" or "acrylamide", not only a compound in which the α -position is a hydrogen atom, but also a compound in which the α -position is substituted with another group (for example, a monovalent organic group including a methyl group or a halogen atom) are included. In the present specification, "(meth) acrylate" means acrylate or methacrylate, and "(meth) acrylamide" means acrylamide or methacrylamide.
The monomers (a), (b), and (c) (for example, the monomers (c 1) and (c 2) may each be 1 kind alone or may be a combination of 2 or more kinds.
In the fluoropolymer, the amount of the fluoromonomer (a) may be 20 to 90% by weight, preferably 30 to 80% by weight, relative to the fluoropolymer.
In the fluoropolymer, relative to 100 parts by weight of the fluoromonomer (a),
The amount of the haloalkene monomer (b) is 5 to 300 parts by weight, for example, 10 to 200 parts by weight, particularly 20 to 100 parts by weight, particularly 30 to 80 parts by weight,
The amount of the other monomer (c) is 0 to 800 parts by weight, for example, 1 to 300 parts by weight, particularly 2 to 200 parts by weight, and particularly 3 to 100 parts by weight.
In the fluoropolymer, relative to 100 parts by weight of the fluoromonomer (a),
The amount of the non-fluorine non-crosslinkable monomer (c 1) may be 0 to 500 parts by weight, for example 1 to 300 parts by weight, particularly 2 to 200 parts by weight, particularly 3 to 100 parts by weight,
The amount of the non-fluorine-crosslinking monomer (c 2) may be 0 to 80 parts by weight, for example, 0 to 50 parts by weight, particularly 0.1 to 30 parts by weight, particularly 1 to 20 parts by weight.
The number average molecular weight (Mn) of the fluoropolymer may generally be 1000 to 1000000, for example 5000 to 500000, in particular 3000 to 200000. The number average molecular weight (Mn) of the fluoropolymer is usually determined by GPC (gel permeation chromatography).
In the present invention, the monomers (a) to (c) are copolymerized to obtain a fluorine-containing treating agent (surface treating agent composition) in which a fluorine-containing polymer is dispersed or dissolved in a medium.
The monomer may be polymerized in the presence of at least 1 compound selected from the group consisting of blocked isocyanate compounds and organopolysiloxane compounds. The amount of the blocked isocyanate compound (or organopolysiloxane compound) may be 0 to 100 parts by weight, for example 1 to 50 parts by weight, relative to 100 parts by weight of the monomer.
By polymerizing the monomer in the presence of the blocked isocyanate compound, a fluoropolymer having blocked isocyanate groups can be obtained. The blocked isocyanate compound is an isocyanate obtained by blocking with at least one blocking agent. Examples of the blocking agent include oximes, phenols, alcohols, thiols, amides, imides, imidazoles, ureas, amines, imines, pyrazoles, and active methylene compounds. Other examples of the end-capping agent may be exemplified by pyridinols, thiophenols, diketones, and esters. The blocked isocyanate compound may be modified with a compound having a hydrophilic group.
The fluorinated polymer having a siloxane group can be obtained by polymerizing a monomer in the presence of an organopolysiloxane compound (e.g., mercapto-functional organopolysiloxane, vinyl-functional organopolysiloxane). In 1 embodiment, the mercapto-functional organopolysiloxane comprises siloxane units having the average formula:
(R2SiO)a(RRNSiO)b(RRSSiO)c
[ wherein a is 0 to 4000, 0 to 1000 or 0 to 400,
B is 1 to 1000, 1 to 100 or 1 to 50,
C is 1 to 1000, 1 to 100 or 1 to 50;
r is independently a monovalent organic group, R is a hydrocarbon having 1 to 30 carbon atoms, R is a monovalent alkyl group having 1 to 12 carbon atoms, or R is a methyl group;
R N is a monovalent amino-functional organic group as defined above,
R S is a monovalent mercapto-functional organic group as defined above. ]
The amount of the fluorine-containing polymer (solid content) may be about 0.01 to 60% by weight, preferably about 0.1 to 40% by weight, particularly preferably about 5 to 35% by weight, relative to the fluorine-containing treating agent or the surface treating agent composition.
The fluoropolymer may be present as a solution in an organic solvent, but is preferably present as an aqueous dispersion.
[ Liquid Medium ]
The liquid medium may be an aqueous medium. The aqueous medium may be water alone or in a mixture with a (water miscible) organic solvent. The amount of the organic solvent may be 30% by weight or less, for example 10% by weight or less (preferably 0.1% or more) with respect to the liquid medium. The liquid medium is preferably water alone. The liquid medium may be an organic solvent only.
The amount of liquid medium may be 30 to 99.1% by weight, particularly 50 to 99% by weight, relative to the fluorine-containing treating agent (or surface treating agent composition).
[ Surfactant ]
The fluorine-containing treatment agent may contain a surfactant. When the fluorine-containing treating agent contains an aqueous medium, the fluorine-containing treating agent preferably contains a surfactant. The fluorine-containing treating agent preferably contains a fluorine-containing polymer, a liquid medium (preferably an aqueous medium), and a surfactant.
In the present invention, the surfactant may be at least 1 selected from the group consisting of nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.
As examples of the nonionic surfactant, ethers, esters, ester ethers, alkanolamides, polyols and amine oxides can be cited.
Examples of ethers are compounds having an oxyalkylene group, preferably a polyoxyethylene group.
Examples of esters are esters of alcohols with fatty acids. Examples of the alcohol include 1 to 6-membered (particularly 2 to 5-membered) alcohols having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.
Examples of the ester ether are compounds in which an ester of an alcohol with a fatty acid is added with an oxyalkylene group, particularly an oxyethylene group. Examples of the alcohol include 1 to 6-membered (particularly 2 to 5-membered) alcohols having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.
Examples of alkanolamides are formed from fatty acids and alkanolamines. The alkanolamide may be a mono-alkanolamide or a di-alkanolamino group. Examples of fatty acids are saturated or unsaturated fatty acids having 2to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamine may be an alkanol having from 2to 50, particularly from 5 to 30, carbon atoms with from 1 to 3 amino groups and from 1 to 5 hydroxyl groups.
The polyol may be a 2-5-membered alcohol having 3 to 30 carbon atoms.
The amine oxide may be an oxide (e.g., having 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).
The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms of the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic surfactant is generally preferably 2 to 100.
The nonionic surfactant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyols and amine oxides, preferably nonionic surfactants having an oxyalkylene group.
The nonionic surfactant may be a linear and/or branched aliphatic (saturated and/or unsaturated) alkylene oxide adduct, a linear and/or branched fatty acid (saturated and/or unsaturated) polyalkylene glycol ester, a Polyoxyethylene (POE)/polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, or the like. Among them, the structures of the alkylene oxide addition moiety and the polyalkylene glycol moiety are preferably Polyoxyethylene (POE), polyoxypropylene (POP) or POE/POP copolymer (which may be a random copolymer or a block copolymer).
In addition, from the viewpoint of environmental problems (biodegradability, environmental hormones, etc.), the nonionic surfactant is preferably a structure containing no aromatic group.
The nonionic surfactant can be of the formula: a compound represented by R 1O-(CH2CH2O)p-(R2O)q-R3.
[ Wherein R 1 is an alkyl group having 1to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms or an acyl group,
R 2 are each independently the same or different and are an alkylene group having 3 or more carbon atoms (for example, 3 to 10),
R 3 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more,
Q is a number of 0 or 1 or more. ]
R 1 has preferably 8 to 20 carbon atoms, particularly preferably 10 to 18 carbon atoms. Preferable specific examples of R 1 include lauryl, tridecyl and oleyl.
Examples of R 2 are propylene and butylene.
In the nonionic surfactant, p may be a number of 3 or more (for example, 5to 200). q may be a number of 2 or more (for example, 5to 200). That is, - (R 2O)q -may form a polyoxyalkylene chain).
The nonionic surfactant may be a polyoxyalkylene alkyl ether having a hydrophilic polyoxyalkylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) in the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, and among these, the oxypropylene chain is preferable.
Preferred nonionic surfactants are of the formula: and R 1O-(CH2CH2O)p -H.
[ Wherein R 1 and p have the same meaning as above. ]
Specific examples of nonionic surfactants are:
C10H21O-(CH2CH2O)p-(C3H6O)q-H
C12H25O-(CH2CH2O)p-(C3H6O)q-H
C16H31O-(CH2CH2O)p-(C3H6O)q-H
C16H33O-(CH2CH2O)p-(C3H6O)q-H
C18H35O-(CH2CH2O)p-(C3H6O)q-H
C18H37O-(CH2CH2O)p-(C3H6O)q-H
C12H25O-(CH2CH2O)p-(C3H6O)q-C12H25
C16H31O-(CH2CH2O)p-(C3H6O)q-C16H31
C16H33O-(CH2CH2O)p-(C3H6O)q-C12H25
iso-C13H27O-(CH2CH2O)p-(C3H6O)q-H
C10H21COO-(CH2CH2O)p-(C3H6O)q-H
C16H33COO-(CH2CH2O)p-(C3H6O)q-C12H25 Etc.
[ Wherein p and q have the same meaning as above. ]
Specific examples of the nonionic surfactant include condensation products of ethylene oxide with hexylphenol, isooctylphenol, cetyl alcohol, oleic acid, alkane (C 12-C16) thiol, sorbitan fatty acid (C 7-C19) or alkyl (C 12-C18) amine, and the like.
The proportion of the polyoxyethylene block may be 5 to 80% by weight, for example 30 to 75% by weight, in particular 40 to 70% by weight, relative to the molecular weight of the nonionic surfactant (copolymer).
The average molecular weight of the nonionic surfactant is generally 300 to 5,000, for example 500 to 3,000.
The nonionic surfactant may be used alone or in combination of at least 2 kinds.
The nonionic surfactant is preferably a combination of 2 or more. Of the combinations of 2 or more, at least 1 nonionic surfactant may be a compound represented by R 1O-(CH2CH2O)p-(R2O)q-R3 [ especially R 1O-(CH2CH2O)p -H ] wherein the R 1 group (and/or R 3 group) is a branched alkyl group (e.g., isotridecyl). The amount of the nonionic surfactant in which the R 1 group is a branched alkyl group may be 5 to 100 parts by weight, for example, 8 to 50 parts by weight, particularly 10 to 40 parts by weight, relative to 100 parts by weight of the total nonionic surfactant. Of the 2 or more combinations, the remaining nonionic surfactants can be compounds represented by R 1O-(CH2CH2O)p-(R2O)q-R3 [ especially R 1O-(CH2CH2O)p -H ] where the R 1 group (and/or R 3 group) is a (saturated and/or unsaturated) straight chain alkyl group (e.g., lauryl (n-lauryl)).
Examples of the nonionic surfactant include: polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerol fatty acid ester, polyoxyethylene glycerol fatty acid ester, polyglycerol fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkyl alcohol amide, alkyl alkanolamide, acetylene glycol, an oxyethylene adduct of acetylene glycol, polyethylene glycol polypropylene glycol block copolymer, and the like. Preferably polyoxyethylene alkyl ethers and polyoxyethylene sorbitan fatty acid esters. More preferred are polyoxyethylene alkyl ethers.
The cationic surfactant may be amine salt, quaternary ammonium salt, or ethylene oxide addition type ammonium salt. Specific examples of the cationic surfactant include, but are not particularly limited to: amine salt type surfactants such as alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazoline, quaternary ammonium type surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzyl ammonium salts, pyridinium salts, alkylisoquinolinium salts, and benzylammonium chloride.
Preferred examples of cationic surfactants are compounds R 21-N+(-R22)(-R23)(-R24)X-.
[ Wherein R 21、R22、R23 and R 24 are hydrocarbon groups having 1 to 30 carbon atoms,
X is an anionic group. ]
Specific examples of R 21、R22、R23 and R 24 are alkyl groups (e.g., methyl, butyl, stearyl, soft-lipidyl). Specific examples of X are halogen (e.g., chlorine), acid (e.g., hydrochloric acid, acetic acid).
The cationic surfactant is particularly preferably a monoalkyl trimethyl ammonium salt (alkyl group having 4 to 30 carbon atoms).
The cationic surfactant is preferably an ammonium salt. The cationic surfactant may be of the formula: and an ammonium salt represented by R 1 p-N+R2 qX-.
[ Wherein R 1 is a linear and/or branched aliphatic (saturated and/or unsaturated) group having not less than C 12 (for example, C 12～C50),
R 2 is H or C 1～C4 alkyl, benzyl, polyoxyethylene (the number of oxyethylene groups is for example 1 (in particular 2, in particular 3) to 50) (particularly preferably CH 3、C2H5),
X is halogen atom, fatty acid salt group of C 1～C4,
P is 1 or 2, q is 2 or 3, and p+q=4. ]
The number of carbon atoms of R 1 may be 12 to 50, for example 12 to 30.
Specific examples of the cationic surfactant include: dodecyl trimethyl ammonium acetate, trimethyl tetradecyl ammonium chloride, hexadecyl trimethyl ammonium bromide, trimethyl octadecyl ammonium chloride, (dodecyl methyl benzyl) trimethyl ammonium chloride, benzyl dodecyl dimethyl ammonium chloride, methyl dodecyl di (hydrogen polyoxyethylene) ammonium chloride, benzyl dodecyl di (hydrogen polyoxyethylene) ammonium chloride, N- [2- (diethylamino) ethyl ] oleoyl amine hydrochloride, dialkyl (reduced tallow) dimethyl ammonium chloride, and the like. Cationic emulsifiers having an ammonium chloride structure are preferred. Further preferred are cationic emulsifiers having an ammonium chloride structure containing a long chain (e.g., a hydrocarbon group having 10 to 30 carbon atoms, particularly 14 to 24 carbon atoms), such as octadecyl or hexadecyl, and particularly an alkyl group.
Specific examples of the anionic surfactant include: sodium lauryl sulfate, triethanolamine lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene nonylphenyl ether sulfate, triethanolamine polyoxyethylene lauryl ether sulfate, sodium cocoyl sarcosinate, sodium N-cocoyl methyl taurate, sodium polyoxyethylene cocoyl ether sulfate, sodium diether hexyl sulfosuccinate, sodium alpha-olefin sulfonate, sodium lauryl phosphate, sodium polyoxyethylene lauryl ether phosphate, perfluoroalkyl carboxylate (trade names Unidyne DS-101, 102 (manufactured by Dain industries, ltd.), and the like. The anionic surfactant is preferably a salt of an organic acid (e.g., a salt of an organic acid with an inorganic base or amine). More preferably an alkyl sulfate (e.g., ROSO 3 -M+) (alkyl (R group) has 8 to 30.M of carbon atoms and is an alkali metal (e.g., sodium or potassium)).
Specific examples of the amphoteric surfactant include amine oxides, anilines, imidazolinium betaines, amidobetaines, and acetic acid betaines, and specific examples include lauryl betaine, stearyl betaine, lauryl Gui Jisuo methyl hydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetic acid betaine, and fatty acid amidopropyl dimethylaminoacetic acid betaine. Amine oxides (for example, R 3 n=o (each R group is, for example, a hydrocarbon group having 1 to 30 carbon atoms (particularly, an alkyl group)) are preferable.
The nonionic surfactant, the cationic surfactant, the anionic surfactant, and the amphoteric surfactant may be 1 kind or a combination of 2 or more kinds, respectively.
The fluorine-containing treating agent may contain additives in addition to the fluorine-containing polymer, the liquid medium and the surfactant. Examples of additives are silicon-containing compounds, waxes, acrylic emulsions, and the like. Other examples of additives are other fluoropolymers, drying rate modifiers, crosslinking agents, film forming aids, phase solvents, surfactants, anti-freeze agents, viscosity modifiers, ultraviolet light absorbers, antioxidants, pH modifiers, defoamers, hand modifiers, slip modifiers, antistatic agents, hydrophilizing agents, antimicrobial agents, preservatives, insect repellents, fragrances, flame retardants, and the like.
The fluoropolymer and the non-fluoropolymer in the present invention can be produced by any of usual polymerization methods, and the conditions of the polymerization reaction can be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization.
In the solution polymerization, a method of dissolving a monomer in an organic solvent in the presence of a polymerization initiator, and heating and stirring the solution at 30 to 120 ℃ for 1 to 10 hours after nitrogen substitution may be employed. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and the like. The polymerization initiator is used in a range of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, relative to 100 parts by weight of the monomer.
The organic solvent is inactive to the monomer and can dissolve the monomer, and may be, for example, an ester (for example, an ester having 2 to 30 carbon atoms, specifically ethyl acetate or butyl acetate), a ketone (for example, a ketone having 2 to 30 carbon atoms, specifically methyl ethyl ketone or diisobutyl ketone), or an alcohol (for example, an alcohol having 1 to 30 carbon atoms, specifically isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1, 4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1, 2-tetrachloroethane, 1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, and the like. The organic solvent is used in a range of 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight, relative to 100 parts by weight of the total of the monomers.
In emulsion polymerization, a method of emulsifying a monomer in water in the presence of a polymerization initiator and an emulsifier, and then stirring the mixture at 50 to 80℃for 1 to 10 hours to polymerize the monomer may be employed. As the polymerization initiator, there may be used water-soluble polymerization initiators such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutyrimidine dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate and the like, or oil-soluble polymerization initiators such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate and the like. The polymerization initiator is used in a range of 0.01 to 10 parts by weight relative to 100 parts by weight of the monomer.
In order to obtain an aqueous polymer dispersion excellent in storage stability, it is preferable to use an emulsifying device capable of applying powerful pulverizing energy, such as a high-pressure homogenizer or an ultrasonic homogenizer, to atomize and polymerize the monomer in water. As the emulsifier, various emulsifiers of anionic type, cationic type or nonionic type may be used, and the emulsifier is used in the range of 0.5 to 20 parts by weight based on 100 parts by weight of the monomer. Preferably, anionic and/or nonionic and/or cationic emulsifiers are used. In the case where the monomers are not completely compatible, it is preferable to add a phase solvent which makes these monomers sufficiently compatible, for example, a water-soluble organic solvent or a low molecular weight monomer. By adding the phase solvent, the emulsifying property and the copolymerization property can be improved.
Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and ethanol, and the water-soluble organic solvent may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, based on 100 parts by weight of water. Examples of the low molecular weight monomer include methyl methacrylate, glycidyl methacrylate, and 2, 2-trifluoroethyl methacrylate, and the like, and the monomer may be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, based on 100 parts by weight of the total amount of the monomers.
Chain transfer agents may be used in the polymerization. The molecular weight of the polymer may be changed corresponding to the amount of the chain transfer agent used. Examples of the chain transfer agent include thiol group-containing compounds (particularly (for example, alkyl mercaptans having 1 to 30 carbon atoms)) such as lauryl mercaptan, thioglycol and thioglycerol, inorganic salts such as sodium hypophosphite and sodium bisulphite. The amount of the chain transfer agent to be used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, relative to 100 parts by weight of the total amount of the monomers.
The fluorine-containing treatment agent of the present invention may be in the form of a solution, an emulsion (particularly an aqueous dispersion) or an aerosol, and is preferably an aqueous dispersion. The fluorine-containing treatment agent contains a polymer (active ingredient of the surface treatment agent) and a medium (particularly a liquid medium such as an organic solvent and/or water). For example, the amount of the medium may be 5 to 99.9% by weight, particularly 10 to 80% by weight, relative to the fluorine-containing treating agent.
In the fluorine-containing treating agent, the concentration of the polymer may be 0.01 to 95% by weight, for example, 5 to 50% by weight.
The fluorine-containing treating agent of the present invention can be applied to a nonwoven fabric substrate by a conventionally known method. In general, the fluorine-containing treating agent may be diluted with an organic solvent or water, and then attached to the surface of the object to be treated by a known method such as dip coating, spray coating, or foam coating, and dried. In addition, the polymer may be used together with an appropriate crosslinking agent as needed, and cured. The fluorine-containing treating agent of the present invention may be used in combination with an insect repellent, a softening agent, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixative, an anti-wrinkling agent, etc. The concentration of the polymer in the treatment liquid in contact with the substrate may be 0.01 to 10% by weight (in particular in the case of dip coating), for example 0.05 to 10% by weight.
[ Nonwoven fabric substrate ]
The nonwoven fabric of the present invention can be produced by applying a fluorine-containing treating agent to a nonwoven fabric substrate. The nonwoven substrate is typically an untreated nonwoven, particularly a nonwoven that has not been applied with a pharmaceutical agent.
Examples of the fibers constituting the nonwoven fabric substrate are natural fibers, synthetic fibers, semisynthetic fibers, regenerated fibers, and inorganic fibers. The fibers may be used alone or in combination of 2 or more.
Examples of natural fibers are cellulose fibers such as cotton, flax, wood pulp, chitin, chitosan, wool, and silk. Specific examples of the wood pulp include mechanical pulp such as fine ground wood pulp (GP), pressure ground wood Pulp (PGW), thermomechanical pulp (TMP), and the like, needle-leaved tree high-yield unbleached kraft pulp (HNKP, N-material), needle-leaved tree bleached kraft pulp (NBKP, N-material, NB-material), broad-leaved tree unbleached kraft pulp (LUKP, L-material), chemical pulp such as broad-leaved tree bleached kraft pulp (LBKP, L-material), and the like, and old pulp such as deinked pulp (DIP), waste paper pulp (WP), and semi-Chemical Pulp (CP), and the like.
Examples of the synthetic fibers are polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and copolyesters; polyolefin such as linear low density polyethylene, high density polyethylene, polypropylene, etc.; polyamides such as nylon 6, nylon 66, nylon 610, nylon 46, etc.; acrylic fibers such as polyacrylonitrile; polyvinyl alcohol, polyurethane, polyvinyl chloride.
Examples of semi-synthetic fibers are acetate fibers, triacetate fibers.
Examples of regenerated fibres are rayon, cuprammonium fibres (cupronion), viscose fibres (Lyocell), lyocell, tencel.
Examples of inorganic fibers are glass fibers and carbon fibers.
The fibers constituting the nonwoven fabric substrate are preferably a combination of natural fibers and synthetic fibers, for example, a combination of cellulose-based fibers and polyester fibers, particularly a combination of wood pulp fibers and polyester fibers (for example, polyethylene terephthalate fibers). In the combination of natural fibers and synthetic fibers, the weight ratio of natural fibers to synthetic fibers may be 5: 95-95: 5, for example 30: 70-70: 30. or in the case where strength, durability, etc. are required of the nonwoven fabric, the weight ratio of the natural fibers to the synthetic fibers may be 5: 95-70: 30, for example 10: 90-50: 50, in particular 15: 85-45: 55.
The fluoropolymer may be applied to the nonwoven substrate by any method known for treating fibrous articles with liquids. The nonwoven fabric substrate may be immersed in a liquid (a liquid containing a fluoropolymer, for example, a solution or dispersion), or the liquid may be adhered to or sprayed on the nonwoven fabric substrate. The nonwoven fabric substrate to be treated is dried to exhibit water repellency and oil repellency, and is preferably heated at, for example, 100 to 200 ℃.
Alternatively, the polymer may be applied to the nonwoven substrate by a cleaning method, for example, in a washing application, a dry cleaning method, or the like.
The amount of the fluoropolymer to be adhered to the nonwoven fabric substrate may be usually 0.001 to 20 parts by weight, for example 0.01 to 5 parts by weight, particularly 0.05 to 1 part by weight, relative to 100 parts by weight of the nonwoven fabric substrate.
The term "treatment" refers to the application of a treatment agent to an object to be treated by dipping, spraying, coating, or the like. By the treatment, the polymer as an active ingredient of the treatment agent permeates into the object to be treated and/or adheres to the surface of the object to be treated.
Examples
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
Hereinafter, unless otherwise specified, parts,% or ratios refer to parts by weight, wt% or ratios by weight.
The procedure of the test is as follows.
Spray water repellency test (Spray)
The spray water repellency test was conducted in accordance with JIS-L-1092. The shower water repellency test (shown in Table 1 described below) is indicated by water repellency No. s.
A glass funnel having a volume of at least 250ml and a nozzle capable of ejecting 250ml of water for 20 to 30 seconds were used. The test piece frame was a metal frame having a diameter of 15 cm. 3 test pieces having a size of about 20cm×20cm were prepared, and the pieces were fixed to a test piece fixing frame so that the pieces were free from wrinkles. The center of the spray was placed in the center of the sheet. To the glass funnel was added room temperature water (250 mL) and the test sheet (25 to 30 seconds elapsed) was sprayed. The holding frame is removed from the table, and one end of the holding frame is grasped so that the front surface is the lower side, and the opposite end is tapped with a hard object. The holding frame was further rotated 180 °, and the same procedure was repeated to drop the excessive water. Wet test pieces were compared with wet comparison standards in order of poor water repellency to scores of 0, 50, 70, 80, 90, and 100. The results were obtained from the average of 3 determinations.
[ Table 1]
Water repellency test (IPA)
The treated test cloth was stored in a constant temperature and humidity machine at a temperature of 21℃and a humidity of 65% for 4 hours or more. The test solutions (isopropyl alcohol (IPA), water, and mixtures thereof, as shown in Table 2) were also used, and the test solutions were stored at a temperature of 21 ℃. The test was carried out in a constant temperature and humidity chamber at a temperature of 21℃and a humidity of 65%. After the test piece was left for 30 seconds, 50. Mu.l of the test piece was smoothly dropped onto the test piece, and if the droplet remained on the test piece, the test piece was accepted. Regarding the water repellency, the maximum value of isopropyl alcohol (IPA) content (vol%) of the acceptable test liquid was evaluated as the number of points, and twelve grades of FAIL, 0, 1,2, 3, 4, 5, 6, 7, 8, 9, and 10 were evaluated in terms of the degree of poor water repellency.
[ Table 2]
IPR (WATER IMPACT Penetration Resistance) test
IPR test was performed according to AATCC TEST Method 42-2000.
Hydrostatic test (Hydro Head)
The water resistance was measured using a water resistance measuring device according to AATCC 127-2003 water resistance test method.
Tensile Strength test
The treated test cloth was cut into 15cm×5cm pieces, and the tensile strength in the machine direction and the tensile strength in the transverse direction were measured by a tensile tester.
Production example 1
To a 1000ml autoclave were added CF3CF2-(CF2CF2)n-CH2CH2OCOC(Cl)＝CH2(n＝2.0)97.2g、 g of lauryl acrylate 73.66g, pure water 405g, an aqueous glycol solvent 34.8g, an alkylamine oxide 11.75g and a polyoxyethylene alkyl ether 6.17g, and the mixture was dispersed by ultrasonic emulsification at 60℃for 15 minutes under stirring. After nitrogen substitution was performed in the autoclave, 43g of vinyl chloride was added, and a solution of 0.86g of an azo group-containing water-soluble initiator and 9g of water was added to the mixture to react at 60℃for 5 hours to obtain an aqueous polymer dispersion. The composition of the polymer is substantially identical to the composition of the feed monomer.
Production example 2
To a 1000ml autoclave were added CF3CF2-(CF2CF2)n-CH2CH2OCOC(Cl)＝CH2(n＝2.0)97.2g、 g of butyl acrylate 73.66g, 405g of pure water, 34.8g of an aqueous glycol solvent, 11.75g of an alkylamine oxide and 6.17g of polyoxyethylene alkyl ether, and the mixture was dispersed by ultrasonic emulsification at 60℃for 15 minutes under stirring. After nitrogen substitution was performed in the autoclave, 43g of vinyl chloride was added, and a solution of 0.86g of an azo group-containing water-soluble initiator and 9g of water was added to the mixture to react at 60℃for 5 hours to obtain an aqueous polymer dispersion. The composition of the polymer is substantially identical to the composition of the feed monomer.
Production example 3
To a 1000ml autoclave were added CF3CF2-(CF2CF2)n-CH2CH2OCOC(Cl)＝CH2(n＝2.0)97.2g、 g of lauryl acrylate, 24.5g of isobornyl methacrylate, 405g of pure water, 34.8g of an aqueous glycol solvent, 11.75g of an alkylamine oxide and 6.17g of polyoxyethylene alkyl ether, and the mixture was dispersed by ultrasonic emulsification at 60℃for 15 minutes under stirring. After nitrogen substitution was performed in the autoclave, 43g of vinyl chloride was added, and a solution of 0.86g of an azo group-containing water-soluble initiator and 9g of water was added to the mixture to react at 60℃for 5 hours to obtain an aqueous polymer dispersion. The composition of the polymer is substantially identical to the composition of the feed monomer.
Comparative production example 1
To a 1000ml autoclave were added CF3CF2-(CF2CF2)n-CH2CH2OCOC(CH3)＝CH2(n＝2.0)133g、 g of lauryl acrylate, 405g of pure water, 34.8g of an aqueous glycol solvent, 11.75g of an alkylamine oxide and 6.17g of polyoxyethylene alkyl ether, and the mixture was dispersed by ultrasonic emulsification at 60℃for 15 minutes under stirring. After nitrogen substitution was performed in the autoclave, 43g of vinyl chloride was added, and a solution of 0.86g of an azo group-containing water-soluble initiator and 9g of water was added to the mixture to react at 60℃for 5 hours to obtain an aqueous polymer dispersion. The composition of the polymer is substantially identical to the composition of the feed monomer.
Comparative production example 2
To a 1000ml autoclave were added CF3CF2-(CF2CF2)n-CH2CH2OCOC(Cl)＝CH2(n＝2.0)97.2g、 g of stearyl acrylate 73.66g, pure water 405g, an aqueous glycol solvent 34.8g, an alkylamine oxide 11.75g and a polyoxyethylene alkyl ether 6.17g, and the mixture was dispersed by ultrasonic emulsification at 60℃for 15 minutes under stirring. After nitrogen substitution was performed in the autoclave, 43g of vinyl chloride was added, and a solution of 0.86g of an azo group-containing water-soluble initiator and 9g of water was added to the mixture to react at 60℃for 5 hours to obtain an aqueous polymer dispersion. The composition of the polymer is substantially identical to the composition of the feed monomer.
Example 1
The aqueous liquid prepared in production example 1 was diluted with pure water so that the fluoropolymer concentration became 30% as a solid component, and then 1.8g of the 30% diluted liquid and 0.20g of the crosslinking agent (blocked isocyanate) were diluted with pure water to prepare 100g of a test liquid. 4 pieces of wood pulp/polyester nonwoven fabric (510 mm. Times.205 mm, weight ratio of wood pulp/polyester: 30/70) were immersed in the test solution, passed through a calender, dried at 100℃for 30 seconds, and then treated with a pin tenter at 170℃for 2 minutes. Then, the test cloth was subjected to a shower water repellency test, a water pressure resistance test, an IPA test, and a tensile strength test. The results are shown in Table 3.
Examples 2 to 4 and comparative example 1
The polymers produced in production examples 2 to 4 and comparative production example 1 were treated in the same manner as in example 1, and were subjected to a shower water repellency test, a water pressure resistance test, an IPA test, and a tensile strength test. The results are shown in Table 3.
In the table, the abbreviations have the following meanings.
Short for short Compound name chemical formula
C6SFClA C6F13CH2CH2OCOC(Cl)＝CH2
C6SFMA C6F13CH2CH2OCOC(CH3)＝CH2
LA Lauryl acrylate
BA Butyl acrylate
StA Stearyl acrylate
VCM Vinyl chloride
IBMA Isobornyl methacrylate
[ Table 3]
Industrial applicability
The nonwoven fabric of the present invention can be used for medical use, industrial material use, civil engineering and construction use, agronomic gardening use, and the like. Specific uses include surgical gowns, wrapping cloths, bedsheets, pillowcases, paper diapers, sanitary napkins and the like.

Claims (12)

1. A nonwoven fabric, characterized in that:
Comprising (i) a nonwoven fabric substrate, and (ii) a fluoropolymer attached to the nonwoven fabric substrate,
The fluoropolymer has:
(a) Repeating units derived from a fluoromonomer that is an alpha-chloroacrylate having a fluoroalkyl group;
(b) Repeating units derived from a haloalkene monomer; and
(C1) Repeat units derived from non-fluorine non-crosslinking monomers,
The fluorine-containing monomer (a) is a compound represented by the following formula,
CH2＝C(-Cl)-C(＝O)-Y-Z-Rf
Wherein Y is-O-,
Z is a direct bond or a divalent organic group,
Rf is a fluoroalkyl group having 1 to 20 carbon atoms,
The halogenated olefin monomer (b) is an olefin having 2 to 20 carbon atoms and substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms,
The non-fluorine non-crosslinkable monomer (c 1) is a (meth) acrylate monomer having a linear or branched hydrocarbon group having 17 or less carbon atoms and having no fluoroalkyl group represented by the following formula (c 1-i),
(C 1-i) formula: the number of bits of the CH 2＝CA1 COOA2,
Wherein A 1 is a hydrogen atom, a methyl group or a halogen atom other than fluorine atom,
A 2 is an alkyl group shown as C nH2n+1, wherein n=4 to 13,
The fluoropolymer does not have a repeating unit derived from a (meth) acrylic acid ester having a linear or branched hydrocarbon group having 18 or more carbon atoms,
In the fluoropolymer, the amount of the fluoromonomer (a) is 20 to 90% by weight relative to the fluoropolymer,
In the fluoropolymer, the amount of the halogenated olefin monomer (b) is 10 to 200 parts by weight and the amount of the non-fluorine non-crosslinkable monomer (c 1) is 3 to 100 parts by weight relative to 100 parts by weight of the fluorine-containing monomer (a),
The nonwoven fabric base material is a combination of cellulose fibers as natural fibers and polyester fibers as synthetic fibers, and the weight ratio of the natural fibers to the synthetic fibers is 15:85 to 45:55.
2. The nonwoven fabric according to claim 1, wherein:
Z is a direct bond,
A linear or branched aliphatic group having 1 to 20 carbon atoms,
An aromatic group or a cyclic aliphatic group having 6 to 18 carbon atoms,
A group of the formula-R 2(R1)N-SO2 -or-R 2(R1) N-CO-,
A group of the formula-CH 2CH(OR3)CH2-[Ar-(O)q]p -, a radical of the formula,
A group of the formula- (CH 2)n-Ar-(O)q -or
- (CH 2)m-SO2-(CH2)n -group or- (CH 2)m-S-(CH2)n -group),
Wherein in the formula-R 2(R1)N-SO2 -and the formula-R 2(R1) N-CO-, R 1 is an alkyl group having 1 to 10 carbon atoms, R 2 is a linear alkylene group or a branched alkylene group having 1 to 10 carbon atoms,
In the formula-CH 2CH(OR3)CH2-[Ar-(O)q]p -, R 3 is a hydrogen atom or an acyl group having 1 to 10 carbon atoms, ar is an arylene group having a substituent as required, p is 0 or 1, q is 0 or 1,
In the formula- (CH 2)n-Ar-(O)q -, ar is arylene having a substituent according to need, n is 0 to 10, q is 0 or 1,
In the formulae- (CH 2)m-SO2-(CH2)n -and- (CH 2)m-S-(CH2)n) -m is 1 to 10 and n is 0 to 10.
3. The nonwoven fabric according to claim 1 or 2, characterized in that:
The halogenated vinyl monomer (b) is at least one selected from vinyl chloride and vinylidene chloride.
4. The nonwoven fabric according to claim 1 or 2, characterized in that:
in the (meth) acrylate monomer (c 1-i), A 2 is butyl or lauryl.
5. The nonwoven fabric according to claim 1 or 2, characterized in that:
the fluoropolymer also has (c 2) repeating units derived from a non-fluorine crosslinkable (meth) acrylate or (meth) acrylamide monomer.
6. The nonwoven fabric according to claim 1 or 2, characterized in that:
the fluoropolymer does not have a repeating unit derived from a (meth) acrylate having a linear or branched hydrocarbon group having 14 or more carbon atoms.
7. The nonwoven fabric of claim 4 wherein:
the fluoropolymer does not have a repeating unit derived from a (meth) acrylate having a linear or branched hydrocarbon group having 14 or more carbon atoms.
8. The nonwoven fabric according to claim 1 or 2, characterized in that:
the nonwoven fabric is obtained by crosslinking blocked isocyanates as crosslinking agents.
9. The nonwoven fabric according to claim 1 or 2, characterized in that:
The amount of the non-fluorine non-crosslinkable monomer (c 1) is1 to 300 parts by weight based on 100 parts by weight of the fluorine-containing monomer (a).
10. The nonwoven fabric according to claim 1 or 2, characterized in that:
The amount of the fluoropolymer attached to the nonwoven fabric substrate is 0.01 to 5 parts by weight relative to 100 parts by weight of the nonwoven fabric substrate.
11. A method of producing the nonwoven fabric according to any one of claims 1 to 10, characterized in that:
The fluoropolymer is applied to a nonwoven substrate.
12. The method for producing a nonwoven fabric according to claim 11, wherein:
The fluoropolymer is present in the form of an aqueous dispersion.
CN202410220458.1A 2016-08-02 2016-08-02 Nonwoven fabric Pending CN118087269A (en)

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