Patent Publication Number: US-2018038044-A1

Title: Nonwoven fabric

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application claims benefit of Chinese Patent Application No. 201610626325.X filed Aug. 2, 2016, incorporated herein by reference in its entirety. 
     TECHNICAL FIELD 
     The present invention relates to a nonwoven fabric, particularly a nonwoven fabric to which a fluorine-containing polymer is adhered. 
     BACKGROUND ART 
     Hitherto, treatments of textiles with a fluorine-containing treatment agent are proposed. 
     WO 2010/030044 discloses a treatment composition comprising a fluorine-containing polymer having repeating units formed from a fluorine-containing monomer, and a (meth)acrylate monomer containing a cyclic hydrocarbon group. WO 2011/122442 discloses a treatment composition comprising a fluorine-containing polymer having repeating units formed from alpha-chloro acrylate, and a (meth)acrylate monomer containing a hydrocarbon group. These publications do not consider the application to a nonwoven fabric. 
     WO 2013/99611 discloses treatment of a nonwoven fabric with a fluorine-containing treatment agent. However, sufficient water- and oil-repellency for the nonwoven fabric is not obtained. 
     SUMMARY OF THE INVENTION 
     One of objects of the present invention is to provide a nonwoven fabric having high water- and oil-repellency and high mechanical strength. 
     The present invention relates to the nonwoven fabric to which the fluorine-containing polymer adhered. 
     The present invention provides a nonwoven fabric comprising (i) a nonwoven fabric substrate and (ii) a fluorine-containing polymer adhering to the nonwoven fabric substrate, 
     wherein the fluorine-containing polymer comprises:
 
(a) repeating units formed from a fluorine-containing monomer which is alpha-chloro acrylate or alpha-chloro acrylamide containing a fluoroalkyl group, and
 
(b) repeating units formed from a halogenated olefin monomer, and
 
the fluorine-containing polymer is free from repeating units formed from a (meth)acrylate containing a linear or branched hydrocarbon group having at least 18 (for example, at least 16, particularly at least 14) carbon atoms.
 
     The fluorine-containing polymer gives high water repellency, oil repellency, and/or soil resistance to the nonwoven fabric substrate. 
     Effect of the Invention 
     The nonwoven fabric of the present invention has excellent water- and oil-repellency, for example, excellent strong water-repellency and high water pressure resistance, and excellent mechanical strength, for example, high tensile strength. 
    
    
     MODES FOR CARRYING OUT THE INVENTION 
     In the present invention, the fluorine-containing polymer has adhered to the nonwoven fabric. The nonwoven fabric to which the fluorine-containing polymer is adhered can be produced, for example by applying a fluorine-containing treatment agent to a nonwoven fabric substrate (an untreated nonwoven fabric substrate). 
     The fluorine-containing treatment agent comprises the fluorine-containing polymer and a liquid medium. 
     (1) Fluorine-Containing Polymer 
     The fluorine-containing polymer comprises: 
     (a) repeating units formed from a fluorine-containing monomer which is alpha-chloro acrylate or alpha-chloro acrylamide containing a fluoroalkyl group, and
 
(b) repeating units formed from a halogenated olefin monomer.
 
     The fluorine-containing polymer is free from repeating units formed from a (meth)acrylate, preferably a (meth)acrylate or (meth)acrylamide, which contains a linear or branched hydrocarbon group having at least 18 carbon atoms. 
     (a) Fluorine-containing monomer 
     The fluorine-containing monomer (a) may be a compound represented by the formula: 
       CH 2 ═C(—Cl)—C(═O)—Y—Z—Rf
 
     wherein Y is —O— or —NH—;
 
Z is a direct bond or divalent organic group; and
 
Rf is a fluoroalkyl group having 1 to 20 carbon atoms.
 
     The fluorine-containing monomer (a) is preferably a compound represented by the formula: 
       CH 2 ═C(—Cl)—C(═O)—Y—Z—Rf
 
     wherein Y is —O— or —NH—; 
     Z is a direct bond, 
     a linear or branched aliphatic group having 1-20 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 cycloaliphatic group having 6-30 carbon atoms,
 
a group represented by the formula —R 2 (R 1 )N—SO 2 — or the formula —R 2  (R 1 )N—CO— wherein R 1  is an alkyl group having 1 to 10 carbon atoms and R 2  is a linear alkylene group or branched alkylene group having 1 to 10 carbon atoms,
 
a group represented by the formula —CH 2 CH(OR 3 )CH 2 —(Ar—O) 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), Ar is an arylene group (for example, a phenylene group) optionally having a substituent group, and p is 0 or 1,
 
a group represented by the formula —(CH 2 ) n —Ar—(O) q — wherein Ar is an arylene group optionally having a substituent group, n is 0 to 10, and q is 0 or 1, or
 
a —(CH 2 ) m —SO 2 —(CH 2 ) n — group or a —(CH 2 ) m —S—(CH 2 ) n — group wherein m is 1-10, and
 
n is 0-10, and
 
Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms.
 
     In the fluorine-containing monomer, the Rf group is preferably a perfluoroalkyl group. The carbon number of the Rf group is preferably from 1 to 12, for example, 1 to 6, particularly from 4 to 6, more preferably 6. Examples of the Rf group include —CF 3 , —CF 2 CF 3 , —CF 2 CF 2 CF 3 , —CF(CF 3 ) 2 , —CF 2 CF 2 CF 2 CF 3 , —CF 2 CF(CF 3 ) 2 , —C(CF 3 ) 3 , —(CF 2 ) 4 CF 3 , —(CF 2 ) 2 CF(CF 3 ) 2 , —CF 2 C(CF 3 ) 3 , —CF(CF 3 )CF 2 CF 2 CF 3 , —(CF 2 ) 5 CF 3 , —(CF 2 ) 3 CF(CF 3 ) 2 , —(CF 2 ) 4 CF(CF 3 ) 2  and —C 8 F 17 . 
     Preferably, the fluorine-containing monomer is an acrylate ester wherein the Y group is —O—. 
     The Z group may be, specifically, a linear or branched aliphatic group having 1-20 carbon atoms (for example, 1-10 carbon atoms, particularly 1-4 carbon atoms, especially 1 or 2 carbon atoms) (for example, an alkylene group), such as a group represented by the formula —(CH 2 ) x — wherein x is 1 to 10, 
     an aromatic group or cycloaliphatic group having 6-18 carbon atoms,
 
a group represented by the formula —R 2 (R 1 )N—SO 2 — or the formula —R 2  (R 1 )N—CO— wherein R 1  is an alkyl group having 1 to 10 carbon atoms and R 2  is a linear alkylene group or branched alkylene group having 1 to 10 carbon atoms, for example, by a —CH 2  CH 2  N(R 1 )SO 2 — group wherein R 1  is an alkyl group having 1 to 4 carbon atoms,
 
a group represented by the formula —CH 2 CH(OR 3 )CH 2 —[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), Ar is an arylene group (for example, a phenylene group) optionally having a substituent group, p is 0 or 1, and q is 0 or 1, a group represented by the formula —(CH 2 ) n —Ar—(O) q — (wherein Ar is an arylene group (for example, phenylene group) optionally having a substituent group, n is 0-10, and q is 0 or 1), or
 
a —(CH 2 ) m —SO 2 —(CH 2 ) n — group or a —(CH 2 ) m —S—(CH 2 ) n — group wherein m is 1-10, and n is 0-10.
 
     The aromatic group or the cycloaliphatic group may be substituted or unsubstituted. The S group or the 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 followings: 
       CH 2 ═C(—Cl)—C(═O)—O—(CH 2 ) 2 —Rf
 
       CH 2 ═C(—Cl)—C(═O)—O—(CH 2 ) 4 —Rf
 
       CH 2 ═C(—Cl)—C(═O)—O—(CH 2 ) 2 —S—Rf
 
       CH 2 ═C(—Cl)—C(═O)—O—(CH 2 ) 2 —S—(CH 2 ) 2 —Rf
 
       CH 2 ═C(—Cl)—C(═O)—O—(CH 2 ) 2 —SO 2 —Rf
 
       CH 2 ═C(—Cl)—C(═O)—O—(CH 2 ) 2 —SO 2 —(CH 2 ) 2 —Rf
 
       CH 2 ═C(—Cl)—C(═O)—NH—(CH 2 ) 2 —Rf
 
       CH 2 ═C(—Cl)—C(═O)—O—(CH 2 ) 3 —S—Rf
 
       CH 2 ═C(—Cl)—C(═O)—O—(CH 2 ) 3 —S—(CH 2 ) 2 —Rf
 
       CH 2 ═C(—Cl)—C(═O)—O—(CH 2 ) 3 —SO 2 —Rf
 
       CH 2 ═C(—Cl)—C(═O)—O—(CH 2 ) 3 —SO 2 —(CH 2 ) 2 —Rf
 
       CH 2 ═C(—Cl)—C(═O)—O—CH 2 CH 2 N(CH 3 )SO 2 —Rf
 
       CH 2 ═C(—Cl)—C(═O)—O—CH 2 CH(OCOCH 3 )CH 2 —Rf
 
       CH 2 ═C(—Cl)—C(═O)—O—CH 2 -Ph-O—Rf (wherein Ph is 1,4-phenylene.)
 
       CH 2 ═C(—Cl)—C(═O)—O—CH 2 CH(OH)CH 2 -Ph-O—Rf
 
       CH 2 ═C(—Cl)—C(═O)—O—CH 2 -Ph-Rf
 
       CH 2 ═C(—Cl)—C(═O)—O—CH 2 CH(OCOCH 3 )CH 2 -Ph-Rf
 
     wherein Ph is a phenylene group, and
 
Rf is a fluoroalkyl group having 1-20 carbon atoms.
 
     (b) Halogenated Olefin Monomer 
     Preferably, the halogenated olefin is free from a fluorine atom. 
     Preferably, the halogenated olefin is an olefin having 2-20 carbon atoms and substituted by 1-10 chlorine atoms, bromine atoms or iodine atoms. Preferably, the halogenated olefin is a chlorinated olefin having 2-20 carbon atoms, particularly an olefin having 2-5 carbon atoms carbon and having 1-5 chlorine atoms. Preferable examples of the halogenated olefin are a vinyl halide such as vinyl chloride, vinyl bromide and vinyl iodide, and a vinylidene halide such as vinylidene chloride, vinylidene bromide and vinylidene iodide. Vinyl chloride and vinylidene chloride are preferred, and vinyl chloride is particularly preferred. 
     (c) Other Monomer 
     The other monomer (c) does contain a fluoroalkyl group. Preferably, the other monomer (c) other than the monomers (a) and (b) does not contain fluorine. Examples of the other monomer (c) include (c1) a fluorine-free non-crosslinkable monomer and (c2) a fluorine-free crosslikable monomer. 
     The other monomer (c) do not comprise the (meth)acrylate containing a linear or branched hydrocarbon group having at least 18 (for example, at least 16, particularly at least 14) carbon atoms. That is, the present invention does not use the (meth)acrylate containing a linear or branched hydrocarbon group having at least 18 (for example, at least 16, particularly at least 14) carbon atoms, for example, stearyl (meth)acrylate and behenyl (meth)acrylate. 
     (c1) Fluorine-Free Non-Crosslinkable Monomer 
     The fluorine-free non-crosslinkable monomer (c1) is a monomer which does not contain a fluorine atom. The fluorine-free non-crosslinkable monomer (c1) does not have a crosslinkable functional group. Unlike the crosslinkable monomer (c2), the fluorine-free non-crosslinkable monomer (c1) has no crosslinkability. Preferably, the fluorine-free non-crosslinkable monomer (c1) is a fluorine-free monomer having an ethylenically unsaturated carbon-carbon double bond. The fluorine-free non-crosslinkable monomer (c1) is preferably a vinyl monomer free from fluorine. Generally, the fluorine-free non-crosslinkable monomer (c1) is a compound having one ethylenically unsaturated carbon-carbon double bond. 
     The fluorine-free non-crosslinkable monomer (c1) may be: 
     (c1-i) a (meth)acrylate or (meth)acrylamide monomer containing a linear or branched hydrocarbon group having 17 or less carbon atoms, and/or
 
(c1-ii) a (meth)acrylate or (meth)acrylamide monomer containing a cyclic hydrocarbon group.
 
     A preferable fluorine-free non-crosslinkable monomer, which includes the (meth)acrylate or (meth)acrylamide monomers (c1-i) and (c1-ii), is a compound represented by the formula: 
       CH 2 ═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, an open-chain (linear or branched) hydrocarbon group having 1 to 17 (for example, 2 to 15, particularly 3 to 14, especially 4 to 13) carbon atoms, a cyclic organic group having 4 to 30 carbon atoms, or an open-chain or cyclic organic group having 1 to 31 carbon atoms and an ester bond or amide bond. 
     In the (meth)acrylate or (meth)acrylamide monomer (c1-i), the T group is an open-chain group having 1 to 17 carbon atoms and an ester bond. In the (meth)acrylate or (meth)acrylamide monomer (c1-ii), the T group is a cyclic organic group having 4 to 30 carbon atoms and an amide bond. 
     Examples of the cyclic hydrocarbon group having 4-30 carbon atoms are a cycloaliphatic group having 4-30 carbon atoms, an aromatic hydrocarbon group having 6-30 carbon atoms, and an araliphatic hydrocarbon group having 7-30 carbon atoms. 
     Examples of the open-chain or cyclic organic group having 1-31 carbon atoms and an ester bond are: —C(═O)—O-Q and —O—C(═O)-Q wherein Q is a open-chain (linear or branched) aliphatic hydrocarbon group having 1 to 17 (for example, 2 to 15, particularly 3 to 14, especially 4 to 13) carbon atoms, a cyclic aliphatic group having 4-30 carbon atoms, an aromatic hydrocarbon group having 6-30 carbon atoms, or an araliphatic hydrocarbon group having 7-30 carbon atoms. 
     Examples of the open-chain or cyclic organic group having 1-31 carbon atoms and an amide bond are: —C(═O)—NH-Q and —NH—C(═O)-Q wherein Q is a open-chain (linear or branched) aliphatic hydrocarbon group having 1 to 17 (for example, 2 to 15, particularly 3 to 14, especially 4 to 13) carbon atoms, a cyclic aliphatic group having 4-30 carbon atoms, an aromatic hydrocarbon group having 6-30 carbon atoms, or an araliphatic hydrocarbon group having 7-30 carbon atoms. 
     Preferable Examples of the fluorine-free non-crosslinkable monomer (c1) include ethylene, vinyl acetate, acrylonitrile, styrene, polyethyleneglycol (meth)acrylate, polypropyleneglycol (meth)acrylate, methoxypolyethyleneglycol (meth)acrylate, methoxypolypropyleneglycol (meth)acrylate and vinyl alkyl ether. The fluorine-free non-crosslinkable monomer (c1) is not limited to these examples. 
     The fluorine-free non-crosslinkable monomer (c1) may be a (meth)acrylate ester or (meth)acrylamide containing an alkyl group. The number of the carbon atoms in the alkyl group may be from 1 to 17, for example, from 2 to 15 (e.g., from 3 to 14, particularly 4 to 13). The fluorine-free non-crosslinkable monomer (c1) may be an acrylate represented by the formula: 
       CH 2 ═CA 1 CO—Z 1 -A 2  
 
     wherein A 1  is a hydrogen atom, a methyl group, or a halogen atom (for example, a chlorine atom, a bromine atom, and an iodine atom) other than a fluorine atom, 
     Z 1  is —O— or —NH—, and 
     A 2  is an alkyl group represented by C n H 2n+1  wherein n is 1 to 17. 
     Preferable examples ofA 2  include butyl and lauryl. 
     The fluorine-free non-crosslinkable monomer (c1) may be a (meth)acrylate or (meth)acrylamide monomer containing a cyclic hydrocarbon group. 
     The cyclic hydrocarbon group-containing (meth)acrylate ester monomer is preferably a compound represented by the formula: 
       CH 2 ═CA 21 -C(═O)—O-A 22  
 
     wherein A 21  is a hydrogen atom or a methyl group, and
 
A 22  is a cyclic hydrocarbon containing group having 4-30 carbon atoms.
 
     The cyclic hydrocarbon group-containing (meth)acrylate ester monomer is a monomer having a high glass transition temperature (for example, at least 50° C., particularly at least 80° C.) of a homopolymer thereof. 
     The cyclic hydrocarbon group-containing (meth)acrylate ester monomer does not have a fluoroalkyl group. The cyclic hydrocarbon group-containing (meth)acrylate ester 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 an open-chain group (for example, a linear or branched hydrocarbon group). Examples of the cyclic hydrocarbon group include a saturated or unsaturated, monocyclic group, polycyclic group or bridged ring group. The cyclic hydrocarbon group is preferably a saturated group. The cyclic hydrocarbon group preferably has 4 to 30, more preferably 6 to 20 carbon atoms. Examples of the cyclic hydrocarbon group include a cycloaliphatic group having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an araliphatic group having 7 to 20 carbon atoms. The number of carbon atoms in the cyclic hydrocarbon group is particularly preferably at most 15, for example, at most 12. The cyclic hydrocarbon group is preferably a saturated cycloaliphatic group. Specific examples of the cyclic hydrocarbon group include a cyclohexyl group, a t-butyl cyclohexyl group, an isobornyl group, a dicyclopentanyl group and a dicyclopentenyl group and an adamantyl group. 
     Specific examples of the monomer containing cyclic hydrocarbon group include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamanthyl (meth)acrylate and 2-ethyl-2-adamanthyl (meth)acrylate. 
     The presence of the cyclic hydrocarbon group-containing acrylate ester monomer gives higher water repellency and oil repellency imparted by the copolymer. 
     (c2) Fluorine-Free Crosslinkable Monomer 
     The fluorine-containing polymer of the present invention may have repeating units formed from the fluorine-free crosslinkable monomer (c2). The fluorine-free crosslinkable monomer is a monomer free from a fluorine atom. The fluorine-free crosslinkable monomer (c2) has at least two reactive groups and/or ethylenically unsaturated carbon-carbon double bonds. The fluorine-free crosslinkable monomer (c2) may be a compound which has at least two ethylenically unsaturated carbon-carbon double bonds or a compound which has at least one ethylenically unsaturated carbon-carbon double bond and at least one reactive group. Examples of the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group and a carboxyl group. The fluorine-free crosslinkable monomer (c2) may be a mono(meth)acrylate, di(meth)acrylate, or mono(meth)acrylamide containing a reactive group. Alternatively, the fluorine-free crosslinkable monomer (c2) may be di(meth)acrylate free from a reactive group. 
     Examples of the fluorine-free crosslinkable monomer (c2) include, but are not limited to, diacetone(meth)acrylamide, (meth)acrylamide, N-methylol(meth)acrylamide, hydroxymethyl (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, and neopentylglycol di(meth)acrylate. 
     When the fluorine-free non-crosslinkable monomer (c1) and/or the fluorine-free crosslinkable monomer (c2) are copolymerized, various properties such as water- and oil-repellency, stain-proofing properties, cleaning durability and washing durability of said properties, solubility in solvents, hardness and feeling may be improved depending on the necessity. 
     Herein, “acrylate” or “acrylamide” includes not only a compound containing a hydrogen atom at an alpha-position but also a compound in which the alpha position is substituted by another group (for example, a monovalent organic group including a methyl group, or a halogen atom). The term “(meth)acrylate” as used herein means an acrylate or methacrylate, and the term “(meth)acrylamide” as used herein means an acrylamide or methacrylamide. 
     Each of the monomer (a), the monomer (b), and the monomer (c) (for example, each of the monomer (c1) and the monomer (c2)) may be one alone or a combination of at least two. 
     In the fluorine-containing polymer, the amount of the monomer (a) is 20% to 90% by weight, preferably 30% to 80% by weight, based on the fluorine-containing polymer. 
     In the fluorine-containing polymer, the amount of the halogenated olefin monomer (b) may be 5 to 300 parts by weight, for example, 10 to 200 parts by weight, particularly 20 to 100 parts by weight, especially 30 to 80 parts by weight, and 
     the amount of other monomer (c) may be 0 to 800 parts by weight, for example, 1 to 300 parts by weight, particularly 2 to 200 parts by weight, especially 3 to 100 parts by weight, based on 100 parts by weight of the fluorine-containing monomer (a). 
     In the fluorine-containing polymer, the amount of the fluorine-free non-crosslinkable monomer (c1) may be 0 to 500 parts by weight, for example, 1 to 300 parts by weight, particularly 2 to 200 parts by weight, especially 3 to 100 parts by weight, and 
     the amount of the fluorine-free crosslikable monomer (c2) may be 0 to 80 parts by weight, for example, 0 to 50 parts by weight, particularly 0.1 to 30 parts by weight, especially 1 to 20 parts by weight, based on 100 parts by weight of the fluorine-containing monomer (a). 
     The amount of each of the fluorine-free non-crosslinkable monomers (c1-i) and (c1-ii) may be 0 to 500 parts by weight, for example, 1 to 300 parts by weight, particularly 2 to 200 parts by weight, especially 3 to 100 parts by weight, based on 100 parts by weight of the fluorine-containing monomer (a). 
     The number-average molecular weight (Mn) of the fluorine-containing polymer may be 1,000 to 1,000,000, for example, from 5,000 to 500,000, particularly from 3,000 to 200,000. The number-average molecular weight (Mn) of the fluorine-containing polymer can be generally measured by GPC (gel permeation chromatography). 
     In the present invention, the monomers (a) to (c) are polymerized to obtain the fluorine-containing treatment agent (or the surface treatment agent composition) wherein the fluorine-containing polymer is dispersed or dissolved in the liquid medium. 
     The monomer(s) may be polymerized in the presence of at least one compound selected from the group consisting of a blocked isocyanate compound and an organopolysiloxane compound. The amount of the blocked isocyanate compound (or the organopolysiloxane compound) may be 0 to 100 parts by weight, for example, 1 to 50 parts by weight, based on 100 parts by weight of monomers. 
     A fluorine-containing polymer containing a blocked isocyanate group is obtained by polymerizing the monomer in the presence of the blocked isocyanate compound. The blocked isocyanate compound is an isocyanate blocked by at least one blocking agent. Examples of the blocking agent include oximes, phenols, alcohols, mercaptans, amides, imides, imidazoles, ureas, amines, imines, pyrazoles, and active methylene compounds. Other examples of the blocking agent include pyridinols, thiophenols, diketones, and esters. The blocked isocyanate compound may be modified with a compound containing a hydrophilic group. 
     A fluorine-containing polymer containing a siloxane group is obtained by polymerizing the monomer in the presence of an organopolysiloxane compound (for example, a mercapto-functional organopolysiloxane and a vinyl-functional organopolysiloxane). In one embodiment, the mercapto-functional organopolysiloxane comprises siloxy units having the average formula: 
       (R 2 SiO) a (RR N SiO) b (RR S SiO) c    
     where; a is 0-4000, alternatively 0 to 1000, alternatively 0 to 400,
 
b is 0-1000, alternatively 1 to 100, alternatively 1 to 50,
 
c is 1-1000, alternatively 1 to 100, alternatively 1 to 50;
 
R is independently a monovalent organic group,
 
alternatively R is a hydrocarbon containing 1-30 carbon atoms,
 
alternatively R is a monovalent alkyl group containing 1-12 carbons, or
 
alternatively R is a methyl group;
 
R N  is a monovalent amino-functional organic group,
 
R S  each is a monovalent mercapto-functional organic group (R S ).
 
     The amount of the fluorine-containing polymer (a 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, based on the fluorine-containing treatment agent or the surface treatment agent composition. 
     Although the fluorine-containing polymer may be present in the form of a solution dissolved in an organic solvent, the fluorine-containing polymer is preferably present in the form of an aqueous dispersion. 
     (2) Liquid Medium 
     The liquid medium may be an aqueous medium. The liquid medium may be water alone, or a mixture of water and an (water-soluble) organic solvent. The amount of the organic solvent may be at most 30% by weight, for example, at most 10% by weight (preferably at least 0.1%), based on the liquid medium. The liquid medium is preferably water alone. The liquid medium may be the organic solvent alone. 
     The amount of the liquid medium may be, for example, from 30 to 99.9% by weight, particularly 50 to 99% by weight, based on the fluorine-containing treatment agent (or the surface treatment agent composition). 
     (3) Surface Active Agent 
     The fluorine-containing treatment agent may contain a surface active agent. In case that a fluorine-containing treatment agent contains an aqueous medium, the fluorine-containing treatment agent preferably contains the surface active agent. The fluorine-containing treatment agent preferably comprises the fluorine-containing polymer, the liquid medium (preferably the aqueous medium), and the surface active agent. 
     In the present invention, the surface active agent may be at least one selected from a nonionic surface active agent, a cationic surface active agent, an anionic surface active agent, and an amphoteric surface active agent. 
     Examples of the nonionic surface active agent include an ether, an ester, an ester ether, an alkanolamide, a polyhydric alcohol and an amine oxide. 
     An example of the ether is a compound containing an oxyalkylene group (preferably a polyoxyethylene group). 
     An example of the ester is an ester from an alcohol and a fatty acid. An example of the alcohol is a monovalent-haxavalent (especially divalent-pentavalence) alcohol (for example, an aliphatic alcohol) having 1 to 50 carbon atoms (especially 3 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms. 
     An example of ester ether is a compound obtained by adding an alkylene oxide (especially ethylene oxide) to an ester from an alcohol and a fatty acid. An example of the alcohol is a monovalent-haxavalent (especially divalent-pentavalence) alcohol (for example, an aliphatic alcohol) having 1 to 50 carbon atoms (especially 3 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms. 
     An example of the alkanolamide is a compound formed from a fatty acid and an alkanolamine. The alkanolamide may be a monoalkanol amide or a dialkanol amide. An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2-50, especially 5-30 carbon atoms which has 1-3 amino groups and 1-5 hydroxyl groups. 
     The polyhydric alcohol may be a dihydric to pentahydric alcohol having 3-30 (or 10-50) carbon atoms. 
     The amine oxide may be an oxide (for example, having 5-50 carbon atoms) of an amine (a secondary amine or preferably a tertiary amine) 
     Preferably, the nonionic surface active agent is a nonionic surface active agent containing an oxyalkylene group (preferably a polyoxyethylene group). Preferably, the carbon number of an alkylene group in the oxyalkylene group is from 2 to 10. Preferably, the number of the oxyalkylene groups in a molecule of the nonionic surface active agent is generally from 2 to 100. 
     Preferably, the nonionic surface active agent is a nonionic surface active agent containing an oxyalkylene group and selected from the group consisting of an ether, an ester, an ester ether, an alkanolamide, a polyhydric alcohol and an amine oxide. 
     The nonionic surface active agent may include an alkylene oxide addition product of a linear and/or branched aliphatic (saturated and/or unsaturated) group, a polyalkylene glycol ester of linear and/or branched (saturated and/or unsaturated) fatty acid, a polyoxyethylene (POE)/polyoxypropylene (POP) copolymer (a random copolymer or a block copolymer), and an alkylene oxide addition product of acetyleneglycol. Among them, preferable is one wherein a structure of an alkylene oxide addition portion and a polyalkylene glycol portion are polyoxyethylene (POE), polyoxypropylene (POP), or a POE/POP copolymer (which may be a random copolymer or may be a block copolymer). 
     Preferably, the nonionic surface active agent has a structure which does not have an aromatic group in view of environmental problems (such as biodegradability and environmental hormone). 
     The nonionic surfactant may be a surfactant of the formula: 
       R 1 O—(CH 2 CH 2 O) p —(R 2 O) q —R 3  
 
     wherein R 1  is an alkyl group having 1 to 22 carbon atoms or an alkenyl or acyl group having 2 to 22 carbon atoms,
 
R 2  is independently, the same or different, an alkylene group having at least 3 (for example, 3 to 10) carbon atoms,
 
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 the number of at least 2, and
 
q is 0 or the number of at least 1.
 
     R 1  is preferably has 8 to 20 carbon atoms, especially 10 to 18 carbon atoms. Preferable examples of R 1  include a lauryl group, a tridecyl group and an oleyl group. 
     Examples of R 2  are a propylene group and a butylene group. 
     In the nonionic surfactant, p may be the number of at least 3 (for example, 5 to 200). q may be the number of at least 2 (for example, 5 to 200). That is, —(R 2 O) q — may form the polyoxyalkylene chain. 
     The nonionic surfactant is a polyoxyethylenealkylene alkyl ether containing a hydrophilic polyoxyethylene chain in the molecular center and hydrophobic oxyalkylene chains (particularly, polyoxyalkylene chains). Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain and a styrene chain. Among them, the oxypropylene chain is preferable. 
     A preferable nonionic surfactant is the formula: 
       R 1 O—(CH 2 CH 2 O) p —H
 
     wherein R 1  and p are the same as the above. 
     Examples of the nonionic surfactant include the followings: 
       C 10 H 21 O—(CH 2 CH 2 O) p —(C 3 H 6 O) q —H
 
       C 12 H 25 O—(CH 2 CH 2 O) p —(C 3 H 6 O) q —H
 
       C 16 H 31 O—(C H 2 CH 2 O) p —(C 3 H 6 O) q —H
 
       C 16 H 33 O—(CH 2 CH 2 O) p —(C 3 H 6 O) q —H
 
       C 18 H 35 O—(CH 2 CH 2 O) p —(C 3 H 6 O) q —H
 
       C 18 H 37 O—(CH 2 CH 2 O) p —(C 3 H 6 O) q —H
 
       C 12 H 25 O—(CH 2 CH 2 O) p —(C 3 H 6 O) q —C 12 H 25  
 
       C 16 H 31 O—(C H 2 CH 2 O) p —(C 3 H 6 O) q -C 16 H 31  
 
       C 16 H 33 O—(CH 2 CH 2 O) p —(C 3 H 6 O) q -C 12 H 25  
 
       iso-C 13 H 27 O—(CH 2 CH 2 H 2 O) p —(C 3 H 6 O) q —H
 
       C 10 H 21 COO—(CH 2 CH 2 O) p —(C 3 H 6 O) q —H
 
       C 16 H 33 COO—(CH 2 CH 2 O) p —(C 3 H 6 O) q -C 12 H 25  
 
     wherein p and q are the same as defined in the above. 
     Examples of the nonionic surfactant include a condensation product of ethylene oxide with, for example, hexyl phenol, isooctyl phenol, hexadecanol, oleic acid, alkane (C 12 -C 16 ) thiol, a sorbitan mono-fatty acid (C 7 -C 19 ) or an alkyl (C 12 -C 18 ) amine. 
     The amount of the polyoxyethylene block may be 5 to 80% by weight, for example, 30 to 75% by weight, especially 40 to 70% by weight, based on the molecular weight of the nonionic surfactant (copolymer). 
     Generally, the average molecular weight of the nonionic surfactant is from 300 to 5,000, for example, from 500 to 3,000. 
     The nonionic surfactant can be used alone or in combination of at least two. 
     Preferably, the nonionic surfactant is a combination of at least two. In the combination of at least two, at least one nonionic surfactant may be a compound represented by R 1 O 1 —(CH 2 CH 2 O) p —(R 2 O) q —R 3  [especially, R 1 O—(CH 2 CH 2 O) p —H] wherein the R 1  group (and/or, the R 3  group) is a branched alkyl group (for example, an isotridecyl group). The amount of the nonionic surfactant wherein the R 1  group is the branched alkyl group may be 5 to 100 parts by weight, for example, 8 to 50 parts by weight, especially 10 to 40 parts by weight, based on the total of 100 parts by weight of the nonionic surfactant. In the combination of at least two, the remaining nonionic surfactant may be a compound represented by R 1 O—(CH 2 CH 2 O) p —(R 2 O) q —R 3  [especially, R 1 O—(CH 2 CH 2 O) p —H] wherein the R 1  group (and/or, the R 3  group) is a (saturated and/or unsaturated) linear alkyl group (for example, a lauryl group (a n-lauryl group)). 
     Examples of the nonionic surface active agent include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene 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 alkylol amide, alkyl alkanolamide, acetyleneglycol, an oxyethylene addition product of acetyleneglycol, a polyethylene glycol polypropylene glycol block copolymer. Polyoxyethylene alkyl ether and polyoxyethylene sorbitan fatty acid ester are preferable. Polyoxyethylene alkyl ether is more preferable. 
     The cationic surface active agent may be an amine salt, a quarternary ammonium salt, and an oxyethylene addition-type ammonium salt. Although not limited, specific examples of the cationic surface active agent particularly include amine salt-type surface active agents, such as an alkylamine salt, an amino alcohol fatty acid derivative, a polyamine fatty acid derivative, and imidazoline; and quarternary ammonium salt-type surface active agents, such as an alkyl trimethyl ammonium salt, a dialkyl dimethyl ammonium salt, an alkyl dimethyl benzyl ammonium salt, a pyridinium salt, an alkyl isoquinolinium salt and benzethonium chloride. 
     A preferable example of the cationic surface active agent is: 
       R 21 —N + (—R 22 )(—R 23 )(—R 24 )X − 
 
     wherein R 21 , R 22 , R 23  and R 24  are a hydrocarbon groups having 1 to 30 carbon atoms, and
 
X is an anionic group.
 
     Specific examples of R 21 , R 22 , R 23  and R 24  are an alkyl group (for example, a methyl group, a butyl group, a stearyl group, a palmityl group). Specific examples of X are halogen (for example, chlorine) and an acid (for example, hydrochloric acid and acetic acid). 
     The cationic surface active agent is particularly preferably a monoalkyltrimethyl ammonium salt (the carbon number of the alkyl is 4 to 30). 
     Preferably, the cationic surfactant is an ammonium salt. The cationic surfactant may be an ammonium salt of the formula: 
       R 1   p —N + R 2   q X − 
 
     wherein R 1  is a linear and/or branched aliphatic (saturated and/or unsaturated) group having at least 12 carbon atoms (for example, C 12 -C 50 ),
 
R 2  is H, an alkyl group having 1 to 4 carbon atoms, a benzyl group, or a polyoxyethylene group (the number of the oxyethylene groups is, for example, at least 1 (particularly at least 2, especially at least 3) and up to 50) (CH 3  and C 2 H 5  are particularly preferable),
 
X is a halogen atom or a C 1 -C 4  fatty-acid-salt group,
 
p is 1 or 2,
 
q is 2 or 3, and
 
p+q=4.
 
     The carbon number of R 1  may be from 12 to 50, for example, from 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, (dodecylmethylbenzyl) trimethyl ammonium chloride, benzyl dodecyl dimethyl ammonium chloride, methyl dodecyl di(hydropolyoxyethylene) ammonium chloride, benzyl dodecyl di(hydropolyoxyethylene) ammonium chloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride and dialkyl (hydrogenated beef tallow) dimethyl ammonium chloride. A cationic surfactant having an ammonium chloride structure is preferable. A cationic surfactant having an ammonium chloride structure and having a long-chain (for example, 10-30, particularly 14-24 carbon atoms) hydrocarbon group (particularly an alkyl group) such as octadecyl and hexadecyl is more preferable. 
     Specific examples of the anionic surfactant include sodium lauryl sulfate, triethanolamine lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene nonyl phenyl ether sulfate, triethanolamine polyoxyethylene lauryl ether sulfate, sodium cocoyl sarcosinate, sodium N-cocoyl methyl taurine, sodium polyoxyethylene cocoalkyl ether sulfate, sodium diethylhexyl sulfosuccinate, sodium α-olefin sulfonate, sodium lauryl phosphate, sodium polyoxyethylene lauryl ether phosphate, a perfluoroalkyl carboxylate salt (trade name Unidyne DS-101 and 102 (manufactured by Daikin Industries, Ltd.)). The anionic surface active agent is preferably a salt of an organic acid (for example, a salt of an organic acid with an inorganic base or an amine). More preferable is an alkyl sulfate ester salt, for example, ROSO 3   − M +  wherein the carbon number of the alkyl group (R group) is, for example, 8 to 30, and M is an alkali metal (for example, sodium or potassium). 
     Examples of the amphoteric surfactant include amine oxides, alanines, imidazolinium betaines, amidobetaines, and betaine acetate. Specific examples thereof include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryldimethylaminoacetic acid betaine, and fatty acid amidopropyldimethylaminoacetic acid betaine. Preferable are amine oxides, for example, R 3 N═O wherein each R group is, for example, a hydrocarbon group (particularly an alkyl group) having 1-30 carbon atoms. 
     Each of the nonionic surface active agent, the cationic surface active agent, the anionic surface active agent, and the amphoteric surface active agent may be used alone or in a combination of at least two. 
     The fluorine-containing treatment agent may comprise an additive, in addition to the fluorine-containing polymer, the liquid medium and the surface active agent. Examples of the additive include silicon-containing compounds, waxes and acrylic emulsions. Other examples of the additive include other fluorine-containing polymers, drying rate regulators, crosslinking agents, film formation aids, compatibilizers, surfactants, anti-freezing agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusting agents, defoaming agents, texture regulating agents, slippage adjusting agents, antistatic agents, hydrophilizing agents, antimicrobial agents, antiseptics, insecticides, fragrances and flame retardants. 
     The polymer (the fluorine-containing polymer) in the present invention can be produced by any of conventional polymerization methods and the polymerization condition can be optionally selected. The polymerization method includes, for example, a solution polymerization, a suspension polymerization and an emulsion polymerization. 
     In a solution polymerization, there can be used a method of dissolving the monomer(s) into an organic solvent in the presence of a polymerization initiator, replacing the atmosphere by nitrogen, and stirring the mixture with heating at the temperature within the range from 30° C. to 120° C. for 1 hour to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate and diisopropyl peroxydicarbonate. The polymerization initiator may be used in the amount within the range from 0.01 to 20 parts by weight, for example, from 0.01 to 10 parts by weight, based on 100 parts by weight of total of the monomers. 
     The organic solvent is inert to the monomer, and dissolves the monomer, and examples of the organic solvent include an ester (for example, an ester having 2-30 carbon atoms, specifically ethyl acetate and butyl acetate), a ketone (for example, a ketone of 2-30 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), and an alcohol (for example, an alcohol having 1-30 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, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane and trichlorotrifluoroethane. The organic solvent may be used in the amount within the range from 10 to 2,000 parts by weight, for example, from 50 to 1,000 parts by weight, based on 100 parts by weight of total of the monomers. 
     In an emulsion polymerization, there can be used a method of emulsifying monomers in water in the presence of a polymerization initiator and an emulsifying agent, replacing the atmosphere by nitrogen, and polymerizing with stirring, for example, at the temperature within the range from 50° C. to 80° C. for 1 hour to 10 hours. Examples of the polymerization initiator include water-soluble initiators such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate and ammonium persulfate; and oil-soluble initiators such as azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate and diisopropyl peroxydicarbonate. The polymerization initiator may be used in the amount within the range from 0.01 to 10 parts by weight, based on 100 parts by weight of the monomers. 
     In order to obtain a polymer dispersion in water, which is superior in storage stability, it is preferable that the monomers are dispersed in water by using an emulsifying device capable of applying a strong shearing energy (e.g., a high-pressure homogenizer and an ultrasonic homogenizer) and then polymerized. As the emulsifying agent, various emulsifying agents such as an anionic emulsifying agent, a cationic emulsifying agent and a nonionic emulsifying agent can be used in the amount within the range from 0.5 to 20 parts by weight based on 100 parts by weight of the monomers. The anionic emulsifying agent and/or the cationic emulsifying agent and/or the nonionic emulsifying agent are preferable. When the monomers are not completely compatibilized, a compatibilizing agent (e.g., a water-soluble organic solvent and a low-molecular weight monomer) capable of sufficiently compatibilizing them is preferably added to these monomers. By the addition of the compatibilizing agent, the emulsifiability and polymerizability 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. The water-soluble organic solvent may be used in the amount within the range from 1 to 50 parts by weight, e.g., from 10 to 40 parts by weight, based on 100 parts by weight of water. Examples of the low-molecular weight monomer include methyl methacrylate, glycidyl methacrylate and 2,2,2-trifluoroethyl methacrylate. The low-molecular weight monomer may be used in the amount within the range from 1 to 50 parts by weight, e.g., from 10 to 40 parts by weight, based on 100 parts by weight of total of monomers. 
     A chain transfer agent may be used in the polymerization. The molecular weight of the polymer can be changed according to the amount of the chain transfer agent used. Examples of a chain transfer agent include a mercaptan group-containing compound (especially alkyl mercaptan (for example, having 1-30 carbon atoms)), such as lauryl mercaptan, thioglycol, and thioglycerol, and an inorganic salt such as sodium hypophosphite and sodium hydrogen sulfite. The amount of the chain transfer agent may be within the range from 0.01 to 10 parts by weight, for example, from 0.1 to 5 parts by weight, based on 100 parts by weight of total 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, but is preferably in the form of an aqueous dispersion. The surface treatment agent generally comprises the fluorine-containing polymer (active ingredient of the surface treatment agent) and a medium (particularly a liquid medium, for example, an organic solvent and/or water). The amount of the liquid medium may be 5 to 99.9% by weight, particularly 10 to 80% by weight, based on the fluorine-containing treatment agent. 
     In the fluorine-containing treatment agent, the concentration of the fluorine-containing polymer may be 0.01 to 95% by weight, for example, 5 to 50% by weight. 
     The surface treatment agent can be applied to a substrate to be treated by a known procedure. Usually, the surface treatment agent is diluted with an organic solvent or water, is adhered to surfaces of the substrate by a well-known procedure such as an immersion coating, a spray coating and a foam coating, and is dried. If necessary, the treatment liquid is applied together with a suitable crosslinking agent, followed by curing. It is also possible to add mothproofing agents, softeners, antimicrobial agents, flame retardants, antistatic agents, paint fixing agents, crease-proofing agents, etc. to the surface treatment agent. The concentration of the polymer in the treatment liquid contacted with the substrate may be from 0.01 to 10% by weight (particularly for immersion coating), for example, from 0.05 to 10% by weight, based on the treatment liquid. 
     (4) Nonwoven Fabric Substrate 
     The nonwoven fabric of the present invention can be produced by applying the fluorine-containing treatment agent to the nonwoven fabric substrate. Generally, the nonwoven fabric substrate is an untreated nonwoven fabric, particularly a nonwoven fabric to which agents are not applied. 
     Examples of fibers constituting the nonwoven fabric substrate include natural fibers, synthetic fibers, semi-synthetic fibers, regenerated fibers, and inorganic fibers. The fibers may be used alone or in a combination of at least two. 
     Examples of natural fibers include cellulosic fibers, such as cotton, flax and wood pulp; and chitin, chitosan, wool, and silk. Examples of the wood pulp include mechanical pulp such as ground wood pulp (GP), pressure ground wood pulp (PGW) and thermomechanical pulp (TMP); chemical pulp such as needle-leaf tree high-yield unbleached kraft pulp (HNKP; N material), needle-leaf tree bleached kraft pulp (NBKP; N material, NB material), broad-leaf tree unbleached kraft pulp (LUKP; L material) and broad-leaf tree bleached kraft pulp (LBKP, L material); recycled pulp such as deinked pulp (DIP) and waste pulp (WP); and semi-chemical pulp (CP). 
     Examples of synthetic fibers include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate and copolyester; polyolefins such as linear low-density polyethylene, low-density polyethylene, high-density polyethylene and polypropylene; polyamides such as nylon 6, nylon 66, nylon 610 and nylon 46; acrylic fibers such as polyacrylonitrile; polyvinyl alcohol, polyurethane, and polyvinyl chloride. 
     Examples of semi-synthetic fibers include acetate and triacetate. 
     Examples of regenerated fibers include rayon, cupra, polynosic rayon, lyocell and tencel. 
     Examples of inorganic fibers include glass fibers and carbon fibers. 
     The fibers constituting the nonwoven fabric substrate is preferably a combination of natural fibers and synthetic fibers, for example, a combination of cellulosic 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 the natural fibers to the synthetic fibers may be 5:95-95:5, for example, 30:70-70:30. Alternatively, in case that the intensity or durability is required of the nonwoven fabric, the weight ratio of the natural fiber to the synthetic fiber may be 5:95-70:30, for example, 10:90-50:50, especially 15:85-45:55. 
     The fluorine-containing polymer can be applied to the nonwoven fabric substrate by any of known methods of treating textiles with a liquid. The nonwoven fabric substrate may be dipped in the liquid (a liquid, for example, a solution, or dispersion liquid comprising the fluorine-containing polymer), or the liquid may be adhered or sprayed on the nonwoven fabric substrate. The treated nonwoven fabric substrate is dried and preferably heated at, for example, 100° C.-200° C., so as to exhibit water- and oil-repellency. 
     Alternatively, the fluorine-containing polymer may be applied to the nonwoven fabric substrate by a cleaning method, for example, may be applied to the nonwoven fabric substrate in a laundry application or a dry cleaning method. 
     The amount of the fluorine-containing polymer adhering to the nonwoven fabric substrate may be generally 0.001 to 20 parts by weight, for example, 0.01 to 5 parts by weight, particularly 0.05 to 1 part by weight, based on 100 parts by weight of the nonwoven fabric substrate. 
     The term “treatment” means that the treatment agent is applied to the substrate by immersion, spray, coating or the like. The treatment gives the result that the polymer which is an active component of the treatment agent is penetrated into internal parts of the substrate and/or adhered to surfaces of the substrate. 
     EXAMPLES 
     The followings are examples which specifically explain the present invention. These examples are for the explanation of the present invention, but do not limit the present invention. 
     In the following Examples, parts, % and ratio are parts by weight, % by weight and weight ratio, unless otherwise specified. 
     The procedures of the tests were performed in the following manner. 
     Shower Water Repellency Test (Spray) 
     A shower water repellency test was conducted according to JIS-L-1092. The shower water repellency was expressed by water repellency No. (as shown in the below-described Table 1). 
     A glass funnel which has a volume of at least 250 mL and a spray nozzle which can spray 250 mL of water for 20-30 seconds are used. A test piece flame is a metal flame having a diameter of 15 cm. Three sheets of a test piece having a size of about 20 cm×20 cm are prepared and the sheet is mounted on a test piece holding flame so that the sheet has no wrinkle. The center of the spray is located on the center of the sheet. Room temperature water (250 mL) is charged into the glass funnel and sprayed on the test piece sheet (for time of 25-30 seconds). The holding flame is removed from a stand, one edge of the holding flame is grasped so that a front surface is downside and the other edge is lightly hit with a stiff substance. The holding flame is further rotated 180° and the same procedure is repeated to drop excess water droplets. The wet test piece is compared with a wet comparison standard to grade 0, 50, 70, 80, 90 and 100 points in order of poor water-repellency to excellent water repellency. The results are obtained from an average of three measurements. 
     
       
         
           
               
               
             
               
                 TABLE 1 
               
               
                   
               
               
                 Water  
                   
               
               
                 repellency 
                   
               
               
                 No. 
                 State 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
            
               
                 100 
                 No wet or water droplets adhesion on surface 
               
               
                 90 
                 No wet but small water droplets adhesion on surface 
               
               
                 80 
                 Separate small water droplets-like wet on surface 
               
               
                 70 
                 Wet on half of surface and separate small wet which 
               
               
                   
                 penetrates fabric 
               
               
                 50 
                 Wet on whole surface 
               
               
                 0 
                 Wet on front and back whole surfaces 
               
               
                   
               
            
           
         
       
     
     Water-Repellency Test (IPA) 
     The treated cloth is kept for at least 4 hours in a constant temperature and humidity machine having a temperature of 21° C. and a humidity of 65%. A test liquid (shown in Table 3) which has been also stored at 21° C. is used. The test is conducted in an air-conditioned room having a temperature of 21° C. and a humidity of 65%. A droplet of the test liquid in an amount of 0.05 mL is softly dropped by a micropipette on the fabric. If the droplet remains on the fabric after standing for 30 seconds, the test liquid passes the test. The water-repellency is expressed by a point corresponding to a maximum content (% by volume) of isopropyl alcohol (IPA) in the test liquid which passes the test. The water-repellency is evaluated as twelve levels which are Fail, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 in order of a poor level to an excellent level. 
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 Water-repellency test liquid 
               
            
           
           
               
               
            
               
                   
                 (% by volume) 
               
            
           
           
               
               
               
            
               
                 Point 
                 Isopropyl alcohol 
                 Water 
               
               
                   
               
            
           
           
               
               
               
            
               
                 10 
                 100 
                 0 
               
               
                 9 
                 90 
                 10 
               
               
                 8 
                 80 
                 20 
               
               
                 7 
                 70 
                 30 
               
               
                 6 
                 60 
                 40 
               
               
                 5 
                 50 
                 50 
               
               
                 4 
                 40 
                 60 
               
               
                 3 
                 30 
                 70 
               
               
                 2 
                 20 
                 80 
               
               
                 1 
                 10 
                 90 
               
               
                 0 
                 0 
                 100 
               
            
           
           
               
               
            
               
                 Fail 
                 Inferior to isopropyl alcohol 0/water 100 
               
               
                   
               
            
           
         
       
     
     IPR (Water Impact Penetration Resistance) Test 
     The IPR test was conducted according to AATCC Test Method 42-2000. 
     Water Pressure Resistance Test (Hydro Head) 
     According to an AATCC 127-2003 water pressure resistance test method, a water pressure resistance measuring apparatus was used to measure the water pressure resistance. 
     Tensile Strength Test 
     A treated test fabric was cut to 15 cm×5 cm and pulled by a tensile testing machine to measure a tensile strength in a lengthwise direction and a tensile strength in a transverse direction. 
     Preparative Example 1 
     CF 3 CF 2 —(CF 2 CF 2 ) n —CH 2 CH 2 OCOC(Cl)═CH 2  (n=2.0) (97.2 g), lauryl acrylate (73.66 g), pure water (405 g), aqueous glycol solvent (34.8 g), alkylamine oxide (11.75 g), and polyoxyethylene alkyl ether (6.17 g) were charged into a 1000 mL autoclave, and ultrasonically emulsification-dispersed at 60° C. for 15 minutes with stirring. After the atmosphere in the autoclave was replaced with nitrogen, vinyl chloride (43 g) was injected, and a solution of an azo group-containing water-soluble initiator (0.86 g) in water (9 g) was added to conduct a reaction at 60° C. for 5 hours, whereby obtaining an aqueous dispersion of polymer. The composition of the polymer was almost the same as the formulations of charged monomers. 
     Preparative Example 2 
     CF 3 CF 2 —(CF 2 CF 2 ) n —CH 2 CH 2 OCOC(Cl)═CH 2  (n=2.0) (97.2 g), butyl acrylate (73.66 g), pure water (405 g), aqueous glycol solvent (34.8 g), alkylamine oxide (11.75 g), and polyoxyethylene alkyl ether (6.17 g) were charged into a 1000 mL autoclave, and ultrasonically emulsification-dispersed at 60° C. for 15 minutes with stirring. After the atmosphere in the autoclave was replaced with nitrogen, vinyl chloride (43 g) was injected, and a solution of an azo group-containing water-soluble initiator (0.86 g) in water (9 g) was added to conduct a reaction at 60° C. for 5 hours, whereby obtaining an aqueous dispersion of polymer. The composition of the polymer was almost the same as the formulations of charged monomers. 
     Preparative Example 3 
     CF 3 CF 2 —(CF 2 CF 2 ) n —CH 2 CH 2 OCOC(Cl)═CH 2  (n=2.0) (97.2 g), lauryl acrylate (49.1 g), isobornyl methacrylate (24.5 g), pure water (405 g), aqueous glycol solvent (34.8 g), alkylamine oxide (11.75 g), and polyoxyethylene alkyl ether (6.17 g) were charged into a 1000 mL autoclave, and ultrasonically emulsification-dispersed at 60° C. for 15 minutes with stirring. After the atmosphere in the autoclave was replaced with nitrogen, vinyl chloride (43 g) was injected, and a solution of an azo group-containing water-soluble initiator (0.86 g) in water (9 g) was added to conduct a reaction at 60° C. for 5 hours, whereby obtaining an aqueous dispersion of polymer. The composition of the polymer was almost the same as the formulations of charged monomers. 
     Comparative Preparative Example 1 
     CF 3 CF 2 —(CF 2 CF 2 ) n —CH 2 CH 2 OCOC(CH 3 )═CH 2  (n=2.0) (133 g), lauryl acrylate (37.6 g), pure water (405 g), aqueous glycol solvent (34.8 g), alkylamine oxide (11.75 g), and polyoxyethylene alkyl ether (6.17 g) were charged into a 1000 mL autoclave, and ultrasonically emulsification-dispersed at 60° C. for 15 minutes with stirring. After the atmosphere in the autoclave was replaced with nitrogen, vinyl chloride (43 g) was injected, and a solution of an azo group-containing water-soluble initiator (0.86 g) in water (9 g) was added to conduct a reaction at 60° C. for 5 hours, whereby obtaining an aqueous dispersion of polymer. The composition of the polymer was almost the same as the formulations of charged monomers. 
     Comparative Preparative Example 2 
     CF 3 CF 2 —(CF 2 CF 2 ) n —CH 2 CH 2 OCOC(Cl)═CH 2  (n=2.0) (97.2 g), stearyl acrylate (73.66 g), pure water (405 g), aqueous glycol solvent (34.8 g), alkylamine oxide (11.75 g), and polyoxyethylene alkyl ether (6.17 g) were charged into a 1000 mL autoclave, and ultrasonically emulsification-dispersed at 60° C. for 15 minutes with stirring. After the atmosphere in the autoclave was replaced with nitrogen, vinyl chloride (43 g) was injected, and a solution of an azo group-containing water-soluble initiator (0.86 g) in water (9 g) was added to conduct a reaction at 60° C. for 5 hours, whereby obtaining an aqueous dispersion of polymer. The composition of the polymer was almost the same as the formulations of charged monomers. 
     Example 1 
     After diluting the aqueous dispersion produced in Preparative Example 1 with pure water to give a fluorine-containing polymer solid concentration of 30%, 1.8 g of the 30% diluted liquid and 0.20 g of a crosslinking agent (a blocked isocyanate) were diluted with pure water to prepare 100 g of a test liquid. Four sheets of wood pulp/polyester nonwoven fabric (510 mm×205 mm, 30/70 of wood pulp/polyester weight ratio) were dipped in this test liquid, passed through a mangle, dried at 100° C. for 30 seconds, and treated by a pin tenter at 170° C. for 2 minutes. Then, a shower water repellency test, a water repellency test, a water pressure resistance test, an IPR test, and a tensile strength test were conducted for the test fabrics. Results are shown in Table 3. 
     Examples 2 to 4 and Comparative Examples 1 to 2 
     The polymers produced in Preparative Examples 2-4 and Comparative Preparative Examples 1-2 were used for the treatment as in Example 1, and the shower water repellency test, the water repellency test, the water pressure resistance test, the IPR test, and the tensile strength test were conducted. Results are shown in Table 3. 
     The meanings of abbreviations in the Tables are as follows: 
     
       
         
           
               
               
               
             
               
                   
                   
               
               
                   
                 Abbreviation 
                 Compound name/Chemical formula 
               
               
                   
                   
               
             
            
               
                   
                 C6SFCIA 
                 C 6 F 13 CH 2 CH 2 OCOC(Cl)═CH 2   
               
               
                   
                 C6SFMA 
                 C 6 F 13 CH 2 CH 2 OCOC(CH 3 )═CH 2   
               
               
                   
                 LA 
                 Lauryl acrylate 
               
               
                   
                 BA 
                 Butyl acrylate 
               
               
                   
                 StA 
                 Stearyl acrylate 
               
               
                   
                 VCM 
                 Vinyl chloride 
               
               
                   
                 IBMA 
                 Isobornyl methacrylate 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
             
               
                 TABLE 3 
               
             
            
               
                   
               
               
                   
                   
                   
                   
                 Com. Ex. 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                   
                   
                 Ex. 
                 Com. 
                 Com. 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                   
                   
                   
                 Pre. 
                 Pre. 
                 Pre. 
                 Pre. 
                 Pre. 
               
               
                   
                   
                   
                 Ex. 1 
                 Ex. 2 
                 Ex. 3 
                 Ex. 1 
                 Ex. 2 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 Polymer  
                 C6SFCIA 
                   
                 50 
                 50 
                 50 
                   
                 50 
               
               
                 components 
                 C6SFMA 
                   
                   
                   
                   
                 70 
                   
               
               
                   
                 VCM 
                   
                 20 
                 20 
                 20 
                 20 
                 20 
               
               
                   
                 LA 
                   
                 30 
                   
                 20 
                 10 
                   
               
               
                   
                 BA 
                   
                   
                 30 
                   
                   
                   
               
               
                   
                 StA 
                   
                   
                   
                   
                   
                 30 
               
               
                   
                 IBMA 
                   
                   
                   
                 10 
                   
                   
               
               
                 Treatment  
                 Sample 
                 g/20% 
                 1.8% 
                 1.8% 
                 1.8% 
                 1.8% 
                 1.8% 
               
               
                 recipe 
                   
                 solid 
                   
                   
                   
                   
                   
               
               
                   
                   
                 content 
                   
                   
                   
                   
                   
               
               
                   
                 Cross linking 
                   
                 0.2% 
                 0.2% 
                 0.2% 
                 0.2% 
                 0.2% 
               
               
                   
                 agent (blocked 
                   
                   
                   
                   
                   
                   
               
               
                   
                 isocyanate) 
                   
                   
                   
                   
                   
                   
               
               
                 Wood pulp/ 
                 IPA 
                 % 
                 90 
                 90 
                 90 
                 80 
                 90 
               
               
                 polyester 
                 Spray 
                   
                 90 
                 90 
                 90 
                 70 
                 80 
               
               
                 nonwoven  
                 IPR 
                 g 
                 0.22 
                 0.41 
                 0.21 
                 0.65 
                 0.22 
               
               
                 fabric 
                 Hydro Head 
                 mbar 
                 21.3 
                 21.4 
                 20.4 
                 21.7 
                 21.5 
               
               
                 Wet pick up  
                   
                   
                   
                   
                   
                   
                   
               
               
                 110% 
                   
                   
                   
                   
                   
                   
                   
               
               
                 Tensile  
                 Lengthwise 
                 N 
                 241 
                 233 
                 211 
                 194 
                 192 
               
               
                 strength 
                 direction (MD) 
                   
                   
                   
                   
                   
                   
               
               
                   
                 Transverse 
                 N 
                 43 
                 38 
                 36 
                 35 
                 30 
               
               
                   
                 direction (CD) 
               
               
                   
               
            
           
         
       
     
     INDUSTRIAL APPLICABILITY 
     The nonwoven fabric of the present invention can be used in, for example, a medical use, an industrial material use, a civil engineering and construction use, and an agricultural and horticultural use. Specific uses include a surgical cloth, a package cloth, a bedsheet, a pillow case, a disposable diaper and a sanitary napkin. 
     Embodiments of the present invention are as follows: 
     1) A nonwoven fabric to which a fluorine-containing polymer is adhered,
 
wherein the fluorine-containing polymer comprises:
 
(a) repeating units derived from a fluorine-containing monomer which is alpha-chloro acrylate or alpha-chloro acrylamide having a fluoroalkyl group, and
 
(b) repeating units derived from a halogenated olefin monomer, and the fluorine-containing polymer is free from repeating unit derived from a (meth)acrylate containing a linear or branched hydrocarbon group having at least 18 carbon atoms.
 
2) The nonwoven fabric according to any embodiment above, wherein the fluorine-containing monomer (a) is a compound represented by the formula:
 
       CH2═C(—Cl)—C(═O)—Y—Z—Rf
 
     wherein Y is —O— or —NH—;
 
Z is a direct bond or divalent organic group; and
 
Rf is a fluoroalkyl group having 1 to 20 carbon atoms.
 
3) The nonwoven fabric according to any embodiment above, wherein the halogenated olefin is an olefin having 2-20 carbon atoms substituted by 1-10 chlorine atoms, bromine atoms or iodine atoms.
 
4) The nonwoven fabric according to any embodiment above, wherein the fluorine-containing polymer further comprises:
 
(c) repeating unit derived from a (meth)acrylate containing a linear or branched hydrocarbon group having 17 or less carbon atoms.
 
5) The nonwoven fabric according to any embodiment above, wherein the fluorine-containing polymer further comprises at least one selected from the group consisting of:
 
(d) repeating units derived from a (meth)acrylate or (meth)acrylamide monomer having a cyclic hydrocarbon group, and
 
(e) repeating units derived from a fluorine-free crosslinking (meth)acrylate or (meth)acrylamide monomer.
 
6) The nonwoven fabric according to any embodiment above, wherein the substrate is a combination of cellulosic fibers and polyester fibers.
 
7) The nonwoven fabric according to any embodiment above, wherein the amount of the fluorine-containing monomer (a) is 20% to 90% by weight, based on the fluorine-containing polymer, and
 
the amount of the halogenated olefin monomer (b) is 5 to 300 parts by weight, based on 100 parts by weight of the fluorine-containing monomer (a).
 
8) The nonwoven fabric according to any embodiment above, wherein the amount of the fluorine-containing polymer adhering to the nonwoven fabric substrate is 0.01 to 5 parts by weight, based on 100 parts by weight of nonwoven fabric substrate.
 
9) A method of producing the nonwoven fabric according to any embodiment above, which comprises applying the fluorine-containing polymer to the substrate.