U.S. patent application number 15/662437 was filed with the patent office on 2018-02-08 for nonwoven fabric.
This patent application is currently assigned to DAIKIN INDUSTRIES, LTD.. The applicant listed for this patent is DAIKIN INDUSTRIES, LTD.. Invention is credited to Takashi ENOMOTO, Masaki FUKUMORI, Shinichi MINAMI, Ikuo YAMAMOTO, Min ZHU.
Application Number | 20180038044 15/662437 |
Document ID | / |
Family ID | 61070263 |
Filed Date | 2018-02-08 |
United States Patent
Application |
20180038044 |
Kind Code |
A1 |
MINAMI; Shinichi ; et
al. |
February 8, 2018 |
NONWOVEN FABRIC
Abstract
Disclosed is a nonwoven fabric formed from (i) a nonwoven fabric
substrate and (ii) a fluorine-containing polymer adhering to the
nonwoven fabric substrate, wherein the fluorine-containing polymer
contains: (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 carbon atoms.
Inventors: |
MINAMI; Shinichi; (Shanghai,
CN) ; FUKUMORI; Masaki; (Osaka-shi, JP) ;
ENOMOTO; Takashi; (Osaka-shi, JP) ; YAMAMOTO;
Ikuo; (Osaka-shi, JP) ; ZHU; Min; (Shanghai,
CN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
DAIKIN INDUSTRIES, LTD. |
Osaka |
|
JP |
|
|
Assignee: |
DAIKIN INDUSTRIES, LTD.
Osaka
JP
|
Family ID: |
61070263 |
Appl. No.: |
15/662437 |
Filed: |
July 28, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
D01F 6/16 20130101; D06M
15/295 20130101; D06M 15/263 20130101; D06M 2200/11 20130101; D06M
2200/10 20130101; D06M 2101/22 20130101; D06M 15/248 20130101; D06M
2200/01 20130101; D06M 15/244 20130101; D06M 15/277 20130101; D06M
2101/06 20130101; D06M 15/267 20130101; D01F 6/32 20130101; D06M
2101/32 20130101; D06M 2200/12 20130101 |
International
Class: |
D06M 15/277 20060101
D06M015/277; D01F 6/32 20060101 D01F006/32; D01F 6/16 20060101
D01F006/16; D06M 15/267 20060101 D06M015/267 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 2, 2016 |
CN |
201610626325.X |
Claims
1. 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 carbon
atoms.
2. The nonwoven fabric according to claim 1, wherein the
fluorine-containing monomer (a) is a compound represented by the
formula: CH.sub.2.dbd.C(--Cl)--C(.dbd.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 claim 1, wherein Z is a direct
bond, a linear or branched aliphatic group having 1-20 carbon
atoms, an aromatic group or cycloaliphatic group having 6-18 carbon
atoms, a group represented by the formula
--R.sup.2(R.sup.1)N--SO.sub.2-- or the formula
--R.sup.2(R.sup.1)N--CO-- wherein R.sup.1 is an alkyl group having
1 to 10 carbon atoms and R.sup.2 is a linear alkylene group or
branched alkylene group having 1 to 10 carbon atoms, for example,
by a --CH.sub.2CH.sub.2N(R.sup.1)SO.sub.2-- group wherein R.sup.1
is an alkyl group having 1 to 4 carbon atoms, a group represented
by the formula
--CH.sub.2CH(OR.sup.3)CH.sub.2--[Ar--(O).sub.q].sub.p-- wherein
R.sup.3 is a hydrogen atom or an acyl group having 1 to 10 carbon
atoms, Ar is an arylene group optionally having a substituent
group, p is 0 or 1, and q is 0 or 1, a group represented by the
formula --(CH.sub.2).sub.n--Ar--(O).sub.q-- (wherein Ar is an
arylene group optionally having a substituent group, n is 0-10, and
q is 0 or 1), or a --(CH.sub.2).sub.m--SO.sub.2--(CH.sub.2).sub.n--
group or a --(CH.sub.2).sub.m--S--(CH.sub.2).sub.n-- group wherein
m is 1-10, and n is 0-10.
4. The nonwoven fabric according to claim 1, wherein the
halogenated olefin monomer (b) is an olefin having 2-20 carbon
atoms and substituted by 1-10 chlorine atoms, bromine atoms or
iodine atoms.
5. The nonwoven fabric according to claim 4, wherein the
halogenated olefin monomer (b) is at least one selected from the
group consisting of vinyl chloride and vinylidene chloride.
6. The nonwoven fabric according to claim 1, wherein the
fluorine-containing polymer further comprises a fluorine-free
non-crosslinkable monomer, and the fluorine-free non-crosslinkable
monomer is at least one selected from the group consisting of:
(c1-i) repeating units formed from a (meth)acrylate or
(meth)acrylamide monomer containing a linear or branched
hydrocarbon group having 17 or less carbon atoms, and (c1-ii)
repeating units formed from a (meth)acrylate or (meth)acrylamide
monomer containing a cyclic hydrocarbon group.
7. The nonwoven fabric according to claim 6, wherein the
(meth)acrylate or (meth)acrylamide monomers (c1-i) and (c1-ii) are
a compound represented by the formula: CH.sub.2.dbd.CA-T wherein A
is a hydrogen atom, a methyl group, or a halogen atom other than a
fluorine atom, T is an open-chain or cyclic organic group having 1
to 31 carbon atoms and an ester bond or amide bond.
8. The nonwoven fabric according to claim 6, wherein the
(meth)acrylate or (meth)acrylamide monomer containing a linear or
branched hydrocarbon group having 17 or less carbon atoms (c1-i) is
an acrylate represented by the formula:
CH.sub.2.dbd.CA.sup.1CO--Z.sup.1-A.sup.2 wherein A.sup.1 is a
hydrogen atom, a methyl group, or a halogen atom other than a
fluorine atom, Z.sup.1 is --O-- or --NH--, and A.sup.2 is an alkyl
group represented by C.sub.nH.sub.2n+1 wherein n is 1 to 17.
9. The nonwoven fabric according to claim 1, wherein the
fluorine-containing polymer further comprises: (c2) repeating units
formed from a fluorine-free crosslinking (meth)acrylate or
(meth)acrylamide monomer.
10. The nonwoven fabric according to claim 1, wherein the nonwoven
fabric substrate is a combination of natural fibers and synthetic
fibers,
11. The nonwoven fabric according to claim 10, wherein the nonwoven
fabric substrate is a combination of cellulosic fibers and
polyester fibers.
12. The nonwoven fabric according to claim 10, wherein the weight
ratio of the natural fiber to the synthetic fiber is
15:85-45:55.
13. The nonwoven fabric according to claim 1, 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).
14. The nonwoven fabric according to claim 6, wherein the amount of
each of the fluorine-free non-crosslinkable monomers (c1-i) and
(c1-ii) is 0 to 500 parts by weight, based on 100 parts by weight
of the fluorine-containing monomer (a).
15. The nonwoven fabric according to claim 1, 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 the nonwoven fabric substrate.
16. A method of producing the nonwoven fabric according to claim 1,
which comprises applying the fluorine-containing polymer to the
nonwoven fabric substrate.
17. The method according to claim 16, wherein the
fluorine-containing polymer is in the form of an aqueous
dispersion.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims benefit of Chinese Patent
Application No. 201610626325.X filed Aug. 2, 2016, incorporated
herein by reference in its entirety.
TECHNICAL FIELD
[0002] The present invention relates to a nonwoven fabric,
particularly a nonwoven fabric to which a fluorine-containing
polymer is adhered.
BACKGROUND ART
[0003] Hitherto, treatments of textiles with a fluorine-containing
treatment agent are proposed.
[0004] 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.
[0005] 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
[0006] One of objects of the present invention is to provide a
nonwoven fabric having high water- and oil-repellency and high
mechanical strength.
[0007] The present invention relates to the nonwoven fabric to
which the fluorine-containing polymer adhered.
[0008] 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.
[0009] The fluorine-containing polymer gives high water repellency,
oil repellency, and/or soil resistance to the nonwoven fabric
substrate.
Effect of the Invention
[0010] 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
[0011] 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).
[0012] The fluorine-containing treatment agent comprises the
fluorine-containing polymer and a liquid medium.
(1) Fluorine-Containing Polymer
[0013] 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.
[0014] 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
[0015] The fluorine-containing monomer (a) may be a compound
represented by the formula:
CH.sub.2.dbd.C(--Cl)--C(.dbd.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.
[0016] The fluorine-containing monomer (a) is preferably a compound
represented by the formula:
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--Y--Z--Rf
wherein Y is --O-- or --NH--;
[0017] 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.sub.2).sub.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.sup.2(R.sup.1)N--SO.sub.2-- or the
formula --R.sup.2 (R.sup.1)N--CO-- wherein R.sup.1 is an alkyl
group having 1 to 10 carbon atoms and R.sup.2 is a linear alkylene
group or branched alkylene group having 1 to 10 carbon atoms, a
group represented by the formula
--CH.sub.2CH(OR.sup.3)CH.sub.2--(Ar--O).sub.p-- wherein R.sup.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.sub.2).sub.n--Ar--(O).sub.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.sub.2).sub.m--SO.sub.2--(CH.sub.2).sub.n-- group or a
--(CH.sub.2).sub.m--S--(CH.sub.2).sub.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.
[0018] 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.sub.3, --CF.sub.2CF.sub.3, --CF.sub.2CF.sub.2CF.sub.3,
--CF(CF.sub.3).sub.2, --CF.sub.2CF.sub.2CF.sub.2CF.sub.3,
--CF.sub.2CF(CF.sub.3).sub.2, --C(CF.sub.3).sub.3,
--(CF.sub.2).sub.4CF.sub.3, --(CF.sub.2).sub.2CF(CF.sub.3).sub.2,
--CF.sub.2C(CF.sub.3).sub.3,
--CF(CF.sub.3)CF.sub.2CF.sub.2CF.sub.3, --(CF.sub.2).sub.5CF.sub.3,
--(CF.sub.2).sub.3CF(CF.sub.3).sub.2,
--(CF.sub.2).sub.4CF(CF.sub.3).sub.2 and --C.sub.8F.sub.17.
[0019] Preferably, the fluorine-containing monomer is an acrylate
ester wherein the Y group is --O--.
[0020] 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.sub.2).sub.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.sup.2(R.sup.1)N--SO.sub.2--
or the formula --R.sup.2 (R.sup.1)N--CO-- wherein R.sup.1 is an
alkyl group having 1 to 10 carbon atoms and R.sup.2 is a linear
alkylene group or branched alkylene group having 1 to 10 carbon
atoms, for example, by a --CH.sub.2 CH.sub.2 N(R.sup.1)SO.sub.2--
group wherein R.sup.1 is an alkyl group having 1 to 4 carbon atoms,
a group represented by the formula
--CH.sub.2CH(OR.sup.3)CH.sub.2--[Ar--(O).sub.q].sub.p-- wherein
R.sup.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.sub.2).sub.n--Ar--(O).sub.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.sub.2).sub.m--SO.sub.2--(CH.sub.2).sub.n-- group or a
--(CH.sub.2).sub.m--S--(CH.sub.2).sub.n-- group wherein m is 1-10,
and n is 0-10.
[0021] The aromatic group or the cycloaliphatic group may be
substituted or unsubstituted. The S group or the SO.sub.2 group may
be directly bonded to the Rf group.
[0022] Specific examples of the fluorine-containing monomer (a)
include, but are not limited to, the followings:
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--O--(CH.sub.2).sub.2--Rf
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--O--(CH.sub.2).sub.4--Rf
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--O--(CH.sub.2).sub.2--S--Rf
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--O--(CH.sub.2).sub.2--S--(CH.sub.2).sub.-
2--Rf
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--O--(CH.sub.2).sub.2--SO.sub.2--Rf
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--O--(CH.sub.2).sub.2--SO.sub.2--(CH.sub.-
2).sub.2--Rf
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--NH--(CH.sub.2).sub.2--Rf
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--O--(CH.sub.2).sub.3--S--Rf
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--O--(CH.sub.2).sub.3--S--(CH.sub.2).sub.-
2--Rf
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--O--(CH.sub.2).sub.3--SO.sub.2--Rf
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--O--(CH.sub.2).sub.3--SO.sub.2--(CH.sub.-
2).sub.2--Rf
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--O--CH.sub.2CH.sub.2N(CH.sub.3)SO.sub.2--
-Rf
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--O--CH.sub.2CH(OCOCH.sub.3)CH.sub.2--Rf
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--O--CH.sub.2-Ph-O--Rf (wherein Ph
is 1,4-phenylene.)
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--O--CH.sub.2CH(OH)CH.sub.2-Ph-O--Rf
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--O--CH.sub.2-Ph-Rf
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--O--CH.sub.2CH(OCOCH.sub.3)CH.sub.2-Ph-R-
f
wherein Ph is a phenylene group, and Rf is a fluoroalkyl group
having 1-20 carbon atoms.
(b) Halogenated Olefin Monomer
[0023] Preferably, the halogenated olefin is free from a fluorine
atom.
[0024] 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
[0025] 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.
[0026] 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
[0027] 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.
[0028] 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.
[0029] 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.sub.2.dbd.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.
[0030] 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.
[0031] 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.
[0032] Examples of the open-chain or cyclic organic group having
1-31 carbon atoms and an ester bond are: --C(.dbd.O)--O-Q and
--O--C(.dbd.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.
[0033] Examples of the open-chain or cyclic organic group having
1-31 carbon atoms and an amide bond are: --C(.dbd.O)--NH-Q and
--NH--C(.dbd.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.
[0034] 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.
[0035] 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.sub.2.dbd.CA.sup.1CO--Z.sup.1-A.sup.2
wherein A.sup.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.sup.1 is --O-- or --NH--, and
[0036] A.sup.2 is an alkyl group represented by C.sub.nH.sub.2n+1
wherein n is 1 to 17.
[0037] Preferable examples ofA.sup.2 include butyl and lauryl.
[0038] The fluorine-free non-crosslinkable monomer (c1) may be a
(meth)acrylate or (meth)acrylamide monomer containing a cyclic
hydrocarbon group.
[0039] The cyclic hydrocarbon group-containing (meth)acrylate ester
monomer is preferably a compound represented by the formula:
CH.sub.2.dbd.CA.sup.21-C(.dbd.O)--O-A.sup.22
wherein A.sup.21 is a hydrogen atom or a methyl group, and A.sup.22
is a cyclic hydrocarbon containing group having 4-30 carbon
atoms.
[0040] The cyclic hydrocarbon group-containing (meth)acrylate ester
monomer is a monomer having a high glass transition temperature
(for example, at least 50.degree. C., particularly at least
80.degree. C.) of a homopolymer thereof.
[0041] 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.
[0042] A.sup.21 may be a hydrogen atom.
[0043] A.sup.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.
[0044] 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.
[0045] 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
[0046] 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.
[0047] 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.
[0048] 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.
[0049] 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.
[0050] 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.
[0051] 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.
[0052] 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).
[0053] 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).
[0054] 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).
[0055] 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).
[0056] 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.
[0057] 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.
[0058] 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.
[0059] 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.sub.2SiO).sub.a(RR.sup.NSiO).sub.b(RR.sup.SSiO).sub.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.sup.N is a monovalent amino-functional organic
group, R.sup.S each is a monovalent mercapto-functional organic
group (R.sup.S).
[0060] 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.
[0061] 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
[0062] 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.
[0063] 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
[0064] 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.
[0065] 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.
[0066] Examples of the nonionic surface active agent include an
ether, an ester, an ester ether, an alkanolamide, a polyhydric
alcohol and an amine oxide.
[0067] An example of the ether is a compound containing an
oxyalkylene group (preferably a polyoxyethylene group).
[0068] 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.
[0069] 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.
[0070] 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.
[0071] The polyhydric alcohol may be a dihydric to pentahydric
alcohol having 3-30 (or 10-50) carbon atoms.
[0072] 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)
[0073] 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.
[0074] 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.
[0075] 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).
[0076] 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).
[0077] The nonionic surfactant may be a surfactant of the
formula:
R.sup.1O--(CH.sub.2CH.sub.2O).sub.p--(R.sup.2O).sub.q--R.sup.3
wherein R.sup.1 is an alkyl group having 1 to 22 carbon atoms or an
alkenyl or acyl group having 2 to 22 carbon atoms, R.sup.2 is
independently, the same or different, an alkylene group having at
least 3 (for example, 3 to 10) carbon atoms, R.sup.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.
[0078] R.sup.1 is preferably has 8 to 20 carbon atoms, especially
10 to 18 carbon atoms. Preferable examples of R.sup.1 include a
lauryl group, a tridecyl group and an oleyl group.
[0079] Examples of R.sup.2 are a propylene group and a butylene
group.
[0080] 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.sup.2O).sub.q-- may form the
polyoxyalkylene chain.
[0081] 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.
[0082] A preferable nonionic surfactant is the formula:
R.sup.1O--(CH.sub.2CH.sub.2O).sub.p--H
wherein R.sup.1 and p are the same as the above.
[0083] Examples of the nonionic surfactant include the
followings:
C.sub.10H.sub.21O--(CH.sub.2CH.sub.2O).sub.p--(C.sub.3H.sub.6O).sub.q--H
C.sub.12H.sub.25O--(CH.sub.2CH.sub.2O).sub.p--(C.sub.3H.sub.6O).sub.q--H
C.sub.16H.sub.31O--(C
H.sub.2CH.sub.2O).sub.p--(C.sub.3H.sub.6O).sub.q--H
C.sub.16H.sub.33O--(CH.sub.2CH.sub.2O).sub.p--(C.sub.3H.sub.6O).sub.q--H
C.sub.18H.sub.35O--(CH.sub.2CH.sub.2O).sub.p--(C.sub.3H.sub.6O).sub.q--H
C.sub.18H.sub.37O--(CH.sub.2CH.sub.2O).sub.p--(C.sub.3H.sub.6O).sub.q--H
C.sub.12H.sub.25O--(CH.sub.2CH.sub.2O).sub.p--(C.sub.3H.sub.6O).sub.q--C-
.sub.12H.sub.25
C.sub.16H.sub.31O--(C
H.sub.2CH.sub.2O).sub.p--(C.sub.3H.sub.6O).sub.q-C.sub.16H.sub.31
C.sub.16H.sub.33O--(CH.sub.2CH.sub.2O).sub.p--(C.sub.3H.sub.6O).sub.q-C.-
sub.12H.sub.25
iso-C.sub.13H.sub.27O--(CH.sub.2CH.sub.2H.sub.2O).sub.p--(C.sub.3H.sub.6-
O).sub.q--H
C.sub.10H.sub.21COO--(CH.sub.2CH.sub.2O).sub.p--(C.sub.3H.sub.6O).sub.q--
-H
C.sub.16H.sub.33COO--(CH.sub.2CH.sub.2O).sub.p--(C.sub.3H.sub.6O).sub.q--
C.sub.12H.sub.25
[0084] wherein p and q are the same as defined in the above.
[0085] Examples of the nonionic surfactant include a condensation
product of ethylene oxide with, for example, hexyl phenol, isooctyl
phenol, hexadecanol, oleic acid, alkane (C.sub.12-C.sub.16) thiol,
a sorbitan mono-fatty acid (C.sub.7-C.sub.19) or an alkyl
(C.sub.12-C.sub.18) amine.
[0086] 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).
[0087] Generally, the average molecular weight of the nonionic
surfactant is from 300 to 5,000, for example, from 500 to
3,000.
[0088] The nonionic surfactant can be used alone or in combination
of at least two.
[0089] 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.sup.1O.sup.1--(CH.sub.2CH.sub.2O).sub.p--(R.sup.2O).sub.q--R.sup.3
[especially, R.sup.1O--(CH.sub.2CH.sub.2O).sub.p--H] wherein the
R.sup.1 group (and/or, the R.sup.3 group) is a branched alkyl group
(for example, an isotridecyl group). The amount of the nonionic
surfactant wherein the R.sup.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.sup.1O--(CH.sub.2CH.sub.2O).sub.p--(R.sup.2O).sub.q--R.sup.3
[especially, R.sup.1O--(CH.sub.2CH.sub.2O).sub.p--H] wherein the
R.sup.1 group (and/or, the R.sup.3 group) is a (saturated and/or
unsaturated) linear alkyl group (for example, a lauryl group (a
n-lauryl group)).
[0090] 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.
[0091] 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.
[0092] A preferable example of the cationic surface active agent
is:
R.sup.21--N.sup.+(--R.sup.22)(--R.sup.23)(--R.sup.24)X.sup.-
wherein R.sup.21, R.sup.22, R.sup.23 and R.sup.24 are a hydrocarbon
groups having 1 to 30 carbon atoms, and X is an anionic group.
[0093] Specific examples of R.sup.21, R.sup.22, R.sup.23 and
R.sup.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).
[0094] The cationic surface active agent is particularly preferably
a monoalkyltrimethyl ammonium salt (the carbon number of the alkyl
is 4 to 30).
[0095] Preferably, the cationic surfactant is an ammonium salt. The
cationic surfactant may be an ammonium salt of the formula:
R.sup.1.sub.p--N.sup.+R.sup.2.sub.qX.sup.-
wherein R.sup.1 is a linear and/or branched aliphatic (saturated
and/or unsaturated) group having at least 12 carbon atoms (for
example, C.sub.12-C.sub.50), R.sup.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.sub.3 and C.sub.2H.sub.5 are particularly preferable), X is a
halogen atom or a C.sub.1-C.sub.4 fatty-acid-salt group, p is 1 or
2, q is 2 or 3, and p+q=4.
[0096] The carbon number of R.sup.1 may be from 12 to 50, for
example, from 12 to 30.
[0097] 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.
[0098] 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 .alpha.-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.sub.3.sup.-M.sup.+ 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).
[0099] 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.sub.3N.dbd.O wherein each R group is, for
example, a hydrocarbon group (particularly an alkyl group) having
1-30 carbon atoms.
[0100] 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.
[0101] 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.
[0102] 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.
[0103] 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.degree. C. to 120.degree. 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.
[0104] 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.
[0105] 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.degree. C. to 80.degree. 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.
[0106] 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.
[0107] 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.
[0108] 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.
[0109] 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.
[0110] 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.
[0111] 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
[0112] 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.
[0113] 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.
[0114] 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).
[0115] 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.
[0116] Examples of semi-synthetic fibers include acetate and
triacetate.
[0117] Examples of regenerated fibers include rayon, cupra,
polynosic rayon, lyocell and tencel.
[0118] Examples of inorganic fibers include glass fibers and carbon
fibers.
[0119] 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.
[0120] 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.degree. C.-200.degree. C., so as to exhibit
water- and oil-repellency.
[0121] 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.
[0122] 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.
[0123] 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
[0124] 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.
[0125] In the following Examples, parts, % and ratio are parts by
weight, % by weight and weight ratio, unless otherwise
specified.
[0126] The procedures of the tests were performed in the following
manner.
Shower Water Repellency Test (Spray)
[0127] 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).
[0128] 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.times.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.degree. 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-US-00001 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)
[0129] The treated cloth is kept for at least 4 hours in a constant
temperature and humidity machine having a temperature of 21.degree.
C. and a humidity of 65%. A test liquid (shown in Table 3) which
has been also stored at 21.degree. C. is used. The test is
conducted in an air-conditioned room having a temperature of
21.degree. 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-US-00002 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
[0130] The IPR test was conducted according to AATCC Test Method
42-2000.
Water Pressure Resistance Test (Hydro Head)
[0131] 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
[0132] A treated test fabric was cut to 15 cm.times.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
[0133]
CF.sub.3CF.sub.2--(CF.sub.2CF.sub.2).sub.n--CH.sub.2CH.sub.2OCOC(Cl-
).dbd.CH.sub.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.degree. 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.degree. 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
[0134]
CF.sub.3CF.sub.2--(CF.sub.2CF.sub.2).sub.n--CH.sub.2CH.sub.2OCOC(Cl-
).dbd.CH.sub.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.degree. 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.degree. 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
[0135]
CF.sub.3CF.sub.2--(CF.sub.2CF.sub.2).sub.n--CH.sub.2CH.sub.2OCOC(Cl-
).dbd.CH.sub.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.degree. 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.degree. 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
[0136]
CF.sub.3CF.sub.2--(CF.sub.2CF.sub.2).sub.n--CH.sub.2CH.sub.2OCOC(CH-
.sub.3).dbd.CH.sub.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.degree. 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.degree. 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
[0137]
CF.sub.3CF.sub.2--(CF.sub.2CF.sub.2).sub.n--CH.sub.2CH.sub.2OCOC(Cl-
).dbd.CH.sub.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.degree. 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.degree. 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
[0138] 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.times.205 mm,
30/70 of wood pulp/polyester weight ratio) were dipped in this test
liquid, passed through a mangle, dried at 100.degree. C. for 30
seconds, and treated by a pin tenter at 170.degree. 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
[0139] 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.
[0140] The meanings of abbreviations in the Tables are as
follows:
TABLE-US-00003 Abbreviation Compound name/Chemical formula C6SFCIA
C.sub.6F.sub.13CH.sub.2CH.sub.2OCOC(Cl).dbd.CH.sub.2 C6SFMA
C.sub.6F.sub.13CH.sub.2CH.sub.2OCOC(CH.sub.3).dbd.CH.sub.2 LA
Lauryl acrylate BA Butyl acrylate StA Stearyl acrylate VCM Vinyl
chloride IBMA Isobornyl methacrylate
TABLE-US-00004 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
[0141] 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.
[0142] 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.dbd.C(--Cl)--C(.dbd.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.
* * * * *