U.S. patent application number 10/181897 was filed with the patent office on 2003-06-12 for treatment of textile product for imparting water and oil repellency.
Invention is credited to Enomoto, Takashi, Fukuda, Teruyuki, Otsuki, Norihito, Yamamoto, Ikuo.
Application Number | 20030106161 10/181897 |
Document ID | / |
Family ID | 18543011 |
Filed Date | 2003-06-12 |
United States Patent
Application |
20030106161 |
Kind Code |
A1 |
Enomoto, Takashi ; et
al. |
June 12, 2003 |
Treatment of textile product for imparting water and oil
repellency
Abstract
A textile having sufficient water repellency, oil repellency and
soil releasability before and after cleaning can be prepared by a
method of preparing a treated textile has the steps of (1)
preparing a treatment liquid containing a water- and oil-repellent
agent and a stain blocking agent, (2) bringing the pH of the
treatment liquid to at most 7, (3) applying the treatment liquid to
the textile, (4) thermally treating the textile with steam, and (5)
washing the textile with water and dehydrating the textile, wherein
the water- and oil-repellent agent has a combination of (A) a
fluorine-containing polymer comprising a repeat unit derived from
vinyl chloride and/or vinylidene chloride, and (B) a
fluorine-containing polymer free from a repeat unit derived from
vinyl chloride and/or vinylidene chloride.
Inventors: |
Enomoto, Takashi;
(Settsu-shi, JP) ; Yamamoto, Ikuo; (Settsu-shi,
JP) ; Fukuda, Teruyuki; (Settsu-shi, JP) ;
Otsuki, Norihito; (Settu-shi, JP) |
Correspondence
Address: |
SUGHRUE MION, PLLC
2100 PENNSYLVANIA AVENUE, N.W.
WASHINGTON
DC
20037
US
|
Family ID: |
18543011 |
Appl. No.: |
10/181897 |
Filed: |
July 24, 2002 |
PCT Filed: |
January 17, 2001 |
PCT NO: |
PCT/JP01/00243 |
Current U.S.
Class: |
8/115.51 |
Current CPC
Class: |
D06M 15/248 20130101;
D06M 2200/12 20130101; D06M 15/277 20130101; D06M 2200/11 20130101;
D06M 2101/16 20130101 |
Class at
Publication: |
8/115.51 |
International
Class: |
D06M 010/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 25, 2000 |
JP |
2000-015769 |
Claims
1. A method of preparing a treated textile, comprising steps of:
(1) preparing a treatment liquid comprising a water- and
oil-repellent agent, (2) adjusting pH of the treatment liquid to at
most 7, preferably at most 2, (3) applying the treatment liquid to
the textile, (4) thermally treating the textile with steam, and (5)
washing the textile with water and dehydrating the textile, wherein
the water- and oil-repellent agent comprises a combination of (A) a
fluorine-containing polymer comprising a repeat unit derived from
vinyl chloride and/or vinylidene chloride, and (B) a
fluorine-containing polymer free from a repeat unit derived from
vinyl chloride and/or vinylidene chloride.
2. The method according to claim 1, wherein the fluorine-containing
polymer (A) comprises: (A-I) a repeat unit derived from a monomer
having a fluoroalkyl group, and (A-II) a repeat unit derived from
vinyl chloride and/or vinylidene chloride.
3. The method according to claim 1, wherein the fluorine-containing
polymer (A) comprises: (A-I) a repeat unit derived from a monomer
having a fluoroalkyl group, (A-II) a repeat unit derived from vinyl
chloride and/or vinylidene chloride, (A-III) a repeat unit derived
from a fluorine-free monomer, and (A-IV) a repeat unit derived from
a crosslinkable monomer.
4. The method according to claim 1, wherein the fluorine-containing
polymer (B) comprises (B-I) a repeat unit derived from a monomer
having a fluoroalkyl group, and does not comprise a repeat unit
derived from vinyl chloride and/or vinylidene chloride.
5. The method according to claim 1, wherein the fluorine-containing
polymer (B) comprises: (B-I) a repeat unit derived from a monomer
having a fluoroalkyl group, (B-II) a repeat unit derived from a
fluorine-free monomer, and (B-III) a repeat unit derived from a
crosslinkable monomer, and does not comprise a repeat unit derived
from vinyl chloride and/or vinylidene chloride.
6. A textile obtainable by the method according to claim 1.
7. A carpet obtainable by the method according to claim 1.
8. The carpet according to claim 7, wherein the carpet comprises a
nylon fiber, a propylene fiber and/or a polyester fiber.
9. The carpet according to claim 7, which has the water repellency
of at least 90 and the oil repellency of at least 5 before the
cleaning, and the water repellency of at least 40 and the oil
repellency of at least 2 after 10 times of the cleaning, wherein
the numerical value of the water repellency is a maximum content of
IPA (% by volume) in a test solution resulting from the test that
five droplets of an isopropyl alcohol (IPA)/water mixture test
solution are softly positioned on a carpet surface, the penetration
state of the droplets after 10 seconds are observed and at least
four droplets do not exhibit the penetration, and the numerical
value of the oil repellency is a maximum value of oil repellency
according to AATCC-TM-118-1992 resulting from the test that five
droplets of a test solution are softly positioned on a carpet
surface, the penetration state of the droplets after 30 seconds are
observed and at least four droplets do not exhibit the
penetration.
10. A water- and oil-repellent agent used in a method of preparing
a treated textile, comprising steps of: (1) preparing a treatment
liquid comprising a water- and oil-repellent agent, (2) adjusting
pH of the treatment liquid to at most 7, preferably at most 2, (3)
applying the treatment liquid to the textile, (4) thermally
treating the textile, and (5) washing the textile with water and
dehydrating the textile, wherein the water- and oil-repellent agent
comprises a combination of (A) a fluorine-containing polymer
comprising a repeat unit derived from vinyl chloride and/or
vinylidene chloride, and (B) a fluorine-containing polymer free
from a repeat unit derived from vinyl chloride and/or vinylidene
chloride.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a treatment for imparting
water repellency, oil repellency, soil releasability and durability
thereof to a textile. A method of the present invention is
particularly useful for carpet.
RELATED ART
[0002] Hitherto, various treatment methods have been proposed in
order to impart water repellency, oil repellency and soil
releasability to a textile such as a carpet. For example, a process
of treating a textile comprising decreasing the pH of a treatment
liquid, applying the treatment liquid to the textile, thermally
treating the textile with steam, washing the textile with water,
and dehydrating the textile (hereinafter, sometimes referred to as
"Exhaust process") is proposed.
[0003] A method comprising the Exhaust process is proposed in U.S.
Pat. Nos. 5,073,442, 5,520,962 and 5,516,337, and International
Publication WO 98/50619.
[0004] U.S. Pat. No. 5,073,442 discloses a method of treating a
textile, comprising conducting an Exhaust process by using a water-
and oil-repellent agent comprising a fluorine-containing compound,
a formaldehyde condensation product and an acrylic polymer. U.S.
Pat. No. 5,520,962 discloses a method of treating a carpet,
comprising conducting an Exhaust process by using a
fluorine-containing compound and a polymeric binder. U.S. Pat. No.
5,516,337 discloses a method of treating a textile, comprising
conducting an Exhaust process by using a fluorine-containing water-
and oil-repellent agent and a metal compound such as aluminum
sulfate. International Publication WO 98/50619 discloses a method
of treating a carpet, comprising conducting an Exhaust process by
using a fluorine-containing water- and oil-repellent agent and a
salt such as a magnesium salt.
[0005] Sufficient water repellency, oil repellency and soil
releasability cannot be obtained by conducting the Exhaust process
in accordance with these methods.
SUMMARY OF THE INVENTION
[0006] An object of the present invention is to give a textile
excellent in water repellency, oil repellency, soil releasability
and durability thereof, when an Exhaust process is conducted with
using a water- and oil-repellent agent having a specified
composition.
[0007] The present invention provides a method of treating a
textile, comprising steps of:
[0008] (1) preparing a treatment liquid comprising a water- and
oil-repellent agent,
[0009] (2) adjusting pH of the treatment liquid to at most 7,
preferably at most 2,
[0010] (3) applying the treatment liquid to the textile,
[0011] (4) thermally treating the textile with steam, and
[0012] (5) washing the textile with water and dehydrating the
textile,
[0013] wherein the water- and oil-repellent agent comprises a
combination of (A) a fluorine-containing polymer comprising a
repeat unit derived from vinyl chloride and/or vinylidene chloride,
and (B) a fluorine-containing polymer free from a repeat unit
derived from vinyl chloride and/or vinylidene chloride.
[0014] The present invention also provides a textile prepared by
the above-mentioned method.
DETAILED DESCRIPTION OF THE INVENTION
[0015] The procedure used in the present invention is an Exhaust
process which comprises decreasing the pH of the treatment liquid
comprising the fluorine-containing polymer, applying the treatment
liquid to the textile, washing the textile with water, and
dehydrating the textile.
[0016] In the step (1) of the method of the present invention, the
treatment liquid comprising the water- and oil-repellent agent,
which is applied to the textile, is prepared. The treatment liquid
comprising the water- and oil-repellent agent may be in the form of
a solution or an emulsion, particularly an aqueous emulsion.
[0017] In the step (2) in the method of the present invention, the
pH of the treatment liquid is brought to at most 7. The pH of the
treatment liquid is preferably at most 3, more preferably at most
2. The pH can be decreased by addition of an acid, such as an
aqueous solution of citrconic acid and an aqueous solution of
sulfamic acid, to the treatment liquid.
[0018] In the step (3) of the method of the present invention, the
treatment liquid is applied to the textile. The water- and
oil-repellent agent can be applied to a substrate to be treated
(that is, the textile) by a know procedure. The application of the
treatment liquid can be conducted by immersion, spraying and
coating. Usually, the treatment liquid is diluted with an organic
solvent or water, and is adhered to surfaces of the substrate by a
well-known procedure such as an immersion coating, a spray coating
and a foam coating to a fabric (for example, a carpet cloth), a
yarn (for example, a carpet yarn) or an original fiber. 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 treatment liquid. The concentration of the
water- and oil-repellent agent active component (that is, the
fluorine-containing polymer) in the treatment liquid contacted with
the substrate may be from 0.05 to 10% by weight. The stain blocking
agent may be used in the concentration of, for example, 0 to 1,000
parts by weight, particularly 1 to 500 parts by weight, in terms of
the solid content, based on 100 parts by weight of the
fluorine-containing polymer.
[0019] In the step (4) of the method of the present invention, the
textile is thermally treated. The thermal treatment can be
conducted by applying a steam (for example, 90.degree. C. to
110.degree. C.) to the textile under a normal pressure for e.g., 10
seconds to 10 minutes.
[0020] In the step (5) of the method of the present invention, the
textile is washed with water and dehydrated. The thermally treated
textile is washed with water at least once. Then, in order to
remove excess water, the textile is dehydrated by a usual
dehydration procedure such as a centrifuging and vacuuming
procedure.
[0021] After the step (5), the textile can be dried.
[0022] The water- and oil-repellent agent used in the present
invention comprises two fluorine-containing polymers, that is, the
fluorine-containing polymer (A) and the fluorine-containing polymer
(B).
[0023] The fluorine-containing polymer (A) is the
fluorine-containing polymer comprising a repeat unit derived from
vinyl chloride and/or vinylidene chloride. The fluorine-containing
polymer (B) is the fluorine-containing polymer free from a repeat
unit derived from vinyl chloride and/or vinylidene chloride.
[0024] The fluorine-containing polymers (A) and (B) may be a
polymer derived from a fluoroalkyl group-containing monomer such as
a fluoroalkyl group-containing (meth)acrylate, a fluoroalkyl
group-containing maleate or fumarate, and a fluoroalkyl
group-containing urethane.
[0025] The fluorine-containing polymer (A) may be, for example, a
polymer comprising:
[0026] (A-I) a repeat unit derived from a monomer having a
fluoroalkyl group, and
[0027] (A-II) a repeat unit derived from vinyl chloride and/or
vinylidene chloride. An example of the fluorine-containing polymer
(A) is a copolymer comprising:
[0028] (A-I) a repeat unit derived from a monomer having a
fluoroalkyl group,
[0029] (A-II) a repeat unit derived from vinyl chloride and/or
vinylidene chloride,
[0030] (A-III) a repeat unit derived from a fluorine-free monomer,
and
[0031] (A-IV) a repeat unit derived from a crosslinkable
monomer.
[0032] The fluorine-containing polymer (B) may be, for example, a
copolymer which comprises
[0033] (B-I) a repeat unit derived from a monomer having a
fluoroalkyl group, and which does not comprise a repeat unit
derived from vinyl chloride and/or vinylidene chloride. An example
of the fluorine-containing polymer (B) is a copolymer which
comprises:
[0034] (B-I) a repeat unit derived from a monomer having a
fluoroalkyl group,
[0035] (B-II) a repeat unit derived from a fluorine-free monomer,
and
[0036] (B-III) a repeat unit derived from a crosslinkable monomer,
and which does not comprise a repeat unit derived from vinyl
chloride and/or vinylidene chloride.
[0037] The repeat units (A-I) and (B-I) are preferably a repeat
unit derived from a (meth)acrylate ester having a fluoroalkyl
group.
[0038] The fluoroalkyl group-containing (meth)acrylate ester may be
of the formula:
Rf--A--OCOCR.sup.11.dbd.CH.sub.2
[0039] wherein Rf is a fluoroalkyl group having 3 to 21 carbon
atoms, R.sup.11 is a hydrogen atom or a methyl group, and A is a
divalent organic group.
[0040] In the above formula, A may be a linear or branched alkylene
group having 1 to 20 carbon atoms, a
--SO.sub.2N(R.sup.21)R.sup.22-- group or a
--CH.sub.2CH(OR.sup.23)CH.sub.2-- group (R.sup.21 is an alkyl group
having 1 to 10 carbon atoms, R.sup.22 is a linear or branched
alkylene group having 1 to 10 carbon atoms, and R.sup.23 is a
hydrogen atom or an acyl group having 1 to 10 carbon atoms).
[0041] Examples of the fluoroalkyl group-containing (meth)acrylate
are as follows: 1 Rf--(CH.sub.2).sub.nOCOCR.sup.3.dbd.CH.sub.2
(2)
[0042] 2 Rf--O--Ar--CH.sub.2OCOCR.sup.3.dbd.CH.sub.2 (6)
[0043] wherein Rf is a fluoroalkyl group having 3 to 21 carbon
atoms, R.sup.1 is a hydrogen atom or an alkyl group having 1 to 10
carbon atoms, R.sup.2 is an alkylene group having 1 to 10 carbon
atoms, R.sup.3 is a hydrogen atom or a methyl group, and Ar is
arylene group optionally having a substituent, and n is an integer
of 1 to 10.
[0044] Specific examples of the fluoroalkyl group-containing
(meth)acrylate are as follows:
[0045]
CF.sub.3(CF.sub.2).sub.7(CH.sub.2).sub.10OCOCH.dbd.CH.sub.2
[0046]
CF.sub.3(CF.sub.2).sub.7(CH.sub.2).sub.10OCOC(CH.sub.3).dbd.CH.sub.-
2
[0047] CF.sub.3(CF.sub.2).sub.6CH.sub.2OCOCH.dbd.CH.sub.2
[0048]
CF.sub.3(CF.sub.2).sub.8CH.sub.2OCOC(CH.sub.3).dbd.CH.sub.2
[0049]
(CF.sub.3).sub.2CF(CF.sub.2).sub.6(CH.sub.2).sub.2OCOCH.dbd.CH.sub.-
2
[0050]
(CF.sub.3).sub.2CF(CF.sub.2).sub.8(CH.sub.2).sub.2OCOCH.dbd.CH.sub.-
2
[0051]
(CF.sub.3).sub.2CF(CF.sub.2).sub.10(CH.sub.2).sub.2OCOCH.dbd.CH.sub-
.2
[0052]
(CF.sub.3).sub.2CF(CF.sub.2).sub.6(CH.sub.2).sub.2OCOC(CH.sub.3).db-
d.CH.sub.2
[0053]
(CF.sub.3).sub.2CF(CF.sub.2).sub.8(CH.sub.2).sub.2OCOC(CH.sub.3).db-
d.CH.sub.2
[0054]
(CF.sub.3).sub.2CF(CF.sub.2).sub.10(CH.sub.2).sub.2OCOC(CH.sub.3).d-
bd.CH.sub.2
[0055]
CF.sub.3CF.sub.2(CF.sub.2).sub.6(CH.sub.2).sub.2OCOCH.dbd.CH.sub.2
[0056]
CF.sub.3CF.sub.2(CF.sub.2).sub.8(CH.sub.2).sub.2OCOCH.dbd.CH.sub.2
[0057]
CF.sub.3CF.sub.2(CF.sub.2).sub.10(CH.sub.2).sub.2OCOCH.dbd.CH.sub.2
[0058]
CF.sub.3CF.sub.2(CF.sub.2).sub.6(CH.sub.2).sub.2OCOC(CH.sub.3).dbd.-
CH.sub.2
[0059]
CF.sub.3CF.sub.2(CF.sub.2).sub.8(CH.sub.2).sub.2OCOC(CH.sub.3).dbd.-
CH.sub.2
[0060]
CF.sub.3CF.sub.2(CF.sub.2).sub.10(CH.sub.2).sub.2OCOC(CH.sub.3).dbd-
.CH.sub.2
[0061]
CF.sub.3(CF.sub.2).sub.7SO.sub.2N(CH.sub.3)(CH.sub.2).sub.2OCOCH.db-
d.CH.sub.2
[0062] CF.sub.3(CF.sub.2).sub.7SO.sub.2N
(C.sub.2H.sub.5)(CH.sub.2).sub.2O- COCH.dbd.CH.sub.2
[0063] (CF.sub.3).sub.2CF(CF.sub.2).sub.8CH.sub.2CH(OCOCH.sub.3)
CH.sub.2OCOC(CH.sub.3).dbd.CH.sub.2
[0064]
(CF.sub.3).sub.2CF(CF.sub.2).sub.6CH.sub.2CH(OH)CH.sub.2OCOCH.dbd.C-
H.sub.2 3
[0065] The repeat units (A-III) and (B-II) are preferably derived
from a fluorine-free vinyl monomer. Non-limiting examples of
preferable monomer constituting the repeat units (A-III) and (B-II)
include, for example, ethylene, vinyl acetate, acrylonitrile,
styrene, alkyl (meth)acrylate, polyethyleneglycol (meth)acrylate,
polypropyleneglycol (meth)acrylate, methoxypolyethyleneglycol
(meth)acrylate, methoxypolypropyleneglycol (meth)acrylate, vinyl
alkyl ether and isoprene.
[0066] The monomer constituting the repeat units (A-III) and (B-II)
may be a (meth)acrylate ester having an alkyl group. The number of
carbon atoms of the alkyl group may be from 1 to 30, for example,
from 6 to 30, e.g., from 10 to 30. For example, the monomer
constituting the repeat units (A-III) and (B-II) may be acrylates
of the general formula:
CH.sub.2.dbd.CA.sup.1COOA.sup.2
[0067] wherein A.sup.1 is a hydrogen atom or a methyl group, and
A.sup.2 is an alkyl group of C.sub.nH.sub.2n+1 (n=1 to 30). The
copolymerization with this monomer can improve various properties
such as water- and oil-repellency and soil releasability; cleaning
durability, washing durability and abrasion resistance of said
repellency and releasability; solubility in solvent; hardness; and
feeling, according to necessity.
[0068] The crosslinkable monomer constituting the repeat units
(A-IV) and (B-III) may be a fluorine-free vinyl monomer having at
least two reactive groups. The crosslinkable monomer may be a
compound having at least two carbon-carbon double bonds, or a
compound having at least one carbon-carbon double bond and at least
one reactive group.
[0069] Examples of the crosslinkable monomer include
diacetoneacrylamide, (meth)acrylamide, N-methylolacrylamide,
hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate,
3-chloro-2-hydroxypropyl (meth)acrylate, N,N-dimethylaminoethyl
(meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, butadiene,
chloroprene and glycidyl (meth)acrylate, to which the crosslinkable
monomer is not limited. The copolymerization with this monomer can
improve various properties such as water- and oil-repellency and
soil releasability; cleaning durability and washing durability of
said repellency and releasability; solubility in solvent; hardness;
and feeling, according to necessity.
[0070] The fluorine-containing polymer (A) and the
fluorine-containing polymer (B) preferably has a weight average
molecular weight of 2,000 to 1,000,000, for example, 10,000 to
200,000.
[0071] Preferably, the amount of the repeat unit (A-I) is from 40
to 89.9% by weight, more preferably from 50 to 79.5% by weight,
[0072] the amount of the repeat unit (A-II) is from 5 to 50% by
weight, more preferably from 10 to 40% by weight,
[0073] the amount of the repeat unit (A-III) is from 5 to 54.9% by
weight, more preferably from 10 to 40% by weight, and
[0074] the amount of the repeat unit (A-IV) is from 0.1 to 10% by
weight, more preferably 0.5 to 5% by weight,
[0075] based on the fluorine-containing polymer (A).
[0076] Preferably, the amount of the repeat unit (B-I) is from 39
to 94.9% by weight, more preferably from 50 to 89.5% by weight,
[0077] the amount of the repeat unit (B-II) is from 5 to 60% by
weight, more preferably from 10 to 40% by weight, and
[0078] the amount of the repeat unit (B-III) is from 0.1 to 10% by
weight, more preferably from 0.5 to 5% by weight,
[0079] based on the fluorine-containing polymer (B).
[0080] A weight ratio of the fluorine-containing polymer (A) to
fluorine-containing polymer (B) in this mixture may be from 1:99 to
99:1, for example, from 10:90 to 90:10, particularly from 70:30 to
90:10.
[0081] The fluorine-containing polymer (A) and (B) in the present
invention can be produced by any polymerization method, and the
conditions of the polymerization reaction can be arbitrary
selected. The polymerization method includes, for example, solution
polymerization and emulsion polymerization. Among them, emulsion
polymerization is particularly preferred.
[0082] The method of producing the fluorine-containing polymer (A)
is explained hereinafter.
[0083] In the solution polymerization, there can be used a method
of dissolving a monomer (A-I), a monomer (A-III) and a crosslinking
monomer (A-IV) in an organic solvent in the presence of a
polymerization initiator, replacing the atmosphere by nitrogen,
charging vinyl chloride and/or vinylidene chloride (A-II) and
stirring the mixture with heating at the temperature within the
range from 50.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 is used
in the amount within the range from 0.01 to 5 parts by weight based
on 100 parts by weight of the monomers.
[0084] The organic solvent is inert to the monomer and dissolves
them, and examples thereof include pentane, hexane, heptane,
octane, cyclohexane, benzene, toluene, xylene, petroleum ether,
tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl
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 50 to 1,000
parts by weight based on 100 parts by weight of the monomers (A-I)
to (A-IV).
[0085] In the emulsion polymerization, there can be used a method
of emulsifying a monomer (A-I), a monomer (A-III) and a
crosslinking monomer (A-IV) in water in the presence of a
polymerization initiator and an emulsifying agent, replacing the
atmosphere by nitrogen, charging vinyl chloride and/or vinylidene
chloride (A-II) and copolymerizing with stirring at the temperature
within the range, for example, from 50.degree. C. to 80.degree. C.
for 1 hour to 10 hours. As the polymerization initiator, for
example, water-soluble initiators (e.g., benzoyl peroxide, lauroyl
peroxide, L-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide,
3-carboxypropionyl peroxide, acetyl peroxide,
azobisisohtitylamidine dihydrochloride, azobisisobutyronitrile,
sodium peroxide, potassium persulfate and ammonium persulfate) and
oil-soluble initiators (e.g., azobisisobutyronitrile, benzoyl
peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene
hydroperoxide, t-butyl peroxypivalate and diisopropyl
peroxydicarbonate) are used. The polymerization initiator is used
in the amount within the range from 0.01 to 5 parts by weight based
on 100 parts by weight of the monomers.
[0086] In order to obtain a copolymer dispersion ill water, which
is superior in storage stability, it is desirable that the monomers
are atomized in water by using an emulsifying device capable of
applying a strong shattering energy (e.g., a high-pressure
homogenizer and an ultrasonic homogenizer) and then polymerized
with using the oil-soluble polymerization initiator. 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 10 parts by weight based on 100 parts by weight of the
monomers. When the monomers (A-I) to (A-IV) are not completely
compatibilized, a compatibilizing agent capable of sufficiently
compatibilizing them (e.g., a water-soluble organic solvent and a
low-molecular weight monomer) is preferably added to these
monomers. By the addition of the compatibilizing agent, the
emulsifiability and copolymerizability can be improved.
[0087] 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.
[0088] The fluorine-containing polymer (B) can be prepared in the
same manner as in the fluorine-containing polymer (A), except that
vinyl chloride or vinylidene chloride is not used.
[0089] A liquid containing the fluorine-containing polymer (A) and
a liquid containing the fluorine-containing polymer (B), which are
separately prepared, are mixed and optionally a medium (for
example, water or an organic solvent) is added to give the water-
and oil-repellent agent.
[0090] The substrate to be treated in the present invention is
preferably a textile, particularly a carpet. The textile includes
various examples. Examples of the textile include animal- or
vegetable-origin natural fibers such as cotton, hemp, wool and
silk; synthetic fibers such as polyamide, polyester, polyvinyl
alcohol, polyacrylonitrile, polyvinyl chloride and polypropylene;
semisynthetic fibers such as rayon and acetate; inorganic fibers
such as glass fiber, carbon fiber and asbestos fiber; and a mixture
of these fibers. The present invention can be suitably used in
carpets made of nylon fibers, polypropylene fibers and/or polyester
fibers, because the present invention provides excellent resistance
to a detergent solution and brushing (mechanical).
[0091] The textile may be in any form such as a fiber and a fabric.
When the carpet is treated with the water- and oil-repellent agent,
the carpet may be formed after the fibers or yarns are treated with
the water- and oil-repellent agent, or the formed carpet may be
treated with the water- and oil-repellent agent. Examples of the
substrate to be treated include glass, paper, wood, leather, fur,
asbestos, brick, cement, metal and oxide, ceramics, plastic, coated
surface and plaster, in addition to the textile.
EXAMPLES
[0092] The following Examples further illustrate the present
invention in detail but are not to be construed to limit the scope
thereof. The water repellency, oil repellency, soil releasability
and fluorine adhesion amount of the carpets obtained in the
Examples and Comparative Example were evaluated.
[0093] Test procedures of the water repellency, the oil repellency,
the soil releasability, fluorine adhesion amount and cleaning are
as follows.
[0094] (1) Water repellency
[0095] A droplet of a isopropyl alcohol (IPA)/water mixture liquid
shown in Table 1 is softly positioned on a carpet surface, and a
maximum content of IPA (% by volume) in the liquid which maintains
the droplet shape is taken as the result of the water
repellency.
[0096] Specific procedure is as follows.
[0097] A carpet treated for giving repellency is stored in a
therio-hyqrostat having a temperature of 21.degree. C. and a
humidity of 65% for at least 4 hours. A test liquid (having the
composition shown in Table 1) which has been also stored at
21.degree. C. is used. The temperature of a measurement room is
controlled to be 21.degree. C. Droplets of the test liquid in an
amount of 50 .mu.L are softly dropped by a micropipette on the
carpet and the diameter of the droplets is 5 mm. The micropippete
is vertically stood and droplets are softly dropped. Five droplets
are positioned. If 4 or 5 droplets remain on the carpet after
standing for 10 seconds, it is evaluated that the test liquid
passes the test. The maximum content of IPA (% by volume) in the
test liquid which passes the test is taken as the result of the
water repellency.
1TABLE 1 Mixing composition (% by volume) Isopropyl alcohol Water
100 0 90 10 80 20 70 30 60 40 50 50 40 60 30 70 25 75 20 80 15 85
10 90 5 95 2 98 0 100
[0098] (2) Oil repellency
[0099] According to AATCC-TM-118-1992, five droplets of the test
solution shown in Table 2 are positioned on a carpet and the
penetration state after 30 seconds is observed. A maximum point
corresponding to the test solution, four droplets of which exhibit
no penetration, is taken as the oil repellency.
2TABLE 2 Surface tension Point Test solution (mN/m, 25.degree. C.)
0 Inferior to 1 -- 1 Nujol 31.2 2 Mixture liquid of 29.6
n-Hexadecane (35 wt. parts)/ nujol (65 wt. parts) 3 n-Hexadecane
27.3 4 n-Tetradecane 26.7 5 n-Dodecane 25.0 6 n-Decane 23.5
[0100] (3) Soil releasability (Stain proof property)
[0101] A carpet sample piece (size: 18.2 cm in a direction of
tufting, and 8.9 cm in a direction perpendicular to a tufting
direction) treated with a water- and oil-repellent agent and a
blank carpet piece (size: 18.2 cm in direction of tufting, and 8.9
cm in a direction perpendicular to tufting direction) are kept to
stand for at least 4 hours in an atmosphere of 21.degree. C. and
65% RH. Before the soil releasability test, L*, a* and b* of the
carpet pieces are measured at five spots. Two carpet pieces are
adhered with a double-sided tape to an internal surface of a pot of
a ball mill. 10 g of dry soil (artificial soil having the
composition shown in Table 3, dried in a desiccator for at least 48
hours) is charged in the pot and then a lid is put on the pot. The
pot is slightly shaken so that the dry soil is positioned almost
uniformly on the carpet test piece. The lid of the pot is taken
off, the carpet samples are removed, and then 50 ceramic balls
(according to AATCC Test Method 123-1989) are charged into the pot,
and the lid is firmly put on the pot. In the ball mill apparatus,
the pot is rotated at 80 rpm for 7 minutes and 30 seconds. The lid
of the pot is taken off, the carpet samples are removed, and then
the double-sided tapes are peeled off. Excess dry soil on a front
surface of the carpet test piece is removed by a vacuum cleaner.
The vacuum cleaner is applied to the front surface in each
direction (longitudinal and transverse directions) for back and
forth five times. Finally, the vacuum cleaner is applied also to
the back surface for back and force once. L*, a* and b* of each
carpet piece without excess dry soil are measured at five spots by
a color difference meter (CR-310 manufactured by MINOLTA Co., Ltd.,
having a circular detection part having the diameter of 50 mm).
[0102] A color difference (AE*ab) of the carpet surface is
calculated according to the following equation from L*, a* and b*
before soil releasability test and L*, a* and b* after soil
releasability test. Since the measurement for each carpet sample is
conducted at five spots, the calculation is conducted by using a
value at the same spot.
.DELTA.E*ab=[(.DELTA.L*).sup.2+(.DELTA.a*).sup.2+(.DELTA.b*).sup.2].sup.1/-
2
[0103] .DELTA.L*: difference of L* before and after soil
releasability test
[0104] .DELTA.a*; difference of a* before and after soil
releasability test
[0105] .DELTA.b*. difference of b* before and after soil
releasability test
[0106] An average of .DELTA.E*ab is determined for each carpet test
sample, and this average is taken as .DELTA.E, which is a result of
soil releasability.
3 TABLE 3 Components of artificial soil Amount (wt %) Peat moss
(dark) 38.4 Portland cement 18 Kaolin clay 18 Silica (200 mesh) 18
Carbon black 1.05 Red iron oxide 0.30 Mineral oil 6.25
[0107] (4) Adhesion amount of fluorine
[0108] The content of fluorine (ppm) present on a carpet fiber
after the Exhaust treatment is measured by an oxygen combustion
method.
[0109] (5) Cleaning
[0110] A carpet fabric treated with a water- and oil-repellent
agent is cleaned according to AATCC-TM-171-1995. The detail of the
cleaning procedure is as follows. A carpet piece having a size of
8.9 cm.times.18.2 cm is fixed on a test pedestal. A steam cleaner
(having functions of suction and warm water injection) is applied
to the carpet surface from back and forth once, with suction and
spraying of 60.degree. C. water, and then applied to the carpet
surface from back and forth once, with suction alone. The above
procedure is defined as once of the cleaning. After a given number
of times of the cleaning is conducted, the carpet is dried at
105.degree. C. for 15 minutes in hot-air dryer to complete the
cleaning.
[0111] The water repellency, the oil repellency, the soil
releasability and the fluorine adhesion amount are measured before
and after the cleaning.
[0112] The carpet of the present invention preferably has the water
repellency of at least 90 and the oil repellency of at least 5
before the cleaning, and the water repellency of at least 40 and
the oil repellency of at least 2 after 10 times of the
cleaning.
Preparative Example 1
Preparation of (a) a Fluorine-containing Water- and Oil-repellent
Agent Containing Vinyl Chloride
[0113]
CH.sub.2.dbd.CHCOO(CH.sub.2).sub.2(CF.sub.2CF.sub.2).sub.nCF.sub.2C-
F.sub.3 (a mixture of compounds wherein n is 3, 4 and 5 in a weight
ratio of 5:3:1) (FA), stearyl acrylate (StA), N-methylolacrylamide
(N-MAM), 3-chloro-2-hydroxypropyl methacrylate (TOPOLEN M),
deionized water, n-laurylmercaptan (LSH, a chain transfer agent),
octadecyltrimethyl ammonium chloride (CATION 2ABT, a cationic
emulsifier), polyoxyethylenealkylphenyl ether (EMULGEN 985, a
nonionic emulsifier), polyoxyethylene-alkylphenyl ether (NONION
HS-208, a nonionic emulsifier), sorbitan monopalmitate (NONION
PP-40R, a nonionic emulsifier) and dipropyleneglycol monomethyl
ether (DPM) were mixed in the amounts shown in Table 4 to give a
mixture liquid.
[0114] This mixture liquid was heated at 60.degree. C. and
emulsified by a high pressure homogenizer. The resultant emulsion
was charged into a 1 L autoclave and subjected to a nitrogen gas
replacement to remove a dissolved oxygen. Vinyl chloride having a
purity of 99% (VCl) was charged in the amount shown in Table 4 and
then an initiator, azobisamide dipropane (V-50) was charged in the
amount shown in Table 4. With stirring, the copolymerization
reaction was conducted for 60.degree. C. at 8 hours to give a vinyl
chloride-containing copolymer emulsion, which was diluted with
water to give an emulsion having a solid content of 30% by
weight.
Preparative Example 2
Preparation of (b) a Fluorine-containing Water- and Oil-repellent
Agent Free of Vinyl Chloride
[0115]
CH.sub.2.dbd.CHCOO(CH.sub.2).sub.2(CF.sub.2CF.sub.2).sub.nCF.sub.2C-
F.sub.3 (a mixture of compounds wherein n is 3, 4 and 5 in a weight
ratio of 5:3:1) (FA), stearyl acrylate (StA), 2-hydroxyethyl
methacrylate (2ERA), glycidyl methacrylate (BLENMER G),
N-methylolacrylamide (N-MAM), 3-chloro-2-hydroxypropyl methacrylate
(TOPOLEN M), deionized water, n-laurylmercaptan (LSH),
polyoxyethylene-alkylphenyl ether sulfate ammonium (HITENOL N-17,
an anionic emulsifier), polyoxyethylenealkylpheny- l ether (NONION
HS-220, a nonionic emulsifier), sorbitan monolaurate (LP-20R, a
nonionic emulsifier) and dipropylene glycol monomethylether (DPM)
were mixed in the amounts shown in Table 4 to give a mixture
liquid.
[0116] This mixture liquid was heated at 60.degree. C. and
emulsified by a high pressure homogenizer. The resultant emulsion
was charged into a 1 L autoclave and subjected to a nitrogen gas
replacement to remove a dissolved oxygen. Then, an initiator,
ammonium persulfate (APS) was charged in the amount shown in Table
4. With stirring, the copolymerization reaction was conducted for
60.degree. C. at 8 hours to give a fluorine-containing copolymer
emulsion, which was diluted with water to give an emulsion having a
solid content of 30% by weight.
4TABLE 3 Composition ratio of charged monomers (weight (g)) Pre.
Pre. Ex. 1 Ex. 2 SFA 90.4 79.2 STA 6.0 19.1 VCl (vinyl chloride)
14.7 -- 2EHA -- 19.1 BLENMER G -- 2.6 N-MAM 2.4 3.0 TOPOLEN M 0.6
1.3 LSH 0.8 0.24 Ammonium persulfate -- 0.56 azobisamide dipropane
0.76 NONION PP-40R 1.92 -- NONION HS-208 4.20 -- NONION HS-220 --
1.72 LP-20R -- 2.16 EMULGEN 985 1.92 -- CTION 2ABT 2.0 -- HITENOL
N-17 -- 5.20 Pure water 236 244
Example 1
[0117] 0.9 Grams of a mixture liquid of the fluorine-containing
water- and oil-repellent agent (a) (which is a fluorine-containing
water- and oil-repellent agent containing vinyl chloride) produced
in Preparative Example 1 and the fluorine-containing water- and
oil-repellent agent (b) (which is a water- and oil-repellent agent
free of vinyl chloride) produced in Preparative Example 2 (the
mixing weight ratio of 8 to 2 in terms of solid) and 5 g of a stain
blocking agent FX-657 (manufactured by 3M) were diluted with water
to 1,000 g to give a mixture liquid. The solid weight ratio of the
water- and oil-repellent agent and the stain blocking agent was
1:5.6. The pH of the mixture liquid was adjusted to 1.5 by adding a
10% aqueous solution of sulfamic acid to give a treatment
liquid.
[0118] A carpet (8.9 cm.times.18.2 cm, nylon 6,6, cut piled,
density: 36 oz/yd.sup.2) was immersed in the treatment liquid for
30 seconds. Then, the carpet was squeezed to give the WPU (wet pick
up) of 300%. Then, a normal pressure steamer treatment (the
temperature of 100.degree. C. to 107.degree. C.) was conducted for
90 seconds under the state that a pile surface of the carpet is
upward. Then, the carpet was lightly rinsed with 2 L of water, and
centrifugally dehydrated to give the WPU of about 25%. Finally, the
carpet was thermally cured at 110.degree. C. for ten minutes. Then,
this carpet was cleaned (five times or ten times). The water
repellency, the oil repellency, the soil releasability and the
fluorine adhesion amount were evaluated before and after the
cleaning. The results are shown in Tables A to D.
Comparative Example 1
[0119] 0.8 Grams of the fluorine-containing water- and oil
repellent agent (a) and 5 g of the stain blocking agent FX-657
(manufactured by 3M) were diluted with water to 1,000 g to give a
mixture liquid. The solid weight ratio of the water- and
oil-repellent agent and the stain blocking agent was 1:6.3. The pH
of the mixture liquid was adjusted to 1.5 by adding a 10% aqueous
solution of sulfamic acid. Then, the treatment and evaluation were
conducted in the same manner as in Example 1. The results are shown
in Tables A to D.
Comparative Example 2
[0120] 1.0 Grams of the fluorine-containing water- and oil
repellent agent (b) and 5 g of the stain blocking agent FX-657
(manufactured by 3M) were diluted with water to 1,000 g to give a
mixture liquid. The solid weight ratio of the water- and
oil-repellent agent and the stain blocking agent was 1:5. The pH of
the mixture liquid was adjusted to 1.5 by adding a 10% aqueous
solution of sulfamic acid. Then, the treatment and evaluation were
conducted in the same manner as in Example 1. The results are shown
in Tables A to D.
Comparative Example 3
[0121] 5.7 Grams of a commercially available emulsion repellent
agent (solid concentration: 21% by weight) [a mixture of a
fluorine-containing oil repellent agent containing chlorine (6% by
weight) and a stain blocking agent (a phenol-formaldehyde
condensation product) (15% by weight)] was diluted with water to
1,000 g to give a mixture liquid. The pH of the mixture liquid was
adjusted to 1.5 by adding a 10% aqueous solution of sulfamic acid.
Then, the treatment and evaluation were conducted in the same
manner as in Comparative Example 1. The results are shown in Tables
A to D.
Comparative Example 4
[0122] 5.7 Grams of a commercially available emulsion repellent
agent (solid concentration: 21% by weight) [a mixture of a
fluorine-containing oil repellent agent containing chlorine (6% by
weight) and a stain blocking agent (a phenol-formaldehyde
condensation product) (15% by weight)] and 12.5 g of MgSO.sub.4
were diluted with water to 1,000 g to give a mixture liquid. The pH
of the mixture liquid was adjusted to 1.5 by adding a 10% aqueous
solution of sulfamic acid. Then, the treatment and evaluation were
conducted in the same manner as in Comparative Example 1. The
results are shown in Tables A to D.
5TABLE A Results of water repellency evaluation Number of times
Com. Com. Com. Com. of cleaning Ex. 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 0 90
80 100 X 40 5 90 70 90 X 30 10 40 40 40 X 30 Note) X: cannot pass a
test liquid (IPA:water = 0:100 (vol %))
[0123]
6TABLE B Results of oil repellency evaluation Number of times Com.
Com. Com. Com. of cleaning Ex. 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 0 5 3 6 0
5 5 4 2 6 0 4 10 2 0 4 0 4
[0124]
7TABLE C Results of soil releasability (delta E value) Number of
times Com. Com. Com. Com. of cleaning Ex. 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4
0 16.5 16.5 19.8 24.9 18.9 5 18.0 16.7 21.7 25.7 19.6 10 19.5 19.6
22.8 25.1 21.1 Delta E value of untreated carpet is 25.6 at the
number of cleaning times of 0.
[0125]
8TABLE D Results of fluorine adhesion amount measurement (ppm)
Number of times Com. Com. Com. Com. of cleaning Ex. 1 Ex. 1 Ex. 2
Ex. 3 Ex. 4 0 292 273 300 10 259 5 285 262 300 9 225 10 235 173 279
8 216
* * * * *