HK1136853A - Low temperature cure repellents - Google Patents
Low temperature cure repellents Download PDFInfo
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- HK1136853A HK1136853A HK10100513.6A HK10100513A HK1136853A HK 1136853 A HK1136853 A HK 1136853A HK 10100513 A HK10100513 A HK 10100513A HK 1136853 A HK1136853 A HK 1136853A
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Description
Technical Field
The present invention relates to an improved method of treating fibrous substrates with fluorinated (meth) acrylate copolymers that dry and cure at ambient temperatures without the need for in-oven curing at elevated temperatures to provide water and alcohol repellency.
Background
A variety of fluorinated polymer compositions are known to be useful as treating agents to provide surface benefits to substrates. Most commercially available fluorinated polymers that can be used as a treatment to impart repellency to a substrate require oven drying and curing at about 140 ℃ to provide the desired repellency properties. These commercially available fluorinated polymers typically contain perfluoroalkyl chains having predominantly eight or more carbon atoms.
Poly (fluorinated alkyl acrylates) comprising perfluoroalkyl groups having less than six carbon atoms typically have poor kinetic water repellency. Koji Honda et al in "Molecular aggregation structures and Surface Properties of Poly (fluoroalkylacrylate) Thinfilms" ("Macromolecules", 2005, 38(13), pp. 5699 to 5705) propose that for perfluoroalkyl chains with more than 8 carbons, the orientation of the perfluoroalkyl groups represented by the Rf group is maintained in a parallel configuration, while for such chains with less than 6 carbons, reorientation occurs. This reorientation reduces surface characteristics such as contact angle. Thus, shorter chain perfluoroalkyl groups have traditionally not been commercially successful.
Drying and curing the treated substrate helps to gradually achieve optimal water/alcohol repellency properties. The curing process enables melt spreading of the repellent and orientation of the fluorochemical polymer. Drying and curing generally requires high temperature thermal curing, as described by Charles L.Strickler in the fluorescent laboratory Fabrics for nonwovens "(" Journal of Industrial Fabrics ", 1984, 3(2), 10-18).
U.S. patent 7,008,993 describes a composition for providing alcohol and water repellency comprising: (a) a cationic fluorinated acrylate copolymer having a glass transition temperature near ambient temperature; (b) a cationic fluorinated acrylate copolymer having a glass transition temperature of about 80 ℃ to about 100 ℃; (c) a nonionic hydrophilic softener; and (d) an inorganic additive. The above compositions do not provide a low enough surface tension to treat nonwoven fabrics such as polypropylene nonwovens or polyethylene nonwovens.
It would be desirable to have a method of providing water repellency and alcohol repellency to fibrous substrates that employs drying and curing at ambient temperatures without the need for in-oven curing at elevated temperatures. This method requires less energy. It would be desirable to have such a process that is particularly effective for nonwoven substrates having a low glass transition temperature. The present invention provides such methods.
Brief description of the invention
The present invention includes a method of treating a fibrous substrate with a copolymer comprising a fluorinated acrylate or fluorinated methacrylate to provide water and alcohol repellency, wherein the improvement comprises contacting the substrate with a composition comprising repeating units of any sequence of formula 1, formula 2, formula 3, or formula 4, wherein
A. Formula 1 is
[Rf-X-Y-C(O)-CH-CH2]k-[Rf-X-Y-C(O)-CT-CH2]a-[CCl2-CH2]b-[R1-Y-C(O)-CZ-CH2]p-Formula 1
Wherein
RfIs a linear or branched perfluoroalkyl group having 6 carbon atoms, optionally interrupted by at least one oxygen atom, or a mixture thereof,
x is an organic divalent linking group having from about 1 to about 20 carbon atoms optionally comprising triazole, oxygen, nitrogen, or sulfur, or a combination thereof,
y is O, S or N (R), wherein R is H or C1To C20An alkyl group, a carboxyl group,
t is a straight or branched alkyl group having from about 1 to about 4 carbon atoms, or a halide,
k is a positive integer which is a positive integer,
a is zero or a positive integer,
b is zero or a positive integer,
p is zero or a positive integer, and
z is H, a linear, branched or cyclic alkyl group having from about 1 to about 10 carbon atoms, or a halide,
R1is H, CnH2n+1、CnH2n-1、CmH2m-CH(O)CH2、[CH2CH2O]iR2、[CH2CH(CH3)O]iR2、[CmH2m]N(R2)2，
n is in the range of from about 8 to about 40,
m is in the range of from 1 to about 40,
each R2Independently H, CH2OH or CsH2s+1，
s is 0 to about 40, and
i is from 1 to about 200,
provided that
1) The repeating unit [ R ] in the formula 1f-X-Y-C(O)-CH-CH2]k-is present in an amount of at least about 7 wt.%,
2) repeating unit [ R ]f-X-Y-C(O)-CH-CH2]k+[Rf-X-Y-C(O)-CT-CH2]a+[CCl2-CH2]bIs present in an amount of at least about 70% by weight, and
3) all repeating units [ R ]f-X-Y-C(O)-CH-CH2]k+[Rf-X-Y-C(O)-CT-CH2]a+[CCl2-CH2]b+[R1-Y-C(O)-CZ-CH2]p+ the total amount of optional monomers is 100 wt%;
B. formula 2 is
[Rf-X-Y-C(O)-C(CH3)-CH2]a-[CCl2-CH2]b-[CH3(CH2)3CH(C2H5)CH2-O-C(O)-CH-CH2]q-[R1-Y-C(O)-CZ-CH2]p-
Wherein
Rf、X、Y、Z、R1A, b and p are each as defined for formula 1, and
q is a positive integer and q is a positive integer,
provided that
1) The repeating unit in the formula 2- [ R ]f-X-Y-C(O)-C(CH3)-CH2]a-is present in an amount of about 48% by weight,
2) the repeating unit in formula 2- [ CCl2-CH2]b-And a repeating unit- [ CH ]3(CH2)3CH(C2H5)CH2-O-C(O)-CH-CH2]qEach present in an amount of about 24% by weight, and
3) all repeating units [ R ]f-X-Y-C(O)-C(CH3)-CH2]a+[CCl2-CH2]b+[CH3(CH2)3CH(C2H5)CH2-O-C(O)-CH-CH2]q+[R1-Y-C(O)-CZ-CH2]p-The total amount of (a) is 100 wt%;
C. formula 3 is
[Rf-X-Y-C(O)-C(CH3)-CH2]a-[CCl2-CH2]b-[CH3(CH2)17-O-C(O)-C(CH3)-CH2]q-[CH3(CH2)17-O-C(O)-CH-CH2]t-[R1-Y-C(O)-CZ-CH2]p-
Wherein
Rf、X、Y、Z、R1A, b and p are each as defined for formula 1,
q is a positive integer, and
t is a positive integer and is a negative integer,
provided that
1) A repeating unit of formula 3- [ R ]f-X-Y-C(O)-C(CH3)-CH2]a-is present in an amount of about 48% by weight,
2) repeat Unit- [ CCl2-CH2]b-Is present in an amount of about 24% by weight,
3) the repeating unit- [ CH ] in formula 33(CH2)17-O-C(O)-C(CH3)-CH2]q-and repeating unit- [ CH3(CH2)17-O-C(O)-CH-CH2]tEach present in an amount of about 12% by weight, and
4) all repeating units [ R ]f-X-Y-C(O)-C(CH3)-CH2]a+[CCl2-CH2]b+-[CH3(CH2)17-O-C(O)-C(CH3)-CH2]q+[CH3(CH2)17-O-C(O)-CH-CH2]t+[R1-Y-C(O)-CZ-CH2]p-The total amount of (a) is 100 wt%; and is
D. Formula 4 is
[Rf-X-Y-C(O)-CH-CH2]k-[Rf-X-Y-C(O)-C(CH3)-CH2]a-[CH3(CH2)17-O-C(O)-C(CH3)-CH2]q-[CH3(CH2)17-O-C(O)-CH-CH2]t-[CH3(CH2)3CH(C2H5)CH2-O-C(O)-CH-CH2]u-[CH3(CH2)3CH(C2H5)CH2-O-C(O)-C(CH3)-CH2]v-[R1-Y-C(O)-CZ-CH2]p-
Wherein
RfX, Y, Z, and R1K, a, p are each as defined for formula 1,
q is a positive integer and q is a positive integer,
t is a positive integer and is a negative integer,
u is a positive integer, and
v is a positive integer which is a whole number,
provided that
1) The repeating unit [ R ] in the formula 4f-X-Y-C(O)-CH-CH2]k-and a repeating unit- [ R [ ]f-X-Y-C(O)-C(CH3)-CH2]aEach present in an amount of about 32 wt%,
2) the repeating unit in formula 4- [ CH ]3(CH2)17-O-C(O)-C(CH3)-CH2]q-, repeating unit- [ CH ]3(CH2)17-O-C(O)-CH-CH2]t-, repeating unit- [ CH ]3(CH2)3CH(C2H5)CH2-O-C(O)-CH-CH2]u-, and repeating units- [ CH ]3(CH2)3CH(C2H5)CH2-O-C(O)-C(CH3)-CH2]vEach present in an amount of about 8 wt%, and
3) all repeating units [ R ]f-X-Y-C(O)-CH-CH2]k+[Rf-X-Y-C(O)-C(CH3)-CH2]a+[CH3(CH2)17-O-C(O)-C(CH3)-CH2]q+[CH3(CH2)17-O-C(O)-CH-CH2]t+[CH3(CH2)3CH(C2H5)CH2-O-C(O)-CH-CH2]u+[CH3(CH2)3CH(C2H5)CH2-O-C(O)-C(CH3)-CH2]v+[R1-Y-C(O)-CZ-CH2]p-The total amount of (B) is 100 wt%.
The invention also includes a substrate treated according to the above method.
Detailed Description
All trademarks are indicated in capital letters. In all instances herein, the term "(meth) acrylate" is used to denote either or both acrylate or methacrylate.
Herein, the term "ambient temperature" is used to mean a temperature of about 15 ℃ to about 25 ℃.
The present invention includes an improved method of using fluorinated (meth) acrylate copolymers to treat fibrous substrates, particularly nonwoven substrates having low glass transition temperatures, to impart water and alcohol repellency. In the improved method of the present invention, the treated substrate is air dried and cured at ambient temperature.
To produce good fibers and fabrics, the lowest thermal property of the polymer is the melting temperature Tm above ambient temperature; otherwise the polymer will not have the structural integrity of the formed fiber and fabric. If the fabric reaches a temperature near or above its Tm during drying or curing, the fabric will lose many of its properties, such as breathability, handleability, and tensile strength. Between the glass transition temperatures Tg and Tm, the polymer fiber or fabric can be mechanically stressed to produce useful properties such as bulk, crimp, spatial strength, uniformity, and other properties. Drying or curing at temperatures close to Tm risks the loss of these beneficial properties imparted to the fiber or fabric at early treatment. Examples of the Tg and Tm of the various polymers are set forth below.
| Polymer and method of making same | Glass transition temperature (Tg) | Melting Point (Tm) |
| Polyethylene | -125C | 137C |
| Polyisobutenes | -73C | 44C |
| Polypropylene | -13C | 176C |
| Polyvinyl chloride | -18C | 200C |
| Nylon-6 | 52C | 223C |
| Nylon-66 | 50C | 265C |
| Polyester (PET) | 69C | 270C |
| Polystyrene | 100C | 240C |
The data are from "Polymer Handbook" from J.Brantup, E.H.Immergut, Chapter III, pages 1 to 193 (Wiley-Interscience, New York, 1975). Further description can be found in "Principles of Polymerization" by G.Odian, Wiley-Interscience, New York, 1981, pages 29 to 36.
The process of the present invention is particularly useful for treating polymers having a Tg near ambient temperature, especially polypropylene nonwoven fabrics and polyethylene nonwoven fabrics.
As defined below, the fluorinated (meth) acrylate copolymer used in the present invention comprises a repeating unit of any sequence of formula 1, formula 2, formula 3, or formula 4. The polymer sequence includes random, statistical, block, multiple block, gradient, or alternating. The weight percentages given herein for formula 1, formula 2, formula 3, and formula 4, respectively, are based on the weight of the copolymer.
Formula 1 is
[Rf-X-Y-C(O)-CH-CH2]k-[Rf-X-Y-C(O)-CT-CH2]a-[CCl2-CH2]b-[R1-Y-C(O)-CZ-CH2]p-
Wherein
RfIs a linear or branched perfluoroalkyl group having 6 carbon atoms, or a mixture of linear or branched perfluoroalkyl groups having 6 carbon atoms, optionally interrupted by at least one oxygen atom,
x is an organic divalent linking group having from about 1 to about 20 carbon atoms optionally comprising triazole, oxygen, nitrogen, or sulfur, or a combination thereof,
y is O, S or N (R), wherein R is H or linear, branched or cyclic C1To C20An alkyl group, a carboxyl group,
t is a straight or branched alkyl group having from about 1 to about 4 carbon atoms, or a halide,
k is a positive integer which is a positive integer,
a is zero or a positive integer,
b is zero or a positive integer,
p is zero or a positive integer, and
z is H, a linear, branched or cyclic alkyl group having from about 1 to about 10 carbon atoms, or a halide,
R1is H, CnH2n+1、CnH2n-1、CmH2m-CH(O)CH2、[CH2CH2O]iR2、[CH2CH(CH3)O]iR2、[CmH2m]N(R2)2，
n is in the range of from about 8 to about 40,
m is in the range of from 1 to about 40,
R2is H, CH2OH or CsH2s+1，
s is 0 to about 40, and
i is from 1 to about 200,
provided that
1) The repeating unit [ R ] in the formula 1f-X-Y-C(O)-CH-CH2]k-is present in an amount of at least about 7 wt.%,
2) repeating unit [ R ]f-X-Y-C(O)-CH-CH2]k+[Rf-X-Y-C(O)-CT-CH2]a+[CCl2-CH2]bIs present in an amount of at least about 70% by weight, and
3) all repeating units [ R ]f-X-Y-C(O)-CH-CH2]k+[Rf-X-Y-C(O)-CT-CH2]a+[CCl2-CH2]b+[R1-Y-C(O)-CZ-CH2]pPlus the total amount of any other optional monomers is 100%.
In the copolymer of formula 1, the repeating unit [ R ]f-X-Y-C(O)-CT-CH2]aIs present in an amount of at least 7 wt.% and may be present in the copolymer in an amount ranging up to 100 wt.%, preferably from about 7 wt.% to about 97 wt.%, more preferably from about 7 wt.% to about 50 wt.%. In formula 1, a repeating unit [ R ]f-X-Y-C(O)-CH-CH2]k+[Rf-X-Y-C(O)-CT-CH2]a+[CCl2-CH2]bIs present in a total amount of at least about 70 wt.%. All of these repeat units [ R ]f-X-Y-C(O)-CH-CH2]k+[Rf-X-Y-C(O)-CT-CH2]a+[CCl2-CH2]bThe content in the copolymer used in the present invention is in the range of about 70 to 100% by weight. This total content is preferably from about 70 to about 90 wt%, more preferably from about 70 to 80 wt%. The total of all repeating units plus any other optional monomers in formula 1 is 100 weight percent.
Formula 2 is [ R ]f-X-Y-C(O)-C(CH3)-CH2]a-[CCl2-CH2]b-[CH3(CH2)3CH(C2H5)CH2-O-C(O)-CH-CH2]q-[R1-Y-C(O)-CZ-CH2]p-
Wherein
Rf、X、Y、Z、R1A, b and p are each as defined for formula 1, and q is a positive integer,
provided that
1) The repeating unit in the formula 2- [ R ]f-X-Y-C(O)-C(CH3)-CH2]a-is present in an amount of about 48% by weight,
2) the repeating unit in formula 2- [ CCl2-CH2]b-and repeating unit- [ CH3(CH2)3CH(C2H5)CH2-O-C(O)-CH-CH2]qEach present in an amount of about 24 wt%, and
3) all repeating units [ R ]f-X-Y-C(O)-C(CH3)-CH2]a+[CCl2-CH2]b+[CH3(CH2)3CH(C2H5)CH2-O-C(O)-CH-CH2]q+[R1-Y-C(O)-CZ-CH2]p-The total amount of (B) is 100 wt%.
Formula 3 is
[Rf-X-Y-C(O)-C(CH3)-CH2]a-[CCl2-CH2]b-[CH3(CH2)17-O-C(O)-C(CH3)-CH2]q-[CH3(CH2)17-O-C(O)-CH-CH2]t-[R1-Y-C(O)-CZ-CH2]p-
Wherein
Rf、X、Y、Z、R1A, b and p are each as defined for formula 1,
q is a positive integer, and
t is a positive integer and is a negative integer,
provided that
1) A repeating unit of formula 3- [ R ]f-X-Y-C(O)-C(CH3)-CH2]a-is present in an amount of about 48% by weight,
2) repeat Unit- [ CCl2-CH2]b-Is present in an amount of about 24% by weight,
3) the repeating unit- [ CH ] in formula 33(CH2)17-O-C(O)-C(CH3)-CH2]q-and repeating unit- [ CH3(CH2)17-O-C(O)-CH-CH2]tEach present in an amount of about 12% by weight, and
4) all repeating units [ R ]f-X-Y-C(O)-C(CH3)-CH2]a+[CCl2-CH2]b+-[CH3(CH2)17-O-C(O)-C(CH3)-CH2]q+[CH3(CH2)17-O-C(O)-CH-CH2]t+[R1-Y-C(O)-CZ-CH2]p-The total amount of (B) is 100 wt%.
Formula 4 is
[Rf-X-Y-C(O)-CH-CH2]k-[Rf-X-Y-C(O)-C(CH3)-CH2]a-[CH3(CH2)17-O-C(O)-C(CH3)-CH2]q-[CH3(CH2)17-O-C(O)-CH-CH2]t-[CH3(CH2)3CH(C2H5)CH2-O-C(O)-CH-CH2]u-[CH3(CH2)3CH(C2H5)CH2-O-C(O)-C(CH3)-CH2]v-[R1-Y-C(O)-CZ-CH2]p-
Wherein
RfX, Y, Z, and R1K, a, p are each as defined for formula 1,
q is a positive integer and q is a positive integer,
t is a positive integer and is a negative integer,
u is a positive integer, and
v is a positive integer which is a whole number,
provided that
1) The repeating unit [ R ] in the formula 4f-X-Y-C(O)-CH-CH2]k-and a repeating unit- [ R [ ]f-X-Y-C(O)-C(CH3)-CH2]aEach present in an amount of about 32 wt%,
2) the repeating unit in formula 4- [ CH ]3(CH2)17-O-C(O)-C(CH3)-CH2]q-, repeating unit- [ CH ]3(CH2)17-O-C(O)-CH-CH2]t-, repeating unit- [ CH ]3(CH2)3CH(C2H5)CH2-O-C(O)-CH-CH2]u-, and repeating units- [ CH ]3(CH2)3CH(C2H5)CH2-O-C(O)-C(CH3)-CH2]vEach present in an amount of about 8 wt%, and
3) all repeating units [ R ]f-X-Y-C(O)-CH-CH2]k+[Rf-X-Y-C(O)-C(CH3)-CH2]a+[CH3(CH2)17-O-C(O)-C(CH3)-CH2]q+[CH3(CH2)17-O-C(O)-CH-CH2]t+[CH3(CH2)3CH(C2H5)CH2-O-C(O)-CH-CH2]u+[CH3(CH2)3CH(C2H5)CH2-O-C(O)-C(CH3)-CH2]v+[R1-Y-C(O)-CZ-CH2]pThe total amount of-is 100% by weight.
In each of formulae 1 to 4, RfPreferably a linear or branched perfluoroalkyl group having 6 carbon atoms, or a mixture of linear or branched perfluoroalkyl groups having 6 carbon atoms, optionally interrupted by at least one oxygen atom. RfMore preferably straight or branched C6F13-Or mixtures thereof. RfMost preferably CF3(CF2)5。
In formulas 1 through 4, subscripts k, a, b, p, q, t, u, and v are each independently 1 to about 10,000, more preferably about 5 to about 2000, or a mixture thereof.
In formulae 1 to 4, examples of suitable linking groups X include linear, branched or cyclic alkylene, phenyl, arylene, aralkylene, sulfonyl, sulfenyl, sulfonamido, carbonamide, carbonyloxy, urethanylene, ureylene, and combinations thereof such as sulfonamidoalkylene.
Examples of preferred groups Y in formulae 1 to 4 are O, S or N (R), wherein R is H or C1To C4An alkyl group.
The copolymers used in the present invention are prepared by polymerization of fluorinated (meth) acrylate monomers with other monomers, as described in detail below.
The copolymer of formula 1 used in the present invention comprises the following monomers copolymerized in the following percentages by weight with respect to the copolymer product:
(a) from about 7% to about 100% of formula 5, or mixtures thereof
Rf-X-Y-C(O)-CH＝CH2Formula 5
Wherein
RfX and Y are as defined above for formula 1;
(b) from about 0% to about 93% of formula 6, or a mixture thereof:
Rf-X-Y-C(O)-CT＝CH2formula 6
Wherein
RfX, Y and T are defined above for formula 1;
(c) from about 0% to about 93% vinylidene chloride;
(d) from about 0% to about 30% of formula 7, or a mixture thereof:
R1-Y-C(O)-CZ-CH2formula 7
Wherein
Y、R1And Z are each as defined above for formula 1; and
(e) from about 0% to about 93% of additional optional monomers. Thus the copolymer of formula 1 may comprise repeat units derived from 100% of formula 5; a mixture of formula 5 and formula 6; a mixture of formula 5 with vinylidene chloride; a mixture of formula 5 and formula 7; a mixture of formula 5 and optional monomers; a mixture of formula 5 with any two of formula 6, formula 7, vinylidene chloride, and optionally a monomer; a mixture of formula 5 with any three of formula 6, formula 7, vinylidene chloride, and optionally a monomer; or a mixture of formula 5, formula 6, formula 7, vinylidene chloride, and optional monomers. For any such mixture, the weight percentages of all repeating units add up to 100%.
The copolymer of formula 2 used in the present invention comprises the following monomers copolymerized in the following percentages by weight with respect to the copolymer product:
(a) about 48% of formula 8
Rf-X-Y-C(O)-C(CH3)＝CH2Formula 8
Wherein
RfX and Y are as defined above for formula 1;
(b) about 24% vinylidene chloride;
(c) about 24% 2-ethylhexyl acrylate; and
(d) about 4% of formula 7 as defined above.
The copolymer of formula 3 used in the present invention comprises the following monomers copolymerized in the following percentages by weight with respect to the copolymer product:
(a) about 48% of formula 8
Rf-X-Y-C(O)-C(CH3)＝CH2Formula 8
Wherein
RfX and Y are as defined above for formula 1;
(b) about 24% vinylidene chloride;
(c) about 12% stearyl methacrylate;
(d) about 12% stearyl acrylate; and
(e) about 4% of formula 7 as defined above.
The copolymer of formula 4 used in the present invention comprises the following monomers copolymerized in the following percentages by weight with respect to the copolymer product:
(a) about 32% of a compound of formula 5, as defined above, or mixtures thereof,
(b) about 32% of a compound of formula 8, as defined above, or mixtures thereof,
(c) about 8% stearyl methacrylate,
(d) about 8% of stearyl acrylate,
(e) about 8% of 2-ethylhexyl acrylate,
(f) about 8% of 2-ethylhexyl methacrylate, and
(g) about 4% of formula 7 as defined above, or a mixture thereof.
In formula 5 and formula 8, Rf is preferably a linear or branched perfluoroalkyl group having 6 carbon atoms, or a mixture thereof, more preferably a linear or branched C6F13-Or mixtures thereof, most preferably CF3(CF2)5-. Examples of formula 5 suitable for use in the present invention are:
CF3(CF2)5-CH2CH2-OC(O)-CH＝CH2，
C6F13-CH2CH2-OC(O)-CH＝CH2，
C6F13-R2-SC(O)-CH＝CH2，
C6F13-R2-OC(O)-CH＝CH2，
C6F13-SO2-N(R1)-R2-OC(O)-CH＝CH2，
C6F13-CO-N(R1)-R2-OC(O)-CH＝CH2，
C6F13-CH2CH(OR3)CH-OC(O)-CH＝CH2，
C6F13-R2-SO2-N(R1)-OC(O)-CH＝CH2，
C6F13-R2-O-CON(R1)-R2-OC(O)-CH＝CH2，
wherein
R1Is H or C1-C4An alkyl group;
R2is C1-C10An alkylene group; and is
R3Is H or C1-C4An acyl group.
Examples of suitable formula 6 suitable for use in the present invention are:
CF3(CF2)5-CH2CH2-OC(O)-C(CH3)＝CH2，
C6F13-CH2CH2-OC(O)-C(CH3)＝CH2，
C6F13-R2-SC(O)-C(CH3)＝CH2，
C6F13-R2-OC(O)-C(CH3)＝CH2，
C6F13-SO2-N(R1)-R2-OC(O)-C(CH3)＝CH2，
C6F13-CO-N(R1)-R2-OC(O)-C(CH3)＝CH2，
C6F13-CH2CH(OR3)CH-OC(O)-C(CH3)＝CH2，
C6F13-R2-SO2-N(R1)-OC(O)-C(CH3)＝CH2，
C6F13-R2-O-CON(R1)-R2-OC(O)-C(CH3)＝CH2，
wherein
R1Is H or C1-C4An alkyl group;
R2is C1-C10An alkylene group; and
R3is H or C1-C4An acyl group.
Examples of formula 8 suitable for use in the present invention are:
CF3(CF2)5-CH2CH2-OC(O)-C(CH3)＝CH2，
C6F13-CH2CH2-OC(O)-C(CH3)＝CH2，
C6F13-R2-SC(O)-C(CH3)＝CH2，
C6F13-R2-OC(O)-C(CH3)＝CH2，
C6F13-SO2-N(R1)-R2-OC(O)-C(CH3)＝CH2，
C6F13-CO-N(R1)-R2-OC(O)-C(CH3)＝CH2，
C6F13-CH2CH(OR3)CH-OC(O)-C(CH3)＝CH2，
C6F13-R2-SO2-N(R1)-OC(O)-C(CH3)＝CH2，
C6F13-R2-O-CON(R1)-R2-OC(O)-C(CH3)＝CH2
wherein
R1Is H or C1-C4An alkyl group;
R2is C1-C10An alkylene group; and
R3is H or C1-C4An acyl group.
Non-fluorinated (meth) acrylate monomers of formula 7 suitable for use in the process of the present invention include alkyl (meth) acrylates wherein the alkyl group is a straight or branched chain containing from 8 to 40 carbon atoms, or mixtures thereof. Preferred alkyl groups in the alkyl (meth) acrylates contain 8 to 20 carbon atoms. Examples of alkyl (meth) acrylates (straight or branched) are, but not limited to, alkyl (meth) acrylates wherein the alkyl group is octyl, 2-ethylhexyl, decyl, isodecyl, lauryl, cetyl, or stearyl. Preferred examples are 2-ethylhexyl acrylate, lauryl acrylate and stearyl acrylate.
Examples of other non-fluorinated (meth) acrylate monomers of formula 7 suitable for use in the method of the present invention include N-methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, alkoxy (meth) acrylate, glycidyl (meth) acrylate, stearyl acrylate, aminoalkyl methacrylate hydrochloride, acrylamide, alkylacrylamides. Among them, examples of the N-methylol monomer are, but not limited to, N-methylolacrylamide and N-methylolmethacrylamide. Hydroxyalkyl (meth) acrylates have an alkyl chain length in the range of from 2 to 4 carbon atoms and examples are 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. Alkoxy (meth) acrylates also have alkyl chain lengths in the range of 2 to 4 carbon atoms and contain 1 to 12 oxyalkylene units per molecule, preferably 4 to 10 oxyalkylene units per molecule, and most preferably 6 to 8 oxyalkylene units per molecule.
Other suitable additional optional monomers that may be used to prepare the copolymer of formula 1 include vinyl acetate, vinyl stearate, alkyl vinyl sulfones, styrene, vinyl benzoic acid, alkyl vinyl ethers, maleic anhydride, vinyl chloride, and other olefins.
The fluorinated (meth) acrylate copolymers of formula 1, 2, 3 or 4 useful in the present invention can be prepared by free radical initiated polymerization of the fluorinated (meth) acrylate mixtures of formula 5, 6 and/or 8, where appropriate, with other monomers listed separately above in an organic solvent or water containing one or more surfactants. The fluorinated copolymers useful in the present invention are prepared by stirring the above monomers in an organic solvent or water containing one or more surfactants in a suitable reaction vessel equipped with stirring means and external heating and cooling means. A free radical initiator is added and the temperature is raised to about 20 ℃ to about 70 ℃. Examples of the polymerization initiator are 2, 2 '-azobis (2-amidinopropane) dihydrochloride or 2, 2' -azobis (isobutylamidine) dihydrochloride. These initiators are sold under the name "VAZO" by E.I. du Pont de Nemours and Company (Wilmington, Delaware). An example of a suitable polymerization regulator or chain transfer agent is dodecanethiol. Organic solvents useful in the process of the present invention for preparing the copolymer of formula 1, 2, 3 or 4 include tetrahydrofuran, acetone, methyl isobutyl ketone, isopropanol, ethyl acetate, and mixtures thereof. Tetrahydrofuran is preferred. To exclude oxygen, the reaction is carried out under an inert gas such as nitrogen. The polymer is isolated by precipitation and optionally purified, for example by recrystallization. The solvent is removed by evaporation, or the solution is retained, for dilution and application to a substrate. The reaction product is a fluorinated (meth) acrylate copolymer of formula 1, 2, 3, or 4.
The resulting fluorinated (meth) acrylate copolymer of formula 1, 2, 3 or 4 is then diluted with water or further dispersed or dissolved in a solvent selected from simple alcohols and ketones suitable for final application to a substrate (hereinafter referred to as "application solvent"). Alternatively, aqueous dispersions prepared by conventional methods using surfactants can be prepared by removing the solvent (by evaporation) and using emulsification or homogenization steps known to those skilled in the art. Such solvent-free emulsions are preferred to minimize flammability and Volatile Organic Compound (VOC) related problems. The final product applied to the substrate is a dispersion (if water-based) or a solution (if a solvent other than water is used) of the fluorinated (meth) acrylate copolymer of formula 1, 2, 3 or 4.
In the improved process of the present invention, water and alcohol repellency is provided to a fibrous substrate by contacting the fluorinated (meth) acrylate copolymer solution or dispersion of formula 1, 2, 3, or 4 to the substrate. Suitable substrates include fibrous substrates, particularly nonwoven substrates as defined below.
The fluorinated (meth) acrylate copolymer solution or dispersion of formula 1, 2, 3, or 4 can be contacted with the substrate via any suitable method. Such methods are known to those skilled in the art and include, for example, application by foam, nip, cushion, wet roller, spray, dip, immersion, brush, nip roller, sponge, pad, and similar conventional methods. The dispersion of the fluorinated (meth) acrylate copolymer of formula 1, 2, 3 or 4 may be applied to the substrate as such or in combination with other optional fabric finishes or surface treatments.
Such optional additional components include treatments or finishes that can achieve additional surface effects, or additives commonly used with such treatments or finishes. Such additional components include compounds or compositions that can provide surface effects such as easy-care, shrink control, anti-wrinkle, permanent-set, moisture control, softness, strength, anti-slip, anti-static, anti-snag, anti-pilling, stain repellency, stain release, alcohol repellency, alcohol release, water repellency, alcohol repellency, odor control, antimicrobial, sun protection, cleanability, and the like. One or more such treatments or finishes may be applied to the substrate before, after, or simultaneously with the application of the copolymers of the present invention. Such optional components are typically blended into the treatment bath.
Other additives commonly used with such treatments or finishes may also be present, such as surfactants, pH adjusters, cross linkers, wetting agents, wax extenders, and other additives known to those skilled in the art. Suitable surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, N-oxides, and amphoteric surfactants. Examples of such additives include processing aids, blowing agents, lubricants, anti-fouling agents, and the like. Such additives are typically blended with the treatment bath.
The rate of application of the fluorinated (meth) acrylate copolymer solution or dispersion of formula 1, 2, 3 or 4 used in the present invention depends on the substrate porosity and is applied in an amount to provide the desired fluorine content in the treated substrate. The treated fibrous substrate typically has a fluorine content of about 100 μ g/g to about 10,000 μ g/g by weight. The fluorine content is preferably from about 1,000 μ g/g to about 4,000 μ g/g.
Optionally, a non-fluorinated extender composition is also included in the application composition to potentially increase fluorine efficiency. Examples of such optional additional extender polymer compositions are those disclosed in co-pending U.S. provisional application 60/607,612(CH2996), filed on 7/9/2004, and U.S. serial No. 11/175680(CH3048), filed on 6/7/2005.
The invention also includes substrates treated with the method of the invention using the fluorinated (meth) acrylate copolymer solutions or dispersions of formula 1, 2, 3 or 4. Suitable substrates include fibrous substrates. The fibrous substrates include woven, knitted, and nonwoven fabrics or other textiles. In particular, the fluorinated (meth) acrylate copolymer solutions or dispersions of formula 1, 2, 3 or 4 used in the process of the present invention are suitable for providing excellent water and alcohol repellency to woven, knitted, and non-woven fabrics, especially those made from polyolefin fibers such as polypropylene, polyethylene, and low melt blend polymers, fibers made therefrom, and blends comprising these fibers. The present invention is particularly applicable to polypropylene fabrics or polyethylene fabrics, and is most suitable for polypropylene nonwoven fabrics or polyethylene nonwoven fabrics. Types of nonwoven fabrics include spunbond, meltblown, and laminates comprising any type of nonwoven structure. The type of nonwoven material is described in "Encyclopedia of textile finishing" (Rouette, Hans-Karl, 2001, Springer-Verlag, ISBN: 3540654909). Such nonwoven materials typically have a low glass transition temperature, and therefore the nonwoven materials soften during heating when conventional processing with a thermal curing step is employed. Thus, the improved method of the present invention is capable of providing surface benefits to nonwoven materials without this disadvantage. The fluorinated (meth) acrylate copolymer solutions or dispersions of formula 1, 2, 3 or 4 used in the method of the present invention can provide excellent water and alcohol repellency to substrates treated therewith.
The fluorinated (meth) acrylate copolymer compositions used in the methods of the present invention can be used to provide excellent water and alcohol repellency to substrates that are air dried or cured at ambient temperatures. No high temperatures are required to achieve effective repellency. The fluorinated (meth) acrylate copolymers used in the process of the present invention can use shorter chain fluoroalkyl groups containing, for example, 6 carbon atoms, while commercially available conventional (meth) acrylates typically exhibit poor alcohol and water repellency if the fluoroalkyl groups contain less than 8 carbon atoms.
Test method
Test method 1
The fabric is treated with a pad bath (dipping) process using the copolymer dispersion for emulsion pad application. The fluorinated (meth) acrylate copolymer of formula 1, 2, 3 or 4 was applied to a spunbond-meltblown-spunbond polypropylene (SMS PP) nonwoven fabric weighing 76 grams per square meter of fabric made by Kimberly-Clark (Roswell, GA). After application, the fabric was allowed to air dry and cure. The water and alcohol repellency of the fabric was determined using test method 2 described below.
Test method 2 Water repellency/alcohol repellency
The water/alcohol repellency of the treated substrates was determined according to the INDA standard test used in Water/alcohol repellency test method IST 80.6-92. The test determines the resistance of the treated substrate to wetting by aqueous liquids. Three drops of a hydroalcoholic mixture having different surface tensions were placed on the substrate and the degree of surface wetting was determined visually.
The composition of the water repellency test liquid is shown in table 1.
Table 1: water/alcohol repellency test liquid
Three drops of test liquid 1 were placed on the treated substrate. If no liquid penetration or partial absorption (appearance of a deeper wet spot on the substrate) is observed after 5 minutes, the test is repeated with test liquid 2. The test was repeated with test liquid 3 and progressively higher test liquid numbers were used until liquid penetration (deeper wet spots on the substrate) was observed. The test result is the highest number of test liquids that do not penetrate into the substrate. Higher values indicate greater water repellency.
Examples
Unless otherwise indicated, for all lists in the examples section, the fluorine measured is the weight ratio of fluorine to the total fabric weight treated. All chemicals used below were reagent grade and were obtained from Sigma-Aldrich (st. louis, MO) unless otherwise indicated.
Example 1
In a plastic beaker, mix 200 grams deionized water, 4.0 grams fromMazerMAPEG 600MS polyalkylene glycol ester from Mazer Chemicals, Inc. (Gurnee, Illinois), 6.0 grams of AVITEX surfactant from E.I.du Pont DE Nemours and Company (Wilmington, DE), 7.1 grams of CF from E.I.du Pont DE Nemours and Company (Wilmington, DE)3(CF2)5CH2CH2OC(O)CHCH27.1 grams of CF from E.I. duPont DE Nemours and Company (Wilmington, DE)3(CF2)5CH2CH2-OC(O)C(CH3)CH21.0 g of poly (ethylene glycol) methacrylate with an average of 8 ethoxy groups (8EO-MA) from NOF-America (White Plains, NY) under the product name BLEMMER 350 as comonomer, 7.1 g of stearyl methacrylate from Sigma-Aldrich (Milwaukee, WI), 1.0 g of methylolacrylamide from Sigma-Aldrich (Milwaukee, WI), 0.50 g of hydroxyethyl methacrylate from Sigma-Aldrich (Milwaukee, WI), 0.25 g of dodecanethiol from Sigma-Aldrich (Milwaukee, WI), 10.0 g of hexanediol from Sigma-Aldrich (Milwaukee, WI) and 0.10 g of sulfamic acid from Sigma-Aldrich (Milwaukee, WI). The reaction mixture was heated to 55 ℃ and emulsified twice in a sonicator for two minutes each time until a homogeneous milky white emulsion was obtained. The solution was added to a 500mL flask equipped with a nitrogen blanket, condenser, overhead stirrer, and temperature probe, nitrogen bubbling was initiated, and stirring was performed at 170 rpm. When the temperature dropped below about 30 deg.C, the flask was switched to a nitrogen blanket and 14.3 grams of vinylidene chloride (VDC) from Sigma-Aldrich (Milwaukee, Wis.) and 10.0 grams of deionized water were added. The solution was stirred for 15 minutes. After 15 minutes, a solution of 0.50 grams of VAZO-50 initiator in 10.0 grams of deionized water was added. The reaction mixture was then heated to 50 ℃ over 30 minutes. The solution was stirred at 50 ℃ for 8 hours. The solution was then allowed to cool to room temperature, followed by gravity filtration through a milk filter into a narrow neck bottle to obtain an emulsion copolymer having 13.2 wt% solids and 3.2 wt% fluorine.
Spunbond-meltblown-spunbond polypropylene fabric (SMSPP) was treated with the copolymer according to test method 1. The amount of fluorinated copolymer dispersion used in the pad bath was calculated to obtain a fluorine content on the fabric of about 1200 micrograms per gram of fluorine by weight. In addition to the fluorinated copolymer emulsion prepared as described above, the padding bath contained 0.15% by weight of potassium ZELEC TY butyl phosphate from e.i.du Pont DE Nemours and Company (Wilmington, DE) and 0.6% n-hexanol from Sigma-Aldrich (Milwaukee, WI). After pad application of the fluorinated copolymer emulsion prepared as described above (total bath wet pick-up of about 140%), the nonwoven SMS PP fabric was allowed to air dry, or dried and cured in an oven until the fabric reached 140 ℃ and held at that temperature for 3 minutes. After treatment and curing, the fabric is allowed to "rest". The water and alcohol repellency of the nonwoven SMS PP fabric was determined using test method 2. The results are shown in Table 2.
TABLE 2
| Examples | Air drying/curing at ambient temperature | Air drying/curing at 140 ℃ |
| 1 | 8 | 9 |
| Untreated | 2 | 2 |
The data in table 2 shows that the method of the present invention provides excellent water and alcohol repellency on SMS PP nonwoven fabrics air dried at ambient temperature, which is substantially comparable to drying with high temperature.
Examples 2 to 27 and comparative examples A to P
For each of examples 2 to 27 and comparative examples a to P, the copolymers were prepared using the monomers listed in table 3 as weight percent in the copolymer and using the method of example 1. Using test method 1, the copolymers from examples 2 to 27 and from comparative examples a to P were applied to nonwoven spunbond-meltblown-spunbond polypropylene (SMS PP) fabrics, respectively. The water/alcohol repellency of the treated fabrics was determined according to test method 2. The results are shown in Table 5.
The comparative examples provide copolymer compositions that are not within formulas 1, 2, 3, or 4, and do not provide ambient temperature cure repellency. For comparative examples A, F, J, K, L, M and O, no repeating unit [ R ] is presentf-X-Y-C(O)-CH-CH2]kOr- [ R ]f-X-Y-C(O)-C(CH3)-CH2]a. For comparative examples B, C, D, G, H, I and P, [ R ]f-X-Y-C(O)-CH-CH2]k+[Rf-X-Y-C(O)-CT-CH2]a+[CCl2-CH2]bThe total amount is less than 70 wt%. For comparative example E, R1Is C4H9And chain lengths shorter than those desired in formulas 1, 2, 3 or 4. For comparative examples N, R1Is C6H11And chain lengths shorter than those desired in formulas 1, 2, 3 or 4.
TABLE 3 monomers used in the copolymerization
| Monomer | A | B | VDC | D | E | F | G | H | I |
| Chemical formula (II) | 5 | 6 | - | 7 | 7 | 7 | 7 | 7 | 7 |
| Examples | |||||||||
| 2 | 19％ | 19％ | 39％ | 19％ | 4％ | ||||
| 3 | 7％ | 18％ | 50％ | 21％ | 4％ | ||||
| 4 | 38％ | 24％ | 30％ | C12 4％ | 4％ | ||||
| 5 | 48％ | 24％ | 24％ | 4％ | |||||
| 6 | 48％ | 24％ | 12％ | 12％ | 4％ | ||||
| 7 | 24％ | 24％ | 24％ | 24％ | 4％ | ||||
| 8 | 38％ | 38％ | 9％ | 10％ | 4％ | ||||
| 9 | 38％ | 38％ | 19％ | 4％ | |||||
| 10 | 48％ | 24％ | 12％ | 12％ | 4％ | ||||
| 11 | 38％ | 48％ | 10％ | 4％ | |||||
| 12 | 38％ | 38％ | 9％ | 10％ | 4％ | ||||
| 13 | 44％ | 31％ | 22％ | 4％ | |||||
| 14 | 58％ | 29％ | 10％ | 4％ | |||||
| 15 | 48％ | 24％ | 24％ | 4％ | |||||
| 16 | 19％ | 67％ | 10％ | 4％ | |||||
| 17 | 13％ | 17％ | 40％ | C of a branched chain13 26％ | 4％ | ||||
| 18 | 13％ | 17％ | 40％ | C18-C24Blend 26% | 4％ | ||||
| 19 | 32％ | 42％ | 22％ | 4％ | |||||
| 20 | 48％ | 24％ | 24％ | 4％ | |||||
| 21 | 48％ | 24％ | 12％ | 12％ | 4％ | ||||
| 22 | 70％ | 10％ | 16％ | 4％ | |||||
| 23 | 44％ | 31％ | 22％ | 4％ | |||||
| 24 | 38％ | 24％ | 30％ | Branched chain C10 4％ | 4％ | ||||
| 25 | 32％ | 32％ | 8％ | 8％ | 8％ | 8％ | 4％ | ||
| 26 | 58％ | 19％ | 19％ | 4％ | |||||
| 27 | 24％ | 26％ | 46％ | 4％ |
| A | 44％ | C12 52％ | 4％ | ||||||
| B | 48％ | 24％ | 24％ | 4％ | |||||
| C | 64％ | 32％ | 4％ | ||||||
| D | 38％ | 29％ | 29％ | 4％ | |||||
| E | 38％ | 24％ | 30％ | C4 4％ | 4％ | ||||
| F | 64％ | 32％ | 4％ | ||||||
| G | 19％ | 48％ | 29％ | 4％ | |||||
| H | 44％ | 52％ | 4％ | ||||||
| I | 44％ | 52％ | 4％ | ||||||
| J | 51％ | 24％ | 21％ | 4％ | |||||
| K | 38％ | 38％ | 19％ | 4％ | |||||
| L | 58％ | 19％ | 19％ | 4％ | |||||
| M | 36％ | 36％ | 25％ | 4％ | |||||
| N | 13％ | 17％ | 40％ | Cyclic C6 26％ | 4％ | ||||
| 0 | 48％ | 24％ | 24％ | 4％ | |||||
| P | 19％ | 29％ | 48％ | 4％ |
Monomer A-CF3(CF2)5CH2CH2OC(O)CHCH2
Monomer B-CF3(CF2)5CH2CH2OC(O)C(CH3)CH2
Monomer VDC-vinylidene chloride
Monomeric stearyl D-methacrylate
Monomer E stearyl acrylate
Monomeric F-2-ethylhexyl acrylate
Monomer G-2-ethylhexyl methacrylate
Monomeric H-alkyl methacrylates
Monomer I-1.6% poly (ethylene glycol) methacrylate with an average of seven ethoxylates (7EO methacrylate), 1.0% hydroxyethyl methacrylate, 1.0% methylolacrylamide and 0.4% dodecanethiol.
Comparative examples Q and R
For each of comparative example Q and comparative example R, the method of example 1 was employed, but using formula F (CF)2)aCH2CH2OC(O)CHCH2As the fluorine-containing compound, a is in the range of 4 to 12, and is mainly 6, 8 and 10. A typical mixture is as follows: from 27% to 37% of a ═ 6, from 28% to 32% of a ═ 8, from 14% to 20% of a ═ 10, from 8% to 13% of a ═ 12, and from 3% to 6% of a ═ 14, available from e.i. dupont DE Nemours and Company (Wilmington, DE). Thus, for comparative examples Q and R, the radical RfIs C6F13、C8F17、C10F21、C12F25、C14F29Is not within formula 1, 2, 3, or 4. The monomers used are listed in table 4 as a weight percent of the copolymer. The resulting copolymers were applied to nonwoven spunbond-meltblown-spunbond polypropylene SMS PP fabrics using test method 1, respectively. The water/alcohol repellency of the treated fabrics was determined according to test method 2. The results are shown in Table 5.
TABLE 4 monomers used in the copolymerization
| Example numbering | F(CF2)aCH2CH2-OC(O)CHCH2 | Stearyl methacrylate | Vinylidene chloride | I* |
| Comparative example-Q | 19％ | 29％ | 48％ | 4％ |
| Comparative example-R | 59％ | 18％ | 18％ | 4％ |
Monomer I was a mixture of 1.6% poly (ethylene glycol) methacrylate with an average of seven ethoxylates (7EO methacrylate), 1.0% hydroxyethyl methacrylate, 1.0% hydroxymethyl acrylamide and 0.4% dodecanethiol.
TABLE 5 Water repellency/alcohol repellency
| Examples | Repellency property | Examples | Repellency property | Examples | Repellency property |
| 2 | 8 | 17 | 6 | Comparative example E | 2 |
| 3 | 8 | 18 | 5 | Comparative example F | 2 |
| 4 | 8 | 19 | 5 | Comparative example G | 2 |
| 5 | 8 | 20 | 5 | Comparative example-H | 2 |
| 6 | 8 | 21 | 5 | Comparative example-I | 1 |
| 7 | 8 | 22 | 5 | Comparative example-J | 1 |
| 8 | 8 | 23 | 5 | Comparative example-K | 1 |
| 9 | 7 | 24 | 4 | Comparative example-L | 1 |
| 10 | 7 | 25 | 4 | Comparative example-M | 1 |
| 11 | 7 | 26 | 4 | Comparative example-N | 1 |
| 12 | 7 | 27 | 3.5 | Comparative example-O | 1 |
| 13 | 6 | Comparative example-A | 3 | Comparative example P | 0 |
| 14 | 6 | Comparative example-B | 3 | Comparative example-Q | 1 |
| 15 | 6 | Comparative example C | 3 | Comparative example-R | 1 |
| 16 | 6 | Comparative example D | 2 | Untreated | 2 |
In table 5, formula 1 is represented by examples 1 to 19, 22 to 24, and 26 to 27. Formula 2 is represented by example 20. Formula 3 is represented by example 21. Formula 4 is represented by example 25. The data in table 5 show that very high repellency is obtained in examples 1 to 23, while moderate repellency is obtained in examples 24 to 27. The comparative examples show unacceptably low or no rejection.
Claims (10)
1. A method of treating a fibrous substrate with a copolymer comprising a fluorinated acrylate or fluorinated methacrylate to provide water and alcohol repellency, wherein the improvement comprises contacting the substrate with a composition comprising repeating units of any sequence of formula 1, formula 2, formula 3, or formula 4, wherein
A. Formula 1 is
[Rf-X-Y-C(O)-CH-CH2]k-[Rf-X-Y-C(O)-CT-CH2]a-[CCl2-CH2]b-
[R1-Y-C(O)-CZ-CH2]p-Formula 1
Wherein
RfIs a linear or branched perfluoroalkyl group having 6 carbon atoms, optionally interrupted by at least one oxygen atom, or a mixture thereof,
x is an organic divalent linking group having from about 1 to about 20 carbon atoms optionally comprising triazole, oxygen, nitrogen, or sulfur, or a combination thereof,
y is 0, S or N (R), wherein R is H or C1To C20An alkyl group, a carboxyl group,
t is a straight or branched alkyl group having from about 1 to about 4 carbon atoms, or a halide,
k is a positive integer which is a positive integer,
a is zero or a positive integer,
b is zero or a positive integer,
p is zero or a positive integer, and
z is H, a linear, branched or cyclic alkyl group having from about 1 to about 10 carbon atoms, or a halide,
R1is H, CnH2n+1、CnH2n-1、CmH2m-CH(O)CH2、[CH2CH2O]iR2、[CH2CH(CH3)O]iR2、[CmH2m]N(R2)2，
n is in the range of from about 8 to about 40,
m is in the range of from 1 to about 40,
each R2Independently H, CH2OH or CsH2s+1，
s is 0 to about 40, and
i is from 1 to about 200,
provided that
1) The repeating unit [ R ] in formula 1f-X-Y-C(O)-CH-CH2]k-is present in an amount of at least about 7 wt.%,
2) repeating unit [ R ]f-X-Y-C(O)-CH-CH2]k+[Rf-X-Y-C(O)-CT-CH2]a+[CCl2-CH2]bIs present in an amount of at least about 70% by weight, and
3) all repeating units [ R ]f-X-Y-C(O)-CH-CH2]k+[Rf-X-Y-C(O)-CT-CH2]a+[CCl2-CH2]b+[R1-Y-C(O)-CZ-CH2]p+ the total amount of optional monomers is 100 wt%;
B. formula 2 is
[Rf-X-Y-C(O)-C(CH3)-CH2]a-[CCl2-CH2]b-[CH3(CH2)3CH(C2H5)CH2-O-C(O)-CH-CH2]q-[R1-Y-C(O)-CZ-CH2]p-
Wherein
Rf、X、Y、Z、R1A, b and p are each as defined for formula 1, and
q is a positive integer and q is a positive integer,
provided that
1) The repeating unit- [ R ] in formula 2f-X-Y-C(O)-C(CH3)-CH2]a-is present in an amount of about 48% by weight,
2) the repeating unit- [ CCl ] in formula 22-CH2]b-And said repeating unit- [ CH ]3(CH2)3CH(C2H5)CH2-O-C(O)-CH-CH2]. Each present in an amount of about 24 wt%, and
3) all repeating units [ R ]f-X-Y-C(O)-C(CH3)-CH2]a+[CCl2-CH2]b+[CH3(CH2)3CH(C2H5)CH2-O-C(O)-CH-CH2]q+[R1-Y-C(O)-CZ-CH2]p-The total amount of (a) is 100 wt%;
C. formula 3 is
[Rf-X-Y-C(O)-C(CH3)-CH2]a-[CCl2-CH2]b-[CH3(CH2)17-O-C(O)-C(CH3)-CH2]q-[CH3(CH2)17-O-C(O)-CH-CH2]t-[R1-Y-C(O)-CZ-CH2]p-
Wherein
Rf、X、Y、Z、R1A, b and p are each as defined for formula 1,
q is a positive integer, and
t is a positive integer and is a negative integer,
provided that
1) The repeating unit- [ R ] in formula 3f-X-Y-C(O)-C(CH3)-CH2]a-is present in an amount of about 48% by weight,
2) the repeating unit- [ CCl2-CH2]b-is present in an amount of about 24% by weight,
3) the repeating unit- [ CH ] of formula 33(CH2)17-O-C(O)-C(CH3)-CH2]q-and the repeating unit- [ CH3(CH2)17-O-C(O)-CH-CH2]tEach present in an amount of about 12% by weight, and
4) all repeating units [ R ]f-X-Y-C(O)-C(CH3)-CH2]a+[CCl2-CH2]b+[CH3(CH2)17-O-C(O)-C(CH3)-CH2]q+[CH3(CH2)17-O-C(O)-CH-CH2]t+[R1-Y-C(O)-CZ-CH2]p-The total amount of (a) is 100 wt%; and
D. formula 4 is
[Rf-X-Y-C(O)-CH-CH2]k-[Rf-X-Y-C(O)-C(CH3)-CH2]a-[CH3(CH2)17-O-C(O)-C(CH3)-CH2]q-[CH3(CH2)17-O-C(O)-CH-CH2]t-[CH3(CH2)3CH(C2H5)CH2-O-C(O)-CH-CH2]u-[CH3(CH2)3CH(C2H5)CH2-O-C(O)-C(CH3)-CH2]v-[R1-Y-C(O)-CZ-CH2]p-
Wherein
RfX, Y, Z, and R1K, a, p are each as defined for formula 1,
q is a positive integer and q is a positive integer,
t is a positive integer and is a negative integer,
u is a positive integer, and
v is a positive integer which is a whole number,
provided that
1) The repeating unit [ R ] in formula 4f-X-Y-C(O)-CH-CH2]k-and said recurring unit- [ R [ ]f-X-Y-C(O)-C(CH3)-CH2]aEach present in an amount of about 32 wt%,
2) the repeating unit- [ CH ] of formula 43(CH2)17-O-C(O)-C(CH3)-CH2]q-, the repeating unit- [ CH ]3(CH2)17-O-C(O)-CH-CH2]t-, the repeating unit- [ CH ]3(CH2)3CH(C2H5)CH2-O-C(O)-CH-CH2]u-, and the repeating unit- [ CH ]3(CH2)3CH(C2H5)CH2-O-C(O)-C(CH3)-CH2]vEach present in an amount of about 8 wt%, and
3) all repeating units [ R ]f-X-Y-C(O)-CH-CH2]k+[Rf-X-Y-C(O)-C(CH3)-CH2]a+[CH3(CH2)17-O-C(O)-C(CH3)-CH2]q+[CH3(CH2)17-O-C(O)-CH-CH2]t+[CH3(CH2)3CH(C2H5)CH2-O-C(O)-CH-CH2]u+[CH3(CH2)3CH(C2H5)CH2-O-C(O)-C(CH3)-CH2]v+[R1-Y-C(O)-CZ-CH2]pThe total amount of-is 100% by weight.
2. The method of claim 1, wherein the repeat unit [ R ]f-X-Y-C(O)-CH-CH2]k+[Rf-X-Y-C(O)-CT-CH2]a+[CCl2-CH2]bIn a total amount of about 70 to 100% by weight of the copolymer.
3. The method of claim 1, wherein the substrate is air dried and cured at a temperature of about 15 ℃ to about 25 ℃ after treatment.
4. The method of claim 1, wherein RfIs straight-chain or branched C6F13-, or wherein RfIs CF3(CF2)5-。
5. The method of claim 1, wherein k, a, b, p, q, t, u, and v are each independently from about 5 to about 2,000, or mixtures thereof.
6. The method of claim 1, wherein the composition is administered in the presence of at least one of:
A) an agent that provides a surface effect that is non-permanent press, easy-care, shrink control, anti-wrinkle, permanent set, moisture control, softness, strength, anti-slip, anti-static, anti-snag, anti-pilling, anti-soiling, stain release, alcohol repellency, alcohol release, water repellency, alcohol repellency, odor control, antimicrobial, or sunscreen,
B) surfactants, antioxidants, light stabilizers, color fixatives, water, pH adjusters, cross-linking agents, wetting agents, extenders, blowing agents, processing aids, lubricants, blocked isocyanates, non-fluorinated extenders, or
C) Combinations thereof.
7. The method of claim 1, wherein the composition of formula 1 further comprises repeat units from an optional monomer selected from the group consisting of vinyl acetate, vinyl stearate, alkyl vinyl sulfones, styrene, vinyl benzoic acid, alkyl vinyl ethers, maleic anhydride, vinyl chloride, and other olefins.
8. The method of claim 1, wherein the composition is applied as an aqueous dispersion or solution.
9. A substrate treated according to the method of claim 1.
10. The substrate of claim 9 which is a woven, knit, or nonwoven fabric made from polyolefin fibers selected from the group consisting of polyethylene, polypropylene, and blends thereof, and wherein the nonwoven fabric is selected from the group consisting of spunbond nonwoven fabrics, meltblown nonwoven fabrics, and laminates comprising spunbond nonwoven materials or meltblown nonwoven materials, or combinations thereof.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/638,916 | 2006-12-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| HK1136853A true HK1136853A (en) | 2010-07-09 |
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