U.S. patent application number 11/553055 was filed with the patent office on 2007-03-08 for hydrophobic, oleophobic and alcohol-resistant fluorochemical additive.
Invention is credited to James F. DAY.
Application Number | 20070051915 11/553055 |
Document ID | / |
Family ID | 35541711 |
Filed Date | 2007-03-08 |
United States Patent
Application |
20070051915 |
Kind Code |
A1 |
DAY; James F. |
March 8, 2007 |
Hydrophobic, Oleophobic and Alcohol-Resistant Fluorochemical
Additive
Abstract
A fluorochemical additive is the reaction product under
polymerization conditions of monomers that include: (a) an aromatic
polycarboxylic acid as an anhydride, ester, or ester chloride; (b)
at least one fluorinated reactant; and (c) at least one aliphatic
amine, mercaptan, or alcohol. Optionally, a crosslinking agent can
be used. The components of the additive all can be viewed as
contributing to the performance of the disclosed additive. The
fluorine-containing component is generally insoluble in molten
polymers and will tend to migrate to the cooled surface thereof
where the fluorinated moieties provide repellency characteristics
when used in adequate quantities, generally at least about 30 wt %
depending on the fluorinated reactant used to make the additive.
The aromatic component appears to facilitate solubility and speed
up the orientation process of the additive within the molten
polymer. The aliphatic component to the reaction mixture appears to
assist in anchoring the reaction product additive in the bulk
polymer structure. Together, the components form a fluorinated
reaction product additive that can be added to a molten polymer for
integration into the resulting product to impart improved
resistance to oil, water, and alcohol.
Inventors: |
DAY; James F.;
(Winston-Salem, ND) |
Correspondence
Address: |
ROYLANCE, ABRAMS, BERDO & GOODMAN, L.L.P.
1300 19TH STREET, N.W.
SUITE 600
WASHINGTON,
DC
20036
US
|
Family ID: |
35541711 |
Appl. No.: |
11/553055 |
Filed: |
October 26, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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10887451 |
Jul 9, 2004 |
|
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11553055 |
Oct 26, 2006 |
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Current U.S.
Class: |
252/8.62 ;
525/418 |
Current CPC
Class: |
C08F 259/08 20130101;
D04H 1/4291 20130101; D04H 3/16 20130101; D04H 1/56 20130101; Y10T
428/3154 20150401; C08L 67/02 20130101; D04H 1/4318 20130101; D04H
1/435 20130101; B32B 5/26 20130101; C08L 2666/02 20130101; D04H
1/4374 20130101; C08L 67/02 20130101; D01F 1/10 20130101; D04H
1/4334 20130101 |
Class at
Publication: |
252/008.62 ;
525/418 |
International
Class: |
D06M 15/263 20060101
D06M015/263; C08L 67/00 20060101 C08L067/00 |
Claims
1. A polymeric product comprising a synthetic organic polymer and a
fluorochemical additive, said fluorochemical additive comprising
the reaction product under polymerization conditions of monomers
that comprise: (a) an aromatic polycarboxylic acid as an anhydride,
ester, or ester chloride; (b) at least one fluorinated reactant;
and (c) at least one reactive aliphatic amine, mercaptan, or
alcohol.
2. A polymeric product according to claim 1, wherein said
fluorochemical additive comprising the reaction product under
polymerization conditions of monomers that comprise: (a)
trimellitic anhydride, (b) a fluorotelomer comprising a mixture of
even-numbered C.sub.6-C.sub.18
1,1,2,2-tetrahydroperfluoro-1-alcohols, and (c) stearyl alcohol
that has been polymerized at a temperature within the range from
about 140.degree.-180.degree. C.
3. A polymeric product according to claim 1, wherein said
fluorochemical additive comprises the polymeric reaction under
polymerization conditions of monomers that comprise: (a) an
anhydride monomer that contains at least one anhydride functional
group or is capable of forming an anhydride functional group under
polymerization conditions, (b) a fluorine-containing amine,
alcohol, or mercaptan, and (c) a reactive aliphatic alcohol or
amine.
4. A polymeric product according to claim 3, wherein said anhydride
monomer is a carboxylic acid having 2-4 carboxylic acid groups or a
carboxylic acid anhydride.
5. A polymeric product according to claim 4, wherein said anhydride
monomer comprises maleic acid, maleic anhydride, itaconic acid,
itaconic anhydride, 3-butene-1,2,3-tricarboxylic acid, acrylic
anhydride allylsuccinic anhydride, citraconic anhydride,
methacrylic anhydride, trimellitic anhydride, fumaric acid, fumaric
anhydride, vinyl acetic acid, vinyl acetic anhydride, norbornene
dicarboxylic acid, norbornene tricarboxylic acid, norbornene
anhydride, cyclopentadiene dicarboxylic acid, cyclopentadiene
tricarboxylic acid, cyclopentadiene anhydride, cyclohexyl
dicarboxylic acid, cyclohexyl tricarboxylic acid, or cyclohexyl
anhydride.
6. A polymeric product according to claim 5, wherein said anhydride
monomer comprises maleic anhydride, acrylic anhydride,
allylsuccinic anhydride, citraconic anhydride, methacrylic
anhydride, or trimellitic anhydride.
7. A polymeric product according to claim 3, wherein said
fluorine-containing reactant is a partially fluorinated or
perfluorinated straight or branched chain alcohol comprising about
2 to about 40 carbon atoms in length.
8. A polymeric product according to claim 7, wherein said
fluorine-containing reactant is a partially fluorinated or
perfluorinated straight or branched chain alcohol comprising about
6 to about 18 carbon atoms.
9. A polymeric product according to claim 7, wherein said
fluorine-containing reactant is an alcohol that is completely
fluorinated.
10. A polymeric product according to claim 7, wherein said
fluorine-containing reactant has between 2 and about 6 hydrogen
substituents.
11. A polymeric product according to claim 7, wherein said
fluorine-containing reactant is a tetrahydro- substituted alcohol
with remaining substituents being fluorine.
12. A polymeric product according to claim 7, wherein said
fluorine-containing reactant is an alcohol that contains a terminus
of either (CH.sub.3--) or (CHF.sub.2--).
13. A polymeric product according to claim 7, wherein said
fluorine-containing reactant is a fluorotelomer.
14. A polymeric product according to claim 13, wherein said
fluorine-containing reactant is a mixture of even-numbered
C.sub.6-C.sub.18 1,1,2,2 - tetrahydroperfluoro-1-alcohols.
15. A polymeric product according to claim 3, wherein said reactive
alcohol or amine is a straight or branched alcohol with one or more
hydroxyl moieties.
16. A polymeric product according to claim 15, wherein the reactive
alcohol has 12-30 carbon atoms.
17. A polymeric product according to claim 16, wherein the reactive
alcohol has 15-20 carbon atoms.
18. A polymeric product according to claim 1, wherein said
polymerization conditions comprise a temperature within the range
from about .sub.140.degree.-180.degree. C.
19. A polymeric product according to claim 1, that comprises the
reaction product of: (a) trimellitic anhydride, (b) a fluorotelomer
comprising a mixture of even-numbered C.sub.6-C.sub.18 1,1,2,2-
tetrahydroperfluoro-1-alcohols, and (c) stearyl alcohol that has
been polymerized a temperature within the range from about
140.degree.-180.degree. C.
20. A polymeric product of claim 1, wherein said polymeric product
is a mixture of said synthetic organic polymer and said
fluorochemical additive.
21. A polymeric product according to claim 20 wherein said
synthetic organic polymer is a thermoplastic polymer or a thermoset
polymer.
22. A polymeric product according to claim 21, wherein said
thermoplastic polymer is a polyamide, a polyester, a polyolefin, a
thermoplastic urethane, a polystyrene, or an acrylic.
23. A polymeric product according to claim 21, wherein said
thermoset polymer is an epoxy, or a thermoset polyurethane.
24. A polymeric product according to claim 1, wherein said
synthetic organic polymer is in the form of a fiber, a film, a
nonwoven web, or a molded article.
25. A polymeric product according to claim 1, wherein said
synthetic organic polymer is in the form of a nonwoven web.
26. A polymeric product according to claim 1, wherein said
synthetic organic polymer is selected from the group consisting of
nylon, polyethylene, polypropylene, and polyethylene
terephthalate.
27. A polymeric product according to claim 24, wherein said
nonwoven web is a multilayer laminate comprising an inner layer, at
least one middle layer, and an outer layer.
28. A polymeric product according to claim 27, wherein said outer
layer comprises a thermoplastic with said fluorochemical additive
and said inner layer comprises a thermoplastic without said
fluorochemical additive.
29. A polymeric product according to claim 28, wherein said
nonwoven web comprises two middle layers.
30. A polymeric product according to claim 28, wherein said inner
layer and said outer layer each have a spun bond structure.
31. A polymeric product of claim 1 wherein said synthetic organic
polymer is an article in the form of a fiber, film, non-woven web
or molded article and wherein said fluorochemical additive is
applied as a surface treatment on said article.
32. A polymeric product of claim 1 wherein said synthetic organic
polymer is an article in the form of a fiber, film, non-woven web
or molded article and wherein said fluorochemical additive is
formed as a mixture.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional application of Ser. No.
10/887,451, filed Jul. 9, 2004, which are hereby incorporated by
reference in their entirety.
FIELD OF THE INVENTION
[0002] This invention relates to a fluorochemical additive that is
useful for incorporation into fibers, films and molded articles to
enhance resistance to water, oil, and alcohol.
BACKGROUND OF THE INVENTION
[0003] Synthetic organic polymers are employed widely to create a
variety of products. Included among such varied products are blown
and cascade films, extruded sheets, foams, fibers, products made
from foam and fibers, woven and knitted fabrics, non-woven fibrous
webs and molded articles for garment, upholstery and medical uses,
to name a few. Many polymers used in these products, such as
polypropylene, exhibit some water and/or alcohol resistance but
exhibit no oil resistance.
[0004] The use of various fluorochemical agents to topically treat
a variety of fibers and fibrous substrates such as textiles,
carpet, leather, paper and non-woven webs, to impart desirable
properties to these materials, is known. See for example Mason
Hayek, Waterproofing and Water/Oil Repellency, 24, Kirk-Othmer
Encyclopedia of Chemical Technology, pp. 448-455 (3.sup.rd Edition
1979) or Banks, Ed., Organofluorine Chemicals and Their Industrial
Applications, Ellis Horwood Ltd., Chichester, England, pp. 226-234
(1979). Such fluorochemical compositions include fluorochemical
urethane and urea-based oligomers as disclosed in U.S. Pat. No.
3,398,182 of Guenthner et al.; U.S. Pat. No. 4,001,305 of Dear et
al.; U.S. Pat. No. 4,215,205 of Landucci et al.; U.S. Pat. No.
4,606,737 of Stern; U.S. Pat. No. 4,668,406 of Chang; U.S. Pat. No.
4,792,354 of Matsuo et al. and U.S. Pat. No. 5,410,073 of Kirchner;
compositions of cationic and non-cationic fluorochemicals as
disclosed in U.S. Pat. No. 4,566,981 of Howells; and compositions
containing fluorochemical carboxylic acid and epoxidic cationic
resin as disclosed in U.S. Pat. No. 4,426,466 of Schwartz and U.S.
Pat. No. 6,127,485 of Klun et al., as well as in PCT application WO
99/05345, also of Klun et al.
[0005] Also known are fluorochemical esters as disclosed in U.S.
Pat. No. 6,063,474 of Raiford et al.; U.S. Pat. No. 5,859,126 of
Anton et al.; U.S. Pat. Nos. 3,923,715 and 4,029,585, both of
Dettre; U.S. Pat. No. 3,716,401 of Axelrod; and U.S. Pat. No.
4,264,484 of Pattel; and fluorochemical esters derived from
dimerized unsaturated fatty acids as disclosed by U.S. Pat. No.
4,539,006 of Langford and WO 93/10085 of Coppens et al. These
fluorochemicals can be applied to various substrates by methods
known in the art, including spraying, padding, and finish bath
immersion, or can be applied directly to the fiber before the fiber
is woven by incorporating the fluorochemical into the fiber spin
finish.
[0006] Blending a variety of fluorochemicals with synthetic organic
polymers and melt extruding fibers from the molten blend to produce
fiber and fibrous substrates exhibiting hydrophobicity (water
resistance) and oleophilicity (oil resistance) is also known. Such
patents include U.S. Pat. No. 5,025,052 of Crater et al.; U.S. Pat.
No. 5,380,778 of Buckanin; U.S. Pat. No. 5,451,622 of Boardman et
al.; U.S. Pat. No. 5,411,576 of Jones et al.; U.S. Pat. No.
5,300,587 of Mascia et al.; and U.S. Pat. No. 5,336,717 of Rolando
et al.
[0007] While these various fluorochemical melt additives can in
some cases impart satisfactory hydrophobicity and/or oleophobicity
to resins, many suffer poor thermal stability above the 200.degree.
C. melt processing temperature which is often encountered in the
industry. It would be desirable to have a fluorochemical additive
that was stable at the temperatures used in commercial polymer
processing and forming equipment.
[0008] Others, such as the melt additives of Klun et al., U.S. Pat.
No. 6,127,485 and WO 99/05345, are thermally stable at high
processing temperatures but are required to be used in unacceptably
high amounts so as to make them economically undesirable.
[0009] It would be desirable to have a fluorochemical additive that
could be incorporated into molten polymers or curable thermoset
polymers that could be formed into fibers, films, fabrics (woven or
nonwoven) or cast articles to enhance the inherent water, oil,
and/or alcohol resistance of the resulting product.
SUMMARY OF THE INVENTION
[0010] It is an object of the invention to provide a polymeric
fluorochemical additive that is stable at the elevated temperatures
used in commercial polymer processing and forming equipment.
[0011] It is another object of the invention to provide a
fluorochemical additive that can be incorporated into thermoplastic
and thermoset polymers that can be formed into fibers, films,
textiles (woven or nonwoven), and castings that will enhance the
inherent water, oil, and/or alcohol resistance of the resulting
product.
[0012] It is further an object of the invention to provide fibers,
films, textiles (woven or nonwoven), and castings made of
thermoplastic and thermoset polymers that exhibit enhanced
resistance to water, oil, and or alcohol exposure than the same
product made with the same polymeric components but without the
fluorochemical additive of the present invention.
[0013] In accordance with these and other objects of the invention
that will become apparent from the description herein, the
fluorochemical additive of the present invention comprises the
reaction product under polymerization conditions of components that
include: (a) an aromatic polycarboxylic acid as an anhydride,
ester, or ester chloride; (b) at least one fluorinated reactant;
and (c) at least one aliphatic amine, mercaptan, or alcohol.
Optionally, a crosslinking agent can be used in addition to the
above components.
[0014] The three components of the additive all can be viewed as
contributing to the performance of the additive. The
fluorine-containing component is generally insoluble in molten
polymers and will tend to migrate to the cooled surface thereof
where the fluorinated moieties provide repellency characteristics
when used in adequate quantities. The aromatic component appears to
facilitate solubility and speed up the orientation process of the
additive within the molten polymer. The aliphatic component to the
reaction mixture appears to assist in anchoring the reaction
product additive in the bulk polymer structure. Together, the
components form a fluorinated reaction product additive that can be
added to a molten polymer for integration into the resulting
product to impart improved resistance to oil, water, and
alcohol.
DETAILED DESCRIPTION OF THE INVENTION
[0015] The fluorochemical additive of the present invention
comprises the reaction product formed under polymerization
conditions of components that include: (a) an aromatic
polycarboxylic acid as an anhydride, ester, or ester chloride; (b)
at least one fluorinated reactant; and (c) at least one aliphatic
amine, mercaptan, or alcohol. Preferably, the monomers include, and
preferably consist essentially of: (a) an anhydride monomer; (b) a
fluorine-containing amine, alcohol, or mercaptan; and (c) a
reactive aliphatic amine, mercaptan or alcohol.
[0016] The resulting fluorochemical additive product of the present
invention is in the form of a polymer or oligomer, preferably a
solid, that can be ground to a fine powder (if needed) and can be
added to thermoplastic and thermoset monomer mixtures for reactive
incorporation into products made from these monomers. The
fluorochemical additive of the invention is thermally stable and
remains effective despite exposure to elevated melt processing or
exothermic curing temperatures. When added to a molten polymer for
incorporation therein, the fluorochemical additive of the invention
imparts increased resistance to water, oil, and alcohol.
[0017] The anhydride monomer is intended to refer to monomers that
contain at least one anhydride functional group or are capable of
forming an anhydride functional group under the polymerization
conditions of the present invention. Such monomers can include
acids, anhydrides, chlorides, or esters. Carboxylic acids
preferably have 2-4 carboxylic acid groups and carboxylic acid
anhydrides. Suitable anhydride monomers include aliphatic,
cycloaliphatic, and aromatic anhydrides. Examples include maleic
acid, maleic anhydride, itaconic acid, itaconic anhydride,
3-butene-1,2,3-tricarboxylic acid, acrylic anhydride, allylsuccinic
anhydride, citraconic anhydride, methacrylic anhydride, trimellitic
anhydride, fumaric acid, fumaric anhydride, vinyl acetic acid,
vinyl acetic anhydride, norbornene dicarboxylic acid, norbornene
tricarboxylic acid, norbornene anhydride, cyclopentadiene
dicarboxylic acid, cyclopentadiene tricarboxylic acid,
cyclopentadiene anhydride, cyclohexyl dicarboxylic acid, cyclohexyl
tricarboxylic acid, cyclohexyl anhydride, and the like. Preferably,
the anhydride monomer is an anhydride selected from the group
maleic anhydride, acrylic anhydride, allylsuccinic anhydride,
citraconic anhydride, methacrylic anhydride, and trimellitic
anhydride including the acid chlorides thereof.
[0018] Aromatic acids, anhydrides, chlorides, or esters are
particularly preferred. Recommended aromatic forms include
phthalic, isophthalic, terephthalic, and pyromellitic with specific
note of napthalene dicarboxylic acid and the dimethyl ester
thereof.
[0019] The fluorine-containing reactant is conveniently described
by the general formula RfQ in which the Rf moiety may be a
partially fluorinated or perfluorinated straight or branched chain
group comprising about 2 to about 40 carbon atoms in length, more
typically about 6 to about 18 carbon atoms. This fluorochemical
group may be completely fluorinated or may have some hydrogen
substituents, i.e., between 2 and about 6. In a preferred
embodiment, the Rf portion is tetrahydro- substituted, with the
remaining substituents being fluorine. In still other embodiments,
the fluorochemical group of the fluorochemical reactant may
comprise a long chain perfluoro- group, optionally partially
hydrogen substituted, at one end of which is a sulfonamide group.
In yet other embodiments, all of the carbon atoms of the reactive
fluorochemical portion of the reactant may be completely
fluorinated. In still other embodiments, the fluorochemical portion
of the reactant may be branched, e.g., by up to about 1/3, as
described in U.S. Pat. No. 6,048,952 of Behr et al., herein
incorporated by reference.
[0020] The group Q which is joined to Rf portion may be a
terminating (CH.sub.3--) or (CHF.sub.2--) group, or may be a
divalent or a trivalent linking group, may be a branched or
straight chain alkyl, alkoxy, or alkylthio group, optionally
interrupted by other heteroatoms. In some embodiments, the Q group
may comprise a combination of the above-described moieties. The
chemical makeup of the linking group Q is not important so long as
it neither interferes with the polymerization of the fluorochemical
reactant with the anhydride monomer and reactive alcohol/amine
reactants used in the present invention, nor deleteriously effects
the properties of the end product.
[0021] In addition to relatively simple fluorochemical reactant
compounds in which the fluorochemical group is bonded to a single
reactive group by a covalent bond, there may be used compounds
which contain more than one reactive group; compounds that are
branched; and compounds that include Q groups which may contain
carbon, hydrogen, and heteroatoms. A non-limitative group of other
such fluorochemical reactants is listed below: [0022] I.
(Rf)--CH.sub.2CH.sub.2CH.sub.2--O--(CH.sub.2CH.sub.2CH.sub.2--O).sub.zH
[0023] II. (Rf)--CH.sub.2CH.sub.2CH.sub.213
S--(CH.sub.2CH.sub.2CH.sub.2O).sub.zH [0024] III.
(Rf)--CH.sub.2CH.sub.213 O--(CH.sub.2CH.sub.2CH.sub.2O).sub.zH
[0025] IV.
(Rf)--CH(CH.sub.3)--O--(CH.sub.2CH.sub.2CH.sub.2O).sub.zH [0026] V.
(Rf)--(CH.sub.2CH.sub.2O).sub.zC(O)--OH [0027] VI.
(Rf)--CH.sub.2CH.sub.2).sub.zC(O)--OH [0028] VII.
(Rf)--(CH.sub.2CH.sub.2CH.sub.2O).sub.zC(O)--OH [0029] VIII.
(Rf)--(CH.sub.2CH.sub.2O).sub.zCH.sub.213 NH.sub.2 [0030] IX.
(Rf)--(CH.sub.2CH.sub.2CH.sub.2O).sub.zCH.sub.213 NH.sub.2 [0031]
X. (Rf)--(CH.sub.2CH.sub.213 S--CH.sub.2O).sub.zCH.sub.213 NH.sub.2
[0032] XI. (Rf)--CH(CH.sub.3)CH.sub.213 NH.sub.2 [0033] XII.
(Rf)--CH.sub.2CH.sub.2CH.sub.213 NH.sub.2 [0034] XIII.
(Rf)--CH.sub.2CH.sub.213 S--CH.sub.213 NH.sub.2 [0035] XIX.
(Rf)--(CH.sub.2CH.sub.2O).sub.z--C(O)--NH_CH.sub.2CH.sub.2--OH
[0036] XX. (Rf)--(CH.sub.2CH.sub.2CH.sub.2O).sub.zCH.sub.2--SH
[0037] XXI. (Rf)--CH.sub.2CH.sub.2CH.sub.2CH.sub.2--SH [0038] XXII.
(Rf)--(CH.sub.2CH.sub.2CH.sub.2O).sub.z--C(O)--NH
CH.sub.2CH.sub.2--OH [0039] XXIII. (Rf)--CH.sub.2CH.sub.213
C(O)--NHCH.sub.2CH.sub.2--OH [0040] XXIV.
(Rf)--C(O)--CH.sub.2CH.sub.2--SH [0041] XXV.
(Rf)--C(O)--CH.sub.2CH.sub.2CH.sub.2CH.sub.2--SH [0042] XXVI.
(Rf)--C(O)--(CH.sub.2CH.sub.2CH.sub.2O).sub.z--CH.sub.2CH.sub.2CH.sub.2O--
-NH.sub.2 [0043] XXVII. (Rf)--C(O)--CH.sub.2CH.sub.2O
CH.sub.2CH.sub.2O--NH.sub.2 [0044] XXVIII. (Rf)--NH.sub.213
CH.sub.2CH.sub.2CH.sub.2OCH.sub.2--C(O)OH ##STR1## wherein z may be
a number from 1 to about 40 and wherein Rf is a branched or
straight chain fluorinated group as defined elsewhere herein. Also,
epoxidized variants of the above may be used.
[0045] Preferably, the fluorine-containing reactant is an alcohol
may be a partially fluorinated or perfluorinated straight or
branched chain comprising about 2 to about 40 carbon atoms in
length, more typically about 6 to about 18 carbon atoms. This
fluorochemical group may be completely fluorinated or may have some
hydrogen substituents, i.e., between 2 and about 6. In a preferred
embodiment the fluorine-containing alcohol is tetrahydro-
substituted, with the remaining substituents being fluorine. A
commercially available form of such a telomere is sold under the
name Zonyl.RTM. BA fluorotelomer from DuPont Chemical Enterprises,
Wilmington, Del. This is a mixture of even numbered 6-18 carbon
atom 1,1,2,2 - tetrahydroperfluoro 1-alcohols, the majority of
which are eight to twelve carbon atoms in length. The mixture has a
boiling point of 145-245.degree. C. at 1 atm; a melting point of
55-65.degree. C. and a specific gravity of 1.7.
[0046] In still other embodiments, the fluorochemical group of the
fluorochemical reactant may comprise a long chain perfluoro- group,
optionally partially hydrogen substituted. In yet other
embodiments, all of the carbon atoms of the reactive fluorochemical
portion of the reactant may be completely fluorinated. In still
other embodiments, the fluorochemical portion of the reactant may
be branched, e.g., by up to about 1/3, as described in U.S. Pat.
No. 6,048,952 of Behr et al., herein incorporated by reference.
[0047] A perfluorinated alcohol can be prepared either by a
telomerization process, or by direct fluorination as described in
one or more of U.S. Pat. Nos. 5,506,309; 5,523,496; 5,539,059;
5,543,567; 5,557,012; 5,571,870; 5,674,949, the contents of each of
which are incorporated herein by reference. Telomerization
generally resulted in a product with a distribution of different
fluorocarbon lengths, e.g., a preferred fluorotelomer is a mixture
of even-numbered C.sub.6- C.sub.18 1,1,2,2 -
tetrahydroperfluoro-1-alcohols, the majority of which are between 8
and 12 carbon atoms in length. Monomers with a single chain length
are generally obtained by direct fluorination.
[0048] The reactive aliphatic alcohol may be straight or branched
with one or more hydroxyl moieties. Preferred aliphatic alcohols
have 1-24 carbon atoms and most preferably have 10-20 carbon
atoms.
[0049] The reactive amine is preferably a long chain amine that is
capable of reacting with the anhydride monomer and perfluorinated
alcohol under polymerization conditions. Suitable reactive amines
have about 10-20, preferably 12-18, and most preferably 16-18
carbon atoms.
[0050] The ratio of anhydride monomer, fluorine-containing
reactant, and reactive alcohol or amine can be almost any ratio
that will form a fluorine-containing polymer or oligomer at
polymerization conditions. In general, these components can be used
within the molar range of 1:0.1-10:0.1-10 of anhydride monomer:
fluorine-containing reactant: reactive alcohol or amine.
[0051] If desired, one or more crosslinking agents can be used in
the polymerization process to make the fluorochemical additive of
the present invention. Short chain diols are useful, e.g.
monoethylene glycol, monopropylene glycol, 1,3-butylene glycol,
1,4-butylene glycol. One could also use a fluorinated diol as a
crosslinking agent, e.g., the reaction product of a fluorinated
mercaptan (2 moles) with I mole dibromoneopentyl alcohol as well as
the addition of the fluoroalkyl mercaptan to 1,4-butyne-2- diol.
One could also add to allyl alcohol to the combination of a
fluoroalkyl mercaptan and 1,4-butyne-2-diol to make a new
fluoro-alcohol that would be a useful crosslinking agent according
to the invention.
[0052] The monomers are reacted under polymerization conditions to
form the fluorinated additive of the present invention. Exemplary
conditions include a temperature within the range from about
140.degree.-180.degree. C. with stirring and water removal until an
acid value of less than about 10, preferably less than about 5 mg
KOH/g.
[0053] Catalysts are desirably used to speed up the reaction and
help drive the polymerization toward completion. Any of the
esterification or transesterification catalysts well known in the
art. Suitable examples include toluene sulfonic acid, sulfuric
acid, tin catalysts, zirconium catalysts, titanium catalysts (e.g.,
tetra-n-butyl titanate), and methanesulfonic acid.
[0054] The result of the polymerization process of the invention is
a polymer or oligomer containing 40-60% fluorine based on weight.
Preferably, the resulting product is a solid that is subsequently
ground to chips or a powder of a size suitable for addition to a
melt extruder, spinning, or other polymer product forming
equipment. Finely divided powders can be added to melt processes or
to thermoset polymers.
[0055] As used herein, the terms "fiber" and "fibrous" refer to an
elongated article, generally made of a thermoplastic resin, wherein
the length to diameter ratio of the article is greater than or
equal to about 10. Fiber diameters may range from about 0.5 micron
up to at least 1,000 microns. Each fiber may have a variety of
cross-sectional geometries, may be solid or hollow, and may
optionally be colored. "Yarns" are made with a plurality of fibers.
The fluorochemicals of this invention modify the individual fibers
internally from core to outer surface for uniform properties across
the fiber cross section for consistent properties despite removal
of external fiber material due to wear.
[0056] The fluorochemical additive of the invention is particularly
useful when incorporated into synthetic organic polymers, with or
without reaction into the polymeric backbone. Such synthetic
organic polymers include but are not limited to polyamides
including nylon 6 and nylon 66; polyesters such as polyethylene
terephthalate; polyolefins such at polyethylene, polypropylene and
polybutylene; epoxy resins; urethanes (thermoplastic or thermoset);
acrylics; polystyrenes and the like.
[0057] Synthetic organic polymeric films, fibers, and molded
articles into which the fluorochemicals are added have low surface
energy, excellent oil and water repellency, and resistance to
soiling. The fluorochemical additive of the invention can also be
used as blends with other fluorochemicals or other additives.
[0058] Fibers, films, and molded articles containing the
fluorochemical additive of the invention can be made by preparing a
blend of the fluorochemical additive with a chosen solid synthetic
organic polymer by intimately mixing the fluorochemical additive
with pelletized or powdered polymer, and melt processing (extrusion
or spinning) the blend into fibers or films. The fluorochemical
additive can be mixed directly with the synthetic organic polymer
as needed or it can be mixed in a "master batch" that is
subsequently melted and formed. Alternatively, the fluorochemical
additive can be injected with sufficient mixing into a molten
polymer stream to form a blend immediately prior to extrusion.
[0059] The amount of fluorochemical additive of the invention that
should be used is an amount sufficient to enhance the water, oil,
and/or alcohol resistance of the resulting polymeric product
relative to the same product made with the same polymer but without
the fluorochemical of the present invention. Suitable amounts for
any specific process, product, and base polymer is readily
determined by those with no more than the existing level of
ordinary skill in the art with no more than the exercise of routine
experimentation. In general, the amount of fluorochemical additive
will be that amount which provides from about 100 to 20,000 ppm of
fluorine, more preferably 200 to 10,000 ppm fluorine, based on the
unit weight of fiber, film, textile, or cast product. It is noted
that the fluorochemicals of the present invention may be more
efficient than those of the prior art and may therefore be
effective in lower than expected doses.
[0060] After extrusion, spinning, casting, or other product forming
operation, the formed product may be annealed and/or the extrudate
embossed by methods known in the art.
[0061] The fluorochemical additive of the invention also may be
used as aqueous suspensions or emulsions, or as organic solvent
solutions in the treatment of textile fibers or filaments during
manufacture, e.g., in combination with spin finishes, or in the
treatment of porous or fibrous substrates such as textiles,
carpets, paper and leather to impart oil, alcohol and water
repellency and anti-soiling properties thereto. The fluorochemical
treatment may, for example, be carried out by immersion in a
cationic, anionic or nonionic bath, and spin finishing.
Alternatively, the fluorochemical additive can be co-applied with
conventional fiber treating agents such as anti-static or
lubricating agents.
[0062] The fluorochemical additive of this invention also has
utility in making non- woven fabrics, melt- or spun- bonded webs,
or laminate structures using a combination of webs, e.g., spun
bond/melt blown/spun bond laminates wherein one or more layers in a
composite contain the fluorochemical additive of the invention.
Multi-layer constructions made from non-woven fabrics enjoy wide
industrial and commercial utility and include uses such as medical
fabrics, apparel, industrial apparel, outdoor fabrics, home
furnishings, table linens, shower curtains, and many other uses.
Embossing can be added to one or more layers within a composite for
enhanced aesthetic appeal as well as functional characteristics
that add loft to rolls or superimposed layers of composite.
[0063] Non-wovens fabrics are typically a multi-layer laminate
construction of one or more types of thermoplastic polymers. The
inner and outer layers have a spun bond (SB) structure. At least
one middle layer, often 1-2 layers, is made of melt blown (MB)
fibers. When two middle MB layers are used, the web is said to have
a "SMMS" construction are typically described according to the
following system: TABLE-US-00001 Layer Nomenclature Type Inner B SB
Middle 1 C MB Middle 2 D MB Outer E SB
[0064] There is also an "SMS" construction where there is only one
melt blown layer between two spun bond layers. These SMMS and SMS
constructions are used in medical drapes or masks. The E layer
would be the side towards the embossing roll.
[0065] For the present invention with the present fluorochemical
additive, the B layer (the one away from the embossing roller) does
not require use of the fluorochemical additive of the present
invention although it can be used, if desired. The ability to make
a nonwoven web having enhanced water, oil, and alcohol resistance
without the use of fluorochemical additive in both inner and outer
layers allows a savings in additive for the manufacture of fabrics,
drapes, and similar products made from a nonwoven web according to
the invention.
[0066] Films of the invention can be made from blends of synthetic
organic polymer and the described fluorochemical additive by any
film making method commonly employed in the art. Such films may be
non-porous, porous or microporous, where the presence and degree of
porosity is selected according to desired performance
characteristics.
Test Methods
[0067] Each of the test methods employed herein were the same as
described in WO 99/05345, herein incorporated by reference in its
entirety.
[0068] Melt-Blown Extrusion Procedure: The melt-blown extrusion
procedure was the same as described in U.S. Pat. No. 5,300,357,
col. 10, herein incorporated by reference. The extruder that was
used is a Brabender 42 mm conical twin-screw extruder, with maximum
extrusion temperature of 270-280.degree. C. and distance to the
collector of 12 inches (30 cm).
[0069] Mixtures of the fluorochemical additive and the synthetic
thermoplastic polymer were made by blending in a paperboard
container using a mixer head affixed to a hand drill for about one
minute until a visually homogeneous mixture was obtained.
[0070] The process conditions for each mixture were the same,
including the melt blowing die construction used to blow the
microfiber web (50.+-.5 gm/cm.sup.2) and the diameter of the
microfibers (5-518 micrometers). Unless otherwise stated, the
extrusion temperature was 210.degree. C., the pressure was 124 kPa
(18 psi) with a 0.076 cm air gap width, and the polymer throughput
was about 180 g/hr/cm.
[0071] Spunbond Extrusion Procedure: The extruder used was a
Reifenhauser Extruder Model Number RT 381 (available from
Reifenhauser Co., Troisdorf, Nordrhein Wesfalen, Germany). The
extruder was driven by an infinitely variable 3o shunt wound DC
motor, 37.3 kW& 2200 rev/min max. The maximum screw speed was
reduced to 150 rev/min. The screw was 70 mm in diameter and 2100 mm
in length. The entire extruder was 2.3 m in length by 1.3 m in
width by 1.6 m in height, weighing 2200 kg. There were five 220 V
heating zones at a total 22.1 kW of heating power, giving a maximum
heating zone temperature of 210.degree. C.
[0072] The bonder was a Kusters Two-Bowl-Thermobonding-Calendar
(available from Kusters Corp., Nordrhein Westfalen, Germany). The
effective bonding width was 1.2 m. The upper patterned metal roll
had a 15% bonding area and a temperature of 270.degree. F.
(132.degree. C.), while the lower rubber roll had a slick surface
and a temperature of 265.degree. F. (129.degree. C.), the bonding
nip pressure was 57-860 pounds of force per linear inch
(3000-46,000 J/cm). The rolls were heated by convection from
continuously circulating furnace oil. The temperature range of the
nips was 200-300.degree. F. (93-149.degree. C.). The bonder's speed
was directly synchronized to the speed of the collection belt that
had a range of 3.6 to 65 linear meters per minute.
[0073] The basis weight for the nonwoven web (in g/m2 ) can be
calculated by multiplying the speed of the spin pump (rev/m) times
the constant 71.
[0074] Embossing Procedure: Nonwoven samples were embossed using a
top roll with a 15% contact area diamond pattern metal top roll set
at 98.degree. C. and a rubber bottom roll set at 104.degree. C.,
with a gap between the rolls of less the 2 mil (50 microns), at a
pressure of 30 psi (1550 torr) between the top and bottom rolls,
and at a linear speed of 8.3 ft/min(2.5 m/min).
[0075] Thermal Gravimetric Analysis (TGA) Test: Unless otherwise
stated, a DuPont Instruments Model 951 Thermogravimetric Analyzer
was used, and the sample was heated from room temperature at a rate
of 10.degree. C./min. The percent of the sample left when a given
temperature was reached (usually 220.degree. C., 280.degree. C.,
320.degree. C. and 340.degree. C.) was reported. It is desirable to
have at least about 90% of the sample remaining after heating to
320.degree. C. so that the fluorochemical additive is resistant to
high temperature processing.
[0076] In a variant of this test, a sample of fluorochemical
additive is heated at a rate of 100.degree. C./min to 220.degree.
C., 280.degree. C. or 320.degree. C. and held at the respective
temperature. The percent of the sample left after different numbers
of minutes was measured and recorded as "% TGA remaining".
[0077] Water Repellency Test: Nonwoven web samples were evaluated
for water repellency using 3M Water Repellency Test V for
Floorcoverings (February 1994), available from 3M Company. In this
test, samples are challenged to penetrations by blends of deionized
water and isopropyl alcohol (IPA). Each blend was assigned a rating
number as shown below: TABLE-US-00002 Water Blend (% by Repellency
Rating volume, water/IPA) 0 100% water 1 90/10 2 80/20 3 70/30 4
60/40 5 50/50 6 40/60 7 30/70 8 20/80 9 10/90 10 100% IPA
[0078] In running the Water Repellency Test, a nonwoven web sample
was placed on a flat, horizontal surface. Five small drops of water
or a water/fluorochemical additive sample were gently placed at
points at least two inches apart on the sample. If, after observing
for ten seconds at a 45.degree. angle, four of the five drops were
visible as a sphere or a hemisphere, the nonwoven web sample was
deemed to have passed the test. The reported water repellency
rating corresponds to the highest numbered water or water/mixture
for which the nonwoven sample passed the described test.
[0079] It is desireable to have a water repellency rating of at
least four, preferably at least six.
[0080] Oil Repellency Test: Nonwoven web samples were evaluated for
oil repellency using 3 M Oil Repellency Test III (February 1994),
available from 3M Company, St. Paul, Minn. In this test, samples
are challenged to penetration by oil or oil mixtures of varying
surface tensions. Oils and oil mixtures are given a rating
corresponding to the following: TABLE-US-00003 Repellency Rating
No. Oil Composition 0 (fails Kaydol .TM. mineral oil) 1 Kaydol .TM.
mineral oil 2 65/35 (vol.) mineral oil/n-hexadecane 3 n-hexadecane
4 n-tetradecane 5 n-dodecane 6 n-decane 7 n-octane 8 n-heptane
[0081] The following examples are offered by way by of illustration
only and to aid in the understanding of the invention. They are not
to be construed as limiting the scope of the invention.
EXAMPLES
[0082] In the examples below, unless otherwise indicated, the acid
starting material is 1,2,4-Benzenetericarboxylic anhydride, also
called trimellitic anhydride (CAS Registry Number 552-30-7).
[0083] Alcohol 1 identified in the examples as Zonyl.RTM. BA is a
fluorotelomer from Dupont Chemical Enterprises, Wilmington, Del. It
is a mixture of even-numbered C.sub.6 -C.sub.18
1,1,2,2-tetrahydroperfluoro-1-alcohols, the majority of which are
between 8 and 12 carbon atoms in length. The mixture has a boiling
point of 145-245.degree. C. (293-473.degree. F.) at 1 atm; a
melting point of 55-65.degree. C. (131-149.degree. F.) and a
specific gravity of 1.7.
[0084] Alcohol 2 identified in the examples is 1-Octadecanol, also
called stearyl alcohol (CAS Registry Number 112-92-5). This
material may be derived from natural (e.g. animal or
vegetable-based) or petrochemical feedstocks.
[0085] Escorene.TM. PP3505 is polypropylene having a melt flow rate
of 400, which is commercially available from Exxon Chemical
Company, Baytown, Tex.
[0086] Aspun.TM.6806 is polyethylene having a melt index of 105
g/10 min (as measured by Test Method ASTM D-1238) and a peak
melting point of 124.8.degree. C. It is commercially available from
Dow Chemical Company, Midland Mich.
[0087] Morthane.TM.PS 400 is a thermoplastic polyurethane resin
having a Shore A Hardness (one sec delay) of 89 and a melting point
range of 140-210.degree. and is commercially available from Shell
Chemical Company.
[0088] PET 35 is polyethylene terephthalate that is commercially
available from BASF Corporation, Mt. Olive, N.J.
[0089] Ultramid.TM.B-3 is nylon 6 polyamide resin having a melting
point of 220.degree. C., a number average molecular weight of
15,000 and a melt viscosity of 140 Pas at 250.degree. C. (D=1000
s.sup.-1). It is commercially available from BASF Corp.,
Parsippany, N.J.
[0090] Unless otherwise indicated in the examples, all parts and
percentages are by weight. Whenever a "control" is designated, it
signifies a composition identical to the one which is tested but
lacking the additive described in that example.
[0091] Synthesis of Fluorochemical Additives
Example 1
[0092] A 50 gallon glass-lined reactor is charged with 38.5 pounds
trimellitic anhydride (BP-Amoco); 220 pounds Zonyl.RTM. BA C6-C18
tetrahydroperfluoro-1-alcohol telomer (DuPont Chemical
Enterprises); 64 pounds 1-Octadecanol (Sasol); 322 grams 70%
aqueous methanesulfonic acid; and 304 grams Irgafos 168 (Ciba
Specialties). The reaction mass is heated, with stirring, to
150-160.degree. C. and reaction water is distilled out until an
acid value is less than 4 mg KOH/g sample is obtained. The molten
reaction mass is flaked or discharged to trays and allowed to
freeze. The product is then ground to a powder. The yield is 272
pounds of a light tan solid, melting at 52.degree. C. The fluorine
content was determined to be 47.1% by weight. The TGA profile as
percent product remaining was determined at the following
temperatures. This fluorochemical additive product is referred to
hereinbelow as FC-1. TABLE-US-00004 Temperature 220.degree. C.
280.degree. C. 320.degree. C. 340.degree. C. % Remaining 98 97 95
93
Example 2
[0093] Example 1 was repeated in a vented rotary ball mill/dryer
with external heating. The reaction mass was heated at 155.degree.
C. until the acid value was less than 4 mg KOH/gram sample. The
yield was 5160 grams of tan power with a melting point of
52.4.degree. C. and a fluorine content of 46.7% by weight.
Example 3
[0094] Example 2 was repeated on a laboratory scale in a Brabender
Prep Center. The machine was charged with 220 grams Zonyl BA, 64
grams 1-Octadecanol, 38.5 grams Trimellitic anhydride, 0.3 grams
70% Methanesulfonic acid and 0.3 grams Irgafos 168. The reaction
mass was held at 160.degree. C. until the acid value was less than
4 mg KOH/gram sample. The yield was 270 grams of a tan solid
melting at 54.degree. C. with a fluorine content of 46.1% by
weight.
Use of Flurochemical Additive to Confer Hydrophobicity and
Oleophobicity to Synthetic Organic Polymers
Non-woven Fabrics
[0095] Escorene.TM. PP 3505 chips were blended with the
fluorochemical additive FC-1 described in Example 1 above at 1.00
percent by weight solids and thermally extruded into non-woven webs
using the Melt-Blown Extrusion Procedure. The non-woven webs were
evaluated for repellency using the above-described Water Repellency
and Oil Repellency Tests. Both tests were done immediately after
extrusion; after holding for ten days at room temperature; and
after the above-described Embossing Procedure was performed.
[0096] Escorene.TM. PP 3505 TABLE-US-00005 Water Repellency Oil
Repellency Initial 10 days Embossed Initial 10 days Embossed
Control 2 2 2 0 0 0 FC-1 8 8 9 3 1 4
[0097] The procedure described immediately above was repeated
except using four different polymers: Aspun.TM. 6806 polyethylene;
Morthane PS 400 polyurethane; PET 35 polyethylene terephthalate;
and BASF Ultramid.TM. B-3 nylon; the results are described
below.
[0098] Aspun.TM. 6806 Polyethylene TABLE-US-00006 Water Repellency
Oil Repellency Initial 10 days Embossed Initial 10 days Embossed
Control 2 2 2 0 0 0 FC-1 9 9 9 3 1 2
[0099] Morthane.TM. PS 400 Polyurethane TABLE-US-00007 Water
Repellency Oil Repellency Initial 10 days Embossed Initial 10 days
Embossed Control 2 2 3 0 0 0 FC-1 7 8 9 4 5 6
[0100] PET 35 Polyethylene Terephthalate TABLE-US-00008 Water
Repellency Oil Repellency Initial 10 days Embossed Initial 10 days
Embossed Control 1 1 1 0 0 1 FC-1 3 4 4 2 3 3
[0101] BASF Ultramid.TM.B-3 Nylon TABLE-US-00009 Water Repellency
Oil Repellency Initial 10 days Embossed Initial 10 days Embossed
Control 0 0 0 0 0 0 FC-1 2 2 2 1 1 1
Concentration Dependence of Fluorochemical Additive Polymer in
Non-Woven Fabric
[0102] The polymer used above, Escorene.TM.PP3505, was subjected to
Water Repellency tests at 5 and 120 min. and Oil Repellency tests
at 5 min. at 0.5, 0.75, 1.00 and 1.5 weight percent, based on total
weight. The following values were noted:
[0103] Escorene.TM.PP 3505 TABLE-US-00010 Water Repellency Oil
Repellency Concentration 5 Minutes 120 Minutes 5 Minutes 0.5 3 4 0
0.75 5 4 3 1.00 8 7 4 1.5 8 8 5
Films Incorporating Fluorochemical Additive
[0104] To the polymer used above and identified as Escorene.TM. PP
3505 from Exxon Chemical Company, was added 1.25% by weight of
FC-1. The mixture was made into a film, according to the following
procedure, as was the control material, which comprised the
Escorene polymer with no additive.
[0105] A sandwich construction was assembled consisting of a
rectangular steel plate of 25.4 cm length and 15.3 cm width, a
copper foil of dimensions similar to those of the steel plate, and
a rectangular steel shim of 25.4 cm length, 15.3 cm width and 254
microns thickness in which a centered rectangular cutout of 10.1 cm
by 8.7 cm was made. Next, 2.5 g of spunbond polypropylene was
folded into the center of the cutout area with approximate open
margin border of approximately 1 cm on each side. The fabric was
covered with more copper foil and another rectangular steel plate
of the same dimensions used in the rest of the construction. The
sandwich construction was placed between the plates of a press,
each plate being heated to 200.degree. C., and the plates were
brought together with a force of 5 tons for a 4 inch (10.2 cm)
diameter circle (587,000 kg/m.sup.2) for 2 minutes. Afterwards, the
sandwich construction was removed form the heated plates and was
placed between two unheated plates on the press at a much lower
pressure to cool for 1 minute. The construction was disassembled
and the film extracted for testing.
[0106] The films were subjected to Water, Alcohol and Oil
Repellency tests as described above. The following properties were
noted. TABLE-US-00011 Film Water Alcohol Oil Thickness Repellency
Repellency Repellency Control 10.6 4 1 0 1.0% FC-1 11.0 10 7 5
Epoxy Castings Using Fluorochemical Additive
[0107] A composition containing 1.25% of FC-1 was made into epoxy
castings from a part, room temperature curable, thermoset epoxy
resin system (3M Scotch-Weld.TM. 2158 B/A Epoxy Adhesive Tube Kit)
with and without the fluorochemical additive (for control). After
curing, the castings were submitted to testing as reported below.
TABLE-US-00012 Water Repellency Oil Repellency Control 2 1 1.0%
FC-1 10 8
[0108] Various modifications and alterations of this invention will
be apparent to those skilled in the art without departing from the
scope and spirit of this invention, and it should be understood
that this invention is not limited to the illustrative embodiments
as set forth herein.
* * * * *