U.S. patent application number 17/228835 was filed with the patent office on 2021-07-29 for solid polymeric articles having hydrophobic compounds intermixed therein.
This patent application is currently assigned to THE CHEMOURS COMPANY FC, LLC. The applicant listed for this patent is THE CHEMOURS COMPANY FC, LLC. Invention is credited to GERALD ORONDE BROWN, JOHN CHRISTOPHER SWOREN.
Application Number | 20210230395 17/228835 |
Document ID | / |
Family ID | 1000005512112 |
Filed Date | 2021-07-29 |
United States Patent
Application |
20210230395 |
Kind Code |
A1 |
BROWN; GERALD ORONDE ; et
al. |
July 29, 2021 |
SOLID POLYMERIC ARTICLES HAVING HYDROPHOBIC COMPOUNDS INTERMIXED
THEREIN
Abstract
The present invention relates to a three-dimensional solid
polymeric article having surface effects comprising a polymer
composition and 0.1 to 20% by weight of a hydrophobic compound,
based on the total weight of the solid polymeric article, where the
hydrophobic compound is intermixed throughout the polymer
composition and throughout three-dimensional solid polymeric
article; and where the hydrophobic compound is selected from a
cyclic alcohol which is substituted with at least two hydrophobic
groups.
Inventors: |
BROWN; GERALD ORONDE;
(Swedesboro, NJ) ; SWOREN; JOHN CHRISTOPHER;
(Lincoln University, PA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
THE CHEMOURS COMPANY FC, LLC |
Wilmington |
PA |
US |
|
|
Assignee: |
THE CHEMOURS COMPANY FC,
LLC
Wilmington
DE
|
Family ID: |
1000005512112 |
Appl. No.: |
17/228835 |
Filed: |
April 13, 2021 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
15764901 |
Mar 30, 2018 |
11008439 |
|
|
PCT/US16/54584 |
Sep 30, 2016 |
|
|
|
17228835 |
|
|
|
|
62236335 |
Oct 2, 2015 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B29C 45/14639 20130101;
C08K 5/1535 20130101; H01B 3/30 20130101; B29K 2067/00 20130101;
B29L 2031/3462 20130101; H01B 7/0275 20130101; B29C 45/0001
20130101; B29K 2705/10 20130101; B29K 2105/0005 20130101; B29K
2995/0093 20130101; B29C 45/14549 20130101 |
International
Class: |
C08K 5/1535 20060101
C08K005/1535; B29C 45/00 20060101 B29C045/00; B29C 45/14 20060101
B29C045/14; H01B 3/30 20060101 H01B003/30; H01B 7/02 20060101
H01B007/02 |
Claims
1. A three-dimensional solid polymeric article having surface
effects comprising 60 to 99.9% of a polymer composition and 0.1 to
20% by weight of a hydrophobic compound, based on the total weight
of the solid polymeric article, where the hydrophobic compound is
intermixed throughout the polymer composition and throughout the
three-dimensional solid polymeric article; where the hydrophobic
compound is selected from Formula (Ia): ##STR00003## wherein each R
is independently --H; --R.sup.1; --C(O)R.sup.1; or
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mC(O)R.sup.1;
each n is independently 0 to 20; each m is independently 0 to 20;
m+n is greater than 0; r is 1 to 3; a is 0 or 1; p is independently
0 to 2; provided that a is 0 when r is 3; and each R.sup.1 is
independently a linear or branched alkyl group having 5 to 29
carbons; provided at least one R is H and at least two R groups are
a --R.sup.1; --C(O)R.sup.1; or
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mC(O)R.sup.1;
wherein the polymer composition is a polymer resin selected from
thermoplastic urethanes; thermoplastic elastomer polyesters; or a
thermoplastic resin, a thermoset resin, an elastomer resin, or an
amorphous polymer selected from linear polyamides, polystyrene and
polystyrene copolymers, poly(acrylic acid) and poly(acrylic acid)
copolymers, poly(methyl methacrylate) and poly(methyl methacrylate)
copolymers, poly(methyl acrylate) and poly(methyl acrylate)
copolymers, polymethacrylate and polymethacrylate copolymers,
polyacrylate and polyacrylate copolymers, polyvinyl chloride and
polyvinyl chloride copolymers, polycarbonates and polycarbonate
copolymers, polycaprolactones and polycaprolactone copolymers,
silicones, fluoroolefins, and fluoroelastomers.
2. (canceled)
3. The solid polymeric article of claim 1, where the hydrophobic
compound is selected from Formula (Ia) to be Formula (Ia'):
##STR00004## wherein R is further limited to independently --H;
--R.sup.1; or --C(O)R.sup.1.
4. The solid polymeric article of claim 1, where the hydrophobic
compound is selected from Formula (Ia) to be Formula (Ia'):
##STR00005## wherein R is further limited to independently --H; or
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mC(O)R.sup.1.
5. The solid polymeric article of claim 1, where the hydrophobic
compound is substituted with at least three --R.sup.1,
--C(O)R.sup.1,
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mC(O)R.sup.1,
or mixtures thereof.
6. The solid polymeric article of claim 1, further comprising at
least one hydrophobic surface effect agent which provides a surface
effect, where the hydrophobic surface effect agent is intermixed
with the polymer composition and the hydrophobic compound.
7. The solid polymeric article of claim 1, comprising 1 to 10% by
weight of the hydrophobic compound, based on the total weight of
the polymeric article.
8. The solid polymeric article of claim 6, comprising 1 to 5% by
weight of the hydrophobic compound, and 1 to 5% by weight of the
hydrophobic surface effect agent, based on the total weight of the
polymeric article.
9. The solid polymeric article of claim 6, wherein the hydrophobic
surface effect agent is selected from the group consisting of
non-fluorinated or fluorinated cationic acrylic polymers,
non-fluorinated or fluorinated anionic acrylic polymers,
non-fluorinated or fluorinated nonionic acrylic polymers, partially
fluorinated urethanes, fluorinated ethoxylates, fluorinated
alcohols, fluorinated phosphate acids, non-fluorinated urethanes,
silicones, waxes, and mixtures thereof.
10. (canceled)
11. (canceled)
12. A method of imparting a surface effect to a polymeric article
comprising contacting 60 to 99.9% of a flowable or liquid polymer
composition with 0.1% by weight to 20% by weight of a hydrophobic
compound, based on the total weight of the polymer composition, to
form a treated polymer composition, and allowing or causing the
treated polymer composition to solidify to form a treated polymeric
article, where the hydrophobic compound is selected from Formula
(Ia): ##STR00006## wherein each R is independently --H; --R.sup.1;
--C(O)R.sup.1; or
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mC(O)R.sup.1;
each n is independently 0 to 20; each m is independently 0 to 20;
m+n is greater than 0; r is 1 to 3; a is 0 or 1; p is independently
0 to 2; provided that a is 0 when r is 3; and each R.sup.1 is
independently a linear or branched alkyl group having 5 to 29
carbons; provided at least one R is --H and at least two R groups
are a --R.sup.1; --C(O)R.sup.1; or
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mC(O)R.sup.1;
wherein the polymer composition is a polymer resin selected from
thermoplastic urethanes; thermoplastic elastomer polyesters; or a
thermoplastic resin, a thermoset resin, an elastomer resin, or an
amorphous polymer selected from linear polyamides, polystyrene and
polystyrene copolymers, poly(acrylic acid) and poly(acrylic acid)
copolymers, poly(methyl methacrylate) and poly(methyl methacrylate)
copolymers, poly(methyl acrylate) and poly(methyl acrylate)
copolymers, polymethacrylate and polymethacrylate copolymers,
polyacrylate and polyacrylate copolymers, polyvinyl chloride and
polyvinyl chloride copolymers, polycarbonates and polycarbonate
copolymers, polycaprolactones and polycaprolactone copolymers,
silicones, fluoroolefins, and fluoroelastomers.
13. The method of claim 12, further comprising the step of molding,
extruding, or spinning the treated polymer composition prior to
solidification.
14. The method of claim 12, further comprising the step of
thermoforming the treated polymeric article to form a treated three
dimensional polymeric article.
Description
FIELD OF THE INVENTION
[0001] Hydrophobic cyclic sugar alcohols are employed as polymer
resin additives to provide repellency surface effects to the
finished solid articles.
BACKGROUND OF THE INVENTION
[0002] Various compositions are known to be useful as treating
agents to provide surface effects to substrates. Surface effects
include repellency to moisture, soil and stain resistance, and
other effects which are particularly useful for hard or fibrous
substrates such as fibers, fabrics, textiles, carpets, paper,
leather, stone and tile, glass, metal, and other such substrates.
Many such treating agents are partially fluorinated polymers or
copolymers.
[0003] Fluorinated polymer compositions having utility as fibrous
substrate treating agents generally contain pendant perfluoroalkyl
groups of three or more carbon atoms, which provide oil- and
water-repellency when the compositions are applied to fibrous
substrate surfaces. The perfluoroalkyl groups are generally
attached by various connecting groups to polymerizable groups not
containing fluorine. The resulting monomer is then generally
copolymerized with other monomers which confer additional favorable
properties to the substrates. Various specialized monomers may be
incorporated to impart improved cross-linking, latex stability and
substantivity. Since each ingredient may impart some potentially
undesirable properties in addition to its desirable ones, the
specific combination is directed to the desired use. These polymers
are generally marketed as aqueous emulsions for easy application to
the fibrous substrates.
[0004] Various attempts have been made to increase the oil- and
water-repellency imparted an article while reducing the amount of
fluorinated polymer required, i.e., boost the efficiency or
performance of the treating agent. One method is to incorporate
blocked isocyanates or melamine resins. However, only limited
amounts can be used because these ingredients tend to adversely
affect the handle (the feel) of the fibrous substrate. Another
approach employs use of various extender polymers. These are
typically hydrocarbon polymers in aqueous emulsions, which are
blended with the fluorinated polymer emulsion before application to
the substrate.
[0005] Jariwala et al. (U.S. Pat. No. 5,228,157) discloses
fluorochemical compounds for use as treating agents or polymer melt
additives for the purposes of providing oil-, water-, or stain
repellency to shaped articles such as fibers.
BRIEF SUMMARY OF THE INVENTION
[0006] There is a need for surface effect compositions which
provide hydrophobicity performance with improved fluorine
efficiency in polymeric resin articles. The present invention
provides such a composition.
[0007] The present invention relates to a three-dimensional solid
polymeric article having surface effects comprising a polymer
composition and 0.1 to 20% by weight of a hydrophobic compound,
based on the total weight of the solid polymeric article, where the
hydrophobic compound is intermixed throughout the polymer
composition and throughout three-dimensional solid polymeric
article; where the hydrophobic compound is selected from a cyclic
sugar alcohol which is substituted with at least two R.sup.1,
--C(O)R.sup.1,
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mR.sup.2,
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mC(O)R.sup.1,
or mixtures thereof; where the cyclic sugar alcohol is selected
from a saccharide, reduced sugar, aminosaccharide, aldonic acid, or
aldonic acid lactone; wherein each n is independently 0 to 20; each
m is independently 0 to 20; m+n is greater than 0; each R.sup.1 is
independently a linear or branched alkyl group having 5 to 29
carbons; and each R.sup.2 is independently H, a linear or branched
alkyl group having 6 to 30 carbons.
[0008] The invention further relates to a method of imparting a
surface effect to a polymeric article comprising contacting a
flowable or liquid polymer composition with 0.1% by weight to 20%
by weight of a hydrophobic compound, based on the total weight of
the polymer composition, to form a treated polymer composition, and
allowing or causing the polymer composition to solidify to form a
treated polymeric article, where the treatment composition
comprises a hydrophobic compound selected from a cyclic sugar
alcohol which is substituted with at least two R.sup.1,
--C(O)R.sup.1,
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mR.sup.2,
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mC(O)R.sup.1,
or mixtures thereof; where the cyclic sugar alcohol is selected
from a saccharide, reduced sugar, aminosaccharide, aldonic acid, or
aldonic acid lactone; wherein each n is independently 0 to 20; each
m is independently 0 to 20; m+n is greater than 0; each R.sup.1 is
independently a linear or branched alkyl group having 5 to 29
carbons; each R.sup.2 is independently H, a linear or branched
alkyl group having 6 to 30 carbons.
DETAILED DESCRIPTION OF THE INVENTION
[0009] Trademarks are indicated herein by capitalization.
[0010] The present invention provides three-dimensional solid
polymeric articles having improved water repellency, oil or stain
repellency, and/or other hydrophobic surface effects. The treated
articles provide enhanced performance and durability compared to
traditional non-fluorinated commercially available treatment
agents. Furthermore, the hydrophobic compound additives of the
present invention can be derived from bio-sourced materials.
[0011] The present invention relates to a three-dimensional solid
polymeric article having surface effects comprising a polymer
composition and 0.1 to 20% by weight of a hydrophobic compound,
based on the total weight of the solid polymeric article, where the
hydrophobic compound is intermixed throughout the polymer
composition and throughout three-dimensional solid polymeric
article; where the hydrophobic compound is selected from a cyclic
sugar alcohol which is substituted with at least two R.sup.1,
--C(O)R.sup.1,
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mR.sup.2,
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mC(O)R.sup.1,
or mixtures thereof; where the cyclic sugar alcohol is selected
from a saccharide, reduced sugar, aminosaccharide, aldonic acid, or
aldonic acid lactone; wherein each n is independently 0 to 20; each
m is independently 0 to 20; m+n is greater than 0; each R.sup.1 is
independently a linear or branched alkyl group having 5 to 29
carbons; and each R.sup.2 is independently H, a linear or branched
alkyl group having 6 to 30 carbons. The --(CH.sub.2CH.sub.2O)--
represents oxyethylene groups (EO) and --(CH(CH.sub.3)CH.sub.2O)--
represents oxypropylene groups (PO). These compounds can contain
only EO groups, only PO groups, or mixtures thereof. These
compounds can also be present as a tri-block copolymer designated
PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene
glycol), for example. In one embodiment, n+m is 1 to 20; in another
embodiment, n+m is 1 to 15; and in a third embodiment, n+m is 1 to
12.
[0012] The cyclic alcohol is selected from a saccharide, reduced
sugar, aminosaccharide, aldonic acid, or aldonic acid lactone.
Mixtures of these compounds may also be used. The hydrophobic
compounds are substituted with at least two --R.sup.1;
--C(O)R.sup.1;
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mR.sup.2;
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mC(O)R.sup.1;
or mixtures thereof. Such a substitution lends hydrophobic
character to the monomer, and to the polymer molecules. In one
embodiment, the hydrophobic compound is substituted with at least
three --R.sup.1; --C(O)R.sup.1;
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mR.sup.2;
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mC(O)R.sup.1;
or mixtures thereof.
[0013] These substituted compounds can be made by the reaction of a
sugar alcohol with at least one fatty acid or alkoxylated fatty
acid, such as by esterification of a fatty acid. Examples of such
sugar alcohols include but are not limited to aldoses and ketoses
such as those compounds derived from tetroses, pentoses, hexoses,
and heptoses. Specific examples include glucose, allose, altrose,
mannose, xylose, lyxose, galactose, talose, fructose,
1,4-anhydro-D-glucitol, 2,5-anhydro-D-mannitol,
2,5-anhydro-L-iditol, sorbitan, mannoheptulose, glucopyranose,
mannopyranose, talopyranose, allopyranose, altropyranose,
idopyranose, gulopyranose, inositol, ascorbic acid, gluconic acid
lactone, glyceric acid lactone, xylonic acid lactone, isosorbide,
glucosamine, galactosamine, or mixtures thereof.
[0014] Suitable fatty acids include, but are not limited to,
caprylic acid, capric acid, lauric acid, mysteric acid, palmitic
acid, stearic acid, arachidic acid, behenic acid, lignoceric acid,
alkoxylated versions of these acids, and mixtures thereof.
[0015] In one embodiment, R.sup.1 is a linear or branched alkyl
group having 11 to 29 carbons, and in another embodiment, R.sup.1
is a linear or branched alkyl group having 17 to 21 carbons. In one
embodiment, R.sup.2 is a linear or branched alkyl group having 12
to 30 carbons, in another embodiment, R.sup.2 is a linear or
branched alkyl group having 18 to 30 carbons, and in another
embodiment, R.sup.2 is a linear or branched alkyl group having 18
to 22 carbons. In one embodiment, the fatty acid or long-chain
alcohol substitution of the cyclic sugar alcohols has a melting
point of at least -59.degree. C. In another embodiment, it has a
melting point of at least 0.degree. C., and in a third embodiment,
it has a melting point of at least 40.degree. C.
[0016] In one embodiment, the hydrophobic compound is selected from
Formula (Ia):
##STR00001##
wherein each R is independently H; --R.sup.1; --C(O)R.sup.1;
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mR.sup.2; or
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mC(O)R.sup.1;
each n is independently 0 to 20; each m is independently 0 to 20;
m+n is greater than 0; r is 1 to 3; a is 0 or 1; p is independently
0 to 2; provided that a is 0 when r is 3; each R.sup.1 is
independently a linear or branched alkyl group having 5 to 29
carbons; and each R.sup.2 is independently H, or a linear or
branched alkyl group having 6 to 30 carbons; provided at least one
R is H and at least two R groups are a --R.sup.1; --C(O)R.sup.1;
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mR.sup.2; or
[0017]
(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mC(O)R.sup.1.
[0018] Where the hydrophobic compound is Formula (Ia), any suitable
substituted reduced sugar alcohol may be employed, including esters
of 1,4-sorbitan, esters of 2,5-sorbitan, and esters of
3,6-sorbitan. In one embodiment, the hydrophobic compound is
selected from Formula (a) to be Formula (Ia'):
##STR00002##
wherein R is further limited to H; --R.sup.1; or --C(O)R.sup.1 and
at least two R groups are C(O)R.sup.1 or R.sup.1. Compounds used to
form residues of Formula (Ia'), having at least one of R is H and
at least one R is selected from --C(O)R.sup.1, are commonly known
as alkyl sorbitans. These sorbitans can be di-substituted or
tri-substituted with --C(O)R.sup.1. It is known that commercially
available sorbitans, such as SPAN, contain a mixture of the various
sorbitans ranging from where each R is H (un-substituted), and
sorbitans where each R is --C(O)R.sup.1 (fully substituted);
wherein R.sup.1 is a linear or branched alkyl group having 5 to 29
carbons; and mixtures of various substitutions thereof. The
commercially available sorbitans may also include amounts of
sorbitol, isosorbide, or other intermediates or byproducts.
[0019] In one embodiment, at least two R groups are C(O)R.sup.1,
and R.sup.1 is a linear branched alkyl group having 5 to 29
carbons. In another embodiment, R.sup.1 is a linear or branched
alkyl group having 7 to 21 carbons, and in a third embodiment,
R.sup.1 is a linear or branched alkyl group having 11 to 21
carbons. Preferred compounds used to form these residues include
di- and tri-substituted sorbitans derived from caprylic acid,
capric acid, lauric acid, mysteric acid, palmitic acid, stearic
acid, arachidic acid, behenic acid, lignoceric acid, and mixtures
thereof. Particularly preferred compounds include di- and
tri-substituted sorbitan stearates or sorbitan behenins.
[0020] In one embodiment, a compound of Formula (Ia) is employed,
wherein at least two R groups are independently
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mR.sup.2 or
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mC(O)R.sup.1.
Compounds of Formula (Ia), wherein at least two R groups are
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mR.sup.2 or
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mC(O)R.sup.1,
wherein each m is independently 0 to 20, each n is independently 0
to 20, and n+m is greater than 0 are known as polysorbates and are
commercially available under the tradename TWEEN. These
polysorbates can be di-substituted or tri-substituted with alkyl
groups R.sup.1 or R.sup.2. It is known that commercially available
polysorbates contain a mixture of the various polysorbates ranging
from where each R.sup.2 is H (unsubstituted), and polysorbates
where each R.sup.1 is a linear or branched alkyl group having 5 to
29 carbons (fully substituted); and mixtures of various
substitutions thereof. Examples of compounds of Formula (Ia)
include polysorbates such as polysorbate tristearate and
polysorbate monostearate. Reagents may include mixtures of
compounds having various values for R, R.sup.1, and R.sup.2, and
may also include mixtures of compounds where R.sup.1 comprises at
least one unsaturated bond with compounds where R.sup.1 is fully
saturated.
[0021] Compounds of Formula (Ia) can all be bio-based derived. By
"bio-based derived", it is meant that at least 10% of the material
can be produced from non-crude oil sources, such as plants, other
vegetation, and tallow. In one embodiment, the hydrophobic compound
is from about 10% to 100% bio-based derived. In one embodiment,
hydrophobic compound is from about 35% to 100% bio-based derived.
In another embodiment, hydrophobic compound is from about 50% to
100% bio-based derived. In one embodiment, hydrophobic compound is
from about 75% to 100% bio-based derived. In one embodiment,
hydrophobic compound is 100% bio-based derived. The average OH
value of the hydrophobic compounds can range from just greater than
0 to about 230. In one embodiment, the average OH value is from
about 10 to about 175, and in another embodiment, the average OH
value is from about 25 to about 140.
[0022] The three-dimensional solid polymeric article comprises 0.1
to 20% by weight of the hydrophobic compound, based on the total
weight of the solid polymeric article. In a second aspect, the
article comprises 1 to 10% by weight of the hydrophobic compound;
and in a third aspect, 1 to 5% by weight of the hydrophobic
compound based on the total solids weight of the solid polymeric
article. The polymer composition used to form the three-dimensional
solid polymeric article may further comprise aqueous or organic
solvents, additional polymer resins, pigments, functional
additives, surfactants, and hydrophobic surface effect agents.
[0023] The polymer composition used to form the body of the
polymeric article may be any polymer resin which forms a solid
material at room temperature, including but not limited to
thermoplastic resins, thermoset resins, elastomeric resins, or
amorphous polymers. Such polymer resins are synthetic. These
include polyamide, polyester, polyepoxide, polystyrene, styrene
copolymer, polyolefin, polyolefin copolymer, thermoplastic
urethane, fluoroelastomers, polyfluoroolefins, acrylic polymers and
copolymers, silicone, polyesters, and polycarbonate. The
thermoplastic resins may be melted and shaped as desired. More
specific polyamides include linear polyamide such as nylons
(nylon-6 or nylon-66), polystyrene and polystyrene copolymers
including ABS polymers, polyethylene and polyethylene copolymers,
polypropylene and polypropylene copolymers, thermoplastic
urethanes, poly(acrylic acid), poly(methyl methacrylate),
poly(methyl acrylate), polymethacrylate, polyacrylate, polyesters
including thermoplastic polyesters, polyethylene terephthalate,
polypropylene terephthalate, and polybutylene terephalate,
polyvinyl chloride, polycaprolactones, polylactic acid, and
copolymers of any of the preceding polymers. The term
"thermoplastic" includes thermoplastic elastomers as well. In one
aspect, the polymer composition may be present in the
three-dimensional solid polymeric article in an amount of 60 to
99.9% by weight; in a second aspect, 60 to 99% by weight; and in a
third aspect, 75 to 99% by weight, based on the total weight of the
solid polymeric article. The balance of the three-dimensional
article composition comprises additives including but not limited
to pigments, viscosity modifiers, dyes, and other functional
additives. In one aspect, the polymer composition contains no
liquid carrier, including water or solvent. In another aspect, the
polymer composition contains no more than 5% of a liquid
carrier.
[0024] In one embodiment, the three-dimensional solid polymeric
article further comprises a hydrophobic surface effect agent to
provide further surface effects to the solid polymeric article. In
this case, three-dimensional solid polymeric article comprises 0.1
to 20% by weight of the hydrophobic surface effect agent, based on
the total weight of the solid polymeric article. In a second
aspect, the article comprises 1 to 10% by weight of the hydrophobic
surface effect agent; and in a third aspect, 1 to 5% by weight of
the hydrophobic surface effect agent based on the total solids
weight of the solid polymeric article. Hydrophobic surface effect
agents provide surface effects such as shrinkage control, wrinkle
free, permanent press, moisture control, softness, strength,
anti-slip, anti-static, anti-snag, anti-pill, stain repellency,
stain release, soil repellency, soil release, water repellency, oil
repellency, odor control, antimicrobial, sun protection, and
similar effects. In one aspect, such materials can be in the form
of non-fluorinated or fluorinated cationic acrylic polymers,
non-fluorinated or fluorinated anionic acrylic polymers,
non-fluorinated or fluorinated nonionic acrylic polymers, partially
fluorinated urethanes, fluorinated ethoxylates, fluorinated
alcohols, fluorinated phosphate acids, non-fluorinated urethanes,
silicones, waxes, or mixtures thereof.
[0025] Superior properties, along with desirable properties of low
yellowing and good durability, are imparted to articles by the
combination of the hydrophobic compounds and hydrophobic surface
effect agents within the solid polymeric articles. These combined
blends may be, for example, contacted with the polymer composition
in the form of a dispersion in water or other solvents.
[0026] Of particular interest are fluorinated polymers to provide
repellency properties to the surface of treated articles. These
include fluorochemical compounds or polymers containing one or more
fluoroaliphatic groups (designated here as R.sub.f groups) which
are fluorinated, stable, inert, and non-polar, preferably
saturated, monovalent, and both oleophobic and hydrophobic. The
R.sub.f groups contain at least 3 carbon atoms, preferably 3 to 20
carbon atoms, more preferably 4 to 12 carbon atoms, and most
preferably about 4 to about 6 carbon atoms. The R.sub.f groups may
contain straight or branched chain or cyclic fluorinated alkylene
groups or combinations thereof. The terminal portion of the R.sub.f
groups is preferably a perfluorinated aliphatic group of the
formula C.sub.nF.sub.2n+1 wherein n is from about 3 to about 20.
Examples of fluorinated polymer treating agents are CAPSTONE and
ZONYL available from The Chemours Company, Wilmington, Del.; ASAHI
GARD from Asahi Glass Company, Ltd., Tokyo, Japan; UNIDYNE from
Daikin America, Inc., Orangeburg, N.Y.; SCOTCHGARD from 3M Company,
St. Paul, Minn.; and NANO TEX from Nanotex, Emeryville, Calif.
[0027] Examples of such fluorinated polymers include
R.sub.f-containing polyurethanes and poly(meth)acrylates.
Especially preferred are copolymers of fluorochemical
(meth)acrylate monomers with a co-polymerizable monovinyl compound
or a conjugated diene. The co-polymerizable monovinyl compounds
include alkyl (meth)acrylates, vinyl esters of aliphatic acids,
styrene and alkyl styrene, vinyl halides, vinylidene halides, alkyl
esters, vinyl alkyl ketones, and acrylamides. The conjugated dienes
are preferably 1,3-butadienes. Representative compounds within the
preceding classes include the methyl, propyl, butyl,
2-hydroxypropyl, 2-hydroxyethyl, isoamyl, 2-ethylhexyl, octyl,
decyl, lauryl, cetyl, and octadecyl acrylates and methacrylates;
vinyl acetate, vinyl propionate, vinyl caprylate, vinyl laurate,
vinyl stearate, styrene, alpha methyl styrene, p-methylstyene,
vinyl fluoride, vinyl chloride, vinyl bromide, vinylidene fluoride,
vinylidene chloride, allyl heptanoate, allyl acetate, allyl
caprylate, allyl caproate, vinyl methyl ketone, vinyl ethyl ketone,
1,3-butadiene, 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene,
isoprene, N-methylolacrylamide, N-methylolmethacrylamide, glycidyl
acrylate, glycidyl methacrylate, amine-terminated (meth)acrylates,
and polyoxy(meth)acrylates.
[0028] Hydrophobic non-fluorinated acrylic polymers include
copolymers of monovinyl compounds, including alkyl (meth)acrylates,
vinyl esters of aliphatic acids, styrene and alkyl styrene, vinyl
halides, vinylidene halides, alkyl esters, vinyl alkyl ketones, and
acrylamides. The conjugated dienes are preferably 1,3-butadienes.
Representative compounds within the preceding classes include the
methyl, propyl, butyl, 2-hydroxypropyl, 2-hydroxyethyl, isoamyl,
2-ethylhexyl, octyl, decyl, lauryl, cetyl, and octadecyl acrylates
and methacrylates; vinyl acetate, vinyl propionate, vinyl
caprylate, vinyl laurate, vinyl stearate, styrene, alpha methyl
styrene, p-methylstyene, vinyl fluoride, vinyl chloride, vinyl
bromide, vinylidene chloride, allyl heptanoate, allyl acetate,
allyl caprylate, allyl caproate, vinyl methyl ketone, vinyl ethyl
ketone, 1,3-butadiene, 2-chloro-1,3-butadiene,
2,3-dichloro-1,3-butadiene, isoprene, N-methylolacrylamide,
N-methylolmethacrylamide, glycidyl acrylate, glycidyl methacrylate,
amine-terminated (meth)acrylates, and polyoxy(meth)acrylates.
[0029] Hydrophobic non-fluorinated urethanes include, for example,
urethanes synthesized by reacting an isocyanate compound with the
hydrophobic compounds described above as an alcohol reagent. These
compounds are described in US2014/0295724 and US2016/0090508.
Hydrophobic non-fluorinated nonionic acrylic polymers include, for
example, polymers made by polymerizing or copolymerizing an acrylic
ester of the hydrophobic compounds described above. Such compounds
are described in US2016/0090686.
[0030] In one embodiment the hydrophobic surface effect agent can
be a fluorinated alcohol which may be used to improve stain release
properties of the end product. Any suitable fluorinated alcohol may
be used. In one embodiment, the fluorinated alcohol has the
formula
R.sub.f-A.sub.x-Z--H (II)
wherein R.sub.f is a C1 to C20 linear or branched perfluoroalkyl
optionally interrupted by one, two or three ether oxygen atoms; x
is 0 or 1; A is (CH.sub.2).sub.k,
(CH.sub.2CF.sub.2).sub.m(CH.sub.2).sub.n,
(CH.sub.2).sub.oSO.sub.2N(CH.sub.3)(CH.sub.2).sub.p,
O(CF.sub.2).sub.2(CH.sub.2).sub.r, or OCHFCF.sub.2OE; Z is O, S, or
NH; m is 1 to 4; k, n, o, p, and r are each independently 1 to 20;
and E is a C2 to C20 linear or branched alkyl group optionally
interrupted by oxygen, sulfur, or nitrogen atoms; a cyclic alkyl
group, or a C6 to C10 aryl group. In one embodiment, the
fluorinated alcohol has Formula (II) where Z is O and where R.sub.f
is a C1 to C20 perfluoroalkyl group optionally interrupted by
CH.sub.2, CH.sub.2CH.sub.2, SO.sub.2N, CFH, S, or O; and A is a
direct bond or a C.sub.1 to C.sub.6 alkylene group. R.sub.f and A
may be linear or branched. In one aspect, the fluorinated alcohol
is a telomer-based alcohol, where R.sub.f is a linear
perfluoroalkyl group and A is CH.sub.2CH.sub.2. In one aspect,
R.sub.f is a C.sub.2 to C.sub.6 linear or branched perfluoroalkyl
group. Specific examples of fluorinated alcohols include but are
not limited to R.sub.fOH, R.sub.fCH.sub.2CH.sub.2OH,
R.sub.fSO.sub.2NHCH.sub.2CH.sub.2OH,
R.sub.fCH.sub.2CH.sub.2SCH.sub.2CH.sub.2OH,
R.sub.fCH.sub.2CH.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2OH,
R.sub.fCH.sub.2CH.sub.2(CF.sub.2CF.sub.2CH.sub.2CH.sub.2).sub.2OH,
R.sub.fCH.sub.2CF.sub.2CH.sub.2CH.sub.2OH,
R.sub.fCH.sub.2CF.sub.2CH.sub.2CF.sub.2CH.sub.2CH.sub.2OH,
R.sub.fOCF.sub.2CF.sub.2CH.sub.2CH.sub.2OH,
R.sub.fCH.sub.2OCH.sub.2CH.sub.2OH, R.sub.fCHFCH.sub.2CH.sub.2OH,
R.sub.fCH.sub.2O(CH.sub.2).sub.6OH,
(CF.sub.3).sub.2CFCH.sub.2CH.sub.2OH,
(CF.sub.3).sub.2CFCH.sub.2CH.sub.2 CH.sub.2OH,
R.sub.fCH.sub.2CH.sub.2SO.sub.2NHCH.sub.2CH.sub.2OH,
R.sub.fCH.sub.2CH.sub.2SO.sub.2N(CH.sub.3)CH.sub.2CH.sub.2OH,
R.sub.fCH.sub.2CH.sub.2SO.sub.2N(CH.sub.2CH.sub.3)CH.sub.2CH.sub.2OH,
R--(CF(CF.sub.3)CF.sub.2O).sub.yCH.sub.2OH,
CF.sub.2.dbd.CFOCF.sub.2CF(CF.sub.3)OCF.sub.2CF.sub.2CH.sub.2OH, or
R.sub.fCH.sub.2OC.sub.2F.sub.4CH.sub.2OCH.sub.2CH.sub.2OH.
Alkoylated compounds made from these alcohols are also useful as
hydrophobic surface effect agents.
[0031] The three-dimensional solid polymer articles of the present
invention optionally further comprise additional components such as
surfactants, pH adjusters, cross linkers, wetting agents, pigments,
and other functional additives known by those skilled in the
art.
[0032] The invention further relates to a method of imparting a
surface effect to a polymeric article comprising contacting a
flowable or liquid polymer composition with 0.1% by weight to 20%
by weight of a hydrophobic compound, based on the total weight of
the polymer composition, to form a treated polymer composition, and
allowing or causing the polymer composition to solidify to form a
treated polymeric article, where the treatment composition
comprises a hydrophobic compound selected from a cyclic sugar
alcohol which is substituted with at least two R.sup.1,
--C(O)R.sup.1,
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mR.sup.2,
--(CH.sub.2CH.sub.2O).sub.n(CH(CH.sub.3)CH.sub.2O).sub.mC(O)R.sup.1,
or mixtures thereof; where the cyclic sugar alcohol is selected
from a saccharide, reduced sugar, aminosaccharide, aldonic acid, or
aldonic acid lactone; wherein each n is independently 0 to 20; each
m is independently 0 to 20; m+n is greater than 0; each R.sup.1 is
independently a linear or branched alkyl group having 5 to 29
carbons; each R.sup.2 is independently H, a linear or branched
alkyl group having 6 to 30 carbons.
[0033] The contacting step may occur by any conventional method,
including standard mixing, with a molten polymer composition, with
a flowable polymer composition, with a polymer composition
dispersion, or with a polymer composition solution. Following the
contacting step, the polymer composition having the hydrophobic
compound intermixed may be solidified by any conventional method,
including by drying, by cooling, or by causing to cool. Drying may
be completed with or without heating. Solidification may occur
before or after the formation and shaping of the three-dimensional
article. The three-dimensional article is formed by any
conventional method, including molding, extruding, or spinning a
liquid polymer composition having the hydrophobic compound
intermixed therein; by thermoforming sheets of the polymeric
composition having the hydrophobic compound intermixed therein. For
example, a thermoplastic polymer resin may be mixed with the
hydrophobic compound while molten, may be extruded and shaped into,
for example, fibers, and may be cooled to form the
three-dimensional article. The solid three-dimensional polymeric
articles are useful in applications including, but not limited to,
moisture and grease-resistant packaging, release liners, multilayer
constructions, oil- and water-repellent carpet fibers, oil- and
water-repellent textile fibers, repellent medical non-woven
fabrics, and repellent caulks and other filling sealers.
Materials and Test Methods
[0034] All solvents and reagents, unless otherwise indicated, were
purchased from Sigma-Aldrich, St. Louis, Mo., and used directly as
supplied.
[0035] Sorbitan tristearate is available from DuPont Nutrition
& Health, Copenhagen, Denmark.
[0036] HYTREL 3078 is a thermoplastic polyester elastomer copolymer
commercially available from DuPont, Wilmington, Del.
Test Method 1. Evaluation of Water Repellency Via Contact Angle
Measurement
[0037] Water contact angle measurements are used to test for the
migration of additive to the surface of the compression molded
sheet samples. Testing is performed by a Ramo-Hart Standard
Automated Goniometer Model 200 employing DROPimage standard
software and equipped with an automated dispensing system, 250
.mu.l syringe, and illuminated specimen stage assembly is used. The
goniometer camera is connected through an interface to a computer,
allowing the droplet to be visualized on a computer screen. The
horizontal axis line and the cross line can both be independently
adjusted on the computer screen using the software.
[0038] Prior to contact angle measurement, the sample is placed on
the sample stage and the vertical vernier is adjusted to align the
horizontal line (axis) of the eye piece coincident to the
horizontal plane of the sample. The horizontal position of the
stage relative to the eye piece is positioned so as to view one
side of the test fluid droplet interface region at the sample
interface.
[0039] To determine the contact angle of the test fluid on the
sample, approximately one drop of test fluid is dispensed onto the
sample using a 30 .mu.L pipette tip and an automated dispensing
system to displace a calibrated amount of the test fluid. Deionized
water is used for water contact angle measurements. Horizontal and
cross lines are adjusted via the software in case of the Model 200
after leveling the sample via stage adjustment, and the computer
calculates the contact angle based upon modeling the drop
appearance. The initial contact angle is the angle determined
immediately after dispensing the test fluid to the sample surface.
Initial contact angles above 30 degrees are indicators of effective
oil repellency.
Test Method 2. Friction Coefficient Measurement
[0040] The friction coefficient was measured according to ASTM
D1894 "Standard Test Method for Static and Kinetic Coefficients of
Friction of Plastic Film and Sheeting".
[0041] The sample is cut to a size of 250 mm.times.130 mm and
secured on the test plane. A second test piece is cut to 120 mm
square if the specimen is defined as a film, and 63.5 mm square if
defined as sheeting, and attached to the sled. Care is taken not to
contaminate the test pieces by handling or foreign matter and
condition according to ASTM D618.
[0042] The sled is attached to the friction tester crosshead, and
the driving mechanism is set to a speed of 150.+-.30 mm/min
(6.0.+-.1.2 in./min). The initial maximum force reading is
recorded, which is the static frictional force. The sliding is
continued for another 130 mm. An average force reading is obtained
for the kinetic friction. Five data sets are taken on separate
samples. The mean coefficient of friction is calculated as
.mu.=F/mg, where mg is the sled weight.
Test Method 3. Evaluation of Stain Cleanability
[0043] There are seven stains used to evaluate easy clean
performance on untreated and treated shims, including grape juice,
ketchup, corn oil, mustard, cola, coffee, and ink. The stains were
applied in the same layout for each substrate, using a disposable
pipette. The volume of the stains applied with a pipette was about
50 .mu.L in order to keep the stain quantity and drop size
consistent. The stains were left to dwell for about 15 hours. Using
an aspirator, the liquid stains were vacuumed one at a time, wiping
the end of the tubing to avoid contaminating different stains.
[0044] Once all of the solid and liquid stains were removed, the
substrate was placed under a running faucet with warm water to
remove some of the stains, and the substrate was wiped and dried
with a SONTARA wipe. The samples were placed on the lab bench face
up to dry for 4 hours.
[0045] Rating Performance:
[0046] After the tile is dry rate the stains on a score of 0-4.
[0047] 0--No visible stain
[0048] 1--Slight stain perceptible
[0049] 2--Visible stain without clearly defined outline
[0050] 3--Stain with a clearly defined outline but not very deep in
color
[0051] 4--Stain with a clearly defined outline, deep in color or
stains that penetrated the tile.
Percent Easy Clean Factor (% ECF) is calculated as % ECF=[(40-sum
of scores)/40]*100%. A higher % ECF indicates better stain
release.
Examples 1-2
[0052] Pellets of HYTREL 3078 were dried at 130.degree. F. and
blended with sorbitan tristearate, which was in the form of a dry
powder, to yield a blend of 2.5% by weight sorbitan tristearate
(Example 1) and 5% by weight sorbitan tristearate (Example 2). The
powder/pellet blends were fed to a Davis Standard 1.5'' extruder
operating at 25 rpm. The extruder had a length/diameter ratio of
24:1 and was equipped with a screw fitted with a Saxton mixer
located at the end of the metering section in order to provide
uniform temperature and dispersion of the additives within the
melt. The compression ratio of the screw (depth of the feed section
to the depth of the metering section) was approximately 3.2 to 1.
The temperature profile for the extruder was kept at or below
410.degree. F. (210.degree. C.) to minimize any potential thermal
degradation.
[0053] Extrudate was processed on a wire-line to produce an
insulation .about.25 mil (.about.0.64 mm) in thickness on a 7
stranded 18 AWG bare copper conductor have a diameter of .about.48
mils (.about.1.2 mm). The material was extruded onto wire at a
speeds of .about.60 to 65 ft/min via a tubing configuration
consisting of a die have an inner diameter of 180 mils (4.6 mm) and
a guider tip outer diameter of 90 mils (2.3 mm). The die and guider
tip combinations yielded draw down ratios (cross-sectional area of
the die area/cross-sectional area of the finished extrudate) of
.about.3.5.
[0054] Additionally, extrudate was collected to be utilized in post
extrusion molding operations to create small flat sheets for
testing. The resulting extrudates were dried overnight at
130.degree. F. where they were compression molded into sheets
approximately 6 inches (.about.152 mm) square with a thickness of
.about.30 mils (.about.0.76 mm). Approximately 16.5 to 17 grams of
material was placed between two sheets of polytetrafluoroethylene
(PTFE) within a picture frame shim used to achieve the desired
dimensions. The stack consisting of the PTFE sheeting, shim, and
material was placed between 2 metal plates and then transferred to
a hot press with platens set to a temperature of 392.degree. F.
(200.degree. C.). The pressure within the press was raised and
maintained at .about.5 lbs for a time period of 8 minutes. After
this time period allowing the material to soften, the pressure was
raised to 10 tons and released multiple times within a one minute
period and then maintained at 10 tons for an additional minute
allowing the material to flow and acquire the desired dimensions.
The pressure was then released and the stack transferred to a water
cooled press where the material was held for approximately 5
minutes under low pressure until the sample cooled for removal from
the shims. The sheets were tested according to the test methods
above.
Comparative Example A
[0055] Example 1 was repeated, without the addition of sorbitan
tristearate.
TABLE-US-00001 TABLE 1 Contact Angle and Friction Coefficient
Measurement of Sheets Example Water Contact Angle Coefficient of
Friction 1 134.75 0.314 2 136.00 0.383 A 116.43 0.479
TABLE-US-00002 TABLE 2 Stain Cleanability Ratings of Sheets Example
A 1 2 Grape juice 1 0 0 ketchup 2 0 0 Corn oil 2 2 2 Mustard 4 4 3
Coke 0 0 0 Coffee 3 1 2 Ink 0 0 0 Average Rating 1.71 1.00 1.00 %
ECF 66.67 80.56 80.56
TABLE-US-00003 TABLE 3 Stain Cleanability Ratings of Extruded Wire
Example A 1 2 Grape juice 1 0 0 ketchup 2 0 0 Corn oil 2 2 2
Mustard 4 4 3 Coke 0 0 0 Coffee 3 1 2 Ink 0 0 0 Average Rating 1.71
1.00 1.00 % ECF 66.67 80.56 80.56
* * * * *