U.S. patent application number 15/946813 was filed with the patent office on 2018-08-23 for multifunctional polymers.
The applicant listed for this patent is ISP INVESTMENTS LLC. Invention is credited to Jui-Chang Chuang, Xuejun Liu, Osama M. Musa, Karen Winkowski.
Application Number | 20180237568 15/946813 |
Document ID | / |
Family ID | 49483740 |
Filed Date | 2018-08-23 |
United States Patent
Application |
20180237568 |
Kind Code |
A1 |
Chuang; Jui-Chang ; et
al. |
August 23, 2018 |
MULTIFUNCTIONAL POLYMERS
Abstract
Described herein are multifunctional polymers comprising a first
repeating unit having at least one pseudo-cationic moiety, a second
repeating unit having at least a hydrophobic moiety, and a third
repeating unit, where the weight-average molecular weight is less
than about 10,000 Da. In one embodiment the polymers exhibit
antimicrobial activity. Also provided are compositions formulated
with the multifunctional polymers, and a method of providing
antimicrobial activity.
Inventors: |
Chuang; Jui-Chang; (Wayne,
NJ) ; Liu; Xuejun; (Whippany, NJ) ; Musa;
Osama M.; (Kinnelon, NJ) ; Winkowski; Karen;
(Springfield, NJ) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ISP INVESTMENTS LLC |
Wilmington |
DE |
US |
|
|
Family ID: |
49483740 |
Appl. No.: |
15/946813 |
Filed: |
April 6, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14384111 |
Sep 9, 2014 |
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PCT/US2013/032219 |
Mar 15, 2013 |
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15946813 |
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61638670 |
Apr 26, 2012 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08F 226/10 20130101;
A01N 43/36 20130101; C08F 220/60 20130101; C08F 220/18 20130101;
C08F 220/60 20130101; C08F 220/18 20130101; C08F 226/08
20130101 |
International
Class: |
C08F 226/10 20060101
C08F226/10; C08F 220/18 20060101 C08F220/18; A01N 43/36 20060101
A01N043/36; C08F 220/60 20060101 C08F220/60; C08F 226/08 20060101
C08F226/08 |
Claims
1-13. (canceled)
14. A terpolymer having structure ##STR00044## wherein: R.sub.1 and
R.sub.4 are independently selected from the group consisting of
hydrogen, methyl, and combinations thereof, R.sub.2 and R.sub.3 are
independently selected C1-C20 alkyl, R.sub.5 is selected from the
group consisting of functionalized and unfunctionalized alkyl,
alkoxy, cycloalkyl, alkenyl, and aryl, R.sub.6 and R.sub.7 are
selected from the group consisting of functionalized and
unfunctionalized alkyl, alkoxy, cycloalkyl, alkenyl, and aryl, and
wherein R.sub.6 and R.sub.7 may form a 5 to 7-membered ring, Q is
selected from the group consisting of functionalized and
unfunctionalized alkylene, alkyleneoxy, cycloalkylene, alkenylene,
and arylene, X is O, NH, or combinations thereof, and a, b, and c
are molar ratios equaling 100%.
15. The terpolymer according to claim 14 wherein said a ranges from
about 5% to about 80%, said b ranges from about 5% to about 60%,
and said c ranges from about 5% to about 80% (all molar
ratios).
16. (canceled)
17. The terpolymer according to claim 14, wherein said terpolymer
exhibits antimicrobial activity against a microbe selected from the
group consisting of S. aureus, E. coli, P. aeruginosa, A. niger, C.
albicans, and mixtures thereof.
18-21. (canceled)
22. A composition comprising a terpolymer having the structure:
##STR00045## wherein: R.sub.1 and R.sub.4 are independently
selected from the group consisting of hydrogen, methyl, and
combinations thereof, R.sub.2 and R.sub.3 are independently
selected C1-C20 alkyl, R.sub.5 is selected from the group
consisting of functionalized and unfunctionalized alkyl, alkoxy,
cycloalkyl, alkenyl, and aryl, R.sub.6 and R.sub.7 are selected
from the group consisting of functionalized and unfunctionalized
alkyl, alkoxy, cycloalkyl, alkenyl, and aryl, and wherein R.sub.6
and R.sub.7 may form a 5 to 7-membered ring, Q is selected from the
group consisting of functionalized and unfunctionalized alkylene,
alkyleneoxy, cycloalkylene, alkenylene, and arylene, X is O, NH, or
combinations thereof, and a, b, and c are molar ratios equaling
100%.
23. The composition according to claim 22 that is a nutrition,
food, beverage, pharmaceutical, cleaning, coating, paint, biocide,
construction, energy, industrial, oilfield, personal care,
household, performance, agricultural, pesticide, veterinary, fuel,
lubricant, adhesive, electronic, textile, ink, or membrane
composition.
24. The composition according to claim 23, wherein said personal
care composition is a skin lotion, skin creme, skin ointment, skin
salve, anti-aging creme, moisturizer, deodorant, tanning agent, sun
block, sunscreen, foundation, concealer, eyebrow pencil, eye
shadow, eye liner, mascara, rouge, finishing powder, lipstick, lip
gloss, nail polish, make-up remover, nail polish remover, shampoo,
rinse-off conditioner, leave-on conditioner, hair styling gel, hair
mousse, hair spray, styling aide, hair color, or hair color
remover.
25. The composition according to claim 22, wherein the terpolymer
exhibits antimicrobial activity against a microbe selected from the
group consisting of S. aureus, E. coli, P. aeruginosa, A. niger, C.
albicans, and mixtures thereof.
26. (canceled)
27. A method of providing antimicrobial activity, said method
comprising the step: contacting a composition with at least one
terpolymer having the structure: ##STR00046## wherein: R.sub.1 and
R.sub.4 are independently selected from the group consisting of
hydrogen, methyl, and combinations thereof, R.sub.2 and R.sub.3 are
independently selected C1-C20 alkyl, R.sub.5 is selected from the
group consisting of functionalized and unfunctionalized alkyl,
alkoxy, cycloalkyl, alkenyl, and aryl, R.sub.6 and R.sub.7 are
selected from the group consisting of functionalized and
unfunctionalized alkyl, alkoxy, cycloalkyl, alkenyl, and aryl, and
wherein R.sub.6 and R.sub.7 may form a 5 to 7-membered ring, Q is
selected from the group consisting of functionalized and
unfunctionalized alkylene, alkyleneoxy, cycloalkylene, alkenylene,
and arylene, X is O, NH, or combinations thereof, and a, b, and c
are molar ratios equaling 100%.
28. The method according to claim 27 that provides antimicrobial
activity against a microbe selected from the group consisting of S.
aureus, E. coli, P. aeruginosa, A. niger, C. albicans, and
combinations thereof.
29. The terpolymer according to claim 14 wherein said Q is C2-C20
alkylene.
30. The composition according to claim 22 wherein in the terpolymer
said Q is C2-C20 alkylene.
31. The method according to claim 27 wherein in the terpolymer said
Q is C2-C20 alkylene.
32. The terpolymer according to claim 14 wherein said R.sub.5 is
C1-C20 alkyl.
33. The composition according to claim 22 wherein in the terpolymer
said R.sub.5 is C1-C20 alkyl.
34. The method according to claim 27 wherein in the terpolymer said
R.sub.5 is C1-C20 alkyl.
Description
BACKGROUND
Field of the Invention
[0001] The invention provides multifunctional polymers comprising a
repeat unit having a pseudo-cationic moiety, a repeat unit having a
hydrophobic moiety, and a third repeat unit. In one embodiment the
polymer has a weight-average molecular weight of less than about
10,000 Da. In another embodiment the polymers exhibit antimicrobial
activity. The polymers may be prepared by known polymerization
methods, such as radical or condensation polymerization. Depending
upon the repeating unit types and ratios, the resulting polymers
can have a wide variety of physical and chemical properties. The
multifunctional polymers of the invention can be employed in a wide
variety of compositions. Also disclosed is a method of providing
antimicrobial activity through the use of the multifunctional
polymers.
Description of Related Art
[0002] Antimicrobial compounds are widely used in many
formulations, where they may assist in killing or inhibiting the
growth and presence of microbes as bacterium, fungus, or protozoan,
or combinations thereof. In the personal care arts antimicrobial
compounds may be called "preservatives," while in non-personal care
applications-such as adhesives, coatings, inks, membranes,
textiles, and paints-antimicrobial compounds may be called
"biocides." Regardless, regulatory and environmental concerns have
put limits on the selection and usage of traditional preservatives.
Non-traditional antimicrobial compounds, such as multifunctional
polymers, have attracted much attention in the chemical industry.
Antimicrobial polymers are nonvolatile, do not penetrate the skin,
have better long-term efficiency and possibly higher selectivity
compared to traditional preservatives. Antimicrobial polymers also
minimize environmental problems by minimizing residual
toxicity.
[0003] Multifunctional polymers are described in the following
disclosures, each of which is incorporated herein by reference. De
Grado, et al., in J. Am. Chem. Soc., 2005, 127, 4128, and U.S. Pat.
Appl. No. 2006/0024264 disclose the synthesis and uses of
amphiphilic polymethacrylate derivatives as antimicrobial agents.
Kuroda, et al., in Chem. Eur. J. , 2009, 15, 1123, describes the
role of hydrophobicity in the antimicrobial and hemolytic
activities of polymethacrylate derivatives. Gellman, et al., in
Org. Lett., 2004, 4, 557, discloses the biocidal activity of
polystyrene derivatives bearing cationic properties through
reversible amine protonation. U.S. Pat. No. 6,214,885 describes the
use of polymers containing .beta.-hydroxyalkylvinylamine units as
biocides. U.S. Pat. No. 5,208,016 discloses antimicrobial resin
compositions containing ethylene copolymer from radical
polymerization of ethylene and dialkylaminoalkylacrylamide
co-repeating units.
[0004] Other references related to these polymers include the
following patents and patent applications: EP 40,498; GB 686,381;
730,463; 870,398; 922,878; 1,286,966; 1,329,033; JP 53,090,397;
57,161,859; U.S. Pat. Nos. 3,449,250; 3,555,001; 4,048,422;
4,058,491; 4,734,446; 4,767,616; 5,229,458; 5,352,729; 5,408,022;
5,449,775; 5,492,988; 5,756,181; 6,025,501; 6,071,993; 6,075,107;
6,299,866; 6,646,082; 6,682,725; 6,737,049; 6,838,078; 6,951,598;
7,033,607; 7,041,281; 7,323,163; 7,326,262; 7,592,040; 7,955,594;
US 2005/0152855; 2006/0024264; 2007/0082196; 2007/0161519;
2007/0238807; 2009/0029129; 2009/0312214; 2010/00029838;
2010/00298504; 2010/0130678; 2010/0137455; 2010/0174040;
2011/0060166, and WO 2010/0014655; 2010/031144 and
PCT/U513/030115.
[0005] Accordingly, there is a need for multifunctional polymers to
alter or improve the physicochemical properties of such
polymers.
SUMMARY
[0006] The invention provides polymers that are polymerized from
(A) a first repeating unit A comprising at least one
pseudo-cationic moiety, (B) a second repeating unit B comprising at
least one hydrophobic moiety, and (C) a third repeating unit C, and
wherein the weight-average molecular weight of said polymer is less
than about 10,000 Da. The polymer may be a terpolymer or comprise
more than three repeating units. Additionally, the polymers may be
synthesized via radical or condensation polymerization
techniques.
[0007] In one embodiment, the polymers may exhibit antimicrobial
activity.
[0008] Also provided are compositions having one or more of the
multifunctional polymers, as well as a method of providing
antimicrobial activity.
DETAILED DESCRIPTION
[0009] Described herein are polymers that are polymerized from at
least three repeating unit types that are distinctly different from
those known in the related art. In one embodiment, the polymers may
exhibit antimicrobial properties, such as being microbiocidal
and/or microbiostatic, which may lend their use in any number of
formulations that may benefit from this effect. As a non-limiting
aspect of this embodiment, the polymers may exhibit a broad
spectrum of activity against many different types of microbes,
including activity against S. aureus, E. coli, and P. aeruginosa.
In another non-limiting aspect, the polymers may be formulated into
compositions.
[0010] As used herein, the following terms have the meanings set
out below.
[0011] The term "microbe" refers to any bacterium, fungus,
protozoan, and any combination thereof.
[0012] The term "antimicrobial" refers to a substance that kills or
inhibits the growth of microbes such as bacterium, fungus, or
protozoan, or combinations thereof. Antimicrobials may kill
microbes (microbiocidal) and/or prevent the growth of microbes
(microbiostatic). The term "antimicrobial activity" refers to
activity that kills and/or inhibits the growth of one or more
microbes.
[0013] The term "functionalized" refers to replacing one or more
hydrogens with one or more non-hydrogen groups, for e.g., alkyl,
alkoxy, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, and/or aryl
groups. Alkyl, alkenyl and/or alkynyl groups include
C.sub.1-C.sub.60, more particularly C.sub.1-C.sub.36, and most
particularly C.sub.1-C.sub.18 groups. Cycloalkyl groups include
cyclopentane, cyclohexane, cycloheptane, and the like. Alkoxy
groups include methoxy, ethoxy, n-propoxy, isopropoxy, and the
like. Aryl groups include benzenes, naphthalenes (2 rings),
anthracenes (3 rings), and the like.
[0014] The term "anion" refers to an ion with more electrons than
protons, giving it a net negative charge.
[0015] The term "cation" refers to an ion with fewer electrons than
protons, giving it a net positive charge.
[0016] The term "halogenated" refers to chloro, bromo, iodo and
fluoro. In one embodiment halogen may be bromo and/or chloro.
[0017] The term "branched and unbranched alkyl groups" refers to
alkyl groups which may be straight chained or branched. The alkyl
group may have from 1 to about 18 carbon atoms, more particularly,
from 1 to about 10 carbon atoms, and yet more particularly from 1
to about 6 carbon atoms. Branched groups include iso-propyl,
tert-butyl, sec-butyl, and the like.
[0018] The term "hydrocarbyl" refers to straight-chain and/or
branched-chain groups comprising carbon and hydrogen atoms with
optional heteroatom(s). Particularly, the hydrocarbyl group
includes C.sub.1-C.sub.60, more particularly C.sub.1-C.sub.36, and
most particularly C.sub.1-C.sub.18 alkyl and alkenyl groups
optionally having one or more hetero atoms. The hydrocarbyl group
may be mono-, di- or polyvalent.
[0019] The term "heteroatom" refers to oxygen, nitrogen, sulfur,
silicon, and/or phosphorous. The heteroatom may be present as a
part of one or more functional groups on the hydrocarbyl chain
and/or as a part of the hydrocarbyl chain itself. When the
heteroatom is a nitrogen atom, the nitrogen atom may be present in
the form of a quaternary amine.
[0020] The term "generic substituent(s)" refer(s) to substituent(s)
such as R.sub.1-R.sub.6, and subscripts a, b, and c used and
defined in the invention.
[0021] The term "amphiphilic" refers to a compound possessing both
hydrophilic (water-loving, polar) and hydrophobic (lipophilic,
fat-loving, non-polar) properties. Such compounds are also referred
to as amphipathic.
[0022] The term "C1-C20 alkyl" refers to groups such as: methyl,
ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl,
tert-butyl, n-pentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl,
n-octyl, 2-ethylhexyl, n-nonyl, iso-nonyl, 2-propylheptyl, n-decyl,
n-dodecyl, n-tridecyl, iso-tri-decyl, n-tetradecyl, n-hexydecyl,
n-octadecyl and eicosyl.
[0023] The term "C1-C20 alkylene" refers to groups such as:
methylene, ethylene, n-propylene, iso-propylene, n-butylene,
iso-butylene, sec-butylene, tert-butylene, n-pentylene,
sec-pentylene, tert-pentylene, n-hexylene, n-heptylene, n-octylene,
2-ethylhexylene, n-nonylene, iso-nonylene, 2-propylheptylene,
n-decylene, n-dodecylene, n-tridecylene, iso-tri-decylene,
n-tetradecylene, n-hexydecylene, n-octadecylene and eicosylene.
[0024] The term "pseudo-cationic moiety" refers to moiety
comprising one or more functionalized and unfunctionalized nitrogen
or phosphorus.
[0025] The term "repeating unit" refers to a small molecule that
chemically bonds during polymerization to one or more repeating
units of the same or different kind to form a polymer.
[0026] The term "(meth)acrylate" refers to both methacrylate and
acrylate. Similarly, the term "(meth)acrylamide" refers to both
methacrylamide and acrylamide.
[0027] The term "polymer" refers to a large molecule
(macromolecule) comprising repeating structural units polymerized
from one or more repeating units connected by covalent chemical
bonds.
[0028] The term "polymerization" refers to methods for chemically
reacting repeating units to form polymer chains. The type of
polymerization method may be selected from a wide variety of
methods. Such methods include, but are not limited to, free radical
polymerization, such as classical radical polymerization and
controlled radical polymerization, Nitroxide Mediation
Polymerization (NMP), Atom Transfer Radical Polymerization (ATRP),
and Reversible Addition Fragmentation Chain-Transfer (RAFT). The
term polymerization" also refers to condensation polymerization
methods.
[0029] The term "homopolymer" refers to a polymer comprising
essentially one type of repeating unit. Homopolymers include
polymers polymerized from one repeating unit that may be modified
during or after polymerization, for example, by grafting,
hydrolyzing, or end-capping. Homopolymers may be associated with
solvent adducts.
[0030] The term "non-homopolymer" refers to a polymer obtained by
polymerization of two or more different kinds of repeating units.
The definition includes essentially all polymers that are not
homopolymers. Nonlimiting examples of non-homopolymers include
copolymers, terpolymers, tetramers, and the like, wherein the
non-homopolymer may be a random, block, or an alternating
polymer.
[0031] The term "hydrophilic" refers to a molecular entity that
tends to be polar and water-soluble or water-miscible. A
hydrophilic molecule or portion of a molecule may be
charge-polarized and/or capable of hydrogen bonding enabling it to
dissolve in water.
[0032] The term "hydrophobic" refers to a molecular entity that
tends to be non-polar and non-water-soluble.
[0033] The term "inert solvent" refers to a solvent that does not
interfere chemically with the reaction.
[0034] The term "lower molecular weight alcohols" refers to
alcohols having from one to four carbon atoms. Examples of lower
molecular weight alcohols include: methanol, ethanol, 1-propanol,
2-propanol, allyl alcohol, propargyl alcohol, 2-aminoethanol,
ethylene glycol, methyl propargyl alcohol, 1-butyn-4-ol,
2-butyn-1-ol, 2-buten-1-ol, 2-butanol, 2-methyl-2-propanol, and
tert-butanol. In various embodiments of the invention, the lower
molecular weight alcohol may be methanol, ethanol, 1-propanol,
2-propanol, or tert-butanol, or combinations thereof.
[0035] The term "quaternary ammonium cation" , also known as
"quat," refers to a positively charged polyatomic ion having the
structure NR'.sub.4.sup.+, wherein each of the four R'
independently can be an alkyl group or an aryl group. Unlike the
ammonium ion (NH.sub.4.sup.+) and primary, secondary, and tertiary
ammonium cations, the quaternary ammonium cations are permanently
charged, independent of the pH value of their solution.
Accordingly, quaternary ammonium cations are accompanied by an
anion (negative charge) to balance the overall charge.
[0036] The term "each independently selected from the group
consisting of" means that when a group appears more than once in a
structure, that group may be independently selected each time it
appears. For example, in the structure below:
##STR00001##
the generic substituent R.sub.6 appears more than once. The term
"each independently selected from the group consisting of" means
that each generic substituent may be the same or different.
[0037] The term "weight-average molecular weight" refers to a
method of describing the molecular weight of a polymer, and may be
calculated by the equation:
M w = i N i M i 2 i N i M i ##EQU00001##
wherein N.sub.i is the number of molecules having molecular weight
M.sub.i.
[0038] The term "number-average molecular weight" refers to another
method of describing the molecular weight of a polymer, and may be
calculated by the equation:
M n = i N i M i i N i ##EQU00002##
wherein N.sub.i is the number of molecules having molecular weight
M.sub.i.
[0039] The term "personal care composition," also referred to as
"cosmetics," refer to such illustrative non-limiting compositions
as skin, sun, oil, hair, and preservative compositions, including
those to alter the color, condition, or appearance of the skin.
Potential personal care compositions include, but are not limited
to, compositions for increased flexibility in styling, durable
styling, increased humidity resistance for hair, skin, color
cosmetics, water-proof/resistance, wear-resistance, and thermal
protecting/enhancing compositions. Examples of personal care
compositions include: skin lotion, skin creme, skin ointment, skin
salve, anti-aging creme, moisturizer, deodorant, tanning agent, sun
block, sunscreen, foundation, concealer, eyebrow pencil, eye
shadow, eye liner, mascara, rouge, finishing powder, lipstick, lip
gloss, nail polish, make-up remover, nail polish remover, shampoo,
rinse-off conditioner, leave-on conditioner, hair styling gel, hair
mousse, hair spray, styling aide, hair color, or hair color
remover.
[0040] The term "performance chemicals composition" refers to any
non-personal care composition. Performance chemicals compositions
serve a broad spectrum of arts, and include non-limiting
compositions such as: adhesives; agricultural, biocides, coatings,
electronics, household-industrial-institutional (HI&I), inks,
membranes, metal fluids, oilfield, paper, paints, plastics,
printing, plasters, and wood-care compositions.
[0041] The term "oilfield formulation" refers to a composition that
may be used in the exploration, extraction, recovery, or completion
of any hydrocarbon-based fuel. Non-limiting examples of oilfield
formulations include anti-agglomerants, emulsifiers,
de-emulsifiers, gas hydrate inhibitors, kinetic hydrate inhibitors,
shale swelling inhibitors, drilling fluids, drilling muds, friction
reducers, rheology modifier, fracturing fluids, and/or scale
inhibitors.
[0042] The term "coating formulation" refers to any composition
suitable for application on a substrate in order to provide one or
more desired functions, including, but not limited to protecting,
smoothing, strengthening, decorating, color enhancing/altering,
substrate preparing and/or texturizing. The substrate for a coating
formulation may include, without limitation, paper, paper board,
wood, inorganic substrate, woven and non-woven textiles, metal,
leather, powder, plastic, polymer, glass, cement, ceramic, traffic,
tile, rubber, sealant, cable, concrete, plasterboard, adhesives,
fillers, primers, inks, fertilizers, pharmaceuticals, structural
materials, molding, printing, inks, and the like. Examples of
coating formulations include, without limitation, the following:
paints, primers, stains, sealers, varnishes/polyurethanes,
adhesives, waterproofers, wood hardeners. Coating formulations may
be applied by brush, dauber, roll, strip/sheet, and/or trowel, or
may be atomized and applied as a spray, mist, or droplet.
[0043] A "paint formulation" is a non-limiting, specific type of a
"coating formulation". Paints may be water based or non-water based
(i.e., solvent based). Paint formulations may be designed for any
number of substrates, including wood, siding, dry wall, plaster,
plastics, masonry, brick, tile, particle board, glass, stucco,
concrete, and the like. Non-limiting examples of paints include
exterior paints, interior paints, architectural paints, and
automotive paints.
[0044] The term "imide" refers to an organic compound comprising
two carbonyl groups (acyl groups) bound to a common nitrogen atom.
The nitrogen atom in the imide functional group may or may not be
substituted with an organic functional group.
[0045] The term "Jeffamine" is a brand name of The Huntsman
Corporate and refers to polyetheramines containing primary amino
groups attached to the end of a polyether backbone. The polyether
may be based on either propylene oxide (PO), ethylene oxide (EO),
or mixed PO/EO. The polyetheramines undergo typical amine
reactions, often imparting increased flexibility, toughness, low
viscosity, and low color. The wide range of molecular weight, amine
functionality, repeating unit type, and distribution can provide
flexibility in the design of new compounds or mixtures. Jeffamines
are available from Huntsman Corporation, The Woodlands, Tex.
[0046] Multifunctional polymers have been discovered that are
polymerized from at least repeating unit (or repeat unit) types: A
first repeating unit A comprising at least one pseudo-cationic
moiety, a second repeating unit B that comprises at least one
hydrophobic moiety, and a third repeating unit C, and wherein the
weight-average molecular weight of the polymer is less than about
10,000 Da. Without being bound by theory, it is believed that the
combination of repeating units A and B contribute antimicrobial
activity, and repeating unit C allows for additional performance
functionality.
[0047] The polymers may be random, block, or alternating, or
combinations thereof.
[0048] At least two broad categories of polymers are embraced by
the invention, their repeating unit (or repeat unit) types
determined in part by the polymerization method. Multifunctional
polymers prepared by a radical polymerization approach are
summarized first, followed by polymers synthesized by condensation
polymerization. These polymers comprise at least one first
repeating unit A, at least one second repeating unit B, and at
least one third repeating unit C.
[0049] By a radical polymerization method, repeating unit A may be
any repeating unit having at least one pseudo-cationic moiety. For
example, repeating unit A may be an amino (meth)acrylate, amino
(meth)acrylamide, or a repeating unit comprising a nitrogen or
phosphorus heterocyclic ring, or combinations of these repeating
units. These repeating units may exhibit pseudo-cationic behavior,
e.g., in acid conditions, e.g., by protonation under acidic
conditions.
[0050] In the embodiments wherein repeating unit A is an amino
(meth)acrylate or an amino (meth)acrylamide , it may be represented
by the structure:
##STR00002## [0051] wherein [0052] R.sub.1, is selected from the
group consisting of hydrogen, methyl, and combinations thereof;
[0053] R.sub.2 and R.sub.3 are independently selected from the
group consisting of C1-C20 alkyl, [0054] Q is selected from the
group consisting of functionalized and unfunctionalized alkylene,
cycloalkylene, alkyleneoxy, alkenylene, and arylene; and [0055] X
is O or NH or combinations thereof.
[0056] In the amino (meth)acrylate and amino (meth)acrylamide
structure presented earlier, R.sub.1 may be hydrogen or methyl,
such that repeating unit A may be regarded as an amino
(meth)acrylate or amino (meth)acrylamide:
##STR00003##
where R.sub.2, R.sub.3, and Q retain their earlier definitions.
Particularly, Q may be C1-C8 alkylene, more particularly C2-C5
alkylene. R.sub.2 and R.sub.3 may be C1-C4 alkyl groups.
Non-limiting examples of the second repeating unit include:
##STR00004##
[0057] Optionally, repeating unit A may comprise a nitrogen or
phosphorus heterocyclic ring, such as functionalized and
unfunctionalized N-vinyl lactams, vinyl pyridines, vinyl
imidazoles, and/or vinyl pyrazoles. Included in this aspect of the
invention are the following polymerizable compounds: N-vinyl
imidazole, N-vinyl benzimidazole, N-vinyl-pyrazole,
N-vinyl-3-imidazoline, N-(C1-C20-alkyl)-N'-vinyl piperazine or 2-,
3- or 4-vinyl pyridine, and hydroxyethylimidazole (meth)acrylate.
One or more C1-C20-alkyl groups, which can be substituents in the
aforementioned repeating units can be methyl, ethyl, n-propyl,
iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl,
sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl,
n-nonyl, iso-nonyl, 2-propylheptyl, n-decyl, n-dodecyl, n-tridecyl,
iso-tri-decyl, n-tetradecyl, n-hexydecyl, n-octadecyl and
eicosyl.
[0058] Combinations of the repeating units may be used.
[0059] Turning now to repeating unit B, it is repeating unit
comprising at least one hydrophobic moiety. Thus, repeating unit B
may be any polymerizable repeating unit that exhibits hydrophobic
character, or another polymer having been functionalized with one
or more hydrophobic moieties. Within the context of radical
polymerization, repeating unit B may be any functionalized and
unfunctionalized: (meth)acrylates, (meth)acrylamides, styrenes,
4-vinyl-1,2,3-triazoles, 5-vinyl-1,2,3-triazoles, vinyls, allyls,
maleic anhydrides, fumarates, maleates, maleimides,
.alpha.-.beta.-olefinically unsaturated carboxylic nitriles,
styrenes, vinyl ethers, vinyl esters, vinyl acetates, vinyl amides,
vinyl alcohols, vinyl carbonates, vinyl carbamates, vinyl
thiocarbamates, vinyl ureas, vinyl halides, vinyl imidazoles, vinyl
lactams, vinyl pyridines, vinyl silanes, vinyl siloxanes, vinyl
sulfones, and/or allyl ethers.
[0060] Examples of hydrophobic alpha-olefins include isobutene,
diisobutene, butene, pentene, hexene and additional olefins having
5 or more carbon atoms or mixtures thereof, such as, for example,
1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene,
1-eicosene, 1-docosene, 1-tetracosene and 1-hexacosene. The
hydrophobic alpha-olefin may be a C.sub.22-alpha-olefin, a mixture
of C.sub.20-C.sub.24-alpha-olefins and polyisobutene with, on
average, 12 to 100 carbon atoms.
[0061] Further examples of hydrophobic repeating units B are known,
including the (meth)acrylate and (meth)acrylamide families of
repeating units. Includes in these classes are those repeating
units represented by the structure:
##STR00005## [0062] wherein [0063] R.sub.4 is selected from the
group consisting of hydrogen, methyl, and combinations thereof,
[0064] R.sub.5 is selected from the group consisting of
functionalized and unfunctionalized alkyl, alkoxy, cycloalkyl,
alkenyl, and aryl, and [0065] X is selected from the group
consisting of O, NH, and combinations thereof.
[0066] Non-limiting examples of hydrophobic (meth)acrylates
include: ethyl methacrylate, butyl methacrylate, hexyl
methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate,
lauryl methacrylate, isobutyl methacrylate, isodecyl methacrylate,
phenyl methacrylate, decyl methacrylate, 3,3,5-trimethylcyclohexyl
methacrylate, benzyl methacrylate, cyclohexyl methacrylate, stearyl
methacrylate, tert-butyl methacrylate, tridecyl methacrylate,
2-naphthyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate,
1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 2,2,2-trifluoroethyl
methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate,
2,2,3,4,4,4-hexafluorobutyl methacrylate,
2,2,3,3,4,4,4-heptafluorobutyl methacrylate,
2,2,3,3,4,4,5,5-octafluoropentyl methacrylate,
3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl methacrylate, and
3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl
methacrylate.
[0067] Hydrophobic repeating units B also are provided when X is
NH. As with the (meth)acrylates, in particular embodiments R.sub.5
may comprise 2 or more carbon atoms, and more particularly, from
about 4 to about 50 or even more carbon atoms, and yet more
particularly from about 4 to 30 carbon atoms. Non-limiting examples
of hydrophobic (meth)acrylamides include: ethyl (meth)acrylamide,
butyl (meth)acrylamide, hexyl (meth)acrylamide, 2-ethylhexyl
(meth)acrylamide, octyl (meth)acrylamide, lauryl (meth)acrylamide,
isobutyl (meth)acryl amide, isodecyl (mcth)acrylamidc, phenyl
(meth)acrylamide, decyl (mcth)acrylamidc,
3,3,5-tri(methyl)cyclohexyl (meth) acrylamide, benzyl
(meth)acrylamide, cyclohexyl (meth)acrylamide, stearyl
(meth)acrylamide, tert-butyl (meth) acrylamide, tridecyl
(meth)acrylamide, 2-naphthyl (meth)acrylamide,
2,2,3,3-tetrafluoropropyl (meth)acrylamide,
1,1,1,3,3,3-hexafluoroisopropyl (meth)acrylamide,
2,2,2-trifluoroethyl (meth)acrylamide, 2,2,3,3,3-pentafluoropropyl
(meth)acrylamide, 2,2,3,4,4,4-hexafluorobutyl (meth)acrylamide,
2,2,3,3,4,4,4-heptafluorobutyl (meth)acrylamide,
2,2,3,3,4,4,5,5-octafluoropentyl (meth)acrylamide,
3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl (meth)acrylamide, and
3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl
(meth)acrylamide.
[0068] The invention embraces other hydrophobic repeating units,
such as the styrene family of repeating units. Non-limiting
examples thereof include the following: 1-vinyl naphthalene,
2-vinyl naphthalene, a-methyl styrene, 3-methyl styrene, 4-propyl
styrene, t-butyl styrene, 4-cyclohexyl styrene, 4-dodecyl styrene,
2-ethyl-4-benzyl styrene, and 4-(phenyl butyl) styrene.
[0069] Examples of hydrophobic alkyl vinyl ethers that may be used
as repeating unit B include methyl vinyl ether, ethyl vinyl ether,
iso-propyl vinyl ether, n-butyl vinyl ether, iso-butyl vinyl ether,
sec-butyl vinyl ether, octyl vinyl ether, decyl vinyl ether,
dodecyl vinyl ether, hexadecyl vinyl ether, octadecyl vinyl ether,
and combinations thereof.
[0070] It was mentioned earlier that the hydrophobic repeating unit
B may be a repeating unit that is functionalized to impart
hydrophobic character. Such functionalization includes those
reactions to graft, add, or substitute one or more hydrophobic
moieties to the repeating unit or polymer. To help illustrate this
point, a suitable hydrophobic repeating unit B may be attained by
reacting a polymerizable anhydride with a compound having at least
one moiety that is reactive to the anhydride. The anhydride may be
maleic anhydride, methyl maleic anhydride, dimethyl maleic
anhydride, itaconic anhydride, citraconic anhydride, and
tetrahydrophthalic anhydride, as well as their functionalized
analogues. The moiety reactive to the anhydride may be a hydroxyl,
amine, or thiol moiety so that a hydrophobically-modified anhydride
results. The hydrophobic moiety may be any functionalized or
unfunctionalized alkylene, alkyleneoxy, cycloalkylene, alkenylene,
arylene with or without heteroatoms, and combinations thereof.
Particularly, the hydrophobic moiety may comprise 2 to 50 carbon
atoms, more particularly from 2 to 20 carbon atoms. The
modification may be realized through the hydrophobic modification
of the pre-polymerized repeating unit, or after polymerization with
intact reactive groups on the polymer.
[0071] Polymers of the invention are polymerized from at least a
repeating unit C that is chosen in order to modulate the polymer's
properties as appropriate. Monomer C may be hydrophobic,
hydrophilic, or amphiphilic; combinations may be used. One or more
repeating unit C may be selected from the group consisting of
functionalized and unfunctionalized: (meth)acrylates,
(meth)acrylamides, styrenes, 4-vinyl-1,2,3-triazoles,
5-vinyl-1,2,3-triazoles, vinyls, allyls, maleic anhydrides,
fumarates, maleates, maleimides, .alpha.-.beta.-olefinically
unsaturated carboxylic nitriles, styrenes, vinyl ethers, vinyl
esters, vinyl acetates, vinyl amides, vinyl alcohols, vinyl
carbonates, vinyl carbamates, vinyl thiocarbamates, vinyl ureas,
vinyl halides, vinyl imidazoles, vinyl lactams, vinyl pyridines,
vinyl silanes, vinyl siloxanes, vinyl sulfones, allyl ethers, and
combinations thereof. One skilled in the art understands how to
polymerize these repeating units with repeating units A and B,
e.g., radical, emulsion, cationic, anionic polymerization
methods.
[0072] In one non-limiting example, repeating unit C is an amide,
and may be an N-vinyl amide represented by the structure:
##STR00006##
wherein R.sub.6 and R.sub.7 are selected from the group consisting
of functionalized and unfunctionalized alkyl, alkoxy, cycloalkyl,
alkenyl, and aryl groups, and where R.sub.6 and R.sub.7 may form a
ring having from 5 to 7 carbon atoms.
[0073] In one embodiment, R.sub.6 and R.sub.7 may be independently
selected from the group consisting of hydrogen and methyl. Examples
of repeating unit C in this embodiment may include repeating units
represented by the structure:
##STR00007##
and combinations thereof.
[0074] Alternatively, R.sub.6 and R.sub.7 may form a ring
structure, and repeating unit C may be represented by the
structure:
##STR00008##
where n is an integer from 1 to 3. Examples of such repeating units
include those having the structures:
##STR00009##
and combinations thereof.
[0075] In another embodiment, repeating unit C may be a
(meth)acrylate and/or (meth)acrylamide, such as those described
earlier for repeating unit B except repeating unit C does not have
to be hydrophobic.
[0076] Other examples of repeating unit C include, without
limitation:
##STR00010## ##STR00011## ##STR00012##
wherein each R is independently selected from the group consisting
of hydrogen, and functionalizcd and unfunctionalized alkyl,
cycloalkyl, alkenyl, and aryl groups, wherein any of the
beforementioned groups may be with or without heteroatoms, and m
and n are integers greater than or equal to 1.
[0077] Combinations of repeating units A, B, and/or C may be used
(i.e., the multifunctional polymer may be a terpolymer, a
tetrapolymer, or comprise more than 4 repeat units).
[0078] In addition to radical polymerization, polymers embraced by
the invention include those synthesized by condensation
polymerization. Maintained in this aspect of the invention are the
descriptions of repeating units A (comprises a pseudo-cationic
moiety), B (comprises a hydrophobic moiety), and repeating unit C.
Polymers having a weight-average molecular weight of less than
about 10,000 Da can be made by either radical or condensation
polymerization methods; the slower reaction rate for condensation
may allow better control of the final polymer properties.
[0079] Next, a brief description is provided for the repeating
units when the multifunctional polymer is a condensation
polymer.
[0080] Monomer A may be any multifunctional compound comprising at
least one pseudo-cationic moiety and at least two reactive groups
suitable for condensation polymerization. Examples of these
reactive groups include, but are not limited to, hydroxyl and thiol
groups. The pseudo-cationic moiety may comprise a nitrogen atom,
such as amino or comprise a nitrogen or phosphorus heterocyclic
ring. Examples of nitrogen heterocyclic rings include lactamyl,
pyridinyl, imidazolyl, and pyrazolyl moieties. Typical condensation
repeating units A may have the structure:
X-Q.sub.2-X [0081] wherein [0082] Q.sub.2 is selected from the
group consisting of functionalized and unfunctionalized alkylene,
cycloalkylene, alkyleneoxy, alkenylene, and arylene, wherein
Q.sub.2 comprises one or more pseudo-cationic moieties pendant to
or part of the final polymer backbone; [0083] each X is
independently selected from the group consisting of O and SH;
and
[0084] Examples of condensation repeating units A include, but arc
not limited to:
##STR00013##
and combinations thereof.
[0085] Condensation repeating units B are those repeating units
comprising at least one hydrophobic moiety, which may be pendant to
or part of the final polymer backbone. In one embodiment,
condensation repeating unit B is a polymerizable condensation
repeating unit also having at least two reactive groups suitable
for condensation polymerization. The hydrophobic group may or may
not be pendant to the final polymer backbone. Such condensation
repeating units B may have the structure:
X-Q.sub.3-X [0086] wherein [0087] Q.sub.3 is selected from the
group consisting of functionalized and unfunctionalized alkylene,
cycloalkylene, alkyleneoxy, alkenylene, and arylene, wherein
Q.sub.3 comprises one or more hydrophobic moieties pendant to or
part of the final polymer backbone; [0088] each X is independently
selected from the group consisting of O and SH; and
[0089] Examples of condensation repeating units B include, but are
not limited to:
##STR00014##
and combinations thereof.
[0090] Alternatively, the condensation repeating unit B is not a
polymerizable condensation repeating unit per se, yet still repeats
more than one throughout the polymer. The hydrophobic moiety may be
provided by end-capping or grafting one or more hydrophobic
moieties onto a condensation polymer. Such reactions are known to
one skilled in the art, and may be accomplished, e.g., by reacting
a polymer bearing reactive hydroxyl or amino groups with a compound
having the structure:
R*-W [0091] wherein [0092] R* is a hydrophobic moiety selected from
the group consisting of alkyl, alkoxyl, cycloalkyl, alkenyl, and
aryl, wherein any of the beforementioned groups may be with or
without one or more heteroatoms, and [0093] W is halogen, [0094]
under alkaline conditions (for example, with NaOH addition).
[0095] Multifunctional polymers that are condensation polymers also
comprise repeating unit C, which can be any functional repeating
unit having the structure:
X-Q.sub.4-X [0096] wherein [0097] Q.sub.4 is selected from the
group consisting of functionalized and unfunctionalized alkylene,
cycloalkylene, alkyleneoxy, alkenylene, and arylene; [0098] each X
is independently selected from the group consisting of O and SH;
and
[0099] Non-limiting examples of condensation repeating units C
include the following compounds:
##STR00015##
and combinations thereof.
[0100] Also suitable are polyetheramines, such as those based on
propylene oxide and/or ethylene oxide, such as those sold into
commercial sale under the trade name "Jeffamine" by The Huntsman
Corporation.
[0101] Condensation multifunctional polymers may be prepared by
reacting repeating units A, B, and C in the presence of one or more
hydrocarbyl compounds having at least two halogens:
W-Q*W [0102] wherein [0103] Q* is functionalized and
unfunctionalized hydrocarbylene optionally having one or more
heteroatoms, and [0104] each W is independently selected
halogen.
[0105] A non-limiting reaction scheme illustrating condensation
multifunctional polymers is given by:
##STR00016##
wherein A, B, C, and k represent the molar quantities of each
reactant type. The silicone-containing compound is disclosed in
Journal of the American Chemical Society, 1959 , vol. 81, p.
2632.
[0106] As mentioned earlier, the reactive hydroxyl and amine groups
may be subject to one or more further reactions, e.g., to produce
an end-capped or grafted condensation polymer.
[0107] Additionally, multifunctional polymers comprising repeating
units A, B, and C may be prepared by ring-opening polymerization of
functionalized and unfunctionalized cyclic compounds. For example,
monomer A may be a functionalized ethylene oxide having a
pseudo-cationic moiety, such as:
##STR00017##
monomer B may be a functionalized ethylene oxide having at least
one hydrophobic moiety, such as:
##STR00018##
and monomer C may be any functionalized or unfunctionalized
ethylene oxide, such as:
##STR00019##
[0108] Other functionalized and unfunctionalized cyclic compounds
with and without heteroatoms, including oxetanes, tetrahydrofurans,
oxazines, and oxazolines, may be polymerized to yield corresponding
multifunctional polymers according to the invention.
[0109] In one embodiment, the multifunctional polymer comprising
repeating units A, B, and C may be a terpolymer, whether it be a
radical polymerization polymer or a condensation polymer. It may be
represented as:
##STR00020## [0110] wherein: [0111] said M.sub.pseudo-cationic is a
repeating unit comprising at least one pseudo-cationic moiety,
[0112] said M.sub.hydrophobic is a repeating unit comprising at
least one hydrophobic moiety, [0113] said M.sub.funcational is a
functional repeating unit, [0114] and wherein said a, b, and c are
molar ratios totaling 100%.
[0115] The reader will recognize that M.sub.pseudo-cationic is
repeating unit A, M.sub.hydrophobic is repeating unit B, and
M.sub.functional is repeating unit C as described earlier. For
brevity, non-limiting descriptions for these repeating units will
be understood to apply for terpolymer embodiments.
[0116] An aspect of this embodiment is a multifunctional radical
polymerization polymer represented by the structure:
##STR00021## [0117] wherein: [0118] R.sub.1, R.sub.4, and R.sub.5
are independently selected from the group consisting of
functionalized and unfunctionalized alkyl, alkoxy, cycloalkyl,
alkenyl, and aryl groups; [0119] R.sub.2 and R.sub.3 are
C.sub.1-C.sub.5 alkyl groups, [0120] R.sub.6 and R.sub.7 are
independently selected from the group consisting of functionalized
and unfunctionalized alkyl, alkoxy, cycloalkyl, alkenyl, and aryl
groups, and R.sub.6 and R.sub.7 may form a 5 to 7-membered
ring,
[0121] X is O or NH or combinations thereof, [0122] Q is selected
from the group consisting of functionalized and unfunctionalized
alkylene, alkyleneoxy, cycloalkylene, alkenylene, and arylene
groups, and [0123] and the subscripts a, b, and c refer to the
molar amounts of the three repeating units.
[0124] The invention embraces various embodiments with regard to
generic substituent. For example, in various aspects Q may be
C.sub.1-C.sub.5 alkylene, more particularly C.sub.1-C.sub.4
alkylene; or yet more particularly propylene. Various aspects of
R.sub.5 include C.sub.3-C.sub.18 alkyl, more particularly
C.sub.4-C.sub.16 alkyl, and yet more particularly C.sub.4-C.sub.12
alkyl. R.sub.1 and R.sub.4 may be hydrogen or methyl; more
particularly, they are methyl. In one aspect, R.sub.2 and R.sub.3
may be C.sub.1-C.sub.3 alkyl; more particularly C.sub.1-C.sub.2
alkyl; and yet more particularly methyl. Regarding the molar
subscripts, a may range from about 5% to about 80%, b may range
from about 5% to about 60%, and c may range from about 5% to about
80%. More particularly, a may range from about 10% to about 70%, b
may range from about 15% to about 50%, and c may range from about
10% to about 70%. In one aspect, the weight-average molecular
weight of the polymer may be less than 10,000 Da.
[0125] In one of the terpolymer embodiments, the invention provides
amphiphilic, pseudo-cationic multifunctional polymers. The
multifunctional polymers may be prepared by a polymerization of:
(A) a pseudo-cationic vinyl repeating unit such as
N[2-(dimethylamino)ethyl] (meth)acrylamide,
N-[3-(dimethylamino)propyl] (meth)acrylamide, or
N-[4-(dimethylamino)butyl] (meth)acrylamide; with (B) a hydrophobic
vinyl repeating units; such as methyl (meth)acrylate, ethyl
(meth)acrylate, or butyl (meth)acrylate, and (C) N-vinyl amide
repeating unit; such as N-vinyl formamide, N-methyl-N-vinyl
formamide, N-vinyl pyrrolidone, and/or N-vinyl caprolactam. In one
aspect, the polymer may be represented by the structures:
##STR00022##
wherein a, b, and c are as defined above.
[0126] Also embraced by the invention is a method of providing
antimicrobial activity in or on a composition, wherein the method
comprising the step: contacting a composition with at least one
multifunctional polymer synthesized from at least repeating unit
types: a first repeating unit A comprising at least one
pseudo-cationic tertiary amine, a second repeating unit B that is
hydrophobic, and a third repeating unit C. Separately, the
weight-average molecular weight of the polymer may be less than
about 10,000 Da. The molecular weight may be chosen, in part, based
on the addition level of the multifunctional polymer,
multifunctional polymer type, rheology considerations, and desired
level of antimicrobial activity. Descriptions of the method's
repeating units A, B, and C mirror the description provided
earlier, and for the sake of brevity are not repeated here.
[0127] In one embodiment, the method's polymer may be a terpolymer,
and may be represented as:
##STR00023## [0128] wherein: [0129] said M.sub.pseudo-cationic is a
repeating unit comprising at least one pseudo-cationic moiety,
[0130] said M.sub.hydrophobic is a repeating unit comprising at
least one hydrophobic moiety, [0131] said M.sub.functional is a
functional repeating unit, [0132] and wherein said a, b, and c are
molar ratios totaling 100%.
[0133] Particularly but without limitation, the polymer may be
represented by the structure:
##STR00024## [0134] wherein: [0135] R.sub.1, R.sub.4, and R.sub.5
are independently selected from the group consisting of
functionalized and unfunctionalized alkyl, alkoxy, cycloalkyl,
alkenyl, and aryl groups; [0136] R.sub.2 and R.sub.3 are
C.sub.1-C.sub.5 alkyl groups, [0137] R.sub.6 and R.sub.7 arc
independently selected from the group consisting of functionalized
and unfunctionalized alkyl, alkoxy, cycloalkyl, alkenyl, and aryl
groups, and R.sub.6 and R.sub.7 may form a 5 to 7-membered ring,
[0138] X is O or NH or combinations thereof,
[0139] Q is selected from the group consisting of functionalized
and unfunctionalized alkylene, alkyleneoxy, cycloalkylene,
alkenylene, and arylene groups, and [0140] and the subscripts a, b,
and c refer to the molar amounts of the three repeating units.
[0141] Non-limiting examples of polymers that may be used in the
method include:
##STR00025##
wherein a, b, and c arc as defined above.
[0142] The aforementioned method comprises the step, "contacting a
composition with a multifunctional polymer" meaning that the
composition may be molecular blend, a nano/micro/macroscopic
dispersion, and/or nano/micro/macroscopic emulsion with one or more
multifunctional polymer(s). Additionally, the composition may
contact one or more multifunctional polymer(s) at an interface,
e.g., as a film, in one or more layers, and/or along a phase
boundary.
[0143] In one embodiment, the method provides antimicrobial
activity against a microbe selected from the group consisting of S.
aureus, E. coli, P. aeruginosa, A. niger, C. albicans, and
combinations thereof. In a separate embodiment, the multifunctional
polymers express antimicrobial activity at a microorganism
concentration of 10.sup.5-10.sup.6 cfu/mL and a polymer
concentration of 1% (w/w) or greater.
[0144] The polymers may be designed to have a wide variety of
physical and mechanical properties, to suit a particular
application. The polymers may be random, block, or alternating
polymers, or combinations thereof. The properties of the
multifunctional polymers can be further designed by appropriate
selection of the type of the vinyl repeating units employed, the
ratios of the vinyl repeating units employed, and the
weight-average molecular weight of the resulting polymer.
[0145] In another aspect, a wide variety of compositions comprising
the modified polymers are provided, including adhesives, aerosols,
agricultural compositions, beverages, biocides, cleaning
compositions, coating compositions, cosmetic compositions, dental
compositions, detergents, drugs, electronics, encapsulations,
foods, hair sprays, household-industrial-institutional (HI&I),
inks, lithographic solutions, membrane compositions, metal fluids,
oilfield compositions, paints, paper, personal care compositions,
pharmaceuticals, plasters, plastics, printing, and wood-care
compositions.
[0146] Polymers of the invention may be used in a wide variety of
compositions such as in adhesives, agricultural, biocides,
coatings, electronics, household-industrial-institutional inks,
membranes, metal fluids, oilfield, paper, paints, plastics,
printing, plasters, and wood-care compositions.
[0147] Depending on the end application, one or more fillers may be
included in the compositions and may be added for improved
rheological properties and/or stress reduction. Examples of
suitable nonconductive fillers include alumina, aluminum hydroxide,
silica, fused silica, fumed silica, vermiculite, mica,
wollastonite, calcium carbonate, titania, sand, glass, barium
sulfate, zirconium, carbon black, organic fillers, and halogenated
ethylene polymers, such as, tetrafluoroethylene, trifluoroethylene,
vinylidene fluoride, vinyl fluoride, vinylidene chloride, and vinyl
chloride. Examples of suitable conductive fillers include carbon
black, graphite, gold, silver, copper, platinum, palladium, nickel,
aluminum, silicon carbide, boron nitride, diamond, and alumina.
Combinations of these fillers may be used.
[0148] The filler particles may be of any appropriate size,
particularly from the nano to micro range. The choice of such size
for any particular end use is within the expertise of one skilled
in the art. The filler may be present in an amount from about 10%
to about 90% by weight of the total composition. More than one
filler type may be used in a composition and the fillers may or may
not be surface treated. Appropriate filler sizes can be determined
by the practitioner, and, in particular, may be within the range
from about 20 nm to about 100 min.
[0149] Other materials, such as adhesion promoters (e.g. epoxides,
silanes), dyes, pigments, and rheology modifiers may be added as
desired for the modification of the final properties. Such
materials and the amounts needed are within the expertise of those
skilled in the art.
[0150] Compositions belonging to the personal care/cosmetic and
pharmaceutical arts find utility in altering, delivering an active,
enhancing, improving, modifying the appearance, condition, color,
health, style of the skin (including face, scalp, and lips), hair,
nails, and oral cavity. Many examples and product forms of these
compositions are known. These compositions can impart benefits that
include, but are not limited to, hair style flexibility, hair style
durability, humidity resistance for hair, color and/or color
protection, moisturization, wrinkle reduction, protection from
ultraviolet radiation, water proofness, water resistance, wear
resistance, thermal protection, adhesion, active ingredient
delivery, anti-cavity, and/or anti-gingivitis protection. As such,
these compositions are sometimes categorized in the following
areas: skin care, hair care (both styling and non-styling), sun
care, cosmetics (including color cosmetics), antiperspirants,
deodorants, oral hygiene, and men's and women's personal
hygiene/grooming. In some cases these benefits and care areas
overlap with another.
[0151] Skin care compositions include those materials used on the
body, face, hands, lips, and/or scalp, and are beneficial for many
reasons, such as finning, anti-cellulite, moisturizing, nourishing,
cleaning, reducing or eliminating the appearance of wrinkles or
lentigo, toning, and/or purifying. They also can be used to
sanitize.
[0152] Consumers can identify many of the compositions that serve
the sun care area, for example after-fun, children's, beach,
self-tan, sports (i.e., being sweat proof, waterproof, resistant to
running, or having added UV absorbers and/or antioxidants),
sensitive skin products (i.e., having low irritation to the eyes
and/or skin, and/or being free of fragrances and/or dyes), daily
wear, leave-on hair creams, lotions, styling products, and hair
sprays. Typically, sun care products also comprise one or more UV
actives, which are those organic and inorganic materials that
scatter, absorb, and/or reflect radiation having a wavelength from
about 100 nm to about 400 nm. In one aspect, the sun care product
protects against UV-A and/or UV-B radiation. UV-A radiation, from
about 320 nm to about 400 nm, has the longest wavelength within the
UV spectrum, and consequently is the least energetic. While UV-A
rays can induce skin tanning, they are liable to induce adverse
changes as well, especially in the case of sensitive skin or of
skin, which is continually exposed to solar radiation. In
particular UV-A rays cause a loss of skin elasticity and the
appearance of wrinkles, leading to premature skin aging. UV-B rays
have shorter wavelengths, from about 290 nm to about 320 nm, and
their higher energy can cause erythema and skin burns, which may be
harmful. Alternatively, sun care products may omit UV actives, and
may be regarded as a tanning oil or a tan promoter. Some sun care
compositions may promote soothe skin after sun exposure, and/or be
formulated for application to the lips, hair, or the area around
the eyes. Self-tan compositions, which are products that color skin
without requiring full sun exposure, also fit under the sun care
umbrella. The many different sun care product formats include may
assume a consistency ranging from liquid to semi liquid forms
(e.g., milks, creams), to thicker forms like gels, creams, pastes,
and even solid- and wax-like forms. Sun care products also may take
the form of an aerosol, spray, mist, roll-on, or wipe.
[0153] Hair care compositions include shampoos, leave-on and
rinse-out conditioners used for conditioning, moisturizing,
repairing, hair colors, hair relaxers, and deep conditioners and
treatments such as hot oils and waxes, 2-in-1 shampoo/conditioner
combination products, 3-in-1 shampoo/conditioner/styling agent. The
many types of hair care products can be delivered in an array of
formats, including aerosol sprays, pump sprays, gel sprays,
mousses, gels, waxes, creams, pomades, spritzes, putties, lacquers,
de-frizzing serums, perms, relaxants and colorants.
[0154] Color cosmetic compositions include facial make-up, eye
makeup, mascaras, lip and nail products. Facial make-up
compositions include foundation (liquid, solid, and
semi-solid)--skin tinted creams, liquid, sticks, mousses used as a
base under make-up, rouge, face powder, blusher, highlighters, face
bronzers, concealers, and 2-way cake products.
[0155] Personal care/cosmetics also include eye make-up, mascaras,
eyeliners, eye shadows, eyebrow pencils and eye pencils. Lip
products include lipsticks, lip pencils, lip gloss, transparent
bases and tinted lip moisturizers as well as multi-function color
sticks that also can be used for cheeks and eyes. Nail products
include nail varnishes/enamels, nail varnish removers, treatments,
home-manicure products such as cuticle softeners and nail
strengtheners.
[0156] In addition to the skin, hair, and sun care compositions
summarized above, the polymers related herein also find application
in oral care compositions. Non-limiting examples or oral care
compositions include toothpastes (including toothpaste gels),
denture adhesives, whiteners, anesthetics, and dental floss and
related products. These compositions may take any product format,
such as pastes, gels, creams, solutions, dispersions, rinses,
flosses, aerosols, powders, and lozenges.
[0157] Grooming products for men and women include shaving products
and toiletries, which may find use in preparing the skin and/or
hair for dry or wet shaving. In addition, these compositions may
help to moisturize, cool, and/or soothe skin. A variety of product
forms are known, a few of which are foams, gels, creams, sticks,
oils, solutions, tonics, balms, aerosols, mists, sprays, and
wipes.
[0158] The polymer also can be used in other personal care/cosmetic
applications, such as an absorbent material in appropriate
applications such as diapers, incontinence products, feminine
products, and other related products.
[0159] The polymers described herein also find application in bath
and shower compositions, such as foams, gels, salts, oils, balls,
liquids, powders and pearls. Also included are bar soaps, body
washes, shower gels, cleansers, gels, oils, foams, scrubs and
creams. As a natural extension of this category, these compositions
also include liquid soaps and hand sanitizers used for cleaning
hands.
[0160] The polymer of the invention can be used in combination with
one or more additional personal care/cosmetically acceptable
additives chosen from, for example, conditioning agents, protecting
agents, such as, for example, hydrosoluble, liposoluble and
water-insoluble UV filters, antiradical agents, antioxidants,
vitamins and pro-vitamins, fixing agents, oxidizing agents,
reducing agents, dyes, cleansing agents, anionic, cationic,
nonionic and amphoteric surfactants, thickeners, perfumes,
pearlizing agents, stabilizers, pH adjusters, filters, hydroxy
acids, various cationic, anionic and nonionic polymers, cationic
and nonionic polyether associative polyurethanes, preservatives,
vegetable oils, mineral oils, synthetic oils, polyols such as
glycols and glycerol, silicones, aliphatic alcohols, colorants,
bleaching agents, highlighting agents and sequestrants.
[0161] These additives may be present in the composition according
to the invention in proportions that may range from about 0% to
about 20% by weight in relation to the total weight of the
composition. An expert in the field according to its nature and its
function may easily determine the precise amount of each
additive.
[0162] Examples of these co-ingredients and many others can be
found in the following references, each of which is herein
incorporated in its entirety by reference: " Inventory and common
nomenclature of ingredients employed in cosmetic products,"
Official Journal of the European Union, 5.4.2006, pages L 97/1
through L 97/528; and International Cosmetic Ingredient Dictionary
and Handbook, 13th edition, ISBN: 1882621476, published by The
Personal Care Products Council in January 2010.
[0163] Any known conditioning agent is useful in the personal
care/cosmetic compositions of this invention. Conditioning agents
function to improve the cosmetic properties of the hair,
particularly softness, thickening, untangling, feel, and static
electricity and may be in liquid, semi-solid, or solid form such as
oils, waxes, or gums. Similarly, any known skin-altering agent is
useful in the compositions of this invention. A few examples of
conditioning agents include cationic polymers, cationic surfactants
and cationic silicones. Conditioning agents may be chosen from
synthesis oils, mineral oils, vegetable oils, fluorinated or
perfluorinated oils, natural or synthetic waxes, silicones,
cationic polymers, proteins and hydrolyzed proteins, ceramide type
compounds, cationic surfactants, fatty amines, fatty acids and
their derivatives, as well as mixtures of these different
compounds.
[0164] The cationic polymers that may be used as a conditioning
agent according to the invention are those known to improve the
cosmetic properties of hair treated by detergent compositions. The
expression " cationic polymer" as used herein, indicates any
polymer containing cationic groups and/or ionizable groups in
cationic groups. The cationic polymers used generally have a
number-average molecular weight, which falls between about 500 and
5,000,000, for example between 1000 and 3,000,000. Cationic
polymers may be chosen from among those containing units including
primary, secondary, tertiary, and/or quaternary amine groups that
may either form part of the main polymer chain or a side chain.
Useful cationic polymers include known polyamine, polyaminoamide,
and quaternary polyammonium types of polymers, such as: [0165] a.
homopolymers and copolymers derived from acrylic or methacrylic
esters or amides. The copolymers can contain one or more units
derived from acrylamides, methacrylamides, diacetone acrylamides,
acrylic or methacrylic acids or their esters, vinyl lactams such as
vinyl pyrrolidone or vinyl caprolactam, and vinyl esters. Specific
examples include: copolymers of acrylamide and
N,N-dimethylaminoethyl methacrylate quaternized with dimethyl
sulfate or with an alkyl halide; copolymers of acrylamide and
methacryloyloxyethyl trimethyl ammonium chloride; the copolymer of
acrylamide and methacryloyloxyethyl trimethyl ammonium
methosulfate; copolymers of vinyl pyrrolidone/dialkylaminoalkyl
acrylate or methacrylate, optionally quaternized, such as the
products sold under the name Gafquat.RTM. by Ashland Specialty
Ingredients; the N,N-dimethylaminoethyl methacrylate/vinyl
caprolactam/vinyl pyrrolidone terpolymers, such as the product sold
under the name Gaffix.RTM. VC 713 by Ashland Specialty Ingredients;
the vinyl pyrrolidone/methacrylamidopropyl dimethyl amine
copolymer, marketed under the name Styleze.RTM. CC-10 by Ashland
Specialty Ingredients; the vinyl pyrrolidone/quaternized dimethyl
amino propyl methacrylamide copolymers such as the product sold
under the name Gafquat.RTM. HS-100 by Ashland Specialty
Ingredients; and the vinyl pyrrolidone/dimethylaminopropyl
methacrylami de/C.sub.9-C.sub.24 alkyldimethylaminopropyl
methacrylic acid quaternized terpolymers described in U.S. Pat. No.
6,207,778 and marketed under the name Styleze.RTM. W-20 by Ashland
Specialty Ingredients. [0166] b. derivatives of cellulose ethers
containing quaternary ammonium groups, such as hydroxyethyl
cellulose quaternary ammonium that has reacted with an epoxide
substituted by a trimethyl ammonium group. [0167] c. derivatives of
cationic cellulose such as cellulose copolymers or derivatives of
cellulose grafted with a hydrosoluble quaternary ammonium repeating
unit, as described in U.S. Pat. No. 4,131,576, such as the hydroxy
alkyl cellulose, and the hydroxymethyl-, hydroxyethyl- or
hydroxypropyl-cellulose grafted with a salt of methacryloyl ethyl
trimethyl ammonium, methacrylamidopropyl trimethyl ammonium, or
dimethyl diallyl ammonium. [0168] d. cationic polysaccharides such
as described in U.S. Pat. Nos. 3,589,578 and 4,031,307, guar gums
containing cationic trialkyl ammonium groups and guar gums modified
by a salt, e.g., chloride of 2,3-epoxy propyl trimethyl ammonium.
[0169] e. polymers composed of piperazinyl units and alkylene or
hydroxy alkylene divalent radicals with straight or branched
chains, possibly interrupted by atoms of oxygen, sulfur, nitrogen,
or by aromatic or heterocyclic cycles, as well as the products of
the oxidation and/or quatemization of such polymers. [0170] f.
water-soluble polyamino amides prepared by polycondensation of an
acid compound with a polyamine. These polyamino amides may be
reticulated. [0171] g. derivatives of polyamino amides resulting
from the condensation of polyalkylene polyamines with
polycarboxylic acids followed by alkylation by bi-functional
agents. [0172] h. polymers obtained by reaction of a polyalkylene
polyamine containing two primary amine groups and at least one
secondary amine group with a dioxycarboxylic acid chosen from among
diglycolic acid and saturated dicarboxylic aliphatic acids having 3
to 8 atoms of carbon. Such polymers are described in U.S. Pat. Nos.
3,227,615 and 2,961,347. [0173] i. the cyclopolymers of alkyl
diallylamine or dialkyl diallyl ammonium such as the homopolymer of
dimethyl diallyl ammonium chloride and copolymers of diallyl
dimethyl ammonium chloride and acrylamide. [0174] j. quaternary
diammonium polymers such as hexadimethrine chloride. Polymers of
this type arc described particularly in U.S. Pat. Nos. 2,273,780,
2,375,853, 2,388,614, 2,454,547, 3,206,462, 2,261,002, 2,271,378,
3,874,870, 4,001,432, 3,929,990, 3,966,904, 4,005,193, 4,025,617,
4,025,627, 4,025,653, 4,026,945, and 4,027,020. [0175] k.
quaternary polyammonium polymers, including, for example,
Mirapol.RTM. A 15, Mirapol.RTM. AD1, Mirapol.RTM. AZ1, and
Mirapol.RTM. 175 products sold by Miranol. [0176] l. the quaternary
polymers of vinyl pyrrolidone and vinyl imidazole such as the
products sold under the names Luviquat.RTM. FC 905, FC 550, and FC
370 by BASF. [0177] m. quaternary polyamines [0178] n. reticulated
polymers known in the art.
[0179] The conditioning agent can be a protein or hydrolyzed
cationic or non-cationic protein. Examples of these compounds
include hydrolyzed collagens having triethyl ammonium groups,
hydrolyzed collagens having trimethyl ammonium and trimethyl
stearyl ammonium chloride groups, hydrolyzed animal proteins having
trimethyl benzyl ammonium groups (benzyltrimonium hydrolyzed animal
protein), hydrolyzed proteins having groups of quaternary ammonium
on the polypeptide chain, including at least one C1-C18 alkyl.
Hydrolyzed proteins include Croquat.TM. L, in which the quaternary
ammonium groups include a C12 alkyl group, Croquat.TM. M, in which
the quaternary ammonium groups include C10-C18 alkyl groups,
Croquat.TM. S in which the quaternary ammonium groups include a C18
alkyl group and Crotein Q in which the quaternary ammonium groups
include at least one C1-C18 alkyl group. These products are sold by
Croda. The conditioning agent can comprise quaternized vegetable
proteins such as wheat, corn, or soy proteins such as cocodimonium
hydrolyzed wheat protein, laurdimonium hydrolyzed wheat protein and
steardimonium hydrolyzed wheat protein.
[0180] The conditioning agent can be a ceramide type of compound
such as a ceramide, a glycoceramide, a pseudoceramide, or a
neoceramide. These compounds can be natural or synthetic. Compounds
of the ceramide type are, for example, described in Patents pending
DE4424530, DE4424533, DE4402929, DE4420736, WO95/23807, WO94/07844,
EP-A-0646572, WO95/16665, FR-2 673 179, EP-A-0227994, WO 94/07844,
WO 94/24097, and WO 94/10131. Ceramide type compounds useful herein
include 2-N-linoleoyl amino-octadecane-1,3-diol, 2-N-oleoyl
amino-octadecane-1,3-diol, 2-N-palmitoyl amino-octadecane-1,3-diol,
2-N-stearoyl amino-octadecane-1,3-diol, 2-N-behenoyl
amino-octadecane-1,3-diol,
2-N-[2-hydroxy-palmitoyl]-amino-octadecane-1,3-diol, 2-N-stearoyl
amino-octadecane-1,3,4-triol, N-stearoyl phytosphingosine,
2-N-palmitoyl amino-hexadecane-1,3-diol, bis-(N-hydroxy ethyl
N-cetyl) malonamide, N(2-hydroxy ethyl)-N-(3-cetoxyl-2-hydroxy
propyl) amide of cetylic acid, N-docosanoyl N-methyl-D-glucamine
and mixtures of such compounds.
[0181] The conditioning agent can be a cationic surfactant such as
a salt of a primary, secondary, or tertiary fatty amine, optionally
polyoxyalkylenated, a quaternary ammonium salt, a derivative of
imadazoline, or an amine oxide. Suitable examples include mono-,
di-, or tri-alkyl quaternary ammonium compounds with a counter-ion
such as a chloride, methosulfate, tosylate, etc. including, but not
limited to, cetrimonium chloride, dicetyldimonium chloride,
behentrimonium methosulfate, and the like. The presence of a
quaternary ammonium compound in conjunction with the polymer
described above reduces static and enhances combing of hair in the
dry state. The polymer also enhances the deposition of the
quaternary ammonium compound onto the hair substrate thus enhancing
the conditioning effect of hair.
[0182] The conditioning agent can be any fatty amine known to be
useful as a conditioning agent; e.g. dodecyl, cetyl or stearyl
amines, such as stearamidopropyl dimethylamine. The conditioning
agent can be a fatty acid or derivatives thereof known to be useful
as conditioning agents. Suitable fatty acids include myristic acid,
palmitic acid, stearic acid, behenic acid, oleic acid, linoleic
acid, and isostearic acid. The derivatives of fatty acids include
carboxylic esters including mono-, di-, tri- and tetra-carboxylic
acids.
[0183] The conditioning agent can be a fluorinated or
perfluorinated oil. Fluorinated oils include perfluoropolyethers
described in EP-A-486135 and the fluorohydrocarbon compounds
described in WO 93/11103. The fluoridated oils may also be
fluorocarbons such as fluoramines, e.g., perfluorotributylamine,
fluoridated hydrocarbons, such as perfluorodecahydronaphthalene,
fluoroesters, and fluoroethers. Of course, mixtures of two or more
conditioning agents can be used.
[0184] The conditioning agent can be any silicone known by those
skilled in the art to be useful as a conditioning agent. The
silicones suitable for use according to the invention include
polyorganosiloxancs that arc insoluble in the composition. The
silicones may be present in the form of oils, waxes, polymers, or
gums. They may be volatile or non-volatile. The silicones can be
selected from polyalkyl siloxanes, polyaryl siloxanes, polyalkyl
aryl siloxanes, silicone gums and polymers, and polyorgano
siloxanes modified by organofunctional groups, and combinations
thereof. Suitable polyalkyl siloxanes include polydimethyl
siloxanes with terminal trimethyl silyl groups or terminal dimethyl
silanol groups (dimethiconol) and polyalkyl (C1-C20) siloxanes.
Suitable polyalkyl aryl siloxanes include polydimethyl methyl
phenyl siloxanes and polydimethyl diphenyl siloxanes, linear or
branched. The silicone gums suitable for use herein include
polydiorganosiloxanes including those having a number-average
molecular weight between 200,000 and 1,000,000, used alone or mixed
with a solvent. Examples include polymethyl siloxane, polydimethyl
siloxane/methyl vinyl siloxane gums, polydimethyl siloxane/diphenyl
siloxane, polydimethyl siloxane/phenyl methyl siloxane and
polydimethyl siloxane/diphenyl siloxane/methyl vinyl siloxane.
Suitable silicone polymers include silicones with a
dimethyl/trimethyl siloxane structure and polymers of the trimethyl
siloxysilicate type. The organo-modified silicones suitable for use
in the invention include silicones such as those previously defined
and containing one or more organofunctional groups attached by
means of a hydrocarbon radical and grafted siliconated polymers. In
one embodiment the silicones are amino functional silicones. The
silicones may be used in the form of emulsions, nano-emulsions, or
micro-emulsions.
[0185] The conditioning agent or agents can be present in an amount
from about 0.001% to about 20%, particularly from about 0.01% to
about 10%, and even more particularly from about 0.1% to about 3%
by weight based on the total weight of the final composition. The
personal care/cosmetic compositions of the invention can contain
one or more protecting agents in combination with the
above-described polymer to prevent or limit the degrading effects
of natural physical and/or chemical assaults on the keratinous
materials.
[0186] The protecting agent can be chosen from hydrosoluble,
liposoluble and water-insoluble UV filters, antiradical agents,
antioxidants, vitamins and pro-vitamins. The above-described
cationic polymer enhances the deposition of these materials onto
the hair or skin substrate enhancing protection of hair to UV
damage. Organic UV filters (systems that filter out UV rays) can be
chosen from among hydrosoluble or liposoluble filters, whether
siliconated or nonsiliconated, and mineral oxide particles, the
surface of which may be treated. Hydrosoluble organic UV filters
may be chosen from para-amino benzoic acid and its salts,
anthranilic acid and its salts, salicylic acid and its salts,
hydroxy cinnamic acid and its salts, sulfonic derivatives of
benzothiazoles, benzimidizoles, benzoxazoles and their salts,
sulfonic derivatives of benzophenone and their salts, sulfonic
derivatives of benzylidene camphor and their salts, derivatives of
benzylidene camphor substituted by a quaternary amine and their
salts, derivatives of phthalydene-camphosulfonic acids and their
salts, sulfonic derivatives of benzotriazole, and combinations
thereof. Hydrophilic polymers, which have light-protective
qualities against UV rays, can be used. These include polymers
containing benzylidene camphor and/or benzotriazole groups.
[0187] Suitable liposoluble organic UV filters include derivatives
of para-aminobenzoic acid, such as the esters or amides of
para-aminobenzoic acid; derivatives of salicylic acid; derivatives
of benzophenone; derivatives of dibenzoyl methane; derivatives of
diphenyl acrylates; derivatives of benzofurans; UV filter polymers
containing one or more silico-organic residues; esters of cinnamic
acid; derivatives of camphor; derivatives of trianilino-s-triazine;
the ethylic ester urocanic acid; benzotriazoles; derivatives of
hydroxy phenyl triazine; bis-resorcinol-dialkyl amino triazine; and
combinations thereof. The liposoluble (or lipophilic) organic UV
filter can be chosen from octyl salicylate; 4-tert-butyl-4'-methoxy
dibenzoyl methane; octocrylene; 4-methoxy cinnamate; 2-ethylhexyl
[2-ethylhexyl 4-methoxycinnamate]; and
2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3
-tetramethyl-1-[(trimethyl sily)oxy] disiloxanyl]propynyl] phenol.
Other UV filters that may be useful are derivatives of
benzophenones such as 2-hydroxy-4-methoxybenzophenone-5-sulfonic
acid, 2-hydroxy-4-methoxy benzophenone, derivatives of
benzalmalonates such as poly dimethyl/methyl (3(4-(2,2-bis-ethoxy
carbonyl vinyl)-phenoxy)-propenyl) siloxane, derivatives of
benzylidene camphor such as beta-beta' camphosulfonic [1-4
divinylbenzene] acid and derivatives of benzimidazole such as
2-phenyl-benzimidazol-5-sulfonic acid. Water-insoluble UV filters
include various mineral oxides. The mineral oxides may be selected
from among titanium oxides, zinc oxides, and cerium oxides. The
mineral oxides can be used in the form of ultrafine nanoparticles.
For example, the UV filters can include Escalol.RTM. HP-610
(dimethylpabamido propyl laurdimonium tosylate and propylene glycol
stearate) or Crodasorb HP (polyquaternium 59).
[0188] The antioxidants or antiradical agents can be selected from
phenols such as BHA (tert-butyl-4-hydroxy anisole), BHT
(2,6-di-tert-butyl-p-cresol), TBHQ (tert-butyl hydroquinone),
polyphenols such as proanthocyanodic oligomers, flavonoids,
hindered amines such as tetra amino piperidine, erythorbic acid,
polyamines such as spermine, cysteine, glutathione, superoxide
dismutase, and lactoferrin.
[0189] The vitamins can be selected from ascorbic acid (vitamin C),
vitamin E, vitamin E acetate, vitamin E phosphate, B vitamins such
as B3 and B5, vitamin PP, vitamin A, and derivatives thereof. The
provitamins can be selected from panthenol and retinol.
[0190] The protecting agent can be present in an amount from about
0.001% to about 20% by weight, particularly from about 0.01% to
about 10% by weight, and more particularly from 0.1% to about 5% by
weight of the total weight of the final composition.
[0191] The composition of the invention can contain a fixing agent
in combination with the above-described polymer. The fixing agent
can be an anionic polymer chosen from polymers containing
carboxylic units derived from unsaturated carboxylic mono- or
polyacids.
[0192] The fixing agent can he an amphoteric polymer chosen from
the polymer containing recurring units derived from: [0193] i. at
least one co-repeating unit containing carboxylic acid units, and
[0194] ii. at least one basic co-repeating unit, such as esters
with primary, secondary, tertiary, and quaternary amino
substituents of acrylic and methacrylic acids and the product of
quaternization of dimethylaminoethyl methacrylate with dimethyl or
diethyl sulfate.
[0195] The fixing agent can be a nonionic polymer chosen from
polyalkyloxazolines; vinyl acetate homopolymers; vinyl acetate and
acrylic ester copolymers; vinyl acetate and ethylene copolymers;
vinyl acetate and maleic ester copolymers; polyethylene and maleic
anhydride copolymers; homopolymers of alkyl acrylates; homopolymers
of alkyl methacrylates; copolymers of acrylic esters; copolymers of
alkyl acrylates and alkyl methacrylates; copolymers of
acrylonitrile and a nonionic repeating unit chosen from among
butadiene and alkyl (meth)acrylates; copolymers of alkyl acrylate
and urethane; and polyamides. The fixing agent can be a
functionalized or unfunctionalized, silicone or non-silicone
polyurethane. The fixing polymer can be a polymer of the grafted
silicone type containing a polysiloxane portion and a portion
consisting of a nonsilicone organic chain, with one of the two
portions forming the main chain of the polymer, and with the other
being grafted onto the main chain.
[0196] The fixing agent can be present in the composition in a
relative weight concentration between about 0.1% to about 10%, for
example, from about 0.5% to about 5%.
[0197] The personal care/cosmetic composition of the invention can
contain an oxidizing agent in combination with the above-described
polymer. The oxidizing agent can be chosen from the group of
hydrogen peroxide, urea peroxide, alkali metal bromates,
ferricyanides, persalts, and redox enzymes, optionally with their
respective donor or cofactor. For example, the oxidizing agent can
be hydrogen peroxide. The oxidizing agent can be a solution of
oxygenated water whose titer varies from 1 to 40 volumes.
[0198] The personal care/cosmetic composition of the invention can
contain at least one reducing agent in combination with the
above-described polymer in amounts from about 0.01% to about 30%,
particularly from about 0.05% to about 20% of the total weight of
the composition. The reducing agents can be selected from thiols,
like cysteine, thioglycolic acid, thiolactic acid, their salts and
esters, cysteamine, and its salts or sulfites. In the case of
compositions intended for bleaching, ascorbic acid, its salts and
its esters, erythorbic acid, its salts and its esters, and
sulfinates, like sodium hydroxymethanesulfinate can be used.
[0199] The personal care/cosmetic composition of the invention can
contain a dye in combination with the above-described polymer. The
dye can be selected from the group consisting of neutral acid or
cationic nitrobenzene dyes, neutral acid or cationic azo dyes,
quinone dyes, neutral, acid or cationic anthraquinone dyes, azine
dyes, triarylmethane dyes, indoamine dyes and natural dyes. The dye
or dyes can be present in a concentration from about 0.001% to
about 20%, and particularly from about 0.005% to about 10% based on
the total weight of the composition.
[0200] In addition, the personal care/cosmetic compositions can
include at least one surfactant in combination with the
above-described polymer. The surfactant can be present in an amount
from about 0.1% to about 60%, particularly from about 1% to about
40%, and more particularly from about 5% to about 30% by weight
based on the total weight of the composition. The surfactant may be
chosen from among anionic, amphoteric, or non-ionic surfactants, or
mixtures of them known to be useful in personal care/cosmetic
compositions.
[0201] One or more suitable thickeners or viscosity increasing
agents may be included in combination with the above-described
polymer in the personal care/cosmetic compositions of the
invention. Suitable thickeners and/or viscosity increasing agents
include: Acetamide MEA; acrylamide/ethalkonium chloride acrylate
copolymer; acrylamide/ethyltrimonium chloride acrylate/ethalkonium
chloride acrylate copolymer; acrylamides copolymer;
acrylamide/sodium acrylate copolymer; acrylamide/sodium
acryloyldimethyltaurate copolymer; acrylates/acetoacetoxyethyl
methacrylate copolymer; acrylates/beheneth-25 methacrylate
copolymer; acrylates/C10-C30 alkyl acrylate crosspolymer;
acrylates/ceteth-20 itaconate copolymer; acrylates/ceteth-20
methacrylate copolymer; acrylates/laureth-25 methacrylate
copolymer; acrylates/palmeth-25 acrylate copolymer;
acrylates/palmeth-25 itaconate copolymer; acrylates/steareth-50
acryl ate copolymer; acrylates/steareth-20 itaconate copolymer;
acrylates/steareth-20 methacrylate copolymer; acrylates/stearyl
methacrylate copolymer; acrylates/vinyl isodecanoate crosspolymer;
acrylic acid/acrylonitrogens copolymer; adipic acid/methyl DEA
crosspolymer; agar; agarose; alcaligenes polysaccharides; algin;
alginic acid; almondamide DEA; almondamidopropyl betaine;
aluminum/magnesium hydroxide stearate; ammonium
acrylates/acrylonitrogens copolymer; ammonium acrylates copolymer;
ammonium acryloyldimethyltaurate/vinyl formamide copolymer;
ammonium acryloyldimethyltaurate/VP copolymer; ammonium alginate;
ammonium chloride; ammonium polyacryloyldimethyl taurate; ammonium
sulfate; amylopectin; apricotamide DEA; apricotamidopropyl betaine;
arachidyl alcohol; arachidyl glycol; arachis hypogaea (peanut)
flour; ascorbyl methylsilanol pectinate; astragalus gummifer gum;
attapulgite; avena sativa (oat) kernel flour; avocadamide DEA;
avocadamidopropyl betaine; azelamide MEA; babassuamide DEA; babas
suamide MEA; babassuamidopropyl betaine; behenamide DEA; behenamide
MEA; behenamidopropyl betaine; behenyl betaine; bentonite; butoxy
chitosan; caesalpinia spinosa gum; calcium alginate; calcium
carboxymethyl cellulose; calcium carrageenan; calcium chloride;
calcium potassium carbomer; calcium starch octenylsuccinate; C20-40
alkyl stearate; canolamidopropyl betaine; capramide DEA;
capryl/capramidopropyl betaine; carbomer; carboxybutyl chitos an;
carboxymethyl cellulose acetate butyrate; carboxymethyl chitin;
carboxymethyl chitosan; carboxymethyl dextran; carboxymethyl
hydroxyethylcellulose; carboxymethyl hydroxypropyl guar; carnitine;
cellulose acetate propionate carboxylate; cellulose gum; ceratonia
siliqua gum; cetearyl alcohol; cetyl alcohol; cetyl babassuate;
cetyl betaine; cetyl glycol; cetyl hydroxyethylcellulose; chimyl
alcohol; cholesterol/HDUpullulan copolymer; cholesteryl hexyl
dicarbamate pullulan; citrus aurantium dulcis (orange) peel
extract; cocamide DEA; cocamide MEA; cocamide MIPA; cocamidoethyl
betaine; cocamidopropyl betaine; cocamidopropyl hydroxysultaine;
coco-betaine; coco-hydroxysultaine; coconut alcohol;
coco/oleamidopropyl betaine; coco-Sultaine; cocoyl sarcosinamide
DEA; cornamide/cocamide DEA; cornamide DEA; croscarmellose;
crosslinked bacillus/glucose/sodium glutamate ferment; cyamopsis
tetragonoloba (guar) gum; decyl alcohol; decyl betaine;
dehydroxanthan gum; dextrin; dibenzylidene sorbitol;
diethanolaminooleamide DEA; diglycol/CHDM/isophthalates/SIP
copolymer; dihydroabietyl behenate; dihydrogenated tallow
benzylmonium hectorite; dihydroxyaluminum aminoacetate;
dimethicone/PEG-10 crosspolymer; dimethicone/PEG-15 crosspolymer;
dimethicone propyl PG-betaine; dimethylacrylamide/acrylic
acid/polystyrene ethyl methacrylate copolymer;
dimethylacrylamide/sodium acryloyldimethyltaurate crosspolymer;
disteareth-100 IPDI; DMAPA acrylates/acrylic acid/acrylonitrogens
copolymer; erucamidopropyl hydroxysultaine; ethylene/sodium
acrylate copolymer; gelatin; gellan gum; glyceryl alginate; glycine
soja (soybean) flour; guar hydroxypropyltrimonium chloride;
hectorite; hyaluronic acid; hydrated silica; hydrogenated potato
starch; hydrogenated tallow; hydrogenated tallowamide DEA;
hydrogenated tallow betaine; hydroxybutyl methylcellulose;
hydroxyethyl acrylate/sodium acryloyldimethyl taurate copolymer;
hydroxyethylcellulose; hydroxyethyl chitosan; hydroxyethyl
ethylcellulose; hydroxyethyl stearamide-MIPA;
hydroxylauryl/hydroxymyristyl betaine; hydroxypropylcellulose;
hydroxypropyl chitosan; hydroxypropyl ethylenediamine carbomer;
hydroxypropyl guar; hydroxypropyl methylcellulose; hydroxypropyl
methylcellulose stearoxy ether; hydroxypropyl starch; hydroxypropyl
starch phosphate; hydroxypropyl xanthan gum; hydroxystearamide MEA;
isobutylene/sodium maleate copolymer; isostearamide DEA;
isostearamide MEA; isostearamide mIPA; isostearamidopropyl betaine;
lactamide MEA; lanolinamide DEA; lauramide DEA; lauramide MEA;
lauramide MIPA; lauramide/myristamide DEA; lauramidopropyl betaine;
lauramidopropyl hydroxysultaine; laurimino bispropanediol; lauryl
alcohol; lauryl betaine; lauryl hydroxysultaine; lauryl/myristyl
glycol hydroxypropyl ether; lauryl sultaine; lecithinamide DEA;
linoleamide DEA; linoleamide MEA; linoleamide MIPA; lithium
magnesium silicate; lithium magnesium sodium silicate; macrocystis
pyrifera (kelp); magnesium alginate;
magnesium/aluminum/hydroxide/carbonate; magnesium aluminum
silicate; magnesium silicate; magnesium trisilicate; methoxy
PEG-22/dodecyl glycol copolymer; methylcellulose; methyl
ethylcellulose; methyl hydroxyethylcellulose; microcrystalline
cellulose; milkamidopropyl betaine; minkamide DEA; minkamidopropyl
betaine; MIPA-myristate; montmorillonite; Moroccan lava clay;
myristamide DEA; myristamide MEA; myristamide MIPA;
myristamidopropyl betaine; myristamidopropyl hydroxysultaine;
myristyl alcohol; myristyl betaine; natto gum; nonoxynyl
hydroxyethylcellulose; oatamide MEA; oatamidopropyl betaine;
octacosanyl glycol isostearate; octadecene/MA copolymer; oleamide
DEA; oleamide MEA; oleamide MIPA; oleamidopropyl betaine;
oleamidopropyl hydroxysultaine; oleyl betaine; olivamide DEA;
olivamidopropyl betaine; oliveamide MEA; palmamide DEA; palmamide
MEA; palmamide MIPA; palmamidopropyl betaine; palmitamide DEA;
palmitamide MEA; palmitamidopropyl betaine; palm kernel alcohol;
palm kernelamide DEA; palm kernelamide MEA; palm kernelamide MIPA;
palm kernelamidopropyl betaine; peanutamide MEA; peanutamide MIPA;
pectin; PEG-800; PEG-crosspolymer; PEG-150/decyl alcohol/SMDI
copolymer; PEG-175 diisostearate; PEG-190 distearate; PEG-15
glyceryl tristearate; PEG-140 glyceryl tristearate; PEG-240/HDI
copolymer bis-decyltetradeceth-20 ether; PEG-100/IPDI copolymer;
PEG-180/1aureth-50/TMMG copolymer; PEG-10/lauryl dimethicone
crosspolymer; PEG-15/lauryl dimethicone crosspolymer; PEG-2M;
PEG-5M; PEG-7M; PEG-9M; PEG-14M; PEG-20M; PEG-23M; PEG-25M;
PEG-45M; PEG-65M; PEG-90M; PEG-115M; PEG-160M; PEG-180M; PEG-120
methyl glucose trioleate; PEG-180/octoxynol-40/TMMG copolymer;
PEG-150 pentaerythrityl tetrastearate; PEG-4 rapeseedamide;
PEG-150/stearyl alcohol/SMDI copolymer; phaseolus angularis seed
powder; polianthes tuberosa extract; polyacrylate-3; polyacrylic
acid; polycyclopentadiene; polyether-1; polyethylene/isopropyl
maleate/MA copolyol; polyglyccryl-3 disiloxanc dimethicone;
polyglyccryl-3 polydimethylsiloxyethyl dimethicone; polymethacrylic
acid; polyquaternium-52; polyvinyl alcohol; potassium alginate;
potassium aluminum polyacrylate; potassium carbomer; potassium
carrageenan; potassium chloride; potassium palmate; potassium
polyacrylate; potassium sulfate; potato starch modified; PPG-2
cocamide; PPG-1 hydroxyethyl caprylamide; PPG-2 hydroxyethyl
cocamide; PPG-2 hydroxyethyl coco/isostearamide; PPG-3 hydroxyethyl
soyamide; PPG-14 laureth-60 hexyl dicarbamate; PPG-14 laureth-60
isophoryl dicarbamate; PPG-14 palmeth-60 hexyl dicarbamate;
propylene glycol alginate; PVP/decene copolymer; PVP
montmorillonite; pyrus cydonia seed; pyrus malus (apple) fiber;
rhizobian gum; ricebranamide DEA; ricinoleamide DEA; ricinoleamide
MEA; ricinoleamide MIPA; ricinoleamidopropyl betaine; ricinoleic
acid/adipic acid/AEEA copolymer; rosa multiflora flower wax;
sclerotium gum; sesamide DEA; sesamidopropyl betaine; sodium
acrylate/acryloyldimethyl taurate copolymer; sodium
acrylates/acrolein copolymer; sodium acrylates/acrylonitrogens
copolymer; sodium acrylates copolymer; sodium acrylates
crosspolymer; sodium acrylate/sodium acrylamidomethylpropane
sulfonate copolymer; sodium acrylates/vinyl isodecanoate
crosspolymer; sodium acrylate/vinyl alcohol copolymer; sodium
carbomer; sodium carboxymethyl chitin; sodium carboxymethyl
dextran; sodium carboxymethyl beta-glucan; sodium carboxymethyl
starch; sodium carrageenan; sodium cellulose sulfate; sodium
chloride; sodium cyclodextrin sulfate; sodium hydroxypropyl starch
phosphate; sodium isooctylene/MA copolymer; sodium magnesium
fluorosilicate; sodium oleate; sodium palmitate; sodium palm
kernelate; sodium polyacrylate; sodium polyacrylate starch; sodium
polyacryloyldimethyl taurate; sodium polygamma-glutamate; sodium
polymethacrylate; sodium polystyrene sulfonate; sodium
silicoaluminate; sodium starch octenylsuccinate; sodium stearate;
sodium stearoxy PG-hydroxyethylcellulose sulfonate; sodium
styrene/acrylates copolymer; sodium sulfate; sodium tallowate;
sodium tauride acrylates/acrylic acid/acrylonitrogens copolymer;
sodium tocopheryl phosphate; solanum tuberosum (potato) starch;
soyamide DEA; soyamidopropyl betaine; starch/acrylates/acrylamide
copolymer; starch hydroxypropyltrimonium chloride; stearamide AMP;
stearamide DEA; stearamide DEA-distearate; stearamide
DIBA-stearate; stearamide MEA; stearamide MEA-stearate; stearamide
MIPA; stearamidopropyl betaine; steareth-60 cetyl ether;
steareth-100/PEG-136/HDI copolymer; stearyl alcohol; stearyl
betaine; sterculia urens gum; synthetic fluorphlogopite; tallamide
DEA; tallow alcohol; tallowamidc DEA; tallowamide MEA;
tallowamidopropyl betaine; tallowamidopropyl hydroxysultaine;
tallowamine oxide; tallow betaine; tallow dihydroxyethyl betaine;
tamarindus indica seed gum; tapioca starch; TEA-alginate;
TEA-carbomer; TEA-hydrochloride; trideceth-2 carboxamide MEA;
tridecyl alcohol; triethylene glycol dibenzoate; trimethyl pentanol
hydroxyethyl ether; triticum vulgare (wheat) germ powder; triticum
vulgare (wheat) kernel flour; triticum vulgare (wheat) starch;
tromethamine acrylates/acrylonitrogens copolymer; tromethamine
magnesium aluminum silicate; undecyl alcohol; undecylenamide DEA;
undecylenamide MEA; undecylenamidopropyl betaine; welan gum; wheat
germamide DEA; wheat germamidopropyl betaine; xanthan gum; yeast
beta-glucan; yeast polysaccharides; zea mays (corn) starch; and
blends thereof.
[0202] In one such embodiment, the thickeners or viscosity
increasing agents include carbomers, Aculyn.TM. and Stabileze.RTM.,
e.g., crosslinked acrylic acid, crosslinked poly(methylvinyl
ether/maleic anhydride) copolymer, acrylamides, carboxymethyl
cellulose, and the like.
[0203] The personal care/cosmetic composition of the invention can
contain at least one amphoteric polymer or a cationic polymer in
combination with the above-described polymer. The cationic or
amphoteric polymer or polymers can be present in an amount from
about 0.01% to about 10%, particularly from about 0.05% to about
5%, and more particularly from about 0.1% to about 3% by weight of
the total weight of the composition.
[0204] For some embodiments, it may be preferred to add one or more
preservatives and/or antimicrobial agents, such as, but not limited
to, benzoic acid, sorbic acid, dehydroacetic acid, piroctone
olamine, DMDM hydantoin, IPBC, triclosan, bronopol, formaldehyde,
isothiazolinones, nitrates/nitrites, parabens, phenoxyethanol,
potassium sorbate, sodium benzoate, sulphites, and sulphur dioxide.
Combinations of preservatives may be used.
[0205] In other embodiments it may be desirable to incorporate
preservative boosters/solvents, select examples of which include
caprylyl glycol, hexylene glycol, pentylene glycol,
ethylhexylglycerin, caprylhydroxamic acid, and glyceryl
caprylate.
[0206] In other embodiments it may be desirable to include one or
more other ingredients, such as synthetic and natural oils and
waxes. The synthetic oils include polyolefins, e.g.,
poly-.alpha.-olefins such as polybutenes, polyisobutenes and
polydecenes. The polyolefins can be hydrogenated. The mineral oils
suitable for use in the compositions of the invention include
hexadecane and oil of paraffin. Suitable animal and vegetable oils
include sunflower, corn, soy, avocado, jojoba, squash, raisin seed,
sesame seed, walnut oils, fish oils, glycerol tricaprocaprylate,
Purcellin oil or liquid jojoba. Suitable natural or synthetic oils
include eucalyptus, lavender, vetiver, litsea cubeba, lemon,
sandalwood, rosemary, chamomile, savory, nutmeg, cinnamon, hyssop,
caraway, orange, geranium, cade, and bergamot. Suitable natural and
synthetic waxes include carnauba wax, candelila wax, alfa wax,
paraffin wax, ozokerite wax, vegetable waxes such as olive wax,
rice wax, hydrogenated jojoba wax, absolute flower waxes such as
black currant flower wax, animal waxes such as bees wax, modified
bees wax (cerabellina), marine waxes and polyolefin waxes such as
polyethylene wax.
[0207] The personal care/cosmetic compositions may be used to wash
and treat keratinous material such as hair, skin, eyelashes,
eyebrows, fingernails, lips, and hairy skin. The invention provides
a method for treating keratinous material including the skin or
hair, by applying to skin or keratinous materials a personal
care/cosmetic composition as described above, and then eventually
rinsing it with water. Accordingly, the method makes it possible to
maintain the hairstyle, treatment, care, washing, or make-up
removal of the skin, the hair, and any other keratinous
material.
[0208] The personal care/cosmetic compositions described herein are
useful in personal care/cosmetic products, including, but not
limited to, gels, lotions, glazes, glues, mousses, sprays,
fixatives, shampoos, conditioners, 2-in-1 shampoos, temporary hair
dyes, semi-permanent hair dyes, permanent hair dyes, straighteners,
permanent waves, relaxers, creams, putties, waxes, pomades,
moisturizers, mascaras, lip balms and foam enhancers. The personal
care/cosmetic compositions can be detergent compositions such as
shampoos, bath gels, and bubble baths. In this mode, the
compositions will comprise a generally aqueous washing base. The
surfactant or surfactants that form the washing base may be chosen
alone or in blends, from known anionic, amphoteric, or non-ionic
surfactants. The quantity and quality of the washing base must be
sufficient to impart a satisfactory foaming and/or detergent value
to the final composition. The washing base can be from about 4% to
about 50% by weight, particularly from about 6% to about 35% by
weight, and even more particularly from about 8% to about 25% by
weight of the total weight of the final composition. The personal
care/cosmetic compositions may also take the form of after-shampoo
compositions, to be rinsed off or not, for permanents,
straightening, waving, dyeing, or bleaching, or the form of rinse
compositions to be applied before or after dyeing, bleaching,
permanents, straightening, relaxing, waving or even between the two
stages of a permanent or straightening process. The personal
care/cosmetic compositions may also take the form of skin-washing
compositions, and particularly in the form of solutions or gels for
the bath or shower, or of make-up removal products. The personal
care/cosmetic compositions may also be in the form of aqueous or
hydro-alcoholic solutions for skin and/or hair care.
[0209] The pH of the composition applied to the keratinous material
is generally between 2 and 12. In one embodiment, the pH is from
about 3 to about 8, and may he adjusted to the desired value by
means of acidifying or alkalinizing agents that are well known in
the state of the art. Thus, the composition of the invention can
contain at least one alkalizing or acidifying agent in amounts from
about 0.01% to about 30% based on the total weight of the
composition.
[0210] The alkalizing agent can be chosen from ammonia, alkali
hydroxides, alkali carbonates, alkanolamines, like mono-, di- and
triethanolamines, as well as their derivatives, hydroxyalkylamines
and ethoxylated and/or propoxylated ethylenediamines, unsubstituted
and substituted propylenediamines.
[0211] The acidifying agent can be chosen from mineral or organic
acids, like hydrochloric acid, orthophosphoric acid, carboxylic
acids like tartaric acid, citric acid, or lactic acid, or sulfonic
acids, and the like.
[0212] The personal care/cosmetic compositions of the invention may
include a physiological and cosmetically acceptable medium. Such
medium may consist exclusively of water, a cosmetically acceptable
solvent, or a blend of water and a cosmetically acceptable solvent,
such as a lower alcohol composed of C 1 to C4, such as ethanol,
isopropanol, t-butanol, n-butanol, alkylene glycols such as
propylene glycol, and glycol ethers. Alternatively, the personal
care/cosmetic compositions can be anhydrous.
[0213] Generally, personal care/cosmetic compositions can be
prepared by simple mixing procedures well known in the art.
[0214] The invented polymers can be prepared according to the
examples set out below. The examples are presented for purposes of
demonstrating, but not limiting, the preparation of the compounds
and compositions of this invention.
EXAMPLES
[0215] The following non-limiting examples are provided to
illustrate a few methods for preparing multifunctional
polymers.
Example 1
Synthesis of 16% N-(3-dimethylaminopropyl) methacrylamide/20% butyl
methacrylate/64% N-vinyl pyrrolidone (molar ratios) terpolymer
##STR00026##
[0217] Isopropanol (204.0 g), N-vinyl pyrrolidone (VP) (23.47 g),
N-(3-dimethylaminopropyl) methacrylamide (DMAPMA) (1.80 g), and
butyl methacrylate (BMA) (1.88 g) were loaded into a glass kettle
reactor. The mixture was purged with nitrogen and then heated under
nitrogen to 81.degree. C. with stirring at 200 rpm. Meanwhile, a
repeating unit premix was prepared with 96.00 g of isopropanol,
7.19 g of DMAPMA, and 7.51 g of BMA. At t=0, 0.14 g of
Trigonox.RTM. 25C75 (AkzoNobel, t-butyl peroxy-pivalate initiator)
was charged into the reactor. The repeating unit premix was emptied
into the reactor at a constant rate in 3 hours. Additional shots of
Trigonox.RTM. 25C75 were added at t=1, 2, 3 hour (0.14 g each) and
t=4, 6 hour (0.56 g each). After the last initiator addition, the
reactor was kept stirring at 81.degree. C. for 1 hour. The polymer
solution was then cooled and discharged.
Example 2
Synthesis of 12% N-(3-dimethylaminopropyl) methacrylamide/40% butyl
methacrylate/48% N-vinyl pyrrolidone (molar ratios) terpolymer
##STR00027##
[0219] Isopropanol (184.0 g), VP (16.0 g), DMAPMA (1.23 g), and BMA
(3.41 g) were loaded into a glass kettle reactor. The mixture was
purged with nitrogen and then heated under nitrogen to 82.degree.
C. with stirring at 200 rpm. Meanwhile, a repeating unit premix was
prepared with 96.00 g of isopropanol, 4.90 g of DMAPMA, and 13.65 g
of BMA. At t=0, 0.13 g of Trigonox.RTM. 25C75 (AkzoNobel, t-butyl
peroxy-pivalate initiator) was charged into the reactor. The
repeating unit premix was emptied into the reactor at a constant
rate in 3 hours. Additional shots of Trigonox.RTM. 25C75 were added
at t=1, 2, 3 hour (0.13 g each) and t=4, 6 hour (0.53 g each).
After the last initiator addition, the reactor was kept stirring at
82.degree. C. for 1 hour. The polymer solution was then cooled and
discharged.
Example 3
Synthesis 40% N-(3-dimethylaminopropyl) methacrylamide/20% butyl
methacrylate/of 40% N-vinyl pyrrolidone (molar ratios)
terpolymer
##STR00028##
[0221] A quantity of 338.00 g of isopropanol, 22.23 g of VP, 6.81 g
of DMAPMA, and 2.84 g of BMA were loaded into a glass kettle
reactor. The mixture was purged with nitrogen and then heated under
nitrogen to 80.degree. C. with stirring at 200 rpm. Meanwhile, a
repeating unit premix was prepared with 152.00 g of isopropanol,
27.24 g of DMAPMA, and 11.38 g of BMA. At t=0, 0.25 g of
Trigonox.RTM. 25C75 (AkzoNobel, t-butyl peroxy-pivalate initiator)
was charged into the reactor. The repeating unit premix was emptied
into the reactor at a constant rate in 3 hours. Additional shots of
Trigonox.RTM. 25C75 were added at t=1, 2, 3 hour (0.25 g each) and
t=4, 6 hour (1.00 g each). After the last initiator addition, the
reactor was kept stirring at 80.degree. C. for 1 hour. The polymer
solution was then cooled and discharged.
[0222] The relative viscosity was measured for a 1% (wt/v) polymer
solution in ethanol at 25.degree. C., and found to be 1.13. Part of
the polymer solution was then neutralized by 1 M HCl solution (1:1
molar of DMAPMA). The isopropanol was removed by solvent exchange
with water. The water was then removed by vacuum stripping and a
slightly yellow, fine powder was resulted. The polymer was found to
give clear solutions in water for concentration at least up to and
including 10% by weight.
Example 4
Synthesis of 30% N-(3-dimethylaminopropyl) methacrylamide/40% butyl
methacrylate/30% N-vinyl pyrrolidone (molar ratios) terpolymer
##STR00029##
[0224] A quantity of 338.00 g of isopropanol, 16.67 g of VP, 5.11 g
of DMAPMA, and 5.69 g of BMA were loaded into a glass kettle
reactor. The mixture was purged with nitrogen and then heated under
nitrogen to 80.degree. C. with stirring at 200 rpm. Meanwhile, a
repeating unit premix was prepared with 152.00 g of isopropanol,
20.43 g of DMAPMA, and 22.75 g of BMA. At t=0, 0.25 g of
Trigonox.RTM. 25C75 (AkzoNobel, t-butyl peroxy-pivalate initiator)
was charged into the reactor. The repeating unit premix was emptied
into the reactor at a constant rate in 3 hours. Additional shots of
Trigonox.RTM. 25C75 were added at t=1, 2, 3 hour (0.25 g each) and
t=4, 6 hour (1.00 g each). After the last initiator addition, the
reactor was kept stirring at 80.degree. C. for 1 hour. The polymer
solution was then cooled and discharged.
[0225] The relative viscosity was measured for a 1% (wt/v) polymer
solution in ethanol at 25.degree. C., and found to be 1.12. Part of
the polymer solution was then neutralized by 1 M HC1 solution (1:1
molar of DMAPMA). The isopropanol was removed by solvent exchange
with water. The water was then removed by vacuum stripping and a
slightly yellow, fine powder was resulted. The polymer was found to
give clear solutions in water for concentration at least up to and
including 5% by weight. A 10% (w/w) solution in water sometimes was
slightly hazy.
Example 5
Synthesis of 64% N-(3-dimethylaminopropyl) methacrylamide/20% butyl
methacrylate/16% N-vinyl pyrrolidone (molar ratios) terpolymer
##STR00030##
[0227] A quantity of 338.00 g of isopropanol, 8.89 g of VP, 10.90 g
of DMAPMA, and 2.84 g of BMA were loaded into a glass kettle
reactor. The mixture was purged with nitrogen and then heated under
nitrogen to 83.degree. C. with stirring at 200 rpm. Meanwhile, a
repeating unit premix was prepared with 152.00 g of isopropanol,
43.58 g of DMAPMA, and 11.38 g of BMA. At t=0, 0.25 g of
Trigonox.RTM. 25C75 (AkzoNobel, t-butyl peroxy-pivalate initiator)
was charged into the reactor. The repeating unit premix was emptied
into the reactor at a constant rate in 3 hours. Additional shots of
Trigonox.RTM. 25C75 were added at t=1, 2, 3 hour (0.25 g each) and
t=4, 6 hour (1.00 g each). After the last initiator addition, the
reactor was kept stirring at 83.degree. C. for 1 hour. The polymer
solution was then cooled and discharged.
[0228] The relative viscosity was measured for a 1% (wt/v) polymer
solution in ethanol at 25.degree. C., and found to be 1.10. Part of
the polymer solution was then neutralized by 1 M HCl solution (1:1
molar of DMAPMA). The isopropanol was removed by solvent exchange
with water. The water was then removed by vacuum stripping and a
slightly yellow, fine powder was resulted.
Example 6
Synthesis of 48% N-(3-dimethylaminopropyl) methacrylamide/40% butyl
methacrylate/12% N-vinyl pyrrolidone (molar ratios) terpolymer
##STR00031##
[0230] A quantity of 338.00 g of isopropanol, 6.67 g of VP, 8.17 g
of DMAPMA, and 5.69 g of BMA were loaded into a glass kettle
reactor. The mixture was purged with nitrogen and then heated under
nitrogen to 83.degree. C. with stirring at 200 rpm. Meanwhile, a
repeating unit premix was prepared with 152.00 g of isopropanol,
32.69 g of DMAPMA, and 22.75 g of BMA. At t=0, 0.25 g of
Trigonox.RTM. 25C75 (AkzoNobel, t-butyl peroxy-pivalate initiator)
was charged into the reactor. The repeating unit premix was emptied
into the reactor at a constant rate in 3 hours. Additional shots of
Trigonox.RTM. 25C75 were added at t=1, 2, 3 hour (0.25 g each) and
t=4, 6 hour (1.00 g each). After the last initiator add ition, the
reactor was kept stirring at 83.degree. C. for 1 hour. The polymer
solution was then cooled and discharged.
[0231] The relative viscosity was measured for a 1% (wt/v) polymer
solution in ethanol at 25.degree. C., and found to be 1.10. Part of
the polymer solution was then neutralized by 1 M HCl solution (1:1
molar of DMAPMA). The isopropanol was removed by solvent exchange
with water. The water was then removed by vacuum stripping and a
slightly yellow, fine powder was resulted.
[0232] Molecular weights were measured as a 0.15% polymer solution
in methanol/water mobile phase in using PEO/PEG standards. M.sub.w
was found to be 2,640 Da, and M.sub.n was determined to be 1,170
Da.
Example 7
Synthesis of 30% N-(3-dimethylaminopropyl) methacrylamide/40% butyl
methacrylate/30% N-vinyl pyrrolidone (molar ratios) terpolymer
##STR00032##
[0234] A quantity of 30.00 g of ethanol, 33.34 g of VP, 10.22 g of
DMAPMA, and 11.38 g of BMA were loaded into an Autoclave Engineers'
reactor. The mixture was purged with nitrogen and then heated under
nitrogen to 116.degree. C. with stirring at 200 rpm. Meanwhile, a
pump was filled with a mixture of 64.00 g of ethanol, 40.86 g of
DMAPMA, and 45.50 g of BMA. At t=0, 0.58 g of Trigonox.RTM. 121
(AkzoNobel, t-amyl peroxy-2-ethylhexanoate initiator) was charged
into the reactor. Then the contents of the pump were emptied into
the reactor at a constant rate over the next 3 hours. Additional 12
shots of Trigonox.RTM. 121 were added into the reactor every 15 min
(0.58 g each). Then the reaction was cooled to 92.degree. C.
Starting at t=4 hour, 6 shots of Trigonox.RTM. 121 were added into
the reactor every hour (1.17 g each). After the last initiator
addition, the reactor was kept stirring at 92.degree. C. for 3
hours. The polymer solution was then cooled and discharged.
[0235] The relative viscosity was measured for a 1% (wt/v) polymer
solution in ethanol at 25.degree. C., and found to be 1.11. Part of
the polymer solution was then neutralized by 1 M HCl solution (1:1
molar of DMAPMA). The ethanol was removed by solvent exchange with
water. The water was then removed by vacuum stripping and a
slightly yellow, fine powder was resulted.
[0236] Molecular weights were measured as a 0.15% polymer solution
in methanol/water mobile phase in using PEO/PEG standards. M.sub.w
was found to be 5,000 Da, and M.sub.n was determined to be 826
Da.
Example 8
Synthesis of 30% N-(3-dimethylaminopropyl) methacrylamide/40% butyl
methacrylate/30% N-vinyl pyrrolidone (molar ratios) terpolymer
##STR00033##
[0238] A quantity of 130.00 g of ethanol, 33.34 g of VP, 25.54 g of
DMAPMA, and 11.38 g of BMA were loaded into an Autoclave Engineers'
reactor. The mixture was purged with nitrogen and then heated to
116.degree. C. under nitrogen with stirring at 200 rpm. Meanwhile,
a pump was filled with a mixture of 64.00 g of ethanol, 25.54 g of
DMAPMA, and 45.50 g of BMA. At t=0, 0.58 g of Trigonox.RTM. 121
(AkzoNobel, t-amyl peroxy-2-ethylhexanoate initiator) was charged
into the reactor. Then the contents of the pump were emptied into
the reactor at a constant rate over the next 3 hours. Additional 12
shots of Trigonox.RTM. 121 were added into the reactor every 15 min
(0.58 g each). Then the reaction was cooled to 92.degree. C.
Starting at t=4 hour, 5 shots of Trigonox.RTM. 121 were added into
the reactor every hour (1.17 g each for the first 4 shots and 2.33
g for the last shot). After the last initiator addition, the
reactor was kept stirring at 92.degree. C. for 3 hours. The polymer
solution was then cooled and discharged. Part of the polymer
solution was then neutralized by 1 M HCl solution (1:1 molar of
DMAPMA). The ethanol was removed by solvent exchange with water.
The water was then removed by vacuum stripping and a slightly
yellow, fine powder was resulted.
[0239] Molecular weights were measured as a 0.15% polymer solution
in methanol/water mobile phase in using PEO/PEG standards. M.sub.w
was found to be 8,250 Da, and M.sub.n was determined to be 1,180
Da.
Example 9
Synthesis of 30% N-(3-dimethylaminopropyl) methacrylamide/40% butyl
methacrylate/30% N-vinyl pyrrolidone (molar ratios) terpolymer
##STR00034##
[0241] A quantity of 200.00 g of ethanol, 33.34 g of VP, 10.22 g of
DMAPMA, and 1 L38 g of BMA were loaded into a glass kettle reactor.
The mixture was purged with nitrogen and then heated to 80.degree.
C. under nitrogen with stirring at 200 rpm. Meanwhile, a repeating
unit premix was prepared with 40.86 g of DMAPMA and 45.50 g of BMA.
Starting at t=0, 1.70 g of Trigonox.RTM. 121 (AkzoNobel, t-amyl
peroxy-2-ethylhexanoate initiator) was charged into the reactor in
3 hours and the contents of the repeating unit premix were also
emptied into the reactor at a constant rate over the 3 hours.
Starting at t=5 hour, additional 2.85 g of Trigonox.RTM. 121 was
added into the reactor over 2 hours. Then the reactor was kept
stirring at 80.degree. C. for 1 hour. The polymer solution was then
cooled and discharged.
[0242] The relative viscosity was measured for a 1% (wt/v) polymer
solution in ethanol at 25.degree. C., and found to be 1.29.
Example 10
Synthesis of 30% N-(3-dimethylaminopropyl) methacrylamide/40% butyl
methacrylate/30% N-vinyl pyrrolidone (molar ratios) terpolymer
##STR00035##
[0244] A quantity of 85.00 g of ethanol, 33.34 g of VP, 10.22 g of
DMAPMA, and 11.38 g of BMA were loaded into a glass kettle reactor.
The mixture was purged with nitrogen and then heated to 80.degree.
C. under nitrogen with stirring at 200 rpm. Meanwhile, a repeating
unit premix was prepared with 40.86 g of DMAPMA and 45.50 g of BMA.
Starting at t=0, 0.85 g of Trigonox.RTM. 121 (AkzoNobel, t-amyl
peroxy-2-cthylhcxanoatc initiator) was charged into the reactor in
3 hours and the contents of the repeating unit premix were also
emptied into the reactor at a constant rate over the 3 hours.
Starting at t=5 hour, additional 2.85 g of Trigonox.RTM. 121 was
added into the reactor over 2 hours. Then the reactor was kept
stirring at 80.degree. C. for 1 hour. The polymer solution was then
cooled and discharged.
[0245] Molecular weights were measured as a 0.15% polymer solution
in methanol/water mobile phase in using PEO/PEG standards. M.sub.w
was found to be 21,400 Da, and M.sub.n was determined to be 5,220
Da.
[0246] The relative viscosity was measured for a 1% (wt/v) polymer
solution in ethanol at 25.degree. C., and found to be 1.97.
Example 11
Synthesis of 30% N-(3-dimethylaminopropyl) methacrylamide/40%
2-ethylhexyl methacrylate/30% N-vinyl pyrrolidone (molar ratios)
terpolymer
##STR00036##
[0248] A quantity of 130.00 g of ethanol, 28.34 g of VP, 21.71 g of
DMAPMA, and 13.48 g of 2-ethylhexyl methacrylate (EHMA) were loaded
into an Autoclave Engineers' reactor. The mixture was purged with
nitrogen and then heated to 116.degree. C. under nitrogen with
stirring at 200 rpm. Meanwhile, a pump was filled with a mixture of
64.00 g of ethanol, 21.71 g of DMAPMA, and 53.94 g of EIIMA. At
t=0, 0.57 g of Trigonox.RTM. 121 (AkzoNobel, t-amyl
peroxy-2-ethylhexanoate initiator) was charged into the reactor.
Then the contents of the pump were emptied into the reactor at a
constant rate over the next 3 hours. Additional Trigonox.RTM. 121
was charged into the reactor over 2.75 hours (6.83 g). Then the
reaction was cooled to 91.degree. C. Starting at t=4 hour, 4 shots
of Trigonox.RTM. 121 were added into the reactor every hour (1.75 g
each). After the last initiator addition, the reactor was kept
stirring at 91.degree. C. for 3 hours. The polymer solution was
then cooled and discharged.
[0249] The relative viscosity was measured for a 1% (wt/v) polymer
solution in ethanol at 25.degree. C., and found to be 1.10. Part of
the polymer solution was then neutralized by 1 M HC1 solution (1:1
molar of DMAPMA). The ethanol was removed by solvent exchange with
water. The water was then removed by vacuum stripping and a
slightly yellow, fine powder was resulted. The polymer was found to
give a hazy solution at 1% weight addition in water. Cloudy
solutions were produced in water for solutions containing 2.5% to
10% (w/w) polymer.
[0250] Molecular weights were measured as a 0.15% polymer solution
in methanol/water mobile phase in using PEO/PEG standards. M.sub.w
was found to be 2,280 Da, and M.sub.n was determined to be 686
Da.
Example 12
Synthesis of 40% N-(3-dimethylaminopropyl) methacrylamide/20%
2-ethylhexyl methacrylate/40% N-vinyl pyrrolidone (molar ratios)
terpolymer
##STR00037##
[0252] A quantity of 130.00 g of ethanol, 37.79 g of VP, 28.94 g of
DMAPMA, and 6.74 g of EIIMA were loaded into an Autoclave
Engineers' reactor. The mixture was purged with nitrogen and then
heated to 116.degree. C. under nitrogen with stirring at 200 rpm.
Meanwhile, a pump was filled with a mixture of 45.00 g of ethanol,
28.94 g of DMAPMA, and 26.98 g of EHMA. Starting at t=0, 6.90 g of
Trigonox.RTM. 121 (AkzoNobel, t-amyl peroxy-2-ethylhexanoate
initiator) was charged into the reactor over 3 hours. The contents
of the pump were also emptied into the reactor at a constant rate
in 3 hours. Then the reaction was cooled to 91.degree. C. Starting
at t=4 hour, 5 shots of Trigonox.RTM. 121 were added into the
reactor every hour (1.30 g each). After the last initiator
addition, the reactor was kept stirring at 91.degree. C. for 3
hours. The polymer solution was then cooled and discharged. The
relative viscosity was measured for a 1% (wt/v) polymer solution in
ethanol at 25.degree. C., and found to be 1.20. Part of the polymer
solution was then neutralized by 1 M HCl solution (1:1 molar of
DMAPMA). The ethanol was removed by solvent exchange with water.
The water was then removed by vacuum stripping and a slightly
yellow, fine powder was resulted.
[0253] Molecular weights were measured as a 0.15% polymer solution
in methanol/water mobile phase in using PEO/PEG standards. M.sub.w
was found to be 13,100 Da, and M.sub.n was determined to be 1,250
Da.
Example 13
Synthesis of 16% N-(3-dimethylaminopropyl) methacrylamide/20%
lauryl methacrylate/64% N-vinyl pyrrolidone (molar ratios)
terpolymer
##STR00038##
[0255] A quantity of 159.00 g of isopropanol, 17.78 g of VP, 1.36 g
of DMAPMA, and 2.54 g of lauryl methacrylate (LMA) were loaded into
a glass kettle reactor. The mixture was purged with nitrogen and
then heated to 82.degree. C. under nitrogen with stirring at 200
rpm. Meanwhile, a repeating unit premix was prepared with 36.00 g
of isopropanol, 5.45 g of DMAPMA, and 10.18 g of LMA. At t=0, 0.125
g of Trigonox.RTM. 25C75 (AkzoNobel, t-butyl peroxy-pivalate
initiator) was charged into the reactor. The repeating unit premix
was emptied into the reactor at a constant rate in 3 hours.
Additional shots of Trigonox.RTM. 25C75 was added at t=1, 2, 3 hour
(0.125 g each) and t=4, 5, 6, 7 hour (0.25 g each). After the last
initiator addition, the reactor was kept stirring at 82.degree. C.
for 1 hour. The polymer solution was then cooled and
discharged.
[0256] The relative viscosity was measured for a 1% (wt/v) polymer
solution in ethanol at 25.degree. C., and found to be 1.13. Part of
the polymer solution was then neutralized by 1 M HCl solution (1:1
molar of DMAPMA). The isopropanol was removed by solvent exchange
with water. The water was then removed by vacuum stripping and a
slightly yellow, fine powder was resulted.
Example 14
Synthesis of 12% N-(3-dimethylaminopropyl) methacrylamide/40%
lauryl methacrylate/48% N-vinyl pyrrolidone (molar ratios)
terpolymer
##STR00039##
[0258] A quantity of 170.00 g of isopropanol, 13.34 g of VP, 1.02 g
of DMAPMA, and 5.09 g of LMA were loaded into a glass kettle
reactor. The mixture was purged with nitrogen and then heated to
81.degree. C. under nitrogen with stirring at 200 rpm. Meanwhile, a
repeating unit premix was prepared with 80.00 g of isopropanol,
4.09 g of DMAPMA, and 20.36 g of LMA. At t=0, 0.125 g of
Trigonox.RTM. 25C75 (AkzoNobel, t-butyl peroxy-pivalate initiator)
was charged into the reactor. The repeating unit premix was emptied
into the reactor at a constant rate in 3 hours. Additional shots of
Trigonox.RTM. 25C75 were added at t=1, 2, 3 hour (0.125 g each) and
t=4, 5, 6, 7 hour (0.25 g each). After the last initiator addition,
the reactor was kept stirring at 81.degree. C. for 1 hour. The
polymer solution was then cooled and discharged.
[0259] The relative viscosity was measured for a 1% (wt/v) polymer
solution in ethanol at 25.degree. C., and found to be 1.12. Part of
the polymer solution was then neutralized by 1 M HCl solution (1:1
molar of DMAPMA). The isopropanol was removed by solvent exchange
with water. The water was then removed by vacuum stripping and a
slightly yellow, fine powder was resulted.
Example 15
Synthesis of 40% N-(3-dimethylaminopropyl) methacrylamide/20%
lauryl methacrylate/40% N-vinyl pyrrolidone (molar ratios)
terpolymer
##STR00040##
[0261] A quantity of 165.00 g of isopropanol, 11.11 g of VP, 3.41 g
of DMAPMA, and 2.54 g of LMA were loaded into a glass kettle
reactor. The mixture was purged with nitrogen and then heated to
80.degree. C. under nitrogen with stirring at 200 rpm. Meanwhile, a
repeating unit premix was prepared with 60.00 g of isopropanol,
13.62 g of DMAPMA, and 10.18 g of LMA. At t=0, 0.125 g of
Trigonox.RTM. 25C75 (AkzoNobel, t-butyl peroxy-pivalate initiator)
was charged into the reactor. The repeating unit premix was emptied
into the reactor at a constant rate in 3 hours. Additional shots of
Trigonox.RTM. 25C75 were added at t=1, 2, 3 hour (0.125 g each) and
t=4, 5, 6, 7 hour (0.25 g each). After the last initiator addition,
the reactor was kept stirring at 80.degree. C. for 1 hour. The
polymer solution was then cooled and discharged.
[0262] The relative viscosity was measured for a 1% (wt/v) polymer
solution in ethanol at 25.degree. C., and found to be 1.12. Part of
the polymer solution was then neutralized by 1 M HCl solution (1:1
molar of DMAPMA). The isopropanol was removed by solvent exchange
with water. The water was then removed by vacuum stripping and a
slightly yellow, fine powder was resulted.
Example 16
Synthesis of 30% N-(3-dimethylaminopropyl) methacrylamide/40%
lauryl methacrylate/30% N-vinyl pyrrolidone (molar ratios)
terpolymer
##STR00041##
[0264] A quantity of 199.00 g of isopropanol, 8.34 g of VP, 2.55 g
of DMAPMA, and 5.09 g of LMA were loaded into a glass kettle
reactor. The mixture was purged with nitrogen and then heated to
82.degree. C. under nitrogen with stirring at 200 rpm. Meanwhile, a
repeating unit premix was prepared with 76.00 g of isopropanol,
10.22 g of DMAPMA, and 20.35 g of LMA. At t=0, 0.125 g of
Trigonox.RTM. 25C75 (AkzoNobel, t-butyl peroxy-pivalate initiator)
was charged into the reactor. The repeating unit premix was emptied
into the reactor at a constant rate in 3 hours. Additional shots of
Trigonox.RTM. 25C75 were added at t=1, 2, 3 hour (0.125 g each) and
t=4, 5, 6, 7 hour (0.25 g each). After the last initiator addition,
the reactor was kept stirring at 82.degree. C. for 1 hour. The
polymer solution was then cooled and discharged.
[0265] The relative viscosity was measured for a 1% (wt/v) polymer
solution in ethanol at 25.degree. C., and found to be 1.11. Part of
the polymer solution was then neutralized by 1 M HCl solution (1:1
molar of DMAPMA). The isopropanol was removed by solvent exchange
with water. The water was then removed by vacuum stripping and a
slightly yellow, fine powder was resulted.
Example 17
Synthesis of 64% N-(3-dimethylaminopropyl) methacrylamide/20%
lauryl methacrylate/16% N-vinyl pyrrolidone (molar ratios)
tcrpolymcr
##STR00042##
[0267] A quantity of 130.00 g of isopropanol, 4.45 g of VP, 5.45 g
of DMAPMA, and 2.54 g of LMA were loaded into a glass kettle
reactor. The mixture was purged with nitrogen and then heated to
83.degree. C. under nitrogen with stirring at 200 rpm. Meanwhile, a
repeating unit premix was prepared with 120.00 g of isopropanol,
21.79 g of DMAPMA, and 10.18 g of LMA. At t=0, 0.125 g of
Trigonox.RTM. 25C75 (AkzoNobel, t-butyl peroxy-pivalate initiator)
was charged into the reactor. The repeating unit premix was emptied
into the reactor at a constant rate in 3 hours. Additional shots of
Trigonox.RTM. 25C75 were added at t=1, 2, 3 hour (0.125 g each) and
t=4, 5, 6, 7 hour (0.25 g each). After the last initiator addition,
the reactor was kept stirring at 83.degree. C. for 1 hour. The
polymer solution was then cooled and discharged
[0268] The relative viscosity was measured for a 1% (wt/v) polymer
solution in ethanol at 25.degree. C., and found to be 1.13. Part of
the polymer solution was then neutralized by 1 M HCl solution (1:1
molar of DMAPMA). The isopropanol was removed by solvent exchange
with water. The water was then removed by vacuum stripping and a
slightly yellow, fine powder was resulted.
Example 18
Synthesis of 48% N-(3-dimethylaminopropyl) methacrylamide/40%
lauryl methacrylate/12% N-vinyl pyrrolidone (molar ratios)
terpolymer
##STR00043##
[0270] A quantity of 140.00 g of isopropanol, 3.33 g of VP, 4.09 g
of DMAPMA, and 5.09 g of LMA were loaded into a glass kettle
reactor. The mixture was purged with nitrogen and then heated to
83.degree. C. under nitrogen with stirring at 200 rpm. Meanwhile, a
repeating unit premix was prepared with 160.00 g of isopropanol,
16.34 g of DMAPMA, and 20.35 g of LMA. At t=0, 0.125 g of
Trigonox.RTM. 25C75 (AkzoNobel, t-butyl peroxy-pivalate initiator)
was charged into the reactor. The repeating unit premix was emptied
into the reactor at a constant rate in 3 hours. Additional shots of
Trigonox.RTM. 25C75 were added at t=1, 2, 3 hour (0.125 g each) and
t=4, 5, 6, 7 hour (0.25 g each). After the last initiator addition,
the reactor was kept stirring at 83.degree. C. for 1 hour. The
polymer solution was then cooled and discharged.
[0271] The relative viscosity was measured for a 1% (wt/v) polymer
solution in ethanol at 25.degree. C., and found to be 1.09. Part of
the polymer solution was then neutralized by 1 M HCl solution (1:1
molar of DMAPMA). The isopropanol was removed by solvent exchange
with water. The water was then removed by vacuum stripping and a
slightly yellow, fine powder was resulted.
Comparative Example 1
Antimicrobial Activity of Repeating Units Via Streak Plate
Method
[0272] The antimicrobial activity of N-vinyl-2-pyrrolidone (VP),
dimethylaminopropyl methacrylamide (DMAPMA), and butyl methacrylate
(BMA)were evaluated using a streak plate method. Briefly, stock
solution of each microorganism was prepared by growing the
bacterial cells in tryptic soy broth (TSB) or the fungi cells in
yeast malt broth (YM) to reach a concentration of about
10.sup.8-10.sup.9 cfu/mL. Molten agar (TSA or YM) was seeded with
each microorganism to obtain a microbial concentration of about
10.sup.5-10.sup.6 cfu/mL. Plates were allowed to solidify. Monomer
plates were challenged with the following microbes: Staphylococcus
aureus (ATCC 6538), Escherichia coli (ATCC 8730), Pseudomonas
aeruginosa (ATCC 9027), Candida albicans (ATCC 10231) and
Aspergillus niger (ATCC 16404). The repeating units were tested as
a 1% solution in water, and DMAPMA solution was adjusted to pH 6-7
prior to testing. The plates were refrigerated for 24 hours to
allow for the polymer to diffuse and were then placed in the
incubator (32.degree. C. for bacteria plates, 28.degree. C. for
fungal plates) for 24-72 hrs. Growth inhibition along the polymeric
streak or polymer sprinkles was considered as indicative of
antimicrobial activity. Seeded plates without polymers were used as
positive controls for microbial growth.
[0273] No repeating unit showed antimicrobial activity for the
microbes tested.
Example 19
Antimicrobial Testing Via Plate Streak Method
[0274] The antimicrobial activity of the various polymers was
evaluated using a plate streak method. The method of the
Comparative Example was followed, except polymers were tested
either as a 5% solution in water or as powders by streaking the
solution or sprinkling the polymers over the microbial seeded
plate, respectively. The results of the streak test for various
polymers are summarized in the Table 1 below. A "-" symbol
indicates that antimicrobial activity was observed (growth
inhibition) whereas a "+" symbol indicates that no antimicrobial
activity was detected in this assay.
TABLE-US-00001 TABLE 1 Microbial test results of Example 19 growth
inhibition S. E. P. A. C. polymer aureus coli aeruginosa niger
albicans Example 3 - - - + + Example 4 - - - + + Example 5 - - - +
+ Example 6 - - - + + Example 7 - + + + + Example 8 - - - + +
Example 11 - - + + + Example 12 - + + - - Example 13 + + + + +
Example 14 + + + + + Example 15 - + + + + Example 16 - + + + +
Example 17 - + + + + Example 18 - + + + +
[0275] As shown in the Table 1 above, multifunctional polymers
embraced by the invention showed antimicrobial activity.
Example 20
[0276] The antimicrobial activity of selected polymers was further
evaluated by a shake flask method. Briefly, 2% by wt. of the
polymers were added to TSB. The pH of the media was adjusted to a
pH of about 6. Each flask was then inoculated with a microorganism
to achieve an initial concentration of about 10.sup.6 cfu/mL and
incubated with shaking at 32.degree. C. Microbial counts were
conducted after 48 hours by serially diluting and plating onto TSA
media. The log reduction values (Log CFIJ/mL control at t=48 h--Log
CFIJ/mL treated sample at t =48 hours) of the polymer in Example 8
tested against S. aureus, E. coli and P. aeruginosa were >7.2,
>7.2, and 6.0, respectively. Therefore, the antimicrobial
activity of Example 8 polymer when tested at 2% resulted in total
growth inhibition of both S. aureus and E. coli.
Example 21
Compatibility with Formulation Polymers
[0277] The poly(DMAPMA/BMA/VP) multifunctional polymer of Examples
8was evaluated for compatibility with four formulation polymers:
polyquaternium-69 (Aquastyle.TM. 300AF, Ashland Specialty
Ingredients), polyimide-1 (Aquaflex.TM. XL30, Ashland Specialty
Ingredients), and polyquaternium-55 (Styleze.TM. W20, Ashland
Specialty Ingredients). To evaluate compatibility a total of
twenty-five 10 gram samples consisting of a ranging amount of
candidate polymer, existing product and water were prepared. Then,
1-5% of the candidate polymer (based on 10 g total sample) was
mixed with 1-5% of existing product (based on 10 g total sample)
and water was added to bring total mass of sample to ten grams.
Amount of all constituent components were adjusted to reflect
percent solids.
[0278] Overall, the polymer showed good compatibility with the
formulation polymers (Tables 2). In the case of polyquaternium-69
and polyimide-1, clear solutions existed at virtually all evaluated
levels, with only slight haze at the highest concentrations, were
observed (Tables 2). With polyquaternium-5 5 clear solutions were
observed until 2-3% of the multifunctional polymer and existing
product (Table 2).
TABLE-US-00002 TABLE 2 Compatibility of 30% VP/30% DMAPMA/40% BMA
(molar ratios) with formulation polymers. formulation
multifunctional polymer addition level (w/w) polymer 1% 2% 3% 4% 5%
pH polyquaternium-69 1% clear clear clear clear clear 5-6 2% clear
clear clear clear clear 3% clear clear clear clear clear 4% clear
clear clear clear clear 5% clear clear clear clear clear
polyimide-1 1% clear clear clear clear clear 6.5-7.5 2% clear clear
clear clear clear 3% clear clear clear clear clear 4% clear clear
clear clear slightly hazy 5% clear clear clear clear slightly hazy
polyquaternium-55 1% clear clear clear clear clear 4.5-5.0 2% clear
clear clear clear slightly hazy 3% clear clear slightly slightly
hazy hazy hazy 4% clear clear slightly slightly hazy hazy hazy 5%
clear clear slightly slightly hazy hazy hazy
[0279] While a number of embodiments of this invention have been
represented, it was apparent that the basic construction can be
altered to provide other embodiments that utilize the invention
without departing from the spirit and scope of the invention. All
such modifications and variations are intended to be included
within the scope of the invention as defined in the appended claims
rather than the specific embodiments that have been presented by
way of example.
* * * * *