U.S. patent application number 14/916267 was filed with the patent office on 2016-12-29 for anti-dandruff compositions and hair care formulations containing zinc pyrithione and quaternary ammonium salt.
The applicant listed for this patent is JUBILANT LIFE SCIENCES LIMITED. Invention is credited to ASHUTOSH AGARWAL, VINEET SHARMA.
Application Number | 20160374914 14/916267 |
Document ID | / |
Family ID | 51753271 |
Filed Date | 2016-12-29 |
United States Patent
Application |
20160374914 |
Kind Code |
A2 |
SHARMA; VINEET ; et
al. |
December 29, 2016 |
ANTI-DANDRUFF COMPOSITIONS AND HAIR CARE FORMULATIONS CONTAINING
ZINC PYRITHIONE AND QUATERNARY AMMONIUM SALT
Abstract
The present invention discloses a stable biocidal composition
with enhanced anti-fungal activity at low concentration of
active(s) and a process for preparing the same. The composition
comprises: zinc pyrithione, C8-C18 quaternary ammonium salt
(preferably cetylpyridinium chloride), water miscible
glycol/polyol/glycol ether/lactam, organic amine and/or alkanol
amine The composition can be formulated into: hair care
formulations, antidandruff hair care formulations, water based
paints, coatings, adhesives, hard surface cleaners, fabric care
compositions, wood products, plastic products and medical products.
The biocidal compositions and the resulting formulations are
transparent or opaque and are stable at varying pH and humidity
conditions.
Inventors: |
SHARMA; VINEET; (NOIDA,
UTTAR PRADESH, IN) ; AGARWAL; ASHUTOSH; (NOIDA, UTTAR
PRADESH, IN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
JUBILANT LIFE SCIENCES LIMITED |
NOIDA, UTTAR PRADESH |
|
IN |
|
|
Prior
Publication: |
|
Document Identifier |
Publication Date |
|
US 20160220468 A1 |
August 4, 2016 |
|
|
Family ID: |
51753271 |
Appl. No.: |
14/916267 |
Filed: |
September 2, 2014 |
PCT Filed: |
September 2, 2014 |
PCT NO: |
PCT/IN2014/000570 PCKC 00 |
371 Date: |
March 3, 2016 |
Current U.S.
Class: |
514/188 |
Current CPC
Class: |
A01N 33/08 20130101;
A61K 8/4926 20130101; A61K 2800/262 20130101; A01N 43/40 20130101;
A61Q 5/006 20130101; A01N 33/08 20130101; A01N 33/12 20130101; A61K
2800/524 20130101; A01N 33/12 20130101; A01N 59/16 20130101; A01N
25/30 20130101; A61K 8/416 20130101; A01N 43/40 20130101; A01N
59/16 20130101; A61K 8/4933 20130101; A61K 8/345 20130101; A61K
2800/591 20130101; A61K 8/58 20130101; A61K 8/41 20130101; A01N
25/02 20130101; A01N 59/16 20130101; A01N 25/02 20130101; A01N
25/02 20130101; A01N 43/40 20130101; A01N 43/40 20130101; A01N
25/30 20130101; A01N 59/16 20130101; A01N 33/08 20130101; A01N
25/02 20130101; A01N 33/08 20130101; A01N 25/30 20130101 |
International
Class: |
A61K 8/58 20060101
A61K008/58; A61K 8/41 20060101 A61K008/41; A61K 8/49 20060101
A61K008/49; A61Q 5/00 20060101 A61Q005/00 |
Claims
1. A transparent, stable biocidal composition, said composition
comprising: (i) 0.5-35% w/w of zinc pyrithione, (ii) 0-20% w/w of
C.sub.8-C.sub.18 quaternary ammonium salt, (iii) 0.5-20% w/w
organic amines and/or alkanol amine, (iv) 0.5-60% w/w water soluble
glycol/polyol/glycol ether/lactam or mixtures thereof, (v) 0-10%
w/w of a dispersant and/or a rheology modifier and/or a suspending
agent, (vi) 0-60% w/w of water.
2. A transparent, stable biocidal composition, said composition
comprising: (i) 0.5-35% w/w of zinc pyrithione, (ii) 0.05-20% w/w
of a C.sub.8-C.sub.18 quaternary ammonium salt, preferably
cetylpyridinium chloride, (iii) 0.5-20% w/w organic amines and/or
alkanol amine, (iv) 0.5-60% w/w water soluble glycol/polyol/glycol
ether/lactam or mixtures thereof, (v) 0-10% w/w of a dispersant
and/or a rheology modifier and/or a suspending agent, (vi) 0-60%
w/w of water.
3. An opaque, stable biocidal composition, said composition
comprising: (i) 0.01-20% w/w zinc pyrithione, (ii) 0.01-20% w/w
C.sub.8-C.sub.18 quaternary ammonium salt, preferably
cetylpyridinium chloride, (iii) 0.5-60% w/w water soluble
glycol/polyol/glycol ether/lactam or mixtures thereof, (iv) 0-10%
w/w of a dispersant and/or a rheology modifier and/or a suspending
agent, (v) 0-60% w/w of water.
4. A personal care formulation comprising the transparent or opaque
stable biocidal composition as claimed in any one of claim 1, 2 or
3.
5. A personal care formulation, said formulation comprising: (i)
0.01-10% w/w transparent or opaque, stable biocidal composition as
claimed in any one of claim 1, 2 or 3, (ii) 5-45% w/w surfactant
system, (iii) 15-75% water
6. The stable biocidal composition as claimed in any one of claims
1 to 3, wherein the C.sub.8-C.sub.18 quaternary ammonium salt is
cetylpyridinium chloride.
7. The stable biocidal composition and/or personal care formulation
as claimed in any of the claims 1 to 5, wherein the said
composition/formulation is in the form of a solution, suspension or
dispersion.
8. The stable biocidal composition and/or personal care formulation
as claimed in claims 1 to 5, wherein zinc pyrithione is present in
an amount of 0.5% to 20% w/w.
9. The stable biocidal composition and/or personal care formulation
as claimed in claims 1 to 5, wherein the C.sub.8-C.sub.18
quaternary ammonium salt is present in an amount of 0.01% to 20%
w/w.
10. The stable biocidal composition and/or personal care
formulation as claimed in claims 1 to 5, wherein C.sub.8-C.sub.18
quaternary ammonium salt is selected from methyltrioctyl ammonium
chloride, cetyltrimethyl ammonium bromide, cetylpyridinium
chloride, dodecyl(lauryl) pyridinium chloride, tetradecyl(myristyl)
pyridinium chloride, hexadecyl(cetyl) pyridinium chloride, methyl-
or ethyl-cetylpyridinium chloride and octadecyl(stearyl) pyridinium
chloride.
11. The stable biocidal composition and/or personal care
formulation as claimed in any one of claims 1 to 5, wherein organic
amines or alkanol amine is selected form the group comprising
monoethanol amine (MEA), 3-aminopropyldimethyl amine,
3-methoxypropyl amine, bis-(2-hydroxypropyl) amine and combinations
thereof.
12. The stable biocidal composition and/or personal care
formulation as claimed in any one of claims 1 to 5, wherein the
water soluble glycols/polyol/glycol ethers are selected from
propylene glycol, glycerol, sorbitol, PEG 400, polyglycol 500 DME,
ethylene glycol monoethyl ether, diethylene glycol monomethyl
ether, diethylene glycol monoethyl ether, diethylene glycol
dimethyl ether (diglyme), triethylene glycol dimethyl ether
(triglyme), tetraethylene glycol dimethyl ether (tetraglyme) and
combinations thereof; lactam is selected from 2-pyrrolidone,
N-methyl pyrrolidone (NMP), polyvinylpyrrolidone (PVP) and
combinations thereof.
13. A personal care formulation as claimed in claim 4 and/or 5,
further comprising one or more additional component selected from
diluents, suspending agents, humectants, pH regulators,
preservatives, perfumes, skin active agents and/or scalp modifiers,
hair growth and/or hair loss preventive agents, sunscreens, UV
absorbers, vitamins, herbal extracts and the like.
14. A process for preparing a transparent stable biocidal
composition as claimed in claim 1 and/or 2, said process
comprising: (a) adding an organic amine and/or alkanol amine to
zinc pyrithione to obtain a mixture, (b) adding a water soluble
glycol/polyol/glycol ether/lactam or mixtures thereof to the
mixture of step (a), (c) preparing a solution of the
C.sub.8-C.sub.18 quaternary ammonium salt, when present, in a
suitable solvent and mixing it with a solution or suspension of
dispersant, (d) adding the mixture of step (b) to the homogenous
solution of step (c).
15. A process for preparing an opaque stable biocidal composition
as claimed in claim 3, said process comprising: (a) preparing a
solution of C.sub.8-C.sub.18 quaternary ammonium salt, preferably
cetyl-pyridinium chloride in a suitable solvent and mixing it with
a solution or suspension of dispersant to obtain a mixture, (b)
adding zinc pyrithione concentrate to mixture obtained in step
(a).
16. A process for preparing a personal care formulation comprising:
(a) preparing an aqueous solution of one or more surfactants, (b)
adding dispersant and/or a rheology modifier and/or a suspending
agent to the above solution, (c) adding the stable biocidal
composition to the solution obtained in step (b) (d) adding one or
more additional component.
17. The process as claimed in any one of claim 14 or 15, wherein
the suitable solvent is selected from cosmetically acceptable
water, propylene glycol, glycerol, sorbitol, PEG 400, polyglycol
500 DME, ethylene glycol monoethyl ether, diethylene glycol
monomethyl ether, diethylene glycol monoethyl ether, diethylene
glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether
(triglyme), tetraethylene glycol dimethyl ether (tetraglyme),
2-pyrrolidone, N-methyl pyrrolidone (NMP), polyvinylpyrrolidone
(PVP) and combinations thereof.
18. The biocidal composition as claimed in claims 1, 2 and/or 3, as
and when used in the preparation of hair care formulations, in
particular anti-dandruff hair care formulations.
19. The biocidal composition as claimed in claims 1, 2 and/or 3, as
and when used as a biologically active agent for cutting oils and
coolant systems, as an agent for protecting cellulosic fibers from
loss of tensile strength due to action of fungi and as a
preservative for water based paints, coatings, adhesives, wet-state
preservatives, hard surface cleaners, fabric care compositions,
wood products, plastic products, personal care formulations,
medical products, fibers or any other antimicrobial application.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a National Stage of International
Application No. PCT/IN2014/000570, filed on Sep. 2, 2014, which
claims priority to Indian patent application no. 2640/DEL/2013,
filed on Sep. 6, 2013, the disclosures of which are incorporated by
reference in their entirety.
FIELD OF INVENTION
[0002] The present invention relates to a stable, transparent or
opaque biocidal compositions comprising zinc pyrithione alone or in
combination with a C.sub.8-C.sub.18 quaternary ammonium salt,
preferably cetylpyridinium chloride. The compositions possess
higher bio-availability and enhanced antifungal activity and are
capable for being formulated into various personal care and
industrial formulations.
BACKGROUND OF THE INVENTION
[0003] Zinc pyrithione (ZPTO), also known as zinc
pyridine-2-thiol-N-oxide or bis-[1-hydroxy-2(H)
pyridinethionato]-zinc is a broad spectrum antimicrobial agent and
has been used as fungicide and bactericide in various personal care
and pharmaceutical products, particularly in anti-dandruff
shampoos. ZPTO is also used as a biologically active agent for
cutting oils and coolant systems, as an agent for protecting
cellulosic fibres from loss of tensile strength due to action of
fungi and as a preservative for water based paints, coatings,
adhesives, wet-state preservatives, hard surface cleaners, fabric
care compositions, wood products, plastic products, medical
products, fibres or any other application where microorganism
growth must be stopped or slowed.
[0004] The antifungal and antimicrobial activity of ZPTO depends on
the bio-availability of ZPTO molecule on scalp. Because of poor
solubility in water (6-12 ppm), the concentration of ZPTO molecules
in aqueous media and thereafter on hair and scalp also remains low,
leading to poor bio-availability. Also, when used in personal care
formulations, it produces white suspension that precipitate in the
packaging bottle. Therefore, to overcome these disadvantages of low
water solubility, precipitations and poor bio-availability, ZPTO is
generally used in excess (1-2% w/w) but higher concentration of
ZPTO lacks ready consumer acceptability due to harshness.
[0005] There had been many approaches to increase the
solubilisation and antimicrobial efficacy of zinc pyrithione.
[0006] U.S. Pat. No. 3,636,213 discloses solubilisation of heavy
metal pyrithione salts in common organic solvents and/or water by
combination with primary alkyl and aryl monoamines or
polyalkyleneimines, preferably dodecyl amine and diglycol amine for
use in hair dressings. The compositions have pH's from about
8.5-9.0.
[0007] U.S. Pat. No. 3,785,985 and U.S. Pat. No. 3,940,482 describe
the solubilization of heavy metal pyrithione salts in water and
detergent containing compositions with aliphatic polyamine.
However, ZPTO solubilized in alcohol/water system using
polyethylenimine has pH of about 9.0 or above and reducing pH less
than 8.0 leads to precipitation of ZPTO in the system.
[0008] U.S. Pat. No. 4,835,149 discloses the use of alkanol and/or
alkyl amines in the solublizing a metal pyrithione salt in the
preparation of a shampoo effective for the treatment of seborrhea
and dandruff. The amines include ethanolamine, diethanolamine,
monoisopropylamine and others together with a cosmetically
effective amount of an aminopolycarboxylic acid to regulate the pH
of the system between 6.5-7.5.
[0009] U.S. Pat. No. 6,908,912 discloses a stable, soluble,
antimicrobial composition where insoluble metal salts of pyrithione
in combination with a zinc source (zinc salts, -oxides,
-hydroxides, -borates, -sulfates, -chlorides etc.) were solubilised
in an organic amine (1,2-alkanolamines and 1,3-alkanolamines) alone
or in combination with a second organic amine (monomeric and
polymeric forms of 1,2-alkyldiamines and 1,3-alkyldiamines). These
compositions deliver higher concentration of pyrithione and zinc
ions to an application (in-can preservatives and metalworking
fluids) and thus provide enhanced biocidal efficacy against
microorganisms and bio-films.
[0010] It is known that below pH 4.5 zinc complex dissociates into
free pyrithione and above pH 9.5, zinc complex hydrolyzes to yield
ionized pyrithione and zincate species. Both free and ionized
pyrithione are biologically active but being much more water
soluble than the zinc complex they are most susceptible to
degradation from exposure to light or oxygen. In the patent
applications cited above, where different types of amines have been
used to solubilize ZPTO, either require pH adjustment,
pre-formulation of the actives or give precipitate on pH
adjustment. Also these prior arts do not disclose any improved or
enhanced antifungal or antimicrobial activity particularly the
anti-dandruff efficacy for the resulting solubilized ZPTO as
compared to ZPTO suspensions. Further, it is extremely difficult to
simultaneously attain superior hair sensory attributes along with
higher anti-dandruff efficacy from ZPTO containing compositions (US
2006/0182696).
[0011] WO 20010095717 discloses that cationic polymers can increase
the efficacy of zinc pyrithione in an anti-dandruff shampoos by
enhancing the deposition and retention of the water insoluble ZPTO
particles on scalp. Similarly polyethylenimine or the reaction
product of polyethylenimine and ethylene oxide or propylene oxide
(U.S. Pat. No. 3,489,686); water-soluble cationic
nitrogen-containing polymers or nitrogen-substituted cellulose
ether derivatives (U.S. Pat. No. 3,580,853) and piperidinum
chloride (U.S. Pat. No. 3,761,417) have also been disclosed to
increase the efficacy of ZPTO. However, the effect on adsorption of
a metal pyrithione salt such as zinc pyrithione was not found
sufficient for required or enhanced anti-dandruff efficacy.
[0012] U.S. Pat. No. 4,557,928 describes the use of acrylamide
copolymer quaternium 41 and Methocel to create more efficacious
zinc pyrithione anti-dandruff shampoo but these shampoos were found
unstable over a long period of time.
[0013] Cationic surfactants such as amino or quaternary ammonium
hydrophilic moieties has been used as cationic surfactant or
emulsifying agent in hair conditioners, shampoos, anti-static
formulations, fabric softeners and other cosmetics and toiletries
preparations (EP 0034385, EP 0941061, US 2008/0057015, U.S. Pat.
No. 8,506,942, US 2012/0064136, U.S. Pat. No. 8,206,694 and US
2012/0100092). Some of them like cetyl pyridinium chloride, is also
commonly used as antiseptic and/or antimicrobial component at low
concentrations (0.025-0.1%) in many OTC health care products
(creams, dentifrices, deodorizing and antiperspirant preparations
mouth washes, toothpastes, lozenges, throat sprays, cough syrups,
nasal sprays and pre-moistened wipes) deodorant.
[0014] US 2007/0020221 describes the use of cetylpyridinium
chloride (CPC) as a skin lightening or pigmentation reducing
cosmetic agent in cosmetic compositions to regulate the condition
of mammalian keratinous tissue particularly for preventing,
retarding, and/or treating uneven skin tone.
[0015] US 2006/0241190 describes the specific utility of
cetylpyridinium chloride in cosmetic compositions as a keratolytic
active with SLES for the treatment of psoriasis, eczema and like
skin disorders.
[0016] As antimicrobial active in shampoos and/or hair care
products, US 2011/0287074 describes the use of CPC as secondary
antimicrobial agent in the form of a micro-emulsion. US 2012/012172
provides an antimicrobial composition with a synergistic effect of
laurylamine oxide and CPC. This composition which has strong
antimicrobial efficacy can be incorporated into shampoos for the
treatment of fungal and/or bacterial infection on skin or mucosal
surfaces.
[0017] Although the prior art describes that cationic polymers can
enhance the deposition of ZPTO on scalp, it is extremely difficult
to formulate their stable composition as they show problems in
formulation compatibility particularly with ZPTO, resulting in loss
of transparency, drop in viscosity and instability over a long
period of time.
[0018] Thus, there is a need to develop antimicrobial stock
compositions and/or personal care formulations with ZPTO in such a
manner that ZPTO remains solubilised, maintains transparency above
90%, remains stable in wide pH range and storage conditions,
aesthetically more desirable and simultaneously imparts high
anti-dandruff efficacy at low concentration of active(s).
SUMMARY OF THE INVENTION
[0019] The present invention is directed to transparent or opaque
biocidal compositions and their formulations, said composition
comprising zinc pyrithione either alone or in combination with a
C.sub.8-C.sub.18 quaternary ammonium salt, preferably
cetylpyridinium chloride.
[0020] The compositions of the present invention can be transparent
or opaque, possess higher bio-availability and enhanced
anti-dandruff efficacy at lower concentration of active(s), are
stable at varying pH and humidity conditions and can be easily
formulated into various personal care and industrial
formulations.
[0021] An embodiment of the present invention is directed to a
transparent or opaque stable biocidal composition comprising: (i)
0.5-35% w/w of ZPTO, (ii) 0-20% w/w of a C.sub.8-C.sub.18
quaternary ammonium salt, preferably cetylpyridinium chloride (iii)
0.5-20% w/w organic amines and/or alkanol amine, (iv) 0.5-60% w/w
water soluble glycol/polyol/glycol ether/lactam or mixtures
thereof, (v) 0-10% w/w of a dispersant and/or a rheology modifier
and/or a suspending agent, (vi) 0-60% w/w of water.
DETAILED DESCRIPTION OF THE INVENTION
[0022] The present invention provides a stable biocidal composition
with enhanced antifungal activity and efficacy. The present
invention also provides a biocidal composition having one or more
C.sub.8-C.sub.18 quaternary ammonium salt in addition to zinc
pyrithione. The biocidal compositions of the present invention
possess high bio-availability of zinc pyrithione. The compositions
of the present invention is opaque or transparent.
[0023] The inventors of the present invention have surprisingly
found that quaternary ammonium salt, in particular C.sub.8-C.sub.18
quaternary ammonium salt such as cetylpyridinium chloride (CPC)
possess significant anti-malassezia or anti-dandruff activity alone
and shows enhanced anti-dandruff activity in combination with lower
concentrations of ZPTO. The compositions and formulations of the
present invention possess superior anti-dandruff efficacy at lower
concentrations of active (s), ZPTO and C.sub.8-C.sub.18 quaternary
ammonium salt. The compositions of the present invention are stable
and also impart better sensorial benefits.
[0024] The invention described herein in detail using the terms
defined below unless otherwise specified.
[0025] The term "biocidal composition" as used herein refers to a
solution, suspension and/or a dispersion comprising zinc pyrithione
either alone or in combination with a C.sub.8-C.sub.18 quaternary
ammonium salt wherein the said composition is capable of inhibiting
microbial growth.
[0026] The term "stock" as used herein refers to a concentrated
solution, suspension and/or a dispersion comprising zinc pyrithione
either alone or in combination with a quaternary ammonium salt as
active.
[0027] The term "zinc pyrithione concentrate" refers to an aqueous
suspension of zinc pyrithione in an amount from 25-50% w/w.
[0028] The term "personal care formulation" as used herein refers
to various toiletries and cosmetic preparation used for general
health and hygiene and grooming Examples of personal care
formulation includes but are not limited to shower gel, soap,
conditioners, body lotion and shampoo, anti-dandruff shampoo,
anti-dandruff hair gel, and the like.
[0029] The term "C.sub.8-C.sub.18 quaternary ammonium salt" as used
herein refers to salts of quaternary ammonium cations with anions.
The quaternary ammonium cations are positively charged polyatomic
ions in which a central nitrogen atom is attached to same or
different four straight chain or branched alkyl group (having from
8-18 carbon atoms) or a pyridine nitrogen attached to
C.sub.8-C.sub.18 alkyl group. Examples of C.sub.8-C.sub.18
quaternary ammonium salt includes but are not limited to
methyltrioctyl ammonium chloride, cetyltrimethyl ammonium chloride,
decyltrimethyl ammonium chloride, didecyldimethyl ammonium
chloride, trimethyltetradecyl ammonium bromide; dodecyl(lauryl)
pyridinium chloride, tetradecyl(myristyl) pyridinium chloride,
hexadecyl(cetyl) pyridinium chloride, methyl- or ethyl-
cetylpyridinium chloride and octadecyl(stearyl) pyridinium
chloride; alkylbenzyldimethyl ammonium halides or benzalkonium
halides with chain lengths of C.sub.8-C.sub.18, predominantly
C.sub.12 to C.sub.16, like cetalkonium chloride, benzethonium
chloride, lauralkonium halide and stearalkonium chloride.
[0030] The term "surfactant" as used herein refers to substances
which lower the surface tension of the medium in which it is
dissolved, and/or the interfacial tension with other phases, and,
accordingly, is positively adsorbed at the liquid/vapour and/or at
other interfaces. Surfactants have a hydrophobic (water repellent)
part and a hydrophilic (`water loving`) part. The hydrophobic part
consists of an uncharged carbohydrate group that can be straight,
branched, cyclic or aromatic. Depending on the nature of the
hydrophilic part the surfactants are classified as anionic,
cationic, non-ionic, or amphoteric.
[0031] The term "anionic surfactant" as used herein refers to those
surfactants where the hydrophilic part consists of a negatively
charged group like a sulphonate, sulphate or carboxylate the
surfactant. Examples of anionic surfactant include but are not
limited to sodium, potassium or ammonium salts of long chain
sulphates having carbon chain lengths 6-14, preferably sodium
lauryl sulfate (SLS), sodium laureth sulfate (SLES), triethylamine
lauryl sulfate, triethylamine laureth sulfate, triethanolamine
lauryl sulfate, triethanolamine laureth sulfate, monoethanolamine
lauryl sulfate, monoethanolamine laureth sulfate, diethanolamine
lauryl sulfate, diethanolamine laureth sulfate, ammonium lauryl
sulfate, ammonium laureth sulfate, lauric monoglyceride sodium
sulfate, potassium lauryl sulfate, potassium laureth sulfate,
sodium lauryl sarcosinate, sodium lauroyl sarcosinate, lauryl
sarcosine, cocoyl sarcosine, ammonium cocoyl sulfate, ammonium
lauroyl sulfate, sodium cocoyl sulfate, sodium lauroyl sulfate,
potassium cocoyl sulfate, potassium lauryl sulfate,
monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate,
sodium tridecyl benzene sulfonate, sodium dodecyl benzene
sulfonate, sodium cocoyl isethionate, amino acid derived
surfactants and combinations thereof.
[0032] The term "cationic surfactant" as used herein refers to
those surfactants where the hydrophilic part consists of a
positively charged group. Examples of cationic surfactant include
but are not limited to cetyl pyridinium chloride, stearyl
pyridinium chloride, methyl or ethyl cetyl pyridinium chloride,
aralkyl ammonium halides such as benzyl triethyl ammonium chloride,
benzalkonium chloride, cetalkonium chloride, benzethonium chloride,
lauryltrimethyl ammonium halide, cetrimonium halide or
cetyltrimethyl ammonium halide, glycidyltrimethylammonium halide,
tallowtrimethyl ammonium chloride, cocotrimethyl ammonium chloride,
vitamin B6 hydrochloride, behenyltrimethyl ammonium chloride
(BTAC), octyltrimethyl ammonium chloride, octyldimethylbenzyl
ammonium chloride, decyldimethylbenzyl ammonium chloride,
stearyldimethylbenzyl ammonium chloride, didodecyldimethyl ammonium
chloride, dioctadecyldimethyl ammonium chloride,
dipalmitoylethyldimethyl ammonium chloride and combinations
thereof.
[0033] The term "non-ionic surfactant" as used herein refers those
surfactants where the hydrophilic part is not charged. Examples of
non-ionic surfactant include, but are not limited to Lamesoft PO65,
polyoxyethylene (20) sorbitan monooleate (Tween 80),
polyoxyethylene (20) sorbitan monolaurate (Tween 20), ethoxylated
sorbitan monolaurate (Crillet 180) and combinations thereof.
[0034] The term "amphoteric surfactant" as used herein refers to
those surfactants wherein hydrophilic part can be either positively
or negatively charges depending on the pH of the solution. They can
act as anionic surfactant in an alkaline solution or as cationic
surfactant in an acidic solution. Examples of amphoteric surfactant
include but are not limited to cocamidopropyl betaine (CAPB) or
cocamide DEA and combinations thereof.
[0035] The term "surfactant system" as used herein refers to one or
more surfactants selected form anionic surfactant, cationic
surfactant, non-ionic surfactant, amphoteric surfactants or a
combination thereof.
[0036] The term "suspending agents", are as used herein refers to
insoluble particles dispersed in a vehicle and help to reduce the
sedimentation rate of particles in suspension. The term
"dispersants" as used herein are substances which facilitate the
dispersion of aggregates and improve the kinetic stability of the
particles. The term "Theology modifiers" as used herein refers to
compounds/polymers which alter the thickness or viscosity of the
system. Throughout the specification, these terms have been used
interchangeably. Examples of dispersants and/or rheology modifier
and/or suspending agent as used herein include but are not limited
to sodium and potassium salts of alkyl-aryl sulfonic acids and/or
polymerized alkyl-aryl sulfonic acids and/or formaldehyde
complexes, synthetic silicates, castor oil based thixotropes and
organic thixoptropes, carboxymethylcellulose, organoclays,
synthetic clays, polymers of acrylic acid cross-linked with
polyalkenyl ethers or divinyl glycol, Stepan TAB-2, Stepan SAB-2,
Carbopol ETD 2020, Carbopol Aqua SF-1, Carbopol Ultrez 20, Rheocare
TTA, Rheocare C Plus, xanthum gum, dehydroxanthan gum like Amaze
XT, methyl hydroxyethylcellulose like Structure Cell 12000 and
combinations thereof. Sodium and potassium salts of alkyl-aryl
sulfonic acids and/or polymerized alkyl-aryl sulfonic acids and/or
formaldehyde complexes is selected from but not limited to Tytan
series, Tysperse series, DARVAN Series, DEMOL Series, DAXAD Series,
TAMOL Series, HAROL Series, LOMAR Series and the likes; synthetic
silicates is selected from but not limited to sodium aluminium
silicate, magnesium aluminum silicates and the likes; organoclays
such as Claytone, Tixogel and the likes; synthetic clay such as
Veegum, Laponite and the likes.
[0037] The term "suitable solvent" as used herein refers to
cosmetically acceptable water and water miscible solvents such as
glycol, polyol, glycol ethers, lactams and the like. Exemplary
water miscible glycols/polyol/glycol ethers include but are not
limited to propylene glycol, glycerol, sorbitol, PEG 400,
polyglycol 500 DME, ethylene glycol monoethyl ether, diethylene
glycol monomethyl ether, diethylene glycol monoethyl ether,
diethylene glycol dimethyl ether (diglyme), triethylene glycol
dimethyl ether (triglyme), tetraethylene glycol dimethyl ether
(tetraglyme) and combinations thereof; exemplary lactams include
but are not limited to 2-pyrrolidone, N-methyl pyrrolidone (NMP),
polyvinylpyrrolidone (PVP) and combinations thereof.
[0038] In one embodiment, the present invention provides a
transparent, stable biocidal composition of zinc pyrithione. The
said composition comprises (i) 0.5-35% w/w of ZPTO, (ii) 0.5-20%
w/w organic amines and/or alkanol amine, (iii) 0.5-60% w/w water
soluble glycol/polyol/glycol ether/lactam or mixtures thereof, (iv)
0-10% w/w of a dispersant and/or a rheology modifier and/or a
suspending agent, (v) 0-60% w/w of water.
[0039] In another embodiment, the present invention provides a
transparent, stable biocidal composition of zinc pyrithione and a
C.sub.8-C.sub.18 quaternary ammonium salt. The said composition
comprises (i) 0.5-35% w/w of ZPTO, (ii) 0.05-20% w/w of a
C.sub.8-C.sub.18 quaternary ammonium salt, (iii) 0.5-20% w/w
organic amines and/or alkanol amine, (iv) 0.5-60% w/w water soluble
glycol/polyol/glycol ether/lactams or mixtures thereof, (v) 0-10%
w/w of a dispersant and/or a rheology modifier and/or a suspending
agent, (vi) 0- 60% w/w of water.
[0040] In yet another embodiment the present invention provides an
opaque, stable biocidal composition of zinc pyrithione and a
C.sub.8-C.sub.18 quaternary ammonium salt, preferably
cetylpyridinium chloride. The said composition comprises (i)
0.01-10% w/w zinc pyrithione, (ii) 0.01-10% w/w C.sub.8-C.sub.18
quaternary ammonium salt, preferably cetylpyridinium chloride, (iv)
0.5-60% w/w water soluble glycol/polyol/glycol ether/lactam or
mixtures thereof, (v) 0-10% w/w of a dispersant and/or a rheology
modifier and/or a suspending agent, (vi) 0-60% w/w of water.
[0041] The stable biocidal composition of the present invention and
the formulations prepared from it, is in the form of a solution,
suspension or dispersion. They are present in transparent or opaque
form.
[0042] In a preferred embodiment the stable biocidal composition
and the formulations prepared from the same are in transparent
form. The transparent or opaque stable biocidal composition of the
present invention as described herein can be incorporated into
various personal care or industrial formulation.
[0043] In a preferred embodiment, the compositions of the present
invention are incorporated into a personal care formulation.
[0044] In one embodiment the present invention provides personal
care formulation comprising the 0.01% to 20% w/w of the transparent
or opaque, stable biocidal composition of the present invention as
described herein.
[0045] In another embodiment the present invention provides
personal care formulation comprising 0.01% to 10% w/w of the
transparent or opaque, stable biocidal composition of the present
invention as described herein.
[0046] In a preferred embodiment the present invention provides a
personal care formulation, said formulation comprising (i) 0.01-10%
w/w transparent or opaque stable biocidal composition as described
hereinabove, (ii) 5-45% w/w surfactant system, (iii) 15-75%
water.
[0047] In yet another embodiment, the personal care formulation of
the present invention further comprises one or more additional
component selected from diluents, suspending agents, humectants, pH
regulators, preservatives, perfumes, skin active agents and/or
scalp modifiers, hair growth and/or hair loss preventive agents,
sunscreens, UV absorbers, vitamins and/or herbal/fruit
extracts.
[0048] In a preferred embodiment, the compositions of the present
invention are incorporated into a hair care formulation.
[0049] In the most preferred embodiment, the compositions of the
present invention are incorporated into an anti-dandruff hair care
formulation.
[0050] In a yet another embodiment, the present invention provides
a process for the preparation of stable biocidal compositions and
their formulations, in particular personal care formulation.
[0051] In another embodiment, the present invention provides a
process for preparing a transparent, stable biocidal composition as
described hereinabove, said process comprising:
[0052] (a) adding an organic amine and/or alkanol amine to zinc
pyrithione to obtain a mixture,
[0053] (b) adding a water soluble glycol/polyol/glycol ether/lactam
or mixtures thereof to the mixture of step (a),
[0054] (c) preparing a solution of the C.sub.8-C.sub.18 quaternary
ammonium salt, when present, in a suitable solvent and mixing it
with a solution or suspension of dispersant,
[0055] (d) adding the mixture of step (b) to the homogenous
solution of step (c).
[0056] In another embodiment, the present invention provides a
process for preparing an opaque, stable biocidal composition as
described hereinabove, said process comprising:
[0057] (a) preparing a solution of C.sub.8-C.sub.18 quaternary
ammonium salt, preferably cetylpyridinium chloride in a suitable
solvent and mixing it with a solution or suspension of dispersant
to obtain a mixture,
[0058] (b) adding zinc pyrithione concentrate to mixture obtained
in step (a),
[0059] In yet another embodiment, the present invention provides a
process for preparing a personal care formulation, said process
comprising:
[0060] (a) preparing an aqueous solution of one or more
surfactants,
[0061] (b) adding a dispersant and/or a rheology modifier and/or a
suspending agent to the above solution,
[0062] (c) adding the opaque or transparent, stable biocidal
composition as described hereinabove to the solution obtained in
step (b)
[0063] (d) adding one or more additional component.
[0064] The suitable solvent used in the process of the present
invention is selected from cosmetically acceptable water, propylene
glycol, glycerol, sorbitol, PEG 400, polyglycol 500 DME, ethylene
glycol monoethyl ether, diethylene glycol monomethyl ether,
diethylene glycol monoethyl ether, diethylene glycol dimethyl ether
(diglyme), triethylene glycol dimethyl ether (triglyme),
tetraethylene glycol dimethyl ether (tetraglyme), 2-pyrrolidone,
N-methyl pyrrolidone (NMP), polyvinylpyrrolidone (PVP) and
combinations thereof.
[0065] In a preferred embodiment, the present invention provides a
stable biocidal composition and/or personal care formulation
wherein zinc pyrithione is present in an amount of 0.5% to 20%
w/w.
[0066] In a preferred embodiment, the C.sub.8-C.sub.18 quaternary
ammonium salt is selected from methyltrioctyl ammonium chloride,
cetyltrimethyl ammonium bromide, cetylpyridinium chloride,
dodecyl(lauryl) pyridinium chloride, tetradecyl(myristyl)
pyridinium chloride, hexadecyl(cetyl) pyridinium chloride, methyl-
or ethyl-cetylpyridinium chloride and octadecyl(stearyl) pyridinium
chloride.
[0067] In the most preferred embodiment the C.sub.8-C.sub.18
quaternary ammonium salt is cetylpyridinium chloride. The
cetylpyridinium chloride is anhydrous or monohydrate.
[0068] In a preferred embodiment of the present invention, the
C.sub.8-C.sub.18 quaternary ammonium salt is present in an amount
of 0.01% to 20% w/w.
[0069] The organic amines or alkanol amine used in the present
invention is selected from the group comprising monoethanol amine
(MEA), 3-aminopropyldimethyl amine, 3-methoxypropyl amine,
bis-(2-hydroxypropyl) amine and combinations thereof; lactam is
selected from 2-pyrrolidone, N-methyl pyrrolidone (NMP),
polyvinylpyrrolidone (PVP) and combinations thereof.
[0070] In a preferred embodiment, the organic amines or alkanol
amine is selected from one or more of monoethanol amine (MEA),
N-methyl pyrrolidone (NMP), polyvinylpyrrolidone (PVP).
[0071] The water soluble glycols/polyol/glycol ethers used in the
present invention is selected from propylene glycol, glycerol,
sorbitol, PEG 400, polyglycol 500 DME, ethylene glycol monoethyl
ether, diethylene glycol monomethyl ether, diethylene glycol
monoethyl ether, diethylene glycol dimethyl ether (diglyme),
triethylene glycol dimethyl ether (triglyme), tetraethylene glycol
dimethyl ether (tetraglyme) and combinations thereof.
[0072] The compositions of the present invention can be transparent
or opaque, possess higher bio-availability and anti-dandruff
efficacy and at lower concentration of active(s), are stable at
varying pH and humidity conditions and can be easily formulated
into various personal care and industrial formulations.
[0073] The composition of the present invention can be incorporated
into various personal care or industrial formulations such as for
cutting oils and coolant systems, as an agent for protecting
cellulosic fibers from loss of tensile strength due to action of
fungi and as a preservative for water based paints, coatings,
adhesives, wet-state preservatives, hard surface cleaners, hair
care compositions, fabric care compositions, wood products, plastic
products, medical products, fibers or any other antimicrobial
application.
EXAMPLES
[0074] The invention is explained in detail in the following
examples which are given solely for the purpose of illustration
only and therefore should not be construed to limit the scope of
the invention.
Example 1: Preparation of Transparent ZPTO Stock
[0075] To the weighed amount of ZPTO (w/w), monoethanolamine was
added. Thereafter, NMP was added and contents were stirred with
heating at 40-45.degree. C. Propylene glycol, sorbitol and
polyethylene glycol 400 were then added to the above mixture with
continuous stirring to obtain the desired transparent composition.
An exemplary composition obtained from the above process is
tabulated below:
TABLE-US-00001 TABLE 1 Composition of transparent ZPTO stock 15%
ZPTO Stock 10% ZPTO Stock Ingredients Solution Solution ZPTO 15%
10% Monoethanol amine 10% 7% N-methyl pyrrolidone 25% 24% Propylene
glycol 12% 18% Sorbitol 9.5% 8.5% PEG 400 10% 12% Water 18.5%.sup.
20.5%.sup.
Example 2: Preparation of Transparent ZPTO-CPC Stock
[0076] ZPTO solution was prepared by dissolving ZPTO in monoethanol
amine and NMP with stirring at 40-45.degree. C. Similarly, CPC
solution was prepared by dissolving in propylene glycol.
[0077] This solution was added to an aqueous solution of dispersant
(Tytan N) and sorbitol. To this solution, ZPTO solution was added
slowly with continuous stirring to obtain the desired transparent
composition. An exemplary composition obtained from the above
process is tabulated below:
TABLE-US-00002 TABLE 2 Composition of transparent ZPTO - CPC stock:
Ingredients Quantity ZPTO 10% Monoethanol amine 10% N-methyl
pyrrolidine 25% CPC 10% Propylene glycol 25% Sorbitol 3.5% Rheocare
TTA 1% Tytan N 0.5% Water 15%
Example 3: Preparation of Opaque ZPTO-CPC Stock
[0078] CPC was dissolved in water in 1:2.5 ratio. A dispersant
solution was also prepared. In a separate vessel, Ultrez 20 was
sprinkled over the rest of water. After complete wetting (.about.5
min), contents were stirred at slow speed and then dispersant and
CPC compound (10%) solutions were mixed. Mixture was stirred for 15
min at 40.degree. C. Required amount of zinc pyrithione concentrate
was added with continuous mixing at high rpm (600). This mixture
was stirred for 30 min and finally a stable white suspension was
obtained. An exemplary composition obtained from the above process
is tabulated below:
TABLE-US-00003 TABLE 3 Composition of opaque stocks suspension of
ZPTO and CPC: Ingredients Quantity ZPTO (48% suspension) 10% CPC
10% Ultrez 20 1.2% Water 75% Tytan N 3.8%
Example 4: Preparation of Personal Care Formulation
[0079] In a 250 ml capacity kettle (thick walled beaker), weighed
amount of SLES (2EO), SLS (Galaxy 780) and water were taken and
heated till 55.degree. C. with mixing to make a transparent
homogenous mixture. To this hot mixture, weighed amount of suitable
rheology modifier (Carbopol Aqua SF-1, Ultrez 20, Rheocare TTA
etc.) was added slowly with continuous mixing. To this mixture,
required amount of ZPTO solution from the stock solution (as
prepared in example 1 or 2), was added drop-wise to obtain a
transparent composition. The pH of the system was maintained in the
range of 6.5-8. Thereafter, CAPB was added at 50.degree. C.,
followed by addition of glycerin, hydrovance and aqueous solution
of Merquat 3330 (conditioner) below 40.degree. C. with continuous
stirring. After addition of all above mentioned ingredients,
fragrances compatible with aqueous system like Filip ES or Surf ES
(Robertet) is added to the system at room temperature
(25-30.degree. C.). Total weight of kettle was taken and according
to water loss, required amount of water was added. The mixture was
stirred further for 10-15 min and was stored at room temperature in
a container.
TABLE-US-00004 TABLE 4 Transparent hair care formulations
Ingredients Formulation Used (in %) 1 2 3 4 5 6 7 8 SLES (2EO-28%)
20.00 22.50 27.00 24.50 30.00 30.50 30.00 28.50 SLS (28%) 8.00
10.00 9.70 10.75 8.75 10.00 11.00 10.00 DI Water 53.00 21.50 24.00
20.25 22.00 18.00 32.00 40.50 Ultrez 20 -- -- -- -- -- -- 3.25 4.50
Carbopol 6.00 9.00 7.00 -- -- -- -- -- Aqua SF-1 Rheocare TTA -- --
-- 5.25 6.50 8.00 -- -- zinc -- 2.00 (s) 2.00 (s) 2.00 (s) 2.00
2.00 -- -- Pyrithione (15%) (10%) ZPTO-CPC -- -- -- -- -- -- 2.00
2.00 Mix (1:1) (1:1) Monoethanol -- 12.75 1.00 2.50 -- 0.50 -- --
Amine N-methyl -- -- 8.50 -- 4.50 4.00 -- -- Pyrrolidone DEGMEE* --
-- -- 20.50 -- -- 2.25 -- NaOH (18%) 0.90 -- -- -- -- -- -- 0.45
CAPB 6.00 5.00 6.00 5.00 8.00 8.00 6.00 8.00 PEG 400 4.00 8.00 5.00
5.00 6.00 6.00 4.50 -- Glycerin -- -- -- 2.00 -- 2.50 1 -- PG** --
-- 5.00 -- 2.0 2.25 2.50 2.50 Sorbitol -- 2.00 2.00 -- 4.00 -- --
-- Hydrovance 1.00 1.5 1.50 -- 1.00 2.00 2.00 1.55 Merquat Plus
3330 1.10 0.50 1.00 0.50 2.00 1.50 1.00 -- Colaquat CCG -- -- -- --
-- -- -- 2.00 Neutralizer -- 5.25 0.30 1.75 3.25 4.75 2.50 -- Total
formula 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00
*DEGMEE = Diethylene glycol monoethyl ether; **PG = Propylene
Glycol
Example 5: Physical Stability Studies of the Compositions Obtained
in Examples 1-4
[0080] The stability of the compositions and their formulations
with time and varying humidity conditions was tested and the
results show that the compositions are stable in wide pH range
(6.5-12) and show transparency of more than 90%.
Example 6: Antifungal/Anti-Dandruff Activity Studies
[0081] The anti-dandruff efficacy was determined by measuring zone
of inhibition using disc diffusion method against Malassezia furfur
(ATCC No. 14521). In this procedure, 10 .mu.l of sample was added
on the filter paper disc and the disc was kept in the microbial
culture swabbed on the culture media. The culture plates were
incubated at 37.degree. C. for 48 hrs and anti-fungal activity was
evaluated by observing an area of no growth around the disc. An
area of no growth around the swatch is known as a zone of
inhibition. The results are depicted in Table 5. Similarly, the
anti-dandruff activities for ZPTO and ZPTO-CPC stock compositions
and shampoo formulations against M. furfur have been done and data
are summarized below in table 6:
TABLE-US-00005 TABLE 5 Anti-dandruff activities for various ZPTO
containing samples against M. Furfur Anti-dandruff (M. Quantity
furfur) activity tested Zone of Inhibition Example Sample details
(in %) (in mm) 1 ZPTO suspension in water 2% 20 mm ZPTO suspension
in water 0.2%.sup. 20 mm ZPTO solution in MEA + NMP 2% 25 mm ZPTO
solution 0.2%.sup. 25 mm ZPTO in surfactant + water 2% 20 mm ZPTO
in surfactant + water 0.2%.sup. 20 mm ZPTO solution in surfactant +
MEA + NMP 2% 25 mm ZPTO solution in surfactant + MEA + NMP
0.2%.sup. 25 mm Surfactant + water 2% No activity Surfactant + MEA
+ NMP + water No activity
TABLE-US-00006 TABLE 6 Anti-dandruff activities for stock
compositions and shampoo formulations against M. furfur
Anti-dandruff (M. Quantity furfur) activity tested Zone of
Inhibition Example Sample Details (%) (in mm) 1 TSP ZPTO Stock
(10%) 2% 45 TSP ZPTO Stock (10%) 1% 42 TSP ZPTO Stock (10%)
0.5%.sup. 42 TSP ZPTO Shampoo (10%) 0.5%.sup. 40 TSP ZPTO Shampoo
(10%) 2% 48 TSP ZPTO Shampoo (10%) 1% 45 TSP ZPTO Stock (15%) 2% 48
TSP ZPTO Shampoo (15%) 2% 45 2 TSP ZPTO-CPC Stock (10-10%)
1-1%.sup. 64 TSP ZPTO-CPC Stock (10-10%) 0.5-0.5% .sup. 54 TSP
ZPTO-CPC Shampoo (10-10%) 1-1%.sup. 65 TSP ZPTO-CPC Shampoo
(10-10%) 0.5-0.5% .sup. 52 3 Opaque ZPTO Stock (48%) 2% 30 Opaque
ZPTO Stock (48%) 1% 28 Opaque ZPTO Stock (48%) 0.5%.sup. 20 Opaque
ZPTO Shampoo (2%) 2% 25 Opaque ZPTO Shampoo (2%) 1% 22 Opaque
ZPTO-CPC Stock (10-10%) 1-1%.sup. 55 Opaque ZPTO-CPC Stock (10-10%)
0.5-0.5% .sup. 48 Opaque ZPTO-CPC Shampoo (10-10%) 1-1%.sup. 52
Opaque ZPTO-CPC Shampoo (10-10%) 0.5-0.5% .sup. 46 TSP Shampoo
(Blank) -- No Activity Opaque Shampoo (Blank) -- No Activity *TSP:
Transparent
* * * * *