Field of Invention
The present invention relates to a synergistic hair care composition adapted to provide
combination of antidandruff activity with keratoiytic efficacy and conditioning
properties. More particularly the present invention relates to shampoo composition
comprising antifungal agent and keratoiytic agent like papain in defined amount
providing the synergistic effect. The invention also relates to a method of cleansing and
conditioning the hair comprising applying to the hair and scalp and effective amount of
said compositions.
Background and Prior Art
A person's entire body surface continuously sheds dead skin cells at the rate of l-2g/day
(normal cell renewal 24-30 days). Dandruff is the shedding of dead skin cells from the
scalp at an excessive rate (cell renewal 17-20 days). The result is a growing number of
dead skin cells (white flakes) shed by the surface of the scalp and trapped by the hair.
Malassezia furfur is a micro organism implicated to be associated with dandruff. It
generates free fatty acids on the scalp - free fatty acids cause increased cell turnover,
irritation and itching. There are number of Active Ingredients in use today for the control
of the abnormal state or condition of dandruff. These include the following -
climbazole,
coal tar distillate,
colloidal sulphur
dipyrithion magnesium salt
ketoconazole
piroctone olamine (octopirox)
salicylic acid (singular or in combination with other actives)
selenium disulfide
sulphuric tar distillate
usnic acid
zinc pyrithion

WO 2001/019871 teaches delivery of active agents at the target site to combat/ treat and
or prevent dandruff. It teaches use of antibodies /fragments thereof which are capable of
binding to Malassezia furfur to target delivery of the active agents to the site, specially
delivery the actives to the scalp or the treatment of dandruff. It particularly teaches
composition for topical application comprising an active agent conjugated with a
molecule like antibody which specifically binds with the microorganism Malassezia
furfur. It is also applicable to other molecules which function as binding ligands to the
microorganism in a similar way. The direction of this art is to provide actives specifically
to the site of dandruff and thus cause site directed activity without loss of agents.
Moreover this leads to use of less actives and yet achieve high efficacy. Accordingly
compositions which are long active, faster acting and retain the active cane be deposited
at the specific site. Moreover high amount of active directed to scalp rather than the hair
reduces damage and increases better feel.
The actives taught in WO 2001/019871 includes lytic enzymes. Inhibitors of enzymes of
M. furfur, its inhibitory substrate analogue, proteases like papain, pepsin etc which attack
M. furfur or its extra cellular enzymes. Alternatively the antimicrobials include peptides,
metal salts, biphenolic compounds, antifungal agents, metal pyrithiones, etc.
However there is no disclosure as to use of combination of the proteases along with
antifungal agents. Moreover the document is directed to site specific delivery of the
actives to the site and how the actives including papain or antifungal agent is compatible
with the antibodies and other ligands useful for the delivery. There is no disclosure as to
the combination of the two types of agents, leave alone their direct combination without
any use of antibodies/other ligands.
W0 2008/024308, US 6306805, WO 2002/022105 teach various compositions which
include anti dandruff composition where zinc pyrithion is used. The use of papain as
enzyme is mentioned in each of these documents. US 510655 teaches cosmetic skin and
hair care composition. This document mentions presence of zinc pyrithion and hydrolytic
protein.

Accordingly both zinc pyrithion and proteolytic enzyme such as papain are known to be
used in formulations including antidandruff compositions. However the role of papain in
such compositions is not clear. Neither is there mention of the amount of papain present
or how the stability is attained. Moreover the long term stability of proteolytic enzyme
such as papain in solution and in formulations like hair care compositions, shampoo is
limited.
The modern antidandruff formulations are based on the use of individual or combination
of the following mechanisms
Antifungal action - These compounds are a group of drugs with etiological action,
inhibiting the growth of Malesseza furfur such as Zinc Pyrithion
Keratolytic action - These loosen the attachments between the corneocytes and allow
them to be washed away with shampooing. Keratolytics soften, dissolve, and release the
adherent scale seen in dandruff. The agents are Tar, precipitated Sulphur and Salicylic
acid
Cytostatic action. - These act through regulation of the excessive speed of epidermai
cells division inhibiting exaggerated peeling of the scalp area, thus eliminating the scales
being the basic feature of dandruff. The examples are Selenium sulphide, piroktolamine
and Cyclopiroxolamine.
The ideal way of dandruff management is to have a combination of Antifungal activity
supplemented with keratolytic activity in a single formulation.
Use of Antifungal agent such as Zinc pyrithion inhibits the cell wall transport in the
fungal cell what in effect leads to lysis of fungal cell. The keratolytic agents such as
salicylic acid remove the loosened flakes thus providing effective dandruff management.
However it is difficult to stabilize the formulation containing Antifungal agent such as
Zinc pyrithion and keratolytic agents such as Salicylic acid as it lowers the pH of the
formulation, which may lead to instability of the product. Other keratolytic agent such as
Tar has an "earthy" smell, can give light-coloured hair an orange tint and may make
treated skin more sensitive to sunlight.
Thus there is need to provide the antifungal with the proteolytic enzyme in a single
composition which would be stable and would not only ensure the anti-dandruff efficacy
but would also provide better conditioning effect.
It was surprisingly found that synergistic keratolytic action could be delivered by the use
of encapsulated proteolytic enzyme such as papain, in combination with antifungal agent
such as zinc pyrithion in hair cleansing and conditioning composition. It was also found
that such composition could be stabilized by use of sub micron delivery system (200 nm
average particle size) to stabilize proteolytic enzyme to maintain the long term stability
and efficacy throughout the shelf life.
Objects of the invention
Accordingly, an object of the invention is to provide a synergistic hair care composition
which would provide antidandruff and conditioning effect
Another object is to provide a hair care composition where synergistic keratolytic action
could be delivered by the use of encapsulated proteolytic enzyme such as papain, in
combination with antifungal agent
A further object is to provide a stable hair care composition comprising proteolytic
enzyme to maintain the long term stability and efficacy throughout the shelf life.
Summary of the invention
According to one aspect of the present invention there is provided a hair care composition
comprising from about 0.1 to 5% of an antifungal agent, from about 0.001-5%
encapsulated papain alongwith stabilizing agent and cosmetic base comprising anionic
surfactant, cationic polymer, non volatile water insoluble conditioning agent.
According to another aspect of the present invention there is provided method of
cleansing and conditioning the hair comprising applying to the hair and scalp and
effective amount of the said composition.
Detailed Description of the Invention
According to one aspect of the present invention there is provided an antidandruff and
conditioning hair care composition comprising
a) from about 0.1 - 5% antifungal agent such as zinc pyrithion (ZPTO);
b) from about 0.001 - 5% papain encapsulated along with stabilizer;
c) cosmetic base comprising anionic surfactant, cationic polymer, non volatile water
insoluble conditioning agent.
Optionally other conventional components used in hair care composition are present.
Papain is a proteolytic enzyme, characterized by the ability to hydrolyze large protein
molecules into smaller peptides and amino acids. The present invention describes
combination of fungicidal agent with proteolytic enzyme such as papain extracted from
Papaya carica, which has the keratolytic activity similar to salicylic acid, at much lower
dosage. The stability of papain enzyme in cosmetic formulation such as hair care
composition, shampoo is maintained by encapsulating papain using Glycosphere.
Use of antidandruff agent such as zinc pyrithion makes hair dry and dull. However
combination of papain with antifungal agents such as zinc pyrithion not only provides the
keratolytic efficacy on dandruff cells, but also revitalizes hair by removing the uplifted
scales of cuticle, smoothening the hair fiber and restoring shine. Thus the dual effect of
antidandruff efficacy and enhanced hair revitalization is achieved through single product
format.
Glycospheres are biomimetic nano particles, which allow entrapment, protection and
delivery of active ingredients. Glycospheres are made up of 3 parts
1. A hydrophilic solid cationic core made up of cross linked polysaccharides
2. A middle lipophilic layer of fatty acid
3. A natural polar lipid layer of phospholipids
Glycospheres are sub micron (200 nm average particle size delivery system based on
polysaccharide core surrounded with lipid layer (INCI name: palmitoyl hydroxy propyl

trimonium amylopectin/glycerin cross copolymer (and) lecithin). Because the core is
cationic, it can entrap hydrophilic (anionic) molecules, macromolecules such as enzymes
can be entrapped easily within glycospheres. Glycospheres is a Trademark of Kobo
Products. Glycosphere is used as delivery system for incorporating Papain enzyme in
shampoo based formulation, as direct addition of Papain enzyme in shampoo base is not
stable.
Other form of encapsulation such as liposome is unstable and considered being sustained
release whereas the glycospheres has the controlled release of the actives. Glycospheres
are stable at wide pH range and higher temperature whereas the liposomes are bilayers of
phospholipids, which are unstable.
The active mechanism in Glycospheres is by entrapment and encapsulation whereas in
Liposomes it is encapsulation.
Brief Description Of The Accompanying Drawings
Figure 1: Graph showing activity and stability of papain in encapsulated and non
encapsulated form
Figure 2: Flow diagram showing enzyme activity protocol
Figure 3: Graph showing enzymatic activity in formulations A, B and C
The invention is now described with the help of non limiting illustrative examples and
drawings.
Figure 1 describes the activity of papain in the composition of the present invention. Two
compositions were prepared one with papain in solution and the other with papain
encapsulated in glycospheres. The other components were same. The stability test was
performed over 3 months at 40°C. It was found that the encapsulated papain shows
dramatic increase in stability and remaining enzymatic activity. Non entrapped papain
loses its activity in short time as is evident from the graph shown in Figure 1.
Example 1
The formulations A, B and C were prepared according to the details provided in Table 1

Tablel:
The above formulations were tested for enzyme activity to ascertain any synergistic
benefits of the antifungal+keratolytic system.
The protocol followed is described in the flow diagram as in Figure 2 and the results are
shown in figure 3.
The above data clearly demonstrates the surprising synergistic effect found that the
composition of the present invention not only provides in terms of antidandruff efficacy
and enzymatic activity. It would be seen that Formula A which has both zinc pyrithion
and papain shows the best activity compared to formula B and Formula C where both the
components are not present.
Example 2
Formulation A-C were further subjected to sensory evaluation as per an ASTM
protocol on hair tresses for specific attributes/
Reference: ASTM protocol no E 2082-00
From the above results it can be concluded that the product containing papain gives
enhanced conditioning properties with respect to softness, silkiness and gloss.
According to another aspect there is provided a method of cleansing and conditioning
hair by applying the composition of the present invention. The composition not only
provides a synergistic dandruff efficacy and cleans the hair/scalp but also provide
conditioning effect.
We claim:
1. A hair care composition comprising an antifungal agent from about 0.1 to 5%,
encapsulated papain from about 0.001-5% along with a stabilizing agent and
cosmetic base comprising anionic surfactant, cationic polymer, non volatile water
insoluble conditioning agent.
2. The hair care composition as claimed in claim 1 wherein the antifungal agent is
zinc pyrithion (ZPTO).
3. The hair care composition as claimed in claim 1 wherein the hair care
composition is an antidandruff shampoo composition.
4. The hair care composition as claimed in claim 1 wherein the said stabilizing agent
in the encapsulated papain is Glycosphere.
5. The hair care composition as claimed in claim 1 wherein Glycosphere is selected
from polysaccharide, fatty acid derivative and phospholipid.
6. The hair care composition as claimed in claim 1 wherein the polysaccharide is
amylopectin.
7. The hair care composition as claimed in claim 1 wherein the fatty acid derivative
is palmitoyl hydroxypropyl triminium.
8. The hair care composition as claimed in claim 1 wherein the phospholipid is
lecithin.
9. The hair care composition as claimed in claim 1 wherein the average particle size
delivery system of Glycosphere is 200 nm based on polysaccharide core
surrounded with lipid layer.

10. A method of cleansing and conditioning the hair comprising applying to the hair
and scalp and effective amount of the said composition as claimed in claim 1.

A synergistic hair care composition to provide combination of antidandruff activity with
keratolytic activity and conditioning properties. The synergistic keratolytic action is
delivered by using encapsulated proteolytic enzyme such as papain in amount from about
0.001-5%, in combination with antifungal agent such as zinc pyrithion from about 0.1 to
5% along with a stabilizing agent as Glycosphere and a cosmetic base in hair cleansing
and conditioning composition. A method of cleansing and conditioning the hair
comprising applying to the hair and scalp and effective amount of the said composition.