Note: Descriptions are shown in the official language in which they were submitted.
-
1 338378
This invention relates to a process for preparing
5,6-dihydroxyindole dye compositions and to the products
made by this process. More particularly it concerns a
process and products of the aforementioned type that are
useful in dyeing human hair and skin.
The 5,6-dihydroxyindoles have been found to be very
useful in dyeing hair, and particularly human hair on the
head. However, because of their inherent instability
they have presented problems in their practical
application. These instability problems are attested to
in U.K. patent 797,174 and U.S. patent 4,208,183 which
are concerned with ways and means for preparing stable
compositions containing these indole dyes.
U.K. patent 797,174 describes a process for
preparing a dye composition containing 5,6-
dihydroxyindoles and dyeing hair therewith. In
accordance with this patent the 5,6-dihydroxyindoles are
employed in the form of the 5,6-diacetoxyindole compounds
because of the stability of the latter. The diacetoxy
compound is then deacetylated in aqueous solution with an
alkalizing agent like monoethanolamine immediately prior
to use, and the composition so formed is applied to hair.
It is to be noted that this process is carried out in the
presence of atmospheric oxygen.
Whereas 5,6-diacetoxyindole can be used as a stable
precursor for 5,6-dihydroxyindole its use still presents
difficulties. Since the 5,6-dihydroxyindole is sensitive
to oxidation by atmospheric oxygen, this can lead to high
loss of this material due to its auto-oxidation outside
the hair.
It has now been found that the above-mentioned
difficulties can be avoided and stable compositions may
be obtained if the alkaline hydrolysis of the 5,6-
diacyloxyindole is carried out under anaerobic condition.
In the practice of this invention the 5,6-diacyloxyin-
dole will preferably be mixed with the alkaline
hydrolyzing agent in a container which is substantially
- 1 3 3 8 3 7 8
sealed to the atmosphere and the hydrolysis to the
5,6-diacyloxyindole is permitted to take place slowly in
this container.
In accordance with an embodiment of the invention, a
process is provided for preparing a dye composition
containing a 5,6-dihydroxyindole of formula
H0 ~ I ~ Rl (I)
H0 ~ I R2
which comprises mixing in the presence of water a
5,6-diacyloxyindole of formula
R-C
11`~ / Rl
0 1 1 (II)
C'0 ~ N~-~` R2
R~ o
with an alkaline hydrolyzing agent in a container,
rapidly sealing said container and permitting said
5,6-diacyloxyindole of formula II above to be slowly
hydrolyzed to said 5,6-dihydroxyindole of formula I under
anaerobic conditions, wherein:
(a) R in each case is the same or different and is
an alkyl or aryl radical; and
(b) R1 and R2 are the same or different and selected
from the group consisting of hydrogen, alkyl and aryl.
According to another aspect of the invention,
products are provided as made in accordance with above
process.
~ 338378
_ 2a
In accordance with another embodiment of the
invention, an article of manufacture is provided in the
form of a kit comprising an outer container having
enclosed therein in a first inner sealed container
comprising products made by the above process and a
second inner closed container containing a composition
comprising a metal salt solution capable of promoting the
dyeing of hair with and which accelerates the development
of color from, the 5,6-dihydroxyindole when the contents
of the first and second inner sealed containers are
applied to hair.
The acyloxyindoles that may be employed in the
practice of the present invention correspond generally to
the formula:
Il ~\ . / Rl
C~O ~ N ~ R2 (II)
R ~ ~
wherein R in each instance may be the same or different
organic radical and particularly alkyl or aryl radicals.
When R is an alkyl radical it was to be any of a variety
of such groups. This includes such groups as methyl,
ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl,
n-pentyl, n-hexyl etc. Similarly when R is aryl it may
likewise be any of a variety of aryl radical. By way of
example, mention may be made of such aryl radicals as
tosyl, benzoyl, p-nitrobenzoyl, p-methoxybenzoyl etc. In
the preferred forms of this invention R is a lower alkyl
radical having from 1 to 4 carbon atoms and especially
methyl.
R1 and R2 in formula II above may likewise be the
same or different and may be hydrogen or an organic
radical
1 338~-~8
2 b
such as alkyl or aryl. When R1 or R2 is alkyl it may be
such groups as, methyl, ethyl, n-propyl, iso-propyl,
n-butyl, iso-butyl, t-butyl, n-pentyl, n-hexyl, etc. The
preferred alkyl groups are those that contain l - 4
carbon atoms.
Wherein R1 and R2 is aryl it will-usually be phenyl
or substituted phenyl radicals. In the preferred
practice of this invention, however R1 and R2 will be
hydrogen.
Most usually the indole employed will be
5,6-diacetoxyindole.
The quantity of 5,6-diacyloxyindole or
5,6-diacetoxyindole that will be employed in practising
the present invention may vary somewhat. Generally this
will account for from about 0.25% to about 2% by weight
based on the total weight of the composition with the
preferred concentration being from about 1% to about 2%
on the same weight basis.
1 338378
The alkaline hydrolyzing agent that may be employed in carrying
out the process of this invention may be any of a number of alkaline
materials that is compatible with human use. These are exemplified
by such compounds as monoethanolamine, sodium hydroxide, KOH,
diethanolamine, NH40H, triethanolamine, morpholine. Very good
results have been obtained with monoethanolamine which is the
~aterial of choice.
The quantity of alkaline hydrolyzing agent utilized in carrying
out this invention may also vary and will be dependent on the
quantity of diacyloxyindole that is employed. Usually at least the
theoretical quantity of alkaline agent is used which will completely
hydrolyze off the acyl groups from the diacyloxyindole compound i.e.,
at least 2 equivalents of alkaline agent. In the preferred practice
from about 0.5~ to about 10% by weight of alkaline agent is incor-
porated in a sealed container in accordance with the present inven- _
tion.
In adding the alkaline agent to the composition of this invention
the effort is made to add sufficient so that the pH of the composi-
tion is on the alkaline side and in the range from about pH 7 to
about pH 11. The preferred pH will be about pH 9 to about pH 9.5.
Other ingredients may also be included in the compositions of
this invention. Thus an aqueous or dilute aqueous alcoholic vehicle
containing up to 30% by weight of alcohol may be utilized as the
medium in which the hydrolysis of the 5,6-diacyloxyindole takes
place. Still other ingredients may also be employed which will be
determined mainly by the form that the product will take. The
aqueous or aqueous alcoholic vehicle when employed will comprise
from about 0% to about 95% by weight based on the total weight of
the composition.
In the practice of the present invention a variety of sealed
containers may be utilized to provide the anaerobic conditions under
which the 5,6-diacyloxyindole is hydrolyzed. Thus, for example, the
components may be sealed in an aerosol can or included in a dispenser
tube. In preparing the product in an aerosol can the 5,6-diacyloxy-
indole is dispersed or dissolved in an aqueous or aqueous-alcoholic
1 338378
vehicle. To this is added enough alkalizing agent so
that the final pH is about 9-9.5 which will be in excess
of about 2 equivalents. This mixture is then rapidly
sealed in an aerosol can with a propellant (e.g.
hydrocarbon repellant) The hydrolysis of the 5,6-
diacyloxyindole is then allowed to take place slowly in
the aerosol can which would be under anaerobic
conditions. This product then can be dispensed from the
aerosol can when it is desired for use. This product has
been tested for stability at 50 for 3 months and has
been found to be satisfactory.
In addition to the ingredients mentioned above the
aerosol products may also include other ingredients
designed to improved the organoleptic qualities or
facilitate the application of the product. Thus it may
include detergents, foam stabilizers, foaming agents,
cationic polymers to diminish skin staining, etc. When
the aerosol products of this invention are dispensed from
the aerosol can they come out as rich foams that
generally range in color from light yellow or tan to off-
white or white. As is generally understood by those
skilled in the art, rich foams such as those produced by
the product of Example 1 have a density in the range of
0.4 g/cm3 or less.
In an alternative method for preparing the products
of this invention the ingredients are packaged in a
dispenser tube. The conditions within the tube are
anaerobic in character and, as in the case with the
aerosol products, the 5,6-diacyloxyindole is permitted to
slowly react with the alkaline agent to deacylate the
diacyloxyindole compound to produce the 5,6-
dihydroxyindole.
The products made up in the dispenser tubes may take
the form of a gel or a shampoo. In preparing the product
F
1 338378
as a gel, the 5,6-diacyloxyindole is dissolved in an
aqueous vehicle (usually 95% ethanol). This is dissolved
in a thickened aqueous solution (generally 3-6% Carbomer
940, at pH 9.5). As hydrolysis proceeds, the pH will
drop. This is compensated for by adding additional
alkalizing agent (e.g. ca. 2 equivalents). The thickened
solution is sealed in a tube, and hydrolysis is allowed
to proceed slowly. The product is dispensed from the
tube as necessary, and then the tube is resealed. No
loss in the capacity to dye hair of the material
remaining in the tube has been observed.
4a
~-- 1 3383~
In addition to the ingredients mentioned above, the gel product
may also include other ingredients to improve the organoleptic qual-
ities or facilitate application of the product. Thus, it can include
detergents, cationic polymers to diminish skin staining, etc.
In preparing a product as a shampoo formulation, the
5,6-diacyloxyindole is dispensed in a shampoo base (e.g. Clairol
Blue Shampoo), and alkalyzing agent sufficient to hydrolyze the
acyloxy groups and adjust the pH to 9.5 (e.g. greater than 2
equivalents). The mixture is sealed in a suitable container and the
5,6-diacyloxyindole is allowed to hydrolyze slowly.
In addition to the ingredients mentioned above, the shampoo
formulation can also include other ingredients to improve the
organoleptic qualities or facilitate application of the product.
Thus, it can include, for example, cationic poly~ers to diminish
skin staining, etc.
The hydrolysis of the 5,6-diacyloxyindole in accordance with
this invention is not instantaneous but proceeds over time. For
optimum results, sufficient time should be allowed for complete
conversion of the 5,6-diacyloxyindole to the 5,6-dihydroxyindole as
its mono or dianions. This will usually be about 18 hours at pH of
about 9.5.
The package products of this invention and particularly the gel
and shampoo packages containing the 5,6-diacyloxyindole do not have
to be made under anaerobic conditions. All that is necessary is
that they be stored closed to prevent further diffusion of oxygen
into the container.
In applying the products of this invention to the dyeing of hair
it is often advantageous to employ them in conjunction with a
promoter composition which accelerates the development of color from
the 5,6-dihydroxyindole compound. Certain metal salt solutions, and
especially solutions of CuS04 are particularly useful for this
purpose. These solutions will generally be used at a cosmetically
acceptable pH, the optimum being approximately pH 9.5. The concen-
tration of the salts in this solution will generally be in the range
of from about 0.25~ to about 5~ by weight based on the total weight
~ 1 338378
... ..
of the ~olution with the preferred range being from about 1% to
about 2~ on the same weight basis.
In addition to the metal salt, and particularly CuS04,
additional aids may be incorporated in the promoter composition.
These may serve to facilitate the application of the promoter to the
hair, to assist in the dyeing operation or to improve the elegance
of the product or to improve the condition of the hair. Thus, for
example, the distribution of the CuS04 in a liquid shampoo com-
position provides an effective means for getting it into the hair.
The application of the promoter composition wi ~ ordinarily take
place as a separate step from the application of the 5,6-dihydroxy-
indole composition. The order in which these compositions are
applied is not critical, that is to say that the promoter composi-
tion may first be applied to the hair followed by the application of
the 5,6-dihydroxyindole composition or vice versa.
A convenient form for marketing the products of the present
invention are as kits in which the promoter composition and the hair
dye composition i.e., the 5,6-dihydroxyindole composition are each
disposed in its own inner container and that both of these are
packaged together in an outer container. With this arrangement the
product is ready for use in the total hair treating and coloring
operation.
The following examples are given to further illustrate the
present invention. It is understood, however, that the invention is
not limited thereto.
EXAMPLE 1
Aerosol Product
Gms. ~ by Wt.
~1)5,6-diacetoxyindole C.2 1.0
(2) Monoethanolamine0.1 0.5
(3) H20 17.7 88.5
I 338378
*(4) Propellant 152A 1.6 8.0
(5) Cetyl alcohol 0.4 _ 2.
100
* 75% difluoromethane/25% isobutane.
Procedure:
H20 is added to solid 5,6-diacetoxyindole placed in an
aerosol can. The cetyl alcohol and monoethanolamine then are added
to the can which is rapidly capped and sealed. Air then is
evacuated from the can through the aerosol valve and the propellant
then is introduced into the can through the aerosol valve.
EXAMPLE 2
Gel Product
Gms. % by Wt.
(1) 5,6-diacetoxyindole 0.2 1.0
(2) Monoethanolamine 0.1 .5
(3) ** Carbomer 940
(.5% solution in H20) 19.7 98.5
20 100
*~ CTFA nomenclature for cross-linked polymer of acrylic acid.
Procedure:
The Carbomer 940 solution is mixed with the
5,6-diacetoxyindole. The monoethanolamine is then added and the
product is rapidly loaded into a dispenser tube and sealed.
An alternative, preferred procedure is to dis601ve the
5,6-diacetoxyindole (e.g. 1-5% by weight) in alcohol (e.g. 95%
ethanol), then to add this solution to the thickened, alkalized -
Carbomer 940 solution under aerobic conditions. The product is then
loaded into the dispenser tube and sealed.
. ~ , .. . .
1 338378
EXAMPLE 3
Shampoo
Gms~ by Wt.
(1) 5,6-diacetoxyindole 0.2 1.0
(2) Monoethanolamine0.1 .5
(3) Shampoo *~* 19.7 98.5
20.0 100
**~ Shampoo Formula
Ingredient % by Wt.
Disodium monococamide MIPA-Sulfosoccinate 10.0000
Methylparaben .1000
D&C Violet #2 .0008
FD&C Blue ~1 .0009
Quaternium - 6 1.0000
Imidazolidinyl Urea .2000
Ethylenediamine Tetra Acetic Acid .0500
Citric Acid .2000
Sodium Chloride .6000
Amphoteric - 12 4.5000
Quaternium - 22 2.0000
Ammonium Lauryl Sulfate -40.0000
Hydrolyzed Animal Protein .4000
Laureth - 23 .0100
Fragrance .2000
Water QS 100.
.
Procedure:
The 5,6-diacetoxyindole is mixed with the shampoo. Th~
monoethanolamine is then added and the product is rapidly loaded
into a dispenser tube and sealed.
.
t ~- 1 338378
EXAMPLE 4
Promoter Composition
Gms.% by Wt.
CuSO4 5 2 2.0 2
Monoethanolamine 5.0 5
**** Conditioner Formula 93.0 93
100 100
*t** Conditioner Formula
Ingredient ~ by Wt.
Hydroxylethyl Cellulose 2.09250
Sodium Hydroxide 0.01395
Amphoteric - 2 2.38080
Cocamidopropyl Betaine 1.86000
Phosphoric Acid .42780
Quaternium - 40 4.65000
Ethoxydiglycol (and) Glycol (75-25) 2.79000
Sorbic Acid 0.09300
Quaternium - 15 0.09300
Fragrance - 0.03720
Water QS 100
The conditioner 601ution composition is first formed by
sequentially dissolving each of the ingredients in water (or, after
addition of the first ingredlent, the aqueous solution formed by
addition of the previous ingredient).
The CuSO4 is then dissolved in the conditioner solution and
then the monoethanolamine is added. This has the form of a thin
solution. This product is then poured into a bottle and the bottle
i S 8 ealed.
1 3~8378
Kits may be prepared by packaging in the same outer
package the aerosol, gel or shampoo products prepared by
Examples 1, 2 or 3 above with the promoter product
prepared in accordance with Example 4 above. In addition
to the two products, if desired, there may also be
included in the kit any auxiliary equipment or
composition that would be useful in the application of
the products to hair on the human head.
A feature of kits embodied in this invention may be
the inclusion of a solution which may be used to modify
or remove the color that may be generated on the head of
a subject using the hair dye compositions contained in
these kits. One such solution is a freshly prepared
diluted aqueous alkaline hydrogen peroxide (H2O2)
solution, which can affect these changes in a few
minutes.
An illustrative, but not limiting example of hair
dyed by the kits described in Examples 1,2 and 3 is the
following. Hair is treated with an amount of promoter
sufficient to wet the hair. This solution is left on the
hair for ca. 5 minutes. The hair is rinsed thoroughly,
and the dyeing solution (sufficient for coverage) is
applied for 5 minutes. The hair is shampooed and dried,
leaving a black color.
In a separate example, the order of application may
be reversed.
In a further example, hair dyed by either of the
previous methods can be treated with dilute (1-6%)
aqueous H202, adjusted to pH 9.5, to remove or modify the
color as desired.
n.
.~,
11 1 3383~8
8UPPLEMENTARY DISCL08URE
As previously disclosed, 5,6-dihydroxyindoles are
known hair dyeing compositions. As further
exemplification in this regard, United States patent
3,194,734 to Seemuller describes a process for dyeing
hair with methyl substituted dihydroxyindoles which
provide lighter color dyeouts than are provided by
dihydroxyindole itself. The patent further teaches that
alkaline solutions suitable for hair dyeing can be
prepared immediately prior to dyeing by operating in a
nitrogen atmosphere or by adding antioxidants such as
thioglycollate, sulfite or the like. Based on the
teachings of the prior art such solutions are not
believed to have storage stability. The examples of the
patent clearly show that, in presence of antioxidants,
only weak colors such as light ash blond, gray, and
bluish-gray are obtained by use of 5,6 dihydroxyindole
unless extremely high levels of dye are employed. With
the process of the present invention dark black dyeouts
are produced, even after prolonged storage using very low
levels of dye.
U.S. 4,208,183 teaches the preparation of storage
stable solutions of dihydroxyindoles in alcoholic
solvents. Prolonged storage of dihydroxyindoles is
possible by this method, but these alcohol solutions are
not suitable for dyeing hair, which is a serious
disadvantage. Therefore, these storage stable solutions
of the dihydroxyindoles must be mixed with a suitable
cosmetic vehicle immediately prior to dyeing. The
preferred method disclosed involves a dual compartment
aerosol package. The reference does not disclose
employing or storing the dihydroxyindoles under anaerobic
conditions.
The present invention allows for storage in an
aqueous medium which is suitable for dyeing hair directly
rather than requiring a complex change of solvent and
delivery system.
~ 12 l 338378
While 5,6-dihydroxyindole can be used as stable
precursor for 5,6-dihydroxyindole, its use still presents
difficulties since the 5,6-dihydroxyindole in sensitive
to oxidation by atmospheric oxygen. This can lead to
high loss of the dihydroxyindole due to its auto-
oxidation outside the hair.
As already explained in the principal disclosure,
the above mentioned difficulties can be avoided and
stable compositions may be obtained if the alkaline
hydrolysis of the 5,6-dihydroxy protected compound of
formula II is carried out under anaerobic conditions. To
facilitate discussion of further aspects of this
invention, the protected compounds shall be referred to
as O-protected 5,6-dihydroxyindoles. By the term 0-
protected, it is understood to refer to an acyloxy groupof formula II or a sulfur containing group (both of which
are exemplified in the following formula III) where the
protecting group is hydrolyzed to the free hydroxyl under
alkaline conditions by use of a suitable alkaline
hydrolyzing agent.
By the process of the present invention it is
possible to produce storage stable, ready-to-use alkaline
solutions of 5,6-dihydroxyindoles, which surprisingly do
not form melanins until applied to the hair (or skin).
Thus, much lower dye concentrations are needed to obtain
dark dyeout. In the practice of this invention compound
formula (II) or (III) will preferably be mixed with the
hydrolyzing agent in a container which is substantially
sealed to the atmosphere and the hydrolysis of compound
formula (II) or (III) is permitted to slowly take place
in this container. The present invention allows for
storage in an aqueous medium which is suitable for dyeing
hair directly rather than requiring a complex change of
solvent and delivery systems.
According to another aspect of the invention, a
process for preparing a dye composition containing a 5,6-
dihydroxyindole of formula:
1 338378
H ~ R21 (I)
which comprises mixing in the presence of water an O-
protected 5,6-hydroxyindole of formula:
~ N1 ~ R12 (III)
4~11 H
()n
at a level of from about 0.25~ to about 2~ by weight with
an alkaline hydrolyzing agent in a container, rapidly
sealing said container and permitting said compound of
formula (III) above to be slowly hydrolyzed to said 5,6-
hydroxyindole of formula (I) under anaerobic conditions,
wherein
(a) Rl and R2 vary independently and may be
hydrogen, methyl or ethyl, and
(b) when X=S, n=2, R3 and R4 vary independently and
are Cl-C6 alkyl, substituted phenyl, and
(c) when X=C, n=l, R3 and R4 vary independently and
may be Cl-C6 alkyl, substituted phenyl and substituted
benzyl.
According to another aspect of the invention, an
article of manufacture is provided as a kit comprising a
container having enclosed therein in a first sealed
.~
1 338378
14
container containing compositions prepared in accordance
with the above process and a second sealed container
containing a composition comprising a metal salt solution
present in an amount sufficient to promote the dyeing of
hair with and which accelerates the development of color
from the 5,6-di-hydroxyindole when the contents of said
first and second sealed containers are applied to hair.
The O-protected hydroxyindoles that may be employed
in the practice of the present invention correspond
generally to the formula:
R3 X R2
~ ~ Rl (III)
/lXI
R4 ~0)n
wherein R1 and R2 vary independently and may be hydrogen,
methyl or ethyl. When X=S, n=2, R3 and R4 vary
independently and maybe C1-C6 alkyl and substituted
phenyl. When X=C, n=l, R1 and R4 vary independently and
maybe C1-C6 alkyl, substituted phenyl and substituted
benzyl. Typical of the alkyl groups which may be
employed are methyl, ethyl, n-propyl, iso-propyl, n-
butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, etc. In the
preferred forms of this invention lower alkyl radicals
having from 1 to 4 carbon atoms and especially methyl are
employed.
The O-protected 5,6-dihydroxyindole of formula III
can be formulated under anaerobic conditions in
accordance with the methods defined in the principal
disclosure to prepare the various compositions. The O-
protected 5,6-dihydroxyindole is present in the
composition in the amounts ranging from 0.25~ to about 2
by weight and preferably 1~ to about 2~ by weight. The
1 338378
alkaline hydrolyzing agents employed are preferably the
same for effecting the hydrolyzation of the O-protected
5,6-dihydroxyindole. Usually at lest the theoretical
quantity of alkaline agent is used which will completely
hydrolyze off the protecting groups from the O-protected
compound of formula III; that is at least 2 equivalents
of alkaline agent preferably from about 0.5~ to about 10
by weight of alkaline agent is incorporated in a sealed
container in accordance with this present invention. The
O-protected 5,6-dihydroxyindoles are mixed into the
composition in accordance with the procedures of this
invention, such as in aqueous or dilute aqueous alcoholic
vehicles. They may be incorporated in aerosol cans,
dispenser tubes, shampoo bottles or the like. In this
manner, the compounds of formula III are permitted to
slowly react with the alkaline agent to deprotect the O-
protected 5,6-dihydroxyindoles.
The process of this invention provides compositions
by virtue of the anaerobic environment in which they are
formulated to carry out the hydrolysis and provides a
significant advance over the prior art approach of using
reducing agents. It is believed that the reducing agents
typically employed in prior art compositions adversely
affect the dyeout, oxygen being a critical reactant in
the formation of melanin from 5,6-dihydroxyindole and
that the anhydrous organic solvents interfere with hair
dyeing. The stabilized system of the present invention
provides a dark black dyeout after storage. A series of
comparisons using a Cu+2 pre-treatment cléarly demonstrate
these differences and the need for anaerobic conditions.
These comparisons are set forth in Table I.
~?
, ,
~ 16 l 3383~
TABLE I
Hunter tristimulus values*
L a b
Untreated blended gray hair 32.24 -0.64 6.26
1% 5,6-diacetoxyindole 12.19 -0.4 -0.06
(anaerobic, pH 9)
1% 5,6-diacetoxyindole 27.63 -0.64 5.22
(aerobic, pH 9)
2% 5,6-diacetoxyindole 9.93 -0.09 0.12
(anaerobic, pH 9)
1% 5,6-diacetoxyindole 16.69 -0.45 0.75
(in 100% ethanol)
Nice 'n Easy 122~ 9.52 0.23 0.53
Natural black
* Hunter values are a measure of reflected light and
describe the color along three axes:
L = 0 is black, L = 100 is white. The more positive "a"
is, the redder the color, the more negative "a" is, the
greener the color. Yellowness increases with increasing
"b" value. Blueness increased with decreasing "b" value.
Although preferred embodiments of the invention have
been described herein in detail, it will be understood by
those skilled in the art, that variations may be thereto
without departing from the spirit of the invention or the
scope of the appended claims.
