Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
3~52
~:K'~ ND ~F THE INVENTION
Field of the Invention:
__ _ __.
The present invention rela-tes generally to
cleansers, and more particularly to those cleansers
that include o~idizing and bleaching agents.
Description of the Prior Art:
Cleanser compositions have for some time
used o~idizing agents and bleaching agents in concert
to remove visible stains from hard surfaces, while at
the same time effecting the removal of scale or plaque
build-up on those surfaces. Thus, cleaning compositions,
prepared wi-th abrasi~e material for use as scouring
cleansers~ or alone for puxpose of mild surface cleaning
applications, have ernployed a variety of sulfate salts~
eg. bisulfates, monopersulfates, and sulfates as
detergents, oxidizers and the like, and have utilized
alkali metal and alkallne ear-th metal halides as
bleaches.
U.S. Patent Number 3,458,4~6 to Diaz discloses
an abrasive cleansiny composition that utilizes certain
monopersulfate oxidizing agents in combination with a
water-soluble bromide salt, in place of chlorine-
liberating constituents conventionally employed in~such
compositions. The replacement of the chloride constituents
by the bromide constituents was found to eliminate
the unpleasant odor of chlorine. The composition
2C disclosed in Diaz was primarily intended for use in
powdered form, and utili2ed a variety of additives,
such as detergents, builders and the like in i-ts
formulation.
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The preparation of cleansers to be utilized in a solution
for dipplng, or soaking the articles to be cleaned there;n,
presents different problems from those that attend the
preparation and use of cleansing compositions that are
app`lied to the surface o~ the articles to be cleaned.
Thus, whereas one may apply a composition, either in li-
quid or granular form, to a surface and may then agitate
the surface to assist the cleaning operation, the employ-
ment of compositions that operate in a "pass;ve" ~anner
to serve as dipping solutions and the l;ke, gives no indi- -
cation of their efficacy, and of the period of their ac-
tivity. In particular, cleansers u~ilized for the prepar-
ation of dipping solutions for dentures and the like~ :
have conventionally exhibited an effervescent action in
solution that assists in stain and plaque removal by pro-
viding a desired amount of agitation in the solution to
promote cleansing activity. Also, such compositions have
conventionally included colorants such as dyes, incorpor- .
ated into the composition to indicate the presence of the
cleansing composit;on in the solution.
The effervescent activity of these solution-forming
cleansing compositions has conventionally been provided
by the inolusion in the c~mposition of ..the ingredients
sodium bicarbonate and citric acidO Correspondingly,
the react;on of these two ingredients has taken place at
a pH that is weakly acidic or neutral, with a sacrifice
in the efficiency and speed of cle~ning, that wou1d be
achieved by the employment of a composition operable at
a more basic pH.
The employment of the colorant in the composition as an
indicator has ~een for the purpQse Qf not only indicat~
ing the presence and activity of the cleansing co~posi-
tion, but serves to indicate by its disappearance ~he
1~3~
cessation of cleaning activity. For example, :in the
instarlce where denture cleansers are prepared, a dye
component :is .includecl as an indicator to signi.Ey by
colorati.on the presence oE -the cleansing composl-tion and
the commencement o:E i-ts activity. In these appl.ic~tions,
-the actual period of ac-tivity is reasonably firlite,
and is predetermined by the manufacturer.
Accordingly, as the indica-tor or dye signals
the user that the cleaning process has ended, attemp-ts
have been made to control the disappearance of fading
of the dye, so that the disappearance of the dye will
coincide with the comple-tion of -the cleaning cycle~
Attempts -to control the time span of the dye componen-t
have included the addition of limited quantities of
dye, and the inclusion of additional amounts of bleaching
agents to cause the dye to fade more quickly. The
first approach has been generally unsucessful, and the
second approach proved uneconomical; the inclusion
or additional bleach. to fade the dye frequently required
additional dye to be added to the composition to gI~e
the appropriate depth of initial coloration, and in
turn requi~red additional bleach to be added for fade
control.
The present invention is belie~ed to pro~ide
solutions to the aforementioned problem.
SUMMARY OF THE I~ENTION
. .
A cleansing composition is prepared in
accorclance with the present invention which comprises at
least one oxidizing agent including an alkali metal
monopersulfate
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salt, said oxidizing agent present in amounts ranging
from 35 - 60Yo~ a bleaching promoter selected from the
group consisting of alkaline metal and alkal;ne earth
metal halides, said bleachiny promoter present ;n an
amount of up to about 20Cb~ and a compound selected from
the group consisting of alkali metal and alkaline earth
metal perborates, present in an amount suffic;ent to
catalytically promote the effervescence of the cleansing
composition. The composition after dissolut;on, pro-
vides a solution which possesses a pH in the basic range
and includes sodium carbonate in an amount that may
range from 20 - 40%. Sodium hydroxide may also be added
in amounts of up to ~5% to assist in pH maintenance.
Preferably, the oxidizing agen~ may comprise potassium
monopersulfate, and may be present in an amount ranging
from 40 - 50%. Sodium chloride may comprise the bleach-
ing promoter, and may be present in an amount ranging
from 10 - 20%, and the perborate compound may comprise
sodium perborate and may be present in an amount ranging
from 0.5 - 20~. ~
t
Solutions containing the present cleansing composition ',
possess effervesc;ng capability within an alkaline pH,
due to ~he presence of the perborate compound~ The per~
borate is theorized to react with the oxidizing agent
and the bleaching promoter to initiate effervescence.
The ability of these solutions to achieve effervescence
within a basic pH range yields improved cleaning effi
ciency at reduced cost.
The present cleansing composition may also contain var-
ious additives, such as colorants, including dyes 9
~L83~S'~
perEumes, alld the like. The cleansing compos;tic)n ma~
be prepared in tablet forin, and may accord:ingly aLso
include -tabletlng acJents, excipien-ts, disintegrants ~nd
the li~e. In this latter ~orm, the cleansing com-
position is particularly useful as a c1enture cleanser.
In accordance with the further embodiment
of the present inven-tion, a cleansing composition may
be prepared which comprises an oxidizing agent containing
a monopersulfate salt in an amoun-t of from 35% - 60~,
a bleaching promoter selected from the group consisting
of alkali metal and alkaline earth me-tal halides, presen-t
in an arnount ranging up to about 20~, an effervescence
promcti:ng compound selected from alkaline eaxth metal
and alkali metal perborates, present in amounts from
about 0.5 to 20go~ a colorant selected from pigments and
dyes, and preferably comprising non-toxic dyes, the
colorant present in an amount tha-t may range as high as
1%, and a fade control agent comprising a compound
~0 capable of providiny soluble halide ion. The halide
component of said fade control agent may ~e selected
from bromide, iodide and chloride ion, and is preferably
selected ~rom bromide ana iodide.
The fade control agent is theorized to
coact with the oxidizing agent in a catalytic manner
that may abruptly accelerate the fading of the colorant.
The fade control agent is particularly useful in the
instance where the colorant comprises those dyes
certified by the Food and Drug Administration as
acceptable for use in foods, drugs and cosmetics r
and known as F.D. & C. grade dyes. Also D. ~ C. grade
dyes, and insoluble dyes, such as F.D. ~ C. and D.
C. grade la]ces may be utilized. C.
mab/~
, ~",
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10894
grade may also be used.
The amount of fade control agent present in the cleans-
~ng composition of the present invent1on varies with the
amount of dye and oxidizing agent present in the composi-
tion, and to a lesser extent, the amount of perborate salt :--
included therein. In a preferred embodiment, the fade con- .:
trol agent may comprise potassium bromide, and may be pre- i
sent in amounts ranging from 0.04 to 0.3%. ~'`
, .
The fade control agent acts in an unexpected catalytic ~:
manner and is particularly useful in the instance where ~`.
the composition is prepared in tab1et form as a denture t~
cleanser~ The disso1ving tablet has been found to pro- '
vide an initia71y strong, intensely colore~ solution. :... `
This intense collor may be maintained for varying periods t
1~ of time, depending on the desired quantities of colorant~
perborate, oxidizing agent and fade control agent utili7ed.
By use of a particular quantity of the fade control agent, .-
the color intensity of the solution can be maintained for .... `-.
a predetermined period of ~ime; after which the fading . .I
of the color becomes noticeably a~celerated, and a sub- t'''''"'`''
stantially color1ess solution i5 thereafter rapidly ob- I
tained. For example, increments of as little as .1 mil- .... ;.
1igram of the fade control agent have been found ~o vary !:.
the fade time of the dyes utilized in denture cleanser ...
tablets prepared in accordance herewith, by as much as 1 ... `.
minute; thus~ the addition of .1 milligram of the fade con- ......
trol agen-~ has been found to reduce the time it takes for -
the dyes to comp1etely disappear by as much as 1 minute `
....
, ...:. .: ..:
The foregoing compositions are useful in a variety of ...
applieatlons, apart from their preparation into denture .........
..... .
.
11~33 ,~SZ
cleanser Lablets. Thus, for example, -the cornposikions
of the present inverltion may aclditiorlally be preparecl
as household c~Leatlsers, such as launclry bleaches and
toilet bowl cLeansers, ancl the l:ike. Depending upon
the desired appLications, the cleansing composi-tions
incluclincJ those havirlg -the Eade con-tro], agent, may
include additional ingredients, such as soaps, perEumes,
flavorings, and the like -that may ranye in total arnount
as high as 5 - 10~. Preferably, these addi-tional
ingredients are present in amounts of up to about 5%.
~ s used throughout -the present specification,
all percentages are intended to be percent by weigh-t.
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~ t~Sj~ 1 0894
g
DETAILED DESCRIPTION
... . _ _
The effervescing cleansing compositions of the present
invention comprise an oxidizing agent that may be an al-
kali metal monopersulfate salt, present in an amount
ranging from 35 - 60%3 and preferably 40 - 50% by weight.
The alkali meta1 monopersulfate salts are preferably the
potassium or sodium salts, which are commercially avail-
able. The potassium salt is preferred, and may, if de-
sired, be employed in the form of a triple salt with po-
tassium bisulFate and potassium sulfate, e~g~, KHS05.
KHS04.K2S04.
In ~he mole ratio oF about 2:1:1, the foregoing triple
salt is known commercially by the trademark "OXONE~"
and is sold b.y E~Io duPont DeNemours & CoO, Inc.
The bleaching prsmot~r or component ;s likewise well
known~ and may be selected from the group cons;sting of
alkali and alkaline earth metal halides, in amounts
ranging up to 20%, and preferably ranging from 10 - 20%
by weight of the composition~ The halide salt is prefer-
ably selected from alkaline me~al halides such as the sod-
7um and potassium salts. `In a preferred embodiment, sodi~
um chloride is utilized in an amount ranging between 10
and 20%.
The e~fervescence promoting compounds comprise the per-
borate salts, including the alkali metal and alkaline
earth ~etal perborates. Preferably~ the perborate salts
are selected From ~he alkali metal salts, such as sodium .
and po,assium, and a preferred embodiment~ sodium perbor-
ate monohydrate is utilized~ The perborate compounds un-
expectedly promote effervescence by kheir reacti on wi th
the halide component. The perborate compounds are
~83'75~ 1 0~94
-1 O-
theorized to react as reducing agents, thereby recycling
the halide to react in turn with the oxidizing agent to
promote greater effervescence.
The perborate compnunds may be present in amounts ranging
from about 0.5 to 20%, and preferably from 0,7 to 15%.
As noted earlier, solutions obtained from the cleansing
eomposltions possess a pH in the basic or alkaline range,
which results in improved stain and soil removing capabil- I
ities. In a preferred embodiment, the pH of solutions ob- i
tained from the present compositions may range as high as
pH 11, and preferably resides within the pH of 8 to 10 .
In the instance where the present composi$ions are formu-
lated as denture cleansers, the preparation of compositions
whose solutions will possess a p~l within.the aforem~ntioned
range facili~at~s the rapid removal of stains, with a re-
- duction in the time that the dentur.es must reside in the
cleansing solution, to as low as five minutes in some in-
stances.
. In addition to promoting effervescence in an alkaline 1.
or basic pH, the perborate compounds react favorably wi th
the chl.oride bleaching promotors to reduce or eliminate
the irri~ating odor and aftertaste caused by the presence
of the hyphochlorite resulting from the reaction of the
chloride salt with the oxidizing agent. The elimination
of the hypochlorite odor~permits the present compositions
to ~e modified by the addition of perfuming agents and
flavors, in the instanoe where the present oomposit~ons-
arP to be formulated for.use as denture cleansers.
As noted earlier, the cleansing compositi~ns described
above may be prepared in various formulationsa and,
j
I
~33~SZ
accordingly, ma~ contain certain additional ingredients
selected on the basis oE desired end use. Thus, ~or
e~an~ple, the composi.t:ions may incl~lde additio,lal detergent
compounds, includillcJ orgarlic and ;.nor~anic detergents,
including non-ionic de-tergents such as the various poly-
ox~ethylene e-thers of aromatic ancl alipha-tic alcohols,
as well as the polyo~yethylene ethers of hydropho~ic
propylene o~ide polymers. These compounds assist in
maintaining a Eoaming ac-tion, in the instance where the
cleansing compositions are placed in aqueous solution.
Also, the compositions may con-tain other
adjuvant materials, that may be inorganic or organic in
structure. Thus, inorganic water-soluble alkaline
builders such as alkal and alkaline ear';h met~l car-
bonates, tetrapyophosphates, tripolyphosphates,
phosphates, metasilicates and hydroxides, and mixtures
of these may be added. Particularly, sodium carbonate
may be present in an amount rangi~ng from 20 to 40~,
and preferably in an amount of from 25 to 30~, as it
functions not only as a builder, but enhances efferves-
cence and assists in stabilizing the pH of the solutions
obtained from the composition. In this latter capacity~
sodium hydroxide may be added to assist in pH
stabili~ation and may be presen-t in amounts of up to
about 0.5~, and preferably 0.3gO to 0.5%.
The present compositions may also contain
sequestrants for the purpose of maintaining solution
clarity, in the instance where the compositions are
placed in solution. Sequestran-ts useful in the present
invention include ethylene diamine tetraacetic acid
(EDTA) and its corresponding alkali sal~s, as well as
other polyfunctional organic acids r such as citric acid,
malelc acid, and their corresponding salts. The
seques-trants may be present i.n amounts OL UP to abou-t
I mab/ ~
~IL115 ~75;~
3.5~;, and preferably ~.3% to 3.5~ by we:ight oE the
compos:ition.
In the i.n~tance where the comyos:i.ion is to
be preparecl for use as a clenture cleanser, other
addi-tives such as E:LavorincJs, coloran-ts, per~umes and
the like may be added in various amounts, as men-tioned
earl:ier. For example, the :Elavor:ings may include
varieties of min-t. These materials may be included
and blended in various combinations within the scope
of the present invention. The choice o:E the required
amoun-ts is likewise within the ski:Ll of the ar-t.
In the instance where the presen-t cleansing
compositions are Eormulated for use as denture cleansers~
the colorants useful herein are those known as F.D~ &
C. and D. & C. dyes and lakes. These materials are
certified by the Federal Food and Drug Ad~inistration
as acceptable for use in food, dru.g and cosmetic
applications, and drug and cosmetic colorings. The
materials acceptable for the foregoing spectrum of use
are preferably water-soluble, and include indigoid dye
known as F.D. & C. Blue No. 2, which is the disodium
salt of 5,5'-indigotindisulfonic acid. Similarly,
the dye known as F.D. & C. Green No. l. comprises a
triphenylmethane dye and is the monosodium salt o-f
4 14-(N-ethyl-p-sulfobenzylamino)diphenylmethylene~--
~l-(N-ethyl-.N-p-~sulfoniumbenzyl)-Q~2/5-cyclohexadieniminel.
A full recitation of all F.D. & C. and D. & C. and their
corresponding chemical structures may be found in the
Kirk-Othmer Encyclopedia of Chemical Technology~ at
Volume 5, pages 857-884. Dyes and colorants will fade
at different ra-tes and may be chosen to provi~e specific
end points.
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The foregoiny colorants may be blended w;th each other
in a variety of combinations. It is particularly desir-
able that the colorants be chosen so that the composition
when initially dissolved w;ll present a deep hue. This
;s ;mportant ;n the ;nstance where the composition serves
as a denture cleanser, as the fading phenomenon embod;ed
in denture cleansers can be more easily observed by the
end user.
In accordance with a further embodiment of the ;nvention,
the effervescing cleans;ng composit;ons may be prepared
to ;nclude a fade control agent, ;n the instance where
the composit;ons contain a co10rant such as previously des- ¦
cr;bed, and are ~o be utilized in applications where ces-
sation of composition activity is signif;ed by disappear-
1~ ance of the color. ~he fade control agent comprises a
compound providing soluble halide ion. The halide com-
-~- ponent of the fade control agent may be selected from
brom;de, iodide and chloride ion, and is preferably se- ~f
lected from bromide and iodide ion.
The amount of fade control agent present in the composi-
tion may vary, depending upon the end utility of the com-
pos;tion, as the fade time of the colorants employed will
Yary with the colorants, and with the end use to which the
composit;on is put~ For example~ in the instance where
the compos;tion is to be ut;lized as a denture cleanser3
it is desirable that the fade control agent be present
in an amount sufficient to cause the total disappearance
of the colorant within 18 minutes after a compos;tion con-
tain;ng the colorant is placed in solutinn. Naturally,
the amount of fade control agent present may be adjusted
to accelerate the fading reaction and correspondingly to
reduce the fade time.
~L183752
One of the surprisincJ aspects of the present invention,
is that the :Eade control a~ents set :Eorth herein operate
in a catalytic manner, in that minute quantities of the
fade control agerlts can achieve substantial and precise
facle time control. For example, in -the ins-tance
where a dentu:re cleanser tablet is prepared having a
weiyht of approximately 3.3 cJrams, with a content of
about 4 milligrams of coloran-t, -the addition of 1 milli-
gram of the fade control agen-t can effect the reduc-tion
of the fade time of the colorant -to wi-thin about 12
minutes. Moreover, the inclusion of an additional 0.1
milligram of the fade con-trol agent -to the denture
cleanser tablet causes a recluction of 1 minute in the
fade -time.
The foregoi`ng resul-ts are par-ticularly
advantageous in that -the addition of the presen-t Eade
con-trol agent does not adversely effec-t the ini-t~al
color reaction of -the composi~tion when placed in an
aqueous solution. Prior art attemps to con-trol fade
time by the addition of greater quantities of bleaches
and -the like, have adversely effected the initial color
reaction of the tablet, and have therefore been
undesirable for use.
The particular fade control agents useful in
accordance with the presen-t inven-tion c~mprise those
compounds selected from the group consistin~ o:E the
alkali metal sal-ts of bromine, chloride and iodine,
individually or in mixtures wi-th each o-ther. The
potassium salts o-E these compounds are generally
preferred, and more particularly, the compounds pctassium
bromide and potassium iodide have been found to be
most eEEective.
The fade control agents may ~e added to
-the cleansing
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~ 75Z' 1 0~94
-15-
compositions in amounts ranging from about 0.04 to about
0~3% by weight of the compositon. Preferably, the fade
control agents may be present in an amount rang;ng from
0.04 to 0.18% by weight.
The compositions of the present invention are capable of
preparation by a variety of techniques, depending upon
the intended end use. In the instance w~ere the present
compositions are to serve as denture cleansers~ it is
desirable to prepare the compositions in tablet form. The
use of the present compositions in table~ ~orm is commer-
cially preferred9 as it is easier to achieve the uniformityof quantity and distribution of the ingredients of the com-
positions that is necessary to assure the corresponding un-
iform;ty of performance of the denture cleanser. Thus,
cleanser tablets have been found to exhibit uniformity of
color reaction, disintegration and fade time, and clean-
ing ability on a tablet-to-tablet basis.
To enable the present composition to be prepared in tablet
form, certain ingredients, including excipients9 tableting
agents and the like are added, and the resulting composi-
tion is then compressed to form the final tablet. ThPparticular tableting additives utilized herein comprise
conventional materials normally utilized for such purpose,
and may be selected and employed in amounts determined '
within the skill of the art.
In the instance where the contemplated composition is`to
contain a halide such as sodium chloride, it is advisable
to add the basic component such as sodium carbonate to
the ingredients prior to adding the monopersulfate salt,
75'~
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;n order to avoid undue or premature reactivity of the re-
sult;ng mixture.
A fuller understanding of the present ;nvention will be
gained from a rev;ew of the follow;ng illustrat;ve exam-
ples~ Compositions representing both the alkaline effer-
vescing system, and the fade control agent-are included.
Unless specified otherwise? all amounts expressed as per-
~ cent are deemed to be percent by weight of-the total com-
position, .
EXAMPLES 1-9
-~ A series of compositions were prepared for use as denture
cleansers3 and comprised the jngredients set forth in
Table 1, below.
' ' ' '' ~
The compositions were prepared in tablet form~ each tablet ,.
weighing approximately 3.3 gramsO The tablets were there-
after immersed in approximately 125 milliliters of water
maintained at a temperature of about 45~ C. The color re-
action, disin~egration time, pH and fade time were noted. L
~:18;~5~
N ~ ~ N ~ ~ ¦ N
L~ Il') L~ O O ~1 In ~1 t~ t`~l ~ e;l~ r--l 1
r--I Ll') O O t'~l Lr~ ~1 lS7 O ~ ~ CO ~
~) r--~ (~ O Lr) ~ cn ~0 S~ O ~r r--~ r ~ 00
~1 r--I ~ O Il') ~1 ~ O ~ O r--i ~1 0~ CO
O ~ ~ O 1~ ~ L~ ~1 U~ N N ~ r~
æ
X ~ au D 1d ~r I
O~o a) ,~ r ~ r O ~ t)
Z ~ } o ~ ~ ~
æ ~ ~ r~ U~ ~ ~ rd r h r U~ O ~1 ~:J ~:; U O S ?
rd rd r-l O ~c r~ ~ r-l td O O :~r ~ r~; !~1 r-l ~ Q
r; ~ (`~) ~r 1~~) ~ 1_ CO ~ r--I i r--I rt
-- 17 --
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~183'7S,2
~ach of the tablets disintegrated within 5 minutes, and
e~hibited initially a strong color reactiorl, yenerally
bluisll on the basis of the dyes included in the
colorants.
Favorable effervescence ~as likewise observed,
and the pH of the solutions of each of the compositions
ranged between 9.0 and 9.6. In the lnstance where the
compositions contained -the fade control agent, fade time
for -the colorant ranged between 7 and 17 minutes.
EXAMPLE 10
_
The compos:ition similar to tha-t oE Example 1,
incremen-tal additions of potassium iodide were made,
after -tablets of the composition were placed in ~eparate
containers holding 125 milliliters of water, maintained
at a tempera-ture of 45 degrees C. Four such containers
were prepared having the incremental additions of
potassium iodide se-t for-th in Table 2 below.
TABLE _
SAMPLE NO. POTASSIUM IODIDE ADDED (mg) FADE TIME (min.
....
1 0 (Control) 12
2 0.5 lQ
3 1.0 9
4 1.5 8
2.0 7
It is apparent from a review of Table 2, above
that .5 milligram incremental a~ditions of potassium
iodide effec-ted subs-tan-tial incremen-tal reduc-tions in
-the fade time, the most signi-ficant change being that
of 2 minutes reduction upon the addition of -the firs~
.5 milligram increment. It is apparent from the above
that substantial fade time reductions can be achieved
with minimal incremental additions
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of the fade control agents.
This invention may be embodied in other forms or carried
out in other ways without departing from the sp;r;t or
essential characteristics thereof. The present invention
is therefore to be considered as in all respects
illustrative and not restrictive, the scope of the
invention being indicated by the appended claims, and
all changes which corne with;n the meaning and range ~,
of equivalency ere intended to be embraced therein.
