Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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SILICONE COMPOSlTIONS
TECHNICAL FIELD
The present invention relates to silicone-con~ining compositions and to
use thereof in various household products such as personal care products,
laundry and household cleaners, bleaching compositions and the like. In
particular, it relates to silicone-cont~ininE lipophilic compositions based
on flavorants, pelrunles, coolants or antimicrobial agents as lipophile and
which display improved residn~lity, imr~ct and/or efficacy on surfaces
treated therewith, for example teeth, dentures, skin, hair, laundry,
dishware, working surfaces and the like. In addition, it relates to
silicone-cont~inin~ bleach compositions which ~d~itionally contain bleach-
sensitive ingredients such as pel~mes, flavorants and the like and which
display imp,oved stability.
BACKGRQUND
Lipophilic compositions such as flavor, l,e~rume, coolant and disinfectant
compositions are widely used either directly or in a variety of household
products inclusive of cosmetics~ oral and denlure compositions, bleach,
dishw~shing, hard surface cle~ning and laundry delelgc;nt products, etc.
A common problem enc~untered with lipophilic compositions is that of
improving surface sub~livil~r or resi~ lity of the lipophilic component.
It would be desirable in many if not most household applications to
enh~nce the surface resi~ lity of the lipophile in order, for example, to
provide iuc~eased flavor or perfume impact or increased antimicrobial
efficacy.
Modern dental hygiene and denture preparations, for example, typically
contain antiplaque and/or antitartar agents, as well as antimicrobial agents
and flavol~. Antimicrobial action could affect plaque formation by
either reducing the mlmber of bacteria in the mouth/delllures or by killing
those bacteria llapped in the film to prevent further growth and
metabolism. Flavorants may alleviate the problem of bad breath via a
deodorizing action. Some antimicrobial agents, e.g. menthol may, also
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serve as breath deodorizers. However, the efficacy of antimicrobial
agents depends largely on their intraoral/denture retention~ particularly
their retention on the surface of the teeth or dentures where plaque is
formed.
A typical disadvantage of known dental preparations is that only a
relatively short time during which the teeth are being cleaned or the
mouth is being rinsed is available for ~ntimicrobial agents in the
~repalations to take effect. The problem is compounded by the fact that
~i~ntifrice preparations are used infrequently; most are used once or,
,elLaps, twice daily. Consequently, the long time period between
brll~hin~c for a majority of the population provides opt;....~ plaque
îo~uung conditions.
In many other personal and household applications, it would be desirable
to provide enh~nce~ surface sub~ ivily. ~ n~ry deler~nts, for
e~mrle, would benefit by increasing l,elruule subs~ntivily on fabrics so
as to provide increased pelruule imp~ct on clothing after l~nn~lering or
rin~ use. Increased ~ntimicrobial sul,s~livily would also be beneficial
from the viewpoint of reducing malodors associated with sweat or other
soils. Fnh~nce l perfume subs~nlivily would also be valuable in fine
fragrance and pelruuued cosmetics. Pnh~nce~l coolant sllbs~ ;vily, on
the other hand, would be beneficial in cough/cold products.
There has been a need, thererolG, for developing lipophilic compositions
which have h~ oved surface residu~lity, imp~ct and/or antimicrobial
efficacy.
The use of lipophilic compounds such as pe.rumes, flavorants and the like
in bleachcont~inin~ coul~osilions can also raise a number of problems,
especially loss of l,clruule or flavorant character or inten~ity as a result of
interaction with the bleach. The efficacy of the blç~c-hin~ agent can also
be adversely effecte~l. It would thus be desirable to i,llprove the stability
and effectiveness of bleach compositions cont~iniT~ bleachsensitive
ingredients.
-
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It is known to include silicones in ~l~ntifrice compositions, allegedly to
coat the teeth and prevent cavities and st~inin~. For inctance, GB-A-
689,679 discloses a mouthwash cont~ining an organopolysiloxane for
~reventillg adhesion of, or for removing tars, stains, tartar and food
particles from the teeth. The mouthwash may include antiseptic
compounds, such as thymol, and flavoring and perfuming agents.
US-A-2,806,814 discloses dental preparations including, in combination,
a higher aliphatic acyl amide of an amino carboxylic acid compound as an
active and a silicone compound. The patent notes that silicone
compounds have been proposed for prevention of adhesion or to facilitate
the removal of tars, stains, tartar and the like from teeth. The silicone
col~oulld is said to act as a synergist in improving the ~ntib~cterial and
acid inhibiting activity of the active ingre~lient. Dilllc~yl polysiloxanes
are said to be particularly erre-;live. Flavoring oils and/or m~nthol may
be included.
US-A-3624120 discloses quatel~aly ammonium salts of cyclic siloxane
polymers for use as cationic surfact~nts, bactericides and as
antiC~riogeniC agents.
Accor~ gly, the present invention provides a flavor, pelr~ le, coolant,
antimicrobial or other lipophilic composition having improved surface-
s~ll)s~ t;vily, jmp~ct and/or efficacy.
The invention further provides a bleach composition colllprising an
inorganic persalt bleaching agent, and a lipophilic compound such as a
flavorant and/or perfume and which has improved stability.
SUMMARY OF T~F INVFNTION
~ Acco~i~g to a first aspect of the invention, there is provided a flavor,
pc~runle, coolant, antimicrobial or other lipophilic composition
co~ ising an ~mino~ ylsilicone having an ~mino~lkylsilo~cane content of
from about 0.1%-2% on a repe~tin~ unit basis.
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The invention also relates to the use of an aminoalkylsilicone with a
lipophile selected from flavorants, perfumes, physiological coolants,
antimicrobial agents and mi~lres thereof to provide i...~.o~ed surface
resi~ lity, wherein the ~mino~lkylsilicone is selected from
~mino~lkylsilicones having an ~mino~lkylsilo~cane content of from about
0.1%-2% on a repe~tin~ unit basis.
According to a further aspect of the invention, there is provided a bleach
composition co..lp.ising an inorganic persalt ble~chin~ agent, a lipophile
selected from flavorants, pe-ru.lles, physiological coolants, ~ntimicrobial
agents and mixtures thereof, and an ~mino~lkylsilicone having an
~mino~lkylsilo~cane content of from about 0.1%-2% on a repe~tin~ unit
basis.
The invention also relates to the use of an ~mino~lkylsilicone with an
inorganic persalt ble~chin~ agent and a lipophile selecteA from flavorants,
perfumes, physiological coolants, ~ntimicrobial agents and mi~hlres
thereof to provide i.~roved lipophile stability, wherein the
~mino~lkylsilicone is selected from ~mino~lkylsilicones having an
~mino~lkylsilo~cane content of from about 0.1%-2% on a repeating unit
basis.
All ~erce~ ges and ratios herein are by weight of total composition,
unless otherwise in~ic~te~l
The co~osilions of the invention thus comp-ise an ~mino~lkylsilicone
antiplaque agent and a lipophile sclcctel from flavorants, perfumes,
physiological coolants, antimicrobial agents and m~ res thereof. Other
compositions of the invention take the form of bleach and/or delel~ent
compositions which co~l,.ise the ~mino~lkylsilicone antiplaque agent and
lipophile.
In general terms, the ~mino~lkylsilicone is selected from noncyclic,
hydrophobic ~mino~lkysilicones having a formula co-nprising two basic
units:
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1) (Rl)m(R)nSiO(~m n)/2 wherein m+n is 1, 2 or 3; n is 1, 2 or 3;
m is 0,1,2; and
2) (R1)a(R2)bSio(~a-b)/2 wherein a+b is 1, 2, or 3, and a and b are
integers,
wherein Rl and R2 are indepen~e.lltly selected from H ,alkyl and alkenyl
of about 1 to about 10 carbons optionally subs~ ~l with fluoro or cyano
groups, hydro~cy, alkoxy, and acetoxy, for e~cample, wherein Rl and R2
are indepen~l~ntly selected from methyl, ethyl, phenyl, vinyl,
trifluor~pro~yl and cyanopropyl, and R is
R4 R4
--R3--N-R5 or --R3--N-R5 X
R6
wherein R3 is a divalent alkylene of about 1-20, ~reîerably about 3-5
carbon atoms optionally sul,~ .te~ or mte~lu~led by O atoms, R4, R5
and R6 which may be the same or dirrelent are selected from H, alkyl of
about 1-20, l,~ere~dbly about 1-10, more l,rcfelably about 14 carbons
optionally sul,s~ le~ or intellu~ted by N and/or O atoms, and X~ is a
monovalent anion such as halide, hydro~cide, and tosylate, said
aminoalkylsilicone including from about 0.1-2 %, yrererably from about
0.5-2% of unit (1) on a repe~tin~ unit basis.
In a ~lere~ embo~ ent, the ~mino~lkylsilicones comprise
~moAimethicones. ~mo.limethicones are poly~limPthylsilo~ane polymers
co~ mino~llryl groups. The ~mino~lkyl ~r~,~s may be present
either pen~l~nt or at one or more ends of the poly limetllylsiloxane chain.
Pr~felr~d are ~mino~lkylsilicones in which ~mino~lkyl moiety R is
selected from (cH2)3NH2~ (cH2)3NHcH2cH2NH2
(CH2)3N(CH2CH2OH)2, (CH2)3NH3+X-, and
(CH2)3N(CH3)2(C18H37)+X-, and especially from (CH2)3NH2 and
(CH2)3NHCH2CH2NH2. Also p.er~ed are aminoalkyl silicones having
an average molecnl~r weight of about S,000 and above, preferably from
about 5000 to about 100,000, more plel~lably from about S000 to about
30,00~.
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,AminQ~lkylsilicone compounds suitable for use herein are well known.
Methods of preparing ~mino~lkylsilicones are given in, for example, US-
A-2,930,809.
F.~mpleS of amo~limethicones include OSI's M~n~oft fluid. These
polymers colllprise ~min~llcyl groups :lfflXe~ to a predo--~inA.~tly
poly~limethylsiloxane structure. The typical structure of ~n~oft's
~mino~llryl group-cont~inin~ units is
-OSi(Me)C3H6NHCH2CH2NH2.
The ~mino~ ylsilicone is generally present in a level of from about
0.01% to about 25 % , p~ere~ably from about 0. 1% to about 5 %, more
prefelably from about 0.5% to about 1.5% by weight.
The compositions of the invention prefe~dbly also include a lipophilic
compound. In general terms, lipophilic compounds suitable for use
herein are oil-like materials which are soluble or solubilisable in the
~min~ ylsilicone, prerel~bly at a level of at least about 1%, more
~rererably at least about 5% by weight at 25~C. rrerelled lipophilic
compounds are selected from flavorants, perfumes, physiological cooling
agents and ~ntimicrobial compounds. The aminoalkylsilicone acts to
enh~nGe the snbsl~t;vily of the lipophilic compound to a surface treated
there~vi~, thereby providing enh~nce~ and/or sllst~in~A flavor, perfume
or coolant imr~ct and/or antimicrobial efficacy.
Lipophilic flavorants suitable for use herein comp~ise one or more flavor
colll~one.~ls selected from willtergreen oil, olcgallo oil, bay leaf oil,
~ int oil, s~ealll~i~t oil, clove oil, sage oil, s~ss~fras oil, lemon oil,
orange oil, anise oil, ben7~ldehyde, bitter almond oil, camphor, cedar leaf
oil, marjoram oil, citronella oil, lavendar oil, mns~rd oil, pine oil, pine
nee~le oil, rosemary oil, thyme oil, cinn~mQn leaf oil, and mi~ctures
thereof.
Lipophilic ~lrumes suitable for use herein comprise one or more known
pelrullle com~ollents inclusive of natural products such as essenti~l oils,
absolutes, resins, etc., and synthetic perfume components such as
=
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hydrocarbons, alcohols, aldehydes, ketones, ethers, acids, esters, acet~
ketals, nitriles etc., including saturated and llne~tllrated compounds,
aliphatic, carboxylic and heterocyclic compounds. F.x~mples of perfume
materials suitable for use herein include geranyl ~cet~te, linalyl acetate,
citronellyl ~cet~te, dihydromyrcenyl ~cet~te, terpinyl ~cet~te,
tricyclo~lecenyl ~cet~te, tricyclodecenyl propionate, 2-phenylethyl ~cet~te,
benzyl ~cet~te, benzyl salicylate, benzyl ben~o~te, styrallyl ~cePte, amyl
salicylate, methyl dihydrojasmonate, phenoxyethyl isobulylate~ neryl
~cet~te, trichloromethyl-phenylcarbinyl ~cePte, p-tertiary butyl-
cyclohe~yl ~cet~te, isononyl ~cet~te, cedryl ~cet~te, vetiveryl ~cet~te,
benzyl alcohol, 2-phenyleth~nol, linalool, tetrahydrolinalool, citronellol,
~limethylbenzylcarbinol, dihydromyrcenol, tetrahydromyrcenol, terpineol,
eugenol, geraniol, vetiverol, 3-isocamphyl-cyclohexanol, 2-methyl-3-(p-
tertiary butylphenyl)-propanol, 2-methyl-3-(p-isopropylphenyl)-~ropanol,
3-(p-tertiary butylphenyl)-yrop~ol, nerol, alpha-n-amylcinn~mic
aldehyde, alpha-he~cyl-cinn~mic aldehyde, ~(~hydroxy~methylpentyl)-
3-cyclohP~enec~rb~l~lehyde, ~(~methyl-3-pentenyl)-3-
cyclohe~enec~rb~l~lehyde, ~acetoxy-3-pentyl-tetrahydropyran, 2-n-
heptyl-cyclopçnt~none, 3-methyl-2-pentyl-cyclopent~nQne, n~lec~n~l, n-
~lo~ec~n~l, hydroxycitronellal, phenyl~cet~ldehyde ~lim~thyl ~cet~l,
phenyl~c~al~lehyde diethyl acet~l, ger~nonitrile, citronellonitrile, cedryl
methyl ether, isolongifolanone, aubepine nitrile, aubepine, heliolropille,
CO.llllalln, v~nillin, ~lirh~nyl oxide, ion~.ne~, methyl ionones, isomethyl
ionones, irones, cis-3-h~x~n~l and esters thereof, ind~ne musks, tetralin
musks, isochro~n musks, macrocyclic ketones, macrol~ctone musks,
ethylene brassylate, aromatic nillol,lusks and mi~ res thereof.
Lipophilic antimicrobial compounds suitable for use herein include
thymol, m.o.nth~l, triclosan, ~hexylresorcinol, phenol, eucalyptol, benzoic
acid, be~oyl peroxide, butyl paraben, methyl paraben, propyl paraben,
salicyl~mides, and n~ res thereof.
~.~
Physiological cooling agent suitable for use herein inclllde carbo~amides,
m~ ..e esters and mrn~ . ethers, and mixtures thereof.
Suitable n~ n1l.~ne ethers for use herein are selected from those with the
formula:
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OR~
where Rs is an optionally hydro~y substi~lteA aliphatic radical cont~ining
up to 25 carbon atoms, ~rere~ably up to 5 carbon atoms, and where X is
hydrogen or hydro~cy, such as those commercially available under the
trade nameT~ o, fromT~ o Inle~llational Corporation. A
particularly l,rerelled cooling agent for use in the compositions of the
presenl invention is T~k~ o 10 [3~ .o~cy pr~pan-1,2-diol (MPD)].
MPD is a monoglycelin delivalive of l-m~.ntllrll and has e~cellent cooling
activity.
The carboY~mides found most useful are those described in US-A-
4,136,163, January 23, 1979 to Wason et al., and US-A~,230, 688,
October 28, 1980 to Rawsell et al.
The level of lipophilic com~G.~nd in the con~osilions of the invention is
generally in the range from about 0.01% to about 10%, ~referably from
about 0.05% to about 5%, more ~refelably from about 0.1% to about 3%
by weight.
The co~l~osil;ons of the invention optionally include one or more
surf~ct~n~, these being especially prefe~d in lipophilic compositions of
the illvention for the ~ ,ose of solubili7~tio~ of the lipophile and for
providing illl~JrOVed efficacy. Suitable surf~ct~nt~ include non-soap
anionic, nonionic, cationic, ;~willerionic and amphoteric organic synthetic
delelge~ . Many of these suitable agents are disclosed by Gieske et al. ~-
in US-A-4,051,234, Se~tember 27, 1977.
F.~mrles of surf~ct~nts suitable for use herein include C6-Clg alkyl
s~llf~tes and alkyl ether s~llf~tes etho~cylated with from about 0.5 to about
20 moles of ethylene o~cide per mole; anionic sulro-~ates inclusive of Cs-
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C20 linear alkylben7ene sulfonates, alkyl ester sulfonates, C6-C22
primary or secondary alkane sulfonates, C6-C24 olefin sulfonates,
sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl
glycerol sulfonates, and mixtures thereof; anionic carboxylates inclusive
of primary and secondary C6 to Clg alkyl carboxylate, ethoxy
carboxylate and polyetho~cy polycarboxylate surf~ct~nts having an average
degree of ethoxylation of from about 0 to about 10; Cs-C17 sarcosm~tes
such as sodium cocoylsarcosinate, sodium lauroyl sarcosinate (Hamposyl-
95 e~c W. R. Grace); con~1en~tion products of ethylene or pro~ylene
oxide with fatty acids, fatty alcohols, fatty ~mirles, polyhydric alcohols
(e.g. sorbitan monostearate, sorbitan oleate), alkyl phenols (e.g. Tergitol)
and polypropyleneoxide or polyo~cybutylene (e.g. Pluronics);
alkylpolys~cch~rides as disclosed in US-A ~1,565,647; amine oxides such
as ~1imetllyl coc~mine oxide, t1imetllyl lauryl amine o~cide and
cocoalkylllimet!~yl amine oxide (Aromox); polysorbates such as Tween 40
and Tween 80 (Hercules); sorbitan stearates, so~ dll monooleate, etc;
cationic surf~ct~nts such as cetyl pyri~linil.m chloride, cetyl trimethyl
ammonium bromide, di-isobutyl phenoxy ethoxy ethyl-dimethyl benzyl
ammonium chloride and coconut alkyl trimethyl ammonium nitrate.
Highly prefclr~l herein from the view point of lipophile solubilization are
the nonionic surf~ct~ntc. One class of nonionic surf~cPnt suitable for use
herein are those having the general formula:
Rl--(OCHCH2)m (OCH2CH2) n OH
CH3
in which Rl is an alk(en)yl or alk(en)yl phenyl group having 8 to 22,
prefe~dbly 10 to 20 carbon atoms ion the aLk(en)yl moiety and m and n
r~resent weight-averages in the range 0-80 and 2-80 respectively.
Shorter chain length alkyl grou~s are generally to be avoided for efficacy
re~on.c and bec~se unreacted fatty alcohol in such surf~ct~nts is a source
of malodour and occasionally of skin irritation. It will be understood that
surf~ct~nts of this type are usually mixtures of varying degrees of
etho~cylation / propoxylation, accordingly m and n represent the
respective weight-averages of the number of propoxylate and ethoxylate
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groups. Nonionic surfact~nt~ of the above general type include mixed
alkoxylates in which m and n are both in the range from about 2 to about
80, with m preferably being in the range from about 2 to about 20, more
prererably from about 3 to about 10 and with n preferably being in the
range from about 2 to about 60, more preferdbly from about 5 to about
50. One such malerial is PPG-5-ceteth-20 (available from Croda Inc as
Procetyl AWS), where m and n have the values 5 and 20 respectively.
Other suitable nonionic surf~ctant~ include polyetho~ylated surf~ctants,
e.g. etho~cylated alkylphenol ethers, particularly octyl- and nonylphenol
ethers cont~inin~ 8-16 EO; ethoxylated aliphatic Cg-C20 alcohols, which
may be linear or branched and contain 8-16, pleferably 9-15 EO; and
ethoxylated hydrogenated castor oils.
In general, the ratio of surf~ct~nt to the pelrullle, coolant or other oily
material will be in the range of from about 50:1 to about 1:10, prefe~ably
from about 20:1 to about 1:2, more prere~ably from about 10:1 to about
1:1.
Ble~c.hing compositions of the invention additionally include one or more
ble~c.hing agents optionally together with organic pero~cyacid precursors,
err~ escence generatol~, chelating agents, etc
The ble~c.hing agent takes the form of an inorganic persalt and can be
selected from any of the well-known ble~chin~ agents known for use in
household ble~c.hes, dele~en~, delllurG clç~n.cers and the like such as the
alk~ali metal and ammonium perslllf~tes, perborates inclusive of mono-and
tetrahy~lates~ ~ere~lbonates (optionally coated as described in GB-A-
1,466,799) and perphosph~tes and the alkali metal and ~lk~lin~ earth
metal pero~cides. F.~mples of suitable ble~chin~ agents include
po~.csjllm~ ammonium, sodium and lithillm perslllf~te~ and perborate
mono- and tetrahydrates, sodium pyrophosphate pero~cyhydrate and
m?~pnesjllm, calcium, strontium and zinc pero~cides. Of these, however,
the alkali metal perslllf~tes, perborates, percarbonates and nnixtures
thereof are l.rere-ed for use herein, highly p~erer,ed being the alkali metal
perborates and percarbonates.
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The amount of ble~ching agent in the bleaching compositions of the
invention is generally from about S to about 70% preferably from about
10% to about 50%.
The ble~chin~ compositions can also incorporate an effervescence
generator which in prc;rer~ed embo~iment~s takes the form of a solid base
material which in the presence of water releases carbon dioxide or oxygen
with effervescence. The effervescence generator can be selected from
generatoLs which are effective under acid, neutral or ~lk~linP pH
conditions, but ~lefelably it consists of a combination of a generator
which is effective or most effective under acid or neutral pH conditions
and a generator which is effective or most effective under ~ line pH
conditions. EffervescenGe generators which are effective under acid or
neutral pH conditions include a combination of at least one alkali metal
carbonate or bicall,onate, such as sodium bicarbonate, sodium carbonate,
soAillm sesquicarbonate, pot~sium carbonate, pot~ssillm bicarbonate, or
mi~tures thereof, in ~rimi~ re with at least one non-to~cic,
physiologically-acceptable organic acid, such as tartaric, fumaric, citric,
malic, maleic, gluconic, succinic, salicylic, adipic or sulphamic acid,
sodium fumarate, sodium or potassium acid phosphates, betaine
hydrochloride or mi~ctures thereof. Of these, malic acid is ~refe~cd.
EffervescenGe generators which are erreclive under ~ line pH conditions
include persalts such as alkali and ~ line earth metal peroxoborates as
well as ~cl~orates~ pers~llph~tes, percarbonates, perphosphates and
mi~ res thereof as previously described, for e~ample, a mixture of an
alkali metal perborate (anhydrous, mono- or tetrahydrate) with a
mono~el~.Jlrh~te such as Caroat R marketed by E I du Point de Nemours
Co. and which is a 2:1:1 mi~tllre of monopcl~vlrh~te, pot~csillm sulphate
and pot~c~sillm bisulphate and which has an active o~cygen colltent of about
4.5%.
In ~refelr~d bleaching compositions suitable for use as denture cleansers,
the solid base material incorporates a (bi)carbonate/acid effervescent
couple optionally in combination with a perborate/persulphate oxygen
effervescence generator. The combination of generators is valuable for
achieving ~timum dissolution characteristics and pH conditions for
achieving ~limum clç~nin~ and antimicrobial activity. The (bi)carbonate
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components generally coll,ylise from about S~ to about 65%, preferably
from about 25 % to 55% of the total composition; the acid components
generally colll~iise from about S % to about 50%, preferably from about
10% to about 30% of the total composition.
The ble~hin~ compositions of the invention can be supplemented by
other known compollents of such form~ tions. An especially preferred
additional component is an organic pero~yacid precursor, which in
general terms can be defined as a compound having a titre of at least
1 .Sml of 0. lN sodium thiosulfate in the following peracid formation test.
A test solution is pr~ared by dissolving the following materials in 1000
mls ~iictille~ water:
sodium pyrophosphate
(Na4P2O7- l~H2~) 2.5g
so~ m pell,o~ate
(NaBO2.H2O2.3H2O) having
10.4% available o~cygen 0.615g
sorlillm dodecylbe~
sulphonate O.Sg
To this solution at 60~C an amount of activator is added such that for
each atom of available o~cygen present one molecular equivalent of
aclivat~r is intro~luGed.
The ~ vre obt~ine~ by ~d~lition of the activator is vigorously stirred and
",s~i"t~i~,e~ at 60~C. After S .~in~tes from addition, a 100 ml portion of
the solution is wilhdla~n and imme~i~tely pipetted onto a mi~ture of 250
g cracked ice and 15 ml glacial acetic acid. PoPssi~lm iodide (0.4 g) is
then added and the lil~eiated iodine is imm~li~tely titrated with 0.1 N
so~ m t~ios~11rhate with starch as in~lic~tQr until the first disappearance
of the blue colour. The amount of sodium thioslllrh~te solution used in
ml is the titre of the bleach activator.
The organic peracid ~rec.lrjors are typically compounds cont~ining one or
more acyl groups, which are sllsceptible to perhydrolysis. The preferled
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activators are those of the N-acyl or O-acyl compound type cont~ining a
acyl radical R-CO wherein R is a hydrocarbon or sul~sl;lule~l hydrocarbon
group having plc~lably from about 1 to about 20 carbon atoms.
Examples of suitable peracid precursors include:
1) Acyl or~no~mi~es of the formula RCONRlR2, where RCO is
carbo~cylic acyl radic~1, Rl is an acyl radical and R2 is an organic
radical, as disclosed in US-A-3,117,148. Fs~mrles of compounds
falling under this group include:
a) N,N - diacetyl~niline and N-acetylphth~limi~e;
b) N-acylhydanloins, such as
N,N' -diacetyl-5,5~limethylhydantoin;
c) Polyacylated alkylene ~i~mines~ such as
N,N,N'N' -tetraacetylethylen~i~mine (TAED) and the
colle~onding he~methyleneAi~mine (TAHD) derivatives, as
disclosed in GB-A-907,356, GB-A-907,357 and GB-A-
907,358;
d) Acylated glycolurils, such as tetraacetylglycoluril, as disclosed
in GB-A-1,246,338, GB-A-1,246,339 and GB-A-1,247,429.
2) Acylated sulrhon~mi~les, such as N-methyl-N-benzoyl-m~nt~ne
sulphon~mi~le and N-phenyl-N-acetyl nlPnth~ne sulphon~mi~le, as
disclosed in GB-A-3,183,266.
3) Carbo~cylic esters as disclosed in GB-A-836,988, GB-A-963,135
and GB-A-1,147,871. F.~mrles of compounds of this type include
phenyl ~Get~te, so~ m aceto~y l,e~ene sulphonate,
trichloroethyl~cePte, sorbitol he~cet~te, fructose pent~cet~te, p-
nilfol,c~ lehyde ~ cet~te, iso~ropcneyl ~cet~te, acetyl aceto
hydro~amic acid, and acetyl salicylic acid. Other examples are
esters of a phenol or subsl;~v~eA phenol with an alpha-chlorinated
lower aliphatic carb~ylic acid, such as chloroacetylphenol and
chloroacetylsalicylic acid, as disclosed in US-A-3,130,165.
4) Carbo~cylic esters having the gernal formal Ac L wherein Ac is the
acyl moiety of an organic carbo~cylic acid comprising an optionally
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sul~sl;~u~ , linear or br~nche~l C6-C20 alkyl or alkenyl moiety or a
C6-C20 alkyl-substit~lte~l aryl moiety and L is a leaving group, the
conjugate acid of which has a pKa in the range from 4 to 13, for
example oxybçn7enesl)lfonate or oxybenzoate. rrerel~ed
compounds of this type are those wherein: ,~
a) Ac is R3-CO and R3 is a linear or br~nchPA alkyl group
cont~ining from 6 to 20, l.refeiably 6 to 12, more ~rererdbly 7
to 9 carbon atoms and wherein the longest linear alkyl chain
e~te.n~linP from and including the carbonyl carbon contains
from S to 18, ~reftlably 5 to 10 carbon atoms, R3 optionally
being substi~te~ )r~ Çelably alpha to the carbonyl moiety) by
Cl, Br, OCH3 or OC2Hs. F.~mrles of this class of material
include sodium 3,5,5-kimethylhe~noylo~cyben~en-P sulfonate,
sot~ m 3,5,5-trimethylhexanoylo~cyl,c..~o~te, sodium 2-
ethylhe~canoyl o~yl,e..~~~ Pslllfonate, sodium nonanoyl
o~ybe..,e.~-~. sulfonate and sodium octanoyl
o~cybenP~Pnesl)lfollate, the acyloxy group in each incpnce
pre~e~ably being p-slll s~ e~l;
b) Ac has the formula R3(AO)mXA wherein R3 is a linear or
br~n~h~l alkyl or alkylaryl group cont~ininp from 6 to 20,
e~elably from 6 to 15 carbon atoms in the alkyl moiety, Rs
being optionally sul,s~ leA by Cl, Br, OCH3, or OC2Hs, AO
is oxyethylene or o-~ypro~ylene, m is from 0 to 100, X is O,
NR4 or CO-NR4, and A is CO, CO-CO, R6-CO, CO-R6-CO,
or CO-NR4-R6-CO wherein R4 is Cl-4 alkyl and R6 is
alkylene, alkenylene, arylene or alkarylene cont~ininp from 1
to 8 carbon atoms in the alkylene or alkenylene moiety.
Bleach activator compounds of this type include carbonic acid
derivatives of the formula R3(AO)mOCOL, succinic acid
de~ivalives of the formula R3OCO(CH2)2COL, glycollic acid
derivatives of the formula R3OCH2COL, hydro~y~ropionic
acid delivalives of the formula R30CH2CH2COL, o~calic acid
delivatives of the formula R30COCOL, maleic and fumaric
acid de~ivalives of the formula R30COCH=CHCOL,acyl
aminocaproic acid derivatives of the formula
R3CONRl(CH2)6COL, acyl glycine derivatives of the
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formula R3CONR1CH2COL, and amino-~oxocaproic acid
derivatives of the formula R3N(R1)CO(CH2)4COL. In the
above, m is preferably from 0 to 10, and R3 is prererably C6-
C12, more ~refeiably C6-Clo alkyl when m is zero and Cg-
C1s when m is non-zero. The leaving group L is as defined
above.
S) Acyl-cya~ rates, such as triacetyl- or tribenzoylcyanurates, as
disclosed in US patent specification No. 3,332,882.
6) Optionally substi~ute~ anhydrides of benzoic or phthalic acid, for
e~cample, benzoic anhydride, m-chlorobenzoic anhydride and
phthalic anhydride.
7) N-acylated precursor compounds of the l~ct~m class as disclosed
generally in GB-A-855735, especially caprol~ct~m~ and
valerol~ct~ms such as bc~oyl valerol~ct~m, benzoyl caprolactam
and their Sl)bS~ Jle~ be~l:)yl analogs such as the chloro, amino,
alkyl, aryl and alkoxy delivatives.
Of all the above, prefelled are organic peracid precursors of types 1(c),
4(a) and 7.
Where present, the level of pero~cyacid bleach precursor by weight of the
total composition is prere.ably from about 0.1% to about 10%, more
ere.~bly from about 0.5% to about 5% and is generally added in the
form of a bleach prec.llsor agglomerate.
The bleach precursor agglomerates pfefclred for use herein generally
coln~lise a binder or agglomerating agent in a level of from about 5% to
about 40%, more especially from about 10% to about 30% by weight
thereof. Suitable agglomerating agents include polyvinyl~ylr()lidone, poly
(o~cyethylene) of molecular weight 20,000 to 500,000, polyethyleneglycols
of molecular weight of from about 1000 to about 50,000, Carbowax
having a molecnl~r weight of from 4000 to 20,000, nonionic surf~ct~nt~,
fatty acids, sodium carboxymethyl cellulose, gelatin, fatty alcohols,
phosphates and polyphosphates, clays, ~ minosilicates and polymeric
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polycarboxylates. Of the above, polyethyleneglycols are highly
prefe~red, especially those having molecular weight of from about 1,000
to about 30,000, preferably 2000 to about 10,000.
rrefe~red from the viewpoint of op~ lum dissolution and pH
characteristics are bleach ~re~.lr~or agglomerates which collll,lise from
about 10% to about 75%, pieferably from about 20% to about 60% by
weight thereof of peroxyacid bleach precu.sor, from about 5% to about
60% prcfeldbly from about 5% to about 50%, more preferably from
about 10% to about 40% of a (bi) carbonate/acid effervescent couple,
from about 0% to about 20% of a pero~coboroate, and from about 5% to
about 40%, ~referably from about 10% to about 30% of an agglomerating
agent. The final bleach precursor granules desirably have an average
particle size of from about 500 to about 1500, preferably from about S00
to about 1,000 um, this being valuable from the viewpoint of optimllm
dissolution yelror~ nce and ~sthetics. The level of bleach precursor
agglomerates, moreover, is pre~lably from about 1% to about 20%,
more prefe~dbly from about 5% to about 15% by weight of composition.
The ble~chin~ compositions of the invention can be in paste, tablet,
granular or powder form. Compositions in tablet form can be single or
multiple layered tablets.
Ble~chin~ compositions of the invention can be supplement~l by other
usual components of such formulations, especially surf~ct~nt~ as generally
described above, ch~l~ti~ agents, enzymes, dyes(iJrr~ sweeteners, tablet
binders and fillers, foam depress~nts such as ~limell~ylpolysiloxanes~ foam
stabilizers such as the fatty acid sugar esters, preservatives, lubricants
such as talc, m~gnps;ulll stearate, finely divided amorphous pyrogenic
silicas, etc.
Tablet binders and fillers suitable for use herein include
poly~inyl~y~lolidone, poly (o~cyethylene) of molecul~- weight 20,000 to
500,000, polyethyleneglycols of molec~ r weight of from about 1000 to
about 50,000, Carbowax having a molecul~- weight of from 4000 to
20,000, nonionic surf~ct~nts, fatty acids, sodium carboxymethyl cellulose,
g~l~tin, fatty alcohols, clays, polymeric polycarbo~cylates, sodium
-
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carbonate, calcium carbonate, calcium hydroxide, magnesillm oxide,
m~ne.sium hydroxide carbonate, sodium s~llf~te, proteins, cellulose
ethers, cellulose esters, polyvinyl alcohol, alginic acid esters, vegetable
fatty materials of a pseudocolloidal character. Of the above,
polyethyleneglycols are highly plefelred, especially those having
molecular weight of from about 1,000 to about 30,000, l,le~efably from
about 12,000 to about 30,000.
Chel~tin~ agents beneficially aid cle~ni~ and bleach stability by keeping
metal ions, such as calcium, m~nesium, and heavy metal cations in
solution. E~camples of suitable chel~ting agents include sodium
tripolyphosphate, sodium acid pyrophosphate, tetrasodium pyrophosphate,
aminopolycarboxylates such as nitrilotriacetic acid and ethylen~i~minç
tetracetic acid and salts thereof, ethylenP~ mine-N~Nl-disuccinic acid
(EDDS) and salts thereof, and polyphosphonates and
aminopolyphosphon~tes such as hydroxyeth~ne~liphosphonic acid,
ethyle~P~i~mine tetramethylenephosphonic acid,
diethylelletf;~...inepe.~ ell.ylenephQsphonic acid and salts thereof. The
chP!~ting agent selected is not critical except that it must be comp~tible
with the other ingre~lient~ of the denture cleanser when in the dry state
and in aqueous solution. Advantageously, the chelating agent con~lises
between 0.1 and 60 percent by weight of the composition and preferably
between 0.5 and 30 percellt. Phosphonic acid chelating agents, however,
preferably co~ ise from about 0.1 to about 1 percent, ~refe.ably from
about 0. 1% to about 0.5 % by weight of composition.
E~es suitable for use herein are exemplified by proteases, ~lk~l~ses,
amylases, fungal and bacterial lir~es, dextr~n~res, ... ~ es,
c~n~ses, esterases, cellulases, pectin~ces~ l~ct~Qes and peroxi~ es,
etc. Suitable enzymes are rliscl~sse~l in US-A-3,519,570 and US-A-
3,533,139.
The following F~mrles further describe and demonstrate the preferred
embo~limPnts within the scope of the present invention.
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EXAMPLES I TO V
The following are f~rese~t~tive denture cle~n~in~ tablets according to
the invention. The percentages are by weight of the total tablet. The
tablets are made by co~ ressi~g a mixt~re of the gr~m)l~te~ components
in a punch and dye tabletting press at a ples~ure of about 105 kPa.
II m IV V
Malic Acid 12 10 15 - 14
Citric Acid - 10 - 15
Sodium Carbonate 10 8 10 6 10
Sulphamic Acid 5 - - 3 3
PEG 20,000 - 3 7 8 5
PVP 40,000 6 3
Sodium Bicarbonate 23 24 25 23 24
Sodium Pell,orate Mono~drate 15 12 16 30 15
Pot~c.~illm Mono~e~ ph~te 15 18 13 14
Pyrogenic Silica - 3
Talc 2
EDTA - - 1 - 3
EDTMPl
FlavorS 2 1 2 1 2
~ n~soft Fluid4 1 1.5 0.5 2
Bleach I'rec.llsor Agglomerate 9 8 10 12 10
RleaCh rr~c.~rsor A~lomerate I II III IV V
TAED2 2 - 4 5 2.5
TMHoS3 2 3
Sulphamic Acid 2 2 2 2 3.5
Sodium Bicarbonate 0.5 0.2 0.2 0.5 2
PEG 6000 2.5 2 2.4 2.5 1.5
Dye - 0.8 1.4 2 0.S
1. Ethylçn~li~minetetramethylenephosphonic acid
2. Tetraace~lethylene ~ mine
3. Sodium 3,5,5-trimethylhe~noylo~ybe~.,e..~ sulfonate
4. M~n~coft Fluid - supplied by OSI
S r~pe~l~int-based flavor
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19
In F~mples I to V above, the overall tablet weight is 3 g; di~m~ter 25
mm.
The de.llule cle~ncins~ tablets of Px~mrles I to V display improved
antiplaque,clçqnci~ and anti-bacterial activity together with e.~cellent
cohesion and other physical and in-use pelrolll~ce characteristics.
FXAMP!.F.~ VI TO TX
The following are represeI t~tive perfume, flavour, coolant and
antimicrobial compositions according to the invention. The pelce.llages
are by weight of total composition.
VI VII vm ~
PPG-5-ceteth-20 3.0 3.0 4.5 3.0
PEG-40 hydroge,lated castor - 1.8 4.5 3.0
oil
Tri~leceth-12 2.0
Trideceth 9 2.0 - 3.0
Flavor5 2.0 3.0
Perfume6 - 3.0
T~ c~yl l~ mi-le 0.3 O.S
Triclos-q-n - - 1.0 0.5
~agnq~oft Fluid4 1.0 1.5 5.0 1.0
Water ~-- -- - to 100%-- ----->
6. relrul~le is a comple.~ mishlre of ingre~iiçnt~ used primarily for
- olfactory purposes.
The perfume, flavor, coolant and/or antimicrobial compositions of
F~sqmples VI to IX display impfo~ed surface-substantivity, impact and/or
efficacy.
