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Patent 2094604 Summary

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(12) Patent: (11) CA 2094604
(54) English Title: LIQUID DETERGENT COMPOSITIONS CONTAINING A SUSPENDED PEROXYGEN BLEACH
(54) French Title: COMPOSITIONS LIQUIDES DETERGENTES RENFERMANT UN AGENT DE BLANCHIMENT PEROXYGENE EN SUSPENSION
Status: Deemed expired
Bibliographic Data
(51) International Patent Classification (IPC):
  • C11D 3/39 (2006.01)
  • C11D 3/08 (2006.01)
  • C11D 3/43 (2006.01)
(72) Inventors :
  • THOEN, CHRISTIAAN A. J. K. (Belgium)
(73) Owners :
  • THE PROCTER & GAMBLE COMPANY (Not Available)
(71) Applicants :
(74) Agent: KIRBY EADES GALE BAKER
(74) Associate agent:
(45) Issued: 1997-12-23
(86) PCT Filing Date: 1991-10-15
(87) Open to Public Inspection: 1992-04-23
Examination requested: 1993-04-21
Availability of licence: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): Yes
(86) PCT Filing Number: PCT/US1991/007606
(87) International Publication Number: WO1992/007055
(85) National Entry: 1993-04-21

(30) Application Priority Data:
Application No. Country/Territory Date
90870197.2 United Kingdom 1990-10-22

Abstracts

English Abstract






Liquid detergent compositions are disclosed, which contain a solid peroxygen compound suspended in a liquid phase containing
water and at least one water-miscible solvent, and low levels of silicate which provide adequate suspension for the solid
peroxygen compound in the liquid phase.


French Abstract

Compositions détergentes liquides, renfermant un composé peroxygéné solide en suspension dans une phase liquide contenant de l'eau et au moins un solvant miscible à l'eau, ainsi que de faibles concentrations de silicate permettant une suspension efficace du composé peroxygéné solide dans la phase liquide.

Claims

Note: Claims are shown in the official language in which they were submitted.





CLAIMS:

1. A stable liquid detergent composition having a pH of at least 8 and less
than about 11, characterized by comprising a solid, water-soluble peroxygen compound
suspended in a liquid phase containing water and at least one water miscible organic
solvent, the amount of the solid water-soluble peroxygen compound being such that
the amount of available oxygen provided by said peroxygen compound is from 0.5% to
3%, said composition containing from 0.5% to 5% by weight of silicate.

2. A detergent composition, according to Claim 1, wherein the silicate is
present at a level of from 1% to 3%.

3. A liquid detergent composition according to Claim 1 wherein the
water-miscible organic solvent is an aliphatic monoalcohol.

4. A liquid detergent composition according to Claim 2 wherein the
water-miscible organic solvent is an aliphatic monoalcohol.

5. A liquid detergent composition according to Claim 2 wherein the
water-miscible organic solvent is ethanol, and the water:ethanol ratio of from 8:1 to 1:3,
preferably 5:1 to 1:2.

6. A liquid detergent composition according to Claim 1, 2, 3 or 4 wherein
the solid, water-soluble peroxygen compound is perborate tetrahydrate, and present at
levels of from 5% to 30% by weight of the total composition.

7. A composition according to Claim 6 wherein the perborate tetrahydrate
bleach is in the form of particles having a weight-average particle diameter of from 0.5
micrometer to 20 micrometer.

8. A composition according to Claim 6 wherein the perborate tetrahydrate
particles have been formed by recrystallization of a perborate monohydrate.

9. A composition according to Claim 1, 2, 3 or 4, wherein the solid,
water-soluble peroxygen compound is a percarbonate.

Description

Note: Descriptions are shown in the official language in which they were submitted.


WO 92/070~5 PCT/~591/07606

~: 2 ~
- 1
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LIQUID D~Tk~GENT CO~POSITIONS CONTAINING
. ~
~ A SUSP~NDED PEROXYGEN BLEACH


~ ' : ' ' '

: - TPrl~n;~l Field

: .

... .
e invention relates to liquid detergent compositions
which contain a s~lcp~n~;n~ solid peroxygen -~ -nn~, and
low levels of silicate.


Bac3~L U~ d

Answering the long-felt need for bleach-containing
aqueous liquid detergent c~.rositions, European Patent
' : Application 293 040 and 294 904, have described aqueous
: ; detergent compositions having a pH above 8, cont~;n;ng an
anionic surr~actant at conventional levels, and a solid

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WO 92/07055
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peroxygen bleach, 5~lcp~nd~d ln a specific watPr/solvent
medium, which medium was found to give the requir2d
~;c~l stability to the composition.

In such compositions however, particular attention has
to be given to the physical stability of susr,end2d
i~ particles in the liquid medium.
.




One option is eprPsented by e.g. copending U.~.
Application No. 8926620.9, descri~ing liquid d2t2rsent
compositions in which solid particles, in particular
particlss of a peroxygen compound, are suspended by means
of a structured surfactant phase tsurfactant "neat phas2").
ere is a need, however, for suspending systems which
involve easier ~loc~sci~g, compared to ~Lu~uL~d
surfactant phases.

Although not for the ~UL~oS~ of sUcp~n~;n~ peroxygen
bleach particles, strucLul~d surfactant phases have been
described in variou_ patent ~ S; In particular
E~-A-79 646, EP-A-86 614, EP-A-203 660 and~EP-A-295 021
describe liquid detergent compositions containing suspended
builder particles where one or more "salting-out"
electrolytes, or i'surfactant desolubilizing" electrolytes
are used, to build ~L u~Lured phases with the surfactant
materials;

; Such electrolytes includej among many other substances,
silicates, and need to be used at substantial levels, i.e.
above 5%, in o~der 'o perform their~"salting-out" effect.

Other patent doc~ nts disclosing ~h8 use of silicates
in cle~ning/detergent compositions of the suspending type
include G~-A-2031455, and GB-A-1342612 wherein the solid
materials to be s .cp~n~d include abrasives and

~ ' ' ' , ' .

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WO 92/07055 PCT/US91/076~6

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-- 3 --

T.~at2r-insolubl2 phosphate h~ Pr salts, but do not
~ncomDas~ pero~ygen blsach particles; actually,
GB-A-2158453 which mentions perborate as a possible
~l~aching ~rgr~dient in liquid c ,itions of the
suspendirAg t~pe specirically advocates that the
comDositioms must -e free of silicate', and instead must
contain ~ c-a~o~Ilic antigelling agent.

Silica.es nave also '~een widely described as
alkalinity-building ingredients of aqueous thixotropic
li~uid'c~.~osilions used for e.g. automatic dishwashing
pUrpOSQS. ~epres2ntatiYs of this art is EP 315 024,
disclosing levels of silicate in the range of 25~ to 40%.

It has naw surprisingly been found that low levels of
silicate can effi~ ntly ~-~P-,-~ peroxygen-bleach particles
in liquid de~e~yer.L compositions of the type described in
EP-A-293 040, with only a l~a~e increase in~the
viscosity of the composition.
The present sllcp~n~ion system does not involve any specific
processing ~iLLicul~y; 'u~-th~rmore the presence of silicate
brings such advantages as increased alkality and increased
washing-machine compatibility.

e present invention therefore provides perfectly
phase-stable aqueous liquid detergent compositions
cont~;n;n~ a solid peroxygen bleach c ~ ', a.liquid
phase consisting of water and a water-miscible organic
solvent, and lo~b~ levels o~ silicate to suspend the
- ~ peroxyg~n 'oleach particles in the liguid phase.
": :




,,



:

WO92/0705S
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2~4~0~
4 ~

SummarY

m e present invention relates to s~able liquid
deterg2n~ com~ositions having a pH of at least 8 and less
than about 11, comprising a solid, water-solubIe pzro~g
~ suspended in a liguid phase containing water and
at least one T~ater-miscible organic solvent, the amount o~
the solid water-soluble peroxygPn compound being such ~ha~
the amount of available oxygan provided by said peroxlgen
c _ ld is from 0.5% to 3%, said compositions containing
from 0.5% to 5%, preferably I% to 3%, by weight of
silicate.

~etailed Description

The water-soluble pe~uxY5~sl~ c , ~-d

The water-soluble solid peroxygen ~ n~5 is present
in the compositions herein pref~rably at 1eYe1S of from 5
to 50% by weight of the total composition, more preferably
from 5 to 40%, even more preferably from 5% to 30%, most
praferably from 10~ to 30% by weight.

Examples of suitable water-soluble solid peroxygen
,_ m~c include the peLLuL~es, persulfates,
,ox~Slisulfates, y~L~hn~h~teS and the crystalline
peroxyhydrates formed by reacting hydrogen peroxide~with
sodium carbonac_ (forming percar~onate) or urea. Pre~erred
peroxygen ble~ach c ,_~-dç are perborates and
per~rhon~tes.

Most prererred in the present context is a perborate
bleach in the form of particles having a weight-average an




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W092~0705~ PCT/US91/07606

_ 5 _ 2 ~ 9 ~ ~ u ~


average ~artlcl~ di~met~r of from o.5 to 20 micrometers,
pr ferably 3 to 15 micrometers.

The small ~ rage ~article size can best be achieved by
in-situ cxys.~lii~acion, t~pically of perborate
monohydra~e.

In-sltu c~ystallization encom~s~ processes involving
-dissoiu~lon ar.d rec-~ys~allization, as in the dissolution of
perborate monohydrate and subsequent formation of pel~,dLe
tet-ahydrate~ ~ec~s~ ;7ation may also take place by
allowi.-~ p2 ~_rat~ monohydrate to take up crystal water,
whereby the monohydrate directly recrystallizes into the
tetrahydrate~ without dissolution step.

~In-situ cryst~ tion also ~ ~ec~c ~oc~ccPc
i~involving rh~mi~l re~c~;~ncr as when sodium ~Lu,dLe is
,
formed by reacting stoichiometric amounts of hy~ e
peroxide and sodium metaborate or borax.
~:

The water-miscible organic solvent

~ he suspansion system for the solid peroxygen component
hereln consists in a-liquid phas2 tha_ comprises water and
a water-miscible organic solvent. This makes it possih~e
to in~uL~o-~te in the liquid detergent ~ ~sitlons herein
a high ~mount of solid water-soIuble-peroxygen c _lnd,
while ke~ping the amount of available oxygen in soiution
~elow 0.5~ by weigh~ OI the liquid phase, preferably below
0.1%. Less than one tenth of the total amount of peroxygen
c~ d is d~ssolved in the liquid p;nase; the low level of
available oxygen in solution is in fact critical for the
stability of the syst2m.
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WO92/07~55
PCT/~S91/07606
2~a ~G~


m e standard icdometric methcd (as described for
instanca in ~ethoden der Or~n;~rhPn Chemia, Houben Weyl,
1953, Vo. 2, page 562) is suitable to deter~ine tne
aYaila~le o~gPn (AVO) content of the composition.

In order to ~nsura complet~ ~quil~bration between
liquid and solid phases, the compositions are to be kept
after mixing ror thrae days at room temperature b~LoL~ the
~VO titration. ~efore measuring ~he products are
thoroughly shaken in order to ensure correct sa~pling.

For the det~rm;n~tion of the available oxygen (AVO) in
the liquid phase, s~les of the compositions are
centri~uged for 10 minutes at 10.000 rpm. The liquid is
then s~a-~ed from the solid and titrated for available
oxygen.

It is not nPc~e~y that the organic solvent be fully
mlscible with water, provided that enough of the sol~ent
mixes with the water of the composition to affect the
solubility OL ~h2 p~roxygan ~ ~o~d in the descri~ed
manner. Fully water-soluble solvents are preferred for use
herein.
.
- Ihe water-misci~le organic sol~ent must, of course, be
compatible with the peroxygen hleach c~mpound at the pH
that is used. Therefore, polyalcohols having vicinal
ydluxy groups (e.g. 1,2-propanediol and glycerol~ are less
' desirable when the peroxygen bleach co~ol~n~ is perborate.

Examples of suitable water-miscible organic solvents
include the lower a}iphatic monoalcohols; ethers of
diPthylene glycol and lower monoaliphatic monoalcohols;
specirically ~thanol, n-propanol; iso-propanol; butanol;
,
:
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WO92/07055 PCT/US91/07606

2~6~


polyethylen3 glycol (e.g., PEG 150, 200, 300, 400);
dipropylQ~ne glycol; ha~ylene glycol; methoxyethanol;
e~hoxye~tanol; buto~yethar.ol; e~hyldiglycolether;
bPn%ylalcohol; btltO~I?rOp2nOl; butoxypropoxypropanol; and
mixturas thereof. Pri3f2rrzd solvents include ethanol;
isopropanol~ l-me~ho~-2-propanol and butyldiglycolether.
A prefP~r_~ ,ol-t~n t syi~t2m ls ethanol. Ethanol may be
prararably ~re3ent in a r~at_r.a~hanol ratlo o- ~:1 to 1:3.

Altnough ~le presence or absenc2 of other ingredients
sl2ys 2 rolo, tho amount of available oxygen in solution is
largsly ~ste~ ~ed by the ratio water:organic solvent. It
is not necPss~ry however to use more organic solvent than
is needed to keep the amount of available oxygen in
solution below 0.5%, preferably below 0.1%.

In practical terms, the~ratio water:organic solvent is,
for most systems, in the range from 5:1 to 1:3, preferably
from 4:1 to 1:2.

1~12 ~.licatQ
~'
The silicates are present in the present c -~;tion at
levels or from 0.5%-to 5%, preferably from 1% to 3%. The
addition of silicates at such low levels cannot promote the
formation of a structured surfactant phase, but
surprisir.gly allows for an efficient and stable s~1CpPnCi ~n
of the peroxygen bleach particles, with only a moderate
increase in the viscosity of the composition.
, ~
The silicate materials for use-herein can be natural
silicates with a ratio of SiO2 to Na~0 of from 1:1 to
4:1, preferably 1:1 (metasilicate), 1.6:1 or 2:1.



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Preforr2d is sodium silicate, while potassium silicate
can also be used.

Syn~hetic silicates can be used for the purpose of the
presen~ ~nYe~tiOn, such as Sydo ~ 120, ~ith a ratio of
SiO2 to ~go of 3.~

The pr25~n~ d d~torg2nt s~mpositions with blQach
_xhi~it a pH (1% solution in distill~d wator) of at least 8
and less ~han aboul 11, prererably of at least 9, more
preferably at least 9.5. The al~aline pH allows good
bleach mg action of the peroxygen cu~l~o~.d, particularly
when the peroxygen is a perborate.

,
Surfactants

The compositions herein preferably contain a nonionic
or cationic surfactant, or a mixture thereof, at total
Ievels of from 1% to 20%, most preferably from 3% to 10%.
'
The nonionic surfactants are convention~l1y produced by
condensing ethylene oxide with a hydror~rhon having a
reactive hydrogen atom, e.g., a hydroxyl, carboxyl, or
amido group, in the presence of an acidic or basic
catalyst, and include compounds having the general formula
RA(C~2CH2Q~nH wherein R represents the i~dluphobic
moiety, A represents the group carrying the reactive
hy~ atom and n represents the average number of
ethylene oxide moletles. R typically contains from about 8
to 22 carbon atoms. They can also be formed by the
condensation oI propylene oxide with a lower molecular
wei~ht cu.ru~ld. n usually varies from about 2 to about
24.

,



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WO 92/070S5 PCT/US91/07606


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Tha ~ydrc~hobic ~oi~ty of the nonionic c~o~ln~ is
prPfera~ly a prima~ or secondary, straight or branched,
aliphatic alcohol having _rom abou~ 8 co a~out 24,
praf~rably fmo~ ~bout 12 to oout 20 carbon atoms. A more
com~leta disclosuro of sui~abl~ nonionic surfactants can be
found in U.S. ~atont 4,111,855. Mi~tures of nonionic
surfac'~nt3 ~-~n '._~ desir~

A pr~~2~red class ~f nonionic ~cho~lla~es is
represented by ~he condensation pr~duct or a ratty alcohol
having from 12 to 15 carbon atoms and from about 4 to 10
moles or ethyl~e oxide per mole of fatty alcohol.
Suitable species of this class of ethoxylates include :
the cn~ncation product of C12-C15 oxo-alcohols and 7
moles of ethylene oxide per molè of alcohol; the
CQn~PnC~tioll ~Lv~e~ of narrow cut C14-C15 oxo-alcohals
and 7 or 9 moles of ethylene oxide per mole of
fat~(oxo)~lc~hnl; the co,.~ Lion ~LU~U~L of a narrow cut
C12-C13 fatty(oxo)~lc~hol and 6,5 moles of ethylene
oxide per mole of fatty alcohol; and the condensation
produc'.s of a C~O-C14 coc~!h~ fatty alcohol with a
degree of ethoxylation (moles EO/mole fatty alcohol) in the
range from 5 to 8. The fatty oxo-alcohols while mainly
linear can have, depending upon ,he processing conditions
and raw material olefins, a certain degree of branching,
particularly short chain such as methyl br~n~h;ng.

A degree of br~n~h;n~ in the range from 15% to 50%
(weight %) is frequently found in commercial oxo alcohols.

~ PreferrDd nonionic ethoxylated c~ ts can alco be
:~ ~ represented by a mixture of 2 s2~aratoly ethoxylated
nonionic surfactants having a difîerent degree of
ethoxylation. For Pxample, thP nonionic ethoxylate
;


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WO 92tO70SS
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-- 10 --

surI ct~nt con~ainlng from 3 to 7 moles of ethylene oxide
per ~012 0~ hydrophobic moiety and a second ethoxylated
sp~cies havil.g ,r~m ~ to 1~ ~013s or e~hylQne oxide ~er
mole of hy~roohobic moiety. A prsfsrred nonionic
e~ho~ylat2d ~-~ contains a l~w2r etho~ylate ~hich is
~h~ cor.d~ns2tion prcd1lct of a C12-Cl5 oxo-alcohol, wi~h
u~ to ~0-~ r2rchlr.~, and from a~out 3 to 7 moles of
a~lene oxid- per mola o~ ~a'cty oxo-alcohol, and a high2r
a~ho.~lat2 ~hlGh is ~o cor.d~nsatlon prcduct of a
C16-Clg oxo-alcohol wi-.h mor2 ~han 50% (wt) branching
and frcm a~out 8 to 14 moles of ethylene oxide per mole or
branched oxo-~lcohol.

Semi-polar nonionic surfactants include water-soluble
amine oxides contA;nin~ one alkyl or lly~u~y alkyl moiety
of ~rom about 8 to about 28 carbon atoms and two moieties
~P1 P~t~ from the group consisting of alkyl groups and
hy~L~xy alkyl gro~ps, con~inin~ from 1 to about 3 carbon
at = which can opti~nAlly be joined into ring structures.

Th~ liq~id dete~gent compoisltions of the present
invention optionally contain a cationic surfactant,
preferably from 0.1% to 10%, more preferably 0.1% to 5~, by
weight of tha comro-~ition.
.
Examples of suitable cationic surfactants include
quaternary ~ n~ , ac of the formula
RlR2R3R4N+X , wherein Rl is C12 C20 alkyl
or hydroxyalXyl; R2 is Cl-C4 alkyl or hydroxyalkyl or
C12-Czo alkyl or hydroxyal~yl or Cl-C4
hydroxyalkyl; ~3 and R4 are each Cl-C4 alkyl or
y~Luxy~l~yl, or C5-C8 aryl or alkylarvl; and X is
h~lc~n. Preferred are mono-long cnain quaternary ammonium
cu~u~.ds (i.e., cu~ ds of the above formula wheren R2
is Cl-C4 alkyl or hydroxyalkyl).

.
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WO 92/~7055 PCT/US91/07606

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Zwitterionic surfact~nts T.~hich could bQ used in the
~ --;tions of ~e pros2nt invention includQ dQrivatives
of ali~hatic quat~rn ~y ammonium, phosphn~ m~ and
culph~n~m ~ ds ln ~,~ich t~e al~phatic moiQty can be
straight or branch~d chain and wherein one o~ ~he aliphatic
substit~l~nts ccntains Lrcm about ,3 to about 24 carhon atoms
and ano~he:r ;~l~st.itu~nt contaii~3l a~ 12ast~ ~ anionic
water-solubili~ing group. ~ar~ rly pr2~P-s~:ed
zwittarionic -macerials ~re ~ o~lat-d a~moni~m
sulfonates and sul~ates disclosed in U.S. Patents
3,925,~52, ~au~hlin et al., i.ssued Ooc~ber 9, 1975 and
3,929,678, Laughlin _t al. t is5ued nec~mher 3~, 1975.

The c~rositions herein may also contain anionic
~ d~ Ls. me ~ nic deLe~y~,Ls are well-known in the
d~eLy~.L arts and have found wide-spread application in
commercial d~te-~r,Ls. & itable Ani nni C synthetic
Lac~ acti~e salts are selected from the group of
sulfonates and sulfates. Preferred ~ninn;c synthetic
water-soluble sulfonate or sulfate sal's have in their
molecular struc'~ure an al'~yl radical cont~ning fro~ a~out
8 to about 22 carbon atoms.
,
Accord mgly, anionic surractants, if used, are present
at levels up to 40% by weight, prefzrably fr~m 1% to 30% by
weight, even more preferably from 5% to 20% by weight.

Synthetic ~n;onic surfactants, can be represented by
the general formula RlSo3M wherein R1 represents a
hydror~r~on group selected rrom ~he group consisting of
straight or branched alXyl ra~;c~l~ con~;n;ng from about 8
to about 24 car~on atoms and alXyl phenyl r~;c~l~
cont~;n;ng ~rom about g to akout 15 carbon atoms in the
al~yl group. ~ is a salt ~orming catlon which typically is
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W092/07~55 PCT/US91/07606


. - 12 -

salsct~d ~om ~h~ group consisting or sodium, potassium,
ammonium, and mix~ures ~hereof.

A referred sYnthetic anionic surfactant is a
-~ter-sol~l? ~alt of ~n al~rylb2nz~ne sulfonic acid
contain1n~ f-om ~ ~o 1~ carhon atoms in the alXyl group.
r.othe- p~ d s;~.~h~_ic anionic ~urfactant is a
wat-r-sol~le salt OL~ ~l al~-l sulLate or an alkyl
polyelho~r~Jl~tt~t a-~ah~r 31.1i~;~''t Wi'?~eln thg al3~yl group
con~ains r~-om about ~ to a~out 2~, prer2rably from akout 10
to a~out 20 carbon a-coms, and praferably from about 1 to
about 12 ~ho~v sroups. Other suitable anionic surfactants
are disclosed m U.S. Patent 4,170,5~5, Flesher et al.,
issued October 9, 1979.
: ,
Examples of such preferred ~n;o~;G surfactant salts are
the reaction products ob~ained by sulfatLng C8-C18
fatty alcohols derived from tallow and coc~ oil;
alkylh~ sulfu.l~Les wherein the alkyl group contains
from about 9 to 15 car~on atoms; sodium alkylglyceryl ether
sulfonates; ether sulfates of fattv alcohols derived from
tallow and coconut oils; COCullu~ fatty acid monoglyceride
sulfates ar.d sulfonates; and water-soluble salts of
paraffin sulfonates having from about 8 to about 22 carbon
atams in ~he alkyl cha m. Sulfonated oIefin surfactants as
more fully described in e.g. U.S. Patent Specification
3,332,880 can also ~e used. The neutr~l;7;~ cation for
the ~n; oni C synthetic sulfonates and/or sulfates is
represented by conventional cations which are widely used
: in deter~srt tsc~3.01cgy such as scdium and potassium.
.: .
A par~ riy ~rororr~d anionic syn~hetic surfactant
herein is represented by the water-soluble salts
~ of an alX~l~enzsne sulfonic acid, prererably sodium

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alkylbenzen2 sulîonat~s having L om abcut 10 to 13 carbon
atcms in the al~yl group.

Builders

The pr~s2nt com~osltions may contaln a builder,
preferably at a le~ 1 r.o morQ t~an ~4~ ~ mor ~ref~rabl~ at
a level or ~om 5~ to ~0~4 0~- '' h- 'cotal _~.,.pc~l'icn~
If prasent, such builders can consist o~ ~he inorganic
or organic types alraady described in tn~ art.

The liquid detergent cnm~ositions herein optionally may
contain, as a bu;1de~, a fatty acid cn~ronPnt. Preferably,
v~ the amount cf fatty acid is less than 10% by
weight of the ' ~7sition, more preferably less than 4%.
Preferred sdLuLa~ed fatty acids have from 10 to 16,
more preferably 12 to 14 carbon atoms. Pre~erred
~,aa~u~dted fatty acids are oleic~acid and palmitoleic
acid.
. .

Examples of inorganic builders include the
-~-~us-based ~ d~rs~ e.g., sodium tripolyrho~phate,
sodium pyrorhnsrh~te, and aluminosilicates (zeolites).

Examples of organic builders are L2~eSent d by
polyacids such as citric acid, nitrilotriacetic acid, and
~ixtures of tartrate ~s~ccinate wi~h tartrate
ccin~te. Preferred builders for use herein are citric
acid and alk(en)yl-substitut~d succinic acid cu..,~o~lds,
wherein aik(en)yl contains from 10 to 16 car~on atoms. An
example o~ this group o~ cu.l~u~lds is dcdecenyl succinic
acid. Polymeric car~oxylate builders inclusiva o~
polyacrylatss, polyhydroxy acrylates and
polyacrylates/polymaleates copolymers can also be used,



.

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WO 92/07055 PCT~US91~07606

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- 14 -

preferably in c~m3ination ~i-~h the pre~erred builders
above, i.2. ci'_ric acid znd akl(en)yl substituted succinic
acid co~pG~ds.
.
G~her co.-.,~on-~nts~additi~es

The c_~os ' t~ s herein ~ay also contain other
n~ncs nd,~or addi~ci~s a-c a ievel prererably less than
about 5~ Tor,~ l~lng a~~mples o~ such additivesf which
can more pref2ra~1y ~e used at levels from 0.05% to 2%,
include ~olyaminccar~o~late addlti~es such zs ethylene-.
inn~etracetic acid, die~hyl3netriamino-pentac tic acid,
ethylf~nPAi~;no ~i~UCCiniC acid or the water-soluble alkali
metals thereoI. Other additives useful at these levels
include org~ phn~.h..l.ic acids; particularly preferred are
ethyl~n~ mi no tetramethylen~rh~sFhnnic acid,
diethylenetriamino ~P~Ii Ulyl~n~l'h~ h'~ c acid and
'aminotrimethylPl~L-hnsl-hn-.ic acid, hydroxyethylidene
~iphos~hnn;c acid. Bleach s~hili7~rs such as ~ccorhic
acid, dip;colin;c acid, sodium stannates,
8 h~dL~.cyq~inol~ne, hydro~ye~hyl-d2ne diphosphonic acid
(HEDPj, and diethylenetriamine penta(methylene phosphonic
acid) can also be included in these compositions at these
levels, more preferably at levels from between 0.01 to 1%.

m e compositions herein can contain a series of further
optional ingredients whi&h are mostIy used in additive
levels, usually below about 5%. ExamDles of the like
include : polyacids, enzymes and enzymatic stabilizing
ag~nts, suds r2sulants, opacifi2rs, ag~nts to improve the
~--h1~n~ compati~ y in relation to enamel-coated
surfaces, ~act_ricides, dyes, perf-~mes, brighteners,
softeners and the like.



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WO 92/07055 PCT/US91/07606
2 ~

- 15 -

~ s descri~ed abo~e, d2t2rg2nt en~imss can ~2 used in
the lic~id det~rgsnt c~m~csicior.s a~ ~hls ~v2r.c cn. in
fact, one of the d~sirable features of the present
compositions is that ~h2y A~Y2 compatible with such
detergent en~ymes. Suitable enzymes include the dstergenc
proteases, amylases, lipases and c~llulas2s. Enz~nmatic
stabili2ir.g ag~nts for us~ n li~-ld dete ger.-a are ~ell
kncwn. E~z~me s~Ah;li~;ng ag-~rts, 1L ',1._~d~ ar~ orefe-ably
in a range of from about 0. 57 CO ~ . Preiarr~d enzymatic
stabil; ~;ng agents for use hersin are formic acid, acetic
acid, and salts thereof, e.y. sodium formate and sodium
acetate. More preferred stabilizing agents are sodium
formate and acetic acid.

Use of the compositions

.
The present compositions are mainly intended to be used
in the wash cycle of a washing machine; how2ver, o~her U525
can be contemplated, such as pretreatment product for
heavily-soiled fabrics, or soaking product; the use is not
n~cP~s~rily limited to the washing-machine context, and ~he
c~osltions of the prssent invention can be used alone or
in combination with compatible han~wash compositions.
.




Some typical liquid detergent compositions of the
yLeg~lL invention ha~e the folIowing formulae :




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WO 92/07055

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Lnq~ .2n~ Com~osit.ion ~

II III I'l V ~II

Linaar al~yl ;~ene ~ 13".~ '2 10 ~3 10 12
C, 3--C15 alconol ~r'~r~ 3 ~ 10 5 3
C13-C15 alcoh~1 a~ y~ 3 ~ 7 ) ~ 2 4
Citric ~cid 2 . 5 3 . 5 4 1 2 . 5 3
~c~lPc-~nyl succ~;llo aci~. 8 . 5 7 6 . 5 10 8 . 5 8
Polymeric car~oxylat2 ~uilder 1.5 1.5 2 1.5 1.5
Tallow fatty acid - 1. 5 2 - - 1
Diethylenetriam~no penta(methylene
~h~ .hn.1it~ acid) 0.5 0.5 0.4 0.5
lL~cU-yl~lene A~i~ho~ .n~i C acid O.2 0.2 o.3 0.2 0.3 0.4
Sodium formate 1.5 1 1.5 1.5 1 2
A~etic acid : 1. 4 1. 5 1. 41. 4 2
~ol 8 10 12 10 14 14
S~diU~ p2L~lc~e ~lo.,y~LcLo ~ 14
Sodium perborat 3 tetra~ydrate - 20 - 22 20
Silicate SiO2 to Na2O ratio 1.6 1 3
Silicate Sio2 to Na2O _atio 2 . 0 - ~ . 1. 5 3 _ _
Sydec~ 120 - - - - 1 4
So~ium hydroxyde up pH 9.5
Water ~ minore (perfume, brightener,
enzymes,.. ) h~lAnf~e to 100
,

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Representative Drawing

Sorry, the representative drawing for patent document number 2094604 was not found.

Administrative Status

For a clearer understanding of the status of the application/patent presented on this page, the site Disclaimer , as well as the definitions for Patent , Administrative Status , Maintenance Fee  and Payment History  should be consulted.

Administrative Status

Title Date
Forecasted Issue Date 1997-12-23
(86) PCT Filing Date 1991-10-15
(87) PCT Publication Date 1992-04-23
(85) National Entry 1993-04-21
Examination Requested 1993-04-21
(45) Issued 1997-12-23
Deemed Expired 1999-10-15

Abandonment History

There is no abandonment history.

Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Application Fee $0.00 1993-04-21
Maintenance Fee - Application - New Act 2 1993-10-15 $100.00 1993-04-21
Registration of a document - section 124 $0.00 1993-11-05
Registration of a document - section 124 $0.00 1993-11-05
Maintenance Fee - Application - New Act 3 1994-10-17 $100.00 1994-09-26
Maintenance Fee - Application - New Act 4 1995-10-16 $100.00 1995-09-22
Maintenance Fee - Application - New Act 5 1996-10-15 $150.00 1996-09-23
Final Fee $300.00 1997-08-29
Maintenance Fee - Application - New Act 6 1997-10-15 $150.00 1997-09-17
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
THE PROCTER & GAMBLE COMPANY
Past Owners on Record
PROCTER & GAMBLE EUROPEAN TECHNICAL CENTER
THOEN, CHRISTIAAN A. J. K.
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Cover Page 1997-12-16 1 28
Description 1997-03-04 16 587
Claims 1997-03-04 1 38
Cover Page 1994-05-21 1 23
Claims 1994-05-21 1 38
Abstract 1994-05-21 1 54
Description 1994-05-21 16 674
National Entry Request 1993-04-21 8 302
Prosecution Correspondence 1993-04-21 1 23
International Preliminary Examination Report 1993-04-21 15 524
Prosecution Correspondence 1996-03-29 8 416
Prosecution Correspondence 1996-03-29 2 84
Correspondence Related to Formalities 1997-08-29 1 55
Examiner Requisition 1995-09-29 2 77
Prosecution Correspondence 1993-04-21 6 288
Fees 1993-04-21 1 38
Fees 1996-09-23 1 57
Fees 1995-09-22 1 51
Fees 1994-09-26 2 117