Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~ WO 96/05283 r ~ . 7n
21 96423
DETERGENT COMPOSITION
Field of the InvPntitm
The present invention relates to detergent compositions COllluli~il g
a bleach, a builder system and a snrf~nt~nt system having improved
overall cleaning pclru--..ance on a range of soils, particularly oily soils
and bleachable soils.
Bac~ uul~d of the Inv~ntirm
In~ commonly employed in the detergent comrocitinnc for
fabric washing are surfactants, dc~ .cy builders and bleaches. Builders
serve a number of functions such as assisting in the control of mineral
hardness, pepti7~tifn and pH control. The level of builder required in
granular comrocitirmc for example is typically in the range of from 10%
to 90% by weight of the detergent cnmrociti~n and builders are
commonly employed at levels up to 50% .
However, there are a number of disad~all~dges related to the use of
high levels of builders in detergent comrocitionc Firstly, certain types of
builders such as c~.l,u--a~es and silicates form insoluble salts with the
calcium or m!lpn~cillm hardness ions present in the wash solution.
Dependant on the nature of the composition at least a proportion of these
insoluble salts are cllbseq~ ntly deposited upon the fabric and may also be
deposited onto the heater elements of the washing machine. Secondly, in
terms of weight ratio with respect to certain other ingredients such as
en_ymes, soil release polymers and surfactants, an increase in the builder
WO 96/05283 r~ C ~~
2 2 1 96423
levels beyond a certain level does not ~ignific~ntly increase the bleachable
stain removal p. .rullllance of the composition. The presence of high
levels of builders therefore reduces the formula space that might with
advantage be filled by other COlll~ Glll~t of more value to the stain
removal pc.rullllallcc capability of the composition.
There is accoldill~ly a need for a detergent composition Culll~ illg a
builder system at a reduced level to that conventionally employed, that
provides improved cleaning pc.rullllance on everyday body soils, greasy
soils and bleachable stains.
It has now been surprisingly found that this aim may be achieved by
the use of a bleach detergent composition colll~ g a builder system in
cnmhin~tinn with a ~,.., r~ ,.l system wherein the weight ratio of the
surfactant system to the builder system differs from that conventionally
employed and wherein the cu",l,o~ "~ has a specific lower pH range.
One advantage of the present invention is that the p~,.rullll~ c of
certain dGL~.~",ncy enzymes is also improved thus resulting in an
)lu~G~ llL of the removal E~c.rulllldllce of enzymatic stairls.
Another ad~.llL~.~,e of the present invention is the overall improved
bleaching pe.rullll~.llce of the hydluphobic peracids in the compositions of
the present invention at pH 8 to 9.8, despite the reduction in the rate of
perhydrolysis.
Furthermore, the fu~ liull of unsightly dark polyphenolic stains
produced by the complexation between polyphenol anions and metal ions
is reduced at lower pH values.
A further a-lv~llL~,e is that the amount of soaps formed from
hardness ions and soils CUIIIAhI;IIg fatty acids is reduced by the use of the
compocitir)nc of the present invention.
The use of various builder and ~ulr~ L~Ill systems in detergent
comrocitionc has been extensively described in the art. For example EPO
313 143 describes non rho~ph~tP ~hlminncilir~t~ built detergent bleach
~ W096/05283 2 1 9 6 4 2 3 F~ c, -~n
compositions having effective cleaning and stain removal p-,lru~ ncc at
40~C. The ct7mrncitionc may ~rlitinn~lly comprise 5-40% detergent
active and are described as alkaline pH 8-10.5, preferably 8-9.
DE 42 42 185 relates to granular wash- and cleaning compositions
having a high S",r~ l~"l content and a high density. The culll~u~ilio-ls
comprise 20-55% anionic and nonionic ~ulraulallL~ and optionally soap
and may optionally comprise builders, bleach and enzymes. The pH value
of the compositions are not tliccios~t~
EPO 219 314 relates to granular detergent colllpo~i~iolls having
improved solubility. The compositions comprise 30-85 % linear alkyl
sulrhon~t~ (LAS) and alkyl sulphate (AS), alkali metal silicate, wherein
the ratio of LAS/AS to silicate is 1.5:1 to 6:1, 15-60% sulphate and 0-
20% phocrh~t,~ Optionally the cu~ o~:l;n~c may comprise bleaching
agents and other d.,t~ .,n~,y builders. The examples disclose compositions
in which the ratio of total builder to snrf~rt~nt is high. The pH of the
compositions are not ~icclosed
European Patent Application number 94914042.0 relates to layered
silicate builders in cu~l)hl~l;ol~ with secv--d~..y alkyl sulphates to
minimise ~iepncition The compositions may 2~1~ition~11y comprise 5-30%
nnninnicc, percarbonate bleach and have a pH of 7.5-11.
Broad pH ranges which ~llculll~a~S the pH range of the present
invention have been disclosed in the art. However, the pH range typically
utilised in laundry detergent co~ oji~iulls and ~Y~mplifi~d in the prior art
has a highly alkaline pH value and is typically in excess of 10. Indeed it is
known that a high pH value is generally required for the ~lli~; .... ~l of
overall peLrullll~lllce and fabric compatibility. In contrast the colll~o~iliolls
of the present invention have pH ranges which are less alkaline.
Detergent compositions having lower pH values than are commonly
employed in detergent compositions have been described in the art. For
example WO 95/02673 discloses low pH (8-9) granular detergent
comrrlSitione having improved biodegradability. The cu~ l-o~;~innC
comprise 5-50% detergent surfactant, 5-50% non phosphorous builder
WO 96/05283 1'~ 5N' -~n~
4 21 96423
and 0-5 % enzymes. All the exemplified comrociti~nc contain a high
builder to aul L~ ratio. European Patent Application number
91201057.6 also relates to low pH (~-9.3) granular detergent
compositions comprising a low level of chlorine scavenger which
",i"i"~;crS fading of fabric colours. The composition cull"uli~es 15-25%
linear alkyl 5111rhon~t~ and alkyl sulphate, 20-30% alumino silicate, 1-3%
alkali metal silicate, ~10% citric acid and 5-20% alkali metal carbonate.
The compositions may also comprise 5-50% detergent surfactant and 5-
95% det~ cy builders. All of the exemplified compositions comprise
high builder to surfactant ratios.
However in contrast to the present invention, none of the identified
prior art docllmr~ntc disclose a detergent composition co...l,i. i-.g a
surfactant system and a builder system at ratios greater than
cull~ iondlly employed and having a specific lower pH level range.
r,~lLll~,llllole, none of these docnm~nte provide any teaching as to the
p~lr~ .llce benefits that the comr~ citionc of the present invention
deliver.
S--mm ~ry of the Invention
The present invention is a granular detergent cullluù~;~iOn
cOlll~uliaihlg a bleach system, a builder system and a ~l~lrac~ system,
wherein the ratio of said surfactant system to said builder system is
0.8:1.0 or greater, ch~l.a~t~,.ised in that the pH of a 1% solution of said
composition at 20~C is from 8 to 9.8.
All amounts, weights, p~ .-Lges and ratios are given as a %
weight of the detergent composition unless otherwise stated.
D~t~ilP~ Description of the Invention
Surfactant system
According to the present invention the detergent composition
culll~uli~es as essential COlllluOl1~.lL~ a surfactant syste~. The term
~."I~ system as used herein refers to a system which cu'lllll;cr c at
WO 96105283 1~ n
21 96423
s
least one surfactant selected from anionic, nonionic, cationic,
zwitterionic, ~mphotpri~ surfactants and any mixhures thereof. Preferably
the sllrf~t~nt system is selected from anionic, nonionic, cationic
surfactants and mixtures thereof, more preferably from anionic and
nonionic ~ ~, rA~ According to the present invention said sllrf~rt~nt
system is preferably a non soap ~.,. r~ ...l system.
According to the present invention the detergent compn~ifion
Co~ iscs at least 1% of a sulrd~;ldll~ system, preferably from 10% to
50%, more preferably from 15% to 35%, most preferably from 20% to
30% of a sllrf~rt~nt system.
Aninni~ Snrf:lrt~nt~
Anionic i,... r.~ useful herein include the coll~ iulldl primary,
branched-chain and random C1o-C20 alkyl sulphates ("AS"), the
C10-C18 s~c~llddly (2,3) alkyl sulphates of the formula
CH3(CH2)x(CH~SO3~M+) CH3 and CH3(CH2)y(CHOSO3~M+)
CH2CH3 where x and (y + 1) are integers of at least about 7, p~r.,ldbly
at least about 9, and M is a water-solubilizing cation, especially sodium,
Ull~dlUIdll d sulphates such as oleoyl sulphate, the C1o-C1g alkyl alkoxy
sulphates ("AEXS"; especially EO 1-7 ethoxy sulphates), C1û-Clg alkyl
alkoxy cdlbo~yldt~,~ (especially the EO 1-5 ethoxycarboxylates), sulphated
C1o-C1g alkyl poly~;lycosilles, and C12-C1g alpha-~ h,.. ~Ird fatty acid
esters.
According to the present invention suitable alkyl or hydroxyalkyl
alkoxylated sulphates for use herein are of the formula RO(A)mSO3M,
wherein R is an nn~llbstihltpd Cll-C24 alkyl or hydroxyalkyl COIl~
preferably a C12-C20 alkyl or hydroxyalkyl, more preferably a C12-C1g
alkyl or hydroxyalkyl co..lpun~ l, A is an ethoxy or propoxy group, m is
from 1 to 15, more preferably from 1 to 10, and M is H or a cation which
may be selected from metal cations such as sodium, puL~siu~u, lithium,
calcium, mslgnPei~lm ~.... ,.. i"... or ~h~ Specific
examples of ~ s~ d ~"........ "i,., .cations include methyl-, dimethyl-,
trimethyl-~..,---"-.i---.- and quaternary ~ .n,~ .. cations such as
tetramethyl-:~mmoni--m, dimethyl piperidium and cations derived from
WO 96105283 E~,l/u~. _ JG2q~
21 96423
alkanolamines, e.g. monoethanolamine, diethanolamine and
tri~qthqnnlqmin~ and mixtures thereof. EAe~ IaIY surfactants are C12
C1g alkyl polyethoxylate (2.25) sulphate, C12-C1g alkyl polyethoxylate
(3) sulphate and C12-Clg alkyl polyethoxylate (4) sulphate wherein M is
selected from sodium or pu~ c;~ C12-C14 alkyl sulphate which has
been ethoxylated with an average of from 0.5 to 4 moles of ethylene oxide
per molecule is especially preferred.
Other suitable anionic surfactants for use herein include salts (e.g.
alkali metal and qmmonillm salts) of Cll-C24, preferably C12-C20 alkyl
sdlcosilldl~s, linear alkylaryl s~lrhnn-qtf~s, particularly linear alkyl
benzene slllrh~mqt~c, primary or secondary alkane sulphonates, alkene
snlrhnnqtfs such as o-olefin snlrhonDt~c, ether sulphonates, snlrhnnqtfd
polyl ~ JoAylic acids, oxyalkane 5nlrhon-qtf s (fatty acid ;~r~ tf ~),
acylamino alkane s~lphnnqt~s (taurides), alkyl glycerol slllrhonqt~s and
Cl-lrhqtf s, fatty acyl glycerol slllrhonqt~s, fatty oleoyl glycerol
s--lphnnDt~s, and any mixtures thereof. Also suitable as anionic
5--rfqrtqntc are fatty acids and the salts thereof, particularly
mono~.ll,oAylic fatty acids and the salts thereof. Preferred anionic
~ulr~u~ ~ for use herein are alkyl snlrhqfP~, alkyl alkoxylated sulphates
and mixtures thereof.
According to the present invention the colllposiliùlls comprise from
3% to 30%, preferably from 10% to 20%, most preferably from 12% to
18 % of a anionic surfactant.
Noninnin S", r;.~ Ii."~
According to the present invention another CGIllpOn,-ll of the
.~, r~ 1 system is a nonionic cllrfP~ tqnt
Nonionic condensates of alkyl phenols
The polyethylene, poly~.u,uylt;nc, and polybutylene oxide
cnn~f ncqtf s of alkyl phenols are suitable for use herein. In general, the
polyethylene oxide con~ifncqtes are preferred. These compounds include
the cnn~enc-qtion products of alkyl phenols having an alkyl group
WO 96/05283
2 1 9 6 4 2 3 ~ J s ~ n
C~JIII;I;II;IIg from about 6 to about 12 carbon atoms in either a straight
chain or branched chain cnnfigl-r~ n with the alkylene oxide.
W0 96/05283 1.~
8 2 1 96423
Nonionir Pth~xylated alcohol surfactant
The alkyl ethoxylate co.~ c~ n products of aliphatic alcohols with
from about 1 to about 25 moles of ethylene oxide are suitable for use
herein. The alkyl chain of the aliphatic alcohol can either be straight or
branched, primary or secul.da~y, and generally contains from 6 to 22
carbon atoms. Particularly preferred are the c~-n~nC~tion products of
alcohols having an alkyl group Çl~ll(A;II;IIg from 8 to 20 carbon atoms with
from about 2 to about 10 moles of ethylene oxide per mole of alcohol.
Most preferred are the CI III~ products of alcohols having an alkyl
group C.lJIIIA;II;IIg from 8 to 15 carbon atoms with from about 3 to about 9
moles of ethylene oxide per mole of alcohol. FY~mrl.oc of CO~lllll~,.~ ially
available nonionic surfactant of this type include TergitolTM 15-S-9 (the
çon~ nc~tion product of C11-C1s linear alcohol with 9 moles ethylene
oxide), TergitolTM 24-L-6 NMW (the contllong~til)n product of C12-C14
primary alcohol with 6 moles ethylene oxide with a narrow mo!Pc~ r
weight di~llibuliull), both marketed by Union Carbide Col~ulaliûn;
NeodolTM 45-9 (the cO,l~f ~c~l;nn product of C14-C1s linear alcohol with
9 moles of ethylene oxide), NeodolTM 23-6.5 (the c-m~onc~tion product
of C12-C13 linear alcohol with 6.54 moles of ethylene oxide), NeodolTM
45-7 (the con~lPnc~tinn product of C14-C1s linear alcohol with 7 moles of
ethylene oxide), NeodolTM 45 4 (the con~PnCAtion product of C14-C1s
linear alcohol with 4 moles of ethylene oxide), NeodolTM23-3 (the
c~n~oncAtinn product of C12-C13 linear alcohol with 3 moles of ethyene
oxide) marketed by Shell Chemical Company, KyroTM EOBN (the
CO~ product of C13-C15 alcohol with 9 moles ethylene oxide),
marketed by The Procter ~: Gamble Company, Dobanol 91 and Dobanol
25 marketed by the Shell Chemical Company and Lial 111 marketed by
Enichem.
Nonioniç EO/PO c~ (rS with propylene elycol
The conti~nc~tion product~s of ethylene oxide with a hydrophobic
base formed by the col~ cAI;on of propylene oxide with propylene
glycol are suitable for use herein. ~mpl~s of cul.l~oullds of this type
include certain of the c~,llllll~.cially-aYailable PluronicTM
marketed by BASF.
W0 96/05283 2 1 9 6 4 2 3 r~ J c ~ .
Nnni~mir E0 con~lensatjon products with propylene oxide/ethylene
tli~minr adducts
~ The c o ~ . . products of ethylene oxide with the product
resulting from the reaction of propylene oxide and ethyl~ ~e~ ..,;n~ are
suitable for use herein. FY~mrleS of this type of nonionic mrf~t~nf
include certain of the co.,..ll~.cially available TetronicTM c~....l.o~",.1c,
marketed by BASF.
Nonionic ~lkylpoly-g~rrh~ride ~ulr~
Suitable alkylpolysaccharides for use herein are disclosed in U.S.
Patent 4,565,647, Llenado, issued January 21, 1986, having a
hydrophobic group crnt~inin~ from about 6 to about 30 carbon atoms,
preferably from about 10 to about 16 carbon atoms and a poly~ic~
e.g., a polygly~oside, hydrophilic group c..~ ;";,-g from about 1.3 to
about 10, preferably from about 1.3 to about 3, most preferably from
about 1.3 to about 2.7 g~r,rh~ri~lr units. Any reducing cq~rhqri~lr
crlnt~ining 5 or 6 carbon atoms can be used, e.g., glucose, galactose and
galactosyl moieties can be ~b~ d for the glucosyl moieties.
(Optionally the hyd.u~hob:c group is attached at the 2-, 3-, ~, etc.
positions thus giving a glucose or galactose as opposed to a glucoside or
g~l~rtoci~le ) The hl~ r,~ e bonds can be, e.g., between the one
position of the q~lrlitit)nql ~c:?rch~ri~le units and the 2-, 3-, 4-, and/or ~
positions on the pl~ccdillg ~~nll~ units. The preferred
alkylpolyglycosides have the formula
R20(CnH2nO)t(glYC~sYl)x
wherein R2 is selected from the group c~-ncicting of alkyl, alkylphenyl,
hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the
alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon
atoms; n is 2 or 3, x is from 0 to 10 preferably from about 1.3 to about 3,
most preferably from about 1.3 to about 2.7 and t is from 0 to 10. The
glycosyl is preferably derived from glucose.
W 0 96/05283 2 ~ 9 6 4 ~ ~ F~ 520 ~
Nonionic f~tty acid amide surfactant
Fatty acid amide surfactants suitable for use herein are those
having the formula:
o R1
R2--C--N--Z
wherein Rl is H or a C1-C4 hydluc~llbyl, 2-hydroxy ethyl, 2-hydroxy
propyl and R2 is a CS-C31 Lydluc~.lbyl and Z is a
polyhydroxyhydrocarbyl having a linear lly~llu~ ~llbyl chain with at least 3
hydroxy groups directly connect~d to the chain or an alkoxylated
derivative thereof. Preferably R is a methyl, R is a straight chain C11-
C15 alkyl or alkenyl such as coconut alkyl or mixtures thereof and Z is
derived from a reducing sugar such as glucose, fructose, maltose, lactose
in a reductive amination reaction
Other polyllydluxy fatty acid amides suitable for use herein are
gemini polyllyd~ y fatty acid amides having the formula:
I--X--I
O= l l =O
R R'
wherein: X is a bridging group having from about 2 to about 200 atoms; Z
and Z' are the same or different alcohol-c-,..;~;";,.g moieties having two or
more hydroxyl groups (e.g., glycerol, and units derived from reducing
sugars such as glucose, maltose and the like), or either one (but not both) of
Z or Z' is hydrogen; and R and R' are the same or different L.ydlul albyl
moieties having from about 1 to about 21 carbon atoms and can be
saturated, branched or ull~ ul~lted (e.g., oleoyl) and mixtures thereof.
Preferred X groups are selected from ~ub~ t~ or u~
branched or linear alkyl, ether alkyl, amino alkyl, or arnido alkyl moieties
having from about 2 to about 15 carbon atoms. Preferred alkyl moieties
WO 96/05283 P',~ ?/1
2 1 96423
11
are nn~bstihltpd) linear alkyl moieties having the formula -(CH2)n-,
wherein n is an integer from 2 to about 15, preferably from 2 to about 10,
and most preferably from 2 to about 6; and also nngllhstihlt~p~l~ branched
alkyl moieties having from 3 to about 15 carbon atoms, preferably from 3
to about 10 carbon atoms, and most preferably from 3 to about 6 carbon
atoms. Most preferred are ethylene and propylene (branched or linear)
alkyl moieties. Also preferred are .~ h~ "~d~ branched or linear ether
alkyl moieties having the formula -R2-(O-R2)m-, wherein each R2 is
in-lPpen-lPntly selected from C2-Cg branched or linear alkyl and/or aryl
moieties (preferably ethyl, propyl or colllbilldlio.ls thereof) and m is an
integer from 1 to about 5. X may also be nn~llhstihltpd~ branched or linear
amino and/or amido alkyl moieties having the formula -R2-(N(R3)-R2)m-,
wherein each R2 is i~ lly selected from C2-Cg branched or linear
alkyl and/or aryl moieties (preferably ethyl, propyl or combinations
thereof), m is an integer from 1 to about 5, and R3 is selected from
hydrogen, C1-Cs alkyl, and -C(o)R4-, wherein R4 is C1-C21 alkyl,
including -C(O)R. The X moiety may be derived from cullllll~.ci~lly
available amine compounds such as, for example, J~rr~ll.i..~,sR (supplied by
Texaco) such as JED600, JEDR148, JEDR192, JED230, JED2000, J-D230
and J-D400.
Preferred X moieties therefore include: -(CH2)2-, -(CH2)3-, -
(CH2)4-, -(CH2)5-, -(CH2)6-, -cH2cH(cH3)(cH2)3-~ -(CH2)2-0-(CH2)2-
~ -(CH2)3-0-(CH2)3-, -(cH2)2-o-(cH2)3-~ -(CH2)2-0-(CH2)2-0-(CH2)2-,
-(CH2)3-0-(CH2)2-0-(CH2)3-, -(cH2)2-o-(cH2)3-o-(cH2)2-~ -(CH2)2-
NH-(CH2)2-, -(cH2)3-NH-(cH2)3-~ -(CH2)2-NH-(CH2)3-, -(CH2)2-
N(C(O)R)-(CH2)2-, -(cH2)3-N(c(o)R)-(cH2)3-~ -(CH2)2-N(C(O)R)-
(CH2)3-, -(cH2)2-NH(c6H4)NH4cH2)2-~ -(CH2)3-NH(C6H4)NH-
(CH2)3-, -(CH2)2-NHCH2(C6H4)CH2NH-(CH2)2-, -(CH2)3-
NHCH2(C6H4)CH2NH-(CH2)3-, etc.
Preferred Z and Z' groups are intlepçnriPntly selected from
polyllydlu~yllydlu. ~.~byl moieties having a linear Lylllul all)yl chain with atleast 2 hydlùAyls (in the case of glycerol) or at least 3 Ly-lrù;~yl~ ( in the
case of other sugars) directly connPcte~i to the chain, or an alkoxylated
derivative (preferably t~hOxyla~d or propoxylated) thereof. Z and Z'
preferably will be derived from a reducing sugar, more preferably Z and/or
W096/05283 ~ J., C.C5~
2 ~ q642~
12
Z' is a glycityl moiety. Suitable reducing sugars include glucose, fructose,
maltose, lactose, ~ q~tos~, mannose, and xylose, as well as
glyceraldehyde. As raw materials, high dextrose corn syrup, high fructose
corn syrup, and high maltose corn syrup can be utilised as well as the
individual sugars listed above. These corn syrups may yield a mix of sugar
co~ lL~ for Z and Z'. It should be understood that it is by no means
intended to exclude other suitable raw materials. Z and/or Z' preferably
will be selected from the group c.on~ of -CH2-(CHOH)-p-CH20H, -
CH(CH20H)-(CHOH)pl-CH20H, -CH2-(CHOH)2(CHORl)(CHOH)-
CH20H, where p is an integer from 1 to 5, inclusive, and Rl is H or acyclic mono- or poly~ e, and alkoxylated d.,~ cs thereof. Most
preferred are glycit-yls wherein p is 4, particularly -CH2-(CHOH)4-
CH20H.
Preferred R and R' groups are inA~p~n~ntly selected from C3-C21
hydrocarbyl moieties, preferably straight or branched chain C3-C13 allyl
or alkenyl, more preferably straight chain Cs-C11 alkyl or alkenyl, most
preferably straight chain Cs-Cg alkyl or alkenyl, or mixtures thereof. R-
CO-N< and/or R'-CO-N< can be, for example, cocqm~
oleamide, lauramide, llly~ ie~ c~ de~ rqimitqmi-lP, tallowamide,
etc.
FYqmrl~s of such c~ ulllll1c therefore include, but are not limited
to: CH3(CH2)6C(O)N[CH2(CHOH)4CH20Hl-(CH2)2-
[CH2(CHOH)4CH20H]NC(O)(CH2)6CH3;
CH3(CH2)8C(O)N[CH2(CHOH)4CH20H]-(CH2)2-
[CH2(CHOH)4CH20H]NC(O)(CH2)8CH3;
CH3(CH2)10C(O)N[CH2(CHOH)4CH20H]-(CH2)2-
[CH2(CHOH)4CH20H]NC(O)(CH2)10CH3;
CH3(CH2)8C(O)N[CH2(CHOH)4CH20H]-(CH2)2-0-(CH2)2-o-(cH2)2
[CH2(CHOH)4CH20H]NC(O)(CH2)gCH3;
CH3(CH2)8C(O)N[CH2(CHOH)4CH20Hl-CH2CH(CH3)(CH2)3-
[CH2(CHOH)4CH20H]NC(O)(CH2)gCH3;
CH3(CH2)8C(O)N[CH2(CHOH)4CH20H]-(CH2)3-0-(CH2)2-0-(CH2)3-
[CH2(CHOH)4CH20H]NC(O)(CH2)gCH3;
CH3(CH2)3CH(CH2CH3)C(O)N[CH2(CHOH)4CH20H]-(CH2)2-
[CH2(CHOH)4CH20H]NC(O)CH(CH2CH3)(CH2)3CH3;
WO 96105283 P'~
21 ~6423
13
CH3(cH2)6c(o)N[cH2(cHoH)4cH2oH]-(cH2)3-o-(cH2)2-o-(cH2)3
[CH2(CHOH)4CH20H]NC(O)(CH2)6CH3;
CH3(CH2)4C(O)N[CH2(CHOH)4CH20H]-(CH2)3-0-(CH2)2-o-(cH2)3
[CH2(CHOH)4CH20H]NC(O)(CH2)8CH3;
C6H5c(o)N[cH2(cHoH)4cH2oH]-(cH2)3-o-(cH2)2-o-(cH2)3
[CH2(CHOH)4CH20H]NC(O)C6H5;
C H3(c H2)4c(o)N[c H2(c H o H)4c H2o H]-(c H2)
[cH2(cHoH)4cH2oH]Nc(o)(cH2)8cH3 -
These CG~ UulldS can be readily ~yllLh~,;,;~ from the following
disugar diamines: HN[CH2(CHOH)4CH2OH]-(CH2)2-
[CH2(CHOH)4CH20H]NH; HN[CH2(CHOH)4CH20H]-
CH2CH(CH3)(CH2)3-[CH2(CHOH)4CH20H]NH;
HN[CH2(CHOH)4CH20H]-(CH2)2-0-(CH2)2-o-(cH2)2-
[CH2(CHOH)4CH20H]NH; HN[CH2(CHOH)4CH20H]-(CH2)3-0-
(CH2)2-o-(cH2)3-[cH2(cHoH)4cH2oH]NH; and
HN[cH2(cHoH)4cH2oH]-(cH2)3-[cH2(cHoH)4cH2oH]NH
Preferred nonionic snrf~rt~nf for use herein are polyl,yd.~Ayr~ly
acid amides, ethoxylated alcohols, aikylpoly~ ro~:fie~ and miYtures
thereof.
The compositions of the present invention comprise from 1% to
20%, preferably from 3% to 18%, more preferably from 5% to 15% of
said nonionic surfactants.
According to the present invention the anionic and nonionic
surfactant are present in the detergent composition at a ratio of from
1.0:9.0 to 1.0:0.25, preferably from 1.0:1.5 to 1.0:0.4 .
Cationic surfactant
Cationic detersive surfactants suitable for use herein are those having
one long chain hydrocarbyl group. FY~mrl~s of such cationic 5llrf~rf~n~c
include the ~.""~-.li"lll surfactants such as alkyldil-.~ll,yl~,ll...--nillm
h~lng~nillr~ and surfactants having the formula:
W0 96/05283 r~ 5--7a~
2~ q6423
14
[R2(oR3)y] [R4(oR3)y]2RSN + X-
wherein R2 is an alkyl or alkyl benzyl group having from about 8 to about
18 carbon atoms in the alkyl chain, each R3 is selected from the group
cnn~icting of CH2CH2-, -CH2CH(CH3)-, -CH2CH(CH20H)-, -
CH2CH2CH2-, and m-ixtures thereof; each R4 is selected from the group
cnncietin~ of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl ring ~IIUUIU1~
formed by joining the two R4 groups, -CH2CHOH-
CHoHCOR5CHOHCH20H wherein R6 is any hexose or hexose polymer
having a molecular weight less than about 1000 and hydrogen when y is
not O; RS is the same as R4 or is an alkyl chain wherein the total number
of carbon atoms of R2 plus RS is not more than about 18; each y is from
about O to about 10 and the sum of the y values is from O to about 15; and
X is any comp~tihle anion.
Preferred cationic sllrf~t~ntc are the water soluble llual~.l,aly
allllllul.iulll compounds useful in the present comrocition have the
formula:
Rl R2R3R4N + X-
wherein Rl is a Cg-C16 alkyl, each of R2 R3 and R4 is in-lep~n~l.ontly
C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl and (C2H40)XH where x has
a value of from 1 to 5 and X is an anion. Not more than one of the R2,
R3 or R4 should be benzyl.
The preferred alkyl chain length for R1 is from C12-C1s,
particularly where the alkyl group is a mixture of chain lengths derived
from coconut or palm kernel fat or is derived from synthetically by olefin
build up or OXO alcohols synthesis. Preferred groups for the R2R3 and
R4 are methyl and h~Yd1OA~ 1YI groups and the anion X may be selected
from halide, m~thn5nlrh~t~, acetate and rlhn~l.h~lr ions.
~ xamples of suitable ~IU~,t~,lllaly a, .-n;~ cOIIIL)uulldS for use
herein are: -
coconut trimethyl ~.. -";"", chloride or bromide; coconut methyl
dihydloA~ yl :1llllllnll;lllll chloride or bromide; decyl trimethyl
~mmnninm chloride; decyl dimethyl hydroxyethyl Allllllllllilllll chloride or
bromide; C12-C1s dimethyl hydroxyethyl ~"",..-";~,., chloride or
~ W0 96/OS283 ~ C.'t, ''~l)
21 96423
bromide; coconut dirnethyl hydroxyethyl ~ ,., chloride or bromide;
myristyl trimethyl :~mmr)ninm methyl sulphate; lauryl dimethyl benzyl
i1lllllll~llhllll chloride or bromide; lauryl dimethyl (ethoxy)4 ~"""""~
chloride or bromide and choline esters.
According to the present invention the detergent composition may
comprise from 0.1% to 6%, preferably from 1.0% to 3.5% of a cationic
snl-fzlrt~nt
The ~UIfa~ system of the present invention may also comprise
~fill~,,iul.ic and/or amphoteric surfactants such as C12-C1g betaines,
sulphobetaines ("sultaines") and C1o-C1g amine oxides.
Builder systf m
According to the present invention the detergent composition
co.u~lises as an essential i..gl~,dil.ll a builder system. The term builder
system as used herein refers to a system culll~ illg at least one builder
selected from the builders defmed herein below and any mixtures thereof.
According to the present invention the builder system may
comprise inorganic as well as organic builders and which are selected
from the group cu"~;~l;"E of alkali metal silicates, layered silicates,
minrl.cilic~tf~5, rl~ 5, citrates, ~IIC~,illa~ hpyorliq~tf~c and
mixtures thereof.
Suitable rhosphotf builders for use herein include the alkali metal,
i.l.. l.. "~;~."~ and alkanol~.. ,";"", salts of poly~hr~ h~l ~ (f~Y~mrlifi~ by
the tripolyl.hn~l,h,,t .s, ~Jylophr~llh~ , olLhl)~hr~ f s and glassy
polymeric meta-pl-r,~ At ,) and rhosrhfm~tf s
Inorganic detergent builders include, but are not limited to, phytic
acid, silicates and ~hlminr cili~tf c (see, for example, U.S. Patents
3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) and the so-
called "weak" builders (as compared with pho~ c) such as citrate, or
in the so-called "underbuilt" situation that may occur with zeolite or
layered silicate builders.
WO 96/05283 I ~ u~
21 96423
16
Examples of silicate builders are the alkali metal silicates,
particularly those having a SiO2:Na2O ratio in the range 1.6:1 to 3.2:1
and layered silicates, such as the layered sodium silicates described in
U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 is
the trademark for a crystalline layered silicate marketed by Hoechst
(commonly abbl~vial~d herein as "SKS-6"). Unlike zeolite builders, the
Na SKS-6 silicate builder does not contain ~lnmini-lm NaSKS-6 has the
delta-Na2Si2Os lllul~,holo~y form of layered silicate. It can be prepared
by methods such as those described in German DE-A-3,417,649 and DE-
A-3,742,043. SKS-6 is a highly preferred layered silicate for use herein,
but other such layered silicates, such as those having the general formula
NaMSix~2x+1 YH2O wherein M is sodium or hydrogen, x is a number
from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0
can be used herein. Various other layered silicates from Hoechst include
NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
As noted above, the delta-Na2Si2Os (NaSKS-6 form) is most preferred
for use herein. Other silicates may also be useful such as for example
mognPcillm silicate, which can serve as a ~ g agent in granular
formlll~tinng, as a stabilizing agent for oxygen bleaches, and as a
Culll~)ullC.Il of suds control systems.
~ hlmin~ci~ t~o. builders are useful in the present invention.
~IIlminncilir~tr builders are of great hll~Ollallcc in rnost currently
marketed heavy duty granular detergent comrocitiûncJ and can also be a
ci~nifir~nt builder hlgredicllt in liquid detergent fnrml~ firmc
~Alnmint)gilir~tP builders include those having the empirical formula:
MZ[(sio2)w(zAlo2)y] XH20
wherein w, z and y are integers of at least 6, the molar ratio of z to y is in
the range from 1.0 to about 0.5, and x is an integer from about 15 to
about 264.
Useful alnminncilic~tr ion exchange materials are collllll~.~;ally
available. These ~lllminncilir~trs can be crystalline or dlllu-L,huus in
structure and can be naturally-occurring ~hlminncilir~trc or synthetically
derived. A method for producing ~lllminncilic~t~ ion exchange materials
is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12,
~ W0 96/0~283 r~ . J~-7n
2 1 9~23
17
1976. Preferred synthetic crystalline alllminncilir~tr ion exchange
materials useful herein are available under the d~;g,i~l;o,~ Zeolite A,
Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred
embodiment, the crystalline :Ihlminncilir~tf ion exchange material has the
formula:
Nal2[(A102)12(SiO2)12] XH20
wherein x is from about 20 to about 30, especially about 27. This
material is known as Zeolite A. Dehyd~d~f,d zeolites (x = O - 10) may
also be used herein. Preferably, the ;~lllminncilic~tf has a particle size of
about 0.1-10 microns in diameter.
Citrate builders, e.g., citric acid and soluble salts thereof
(particularly sodium salt), are also useful as builders in the detergent
compositions of the present invention, especially in combination with
zeolite and/or layered silicate builders. Oxy~licllcçin~te s are also
especially useful in such comrn~itionc and co l~ ;n ~
Also suitable in the detergent compositions of the present invention
are the 3~3-dicarboxy-4-oxa-l~6-h~ oAlf~ and the related CO...1.U~
disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986.
Useful succinic acid builders include the Cs-C20 alkyl and alkenyl
succinic acids and salts thereof. A particularly preferred cu.l.~uu..d of this
type is dodecenylsuccinic acid. Specific examples of succinate builders
include: laurylsuccinate, ~y~i~Lyl~ r~ palmitylcucrin~t~. 2-
dodc;~ .yl~lccin~fP (preferred), 2-F~ 1e~f uyl~.lçcinotr, and the like.
Laury1cucrin~t.oc are the preferred builders of this group, and are
described in European Patent Application 86200690.5/0,200,263,
published November 5, 1986.
According to the present invention the builder system preferably
cu...l...~ builders selected from alkali metal silicates, layered silicates,
minrJ.cilir~t!~c, citrates, phn~ , s~lccin~tf s and mixtures thereof,
more preferably selected from alkali metal silicates, layered silicates,
nminncilir~tf s, citrates and mixtures thereof.
According to the present invention the compositions will typically
comprise at least 1% builder, preferably 5% to 50%, most preferably
WO 96/05283 2 1 9 6 4 2 3 r~ . 70~
18
from 15% to 35%, more preferably 18% to 28%. The ratio of said
surfactant system to said builder system is 0.8:1.0 or more, preferably
0.9:1.0 to 4.0:1.0, more preferably from 0.95:1.0 to 3.0:1.0, most
preferably from 1.0:1.0 to 2.0:1Ø
~ WO 96/05283 P'~
21 96423
19
Bleach system - Bleachin~ A~ents :3n(1 Bleach Activators
The detergent compositions herein comprise as an essential
ingredient a bleach system. The term bleach system as used herein refers
to a system co, I;lh~;,,g a bleaching agent and one or more bleach
activators. Bleaching agents will typically be at levels of from 1% to
40%, more typically from S~c to 30%, of the detergent composition,
especially for fabric laundering. If present, the amount of bleach
activators will typically be from 0.1% to 60%, more typically from 0.5%
to 40% of the bleaching composition c~ g the bleaching agent-plus-
bleach activator.
The bleach system used herein can be any of the bleaching agents
useful for detergent compositions in textile cleaning, hard surface
cleaning, or other cleaning purposes that are now known or become
known. These include oxygen bleaches as well as other bleaching agents.
PcrùA~ bleaching agents can also be used. Suitable p~.UAy~
bleaching cu~ uullds include sodium carbonate pero~yl.y~llal~ and
equivalent "pel~ allJunàt~," bleaches, sodium ~y.ul,ho~ "
p~,lu1Lyllydldl~, urea P~lUAYI1Yd1al~ and sodium peroxide. Persulfate
bleach (e.g., OXONE, m~mlf~tllred cullllllcl-;idlly by DuPont) can also
be used.
A preferred p~ .albolldl~ bleach cu...~ cs dry particles having an
average particle size in the range from about 500 IlliCIUIIIc;lu~ to about
1,000 Illi~,lulllct~.~, not more than about 10% by weight of said particles
being smaller than about 200 ...i. .u..-~t. .~ and not more than about 10%
by weight of said particles being larger than about 1,250 mi.~ ,t~
Optionally, the percarbonate can be coated with silicate, borate or water-
soluble surfactants. Preferred coatings are based on carbonate/sulphate
mixtures. Percarbonate is available from various cullllll~ idl sources such
as FMC, Solvay and Tokai Denka.
Another category of h' ' g agent that can be used without
restriction ~l-co---~a;~es p~ ll,oAylic acid bleaching agents and salts
thereof. Suitable examples of this class of agents include m~gn~illm
WO 96/05283 2 1 q 6 4 2 3
monoperoxyphthalate hexahydrate, the m~qgnpcillm salt of metachloro
p~lbell,u C acid, 4-nonylamino~-oxoperoxybutyric acid and
diperoxy~orle.~ e.1i~-ic acid. Such bleaching agents are disclosed in U.S.
Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent
Application 740,446, Burns et al, filed June 3, 1985, European Patent
Application 0,133,354, Banks et al, published February 20, 1985, and
U.S. Patent 4,412,934, Chung et al, issued November 1, 1983. Highly
preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic
acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to
Burns et al.
Mixtures of bleaching agents can also be used. Peroxygen
bleaching agents, the p~lbo~ s, e.g., sodium perborate (e.g., mono- or
tetra-hydrate), the p~,lcall,unaL~;" etc., are preferably combined with
bleach activators, which lead to the in si~u production in aqueous solution
(i.e., during the washing process) of the peroxy acid co--~ uolldi--g to the
bleach activator. Various non limiting examples of activators are
disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al,
and U.S. Patent 4,412,934. The nonanoylo~yl,~ ne sulfonate (NOBS)
and L~ .dce~y! ethylene diamine (TAED) activators are typical, and
mixtures thereof can also be used. See also U.S. 4,634,551 for other
typical bleaches and activators useful herein.
Highly preferred amido-derived bleach activators are those of the
formulae:
R1N(R5)C(o)R2C(o)L or R1C(O)N(R5)R2C(o)L
wherein Rl is an alkyl group co"~ ,g from about 6 to about 12 carbon
atoms, R2 is an alkylene c~ i.,."g from 1 to about 6 carbon atoms, R5
is H or alkyl, aryl, or alkaryl cr~ h~g from about 1 to about 10 carbon
atoms, and L is any suitable leaving group. A leaving group is any group
that is displaced from the bleach activator as a c~",~ ce of the
mlr~l~ophilic attack on the bleach activator by the perhydroxyl anion. A
preferred leaving group is phenol sulfonate.
Preferred examples of bleach activators of the above formulae
include (6-o~tqnqmi~o-caproyl)o~y~ fnmqt~
nr)n,qnqmirlocqrroyl)- oxyl,e ~ r~ fonqt~, (6-~ler~qn~qmir1r)
WO 96/05283 p~ n
21 96423
21
caproyl)oxyb~ , nf ,,llfonate, and mixtures thereof as described in U.S.
Patent 4,634,551, incu.~o,at~ d herein by reference.
Another class of bleach activators COlll~ s the bc.~uAd~ type
activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued
October 30, 1990, incorporated herein by reference. A highly preferred
activator of the b~ A~in-type is:
101
[~N"C~
Still another class of preferred bleach activators includes the acyl
lactam activators, especially acyl caprolactams, acyl pyrolidone and acyl
valerolactams of the formulae:
O O
O C--CH2--CH2 0 C--CH2--CH2
R6--C--N~ CH2 R6--C--N~
CH2--CH2~ CH2--CH2
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group c~nt~ining
from 1 to about 12 carbon atoms. Highly preferred lactam activators
include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-
trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl
caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl
valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl
valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof.
See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985,
hlcOl~lat~i herein by reference, which discloses acyl ca~lùlacLall~,
adsorbed into sodium perborate. Other preferred activators are cationic
bleach activators.
Bleaching agents other than oxygen bleaching agents are also
known in the art and can be utilised herein. One type of non-oxygen
bleaching agent of particular interest includes ph~L~ ivaLt;d bleaching
agents such as the sulfonated zinc and/or ~IIlminillm phthalocyanines. See
U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used,
WO 96/05283 r~
21 96423
22
detergent compositions will typically contain from 0.0259~ to 1.25%, by
weight, of such bleaches, especially sulfonate zinc phthalocyanine.
If desired, the bleaching compounds can be catalysed by means of a
mqng:~n~e compound. Such cu~ Juulld~ are well known in the art and
include, for example, ~e ~ n~e-based catalysts disclosed in U.S.
Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat.
5,114,606; and European Pat. App. Pub. Nos. 549,271Al, 549,272A1,
544,440A2, and 544,490A1; Preferred examples of these catalysts include
MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclonnnqn~ )2(PF6)2,
MnIII2(u-0) 1 (u-OAc)2(1 ,4,7-trimethyl 1 ,4,7-triazacyclnnc.nqnP.)2
(C104)2, MnIV4(u-0)6(1,4,7-triaza~,y~,lollo~ c)4(Cl04)4, MnIIIMnIV4
(u-O)1(u-OAc)2 (I ,4,7-trimethyl-1,4~7-triazacyclonnnone)2(clo4)3~
MnIV(l ,4,7-trimethyl-1,4,7-triazacyclnnon~n~)- (OCH3)3(PF6), an
mixtures thereof. Other metal-based bleach catalysts include those
disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The use of
m~ng~n-oge with various complex ligands to enhance bleaching is also
reported in the following United States Patents: 4,728,455; S,284,944;
5,246,612; S,256,779; 5,280,117; 5,274,147; 5,153,161; S,227,084.
pH of th~ com~osition
According to the present invention it has been found that the
pclrulllldilce of the comrosi~ion is improved by the use of specific pH
values. Thus it is essential to the present invention that the c~,lllpù~ s
have a pH of from 8 to 9.8, preferably from 8.5 to 9.8, more preferably
from 9 to 9.8, measured at 20~C at 1 % cunccll~l~,Lioll.
The required pH value of the comrncitionC of the present invention
may be achieved by methods known in the art such as mo~lific~inn of the
buffer system and/or hlcul~uidtion of acidic species. Typically the buffer
system is based on carbonate, bicarbonates, protonic acids and/ or
coordinatively unsaturated metals or non metals.
According to the present invention the detergent composition may
comprise any number of optional ingredients commonly employed in
. .
WO 96/OS283 2 1 9 6 4 2 3 r~ 5 -'~0
detergent compositions such as chelants, soil release agents, enzymes,
suds :jU~)~)lt;SSUl:~i, softeners and brighteners and the like.
WO 96/05283 ~ 0~
21 ~ 6423
24
Ch~l~tinF Agents
The detergent compositions herein may also optionally contain one
or more iron and/or ~ g~l~fse chelating agents. Such chelating agents
can be selected from the group concictin~ of amino carboxylates, amino
phnsl)hn.~ .t~ " polyfilnrtinn~lly-~ Ih~ rd aromatic chelating agents and
mixtures therein, all as hc,~ drL~. defined. Without intending to be bound
by theory, it is believed that the beneflt of these materials is due in part to
their eYceptiC)nol ability to remove iron and ,ll~ng~1llfce~ ions from washing
solutions by formation of soluble chelates.
Amino carboxylates useful as optional chelating agents include
ethy~ p~ h~rLldcetates~ N-hy-llu~yeLllylethyl~ P~ nGl1t~c~
nitriluLl;~r~l;.lrs, ethylPn~ min~ Lulla~lu~lionates, triethylenetetra-
fllf ~ lrs, diethyl~ L,;~",;"~ I,. lh~ ;,t~ ,, and eth~nr'-l;~ly.;il.~,s,
alkali metal, ~"""". ;""" and ~ Il.;;l~lrd ~mmnnillm salts therein and
mixtures therein.
Amino phncrhnn~tPc are also suitable for use as chelating agents in
the compositions of the invention when at least low levels of total
phosphorus are permitted in detergent compositions, and include
ethyl~ ll;ll hL-dkis (methyl~ hn~l,h-", .t. ~) as DEQUEST.
Preferred, these aminû rhocrholl~t~c tû nût cûntain alkyl or alkenyl
groups with more than about 6 carbon atoms.
Polyfi-nction~lly-snhstihJtpd aromatic chelating agents are also
useful in the comrocitinnc herein. See U.S. Patent 3,812,044, issued
May 21, 1974, to Connor et al. Preferred compounds of this type in acid
form are ~lihyd~u7~y~ ulrub~ ,nes such as 1,2-dihydroxy-3,5-
~licnlrub~ r
A preferred biodegradable chelator for use herein is
ethyl- ,r.l; ",;,~r ll;~lc~ r ("EDDS"), especially the [S,S] isomer as
described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and
Perkins.
WO g6105283 P~ 520
2~ 96~23
If utilised, these chelating agents will generally comprise from
0.1% to 10% more preferably, from 0.1% to 3.0% by weight of such
Co~ uO~iLiOI~S.
Polymeric Soil Release A~ent
Any polymeric soil release agent known to those skilled in the art
can optionally be employed in the cnmrn~itinn~ and processes of this
invention. Polymeric soil release agents are chala~ ed by having both
hydrophilic segments, to hydrophilize the surface of hydluuhob:c fibres,
such as polyester and nylon, and hydrophobic segmPnt~, to deposit upon
hydrophobic fibres and remain adhered thereto through completion of
washing and rinsing cycles and, thus, serve as an anchor for the
hydrophilic segmfnt~ This can enable stains occurring 5nh~fqll~ont to
treatment with the soil release agent to be more easily cleaned in later
washing p~uCf lures.
The polymeric soil release agents useful herein especially include
those soil release agents having: (a) one or more nonionic hydrophile
COIII~UUII~ Cu~ lllg essentially of (i) polyoxyethylene segments with a
degree of polymf~ri7~tinn of at least 2, or (ii) uAy~ulu,uylene or
polyuA~.u~uylene segments with a degree of polymerization of from 2 to
10, wherein said hydrophile segment does not e '~ any
oAylulu~ylene unit unless it is bonded to adjacent moieties at each end by
ether linkages, or (iii) a mixture of oxyalkylene units c. ~ 'l" ;.~;- g
oxyethylene and from I to about 30 oxypropylene units wherein said
mixture contains a sufficient amount of oxyethylene units such that the
hydrophile culllpull-,.ll has hydrophilicity great enough to increase the
hydrophilicity of conventional polyester synthetic fbre surfaces upon
deposit of the soil release agent on such surface, said hydrophile segments
preferably cuulpli~iulg at least about 25% uA~.,Lllylu-lG units and more
preferably, especially for such Cu...pu..~,..L~ having about 20 to 30
uAy~ulu~ylene units, at least about 50% oxyethylene units; or ~b) one or
more hydrophobe culllpu-lf,.l~ "o...~ i..g (i) C3 oxyalkylene
terephth~l~t~ segm~ntc, wherein, if said hydlu,uhobe c.J",l.,:"~f ,l~ also
comprise oxyethylene terf~phth~l~tf, the ratio of oxyethylene
terephth~l~t~ C3 oxyalkylene terephth~ tf units is about 2:1 or lower, (ii)
W0 96/05283 2 1 q 6 4 2 3 E ~ c ~c ~
26
C4-C6 alkylene or oxy C4-C6 alkylene segm~ntc, or mixtures therein,
(iii) poly (vinyl ester) segments, preferably polyvinyl acetate), having a
degree of polymerization of at least 2, or (iv) C1-C4 alkyl ether or C4
hydroxyalkyl ether ~ ;l "~ , or mixtures therein, wherein said
s~ll stih~nt~ are present in the form of Cl-C4 alkyl ether or C4
hydroxyalkyl ether cellulose derivatives, or mixtures therein, and such
cellulose deli~ati~ are qmphirhili~-, whereby they have a sufficient level
of C1-C4 alkyl ether and/or C4 hydroxyalkyl ether units to deposit upon
conventional polyester synthetic fibre surfaces and retain a sufficient level
of LydiuAyl~, once adhered to such cull~ iullal synthetic fibre surface,
to increase flbre surface hydrophilicity, or a combination of (a) and (b).
Typically, the polyoxyethylene segments of (a)(i) will have a degree
of polymerization of from about 200, although higher levels can be used,
preferably from 3 to about 150, more preferably from 6 to about 100.
Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not
limited to, end-caps of polymeric soil release agents such as
MO3S(CH2)nOCH2CH2O-, where M is sodium and n is an integer from
4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to
Gosselink.
Polymeric soil release agents useful in the present invention also
include cellulosic dc.ivdLi~,s such aS hydroxyether cellulosic polymers,
copolyrneric blocks of ethylene tererhtllqlqfl~ or propylene terephthql-t~
with polyethylene oxide or polypropylene oxide terephthqlqt~ and the
like. Such agents are cull~ ;ally available and include hydroxyethers of
cellulose such as METHOCEL (Dow). Cellulosic soil release agents for
use herein also include those selected from the group conci~ting of Cl-C4
alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued
December 28, 1976 to Nicol, et al.
Soil release agents chala~ ed by poly(vinyl ester) hydrophobe
segments include graft copolymers of poly(vinyl ester), e.g., C1-C6 vinyl
esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide
backbones, such as polyethylene oxide backl,ollcs. See European Patent
Application 0 219 048, published April 22, 1987 by Kud, et al.
Collllllc.cially available soil release agents of this kind include the
_ _ . . _ . ... .. . .. . .. _ .. . . .. . . . . . . .. . . ..
WO96/05283 21 96423 ~I/u -~n
21 ~7423
SOKALAN type of material, e.g., SOKALAN HP-22, available from
BASF (West Germany).
One type of preferred soil release agent is a copolymer having
random blocks of ethylene terephth~l~tP and polyethylene oxide (PEO)
terephth~ tP. The molecular weight of this polymeric soil release agent is
in the range of from about 25,000 to about 55,000. See U.S. Patent
3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to
Basadur issued July 8, 1975.
Another preferred polymeric soil release agent is a polyester with
repeat units of ethylene terephthalate units contains 10-15% by weight of
ethylene terephth~l~tP units together with 90-80% by weight of
polyoxyethylene terpphth~l~tp units, derived from a polyu~ l,ylene
glycol of average molecular weight 300-5,000. FY~mphPs of this polymer
include the coll,."~rc;ally available material ZELCON 5126 (from
Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857,
issued October 27, 1987 to Gosselink.
Another preferred polymeric soil release agent is a s~lfon~tPd
product of a substantially linear ester oligomer colll,ulii,ed of an
oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat
units and terminal moieties covalently attached to the backbone. These
soil release agents are described fully in U.S. Patent 4,968,451, issued
November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Other suitable
polymeric soil release agents include the terpphth~l~tp polyesters of U.S.
Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic
end-capped oligomeric esters of U.S. Patent 4,721,580, issued January
26, 1988 to Gosselink, and the block polyester oligomeric CUIIIIJUUIId~ of
U.S. Patent 4,702,857, issued October 27, 1987 to GnccPlink
Preferred polymeric soil release agents also include the soil release
agents of U.S. Patent 4,877,896, issued October 31, 1989 to M:~lrh~n:~rlo
et al, which discloses anionic, especially sulfoarolyl, end-capped
terephth~l~tP esters.
WO 96/05283 2 1 q 6 4 2 3 P~""~ C.,,~ -7Q~
28
If utilised, soil release agents will generally comprise from about
0.01% to about 10.0%, by weight, of the detergent compositions herein,
typically from about 0.1% to about 5%, preferably from about 0.2% to
about 3.0%.
Still another preferred soil release agent is an oligomer with repeat
units of terephthaloyl units, sulruisot..~,~hll-dloyl units, oxyethyleneoxy
and oxy-1,2-propylene units. The repeat units form the backbone of the
oligomer and are preferably t~ lh~ ,d with modified i~ethion~t~ end-
caps. A particularly preferred soil release agent of this type co~
about one sulruiso~h~llaloyl unit, S terephthaloyl units, oxyethyleneoxy
and oxy-1,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8,
and two end-cap units of sodium 2-(2-hydroxyethoxy)-eth~n~slllfonate.
Said soil release agent also co,.lp.ises from about 0.5% to about 20%, by
weight of the oligomer, of a crystalline-reducing stabiliser, preferably
selected from the group cl~ h,~ of xylene sulfonate, cumene sulfonate,
toluene sulfonate, and mixtures thereof.
As a practical matter, and not by way of limit~ti~n, the cu.~ c
and processes herein can be adjusted to provide on the order of at least
one part per ten million of the active bleach catalyst species in the
aqueous washing liquor, and will preferably provide from about 0.1 ppm
to about 700 ppm, more preferably from about I ppm to about 500 ppm,
of the catalyst species in the laundry liquor.
Polymeric Dispersing A~ents
Polymeric dispersing agents can advantageously be utilised at levels
from 0.1% to 7%, by weight, in the compositions herein, especially in the
presence of zeolite and/or layered silicate builders. Suitable polymeric
dispersing agents include polymeric poly~dllJo~yldl.,;, and polyethylene
glycols, although others known in the art can also be used. It is believed,
though it is not intended to be limited by theory, that polymeric ~ E
agents enhance overall detergent builder pclru~ dnce, when used in
combination with other builders by crystal growth inhibition, particulate
soil release pepti7.~tion, and anti-redeposition.
WO 96105283 2 1 9 6 4 2 3 r~ c,620
29
Polymeric polycarboxylate materials can be prepared by
polymerizing or copolyl--~ liGi..g suitable ~ d monomers,
preferably in their acid form. U~ ulated monomeric acids that can be
polymerised to form suitable polymeric polycarboxylates include acrylic
acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid,
aconitic acid""~ o"i,-- acid, citraconic acid and methyl~n~mrloni.- acid.
The presence in the polymeric polycarboxylates herein of m~ nnm~ric
segmrntc, C91l~ no carboxylate radicals such as villyllll~lllyl ether,
styrene, ethylene, etc. is suitable provided that such segments do not
constitute more than about 40% by weight.
Particularly suitable polymeric poly~dllJo~;ylal~i, can be derived
from acrylic acid. Such acrylic acid-based polymers which are useful
herein are the water-soluble salts of polymerised acrylic acid. The
average molecular weight of such polymers in the acid form preferably
ranges from about 2,000 to 10,000, more preferably from about 4,000 to
7,000 and most preferably from about 4,000 to 5,000. Water-soluble salts
of such acrylic acid polymers can include, for example, the alkali metal,
~mm~-,ninm and ~ ;l,.t~.d ~mm~,ninm salts. Soluble polymers of this type
are known materials. Use of poly, c l.yl, t~ i, of this type in detergent
compositions has been ~licclose~l, for example, in Diehl, U.S. Patent
3,308,067, issued march 7, 1967.
Acrylic/maleic-based copolymers may also be used as a preferred
Cvlll~vll~,.ll of the di~ g/anti-redeposition agent. Such materials
include the water-soluble salts of copolymers of acrylic acid and maleic
acid. The average m~ cnl~r weight of such copolymers in the acid form
preferably ranges from about 2,000 to 100,000, more preferably from
about 5,000 to 90,000, most preferably from about 7,000 to 80,000. The
ratio of acrylate to maleate segments in such copolymers will generally
range from about 30:1 to about 1:1, more preferably from about 70:30 to
30:70. Water-soluble salts of such acrylic acid/maleic acid copolymers
can include, for example, the alkali metal, ~mmt-nillm and ~,l,sli~
~mmsnillm salts. Soluble acrylate/maleate copolymers of this type are
known materials which are described in European Patent Application No.
66915, published December 15, 1982, as well as in EP 193,360,
published Sc~ bcl 3, 1986, which also describes such polymers
WO 96105~83 2 1 ~ 6 4 2 3 r~
Culll,ul;~L~g hydroxypropylacrylate. Still other useful disl,eL~ing agents
include the maleic/acrylic/vinyl alcohol or acetate terpolymers. Such
materials are also disclosed in EP 193,360, inrln~ing, for example, the
45/45110 terpolymer of acrylic/maleiclvinyl alcohol.
Another polymeric material which can be included is polyethylene
glycol (PEG). PEG can exhibit dispersing agent p~.rull-lance as well as
act as a clay soil removal-antiredeposition agent. Typical molecular
weight ranges for these purposes range from about 500 to about 100,000,
preferably from about 1,000 to about 50,000, more preferably from about
1,500 to about 10,000.
Polyamino acid ~ h~g agents such as polyaspartate and
polyglutamate may also be used, especially in conjllnnti()n with zeolite
builders. Dispersing agents such as polya~Jdl L~L~ preferably have a
m~llrclll~r weight (avg.) of about 10,000.
Cl~y Soil R.orn-val/~nti-redeposition A~ents
The comrclcitinnc of the present invention can also optionally contain
water-soluble etho~ylated amines having clay soil removal and antire-
deposition properties. Granular detergent colll~o~iLions which contain
these compounds typically contain from about 0.01% to about 10.0% by
weight of the water-soluble ethoxylated amines.
The most preferred soil release and anti-redeposition agent is
elLo~.ylat~;d ~ aelLyl~ l,,;nr Exemplary ethoxylated amines are
further described in U.S. Patent 4,597,898, V~n-l~r~rer, issued July 1,
1986. Another group of preferred clay soil removal-~ h~d~,~o~iLiull
agents are the cationic compolln(lc disclosed in European Patent
Application 111,965, Oh and Gosselink, published June 27, 1984. Other
clay soil removal/alllilcd~,o~iLioll agents which can be used include the
ethoxylated amine polymers disclosed in European Patent Application
111,984, Gosselink, published June 27, 1984; the L~iLLeliullic polymers
disclosed in European Patent Application 112,592, Gosselink, published
July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744,
Connor, issued October 22, 1985. Other clay soil removal and/or anti
WO 96/05283 2 1 9 6 4 2 3 ~ 7n
redeposition agents known in the art can also be utilised in the
compositions herein. Another type of preferred antiredeposition agent
includes the carboxy methyl cellulose (CMC) materials. These materials
are well known in the art.
W0 96/05283 2 ~ q 6 4 2 3 ~ ). 67q~
Dye Tr~ncfer Inhihi~in~ Agents
The co,ll~os;lions of the present invention may also include one or
more materials effective for inhibiting the transfer of dyes from one fabric
to another during the cleaning process. Generally, such dye transfer
inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-
oxide polymers, copolymers of N-vhlyll~yllulidone and N-vhlyli~
5e phthalocyanine, pelù~idascs, and mixtures thereof. If used,
these agents typically comprise from 0.01% to lO~o by weight of the
composition, preferably from 0.01% to 5%, and more preferably from
O.OS~o to 2%.
More specifically, the polyamine N-oxide polymers preferred for
use herein contain units having the following structural formula: R-AX-P;
wherein P is a polymerizable unit to which an N-O group can be attached
or the N-O group can form part of the polyl-l~,iLdble unit or the N-O
group can be attached to both units; A is one of the following 2tLlU-,lU-
~
NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1; and R is aliphatic,
ethoxylated ~ .h~irs, aromatics, hct. .u~ ~ lic or alicyclic groups or any
comhin~ion thereof to which the nitrogen of the N-O group can be
attached or the N-O group is part of these groups. Preferred polyamine
N-oxides are those wherein R is a h~,t~lu~ ~ lic group such as pyridine,
pyrrole, imidazole, pyrrolidine, pilJ."idin~ and de,ivdli~,s thereof.
The N-O group can be l~ sc;,lled by the following general
structures:
~l
~X 7 (R2)y; =N (Rl)x
(R3)z
wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic
groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of
the N-O group can be attached or form part of any of the arOl~ ionf~d
groups. The amine oxide unit of the polyamine N-oxides has a pKa < 10,
preferably pKa <7, more preferred pKa <6.
~ W0 96105283 7 ~ f 2 3 r~ n
Any polymer backbone can be used as long as the amine oxide
polymer formed is water-soluble and has dye transfer inhibiting
properties. Examples of suitable polymeric backbones are polyvinyls,
polyalkylenes, polyesters, polyethers, polyamide, polyimides,
- polyacrylates and mixtures thereof. These polymers include random or
block copolymers where one monomer type is an amine N-oxide and the
other monomer type is an N-oxide. The amine N-oxide polymers typically
have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000.
However, the number of amine oxide groups present in the polyamine
oxide polymer can be varied by dl)lUlU~ copoly""~;"~inn or by an
a~,ululu~ degree of N-oxidation. The polyamine oxides can be obtained
in almost any degree of polylll~ ation. Typically, the average molecular
weight is within the range of 500 to 1,000,000; more preferred 1,000 to
500,000; most preferred 5,000 to 100,000. This preferred class of
materials can be referred to as "PVNO".
The most preferred polyamine N-oxide useful in the detergent
compositions herein is poly(4-vhlyl~u.yli-lillc-N-oxide) which as an average
mnleclllqr weight of about 50,000 and an amine to amine N-oxide ratio of
about 1:4.
Copolymers of N-vh~ylluyllulidone and N-vinylimidazole polymers
(referred to as a class as "PVPVI") are also preferred for use herein.
Preferably the PVPVI has an average molecular weight range from 5,000
to 1,000,000, more preferably from 5,000 to 200,000, and most
preferably from 10,000 to 20,000. (The average molecular weight range
is determined by light scattering as described in Barth, et al., Chemical
Analysis, Vol 113. "Modern Methods of Polymer Cl--"- Ir,;,~ m", the
clo;,.~, of which are hlcol,uul~.it;d herein by reference.) The PVPVI
copolymers typically have a molar ratio of N-vhlylilllid~ùle to N-
vhlyl,uyllùlidone from l:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1,
most preferably from 0.6:1 to 0.4:1. These copolymers can be either
linear or branched. It has also been observed that q~-litinnql dye transfer
inhibition benefits are provided by compositions COIll~ul i~hlg nonionic
polysaccharide ethers and dye transfer inhibitors such as PVNO and
PVPVI such as illustrated in Example 1, reference B and f )-mlllqfinn B. It
is believed that a synergic effect due to the combination of
WO 96105283 2 1 9 6 4 2 3
34
poly~c~ s and dye transfer inhibitors provides the unP~rec~d
wLil~lless ~ ,re p~lru~lllance benefits to white fabrics which have
been subjected to repetitive washing.
The present invention compositions also may employ a
polyvillyl~y-lulidone ("PVP") having an average molccnl~r weight of
from about 5,000 to about 400,000, preferably from about 5,000 to about
200,000, and more preferably from about 5,000 to about 50,000. PVP's
are known to persons skilled in the detergent field; see, for example, EP-
A-262,897 and EP-A-256,696, hlcul~ol~.~td herein by reference.
Compositions cont~ining PVP can also contain polyethylene glycol
("PEG") having an average molecular weight from about 500 to about
100,000, preferably from about 1,000 to about 10,000. Preferably, the
ratio of PEG to PVP on a ppm basis delivered in wash solutions is from
about 2:1 to about 50:1, and more preferably from about 3:1 to about
10:1.
The detergent compositions herein may also optionally contain from
0.005 % to 5 % by weight of certain types of hydrophilic optical
bli~llt~,.l.l~ which also provide a dye transfer inhibition action. If used,
the compositions herein will preferably comprise from 0.01% to 1% by
weight of such optical bli~ ,n~
The hydrophilic optical brighteners useful in the present invention
are those having the structural formula:
N~ ~C=C~NI ~NO<N
R2 SO3M SO3M Rl
wherein Rl is selected from anilino, N-2-bis-hydlu~ ;llyl and NH-2-
hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-
hydlu~ yl-N-lll.,.llylalllillo, morphilino, chloro and amino; and M is a
salt-forming cation such as sodium or pU~ lsiUIII.
~ W096/05283 2 1 9 6423 r~ r~s.~
When in the above formula, R1 is anilino, R2 is N-2-bis-
hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-
bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2 ,2 ' -
stilh~nf ~ lfonic acid and disodium salt. This particular brightener
species is co.. ~ially marketed under the tr~en~m~ Tinopal-UNPA-
GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred
hydrophilic optical biikl~ . useful in the detergent comrociti~ nc herein.
When in the above formula, Rl is anilino, R2 is N-2-h.~ u~ l-yl-
N-2-1llG~hylal~ o and M is a cation such as sodium, the brightener is 4,4'-
bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-
yl)amino]2,2'-stilh~n~ lfonic acid disodium salt. This particular
brightener species is co------c.~ ially marketed under the tradename Tinopal
SBM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M
is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-
morphilino-s-triazine-2-yl)amino]2,2'-stilhPn.o~ 1fonic acid, sodium salt.
This particular brightener species is Collllll~l, ;ally marketed under the
tradename Tinopal AMS-GX by Ciba Geigy Corporation.
The specific optical brightener species selected for use in the
present invention provide especially effective dye transfer inhibition
pGIru----allcc benefits when used in combination with the selected
polymeric dye transfer inhibiting agents herein before ~crihçd The
cclllbillation of such selected polymeric materials (e.g., PVNO and/or
PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX,
Tinopal SBM-GX and/or Tinopal AMS-GX) provides cignifi~ntly better
dye transfer inhibition in aqueous wash solutions than does either of these
two detergent composition Culllpùll~,-lt~ when used alone. Without being
bound by theory, it is believed that such h. ;~ work this way
because they have high affinity for fabrics in the wash solution and
therefore deposit relatively quick on these fabrics. The extent to which
brighteners deposit on fabrics in the wash solution can be defined by a
p,.. ,.. t", called the "çYh~lleti~n coeffficient". The eYh~nstion coefficient
is in general as the ratio of a) the brightener material deposited on fabric
to b) the initial b.igl-t~,.-er c~1llcGIltldLion in the wash liquor. Bright~n~nc~
WO96/05_83 21 9 6423 r~ 70~
36
with relatively high f~h:lnctiQn coefficients are the most suitable for
inhibiting dye transfer in the context of the present invention.
Of course, it will be d~ ted that other, conventional optical
bligl~ er types of compounds can optionally be used in the present
compositions to provide conventional fabric "brightness" benefits, rather
tban a true dye transfe} inhibiting effect. Such usage is conventional and
well-known to detergent form~ tinnc
~zYm~
Enzymes can be included in the formulations herein for a wide
variety of fabric laundering purposes, including removal of protein-based,
carbohydrate-based, or triglyceride-based stains, for example, and for the
prevention of refugee dye transfer, and for fabric ~ u~ The
enzymes to be h.co.~ .t~,d include proteases, amylases, lipases,
cf~ c,~c, and peroxidases, as well as mixtures thereof. Other types of
enzymes may also be included. They may be of any suitable origin, such
as vegetable, animal, bacterial, fungal and yeast origin. However, their
choice is governed by several factors such as pH-activity and/or stability
optima, thermostability, stability versus active detergents, builders and so
on. In this respect bacterial or fungal enzymes are preferred, such as
bacterial amylases and prûteases~ and fungal ce~ ces
Enzymes are normally hlcGl~oldt~ at levels sufficient to provide
from 0.01mg to 5 mg by weight of active enzyme per grarn of the
CGlll~o~ilioll. Stated otherwise, the csmpscitinnc herein will typically
comprise from about 0.001% to about 5%, preferably 0.01%-1% by
weight of a co.l....~ l enzyme preparation. Protease enzymes are
usually present in such cGlllll..,.~ ;al preparations at levels sufficient to
provide from 0.005 to 0.1 Anson units (AU) of activity per gram of
C~)1 l l1l95~
Suitable examples of proteases are the s~lb~ilicinc which are obtained
from particular strains of B. subtilis and B. Iicl,c,liru..lls. Another
suitable protease is obtained from a strain of Bacillus, having m~imnm
activity throughout the pH range of 8-12, developed and sold by Novo
2 1 96423
~ W0 96105283 F~ ,,5,~, -7n
Tn~1llctriPs A/S under the registered trade name ESPERASE. The
preparation of this enzyme and analogous enzymes is described in British
~ Patent Sperifi~qfion No. 1,243,784 of Novo. Proteolytic enzymes suitable
for removing protein-based stains that are co.,l,..e,ci~lly available include
those sold under the tra~lPnqmPc ALCALASE and SAVINASE by Novo
Tn~ ctries A/S (Denmark) and MAXATASE by ~ntPnn~ti~mql Bio-
Synthetics, Inc. (The Ne~lle.ldnds). Other proteases include Protease A
(see European Patent Application 130,756, published January 9, 1985)
and Protease B (see European Patent Application Serial No. 87303761.8,
filed April 28, 1987, and European Patent Application 130,756, Bott et
al, published January 9, 1985).
Amylases include, for example, oc-amylases described in British
Patent Specification No. 1,296,839 (Novo), RAPIDASE, TntPrn~tion~l
Bio-Synthetics, Inc. and TERMAMYL, Novo ~n-lllctriPs Typically,
bacterial amylases are present so as to provide from 0.001KNU to
1000KNU, preferably from 0.01KNU to 100KNU activity per gram of
detergent composition. Fungal amylases if present in the compositions of
the present invention preferably provide from 0.01FAU to 10000FAU,
more preferably from 0.1FAU to 1000FAU (Fungal alpha amylase units)
per gram of detergent composition.
The cellulase usable in the present invention include both bacterial or
fungal cellulase. Suitable cellulases are disclosed in U.S. Patent
4,435,307, Balbest~,a,.l et al, issued March 6, 1984, which discloses
fungal cellulase produced from ~nmi~olq insolens and ~Tnmi-~olq strain
DSM1800 or a cellulase 212-producing fungus belonging to the genus
Aeromonas, and cellulase extracted from the hr~ p~ ,ds of a marine
mollusk (Dolabella Auricula Solander). Suitable cellulases are also
disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
CAREZYME (Novo) is especially useful. Typically cellulase enzyems are
present in the detergent composition from 0.0001% to 2%, preferably
from 0.01 % to 1 % as 1000CEVU active cellulase.
Suitable lipase enzymes for detergent usage include those produced
by microolga..is~..s of the Pseudomonas group, such as Pseudomonas
stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. See also
WO 96/05283 2 1 ~ 6 4 2 3 p~"~ 70~
Iipases in Japanese Patent Application 53,20487, laid open to public
inspection on February 24, 1978. This lipase is available from Amano
Phal",~r~ ir~l Co. Ltd., Nagoya, Japan, under the trade name Lipase P
"Amano," hcl~in~.rl~r referred to as "Amano-P." Other co-ll---c~
lipases include Amano-CES, lipases ex Cl--. ",nba~lr~ viscosum, e.g.
Chromobacter viscosum var. Iipolyticum NRRLB 3673, COllllllCl- i~.lly
available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter
viscosum lipases from U.S. Billrhkmir~l Corp., U.S.A. and Disoynth
Co., The Nethkrl~n~lc~ and lipases ex Pseu(lnmrn~c gladioli. The
LIPOLASE enzyme derived from Humicola l~mlginos~ and l ullllllcl~;ally
available from Novo (see also EPO 341,947) is a preferred lipase for use
herein. Typically the lipase enzymes are present at from 0.001LU to
100LU, preferably from 0.005LU to 10LU per milligram of detergent
composition.
Peroxidase enzymes are used in combination with oxygen sources,
e.g., pel.;~.ll,on~L~, perborate, persulfate, hydrogen peroxide, etc. They
are used for "solution bleaching," i.e. to prevent transfer of dyes or
pigments removed from substrates during wash operations to other
substrates in the wash solution. Peroxidase enzymes are known in the art,
and include, for example, horseradish peroxidase, ligninase, and
haloperoxidase such as chloro- and hromo-p(,lùAiddse. PGlo~idase-
cont~ining detergent compositions are ~1icclose~ for example, in PCT
Tnn~rn~tion:ll Application WO 89/099813, published October 19, 1989, by
0. Kirk, assigned to Novo Tnthlctrie$ A/S.
A wide range of enzyme materials and means for their hlcOl~ulalioll
into synthetic detergent compositions are also disclosed in U.S. Patent
3,553,139, issued January 5, 1971 to McCarty et al. Enzymes are further
disclosed in U.S. Patent 4,101,457, Place et al, issued July 18, 1978, and
in U.S. Patent 4,507,219, Hughes, issued March 26, 1985, both.
Enzymes for use in detergents can be stabilised by various l~rl~ s
Enzyme stabilisation tkrhnirlukc are disclosed and exemplified in U.S.
Patent 3,600,319, issued August 17, 1971 to Gedge, et al, and European
Patent Application Publication No. 0 199 405, Application No.
86200586.5, published October 29, 1986, Venegas. Enzyme stabilisation
systems are also ~Ik5cribet1, for example, in U.S. Patent 3,519,570.
~ W0 96/OS283 r ~ n
2 1 96423
39
Enzyme Stab;lic~rs
The enzymes employed herein are stabilised by the presence of
water-soluble sources of calcium and/or mA~nf-cillm ions in the finished
culll~o~i~ions which provide such ions to the enzymes. (Calcium ions are
generally SOlll~ ~L~.~ more effective than mognl~ci~m ions and are
preferred herein if only one type of cation is being used.) Additional
stability can be provided by the presence of various other art-disclosed
stabilisers, especially borate species: see Severson, U.S. 4,537,706. The
level of calcium or m,n~n~cillm ions should be selected so that there is
always some minimum level available for the enzyme, after allowing for
complexation with builders, fatty acids, etc., in the c~ o~:i;nl~ Any
water-soluble calcium or IllAgll/~;lllll salt can be used as the source of
calcium or IllAgll~ II ions, inAhl~ing, but not limited to, calcium
chloride, calcium sulfate, calcium malate, calcium maleate, calcium
hydroxide, calcium fvrmate, and calcium acetate, and the c~ ollding
mAgn- cillm salts. A small amount of calcium ion, generally from about
0.05 to about 0.4 millimo!Ps per litre, is often also present in the
compocition due to calcium in the enzyme slurry and formula water. In
solid detergent compositions the formulation may include a sufficient
quantity of a water-soluble calcium ion source to provide from 1 to 30,
preferably from 2 to 20 millimoles per litre in the laundry liquor. In the
alternative, natural water hardness may suffice.
It is to be nn/1(~r.ctood that the foregoing levels of calcium and/or
f~ ions are sufficient to provide enzyme stability. More calcium
and/or IllAg~ ions can be added to the compositions to provide an
"tl~1iti~nAl measure of grease removal pclr~ c Accoldill61y, as a
general ~roposi~ion the COIIl~uO~i~iull:, herein will typically comprise from
about 0.05% to about 2% by weight of a water-soluble source of calcium
or IIIA~ IIIIII ions, or both. The amount can vary, of course, with the
amount and type of enzyme employed in the composition.
The compositions herein may also optionally, but preferably, contain
various A~iti~nAl CtAhili~rs, especially borate-type stabilisers. Typically,
such stabilisers will be used at levels in the c~,...l~o~ oll~ from about
0.25% to about 10%, preferably from about 0.5% to about 5%, more
WO96/05283 2 1 9 6423
preferably from about 0.75% to about 3%, by weight of boric acid or
other borate compound capable of forming boric acid in the composition
(cqlrnlqt~d on the basis of boric acid). Boric acid is preferred, although
other c-~""l.u~ e such as boric oxide, borax and ~ther alkali metal
borates (e.g., sodium ortho-, meta- and ~lylvbolale, and sodium
perlLabvlal~) are suitable. S~ t~ d boric acids (e.g., ph~.lylbol~Jnic
acid, butane boronic acid, and p-bromo ph~.lylboluilic acid) can also be
used in place of boric acid.
Suds Suv~ressol~
Coul~vullds for reducing or ~U~ sillg the formation of suds may
also be hlcOl~vlal~d into the comrr)citinnc of the present invention. Suds
~U~ sDiull can be of particular hllpul lancc in the so-called "high
Co~ .. ,1 "~ n cleaning process" and in front-loading European-style
washing mqrhin~s
A wide variety of materials may be used as suds ::Iu~ lUl~, and
suds bu~ ul~ are well known to those skilled in the art. See, for
example, Kirk Othmer Encyclopaedia of Chemical Technology, Third
Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One
category of culllpuullds which may be employed for suds :,u~ iug
benefits is fatty acids and the salts thereof, see U.S. Patent 2,954,347,
issued Se~,t~ "I,e 27, 1960 to Wayne St. John. However, whilst such
compounds may assist in suds suppression, for the purposes of the present
invention such cv.ll~vu--ds are to be considered as COIll~vlle-lL~ of the
s~rfqctqnt system.
The detergent cullll,o~ilivns herein may also contain non-~u.Lc~a.ll
suds :~U~ Ul~. These include, for example: high molecular weight
hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid
triglycerides), fatty acid esters of monovalent alcohols, aliphatic C1g-C40
ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated
amino triazines such as tri- to hexa-alkyl",~lA",;"~s or di- to tetra-
alkyldiamine chlo-l-ia~ es formed as products of cyanuric chloride with
two or three moles of a primary or secondary amine COIIIA;II;IIg I to 24
carbon atoms, propylene oxide, and l~ t~A~yl ph~crhqtes such as
W096105283 2 1 9 6 423 F~ n
41
l~u~o~ l yl alcohol pho~hal~ ester and mon~lstP~ryl di-aL~ali metal
(e.g., K, Na, and Li) phosphates and phocrh~te esters. The hydlu~allJolls
such as paraffm and haloparaffm can be utilised in liquid form. The liquid
hydrocarbons will be liquid at room t~ "l .,~",c and sfmocrhf~ric
pressure, and will have a pour point in the range of about -40~C and
about 50~C, and a minimum boiling point not less than about 110~C
(;Il,~n~l~hf .ic pressure). It is also known to utilise waxy hy-llu~ albons~
pl~r~lably having a melting point below about 100~C. The hydrocarbons
constitute a preferred category of suds ~ yl~ vr for detergent
comrocitionc Hydlu~ allJ~ll suds ~"U~l~.oSOl~ are desrrihe~l, for example,
in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The
hydlucall)ons, thus, include aliphatic, alicyclic, aromatic, and
heterocyclic saturated or "~l~Al"l,ll~d hydi~callJolls having from about 12
to about 70 carbon atoms. The term "paraffin," as used in this suds
,sul ~ - nn, is intended to include mixtures of true paraffins
and cyclic hydlu-,all~Olls.
Another preferred category of non-surfactant suds ~ SVl:~
Cu~ fs silicone suds ~ sol~. This category includes the use of
polyorganosiloxane oils, such as polydi---~.;llybiloxane, ~ ;u"c or
PmlllQi~mc of polyu~ .an~,lnYsnP oils or resins, and combinations of
polyv~ n~iloY~nf with silica particles wherein the polyorg~nocilo~np is
cLe.--i~o-l ed or fused onto the silica. Silicone suds a~l~pl~ Sul:~ are well
known in the art and are, for example, disclosed in U.S. Patent
4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent
Application No. 89307851.9, published February 7, 1990, by Starch, M.
S.
Other silicone suds ;~-I,u~ ,SOl~ are disclosed in U.S. Patent
3,455,839 which relates to comroci~iong and processes for tlPfosming
aqueous solutions by hlcOl~ulalillg therein small amounts of
polydi---~ll.yl~iloxane fluids.
Mixtures of silicone and silanated silica are described, for instance,
in German Patent Application DOS 2,124,526. Silicone defoamers and
suds controlling agents in granular detergent compositions are disclosed in
WO 96/OS283 2 1 q 6 4 2 3 . ~I/L _ ~ ~3 -~o ~
42
U.S. Patent 3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392,
Baginski et al, issued March 24, 1987.
An exemplary silicone based suds suppressor for use herein is a suds
p~JI. ;t~iug amount of a suds controlling agent congie~ins~ essentially of:
(i) poly~ .l.ylsiloxane fluid having a viscosity of
from about 20 cs. to about 1,S00 cs. at 25~C;
(ii) from about 5 to about S0 parts per 100 parts by
weight of (i) of siloxane resin cu...L"~sed of (CH3)3SiOl/2
units of SiO2 units in a ratio of from (CH3)3 SiO1/2 units and
to SiO2 units of from about 0.6:1 to about 1.2:1; and
(iii) from about 1 to about 20 parts per 100 parts by
weight of (i) of a solid silica gel.
In the preferred silicone suds supp..ssor used herein, the solvent for
a c~ c phase is made up of certain polyethylene glycols or
polyethylene-polypropylene glycol copolymers or mixtures thereof
(preferred), or polypropylene glycol. The primary si}icone suds
~u~.cssu. is branched/crosslinked and preferably not linear.
The silicone suds ~uy~ su. herein preferably Colll~liscs
polyethylene glycol and a copolymer of polyethylene
glycol/polypropylene glycol, all having an average molecular weight of
less than about 1,000, preferably between about 100 and 800. The
polyethylene glycol and polyethylene/polypropylene copolymers herein
have a solubility in water at room t~lllpclalul~ of more than about 2
weight %, preferably more than about S weight %.
The preferred solvent herein is pol~ ll-yl~lc glycol having an
average IllO'~ l~r weight of less than about 1,000, more preferably
between about 100 and 800, most preferably between 200 and 400, and a
copolymer of polyethylene glycol/polypropylene glycol, preferably PPG
200/PEG 300. Preferred is a weight ratio of between about 1: 1 and 1: 10,
most preferably between 1:3 and 1:6, of polyethylene glycol:copolymer of
polyethylene-polypropylene glycol.
~ W096105283 2 1 9 6423 r~ c ~ n
The preferred silicone suds suppressors used herein do not contain
polypropylene glycol, particularly of 4,000 molecular weight. They also
preferably do not contain block copolymers of ethylene oxide and
propylene oxide, like PLURONIC L101.
Other suds bU~lpl'U~SOl:~ useful herein comprise the sccond.~ly
alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with
silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118
and EP 150,872. The secull-hly alcohols include the C6-C16 alkyl
alcohols having a C1-C16 chain. A preferred alcohol is 2-butyl octanol,
which is available from Condea under the trademark ISOFOL 12.
Mixtures of secondary alcohols are available under the trademark
ISALCHEM 123 from Enichem. Mixed suds ~U~ D5UI~ typically
comprise mixtures of alcohol + silicone at a weight ratio of 1:5 to 5:1.
For any detergent c~ o~ u~c to be used in qntnmqti(~ laundry
washing mqrhinoS, suds should not form to the extent that they overflow
the washing machine. Suds s-,u~ul~Daul~, when utilized, are preferably
present in a "suds ~u~u~ ,hlg amount. By "suds ~u~u~ul~i~aillg amount" is
meant that the formulator of the comrociti~m can select an amount of this
suds controlling agent that will 5nffi~i~ntly control the suds to result in a
low-sudsing laundry detergent for use in automatic laundry washing
m~rhinf~s
The cullluosilions herein will generally comprise from 0.01 % to
about 5% of suds ~U,U~ Ol. Silicone suds ~U~U~UI~DDOI~ are typically
utilised in amounts up to about 2.0%, by weight, of the detergent
compncitinn, although higher amounts may be used. This upper limit is
practical in nature, due primarily to concern with keeping costs lllh~;...;~e~1
and ~rrt;u~ ,D~ of lower amounts for effectively controlling sudsing.
Preferably from about 0.01% to about 1% of silicone suds ~u,u,ul~ur is
used, more preferably from about 0.25% to about 0.5%. As used herein,
these weight p~LcellLge values include any silica that may be utilised in
combination with polyulg,...o~;loYqn~ as well as any adjunct materials
that may be utilised. M~ yl rhocrhqte suds ~u~essvl~ are
generally utilised in amounts ranging from about 0.1% to about 2%, by
weight, of the composition. Hydrocarbon suds suppressors are typically
WO96/05283 21 96423 F~~ .,,r,~
44
utilised in amounts ranging from about 0.01% to about 5.0%, although
higher levels can be used. The alcohol suds ~u~e~ol~ are typically used
at 0.2%-3% by weight of the finished compositions.
The compositions of the present invention may be used in laundry
detergent compositions, fabric treatment compositions and fabric
softening comrocitionc In particular the compocitionC of the present
invention find particular utility in automatic laundry washing m~rhin~c
The cnmrncitinnc may be formulated as conventional granules, bars,
pastes or powders. The detergent compositions are ",-,..,r~.l",~ in
conventional manner, for example in the case of powdered detergent
compositions, spray drying, agglomeration or spray mixing processes
may be utilised.
Preferably granular detergent co~ osi~iolls accurdil.g to the present
invention have a density of from 400g/1 to 1200g/1, more preferably
from SOOg/l to lOOOg/l, most preferably from 600g/1 to lOOOg/l.
F~m~ples
~hbrevi:ltinnc lle~l in FY~m~les
Ln the detergent comrocitionc~ the abbreviated COIll!)On~ c~lio,~.c
have the following ~ c~
XYAS : Sodium C1x - C1y alkyl sulphate
XYEZ : A C1x - Cly predo"~ "~ly linear primary
alcohol con~ nced with an average of Z moles
of ethylene oxide
XYEZS : Clx - Cly sodium alkyl sulphate con~ nced
with an average of Z moles of ethylene oxide
per mole
TFAA : C16-C1g alkyl N-methyl gl--c~mi~e
W096/05283 2 1 9 6 4 2 3 P~ G20
Silicate : Amorphous Sodium Silicate (SiO2:Na2O ratio
= 2.0)
NaSKS-6 : Crystalline layered silicate of formula ~-
Na2Si205
Carbonate : Anhydrous sodiumcarbonate
MA/AA : Copolymer of 30:70 maleic/acrylic acid,
average mnlrc~ r weight about 70,000.
AA : Polymer of acrylic acid
Zeolite A : Hydrated Sodium ~IIlminncili-Plti~ of formula
Nal2(A102SiO2)12. 27H20 having a primary
particle size in the range from 1 to 10
IlliCl u...~,t~
Citrate : Tri-sodium citrate dihydrate
PelcdllJondle : Anhydrous sodium p~ ,albOIIal~ bleach coated
with a coating of sodium silicate (Si2O:Na2O
ratio = 2:1) at a weight ratio of pc.~albulldl~
to sodium silicate of 39:1
Cellulase : Cellulolytic enzyme sold under the lla~:lcnalllc
of Carezyme or Celluzyme by Novo Nordisk
A/S
DETPMP : Diethylene triaminepenta (Methylene
rhncrhnnit~ acid), marketed by Mnnc~nh:? under
the Tradename Dequest 2060
DTPA : Diethylene triamine penta acetic acid
WO 96/05283 2 1 9 6 4 2 3 r ~ n ~
46
Granular Suds : 12 % Silicone/silica, 18 % stearyl alcohol,70%
S~ ,sol starch in granular form
LAS : Sodium linear C12 alkyl ber~7ene snlrho
TAS : Sodium tallow alkyl sulphate
Phosphate : Sodium tripolyphncrhqt~.
TAED : Tetraacetyl ethylene diamine
Sulphate : Sodium sulphate
EDDS : [s,s] ethylene diamine ~ic~l~cinqtf~.
PVNO : Poly (4-vinylpyridine)-N-oxide ~,opolyll-~,. of
vinylh..id~ulillc and vhlyl~Jyllulidine having an
average mrl~ lqr weight of 10000
DHAC : Dimethyl hydroxyethyl ammcrlinm chloride
F~,qm,rle 1:
The following granular comrncitirlns of the present invention were
prepared by COII~h ~ g the listed hl~l.,die.l~ in the given amounts.
% weight
Ingredient I II III IV V VI VII vm
PIIG~haI~ ' 14 - - - 13
Zeolite A 4 10 8 10 5 8 17.8 9
Sulphate 9 6 6 5 8 7 12.3
MA/AA 4 4 2 3 4 3 - 7.5
WO 96/05283 2 1 9 6 4 2 3 P~ 71~
47
AA - - - - - - 0.2
LAS - 2 4 - 4 2 10.5 26.4
TAS - 1 2
Silicate 2 1 1 2 0.5 - 0.6
CMC
Brightener 0.3 0.3 0.3 0.3 0.3 0.3 0.17 0.2
DETPMP 0.3 0.3 0.3 0.3 0.3 0.3
24E3S 2 2 - 3 2 2 1.4
28AS 10 8 14 11 8 12 9 7.9
28E5 4 8 4 8 8 7 1.4 3.5
28E3 4
TFAA 6 4 2 4 4 2
Granular suds 0.5 0.5 0.5 0.5 0.5 0.5 0.2 0.4
~U~ Ol
Perfume 0.4 0.4 0.4 0.4 0.4 0.4 0.2 0.3
Bicarbonate 12 14 10 12 12 13 12 14
Carbonate
PBl - - - - 15 - 2.6 4.35
TAED& 6 8.5 6 7 5 6 4.5 4.5
activator
Zinc 0.02 0.02 0.02 0.02 0.02 0.02
Phtalocyanine
enr.~rs~ tp~
Savinase 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2
protease(TM)
(4.0 KNPU /
g)
Lipolase lipase 0.4 0.4 0.4 0.4 0.4 0-4
CrM)
(100.000 LU/I)
Termamyl 0.3 0.3 0.3 0.3 0.3 0-3
amylase )TM)
60KNU/g
Cellulase 0.2 0.2 0.2 0.2 0.2 0.2 0.2
PEG - - - - - - 1.2 0.9
DTPA - - - - - ~ 0-5
Na-SKS-6 - 8 10 8 3 12 - 12
r~Ca~ 16 14 18 18 - 15
Citrate - 2 2
WO 96105283 2 1 9 6 4 2 3 ~ n ~
48
DHAC - - - - - 4 - 0.5EDDS 0.4 0.4 0.4 0.4 0.4 0-4
PVNO - - - 0.1 - - - 0.25
Dry mixed 1 - 3 - 1 2 13
Sulphate
Balance 100 100 100 100 100 100 100 100
(moisture &
micc~ n~:On~)
Surfactant 1.30: 1.19: 1.24: 1.30: 1.16: 1.50: 1.21: 1.80:
system:builder
system ratio
All of the exemplified co.l~.u~ n~ above have a pH value of from 8 to
9.8 measured as a 1% solution at 20~C.
