Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CM-224M
~2g2f~
SOFTENING ~N~ 8LE~CHING DE~ERGENT COMPOSITIONS
CONT~INING ~MIDE SOFTENING ~ENT
Hans Raemdonck
Alfred Busch
Frederick E. Hardy
~ n~ C
The present invention rela~es to softening ~eteryent
compositions containing a peroxyacid-bleaching compound, and
a narrowly-defin0d amide softening agent.
The composttions herein, in addition to providing good
cleaning per~rmance, exhibit excellen~ through-the-wash
softening properties, and pro~ide additton~l fabric-care
bene~its such as ~nti-static, anti-wrinkling,
ease-of-ironing, color stability, independently from and in
presence of peroxyacid bleaching agents.
, ' ~
.
13~82~
8ackqround of the ln~ention
Formulators of fabric treatment compositions have long
sought means For simultaneously washing and soFtening
fabrics. ~ong the ~arious approaches suggest~d ~re methods
employing clay softeners, or amine materlals, or both
ingr~dients in combination, such as described in ~.g.:
G~rman Patents 29.64.114, 28.57.~S, ~.39.541, ~3.34.899 and
European Pat~nts 0 026 528 ~nd 0 028 432.
Qmines ha~e been used in combination wlth soaps (U.K.
patent 1 514 276~ fatty acids (published E.P.~. 0 133 804)
or phosphate esters (published E.P.~. 0 168 ~89) as
through-the-wash softeners.
It has been ~ound, howeuer, that the presence of
peroxyacid-bleach compounds in softening detergent
compositions is often detrimental to the stability of the
amine softening agent. ~s a consequ~nce, the utilization of
peroxyacid bl~aching agents, inclusiue of peroxygen
bleach-activator combinations, was in such compositlons
oft~n limit~d in quantity, ~nd optimum performance could
th~refore no~ be obta~ned. In a~dition, the softenlng amine
is not well-compatlble ~ith peroxy~clds, and becomes
deacti~a~ed as a softener~
Carboxy-amides have been used as antistatie agents in
industrlal textil~ treatm~nt ~Garman pa~ent 30 43 618) and
N-alkyl isostearamides as ~ntistatic agents in laundry
application (French patent 2,531,447~.
Japanese patent JS 8144-175-~ discloses the industrial
treatment of textll~ by ca~ionic softening agen~ ~nd
ethoxylat~d fatty ~cid amides.
` :~322~
-- 3 --
~ lkyoxylated f atty amides are known as surfactants
(published ~P~ O 000 595) and as viscosity control agents
(published EPA O 112 719). Published German Pat~nt
Application 19 59 007 discloses the use as softening agent
oE a monoethanolamide. Published German Patent
Application 33 10 417 discloses the use o Eatty acicls
diethallolamides as antistat.ic/non-yellowing agents.
It ls ~n ob~ect of the pres~nt lnuention to provide
d~tergent compositions capable of prouiding excellent
cleaning, softenlng, and f~bric-car~ properties.
It is another ob~ect of the in~ention to formulate
pero~yacid-containing detergent compositions cap~ble of
pro~iding si~ultaneous cleaning and softening benefits.
It has now been disco~ered that the ob~ects set forth
abo~e can be met by using certain amides as softening agents
to thereby auoid interaction with peroxyacid bleaching
agents and thus prouide excellent results in both cleaning
and so~tening of fabric, as well as other "fabric care"
beneflts.
Summary of the ln~ention
Th~ pr~s~nt in~ention r~lates ts detergent compositions
capable of gi~ng through-the-wash ~abrlc-care benefits
inclusive of softeness, cont~ining ~ ~urfact~nt, a
nitrogen-con~ining fabric softener, ~ bleaching compound
and, if desired detersi~e additives, and are ch~racterized
ln that :
a) the nltrogen-contalning softener is an amide ha~ing
the formula:
`I
A
.
.
~3~2~2l~
-- 4 --
~ ~ 3 ..
R2
wherein R1 and R2 are, sQlected independently,
C1 8 alk~n~yl, hydroxyalkyl, aryl, or alkyl~aryl
groups, R3 is hydrog~n, or a C~_22 alktQn)Yl~
aryl or ~lkyl-aryl group, 0-~4, wherein R~ is a
Cl 22 ~lk~en)yl, aryl or alkyl-~ryl group, R3 and
R4 possibly containing functional groups, sQlected
from hydroxy, ester, ether, amide and amine groups,
Rl, R2, R3 each containing from O to 10
ethylen~ oxlde units; the ~ryl group~ can possibly be
deri~ed from hetero-cyclic compounds; with the
pro~iso that the sum of carbon atoms in Rl + R2 +
R3 ~s equal to or greater than 1~;
(ii) R - NH ~ C - R'
O
wherein R and R' are straight chain alk(en)yl ~ryl,
or alkyl-aryl group, e~ch containing from 8 to 22
carbon atoms;
the ble~ching compound is represen~ed by a peroxyacid
bleaching agent.
i
Detailed Description of_the In~ention
The amid~ softenlnq ~q~nt - The amide softenlng agents for
use in the present lnuention can be represented by ~h~
formula:
(~ Rl
N - C - R
~2 ~ o 3
.. . _ ... . , _ _ _ _ _ _ ... . . ..
~3~2~2~
- 5 -
wherein Rl and R2 ~r~ selected independently,
cl a ~lk~en)yl, hydroxy-alkyl, ~ryl, or alkyl aryl
groups, R3 is hydrogen, or a Cl_22 alk(Qn)yl,
aryl or alkyl-aryl group, 0-R4, wherQin R4 is a
Cl 22 alktan~yl, ~ryl or alkyl-aryl group; R3 and
R4 possibly containlng functional groups, sel~cted
from hydroxy, ester, ether, amide and aminQ groups;
Rl, R2, R3 each cont~inlng from 0 to 10
j ethylene oxide units; the aryl groups can possibly be
deri~ed from het~ro-cycl~c compounds; wtth thQ
prouiso that the sum of carbon atoms in Rl + R2
R3 is equal to or gre~ter than 14; or
(ii) R - NH - C - R'
wh~rein R and R' are straight chain alk(en~yl, aryl,
or alkyl aryl groups contalning from 8 to 22 rarbon
atoms .
Preferred amides of the formula (i) ontain more tha~ 8
carbon atoms in th~ R3 group.
Specific ~xamples of preferr~d specles of formula ~i)
include N,N-dimethyl tallowam~d~, N,~-dimethyl lauramide,
N,N-dime~hyl pal~itamide, N,N-d~methyl stear~mide, N,N-
diethyl tallowamide, N,N-dimethyl cocoalkylamide, N,N-di-
ethyl cocoalkylamide, ~,~-di~thanol cocoalkylamidQ,
N-N-diethanol lauramide, polyoxysthylated stearamide,
poly~hoxyethylated tallowamide.
Most pr~erred are N,N-di~Qthylt~llowamide, N-N-dl-
ethylt~llowamide, N-N-di~ethyl cocoalkylamide, N-N-diethyl
cocoalkylamide, N-N-diethanoltallowamide.
Preferred amides of the formula ~i~) in~lud~ N-cocoalkyl
stearamide, N-d~cyl stearamide, N-coco31kyl laur~mlge,
N-tallow t~llowamid~, N-decyl tallowam~d~.
The amide softening agent is used at levels of ~ro~ 0.1
to 15~ by we~ght, preferably form 1 to 10~ by weight o$ the
detergen~ ~omposition, most prsferably from 3% to 6~.
.
- 6 ~ 2~
In ~ highly preferred embodi~ent of the present
in~entlon, the amide softening agent is pre-mixed with a
dispersing agent, and the r~sulting mixture is then added to
the rest of the composition.
~ ny con~entio~al dispersing agent with a suitable HL~
~alue can be used herein. Examples are nonionic surfactants
result-lng ~rom the condensation of primary or secondary
aliphatic alcohols or alkyl phenol, with polyethylene
oxide. Specific examples includ~ the condensation products
of tallow alcohol with 5 to 12 ethylene oxide units in the
molecule.
Suitable as dispersiny agents are also phosphate
esters described in published EPA O l68 889, such as those
oE the formula: R'-O(CH2-CH20)mPo(oH)2l with
R'=Cl2 14 and m=1-5, sold under the Trade ~lark
"Servoxyl vpAæll~
Howe~er, it is a preferred embodiment of the present
lnuentlon to use fatty acids as dispersing agents for the
amide softening agent,
Fatty aclds like lauric, myristic, p~lmit~c, stearlc,
oleic ~cids and mixtures thereof c3n ad~antageously be used
in the present cont~xt.
Especially preferred ls a mixtura of palmitlc and
steartc acids.
Fatty acids dispersing agents are used most preferab~y
in a weight ratio of 1/1 to 10/1 of amide softening agent to
fatty acid.
.
~- ~ 3 2 ~ ~3 r I ~
-- 7 --
Softener Cl~ - The ~mlde softenlng ~gent is preferred but
not llmited, ~or use in combination with a detergent-
compatible clay softener. Such clay softeners are
well-~known in the detergency patent l~terature and are in
broad commercl~l use, both in Europe and in the United
States. Included among such clay softeners are various
ha~t-treated kaolins and varlous multl-layer smectites.
Pref~rraJ clay soft~ners are smectite softener clays that
are describecl in FPo publ1ca~ion No. O l68 889 ancl in
U.K. Patent 1.400.89~, which can be referred to for
details. So~tener clays are used in the preferred
compositi~ns at levels of at least 1X, generally 1~20%,
preferably 2-lOX.
Detersiue surfactants - The compositlons of this in~ention
wlll typically contain organic surfac~-actiue agents
("surfactants") to prouide the usual cleaning bene~lts
associated with the use of such materials.
Detersiue surfact~nts useful herein include well-known
synthetlc anionic, nonionic, amphoteric and zwittenionic
surfactants. Typlcal of these are the alkyl benzene
swlfonates, alkyl- and ~lkylether sulfates, paraf~in
sulfonates, olefin sulfonates, alkoxylated (especially
ethoxylated) alcohols and alkyl phenols, amine oxides,
alpha-sulfonates of fatty ~cids and of fatty acid est¢rs,
and the like, which are well-known From the detergency art.
In general, such detersive surFactants contain an alkyl
group ln th~ Cg-Cl~ r~nge; the anionic det~rs~e
surfactants can be used in the form of their sodium,
potassium or trlethanolammonium salts; the nonlonics
generally contain from about 5 ~o about 17 ethylene oxide
groups. U.S. Patenk 4.111.855 contains detalled listlngs of
such typical detersive surfactant~. C11-C16 alkyl
benzene ~ul~onates, C12-C1~ paraffin-sulfonates and
~32~2~
alkyl sulfates, ~n~ the ethoxylat~d ~lcohols and alkyl
phenols are especially pref~rred in the compositions of the
present type.
~ lso useful herein as th~ surfactant are the
wat~r-soluble ~oaps, e.g. the common sodium ~nd pot~ssium
coconut ~r tallow soaps well-known in the art.
The surfactant component can comprise as little as 1~ of
the composltlons her~in, but pref~rably the compositions
will contain 5% to 40X, ~ore preferably 10~ to 30X, of
surfactant, Mix~ures of the ethoxylated nonionics wlth
anionlcs such a~ th2 alkyl benzene sulfonates, alkyl
sulfates and paraffin sulfonates are pr~ferred for
through-the-wash cleanslng of a broad spectrum of soil~ and
stains from fabrics.
leachin~ comPound - The bleaching compound in the context
of the present inven~ion is represented by a peracid
bleaching agent. In the context of the present invention,
peroxyacid bleaching agent encompassss both a peroxyacid per
se and systems which are able to yield paroxyacid~ ln situ.
Per4xyactds '~per se" are meant h~re to include the
alkaline and alk~lins-earth metal s~lts thereof.
Peroxyacids and dipero~yacids are commonly used; examples
are diperoxydodecanoic acid SDPDQ) or peroxyphthalie acid.
Systems capabl~ of deliuering peracids in situ consist
in a peroxygen bleaching agent ~nd an dctivator therefor.
The peroxygen bleaching agent~ are thos~ capable of
yielding hydrogsn peroxide in an agueous solution; thoss
compounds are well-known in the ~rt, and includ~ hydrog~n
peroxide, alkali-met~l peroxides, organic peroxide blea~hing
. ~
- 9 - ~ 3 2 2 ~ ~ ~
agents such as wrea peroxide, inorganic persalt bleaching
agents such as the alkali metal perborates, percarbonates,
perphosphat2s, persilicates, and the like.
Preferred ar~ sodium perborate, commercially a~ailable
in the form of mono- and tetra-hydrates, sodium carbonate
peroxyhydrate, sodi~m pyrophosphat~ peroxyhydrate, urea
peroxyhydra~e.
The llberated hydrogen peroxtde r~cts with ~he bleach
acti~ator to form the peroxyacid bleach. Classes of bleach
acti~ator~ include esters, lmides, imidazoles, oximes, and
carbona~es. In those classes, preferred materials include
methyl o-acetoxy benzoates; sodium-p-acetoxy benzene
sulfonates such as sodium 4-nonanoxylo~ybenzene sulfonate;
sodtum-4-octanoyloxybenYene sulfonate, and
sodium-4-decanoylo~ybenzenesulfonate: blophenol ~ diacetate;
tetra acetyl ethylene diamine; tetra acetyl hexamethylene
diamine; tetra acetyl methylene dlamine.
Other highly preferred peroxygen bleach acti~ators which
are disclosed in U.S Patents 4.483.778 and 4.539.130, ~re
alpha-substi~uted alkyl or alkenyl es~ers, such as
sodium-4~2-chlorooctanoyloxy~benzen~ sulfonate, sod~um
4-S3,5,5 trimethyl hexanoyloxy)benzane sulfonate. Suitable
peroxyacids are also peroxyg~n bleach acti~tors such as
describ~d in published European Patent ~pllcation N
O 166 571, i.e., eo~po~nds of ~he g~neral type RX~OOH and
RX~L, wherein R is a hydroxcarbyl group, X is ~ het~ro-atom,
is a carbonyl bridging group and ~ is A leau~ng group,
especially oxybenzenesulfonat~.
Detersi~e_ag~ The compositions har~in can contain
other ingredients which aid in their cleaning performance.
Through-the-wash detergent compositions contain a detergent
, _ .
- 10- ~3~2~2fl
builder and/or metal ion sequestrant. Compounds
~lasslfiable and well-known in the art as d~tergent builders
include the nitrilotriAceta~es, polyc~rboxylates, c~tr~tes,
water-soll~ble phosphat~s such ~s tri-polyphosphate ~nd
sodium ortho- ~n~ pyro-phosph~te~, silic~tes, and mixtures
th0rQof. Metal ion sequQstrants lnclude ~11 of th~ ~boue,
plus matQrials lik~ ~thylenedialnin~tetr~acet~te, the
amino-polyphosphonate~ ~nd phosphates (DEQUES~ ~nd a wide
u~riety of othQr poly-functional organic acids ~nd salts too
numerous to mention in d~tall here. SQe U.S. P~tent
3.579.454 for typical exarnplQs of the us~ of such mat~rials
in uarious cleaning compositions. In general, t.h~
builder~sequ~strant will compri~e ~bout 0.5% to 45% of the
composition. Th~ 1-10 micron siz~ zeolit~ (e.g. zeolite ~j
builders disclosed in German Patent 24 22 655 are especially
pref~rred for use in low-phosphate or non-phosphate
compositlons.
The l*undry compositions h~rein also preferably contain
enzymes to enh~nce their through-the-wash cleaning
performance on ~ uariety of soils and ~tains, such as
amyl~s~ & protease enzymes. A~Y1ASe ~nd protease enzymes
suitable for use in detergents are well-known in the art and
ln commerci~lly ~ilable liquid and granular d~tergents. '
Commercial d~tersiue ~nzymes (preferably a mixture of
amyl~se ~nd protease) are ~ypically used ~t l~uels of 0.001%
to 2%, and higher, in the present compositions. Other
highl~ d~lrabl~ d0terg~nt ingr~di~nts ~or use in th~
de~erg~nt composltlons of the pres~nt inuention are
quaternary ~mmonium compounds of the form
R4R3R6R7N X , wh~rain R4 ls ~lkyl hauing from
10 to 20, pref~r~bly from 12-1~ carbon atoms, and R5,R6
~nd R7 ar~ e~ch C1 to C~ alkyl preferably methyl: X~
is an anion, e.g. chlorld~. Examples of such guaternary
ammonlum compounds includ~ C12-C14 ~lkyl trimathyl
ammonium chlorlde and cocoalkyl trlm~thyl ammonium
methosulfate, Th~ qu~tern~ry ammonlum compounds can be used
ht l~vel~ from 0.5~ to 5~, preferably from 1X to 3~.
3~2~
Moreo~er, th~ co~positions herein can contain, in
addition to ingredi~nts already mentioned, uarious other
optlon~l ingr~dients typically used in commercial products
to pro~lde ~esthetic or additional product perform~nce
benefits. Typical ingr~dients includ~ pH regulants,
per~um~s, dy~s, optical brighteners, soil ~uspendlng agents,
hydrotropes ~nd gel-control agents, freeze-thaw stabilizers,
bactericides, preseruatl~es, suds control a~ents, bleach
stabilizing agents.
In a through-the-wash mode, the compositions are
typically usQd at a concentration of at least 500 ppm,
preferrably O.lOX to 1~5%, in an aquaous laundry bath at pH
7-11 to launder fabrics. The laundering can be carried out
ouer the range from 5C to the boil, with excellent results.
Form and Preparation of the comPositions - The detergent
composition~ of the presQnt in~ention can be in granular,
liquid, or sheet-likQ ~orm. They may be prepared in any
way, as appropriate to their physical form, as by mixing the
components, co-agglomerating them, micro-encapsulating them,
dispersing th~m in a liquid carrier, releasably adsorbing or
coatlng th~m onto a no~-particulate su~strate, such as a
non-wo~en or paper she~t.
Preferably, the composi~ions are ~n granular form.
~ highly preferred method of pr~paratlon of said
granular composl~ions consists in preparing a mel~ of the
disperslng agent and the amide, dispersing th~ molten
mixture into a stirred, aqueous crutcher mix comprislng the
balance of the detersiua ingredients, and spray-drylng in
standard fashion. In ~lternat~ but much less pref~rred
modes, the ~elt can b~ atomized onto the detergent granul~
or ~llowQd to solldify, ground ln ~ colloid mill, ~nd
- 12 ~ ~32282~
dry-mixed w~th the balance of ~h0 detergent composition.
The compositions herein may ~lso be sprayed onto particles
of, e.g., sodium perborate mono or tQtrahydrate, sodium
sulfate, sodium carbonata, sodlum sllicate, sodium
phosph~te, or clay of the type dascribed aboue.
Industrial ~pplication
The following examples are typical of the preferred
execution of the in~ention, but are not intended to limit
the scope.
E~MPLE 1
N,N-dim~thyl tallowamide (total 6~ of complete
formulation after spray-drying) and stearic acid (2% of
complete formulation) are admixed, melted in a ~acketed
batch and stirred until homogeneity. ~ standard aqueous
crutcher mix comprising the following ingredi~nts is
prepared ~percentages listed relate to percent ingredients
in the complet~ formulation after spray-drying).
. ~ .
~3~2~
- 13 -
Ingredlents Percent
C11-C12 alkyl benzene sulfonate 6.2
Tallow alcohol ~thoxylate tEO11) l.O
Sodium tripolypho~phate 2~.0
Sodlum sul~ate 15.0
Sodium sl'licate 8.0
Smectite cl~y * 6.5
Carboxymethyl cellulose 0.4
Polyacrylate (soil suspender) 1.7
Enzymes o,~
Optical brightener 0.23
Sulfonated z~nc phthalocyanine ** 25 ppm
EDT~ 0.2
Perfumetcopper salts~minors 0.5
C12~C14 alkyl trimethylammonium chloride1.9
Moisture to 77X
The N-N-dimethyl tallowamide~stearic acid melt is poured
into the crutcher mix (60-90C). The crutcher
mix-plus-N,N-dimethyl tallowamid~stearic acid is then
handled in entirely standard ~ashion, and spray-~ried to
form the final compositio~. ~fter drying sodium perborate,
~20%) and bleach activator ~3% 3-5-5-trimethyl hexamaic
acid, sulfapheryl es~er, sodium salt***) are dry-mtxed with
the granul~s.
* ~atural smectite: ion exchange cap~city aboue
50 meq/100 9 clay
*~ U.S. Patent 3.927.967
*** U.S. Patents 4.483.778 ~ 4.539.130.
~ he composition of Exampl~ 1 pro~ided better softeness
and fabric-car~ benefits, compared to an identic~l
compo~itlon which did not contain the N,N-dimethyl
tallowamidet;tearic acid premix (reference).
~ - 14 - ~322~2~
EX~MPLE 2
The same composition as Exa~ple 1 was prepared, where-ln
N,N-dimethyl tallowamide was replaced by N-tàllow
tallowamide, premixed with st~aric acid in the same
conditions as in Example 1. Uery 900d results were obtained
tn soft~ness and fabric car~ bene~its, compar~d to the same
refer~nce ~s in Example 1.
EX~MPLES 3_~ 4
The following low-phosphate detergent compositlons are
also prepared.
Inqredients Percent
Ex..3 Ex. 4
: Zeolit~l~ (1-10 microns) 26,0 26.0
Sodium nitrilotriacetate 5 0 5.0
Smect~te clay * 3,0 3.C
N,N-dimethyl tallowamide/stearic acid ** 5.0
N,N dl~thanol tallowamideJlauric acid ** - 5.0
C11-C12 alkyl ben2ene sulfonate 6~5 6.5
Tallow ethoxylate (EO 9-11) 0.5 0.5
Sodium perborate 4H~0 *** 20 20
Tetraacetyl ethylenediamine (T~ED~ ~** 3 3
Sodlum sillcate 8 8 ~ :~
CMC
Sodium sulfate 18 18
Enzymes (1:1 amylaseJprotease) *** 1.5 1~5
Optlcal brlghtener 0,5 o.5
Water, minors to 100 to 100
* ~s G~lwhite2GP (TM): CaC03 lon exchange cap~city :~:
70 MeqJ100 9
** Prepared as in Example l
*** Dry-mix~d wlth romposltlon. ::
Zeolite is a -trademark
Gelwhite is a trademark
`:
~ ~7
-- 132~32~i
- 15 -
The composition of Examples 3 and 4 are prepared by
spray-drying in aqueous crutcher mix, in ths manner
describQd for Example ~. The composition of Examples 3 and
4 pro~ide better softeness ~han the composltion wherein the
amlde~fatty acid premixes ha~a been repl~ced by additional
sodium sulfate.
