Note: Descriptions are shown in the official language in which they were submitted.
Wo 93/17084pcr/us93/ol156
2130466
AQUEOUS HARD SURFACE DETERGENT COMPOSITIONS
CONTAINING CALCIUM IONS
TECHNICAL FIELD
The present invention relates to an aqueous hard surface detergent
composition con~ g G~irium ion which provides improved solution feel
without deteriorating storage stability of the composition. The CG~..pGS;lion isparticularly useful for dishwashing liquids, more particularly under soft water
conditions.
BACKGROUND
Anionic swf~ct~ntc such as alkyl ethoxy sulfates with short ethylene
oxide chains, alkyl sl~lf~tes, alkyl benzene sulfonates, a-olefin sulfonates, and
alkyl ethoxy carboxylates are known to be very effective for hard surface
cle~nine but are also known to have more or less unfavorable "slippery" feel in
use. This undeii.~lc attribute is a proble,.. to hard surface cle~ning
compositions, espeçislly for d;~ aslfing purposes.
There is th~ ,fole a considerable demqrld for a hard surface delerg~nl
composition which has good detergency and good storage stability while
having good solution feel when cle~ning and rinsing, particularly for
dishwashing purposes. As defined herein, good solution feel is best defined as
the ~I-se-~ce of "slippery" or "slimy" feel, or a "draggy" kind of feel which one
feels when the composition is in use. "Good solution feel" is an hllpGllanl
attribute for co--..--~ ,;al liquid d~le-g~--l products. Those wash solutions
which have good solution feel on hands and objects to be cleaned allow easy
hqn~iing of the objects, and provide good rinsing characters. Such bencrlls are
most apprecialed for dishwashing purposes.
Many attempts have been made to improve solution feel using various
technology. These all~-"pts are usually directed towards the use of nonionic-
type surf~ct~nts, and other suds e~-h~l-ri~-g-type and solvent-type con.l)onenls.
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213046~
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Generally, these compositions have sacrificed detergency to obtain the
improved solution feel.
Kokoku 46-43550 (Kao Corporation) teaches a liquid detergent
composition which is mild to skin and has good detergency comprising ~Ik~line
earth metal salts of certain alkyl alkylene-oxy sulfate and certain alkyl alkylene-
oxy carboxylates.
Kokai 51-125405 (The Procter & Gamble Company) teaches
compositions comprising calcium and nl~gnesi~m salts of anionic surf~rt~nts
inrluding alkyl ether sulfates and amine oxides, Cl 5 alk~no!e and water,
wherein the weight ratio of amine oxide to anionic surfactant is 1:100 to 1:2.
Up to about 25% ofthe anionic surf~t~nts can be monovalent salts.
U.S. Patent 2,766,212 (General Aniline and Film Colpo~alion) teaches
compositio~e which co"~p.ise alkyl ether alkoxy sulfate salts and water soluble
polyvalent salts of ...~es; ~m, c~lc;~'m~ iron, or al~ u ~ of 5 - 50% by
weight of the surfactant. Examples show CQlnpOSitione colllpli;.ing at least
70% of the anionic surfactant in which .~a~,~c,:~"- and c~lr;~lm ions help
detergency.
U.S. Patent 4,681,704 (The Procter & Gamble Company) teaches a
detergent co",i)osilion with effective grease removal co"""i~i"g 10 - 50%
k~line earth metal salt, preferably ...~ ; lm of anionic surf~rt~nte, 0.5 -
10% amine oxides, and 0.5 - 15% b~laines.
However, the above mentioned diecl~sures use alk~line earth metals
mainly for their cle~ning be~ s, and do not ~lierlose or s~ggest the
improvement to solutio~ feel ben~fitc contributed by c~lci~-m ions. Further, theco,nl)ositions ofthe above mentioned dicclQs~lres have high divalent ion levels,so that they would be unstable upon storage in the context of the present
invention, namely, would form undesirable p,c~,;p;l~les of c~1r;um ~rcf~ ;d
cG."pos;lions and examples shown in the above disclosures also have high
surfactant levels, and thus the amount of calcium needed to reduce or el;~ te
3 ~ 6 ~
the "slippery feel" of the composition would place the composition into a phase
where calcium is believed to easily precipitate.
Here, it has been found that by using calcium ions at a certain low level,
a composition which provides improved solution feel without deteriorating
storage stability is obtained.
SUMMARY OF THE INVENTION
The present invention relates to an aqueous hard surface detergent
composition which provides improved solution feel comprising:
(1) 3 - 35% by weight of a surfactant system selected from the group
consisting of anionic, nonionic, amphoteric surfactants, and mixtures thereof,
comprising:
a. at least 3% by weight of the composition and at least 20% by
weight of the surfactant system alkyl ethoxy sulfate with an alkyl group of Cl0 l6
and an average of 1 - 10 moles of ethylene oxide per molecule;
b. other anionic surfactants selected from the group consisting of
alkyl benzene sulfonates, a-olefin sulfonates, alkyl ethoxy carboxylates, and
mixtures thereof;
c. 0 - 9% by weight of the composition diethanol amide with an
alkyl chain of C8-20;
d. 0 - 10% by weight of the composition amine oxide with an alkyl
chain of C8 ,6; and
(2) 0.01 - 0.5% by weight calcium ion;
wherein at least 20% by weight of the surfactant system comprises the total of
component a, b, c, and d.
t
.~?
J
~ 1! 3 ~ ~ 6 ~
-
-4-
More particularly, the invention relates to an aqueous hard surface
detergent composition which provides improved solution feel comprising: (1) 20
- 30% by weight of a surfactant system selected from the group consisting of
anionic, nonionic, amphoteric surfactants, and mixtures thereof, comprising:
a. at least 35% by weight alkyl ethoxy sulfate with an alkyl group of Cl0 ~6 andan average of 2.5 - 3.5 moles of ethylene oxide per molecule; b. diethanol amidewith an alkyl chain of C8 20; and c. amine oxide with an alkyl chain of C8 ~6; (2)
0.1 - 0.3% by weight calcium ion; and (3) 0.1 - 0.5% by weight magnesium ion;
wherein the composition contains 4 - 7% by weight of the diethanol amide, and
2 - 5% by weight the amine oxide.
The present invention also relates to a method of improving the solution
feel of an aqueous hard surface detergent composition or a wash solution of an
aqueous hard surface detergent composition by adding calcium ion to said
composltlon.
The composition has less of an unacceptable slippery feel, and is easy to
handle when cleaning and rinsing. The compositions of the present invention
have good storage stability, that is, the composition is stable in ordinary use
conditions, more specifically, it does not generate precipitation or gel in the
temperature range of from -5~C to 40~C.
Anionic Surfactant
The compositions of the present invention comprise 15 - 35%, preferably
20 - 30% by weight surfactant system selected from the group consisting of
anionic, nonionic, amphoteric surfactants, and mixtures thereof. At least 20%,
preferably at least 40%, more preferably at least 60%, by weight of the surfactant
is the sum of anionic surfactants, diethanol amide, and amine oxide. Among the
anionic surfactants, at least 3%, preferably at least 8%, more preferably at least
12%, of the composition is alkyl ethoxy sulfate with an alkyl group of Cl0 l6 and
7~ ''
~ ~ 3~4~
-5-
an average of I - 10 moles, more preferably 2 - 5 moles, of ethylene oxide per
molecule.
The anionic surfactants are selected from said alkyl ethoxy sulfates, alkyl
sulfates, alkyl benzene sulfonates, a-olefin sulfonates, alkyl ethoxy carboxylates, and
mixtures thereof.
Alkyl ethoxy sulfate, particularly having an alkyl group of Cl0 l6 and an
average of 1 - 10 moles, preferably 2 - 5 moles, more preferably 2.5 - 3.5 moles,
of ethylene oxide per molecule, provides good detergency and less negative effect
on solution feel. Furthermore, compositions including a considerable amount of
such alkyl ethoxy sulfates are susceptible to the effect of improved solution feel due
to calcium ions. The average number of moles of ethylene oxide per molecule of
the alkyl ethoxy sulfates can change the character of the surfactant. Here, alkyl
sulfate is dealt as an alkyl ethoxy sulfate having 0 moles of ethylene oxide permolecule. Generally, it is known that the longer the ethylene oxide chain contribute
less to poor solution feel, but have poorer detergency performance. Those which
have less than an average ethylene oxide chain of 1 moles per molecule by
themselves will contribute to poor solution feel.
The salts for the anionic surfactant component can be alkali metal, alkali
earth metal, amines, or ammonium salts, preferably sodium or ammonium salts.
Alkali earth metal salts of these surfactants are known for good detergency and
sudsing. Some or all of the calcium ion of the present composition can be
introduced as calcium salts of the anionic surfactant.
Other Surfactants
The compositions of the present invention may also comprise, for the
balance of the surfactant system, other anionic surfactants, nonionic surfactant and
amphoteric surfactants. These surfactants are formulated in the compositions of
the present invention to enhance detergency, and to enhance and stabilize
suds. The species and levels of the other anionic, nonionic and amphoteric
~,..-
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2~3~4~6
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surfactants are chosen in order to obtain optimum balance of detergency,
solution feel, and storage stability.
The compositions of the present invention can contain nonionic
surf~-,t~nts such as dieth~nol amides and amine oxides. 0 - 9%, I)rerelably 4 -
7% by weight of dieth~nol amide and 0 - 10% ~,erel~bly 2 - 5% by weight of
amine oxide is contained in the composition. These two surf~ct~nts are known
to provide good detergency and good storage stability, but can negatively
effect solution feel. The use of calcium ion to improve solution feel is
particularly useful in composition con~l;sing diethanol an~ide and/or amine
oxide.
Diethanol amide useful in the present invention has the formula
HO
l 11
(c2H5oH)2-N-c-Rl I
wherein Rl is sPI~ ,Led from an alkyl chain of Cg 20, pr~,f~.~bly C12 14.
Amine oxide useful in the present invention has the foll.wla
o
1~ II
R2N(OC2H5)2
wherein R2 is s~ lectçd from an alkyl chain of Cg 2o, pr~r~-~bly C12 14.
Calcium
It has been found that by incol~olal;ng low levels of c~lr,ivm ions,
nced benefits in solutiQn feel and storage stability are ob~ained. The effect
of the addition of low levels of c~rium ion into dishwashing compositions is
particularly benefisi~l under low hardness water conditions, where the ~mo~nt
of calcium introduced from tap water is low.
Calri~m ions are added to the co".~)os;lion at levels of 0.01 - 0.5%,
preferably 0.1 - 0.~%, most preferably 0.1 - 0.3%. At lower c~lci--m levels, no
effect on solution feel will be observed. At higher calri~-m levels, storage
~'0 93/17084 21 3 0 ~ 6 6 PCI/US93/011~6
_ ,.
stability will not be good. That is, it is known that calcium ions are relatively
easily p,c;ci~ila~ed at high te",pe,a~-lre conditions, and thus are apt to
deteriorate storage stability when added at high levels. C~lrium ions are
further known to contribute to detergency, particularly to grease removal. By
selectin~ a calcium level in the above range, a composition having all three
important benefits are obtained; good solution feel, good grease removal, and
good storage stability.
The co""~)Gs;lions of the present invention must have less than 35%
total surf~ct~nts to avoid p~ ecip;lalion of the calcium which is present at a level
suffirient to improve solution feel. If the surfactant level is too high? the
m~Yimum amount of calcium that can be added without fo.",ing c~lrium
p, ~cipilalion would not be sufficiçnt to improve solution feel to the
composltion.
The calcium ions can be inco,~o,aled in the co"",os;lion in any
convenient way, so long as the salts CQ~ g cs~lri~lm ions are soluble in
water and do not p,.~ e under oldh~y use conditions. A suitable way of
il~co.~,G,ali.,g c~lrium ions is by adding them as salts selected from the groupcon~ g of chloride, hydroxide, oxide, ~cet~te, nitrate, formate, and mixtures
thereof. Chloride salts are most pn,f~" cd.
Alternately, calcium ions can also be incorporated as counter-ions of
anionic surfactants? such as by neutralizing the acid forrn of anionic surfi-ct~nt.c
with r~lcium oxide or calcium hydroxide, without aa~ling the benefits thereo~
The p,~,fe.,ed composition ofthe present invention co"~.,ises:
(1) 20 - 30% by weight of a surfactant system selected from the group
con.~;cl;.~ of anionic, nonionic, amphoteric sull~cl~"~, and mixtures thereof,
c~"-~ lg.
a. at least 35% by weight of the surfactant system alkyl ethoxy
sulfate with an alkyl group of C10-l6 and an average of 2.5 - 3.5 ethylene
oxide per molecllle;
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2~3a46G -8-
b. 4 - 7% by weight of the composition diethanol amide with an
alkyl chain of C8-20;
c. 2 - 5 by weight of the composition amine oxide with an alkyl
chain of C8-16;
(2) 0.1 - 0.3% by weight calcium ion; and
(3) 0.1 - 1% by weight m~gnPcium ion.
Optional Co",pone"ls
The compositions of the present invention can optionally contain
components in addition to those already disclosed herein.
Optional surf~t~ntc useful in the composition of the present invention
are those such as monoeth~nol arnides, polyhydroxy fatty acid arnides, alkyl
polyglucosidçc, and alkyl ethoxylates.
MOnG~Ih~nOI amide is an optional su,rac~al-t in the present invention,
having the formula
HO
l 11
(c2H5oH)-N-c-R3
wherein R3 is sçlçcted from an alkyl chain of Cg 20, pleI~Iably C12 14.
Polyhydroxy fatty acid arnide is an optional surfactant in the present
invention, having the formula
o R4
Il I .
R5-C-N-Z
wherein R4 is H, Cl 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a
mixture thereof, preferably Cl 4 alkyl, more preferably methyl; and R5 is Cs
31 hydrocarbyl, prel~,~bly straight-chain C10 16 alkyl; and Z is
WO 93/17084 213 0 ~ 6 6 PCI/US93/01156
polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3
hydroxyls directly co~-necled to the chain, or an alkoxylated derivative
(preferably ethoxylated or propoxylated) thereof. Z preferably will be derived
from a reduçing sugar in a reductive amination reaction; more p,erelably Z is
glycityl. Suit?ble reducing sugars include glucose, fructose, mq-ltose, lactose,galactose, mannose, and xylose.
Alkyl polyglucoside is an optional surfactant in the present invention,
having the formula
R6o(cmH2mo)p(glucosyl)q
wherein R6 is selecled from the group con~ .g of alkyl, alkylphenyl,
hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl
groups are C10-l8~ preferably C12 14, m is 2 or 3, preferably 2; p is from 0 to
about 10, preferably 0; and q is 1.3 - 10, plere(ably 1.3 - 3, most prerc,~bly 1.3
- 2.7. To prepare these compounds the alcohol or alkylpolyethoxy alcohol is
formed first and then reacted with glUCOSf~ or a source of g~uGOSç, to form the
g1~lcos;de (attr-hment at the l-position). The nd~itionql glycosyl units can then
be attached ~ ~cn their l-pGS;l;On and the pl ece(~ glycosyl units 2-, 3-, 4-
and/or 6-position, prer~,.ably predo...;.~ely the 2-pos;lion.
Alkyl ethoxylate is an optional surfactant in the present invention. Such
alkyl ethoxylates are aliphatic alcohols with I - 25 moles of ethylene oxide.
The alkyl chain of the aliphatic alcohol can either be straight or b,iu~ched,
primary or secondary, and generally co,.l~;l-C 8 - 22 carbon atoms. Particularlypreft,,cd are the con~1fnC~l;on products of-q-lcohols having an alkyl group
con~ ;ng 8 - 20 carbon atoms with 2 - 10 moles of ethylene oxide per mole of
alcohol. Most ptérelled are the conden~-qtiorl products of alcohols having an
alkyl group cQI.~ ;ng 8 - 14 carbon atoms with 6 - 10 moles of ethylene oxide
per mole of alcohol.
Amphoteric surf~ct~nt~ optionally included in the present invention are
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2~3o~6~
- 10-
betaines having the formula
R8 (R10)2
R7Co-N-R9-N+Rl lcoo-
wherein R7 is a C7 21 alkyl group, or alkylaryl group, prel~,~bly Cg 17; R8 is
hydrogen or a Cl 6 alkyl group, plefe,~bly Cl 3; R9 is a Cl 1o alkylene
group, preferably C2 6, most preferably C3; each R10 is a C1 6 alkyl or
hydroxy alkyl group, preferably C 1_3, most preferably methyl or an ethoxylated
hydroxy alkyl co,.~ g from about 1 to about 10 ethylene oxide units; and
R11 is an C 1 -6 alkylene group, preferably methyl.
~ nPsj-lm ions at a level of 0.1 - 1% are ple~lably inrluded in the
composition of the present invention to improve detergency without ~-;I;np
good solution feel and good storage stability of the co",?o~;lion.
The compositionc of the present invention can also comprise 4 - 8% by
weight of a hydrGIIope selected from the group conC;~ of sodium and
a".l"onium salts of cllm~ne sulfon~t~c~ toluene sulronales, xylene s~lron~
sulfo succ~ lec~ and mixtures thereo~ Such cGnl?onenls are utilized in the
inlere~ls of achieving a desired product phase stability and viscosity.
Other desirable ingredients include solvents, preservatives, dyes, and
perfumes.
Solvents useful in the present invention include water and lower
rnoleclJI~r weight ~lcoholc such as ethanol. Ethanol is also known to reduce
the viscosity of the product, if n~cecc~y for formulation. Solvents other than
water are typically present at levels of 2 - 10% by weight.
Preservatives, dyes, and perfumes can be, and usually will be
forrn~ ted in the composition of the present invention to make products
attractive to the consumer. These co",?on~ s are typically present at levels
not more than 1% resl)eclively.
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Components which are preferably not incl~lded in the composition are
those which generate plc~;l)ilation upon binding with calcium ions. Fysn~pl~s
are those which include sulfate, carboxylate, and fatty acid anions.
EXAMPLES
The following e~n.llec illustrate the compositions of the present
invention, but are not interlded to be limiting thereof. All per~ie.-lsges and
ratios are based on weight unless otherwise specified.
P, epa, ~lion
The liquid delergcnt compositions herein des~i,il,ed can be made
conveniently by one skilled in the art. Surfs-ctsntc hyd,ul~opes, calcium salts,and optionally tt.~gn~si~-m salts are added in an approp,iate amount of water
and are blended. In the present invention, the order of adding the co"")on~,.ds
is not important. If l~ecçsC~ ~, the pH of the mixture is -s~dj~sted with HCI to a
safe level for ho~sPhold products, and viscosity is adjl~sted with alcohol.
Perfume, dye, and preservatives are optionally added, and the co"~,ûsilion is
~slsnced with water. The standard product and c~a. ,Jles 1 - 9 are all p,epa,~d
accord;ng to this Inetllod
EA~;I i"~e.,la~ion
1. Solution feel
- 500g each of 6% solutions of the standard product and compositions of
the present invention are prepared in a 1 liter beaker, and a pûrcelain crucible is
soaked in the solution
- One hand is soaked in the sample solution and the other hand is soaked
in the general standard product solution at the same time, and the feel of the
crucible is evaluated according to the scale as shown below.
- Evaluation is done by three special psnelicts and the average score is
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21~66 12-
obtained.
Evaluation scale
O= There is no diIrerence
I= I think there is a difference
~ 2= I know there is a dia~rence
+ 3= I know there is a big difference
4= I know there is a very big difference
(+): the sample has a better feel (less slippery)
the sample has a worse feel (more slippery)
For those which have higher points than the composition with the same
surfactant system without calcium it is evaluated that the "solution feel was
improved".
2. Storage Stability
The sample is placed in a lO0 ml glass co~ , and stored in rooms
with e~ t~ ed t~..":c.~lules of-5~C and 40~C r~ec~ ely. The cor~ition of
the product after 2 weeks is evaluated as follows.
clear and no change co"",a, ed to before the test - O
p, ec;~ e~l or cloudy - X
AccG,ding to Table 1, it is understood that FY~ IeS 1, 3, 4, and 7
which are compositions of the present invention have both improved solution
feel and good storage stability.
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TABLE 1
Standard 1 2 3 4 5 6 7 8
product
Sodium C,2-l4
alkyl ethoxy (5
ave.) sulfate 11.7 11.7 - - - - - - -
AmmOniUm C12-14
alkyl ethoxy (3
ave.) sulfate - - 12.0 12.0 12.012.0 12.0 12.0 12.0
Cl2-~4 alkyl
dimethyl amine
oxide 3.1 3.13.0 3.0 3.0 3.0 3.0 3.0 3.0
Cl2 alkyl diethanol
amide 4.4 4-4 4-5 4-5 4-5 4-5 4-5 4-5 4-5
Cl2-l4 alkyl N-
methyl glucoamide - - 5.0 5.0 5.0 5.0
Cl2 alkyl ethoxy
(3 ave.) alcohol 2.3 2.3
C9-ll alkyl ethoxy
(8 ave.~ alcohol - - 1.5 1.5 1.5 1.5 1.5 1.5 1.5
Sodium toluene
sulfonate 2.3 2.3
Sodium cumene
sulfonate - - 5-0 5.0 5.0 5.0 5.0 5.0 5.0
Mg++(MgC12-7H20) - - 0.7 0.5 0.36 0.1 0.7 0.5 0.1
Ca+ +(CaC12) - 0.3 - 0.2 0.14 0.6 - 0.2 0.6
Ethanol 2.5 2.54.2 4.2 4.2 4.2 2.8 2.8 2.8
Water and
other minors bal~ bal bal bal bal bal bal bal bal
Solution feel(point) Std+2.0 -1.38 -0.88+0.75+0.75 -1.38 -0.5 +0.13
(comparison example) - Std - ex.2 ex.2 ex.2 - ex.6 ex.6
(improved points) - +2.0 - +0.5 +2.13+2.13 - +0.88+ 1.25
(evaluation) - 0 - 0 0 0 - 0 0
bal = balance
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-- 14 --
TABLE 1
(continuedJ
Standard 1 2 3 4 5 6 7 8
product
Storage stability
(-5~C) 0 0 0 0 0 X 0 0 X
(40~C) 0 0 0 0 0 X 0 0 X
