U.S. patent number 3,676,374 [Application Number 05/091,596] was granted by the patent office on 1972-07-11 for enzyme-containing liquid detergent compositions.
This patent grant is currently assigned to The Procter & Gamble Company. Invention is credited to Daniel Guy Jean Biard, Wahib Nassif Zaki.
United States Patent |
3,676,374 |
Zaki , et al. |
July 11, 1972 |
ENZYME-CONTAINING LIQUID DETERGENT COMPOSITIONS
Abstract
Liquid detergent compositions comprising a mixture of from about
2 percent to about 35 percent of an alkane sulfonate, alpha-olefin
sulfonate, or mixtures thereof having from about 10 to about 26
carbon atoms in the hydrocarbon chain; from about 2 percent to
about 30 percent of an ethoxylated alcohol or alkyl phenol or
sulfate thereof; and from about 0.001 percent to about 5.0 percent
of enzyme. The detergent compositions have desirable enzyme
activity upon storage and exhibit desirable levels of soil-removal
performance.
Inventors: |
Zaki; Wahib Nassif (Bruxelles,
BE), Biard; Daniel Guy Jean (Bruxelles,
BE) |
Assignee: |
The Procter & Gamble
Company (Cincinnati, OH)
|
Family
ID: |
19726203 |
Appl.
No.: |
05/091,596 |
Filed: |
November 20, 1970 |
Foreign Application Priority Data
Current U.S.
Class: |
510/393; 510/321;
510/429; 510/428; 510/424 |
Current CPC
Class: |
C11D
3/38618 (20130101); C11D 1/66 (20130101); C11D
1/83 (20130101); C11D 3/38663 (20130101); C11D
1/29 (20130101); C11D 1/37 (20130101) |
Current International
Class: |
C11D
1/02 (20060101); C11D 1/37 (20060101); C11D
1/66 (20060101); C11D 1/83 (20060101); C11D
3/386 (20060101); C11D 3/38 (20060101); C11D
1/29 (20060101); C11d 001/37 (); C11d 001/83 () |
Field of
Search: |
;252/DIG.12,532,533,536,554,551,552,555,89,535 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Rosdol; Leon D.
Assistant Examiner: Pitlick; Harris A.
Claims
What is claimed is:
1. A liquid detergent composition consisting essentially of, by
weight of the detergent composition, a mixture of:
a. from about 2 percent to about 35 percent of an alkane sulfonate,
or an alpha-olefin sulfonate which consists of a mixture of from
about 30 percent to about 70 percent of Component A, from about 20
percent to about 70 percent of Component B, and from about 2
percent to about 15 percent of Component C, wherein
1. said Component A is a mixture of double-bond positional isomers
of water soluble salts of alkene-1-sulfonic acids containing from
about 10 to about 24 carbon atoms, said mixture of positional
isomers including about 10 percent to about 25 percent of an
alpha-beta unsaturated isomer, about 30 percent to about 70 percent
of a beta-gamma unsaturated isomer, about 5 percent to about 25
percent of a gamma-delta unsaturated isomer, and about 5 percent to
about 10 percent of a delta-epsilon unsaturated isomer;
2. said Component B is a mixture of water soluble salts of
bifunctionally-substituted sulfur-containing saturated aliphatic
compounds, containing from about 10 to about 24 carbon atoms, the
functional units being hydroxy and sulfonate radicals with the
sulfonate radical always being on the terminal carbon and the
hydroxyl radical being attached to a carbon atom at least two
carbon atoms removed from the terminal carbon atom, at least 90
percent of the hydroxy radical substitutions being in the three,
four, and five positions; and
3. said Component C is a mixture comprising from about 30 - 95
percent water soluble salts of alkene disulfonates containing from
about 10 to about 24 carbon atoms, and from about 5 percent to
about 70 percent water soluble salts of hydroxy disulfonates
containing from about 10 to about 24 carbon atoms, said alkene
disulfonates containing a sulfonate group attached to a terminal
carbon atom and a second sulfonate group attached to an internal
carbon atom not more than about six carbon atoms removed from said
terminal carbon atom, the alkene double bond being distributed
between the terminal carbon atom and about the seventh carbon atom,
said hydroxy disulfonates being saturated aliphatic compounds
having a sulfonate radical attached to a terminal carbon, a second
sulfonate group attached to an internal carbon atom not more than
about six carbon atoms removed from said terminal carbon atom, and
a hydroxy group attached to a carbon atom which is not more than
about four carbon atoms removed from the site of attachment of said
second sulfonate group or mixtures of said alkane sulfonate and
said olefin sulfonate, said compounds having from about 10 to about
26 carbon atoms in the hydrocarbon chain;
(b) from about 2 percent to about 30 percent of a compound having
the formula:
AE.sub.n X
wherein A is alkyl of from eight to 30 carbon atoms or alkyl phenyl
with from three to 22 carbon atoms in the alkyl chain; E is an
alkyleneoxy radical selected from the group of ethyleneoxy and
propyleneoxy; n is an integer from 1 - 30 and X is hydroxyl or
sulfate;
(c) from about 0.001 percent to about 5.0 percent of a proteolytic
enzyme,
and the balance of the composition to 100 percent being water.
2. The liquid detergent composition of claim 1 wherein component
(a) is present in an amount from about 10 percent to about 25
percent and component (b) is present in an amount from about 5% to
about 20 percent and wherein X is sulfate.
3. The liquid detergent composition of claim 2 wherein component
(b) has from 10 to 16 carbon atoms in the alkyl chain.
4. The liquid detergent composition of claim 1 wherein the alkane
sulfonate or alpha-olefin sulfonate has from 12 - 20 carbon atoms
in the hydrocarbon chain.
5. The liquid detergent composition of claim 1 wherein the amount
of proteolytic enzyme employed is from about 0.1 percent to about
2.0 percent.
6. The liquid detergent composition of claim 5 wherein the
proteolytic enzyme is from Bacillus subtilis.
Description
This invention pertains to liquid detergent compositions containing
enzymes, particularly proteases.
It is well known that the formulation of enzyme containing liquid
detergent compositions is a very delicate task due to the rapid
decrease of the enzymatic activity in aqueous medium during
storage. In fact, the difficulties flowing from the inherent losses
in enzymatic activity are such that until now, this problem could
not be solved satisfactorily. The significance of these obstacles
will even be better understood when considering that the
desirability of formulating liquid detergent compositions
containing enzymes has long been known. The absence of any
practical solution to this highly unsatisfactory enzymatic activity
retention in aqueous detergent medium confirms all the more the
difficulties in selectively formulating liquid detergent
compositions containing enzymes which might be of commercial
interest.
THE PRIOR ART
The state of the art is scattered with respect to this particular
aspect of detergent technology. So, for example, it is known from
Dutch Pat. application No. 66.08106 that proteolytic enzymes do
only have a limited stability in aqueous medium. In addition to
this, it is expressed that most detergent ingredients such as
phosphates, carbonates, and sulfates have an adverse effect on the
activity of these enzymes as well as on their stability in
detergent solution. This reference amounts to an explanation why
(proteolytic) enzymes are until now only incorporated into granular
detergent compositions. No concrete solution however is suggested
relative to the deficient stability. South African Pat.
specification No. 67/6837 pertains to dishwashing compositions
containing detergent active compounds, builders and amylases. The
compositions, can, among others, be in liquid state but in that
event, they contain alcohol in admixture with nonionics as
stabilizing agent for the amylolytic activity. This use of
alcohols, if desired, in admixture with nonionics as stabilizing
agents for certain enzymes is also known from Dutch Pat.
application No. 68.16356.
SUMMARY OF THE INVENTION
It has now been found that enzyme containing liquid detergent
compositions can be prepared having an unexpected storage stability
and an unforeseeable soil-removal performance versus what can be
obtained from enzyme-containing liquid detergent compositions
currently known. These inventive liquid detergent compositions
comprise a mixture of
A. from about 2 percent to about 35 percent by weight of alkane
sulfonates or alpha-olefin sulfonates or mixtures thereof, both
having from about 10 about 26 carbon atoms in the hydrocarbon
chain;
b. from about 2 percent to about 30 percent by weight of a compound
having the general formula:
AE.sub.n X
wherein A represents an alkyl chain with from eight to 30 carbon
atoms or an alkyl phenyl with from three to 22 carbon atoms in the
alkyl chain; E an alkyleneoxy radical, n an integer from one to 30
and X represents either hydroxyl, or a sulfate radical; and
c. from about 0.001 percent to about 5.0 percent by weight of
enzyme.
DETAILED DESCRIPTION OF THE INVENTION
Ingredient AE.sub.n X should be present in an amount from about 2
percent to about 30 percent by weight and preferably from about 5
percent to about 20 percent by weight. The lower limit reflects
minimum perceptible performance while the 30 percent upper limit
has been set so that any additional incorporation of AE.sub.n X is
only likely to result in an expected performance increase. The
radical A can be an alkyl chain with from about eight to about 30
carbon atoms, preferably from about 10 to about 16 carbon atoms. In
the event A is an alkyl phenyl radical, the alkyl group should
contain from about three to about 22 carbon atoms, and preferably
from about six to about 12 carbon atoms. E represents a
poly(alkyleneoxy) radical preferably derived from ethylene oxide or
propylene oxide or mixtures of both, while n stands for an integer
in the range from one to 30, preferably two to 18. X represents
either a hydroxyl or a sulfate radical.
The preferred surface-active agents, corresponding to the general
formula AE.sub.n X, suitable for being used in the compositions
claimed are derived from the condensation products of fatty
alcohols with from about two to about 18 moles of ethylene oxide,
either bearing a terminal hydroxyl radical or being present in its
sulfated form. Particularly preferred are the alkali metal and
ammonium salts of the sulfated condensation product of one mole of
a mixture of straight chain C.sub.12 to C.sub.14 alcohols with
three moles of ethylene oxide.
The percent compositions should contain from about 2 percent to
about 35 percent by weight, preferably from about 10 percent to
about 25 percent by weight, of alkane sulfonates or alpha-olefin
sulfonates or mixtures thereof, both having from about 10 to about
26 carbon atoms, preferably from about 12 to about 20 carbon atoms
in the hydrocarbon chain. The alkane sulfonates (paraffin
sulfonates) can, for example, be prepared by the sulfoxidation
process. The reaction product obtained from that process after
neutralization and purification steps at temperatures in the range
from 200.degree. C to 300.degree. C is present as an anhydrous melt
having about the following compositions: alkane mono-sulfonates,
from 81 to 83 percent; alkane disulfonates, from 10 to 12 percent;
non-reacted paraffin, 1 percent; sodium sulfate, about 6 percent.
The preferred alkane sulfonate of this invention has the following
chain distribution: C.sub.13 alkane sulfonate: 5 percent; C.sub.14
alkane sulfonate: 16 percent; C.sub.15 alkane sulfonate: 30
percent; C.sub.16 alkanesulfonate: 30 percent; C.sub.17 alkane
sulfonate: 15 percent; C.sub.18 alkane sulfonate: 4 percent. The
alkane sulfonates used in all the Examples correspond to this
composition.
The preferred olefin sulfonate actives are described in detail in
U.S. Pat. No. 3,332,880 issued July 25, 1967 to Kessler et al. They
consist of a mixture of from about 30 to 70 percent of Component A,
preferably 35 to 65 percent; about 20 to 70 percent of Component B,
preferably 25 to 60 percent; and about 2 to 15 percent of Component
C, preferably 3 to 12 percent.
Component A is a mixture of double-bond positional isomers of
water-soluble salts of alkene-1-sulfonic acids containing from
about 10 to about 24 carbon atoms, said mixture of positional
isomers including about 10 percent to about 25 percent of an
alpha-beta unsaturated isomer, about 30 percent to about 70 percent
of a beta-gamma unsaturated isomer, about 5 percent to about 25
percent of a gamma-delta unsaturated isomer, and about 5 percent to
about 10 percent of a delta-epsilon unsaturated isomer. Component B
is a mixture of water-soluble salts of bifunctionally-substituted
sulfur-containing saturated aliphatic compounds containing from
about 10 to about 24 carbon atoms, the functional units being
hydroxy and sulfonate radicals with the sulfonate radical always
being on the terminal carbon and the hydroxyl radical being
attached to a carbon atom at least two carbon atoms removed from
the terminal carbon atom, at least 90 percent of the hydroxy
radical substitutions being in the 3--, 4--, and 5-- positions.
Component C is a mixture comprising from about 30 percent to 95
percent water-soluble salts of alkene disulfonates containing from
about 10 to about 24 carbon atoms, and from about 5 percent to
about 70 percent water-soluble salts of hydroxy disulfonates
containing from about 10 to about 24 carbon atoms, said alkene
disulfonates containing a sulfonate group attached to a terminal
carbon atom and a second sulfonate group attached to an internal
carbon atom not more than about six carbon atoms removed from said
terminal carbon atom, the alkene double bond being distributed
between the terminal carbon atom and about the seventh carbon atom,
said hydroxy disulfonates being saturated aliphatic compounds
having a sulfonate radical attached to a terminal carbon, a second
sulfonate group attached to an internal carbon atom not more than
about six carbon atoms removed from said terminal carbon atom, and
a hydroxy group attached to a carbon atom which is not more than
about four carbon atoms removed from the site of attachment of said
second sulfonate group.
The enzymes suitable for being incorporated into the inventive
compositions can be of any origin, although they are mostly of
animal and vegetable and particularly of bacterial origin. The
enzyme preparations considered are mostly constituted by a mixture
of different active substances all of which are characterized by a
very specific enzymatic activity. They can be classified according
to their activity. Examples of such sub-classes of enzymes are
proteases, carbohydrases, esterases, oxydo-reductases, catalysases,
peroxydases, ureases, demolases, isomerases, nucleases and so on.
As referred to hereinbefore, commercial enzyme preparations are
seldom pure but constitute a mixture of different types of enzymes.
Preferred for use in the detergent compositions of this invention
are proteolytic enzyme preparations. A preferred enzyme component
is a proteolytic enzyme, a serine protease. It is commercially
available under the tradename of "ALCALASE" and manufactured by
Novo Industri A/S, Copenhagen, Denmark. Other enzyme preparations
being almost identical to ALCALASE for use in the detergent
compositions of this invention are:
proteolytic enzyme derived from the genus Bacillus; this component
is described in U.S. Pat. application Ser. No. 761,546, filed on
Sept. 23, 1968, and has been deposited under the number 10 147 with
The National Collection of Industrial Bacteria, Torry Research
Station, Aberdeen Scotland.
protease mixture derived from Bacillus subtilis as sold by KALI
CHEMIE, Germany.
Takeda Fungal Alkaline Protease; Takeda Chemical Industries Ltd.
Osaka, Japan.
The enzyme is to be used in a quantity of from about 0.005 percent
to about 5 percent by weight of the composition. A preferred range
includes a quantity of from about 0.1 percent to about 1.5 percent
by weight of the enzyme preparation. Several non-proteolytic enzyme
components can be mixed in wide ranges with the proteases species
for use in the preferred embodiments of this invention. So for
example, amylolytic enzyme preparations can advantageously be
added. "AMYLASE THC-250" manufactured by Rapidase, Seclin, France,
represents an example of an amylolytic enzyme suitable for being
used.
In addition to the essential ingredients listed hereinbefore, the
inventive compositions can contain usual amounts of other
ingredients and/or minor additives, all having well-defined
functions in detergent technology and all being frequently present
in the type of detergent compositions claimed. So, these
compositions can contain solubilizing compounds which contribute in
maintaining a uniform liquid detergent composition even during
prolonged storage. From zero to 20 percent of the solubilizing
compounds are usually incorporated into liquid detergent
compositions. Typical examples suitable for the compositions
claimed are the sodium salts of benzene sulfonate, toluene
sulfonate, and xylene sulfonate. Lower alcohols can also
satisfactorily be used, preferably those having from one through
five carbon atoms.
Alkaline detergent builders can be employed in the compositions of
this invention. In the event such builders are employed, their
quantity does not normally exceed 20 percent because of the
phase-stability problem which might flow from the use of higher
quantities. Specific examples of inorganic builders suitable for
use herein are alkali metal carbonates, phosphates, polyphosphates
and silicates. The potassium and sodium salts of these builders
are, for solubility reasons, the most suitable ones. Useful
alkaline organic builders include the polyphosphonates,
poly-acetates and polycarboxylates. Examples of polyphosphonates
include the sodium and potassium salts of ethylene diphosphonic
acid, ethane-1-hydroxy-1,1-diphosphonic acid and
ethane-1,1,2-triphosphonic acid. Polyacetate builders useful herein
include the sodium, potassium, lithium, ammonium and substituted
ammonium salts of ethylene diamine tetra-acetic acid;
N-(2-hydroxyethyl)-ethylene diamine triacetic acid;
N-(2-hydroxyethyl)-nitrilo diacetic acid; diethylenetriamine; and
pentacetic acid. Water-soluble salts of polycarboxylate builders
can also be used in these compositions. They are described in more
detail in U.S. Pat. No. 3,308,067.
Enzyme-stabilizing agents in a quantity from 0 to 5 percent can
also be used in the liquid detergent compositions of this
invention. They have been found to be quite useful as they tend to
improve the performance and particularly the storage stability
advantages obtainable from the liquid detergent compositions
claimed. Water-soluble calcium and magnesium chlorides, lactates
and acetates represent the preferred stabilizing agents.
In addition, the liquid detergent compositions of the present
invention can also contain other usual detergents additives not
specifically referred to hereinbefore. For example, perfumes,
anti-tarnishing agents, anti-redisposition agents, bacteriostatic
agents, dyes, optical brighteners, fluorescers, suds depressors,
suds boosters and the like can all be utilized herein without
detracting from the advantageous stability and performance
properties of the compositions of this invention.
The following Examples are illustrative of, but not limitative of,
the claimed invention.
TEST METHOD
The performance advantages of the enzyme-containing detergent
compositions of the invention are apparent from their use in the
decomposition of standardized amounts of soil. In more detail,
egg-soiled microscopic slides are immersed in a water-diluted
solution of the test detergent composition. This detergent solution
is then stirred and kept at 50.degree. C by the aid of a
heater-stirrer. The egg-soil testing slides are prepared by dipping
microscopic slides into an intimately mixed yolk and egg-white.
Then the slides are dried during 45 minutes at 50.degree. C and
cooked for half an hour at 105.degree. C. The enzymatic activity is
expressed as the average time required for achieving 95 percent
soil-removal (T.sub.95). Day-to-day variation of testing results
are minimized by carrying out a reference run with a solution
containing standardized amounts of surface-actives and enzymes.
The enzymatic activity can advantageously be expressed as a
"cleaning index" (CI) corresponding to the following
definition:
This cleaning index comes actually quite close to the real
enzymatic activity in washing solution under current usage
conditions and is not affected by uncontrollable day-to-day
variations.
EXAMPLE I
The cleaning performance superiority of the compositions claimed is
readily recognizable from the following testing results. These
experiments have been carried out with a set of conditions as
listed
washing solution prepared by city water at 20 grains/gallon
hardness
washing solution pH: 8.5; temperature: 50.degree. C
product concentration in solution: see table
enzyme concentration in washing solution: 25 ppm ALCALASE
containing 1.5* *(Anson, Journ. Gen Physiol. 22, 79 (1939).)
AU/g
A B C Composition (reference) % by weight
__________________________________________________________________________
linear C.sub.12 alkylbenzene sulfonate- 19 sodium salt sulfated
(ethoxy).sub.3 coconut alcohol- 19 20 20 sodium salt coconut
monoethanolamide 2 alkane sulfonate-sodium salt (C.sub.15.sub.-16)
20 olefinsulfonate-sodium salt (C.sub.15.sub.-16 20
__________________________________________________________________________
The CI's of the compositions listed are:
Product concentration in solution (% by weight) A B C
__________________________________________________________________________
0.10 110 0.125 140 0.185 140 0.25 100 145 140 0.30 155 0.35 170
__________________________________________________________________________
these results show the performance advantages achievable by the use
of enzymes in combination with the detergent combinations of this
invention.
EXAMPLE II
The inventive performance advantages are brought into prominence by
comparing the CI's (cleaning indexes) measured for various active
systems.
The test conditions are as indicated in Example I except for what
concerns the product concentration in solution which is 0.25
percent by weight.
% by weight surfactant in finished Surfactant system product CI
__________________________________________________________________________
(a) linear C.sub.12 alkyl benzene-sulfonate-Na 20 sulfated
(ethoxy).sub.3 -Coconut alcohol-Na 20 100 (b) alkanesulfonate-Na
(C.sub.15.sub.-16) 20 sulfated (ethoxy).sub.3 -coconut alcohol-Na
20 300 (c) olefin sulfonate-Na (C.sub.15.sub.-16) 20 sulfated
(ethoxy).sub.3 -coconut alcohol-Na 20 380 (d) linear C.sub.12 alkyl
benzene sulfonate-Na 20 sulfate-(ethoxy).sub.12 coconut alcohol-Na
20 100 (e) olefin sulfonate-Na (C.sub.15.sub.-16) 20 sulfated
(ethoxy).sub.12 20 400 coconut alcohol-Na (f) alkanesulfonate-Na
(C.sub.15.sub.-16) 20 sulfated (ethoxy).sub.3 -coconut 20
alcohol-Na condensate of tallow alcohol with 11 moles of ethylene
oxide 10 330 (g) linear C.sub.12 alkyl 40 benzene sulfonate-Na
condensate of tallow alcohol with 11 moles of ethylene oxide 10 100
__________________________________________________________________________
The improvement in cleaning performances as expressed by the CI's
for trails (b), (c), (e) and (f) appears to be significant and also
was unforeseeable.
EXAMPLE III
Different enzyme preparations have successively been incorporated
into a liquid detergent composition with the following detergent
system.
alkanesulfonate-Na (C.sub.15.sub.-16) 20% by weight sulfated
(ethoxy).sub.3 -coconut alcohol-Na 20% by weight
The test conditions and the reference sample composition are the
same as for Example I.
enzyme ppm enzyme activity in washing Enzyme Preparation in AU/g
solution CI ALCALASE 1.5 25 145 Protease mixture 1.5 25 140 derived
from Bacillus subtilis (KALI)* ALCALASE 1.5 12.5 90 MONSANTO DA-10
1.8 12.5 80 KALI 1.5 12.5 90
the CI values confirm that the active system is effective with
different types of enzymes.
EXAMPLE IV/A
Liquid detergent compositions were used for comparative performance
testing thereby maintaining the following conditions:
washing solutions prepared with city water 20 grains/gallon
hardness
solution pH = 7.0
temperature: 50.degree. C
finished product concentration in solution: 0.25 percent
enzyme concentration in washing solution: 25 ppm ALCALASE (1.5
AU/g)
% by weight in Ingredients finished product CI (a) linear C.sub.12
alkyl benzene sulfonate-Na 20 condensate of monylphenol with 9
moles of ethylene oxide 10 100 (b) alkanesulfonate-Na
(C.sub.15.sub.-16) 20 condensate of nonylphenol with 9 moles of
ethylene oxide 10 200 *as sold by KALI CHEMIE, Germany
EXAMPLE IV/B
same conditions as example IV/A above
% by weight in Ingredients finished product CI (a) linear C.sub.12
alkyl benzene sulfonate-Na 20 condensate of tallow alcohol with 25
moles of ethylene oxide 10 100 (b) alkanesulfonate-Na
(C.sub.15.sub.-16) 20 condensate of tallow alcohol with 25 moles of
ethylene oxide 10 140
The unexpected retention of enzymatic activity in liquid detergent
compositions under prolonged storage conditions is apparent from
the following Example.
EXAMPLE V
Liquid detergent samples are stored during one week at 35.degree.
C. The enzymatic activity is determined before and after
storage.
Detergent compositions tested:
active system: see below
ethanol: 12 percent by weight
enzyme preparation: 1 percent by weight ALCALASE (1.5 AU/g)
pH of composition is within the range from 7.0 to 9.0
water: balance to 100.
% of initial % by wt. enzymatic acti- actives in vity remaining
Active System detergent after test (a) linear C.sub.12 alkyl
benzene sulfonate Na salt 19 sulfated (ethoxy).sub.3 coconut
alcohol-Na salt 19 coconut monoethanolamide 2 25 (b) alkane
sulfonate-Na salt (C.sub.15.sub.-16) sulfated (ethoxy).sub.3
coconut alcohol-Na salt 19 coconut monoethanolamide 2 50 (c) olefin
sulfonate-Na salt (C.sub.15.sub.-16) 19 sulfated (ethoxy).sub.3
coconut alcohol-Na salt 19 coconut monoethanolamide 2 50 (d)
C.sub.12 linear alkyl benzene 20 sulfonate-Na salt condensate of
nonylphenol with 9 moles of ethylene oxide 10 (e) alkane
sulfonate-Na salt (C.sub.15.sub.-16) 20 condensate of nonylphenol
with 9 moles of ethylene oxide 10 50 (f) C.sub.12 linear alkyl
benzene sulfonate-Na salt 20 condensate of tallow alcohol with 25
moles of ethylene oxide 10 30 (g) alkane sulfonate-Na salt
(C.sub.15.sub.-16) 20 condensate of tallow alcohol with 25 moles of
ethylene oxide 10 55
The superior stabilization of the active enzymes in (b), (c), (e)
and (g) is related to the choice of the active system.
EXAMPLE VI
Liquid detergent compositions identical to those described in
Example V, except that 0.5 percent by weight of Ca acetate is
added, were used for comparative testing as indicated in Example
V.
% of initial % by wt. enzymatic acti- actives in vity retained
Active System detergent after test (a) linear alkylbenzenesulfonate
Na-salt (C.sub.12) 19 sulfated (ethoxy).sub.3 coconut alcohol-Na
salt 19 coconut monoethanolamide 2 25 (b) alkane sulfonate-Na salt
(C.sub.15.sub.-16) 19 sulfated (ethoxy).sub.3 coconut alcohol-Na
salt 19 coconut monoethanolamide 2 85
These results show the increase in the stabilizing effect attained
with the addition of a calcium salt to a composition as
claimed.
EXAMPLE VII/A
The unforeseeable enzymatic stability can be enhanced as already
apparent from Example VI through the addition of calcium and/or
magnesium salts to the composition claimed. The following data
serve as a further illustration of this.
The active composition used corresponds to composition (b) of
Example V containing ALCALASE as enzyme preparation.
pH liquid composition: 7.0
Stabilizer salt used in detergent at a level of 1.0 percent by
weight.
storage temperature: 20.degree. C.
% of initial enzymatic Stabilizer Salt activity retained after 5
weeks Without 90 Calcium acetate 95 Magnesium acetate 95
EXAMPLE VII/B
The experimental conditions are the same as in Example VII/A above
except:
Storage temperature: 35.degree. C.
% in enzymatic activity Stabilizer Salt retained after 5 weeks
Without 25 Calcium chloride 50 Calcium acetate 75 Magnesium
chloride 50 Magnesium acetate 55
The data show the stabilizing effect obtained from the inventive
compositions through the addition of stabilizing salts. No effect
is noticed, however, when these stabilizers salts are added to the
compositions representing the state of the art.
EXAMPLE VIII
Liquid detergent compositions were stored during two months at
20.degree. C. The enzymatic activity is determined before and after
storage.
Detergent compositions tested:
Active system: see below
ethanol: 12 percent by weight
enzyme preparation: 1 percent by weight ALCALASE (1.5 AU/g)
pH of composition is within the range from 7.0 to 9.0
water: balance to 100
% of initial % by wt. enzymatic actives in activity Active System
detergent retained (a) Linear C.sub.12 alkylbenzene- sulfonate Na
salt 20 Condensate of tallow alcohol with 25 moles of ethylene
oxide 10 75 (b) Alkane sulfonate Na salt (C.sub.15.sub.-16) 20
Condensate of tallow alcohol with 25 moles ethylene oxide 10 90 (c)
Linear C.sub.12 alkylbenzene- sulfonate Na salt 20 Condensate of
nonylphenol with 9 moles of ethylene oxide 10 75 (d) Alkane
sulfonate Na salt (C.sub.15.sub.-16) 20 Condensate of nonylphenol
with 9 moles of ethylene oxide 10 90 (e) Alkane sulfonate Na salt
(C.sub.15.sub.-16) 19 Sulfated (ethoxy).sub.3 coconut alcohol Na
salt 19 Coconut monoethanolamide 2 90
* * * * *