U.S. patent number 3,635,828 [Application Number 04/888,955] was granted by the patent office on 1972-01-18 for enzyme-containing detergent compositions.
This patent grant is currently assigned to The Procter & Gamble Company. Invention is credited to Lawrence Benjamin, John F. Sullivan.
United States Patent |
3,635,828 |
Benjamin , et al. |
January 18, 1972 |
**Please see images for:
( Certificate of Correction ) ** |
ENZYME-CONTAINING DETERGENT COMPOSITIONS
Abstract
Soil- and stain-removing detergent compositions consisting
essentially of a water-soluble synthetic organic detergent and from
0.01 to 2 percent of a lipoxidase having enzymatic activity over
the ranges of 5.degree. C. to 70.degree. C. and pH 5 to 11 are
disclosed. The lipoxidase-containing detergent compositions can
optionally contain a fatty acid substrate having cis-, cis-double
bonds or an alkyl ester thereof for coupled oxidation of stains.
Inorganic peroxy compounds can also be employed. The compositions
of the invention are particularly adapted to the treatment of
textile materials having soils or stains which have a content of
polyunsaturated components.
Inventors: |
Benjamin; Lawrence (Springfield
Township, Hamilton County, OH), Sullivan; John F. (Colerain
Township, Hamilton County, OH) |
Assignee: |
The Procter & Gamble
Company (Cincinnati, OH)
|
Family
ID: |
25394240 |
Appl.
No.: |
04/888,955 |
Filed: |
December 29, 1969 |
Current U.S.
Class: |
510/305; 510/283;
510/491; 510/530; 510/320; 424/94.4; 435/263 |
Current CPC
Class: |
C11D
3/38654 (20130101) |
Current International
Class: |
C11D
3/386 (20060101); C11D 3/38 (20060101); C11d
007/38 () |
Field of
Search: |
;252/99,89,DIG.12
;195/2,63,68 ;424/94 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Weinblatt; Mayer
Claims
What is claimed is:
1. An enzyme-containing detergent composition having soil- and
stain-removal properties consisting essentially of:
A. from 1 percent to 50 percent of a water-soluble synthetic
organic detergent; and
B. from 0.01 percent to 2 percent by weight of the
enzyme-containing detergent composition of a lipoxidase having
lipoxidase enzymatic activity in the temperature range of from
5.degree. C. to 70.degree. C. and in the pH range of from 5 to
11.
2. The enzyme-containing detergent composition of claim 1 wherein
the lipoxidase is a preparation consisting essentially of a mixture
of from 1 percent to 50 percent lipoxidase and from 50 percent to
99 percent of inert carrier or vehicle materials.
3. The composition of claim 2 wherein the lipoxidase preparation
has an activity of from 10,000 to 50,000 activity units/mg.
4. The detergent composition of claim 3 wherein the lipoxidase
preparation is present in an amount by weight of from 0.1 percent
to 20 percent.
5. The detergent composition of claim 4 wherein the lipoxidase is
soybean lipoxidase.
6. The detergent composition of claim 5 wherein a water-soluble
alkaline detergency builder salt is present in a ratio of said
water-soluble alkaline detergency builder salt to water-soluble
synthetic organic detergent of from 1:4 to 20:1.
7. The detergent composition of claim 6 wherein a fatty acid having
from 12 to 20 carbon atoms and methylene-interrupted cis-,
cis-double bonds or a C.sub.1 to C.sub.3 alkyl ester thereof is
present.
8. The detergent composition of claim 7 wherein an inorganic peroxy
compound is present in an amount of from 1 percent to 30
percent.
9. The detergent composition of claim 8 wherein the fatty acid is
linoleic acid.
10. The detergent composition of claim 9 wherein the inorganic
peroxy compound is sodium perborate.
Description
BACKGROUND OF THE INVENTION
This invention relates to enzyme-containing detergent compositions.
More particularly, it relates to enzyme-containing detergent
compositions useful as laundering or presoaking compositions and
containing an organic synthetic detergent and a lipoxidase.
The employment of enzymes in admixture with detergent compositions
is known as described, for example, in U.S. Pat. No. 1,882,279
issued Oct. 11, 1932. Similarly, British Pat. No. 814,772 issued
June 10, 1959, East German Pat. NO. 14,296 published Jan. 6, 1958,
and Jaag, Seifen, Ole Fette, Wachse 88, No. 24, pp. 789-793 (Nov.
1962) disclose detergent compositions containing enzymes. While the
employment of proteolytic and amylolytic enzymes in detergent
compositions to degrade or otherwise alter proteinaceous and
starchy soils and stains has been known, the formulation of
detergent compositions which permit the removal of additional soils
and stains is a desirable objective. It will be appreciated that a
normal household laundering situation presents a complex and
difficult cleaning problem inasmuch as the soils and stains
normally encountered in a household laundering situation are
comprised of a broad spectrum of substance of varying composition.
Notwithstanding the employment of soaking or laundering
compositions containing proteases and/or amylases, certain
difficulty removable soils and stains either do not respond to such
treatment or are not substantially degraded or altered and thereby
rendered more easily removable by the detersive action of a
detergent compound. In some instances these difficulty removable
soils and stains serve as binding agents for nondigestable and
relatively unalterable soils and stains. Examples of difficulty
removable stains are the oily and greasy stains having constituents
of polyunsaturated character. These stains include French salad
dressing, grease, mayonnaise and the like.
The formulation of detergent compositions having enzymes which
facilitate the removal of the soils and stains which frequently
remain notwithstanding the use of conventional enzyme-containing
detergent compositions is desirable from the standpoint of making
possible the removal of a greater range or spectrum of soils and
stains.
It is an object of the present invention to provide detergent
compositions having superior cleaning and laundering
properties.
It is another object of the present invention to provide cleaning
and laundering compositions which facilitate the removal of
difficulty removable soils and stains.
Still another object is the provision of detergent compositions
which facilitate the removal of soils and stains having a content
of polyunsaturated fats or derivatives thereof.
Another object of the invention is the provision of laundering
compositions adapted to the removal of a wide spectrum of soils and
stains.
Other objects of the invention will become apparent from a
consideration of the invention described in detail hereinafter.
SUMMARY OF THE INVENTION
This invention is based in part on the discovery that detergent
compositions comprising a water-soluble organic detergent compound
and a lipoxidase, alternatively termed a lipoxygenase, facilitate
the removal by soaking and laundering methods of soils and stains
having polyunsaturated components from textile materials and
thereby permit the removal of soils and stains which are difficulty
removable by the action of conventional enzyme-containing detergent
compositions. The invention thus involves the provision of
laundering and soaking detergent compositions consisting
essentially of:
A. from 1 percent to 50 percent of a water-soluble synthetic
organic detergent; and
B. from 0.01 percent to 2 percent of a lipoxidase having lipoxidase
enzymatic activity at a temperature of from 5.degree. C. to
70.degree. C. in the pH range of from 5 to 11.
DETAILED DESCRIPTION OF THE INVENTION
The lipoxidase-containing detergent compositions of the invention
contain as an essential component a water-soluble synthetic
detergent. The organic detergent compounds which can be used
include soap and anionic, nonionic, ampholytic and zwitterionic
synthetic detergents and mixtures thereof exemplified as
follows:
a. Water-soluble soap: Examples of suitable soaps for use in this
invention are the sodium, potassium, ammonium and alkanol ammonium
(e.g., triethanolammonium) salts of higher fatty acids containing
from about 10 to about 22 carbon atoms. Particularly useful are the
sodium and potassium salts of the mixture of fatty acids derived
from coconut oil and tallow, i.e., sodium and potassium tallow and
coconut soap.
b. Anionic synthetic nonsoap detergents, a preferred class, can be
broadly described as the water-soluble salts, particularly the
alkali metal salts, of organic sulfuric reaction products having in
their molecular structure an alkyl radical containing from about
eight to about 22 carbon atoms and a radical selected from the
group consisting of sulfonic acid and sulfuric acid ester radicals.
(Included in the term alkyl is the alkyl portion of higher acyl
radicals.) Important examples of the synthetic detergents which
form a part of the preferred compositions of the present invention
are the sodium or potassium alkyl sulfates, especially those
obtained by sulfating the higher alcohols (C.sub.8 -C.sub.18 carbon
atoms) produced by reducing the glycerides of tallow or coconut
oil; sodium or potassium alkyl benzene sulfonates, in which the
alkyl group contains from about nine to about 15 carbon atoms,
including those of the types described in U.S. Pat. Nos. 2,220,099
and 2,477,383 (the alkyl radical can be a straight or branched
aliphatic chain); sodium alkyl glyceryl ether sulfonates,
especially those ethers of the higher alcohols derived from tallow
and coconut oil; sodium coconut oil fatty acid monoglyceride
sulfates and sulfonates; sodium or potassium salts or sulfuric acid
esters of the reaction product of one mole of a higher fatty
alcohol (e.g., tallow or coconut oil alcohols) and about 1 to 6
moles of ethylene oxide; sodium or potassium salts of alkyl phenol
ethylene oxide ether sulfate with about 1 to about 10 units of
ethylene oxide per molecule and in which the alkyl radicals contain
from eight to about 12 carbon atoms; the reaction product of fatty
acids esterified with isethionic acid and neutralized with sodium
hydroxide where, for example, the fatty acids are derived from
coconut oil; sodium or potassium salts of fatty acid amide of a
methyl tauride in which the fatty acids, for example, are derived
from coconut oil; and others known in the art, a number
specifically set forth in U.S. Pat. Nos. 2,486,921, 2,486,922 and
2,396,278. Other important anionic detergents, sulfonated olefins,
are described in the U.S. Pat. No. 3,332,880 to Phillip E. Pflaumer
and Adrian Kessler issued July 25, 1967.
c. Nonionic synthetic detergents: One class can be broadly defined
as compounds produced by the condensation of alkylene oxide groups
(hydrophilic in nature) with an organic hydrophobic compound, which
may be aliphatic or alkyl aromatic in nature. The length of the
hydrophilic or polyoxyalkylene radical which is condensed with any
particular hydrophobic group can be readily adjusted to yield a
water-soluble compound having the desired degree of balance between
hydrophilic and hydrophobic elements. Another class has semipolar
characteristics. Preferred classes of nonionic synthetic detergents
are as follows:
1. A class of nonionic synthetic detergents under the trade name of
"Pluronic." These compounds are formed by condensing ethylene oxide
with a hydrophobic base formed by the condensation of propylene
oxide with propylene glycol. The hydrophobic portion of the
molecule which, of course, exhibits water insolubility, has a
molecular weight of from about 1,500 to 1,800. The addition of
polyoxyethylene radicals to this hydrophobic portion tends to
increase the water solubility of the molecule as a whole and the
liquid character of the product is retained up to the point where
the polyoxyethylene content is about 50 percent of the total weight
of the condensation product.
2. The polyethylene oxide condensates of alkyl phenols, e.g., the
condensation products of alkyl phenols having an alkyl group
containing from about six to 12 carbon atoms in either a
straight-chain or branched-chain configuration with ethylene oxide,
the said ethylene oxide being present in amounts equal to 5 to 25
moles of ethylene oxide per mole of alkyl phenol. The alkyl
substituent in such compounds may be derived from polymerized
propylene, diisobutylene, octene, or nonene, for example.
3. Those nonionic synthetic detergents derived from the
condensation of ethylene oxide with the product resulting from the
reaction of propylene oxide and ethylene diamine. For example,
compounds containing from about 40 percent to about 80 percent
polyoxyethylene by weight and having a molecular weight of from
about 5,000 to about 11,000 resulting from the reaction of ethylene
oxide groups with a hydrophobic base constituted of the reaction
product of ethylene diamine and excess propylene oxide, said base
having a molecular weight of the order of 2,500 to 3,000 are
satisfactory.
4. The condensation product of aliphatic alcohols having from eight
to 22 carbon atoms, in either straight-chain or branched-chain
configuration, with ethylene oxide, e.g., a coconut alcohol
ethylene oxide condensate having from 5 to 40 moles of ethylene
oxide per mole of coconut alcohol, the coconut alcohol fraction
having from 10 to 14 carbon atoms.
5. The ammonia, monoethanol and diethanol amides of fatty acids
having an acyl moiety of from about eight to about 18 carbon atoms.
These acyl moieties are normally derived from naturally occurring
glycerides, e.g., coconut oil, palm oil, soybean oil and tallow,
but can be derived synthetically, e.g., by the oxidation of
petroleum, or by hydrogenation of carbon monoxide by the
Fischer-Tropsch process.
6. Long chain tertiary amine oxides corresponding to the following
general formula
EXAMPLE IV
wherein R.sup.1 is an alkyl radical of from about eight to about 24
carbon atoms, R.sup.2 and R.sup.3 are each methyl, ethyl or
hydroxyethyl radicals, R.sup.4 is ethylene, and n equals from 0 to
about 10. The arrow in the formula is a conventional representation
of a semipolar bond. Specific examples of amine oxide detergents
include: dimethyldodecylamine oxide; cetyldimethylamine oxide;
bis-(2 -hydroxyethyl) dodecylamine oxide; bis-(hydroxyethyl)-3
-dodecoxy-1 -hydroxypropyl amine oxide.
7. Long chain tertiary phosphine oxides corresponding to the
following general formula RR' R" P O wherein R is an alkyl, alkenyl
or monohydroxyalkyl radical ranging from 10 to 24 carbon atoms in
chain length and R' and R" are each alkyl or monohydroxyalkyl
groups containing from one to three carbon atoms. The arrow in the
formula is a conventional representation of a semipolar bond.
Examples of suitable phosphine oxides are found in U.S. Pat. No.
3,304,263 of Feb. 14, 1967, and include: dimethyldodecylphosphine
oxide; diethyldodecylphosphine oxide; dimethyl-(2 -hydroxydodecyl
phosphine oxide.
8. Long chain sulfoxides having the formula
wherein R.sub.5 is an alkyl radical containing from about 10 to
about 28 carbon atoms, from zero to about five ether linkages and
from zero to about two hydroxyl substituents, at least one moiety
of R.sup.5 being an alkyl radical containing zero ether linkages
and containing from about 10 to about 18 carbon atoms, and wherein
R.sup.6 is an alkyl radical containing from one to three carbon
atoms and from one to two hydroxyl groups. Specific examples of
these sulfoxides are: dodecyl methyl sulfoxide; 3 -hydroxy tridecyl
methyl sulfoxide; 3 -methoxy tridecyl methyl sulfoxide; 3
-hydroxy-4 -dodecoxybutyl methyl sulfoxide.
d. Ampholytic synthetic detergents can be broadly described as
derivatives of aliphatic secondary and tertiary amines, in which
the aliphatic radical may be straight-chain or branched and wherein
one of the aliphatic substituents contains from about eight to 18
carbon atoms and one contains an anionic water-solubilizing group,
e.g., carboxy, sulfo, sulfato, phosphato, or phosphono. Examples of
compounds falling within this definition are sodium-3
-dodecylaminopropionate and sodium-3 -dodecylaminopropane
sulfonate.
e. Zwitterionic synthetic detergents can be broadly described as
derivatives of aliphatic quaternary ammonium, phosphonium, and
sulfonium compounds, in which the aliphatic radical may be
straight-chain or branched, and wherein one of the aliphatic
substituents contains from about eight to 18 carbon atoms and one
contains an anionic water-solubilizing group, e.g., carboxy, sulfo,
sulfato, phosphato, or phosphono. Examples of compounds falling
within this definition are 3
-(N,N-dimethyl-N-hexadecylammonio)propane- 1-sulfonate and 3
-(N,N-dimethyl-N-hexadecylammonio) 2 -hydroxy propane-1 -sulfonate
which are especially preferred for their excellent cool water
detergency characteristics. See, for example, Snoddy, et al.,
Canadian Pat. No. 708,148 issued Apr. 20, 1965.
Preferred detergents for use in the compositions of the invention
include the condensation products of 1 mole of aliphatic alcohol
having eight to 22 carbon atoms with from 5 to 40 moles of ethylene
oxide, e.g., tallow alcohol ethoxylated with 11 or 30 moles of
ethylene oxide and coconut alcohol ethoxylated with 6 moles of
ethylene oxide. Also preferred are the 3
-(N,N-dimethyl-N-alkylammonio)-2 -hydroxypropane-1 -sulfonates
wherein the alkyl has from eight to 22 carbon atoms, e.g.,
3-(N,N-dimethyl-N-coconutalkylammonio)-2 -hydroxypropane-1
-sulfonate and the 3 -(N,N-dimethyl-N-alkylammonio) propane-1
-sulfonates wherein the alkyl has from eight to 22 carbon atoms,
e.g., 3 -(N,N-dimethyl-N-hexadecylammonio) propane-1 -sulfonate.
These detergents are especially suitable herein by reason of their
excellent cleaning properties, compatibility with lipoxidase and
ready availability.
The organic detergent employed in the compositions of the invention
can vary in amount from 1 percent to 50 percent by weight of the
total composition. Compositions consisting essentially of a major
proportion of a suitable detergent compound and a minor amount of a
lipoxidase can be suitably employed. Variations in the amount of
detergent will depend on the intended use of the detergent
composition. Thus, compositions intended for use as washing
formulations will normally contain an amount of from 1 percent to
25 percent. Similarly, compositions intended for use as soaking
formulations preparatory to washing with a conventional or
enzyme-containing detergent composition will normally contain a
lesser proportion of detergent active corresponding to an amount of
from 1 percent to 20 percent and, preferably, 3 percent to 10
percent.
The lipoxidases of the invention are those which exhibit lipoxidase
activity under the conditions of temperature and pH normally
encountered in laundry situations. The lipoxidases suitable herein
are those which are characterized by sufficient enzymatic activity
at a temperature of from 5.degree. C. to 70.degree. C. in a pH
range of from 5 to 11 to alter or otherwise render more easily
removable the soils and stains which are normally encountered in a
laundering situation. While the precise mechanism by which the
lipoxidases of the invention function to remove soils and stains in
laundry soaking and washing operations is not completely
understood, it is believed that the lipoxidase is involved in the
oxidation of unsaturated fatty acids and esters containing the cis,
cis-1,4 -pentadiene system. The enzymatic attack appears to involve
the methylene-interrupted multiply-unsaturated system in which the
double bonds are cis, the simplest case of which is as follows:
While applicants do not wish to be bound by any precise theory or
mechanism, it is believed that the formation of hydroperoxide
compounds from unsaturated fatty acids or esters by the action of
lipoxidase and dissolved oxygen is involved. The conversion of such
unsaturated compounds via an oxidative mechanism to species which
are either less colored or are more readily removed from textile
materials is believed to be responsible at least in part for the
desirable soil- and stain-removing properties of the compositions
of the invention. The oxidative mechanism involving lipoxidase
dissolved oxygen and a cis, cis-1,4 -pentadiene system and
described by A. L. Tappel in "Enzymes," Boyer, Lardy and Myrback
(editors) Academic Press, p. 275 (1963) is believed to be in marked
contrast to the degradative, fragmentative and digestive mechanisms
thought to be involved in the removal of stains from textile
materials which are laundered with hydrolytic enzymes such as the
proteases and amylases.
Suitable lipoxidases of the invention include those of plant or
microbiological origin. Suitable plant lipoxidases include those
derived by known methods from legumes, cereals, grains and oil
seeds. Examples of such sources include soybeans, urd beans,
lentils, green peas, ming beans, peanuts, navy beans, red beans,
lima beans, alfalfa, wheat, barley and sunflower seeds.
A preferred lipoxidase of the invention is that derived from
soybeans. Soybean lipoxidase is well known, commercially available
and provides desirable removal of fatty and other stains in
presoaking and washing methods. The lipoxidases of the invention,
e.g., soybean lipoxidase, can be employed in either pure or impure
form, the latter being preferred from the standpoints of
availability and ease of handling. Pure crystalline lipoxidase can
be isolated from legumes such as soybeans or from green peas, pea
seeds, wheat, green beans, green bean seeds and the like by known
methods. A suitable extraction method for soybean lipoxidase
involves aqueous extraction at pH 4.5 from soybean meal, followed
by ammonium sulfate precipitation. Suitable extraction methods are
described by R. T. Holman, et al., "The Enzymes," 1 st ed., Vol.
II, Part I, pp. 564-565 (1951) and by S. A. Hale, et al., "Lipids,"
Vol. 4, No. 3, pp. 209-215 (May 1969 ).
Preferred herein are lipoxidase preparations obtained commercially
in combination with inert carrier or vehicle materials such as
carbohydrates, agglutinating proteins, inorganic salts such as
calcium sulfate, trypsin inhibitor, proteases, and the like. In
such preparations, the lipoxidase constitutes a minor component and
comprises from about 1 percent to 50 percent. The remaining 50
percent to 90 percent is comprised of the hereinbefore described
carrier materials. The commercially available lipoxidase-containing
preparations are preferred herein inasmuch as they are more readily
available than pure crystalline lipoxidase and provide desirable
levels of lipoxidase activity. Suitable examples of such
commercially available lipoxidase-containing preparations include
the soybean lipoxidase preparations available from the following
suppliers: P-L Biochemicals, Inc., Milwaukee, Wis.; Sigma Chemical
Co., St. Louis, Mo.; Nutritional Biochemical Corp., Cleveland,
Ohio; Worthington Biochemical Corp., Freehold, N.J.;
Gallard-Schlesinger Chem. Mfg. Copr., Carle Place, Long Island,
N.Y.; Mann Research Laboratories, New York, N.Y.
Lipoxidases of microbial origin and suitable for use herein include
bacterial and fungal lipoxides derived from fermentation broths.
Suitable examples of such lipoxidases are those obtained from
Aspergillus sojae, Aspergillus flavus, Aspergillus glaucus,
Aspergillus niger, Aspergillus elegans, Rhizopus usamii, Rhizopus
G. 34 Yamasake, Rhizopus G. 36 Yamasake, Rhizopus tritici,
Penicillium rugulosum and Penicillium 15 described by H. Fukuba,
Nippon Nayu Kayuku Kaishi 26, 167 (1952). Also suitable are the
lipoxidases derived from Aspergillus parasiticus (ATCC 11906 ) and
Aspergillus flavus (ATCC 1003 ) which can be obtained from the
permanent collection of the American Type Culture Collection, 12301
Parklawn Drive, Rockville, Md.
The amount of lipoxidase employed in the compositions of the
invention is an amount which provides sufficient lipoxidase
enzymatic activity to alter or otherwise facilitate removal of the
stains and fatty soils normally encountered under laundry
situations. It will be appreciated that the amount of lipoxidase
employed will depend upon enzyme activity and purity or
concentration of the enzyme, conditions of pH and temperature, the
nature of the soils or stains to be removed, substrate
concentration and the like. As used herein, enzyme activity refers
to the property of an enzyme to attack or otherwise alter a
substrate molecule. Pure or substantially pure lipoxidases such as
those obtained by extraction from vegetable sources or from
microbiological sources are characterized by high enzymatic
activity and are employed in smaller amounts than the less active
lipoxidase-containing preparations having present additional
carrier or vehicle materials such as those described hereinbefore.
Pure lipoxidases are employed in an amount of from 0.01 percent to
2 percent and, preferably, from 0.1 percent to 1 percent by weight
of the compositions of the invention.
Lipoxidase-containing preparations wherein the lipoxidase is
combined with carriers or inert materials and comprises from 1
percent to 50 percent by weight of such preparation are normally
employed in a lesser amount of from 0.1 percent to 20 percent by
weight of the detergent compositions of the invention.
The lipoxidase component of the compositions of the invention,
whether incorporated as a pure or substantially pure component or
as a commercially available preparation, is employed in an amount
sufficient to incorporate from 0.01 percent to 2 percent lipoxidase
on a pure enzyme basis. This amount provides sufficient enzymatic
activity to facilitate the removal of soils and stains from
laundered goods.
Lipoxidase activity can be determined by known methods. For
example, oxygen uptake and measurement of peroxide formation by
thiocyanate method can be employed. Assay methods involving
destruction of a substrate such as carotene under prescribed
conditions can also be used. A suitable and preferred method is a
spectrophotometric assay method whereby a homogeneous substrate and
the products of the primary reaction are measured by ultraviolet
light absorption. Peroxide formation is proportional to time and to
enzyme concentration of wide ranges. Lipoxidase activity can be
determined by spectrophotometric assay according to the following
procedure.
To the main compartment of a side arm test tube is added 1.0 ml. of
substrate solution containing 2 mg. linoleic acid in borate buffer
at pH 9.0. The enzyme in 0.2 ml. borate buffer is pipetted into the
side arm, the tube is flushed with O.sub.2 and stoppered. After the
temperature has been adjusted to 20.degree. C. by placing in a
water bath, the tube is rocked to mix the contents, and at the end
of 2 minutes 2.0 ml. absolute ethanol are added to stop the
reaction. The mixture is diluted 10 times with 60 percent alcohol
and the absorption of light at 2340 A. is measured with a Beckman
spectrophotometer. Correction is made for the light absorption of
the enzyme preparation and the substrate. Activity of an enzyme or
enzyme-containing composition is expressed in units/mg. and is
determined according to the following relationship
activity = .DELTA.A/min..times.1,000/ mg. enzyme
wherein .DELTA. A is the change in absorption. Activity values
employed in the specification and claims herein refer to those
determined by the hereinbefore described method. This method is
described by R. T. Holman, et al., "The Enzymes," 1 st ed. Vol. II,
Part I, pp. 563-4 (1951).
The activity of suitable lipoxidases of the invention, determined
by the hereinbefore described spectrophotometric assay method, will
vary depending upon factors hereinbefore mentioned. For example,
pure lipoxidases may have an activity of 100,000 units/mg. or more.
The more readily available lipoxidase-containing preparations such
as the commercially available preparations derived from soybeans
range in activity from about 10,000 to 50,000 units/mg. These
compositions employed in the detergent compositions of the
invention in an amount by weight of from 0.1 percent to 20 percent
as hereinbefore described provide lipid soil and stain removal in
soaking and washing solutions.
The detergent compositions described herein are not restricted or
limited to any special physical form. They can, for example, be
solids such as granular compositions made by spray-drying or
coagglomeration processes or liquid or paste compositions. They can
be employed in the form of liquid compositions for application
directly as by spraying onto stained fabrics or added to
conventional detergent compositions. Granular compositions can be
employed to advantage as presoaking or washing compositions.
The lipoxidase-containing detergent compositions of the invention
can contain additional or minor amounts of materials which make the
compositions more effective or attractive. The usual detergent
adjuvants, diluents and additives can be employed, the following
being mentioned by way of example. Soluble sodium carboxymethyl
cellulose can be added in minor amounts to inhibit soil
redeposition. A tarnish inhibitor such as benzotriazole or
ethylenethiourea can also be added in amounts up to about 2
percent. Fluorescers, perfumes, dyes, suds builders, suds
depressors, bacteriostats and the like can be employed herein
without detracting from the advantageous properties of the
composition of the invention.
The detergent compositions of this invention can contain
water-soluble alkaline detergency builder salts, either of the
organic or inorganic types. The ratio of builder salts to organic
detergent is preferably from about 1:4 to about 20:1, more
preferably from about 0.7:1 to about 9:1. Examples of suitable
water-soluble inorganic alkaline detergency builder salts are
alkali metal carbonates, borates, phosphates, polyphosphates,
bicarbonates and silicates. Specific examples of such salts are
sodium and potassium tetraborates, bicarbonates, carbonates,
tripolyphosphates, pyrophosphates, orthophosphates, and
hexametaphosphates. Examples of suitable organic alkaline
detergency builder salts are: (1) Water-soluble
aminopolycarboxylates [e.g., sodium and potassium
ethylenediaminetetraacetates, nitrilo triacetates, and N-(2
-hydroxyethyl)-nitrilo diacetates]; (2 ) Water-soluble salts of
phytic acid (e.g., sodium and potassium phytates--see U.S. Pat. No.
2,739,942 ); (3 ) Water-soluble salts of ethane-1 -hydroxy-1,1
-diphosphonate (e.g., the trisodium and tripotassium salts--see
U.S. Pat. No. 3,159,581; (4 ) Water-soluble salts of methylene
diphosphonic acid (e.g., trisodium and tripotassium methylene
diphosphonate and the other salts described in the copending
application of Francis L. Diehl, Ser. No. 266,025, filed Mar. 18,
1963, now U.S. Pat. No. 3,213,030 ); (5 ) Water-soluble salts of
substituted methylene diphosphonic acids (e.g., trisodium and
tripotassium ethylidene, isopropylidene, benzylmethylidene, and
halomethylidene diphosphonates and the other substituted methylene
diphosphonates disclosed in U.S. Pat. No. 3,422,021 to Clarence H.
Roy, issued Jan. 14, 1969; (6 ) Water-soluble salts of
polycarboxylate polymers and copolymers as described in the
copending application of Francis L. Diehl, Ser. No. 269,359, filed
Apr. 1, 1963, now U.S. Pat. No. 3,260,153. (Specifically, a
polyelectrolyte builder material comprising a water-soluble salt of
a polymeric aliphatic polycarboxylic acid having the following
structural relationships as to the position of the carboxylate
groups and possessing the following prescribed physical
characteristics: (a) a minimum molecular weight of about 350
calculated as to the acid form; (b) an equivalent weight of about
50 to about 80 calculated as to acid form; (c) at least 45 mole
percent of the monomeric species having at least two carboxyl
radicals separated from each other by not more than two carbon
atoms; (d) the site of attachment to the polymer chain of any
carboxyl-containing radical being separated by not more than three
carbon atoms along the polymer chain from the site of attachment of
the next carboxyl-containing radical. Specific examples are
polymers of itaconic acid, aconitic acid, maleic acid, mesaconic
acid, fumaric acid, methylene malonic acid, and citraconic acid and
copolymers with themselves and other compatible monomers such as
ethylene), and (7) mixtures thereof.
Mixtures of organic and/or inorganic builders can be used and are
generally desirable. Especially preferred are the mixtures of
builders disclosed in U.S. Pat. No. 3,392,121 to Burton H. Gedge,
issued July 9, 1968, e.g., ternary mixtures of sodium
tripolyphosphate, sodium nitrilotriacetate, and trisodium ethane-1
-hydroxy-1,1 -diphosphonate.
It is preferred that the compositions of the invention contain in
addition certain proteolytic and amylolytic enzymes. The enzymes
include the alkaline, neutral and acid proteases and amylases which
aid materially the removal of proteinaceous and starchy soils and
stains from laundered textiles. The employment of proteolytic and
amylolytic enzymes in combination with the lipoxidases of the
present invention is preferred from the standpoint of facilitating
the removal of a broad spectrum of varied soils and stains. The
preferred proteolytic enzymes are the subtilisins obtained from the
bacterial organism, Bacillus subtilis and from Streptomyces
organisms. Preferred amylases are those derived from Bacillus
subtilis by fermentation methods known in the art. Examples of
proteases and amylases are described for example in U.S. Pat. No.
3,451,935 to Roald, et al., issued June 24, 1969. The proteases and
amylases are employed in an amount each of from 0.001 percent to 10
percent by weight, on a pure enzyme basis, of the enzyme-containing
detergent compositions of the invention.
The compositions of the invention preferably contain a
water-soluble inorganic electrolyte salt. It has been found that
the presence of such a salt preserves enzymatic activity in soaking
and washing solutions and in some instances enhances the detergency
properties of the composition. The presence of such salts inhibits
loss of lipoxidase activity thereby maximizing the oxidative and/or
altering effects of lipoxidase. Suitable electrolyte salts,
employed in an amount of from 1 percent to 50 percent by weight of
the compositions of the invention, include the water-soluble alkali
metal, alkaline earth metal and ammonium chlorides, sulfates,
borates, nitrates, acetates and the like. Examples include sodium
chloride, calcium chloride, potassium chloride, magnesium chloride,
sodium sulfate, odium phosphate, sodium borate, magnesium sulfate,
magnesium nitrate, sodium acetate, borax and the like.
According to a preferred embodiment of the invention, the
compositions of the invention contain a fatty acid component, or
lower alkyl ester thereof, characterized by having from 12 to 20
carbon atoms, and preferably 18 to 20 carbon atoms, in the fatty
acid moiety and having methylene-interrupted cis-, cis-double
bonds. Compounds having less than 12 carbons in the fatty acid
chain tend to be less detersive while those having more than 20
tend to be difficulty soluble in water. While applicants do not
wish to be bound by theory, the added fatty acid or derivative is
believed to act as a substrate which is converted by the action of
a lipoxidase and dissolved oxygen to a hydroperoxide specie. This
specie in turn is believed to aid the laundering process by
bleaching, decolorizing and/or removing soils and stains from
laundered goods or by preventing the redeposition of soils and
stains by modification of their color characteristics or affinity
for textile fabrics. The employment of added substrate to
facilitate stain removal by an oxidative mechanism, termed herein
coupled oxidation, makes possible the oxidation of components such
as carotene, chlorophyll, hemiglobin and lycopene which occur in
carrot, grass, blood and tomato stains and the like.
Suitable unsaturated fatty acids for purposes of coupled oxidation
are the fatty acids having from 12 to 20 carbon atoms and include
the readily available linoleic, linolenic and arachidonic acids.
Lower alkyl esters such as the C.sub.1 - to C.sub.3 -alkyl, e.g.,
methyl-, ethyl-, n -propyl- and isopropyl-, esters can also be
employed to advantage.
The compositions of the invention can additionally contain a
component which provides an available source of oxygen for the
lipoxidase of the invention. While the amount of oxygen or air
present in an agitated washing solution is sufficient to permit
stain removal by a lipoxidase, an added source of oxygen can e
incorporated into the compositions of the invention. Suitable
oxygen-yielding compounds are the inorganic peroxy compounds
including the peracids and persalts. Suitable examples are the
alkali metal (e.g. sodium and potassium) and ammonium perborates,
percarbonates, persulfates and perpyrophosphates. These compounds
are employed in an amount of from 1 percent to 30 percent or more
of the total composition. In addition to providing available oxygen
to facilitate lipoxidase catalysis, the presence of a peroxy
compound in some instances tends to reduce the amount of
redeposition of soils and stains onto a soaked or laundered fabric.
The presence of such peroxy compound for its improved
antiredeposition properties, thus, constitutes a preferred
embodiment.
Inorganic or enzymatic catalysts which facilitate evolution of
oxygen or degradation of the peroxy compound to thereby provide
available oxygen can also be employed. Suitable catalysts, employed
in an amount up to 1 percent, include catalase, manganese dioxide,
finely divided metals such as powdered copper or iron,
water-soluble halites and hypohalites as, for example, sodium
chlorite and sodium hypochlorite, molybdates and hemin-type
compounds. Preferred herein is catalase.
The compositions of the invention are illustrated by the examples
which follow. The examples are not to be regarded as limiting the
invention. All amounts, percentages and ratios in the specification
and claims are by weight unless otherwise indicated.
EXAMPLE I
The soil removal properties of lipoxidase-containing detergent
compositions of the invention were evaluated by a detergency test
termed herein the Facial Swatch Test. This test involves a
procedure of soiling a cloth swatch with natural soil by attaching
a swatch (about 5 inches by 5 inches) to the plunger cup of an
electric vibrator massager. Two swatches are soiled from an
individual subject by massaging the right and left halves of the
face respectively of 1 minute each. The soiled swatches are then
randomized into groups to statistically provide equal numbers of
left and right samples. Groups of six swatches each are then
subjected to soaking and washing treatments in the compositions to
be evaluated. Each group of swatches is subjected to four cycles,
each cycle including soiling, soaking and washing. Whiteness
variations are then measured.
The detergent compositions tested were soaking solutions having the
components and soaking conditions described in table I. Amounts
expressed in table I are weight percent.
TABLE I
Components Soaking composition
__________________________________________________________________________
A B C 3 -(N,N-dimethyl-N-hexadecyl ammoniol 0.05 0.05 0.05 -propane
sulfonate Boric Acid, H.sub.3 BO.sub.3 0.31 0.31 0.31 Lipoxidase
preparation (containing 0.01 0.01 0.01 about 10 % soybean
lipoxidase and having an acitivity of about 10,000 units/mg.) Water
Balance to 100 %
Soaking conditions pH 9 7.5 7.5 Temperature (.degree.F.) 80 80 80
U.S. hardness (grains/gallon) 0 1.5 5 Soaking time (hours) 4 4 4
__________________________________________________________________________
Following each soaking, the swatches were rinsed twice in
85.degree. F. water (0 grain/gallon hardness). Each washing
treatment was conducted by washing the swatches in a mechanical
washer equipped with an agitator and which simulates a home washing
machine. The washing composition employed was a conventional built
anionic-containing detergent formulation employed in an amount of
1.75 grams/1.5 gallon water (equivalent to 1 cup/17 gallons water).
Each washing step (10 minutes) was conducted at 140.degree. F., pH
10 in 0 grain/gallon water. The detergent composition employed in
the washing step was as follows:
Ingredient Parts by weight
__________________________________________________________________________
A mixture of 55 % sodium tallow 17.5 alkyl sulfate and 45 % sodium
linear alkyl benzene sulfonate wherein the alkyl chain dis-
tribution is 16 % C.sub.11, 27 % C.sub.12, 35 % C.sub.13, and 22 %
C.sub.14. Sodium tripolyphosphate 50.0 Sodium silicate having an
SiO.sub.2 :Na.sub.2 O 6.0 ratio of 1.8:1 Coconut fatty acid ammonio
amide 2.5 Sodium sulfate 14.0 Water 10.0
__________________________________________________________________________
Following the washing of the swatches, they were rinsed and dried
and then whiteness measurements were made with a commercially
available photoelectric reflectometer, i.e., a Hunter Color and
Color Difference meter (Model D25 ) manufactured by Hunter
Associates Laboratory, Fairfax, Va. This instrument is designed to
distinguish color differences and operates on the tristimulus
colorimeter principle. According to this principle, a 45.degree.
diffuse reflectance of an incident light beam on a test specimen is
measured through a combination of green, blue and amber filters.
The electrical circuitry of the instrument is so designed that
lightness and chromaticity values for the test specimen are read
directly. The departure from white (MgO being taken as a standard
white) of the test specimen is calculated by introducing the
lightness and chromaticity values so obtained into a complex
formula supplied by the manufacturer. An evaluation of relative
whiteness performance compared to a standard treatment is thus
obtained for the test formulations.
The measurements obtained by the foregoing procedure are given
below in table II. The greater the Hunter value, the greater the
whiteness level. A statistically significant difference is
0.24.
The measurements obtained by the foregoing procedure and presented
in table II are compared with those obtained from swatches which
were subjected to two control treatments. In the case of Control-1,
swatches were treated as described above except that no soaking
step was employed, i.e., the soiled swatches were washed in the
conventional anionic-containing detergent formulation. In the case
of Control-2, the swatches were soaked and laundered as described,
the soaking being conducted in the same composition utilized in the
washing step. The soaking step was conducted in a solution of the
detergent composition of 1.75 grams/1.5 gallon water; 0 gram
hardness; 4 hours; 80.degree. F.; and pH 9.6.
---------------------------------------------------------------------------
---------------------------------------------------------------------------
table ii
treatment Hunter whiteness
__________________________________________________________________________
Composition A 0.24 Composition B 0.21 Composition C 0.05 Control-1
-0.09 Control-2 0.00
__________________________________________________________________________
It can be seen from the foregoing table that soaking with
Compositions A, B and C of the invention effects significant soil
removal compared to Controls 1 and 2. Extraction (with chloroform
and methanol) of the fabrics after the last washing step confirmed
the greater soil removal obtained by soaking in Compositions A, B
and C. A lesser amount of soil was extracted from swatches treated
with Compositions A, B or C than was extracted where the Control-1
and -2 treatments were employed.
EXAMPLE II
Muslin swatches were stained by passing strips of muslin through a
padding bath containing the staining solution, passing the muslin
through wringers and a drying oven. The stained strip was cut into
5 .times. 51/4 inch swatches. These swatches were laundered in an
automatic miniature washer at 125.degree. F. in water of 7 grain
hardness for 10 minutes. The composition being tested was used to
wash a soiled load consisting of three swatches each of (1 ) gravy
(a substrate sensitive to proteolytic activity and having a content
of cis-, cis- polyunsaturated component), (2 ) spinach (a substrate
primarily sensitive to proteolytic activity), and (3 ) milk
substitute (a substrate primarily sensitive to proteolytic
activity), and (4 ) licorice (a substrate primarily sensitive to
amylolytic activity) stained muslin in the presence of two
untreated terrycloth swatches added to provide bulk to the
washload.
The control composition used for a comparison was a conventional
built anionic-containing detergent formulation and was employed in
an amount of 6.75 grams/11/2 gal. water (equivalent to 1 cup/17
gal. water). The lipoxidase to be evaluated (0.01 percent by weight
of the washing solution) was added in the form of a water solution
to provide the desired level of enzyme. The swatches were washed,
dried, and ironed and their whiteness levels were measured
employing a Hunter Color-Difference Meter described hereinbefore.
The control detergent for comparison purposes was the
anionic-containing composition described in example I. The
lipoxidase preparation was a commercially available lipoxidase
preparation containing about 20 percent soybean lipoxidase and
having an activity of about 18,000 units/mg.
Results of these stain tests are tabulated in table III as follows:
---------------------------------------------------------------------------
---------------------------------------------------------------------------
TABLE
III Hunter whiteness Gravy Spinach Milk Licorice Stain Stain Stain
Stain
__________________________________________________________________________
Control composition 75.56 37.03 105.43 94.93 Control composition
80.26 36.63 103.30 94.19 + lipoxidase +4.70 -0.40 -2.13 -0.74
__________________________________________________________________________
The effectiveness of the lipoxidase in removing gravy stains is
readily apparent. As respects the gravy stain, a difference of 1.91
Hunter Whiteness units is a visually observable difference; with
spinach stain, an observable difference is 2.47 units; with milk
stain, 5.91 units; and with licorice stains, 2.76 units.
EXAMPLE III
The stain-removing properties of a lipoxidase-containing
composition of the invention were further evaluated by employing a
test involving 10 stains and four fabrics. Duplicate swatches (16.5
cm..times.22 cm.) of cotton, Dacron, nylon and a Dacron/polyester
blend were stained with ten staining materials, each of the fabric
swatches containing one stain from each of such materials. The
following stains were placed onto the fabric swatches: felt-tipped
pen ink (green); ballpoint pen ink (blue); liquid shoe polish
(brown); dirty motor oil; mustard; chocolate; French salad
dressing; lipstick; bacon grease; and grass. Four stained swatches
(four fabrics) were soaked in a composition identical to
Composition A of example I except that the lipoxidase preparation
was a commercially available preparation containing about 35
percent soybean lipoxidase and having an activity of about 35,000
units/mg. Four duplicate swatches were soaked under identical
conditions in a control composition identical to Composition A but
containing no lipoxidase. In each instance soaking was conducted
for 4 hours at 30.degree. C. in water of 0 grain/gallon U.S.
hardness and at a pH of 9.0. Following the soaking period, the
swatches were wrung out by hand and washed in an automatic
miniature washer at 60.degree. C. for 10 minutes in water of 0
grain hardness at a pH of 10. The washing solution was a 0.15
percent solution of the anionic-containing detergent formulation
described in examples I and II. The laundered swatches were rinsed,
dried and ironed and their stain removal properties visually
measured by a panel of three judges. Each stain on each of the
stained and laundered fabrics was compared by each of the three
judges with standard stained swatches having on each type of fabric
a gradation of staining degrees ranging from zero (no stain) to 10
(corresponding to the degree of staining of the test swatches prior
to treatment). The values reported in table IV represent an average
of the three visual grades accorded each stain. A difference of one
unit is considered to represent a visually detectable difference.
##SPC1##
As can be readily seen from the data of table IV, stains having a
content of polyunsaturates, e.g., French salad dressing, are
removed from textile materials by lipoxidase-containing detergent
compositions. Stain removal was also observed in the case of the
treatment of certain fabrics with stains which normally contain
only minor amounts, if any, of polyunsaturated components. Thus,
appreciable mustard stain removal from cotton and Dacron swatches
is observed from the data of table IV. Similarly, stain removal is
observed in the case of cotton, Dacron and nylon swatches stained
with felt-tipped pen ink.
Granular detergent washing compositions having excellent soil and
stain-removing properties in the laundering of textile goods have
the following compositions:
1 2 3
__________________________________________________________________________
Sodium C.sub.12 -alkyl benzenesulfonate 31.8 32.4 35.0 (derived
from tetrapropylene) Sodium tripolyphosphate 30.7 22.7 24.5 Sodium
silicate 6.1 6.2 6.7 Sodium sulfate 8.8 9.0 9.7 Tetrasodium
pyrophosphate (Na.sub.4 P.sub.2 O.sub.7 ) 6.8 6.8 6.8 Alcalase
(pyroteolytic enzyme) 0.72 0.72 0.72 Monsanto DA-10 (mixture of
proteolytic 0.72 0.72 0.72 lytic and amylolytic enzymes) Soybean
lipoxidase preparation (having 1 5 Water (moisture) 8.7 8.8 9.5
Miscellaneous detergent additives Balance to 100%
When in example IV any of the following detergents are substituted
for the sodium alkyl benzene sulfonate detergent substantially
similar results are obtained: sodium coconut soap; sodium linear
alkyl benzene sulfonate having a chain length distribution of 10
percent C.sub.10 , 30 percent C.sub.11 , 35 percent C.sub.12 , 16.5
C.sub.13 , 8 percent C.sub.14 and 0.5 C.sub.15 ; sodium tallow
alkyl sulfate; the condensation product of one mole of coconut
alcohol with 5 moles of ethylene oxide; the condensation product of
one mole of octyl phenol with 20 moles of ethylene oxide; the
condensation product of one mole of coconut alcohol with 20 moles
of ethylene oxide; dimethylhydroxydodecylamine oxide;
cetyldimethylphosphine oxide; sodium-3 -dodecylaminopropionate; and
3-(N,N-dimethyl-N-decylammonio)-2 -hydroxypropane-1 -sulfonate.
EXAMPLE V
An excellent presoaking composition effective in the removal of
proteinaceous and starchy stains and stains having a content of
cis-, cis-polyunsaturates has the following composition in parts by
weight:
Ethoxylated tallow fatty alcohol 30 moles ethylene oxide per mole
of alcohol 4.0 Sodium tripolyphosphate 69.3 Sodium perborate 25.0
Alcalase (proteolytic enzyme) 0.55 Maxatase (proteolytic enzyme)
0.55 Monsanto DA-10 (mixture of proteo- lytic and amyolytic
enzymes) 0.10 Soybean lipoxidase preparation (having 3 an activity
of 39,000 units/mg.) Miscellaneous (brightener, perfume, 0.52 dye,
etc.)
EXAMPLE VI
A granular presoak detergent composition having the following
components in parts by weight provides soil- and stain-removal
properties and improved anti-redeposition properties:
3 -(N,N-dimethyl-N-hexadecylammonio)- propanesulfonate 12.6 Sodium
sulfate 12.6 Sodium tripolyphosphate 37.5 Soybean lipoxidase
preparation (having 6.3 an activity of 50,000 units/mg.) Linoleic
acid 17.6 Sodium perborate, NaBO.sub.3 .sup.. 2 O 3.1 Catalase 0.02
Moisture 10.0
* * * * *